WO2011014210A2 - Liquid phosphite compositions having different alkyl groups - Google Patents
Liquid phosphite compositions having different alkyl groups Download PDFInfo
- Publication number
- WO2011014210A2 WO2011014210A2 PCT/US2009/060213 US2009060213W WO2011014210A2 WO 2011014210 A2 WO2011014210 A2 WO 2011014210A2 US 2009060213 W US2009060213 W US 2009060213W WO 2011014210 A2 WO2011014210 A2 WO 2011014210A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphite
- composition
- alkyl
- butyl
- phenol
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 311
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 title claims description 295
- 125000000217 alkyl group Chemical group 0.000 title claims description 87
- 239000007788 liquid Substances 0.000 title claims description 53
- -1 alkylaryl phosphites Chemical class 0.000 claims description 168
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 65
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims description 40
- 239000003381 stabilizer Substances 0.000 claims description 33
- 150000002989 phenols Chemical class 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 150000001412 amines Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 22
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 19
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 17
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 239000002952 polymeric resin Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 229920003002 synthetic resin Polymers 0.000 claims description 13
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 12
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- 239000004611 light stabiliser Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000000087 stabilizing effect Effects 0.000 claims description 6
- 150000002443 hydroxylamines Chemical class 0.000 claims description 5
- ZMPODEGAECKFEA-UHFFFAOYSA-N tris[2,4-bis(2-methylbutan-2-yl)phenyl] phosphite Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)CC)C(C)(C)CC)OC1=CC=C(C(C)(C)CC)C=C1C(C)(C)CC ZMPODEGAECKFEA-UHFFFAOYSA-N 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043276 diisopropanolamine Drugs 0.000 claims description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 79
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 42
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 37
- 239000007983 Tris buffer Substances 0.000 description 29
- 229920001577 copolymer Polymers 0.000 description 29
- 150000001336 alkenes Chemical class 0.000 description 28
- 235000013824 polyphenols Nutrition 0.000 description 28
- 239000003054 catalyst Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229920002857 polybutadiene Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 9
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 8
- 229920001684 low density polyethylene Polymers 0.000 description 8
- 239000004702 low-density polyethylene Substances 0.000 description 8
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 229920000092 linear low density polyethylene Polymers 0.000 description 7
- 239000004707 linear low-density polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 6
- 229920000515 polycarbonate Polymers 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- 229920006324 polyoxymethylene Polymers 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 229920000915 polyvinyl chloride Polymers 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 150000003739 xylenols Chemical class 0.000 description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- KPZBEZVZFBDKCG-UHFFFAOYSA-N 2,4-dibutylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1 KPZBEZVZFBDKCG-UHFFFAOYSA-N 0.000 description 4
- GKPNMUZVXNHWPX-UHFFFAOYSA-N 2,4-dipentylphenol Chemical compound CCCCCC1=CC=C(O)C(CCCCC)=C1 GKPNMUZVXNHWPX-UHFFFAOYSA-N 0.000 description 4
- CYYZDBDROVLTJU-UHFFFAOYSA-N 4-n-Butylphenol Chemical compound CCCCC1=CC=C(O)C=C1 CYYZDBDROVLTJU-UHFFFAOYSA-N 0.000 description 4
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical compound CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 description 4
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- LGUHMLGBHYNDST-UHFFFAOYSA-N [2,4-ditert-butyl-3,5-bis(4-tert-butylphenyl)phenyl] dihydrogen phosphite Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC(OP(O)O)=C(C(C)(C)C)C(C=2C=CC(=CC=2)C(C)(C)C)=C1C(C)(C)C LGUHMLGBHYNDST-UHFFFAOYSA-N 0.000 description 4
- SSIISAPMNOFEPS-UHFFFAOYSA-N [4-tert-butyl-2,3-bis(2,4-ditert-butylphenyl)phenyl] dihydrogen phosphite Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1C1=C(OP(O)O)C=CC(C(C)(C)C)=C1C1=CC=C(C(C)(C)C)C=C1C(C)(C)C SSIISAPMNOFEPS-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229920002988 biodegradable polymer Polymers 0.000 description 4
- 239000004621 biodegradable polymer Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000000486 o-cresyl group Chemical group [H]C1=C([H])C(O*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 125000000552 p-cresyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1O*)C([H])([H])[H] 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 125000005561 phenanthryl group Chemical group 0.000 description 4
- 230000006641 stabilisation Effects 0.000 description 4
- 238000011105 stabilization Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- SAAMKFBWYWFBNY-UHFFFAOYSA-N tris(4-tert-butylphenyl) phosphite Chemical compound C1=CC(C(C)(C)C)=CC=C1OP(OC=1C=CC(=CC=1)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1 SAAMKFBWYWFBNY-UHFFFAOYSA-N 0.000 description 4
- XGYJGDTVZLADOZ-UHFFFAOYSA-N tris[4-(2-methylbutan-2-yl)phenyl] phosphite Chemical compound C1=CC(C(C)(C)CC)=CC=C1OP(OC=1C=CC(=CC=1)C(C)(C)CC)OC1=CC=C(C(C)(C)CC)C=C1 XGYJGDTVZLADOZ-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- KEUMBYCOWGLRBQ-UHFFFAOYSA-N 2,4-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC=C(O)C(C(C)C)=C1 KEUMBYCOWGLRBQ-UHFFFAOYSA-N 0.000 description 3
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 3
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 3
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Substances CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- VIBRKRRPOGOBCE-UHFFFAOYSA-N [2,3-bis[2,4-bis(2-methylbutan-2-yl)phenyl]-4-(2-methylbutan-2-yl)phenyl] dihydrogen phosphite Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC=C1C1=C(OP(O)O)C=CC(C(C)(C)CC)=C1C1=CC=C(C(C)(C)CC)C=C1C(C)(C)CC VIBRKRRPOGOBCE-UHFFFAOYSA-N 0.000 description 3
- HVLYNTYKOVZACQ-UHFFFAOYSA-N [2,4-bis(2-methylbutan-2-yl)-3,5-bis[4-(2-methylbutan-2-yl)phenyl]phenyl] dihydrogen phosphite Chemical compound C1=CC(C(C)(C)CC)=CC=C1C1=CC(OP(O)O)=C(C(C)(C)CC)C(C=2C=CC(=CC=2)C(C)(C)CC)=C1C(C)(C)CC HVLYNTYKOVZACQ-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- ITUWQZXQRZLLCR-UHFFFAOYSA-N n,n-dioctadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCN(O)CCCCCCCCCCCCCCCCCC ITUWQZXQRZLLCR-UHFFFAOYSA-N 0.000 description 3
- 150000002816 nickel compounds Chemical class 0.000 description 3
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920001084 poly(chloroprene) Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical class C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 2
- XYXJKPCGSGVSBO-UHFFFAOYSA-N 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1CN1C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C(=O)N(CC=2C(=C(O)C(=CC=2C)C(C)(C)C)C)C1=O XYXJKPCGSGVSBO-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- VTFXHGBOGGGYDO-UHFFFAOYSA-N 2,4-bis(dodecylsulfanylmethyl)-6-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCCCCCC)=C1 VTFXHGBOGGGYDO-UHFFFAOYSA-N 0.000 description 2
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 2
- XQESJWNDTICJHW-UHFFFAOYSA-N 2-[(2-hydroxy-5-methyl-3-nonylphenyl)methyl]-4-methyl-6-nonylphenol Chemical compound CCCCCCCCCC1=CC(C)=CC(CC=2C(=C(CCCCCCCCC)C=C(C)C=2)O)=C1O XQESJWNDTICJHW-UHFFFAOYSA-N 0.000 description 2
- SZAQZZKNQILGPU-UHFFFAOYSA-N 2-[1-(2-hydroxy-3,5-dimethylphenyl)-2-methylpropyl]-4,6-dimethylphenol Chemical compound C=1C(C)=CC(C)=C(O)C=1C(C(C)C)C1=CC(C)=CC(C)=C1O SZAQZZKNQILGPU-UHFFFAOYSA-N 0.000 description 2
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 2
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 2
- QFCGHEBLSUPGPF-UHFFFAOYSA-N 4-methyl-2,6-bis(1-phenylethyl)phenol Chemical compound C=1C(C)=CC(C(C)C=2C=CC=CC=2)=C(O)C=1C(C)C1=CC=CC=C1 QFCGHEBLSUPGPF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Chemical class 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- SXAKWNXJBMPVDZ-UHFFFAOYSA-N amino propaneperoxoate Chemical compound C(CC)(=O)OON SXAKWNXJBMPVDZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000006078 metal deactivator Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- IXHMTDIIQNIVBN-UHFFFAOYSA-N n'-(2,2-dihydroxyethyl)oxamide Chemical compound NC(=O)C(=O)NCC(O)O IXHMTDIIQNIVBN-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229940117969 neopentyl glycol Drugs 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000007970 thio esters Chemical class 0.000 description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- VAURMQDVZLSKAA-UHFFFAOYSA-N tris(4-propan-2-ylphenyl) phosphite Chemical compound C1=CC(C(C)C)=CC=C1OP(OC=1C=CC(=CC=1)C(C)C)OC1=CC=C(C(C)C)C=C1 VAURMQDVZLSKAA-UHFFFAOYSA-N 0.000 description 2
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- KJYSXRBJOSZLEL-UHFFFAOYSA-N (2,4-ditert-butylphenyl) 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 KJYSXRBJOSZLEL-UHFFFAOYSA-N 0.000 description 1
- HQEPZWYPQQKFLU-UHFFFAOYSA-N (2,6-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(O)=C1C(=O)C1=CC=CC=C1 HQEPZWYPQQKFLU-UHFFFAOYSA-N 0.000 description 1
- NNUNDQZDGVWLPX-UHFFFAOYSA-N (2-hydroxy-4-propoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCC)=CC=C1C(=O)C1=CC=CC=C1 NNUNDQZDGVWLPX-UHFFFAOYSA-N 0.000 description 1
- ATLWFAZCZPSXII-UHFFFAOYSA-N (2-octylphenyl) 2-hydroxybenzoate Chemical compound CCCCCCCCC1=CC=CC=C1OC(=O)C1=CC=CC=C1O ATLWFAZCZPSXII-UHFFFAOYSA-N 0.000 description 1
- WBSRIXCTCFFHEF-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methyl-ethoxyphosphinic acid Chemical compound CCOP(O)(=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WBSRIXCTCFFHEF-UHFFFAOYSA-N 0.000 description 1
- ZEBMSMUPGIOANU-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl)methylphosphonic acid Chemical class CC(C)(C)C1=CC(CP(O)(O)=O)=CC(C(C)(C)C)=C1O ZEBMSMUPGIOANU-UHFFFAOYSA-N 0.000 description 1
- JAFUHGPESJSRJX-UHFFFAOYSA-N (4-ethoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCC)=CC=C1C(=O)C1=CC=CC=C1 JAFUHGPESJSRJX-UHFFFAOYSA-N 0.000 description 1
- GOZHNJTXLALKRL-UHFFFAOYSA-N (5-benzoyl-2,4-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(O)=C(C(=O)C=2C=CC=CC=2)C=C1C(=O)C1=CC=CC=C1 GOZHNJTXLALKRL-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- DSSWUSNSRXWFBO-UHFFFAOYSA-N 1-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)azepan-2-one Chemical compound C1C(C)(C)N(O)C(C)(C)CC1N1C(=O)CCCCC1 DSSWUSNSRXWFBO-UHFFFAOYSA-N 0.000 description 1
- JDLQSLMTBGPZLW-UHFFFAOYSA-N 1-(1-hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC(O)N1C(C)(C)CC(O)CC1(C)C JDLQSLMTBGPZLW-UHFFFAOYSA-N 0.000 description 1
- MQQKTNDBASEZSD-UHFFFAOYSA-N 1-(octadecyldisulfanyl)octadecane Chemical compound CCCCCCCCCCCCCCCCCCSSCCCCCCCCCCCCCCCCCC MQQKTNDBASEZSD-UHFFFAOYSA-N 0.000 description 1
- BXGUTTFOYJLXCS-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethyl-4-phenylmethoxypiperidine Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OCC1=CC=CC=C1 BXGUTTFOYJLXCS-UHFFFAOYSA-N 0.000 description 1
- TUYBEVLJKZQJPO-UHFFFAOYSA-N 19-(3,5-ditert-butyl-4-hydroxyphenyl)heptatriacontan-19-ylphosphonic acid Chemical compound CCCCCCCCCCCCCCCCCCC(CCCCCCCCCCCCCCCCCC)(P(O)(O)=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 TUYBEVLJKZQJPO-UHFFFAOYSA-N 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- LXWZXEJDKYWBOW-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O LXWZXEJDKYWBOW-UHFFFAOYSA-N 0.000 description 1
- YMSHDOYMWLYKBN-UHFFFAOYSA-N 2,4-ditert-butylphenol;tris(2,4-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1.CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C YMSHDOYMWLYKBN-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- LKALLEFLBKHPTQ-UHFFFAOYSA-N 2,6-bis[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=CC(C)=CC=1CC1=CC(C)=CC(C(C)(C)C)=C1O LKALLEFLBKHPTQ-UHFFFAOYSA-N 0.000 description 1
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 1
- FRAQIHUDFAFXHT-UHFFFAOYSA-N 2,6-dicyclopentyl-4-methylphenol Chemical compound OC=1C(C2CCCC2)=CC(C)=CC=1C1CCCC1 FRAQIHUDFAFXHT-UHFFFAOYSA-N 0.000 description 1
- JBYWTKPHBLYYFJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JBYWTKPHBLYYFJ-UHFFFAOYSA-N 0.000 description 1
- SCXYLTWTWUGEAA-UHFFFAOYSA-N 2,6-ditert-butyl-4-(methoxymethyl)phenol Chemical compound COCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SCXYLTWTWUGEAA-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
- LBOGPIWNHXHYHN-UHFFFAOYSA-N 2-(2-hydroxy-5-octylphenyl)sulfanyl-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(SC=2C(=CC=C(CCCCCCCC)C=2)O)=C1 LBOGPIWNHXHYHN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FDAWMTSIMDNWMP-UHFFFAOYSA-N 2-[(dibenzylamino)oxymethyl]icosanoic acid Chemical compound C=1C=CC=CC=1CN(OCC(CCCCCCCCCCCCCCCCCC)C(O)=O)CC1=CC=CC=C1 FDAWMTSIMDNWMP-UHFFFAOYSA-N 0.000 description 1
- BVNPSIYFJSSEER-UHFFFAOYSA-H 2-[2-(1,3,2-benzodioxastibol-2-yloxy)phenoxy]-1,3,2-benzodioxastibole Chemical compound O([Sb]1Oc2ccccc2O1)c1ccccc1O[Sb]1Oc2ccccc2O1 BVNPSIYFJSSEER-UHFFFAOYSA-H 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- BWKXNZIUYIXMCM-UHFFFAOYSA-N 2-[2-hydroxy-5-(2,2,4-trimethylpentan-3-yl)phenyl]sulfanyl-4-(2,2,4-trimethylpentan-3-yl)phenol Chemical compound CC(C)C(C(C)(C)C)C1=CC=C(O)C(SC=2C(=CC=C(C=2)C(C(C)C)C(C)(C)C)O)=C1 BWKXNZIUYIXMCM-UHFFFAOYSA-N 0.000 description 1
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 description 1
- XUQNLOIVFHUMTR-UHFFFAOYSA-N 2-[[2-hydroxy-5-nonyl-3-(1-phenylethyl)phenyl]methyl]-4-nonyl-6-(1-phenylethyl)phenol Chemical compound OC=1C(C(C)C=2C=CC=CC=2)=CC(CCCCCCCCC)=CC=1CC(C=1O)=CC(CCCCCCCCC)=CC=1C(C)C1=CC=CC=C1 XUQNLOIVFHUMTR-UHFFFAOYSA-N 0.000 description 1
- VZBKFSFRDBYEDW-UHFFFAOYSA-N 2-[[2-hydroxy-5-nonyl-3-(2-phenylpropan-2-yl)phenyl]methyl]-4-nonyl-6-(2-phenylpropan-2-yl)phenol Chemical compound OC=1C(C(C)(C)C=2C=CC=CC=2)=CC(CCCCCCCCC)=CC=1CC(C=1O)=CC(CCCCCCCCC)=CC=1C(C)(C)C1=CC=CC=C1 VZBKFSFRDBYEDW-UHFFFAOYSA-N 0.000 description 1
- KDHQJFCGOUFSRE-UHFFFAOYSA-N 2-[bis[carboxy-(2,2,6,6-tetramethylpiperidin-1-yl)methyl]amino]-2-(2,2,6,6-tetramethylpiperidin-1-yl)acetic acid Chemical compound CC1(CCCC(N1C(C(=O)O)N(C(C(=O)O)N2C(CCCC2(C)C)(C)C)C(C(=O)O)N3C(CCCC3(C)C)(C)C)(C)C)C KDHQJFCGOUFSRE-UHFFFAOYSA-N 0.000 description 1
- HHPDFYDITNAMAM-UHFFFAOYSA-N 2-[cyclohexyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C1CCCCC1 HHPDFYDITNAMAM-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- OMCYEZUIYGPHDJ-UHFFFAOYSA-N 2-hydroxy-N-[(2-hydroxyphenyl)methylideneamino]benzamide Chemical compound OC1=CC=CC=C1C=NNC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-UHFFFAOYSA-N 0.000 description 1
- UORSDGBOJHYJLV-UHFFFAOYSA-N 2-hydroxy-n'-(2-hydroxybenzoyl)benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)C1=CC=CC=C1O UORSDGBOJHYJLV-UHFFFAOYSA-N 0.000 description 1
- WBJWXIQDBDZMAW-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carbonyl chloride Chemical class C1=CC=CC2=C(C(Cl)=O)C(O)=CC=C21 WBJWXIQDBDZMAW-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- NZRSIUKTGLRKIQ-UHFFFAOYSA-N 2-tert-butyl-4-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 NZRSIUKTGLRKIQ-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- RKLRVTKRKFEVQG-UHFFFAOYSA-N 2-tert-butyl-4-[(3-tert-butyl-4-hydroxy-5-methylphenyl)methyl]-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 RKLRVTKRKFEVQG-UHFFFAOYSA-N 0.000 description 1
- MOOLTXVOHPAOAP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-methyl-1-sulfanylpentadecyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(S)(CC(C)CCCCCCCCCCCC)C1=CC(C(C)(C)C)=C(O)C=C1C MOOLTXVOHPAOAP-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- PHOPRYXKLUFKFG-UHFFFAOYSA-N 2-tert-butyl-4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C(C(C)(C)C)=C1 PHOPRYXKLUFKFG-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- UHLYPUYAVHSKBN-UHFFFAOYSA-N 2-tert-butyl-6-[1-[3-tert-butyl-2-hydroxy-5-(2-methylpropyl)phenyl]ethyl]-4-(2-methylpropyl)phenol Chemical compound CC(C)(C)C1=CC(CC(C)C)=CC(C(C)C=2C(=C(C=C(CC(C)C)C=2)C(C)(C)C)O)=C1O UHLYPUYAVHSKBN-UHFFFAOYSA-N 0.000 description 1
- GUCMKIKYKIHUTM-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperazin-1-yl)ethyl]piperazin-2-one Chemical compound O=C1C(C)(C)NC(C)(C)CN1CCN1C(=O)C(C)(C)NC(C)(C)C1 GUCMKIKYKIHUTM-UHFFFAOYSA-N 0.000 description 1
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 1
- YLUZWKKWWSCRSR-UHFFFAOYSA-N 3,9-bis(8-methylnonoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCC(C)C)OCC21COP(OCCCCCCCC(C)C)OC2 YLUZWKKWWSCRSR-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- KJEKRODBOPOEGG-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]propyl]propanamide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 KJEKRODBOPOEGG-UHFFFAOYSA-N 0.000 description 1
- BYMLDFIJRMZVOC-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O BYMLDFIJRMZVOC-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- XVDXXIFPRDPQBG-UHFFFAOYSA-N 4-(2,2,3-trimethylazepane-1-carbonyl)benzamide Chemical compound CC1(C)C(C)CCCCN1C(=O)C1=CC=C(C(N)=O)C=C1 XVDXXIFPRDPQBG-UHFFFAOYSA-N 0.000 description 1
- YDPBRVDCNBTDSA-UHFFFAOYSA-N 4-[1,1-bis(3-tert-butyl-4-hydroxy-5-methylphenyl)butyl]-2-tert-butyl-6-methylphenol Chemical compound C=1C(C)=C(O)C(C(C)(C)C)=CC=1C(C=1C=C(C(O)=C(C)C=1)C(C)(C)C)(CCC)C1=CC(C)=C(O)C(C(C)(C)C)=C1 YDPBRVDCNBTDSA-UHFFFAOYSA-N 0.000 description 1
- WTWGHNZAQVTLSQ-UHFFFAOYSA-N 4-butyl-2,6-ditert-butylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 WTWGHNZAQVTLSQ-UHFFFAOYSA-N 0.000 description 1
- OVARTXYXUGDZHU-UHFFFAOYSA-N 4-hydroxy-n-phenyldodecanamide Chemical compound CCCCCCCCC(O)CCC(=O)NC1=CC=CC=C1 OVARTXYXUGDZHU-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LZAIWKMQABZIDI-UHFFFAOYSA-N 4-methyl-2,6-dioctadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC(C)=CC(CCCCCCCCCCCCCCCCCC)=C1O LZAIWKMQABZIDI-UHFFFAOYSA-N 0.000 description 1
- JJHKARPEMHIIQC-UHFFFAOYSA-N 4-octadecoxy-2,6-diphenylphenol Chemical compound C=1C(OCCCCCCCCCCCCCCCCCC)=CC(C=2C=CC=CC=2)=C(O)C=1C1=CC=CC=C1 JJHKARPEMHIIQC-UHFFFAOYSA-N 0.000 description 1
- JKTORXLUQLQJCM-UHFFFAOYSA-N 4-phosphonobutylphosphonic acid Chemical compound OP(O)(=O)CCCCP(O)(O)=O JKTORXLUQLQJCM-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical class CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- MWJWZXNNLRNCFL-UHFFFAOYSA-N 4-tert-butyl-2-(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)C)=CC=C1O MWJWZXNNLRNCFL-UHFFFAOYSA-N 0.000 description 1
- SXIUYTXSDRIIIQ-UHFFFAOYSA-N 6-methylheptyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)-2-sulfanylpropanoate Chemical compound CC(C)CCCCCOC(=O)C(S)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SXIUYTXSDRIIIQ-UHFFFAOYSA-N 0.000 description 1
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 1
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ZRZFCHCIMYNMST-UHFFFAOYSA-L C=1([O-])C([O-])=CC=CC1.[Zn+2] Chemical compound C=1([O-])C([O-])=CC=CC1.[Zn+2] ZRZFCHCIMYNMST-UHFFFAOYSA-L 0.000 description 1
- JFCVYJORFPTJOB-UHFFFAOYSA-N CC(C)C1=CC(C(C)C)=CC=C1C1=C(OP(O)O)C=CC(C(C)C)=C1C1=CC=C(C(C)C)C=C1C(C)C Chemical compound CC(C)C1=CC(C(C)C)=CC=C1C1=C(OP(O)O)C=CC(C(C)C)=C1C1=CC=C(C(C)C)C=C1C(C)C JFCVYJORFPTJOB-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VSRRGPPFTIJBJG-UHFFFAOYSA-N DL-4-hydroxy stearic acid Chemical compound CCCCCCCCCCCCCCC(O)CCC(O)=O VSRRGPPFTIJBJG-UHFFFAOYSA-N 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000871495 Heeria argentea Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- KIEOSPBEUABEFO-UHFFFAOYSA-N [2,4-dipropyl-3,5-bis(4-propylphenyl)phenyl] dihydrogen phosphite Chemical compound C1=CC(CCC)=CC=C1C1=CC(OP(O)O)=C(CCC)C(C=2C=CC(CCC)=CC=2)=C1CCC KIEOSPBEUABEFO-UHFFFAOYSA-N 0.000 description 1
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 1
- HHFMFWAFQGUGOB-UHFFFAOYSA-N [5-(4-tert-butylbenzoyl)-2,4-dihydroxyphenyl]-(4-tert-butylphenyl)methanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC(C(=O)C=2C=CC(=CC=2)C(C)(C)C)=C(O)C=C1O HHFMFWAFQGUGOB-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- PYHXGXCGESYPCW-UHFFFAOYSA-N alpha-phenylbenzeneacetic acid Chemical class C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- MJMDMGXKEGBVKR-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-3-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1CC(C)(C)N(C)C(C)(C)C1OC(=O)C(C(=O)OC1C(N(C)C(C)(C)CC1)(C)C)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 MJMDMGXKEGBVKR-UHFFFAOYSA-N 0.000 description 1
- SMISHRXKWQZCCQ-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-3-yl) decanedioate Chemical compound CC1(C)N(C)C(C)(C)CCC1OC(=O)CCCCCCCCC(=O)OC1C(C)(C)N(C)C(C)(C)CC1 SMISHRXKWQZCCQ-UHFFFAOYSA-N 0.000 description 1
- SXPLGYBFGPYAHS-UHFFFAOYSA-N bis(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(O)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(O)C(C)(C)C1 SXPLGYBFGPYAHS-UHFFFAOYSA-N 0.000 description 1
- YWDBZVIHZORXHG-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-1-yl) decanedioate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)CCCCCCCCC(=O)ON1C(C)(C)CCCC1(C)C YWDBZVIHZORXHG-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- LDTDSAMMMCLGQR-UHFFFAOYSA-N bis[(4-tert-butyl-3-hydroxy-2,6-dimethylphenyl)methyl] 2-(3h-dithiol-5-yl)benzene-1,4-dicarboxylate Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C)=C1COC(=O)C(C=C1C=2SSCC=2)=CC=C1C(=O)OCC1=C(C)C=C(C(C)(C)C)C(O)=C1C LDTDSAMMMCLGQR-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- OEUVSBXAMBLPES-UHFFFAOYSA-L calcium stearoyl-2-lactylate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C([O-])=O.CCCCCCCCCCCCCCCCCC(=O)OC(C)C(=O)OC(C)C([O-])=O OEUVSBXAMBLPES-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- JCKYGMPEJWAADB-UHFFFAOYSA-N chlorambucil Chemical compound OC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 JCKYGMPEJWAADB-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZJPJECQPVMSILT-UHFFFAOYSA-N chloroethene 3-(2-phenylethenyl)furan-2,5-dione Chemical compound ClC=C.O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 ZJPJECQPVMSILT-UHFFFAOYSA-N 0.000 description 1
- IEJNAGSUKYCWCR-UHFFFAOYSA-N chloroethene;1,1-dichloroethene;ethenyl acetate Chemical compound ClC=C.ClC(Cl)=C.CC(=O)OC=C IEJNAGSUKYCWCR-UHFFFAOYSA-N 0.000 description 1
- VSJDEWYENWWMAV-UHFFFAOYSA-N chloroethene;2-methylprop-2-enoic acid Chemical compound ClC=C.CC(=C)C(O)=O VSJDEWYENWWMAV-UHFFFAOYSA-N 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
- SQNNHEYXAJPPKH-UHFFFAOYSA-N chloroethene;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C SQNNHEYXAJPPKH-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical class C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- SZRLKIKBPASKQH-UHFFFAOYSA-M dibutyldithiocarbamate Chemical compound CCCCN(C([S-])=S)CCCC SZRLKIKBPASKQH-UHFFFAOYSA-M 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- JMFYZMAVUHNCPW-UHFFFAOYSA-N dimethyl 2-[(4-methoxyphenyl)methylidene]propanedioate Chemical compound COC(=O)C(C(=O)OC)=CC1=CC=C(OC)C=C1 JMFYZMAVUHNCPW-UHFFFAOYSA-N 0.000 description 1
- HPLVTKYRGZZXJF-UHFFFAOYSA-N dimethyl 2-benzylidenepropanedioate Chemical compound COC(=O)C(C(=O)OC)=CC1=CC=CC=C1 HPLVTKYRGZZXJF-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- VFFDVELHRCMPLY-UHFFFAOYSA-N dimethyldodecyl amine Natural products CC(C)CCCCCCCCCCCN VFFDVELHRCMPLY-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000004746 geotextile Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- NZYMWGXNIUZYRC-UHFFFAOYSA-N hexadecyl 3,5-ditert-butyl-4-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NZYMWGXNIUZYRC-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000005027 hydroxyaryl group Chemical group 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- WGGBUPQMVJZVIO-XFXZXTDPSA-N methyl (z)-2-cyano-3-(4-methoxyphenyl)but-2-enoate Chemical compound COC(=O)C(\C#N)=C(\C)C1=CC=C(OC)C=C1 WGGBUPQMVJZVIO-XFXZXTDPSA-N 0.000 description 1
- XTNHRWHWTSXJSX-UHFFFAOYSA-N methyl 3-(dibenzylamino)oxy-2-methylpropanoate Chemical compound C=1C=CC=CC=1CN(OCC(C)C(=O)OC)CC1=CC=CC=C1 XTNHRWHWTSXJSX-UHFFFAOYSA-N 0.000 description 1
- HXTAPQWAQZLWIY-UHFFFAOYSA-N methyl 3-(dibenzylamino)oxypropanoate Chemical compound C=1C=CC=CC=1CN(OCCC(=O)OC)CC1=CC=CC=C1 HXTAPQWAQZLWIY-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QITVMFSGIKQAFH-UHFFFAOYSA-N n'-(2,2,6,6-tetramethylpiperidin-1-yl)hexane-1,6-diamine Chemical compound CC1(C)CCCC(C)(C)N1NCCCCCCN QITVMFSGIKQAFH-UHFFFAOYSA-N 0.000 description 1
- YIMHRDBSVCPJOV-UHFFFAOYSA-N n'-(2-ethoxyphenyl)-n-(2-ethylphenyl)oxamide Chemical compound CCOC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1CC YIMHRDBSVCPJOV-UHFFFAOYSA-N 0.000 description 1
- GTIBACHAUHDNPH-UHFFFAOYSA-N n,n'-bis(benzylideneamino)oxamide Chemical compound C=1C=CC=CC=1C=NNC(=O)C(=O)NN=CC1=CC=CC=C1 GTIBACHAUHDNPH-UHFFFAOYSA-N 0.000 description 1
- ZJFPXDGPJMHQMW-UHFFFAOYSA-N n,n'-bis[3-(dimethylamino)propyl]oxamide Chemical compound CN(C)CCCNC(=O)C(=O)NCCCN(C)C ZJFPXDGPJMHQMW-UHFFFAOYSA-N 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- RZFMDNXBQJACKD-UHFFFAOYSA-N n-tricosan-12-ylidenehydroxylamine Chemical compound CCCCCCCCCCCC(=NO)CCCCCCCCCCC RZFMDNXBQJACKD-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- RLUAAOOSMNBCHE-UHFFFAOYSA-N octadecyl 3-(diethylaminooxy)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCON(CC)CC RLUAAOOSMNBCHE-UHFFFAOYSA-N 0.000 description 1
- 125000005474 octanoate group Chemical group 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NTTIENRNNNJCHQ-UHFFFAOYSA-N octyl n-(3,5-ditert-butyl-4-hydroxyphenyl)carbamate Chemical compound CCCCCCCCOC(=O)NC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NTTIENRNNNJCHQ-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NFBAXHOPROOJAW-UHFFFAOYSA-N phenindione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C1=CC=CC=C1 NFBAXHOPROOJAW-UHFFFAOYSA-N 0.000 description 1
- 229960000280 phenindione Drugs 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical class OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003214 poly(methacrylonitrile) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 208000034301 polycystic dysgenetic disease of parotid salivary glands Diseases 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- JWESMTKQFFGIBQ-UHFFFAOYSA-M potassium;3-(dibenzylamino)oxypropanoate Chemical compound [K+].C=1C=CC=CC=1CN(OCCC(=O)[O-])CC1=CC=CC=C1 JWESMTKQFFGIBQ-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- MKWYFZFMAMBPQK-UHFFFAOYSA-J sodium feredetate Chemical compound [Na+].[Fe+3].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O MKWYFZFMAMBPQK-UHFFFAOYSA-J 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920006302 stretch film Polymers 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920006249 styrenic copolymer Polymers 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- UIERETOOQGIECD-ONEGZZNKSA-N tiglic acid Chemical compound C\C=C(/C)C(O)=O UIERETOOQGIECD-ONEGZZNKSA-N 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- YOIAWAIKYVEKMF-UHFFFAOYSA-N trifluoromethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)F.OS(=O)(=O)C(F)(F)F YOIAWAIKYVEKMF-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- RLXXDKQYBGLSLK-UHFFFAOYSA-N tris(2,4-dipropylphenyl) phosphite Chemical compound CCCC1=CC(CCC)=CC=C1OP(OC=1C(=CC(CCC)=CC=1)CCC)OC1=CC=C(CCC)C=C1CCC RLXXDKQYBGLSLK-UHFFFAOYSA-N 0.000 description 1
- DPXMCGQIIKXTKL-UHFFFAOYSA-N tris(2-butan-2-ylphenyl) phosphite Chemical compound CCC(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)CC)OC1=CC=CC=C1C(C)CC DPXMCGQIIKXTKL-UHFFFAOYSA-N 0.000 description 1
- QGICLBHPOLQUBD-UHFFFAOYSA-N tris(4-butan-2-ylphenyl) phosphite Chemical compound C1=CC(C(C)CC)=CC=C1OP(OC=1C=CC(=CC=1)C(C)CC)OC1=CC=C(C(C)CC)C=C1 QGICLBHPOLQUBD-UHFFFAOYSA-N 0.000 description 1
- CNIDDOIZOYGBEM-UHFFFAOYSA-N tris[2,4-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC(C(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)C)C(C)C)OC1=CC=C(C(C)C)C=C1C(C)C CNIDDOIZOYGBEM-UHFFFAOYSA-N 0.000 description 1
- ZBSCMUKWGDDOQK-UHFFFAOYSA-N tris[2-(2-hydroxyethoxy)ethyl] phosphite Chemical compound OCCOCCOP(OCCOCCO)OCCOCCO ZBSCMUKWGDDOQK-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/145—Esters of phosphorous acids with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- the present invention relates to novel phosphite compositions suitable for use as antioxidants in polymer compositions. It also relates to stabilized polymer compositions and stabilizer concentrates comprising the novel liquid phosphite compositions.
- Organic phosphites are well-known and are commonly used as secondary antioxidants in polymer compositions including, for example, polyolefins, polyvinyl chloride, and elastomers. Examples of such phosphites are disclosed in H. Zweifel (Ed) Plastics Additives Handbook, 5th edition, Hanser Publishers, Kunststoff 2000. Phosphite stabilizers, both liquid and solid, are known in the art.
- Solid organic phosphite stabilizers are widely used as secondary antioxidants in polymer compositions.
- One commercially available antioxidant is tris(2,4-di-t-butylphenyl) phosphite, shown below, a solid antioxidant commonly known as AlkanoxTM 240 (Chemtura Corporation, Middlebury, Connecticut, USA), IrgafosTM 168 (Ciba Specialty Chemicals Corp., Tarrytown, New York, USA) and DoverphosTM S-480 (Dover Chemical Corp., Dover, Ohio, USA).
- Tris(2,4-di-t-butylphenyl) phosphite has been demonstrated to effectively reduce peroxide induced oxidative degradation for many polymers including polyolefins, polycarbonates, ABS and polyesters.
- the trialkylaryl phosphite has low volatility that allows for its use at high temperatures commonly required for processing thermoplastic polymers. Owing to its solid form and concomitant processing limitations, however, tris(2,4-di-t- butylphenyl) phosphite is not well-suited for the stabilization of all polymers and has been demonstrated to plateout during processing of some plastics, in particular low melting point plastics, and forming deposits on processing machinery surfaces.
- Liquid phosphite compositions are also well known and do not possess the handling problems associated with solid phosphite compounds.
- liquid phosphite compositions generally exhibit better processability than solid phosphite compositions for polymers that process at low temperatures.
- Tris(p-nonylphenyl) phosphite (TNPP) for example, is one alkylaryl phosphite that is a stable liquid at ambient conditions.
- TNPP is a versatile phosphite stabilizer that is useful in stabilizing a large number of polymers such as HDPE, LLDPE, SBR, ABS, PVC and others. There is, however, a need to replace TNPP owing to the alleged estrogenicity of nonylphenol, which is commonly used in the synthesis of TNPP.
- U.S. Patent No. 7,468,410 describes a mixture of phosphites including a tri(4-sec- butylphenyl)phosphite and a tri(2-sec-butylphenyl)phosphite. Each of these phosphites is a liquid when isolated, and the combination is a liquid.
- U.S. Patent No. 5,254,709 describes various secondary antioxidants including a solid phosphite made from 2:1 molar ratio of 2,4-di-t-amyl phenol and 2,4-di-t-butyl phenol, and a liquid phosphite made from 2-t-butyl-4-nonyl phenol.
- WO 2007/149143 discloses liquid phosphite blends comprising at least two different phosphites.
- a phosphite mixture is prepared by using as alkylated phenol feedstock the product obtained by alkylating phenol with isobutylene and amylene.
- the phosphite composition comprises two or more alkylaryl phosphites having the structure:
- Each Ri is an alkyl group having the same number of carbon atoms and each R 2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R 2 .
- at least one alkylaryl phosphite includes Ri and at least one other alkylaryl phosphite includes R 2 .
- the two or more phosphites preferably include a first phosphite selected from the group consisting of tris(2,4-di-t-butylphenyl)phosphite, tris(4-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)- 4-t-butylphenyl phosphite, and bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite and a second phosphite selected from the group consisting of tris(2,4-di-t-amylphenyl)phosphite, tris(4-t-amylphenyl)phosphite, bis(2,4-di-t-amylphenyl)-4-t-amylphenyl phosphite, and bis(4- t-amylphenyl)
- a, b, c and d are independently selected from 0, 1, and 2.
- Ri and R 2 are independently selected from straight or branched C 1 -C 12 alkyl groups, preferably selected from isopropyl, t-butyl and t-amyl.
- the invention is to a composition
- a composition comprising at least two different alkylaryl phosphites, wherein at least one of the alkylaryl phosphites has two or more alkyl groups having a different number of carbon atoms on different aryl moieties, and wherein the composition is a liquid at ambient conditions.
- the different alkylaryl phosphites optionally is a reaction product of a phosphorous trihalide and a mixture of 2,4-di-t-amyl phenol and 4-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1.
- the two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-butyl phenol and either 4-t-amyl phenol or 2,4-di-t-amyl phenol, in a molar ratio of 1:4 to 4: 1.
- the two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-amyl phenol and either 4-t-butyl phenol or 2,4- di-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1.
- the present invention relates to phosphite compositions comprising at least two different alkylaryl phosphites provided that the phosphite composition includes two or more alkyl groups, whether on the same or different phosphite compounds, the two or more alkyl groups having a different number of carbon atoms.
- the inclusion of two or more alkyl groups having a different number of carbon atoms leads to primarily to two different embodiments of the present invention as follows:
- the two or more alkyl groups having a different number of carbon atoms are on different phosphite compounds.
- One phosphite has an alkyl group having a first number of carbon atoms and another phosphite has an alkyl group having a second number of carbon atoms, where the first and second numbers are different.
- the first embodiment is referred to as the "mixed phosphites" embodiment because such compositions may be formed by mixing two separately synthesized phosphites.
- the two or more alkyl groups having a different number of carbon atoms are on adjacent aryl moieties of specific phosphite compounds.
- Each phosphite has three aryl moieties and one of the aryl moieties is substituted with an alkyl group having the first number of carbon atoms and an adjacent aryl moiety is substituted with an alkyl group having a second number of carbon atoms, where the first and second numbers are different.
- the second embodiment is referred to as "mixed alkylates" embodiment because such phosphite compositions may be formed by reacting an alkylate composition with a phosphorous halide, where the alkylate composition comprises a composition of at least two separately synthesized alkylates.
- first and second embodiments may be combined to form even more diverse phosphite compositions.
- the phosphite compositions are liquid at ambient conditions.
- ambient conditions room temperature, e.g., 25°C, and 1 atmosphere pressure.
- the fact that the phosphite compositions are liquid at ambient conditions is surprising and unexpected because it would be expected that each of the different phosphites contained in the phosphite composition, when isolated, would be a solid at ambient conditions.
- the phosphite compositions of the invention are liquids at ambient conditions even though at least some of the individual components, when isolated, are solid at ambient conditions.
- Table 1 for example, provides the melting points, each of which is above room temperature, for several pure phosphite compounds.
- the phosphite compositions of the invention are liquids at ambient conditions.
- liquid it is meant that the phosphite composition remains liquid after at least three “freeze/thaw” cycles as opposed to “meta-stable liquids,” which do not remain liquid after three or fewer cycles.
- a freeze/thaw cycle is defined as follows: 1) An ambient temperature composition is stirred for 0.5 hours; 2) The stirred composition is then refrigerated at about 5 0 C for three days; and 3) The refrigerated composition is then brought to ambient temperature, and held at ambient for 3 days. Upon completion of step 3, the composition is checked for solids content, e.g., crystallization. Completion of steps 1-3 defines one freeze/thaw cycle.
- the viscosity of the phosphite composition may vary depending on the relative amounts of the various phosphite compounds contained therein.
- the phosphite composition has a viscosity equal to or less than 11,000 cSt, e.g., equal to or less than 7,300 cSt, equal to or less than 5,000 cSt, equal to or less than 4,000 cSt, equal to or less than 3,000 cSt, or equal to or less than 2850 cSt, these viscosities being measured at 30 0 C.
- viscosity of the composition may range from 1 cSt to 15,000 cSt, from 100 cSt to 12,000 cSt, from 500 cSt to 10,000 cSt, from 500 cSt to 6,500 cSt, from 500 cSt to 5,000 cSt, from 500 cSt to 3,000 cSt, from 1,000 cSt to 4,000 cSt, from 1,500 cSt to 3,500 cSt, from 2,000 cSt to 3,000 cSt, or from 2,000 to 2,800 cSt, these viscosities being measured at 30 0 C.
- the embodiments of the invention provide various ways to increase phosphite diversity by incorporating alkyl groups having different numbers of carbon atoms.
- the liquid composition may comprise at least 2, e.g., at least 4 or at least 10, different alkylaryl phosphites, and optionally from 2 to 100 different alkylaryl phosphites, e.g., from 3 to 20 different alkylaryl phosphites or from 4 to 10 different alkylaryl phosphites.
- alkylaryl phosphites derived from mixed alkylates helps to mitigate processing costs due to fluctuations in source alkenes and by eliminating the conventional need for substantially pure starting materials (e.g., olefins and/or alkylated phenolics).
- each phosphite in the composition has the structure:
- a, b, c and d are independently selected from 0, 1, 2 and 3, provided that a
- the aryl moiety (Ar) present in the compounds of the present invention is preferably an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, preferably phenolics such as phenyl.
- Each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2.
- at least one alkylaryl phosphite includes Ri and at least one other alkylaryl phosphite includes R2.
- the phosphite composition comprises at least two phosphite compounds.
- the phosphite composition also preferably contains at least two alkyl groups having a different number of carbon atoms.
- each aromatic moiety is substituted, e.g., Ri or R 2 , with at least one branched or straight chain Ci-Ci 8 alkyl group, e.g., C 4 -C 1 0 alkyl group or C 4 -C5 alkyl group, preferably t-butyl and/or t-amyl, but preferably no aromatic moieties are substituted with any C 9 alkyl groups.
- the two or more alkyl groups having a different number of carbon atoms are selected from branched or straight chain C1-C12 alkyl group, e.g., a C2-C5 alkyl group, a C2-C4 alkyl group, or C3-C5 alkyl group, provided that one alkyl group has a different number of carbon atoms than the another alkyl group.
- the alkyl groups may be selected, for example, from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl (although less preferred), decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and isomers thereof.
- the alkyl group(s) are selected from propyl, especially isopropyl, butyl, especially sec-butyl, t-butyl, and amyl groups, especially sec-amyl, t-amyl and neo-amyl.
- the alkyl groups having different numbers of carbon atoms is Cs-Cio alkyl, e.g., C 9 alkyl.
- the alkyl moieties do not include nonyl, meaning the phosphite composition preferably comprises less than 50 wppm, e.g., less than 10 wppm or less than 5 wppm nonyl substituted aryl phosphite compounds, and most preferably no detectable nonyl substituted aryl phosphite compounds.
- the phosphite composition preferably comprises less than 50 wppm, e.g., less than 10 wppm or less than 5 wppm nonylphenol, and most preferably no detectable nonylphenol.
- the aromatic moieties may be mono, di or tri substituted in the ortho and/or para positions, but preferably the phosphites themselves are not exclusively mono substituted and are not exclusively disubstituted.
- the phosphite compositions of the invention ideally include phosphite compounds having aryl moieties that are monoalkylated and dialkylated.
- the combination of mono and di-substituted aryl moieties in combination with employing different alkyl groups advantageously may lead to very diverse phosphite compositions.
- few if any of the aryl moieties are trisubstituted. For example, in some embodiments fewer than 3 wt. % of the aryl moieties are trisubstituted, e.g., fewer than 2 wt. %, or fewer than 1 wt. %.
- the aryl moieties are monosubstituted in the ortho position.
- the aryl moieties are monosubstituted in the ortho position, if at all, in an amount less than 3 wt. %, e.g., less than 2 wt. % or less than 1 wt.
- the phosphite composition is substantially free of phosphite compounds having aryl groups that are substituted with alkyl groups having hydrogen atoms in the ⁇ position. That is, in preferred embodiments, at least 95%, at least 98% or at least preferably t-butyl and/or t-amyl.
- the phosphite compositions have an overall phosphorus content that is equal to or greater than TNPP, e.g., at least 4.5 mole %, e.g., at least 4.8 mole %, or at least 5.1 mole %.
- the overall phosphorus content of the phosphite composition may range from 4.5 to 10.0 mole %, e.g., from 4.8 to 8.0 mole %, or 5.1 to 6.0 mole %, of all phosphorous containing compounds in the phosphite composition.
- the phosphite composition has a low level or is substantially free of phenolics (e.g., phenols, cresols or xylenols), whether alkylated or unalkylated, which is referred to herein as "free phenolics" when contained in the phosphite composition.
- the phosphite composition preferably comprises less than 5 wt. %, e.g., less than 3 wt. % or less than 1 wt. %, of free phenolics, based on the total weight of the phosphite composition. Any free phenolics, for example, may be removed by distillation.
- the phosphite composition may comprise less than 0.5 wt. %, e.g., less than 0.2 wt. % or less than 0.1 wt. %, of free phenolics, based on the total weight of the phosphite composition.
- a minor amount of free phenolics may be beneficial, for example, as a viscosity reducing agent.
- the phosphite composition comprises a minor amount of free phenolics, e.g., from 1 to 4 weight percent, e.g., from 2 to 3 weight percent, based on the total weight of the phosphite composition.
- the phosphite composition is preferably substantially free of phosphite compounds having unsubstituted aryl moieties, e.g., triphenylphosphites, bis(phenyl)alkylphenyl phosphites or bis(alkylphenyl)phenyl phosphites.
- the phosphite composition preferably comprises less than 2 wt. %, e.g., less than 1 wt. % or less than 0.5 wt. %, phosphite compounds having at least one unsubstituted aryl moiety, based on the total weight of the phosphite composition.
- the alkylate used to prepare the phosphite composition may contain a minor amount of phenol, e.g., from 5 to 10 weight percent phenol, which may react during the phosphite synthesis process to form some phenyl phosphites.
- the phosphite composition (whether of the first, second, or third embodiment) includes one or more hydrolytic stabilizers.
- Preferred stabilizers include amines of the structure:
- R3 is selected from the group consisting of hydrogen, and straight or branched Ci-C ⁇ alkyl
- R 4 is selected from the group consisting of straight or branched Ci- C30 alkyl.
- R3 is selected from the group consisting of straight or branched C 1 -C 4 alkyl, e.g., methyl or ethyl.
- R 4 is selected from the group consisting of straight or branched C5-C 2 0 alkyl, e.g., straight or branched C 1 0-C 2 0 alkyl or straight or branched Ci 2 -Ci 8 alkyl.
- x is 1 and R3 is straight or branched C5-C 2 0 alkyl, e.g., Ci 2 -Ci 8 alkyl. In one embodiment, x is 2 and R 4 is straight or branched C 1 0-C 2 0 alkyl, e.g., Ci 2 -Ci 8 alkyl.
- the amine is selected from the group consisting of triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and
- the amine is selected from the group consisting of octyl-bis(2- ethanol)amine, nonyl-bis(2-ethanol)amine, decyl-bis(2-ethanol)amine, undecyl-bis(2- ethanol)amine, dodecyl-bis(2-ethanol)amine, tridecyl-bis(2-ethanol)amine, tetradecyl-bis(2- ethanol)amine, pentadecyl-bis(2-ethanol)amine, hexadecyl-bis(2-ethanol)amine, heptadecyl- bis(2-ethanol)amine, octadecyl-bis(2-ethanol)amine, octyl-bis(2-propanol)amine, nonyl- bis(2-propanol)amine, decyl-bis(2-propanol)amine, undecyl-bis(2-propanol)amine, dodecyl- bis(2-propanol)amine, tridec
- Additional hydrolytic stabilizers include epoxies such as epoxidized soybean oil (ESBO) commercially available as DrapexTM 39, Drapex 392, Drapex 4.4, and Drapex 6.8 (Chemtura Corp.).
- ESBO epoxidized soybean oil
- the amine may be present in an amount of from 0.01 to 5 wt. %, e.g., from 0.1 to 1.5 wt. % or from 0.2 to 0.8 wt. %, based on the total weight of the phosphite composition.
- the present invention relates to liquid phosphite compositions having at least two different alkylaryl phosphites.
- the phosphite compositions comprise one or more first phosphites having exclusively first alkyl groups and one or more second phosphites having exclusively second alkyl groups, wherein the first alkyl groups have a different number of carbon atoms than the second alkyl groups.
- the phosphite compositions comprise phosphites having at least the following two structures:
- Each Ar is an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, more preferably phenolics such as phenyl.
- each Ar is independently selected from the formula:
- each Ar is a phenolic, more preferably phenyl.
- Each Ri is an alkyl group having the same number of carbon atoms and each R 2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R 2 .
- Ri and R 2 preferably are independently selected from straight or branched Ci- Ci8 alkyl, e.g., Ci-Ci 2 , C2-C5 or C2-C4 alkyl, provided that that Ri has a different number of carbon atoms than R 2 .
- one of Ri or R 2 is C 4 alkyl, e.g., t-butyl, and the other of Ri or R 2 is C5 alkyl, e.g., t-amyl.
- the phosphite composition comprises at least a first phosphite and a second phosphite, wherein the first phosphite comprises an Alkyl-A group and the second phosphite comprises an Alkyl-B group.
- Alkyl-A refers to an alkyl group having A carbon atoms
- Alkyl-B refers to an alkyl group having B carbon atoms, wherein B is a whole number greater than A.
- Alkyl-A may be t-butyl
- Alkyl-B may be t-amyl.
- each of Alkyl-A and Alkyl-B may include multiple isomers of alkyl groups having the same number of carbon atoms.
- Alkyl-A groups may include sec-butyl and t-butyl
- Alkyl-B groups may include sec-amyl and t-amyl.
- the first phosphite may be selected from the group consisting of: tris(Alkyl-A-aryl) phosphite, tris(di-Alkyl-A-aryl)phosphite, bis(Alkyl-A-aryl)di-Alkyl-A- aryl phosphite, and bis(di-Alkyl-A-aryl)Alkyl-A-aryl phosphite.
- the second phosphite may be selected from the group consisting of: tris(Alkyl-B-aryl) phosphite, tris(di-Alkyl-B-aryl) phosphite, bis(Alkyl-B-aryl)di-Alkyl-B-aryl phosphite, and bis(di-Alkyl-B-aryl)Alkyl-B-aryl phosphite.
- the phosphite composition comprises at least three, e.g., at least four or at least five, of the phosphites identified above.
- the relative amounts of the first and second phosphites in the phosphite composition may vary so long as the phosphite composition is a liquid at ambient conditions.
- the molar ratio of Alky 1- A groups to Alkyl-B groups, or alternatively of the first phosphite(s) to the second phosphite(s) is from 1 : 10 to 10: 1, e.g., from 1:4 to 4: 1 or from 2: 1 to 1 : 1.
- the phosphite composition comprises the phosphite having alkyl groups with the lesser number of carbon atoms, i.e., the first phosphite, in an amount greater than the phosphite having alkyl groups with the greater number of carbon atoms, i.e., the second phosphite.
- the phosphite composition preferably comprises the first phosphite in an amount greater than the second phosphite.
- the overall phosphorus content may be advantageously maximized.
- the second phosphite in the phosphite composition preferably in a minor amount, may improve, e.g., lower, the viscosity and processing characteristics for the overall phosphite composition.
- the phosphite composition comprises the first phosphite (containing Alkyl- A groups) in an amount greater than 50 weight percent, greater than 60 weight percent or greater than 75 weight percent, based on the total weight of all phosphites in the phosphite composition, and preferably comprises the second phosphite (containing Alkyl-B groups) in an amount greater than 5 weight percent, greater than 10 weight percent or greater than 25 weight percent, based on the total weight of all phosphites in the phosphite composition.
- the phosphite composition preferably comprises the first phosphite in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the second phosphite in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphites in the phosphite composition.
- the phosphite composition comprises the phosphite having the alkyl groups with the lesser number of carbon atoms in an amount less than the phosphite having the alkyl groups with the greater number of carbon atoms.
- the phosphite composition optionally comprises the second phosphite in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the first phosphite in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphites in the phosphite composition.
- the first phosphite is substituted with propyl groups, e.g., isopropyl groups, and the second phosphite is substituted with butyl groups, e.g., t-butyl groups.
- the first phosphite is substituted with propyl groups, e.g., isopropyl groups, and the second phosphite is substituted with amyl groups, e.g., t-amyl groups.
- the first phosphite is substituted with butyl groups, e.g., t-butyl groups, and the second phosphite is substituted with amyl groups, e.g., t-amyl groups.
- Alkyl-A is isopropyl and Alkyl-B is t-butyl.
- the first phosphite is selected from the group consisting of tris(4-isopropyl phenyl) phosphite, tris(2,4-dipropylphenyl) phosphite, bis(4-propylphenyl)-2,4-dipropylphenyl phosphite, and bis(2,4-di-isopropylphenyl)-4-isopropylphenyl phosphite.
- the second phosphite is selected from the group consisting of tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite.
- Alkyl-A is isopropyl and Alkyl-B is t-amyl.
- the first phosphite is selected from the group consisting of tris(4-isopropyl phenyl) phosphite, tris(2,4-di-isopropyl phenyl) phosphite, bis(4-isopropyl phenyl)-2,4-di-isopropyl phenyl phosphite, and bis(2,4-di-isopropyl phenyl)-4-isopropyl phenyl phosphite
- the second phosphite is selected from the group consisting of tris(4-t-amylphenyl) phosphite, tris(2,4-di- t-amylphenyl) phosphite, bis(4-t-amylphenyl)-2,4
- tertiary olefins such as t-butyl and t-amyl are employed in combination where the aryl moiety is a phenolic, e.g., phenyl.
- the phosphite composition may comprise a first phosphite and a second phosphite where the first phosphite is selected from the group consisting of tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite.
- the first phosphite is selected from the group consisting of tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl
- the second phosphite is selected from the group consisting of tris(4-t-amylphenyl) phosphite, tris(2,4-di-t- amylphenyl) phosphite, bis(4-t-amylphenyl)-2,4-di-t-amylphenyl phosphite, and bis(2,4-di-t- amylphenyl)-4-t-amylphenyl phosphite.
- the phosphite composition comprises at least three, e.g., at least four or at least five, of the phosphites identified above.
- the phosphite compositions of this embodiment may be particularly diverse so long as the overall phosphite composition is a liquid at ambient conditions.
- the phosphite composition optionally comprises tris(monoalkylaryl)phosphites, e.g., tris(Alkyl- A-phenyl) phosphite and tris(Alkyl-B -phenyl) phosphite, in an amount from 20 to 70 weight percent, e.g., from 15 to 55 weight percent, or from 37 to 54 weight percent, based on the total weight of all phosphites in the phosphite composition.
- the phosphite composition optionally comprises bis(monoalkylaryl)dialkylaryl phosphites, e.g., bis(Alkyl-A-phenyl)di- Alkyl-A-phenyl phosphite, and bis(Alkyl-B-phenyl)di-Alkyl-B-phenyl phosphite, in an amount from 15 to 60 weight percent, e.g., from 31 to 50 weight percent, or from 34 to 45 weight percent, based on the total weight of all phosphites in the phosphite composition.
- bis(monoalkylaryl)dialkylaryl phosphites e.g., bis(Alkyl-A-phenyl)di- Alkyl-A-phenyl phosphite, and bis(Alkyl-B-phenyl)di-Alkyl-B-phenyl phosphite, in an amount from 15 to
- the phosphite composition optionally further comprises tris(dialkylaryl) phosphites and/or bis(dialkylaryl)monoalkylaryl phosphites. If present, the phosphite composition preferably comprises bis(dialkylaryl)monoalkylaryl phosphites, e.g., bis(di-Alkyl-A-phenyl)Alkyl-A- phenyl phosphite and bis(di-Alkyl-B-phenyl)Alkyl-B-phenyl phosphite, in an amount of from 2 to 20 weight percent, e.g., from 4 to 20 weight percent or from 5 to 10 weight percent, based on the total weight of all phosphites in the phosphite composition.
- bis(dialkylaryl)monoalkylaryl phosphites e.g., bis(di-Alkyl-A-phenyl)Alkyl-
- the phosphite composition preferably comprises tris(dialkylaryl) phosphites, e.g., tris(di-Alkyl- A-phenyl) phosphite and/or tris(di-Alkyl-B-phenyl) phosphite in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on the total weight of all phosphites in the phosphite composition.
- tris(dialkylaryl) phosphites e.g., tris(di-Alkyl- A-phenyl) phosphite and/or tris(di-Alkyl-B-phenyl) phosphite in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on the total weight of all phosphites in the
- the process for forming the phosphite compositions of the first embodiment comprises separately making each phosphite and blending the separate phosphites together.
- the first phosphite is formed from the reaction of a phosphorous trihalide with a first alkylate composition, which in turn is formed from the reaction between a hydroxyaryl compound and a first olefin.
- the second phosphite is formed from the reaction of a phosphorous trihalide with a second alkylate composition, which in turn is formed from the reaction between a hydroxyaryl compound and a second olefin, wherein the second olefin has a different number of carbon atoms than the first olefin.
- phosphite compositions are obtained in a direct chemical reaction.
- a schematic of one reaction method that may be employed to form such phosphite compositions is as follows. As indicated above, the first phosphite and the second phosphite are separately synthesized according to the below process.
- R is independently any of the groups as defined above (e.g., Ri or R 2 , respectively).
- R is independently any of the groups as defined above (e.g., Ri or R 2 , respectively).
- a minor amount of other alkylated phenols e.g., ortho-substituted monoalkylated phenols, may be included as an additional reactant in the above reaction scheme and would form additional derivative phosphites, but these additional reactants and products have been omitted from this reaction for clarity.
- the phosphorus trihalide preferably is selected from phosphorus trichloride and phosphorus tribromide.
- the catalyst may be selected from the group consisting of pyridine, N,N-dimethyldodecylamine, and dilauryl methyl amine or their hydrochloride salts.
- the molar ratio of alkylate composition (i.e., alkylated phenol compounds) to phosphorus trihalide preferably is from 3: 1 to 5: 1, e.g., from 3: 1 to 4:1 or from 3.1 to 3.7: 1.
- the reaction of the alkylated phenols with a phosphorus trihalide may be conducted under an inert atmosphere (e.g., nitrogen) at a temperature of from 5 to 70 0 C, e.g., from 40 to 70 0 C or from 50 to 70 0 C.
- an inert atmosphere e.g., nitrogen
- the temperature is held at or below 70 0 C during the addition of the alkylate composition to prevent refluxing the phosphorus trihalide.
- the alkylate composition is charged to the reactor and the phosphorus trihalide is added thereto.
- the temperature is optionally held for 10 minutes to 12 hours, e.g., from 30 minutes to 10 hours, or from 1 hour to 3 hours.
- the reaction preferably is conducted at a pressure of 0.8 to 4 atm, e.g., from 0.9 to 3 atm or from 1 to 2 atm.
- the temperature may be ramped a ramped temperature ranging from 70 0 C to 250 0 C, e.g., from 80 0 C to 225°C or from 90 0 C to 200 0 C.
- the reaction is held at the ramped temperature for from 10 minutes to 12 hours, e.g., from 30 minutes to 10 hours, or from 1 hour to 3 hours.
- the reaction preferably is conducted at a reduced pressure of 0.01 to 0.5 atm, e.g. from 0.03 to 0.4 atm or from 0.04 to 0.1 atm.
- hydrochloric or hydrobromic gas will be evolved, and may be removed by reducing the pressure to about 0.05 atm or sweeping an inert gas such as nitrogen over the reaction mixture. In one aspect the removal of such gases may be performed until the total chloride content in the reaction mixture is less than 50 wppm, e.g., less than 25 wppm or less than 10 wppm.
- any free phenol that is not reacted with the phosphorus trihalide may be liberated by raising the reaction temperature to up to 275°C, e.g., up to 250 0 C or up to 225°C, or up to 200 0 C, and in a vacuum at a pressure of 0.0001 to 0.1 atm.
- a wiped- film molecular (Short-Path) still, wiped film evaporator (WFE), thin film evaporator, or similar equipment may be used to further remove the free cresol or phenol to the very low levels indicated above.
- the step of forming the phosphite composition may occur in one or more neutral solvents.
- Typical solvents that may be employed include toluene, xylene, methylene chloride, heptane, chloroform, and benzene.
- the invention of this embodiment comprises two different phosphites having different alkyl groups, one or more of the products shown above in scheme (V), optionally may be separated or partially separated (e.g., through distillation) from the other reaction products.
- two relatively pure phosphites may be optionally heated and blended to form a mixture of phosphite compounds, each having a different alkyl groups.
- the phosphite composition may comprise a first phosphite comprising a substantially pure monosubstituted aryl phosphite that is alkylated with Alkyl- A, and a second phosphite comprising a substantially pure disubstituted aryl phosphite that is dialkylated with Alkyl-B.
- Liquid phosphite compositions may be formed from such first and second phosphite compounds when combined in the proper ratios, as described above.
- the first phosphite includes several compounds that are alkylated with Alkyl-A (e.g., any of those shown in scheme (V) above) and/or the second phosphite includes several compounds that are alkylated with Alkyl-B.
- the invention is to liquid alkylaryl phosphite compositions comprising two or more phosphite compounds, wherein at least some of the phosphite compounds are substituted with multiple alkyl groups including at least a first alkyl group and a second alkyl group, the first alkyl group having a different number of carbon atoms than the second alkyl group, and provided that no individual aryl moiety is substituted with both the first alkyl group and the second alkyl group. That is, each respective aryl moiety is substituted exclusively with either the first alkyl group or the second alkyl group, but not both.
- At least one of the phosphites in the liquid composition would have the structure:
- Each Ar is independently selected from an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, more preferably phenolics such as phenyl.
- each Ar is independently selected from the formula:
- R5, Re, and R7 are either Ri or R2, the reminder being H, Rs is hydrogen or methyl, provided that at least one of R5, Re, R7 and Rs is not hydrogen.
- each Ar is a phenolic, more preferably phenyl.
- Each Ri is an alkyl group having the same number of carbon atoms and each R 2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R 2 .
- Ri and R 2 preferably are independently selected from straight or branched Ci -Ci 8 alkyl groups, e.g., C 1 -C 12 , e.g., C 2 -C5 or C 2 -C 4 alkyl groups, provided that Ri has a different number of carbon atoms than R2.
- one of Ri or R2 is C4 alkyl, e.g., t-butyl, and the other of Ri or R2 is C5 alkyl, e.g., t-amyl.
- the phosphite composition comprises at least two phosphites, wherein the first and second phosphites are independently selected from the group consisting of: bis(Alkyl-A-aryl)di-Alkyl-B-aryl phosphite, bis(Alkyl-B-aryl)di-Alkyl-A-aryl phosphite, bis(di-Alkyl-A-aryl)Alkyl-B-aryl phosphite, bis(di-Alkyl-B-aryl)Alkyl-A-aryl phosphite, (Alkyl-A-aryl)(Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite, (Alkyl-A-aryl)(Alkyl-B-aryl)(di- Alkyl-B-aryl) phosphite, (Alkyl-
- the phosphite composition in this embodiment may also comprise one or more of tris(Alkyl-A-aryl) phosphite, tris(Alkyl-B- aryl) phosphite, tris(di-Alkyl-A-aryl) phosphite, tris(di-Alkyl-B-aryl) phosphite, bis(Alkyl-A- aryl)di-Alkyl-A-aryl phosphite, bis(di-Alkyl-A-aryl)Alkyl-A-aryl phosphite, bis(Alkyl-B- aryl)di-Alkyl-B-aryl phosphite, and bis(di-Alkyl-B-aryl)Alkyl-B-aryl phosphite.
- the relative amounts of Alkyl-A and Alkyl-B groups (or optional additional groups) contained in the phosphite composition may vary so long as the phosphite composition is a liquid at ambient conditions.
- the molar ratio of Alkyl-A groups to Alkyl-B groups e.g., the first alkylated aryl groups to second alkylated aryl groups, is from 1 : 10 to 10: 1, e.g., from 1 :4 to 4:1 or from 2: 1 to 1 : 1.
- the phosphite composition optionally comprises the first alkylated aryl moiety in an amount from 5 to 95 weight percent, e.g., from 25 to 75 weight percent, or from 35 to 60 weight percent, and the second alkylated aryl moiety in an amount from 5 to 95 weight percent, e.g., from 25 to 75 weight percent or from 35 to 60 weight percent. More preferably, the phosphite composition comprises the alkyl groups with the lesser number of carbon atoms, i.e., Alkyl- A, in an amount greater than the alkyl groups with the greater number of carbon atoms, i.e., Alkyl-B.
- the overall phosphorus content may be advantageously maximized.
- the presence of Alkyl-B in the phosphite compositions of the invention allows for a more diverse phosphite composition than a comparable phosphite composition that does not include Alkyl-B.
- Such phosphite composition complexity may improve, e.g., lower, the viscosity and processing
- the phosphite composition comprises the Alkyl- A group in an amount greater than 50 weight percent, greater than 60 weight percent or greater than 75 weight percent, based on the total weight of all phosphite alkyl groups in the phosphite composition, and preferably comprises the Alkyl-B group in an amount greater than 5 weight percent, greater than 10 weight percent or greater than 25 weight percent, based on the total weight of all phosphite alkyl groups in the phosphite composition.
- the phosphite composition preferably comprises the Alkyl-A group in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the Alkyl-B group in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphite alkyl groups in the phosphite composition.
- the phosphite composition comprises the alkyl groups with the lesser number of carbon atoms, i.e., Alkyl-A groups, in an amount less than the alkyl groups with the greater number of carbon atoms, i.e., Alkyl-B groups.
- the phosphite composition optionally comprises the Alkyl-B groups in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the Alkyl-A groups in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphite alkyl groups in the phosphite composition.
- Alkyl-A is propyl, e.g., isopropyl
- Alkyl-B is butyl, e.g., t-butyl.
- Alkyl-A is propyl, e.g., isopropyl
- Alkyl-B is amyl, e.g., t-amyl.
- Alkyl-A is butyl, e.g., t-butyl
- Alkyl-B is amyl, e.g., t-amyl.
- the phosphite compositions may be particularly diverse containing many different phosphite compounds.
- the phosphite composition optionally comprises tris(monoalkylaryl)phosphites, e.g., tris(Alkyl- A-phenyl) phosphite, tris(Alkyl-B -phenyl) phosphite, bis(Alkyl-A-phenyl)Alkyl-B-phenyl phosphite, bis(di-Alkyl-A-phenyl)di-Alkyl-B-phenyl phosphite, and the like, in an amount from 20 to 70 weight percent, e.g., from 15 to 55 weight percent, or from 37 to 54 weight percent, based on the total weight of all phosphites in the phosphite composition.
- the phosphite composition optionally comprises bis(monoalkylaryl)dialkylaryl phosphites, e.g., bis(Alkyl-A-phenyl)di-Alkyl-B-phenyl phosphite, bis(Alkyl-B-phenyl)di-Alkyl-A-phenyl phosphite, bis(Alkyl-A-phenyl)di-Alkyl-A-phenyl phosphite, bis(Alkyl-B-phenyl)di-Alkyl- B-phenyl phosphite, (Alkyl-A-phenyl)(Alkyl-B-phenyl)di-Alkyl-A-phenyl phosphite, and the like, in an amount from 15 to 60 weight percent, e.g., from 31 to 50 weight percent, or from 34 to 45 weight percent, based on the total weight of
- the phosphite composition optionally further comprises tris(dialkylaryl) phosphites and/or bis(dialkylaryl)monoalkylaryl phosphites. If present, the phosphite composition preferably comprises bis(dialkylaryl)monoalkylaryl phosphites, e.g., bis(di- Alkyl-A-phenyl) Alkyl-B -phenyl phosphite, bis(di-Alkyl-B-phenyl)Alkyl-A-phenyl phosphite, bis(di-Alkyl-A-phenyl)Alkyl-A-phenyl phosphite, bis(di-Alkyl-B-phenyl)Alkyl- B-phenyl phosphite, di-Alkyl-A-phenyl-di-Alkyl-B-phenyl-mono-Alkyl-B-
- the phosphite composition preferably comprises tris(dialkylaryl) phosphites, e.g., tris(di-Alkyl-A-phenyl) phosphite, tris(di-Alkyl-B-phenyl) phosphite, bis (di- Alkyl- A- phenyl)di-Alkyl-B-phenyl phosphite, and the like, in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on the total weight of all phosphites in the phosphite composition.
- tris(dialkylaryl) phosphites e.g., tris(di-Alkyl-A-phenyl) phosphite, tris(di-Alkyl-B-phenyl) phosphite, bis (di- Alkyl- A
- a tris(monoalkylaryl) phosphite and a tris(dialkylaryl) phosphite may include tris compounds having exclusively the same alkyl groups (either Alkyl-A or Alkyl-B), or may comprise a mixture of alkyl groups (e.g., Alkyl-A and Alkyl-B) so long as each aryl moiety on the phosphite is similarly substituted, i.e., all are monosubstituted or all or disubstituted, respectively.
- the alkyl groups either Alkyl-A or Alkyl-B
- bis(dialkylaryl)monoalkylaryl phosphites and bis(monoalkylaryl)dialkylaryl phosphites may include exclusively the same alkyl group or different alkyl groups so long as the respective bis(dialkylaryl)monoalkylaryl phosphite compound includes two dialkylaryl groups and one monoalkylaryl group, and the bis(monoalkylaryl)dialkylaryl phosphite compound includes two monoalkylaryl groups and one dialkylaryl group.
- the liquid phosphites of the second embodiment are reaction products of a phosphorous halide and an alkylate composition that is a mixture of alkylated hydroxyaryl compounds, some of which are alkylated with Alkyl-A and some of which are alkylated with Alkyl-B.
- a mixed alkylate composition is employed in forming the desired phosphite composition.
- the alkylated composition comprises a first alkylate and a second alkylate, where the alkyl group on the first alkylate has a different number of carbon atoms than the alkyl groups on the second alkylate.
- the alkylate composition may comprise, for example: (i) a first alkylate composition comprising mono and/or di-Alkyl-A-phenols, and (ii) a second alkylate composition comprising mono and/or di-Alkyl-B-phenols.
- the alkylate composition comprises two or more compounds selected from the group consisting of a propylated hydroxyaryl compound, a butylated hydroxyaryl compound and an amylated hydroxyaryl compound.
- the propylated hydroxyaryl compound preferably is selected from the group consisting of 4-isopropyl phenol and 2,4-di-isopropyl phenol.
- the butylated hydroxyaryl compound preferably is selected from the group consisting of 4-t-butyl phenol and 2,4-di-t-butyl phenol.
- the amylated hydroxyaryl compound preferably is selected from the group consisting of 4-t-amyl phenol and 2,4-di-t-amyl phenol.
- the first alkylate and the second alkylate optionally are separately synthesized and mixed to form the alkylate composition, which is subsequently reacted with the phosphorous halide to form the phosphite composition.
- Each alkylate in one aspect, may be separately formed by the reaction between an olefin, e.g., propylene, butylene or amylene, and a hydroxyaryl compound, e.g., phenol.
- the first alkylate may be derived from a first olefin
- the second alkylate may be derived from a second olefin having a different number of carbon atoms than the first olefin.
- the alkylate composition may be formed in a single reaction between the first and second olefins and the hydroxyaryl compound.
- a mixture of lower alkenes e.g., two or more C3-C6 olefins, such as a mixture of butylene and amylenes
- the phenolic compound may be reacted with the phenolic compound either in parallel (feed in olefin A and B at the same time) or
- olefin A is reacted first followed by olefin B.
- the alkylates may be formed by contacting one or more phenolics with two or more olefins (in separate reactions or in a single reaction process) in the presence of a catalyst and under conditions effective to form the alkylate composition.
- Each of the two or more olefins preferably contains from 1 to 18 carbons, e.g., from 1 to 8 carbons, or from 4 to 6 carbons, provided that the first olefin has a different number of carbon atoms than the second olefin.
- an olefin alkylating agent one or more alkyl halides, alcohols, MTBE or TAME may be employed.
- the alkylating agents that are employed may comprise or be derived from a hydrocarbon stream comprising alkanes and alkenes, such as a petrochemical raffinate stream from a C 4 or C5 fraction, or a dehydrogenation reaction product of an alkane, e.g., isobutane or isopentane.
- the alkanes pass through the alkylating process unaltered and may be easily separated from the product alkylate composition.
- the ratio of olefins to phenolic preferably is such that the resulting alkylate composition is suitable for conversion to the desired phosphite composition when reacted with a phosphorous halide, keeping in mind that the resulting alkylate, e.g., first alkylate, may be blended with another alkylate, e.g., second alkylate, to form the alkylate composition that will be used in synthesizing the phosphite composition.
- the total olefins to phenolic compound mole ratio ranges from 1 : 1 to 6: 1, e.g., from 1.1 : 1 to 2: 1 or from 1.25: 1 to 1.4: 1, although these ratios may very somewhat depending, for example, on the catalyst employed in the alkylation process and the desired composition and viscosity for the ultimately formed phosphite composition.
- the reaction of the phenol and the two or more olefins may occur in an inert atmosphere (e.g., under nitrogen) at a temperature of from 60 to 160 0 C, e.g., from 70 to 145°C or from 80 to 140 0 C.
- the reaction is preferably performed at a pressure of from 0.2 to 10 atm, e.g., from 0.2 to 5 atm or from 0.2 to 4 atm.
- the reaction time may last from 1 to 12 hours, e.g., from 2 to 10 hours, or from 3 to 5 hours.
- the residence time may be from 0.1 to 5 hours, e.g., from 0.2 to 4 hours or from 0.5 to 1 hour.
- the alkylation preferably is performed in the presence of a catalyst.
- the catalyst may, for example, be selected from the group consisting of acid clay catalyst, cationic ion exchange resins, Bronsted acids, e.g., sulfuric acid, trifluoromethanesulfonic acid (triflic acid) and phosphotungstic acid, or Lewis acids, e.g., BF3.
- Suitable commercial acid clay catalysts include FulcatTM 22B (Rockwood Additives).
- the sulfonic acid- type cation-exchange resin catalyst useful in the present invention can be, for example, a sulfonated styrene-divinyl benzene copolymer, a sulfonated crosslmked styrene polymer, a phenol formaldehyde- sulfonic acid resin, or a benzene formaldehyde-sulfonic acid resin.
- Cation exchange resins useful in the present invention include for example styrene- divinylbenzene types of strong acid ion exchange resins such as DowexTM 50WX4, Dowex 50WX2, Dowex M-31, Dowex Monosphere M-31, Dowex DR-2030 and Dowex Monosphere DR-2030 catalysts (Dow Chemical).
- resins include: AmberlystTM 15, Amberlyst 131, Amberlyst 35, Amberlyst 36, and A21 (Rohm and Hass, subsidiary of Dow); DiaionTM WA30, Diaion SK104, Diaion SKlB, Diaion PK208, Diaion PK212 and Diaion PK216 (Mitsubishi); TulsionTM T-38, Tulsion T-62, Tulsion T-66, Tulsion T-3825 and Tulsion T-3830 (Thermax); LewatitTM Kl 131, Lewatit K1221, Lewatit K1261 and Lewatit SC 104 (Sybron Chemicals); IndionTM 180 and Indion 225 (Ion Exchange (India) Limited); and PuroliteTM CT- 175, PuroliteTM CT- 169, and PuroliteTM CT-275(Purolite).
- a batch alkylate synthesis takes place in a pot-type reactor.
- the alkylate synthesis is conducted on a continuous basis in a continuous type reactor.
- the alkylation reaction is optionally quenched using a polar solvent, water, that forms a liquid phase containing most, if not all, of the catalyst and a organic phase containing the alkylated aryl compound, which may be removed by distillation.
- any free phenolic compounds that are not reacted with the olefins may be removed from the mixture of reaction products through distillation at a temperature, for example, of from 70 to 16O 0 C and at a pressure of from 1 to 10 mbar.
- the alkylate composition comprises 4-butyl phenol, e.g., 4-t-butyl phenol, and 2,4-diamyl phenol, e.g., 2,4-di-t-amyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt%.
- the alkylate composition comprises 4-amyl phenol, e.g., 4-t-amyl phenol, and 2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- the alkylate composition comprises 4-isopropyl phenol and 2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- the alkylate composition comprises 4-butyl phenol, e.g., 4-t-butyl phenol, and 2,4-di-isopropyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- the alkylate composition comprises 4-isopropyl phenol and 2,4-diamyl phenol, e.g., 2,4-di-t-amyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- the alkylate composition comprises 4-amyl phenol, e.g., 4-t-amyl phenol, and 2,4-di-isopropyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- the alkylate composition comprises a complex mixture of phenolics, for example, comprising three or four of the following: a 4-butyl phenol (e.g., 4-t-butyl phenol), a 2,4-dibutyl phenol (e.g., 2,4-di-t-butyl phenol), 4-amyl phenol (e.g., 4-t-amyl phenol), and a 2,4-diamyl phenol (e.g., 2,4-di-t-amyl phenol), preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%.
- a 4-butyl phenol e.g., 4-t-butyl phenol
- 2,4-dibutyl phenol e.g., 2,4-di-t-butyl phenol
- 4-amyl phenol e.g., 4-t-amyl phenol
- 2,4-diamyl phenol e.g
- the weight ratio of monosubstituted to disubstituted phenols contained in the alkylate composition preferably are as provided below.
- the alkylate composition may comprise, for example, from 5 to 95 wt %, e.g., from 10 to 70 wt % or from 30 to 65 wt %, of a p-alkylated phenol and from 5 to 95 wt %, e.g., from 10 to 70 wt % or from 30 to 65 wt %, of a o,p- dialkylated phenol.
- the p-alkylated phenol may comprise p-Alkyl-A phenol, p-Alkyl-B phenol or both p-Alkyl-A phenol and p-Alkyl-B phenol.
- the o,p-dialkylated phenol may comprise either o,p-di-Alkyl-A phenol or o,p-di-Alkyl-B phenol, or both o,p-di-Alkyl-A phenol and o,p-di-Alkyl-B phenol.
- the alkylate composition comprises a monoalkyl phenol, e.g., a 4-amyl phenol and/or a 4-butyl phenol, and a dialkyl phenol, e.g., a 2,4-diamyl phenol and/or a 2,4-dibutyl phenol.
- a monoalkyl phenol e.g., a 4-amyl phenol and/or a 4-butyl phenol
- a dialkyl phenol e.g., a 2,4-diamyl phenol and/or a 2,4-dibutyl phenol.
- the 4-alkyl phenol optionally is present in an amount greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt% or greater than 75 wt% and optionally in an amount less than 95 wt%, e.g., less than 85 wt%, less than 80 wt%, less than 75 wt% or less than 65 wt%.
- the 4-alkyl phenol e.g., 4-t-amyl phenol and/or 4-t-butyl phenol
- the dialkyl phenols e.g., 2,4-di-t-amyl phenol and/or 2,4-di-t-butyl phenol
- the dialkyl phenols preferably are present in an amount ranging from 1 wt% to 60 wt%, e.g., from 10 wt% to 50 wt%, from 25 wt% to 40 wt%, or from 25 wt% to 35 wt%.
- the dialkyl phenol is present in an amount less than 60 wt%, e.g., less than 55 wt%, less than 45 wt% or less than 35 wt%.
- dialkyl phenol e.g., 2,4-di-t-amyl phenol and/or 2,4-di-t-butyl phenol
- optionally is present in an amount greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, or greater than 40 wt%.
- the weight ratio of monoalkyl phenols, such as 4-t-amyl phenol or 4-t-butyl phenol, to dialkyl phenols, e.g., 2,4-di-t-amyl phenol or 2,4-di-t-butyl phenol, can be selected or adjusted so as to produce the desired alkylate composition that is suitable for being used as a reactant for forming an alkylaryl phosphite composition that is a liquid at ambient conditions.
- the weight ratio of monoalkyl phenols to dialkyl phenols in the alkylate compositions ranges from 5: 1 to 1 :2, e.g., from 5:1 to 1 : 1, from 3: 1 to 1: 1, or from 1.5: 1 to 1 : 1.
- Alkylate compositions outside of these weight ratio ranges may produce phosphite compositions that are not liquids and/or are meta-stable liquids under ambient conditions.
- the alkylate composition optionally formed from the above-described alkylate composition synthesis process, preferably is further reacted with a phosphorus trihalide, with or without catalyst, to form the liquid phosphite compositions of the invention, as described above in connection with the first embodiment of the invention.
- the liquid phosphite compositions of the present invention are obtained in a direct chemical reaction, in which the molar ratio of the alkylated phenol is adjusted to yield a phosphite composition that is a liquid at ambient conditions.
- a schematic of one reaction method that may be employed to form such phosphite compositions is as follows.
- R and R' are independently any of the groups as defined above (e.g., Ri and R 2 , respectively), but R and R' have a different number of carbon atoms.
- R and R' have a different number of carbon atoms.
- a minor amount of other alkylated phenols e.g., ortho- substituted monoalkylated phenols, may be included as an additional reactant in the above reaction scheme and would form additional derivative phosphites, but these additional reactants and products have been omitted from this reaction for clarity.
- Stabilizers e.g., ortho- substituted monoalkylated phenols
- a stabilizing amount or effective amount of the phosphite composition of the invention may be used as a secondary antioxidant for various types of polymers.
- stabilizing amount and an “effective amount” it is meant when the polymer composition containing the phosphite compositions of the invention shows improved stability in any of its physical or color properties in comparison to an analogous polymer composition which does not include a phosphite composition of the invention.
- improved stability include improved stabilization against, for example, molecular weight degradation, color degradation, and the like from, for example, melt processing, weathering, and/or long term field exposure to heat, light, and/or other elements.
- improved stability is obtained in the form of one or both of lower initial color or additional resistance to weathering, as measured, for example, by initial yellowness index (YI), or by resistance to yellowing and change in color, when compared to a composition without the stabilizer additive.
- YI initial yellowness index
- the additives and stabilizers described herein are preferably present in an amount effective to improve composition stability.
- the composition is generally present in an amount from about 0.001 to about 5 wt. %, e.g., from about 0.0025 to about 2 wt.% or from about 0.005 to about 1 wt.%, based on the total weight of the polymer including the weight of the phosphite composition and any other stabilizers or additives.
- the phosphite compositions of this invention stabilize resins especially during high temperature processing with relatively little change in melt index and/or color, even after multiple extrusions.
- the invention further relates to a stabilized thermoplastics, comprising a base polymer (e.g., polymer resin) and any of the aforementioned phosphite compositions of the invention.
- the polymer resin may be a polymer such as a polyolefin, and the liquid phosphite composition may be used with a costabilizer, for example, hindered phenolics, aromatic amines, hydroxylamines, lactones, and thioethers.
- thermoplastic that is stabilized by the phosphite compositions of the present invention may optionally contain one or more additional stabilizers or mixtures of stabilizers selected from the group consisting of the phenolic antioxidants, hindered amine light stabilizers (HALS), the ultraviolet light absorbers, phosphites, phosphonites, alkaline metal salts of fatty acids, hydrotalcites, metal oxides, epoxydized soybean oils, the hydroxylamines, the tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides, and the thiosynergists.
- HALS hindered amine light stabilizers
- the ultraviolet light absorbers phosphites, phosphonites, alkaline metal salts of fatty acids, hydrotalcites, metal oxides, epoxydized soybean oils, the hydroxylamines, the tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides, and the thio
- Liquid phosphite compositions 0.001-5.0 wt% 0.005-1.0 wt%
- the phosphite compositions of the invention or the resulting stabilized polymer compositions optionally also comprise primary antioxidants such as the following:
- Alkylated monophenols for example: 2,6-di-tert-butyl-4-methylphenol, 2-tert- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-bis( ⁇ - methylbenzyl)-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6- dioctadecyl-4-methylphenol, 2,4,6,-tricyclohexyphenol, and 2,6-di-tert-butyl-4- methoxymethylphenol.
- Commercially available alkylated monophenols include LowinoxTM 624 and NaugardTM 431 made by Chemtura Corp. Other phenols are commercially
- Alkylated hydroquinones for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, and 2,6-diphenyl- 4octadecyloxyphenol.
- Commercially available alkylated hydroquinones include Lowinox AH25 made by Chemtura.
- thiodiphenyl ethers include Lowinox TBM6, and Lowinox TBP6 made by Chemtura.
- Alkylidene-bisphenols for example, 2,2'-methylene-bis-(6-tert-butyl-4- methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-(4- methyl-6-( ⁇ -methylcyclohexyl)phenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(6-( ⁇ -methylbenzyl)-4-nonylphenol), 2,2'-methylene-bis-(6-(alpha,alpha- dimethylbenzyl)-4-nonyl-phenol), 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-methylene-bis-(4,6
- Benzyl compounds for example, l,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, bis-(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithiol-terephthalate, l,3,5-tris-(3,5-di-tert-butyl-4
- benzyl)isocyanurate l,3,5-tris-(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, 1 ,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5- Triazine-2,4,6-(lH,3H,5H)-trione, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, l,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
- Commercially available benzyl compounds include AnoxTM IC- 14, Anox 330 and Lowinox 1790 made by Chemtura.
- (vi) Acylaminophenols, for example, 4-hydroxylauric acid anilide, 4-hydroxy- stearic acid amilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
- 4-hydroxylauric acid anilide 4-hydroxy- stearic acid amilide
- 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine
- octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate
- esters of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid with monohydric or polyhydric alcohols for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris- hydroxyethylisocyanurate, thiodiethyleneglycol, di-hydroxyethyl oxalic acid diamide.
- Such phenols also include tetrakis [methylene ⁇ 3,5-di-tert-butyl-4-hydroxycinnamate ⁇ ]methane.
- Commercially available esters include Anox 20, Anox 1315, Lowinox GP45, Naugalube 38, Naugalube 531, Anox PPl 8, Naugard PS48 and Naugard XL- 1 made by Chemtura.
- thio esters include NaugalubeTM 15 and Anox 70 made by Chemtura.
- phenolic antioxidants include the following phenols.
- Polymeric phenols such as the reaction product of 4-methylphenol with dicyclopentadiene and isobutylene, commercially available as Lowinox CPL; Chemtura.
- Alkylidene-poly-phenols such as 1 ,3 tris(3-methyl-4-hydroxyl-5-t-butyl-phenyl)-butane (Lowinox CA22; Chemtura).
- Thio phenols such as 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-l,3,5-triazin-2-ylamino) phenol (IrganoxTM 565; Ciba), 4,6-bis (octylthiomethyl)-o-cresol (Irganox 1520; Ciba); 4,6- bis(dodecylthiomethyl)-o-cresol (Irganox 1726; Ciba). Hydroxyl amines, such as bis(octadecyl)hydroxylamine (IrgastabTM FS 042; Ciba).
- Ester phenols include bis[3,3-bis(4- hydroxy-3-tert-butyl phenyl)butanoic acid]glycol ester (HostanoxTM 03; Clariant Chemicals). Still other phenols include 2-[l-(2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]-4,6-di-tert- pentylphenyl acrylate (Sumilizer GS; Sumitomo Chemical).
- the stabilizing composition comprises one phenolic selected from the group consisting oftetrakismethylene (3,5-di-t-butyl-4-hydroxylhydrocinnamate) methane (Anox 20), l,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (Anox IC-14), l,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-triazine-2,4,6-(lH,3H,5H)-trione (Lowinox 1790), octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (Anox PP 18), bis(octadecyl)hydroxylamine (Irgastab FS-042), l,3,5-trimethyl-2,4,6-tris (3,5-di-tert-4
- the phosphite compositions and/or the resulting stabilized polymeric compositions optionally also comprise one or more UV absorbers and/or light stabilizers, such as the following:
- 2-Hydroxy-benzophenones for example, the 4-hydroxy, 4-methoxy-, 4- octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 2,4-dihydroxy-, 4,2',4'-trihydroxy- and T- hydroxy-4,4'-dimethoxy- derivative.
- 2-hydroxy-benzophenones include 2- hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2,4- dihydroxybenzophenone, and 2-hydroxy-4-propoxybenzophenone.
- 2-(2'-hydroxyphenyl)-benzotriazoles include Lowilite 20, Lowilite 22, Lowilite 2OS, and
- esters of substituted and unsubstituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl-salicilate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4- tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4- hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
- benzoylresorcinol 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
- UV absorbers and light stabilizers may also comprise acrylates, for example, alpha-cyano-beta, beta-diphenylacrylic acid-ethyl ester or isooctyl ester, alpha- carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester,
- Nickel compounds are also suitable UV absorbers and light stabilizers.
- Exemplary nickel compounds include nickel complexes of 2,2'-thio-bis(4-(l, 1,1,3- tetramethylbutyl)-phenol), such as the 1 :1 or 1 :2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel
- Commercially available nickel compounds include Lowilite Q84 (2,2'-Thiobis(4-tert-octyl-phenolato))-N- butylamine-Nickel(II) made by Chemtura.
- Sterically hindered amines may be used as UV absorbers and light stabilizers.
- Sterically hindered amines for example bis(2,2,6,6-tetramethylpiperidyl)-sebacate, bis- (1 ,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis(l,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1 -hydroxy ethyl- 2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, condensation product of N 3 N'- (2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert-octylamino-2,6-dichloro- 1 ,3,5-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)
- Such amines include hydroxylamines derived from hindered amines, such as di(l-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate: 1 -hydroxy 2,2,6,6- tetramethyl-4-benzoxypiperidine; l-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4- hydroxy hydrocinnamoyloxy)-piperdine; and N-(l-hydroxy-2,2,6,6-tetramethyl-piperidin-4- yl)-epsiloncaprolactam.
- hindered amines include Lowilite 19, Lowilite 62, Lowilite 77, Lowilite 92 and Lowilite 94 made by Chemtura.
- Oxalic acid diamides for examples, 4,4'-dioctyloxy-oxanilide, 2,2'-di- octyloxy-5',5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5',5'di-tert-butyl-oxanilide, 2-ethoxy- 2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'ethyl-5,4-di-tert-butyloxanilide and mixtures of o-and p-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides.
- the polymer resins and phosphite compositions of the invention may also include one or more additional additives, including, for example, one or more of the following:
- Metal deactivators for example, N,N'-diphenyloxalic acid diamide, N- salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4- hydrophenylpropionyl)-hydrazine, salicyloylamino-l,2,4-triazole, bis-benzyliden-oxalic acid dihydrazide.
- N,N'-diphenyloxalic acid diamide for example, N- salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4- hydrophenylpropionyl)-hydrazine, salicyloylamino-l,2,4-triazole, bis-benz
- Additional secondary antioxidants such as additional phosphites and/or phosphonites, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite tristearyl sorbitol triphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and t
- Secondary antioxidants include Naugalube TPP, AlkanoxTM 240, UltranoxTM 626, Naugard P, WestonTM 399, Weston TNPP, Weston 430, Weston 618F, Weston 619F, Weston DPDP, Weston DPP, Weston PDDP, Weston PTP, Weston TDP, Weston TLP, Weston TPP, and Weston TLTTP (trilauryl trithio phosphite) made by Chemtura; DoverphosTM 4, Doverphos 4-HR, Doverphos 4-HR Plus, Doverphos HiPure 4, and Doverphos S-9228 made by Dover Chemical; and Hostanox PEPQ made by Clariant Chemicals.
- Peroxide scavengers for example, esters of betathiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyldithiocaramate, dioctadecyldisulfide,
- Polyamide stabilizers for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese may also be included in the polymer resin and/or phosphite composition.
- Basic co-stabilizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, hydrotalcites, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, Ca stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Zn octoate, Mg stearate, Na ricinoleate and K palmirate, antimony pyrocatecholate or zinc pyrocatecholate.
- Basic co-stabilizers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, hydrotalcites, alkali metal salts and alkaline earth metal salts of higher
- co-stabilizers include MarkTM 6045, Mark 6045ACM, Mark 6055, Mark 6055ACM, Mark 6087ACM, Mark 6102, Mark CE 345, Mark CE 350, and Mark CE 387, made by Chemtura; and DHT-4ATM made by Kisuma Chemicals.
- Nucleating and clarifying agents for example, metal salts of 4-tert butylbenzoic acid, adipic acid, diphenylacetic acid, sorbitol and derivatives thereof, sodium benzoate, and benzoic acid.
- thiosynergists such as dilaurythiodipropionate or distearylthiodipropionate.
- the polymer or polymeric resins may include from 5-50 wt%, e.g., 10-40 wt% or 15-30 wt% fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
- fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
- the invention further pertains to a stabilized polymer, wherein one component comprises a liquid phosphite composition of the present invention and the other a polymer, such as a polyolefin, polyvinyl chloride, etc., or polymeric resins.
- the polymer stabilized by such liquid phosphite compositions may be any polymer known in the art, such as polyolefin homopolymers and copolymers, thermoplastics, rubbers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide-containing polymers, and biodegradable polymers.
- polyolefin homopolymers and copolymers such as polyolefin homopolymers and copolymers, thermoplastics, rubbers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide-containing polymers, and bio
- polystyrene resin blends such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS or other impact modified polymers, such as methacrylonitrile and ⁇ - methylstyrene containing ABS, and polyester/ABS or polycarbonate/ABS and polyester plus some other impact modifier may also be used.
- polymers are available commercially or may be made by means well known in the art.
- the stabilizer compositions of the invention are particularly useful in thermoplastic polymers, such as polyolefins,
- thermoplastic polymers due to the extreme temperatures at which thermoplastic polymers are often processed and/or used.
- the polymers used in combination with liquid phosphite compositions of the present invention are produced using a variety of polymerization processes including solution, high- pressure, slurry and gas phase using various catalysts including Ziegler-Natta, single-site, metallocene or Phillips-type catalysts.
- Non-limiting polymers useful with the liquid phosphite compositions include ethylene based polymers such as linear low density polyethylene, elastomers, plastomers, high density polyethylene, substantially linear long chain branched polymers, and low density polyethylene; and propylene based polymers such as
- polypropylene polymers including atactic, isotactic, and syndiotactic polypropylene polymers, and propylene copolymers such as propylene random, block or impact copolymers.
- the polymers typically ethylene based polymers, have a density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferably greater than 0.925 g/cc.
- the polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than about 8, even more preferably from about 2.2 to less than 5, and most preferably from 2.5 to 4.
- Mw/Mn weight average molecular weight to number average molecular weight
- the ratio of Mw/Mn can be measured by gel permeation chromatography techniques well known in the art.
- the polymers of the present invention in one embodiment have a melt index (MI) or (12) as measured by ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.
- the polymers of the invention in one embodiment have a melt index ratio (121/12) (121 is measured by ASTM-D-1238-F) of from 10 to less than 25, more preferably from about 15 to less than 25.
- the polymers of the invention in a preferred embodiment have a melt index ratio (121/12) (121 is measured by ASTM-D- 1238-F) of from preferably greater than 25, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65.
- Polymers used with liquid phosphites compositions of the invention are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding.
- Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and nonfood contact applications.
- Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc.
- Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.
- the liquid phosphite compositions are used in various rubber based products such as tires, barriers and the like. [0128] In one embodiment, the liquid phosphite compositions are suitable and/or approved for use in polymers, preferably polyolefins, that are used in contact with beverages, foods and other human consumables.
- Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene, or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslmked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used.
- HDPE high density polyethylene
- LDPE low density polyethylene
- LLDPE linear low density polyethylene
- polymers for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE), may also be used.
- copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene,
- the olefin polymers may be produced by, for example, polymerization of olefins in the presence of Ziegler-Natta catalysts optionally on supports such as, for example, MgCk, chromium 20 salts and complexes thereof, silica, silica-alumina and the like.
- the olefin polymers may also be produced utilizing chromium catalysts or single site catalysts, e.g., metallocene catalysts such as, for example, cyclopentadiene complexes of metals such as Ti and Zr.
- polyethylene polymers used herein can contain various comonomers such as, for example, 1-butene, 1- hexene and 1-octene comonomers.
- the polymer may also include styrenic polymers, such as polystyrene, poly-(p- methylstyrene), 5 poly-( ⁇ -methylystyrene), copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene (SBR),
- styrenic polymers such as polystyrene, poly-(p- methylstyrene), 5 poly-( ⁇ -methylystyrene), copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene (SBR),
- SBR styrene/butadiene
- styrene/maleimide styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methylacrylate, mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene/butylene/styrene or
- SBS styrene/butadiene/styrene
- SIS styrene/isoprene/styrene
- Styrenic polymers may additionally or alternatively include graft copolymers of styrene or ⁇ -methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and copolymers thereof; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene- propylene-diene terpolymers,
- Suitable rubbers include both natural rubber and synthetic rubbers, and combinations thereof.
- Synthetic rubbers include, but are not limited to, for example, thermoplastic rubbers, ethylene/alpha-olefin/non-conjugated polyene (EPDM) rubbers, ethylene/alpha-olefin (EPR) rubbers, styrene/butadiene rubbers, acrylic rubbers, nitrile rubbers, polyisoprene, polybutadiene, polychloroprene, acrylonitrile/butadiene (NBR) rubbers, polychloroprene rubbers, polybutadiene rubbers, isobutylene-isoprene copolymers, etc.
- Thermoplastic rubbers include SIS, solution and emulsion SBS, etc.
- Nitrile polymers are also useful in the polymer composition of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs, such as
- polymethacrylonitrile polyacrylonitrile, acrylonitrile/butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS compositions as referred to above in regard to styrenics.
- Polymers based on acrylic acids such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and esters thereof may also be used.
- acrylic acids such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and esters thereof may also be used.
- Such polymers include polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile -type monomer has been replaced by an acrylic acid ester or an acrylic acid amide.
- Polymers including other acrylic-type monomers, such as acrolein, methacrolein, acrylamide and methacrylamide may also be used.
- Halogen-containing polymers may also be stabilized with the phosphite compositions of the present invention.
- polymers such as polychloroprene, epichlorohydrin homo-and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloridestyrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloridestyrene- aery lonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride isoprene copolymer, vinyl chloride- chlorinated propylene copo
- Other useful polymers include homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides;
- cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers
- polyacetals such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer
- polycarbonates and polyester-carbonates polysulfones, polyethersulfones and
- polyetherketones and polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l,4-dimethylol-cyclohexane terephthalate, poly-2-(2,2,4(4-hydroxyphenyl)-propane) terephthalate and polyhydroxybenzoates as well as block copolyetheresters derived from polyethers having' hydroxyl end groups.
- polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l,4-dimethylol-cyclohexane terephthalate, poly-2-(2,2,4(4-hydroxyphenyl)-propane) terephthalate and polyhydroxybenz
- Polyamides and copolyamides which are derived from bisamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m- xylene bisamine and adipic acid; polyamides prepared from hexamethylene bisamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4 trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful.
- copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene glycol, polypropylene glycol or polytetramethylene glycols and polyamides or copolyamides modified with EPDM or ABS may be used.
- the polymer comprises a biodegradable polymer or compostable polymer.
- Biodegradable polymers are those in which the degradation results from the action of naturally occurring microorganisms, such as bacteria, fungi and algae. Compostable polymers undergoes degradation by biological processes during composting to yield CO2, water, inorganic compounds and a biomass at a rate consistent with other compostable materials.
- the biodegradable or compostable polymers are derived from plant sources and are synthetically produced. Examples of biodegradable or compostable polymers include poly(glycolic acid) (PGA), poly(lactic acid) (PLA), and copolymers thereof.
- Biodegradable or compostable polymers may also be derived from a blend of starch of a plant and a conventional petroleum-based polymer. For example, the biodegradable polymer may be blended with a polyolefin.
- Polyolefin, polyalkylene terephthalate, polyphenylene ether and styrenic polymers, and mixtures thereof are more preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether homopolymers and copolymers, polystyrene, high impact polystyrene, polycarbonates and ABS-type graft copolymers and mixtures thereof being particularly preferred.
- liquid phosphite compositions are added to stabilize natural and synthetic waxes, such as n-paraffin waxes, chloroparaffins, ⁇ -olefin waxes,
- microcrystalline waxes may be suitable for making candles.
- polyethylene waxes may be suitable for making candles.
- amide waxes may be suitable for making candles.
- Fisher-Tropsch waxes may be suitable for making candles.
- the instant stabilizers may readily be incorporated into the polymer by conventional techniques at any convenient stage prior to the manufacture of shaped articles therefrom.
- the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
- the stabilized compositions of the invention may optionally also contain from about 0.001 to about 5 wt. %, e.g., from about 0.0025 to about 2 wt. % or from about 0.05 to about 0.25 wt. %, of various conventional additives, such as those described previously, or mixtures thereof.
- the stabilizers of this invention advantageously assist with the stabilization of polymer compositions especially in high temperature processing against changes in melt index and/or color, even though the polymer may undergo a number of extrusions.
- the stabilizers of the present invention may readily be incorporated into the polymer compositions by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom.
- the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
- compositions of the present invention can be prepared by a variety of methods, such as those involving intimate admixing of the ingredients with any additional materials desired in the formulation. Suitable procedures include solution blending and melt blending. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. Examples of equipment used in such melt compounding methods include: co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment. In some instances, the compounded material exits the extruder through small exit holes in a die and the resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.
- All of the ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other or with a portion of the polymer or polymeric resin to make a stabilizer concentrate. Moreover, it is also sometimes
- vent port to allow venting (either atmospheric or vacuum) of the melt.
- the stabilizers of this invention may be conveniently incorporated by conventional techniques into polymers before the fabrication thereof into shaped articles, it is also possible to apply the instant stabilizers by a topical application to the finished articles.
- Articles may comprise the instant stabilizer compounds and polymers and may be made into, for example, head lamp covers, roofing sheets, telephone covers, aircraft interiors, building interiors, computer and business machine housings, automotive parts, and home appliances.
- the articles may be made by extrusion, injection molding, roto-molding, compaction, and other methods. This may be particularly useful with fiber applications where the instant stabilizers are applied topically to the fibers, for example, by way of a spin finish during the melt spinning process.
- the phosphite compositions of the invention may have uses in addition to polymer stabilization. For example, it may be desirable to react the phosphite composition to form a new derivative product, that may of additional uses.
- Transesterification processes for example, such as those disclosed in Hechenbleikner et al., U.S. Patent No. 3,056,823, which is incorporated herein by reference, may also be employed. Specifically, the process described by Hechenbleikner et al. involves transesterifying a triaryl phosphite with a monohydroxy hydrocarbon in the presence of a small but catalytically effective amount of a metal alcoholate or metal phenolate.
- the alcoholate of the particular alcohol to be transesterified is employed.
- the alcoholate can be formed in situ by adding the metal, e.g., sodium, potassium or lithium to the alcohol prior to adding the triaryl phosphite.
- the mono alcohol and triaryl phosphite are reacted in the mol ratio of three mols of the alcohol to one mol of the triaryl phosphite.
- the reaction was then filtered and the phenolic filtrate collected.
- GC analysis identified the following major components: 50.8% 4-t-butyl-phenol, 17.6% 2,4-di-t-butyl-phenol, 15.3% 4-t-amyl-phenol, 10.7% 2-t-amyl-4-t-butyl-phenol and 2- t-butyl-4-t-amyl-phenol, 1.3% 2,4-di-t-amyl-phenol, 1.4% 2-t-butyl-phenol, and 0.3% 2,4,6- tri-t-butyl-phenol.
- the phosphite composition had kinematic viscosity of @ 30 0 C of 8,541 cSt, @ 40 0 C of 3,198 cSt, and @ 50 0 C of 812 cSt.
- reaction temperature is uniformly ramped from 70 0 C to 150 0 C over 1 hour.
- the reaction mass is held at 150 0 C for 1 hour or until the HCl evolution has stopped.
- the reaction mass is further heated from 150 0 C to 200 0 C and held for 1 additional hour.
- the reaction is degassed by applying a vacuum at a pressure from 60-80 mbar until the total chlorine content is less than 50 ppm. Excess phenols may be removed by distillation under a pressure of 7mbar up to an internal temperature of 200 0 C (maximum vapor temperature 127°C).
- the resulting composition of phosphites had a kinematic viscosity at 70 0 C of 97 cSt.
- the total phosphorous content is 5.6%.
- a 1 : 1 molar ratio of 2-t-butyl-p-cresol and 4-t-amylphenol were charged to an oil jacketed flask and heated to 80 0 C under nitrogen.
- PCI3 (73.4 grams, 0.53 mole) was added, below the surface of the phenolics, at a uniform rate over 2 hours.
- the temperature was ramped to 150 0 C and the reaction mass was held at 150 0 C until HCl evolution ceased.
- the reaction mass was heated to over 200 0 C over 1 hour while the pressure was reduced from 1000 to 70 mbar, and held at these conditions until the total Cl content was less than 50 ppm.
- the phenolic excess was then removed by distillation under 8 mbar pressure and an internal temperature of 200 0 C.
- the resulting composition of phosphites had a kinematic viscosity at 70 0 C of 160 cSt.
- the total phosphorous content is 5.9%.
- composition of phosphites from Examples 1 and 2 were tested and compared against a tris(nonylphenyl)phosphite, Weston 399, and showed the following results in Table 3.
- the phosphite were added at the same phosphorous content for comparison (@ 17 ppm).
- Viscosities are provided in Table 4, below.
- Comparative Examples B and C were prepared in a similar amount with different molar ratios of phenols and different phenols as shown in Table 4 below. Comparative
- Examples D and E use 4-t-butylphenol (4-TBP).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Lubricants (AREA)
Description
LIQUID PHOSPHITE COMPOSITIONS HAVING DIFFERENT ALKYL GROUPS
PRIORITY CLAIM
[0001] This application claims priority to U.S. Provisional Application No. 61/230,652, filed July 31, 2009, and to U.S. Application No. 12/534,051, filed on July 31, 2009, which is a continuation in part application of U.S. Application Number 11/787,531, filed April 16, 2007, which claims priority to U.S. Provisional Application Number 60/815,819, filed June 20, 2006. Each of these applications is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to novel phosphite compositions suitable for use as antioxidants in polymer compositions. It also relates to stabilized polymer compositions and stabilizer concentrates comprising the novel liquid phosphite compositions.
BACKGROUND OF THE INVENTION
[0003] Organic phosphites are well-known and are commonly used as secondary antioxidants in polymer compositions including, for example, polyolefins, polyvinyl chloride, and elastomers. Examples of such phosphites are disclosed in H. Zweifel (Ed) Plastics Additives Handbook, 5th edition, Hanser Publishers, Munich 2000. Phosphite stabilizers, both liquid and solid, are known in the art.
[0004] Solid organic phosphite stabilizers are widely used as secondary antioxidants in polymer compositions. One commercially available antioxidant is tris(2,4-di-t-butylphenyl) phosphite, shown below, a solid antioxidant commonly known as Alkanox™ 240 (Chemtura Corporation, Middlebury, Connecticut, USA), Irgafos™ 168 (Ciba Specialty Chemicals Corp., Tarrytown, New York, USA) and Doverphos™ S-480 (Dover Chemical Corp., Dover, Ohio, USA). US Patent No. 5,254,709, the entirety of which is incorporated herein by reference, describes the synthesis of tris(2,4-di-t-butylphenyl) phosphite by reacting 2,4-di-t- butyl phenol with phosphorus trichloride in the presence of catalyst. The isolated phosphite is described as a white crystalline solid having a melting point of 180-1850C.
Tris(2,4-di-t-butylphenyl)phosphite
[0005] Tris(2,4-di-t-butylphenyl) phosphite has been demonstrated to effectively reduce peroxide induced oxidative degradation for many polymers including polyolefins, polycarbonates, ABS and polyesters. The trialkylaryl phosphite has low volatility that allows for its use at high temperatures commonly required for processing thermoplastic polymers. Owing to its solid form and concomitant processing limitations, however, tris(2,4-di-t- butylphenyl) phosphite is not well-suited for the stabilization of all polymers and has been demonstrated to plateout during processing of some plastics, in particular low melting point plastics, and forming deposits on processing machinery surfaces.
[0006] Liquid phosphite compositions are also well known and do not possess the handling problems associated with solid phosphite compounds. In addition, liquid phosphite compositions generally exhibit better processability than solid phosphite compositions for polymers that process at low temperatures. Tris(p-nonylphenyl) phosphite (TNPP), for example, is one alkylaryl phosphite that is a stable liquid at ambient conditions.
Tris(p-nonylphenyl)phosphite
TNPP is a versatile phosphite stabilizer that is useful in stabilizing a large number of polymers such as HDPE, LLDPE, SBR, ABS, PVC and others. There is, however, a need to replace TNPP owing to the alleged estrogenicity of nonylphenol, which is commonly used in the synthesis of TNPP.
[0007] Many commercially available alkylaryl phosphites share a common alkyl group. U.S. Patent No. 5,254,709, for example, the entirety of which is incorporated herein by reference, describes the synthesis of tris(2,4-di-t-butylphenyl) phosphite by reacting a 2,4-di- t-butyl phenol with phosphorus trichloride in the presence of catalyst according to the following reaction:
2,4-di-t-butylphenol tris(2,4-di-t-butylphenyl) phosphite
[0008] U.S. Patent No. 7,468,410 describes a mixture of phosphites including a tri(4-sec- butylphenyl)phosphite and a tri(2-sec-butylphenyl)phosphite. Each of these phosphites is a liquid when isolated, and the combination is a liquid.
[0009] U.S. Patent No. 5,254,709 describes various secondary antioxidants including a solid phosphite made from 2:1 molar ratio of 2,4-di-t-amyl phenol and 2,4-di-t-butyl phenol, and a liquid phosphite made from 2-t-butyl-4-nonyl phenol.
[0010] WO 2007/149143 discloses liquid phosphite blends comprising at least two different phosphites. In one example, a phosphite mixture is prepared by using as alkylated phenol feedstock the product obtained by alkylating phenol with isobutylene and amylene.
[0011] The need remains for novel, safe and effective phosphite stabilizers that can effectively stabilize polymer resins and compositions against heat and light degradation and that are liquid at ambient conditions.
SUMMARY OF THE INVENTION
[0012] In a first embodiment, the phosphite composition comprises two or more alkylaryl phosphites having the structure:
wherein a, b, c and d are independently selected from 0, 1, 2 and 3, provided that a + b + c + d= 3, and wherein each Ar is independently selected from an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, more preferably phenolics such as phenyl. Each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group
having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2. Preferably, at least one alkylaryl phosphite includes Ri and at least one other alkylaryl phosphite includes R2.
[0013] In another preferred embodiment of the invention the phosphite composition comprises a first phosphite wherein a + b =3, and consequently c = 0 and d= 0, and a second phosphite wherein c + d = 3, and consequently a = 0 and b = 0. In this embodiment, the two or more phosphites preferably include a first phosphite selected from the group consisting of tris(2,4-di-t-butylphenyl)phosphite, tris(4-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)- 4-t-butylphenyl phosphite, and bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite and a second phosphite selected from the group consisting of tris(2,4-di-t-amylphenyl)phosphite, tris(4-t-amylphenyl)phosphite, bis(2,4-di-t-amylphenyl)-4-t-amylphenyl phosphite, and bis(4- t-amylphenyl)-2,4-di-t-amylphenyl phosphite.
[0014] In a further preferred embodiment, the alkylaryl phosphite composition comprises at least one alkylaryl phosphite in which a + b - 1 or 2 and c + d= l or 2. In such
embodiments, a, b, c and d are independently selected from 0, 1, and 2.
[0015] In each aspect of the invention, Ri and R2 are independently selected from straight or branched C1-C12 alkyl groups, preferably selected from isopropyl, t-butyl and t-amyl.
[0016] In another embodiment, the invention is to a composition comprising at least two different alkylaryl phosphites, wherein at least one of the alkylaryl phosphites has two or more alkyl groups having a different number of carbon atoms on different aryl moieties, and wherein the composition is a liquid at ambient conditions. The different alkylaryl phosphites optionally is a reaction product of a phosphorous trihalide and a mixture of 2,4-di-t-amyl phenol and 4-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1. In another aspect, the two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-butyl phenol and either 4-t-amyl phenol or 2,4-di-t-amyl phenol, in a molar ratio of 1:4 to 4: 1. In another embodiment, the two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-amyl phenol and either 4-t-butyl phenol or 2,4- di-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1.
DETAILED DESCRIPTION OF THE INVENTION
Introduction
[0017] The present invention relates to phosphite compositions comprising at least two different alkylaryl phosphites provided that the phosphite composition includes two or more alkyl groups, whether on the same or different phosphite compounds, the two or more alkyl
groups having a different number of carbon atoms. The inclusion of two or more alkyl groups having a different number of carbon atoms leads to primarily to two different embodiments of the present invention as follows:
[0018] (i) Mixed Alkylate Embodiment. In the first embodiment, the two or more alkyl groups having a different number of carbon atoms are on different phosphite compounds. One phosphite has an alkyl group having a first number of carbon atoms and another phosphite has an alkyl group having a second number of carbon atoms, where the first and second numbers are different. The first embodiment is referred to as the "mixed phosphites" embodiment because such compositions may be formed by mixing two separately synthesized phosphites.
[0019] (ii) Mixed Phosphite Embodiment. In a second embodiment, the two or more alkyl groups having a different number of carbon atoms are on adjacent aryl moieties of specific phosphite compounds. Each phosphite has three aryl moieties and one of the aryl moieties is substituted with an alkyl group having the first number of carbon atoms and an adjacent aryl moiety is substituted with an alkyl group having a second number of carbon atoms, where the first and second numbers are different. The second embodiment is referred to as "mixed alkylates" embodiment because such phosphite compositions may be formed by reacting an alkylate composition with a phosphorous halide, where the alkylate composition comprises a composition of at least two separately synthesized alkylates.
[0020] It should be appreciated that two or more of the first and second embodiments may be combined to form even more diverse phosphite compositions.
Phosphite Compositions
[0021] While the various embodiments of the present invention will lead to different phosphite compositions, there generally are some shared characteristics for these different phosphite compositions. In preferred embodiments, the phosphite compositions are liquid at ambient conditions. By "ambient conditions" it is meant room temperature, e.g., 25°C, and 1 atmosphere pressure. As discussed herein, in each of the embodiments of the present invention the fact that the phosphite compositions are liquid at ambient conditions is surprising and unexpected because it would be expected that each of the different phosphites contained in the phosphite composition, when isolated, would be a solid at ambient conditions. This is particularly surprising given that the prior art teaches several examples of solid phosphite compositions, the components of which are separately solids at ambient condition, (See JP 59030842; WO 9303092; CA 2,464,551; US 5,254,709). In contrast, the
phosphite compositions of the invention are liquid even though the individual components would be expected to be solid.
[0022] As noted above, the phosphite compositions of the invention are liquids at ambient conditions even though at least some of the individual components, when isolated, are solid at ambient conditions. Table 1, for example, provides the melting points, each of which is above room temperature, for several pure phosphite compounds.
Table 1
Phosphite Melting Point tris(4-t-butylphenyl) phosphite 75-76°C
tris(2,4-di-tertbutylphenyl) phosphite 181-184°C
bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite 63-65°C
bis (2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite 100-1030C
tris(4-t-amylphenyl) phosphite 52-54°C
tris(2,4-di-t-amylphenyl) phosphite 1030C
[0023] As indicated above, the phosphite compositions of the invention are liquids at ambient conditions. As used herein, by "liquid," it is meant that the phosphite composition remains liquid after at least three "freeze/thaw" cycles as opposed to "meta-stable liquids," which do not remain liquid after three or fewer cycles. A freeze/thaw cycle is defined as follows: 1) An ambient temperature composition is stirred for 0.5 hours; 2) The stirred composition is then refrigerated at about 5 0C for three days; and 3) The refrigerated composition is then brought to ambient temperature, and held at ambient for 3 days. Upon completion of step 3, the composition is checked for solids content, e.g., crystallization. Completion of steps 1-3 defines one freeze/thaw cycle.
[0024] The viscosity of the phosphite composition may vary depending on the relative amounts of the various phosphite compounds contained therein. In some exemplary embodiments, the phosphite composition has a viscosity equal to or less than 11,000 cSt, e.g., equal to or less than 7,300 cSt, equal to or less than 5,000 cSt, equal to or less than 4,000 cSt, equal to or less than 3,000 cSt, or equal to or less than 2850 cSt, these viscosities being measured at 300C. In terms of ranges, viscosity of the composition may range from 1 cSt to 15,000 cSt, from 100 cSt to 12,000 cSt, from 500 cSt to 10,000 cSt, from 500 cSt to 6,500 cSt, from 500 cSt to 5,000 cSt, from 500 cSt to 3,000 cSt, from 1,000 cSt to 4,000 cSt, from 1,500 cSt to 3,500 cSt, from 2,000 cSt to 3,000 cSt, or from 2,000 to 2,800 cSt, these viscosities being measured at 300C.
[0025] It has now been discovered that by increasing the diversity of the alkylaryl phosphites in the phosphite composition, handling characteristics (e.g., liquid physical state and viscosity) as well as solubility/compatibility with various polymers can be
advantageously improved. The embodiments of the invention provide various ways to increase phosphite diversity by incorporating alkyl groups having different numbers of carbon atoms. In various optional embodiments, for example, the liquid composition may comprise at least 2, e.g., at least 4 or at least 10, different alkylaryl phosphites, and optionally from 2 to 100 different alkylaryl phosphites, e.g., from 3 to 20 different alkylaryl phosphites or from 4 to 10 different alkylaryl phosphites.
[0026] Another advantage of embodiments of the present invention is that alkylaryl phosphites derived from mixed alkylates helps to mitigate processing costs due to fluctuations in source alkenes and by eliminating the conventional need for substantially pure starting materials (e.g., olefins and/or alkylated phenolics).
[0027] Generally, each phosphite in the composition has the structure:
[0028] wherein a, b, c and d are independently selected from 0, 1, 2 and 3, provided that a
+ b + c + d= 3.
[0029] The aryl moiety (Ar) present in the compounds of the present invention is preferably an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, preferably phenolics such as phenyl.
[0030] Each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2. Preferably, at least one alkylaryl phosphite includes Ri and at least one other alkylaryl phosphite includes R2.
[0031] As indicated above, the phosphite composition comprises at least two phosphite compounds. The phosphite composition also preferably contains at least two alkyl groups having a different number of carbon atoms. Generally, each aromatic moiety is substituted,
e.g., Ri or R2, with at least one branched or straight chain Ci-Ci8 alkyl group, e.g., C4-C10 alkyl group or C4-C5 alkyl group, preferably t-butyl and/or t-amyl, but preferably no aromatic moieties are substituted with any C9 alkyl groups. In one embodiment, the two or more alkyl groups having a different number of carbon atoms are selected from branched or straight chain C1-C12 alkyl group, e.g., a C2-C5 alkyl group, a C2-C4 alkyl group, or C3-C5 alkyl group, provided that one alkyl group has a different number of carbon atoms than the another alkyl group. The alkyl groups may be selected, for example, from the group consisting of methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl (although less preferred), decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and isomers thereof. Most preferably, the alkyl group(s) are selected from propyl, especially isopropyl, butyl, especially sec-butyl, t-butyl, and amyl groups, especially sec-amyl, t-amyl and neo-amyl. Preferably, neither of the alkyl groups having different numbers of carbon atoms is Cs-Cio alkyl, e.g., C9 alkyl. Thus, in a preferred embodiment, the alkyl moieties do not include nonyl, meaning the phosphite composition preferably comprises less than 50 wppm, e.g., less than 10 wppm or less than 5 wppm nonyl substituted aryl phosphite compounds, and most preferably no detectable nonyl substituted aryl phosphite compounds. In addition, the phosphite composition preferably comprises less than 50 wppm, e.g., less than 10 wppm or less than 5 wppm nonylphenol, and most preferably no detectable nonylphenol.
[0032] The aromatic moieties may be mono, di or tri substituted in the ortho and/or para positions, but preferably the phosphites themselves are not exclusively mono substituted and are not exclusively disubstituted. Instead, the phosphite compositions of the invention ideally include phosphite compounds having aryl moieties that are monoalkylated and dialkylated. The combination of mono and di-substituted aryl moieties in combination with employing different alkyl groups advantageously may lead to very diverse phosphite compositions. Ideally, few if any of the aryl moieties are trisubstituted. For example, in some embodiments fewer than 3 wt. % of the aryl moieties are trisubstituted, e.g., fewer than 2 wt. %, or fewer than 1 wt. %.
[0033] Similarly, it is preferred that few if any of the aryl moieties are monosubstituted in the ortho position. Preferably, the aryl moieties are monosubstituted in the ortho position, if at all, in an amount less than 3 wt. %, e.g., less than 2 wt. % or less than 1 wt.
[0034] In one embodiment, the phosphite composition is substantially free of phosphite compounds having aryl groups that are substituted with alkyl groups having hydrogen atoms in the α position. That is, in preferred embodiments, at least 95%, at least 98% or at least
preferably t-butyl and/or t-amyl.
[0035] In some embodiments, the phosphite compositions have an overall phosphorus content that is equal to or greater than TNPP, e.g., at least 4.5 mole %, e.g., at least 4.8 mole %, or at least 5.1 mole %. In terms of ranges, the overall phosphorus content of the phosphite composition may range from 4.5 to 10.0 mole %, e.g., from 4.8 to 8.0 mole %, or 5.1 to 6.0 mole %, of all phosphorous containing compounds in the phosphite composition.
[0036] Preferably, the phosphite composition has a low level or is substantially free of phenolics (e.g., phenols, cresols or xylenols), whether alkylated or unalkylated, which is referred to herein as "free phenolics" when contained in the phosphite composition. In terms of amounts, the phosphite composition preferably comprises less than 5 wt. %, e.g., less than 3 wt. % or less than 1 wt. %, of free phenolics, based on the total weight of the phosphite composition. Any free phenolics, for example, may be removed by distillation. Extremely low levels of free phenolics may be achieved, for example, by employing a wiped-film molecular (Short-Path) still, wiped film evaporator (WFE), thin film evaporator, or similar equipment. In terms of amounts, the phosphite composition may comprise less than 0.5 wt. %, e.g., less than 0.2 wt. % or less than 0.1 wt. %, of free phenolics, based on the total weight of the phosphite composition.
[0037] In other embodiments, a minor amount of free phenolics may be beneficial, for example, as a viscosity reducing agent. Thus, in one embodiment, the phosphite composition comprises a minor amount of free phenolics, e.g., from 1 to 4 weight percent, e.g., from 2 to 3 weight percent, based on the total weight of the phosphite composition.
[0038] In addition, the phosphite composition is preferably substantially free of phosphite compounds having unsubstituted aryl moieties, e.g., triphenylphosphites, bis(phenyl)alkylphenyl phosphites or bis(alkylphenyl)phenyl phosphites. In terms of amounts, the phosphite composition preferably comprises less than 2 wt. %, e.g., less than 1 wt. % or less than 0.5 wt. %, phosphite compounds having at least one unsubstituted aryl moiety, based on the total weight of the phosphite composition. Alternatively, the alkylate used to prepare the phosphite composition may contain a minor amount of phenol, e.g., from 5 to 10 weight percent phenol, which may react during the phosphite synthesis process to form some phenyl phosphites.
[0039] In some preferred embodiments, the phosphite composition (whether of the first, second, or third embodiment) includes one or more hydrolytic stabilizers. Preferred stabilizers include amines of the structure:
wherein x is 1, 2 or 3; R3 is selected from the group consisting of hydrogen, and straight or branched Ci-Cβ alkyl, and R4 is selected from the group consisting of straight or branched Ci- C30 alkyl. Preferably R3 is selected from the group consisting of straight or branched C1-C4 alkyl, e.g., methyl or ethyl. Preferably R4 is selected from the group consisting of straight or branched C5-C20 alkyl, e.g., straight or branched C10-C20 alkyl or straight or branched Ci2-Ci8 alkyl. In one embodiment, x is 1 and R3 is straight or branched C5-C20 alkyl, e.g., Ci2-Ci8 alkyl. In one embodiment, x is 2 and R4 is straight or branched C10-C20 alkyl, e.g., Ci2-Ci8 alkyl.
[0040] In one aspect the amine is selected from the group consisting of triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine, and
tetraisopropanolethylenediamine.
[0041] In another aspect the amine is selected from the group consisting of octyl-bis(2- ethanol)amine, nonyl-bis(2-ethanol)amine, decyl-bis(2-ethanol)amine, undecyl-bis(2- ethanol)amine, dodecyl-bis(2-ethanol)amine, tridecyl-bis(2-ethanol)amine, tetradecyl-bis(2- ethanol)amine, pentadecyl-bis(2-ethanol)amine, hexadecyl-bis(2-ethanol)amine, heptadecyl- bis(2-ethanol)amine, octadecyl-bis(2-ethanol)amine, octyl-bis(2-propanol)amine, nonyl- bis(2-propanol)amine, decyl-bis(2-propanol)amine, undecyl-bis(2-propanol)amine, dodecyl- bis(2-propanol)amine, tridecyl-bis(2-propanol)amine, tetradecyl-bis(2-propanol)amine, pentadecyl-bis(2-propanol)amine, hexadecyl-bis(2-propanol)amine, heptadecyl-bis(2- propanol)amine, octadecyl-bis(2-propanol)amine, and isomers thereof. Commercially available amines include Armostat™ 300 and Armostat 1800 manufactured by Akzo Nobel Polymers.
[0042] Additional hydrolytic stabilizers include epoxies such as epoxidized soybean oil (ESBO) commercially available as Drapex™ 39, Drapex 392, Drapex 4.4, and Drapex 6.8 (Chemtura Corp.).
[0043] The amine may be present in an amount of from 0.01 to 5 wt. %, e.g., from 0.1 to 1.5 wt. % or from 0.2 to 0.8 wt. %, based on the total weight of the phosphite composition.
[0044] The various embodiments of the present invention will now be separately described in more detail below.
Mixed Phosphites Embodiment
[0045] In the first embodiment, the present invention relates to liquid phosphite compositions having at least two different alkylaryl phosphites. Specifically, the phosphite compositions comprise one or more first phosphites having exclusively first alkyl groups and one or more second phosphites having exclusively second alkyl groups, wherein the first alkyl groups have a different number of carbon atoms than the second alkyl groups. The phosphite compositions comprise phosphites having at least the following two structures:
and
wherein a, b, c, and d are independently integers selected from 0, 1, 2, and 3, provided that a+b=3 and c+<i=3. Each Ar is an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, more preferably phenolics such as phenyl.
[0046] It should be understood that structures III and IV are derived from structure I.
Structure III indicates one of the two phosphites wherein a + b =3, and consequently c = 0 and d = 0. Structure IV indicates the another of the two phosphites wherein c + d - 3, and consequently a = 0 and b = 0.
[0047] In one embodiment, each Ar is independently selected from the formula:
wherein one or two of the groups R5, Re, and R7 are either Ri (formula IV) or R2 (formula V), the reminder being H, Rg is hydrogen or methyl, provided that at least one of R5, Re, R7 and Rs is not hydrogen. Preferably, each Ar is a phenolic, more preferably phenyl. Each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2. Thus, Ri and R2 preferably are independently selected from straight or branched Ci- Ci8 alkyl, e.g., Ci-Ci2, C2-C5 or C2-C4 alkyl, provided that that Ri has a different number of carbon atoms than R2. In one embodiment, one of Ri or R2 is C4 alkyl, e.g., t-butyl, and the other of Ri or R2 is C5 alkyl, e.g., t-amyl.
[0048] In one embodiment of the present invention, the phosphite composition comprises at least a first phosphite and a second phosphite, wherein the first phosphite comprises an Alkyl-A group and the second phosphite comprises an Alkyl-B group. As used herein, "Alkyl-A" refers to an alkyl group having A carbon atoms and "Alkyl-B" refers to an alkyl group having B carbon atoms, wherein B is a whole number greater than A. For example, Alkyl-A may be t-butyl, and Alkyl-B may be t-amyl. Thus, the first phosphite will be substituted with alkyl groups that have fewer carbon atoms that the second phosphite. It should be noted that each of Alkyl-A and Alkyl-B may include multiple isomers of alkyl groups having the same number of carbon atoms. For example, Alkyl-A groups may include sec-butyl and t-butyl, and Alkyl-B groups may include sec-amyl and t-amyl.
[0049] For example, the first phosphite may be selected from the group consisting of: tris(Alkyl-A-aryl) phosphite, tris(di-Alkyl-A-aryl)phosphite, bis(Alkyl-A-aryl)di-Alkyl-A- aryl phosphite, and bis(di-Alkyl-A-aryl)Alkyl-A-aryl phosphite. The second phosphite may
be selected from the group consisting of: tris(Alkyl-B-aryl) phosphite, tris(di-Alkyl-B-aryl) phosphite, bis(Alkyl-B-aryl)di-Alkyl-B-aryl phosphite, and bis(di-Alkyl-B-aryl)Alkyl-B-aryl phosphite. Preferably, the phosphite composition comprises at least three, e.g., at least four or at least five, of the phosphites identified above.
[0050] The relative amounts of the first and second phosphites in the phosphite composition may vary so long as the phosphite composition is a liquid at ambient conditions. In one embodiment, the molar ratio of Alky 1- A groups to Alkyl-B groups, or alternatively of the first phosphite(s) to the second phosphite(s), is from 1 : 10 to 10: 1, e.g., from 1:4 to 4: 1 or from 2: 1 to 1 : 1. In a preferred embodiment, the phosphite composition comprises the phosphite having alkyl groups with the lesser number of carbon atoms, i.e., the first phosphite, in an amount greater than the phosphite having alkyl groups with the greater number of carbon atoms, i.e., the second phosphite. For example, if the first phosphite is substituted with t- butyl groups and the second phosphite is substituted with t-amyl groups, the phosphite composition preferably comprises the first phosphite in an amount greater than the second phosphite. By including a greater amount of the first phosphite than the second phosphite, the overall phosphorus content may be advantageously maximized. In addition, the second phosphite in the phosphite composition, preferably in a minor amount, may improve, e.g., lower, the viscosity and processing characteristics for the overall phosphite composition.
[0051] In some embodiments, for example, the phosphite composition comprises the first phosphite (containing Alkyl- A groups) in an amount greater than 50 weight percent, greater than 60 weight percent or greater than 75 weight percent, based on the total weight of all phosphites in the phosphite composition, and preferably comprises the second phosphite (containing Alkyl-B groups) in an amount greater than 5 weight percent, greater than 10 weight percent or greater than 25 weight percent, based on the total weight of all phosphites in the phosphite composition. In terms of ranges, the phosphite composition preferably comprises the first phosphite in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the second phosphite in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphites in the phosphite composition.
[0052] In other embodiments, the phosphite composition comprises the phosphite having the alkyl groups with the lesser number of carbon atoms in an amount less than the phosphite having the alkyl groups with the greater number of carbon atoms. In this embodiment, the phosphite composition optionally comprises the second phosphite in an amount from 50 to 90
weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the first phosphite in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphites in the phosphite composition.
[0053] In one preferred embodiment, the first phosphite is substituted with propyl groups, e.g., isopropyl groups, and the second phosphite is substituted with butyl groups, e.g., t-butyl groups. In another preferred embodiment, the first phosphite is substituted with propyl groups, e.g., isopropyl groups, and the second phosphite is substituted with amyl groups, e.g., t-amyl groups. In still another preferred embodiment, the first phosphite is substituted with butyl groups, e.g., t-butyl groups, and the second phosphite is substituted with amyl groups, e.g., t-amyl groups.
[0054] Thus, in one embodiment, Alkyl-A is isopropyl and Alkyl-B is t-butyl. In this aspect, the first phosphite is selected from the group consisting of tris(4-isopropyl phenyl) phosphite, tris(2,4-dipropylphenyl) phosphite, bis(4-propylphenyl)-2,4-dipropylphenyl phosphite, and bis(2,4-di-isopropylphenyl)-4-isopropylphenyl phosphite. In this aspect, the second phosphite is selected from the group consisting of tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite.
[0055] In another embodiment, Alkyl-A is isopropyl and Alkyl-B is t-amyl. In this aspect, the first phosphite is selected from the group consisting of tris(4-isopropyl phenyl) phosphite, tris(2,4-di-isopropyl phenyl) phosphite, bis(4-isopropyl phenyl)-2,4-di-isopropyl phenyl phosphite, and bis(2,4-di-isopropyl phenyl)-4-isopropyl phenyl phosphite, and the second phosphite is selected from the group consisting of tris(4-t-amylphenyl) phosphite, tris(2,4-di- t-amylphenyl) phosphite, bis(4-t-amylphenyl)-2,4-di-t-amylphenyl phosphite, and bis(2,4-di- t-amylphenyl)-4-t-amylphenyl phosphite.
[0056] In a particularly preferred embodiment, tertiary olefins such as t-butyl and t-amyl are employed in combination where the aryl moiety is a phenolic, e.g., phenyl. For example, the phosphite composition may comprise a first phosphite and a second phosphite where the first phosphite is selected from the group consisting of tris(4-t-butylphenyl) phosphite, tris(2,4-di-t-butylphenyl) phosphite, bis(4-t-butylphenyl)-2,4-di-t-butylphenyl phosphite, and bis(2,4-di-t-butylphenyl)-4-t-butylphenyl phosphite. In this aspect, the second phosphite is selected from the group consisting of tris(4-t-amylphenyl) phosphite, tris(2,4-di-t- amylphenyl) phosphite, bis(4-t-amylphenyl)-2,4-di-t-amylphenyl phosphite, and bis(2,4-di-t- amylphenyl)-4-t-amylphenyl phosphite.
[0057] In some embodiments, the phosphite composition comprises at least three, e.g., at least four or at least five, of the phosphites identified above.
[0058] Because of the presence of multiple phosphite compounds, the phosphite compositions of this embodiment may be particularly diverse so long as the overall phosphite composition is a liquid at ambient conditions. In some exemplary embodiments, the phosphite composition optionally comprises tris(monoalkylaryl)phosphites, e.g., tris(Alkyl- A-phenyl) phosphite and tris(Alkyl-B -phenyl) phosphite, in an amount from 20 to 70 weight percent, e.g., from 15 to 55 weight percent, or from 37 to 54 weight percent, based on the total weight of all phosphites in the phosphite composition. The phosphite composition optionally comprises bis(monoalkylaryl)dialkylaryl phosphites, e.g., bis(Alkyl-A-phenyl)di- Alkyl-A-phenyl phosphite, and bis(Alkyl-B-phenyl)di-Alkyl-B-phenyl phosphite, in an amount from 15 to 60 weight percent, e.g., from 31 to 50 weight percent, or from 34 to 45 weight percent, based on the total weight of all phosphites in the phosphite composition. The phosphite composition optionally further comprises tris(dialkylaryl) phosphites and/or bis(dialkylaryl)monoalkylaryl phosphites. If present, the phosphite composition preferably comprises bis(dialkylaryl)monoalkylaryl phosphites, e.g., bis(di-Alkyl-A-phenyl)Alkyl-A- phenyl phosphite and bis(di-Alkyl-B-phenyl)Alkyl-B-phenyl phosphite, in an amount of from 2 to 20 weight percent, e.g., from 4 to 20 weight percent or from 5 to 10 weight percent, based on the total weight of all phosphites in the phosphite composition. If present, the phosphite composition preferably comprises tris(dialkylaryl) phosphites, e.g., tris(di-Alkyl- A-phenyl) phosphite and/or tris(di-Alkyl-B-phenyl) phosphite in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on the total weight of all phosphites in the phosphite composition.
[0059] The process for forming the phosphite compositions of the first embodiment comprises separately making each phosphite and blending the separate phosphites together. Preferably the first phosphite is formed from the reaction of a phosphorous trihalide with a first alkylate composition, which in turn is formed from the reaction between a hydroxyaryl compound and a first olefin. Similarly, the second phosphite is formed from the reaction of a phosphorous trihalide with a second alkylate composition, which in turn is formed from the reaction between a hydroxyaryl compound and a second olefin, wherein the second olefin has a different number of carbon atoms than the first olefin.
[0060] In the phosphite synthesis reaction, phosphite compositions are obtained in a direct chemical reaction. A schematic of one reaction method that may be employed to form such
phosphite compositions is as follows. As indicated above, the first phosphite and the second phosphite are separately synthesized according to the below process.
wherein R is independently any of the groups as defined above (e.g., Ri or R2, respectively). Note that a minor amount of other alkylated phenols, e.g., ortho-substituted monoalkylated phenols, may be included as an additional reactant in the above reaction scheme and would form additional derivative phosphites, but these additional reactants and products have been omitted from this reaction for clarity.
[0061] The phosphorus trihalide preferably is selected from phosphorus trichloride and phosphorus tribromide. When a catalyst is used, the catalyst may be selected from the group consisting of pyridine, N,N-dimethyldodecylamine, and dilauryl methyl amine or their hydrochloride salts. The molar ratio of alkylate composition (i.e., alkylated phenol compounds) to phosphorus trihalide preferably is from 3: 1 to 5: 1, e.g., from 3: 1 to 4:1 or from 3.1 to 3.7: 1.
[0062] The reaction of the alkylated phenols with a phosphorus trihalide may be conducted under an inert atmosphere (e.g., nitrogen) at a temperature of from 5 to 700C, e.g., from 40 to
700C or from 50 to 700C. Preferably, the temperature is held at or below 700C during the addition of the alkylate composition to prevent refluxing the phosphorus trihalide.
Optionally, the alkylate composition is charged to the reactor and the phosphorus trihalide is added thereto. After the addition of alkylate composition, the temperature is optionally held for 10 minutes to 12 hours, e.g., from 30 minutes to 10 hours, or from 1 hour to 3 hours. The reaction preferably is conducted at a pressure of 0.8 to 4 atm, e.g., from 0.9 to 3 atm or from 1 to 2 atm. Next, the temperature may be ramped a ramped temperature ranging from 700C to 2500C, e.g., from 800C to 225°C or from 900C to 2000C. Preferably, the reaction is held at the ramped temperature for from 10 minutes to 12 hours, e.g., from 30 minutes to 10 hours, or from 1 hour to 3 hours. The reaction preferably is conducted at a reduced pressure of 0.01 to 0.5 atm, e.g. from 0.03 to 0.4 atm or from 0.04 to 0.1 atm. During the reaction time, hydrochloric or hydrobromic gas will be evolved, and may be removed by reducing the pressure to about 0.05 atm or sweeping an inert gas such as nitrogen over the reaction mixture. In one aspect the removal of such gases may be performed until the total chloride content in the reaction mixture is less than 50 wppm, e.g., less than 25 wppm or less than 10 wppm.
[0063] In one aspect of the process, any free phenol that is not reacted with the phosphorus trihalide may be liberated by raising the reaction temperature to up to 275°C, e.g., up to 2500C or up to 225°C, or up to 2000C, and in a vacuum at a pressure of 0.0001 to 0.1 atm. In one embodiment, a wiped- film molecular (Short-Path) still, wiped film evaporator (WFE), thin film evaporator, or similar equipment may be used to further remove the free cresol or phenol to the very low levels indicated above.
[0064] In one embodiment, the step of forming the phosphite composition may occur in one or more neutral solvents. Typical solvents that may be employed include toluene, xylene, methylene chloride, heptane, chloroform, and benzene.
[0065] Since the invention of this embodiment comprises two different phosphites having different alkyl groups, one or more of the products shown above in scheme (V), optionally may be separated or partially separated (e.g., through distillation) from the other reaction products. In this aspect, two relatively pure phosphites may be optionally heated and blended to form a mixture of phosphite compounds, each having a different alkyl groups. For example, the phosphite composition may comprise a first phosphite comprising a substantially pure monosubstituted aryl phosphite that is alkylated with Alkyl- A, and a second phosphite comprising a substantially pure disubstituted aryl phosphite that is dialkylated with Alkyl-B. Liquid phosphite compositions may be formed from such first and
second phosphite compounds when combined in the proper ratios, as described above. In other embodiments the first phosphite includes several compounds that are alkylated with Alkyl-A (e.g., any of those shown in scheme (V) above) and/or the second phosphite includes several compounds that are alkylated with Alkyl-B.
Mixed Alkylates Embodiment
[0066] In the second embodiment, the invention is to liquid alkylaryl phosphite compositions comprising two or more phosphite compounds, wherein at least some of the phosphite compounds are substituted with multiple alkyl groups including at least a first alkyl group and a second alkyl group, the first alkyl group having a different number of carbon atoms than the second alkyl group, and provided that no individual aryl moiety is substituted with both the first alkyl group and the second alkyl group. That is, each respective aryl moiety is substituted exclusively with either the first alkyl group or the second alkyl group, but not both.
[0067] At least one of the phosphites in the liquid composition would have the structure:
wherein a, b, c and d are independently selected from O, 1 and 2, provided that a + b + c + d = 3. In this embodiment, the phosphite composition comprises at least one alkylaryl phosphite in which a + b = 1 or 2, i.e., a + b is not O, and c + d - 1 or 2, i.e., c + dis not O. Optionally, the phosphite composition further comprises one or more alkylaryl phosphites of formula (I) in which a + b = 3 and/or c + d = 3.
[0068] Each Ar is independently selected from an aromatic moiety of from 6 to 18 carbon atoms, e.g., phenyl, naphthyl, phenanthryl, anthracyl, biphenyl, terphenyl, o-cresyl, m-cresyl, p-cresyl, xylenols and the like, more preferably phenolics such as phenyl.
[0069] In one embodiment, each Ar is independently selected from the formula:
wherein one or two of the groups R5, Re, and R7 are either Ri or R2, the reminder being H, Rs is hydrogen or methyl, provided that at least one of R5, Re, R7 and Rs is not hydrogen.
Preferably, each Ar is a phenolic, more preferably phenyl. Each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2. Thus, Ri and R2 preferably are independently selected from straight or branched Ci -Ci 8 alkyl groups, e.g., C1-C12, e.g., C2-C5 or C2-C4 alkyl groups, provided that Ri has a different number of carbon atoms than R2. In one embodiment, one of Ri or R2 is C4 alkyl, e.g., t-butyl, and the other of Ri or R2 is C5 alkyl, e.g., t-amyl.
[0070] In one aspect, the phosphite composition comprises at least two phosphites, wherein the first and second phosphites are independently selected from the group consisting of: bis(Alkyl-A-aryl)di-Alkyl-B-aryl phosphite, bis(Alkyl-B-aryl)di-Alkyl-A-aryl phosphite, bis(di-Alkyl-A-aryl)Alkyl-B-aryl phosphite, bis(di-Alkyl-B-aryl)Alkyl-A-aryl phosphite, (Alkyl-A-aryl)(Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite, (Alkyl-A-aryl)(Alkyl-B-aryl)(di- Alkyl-B-aryl) phosphite, (Alkyl-A-aryl)(di-Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite, (Alkyl- B-aryl)(di-Alkyl-B-aryl)(di-Alkyl-A-aryl) phosphite, bis(di-Alkyl-A-aryl)di-Alkyl-B-aryl phosphite, and bis(di-Alkyl-B-aryl)di-Alkyl-A-aryl phosphite, provided that the second phosphite is different from the first phosphite. The phosphite composition in this embodiment may also comprise one or more of tris(Alkyl-A-aryl) phosphite, tris(Alkyl-B- aryl) phosphite, tris(di-Alkyl-A-aryl) phosphite, tris(di-Alkyl-B-aryl) phosphite, bis(Alkyl-A- aryl)di-Alkyl-A-aryl phosphite, bis(di-Alkyl-A-aryl)Alkyl-A-aryl phosphite, bis(Alkyl-B- aryl)di-Alkyl-B-aryl phosphite, and bis(di-Alkyl-B-aryl)Alkyl-B-aryl phosphite. Other
phosphites, possibly having an alkyl substituents other than Alkyl-A and Alkyl-B, may also be included in the phosphite composition.
[0071] The relative amounts of Alkyl-A and Alkyl-B groups (or optional additional groups) contained in the phosphite composition may vary so long as the phosphite composition is a liquid at ambient conditions. In one embodiment, the molar ratio of Alkyl-A groups to Alkyl-B groups, e.g., the first alkylated aryl groups to second alkylated aryl groups, is from 1 : 10 to 10: 1, e.g., from 1 :4 to 4:1 or from 2: 1 to 1 : 1. In terms of weight percentages, the phosphite composition optionally comprises the first alkylated aryl moiety in an amount from 5 to 95 weight percent, e.g., from 25 to 75 weight percent, or from 35 to 60 weight percent, and the second alkylated aryl moiety in an amount from 5 to 95 weight percent, e.g., from 25 to 75 weight percent or from 35 to 60 weight percent. More preferably, the phosphite composition comprises the alkyl groups with the lesser number of carbon atoms, i.e., Alkyl- A, in an amount greater than the alkyl groups with the greater number of carbon atoms, i.e., Alkyl-B. By including a greater amount of Alkyl-A than Alkyl-B, the overall phosphorus content may be advantageously maximized. In addition, the presence of Alkyl-B in the phosphite compositions of the invention allows for a more diverse phosphite composition than a comparable phosphite composition that does not include Alkyl-B. Such phosphite composition complexity may improve, e.g., lower, the viscosity and processing
characteristics for the overall phosphite composition.
[0072] In some embodiments, for example, the phosphite composition comprises the Alkyl- A group in an amount greater than 50 weight percent, greater than 60 weight percent or greater than 75 weight percent, based on the total weight of all phosphite alkyl groups in the phosphite composition, and preferably comprises the Alkyl-B group in an amount greater than 5 weight percent, greater than 10 weight percent or greater than 25 weight percent, based on the total weight of all phosphite alkyl groups in the phosphite composition. In terms of ranges, the phosphite composition preferably comprises the Alkyl-A group in an amount from 50 to 90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the Alkyl-B group in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphite alkyl groups in the phosphite composition.
[0073] In other embodiments, the phosphite composition comprises the alkyl groups with the lesser number of carbon atoms, i.e., Alkyl-A groups, in an amount less than the alkyl groups with the greater number of carbon atoms, i.e., Alkyl-B groups. In this embodiment, the phosphite composition optionally comprises the Alkyl-B groups in an amount from 50 to
90 weight percent, e.g., in an amount from 60 to 90 weight percent or in an amount from 75 to 90 weight percent, and the Alkyl-A groups in an amount from 10 to 50 weight percent, e.g., from 10 to 40 weight percent or from 10 to 25 weight percent, based on the weight of all phosphite alkyl groups in the phosphite composition.
[0074] In one aspect of this embodiment, Alkyl-A is propyl, e.g., isopropyl, and Alkyl-B is butyl, e.g., t-butyl. In another aspect, Alkyl-A is propyl, e.g., isopropyl, and Alkyl-B is amyl, e.g., t-amyl. In still another preferred aspect, Alkyl-A is butyl, e.g., t-butyl, and Alkyl-B is amyl, e.g., t-amyl.
[0075] In this embodiment, the phosphite compositions may be particularly diverse containing many different phosphite compounds. In some exemplary embodiments, the phosphite composition optionally comprises tris(monoalkylaryl)phosphites, e.g., tris(Alkyl- A-phenyl) phosphite, tris(Alkyl-B -phenyl) phosphite, bis(Alkyl-A-phenyl)Alkyl-B-phenyl phosphite, bis(di-Alkyl-A-phenyl)di-Alkyl-B-phenyl phosphite, and the like, in an amount from 20 to 70 weight percent, e.g., from 15 to 55 weight percent, or from 37 to 54 weight percent, based on the total weight of all phosphites in the phosphite composition. The phosphite composition optionally comprises bis(monoalkylaryl)dialkylaryl phosphites, e.g., bis(Alkyl-A-phenyl)di-Alkyl-B-phenyl phosphite, bis(Alkyl-B-phenyl)di-Alkyl-A-phenyl phosphite, bis(Alkyl-A-phenyl)di-Alkyl-A-phenyl phosphite, bis(Alkyl-B-phenyl)di-Alkyl- B-phenyl phosphite, (Alkyl-A-phenyl)(Alkyl-B-phenyl)di-Alkyl-A-phenyl phosphite, and the like, in an amount from 15 to 60 weight percent, e.g., from 31 to 50 weight percent, or from 34 to 45 weight percent, based on the total weight of all phosphites in the phosphite composition. The phosphite composition optionally further comprises tris(dialkylaryl) phosphites and/or bis(dialkylaryl)monoalkylaryl phosphites. If present, the phosphite composition preferably comprises bis(dialkylaryl)monoalkylaryl phosphites, e.g., bis(di- Alkyl-A-phenyl) Alkyl-B -phenyl phosphite, bis(di-Alkyl-B-phenyl)Alkyl-A-phenyl phosphite, bis(di-Alkyl-A-phenyl)Alkyl-A-phenyl phosphite, bis(di-Alkyl-B-phenyl)Alkyl- B-phenyl phosphite, di-Alkyl-A-phenyl-di-Alkyl-B-phenyl-mono-Alkyl-B-phenyl phosphite, (di-Alkyl-A-phenyl)(di-Alkyl-B-phenyl)(Alkyl-A-phenyl) phosphite, and the like, in an amount of from 2 to 20 weight percent, e.g., from 4 to 20 weight percent or from 5 to 10 weight percent, based on the total weight of all phosphites in the phosphite composition. If present, the phosphite composition preferably comprises tris(dialkylaryl) phosphites, e.g., tris(di-Alkyl-A-phenyl) phosphite, tris(di-Alkyl-B-phenyl) phosphite, bis (di- Alkyl- A- phenyl)di-Alkyl-B-phenyl phosphite, and the like, in an amount from 0.1 to 20 weight percent, e.g., from 0.3 to 5 weight percent or from 0.5 to 1 weight percent, based on the total
weight of all phosphites in the phosphite composition. As suggested by the above example compounds, for purposes of the present specification a tris(monoalkylaryl) phosphite and a tris(dialkylaryl) phosphite may include tris compounds having exclusively the same alkyl groups (either Alkyl-A or Alkyl-B), or may comprise a mixture of alkyl groups (e.g., Alkyl-A and Alkyl-B) so long as each aryl moiety on the phosphite is similarly substituted, i.e., all are monosubstituted or all or disubstituted, respectively. Similarly, the
bis(dialkylaryl)monoalkylaryl phosphites and bis(monoalkylaryl)dialkylaryl phosphites may include exclusively the same alkyl group or different alkyl groups so long as the respective bis(dialkylaryl)monoalkylaryl phosphite compound includes two dialkylaryl groups and one monoalkylaryl group, and the bis(monoalkylaryl)dialkylaryl phosphite compound includes two monoalkylaryl groups and one dialkylaryl group.
[0076] Generally, the liquid phosphites of the second embodiment are reaction products of a phosphorous halide and an alkylate composition that is a mixture of alkylated hydroxyaryl compounds, some of which are alkylated with Alkyl-A and some of which are alkylated with Alkyl-B. Thus, in this embodiment of the invention, a mixed alkylate composition is employed in forming the desired phosphite composition. In one embodiment, the alkylated composition comprises a first alkylate and a second alkylate, where the alkyl group on the first alkylate has a different number of carbon atoms than the alkyl groups on the second alkylate. The alkylate composition may comprise, for example: (i) a first alkylate composition comprising mono and/or di-Alkyl-A-phenols, and (ii) a second alkylate composition comprising mono and/or di-Alkyl-B-phenols.
[0077] In one preferred embodiment, the alkylate composition comprises two or more compounds selected from the group consisting of a propylated hydroxyaryl compound, a butylated hydroxyaryl compound and an amylated hydroxyaryl compound. The propylated hydroxyaryl compound preferably is selected from the group consisting of 4-isopropyl phenol and 2,4-di-isopropyl phenol. The butylated hydroxyaryl compound preferably is selected from the group consisting of 4-t-butyl phenol and 2,4-di-t-butyl phenol. The amylated hydroxyaryl compound preferably is selected from the group consisting of 4-t-amyl phenol and 2,4-di-t-amyl phenol.
[0078] The first alkylate and the second alkylate optionally are separately synthesized and mixed to form the alkylate composition, which is subsequently reacted with the phosphorous halide to form the phosphite composition. Each alkylate, in one aspect, may be separately formed by the reaction between an olefin, e.g., propylene, butylene or amylene, and a hydroxyaryl compound, e.g., phenol. For example, the first alkylate may be derived from a
first olefin, and the second alkylate may be derived from a second olefin having a different number of carbon atoms than the first olefin. Alternatively, the alkylate composition may be formed in a single reaction between the first and second olefins and the hydroxyaryl compound. Thus, to form the alkylate composition, a mixture of lower alkenes (e.g., two or more C3-C6 olefins, such as a mixture of butylene and amylenes) may be reacted with the phenolic compound either in parallel (feed in olefin A and B at the same time) or
consecutively (i.e. olefin A is reacted first followed by olefin B).
[0079] In the alkylate synthesis process, the alkylates may be formed by contacting one or more phenolics with two or more olefins (in separate reactions or in a single reaction process) in the presence of a catalyst and under conditions effective to form the alkylate composition. Each of the two or more olefins preferably contains from 1 to 18 carbons, e.g., from 1 to 8 carbons, or from 4 to 6 carbons, provided that the first olefin has a different number of carbon atoms than the second olefin. As an alternative to using an olefin alkylating agent, one or more alkyl halides, alcohols, MTBE or TAME may be employed. The alkylating agents that are employed may comprise or be derived from a hydrocarbon stream comprising alkanes and alkenes, such as a petrochemical raffinate stream from a C4 or C5 fraction, or a dehydrogenation reaction product of an alkane, e.g., isobutane or isopentane. In this aspect, the alkanes pass through the alkylating process unaltered and may be easily separated from the product alkylate composition.
[0080] The ratio of olefins to phenolic preferably is such that the resulting alkylate composition is suitable for conversion to the desired phosphite composition when reacted with a phosphorous halide, keeping in mind that the resulting alkylate, e.g., first alkylate, may be blended with another alkylate, e.g., second alkylate, to form the alkylate composition that will be used in synthesizing the phosphite composition. In some exemplary embodiments, the total olefins to phenolic compound mole ratio ranges from 1 : 1 to 6: 1, e.g., from 1.1 : 1 to 2: 1 or from 1.25: 1 to 1.4: 1, although these ratios may very somewhat depending, for example, on the catalyst employed in the alkylation process and the desired composition and viscosity for the ultimately formed phosphite composition.
[0081] Although conditions for the alkylation process may vary widely, in some preferred embodiments, the reaction of the phenol and the two or more olefins (whether forming the first and second alkylates separately or together) may occur in an inert atmosphere (e.g., under nitrogen) at a temperature of from 60 to 1600C, e.g., from 70 to 145°C or from 80 to 1400C. The reaction is preferably performed at a pressure of from 0.2 to 10 atm, e.g., from 0.2 to 5 atm or from 0.2 to 4 atm. In a batch reaction, the reaction time may last from 1 to 12
hours, e.g., from 2 to 10 hours, or from 3 to 5 hours. In a continuous reaction, the residence time may be from 0.1 to 5 hours, e.g., from 0.2 to 4 hours or from 0.5 to 1 hour. The alkylation preferably is performed in the presence of a catalyst. The catalyst may, for example, be selected from the group consisting of acid clay catalyst, cationic ion exchange resins, Bronsted acids, e.g., sulfuric acid, trifluoromethanesulfonic acid (triflic acid) and phosphotungstic acid, or Lewis acids, e.g., BF3. Suitable commercial acid clay catalysts include Fulcat™ 22B (Rockwood Additives). In one embodiment, the sulfonic acid- type cation-exchange resin catalyst useful in the present invention can be, for example, a sulfonated styrene-divinyl benzene copolymer, a sulfonated crosslmked styrene polymer, a phenol formaldehyde- sulfonic acid resin, or a benzene formaldehyde-sulfonic acid resin. Cation exchange resins useful in the present invention include for example styrene- divinylbenzene types of strong acid ion exchange resins such as Dowex™ 50WX4, Dowex 50WX2, Dowex M-31, Dowex Monosphere M-31, Dowex DR-2030 and Dowex Monosphere DR-2030 catalysts (Dow Chemical). Other appropriate resins include: Amberlyst™ 15, Amberlyst 131, Amberlyst 35, Amberlyst 36, and A21 (Rohm and Hass, subsidiary of Dow); Diaion™ WA30, Diaion SK104, Diaion SKlB, Diaion PK208, Diaion PK212 and Diaion PK216 (Mitsubishi); Tulsion™ T-38, Tulsion T-62, Tulsion T-66, Tulsion T-3825 and Tulsion T-3830 (Thermax); Lewatit™ Kl 131, Lewatit K1221, Lewatit K1261 and Lewatit SC 104 (Sybron Chemicals); Indion™ 180 and Indion 225 (Ion Exchange (India) Limited); and Purolite™ CT- 175, Purolite™ CT- 169, and Purolite™ CT-275(Purolite).
[0082] In one embodiment, a batch alkylate synthesis takes place in a pot-type reactor. In another embodiment, the alkylate synthesis is conducted on a continuous basis in a continuous type reactor. In the continuous process, the alkylation reaction is optionally quenched using a polar solvent, water, that forms a liquid phase containing most, if not all, of the catalyst and a organic phase containing the alkylated aryl compound, which may be removed by distillation.
[0083] In one aspect of the process, any free phenolic compounds that are not reacted with the olefins may be removed from the mixture of reaction products through distillation at a temperature, for example, of from 70 to 16O0C and at a pressure of from 1 to 10 mbar.
[0084] As indicated above, depending on the desired composition (e.g., propylated, butylated and/or amylated) and target viscosity for the alkylate composition as well as the ultimately formed phosphite composition, the components and component concentrations in the alkylate composition may vary widely. In one embodiment, for example, the alkylate composition comprises 4-butyl phenol, e.g., 4-t-butyl phenol, and 2,4-diamyl phenol, e.g.,
2,4-di-t-amyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt%. In another embodiment, the alkylate composition comprises 4-amyl phenol, e.g., 4-t-amyl phenol, and 2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. In another embodiment, the alkylate composition comprises 4-isopropyl phenol and 2,4-dibutyl phenol, e.g., 2,4-di-t-butyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. In another embodiment, the alkylate composition comprises 4-butyl phenol, e.g., 4-t-butyl phenol, and 2,4-di-isopropyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. In another embodiment, the alkylate composition comprises 4-isopropyl phenol and 2,4-diamyl phenol, e.g., 2,4-di-t-amyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. In another embodiment, the alkylate composition comprises 4-amyl phenol, e.g., 4-t-amyl phenol, and 2,4-di-isopropyl phenol, preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. In still another embodiment, the alkylate composition comprises a complex mixture of phenolics, for example, comprising three or four of the following: a 4-butyl phenol (e.g., 4-t-butyl phenol), a 2,4-dibutyl phenol (e.g., 2,4-di-t-butyl phenol), 4-amyl phenol (e.g., 4-t-amyl phenol), and a 2,4-diamyl phenol (e.g., 2,4-di-t-amyl phenol), preferably in combination in an amount greater than 90 wt% or greater than 95 wt.%. Similar complex alkylate compositions are also possible with propyl/amyl and propyl/butyl. In these embodiments, the weight ratio of monosubstituted to disubstituted phenols contained in the alkylate composition preferably are as provided below.
[0085] In terms of component concentrations, the alkylate composition may comprise, for example, from 5 to 95 wt %, e.g., from 10 to 70 wt % or from 30 to 65 wt %, of a p-alkylated phenol and from 5 to 95 wt %, e.g., from 10 to 70 wt % or from 30 to 65 wt %, of a o,p- dialkylated phenol. The p-alkylated phenol may comprise p-Alkyl-A phenol, p-Alkyl-B phenol or both p-Alkyl-A phenol and p-Alkyl-B phenol. The o,p-dialkylated phenol may comprise either o,p-di-Alkyl-A phenol or o,p-di-Alkyl-B phenol, or both o,p-di-Alkyl-A phenol and o,p-di-Alkyl-B phenol.
[0086] In some preferred embodiments, the alkylate composition comprises a monoalkyl phenol, e.g., a 4-amyl phenol and/or a 4-butyl phenol, and a dialkyl phenol, e.g., a 2,4-diamyl phenol and/or a 2,4-dibutyl phenol. The 4-alkyl phenol optionally is present in an amount greater than 40 wt%, greater than 50 wt%, greater than 60 wt%, greater than 70 wt% or greater than 75 wt% and optionally in an amount less than 95 wt%, e.g., less than 85 wt%, less than 80 wt%, less than 75 wt% or less than 65 wt%. In terms of ranges, in some
embodiments, the 4-alkyl phenol, e.g., 4-t-amyl phenol and/or 4-t-butyl phenol, is present in an amount ranging from 25 wt% to 99 wt%, e.g., from 45 wt% to 80 wt%, from 60 wt% to 75 wt%, or from 65 wt% to 75 wt%. In this aspect, the dialkyl phenols, e.g., 2,4-di-t-amyl phenol and/or 2,4-di-t-butyl phenol, preferably are present in an amount ranging from 1 wt% to 60 wt%, e.g., from 10 wt% to 50 wt%, from 25 wt% to 40 wt%, or from 25 wt% to 35 wt%. Optionally, the dialkyl phenol is present in an amount less than 60 wt%, e.g., less than 55 wt%, less than 45 wt% or less than 35 wt%. In terms of lower range limitations, the dialkyl phenol, e.g., 2,4-di-t-amyl phenol and/or 2,4-di-t-butyl phenol, optionally is present in an amount greater than 10 wt%, greater than 20 wt%, greater than 30 wt%, or greater than 40 wt%.
[0087] The weight ratio of monoalkyl phenols, such as 4-t-amyl phenol or 4-t-butyl phenol, to dialkyl phenols, e.g., 2,4-di-t-amyl phenol or 2,4-di-t-butyl phenol, can be selected or adjusted so as to produce the desired alkylate composition that is suitable for being used as a reactant for forming an alkylaryl phosphite composition that is a liquid at ambient conditions. In some embodiments, the weight ratio of monoalkyl phenols to dialkyl phenols in the alkylate compositions ranges from 5: 1 to 1 :2, e.g., from 5:1 to 1 : 1, from 3: 1 to 1: 1, or from 1.5: 1 to 1 : 1. Alkylate compositions outside of these weight ratio ranges may produce phosphite compositions that are not liquids and/or are meta-stable liquids under ambient conditions.
[0088] The alkylate composition, optionally formed from the above-described alkylate composition synthesis process, preferably is further reacted with a phosphorus trihalide, with or without catalyst, to form the liquid phosphite compositions of the invention, as described above in connection with the first embodiment of the invention. Thus, in one embodiment, the liquid phosphite compositions of the present invention are obtained in a direct chemical reaction, in which the molar ratio of the alkylated phenol is adjusted to yield a phosphite composition that is a liquid at ambient conditions. A schematic of one reaction method that may be employed to form such phosphite compositions is as follows.
wherein R and R' are independently any of the groups as defined above (e.g., Ri and R2, respectively), but R and R' have a different number of carbon atoms. Note that a minor amount of other alkylated phenols, e.g., ortho- substituted monoalkylated phenols, may be included as an additional reactant in the above reaction scheme and would form additional derivative phosphites, but these additional reactants and products have been omitted from this reaction for clarity.
Stabilizers
[0089] As discussed above, a stabilizing amount or effective amount of the phosphite composition of the invention may be used as a secondary antioxidant for various types of polymers. As used herein, by "stabilizing amount" and an "effective amount" it is meant when the polymer composition containing the phosphite compositions of the invention shows improved stability in any of its physical or color properties in comparison to an analogous polymer composition which does not include a phosphite composition of the invention. Examples of improved stability include improved stabilization against, for example, molecular weight degradation, color degradation, and the like from, for example, melt processing, weathering, and/or long term field exposure to heat, light, and/or other elements. In one example, improved stability is obtained in the form of one or both of lower initial color or additional resistance to weathering, as measured, for example, by initial yellowness index (YI), or by resistance to yellowing and change in color, when compared to a composition without the stabilizer additive.
[0090] The additives and stabilizers described herein are preferably present in an amount effective to improve composition stability. When one of the aforementioned phosphite compositions is utilized, the composition is generally present in an amount from about 0.001 to about 5 wt. %, e.g., from about 0.0025 to about 2 wt.% or from about 0.005 to about 1 wt.%, based on the total weight of the polymer including the weight of the phosphite composition and any other stabilizers or additives. The phosphite compositions of this invention stabilize resins especially during high temperature processing with relatively little change in melt index and/or color, even after multiple extrusions.
[0091] The invention further relates to a stabilized thermoplastics, comprising a base polymer (e.g., polymer resin) and any of the aforementioned phosphite compositions of the invention. The polymer resin may be a polymer such as a polyolefin, and the liquid phosphite composition may be used with a costabilizer, for example, hindered phenolics, aromatic amines, hydroxylamines, lactones, and thioethers. Thus, the thermoplastic that is stabilized by the phosphite compositions of the present invention may optionally contain one or more additional stabilizers or mixtures of stabilizers selected from the group consisting of the phenolic antioxidants, hindered amine light stabilizers (HALS), the ultraviolet light absorbers, phosphites, phosphonites, alkaline metal salts of fatty acids, hydrotalcites, metal oxides, epoxydized soybean oils, the hydroxylamines, the tertiary amine oxides, lactones, thermal reaction products of tertiary amine oxides, and the thiosynergists.
[0092] In one embodiment, the amount of each component in the stabilizing mixture, based on the total weight percent of the polymer or polymeric resin, is shown in Table 4.
Table 4
Component Range Preferred Range
Liquid phosphite compositions 0.001-5.0 wt% 0.005-1.0 wt%
Primary antioxidant 0-5.0 wt% 0.005-2.0 wt%
UV or light stabilizers 0-3.0 wt% 0.001-2.0 wt%
Metal deactivators 0-3.0 wt% 0.001-2.0 wt%
Other secondary antioxidants 0-3.0 wt% 0.001-2.0 wt%
Peroxide scavengers 0-3.0 wt% 0.001-2.0 wt%
Polyamide stabilizers 0-3.0 wt% 0.001-2.0 wt%
Basic co-stabilizers 0-3.0 wt% 0.001-2.0 wt%
Nucleating or clarifying agents 0-3.0 wt% 0.001-2.0 wt%
Aminoxy propanoate 0-3.0 wt% 0.001-2.0 wt%
[0093] The phosphite compositions of the invention or the resulting stabilized polymer compositions optionally also comprise primary antioxidants such as the following:
[0094] (i) Alkylated monophenols, for example: 2,6-di-tert-butyl-4-methylphenol, 2-tert- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-bis(α- methylbenzyl)-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6- dioctadecyl-4-methylphenol, 2,4,6,-tricyclohexyphenol, and 2,6-di-tert-butyl-4- methoxymethylphenol. Commercially available alkylated monophenols include Lowinox™ 624 and Naugard™ 431 made by Chemtura Corp. Other phenols are commercially available such as BHEB.
[0095] (ii) Alkylated hydroquinones, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, and 2,6-diphenyl- 4octadecyloxyphenol. Commercially available alkylated hydroquinones include Lowinox AH25 made by Chemtura.
[0096] (iii) Hydroxylated thiodiphenyl ethers, for example, 2,2'-thio-bis-(6-tert-butyl-4- methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3-methylphenol), and 4,4'-thio-bis-(6-tert-butyl-2-methyphenol). Commercially available hydroxylated
thiodiphenyl ethers include Lowinox TBM6, and Lowinox TBP6 made by Chemtura.
[0097] (iv) Alkylidene-bisphenols, for example, 2,2'-methylene-bis-(6-tert-butyl-4- methylphenol), 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis-(4-
methyl-6-(α-methylcyclohexyl)phenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2'-methylene-bis-(6-(α-methylbenzyl)-4-nonylphenol), 2,2'-methylene-bis-(6-(alpha,alpha- dimethylbenzyl)-4-nonyl-phenol), 2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'- ethylidene-bis-(6-tert-butyl-4-isobutylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol), 1 , 1 -bis-(5-tert-butyl-4-hydroxy-2- methylphenol)butane, 1 , 1 -bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,2'- isobutylidene-bis(4,6-dimethylphenol), 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1 , 1 ,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 , 1 -bis-(5-tert- butyl-4-hydroxy-2-methylphenyl)-3-dodecyl-mercaptobutane, ethyleneglycol-bis-(3,3,-bis- (3'-tert-butyl-4'-hydroxyphenyl)-butyrate)-di-(3-tert-butyl-4-hydroxy-5-methylphenyl)- dicyclopentadiene, and di-(2-(3'-tert-butyl-2'hydroxy-5'methyl-benzyl)-6-tert-butyl-4- methylphenyl)terephthalate. Commercially available alkylidene-bisphenols include Lowinox 22M46, Lowinox WSP, Lowinox 44B25, Naugard 536, Naugawhite™, and Lowinox 22IB46 made by Chemtura.
[0098] (v) Benzyl compounds, for example, l,3,5-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, bis-(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, bis-(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithiol-terephthalate, l,3,5-tris-(3,5-di-tert-butyl-4
hydroxybenzyl)isocyanurate, l,3,5-tris-(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)isocyanurate, 1 ,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)- 1,3,5- Triazine-2,4,6-(lH,3H,5H)-trione, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, l,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. Commercially available benzyl compounds include Anox™ IC- 14, Anox 330 and Lowinox 1790 made by Chemtura.
[0099] (vi) Acylaminophenols, for example, 4-hydroxylauric acid anilide, 4-hydroxy- stearic acid amilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine, and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.
[0100] (vii) Esters of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid with monohydric or polyhydric alcohols, for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris- hydroxyethylisocyanurate, thiodiethyleneglycol, di-hydroxyethyl oxalic acid diamide. Such phenols also include tetrakis [methylene {3,5-di-tert-butyl-4-hydroxycinnamate}]methane.
Commercially available esters include Anox 20, Anox 1315, Lowinox GP45, Naugalube 38, Naugalube 531, Anox PPl 8, Naugard PS48 and Naugard XL- 1 made by Chemtura.
[0101] (viii) Thio esters of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydric or polyhydric alcohols, for example, methanol, diethyleneglycol, octadecanol, triethyleneglycol, 1,6-hexanediol, pentaerythritol, neopentylglycol, tris- hydroxyethyl isocyanurate, thiodiethyleneglycol, dihydroxyethyl oxalic acid diamide.
Commercially available thio esters include Naugalube™ 15 and Anox 70 made by Chemtura.
[0102] (ix) Amides of beta-(3,5-di-tert-butyl-4-hydroxyphenol)-propionic acid for example, N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexammethylen-diamine , N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-di-(3,5-di- tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, N,N'-Hexamethylene bis[3-(3,5-di-t-butyl- 4-hydroxyphenyl)propionamide, and l,2-Bis(3,5-di-tert-butyl-4- hydroxyhydrocinnamoyl)hydrazine. Commercially available amides include Lowinox HD98 and Lowinox MD24 made by Chemtura.
[0103] (x) Other phenolic antioxidants include the following phenols. Polymeric phenols such as the reaction product of 4-methylphenol with dicyclopentadiene and isobutylene, commercially available as Lowinox CPL; Chemtura. Alkylidene-poly-phenols, such as 1 ,3 tris(3-methyl-4-hydroxyl-5-t-butyl-phenyl)-butane (Lowinox CA22; Chemtura). Thio phenols such as 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-l,3,5-triazin-2-ylamino) phenol (Irganox™ 565; Ciba), 4,6-bis (octylthiomethyl)-o-cresol (Irganox 1520; Ciba); 4,6- bis(dodecylthiomethyl)-o-cresol (Irganox 1726; Ciba). Hydroxyl amines, such as bis(octadecyl)hydroxylamine (Irgastab™ FS 042; Ciba). Ester phenols include bis[3,3-bis(4- hydroxy-3-tert-butyl phenyl)butanoic acid]glycol ester (Hostanox™ 03; Clariant Chemicals). Still other phenols include 2-[l-(2-hydroxy-3,5-di-tert-pentylphenyl) ethyl]-4,6-di-tert- pentylphenyl acrylate (Sumilizer GS; Sumitomo Chemical).
[0104] In one embodiment, the stabilizing composition comprises one phenolic selected from the group consisting oftetrakismethylene (3,5-di-t-butyl-4-hydroxylhydrocinnamate) methane (Anox 20), l,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (Anox IC-14), l,3,5-tris(4-tert.-butyl-3-hydroxy-2,6-dimethylbenzyl)-l,3,5-triazine-2,4,6-(lH,3H,5H)-trione (Lowinox 1790), octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate (Anox PP 18), bis(octadecyl)hydroxylamine (Irgastab FS-042), l,3,5-trimethyl-2,4,6-tris (3,5-di-tert-4- hydroxybenzyl) benzene (Anox 330), 2,6-bis(α-methylbenzyl)-4-methylphenol (Naugalube 431), 3,5-bis(l,l-dimethylethyl)-4-hydroxy-benzenepropanoic acid (Anox 1315), 2,6-di-t-
butyl-4- ethyl-phenol (BHEB), and mixtures thereof, and the liquid phosphite composition defined herein.
[0105] The phosphite compositions and/or the resulting stabilized polymeric compositions optionally also comprise one or more UV absorbers and/or light stabilizers, such as the following:
[0106] (i) 2-(2'-hydroxyphenyl)-benzotriazoles, for example, the 5'-methyl-, 3'5'-di-tert- butyl-, 3'5'-di-tert-amyl-, 5'-tert-butyl-, 5'-tert-amyl-, 5'(l,l,3,3-tetramethylbutyl)-, 5-chloro-
3',5'-di-tert-butyl-, 5 -chloro-3'-tert-butyl-5 'methyl-, 3'-sec-butyl-5'tert-butyl-,4'-octoxy, 3',5'- ditert-amyl-3',5'-bis-(α,α-dimethylbenzyl)-derivatives. Commercially available 2-(2'- hydroxyphenyl)-benzotriazoles include Lowilite™ 26, Lowilite 27, Lowilite 28, Lowilite 29,
Lowilite 35, Lowilite 55, and Lowilite 234 made by Chemtura.
[0107] (ii) 2-Hydroxy-benzophenones, for example, the 4-hydroxy, 4-methoxy-, 4- octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 2,4-dihydroxy-, 4,2',4'-trihydroxy- and T- hydroxy-4,4'-dimethoxy- derivative. Exemplary 2-hydroxy-benzophenones include 2- hydroxy-4-methoxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2,4- dihydroxybenzophenone, and 2-hydroxy-4-propoxybenzophenone. Commercially available
2-(2'-hydroxyphenyl)-benzotriazoles include Lowilite 20, Lowilite 22, Lowilite 2OS, and
Lowilite 24 made by Chemtura.
[0108] (iii) Esters of substituted and unsubstituted benzoic acids for example, phenyl salicylate, 4-tert-butylphenyl-salicilate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4- tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4- hydroxybenzoate and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate.
[0109] (iv) UV absorbers and light stabilizers may also comprise acrylates, for example, alpha-cyano-beta, beta-diphenylacrylic acid-ethyl ester or isooctyl ester, alpha- carbomethoxy-cinnamic acid methyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy-cinnamic acid methyl ester,
N-(beta-carbomethoxy-beta-cyano-vinyl)-2-methyl-indoline.
[0110] (v) Nickel compounds are also suitable UV absorbers and light stabilizers.
Exemplary nickel compounds include nickel complexes of 2,2'-thio-bis(4-(l, 1,1,3- tetramethylbutyl)-phenol), such as the 1 :1 or 1 :2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel
dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl, ethyl, or butyl ester, nickel complexes of ketoximes such as of 2-hydroxy-4-methyl-penyl undecyl ketoxime, nickel complexes of l-phenyl-4-
lauroyl-5-hydroxy-pyrazole, optionally with additional ligands. Commercially available nickel compounds include Lowilite Q84 (2,2'-Thiobis(4-tert-octyl-phenolato))-N- butylamine-Nickel(II) made by Chemtura.
[0111] (vi) Sterically hindered amines may be used as UV absorbers and light stabilizers. Sterically hindered amines, for example bis(2,2,6,6-tetramethylpiperidyl)-sebacate, bis- (1 ,2,2,6,6-pentamethylpiperidyl)-sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis(l,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1 -hydroxy ethyl- 2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, condensation product of N3N'- (2,2,6,6-tetramethylpiperidyl)-hexamethylendiamine and 4-tert-octylamino-2,6-dichloro- 1 ,3,5-s-triazine, tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate, tetrakis-(2,2,6,6- tetramethyl-4-piperidyl)- 1 ,2,3,4-butane-tetra-carbonic acid, 1 , 1 '(1 ,2-ethanediyl)-bis-(3,3,5,5- tetramethylpiperazinone). Such amines include hydroxylamines derived from hindered amines, such as di(l-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate: 1 -hydroxy 2,2,6,6- tetramethyl-4-benzoxypiperidine; l-hydroxy-2,2,6,6-tetramethyl-4-(3,5-di-tert-butyl-4- hydroxy hydrocinnamoyloxy)-piperdine; and N-(l-hydroxy-2,2,6,6-tetramethyl-piperidin-4- yl)-epsiloncaprolactam. Commercially available hindered amines include Lowilite 19, Lowilite 62, Lowilite 77, Lowilite 92 and Lowilite 94 made by Chemtura.
[0112] (vii) Oxalic acid diamides, for examples, 4,4'-dioctyloxy-oxanilide, 2,2'-di- octyloxy-5',5'-di-tert-butyloxanilide, 2,2'-di-dodecyloxy-5',5'di-tert-butyl-oxanilide, 2-ethoxy- 2'-ethyl-oxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'ethyl-5,4-di-tert-butyloxanilide and mixtures of o-and p-methoxy-as well as of o- and p-ethoxy-disubstituted oxanilides.
[0113] The polymer resins and phosphite compositions of the invention may also include one or more additional additives, including, for example, one or more of the following:
[0114] (i) Metal deactivators, for example, N,N'-diphenyloxalic acid diamide, N- salicylal-N'-salicyloylhydrazine, N,N'-bis-salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4- hydrophenylpropionyl)-hydrazine, salicyloylamino-l,2,4-triazole, bis-benzyliden-oxalic acid dihydrazide.
[0115] (ii) Additional secondary antioxidants such as additional phosphites and/or phosphonites, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonyl-phenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite tristearyl sorbitol triphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and tetrakis(2,4-di-tert-
butylphenyl)4,4'-biphenylene diphosphonite. Commercially available secondary antioxidants include Naugalube TPP, Alkanox™ 240, Ultranox™ 626, Naugard P, Weston™ 399, Weston TNPP, Weston 430, Weston 618F, Weston 619F, Weston DPDP, Weston DPP, Weston PDDP, Weston PTP, Weston TDP, Weston TLP, Weston TPP, and Weston TLTTP (trilauryl trithio phosphite) made by Chemtura; Doverphos™ 4, Doverphos 4-HR, Doverphos 4-HR Plus, Doverphos HiPure 4, and Doverphos S-9228 made by Dover Chemical; and Hostanox PEPQ made by Clariant Chemicals.
[0116] (iii) Peroxide scavengers, for example, esters of betathiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc-dibutyldithiocaramate, dioctadecyldisulfide,
pentaerythritoltetrakis-(beta-dodecylmercapto)-propionate.
[0117] (iv) Polyamide stabilizers, for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese may also be included in the polymer resin and/or phosphite composition.
[0118] (v) Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, hydrotalcites, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example, Ca stearate, calcium stearoyl lactate, calcium lactate, Zn stearate, Zn octoate, Mg stearate, Na ricinoleate and K palmirate, antimony pyrocatecholate or zinc pyrocatecholate. Commercially available co-stabilizers include Mark™ 6045, Mark 6045ACM, Mark 6055, Mark 6055ACM, Mark 6087ACM, Mark 6102, Mark CE 345, Mark CE 350, and Mark CE 387, made by Chemtura; and DHT-4A™ made by Kisuma Chemicals.
[0119] (vi) Nucleating and clarifying agents, for example, metal salts of 4-tert butylbenzoic acid, adipic acid, diphenylacetic acid, sorbitol and derivatives thereof, sodium benzoate, and benzoic acid.
[0120] (vii) Aminoxy propanoate derivatives such as methyl-3-(N,N- dibenzylaminoxy)propanoate; ethyl-3-(N,N-dibenzylaminoxy) propanonoate; 1,6- hexamethylene-bis(3-N,N-dibenzylaminoxy)proponoate); methyl-(2-(methyl)-3(N,N- dibenzylaminoxy)propanoate); octadecyl-3-(N,N-dibenzylaminoxy)propanoic acid; tetrakis (N,N-dibenzylaminoxy)ethyl carbonyl oxymethy)methane; octadecyl-3-(N,N- diethylaminoxy)-propanoate; 3-(N,N-dibenzylaminoxy)propanoic acid potassium salt; and 1 ,6-hexamethylene bis(3-(N-allyl-N-dodecyl aminoxy)propanoate).
[0121] (viii) Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flameproofmg agents, anti-static agents, blowing agents and
thiosynergists such as dilaurythiodipropionate or distearylthiodipropionate.
[0122] Optionally the polymer or polymeric resins may include from 5-50 wt%, e.g., 10-40 wt% or 15-30 wt% fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite.
[0123] The invention further pertains to a stabilized polymer, wherein one component comprises a liquid phosphite composition of the present invention and the other a polymer, such as a polyolefin, polyvinyl chloride, etc., or polymeric resins.
[0124] The polymer stabilized by such liquid phosphite compositions may be any polymer known in the art, such as polyolefin homopolymers and copolymers, thermoplastics, rubbers, polyesters, polyurethanes, polyalkylene terephthalates, polysulfones, polyimides, polyphenylene ethers, styrenic polymers and copolymers, polycarbonates, acrylic polymers, polyamides, polyacetals, halide-containing polymers, and biodegradable polymers. Mixtures of different polymers, such as polyphenylene ether/styrenic resin blends, polyvinyl chloride/ABS or other impact modified polymers, such as methacrylonitrile and α- methylstyrene containing ABS, and polyester/ABS or polycarbonate/ABS and polyester plus some other impact modifier may also be used. Such polymers are available commercially or may be made by means well known in the art. However, the stabilizer compositions of the invention are particularly useful in thermoplastic polymers, such as polyolefins,
polycarbonates, polyesters, polyphenylene ethers and styrenic polymers, due to the extreme temperatures at which thermoplastic polymers are often processed and/or used.
[0125] The polymers used in combination with liquid phosphite compositions of the present invention are produced using a variety of polymerization processes including solution, high- pressure, slurry and gas phase using various catalysts including Ziegler-Natta, single-site, metallocene or Phillips-type catalysts. Non-limiting polymers useful with the liquid phosphite compositions include ethylene based polymers such as linear low density polyethylene, elastomers, plastomers, high density polyethylene, substantially linear long chain branched polymers, and low density polyethylene; and propylene based polymers such as
polypropylene polymers including atactic, isotactic, and syndiotactic polypropylene polymers, and propylene copolymers such as propylene random, block or impact copolymers.
[0126] The polymers, typically ethylene based polymers, have a density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more
preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferably greater than 0.925 g/cc. The polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than about 8, even more preferably from about 2.2 to less than 5, and most preferably from 2.5 to 4. The ratio of Mw/Mn can be measured by gel permeation chromatography techniques well known in the art. The polymers of the present invention in one embodiment have a melt index (MI) or (12) as measured by ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min, more preferably from about 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min. The polymers of the invention in one embodiment have a melt index ratio (121/12) (121 is measured by ASTM-D-1238-F) of from 10 to less than 25, more preferably from about 15 to less than 25. The polymers of the invention in a preferred embodiment have a melt index ratio (121/12) (121 is measured by ASTM-D- 1238-F) of from preferably greater than 25, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65.
[0127] Polymers used with liquid phosphites compositions of the invention are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding. Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and nonfood contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc. In addition to the above, the liquid phosphite compositions are used in various rubber based products such as tires, barriers and the like.
[0128] In one embodiment, the liquid phosphite compositions are suitable and/or approved for use in polymers, preferably polyolefins, that are used in contact with beverages, foods and other human consumables.
[0129] Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene, or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslmked), for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) may be used. Mixtures of these polymers, for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE), may also be used. Also useful are copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as, for example, ethylene/propylene, LLDPE and its mixtures with LDPE, propylene/butene-1, ethylene/hexene, ethylene/ethylpentene, ethylene/heptene, ethylene/octene,
propylene/isobutylene, ethylene/butane-1, propylene/butadiene, isobutylene, isoprene, ethylene/alkyl acrylates, ethylene/alkyl methacrylates, ethylene/vinyl acetate (EVA) or ethylene/acrylic acid copolymers (EAA) and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene- norbornene; as well as mixtures of such copolymers and their mixtures with polymers mentioned above, for example polypropylene/ethylene propylene-copolymers, LDPE/EVA, LDPE/EAA, LLDPE/EVA, and LLDPE/EAA.
[0130] The olefin polymers may be produced by, for example, polymerization of olefins in the presence of Ziegler-Natta catalysts optionally on supports such as, for example, MgCk, chromium 20 salts and complexes thereof, silica, silica-alumina and the like. The olefin polymers may also be produced utilizing chromium catalysts or single site catalysts, e.g., metallocene catalysts such as, for example, cyclopentadiene complexes of metals such as Ti and Zr. As one skilled in the art would readily appreciate, the polyethylene polymers used herein, e.g., LLDPE, can contain various comonomers such as, for example, 1-butene, 1- hexene and 1-octene comonomers.
[0131] The polymer may also include styrenic polymers, such as polystyrene, poly-(p- methylstyrene), 5 poly-(α-methylystyrene), copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene/butadiene (SBR),
styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/maleic anhydride,
styrene/maleimide, styrene/butadiene/ethyl acrylate, styrene/acrylonitrile/methylacrylate,
mixtures of high impact strength from styrene copolymers and another polymer, such as, for example, from a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene, such as, for example, styrene/butadiene/styrene (SBS), styrene/isoprene/styrene (SIS), styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0132] Styrenic polymers may additionally or alternatively include graft copolymers of styrene or α-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene and copolymers thereof; styrene and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene, styrene and alkyl acrylates or methacrylates on polybutadiene, styrene and acrylonitrile on ethylene- propylene-diene terpolymers, styrene and acrylonitrile on polyacrylates or polymethacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the styrenic copolymers indicated above.
[0133] Suitable rubbers include both natural rubber and synthetic rubbers, and combinations thereof. Synthetic rubbers include, but are not limited to, for example, thermoplastic rubbers, ethylene/alpha-olefin/non-conjugated polyene (EPDM) rubbers, ethylene/alpha-olefin (EPR) rubbers, styrene/butadiene rubbers, acrylic rubbers, nitrile rubbers, polyisoprene, polybutadiene, polychloroprene, acrylonitrile/butadiene (NBR) rubbers, polychloroprene rubbers, polybutadiene rubbers, isobutylene-isoprene copolymers, etc. Thermoplastic rubbers include SIS, solution and emulsion SBS, etc.
[0134] Nitrile polymers are also useful in the polymer composition of the invention. These include homopolymers and copolymers of acrylonitrile and its analogs, such as
polymethacrylonitrile, polyacrylonitrile, acrylonitrile/butadiene polymers, acrylonitrile/alkyl acrylate polymers, acrylonitrile/alkyl methacrylate/butadiene polymers, and various ABS compositions as referred to above in regard to styrenics.
[0135] Polymers based on acrylic acids, such as acrylic acid, methacrylic acid, methyl methacrylic acid and ethacrylic acid and esters thereof may also be used. Such polymers include polymethylmethacrylate, and ABS-type graft copolymers wherein all or part of the acrylonitrile -type monomer has been replaced by an acrylic acid ester or an acrylic acid amide. Polymers including other acrylic-type monomers, such as acrolein, methacrolein, acrylamide and methacrylamide may also be used.
[0136] Halogen-containing polymers may also be stabilized with the phosphite compositions of the present invention. These include polymers such as polychloroprene, epichlorohydrin homo-and copolymers, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, fluorinated polyvinylidene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloridestyrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloridestyrene- aery lonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride isoprene copolymer, vinyl chloride- chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride- acrylic acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-methacrylic acid ester copolymers, vinyl chloride- aery lonitrile copolymer and internally plasticized polyvinyl chloride.
[0137] Other useful polymers include homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers; polyacetals, such as polyoxymethylene and those polyoxymethylene which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or methacrylonitrile containing ABS; polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with polystyrene or polyamides;
polycarbonates and polyester-carbonates; polysulfones, polyethersulfones and
polyetherketones; and polyesters which are derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-l,4-dimethylol-cyclohexane terephthalate, poly-2-(2,2,4(4-hydroxyphenyl)-propane) terephthalate and polyhydroxybenzoates as well as block copolyetheresters derived from polyethers having' hydroxyl end groups.
[0138] Polyamides and copolyamides which are derived from bisamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m- xylene bisamine and adipic acid; polyamides prepared from hexamethylene bisamine and isophthalic or/and terephthalic acid and optionally an elastomer as modifier, for example poly-2,4,4 trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide may be useful. Further copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as for instance, with polyethylene
glycol, polypropylene glycol or polytetramethylene glycols and polyamides or copolyamides modified with EPDM or ABS may be used.
[0139] In another embodiment, the polymer comprises a biodegradable polymer or compostable polymer. Biodegradable polymers are those in which the degradation results from the action of naturally occurring microorganisms, such as bacteria, fungi and algae. Compostable polymers undergoes degradation by biological processes during composting to yield CO2, water, inorganic compounds and a biomass at a rate consistent with other compostable materials. Typically the biodegradable or compostable polymers are derived from plant sources and are synthetically produced. Examples of biodegradable or compostable polymers include poly(glycolic acid) (PGA), poly(lactic acid) (PLA), and copolymers thereof. Biodegradable or compostable polymers may also be derived from a blend of starch of a plant and a conventional petroleum-based polymer. For example, the biodegradable polymer may be blended with a polyolefin.
[0140] Polyolefin, polyalkylene terephthalate, polyphenylene ether and styrenic polymers, and mixtures thereof are more preferred, with polyethylene, polypropylene, polyethylene terephthalate, polyphenylene ether homopolymers and copolymers, polystyrene, high impact polystyrene, polycarbonates and ABS-type graft copolymers and mixtures thereof being particularly preferred.
[0141] In one embodiment, the liquid phosphite compositions are added to stabilize natural and synthetic waxes, such as n-paraffin waxes, chloroparaffins, α-olefin waxes,
microcrystalline waxes, polyethylene waxes, amide waxes, and Fisher-Tropsch waxes. These waxes may be suitable for making candles.
[0142] The instant stabilizers may readily be incorporated into the polymer by conventional techniques at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer. The stabilized compositions of the invention may optionally also contain from about 0.001 to about 5 wt. %, e.g., from about 0.0025 to about 2 wt. % or from about 0.05 to about 0.25 wt. %, of various conventional additives, such as those described previously, or mixtures thereof.
[0143] The stabilizers of this invention advantageously assist with the stabilization of polymer compositions especially in high temperature processing against changes in melt index and/or color, even though the polymer may undergo a number of extrusions. The stabilizers of the present invention may readily be incorporated into the polymer
compositions by conventional techniques, at any convenient stage prior to the manufacture of shaped articles therefrom. For example, the stabilizer may be mixed with the polymer in dry powder form, or a suspension or emulsion of the stabilizer may be mixed with a solution, suspension, or emulsion of the polymer.
[0144] The compositions of the present invention can be prepared by a variety of methods, such as those involving intimate admixing of the ingredients with any additional materials desired in the formulation. Suitable procedures include solution blending and melt blending. Because of the availability of melt blending equipment in commercial polymer processing facilities, melt processing procedures are generally preferred. Examples of equipment used in such melt compounding methods include: co-rotating and counter-rotating extruders, single screw extruders, disc-pack processors and various other types of extrusion equipment. In some instances, the compounded material exits the extruder through small exit holes in a die and the resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.
[0145] All of the ingredients may be added initially to the processing system, or else certain additives may be pre-compounded with each other or with a portion of the polymer or polymeric resin to make a stabilizer concentrate. Moreover, it is also sometimes
advantageous to employ at least one vent port to allow venting (either atmospheric or vacuum) of the melt. Those of ordinary skill in the art will be able to adjust blending times and temperatures, as well as component addition location and sequence, without undue additional experimentation.
[0146] While the stabilizers of this invention may be conveniently incorporated by conventional techniques into polymers before the fabrication thereof into shaped articles, it is also possible to apply the instant stabilizers by a topical application to the finished articles. Articles may comprise the instant stabilizer compounds and polymers and may be made into, for example, head lamp covers, roofing sheets, telephone covers, aircraft interiors, building interiors, computer and business machine housings, automotive parts, and home appliances. The articles may be made by extrusion, injection molding, roto-molding, compaction, and other methods. This may be particularly useful with fiber applications where the instant stabilizers are applied topically to the fibers, for example, by way of a spin finish during the melt spinning process.
[0147] The phosphite compositions of the invention may have uses in addition to polymer stabilization. For example, it may be desirable to react the phosphite composition to form a
new derivative product, that may of additional uses. Transesterification processes, for example, such as those disclosed in Hechenbleikner et al., U.S. Patent No. 3,056,823, which is incorporated herein by reference, may also be employed. Specifically, the process described by Hechenbleikner et al. involves transesterifying a triaryl phosphite with a monohydroxy hydrocarbon in the presence of a small but catalytically effective amount of a metal alcoholate or metal phenolate. To avoid contamination, the alcoholate of the particular alcohol to be transesterified is employed. Instead of employing a preformed alcoholate, the alcoholate can be formed in situ by adding the metal, e.g., sodium, potassium or lithium to the alcohol prior to adding the triaryl phosphite. The mono alcohol and triaryl phosphite are reacted in the mol ratio of three mols of the alcohol to one mol of the triaryl phosphite.
[0148] The present invention will now be described by way of the following non-limiting examples.
Comparative Example A
Synthesis of Mixed Amyl/Butyl Phenols
[0149] Phenol (105 grams, 1.12 moles) and Fulcat 22B catalyst (2.25 grams) were charged to an oil jacketed flask and heated to 1300C under nitrogen. Isobutylene (64.6 grams, 1.15 moles) was added via a sintered glass frit below the surface of the phenol at a uniform rate over 30 minutes. During addition, the internal temperature rose to 1400C. Once the addition was completed, the reaction mass was held at a jacket temperature of 1300C for one hour. Amylene (39.2 grams, 0.56 mole) was then added below the surface of the phenolics at a uniform rate over 1.25 hours. After the addition, the reaction mass was held at a jacket temperature of 1300C for two hours. The reaction was then filtered and the phenolic filtrate collected. The mixed butylated/amylated phenol alkylate was subjected to vacuum distillation to reduce the phenol content to less than 0.25% and the water content to less than 50 ppm. Yield = 161.8 grams.
[0150] GC analysis identified the following major components: 50.8% 4-t-butyl-phenol, 17.6% 2,4-di-t-butyl-phenol, 15.3% 4-t-amyl-phenol, 10.7% 2-t-amyl-4-t-butyl-phenol and 2- t-butyl-4-t-amyl-phenol, 1.3% 2,4-di-t-amyl-phenol, 1.4% 2-t-butyl-phenol, and 0.3% 2,4,6- tri-t-butyl-phenol.
Comparative Example B
Conversion to a Phosphite of the Alkylate Obtained as per Example A
[0151] Mixed butylated/amylated phenolic alkylate (148.7 grams, 0.86 mole) was charged to an oil jacketed flask and heated to 800C under nitrogen. PCI3 (35.8 grams, 0.26 mole) was added, below the surface of the phenolics, at a uniform rate over three hours. During the
addition, the temperature was ramped to 1500C. The reaction mass was held at 1500C until HCl evolution ceased, and then was heated to 2000C over one hour while the pressure was reduced from 1000 to 50 mbar. The reaction was held at 2000C / 50 mbar until the total Cl content was less than 50 ppm. The phenolic excess was then removed by distillation under one mbar pressure and an internal temperature of 2400C (vapor temperature 1400C). Yield = 123.1 grams.
[0152] The phosphite composition had kinematic viscosity of @ 300C of 8,541 cSt, @ 400C of 3,198 cSt, and @ 500C of 812 cSt.
Example 1
[0153] 73.4 g (0.53 moles) of phosphorous trichloride and 1.74 ml (6.41 mmols) of N3N- dimethyldodecylamine are charged to a jacketed vessel under nitrogen. The contents of the vessel are agitated and heated to 700C. Separately, a powdered blend of 193.1 g (1.18 moles) of 4-ter?-amylphenol and 121.3 g (0.56 moles) of 2,4-di-ter?-butylphenol is prepared. The powdered blend is added in uniform shots of 26.2 g, every 15 minutes over 3 hours. During the addition the reaction is held at 700C and evolved HCl is absorbed by a scrubber unit.
[0154] Once all the phenols are added, the reaction temperature is uniformly ramped from 700C to 1500C over 1 hour. The reaction mass is held at 1500C for 1 hour or until the HCl evolution has stopped. Next, the reaction mass is further heated from 1500C to 2000C and held for 1 additional hour. Once the reaction mass has reached 2000C, the reaction is degassed by applying a vacuum at a pressure from 60-80 mbar until the total chlorine content is less than 50 ppm. Excess phenols may be removed by distillation under a pressure of 7mbar up to an internal temperature of 2000C (maximum vapor temperature 127°C).
[0155] 1.89g (9.9 mmoles) of triisopropanolamine is added to the phosphite composition.
[0156] The resulting composition of phosphites had a kinematic viscosity at 700C of 97 cSt. The total phosphorous content is 5.6%.
Example 2
[0157] A 1 : 1 molar ratio of 2-t-butyl-p-cresol and 4-t-amylphenol were charged to an oil jacketed flask and heated to 800C under nitrogen. PCI3 (73.4 grams, 0.53 mole) was added, below the surface of the phenolics, at a uniform rate over 2 hours. During the addition the temperature was ramped to 1500C and the reaction mass was held at 1500C until HCl evolution ceased. Next the reaction mass was heated to over 2000C over 1 hour while the pressure was reduced from 1000 to 70 mbar, and held at these conditions until the total Cl content was less than 50 ppm. The phenolic excess was then removed by distillation under 8
mbar pressure and an internal temperature of 2000C. The resulting composition of phosphites had a kinematic viscosity at 700C of 160 cSt. The total phosphorous content is 5.9%.
Example 3
[0158] The composition of phosphites from Examples 1 and 2 were tested and compared against a tris(nonylphenyl)phosphite, Weston 399, and showed the following results in Table 3. The phosphite were added at the same phosphorous content for comparison (@ 17 ppm).
Table 3
Composition Example 1 Example 2 Weston 399
LLDPE 99.93 wt% 99.901 wt% 99.89 wt%
ZnSt 0.05 wt% 0.05 wt% 0.05 wt%
Anox PP18 0.02 wt% 0.02 wt% 0.02 wt%
Phosphite Amount 0.0305 wt% 0.029 wt% 0.04 wt%
YI (ASTM E313Ϊ during multioass (S). 2300C
Initial -1.284 -1.07 -1.249
Pass 1 0.441 0.573 0.06
Pass 3 0.705 0.952 0.718
Pass 5 0.937 1.689 1.203
MFI (α>2.16 kg during multipass (S), 2300C
Initial 0.975 0.958 0.967
Pass 1 0.939 0.909 0.904
Pass 3 0.782 0.781 0.778
Pass 5 0.591 0.629 0.637
MFI (S), 21.6 kg during multipass i (S). 2300C
Initial 23.635 22.817 23.027
Pass 1 23.203 22.986 23.066
Pass 3 22.022 21.656 21.614
Pass 5 21.344 20.694 20.973
MFI ratio during multipass (a), 2300C
Initial 24.229 23.814 23.819
Pass 1 24.698 25.298 25.519
Pass 3 28.149 27.741 27.765
Pass 5 36.113 32.894 32.940
YI, after NOx exposure
2 hours 2.37 2.84 3.26
25 hours 5.48 8.33 6.27
94 hours 8.63 9.14 9.34
120 hours 9.41 9.94 10.11
140 hours 10.19 — 10.52
Examples 4
[0159] Preparation of phosphite composition from a 1 : 1 (Molar) mixture of 4-?-amylphenol (4-TAP) with 2,4-di-?-butylphenol (2,4-DTBP) was prepared similar to Example 1.
Viscosities are provided in Table 4, below.
Comparative Example C
[0160] Reaction of phosphorus trichloride (1/3 mole) with 2,4-di-tertiary amyl phenol (2/3 mole) then with 2,4-ditertiary butyl phenol (1/3 mole) from U.S. Patent No. 5,254,709 produces a solid phosphite composition.
[0161] One -third of a mole of phosphorus trichloride (46 g) was charged into a 500 ml 3- neck flask. One hundred cubic centimeters of toluene and 0.2 g mercaptobenzothiazole were added. Then 156 g (2/3 mole) of melted 2,4-di-tertiary amyl phenol was dropped in over a period of two hours, the temperature being maintained between 55° and 65° C. The
temperature was then increased to 120°- 123° C for two hours. Nitrogen gas was passed through the hot mix to remove residual hydrogen chloride. The mix stood over the weekend at room temperature. An infrared analysis showed no hydroxyl. The mixture was warmed to 60° C and 68.3g (1/3 mole) of solid 2,4-di-tertiary butyl phenol was added. The mix was gradually heated to 127° C (over two hours) and then heated near that temperature for three hours longer. Nitrogen gas was bubbled through the hot mix to remove residual hydrogen chloride. The toluene was removed by heating under diminished pressure. The residual product was a clear liquid that hardened to a clear glassy product on cooling. Three hundred cc of methanol was added and the mixture was stirred and heated to 60° C. The product gradually crystallized to a white powder. After standing in the methanol at room temperature overnight the solid product was filtered off and washed with 100 cc of methanol. The dried produce weighed 197.6 g (90% of theory). The material melted at 89°-93° C.
Comparative Examples D and E
[0162] Comparative Examples B and C were prepared in a similar amount with different molar ratios of phenols and different phenols as shown in Table 4 below. Comparative
Examples D and E use 4-t-butylphenol (4-TBP).
Table 4
Viscosities (cSt)
Ex. Phenol 1 MoI Phenol 2 MoI Ratio @ 400C @ 500C @ 600C
1 2,4-DTBP 0.293 4-TAP 0.588 1 :2 1189 420 175 4 2,4-DTBP 0.288 4-TAP 0.288 1 :1 32,228 7351 1810 D 2,4-DTBP 0.661 4-TBP 0.661 1 :1 10,265 1678 E 2,4-DTBP 2.938 4-TBP 5.878 1 :2 10,486 1853
[0163] As shown in Table 4, replacing 4-TBP with 4-TAP reduces the viscosity at lower temperatures, 30-500C. In addition, providing a molar ratio of 2,4-DTBP to 4-TAP of 1 :2 further reduces the viscosity.
Claims
A liquid composition comprising at least two different alkylaryl phosphites, wherein at least one of the phosphites has the structure:
wherein a, b, c and d are independently selected from O, 1, 2 and 3, provided that a + b + c + d- 3, wherein each Ar is an independently selected aromatic moiety, and wherein each Ri is an alkyl group having the same number of carbon atoms and each R2 is an alkyl group having the same number of carbon atoms, provided that Ri has a different number of carbon atoms than R2, and wherein at least one alkylaryl phosphite includes Ri and wherein at least one other alkylaryl phosphite includes R2.
The composition of claim 1 , wherein Ri and R2 are independently selected from straight or branched C1-C12 alkyl groups.
The composition as in any one of claims 1 and 2, wherein Ri is t-butyl and R2 is t- amyl.
The composition as in any one of claims 1-3, wherein the at least two different alkylaryl phosphites comprise a first alkylaryl phosphite in which a + b = 3, and a second alkylaryl phosphite in which c + d - 3.
The composition of claim 4, wherein the first phosphite and second phosphite do not include tris(2,4-di-t-amyl phenyl)phosphite and tris(2,4-di-t-butyl phenyl)phosphite.
The composition as in any one of claims 1-3, wherein the alkylaryl phosphite composition comprises at least one alkylaryl phosphite in which a + b = 1 or 2, and c + d= 1 or 2.
7. The composition of claim 6, wherein the at least two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 2,4-di-t-amyl phenol and 4-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1.
8. The composition of claim 6, wherein the at least two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-butyl phenol and either 4-t-amyl phenol or 2,4-di-t-amyl phenol, in a molar ratio of 1 :4 to 4: 1.
9. The composition of claim 6, wherein the at least two different alkylaryl phosphites is a reaction product of a phosphorous trihalide and a mixture of 4-t-amyl phenol and 2,4-di-t-butyl phenol, in a molar ratio of 1 :4 to 4: 1.
10. The composition as in any one of claims 1-9, wherein at least 95 wt % of the aryl moieties are substituted with alkyl groups having tertiary α-carbons.
11. The composition as in any one of claims 1-10, wherein the composition further
comprises at least one additional component selected from the group consisting of phenolic antioxidants, amine stabilizers, hindered amine light stabilizers, ultraviolet light absorbers, phosphonites, alkaline metal salts of fatty acids, hydrotalcites, metal oxides, epoxidized oils, epoxidized soybean oils, hydroxylamines, lactones, thermal reaction products of tertiary amine oxides, thiosynergists, and additional phosphites.
12. The composition as in any one of claims 1-11, wherein the composition further
comprises an amine selected from the group consisting of triethanolamine, triisopropanolamine, diethanolamine, diisopropanolamine,
tetraisopropanolethylenediamine, and alkyl dialkanolamines.
13. A method for preparing a liquid phosphite composition as in one of claims 1-12
comprising: reacting a phosphorus polyhalide with alkylated phenols to produce a liquid phosphite composition, wherein alkylated phenols comprise at least two separately synthesized alkylated phenols.
14. A process for stabilizing a polymeric composition comprising adding to the polymeric composition an effective amount of a phosphite composition as in one of claims 1-12.
5. A stabilized polymeric composition comprising:
A) a polymeric resin; and
B) a phosphite composition as in one of claims 1-12.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23065209P | 2009-07-31 | 2009-07-31 | |
US61/230,652 | 2009-07-31 | ||
US12/534,051 US8178005B2 (en) | 2006-06-20 | 2009-07-31 | Liquid phosphite compositions having different alkyl groups |
US12/534,051 | 2009-07-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011014210A2 true WO2011014210A2 (en) | 2011-02-03 |
Family
ID=42025742
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2009/060213 WO2011014210A2 (en) | 2009-07-31 | 2009-10-09 | Liquid phosphite compositions having different alkyl groups |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2011014210A2 (en) |
-
2009
- 2009-10-09 WO PCT/US2009/060213 patent/WO2011014210A2/en active Application Filing
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8178005B2 (en) | Liquid phosphite compositions having different alkyl groups | |
US8008383B2 (en) | Liquid amylaryl phosphite compositions | |
US7947769B2 (en) | Liquid amylaryl phosphite compositions and alkylate compositions for manufacturing same | |
US8008384B2 (en) | Liquid butylaryl phosphite compositions | |
EP2459578B1 (en) | Solid alkylaryl phosphite compositions and methods for manufacturing same | |
EP2459575A2 (en) | Hydrolytically stable phosphite compositions | |
EP2459574B1 (en) | Solid alkylaryl phosphite compositions and methods for manufacturing same | |
EP2459576B1 (en) | Liquid alkylated trisaryl phosphite compositions having two alkyl groups with different carbon number | |
US20100076131A1 (en) | Liquid butylaryl phosphite compositions and alkylate compositions for manufacturing same | |
US20150021523A1 (en) | Processes For Forming Alkylated Aryl Phosphite Compositions From Complex Hydrocarbon Streams | |
US8183311B2 (en) | Liquid phosphite composition derived from cresols | |
WO2011014210A2 (en) | Liquid phosphite compositions having different alkyl groups |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09736363 Country of ref document: EP Kind code of ref document: A2 |
|
NENP | Non-entry into the national phase in: |
Ref country code: DE |
|
122 | Ep: pct app. not ent. europ. phase |
Ref document number: 09736363 Country of ref document: EP Kind code of ref document: A2 |