CA2051469A1 - Polymer composition which masks odor - Google Patents
Polymer composition which masks odorInfo
- Publication number
- CA2051469A1 CA2051469A1 CA 2051469 CA2051469A CA2051469A1 CA 2051469 A1 CA2051469 A1 CA 2051469A1 CA 2051469 CA2051469 CA 2051469 CA 2051469 A CA2051469 A CA 2051469A CA 2051469 A1 CA2051469 A1 CA 2051469A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- poly
- polymer
- methyl
- glutarimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 235000019645 odor Nutrition 0.000 claims abstract description 41
- HLMIVULQFMULRM-UHFFFAOYSA-N 2-cyclohexyloxyethylbenzene Chemical compound C1CCCCC1OCCC1=CC=CC=C1 HLMIVULQFMULRM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000654 additive Substances 0.000 claims abstract description 23
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 42
- -1 poly(glutarimide) Polymers 0.000 claims description 33
- 150000001412 amines Chemical class 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 19
- 229920003023 plastic Polymers 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 18
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical group CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 16
- 239000004609 Impact Modifier Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000012964 benzotriazole Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 8
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 7
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 7
- 229920006243 acrylic copolymer Polymers 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000000873 masking effect Effects 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 4
- 150000008301 phosphite esters Chemical class 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- MPFAYMDFVULHEW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MPFAYMDFVULHEW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical compound [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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 claims description 2
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- NWIKMSABBNGQRG-UHFFFAOYSA-N tris(3,3-dibromopropyl) phosphate Chemical compound BrC(Br)CCOP(=O)(OCCC(Br)Br)OCCC(Br)Br NWIKMSABBNGQRG-UHFFFAOYSA-N 0.000 claims description 2
- YUJCWMGBRDBPDL-UHFFFAOYSA-N 4,4-dimethylpiperidine-2,6-dione Chemical compound CC1(C)CC(=O)NC(=O)C1 YUJCWMGBRDBPDL-UHFFFAOYSA-N 0.000 claims 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 claims 1
- 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 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims 1
- 239000012965 benzophenone Substances 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical group C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 claims 1
- 239000004917 carbon fiber Substances 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 claims 1
- 235000013824 polyphenols Nutrition 0.000 claims 1
- 150000003873 salicylate salts Chemical class 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 13
- 238000002845 discoloration Methods 0.000 abstract description 3
- 238000007086 side reaction Methods 0.000 abstract description 3
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 abstract 1
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical class O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 description 35
- 239000003205 fragrance Substances 0.000 description 33
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 18
- 230000008569 process Effects 0.000 description 15
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 150000003949 imides Chemical class 0.000 description 11
- 238000013022 venting Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 150000008064 anhydrides Chemical group 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 229960001047 methyl salicylate Drugs 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZZDMUVQELXJWCS-UHFFFAOYSA-N 1-propan-2-ylcyclohexan-1-ol Chemical compound CC(C)C1(O)CCCCC1 ZZDMUVQELXJWCS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 150000003973 alkyl amines Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000003016 pheromone Substances 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 239000004597 plastic additive Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000003017 thermal stabilizer Substances 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 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 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 241001177117 Lasioderma serricorne Species 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-UHFFFAOYSA-N 0.000 description 1
- FMGADNVMWHSJDJ-UHFFFAOYSA-N 1,4,4-trimethylpiperidine-2,6-dione Chemical compound CN1C(=O)CC(C)(C)CC1=O FMGADNVMWHSJDJ-UHFFFAOYSA-N 0.000 description 1
- KTEFLEFPDDQMCB-UHFFFAOYSA-N 1,4-bis(4-butylanilino)-5,8-dihydroxyanthracene-9,10-dione Chemical compound C1=CC(CCCC)=CC=C1NC(C=1C(=O)C2=C(O)C=CC(O)=C2C(=O)C=11)=CC=C1NC1=CC=C(CCCC)C=C1 KTEFLEFPDDQMCB-UHFFFAOYSA-N 0.000 description 1
- ZKIVUFFTMWIBCO-UHFFFAOYSA-N 1,5-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC1=CC=CC2=C1C(=O)C1=CC=CC(NC=3C=CC(C)=CC=3)=C1C2=O ZKIVUFFTMWIBCO-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- ZPSZXWVBMOMXED-UHFFFAOYSA-N 2-(2-bromo-5-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC(Cl)=CC=C1Br ZPSZXWVBMOMXED-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- FDTLQXNAPKJJAM-UHFFFAOYSA-N 2-(3-hydroxyquinolin-2-yl)indene-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C1C1=NC2=CC=CC=C2C=C1O FDTLQXNAPKJJAM-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZWRJHWAMESICAF-UHFFFAOYSA-N 3,3,5,5-tetramethyl-1-[2-(3,3,5,5-tetramethyl-2-oxopiperidin-1-yl)ethyl]piperidin-2-one Chemical compound O=C1C(C)(C)CC(C)(C)CN1CCN1C(=O)C(C)(C)CC(C)(C)C1 ZWRJHWAMESICAF-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- DKKRDMLKVSKFMJ-UHFFFAOYSA-N 4-propan-2-ylcyclohexan-1-ol Chemical compound CC(C)C1CCC(O)CC1 DKKRDMLKVSKFMJ-UHFFFAOYSA-N 0.000 description 1
- UZQJQLCWGVJXEE-UHFFFAOYSA-N 5-chlorobenzotriazole Chemical compound [CH]1C(Cl)=CC=C2N=NN=C21 UZQJQLCWGVJXEE-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000725101 Clea Species 0.000 description 1
- 241000042795 Colotes Species 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000182067 Fraxinus ornus Species 0.000 description 1
- 101000852483 Homo sapiens Interleukin-1 receptor-associated kinase 1 Proteins 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
- 102100036342 Interleukin-1 receptor-associated kinase 1 Human genes 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 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 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000000038 blue colorant Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- OCDXZFSOHJRGIL-UHFFFAOYSA-N cyclohexyloxycyclohexane Chemical compound C1CCCCC1OC1CCCCC1 OCDXZFSOHJRGIL-UHFFFAOYSA-N 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical group CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- TWXDDNPPQUTEOV-FVGYRXGTSA-N methamphetamine hydrochloride Chemical compound Cl.CN[C@@H](C)CC1=CC=CC=C1 TWXDDNPPQUTEOV-FVGYRXGTSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005453 pelletization Methods 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
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 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 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004383 yellowing Methods 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
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides polymer compositions such as for instance, polyglutarimide and meth(acrylic)polymers to which is added a phenylethyl cyclohexyl ether of the following structure
The present invention provides polymer compositions such as for instance, polyglutarimide and meth(acrylic)polymers to which is added a phenylethyl cyclohexyl ether of the following structure
Description
2~351~
FIELD OF l'HE INVENTION
This in~ention relates to the use of phenylethyl cyclohexyl ethers f~r masking undesirable odors emitted during the high temperature preparation or processing of certain polymers, and to the reduced odor polyrner compositions containing this odorant. In addition, the phenylethyl cyclohexyl ether (odorant) does not createundesirable results, side reactions and discoloration problems in polymer compositions. The phenylethyl cyclohexyl ether (odorant) is useful in plastics such as polyglutarimides and (meth)acrylic copolyrners.
BAC~GROUND OF THE IN~ENTION
Glutarimides can be prepared by reacting amines or ammonia with (meth)acrylic homopolymers, for example: methyl methacrylate/ethyl acrylate (MMA/EA), methyl methacrylate/methyl acrylate (MMA/MA), methyl methacrylate/methacrylic acid (MMA/MAA~, and methyl methacrylate/butyl acrylate (MMA/BA). Amines and aIIunonia are known to have very low odor thresholds (e.g. parts per million~, and consequently the residual amines or ammonia emit$ed during processing of imides may produce an easily detectable undesirable odor. For example, the odor threshold limits (i.e. when odor is undesirable) for the following compositions are: monomethylamine - 3.2 ppm (parts per million), dimethylamine - 0.34 ppm, trimethylamine - 0.00044 ppm, and ammonia - 5.2 ppm (See "Odors, Helpful Waming and Harmful Effects" by J.lE.
Amoor, Ph. D., R&H Industrial Safety Dir. Conference, Montrëal, Canada, 6~1/87).The undesirable odor of monomethylamine, dimethylamine, trimethylamine and ammonia is therefore easily noticed by the employee or consumer preparing or processing polyglutarimides. Completely eliminating residual amines or ammonia is very desirable, but has not been possible. In the alternative, the next best approach `
., ,: ~ , '~ 0 ~
is to mask the ~mdesirable amine andtor ammonia odors.
U. S. Patent No. 4,246,374 (Kopchik) discloses thermally stable polyglutarimide polyrners and a practic~l process ,for ~eir preparation. I~ese polymers, especially those prepared from poly(methyl metha~ylate~ and monomethylamine or ammonia in a devolatilizing extruder, are use~ul as clear glazing or protective materials and have acceptable impact and modulus properties with a higher service temperature ~han other clea:r thermoplastics. Major markets include: building / construction, electrical / electronlcs, appliances, transportation, business equipment, lightin~" medical devices, optical lenses, and consumer products.
The thermoplastic polymer of Kopchik contains imide units of the structural formula:
xl3 ~ ~N~ Oo X7~CH~ 2 wherein Xl, X2, and X3 independently represent hydrogen or unsubstituted or substituted Cl to C2~ alkyl, aryl, or aralkyl alkaryl, or rrLixtures thereof, said polymer further characterized as non-crosslinlced and soluble in dimethyl formamide, andhaving a degree of thermal stability as measured by Thermal Gravimetric Analysis(TGA) such that the temperature at which said polymer has 1% decomposition in air is above 285C. - ~
The basic reaction for forming irnides is by reacting urea, butylamine, dodecyl amine or octyl amine with poly(methyl methacrylate) or poly(methacrylic acid) asshown in Graves U.S. Patent No. 2,146,209, German Patent No. 1,077,872 and German Patent No. 1,242,369. Schroeder et al. U. S. Patent No. 3,~84,425 and British Patent No. 926,629 show a route toward imidized a~ylics by reacting poly(methyl methacrylate) with ammonium hydroxide, amrnonium phosphate, alkyl amines or a combination of partial reaction with ammonium hydroxide followed by reaction with alkyl amine. British Patent No. 1,045,229 shows chemical modification of methacrylic acid~methacrylc)nitrile (MMA~MAN) copolymers or terpolymers by heating at 180-300C. to give the cyclic imide product, optionally with a dispersing solvent. German Patent Nos. 1,247,517; 2,~41,736; and 2,047,096 show methacrylamide/ methyl methacrylate (MAN~MMA) copolymers, inert solvent, and heat to achieve imide formation accompanied by evolution of ammonia. Most prior patents and literature on processes to imidized acrylics via reaction of ammonia and primary amines with poly(methyl methacrylates~, U. S. P tent No.
FIELD OF l'HE INVENTION
This in~ention relates to the use of phenylethyl cyclohexyl ethers f~r masking undesirable odors emitted during the high temperature preparation or processing of certain polymers, and to the reduced odor polyrner compositions containing this odorant. In addition, the phenylethyl cyclohexyl ether (odorant) does not createundesirable results, side reactions and discoloration problems in polymer compositions. The phenylethyl cyclohexyl ether (odorant) is useful in plastics such as polyglutarimides and (meth)acrylic copolyrners.
BAC~GROUND OF THE IN~ENTION
Glutarimides can be prepared by reacting amines or ammonia with (meth)acrylic homopolymers, for example: methyl methacrylate/ethyl acrylate (MMA/EA), methyl methacrylate/methyl acrylate (MMA/MA), methyl methacrylate/methacrylic acid (MMA/MAA~, and methyl methacrylate/butyl acrylate (MMA/BA). Amines and aIIunonia are known to have very low odor thresholds (e.g. parts per million~, and consequently the residual amines or ammonia emit$ed during processing of imides may produce an easily detectable undesirable odor. For example, the odor threshold limits (i.e. when odor is undesirable) for the following compositions are: monomethylamine - 3.2 ppm (parts per million), dimethylamine - 0.34 ppm, trimethylamine - 0.00044 ppm, and ammonia - 5.2 ppm (See "Odors, Helpful Waming and Harmful Effects" by J.lE.
Amoor, Ph. D., R&H Industrial Safety Dir. Conference, Montrëal, Canada, 6~1/87).The undesirable odor of monomethylamine, dimethylamine, trimethylamine and ammonia is therefore easily noticed by the employee or consumer preparing or processing polyglutarimides. Completely eliminating residual amines or ammonia is very desirable, but has not been possible. In the alternative, the next best approach `
., ,: ~ , '~ 0 ~
is to mask the ~mdesirable amine andtor ammonia odors.
U. S. Patent No. 4,246,374 (Kopchik) discloses thermally stable polyglutarimide polyrners and a practic~l process ,for ~eir preparation. I~ese polymers, especially those prepared from poly(methyl metha~ylate~ and monomethylamine or ammonia in a devolatilizing extruder, are use~ul as clear glazing or protective materials and have acceptable impact and modulus properties with a higher service temperature ~han other clea:r thermoplastics. Major markets include: building / construction, electrical / electronlcs, appliances, transportation, business equipment, lightin~" medical devices, optical lenses, and consumer products.
The thermoplastic polymer of Kopchik contains imide units of the structural formula:
xl3 ~ ~N~ Oo X7~CH~ 2 wherein Xl, X2, and X3 independently represent hydrogen or unsubstituted or substituted Cl to C2~ alkyl, aryl, or aralkyl alkaryl, or rrLixtures thereof, said polymer further characterized as non-crosslinlced and soluble in dimethyl formamide, andhaving a degree of thermal stability as measured by Thermal Gravimetric Analysis(TGA) such that the temperature at which said polymer has 1% decomposition in air is above 285C. - ~
The basic reaction for forming irnides is by reacting urea, butylamine, dodecyl amine or octyl amine with poly(methyl methacrylate) or poly(methacrylic acid) asshown in Graves U.S. Patent No. 2,146,209, German Patent No. 1,077,872 and German Patent No. 1,242,369. Schroeder et al. U. S. Patent No. 3,~84,425 and British Patent No. 926,629 show a route toward imidized a~ylics by reacting poly(methyl methacrylate) with ammonium hydroxide, amrnonium phosphate, alkyl amines or a combination of partial reaction with ammonium hydroxide followed by reaction with alkyl amine. British Patent No. 1,045,229 shows chemical modification of methacrylic acid~methacrylc)nitrile (MMA~MAN) copolymers or terpolymers by heating at 180-300C. to give the cyclic imide product, optionally with a dispersing solvent. German Patent Nos. 1,247,517; 2,~41,736; and 2,047,096 show methacrylamide/ methyl methacrylate (MAN~MMA) copolymers, inert solvent, and heat to achieve imide formation accompanied by evolution of ammonia. Most prior patents and literature on processes to imidized acrylics via reaction of ammonia and primary amines with poly(methyl methacrylates~, U. S. P tent No.
3,2B4,425, for exarnple, are directed to an autoclave batch process requiring lengthy heating time, usually 7 hours or more, in the presence of inert dissolving or suspending solvent. U. S. Patent No. 3,557,û70 describes a process for preparingethylene/methacrylic acid/methacrylimide terpolymers from an ethylene/isopropyl methacrylate copolymer by heating the copolymer to the decomposition temperature ~325C.) of the isopropyl ester to form methacrylic anhydride units which are then reacted with gaseous ammonia to give methacrylimide and methacrylic acid residues in the polymer chain. The reaction_is run neat withoutsolvent. Although U.S. Patent No. 3,557,070 does not mention that these reactions are taking place in an extruder, the Derwent abs~act of the patent mentioned that these reactions may be run in an extruder. The use of extruders as polymer reactors has been shown as a route to copolyesters (Preparation and Properties of ' ~' ' ' ~ ;'' ~ ~3 r;J~
Copolyesters Polymeri7ed in a Vented Extruder, J. Applied Polymer Science 12,2403~1968], nylon products (Direct Extrusion of Nylon Product from Lactams, Modern Plastics, August 1969-Warner Pfleiderer) a;nd graft polymerization of polyolefins (Steinkamp et al. U. S. Patent No. 3,862,265). West German Patent No.
1,077,872 discloses an extruder process of irnid~ing acrylic polymers using a water solution of ammonia, but the product is a foamed strand with defici~e~nt thermalstability and which requires further processing before it can be used to fabricate useful items; futhermore, the process described is not comrs~ercially feasible in that the foamed polymer exits the extruder under high pressure with free ammonia apor. As discussed above, polyglutarimides of the following structure may be prepared and processed with cyclohexyl phenyle~yl ethers:
l3 C ~N~C C) X7~ ~CH2--wherein Xl, X2, and X3 inde~endently represent hydrogen or unsubstituted or substituted Cl to C20 alkyl, aryl, or aralkyl alkaryl, or mixtures t~ereof, said polymer further characterized as non-crosslinked and soluble in dimethyl formamide, and having a degree of thermal stability as measured by TGA such that the temperature at which said polymer has 1~ decomposi~on in air is above 285~C
(Meth)acrylic copolymers (i.e. resins of about 80% or more alkyl acrylate or the like) are known for sparl:ling crystal clarity and outstandillg surface hardness, together with superior weatherability and good chemical resistance. These characteristics have made them the material of choice for a range of applications.
Acrylic monomers are supplied for conversion into coating resins and casting sheet, rods, and tubes. The acrylic resins are supplied as beads or pellets for extruding into 2 n ~
sheet or profiles, or for injection molding into magnifying, automotive tailight, and lighting lenses~ Acrylic monomers can be polymerized by free radical processes with the aid of peroxides and the like~ Methyl methacrylate usually is copolymerized with other acrylates such as methyl or ethyl acsylate for molding and extrusion compounds. There are four basic polymerization processes in use to;:lay: bulk, ~-suspension, emulsion and solution. ~t Phenylethyl cyclohexyl e~er can be used to mask undesirable cdors emitted during high temperature preparation or processing of polymers other than polyglutarimides. l;or example, during the preparation and processing of (meth)acrylic copolymers, t~ere are cases where undesira~le odors become annoying and bothersome due to inadequate venting or no venting. This is quite common with single- and double-screw extruders and injection molding machines which do not have venting. This odor may come from residual monomers and/or mercaptans used in the forIrlulation of the plastic to control molecular weight. For example, in the processing of (meth)acrylic copolymers, methyl methacrylate monomer has an odor threshold range of 50-340 parts per billion (PPB) and n-alkyl mercaptans have an odor threshold range of 0.5-20û PPB (See "Odors, Helpful Warning and Harmful Effects" by J.:E. Amoor, Ph. D., R&H Industrial Safety Dir.
Conference, Montreal, Canada, 6/1/87). Phenylethyl cyclohexyl ethers (PECE) willmask the residual monomer and/or mercaptan odors associated with (meth)acrylic copolymer preparation or professing.
_ . _ .
,. , ~
..
.
:~ ;
The weatherability and optical properties of acrylics are superior to many other plastics available today. They also have good electrical and chemical properties. Acrylics withstand prolonged periods of exposure to weather and sunlight without yellowing or stress-cracking. For extreme cases, lik~ exposure to mercury vapor lamps, adding an ultraviolet absorber ~IJVA) is recommended.
Meth(acrylic) copolymers of the following structure may be prepared and processed with cyclohexyl phenethyl ethers:
,~,CI~
// \Zl 1~
where Zl=H,CH3, CH3C~:[2, CH3CH2CH2, CH3CH2CH2CH2~ and [3 Z2-H, CH3 Z3=~;l n and n' = the same or different repeating units . ' ' ;. ~:
2 ~
DESCRI~ION OF PRIOR ART
Phenylethyl cyclohexyl ethers have been used in perfurnes, and are known to be pheromones and consequenlly can be used in insecticides. For example, U. S.
Patent No. 4,374,746 t~Ciwala et al.) discloses cyclohexyl phenylethyl e~her and its derivatives, for enhancing the aroma of perfumes, perfumed articles, and colognes, and in addition, in combatting tobacco beetles of the spedes Lasioderma serricorne ~F). The pleasant smelling pheromones are also useful for combatldng insects, yet at the same time, are not repulsi~re to individuals or groups of individuals applying the pheromone to the area where the insects are to be combatted.
Kiwala et al., specifically taught the properties of the phenylethyl cyclohexyl ethers having the generic structure:
R2/~ --O
wherein Rl, R2, R3 and R4 are the saIne or different and each represents rnethyl or hydrogen with the proviso ~at when one of R2, R3 and R4 is rnethyl, then the other two of R2, R3 and R~ are hydrogen; or processes for preparing same by reacting the phenethyl als ohol derivatives with cyclohexene.
_ .
Vincent A. Lindgren's article in Modern Plastics Encyclopedia 1989, disdoses fragrance concentrates which can be dispersed in a thermoplastic resin matrix. The fragrances are sold as a dry, pelle~zed additive system, and serve as a clean, safe way to incorporate functional or decorative fragrances into a wide range of plas~c - .. .
, -; , ~ .
2 ~3 ~
processes. The fragrances are disclosed to be available in simple fruits and florals, to complex fine fragrances or hmctional deodorant types, and these concen~ates are produced in resin systems compatible with most olefinic, cellulosic, and poly (vinylchloride) (PVC) compounds. They can be blown or cast into film, injection or blow molded, foamed, or ext~uded.
It is the object of the present invention to produce a plastic composition which masks undesirable odors and does not have undesirable color formation.
Further, it is an object of the present invention to produce an imide composition which masks undesirable amine and anunonia odors. It is a further object to produce a polyglutarimide composition which masks unpleasant amine and ammonia odors, and also does not have undesirable color forma~on. It is a further object to teach a method of producing a plastic composition which masks undesirable odors and does not have undesirable coloT formation.
. .
:
.. , . : , ~
~- .
SU~IMARY OF THE INVENTION
A polymer cornposition has been discovered containing phenylethyl cyclohexyl ethers of the following structure:
.
R~
wherein Rl, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen; resulting in a polymer con position which can simultaneouslymask plastic odors present during high temperature processing, without creating undesirable results, side reactions, and discoloration. ;~
20cr3~l4~3 DETAILED DESCRIPl[~ON
The addition of phenylethyl cyclohexyl ethers (PECE~ to poly~er compositions has been foun~l to greatly improve the masking of odors. For example, the addition of PECE to glutarimides masks amine and/or ammonia which are undesirable to the human sense of smell. Further, PECE has been found to be the most favorable maskant or fragrance with respect to color forma~on (based on yellowness index values) when added to polymer composi~ons (see Example 1).
The level of phenylethyl cyclohexyl ether to b~ effective i5 from abou~ 0.01 -1.0% weight percent, based on the plastic (e.g. polyglutarimide or (meth)acryliccopolyrner) in the polymer composition. At lower levels, ~he odorant will be less effective; and at higher level~, the odorant will be flllly effective, but not at an efficient and economic rate. Preferred is from about 0.01 to about 0.10 weight percent of the odorant. An effective amount of phenylethyl cyclohexyl ether is that amount which people skilled in the art would add, and functions to give the polymer composition the desired characteristics of the odorant.
The plastics of the present invention are useful in applications such as sheet, film, molded articles, or exh uded articles which require high values of clarity or visible light transmittance. Such useful articles where stabiliza~on to light and heat is desirable are windows, protective shields, housings, and the like for heat-emitting light sources, especially those which emit ultraviolet light or are severely exposed to same during use. Such include lighting for cars, truclcs, airplanes, buses, and the like, especially head- or tail-lamp enclosures, high intensity discharge lighting, such as from metallic vapors, mercury sources, sodium vapor, sunroofs for automobiles, ~: :
~ ~) r 1~
buses, trucks, boats, and the like.
The plastics which can be applied to this invention include, but are not limited to polyglutarimides and (meth)acrylics. The glutarimide polymer is preferably prepared by the method of U. S. Patent ~o. 3,246,374, but other processes, such as reaction of poly~me~yl methacrylate) wi~h monomethylam~e in a pressurized kettle at high telnperature, reaction of polymers with a high percentage of methyl methacrylate mers with 2 primary alkyl amine in an appropriate solvent, reaction of polymers with a high percentage of N-methylmethacrylamide mers to eliminate methyl amine, or reaction of polymers having a high percentage of mersof glutaric anhydride with ammonia or methyl amine may be used. Such polymers may not exhibit the thermal stability or clarity of ~ose prepared by the process of U.
S. Patent No. 3,246,374 which thermal stability is expressed by a weight loss of no more than 1% at a temperatllre of 285 degrees C, as measured by thermogravime~ic analysis, as well as by solubility in solvents such as dimethylformamide and tetrahydrofuran.
The acid content of polymers made by the process of U. S. 3,24S,374 will usually exceed about 0.5 weight %, but should not exceed 6%. It is believed thatglutarimide polymers made by other processes will exhibit similar acid contents,with polymers made by ~e solution process on the low side of the range. Typical acid contents of the matrix polymers of the present invention are values of fromabout 2 to about 3.5 weight % (calculated from millequivalents/gram of about 0.10 to about 0.60, the analytical method being taught ln U. ~. Patent No. 4,727,17~).
, .
2 ~
The odorants may be used in combination wi~ plastics, and specifically glutarimide polymers of lower or no ac~d content, such as those taught by U. S.
Copolyesters Polymeri7ed in a Vented Extruder, J. Applied Polymer Science 12,2403~1968], nylon products (Direct Extrusion of Nylon Product from Lactams, Modern Plastics, August 1969-Warner Pfleiderer) a;nd graft polymerization of polyolefins (Steinkamp et al. U. S. Patent No. 3,862,265). West German Patent No.
1,077,872 discloses an extruder process of irnid~ing acrylic polymers using a water solution of ammonia, but the product is a foamed strand with defici~e~nt thermalstability and which requires further processing before it can be used to fabricate useful items; futhermore, the process described is not comrs~ercially feasible in that the foamed polymer exits the extruder under high pressure with free ammonia apor. As discussed above, polyglutarimides of the following structure may be prepared and processed with cyclohexyl phenyle~yl ethers:
l3 C ~N~C C) X7~ ~CH2--wherein Xl, X2, and X3 inde~endently represent hydrogen or unsubstituted or substituted Cl to C20 alkyl, aryl, or aralkyl alkaryl, or mixtures t~ereof, said polymer further characterized as non-crosslinked and soluble in dimethyl formamide, and having a degree of thermal stability as measured by TGA such that the temperature at which said polymer has 1~ decomposi~on in air is above 285~C
(Meth)acrylic copolymers (i.e. resins of about 80% or more alkyl acrylate or the like) are known for sparl:ling crystal clarity and outstandillg surface hardness, together with superior weatherability and good chemical resistance. These characteristics have made them the material of choice for a range of applications.
Acrylic monomers are supplied for conversion into coating resins and casting sheet, rods, and tubes. The acrylic resins are supplied as beads or pellets for extruding into 2 n ~
sheet or profiles, or for injection molding into magnifying, automotive tailight, and lighting lenses~ Acrylic monomers can be polymerized by free radical processes with the aid of peroxides and the like~ Methyl methacrylate usually is copolymerized with other acrylates such as methyl or ethyl acsylate for molding and extrusion compounds. There are four basic polymerization processes in use to;:lay: bulk, ~-suspension, emulsion and solution. ~t Phenylethyl cyclohexyl e~er can be used to mask undesirable cdors emitted during high temperature preparation or processing of polymers other than polyglutarimides. l;or example, during the preparation and processing of (meth)acrylic copolymers, t~ere are cases where undesira~le odors become annoying and bothersome due to inadequate venting or no venting. This is quite common with single- and double-screw extruders and injection molding machines which do not have venting. This odor may come from residual monomers and/or mercaptans used in the forIrlulation of the plastic to control molecular weight. For example, in the processing of (meth)acrylic copolymers, methyl methacrylate monomer has an odor threshold range of 50-340 parts per billion (PPB) and n-alkyl mercaptans have an odor threshold range of 0.5-20û PPB (See "Odors, Helpful Warning and Harmful Effects" by J.:E. Amoor, Ph. D., R&H Industrial Safety Dir.
Conference, Montreal, Canada, 6/1/87). Phenylethyl cyclohexyl ethers (PECE) willmask the residual monomer and/or mercaptan odors associated with (meth)acrylic copolymer preparation or professing.
_ . _ .
,. , ~
..
.
:~ ;
The weatherability and optical properties of acrylics are superior to many other plastics available today. They also have good electrical and chemical properties. Acrylics withstand prolonged periods of exposure to weather and sunlight without yellowing or stress-cracking. For extreme cases, lik~ exposure to mercury vapor lamps, adding an ultraviolet absorber ~IJVA) is recommended.
Meth(acrylic) copolymers of the following structure may be prepared and processed with cyclohexyl phenethyl ethers:
,~,CI~
// \Zl 1~
where Zl=H,CH3, CH3C~:[2, CH3CH2CH2, CH3CH2CH2CH2~ and [3 Z2-H, CH3 Z3=~;l n and n' = the same or different repeating units . ' ' ;. ~:
2 ~
DESCRI~ION OF PRIOR ART
Phenylethyl cyclohexyl ethers have been used in perfurnes, and are known to be pheromones and consequenlly can be used in insecticides. For example, U. S.
Patent No. 4,374,746 t~Ciwala et al.) discloses cyclohexyl phenylethyl e~her and its derivatives, for enhancing the aroma of perfumes, perfumed articles, and colognes, and in addition, in combatting tobacco beetles of the spedes Lasioderma serricorne ~F). The pleasant smelling pheromones are also useful for combatldng insects, yet at the same time, are not repulsi~re to individuals or groups of individuals applying the pheromone to the area where the insects are to be combatted.
Kiwala et al., specifically taught the properties of the phenylethyl cyclohexyl ethers having the generic structure:
R2/~ --O
wherein Rl, R2, R3 and R4 are the saIne or different and each represents rnethyl or hydrogen with the proviso ~at when one of R2, R3 and R4 is rnethyl, then the other two of R2, R3 and R~ are hydrogen; or processes for preparing same by reacting the phenethyl als ohol derivatives with cyclohexene.
_ .
Vincent A. Lindgren's article in Modern Plastics Encyclopedia 1989, disdoses fragrance concentrates which can be dispersed in a thermoplastic resin matrix. The fragrances are sold as a dry, pelle~zed additive system, and serve as a clean, safe way to incorporate functional or decorative fragrances into a wide range of plas~c - .. .
, -; , ~ .
2 ~3 ~
processes. The fragrances are disclosed to be available in simple fruits and florals, to complex fine fragrances or hmctional deodorant types, and these concen~ates are produced in resin systems compatible with most olefinic, cellulosic, and poly (vinylchloride) (PVC) compounds. They can be blown or cast into film, injection or blow molded, foamed, or ext~uded.
It is the object of the present invention to produce a plastic composition which masks undesirable odors and does not have undesirable color formation.
Further, it is an object of the present invention to produce an imide composition which masks undesirable amine and anunonia odors. It is a further object to produce a polyglutarimide composition which masks unpleasant amine and ammonia odors, and also does not have undesirable color forma~on. It is a further object to teach a method of producing a plastic composition which masks undesirable odors and does not have undesirable coloT formation.
. .
:
.. , . : , ~
~- .
SU~IMARY OF THE INVENTION
A polymer cornposition has been discovered containing phenylethyl cyclohexyl ethers of the following structure:
.
R~
wherein Rl, R2, R3 and R4 are the same or different substituents selected from methyl or hydrogen; resulting in a polymer con position which can simultaneouslymask plastic odors present during high temperature processing, without creating undesirable results, side reactions, and discoloration. ;~
20cr3~l4~3 DETAILED DESCRIPl[~ON
The addition of phenylethyl cyclohexyl ethers (PECE~ to poly~er compositions has been foun~l to greatly improve the masking of odors. For example, the addition of PECE to glutarimides masks amine and/or ammonia which are undesirable to the human sense of smell. Further, PECE has been found to be the most favorable maskant or fragrance with respect to color forma~on (based on yellowness index values) when added to polymer composi~ons (see Example 1).
The level of phenylethyl cyclohexyl ether to b~ effective i5 from abou~ 0.01 -1.0% weight percent, based on the plastic (e.g. polyglutarimide or (meth)acryliccopolyrner) in the polymer composition. At lower levels, ~he odorant will be less effective; and at higher level~, the odorant will be flllly effective, but not at an efficient and economic rate. Preferred is from about 0.01 to about 0.10 weight percent of the odorant. An effective amount of phenylethyl cyclohexyl ether is that amount which people skilled in the art would add, and functions to give the polymer composition the desired characteristics of the odorant.
The plastics of the present invention are useful in applications such as sheet, film, molded articles, or exh uded articles which require high values of clarity or visible light transmittance. Such useful articles where stabiliza~on to light and heat is desirable are windows, protective shields, housings, and the like for heat-emitting light sources, especially those which emit ultraviolet light or are severely exposed to same during use. Such include lighting for cars, truclcs, airplanes, buses, and the like, especially head- or tail-lamp enclosures, high intensity discharge lighting, such as from metallic vapors, mercury sources, sodium vapor, sunroofs for automobiles, ~: :
~ ~) r 1~
buses, trucks, boats, and the like.
The plastics which can be applied to this invention include, but are not limited to polyglutarimides and (meth)acrylics. The glutarimide polymer is preferably prepared by the method of U. S. Patent ~o. 3,246,374, but other processes, such as reaction of poly~me~yl methacrylate) wi~h monomethylam~e in a pressurized kettle at high telnperature, reaction of polymers with a high percentage of methyl methacrylate mers with 2 primary alkyl amine in an appropriate solvent, reaction of polymers with a high percentage of N-methylmethacrylamide mers to eliminate methyl amine, or reaction of polymers having a high percentage of mersof glutaric anhydride with ammonia or methyl amine may be used. Such polymers may not exhibit the thermal stability or clarity of ~ose prepared by the process of U.
S. Patent No. 3,246,374 which thermal stability is expressed by a weight loss of no more than 1% at a temperatllre of 285 degrees C, as measured by thermogravime~ic analysis, as well as by solubility in solvents such as dimethylformamide and tetrahydrofuran.
The acid content of polymers made by the process of U. S. 3,24S,374 will usually exceed about 0.5 weight %, but should not exceed 6%. It is believed thatglutarimide polymers made by other processes will exhibit similar acid contents,with polymers made by ~e solution process on the low side of the range. Typical acid contents of the matrix polymers of the present invention are values of fromabout 2 to about 3.5 weight % (calculated from millequivalents/gram of about 0.10 to about 0.60, the analytical method being taught ln U. ~. Patent No. 4,727,17~).
, .
2 ~
The odorants may be used in combination wi~ plastics, and specifically glutarimide polymers of lower or no ac~d content, such as those taught by U. S.
4,727,117. The odorants may ~e added to the plastics and glutarimide polymers bypost-compolmding of additives and unstabilized powder or pellets of, the plastics and glutarimide polymers, or by addition during vr prior to the imidization or acid-reduction steps. For masking odor, it is preferred that the odorant be added at the end of glutarimide production. The odorant and other additives may be added prior to, during, or after the preparation of the polymer and during the imide formation.
An additional method is to add the phenylethyl cyclohexyl ether to the polymer composition, along with other additives such as toners, lubricants, anti-oxidants, colorants, ultraviolet stabilizers, hindered amine light stabilizers, impact modifiers, pigments, fillers, fibers, flame retardants and the like, and for imides to be molten glutarimide or acid-reduced glutarimide polymer prior to extrusion into pellets, strands, sheet, or film. This process exposes the polymer and the additive to less heat history than re-processing of already extruded polymer. An effective amount of an additive is that amount which people skilled in the art would add, and functions to give the polymer composition the desired characteristics of theadditive. The polymer composition cs)ntaining effective amounts of additives maybe blended wi~ ~meth)acrylics, poly(vinyl chloride), poly(arnides), polycarbonates, polyesters, SAN tstyrene/acrylonitrile), ABS (acrylonitrile/butadiene/styrene), MBS
(methyl methacrylate/butadiene/styrene) polymers, or two- or three-stage cor~shell all acrylic impact modifiers.
Very low amounts of toners, colorants (e.g. pigments and dies), and color agents or concentrates can be used to correct undesirable color found in polymers.
The following coloring agen~s expressed by a name or number described in the Color ..-.
Index [in the Society of Dyers and Colourists, U.S.A.] can be chosen for use in polymer compositions described herein: Pigment Black 7, Pigment White 6, PigmentWhite 21, Pigment Gseen 7, Pigment Blue 15, Solvent Orange 60, Solvent Red 179, Solvent Green 28, Solvent Blue 45, 501vent Blue 101, Solvent Violet 14, and Disperse Yellow 54. An example of a useful toner is Irisol NTM (l-p-Toluidino, 4hydroxy an~raquinone). Further, the use of blue colorants are pref~rred for correcting yellowness problems.
Lubricants are well-known components of acrylic-based molding materials, serving to prevent stickage to hot metal surfaces and release from the rnold or die lips. Such lubricants include high molecular weight alcohols, such as those of twelve to twenty-four carbons, esters, especially long-chain alkyl esters of high molecular weight acids, such as bu~yl or stearyl stearate, monoesters of glycols, such as ethylene glycol monostearate, and the like. Preferred is stearyl alcohol. Levels of lubricants, when used, may r ange from about 0.05 to about 0.50 weight percent on polymer; preferred is about ().30%.
Antioxidants (thermal stabilizers) for the processing and molding of the polyglutarimide may be present without detracting from the ultraviolet stability of the stabilized composition. A preferred class of thermal stabilizers are organophosphites, such as tris(aryl)-br tris(alkylaryl)-or tris(alkyl)-phosphites.
Another preferred class is that of organophosphonites, such as trisaryl, trisalkaryl-or aryldialkaryl phosphonites, such as aryl-di(alkylphenyl)phosphonites. Preferred are acid-stable tris(2-alkylaryl) phosphites, such as tris(2-tertiary alkylaryl) phosphite, or aryl di(2-alkylaryl) phosphonite. Especially preferred thermal stabilizers are tris-. _ . . .
(nonylphenyl) phosphite lTNPP], tris~2,4-di-tert-butylphenyl) phosphite [IrgafosTM
168], distearyl pentaerythritol diphosphite [Weston 618TM] and tetrakis (2, ~tert butylphenyl) 4,4'-biphenylene diphosphonite [PEPQ]. Another preferred class of anti-oxidants are thioesters, such as dilauryl thiodipropionate, d;tridecyl thiopropionate, 1~
.
. .
~ ~3 ~
and distearyl ~iodipropionate.
The odor masked polvmer may also contain ultraviolet stabilizers.
Ultl a~iolet ~tabilizers are well-known additives for thermoplastics, including the present glutarimides, and include hydroxy benzophenones, salicylate esters and benzotriazoles. Those pre~erred are benzotriazole stabilizers. The ar~ount of ultraviolet stabilizer needed is from about 0.10 to about 0.50 weight percent of the polymer composition. For ultraviolet light stability (ultraviolet light stabilizers), hindered amines are useful. Preferred are the hinclered amines where Rl=R2=R3=R4= methyl and X=H. Examples of hindered amines which can be employed include: bis-(2,2,6,6-tetramethyl-~piperidirlyl) sebacate; 2,2,6,6-tetramethyl-~piperidinyl) benzoate, 1,2,3,~tetrakis-t2,2,6,6-tetramethyl~piperidinyl)butane tetracarboxylatei 1,2-bis (2-oxo-3,3,5,5-tetramethyl-1-piperidinyl) ethane; 1-(3,~di-tert-butyl-4-hydroxyphenyl)-2,2-bis (2,2,6,6-tetramethyl-~ piperidinyloxycarbonyl)-hexane; poly(1-oxyethylene (2~2,6,6-tetramethyl-l,~piperidinyl) oxysuccinyl; N,N'bis (2,2,6,~ tetramethyl-4-piperidinyl) -1,6-hexanediamine; (4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine) ethanyl;
poly(2-(1,1,3,3- tetraethyl~utylimino)-4,6-triazinediyl-(2,2,6,6-tetramethyl-4-piperi~inyliminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyliminohexamethylene- (2,2,6,6-tetramethyl-4-piperidinyl)imino) or their N-methyl derivatives. Especially preferred for reasons of non-volatility and compatibility are hindered amines containing one or more groups with the structure:
CH2 CR1R\
HC NX
~H2--CR3R4 wherein Rl ,R2,R3"R4 are methyl and X is H, me~ylene or -CH2-CH2~0-. The groups may be joined together by aliphatic ester, aromatic ester, heterocylic carbon-nitrogen materials, such as melamine groups, and the like. Especially preferred is bis(2,2,6,6-tetramethyl-~piperidyl) sebacate. Examples of benzotriazole stabilizers, useful for the protection of glutarimides and other polymers by func'doning as absorbers of the harmful portion of the W spectrum, are 2-(2'-hydrox~-5'-methylphenyl)benzotriazole; 2-(2'-hydroxy-3'-5'-di-t_-butyl)5-chlorobenzotriazole;
2-~2'-hydroxy-3'-tert-butyl-5-5'-methylphenyl)~chlorobenzotriazole; 2-(2'-hydroxy-3'-5'-di-tert-butyl-phenyl~ benzotriazole; 2-(2'-hydroxy-5'-tert-butylphenyl benzotriazole; 2-(2'-hydroxy-5'-octylphenyl) benzotriazole, of which 2-(2'-di-hydroxy-5'-methylphenyl) benzotriazvle and ~-(2'-hydroxy-5'-tert-octylphenyl) benzotriazole :~
(CyasorbTM 5411) are preferred. Preferred is from about 0.10 to about 0.5û percent of the benzotriazole with about 0.05 to about 1.û percent of ~e organophosphite or organophosphonite, based on weight of the glutarimide matrix polymer.
Irnpact modifiers of the ABS ~acrylonitrile/butadiene/styrene) and MBS
(methyl methacrylate/butadiene/styreIIe) types have been found to be useful for ., . .
. .,:
2 ~
improving the impact strength of the imide polymers while retaining high servicetemperature. Further, two- or three stage cor~shell all acrylic impact modifiers are useful for improving the impact strength of imide polymers while retaining high service temperatuI~e. The ratio of impact modifier to imide polymer can be varied over a wide range, depending upon how much impact modification is needed for the particular application. Ratios of impact modifier to irnide polynl,e~r of from about 1:99 to about 70:30 are useful, with t~e preferred range being about 5:95 to 60:40. Impact modifier can be single or multiple stage polymers. In the case of multiple stage polymers, the impact modifier can have a hard or soft first or "core"
stage followed by stages varying in hardness or softness.
From about 0.1 to about 25 percent by weight flame retardant can be employed, preferably compounds of bromine, chlorine, antimony, phosphorus aluminum trihydrate, certain organic compounds containing two or more hydroxyl groups, or mixtures thereof. More specific examples of flame retardants are triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(di-bromo propyl) phosphate, cycloaliphatic chlorides, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromo-diphenyl ether and chlorinated polyphosphonate. The high service temperature of the poly (glutarimide) in its base resin permits larger amounts of fire retardants to be added than can be added toother base resins, while yet maintaining acceptable service temperature.
A wide variety of fillers can be employed, at filler levels of from about 5 to 80 percent. Surprisingly large c~nounts of filler such as hydrated alumina can be blended with the glutarimide polymer base resin, up to about 60 to 70 percent, while main~aining thermoformability. On the other hand, most thermoplastic systems cannot accept more than about 40 percent inert filler with retention of thermo~ormability. The novel imide polymers can be blended with glass reinforcement at glass levels of about 1 to 60 percent to enhance strength, stiffness, .
2 ~ 5c~ '3 creep resistance and deformiltion resistance at high temperatures and to reduce the $hermal expansion c~efficient. The compatibility of the glass reinforcement withthe novel imide polymers is usually high and frequently permits the use of glassreinforcement which has standard coupling agents rather than specially prepared reinforcements. Examples of reinforcing or filler nnaterials which may be used separately, or in combination are glass ~ibers, polymeric fibers, glass ~ads, titanium dioxide, talc, mica, clay, and the like. Ihey may also be used in combination with other polymers wi~ which they are compatible (i.e. with whic~h they may be blended, such as acrylics, poly(vinyl chloride~, polycarbonates, polyesters, and the like.
The resulting polymer blend may be molded at melt temperatures recommended for glutarimide polymers, which range from about 246 to about 330 degrees C, preferably from about 246 to about 316 degrees C, and most preferablyfrom about 274 to about 316 degrees C. The polymers rnay be ex~lded into film, formed into parisons and blown, or may be compression or injection molded into useful articles.
The plastics and polyl,lutarimides of the present invention are also useful in applications as sheet, film, molded articles, or extruded articles not requiring high values of clarity or visible light ~ansrnittance. One such use will be in pigmented or colored articles, such as automotive exterior lighting in yellow, red, orange, and the like such as colored tail-lights. A second use will be in surfac~altered articles having a matte finish to lower reflectance, alter contact behavior with other surfaces, and the like. Such articles may be prepared by surface roughening, such as extrusion over roughened rolls, by use of certain inorganic fillers, or by use of surfac~altering plastic additives with similar refractive indices, such as disclosed in U.S. Patent No. 4,000,216.
'~
"` 2 ~3 ~ 9 EXAMPLES
The following examples are merely intended to illustrate the present invention and not to limit it. All percentages are by weight unless otherwise specified. - , Plaques To measure optical properties, yellowness index (YI) (ASlrM D-1925), % haze, and % total white light transmission (% TWLT) (both by ASTM D-1003), 50.8 mm. x 76.2 mm. x 3.18 mm., plaques were injection molded using a Newbury machine.
Processing conditions are folmd in Table 1.
, ~ ' ~ ' ' `:
~ ~ 5 ~ 9 _able 1: Operations Newb~y Feed (rear), C
Metering ~front), odorant C 299 304 (a,b) Nozzle (va~iac), C 277 Drying Temp. (oYernight), C 121 Mold Temp., C
Stationary 107 - Movable 107 Injection Forward 1st Stage injection (booster) 15 sec.
Cure Mold Closed Mold Open Total Cycle 45 sec.
Injection Speed Screw Speed (rpm) 300-350 Back Pressure (lcPa) Injection (lst stage)(kPa) 2760 Pressure (2nd stage) ~kPa) Cushion (mm.) Feed Setting (mm.~ 82.55 (a) barrel temperature at ~82, C
(b) Glutarimide of 90% degree of imidi~ation: melt temperature 310-316, C
(c) In some experiments, a molding cycle of 215 seconds was used.
, ~' ' , ' '.
'' ': . ' ., .3 A. Polymer Preparations and Incorporation of Stabilizers All of the exemplified polymers containing mers of (N-methyl) dimethylglutarimide and mers of methacrylic acid were prepared by,~ethods known in the art utilizing a poly(methyl methacrylate) of MW ca. 150,000 grams/mole as precursor and monomethylamine. Reactions were carried out to either ca. 66 or ca 84 mol % (76 or 90 weight %) of glutarimide mers. Certain polymers were then further reacted with dimethyl carbonate to form capped glutarimides. An uncapped glutarirnide polymer contains polymethacrylic acid andglutaric anhydride functionality, whereas a capped glutaAmide polymer does not contain polymethacrylic acid and glutaric anhydride functionality.
The polymers of the present study were prepared by the reaction of a poly(methyl methacrylate~ homopolymer of MW ca. 150,000 grams/mole with methylamine in a devolatilizing twin-screw reactor. If reduction of the acid-anhydride content was desired (capped glutarimide polymers), the reaction with the agent for reducing acid/anhydride was conducted on the polymer in a continuous manner, i.e., the glutarimide polymer was not isolated prior to the acid-reducing reactlon, but the molten glutarimide was carried to an adjacent zone in the extruder and ~ere reacted with the agent, after which the acid-reduced glutarimide was isolated by stranding, coolinl3, and pelletizing.
The process for making polyirnides and reducing or substantially eliminating acid and anhydride functionality involves determining the amount of acid and anhydride of the polyimide prior to trea~nent with a capping agent by removing asample of polyimide prior to reaction wit~ the agent for reducing acid and anhydride functionality and titrating the amount of acid and anhydride present. A
. ~ ., . ~
.
. ".
. ~ .
2 ~ '3 calculated amount of ~e agent, based on ~e desired acid and anhydride level is then added. Alternatively, one may determine the amount of agent to add by preparing the polyimide uncler the same conditions to be used in the continuous process, and then measuring the acid and anhydride level. As long as the feed stock is converted to the same polyimide and treated with ~e ageni under the same conditions, the resultant final product is substantially the same.
The extruder used was a 2.0 cm. (0.8 inch~ non-intermeshing counter-rotating twin screw extruder. (C)ther size extruders can be used and they will afford similar results.) The extruder has one sec~ion about six diameters long, for introducing and plasticating the polyglutarimide followed by a closed barrel section about 6 diameters long for pumping and pressure generation, followed by the reaction zone. I~is zone, is about 31.5 diameters long, comprises a ported balTel sec'don for introducing blocking agents, closed barrel sections, and a venting section for removing volatile products. Another vented section, operated at substantially atmospheric pressure, follows the reaction zone, for removing additional volatiles. Larger extruders, such as a 5.0 cm. extruder of the same design, may be used to achieve similar results. The first (imidization) zone is 61 cm. long, and was equipped with means for adding solid polymer and methylanuine. The feed rate of the polymer ~or Example 1 was 72-75 grams/minute. I~e barrel tempera~ure in the imidization zone of Example 1 was280-300C. Example 1 contains data from a 2.0 cm. ex~uder (0.8 inch), and Examples 2 and 3 contain data from a 5.0 cm. ex~ruder (2.0 inch3. For prepara~ons of Example 1, sa~nples 1-13, methylamine was added at a rate of 2~3~ grams/minute, and the gauge pressure was 6û20-6060 kPa; for preparations of Example 1, samples 14-29 the methylamine feed rate was 25-30 grams/minute, and the gauge pressure 600~6200 kPa.
,.
In Example 1, samples 14-~9 (uncapped glutarimides) were isolated at this point wi~out further reaction. Samples 1-13 (capped glutarirnides) of Example 1 were conveyed into the second zone as desibed above. Within this zone of ca. 31cm. in length were means for adding ~e aad-reducing reagent and means for venting volatile products. ~nother venting section followed for further devolatilization. l~e barrel temperature of the capping zone was 28~300C. For samples 1-13 of Example 1, dime~yl carbonate (DMC) was added at a pressure of 3445-3650 kPa; and the feed rate of DMC for samples 1-13 was ~10 cc/minute.
In Example 2, the barrel temperature in the ;midiza~on zone was 260C for samples 3~33, and 275C for samples 3~37. The ~eed rate of the polymer for Example 2 was 240 lbs./hou~. For preparations of Example 2, sa}nples 3~33, methylamine was added at a rate of 85-90 lbs./hour, and the gauge pressure was 7475-7650 kPa; for preparations of Example 2, samples 34-37, ~he methylamine feed rate was 79-80 lbs./hour, and the gauge pressure 7615-76S0 kPa.
Samples 3~37 of Exan~ple 2 were conveyed into the second zone as described above. Within ~is zone were means for adding the acid-reducing reagent and means for venting volatile products. Another venting section followed for further devolatilization. The barrel temperature of the capping zone was 260C for samples 30-33, and 275C for samples 3~37 (although no capping was done wi~ samples 34-37). For samples 3~33 of E~;ample 2, dimethyl carbonate (DMC) was added at a pressure of 5800-5890 kPa; for samples 3~37 of Example 2,1~1Q pressure of nitrogen in the capping zone was 4550 kl'a. The feed rate of DMC for examples 3~33 was 13.5 Ibs./hour.
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In Example 3, the barrel temperature in the imidiza~don zone was 260C for samples 3841. The feed rate of ~e polymer was 2~0 Ibs./hour. For preparations ofExample 3, samples 38-41, methylamine was added at a rate of 85-90 lbs./hour, and ~e gauge pressure was 7475-7650 kPa.
,t Samples 3~41 of Exanlple 3 were conveyed into the second zone as described above. Within ~is zone were means for adding t~e acid-reducing reagent and means for venting volatile products. Another venting section followed for further devolatilization. The barrel temperature of the capping zone was 260C for samples 3~41. For samples 38-41 of Example 3, dimethyl carbonate (DMC) was added at a pressure of 580~5890 kPa. The feed rate of D~C for examples 38~1 was 13.5 lbs./hour.
In Examples 1 3, the plastic additive paclcages (additives and phenylet~yl cyclohexyl ether) were carefully metered into the end of the extruder through anextruder additive port. In Examples 1-3,1~e plastic additives packages were pr~
blended, and then pumped into the extruder as a homogeneous mixture.
2d~
Example 1:
This example demonst~ates the effect of various odor maskants or fragrances on the color (yellownPss index: ASTM D-1925) of glutarimide polymers.
Odor Maskant Sample Number Additive Package~/Odorant~ Yellowness Index -Samples 1-7- J`
no odorant 5.97 2 methyl salicylate 4.35 3 ~isopropyl cyclohexanol 4.76 4 ~isopropyl cyclohexanol 5.95 phenylethyl cyclohexyl ether (PECE) 3.58 (best color) 6 PolyiffTM 13091 6.27 [1]
An additional method is to add the phenylethyl cyclohexyl ether to the polymer composition, along with other additives such as toners, lubricants, anti-oxidants, colorants, ultraviolet stabilizers, hindered amine light stabilizers, impact modifiers, pigments, fillers, fibers, flame retardants and the like, and for imides to be molten glutarimide or acid-reduced glutarimide polymer prior to extrusion into pellets, strands, sheet, or film. This process exposes the polymer and the additive to less heat history than re-processing of already extruded polymer. An effective amount of an additive is that amount which people skilled in the art would add, and functions to give the polymer composition the desired characteristics of theadditive. The polymer composition cs)ntaining effective amounts of additives maybe blended wi~ ~meth)acrylics, poly(vinyl chloride), poly(arnides), polycarbonates, polyesters, SAN tstyrene/acrylonitrile), ABS (acrylonitrile/butadiene/styrene), MBS
(methyl methacrylate/butadiene/styrene) polymers, or two- or three-stage cor~shell all acrylic impact modifiers.
Very low amounts of toners, colorants (e.g. pigments and dies), and color agents or concentrates can be used to correct undesirable color found in polymers.
The following coloring agen~s expressed by a name or number described in the Color ..-.
Index [in the Society of Dyers and Colourists, U.S.A.] can be chosen for use in polymer compositions described herein: Pigment Black 7, Pigment White 6, PigmentWhite 21, Pigment Gseen 7, Pigment Blue 15, Solvent Orange 60, Solvent Red 179, Solvent Green 28, Solvent Blue 45, 501vent Blue 101, Solvent Violet 14, and Disperse Yellow 54. An example of a useful toner is Irisol NTM (l-p-Toluidino, 4hydroxy an~raquinone). Further, the use of blue colorants are pref~rred for correcting yellowness problems.
Lubricants are well-known components of acrylic-based molding materials, serving to prevent stickage to hot metal surfaces and release from the rnold or die lips. Such lubricants include high molecular weight alcohols, such as those of twelve to twenty-four carbons, esters, especially long-chain alkyl esters of high molecular weight acids, such as bu~yl or stearyl stearate, monoesters of glycols, such as ethylene glycol monostearate, and the like. Preferred is stearyl alcohol. Levels of lubricants, when used, may r ange from about 0.05 to about 0.50 weight percent on polymer; preferred is about ().30%.
Antioxidants (thermal stabilizers) for the processing and molding of the polyglutarimide may be present without detracting from the ultraviolet stability of the stabilized composition. A preferred class of thermal stabilizers are organophosphites, such as tris(aryl)-br tris(alkylaryl)-or tris(alkyl)-phosphites.
Another preferred class is that of organophosphonites, such as trisaryl, trisalkaryl-or aryldialkaryl phosphonites, such as aryl-di(alkylphenyl)phosphonites. Preferred are acid-stable tris(2-alkylaryl) phosphites, such as tris(2-tertiary alkylaryl) phosphite, or aryl di(2-alkylaryl) phosphonite. Especially preferred thermal stabilizers are tris-. _ . . .
(nonylphenyl) phosphite lTNPP], tris~2,4-di-tert-butylphenyl) phosphite [IrgafosTM
168], distearyl pentaerythritol diphosphite [Weston 618TM] and tetrakis (2, ~tert butylphenyl) 4,4'-biphenylene diphosphonite [PEPQ]. Another preferred class of anti-oxidants are thioesters, such as dilauryl thiodipropionate, d;tridecyl thiopropionate, 1~
.
. .
~ ~3 ~
and distearyl ~iodipropionate.
The odor masked polvmer may also contain ultraviolet stabilizers.
Ultl a~iolet ~tabilizers are well-known additives for thermoplastics, including the present glutarimides, and include hydroxy benzophenones, salicylate esters and benzotriazoles. Those pre~erred are benzotriazole stabilizers. The ar~ount of ultraviolet stabilizer needed is from about 0.10 to about 0.50 weight percent of the polymer composition. For ultraviolet light stability (ultraviolet light stabilizers), hindered amines are useful. Preferred are the hinclered amines where Rl=R2=R3=R4= methyl and X=H. Examples of hindered amines which can be employed include: bis-(2,2,6,6-tetramethyl-~piperidirlyl) sebacate; 2,2,6,6-tetramethyl-~piperidinyl) benzoate, 1,2,3,~tetrakis-t2,2,6,6-tetramethyl~piperidinyl)butane tetracarboxylatei 1,2-bis (2-oxo-3,3,5,5-tetramethyl-1-piperidinyl) ethane; 1-(3,~di-tert-butyl-4-hydroxyphenyl)-2,2-bis (2,2,6,6-tetramethyl-~ piperidinyloxycarbonyl)-hexane; poly(1-oxyethylene (2~2,6,6-tetramethyl-l,~piperidinyl) oxysuccinyl; N,N'bis (2,2,6,~ tetramethyl-4-piperidinyl) -1,6-hexanediamine; (4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine) ethanyl;
poly(2-(1,1,3,3- tetraethyl~utylimino)-4,6-triazinediyl-(2,2,6,6-tetramethyl-4-piperi~inyliminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyliminohexamethylene- (2,2,6,6-tetramethyl-4-piperidinyl)imino) or their N-methyl derivatives. Especially preferred for reasons of non-volatility and compatibility are hindered amines containing one or more groups with the structure:
CH2 CR1R\
HC NX
~H2--CR3R4 wherein Rl ,R2,R3"R4 are methyl and X is H, me~ylene or -CH2-CH2~0-. The groups may be joined together by aliphatic ester, aromatic ester, heterocylic carbon-nitrogen materials, such as melamine groups, and the like. Especially preferred is bis(2,2,6,6-tetramethyl-~piperidyl) sebacate. Examples of benzotriazole stabilizers, useful for the protection of glutarimides and other polymers by func'doning as absorbers of the harmful portion of the W spectrum, are 2-(2'-hydrox~-5'-methylphenyl)benzotriazole; 2-(2'-hydroxy-3'-5'-di-t_-butyl)5-chlorobenzotriazole;
2-~2'-hydroxy-3'-tert-butyl-5-5'-methylphenyl)~chlorobenzotriazole; 2-(2'-hydroxy-3'-5'-di-tert-butyl-phenyl~ benzotriazole; 2-(2'-hydroxy-5'-tert-butylphenyl benzotriazole; 2-(2'-hydroxy-5'-octylphenyl) benzotriazole, of which 2-(2'-di-hydroxy-5'-methylphenyl) benzotriazvle and ~-(2'-hydroxy-5'-tert-octylphenyl) benzotriazole :~
(CyasorbTM 5411) are preferred. Preferred is from about 0.10 to about 0.5û percent of the benzotriazole with about 0.05 to about 1.û percent of ~e organophosphite or organophosphonite, based on weight of the glutarimide matrix polymer.
Irnpact modifiers of the ABS ~acrylonitrile/butadiene/styrene) and MBS
(methyl methacrylate/butadiene/styreIIe) types have been found to be useful for ., . .
. .,:
2 ~
improving the impact strength of the imide polymers while retaining high servicetemperature. Further, two- or three stage cor~shell all acrylic impact modifiers are useful for improving the impact strength of imide polymers while retaining high service temperatuI~e. The ratio of impact modifier to imide polymer can be varied over a wide range, depending upon how much impact modification is needed for the particular application. Ratios of impact modifier to irnide polynl,e~r of from about 1:99 to about 70:30 are useful, with t~e preferred range being about 5:95 to 60:40. Impact modifier can be single or multiple stage polymers. In the case of multiple stage polymers, the impact modifier can have a hard or soft first or "core"
stage followed by stages varying in hardness or softness.
From about 0.1 to about 25 percent by weight flame retardant can be employed, preferably compounds of bromine, chlorine, antimony, phosphorus aluminum trihydrate, certain organic compounds containing two or more hydroxyl groups, or mixtures thereof. More specific examples of flame retardants are triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(di-bromo propyl) phosphate, cycloaliphatic chlorides, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromo-diphenyl ether and chlorinated polyphosphonate. The high service temperature of the poly (glutarimide) in its base resin permits larger amounts of fire retardants to be added than can be added toother base resins, while yet maintaining acceptable service temperature.
A wide variety of fillers can be employed, at filler levels of from about 5 to 80 percent. Surprisingly large c~nounts of filler such as hydrated alumina can be blended with the glutarimide polymer base resin, up to about 60 to 70 percent, while main~aining thermoformability. On the other hand, most thermoplastic systems cannot accept more than about 40 percent inert filler with retention of thermo~ormability. The novel imide polymers can be blended with glass reinforcement at glass levels of about 1 to 60 percent to enhance strength, stiffness, .
2 ~ 5c~ '3 creep resistance and deformiltion resistance at high temperatures and to reduce the $hermal expansion c~efficient. The compatibility of the glass reinforcement withthe novel imide polymers is usually high and frequently permits the use of glassreinforcement which has standard coupling agents rather than specially prepared reinforcements. Examples of reinforcing or filler nnaterials which may be used separately, or in combination are glass ~ibers, polymeric fibers, glass ~ads, titanium dioxide, talc, mica, clay, and the like. Ihey may also be used in combination with other polymers wi~ which they are compatible (i.e. with whic~h they may be blended, such as acrylics, poly(vinyl chloride~, polycarbonates, polyesters, and the like.
The resulting polymer blend may be molded at melt temperatures recommended for glutarimide polymers, which range from about 246 to about 330 degrees C, preferably from about 246 to about 316 degrees C, and most preferablyfrom about 274 to about 316 degrees C. The polymers rnay be ex~lded into film, formed into parisons and blown, or may be compression or injection molded into useful articles.
The plastics and polyl,lutarimides of the present invention are also useful in applications as sheet, film, molded articles, or extruded articles not requiring high values of clarity or visible light ~ansrnittance. One such use will be in pigmented or colored articles, such as automotive exterior lighting in yellow, red, orange, and the like such as colored tail-lights. A second use will be in surfac~altered articles having a matte finish to lower reflectance, alter contact behavior with other surfaces, and the like. Such articles may be prepared by surface roughening, such as extrusion over roughened rolls, by use of certain inorganic fillers, or by use of surfac~altering plastic additives with similar refractive indices, such as disclosed in U.S. Patent No. 4,000,216.
'~
"` 2 ~3 ~ 9 EXAMPLES
The following examples are merely intended to illustrate the present invention and not to limit it. All percentages are by weight unless otherwise specified. - , Plaques To measure optical properties, yellowness index (YI) (ASlrM D-1925), % haze, and % total white light transmission (% TWLT) (both by ASTM D-1003), 50.8 mm. x 76.2 mm. x 3.18 mm., plaques were injection molded using a Newbury machine.
Processing conditions are folmd in Table 1.
, ~ ' ~ ' ' `:
~ ~ 5 ~ 9 _able 1: Operations Newb~y Feed (rear), C
Metering ~front), odorant C 299 304 (a,b) Nozzle (va~iac), C 277 Drying Temp. (oYernight), C 121 Mold Temp., C
Stationary 107 - Movable 107 Injection Forward 1st Stage injection (booster) 15 sec.
Cure Mold Closed Mold Open Total Cycle 45 sec.
Injection Speed Screw Speed (rpm) 300-350 Back Pressure (lcPa) Injection (lst stage)(kPa) 2760 Pressure (2nd stage) ~kPa) Cushion (mm.) Feed Setting (mm.~ 82.55 (a) barrel temperature at ~82, C
(b) Glutarimide of 90% degree of imidi~ation: melt temperature 310-316, C
(c) In some experiments, a molding cycle of 215 seconds was used.
, ~' ' , ' '.
'' ': . ' ., .3 A. Polymer Preparations and Incorporation of Stabilizers All of the exemplified polymers containing mers of (N-methyl) dimethylglutarimide and mers of methacrylic acid were prepared by,~ethods known in the art utilizing a poly(methyl methacrylate) of MW ca. 150,000 grams/mole as precursor and monomethylamine. Reactions were carried out to either ca. 66 or ca 84 mol % (76 or 90 weight %) of glutarimide mers. Certain polymers were then further reacted with dimethyl carbonate to form capped glutarimides. An uncapped glutarirnide polymer contains polymethacrylic acid andglutaric anhydride functionality, whereas a capped glutaAmide polymer does not contain polymethacrylic acid and glutaric anhydride functionality.
The polymers of the present study were prepared by the reaction of a poly(methyl methacrylate~ homopolymer of MW ca. 150,000 grams/mole with methylamine in a devolatilizing twin-screw reactor. If reduction of the acid-anhydride content was desired (capped glutarimide polymers), the reaction with the agent for reducing acid/anhydride was conducted on the polymer in a continuous manner, i.e., the glutarimide polymer was not isolated prior to the acid-reducing reactlon, but the molten glutarimide was carried to an adjacent zone in the extruder and ~ere reacted with the agent, after which the acid-reduced glutarimide was isolated by stranding, coolinl3, and pelletizing.
The process for making polyirnides and reducing or substantially eliminating acid and anhydride functionality involves determining the amount of acid and anhydride of the polyimide prior to trea~nent with a capping agent by removing asample of polyimide prior to reaction wit~ the agent for reducing acid and anhydride functionality and titrating the amount of acid and anhydride present. A
. ~ ., . ~
.
. ".
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2 ~ '3 calculated amount of ~e agent, based on ~e desired acid and anhydride level is then added. Alternatively, one may determine the amount of agent to add by preparing the polyimide uncler the same conditions to be used in the continuous process, and then measuring the acid and anhydride level. As long as the feed stock is converted to the same polyimide and treated with ~e ageni under the same conditions, the resultant final product is substantially the same.
The extruder used was a 2.0 cm. (0.8 inch~ non-intermeshing counter-rotating twin screw extruder. (C)ther size extruders can be used and they will afford similar results.) The extruder has one sec~ion about six diameters long, for introducing and plasticating the polyglutarimide followed by a closed barrel section about 6 diameters long for pumping and pressure generation, followed by the reaction zone. I~is zone, is about 31.5 diameters long, comprises a ported balTel sec'don for introducing blocking agents, closed barrel sections, and a venting section for removing volatile products. Another vented section, operated at substantially atmospheric pressure, follows the reaction zone, for removing additional volatiles. Larger extruders, such as a 5.0 cm. extruder of the same design, may be used to achieve similar results. The first (imidization) zone is 61 cm. long, and was equipped with means for adding solid polymer and methylanuine. The feed rate of the polymer ~or Example 1 was 72-75 grams/minute. I~e barrel tempera~ure in the imidization zone of Example 1 was280-300C. Example 1 contains data from a 2.0 cm. ex~uder (0.8 inch), and Examples 2 and 3 contain data from a 5.0 cm. ex~ruder (2.0 inch3. For prepara~ons of Example 1, sa~nples 1-13, methylamine was added at a rate of 2~3~ grams/minute, and the gauge pressure was 6û20-6060 kPa; for preparations of Example 1, samples 14-29 the methylamine feed rate was 25-30 grams/minute, and the gauge pressure 600~6200 kPa.
,.
In Example 1, samples 14-~9 (uncapped glutarimides) were isolated at this point wi~out further reaction. Samples 1-13 (capped glutarirnides) of Example 1 were conveyed into the second zone as desibed above. Within this zone of ca. 31cm. in length were means for adding ~e aad-reducing reagent and means for venting volatile products. ~nother venting section followed for further devolatilization. l~e barrel temperature of the capping zone was 28~300C. For samples 1-13 of Example 1, dime~yl carbonate (DMC) was added at a pressure of 3445-3650 kPa; and the feed rate of DMC for samples 1-13 was ~10 cc/minute.
In Example 2, the barrel temperature in the ;midiza~on zone was 260C for samples 3~33, and 275C for samples 3~37. The ~eed rate of the polymer for Example 2 was 240 lbs./hou~. For preparations of Example 2, sa}nples 3~33, methylamine was added at a rate of 85-90 lbs./hour, and the gauge pressure was 7475-7650 kPa; for preparations of Example 2, samples 34-37, ~he methylamine feed rate was 79-80 lbs./hour, and the gauge pressure 7615-76S0 kPa.
Samples 3~37 of Exan~ple 2 were conveyed into the second zone as described above. Within ~is zone were means for adding the acid-reducing reagent and means for venting volatile products. Another venting section followed for further devolatilization. The barrel temperature of the capping zone was 260C for samples 30-33, and 275C for samples 3~37 (although no capping was done wi~ samples 34-37). For samples 3~33 of E~;ample 2, dimethyl carbonate (DMC) was added at a pressure of 5800-5890 kPa; for samples 3~37 of Example 2,1~1Q pressure of nitrogen in the capping zone was 4550 kl'a. The feed rate of DMC for examples 3~33 was 13.5 Ibs./hour.
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In Example 3, the barrel temperature in the imidiza~don zone was 260C for samples 3841. The feed rate of ~e polymer was 2~0 Ibs./hour. For preparations ofExample 3, samples 38-41, methylamine was added at a rate of 85-90 lbs./hour, and ~e gauge pressure was 7475-7650 kPa.
,t Samples 3~41 of Exanlple 3 were conveyed into the second zone as described above. Within ~is zone were means for adding t~e acid-reducing reagent and means for venting volatile products. Another venting section followed for further devolatilization. The barrel temperature of the capping zone was 260C for samples 3~41. For samples 38-41 of Example 3, dimethyl carbonate (DMC) was added at a pressure of 580~5890 kPa. The feed rate of D~C for examples 38~1 was 13.5 lbs./hour.
In Examples 1 3, the plastic additive paclcages (additives and phenylet~yl cyclohexyl ether) were carefully metered into the end of the extruder through anextruder additive port. In Examples 1-3,1~e plastic additives packages were pr~
blended, and then pumped into the extruder as a homogeneous mixture.
2d~
Example 1:
This example demonst~ates the effect of various odor maskants or fragrances on the color (yellownPss index: ASTM D-1925) of glutarimide polymers.
Odor Maskant Sample Number Additive Package~/Odorant~ Yellowness Index -Samples 1-7- J`
no odorant 5.97 2 methyl salicylate 4.35 3 ~isopropyl cyclohexanol 4.76 4 ~isopropyl cyclohexanol 5.95 phenylethyl cyclohexyl ether (PECE) 3.58 (best color) 6 PolyiffTM 13091 6.27 [1]
7 PolyiffTM 41863 3.61 [1]
-Samples 8-13-8 no additives 4.65 9 no additives 3.59 no odorant 2.67 11 ~isopropyl cyclohexanol -0.51 [2]
12 phenylethyl cyclohexyl ether (PECE) 1.51 (bestcolor) 13 methyl salicylate 1.64 . , , : . , 2 ~
-Samples 14-21-14 no addi~ves 4.65 no odorant 3.04 16 methyl salicylate 3.9 17 ~isopropyl cyclohexanol 3.38 18 phenylethyl cyclohexyl ether (PECE) 2.91 ~best color) 19 Poly~ffTM 13091 3.44 [1~
Polyif~TM 41863 4.28 [1]
21 no additives 4.59 -Samples 22-29-22 no additives 5.5 23 no odorant 3.0 24 methyl salicylate 2.34 methyl salicylate 5.50 26 methyl salicylate 4.00 27 4-isopropyl cyclohexanol 2.53 28 phenylethyl cyclohexyl ether (PECE) 2.14 (best color) 29 no additives 6.43 -~
Samples 1-7 (capped ~lutarirnides):
A) The additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.25 wt. % [3;
INPP 0.15 wt. %
~isol NTM ï.OO PPM. [4]
B) The amount of odorant~ was 100 PPM.
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.
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Samples 8-13 (capped glutarimides):
A) l~e additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.25 wt. %
T~PP 0.15 wt. %
Ixisol NTM 1.~)0 PPM. ~"
B) The amount of odorant~ was 200 PPM.
_mples 1~ 21 ~uncapped glutarimides):
A) The additi~e package* was: stearyl alcohol 0.3 wt. %
CyasorbTM 54~L1 0.25 wt. %
Irisol NTM 1.00 PPM.
B~ The amount of odorant~* was 100 PPM.
Samples 22-29 (uncapped glutarimides~:
A) The additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.~5 wt %
Irisol NTM 1.00PPM.
B) The amount of odorant~* was 200 PPM.
[1] PolyiffrM 13û91 and PolyiffTM 41863 are fragrance blends of proprietary ingredients oÇ International Flavors and Fragrances Inc., Ha~lett, N.J. 0~730.
[2] A negative yellawness index denotes that the sample is moving into the ~' blueness region.
[3~ Cyasorb~M 5411 is manufactured by American Cyanamid Co., Wayne, NJ 0747û.
[4] Irisol NTM is also known as Maxrolux Violet B, and is manufactured by Mobay Che~ucal Corp., Dyes and Pi8ments Division, Hawthorne, NJ.
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Example 1 demonstrates that the addition of P~CE to glutarimicles is more preferred than the other fragrances tested, due to the favorable color (yellowness index) results exhibited by ~e addition of PECE.
Example 2: Ratings Odorant Trial (Six Par~cipants) This example demonstrates ~e effect of phenylethyl cydohexy~ ether (PECE) on amine and/or ammonia odors found in ~apped and uncapped glutarimides. An odor panel of SK participants rated odor undesirab;lity (based on smell) from best to worst, of four capped (T-240) and four uncapped ~r-150) glutarimide samples, of which two samples in each group contained PECE. The glutarimide samples were processed on a Cincinnati Milacron molding machine at 530-540 F. The melt droolfrom each sample was immediately placed in a paint can straight from the moldingmachine. Each partîcipant in the odor paLnel of six participants opened a randomly numbered can, smelled ~e contents for about three (3) seconds, and then immediately sealed the can for tlle next p~ticipant of ~e trial. Odor ratings were then rated anonymously amongst the participants.
Sample Number Glutarimide type PECE Present? Additive Package T-240 (capped) yes S/C/TNPP/T/PECE
31 T-~40 (capped) no S/C/770/618/T
32 T-240 (capped) no S/C/TNPP/T
33 T-240 (capped) yes S/C/770/618/T/PECE
34 T-150 (uncapped) no S/C/T
T-150 ~uncapped) no S/C/770/NSDI/T
36 T-150 (uncapped) yes S/C/770/NSDI/T/PECE
37 T-150 (uncapped) yes S/C/T/PECE
2 ~3 ~
where:
S= stearyl alcohol C= CyasorbTM 5411 770= TinuvinTM 770, manufactured by Ciba Geigy Corp., Hawt~orne, NY 10532.
T= toner (Irisol NTM) PECE= phenylethyl cyclohexyl ether 1~
NSDI= designation of an experimental phosphite anti-oxidant manufactured by Uniroyal Inc., Middlebury, CT 06749, in 1990.
TNPP= tris-(nonylphenyl) phosphite Ratings Odorant Trial Results:
a) T-240 (capped2:
Ranking 32 30 32 3132=33 32 33 31 31 3232=33 33 b) T-150 (uncapped):
Participant 1 2 3 4 5 6 Ranking 2 36 37 37 3636 3~
Kev:
1 = least amine and/or ammonia odor 4 = most arnine and/or amrnonia odor .
. .
.;
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Ihe partiapants in general noticed lhat samples 3~33 (T-240 capped glutarimide~, had a milder o~or (with and without the PECE), than samples 3~37 (T-150 uncapped glutarimide). From these results, a definite benefit occurs from the addition of PECE to wncapped glutarimides (T-150). For instance, samples 36 and 37 (whic:h contained PECE) were easily dis~inguished by all six participaAts of ~e odor panel over samples 34 and 3r), which were wil~out PECE~ as being more desirable and pleasant in odor.
Example 3:
This example demonstrates the effect of phenylethyl cyclohexyl ether (PECE) on amine and/or amrnon~a odors found in capped (T-240) glutarimide polymers generated during severe processing conditions (53~540 F). The following sampleswere extruded through a 2.5 inch Prodex extruder equipped with a two-stage screwand 24 inch Johnson sheet die at 530-540 F. The sarnples were ranked in the order of best to worst by the participants of the molding ~ial.
Sample # Rating Glutarimidetype PECEPresent? AdditivePacka~e 38 1 T- 74û yes S/C/770/618/T/PECE
39 ~ T-:240 yes S/C~/lNPP/T/PECE
3 T-~40 no S/C/770/618/T
41 4 T-~40 no S/C~/INPP/T
. . _ :
.. .. ~ . , ;
:ECev:
Rating: 1 = least amine and/or ammonia odor 4 = most ~nine and/or ammonia odor Additive Package (Wt %)~
S= stearyl alcohol (0.3%) C= CyasorbTM 5411 (.11%) C*= CyasorbTM 5411 (0.25%) 770= TinuvinTM 770 (0.12%) T= toner (e.g. Irisol NTM) (1 part per million (PPM)) PECE= phenylethyl cyc1Ohexyl ether (500 PPM) INPP= tris-(nonphenyl) phosphite (0.15%) 618= Weston 618TM (0.12%) (manufactured by Ciba Geigy Corp., Hawthorne, NY
10532).
~:.
-Samples 8-13-8 no additives 4.65 9 no additives 3.59 no odorant 2.67 11 ~isopropyl cyclohexanol -0.51 [2]
12 phenylethyl cyclohexyl ether (PECE) 1.51 (bestcolor) 13 methyl salicylate 1.64 . , , : . , 2 ~
-Samples 14-21-14 no addi~ves 4.65 no odorant 3.04 16 methyl salicylate 3.9 17 ~isopropyl cyclohexanol 3.38 18 phenylethyl cyclohexyl ether (PECE) 2.91 ~best color) 19 Poly~ffTM 13091 3.44 [1~
Polyif~TM 41863 4.28 [1]
21 no additives 4.59 -Samples 22-29-22 no additives 5.5 23 no odorant 3.0 24 methyl salicylate 2.34 methyl salicylate 5.50 26 methyl salicylate 4.00 27 4-isopropyl cyclohexanol 2.53 28 phenylethyl cyclohexyl ether (PECE) 2.14 (best color) 29 no additives 6.43 -~
Samples 1-7 (capped ~lutarirnides):
A) The additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.25 wt. % [3;
INPP 0.15 wt. %
~isol NTM ï.OO PPM. [4]
B) The amount of odorant~ was 100 PPM.
: . ~ .` ,.; ; ~ .;:
.
, "" 2 ~ 6 ~
Samples 8-13 (capped glutarimides):
A) l~e additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.25 wt. %
T~PP 0.15 wt. %
Ixisol NTM 1.~)0 PPM. ~"
B) The amount of odorant~ was 200 PPM.
_mples 1~ 21 ~uncapped glutarimides):
A) The additi~e package* was: stearyl alcohol 0.3 wt. %
CyasorbTM 54~L1 0.25 wt. %
Irisol NTM 1.00 PPM.
B~ The amount of odorant~* was 100 PPM.
Samples 22-29 (uncapped glutarimides~:
A) The additive package~ was: stearyl alcohol 0.3 wt. %
CyasorbTM 5411 0.~5 wt %
Irisol NTM 1.00PPM.
B) The amount of odorant~* was 200 PPM.
[1] PolyiffrM 13û91 and PolyiffTM 41863 are fragrance blends of proprietary ingredients oÇ International Flavors and Fragrances Inc., Ha~lett, N.J. 0~730.
[2] A negative yellawness index denotes that the sample is moving into the ~' blueness region.
[3~ Cyasorb~M 5411 is manufactured by American Cyanamid Co., Wayne, NJ 0747û.
[4] Irisol NTM is also known as Maxrolux Violet B, and is manufactured by Mobay Che~ucal Corp., Dyes and Pi8ments Division, Hawthorne, NJ.
- - . . ~ .
,~
, . ~ ,, ., . .~ ~. . . -, . . .. . .
, ' . '': " ' "
. ..
2 ~
Example 1 demonstrates that the addition of P~CE to glutarimicles is more preferred than the other fragrances tested, due to the favorable color (yellowness index) results exhibited by ~e addition of PECE.
Example 2: Ratings Odorant Trial (Six Par~cipants) This example demonstrates ~e effect of phenylethyl cydohexy~ ether (PECE) on amine and/or ammonia odors found in ~apped and uncapped glutarimides. An odor panel of SK participants rated odor undesirab;lity (based on smell) from best to worst, of four capped (T-240) and four uncapped ~r-150) glutarimide samples, of which two samples in each group contained PECE. The glutarimide samples were processed on a Cincinnati Milacron molding machine at 530-540 F. The melt droolfrom each sample was immediately placed in a paint can straight from the moldingmachine. Each partîcipant in the odor paLnel of six participants opened a randomly numbered can, smelled ~e contents for about three (3) seconds, and then immediately sealed the can for tlle next p~ticipant of ~e trial. Odor ratings were then rated anonymously amongst the participants.
Sample Number Glutarimide type PECE Present? Additive Package T-240 (capped) yes S/C/TNPP/T/PECE
31 T-~40 (capped) no S/C/770/618/T
32 T-240 (capped) no S/C/TNPP/T
33 T-240 (capped) yes S/C/770/618/T/PECE
34 T-150 (uncapped) no S/C/T
T-150 ~uncapped) no S/C/770/NSDI/T
36 T-150 (uncapped) yes S/C/770/NSDI/T/PECE
37 T-150 (uncapped) yes S/C/T/PECE
2 ~3 ~
where:
S= stearyl alcohol C= CyasorbTM 5411 770= TinuvinTM 770, manufactured by Ciba Geigy Corp., Hawt~orne, NY 10532.
T= toner (Irisol NTM) PECE= phenylethyl cyclohexyl ether 1~
NSDI= designation of an experimental phosphite anti-oxidant manufactured by Uniroyal Inc., Middlebury, CT 06749, in 1990.
TNPP= tris-(nonylphenyl) phosphite Ratings Odorant Trial Results:
a) T-240 (capped2:
Ranking 32 30 32 3132=33 32 33 31 31 3232=33 33 b) T-150 (uncapped):
Participant 1 2 3 4 5 6 Ranking 2 36 37 37 3636 3~
Kev:
1 = least amine and/or ammonia odor 4 = most arnine and/or amrnonia odor .
. .
.;
~ . , ;
Ihe partiapants in general noticed lhat samples 3~33 (T-240 capped glutarimide~, had a milder o~or (with and without the PECE), than samples 3~37 (T-150 uncapped glutarimide). From these results, a definite benefit occurs from the addition of PECE to wncapped glutarimides (T-150). For instance, samples 36 and 37 (whic:h contained PECE) were easily dis~inguished by all six participaAts of ~e odor panel over samples 34 and 3r), which were wil~out PECE~ as being more desirable and pleasant in odor.
Example 3:
This example demonstrates the effect of phenylethyl cyclohexyl ether (PECE) on amine and/or amrnon~a odors found in capped (T-240) glutarimide polymers generated during severe processing conditions (53~540 F). The following sampleswere extruded through a 2.5 inch Prodex extruder equipped with a two-stage screwand 24 inch Johnson sheet die at 530-540 F. The sarnples were ranked in the order of best to worst by the participants of the molding ~ial.
Sample # Rating Glutarimidetype PECEPresent? AdditivePacka~e 38 1 T- 74û yes S/C/770/618/T/PECE
39 ~ T-:240 yes S/C~/lNPP/T/PECE
3 T-~40 no S/C/770/618/T
41 4 T-~40 no S/C~/INPP/T
. . _ :
.. .. ~ . , ;
:ECev:
Rating: 1 = least amine and/or ammonia odor 4 = most ~nine and/or ammonia odor Additive Package (Wt %)~
S= stearyl alcohol (0.3%) C= CyasorbTM 5411 (.11%) C*= CyasorbTM 5411 (0.25%) 770= TinuvinTM 770 (0.12%) T= toner (e.g. Irisol NTM) (1 part per million (PPM)) PECE= phenylethyl cyc1Ohexyl ether (500 PPM) INPP= tris-(nonphenyl) phosphite (0.15%) 618= Weston 618TM (0.12%) (manufactured by Ciba Geigy Corp., Hawthorne, NY
10532).
~:.
Claims (31)
1. A polymer composition comprising:
a plastic; and a phenylethyl cyclohexyl ether having the following structure:
wherein R1, R2, R3, and R4 are the same or different substituents selected from methyl or hydrogen.
a plastic; and a phenylethyl cyclohexyl ether having the following structure:
wherein R1, R2, R3, and R4 are the same or different substituents selected from methyl or hydrogen.
2. The polymer composition of Claim 1, wherein the plastic is a polyglutarimide or (meth)acrylic copolymer.
3. The composition of Claim 2 wherein the poly(glutarimide) is poly(N-lower alkyl) dimethylglutarimide or poly(N-hydrogen) dimethylglutarimide.
4. The composition of Claim 3 wherein the poly(N-lower alkyl) dimethylglutarimide is poly(N-methyl) dimethylglutarimide.
5. The composition of Claim 2, wherein the amount of the phenylethyl cyclohexyl ethers is from about 0.01 to about 1.0 weight percent of the polymer.
6. The composition of Claim 2, wherein the amount of phenylethyl cyclohexyl ethers is from about 0.01 to about 0.10.
7. The composition of Claim 1, further containing an effective amount of at least one additive, selected from a toner, lubricant, anti-oxidant, colorant, ultraviolet stabilizer, ultraviolet light stabilizer, impact modifier, pigment, filler, fiber, and flame retardant.
8. The composition of Claim 7, wherein the lubricant is high molecular weight alcohols, or long chain alkyl esters of high molecular weight acids.
9. The composition of Claim 7, wherein the lubricant is stearyl alcohol.
10. The composition of Claim 8, wherein the amount of lubricant is from about 0.05 to about 0.50 weight percent of the polymer.
11. The composition of Claim 7, wherein the ultraviolet stabilizers are benzophenones, salicylate esters or benzotriazoles.
12. The composition of Claim 7, wherein the ultraviolet light stabilizer is a hindered amine.
13. The composition of Claim 12, wherein the hindered amine is bis (2,2,6,6-tetramethyl-4-piperidinyl)-sebacate.
14. The composition of Claim 11, wherein the ultraviolet stabilizers are 2-(2'-di-hydroxy-5'-methylphenyl) benzotriazole and 2-(2'-hydroxy-5'-octylphenyl)benzotriazole.
15. The composition of claim 11, wherein the amount of ultraviolet stabilizer is from about 0.10 to about 0.50 weight percent of the polymer composition.
16. The composition of claim 7, wherein the impact modifier is selected from one or more of acrylonitrile/butadiene/styrene and methyl methacrylate/butadiene/styrene.
17. The composition of claim 7, wherein the impact modifier is a two- or three-stage core-shell all acrylic impact modifier.
18. The composition of claim 16 or 17, wherein the amount of impact modifiers to polymer is from about 5:95 to about 60:40.
19. The composition of claim 7, wherein the antioxidant is from the class of phenolics, amines, phosphites, or thioesters.
20. The composition of claim 19, wherein the phosphite is an organophosphite or organophosphonite.
21. The composition of Claim 20, wherein the organophosphite is tris-(nonylphenyl)phosphite or distearyl pentaerythritol diphosphite or tris(2,4di-tert-butylphenyl) phosphite.
22. The composition of claim 19, wherein the organophosphonite is tetrakis (2,4-tert- butylphenyl) 4,4'-biphenylene diphosphonite.
23. The composition of claim 19, wherein the amount of phosphite is from about 0.05 to about 1.00 weight percent of the polymer composition.
24. The composition of claim 7, wherein the filler is hydrated alumina, glass fibers, polymeric fibers, carbon fibers, glass beads, titanium dioxide, talc, mica, and clay.
25. The composition of claim 7, blended with (meth)acrylics, poly(vinyl chloride), poly(amides), polycarbonates, polyesters, SAN, ABS, MBS polymers or all acrylic impact modifiers.
26. The composition of claim 7, wherein the flame retardant is triphenyl phosphate, phosphonium bromide, phosphonium oxide, tris(di-bromo propyl) phosphate, cycloaliphatic chlorides, chlorinated polyethylene, antimony oxide, ammonium polyphosphate, decabromo-diphenyl ether and chlorinated polyphosphonate.
27. A polymer composition comprising:
a plastic; and an effective amount of phenylethyl cyclohexyl ether to mask undesirable odor having the following structure:
wherein Rl, R2, R3, and R4 are the same or different substituents selected from methyl or hydrogen.
a plastic; and an effective amount of phenylethyl cyclohexyl ether to mask undesirable odor having the following structure:
wherein Rl, R2, R3, and R4 are the same or different substituents selected from methyl or hydrogen.
28. A method of masking amine and ammonia odors in a poly(glutarimide) by combining a poly(glutarimide) and a phenylethyl cyclohexyl ether having the following structure:
wherein Rl, R2, R3, and R4 are the same or different substituent selected from methyl or hydrogen.
wherein Rl, R2, R3, and R4 are the same or different substituent selected from methyl or hydrogen.
29. A method of masking, amine and ammonia odors of a poly(glutarimide) and simultaneously not forming undesirable color by combining a poly(glutarimide) and a phenylethyl cyclohexyl ether having the following structure:
wherein Rl, R2, R3, and R4 are the same or different substiuents selected from methyl or hydrogen.
wherein Rl, R2, R3, and R4 are the same or different substiuents selected from methyl or hydrogen.
30. An article prepared from the composition of Claim 1 in the form of a sheet, film or molded article.
31. An article prepared from the composition of Claim 27 in the form of a sheet,film or molded article.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US58929490A | 1990-09-27 | 1990-09-27 | |
US589,294 | 1990-09-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2051469A1 true CA2051469A1 (en) | 1992-03-28 |
Family
ID=24357413
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2051469 Abandoned CA2051469A1 (en) | 1990-09-27 | 1991-09-16 | Polymer composition which masks odor |
Country Status (3)
Country | Link |
---|---|
JP (1) | JPH04246450A (en) |
BE (1) | BE1005083A3 (en) |
CA (1) | CA2051469A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008042755A1 (en) * | 2008-10-10 | 2010-04-22 | Evonik Röhm Gmbh | Poly (meth) acrylimides with improved optical and color properties |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0049120B1 (en) * | 1980-09-30 | 1985-01-16 | INTERNATIONAL FLAVORS & FRAGRANCES INC. | Phenethylether derivatives, process for preparing same and uses thereof in combatting tobacco beetles and in augmenting or enhancing the aroma of perfumes, colognes and perfumed articles |
FR2641797B1 (en) * | 1988-12-27 | 1991-05-17 | Rhone Poulenc Fibres | SYNTHETIC SCENTED MONOFILAMENT HOMO- OR CO-POLYAMIDE BASED AND MANUFACTURING METHOD |
US5102662A (en) * | 1989-12-08 | 1992-04-07 | Dow Corning Corporation | Insect repellent plastic |
-
1991
- 1991-09-16 CA CA 2051469 patent/CA2051469A1/en not_active Abandoned
- 1991-09-26 BE BE9100896A patent/BE1005083A3/en not_active IP Right Cessation
- 1991-09-26 JP JP24720391A patent/JPH04246450A/en not_active Withdrawn
Also Published As
Publication number | Publication date |
---|---|
JPH04246450A (en) | 1992-09-02 |
BE1005083A3 (en) | 1993-04-13 |
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