CA2384373A1 - Ethylene and/or alpha-olefin/vinyl or vinylidene aromatic interpolymer compositions - Google Patents
Ethylene and/or alpha-olefin/vinyl or vinylidene aromatic interpolymer compositions Download PDFInfo
- Publication number
- CA2384373A1 CA2384373A1 CA002384373A CA2384373A CA2384373A1 CA 2384373 A1 CA2384373 A1 CA 2384373A1 CA 002384373 A CA002384373 A CA 002384373A CA 2384373 A CA2384373 A CA 2384373A CA 2384373 A1 CA2384373 A1 CA 2384373A1
- Authority
- CA
- Canada
- Prior art keywords
- ethylene
- vinyl
- styrene
- interpolymer
- component
- 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
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000005977 Ethylene Substances 0.000 title claims abstract description 45
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 41
- 239000004711 α-olefin Substances 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 title claims description 31
- 239000000178 monomer Substances 0.000 claims abstract description 66
- 229920000642 polymer Polymers 0.000 claims abstract description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 106
- -1 4,5-methylene-phenanthrenyl Chemical group 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 23
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 11
- 229920001519 homopolymer Polymers 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 8
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical group C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 5
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 4
- 125000001475 halogen functional group Chemical group 0.000 claims description 4
- 150000002848 norbornenes Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 3
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- 238000003780 insertion Methods 0.000 description 19
- 230000037431 insertion Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 12
- 238000004811 liquid chromatography Methods 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007795 chemical reaction product Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RKZDZWJDQTZDLD-UHFFFAOYSA-N 4h-cyclopenta[def]phenanthrene Chemical compound C1=CC=C2CC3=CC=CC4=CC=C1C2=C34 RKZDZWJDQTZDLD-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920002959 polymer blend Polymers 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 150000003918 triazines Chemical class 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- YQVACFNDJOYXNG-UHFFFAOYSA-N N-[dimethyl(4-tetracyclo[10.2.1.05,14.08,13]pentadeca-1(14),2,4,6,8(13),9,11-heptaenyl)silyl]-2-methylpropan-2-amine Chemical compound C1=C2C([Si](C)(C)NC(C)(C)C)=CC=C(C3)C2=C2C3=CC=CC2=C1 YQVACFNDJOYXNG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- PGWMBDYEZPHFEM-UHFFFAOYSA-N [Li+].C=C1[CH-]c2ccc3ccccc3c2C=C1 Chemical compound [Li+].C=C1[CH-]c2ccc3ccccc3c2C=C1 PGWMBDYEZPHFEM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000011208 chromatographic data Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 230000010512 thermal transition Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QXALIERKYGCHHA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)borane Chemical compound BC1=C(F)C(F)=C(F)C(F)=C1F QXALIERKYGCHHA-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- GWWHAAHVHHLOQW-UHFFFAOYSA-N 4,5-dimethyl phenanthrene Natural products C1=CC=C(C)C2=C3C(C)=CC=CC3=CC=C21 GWWHAAHVHHLOQW-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UAUDZVJPLUQNMU-UHFFFAOYSA-N Erucasaeureamid Natural products CCCCCCCCC=CCCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-UHFFFAOYSA-N 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
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229940090047 auto-injector Drugs 0.000 description 1
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- AAEHPKIXIIACPQ-UHFFFAOYSA-L calcium;terephthalate Chemical compound [Ca+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 AAEHPKIXIIACPQ-UHFFFAOYSA-L 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
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- 229920002678 cellulose Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000007656 fracture toughness test Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical class C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- CKWOGTUTBSUNSB-UHFFFAOYSA-N n-[chloro(dimethyl)silyl]-2-methylpropan-2-amine Chemical compound CC(C)(C)N[Si](C)(C)Cl CKWOGTUTBSUNSB-UHFFFAOYSA-N 0.000 description 1
- GZMZJJOMZQVSDC-UHFFFAOYSA-N n-butyl-2,2,6,6-tetramethylpiperidin-4-amine;2,4,6-trichloro-1,3,5-triazine Chemical compound ClC1=NC(Cl)=NC(Cl)=N1.CCCCNC1CC(C)(C)NC(C)(C)C1 GZMZJJOMZQVSDC-UHFFFAOYSA-N 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical compound C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/06—Hydrocarbons
- C08F12/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0838—Copolymers of ethene with aromatic monomers
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Abstract
The present invention pertains to an interpolymer comprising; (1) from 5 to 85 mol percent of polymer units derived from one or more vinyl or vinylidene aromatic monomers, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.
Description
ETHYLENE AND/OR ALPHA-OLEFIN/VINYL OR
VINYLIDENE AROMATIC INTERPOLYMER COMPOSITIONS
The present invention relates to compositions comprising interpolymers of vinyl or vinylidene aromatic monomers with ethylene and/or one or more alpha-olefin monomers. The catalyst used to prepare these interpolymers, [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers. The resulting interpolymers, contain successive vinyl or vinylidene aromatic monomer insertions and thus can have vinyl or vinylidene aromatic monomer incorporation in excess of 65 mole percent.
Until recently, the copolymerization of ethylene and vinyl or vinylidene aromatic monomers was not a commercially viable process using the traditional Ziegler alpha-olefin polymerization catalysts based on Ti (III) and Ti (IV) halides. Most earlier attempts to prepare copolymers of vinyl aromatic monomers and alpha-olefins, in particular copolymers of styrene and ethylene, with such catalysts have either failed to obtain substantial incorporation of the vinyl aromatic monomer or else have achieved polymers of low molecular weight. In Polymer Bulletin, 20, 237-241(1988) there is disclosed a copolymer of styrene and ethylene containing 1 mole percent styrene incorporated therein. The reported polymer yield was 8.3 x 10~ grams of polymer per micromole titanium employed. However, with the advent of the metallocene based olefin polymerization catalysts, and in particular the constrained geometry type catalysts, it is now possible to copolymerize ethylene and other alpha-olefins with styrene and other vinyl or vinylidene aromatic monomers to provide interpolymers.
Copolymers of ethylene and styrene including materials with more than 50 mole percent styrene incorporation have been reported using an ansa metallocene catalyst as disclosed by Arai, T.; Ohtsu, T.; Suzuki, S. in Macromolecular Rapid Commute.
1998, and Polym. Prepr., 1998, 39(1), 220-221.
In addition, U.S. Patent No. 5,703,187 describes "pseudo random" ethylene styrene interpolymers characterized by a unique monomer distribution in which successive head-to-tail styrene monomer insertions are not observed that is no SS diads or SSS triads. Except for the absence of sequential head-to-tail styrene monomer insertions, the styrene distribution in interpolymers is still found to be well dispersed hence the term "pseudo-random". A particular distinguishing feature of pseudo-random copolymers was the fact that all phenyl or bulky hindering groups substituted on the polymer backbone are separated by 2 or more methylene units. During the addition polymerization reaction, if a vinyl or vinylidene aromatic monomer is inserted into the growing polymer chain, the next monomer inserted must be ethylene or a vinyl or vinylidene aromatic monomers which is inserted in an inverted fashion (where inverted is taken to mean a 2,1 insertion where a normal insertion is taken to be 1,2, however it is understood by those skilled in the art that the opposite can be true and would not change the_description or properties of the interpolymers of the present invention). After an inverted vinyl or vinylidene aromatic monomer insertion, the next monomer must be ethylene, as the insertion of another vinyl or vinylidene aromatic monomer at this point would place the hindering substituent closer together than the minimum separation as described above. A
consequence of these polymerization kinetics is that the catalysts used did not homopolymerize styrene to any appreciable extent, while a mixture of ethylene and styrene is rapidly polymerized and may give high styrene content (up to 50 mole percent styrene) copolymers. A direct consequence of this monomer distribution was that the practical upper limit of styrene incorporation was approximately 50 mole percent or 79 weight percent styrene.
WO 98/0999 describes the "substantially random" ethylene styrene interpolymers which, while including the aforementioned the pseudo random interpolymers, also included interpolymers prepared using specific metallocene polymerization catalysts. Use of these specific metallocene polymerization catalysts resulted in the formation of interpolymers characterized by a unique monomer distribution. In this distribution, although most of the polymer chains are pseudo random in styrene distribution, a small amount of sequences involving two head-to-tail vinyl aromatic monomer insertions preceded and followed by at least one ethylene insertion were observed. That is an ethylene/styrene/styrene/ethylene tetrad, ESSE, wherein the styrene monomer insertions of said tetrads occur exclusively in a 1,2 manner). Thus these specific substantially random ethylene/styrene interpolymers contain similar peaks in the NMR
spectrum as the pseudo random ethylene/styrene interpolymers, but also are characterized by additional signals with intensities appearing in the chemical shift range 43.70-44.25 ppm. As a result of this unique monomer distribution, the upper limit of styrene incorporation in the substantially random ethylene styrene interpolymers was raised to approximately 65 mole percent or 87.5 weight percent styrene.
We have now suprisingly discovered that that the catalyst, [(4,5-methylene-phenanthrenyl) (tent-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers in their polymerization with ethylene and/or one or more alpha-olefin monomers, and results in the preparation of new interpolymers which include, in the case of ethylene/styrene interpolymers, both SSS
and higher (for example SSSS, SSSSS etc) sequences. As a result of this increased reactivity of the catalyst, the resulting interpolymers are able to exhibit upper limits to their vinyl or vinylidene aromatic monomer contents in excess of 65 mol percent.
The present invention pertains to an interpolymer comprising;
(1) from 5 to 85 mol percent ofpolymer units derived from at least one vinyl or vinylidene aromatic monomer, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3_zo alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from ( 1 ) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.
All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989.
Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.
are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.
The term "interpolymer" is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
The term "detectable vinyl or vinylidene aromatic monomer triads" is used herein to indicate a sequence of three successive vinyl or vinylidene aromatic insertions in the interpolymer. In the case of an ethylene/styrene interpolymer this would correspond to an -SSS- triad. When any atactic polystyrene impurity is separated out from the polymer, these triads are detectable by the presence of a peak in the'3C NMR spectrum which occurs at a chemical shift corresponding to the methine carbons in the polymer backbone of an ethylene/styrene interpolymer at 44.6 ppm (ESSSE) Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS
tetrads, SSSSS pentads. Additional peaks corresponding to the following insertions may also be present in the interpolymers; 46.0 ppm (ESE), 43.75 (ESSE), and 41.6 ppm (>3 successive S insertions). It is understood by one skilled in the art that for such insertions involving a vinyl or vinylidene aromatic monomer other than styrene, and an alpha-olefin other than ethylene, then the interpolymer will give rise to similar'3C NMR
peaks but with slightly different chemical shifts.
The interpolymers of the present invention are prepared using the catalyst , [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane]dimethyl titanium.
CH3~Si/ \ , CH3 CH3~ / ~ CH
OY
We have surprisingly discovered that that this catalyst has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers in their polymerization with ethylene and/or one or more alpha-olefin monomers. This results in the preparation of new interpolymers which include, in the case of ethylene/styrene interpolymers, both SSS
and higher (for example SSSS, SSSSS etc) sequences. As a result of the increased reactivity of the catalyst, the resulting interpolymers are able to exhibit upper limits to vinyl or vinylidene aromatic monomer contents in excess of 65 mol percent.
One method of preparation of the interpolymers of the present invention includes polymerizing a mixture of polymerizable monomers in the presence of [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane]dimethyl titanium and a suitable activating compound. Using this catalyst, the interpolymers of the present invention can be prepared by the processes described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are incorporated herein by reference in their entirety. Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -50°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization. While preparing the interpolymers of the present invention, an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures. The presence of vinyl aromatic homopolymer is in general not detrimental for the purposes of the present invention and can be tolerated. The vinyl aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as liquid chromatography or selective precipitation from solution with a non solvent for either the interpolymer or the vinyl or vinylidene aromatic homopolymer.
The interpolymers of the present invention include interpolymers prepared by polymerizing i) ethylene and/or one or more alpha-olefin monomers and ii) one or more vinyl or vinylidene aromatic monomers and optionally iii) other polymerizable ethylenically unsaturated monomer(s).
Suitable alpha-olefins include for example, alpha-olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms.
Particularly suitable are ethylene, propylene,.butene-1, 4-methyl-1-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1, 4-methyl-1-pentene, hexene-1 or octene-1. These alpha-olefins do not contain an aromatic moiety.
Other optional polymerizable ethylenically unsaturated monomers) include norbornene and C,_,o alkyl or C6_,o aryl substituted norbornenes, with an exemplary interpolymers being ethylene/styrene/norbornene and ethylene/styrene/ethylidene norbornene.
Suitable vinyl or vinylidene aromatic monomers, which can be employed to prepare the interpolymers, include, for example, those represented by the following formula:
Ar ( ~ H2)n Rl - C = C(R2)2 wherein R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl;
each R' is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl;
Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C,_4-alkyl, and C,~-haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Exemplary vinyl aromatic monomers include styrene, vinyl toluene, alpha-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, alpha-methyl styrene, the lower alkyl- (C, - C4) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof. A more preferred vinyl aromatic monomer is styrene.
The resulting interpolymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
The polymers may be readily sulfonated, using processes described in WO 99/20691, the entire contents of which are herein incorporated by reference, chlorinated or otherwise functionalized, as described in copending L1S Application No. 09/244,921 filed on February 42", 1999 by R.
VINYLIDENE AROMATIC INTERPOLYMER COMPOSITIONS
The present invention relates to compositions comprising interpolymers of vinyl or vinylidene aromatic monomers with ethylene and/or one or more alpha-olefin monomers. The catalyst used to prepare these interpolymers, [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers. The resulting interpolymers, contain successive vinyl or vinylidene aromatic monomer insertions and thus can have vinyl or vinylidene aromatic monomer incorporation in excess of 65 mole percent.
Until recently, the copolymerization of ethylene and vinyl or vinylidene aromatic monomers was not a commercially viable process using the traditional Ziegler alpha-olefin polymerization catalysts based on Ti (III) and Ti (IV) halides. Most earlier attempts to prepare copolymers of vinyl aromatic monomers and alpha-olefins, in particular copolymers of styrene and ethylene, with such catalysts have either failed to obtain substantial incorporation of the vinyl aromatic monomer or else have achieved polymers of low molecular weight. In Polymer Bulletin, 20, 237-241(1988) there is disclosed a copolymer of styrene and ethylene containing 1 mole percent styrene incorporated therein. The reported polymer yield was 8.3 x 10~ grams of polymer per micromole titanium employed. However, with the advent of the metallocene based olefin polymerization catalysts, and in particular the constrained geometry type catalysts, it is now possible to copolymerize ethylene and other alpha-olefins with styrene and other vinyl or vinylidene aromatic monomers to provide interpolymers.
Copolymers of ethylene and styrene including materials with more than 50 mole percent styrene incorporation have been reported using an ansa metallocene catalyst as disclosed by Arai, T.; Ohtsu, T.; Suzuki, S. in Macromolecular Rapid Commute.
1998, and Polym. Prepr., 1998, 39(1), 220-221.
In addition, U.S. Patent No. 5,703,187 describes "pseudo random" ethylene styrene interpolymers characterized by a unique monomer distribution in which successive head-to-tail styrene monomer insertions are not observed that is no SS diads or SSS triads. Except for the absence of sequential head-to-tail styrene monomer insertions, the styrene distribution in interpolymers is still found to be well dispersed hence the term "pseudo-random". A particular distinguishing feature of pseudo-random copolymers was the fact that all phenyl or bulky hindering groups substituted on the polymer backbone are separated by 2 or more methylene units. During the addition polymerization reaction, if a vinyl or vinylidene aromatic monomer is inserted into the growing polymer chain, the next monomer inserted must be ethylene or a vinyl or vinylidene aromatic monomers which is inserted in an inverted fashion (where inverted is taken to mean a 2,1 insertion where a normal insertion is taken to be 1,2, however it is understood by those skilled in the art that the opposite can be true and would not change the_description or properties of the interpolymers of the present invention). After an inverted vinyl or vinylidene aromatic monomer insertion, the next monomer must be ethylene, as the insertion of another vinyl or vinylidene aromatic monomer at this point would place the hindering substituent closer together than the minimum separation as described above. A
consequence of these polymerization kinetics is that the catalysts used did not homopolymerize styrene to any appreciable extent, while a mixture of ethylene and styrene is rapidly polymerized and may give high styrene content (up to 50 mole percent styrene) copolymers. A direct consequence of this monomer distribution was that the practical upper limit of styrene incorporation was approximately 50 mole percent or 79 weight percent styrene.
WO 98/0999 describes the "substantially random" ethylene styrene interpolymers which, while including the aforementioned the pseudo random interpolymers, also included interpolymers prepared using specific metallocene polymerization catalysts. Use of these specific metallocene polymerization catalysts resulted in the formation of interpolymers characterized by a unique monomer distribution. In this distribution, although most of the polymer chains are pseudo random in styrene distribution, a small amount of sequences involving two head-to-tail vinyl aromatic monomer insertions preceded and followed by at least one ethylene insertion were observed. That is an ethylene/styrene/styrene/ethylene tetrad, ESSE, wherein the styrene monomer insertions of said tetrads occur exclusively in a 1,2 manner). Thus these specific substantially random ethylene/styrene interpolymers contain similar peaks in the NMR
spectrum as the pseudo random ethylene/styrene interpolymers, but also are characterized by additional signals with intensities appearing in the chemical shift range 43.70-44.25 ppm. As a result of this unique monomer distribution, the upper limit of styrene incorporation in the substantially random ethylene styrene interpolymers was raised to approximately 65 mole percent or 87.5 weight percent styrene.
We have now suprisingly discovered that that the catalyst, [(4,5-methylene-phenanthrenyl) (tent-butylamido) dimethylsilane] dimethyl titanium, has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers in their polymerization with ethylene and/or one or more alpha-olefin monomers, and results in the preparation of new interpolymers which include, in the case of ethylene/styrene interpolymers, both SSS
and higher (for example SSSS, SSSSS etc) sequences. As a result of this increased reactivity of the catalyst, the resulting interpolymers are able to exhibit upper limits to their vinyl or vinylidene aromatic monomer contents in excess of 65 mol percent.
The present invention pertains to an interpolymer comprising;
(1) from 5 to 85 mol percent ofpolymer units derived from at least one vinyl or vinylidene aromatic monomer, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3_zo alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from ( 1 ) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.
All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989.
Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.
Any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.
are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.
The term "interpolymer" is used herein to indicate a polymer wherein at least two different monomers are polymerized to make the interpolymer. This includes copolymers, terpolymers, etc.
The term "detectable vinyl or vinylidene aromatic monomer triads" is used herein to indicate a sequence of three successive vinyl or vinylidene aromatic insertions in the interpolymer. In the case of an ethylene/styrene interpolymer this would correspond to an -SSS- triad. When any atactic polystyrene impurity is separated out from the polymer, these triads are detectable by the presence of a peak in the'3C NMR spectrum which occurs at a chemical shift corresponding to the methine carbons in the polymer backbone of an ethylene/styrene interpolymer at 44.6 ppm (ESSSE) Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS
tetrads, SSSSS pentads. Additional peaks corresponding to the following insertions may also be present in the interpolymers; 46.0 ppm (ESE), 43.75 (ESSE), and 41.6 ppm (>3 successive S insertions). It is understood by one skilled in the art that for such insertions involving a vinyl or vinylidene aromatic monomer other than styrene, and an alpha-olefin other than ethylene, then the interpolymer will give rise to similar'3C NMR
peaks but with slightly different chemical shifts.
The interpolymers of the present invention are prepared using the catalyst , [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane]dimethyl titanium.
CH3~Si/ \ , CH3 CH3~ / ~ CH
OY
We have surprisingly discovered that that this catalyst has a remarkably high reactivity towards vinyl or vinylidene aromatic monomers in their polymerization with ethylene and/or one or more alpha-olefin monomers. This results in the preparation of new interpolymers which include, in the case of ethylene/styrene interpolymers, both SSS
and higher (for example SSSS, SSSSS etc) sequences. As a result of the increased reactivity of the catalyst, the resulting interpolymers are able to exhibit upper limits to vinyl or vinylidene aromatic monomer contents in excess of 65 mol percent.
One method of preparation of the interpolymers of the present invention includes polymerizing a mixture of polymerizable monomers in the presence of [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane]dimethyl titanium and a suitable activating compound. Using this catalyst, the interpolymers of the present invention can be prepared by the processes described in EP-A-0,416,815 by James C. Stevens et al. and US Patent No. 5,703,187 by Francis J. Timmers, both of which are incorporated herein by reference in their entirety. Preferred operating conditions for such polymerization reactions are pressures from atmospheric up to 3000 atmospheres and temperatures from -50°C to 200°C. Polymerizations and unreacted monomer removal at temperatures above the autopolymerization temperature of the respective monomers may result in formation of some amounts of homopolymer polymerization products resulting from free radical polymerization. While preparing the interpolymers of the present invention, an amount of atactic vinyl or vinylidene aromatic homopolymer may be formed due to homopolymerization of the vinyl aromatic monomer at elevated temperatures. The presence of vinyl aromatic homopolymer is in general not detrimental for the purposes of the present invention and can be tolerated. The vinyl aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as liquid chromatography or selective precipitation from solution with a non solvent for either the interpolymer or the vinyl or vinylidene aromatic homopolymer.
The interpolymers of the present invention include interpolymers prepared by polymerizing i) ethylene and/or one or more alpha-olefin monomers and ii) one or more vinyl or vinylidene aromatic monomers and optionally iii) other polymerizable ethylenically unsaturated monomer(s).
Suitable alpha-olefins include for example, alpha-olefins containing from 3 to 20, preferably from 3 to 12, more preferably from 3 to 8 carbon atoms.
Particularly suitable are ethylene, propylene,.butene-1, 4-methyl-1-pentene, hexene-1 or octene-1 or ethylene in combination with one or more of propylene, butene-1, 4-methyl-1-pentene, hexene-1 or octene-1. These alpha-olefins do not contain an aromatic moiety.
Other optional polymerizable ethylenically unsaturated monomers) include norbornene and C,_,o alkyl or C6_,o aryl substituted norbornenes, with an exemplary interpolymers being ethylene/styrene/norbornene and ethylene/styrene/ethylidene norbornene.
Suitable vinyl or vinylidene aromatic monomers, which can be employed to prepare the interpolymers, include, for example, those represented by the following formula:
Ar ( ~ H2)n Rl - C = C(R2)2 wherein R' is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl;
each R' is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms, preferably hydrogen or methyl;
Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C,_4-alkyl, and C,~-haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Exemplary vinyl aromatic monomers include styrene, vinyl toluene, alpha-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds. Particularly suitable such monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, alpha-methyl styrene, the lower alkyl- (C, - C4) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures thereof. A more preferred vinyl aromatic monomer is styrene.
The resulting interpolymers may be modified by typical grafting, hydrogenation, functionalizing, or other reactions well known to those skilled in the art.
The polymers may be readily sulfonated, using processes described in WO 99/20691, the entire contents of which are herein incorporated by reference, chlorinated or otherwise functionalized, as described in copending L1S Application No. 09/244,921 filed on February 42", 1999 by R.
E. Drumright et al., the entire contents of which are herein incorporated by reference. The compositions of the present invention may also be modified by various cross-linking processes. These include, but are not limited to peroxide-, silane-, sulfur-, radiation-, or azide-based cure systems. A full description of the various cross-linking technologies is described in U.S. Patent 5,869,591 and 5977,271, the entire contents of both of which are herein incorporated by reference. Dual cure systems, which use a combination of heat, moisture cure, and radiation steps, may be effectively employed. For instance, it may be desirable to employ peroxide crosslinking agents in conjunction with silane crosslinking agents, peroxide crosslinking agents in conjunction with radiation, sulfur-containing crosslinking agents in conjunction with silane crosslinking agents, etc. Dual cure systems are disclosed and claimed in U. S. Patent 5,911,940, the entire contents of which is incorporated herein by reference.
Additives such as antioxidants (for example, hindered phenols such as, for example, Irganox~ 1010 a registered trademark of Ciba Geigy), phosphites (for example, Irgafos~ 168 a registered trademark of Ciba Geigy), U.V. stabilizers, cling additives (for example, polyisobutylene), slip agents (such as erucamide and/or stearamide), antiblock additives, colorants, pigments, tackifiers, flame retardants, coupling agents, fillers, plastcizers can also be included in the compositions of the present invention.
Also included as a potential component in the compositions of the present invention are various organic and inorganic fillers. Representative examples of such fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, ammonium polyphosphate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B203, nickel powder or chalk.
Other representative organic or inorganic fiber or mineral fillers include carbonates such as barium, calcium or magnesium carbonate; borates such as magnesium or zinc borate, fluorides such as calcium or sodium aluminum fluoride;
hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide;
silicates _7_ such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystals. Mixtures of more than one such filler may be used as well.
The fillers may also be used in conjunction with a coupling agent and/or initiator selected from organic peroxides, silanes, titanates, zirconates,_multi-functional vinyl compounds, organic azides, and mixtures thereof.
Other additives include the hindered amine stabilizers. Such stabilizers include hindered triazines such as substituted triazines and reaction products of triazines. Suitable reaction products include the reaction product of triazine with, for example, diamines and/
or cycloaliphatic compounds such as cyclohexane. A particularly suitable hindered amine stabilizer includes the reaction product of 1, 3-propanediamine, N,N"-1,2-ethanediylbis-, cyclohexane and peroxidized N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine which ismade commercially by Ciba-Geigy and has the name "CG-116 having CAS Reg No. : 191680-81-6.
These additives are employed in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers. Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend. Similarly, the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment. Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the interpolymer. Fillers may suitably be employed in the range 1-90 wt.percent.
The polymers of the present invention can be blended with additional polymers including but not limited to; other interpolymers of different molecular weight and/or _g_ vinyl or vinylidene aromatic monomer content, substantially random interpolymers vinyl and vinylidene halide polymers including but not limited to polyvinyl chloride) and poly(vinylidene chloride), polyethylene, and other polyolefins including but not limited to LDPE, and HDPE, PP, homogeneous ethylene/alpha-olefin copolymers produced by metallocene catalysts, including but not limited to the substantially linear ethylene/alpha-olefin copolymers and heterogeneous and heterogeneous ethylene/alpha-olefin copolymers produced by Ziegler catalysts; styrenic polymers including but not limited to polystyrene, SBS copolymers, polyethers, polycarbonates, polyanilines, asphalt, or any combinations thereof.
The interpolymers of the present invention, or blends thereof, can be fabricated into various forms including but not limited to films, fibers, foams, sheets, injection molded articles, membranes, injection-blow molded articles and extruded profiles, and emulsions. Applications for the interpolymers of the present invention, or blends thereof, include, but are not limited to, ignition resistant articles, pressure sensitive filmstock, coating compositions or paints, floor, ceiling and wall coverings, carpet backing, barriers, gaskets, caps and closures, and, with the addition of conductive additives such as carbon black, various conductive applications including electrical devices, conductor shields, insulation shields, and other wire and cable applications. Other applications include as compatibilizers in blends of polystyrene and ethylene and/or alpha-olefin homo-and copolymers. Also included are applications for the sulfonated derivatives including their use in fuel cell membranes, water absorbent applications and HVAC equipment.
Determining the composition of the ethylene/styrene interpolymers of the present invention can be ambiguous using NMR methods of analysis. This ambiguity arises from the fact that the styrene triads and higher order styrene insertions have peaks in both the 'H and'3C spectra that can not be distinguished from peaks of the ubiquitous amorphous atactic polystyrene homopolymer (aPS) which is present in small amounts in the interpolymers. However use of a liquid chromatography (LC) method using gradient solvent polarity allows separation of the interpolymer from the aPS, and the retention time of the interpolymer peak is indicative of its styrene content.
The interpolymer compositions of the present invention comprise from 5 to 85, preferably from 20 to 85, more preferably from 50 to 85 mole percent of at least one vinyl or vinyl or vinylidene aromatic monomer and from 15 to 95, preferably from 15 to 80, more preferably from 15 to 50 mole percent of ethylene and/or at least one aliphatic alpha-olefin having from 3 to 20 carbon atoms.
The melt index (I2) of the interpolymer of the present invention is greater than 0.05, preferably of from 0.5 to 200, more preferably of from 0.5 to 100 g/10 min.
The molecular weight distribution (Mw/Mn) of the interpolymers of the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to 5.
The interpolymer compositions of the present invention contain detectable vinyl aromatic monomer triads. In the case of an ethylene/styrene interpolymer this would correspond to an -SSS- triad. Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS tetrads, SSSSS
pentads. When any atactic polystyrene impurity is separated out from the polymer, these triads are detectable by the presence of a peak in the'3C NMR which occurs at a chemical shift corresponding to the methine carbons in the polymer backbone of an ethylene/styrene interpolymer at 44.6 ppm (ESSSE).
The following examples are illustrative of the invention, but are not to be construed as to limiting the scope thereof in any manner.
EXAMPLES
Test Methods The molecular weight of the polymer compositions of the present invention is conveniently indicated using Gel Permeation Chromatography using both UV and Refractive Index detectors.
In order to determine the '3C NMR chemical shifts of the interpolymers of the present invention, the following procedures and conditions are employed. A
five to ten weight percent polymer solution is prepared in a mixture consisting of 50 volume percent 1,1,2,2-tetrachloroethane-d2 and 50 volume percent 0.10 molar chromium tris(acetylacetonate) in 1,2,4-trichlorobenzene. NMR spectra are acquired at 130°C using an inverse gated decoupling sequence, a 90°-pulse width and a pulse delay of five seconds or more. The spectra are referenced to the isolated methylene signal of the polymer assigned at 30.000 ppm.
Materials Testing Polymer samples were formed into the shapes required for physical property determination by compression molding at 150°C using a ten minute preheat, 3 minute compression at 10000 pounds force, and immediate cool down.
Differential Scanning Calorimetry (DSC) analysis of this polymer was performed under a nitrogen atmosphere at a heating rate of 5°C/minute using a DuPont Instruments 910 Differential Scanning Calorimeter. All samples were taken through two heating cycles (to remove the effects of previous heat history) and data are reported for the second scan in all cases.
Micro-tensile testing was performed using compression molded micro-tensile bars as per ASTM D638 testing protocol. The samples were pulled using an Instron Series instrument at a cross-head speed of 0.1 inches/minute and a 224.8 lbf load cell at room temperature.
Plain-strain fracture toughness, compact tension single-edge notch geometry samples were compression molded into 1" by 1" by 1/8" squares. These squares were machined to provide a side notch and holes for attachment to the testing apparatus. A pre-crack was formed in each sample by cooling with liquid nitrogen and cracking with a razor blade and hammex. Fracture toughness testing was performed using an Instron 8501 instrument at a cross-head speed of 0.02 in/min with a 224.8 lbf load cell.
Dynamic mechanical spectroscopy was performed on a rectangular bar, which was compression molded at 100°C. Temperature sweeps ranging from -100°C to 150°C were performed at a set frequency of 1 rad/sec with an auto-strain function set by the DMS
instrument.
Density was measured using a helium pycnometer. Rockwell hardness was assessed using ASTM D785-93.
L.C. Analysis.
Between 0.100 and 0.102 grams of polymer were weighed into a 30 ml vial. 10 ml of THF was added. The vial was capped and placed on a heated shaker so as to dissolve the sample. The temperature of the heated shaker was 65° C.
After dissolution, about 1 ml of the solution was transferred to an HP 1090 LC auto-injector vial. A
Hewlett-Packard 1090 LC (serial number 2541A00700) with a diode array detector was used for the collection of all chromatographic data. Signals were collected at 254 nm and 400 nm. The chromatographic data were processed using Grams386 and Excel software.
Two columns were used to determine the styrene contents of the resins by liquid chromatography. Use of either column initially involved determination of the atactic polystyrene content (which peak was clearly discernible). This value was then subtracted from the total styrene content of the sample as determined by 13C N.M.R to give the wtpercent copolymerized styrene. A calibration curve of copolymerized styrene v.
retention time (at the 50'" percentile of the chromatogram peak) was then constructed and the resulting fit was then applied to all new samples. This analysis was performed using two types of column.
The first of these was a C 18 column was obtained from Alltech: Spherisorb ODS
II 5 micron, 250 x 4.60 mm. There was a guard column on the C18 column. It was an RP
8.5 micron. Below are the instrumental conditions used on the HP 1090 with the column).
Solvent A = AcetonitrileAt 24.00 Flow = 1.000 Solvent B = THF At 24.00 percent B =
100.0, C =
Solvent C = 2-Propanol At 25.00 Flow = 1.000 Store Flow 1; At 25.00 percent B =
1.0, C = 0.0 Stop Time=30.00 At 30.00 Flow = 1.000 Post Time = 0.00 At 30.00 percent B =
1.0, C = 0.0 SDS-Config A=1,B=1,C=1 Max Press = 400 Stop time = system Min Press = 8 Post time = 1.00 minute B=1.O,C=0.0 Auto balance = on Injection Volume=10.0 Peak width = 0.100 Oven Temp = 50.0 Spectra Range=240, 600, At 1.00 Flow =1.000 ml/minStore Spectra = peak At 1.00 percent B=1.0,C=0.0Threshold=1.000 At 20.00 Flow =1.000 Signal A=254, 4, 550, At 20.00 percent B=100.0,C=0.0Signal B=400, 4, 550, The second and best column of the two was a nitro column obtained from Phenomenex: Nucleosil 5 N02 250 x 4.60 mm, 5 micron, serial number 243745.
There was a guard column on the nitro column. It was a Phenomenex Nucleosil 5 N02 30 x 4.6 mm, 5 micron 100 angstrom, serial number 2437476. Below are the instrumental conditions used on the HP 1090 with the Nitro2 method (nitro column).
Solvent A = Hexanes At 20.00 Flow=1.000 Solvent B = THF At 20.00 percent B=70.O,C=0.0 Solvent C = 2-propanol At 23.00 Flow=1.000 Store A 1; At 23.00 percent B=70.O,C=0.0 Store B 1; At 24.00 Flow=1.000 Store C 1; At 24.00 percent B=3.O,C=0.0 Store Flow 1; At 30.00 Flow=1.000 Store Temp l; At 30.00 percent B=3.O,C=0.0 Stop Time=30.00 minutes Post Time=0.00 minutes SDS-Config A=1, B=1, Stop Time = System C=1 Flow=1.000 ml/min Post Time=1.00 minute Max Press=400 bar Auto Balance = on Min Press=8 Peakwidth=0.100 percent B=3.O,C=0.0 Spectra Range=240, 600, Inj volum=10.0 1 Store Spectra = peak Oven Temp=30.0 c Threshold=1.000 At 1.00 Flow=1.000 Signal A=254, 4, 550, At 1.00 percent B=3.O,C=0.0Signal B=400, 4, 550, The regression equation used to determine the styrene content on this column was:
[sty] wtpercent = -84.89 + 10.98 * retention time (mins) Preparation of the Examples 1 - 6 of the Inter~olymers of the Present Invention.
1~ Preparation of Catalyst General Syntheses and manipulations were carried out in an inert atmosphere (argon) glove box. Solvents were purchased from Aldrich. Liquid reagents and solvents were first saturated with nitrogen and then dried by passage through activated alumina prior to use as disclosed by Pangborn, A.B.; Giardello, M.A.; Grubbs, R.H.; Rosen, R.K.;
Timmers, F.J. in Organometallics, 1996, I5, 1518- 1520 . Deuterated benzene was dried over sodium/potassium alloy and filtered prior to use. Methylene phenanthrene was purchased from Lancaster. NMR spectra of ligands and metal complexes were recorded on a Varian 300 MHz NMR spectrometer at ambient conditions. '''C NMR spectra of the copolymers were recorded on a Bruker 600 MHz spectrometer.
Synthesis of Lithium Methylenephenanthrenide To 4,5-methylenephenanthrene (0.485 g, 2.55 mmol) in 50 mL of hexanes was added 1.6 M n-BuLi in hexanes ( 1.75 mL, 2.80 mmol). After one day of stirring at ambient conditions the solution appeared darker orange and a small amount of orange precipitated had formed. After 14 days much more precipitate had formed. This was isolated by decanting the supernatant from the solid which stuck to the inside walls of the flask. After drying under reduced pressure, 0.430 g were isolated (86percent yield).
Volatile materials were removed from the supernatant to give an orange solid.
Proton NMR analysis of this material showed it to be the starting methylenephenanthrene.
Synthesis of (4,5-methylenephenanthrenyl)(tert-butylamino)dimethylsilane To (tert-butylamino)dimethylsilyl chloride (0.436 g, 2.63 mmol) in 30 mL THF
was added a cherry red solution of lithium methylenephenanthrenide (0.430 g, 2.19 mmol) in 20 mL THF. The solution was allowed to stir at ambient temperature overnight.
The volatile materials were removed under reduced pressure. The solid residue was slurried in 10 mL hexanes and the volatile materials were removed under reduced pressure. The solid residue was extracted twice with a total of 30 mL hexanes.
The extracts were filtered and the volatile materials were removed from the combined filtrates under reduced pressure to give 0.690 g (99percent yield) of an orange oil.
The'H NMR
spectrum was consistent with the desired product.
Synthesis of [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane]titanium bis(dimethylamide) A solution of the titanium tetrakis amide (0.484 g, 2.16 mmol) and (4,5-methylenephenanthrenyl)(tert-butylamino)dimethylsilane (0.690 g, 2.16 mmol) in 50 mL
n-octane was heated and stirred at reflux. The course of the reaction was monitored by'H
NMR spectroscopy by removing a small aliquot of the solution, removing the volatile materials under reduced pressure, and analyzing the residue in C6D6. Proton NMR
analysis showed clean conversion to the desired product (for example SSpercent conversion after ca. 48 hours reflux.) Several drops of titanium tetrakis amide were added periodically. After seven days at reflux, the reaction appeared not to be progressing past 82percent conversion. The volatile materials were removed from the cooled mixture under reduced pressure. The residue was dissolved in 20 mL of hexanes and the resulting mixture was filtered. The volatile materials were removed from the filtrate under reduced pressure to give a dark powder (0.950 g). Proton NMR analysis of the product showed it to be a mixture of the desired product and the starting ligand, 82/18 mole percent, respectively (87 weight percent of the desired product).
Synthesis of [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane]titanium dichloride To the bis(amide)/ligand mixture isolated above (0.83.g, 1.83 mmol of the bis(amide)) issolved in 40 mL hexanes was added trimethylsilyl chloride (1.33 mL, 10.5 mmol). The solution was stirred at reflux for six hours. A small aliquot of the cooled solution was removed and the volatile materials were removed under reduced pressure.
The residue was dissolved in C6D6 and analyzed by'H NMR spectroscopy. The spectrum showed very clean conversion to the monochloride-monoamide intermediate. An additional 1.3 mL of trimethylsilyl chloride was added and the sealed vessel was stirred at ambient temperature for eight days. The solution was then heated to reflux for six hours.
The cooled solution was placed in the glove box freezer (-25°C). The solids that formed were collected on a glass frit by vacuum filtration. The solid residue was washed once with cold hexanes (ca. 10 mL) and the solid was then dried under reduced pressure to give 0.516 g (65percent yield). Proton NMR analysis showed the material was consistent with very clean desired product.
Synthesis of [(4,5-methylenephenanthrenyl)(tertbutylamido)-dimethylsilane]
dimethyltitanium To the dichloride (0.516 g, 1.18 mmol) in 30 mL of THF was added 3.0 M
methylmagnesium chloride (0.87 mL, 2.6 mmol) which resulted in an immediate color change. After standing overnight, the volatile materials were removed under reduced pressure. The solid residue was slurried in hexanes and the volatile materials were removed under reduced pressure. The residue was extracted several times with hexanes.
The extracts were filtered and the volatile materials were removed from the combined filtrates under reduced pressure to give a bright orange powder, 0.392 g.
Proton and'3C
NMR analysis in C6D6 shows that the desired product was isolated as a 1 to 1 adduct with THF. Assuming a molecular weight was 467.6 g/mol, the isolated yield was 71 percent.
The THF adduct (0.345 g) was dissolved in 50 mL toluene and heated at reflux for six hours. A color change from orange to brown-yellow was observed. The volatile materials were removed under reduced pressure. Proton NMR analysis of the residue showed clean conversion to a new compound.
2.wmerization All transfers of solvents and solutions described below were accomplished using a gaseous pad of dry, purified nitrogen or argon. Gaseous feeds to the reactor were purified by passage through columns of A-204 alumina and QS reactant. Alumina was previously activated at 375°C with nitrogen and QS reactant was activated at 200°C with Spercent hydrogen in nitrogen. Manipulations of catalyst and cocatalyst (tris pentafluorophenyl borane) were carried out in an inert atmosphere glove box.
The semi-batch reactor polymerization was conducted in a two liter Parr reactor with an electrical heating jacket, internal serpentine coil for cooling, and a bottom drain valve. Pressures, temperatures and block valves were computer monitored and controlled.
Isopar E and styrene were measured in a solvent shot tank fitted to a balance.
The resulting solution was then added to the reactor from the solvent shot tank.
The contents of the reactor were stirred at 1200 rpm. Hydrogen was added by differential expansion (ca. 50 psi) from a 75 ml shot tank initially at 300 psig. The contents of the reactor were then heated to the desired run temperature (90°C) under the desired ethylene pressure.
The catalyst, [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane)-dimethyltitanium and cocatalyst, tris(pentafluorophenyl)borane, were combined in the glove box (as 0.0050 M solutions in toluene)and transferred from the glove box to the catalyst shot tank through 1/16 in (0.16 cm) tubing using toluene to aid in the transfer.
The catalyst tank was then pressurized using nitrogen. After the contents of the reactor had stabilized at the desired run temperature, the catalyst solution was injected into the reactor via a dip tube. The temperature was maintained by allowing cold glycol to pass through the internal cooling coils. The reaction was allowed to proceed for the desired time with ethylene provided on demand. Additional injections of catalyst were prepared and added in the same manner during the course of the run.
The contents of the reactor were then expelled into a 4 liter nitrogen purged vessel and quenched with isopropyl alcohol and 100 mg of Irganox 1010 in toluene was added as an antioxidant. Volatile materials were removed from the polymers in a vacuum oven at 140°C overnight and cooled to 50°C prior to removal from the oven. Reactor conditions and polymerization data were given in Table I.
Table I: Reactor Conditions/Run Data Examp Catalyst CocatalStyren IsoparTEthyleTime Yiel 1e ( mol) yst a (g) M E ne (min) d # (g) ( mol) (psig) (g) 1 18.0 18.0 229 538 S00 30 3.9 2 18.0 18.0 455 358 500 39 56.
3 16.0 16.0 457 360 200 30 51.
4 18.0 27.0 602 - 200 30 56.
18.0 27.0 602 - 100 30 34:
6 18.0 27.0 602 - 50 30 22.
5 Polymer Characterization An LC method using gradient solvent polarity was used to separate the interpolymer from the aPS and the retention time of the interpolymer peak was indicative of its styrene content.
Shown in Table II were composition, apparent molecular weight (polystyrene standards) and density data for the polymers reported herein.
Table II: Polymer Composition, Molecular Weight and Density Data ExamplMole percentWt percentperce Mw Mn Mw/Mn Density a # Styrene Styrene t aPS (g/cm3) 1 24.7 54.9 <1 -- -- -- 0.9979 2 45.8 75.9 <1 -- -- -- 1.028 3 53.8" 81.2" (78.1B)1.7 660,000287,0002.30 1.028 (49.0)B
4 56.6" 82.9" (80.4B10.3 684,000198,0003.45 1.031 (52.5)B ) 63.5~ 86.6" (84.9B)18.3 583,000133,0004.38 1.037 (60.2)B
6 74.6A 91.6A (91.0B)33.5 541,00098,500 5.49 1.038 (73.1)B
A From LC data with nitro column.
B From LC data with C 18 column.
5 C From proton NMR data.
With the information that these copolymers contained aPS, the SSS triad peaks in their '3C NMR spectra could be assigned. A very small EEE triad peak indicated that the interpolymers had very few and short ethylene sequences.
These materials all display either low levels of crystallinity, or were amorphous. As a result, the density of these polymers increases with increasing styrene content and approaches 1.06 g/cc, the density of aPS.
The molecular weight data shows that the catalyst can produce high molecular weight polymers. Since a dual detector was used in the GPC analysis, it was possible to examine the ratio of refractive index divided by UV response across the molecular weight range. This ratio was found not to change much indicating that the composition was relatively uniform across the entire molecular weight range; a slight increase in the styrene content at very low molecular weights was seen in all of the samples. This was consistent with the presence of aPS in these materials.
Materials Properties The thermal transition data as determined by DSC were given in Table III.
Table III Thermal Transitions (DSC) ExamplStyrene Styrene Tg; Tm,C Hf, J/g a # (mol percent)(weight C
percent) 1 24.7 54.9 31.9 123 26.5 2 45.8 75.9 32.5 119 1.7 3 53.8" (49.0)B81.2A (78.139.7 - -- --B ) 4 56.6~ (52.5)B82.9" (80.4B44.2 -- --) 63.5A (60.2)B86.6A (84.9B)55.5 -- --6 74.6" (73.191.6" (91.0B)70.3 -- --)B
A From LC data with nitro column.
B From LC data with C18 column.
5 C From proton NMR data.
As expected, the Tg of these materials was found to increase with increasing styrene content. The last two entries, which were well beyond the composition range of earlier pseudo random materials, show that the Tg rapidly approaches that of aPS (ca.
100°C) as the styrene content approaches near 100 percent. It should also be noted that none of the materials showed a pronounced Tg due to aPS homopolymer. The LC data, however, show aPS in the isolated materials. The polymer with the highest crystallinity (the lowest styrene content 55 wt percent S) displayed a peak melting temperature near 120°C and a Tg near 32°C.
Micro-tensile testing and fracture toughness testing was performed to assess the mechanical properties of these materials, Table IV. Short term tensile analysis showed a relatively glassy response with a high modulus at low tensile stress and a relatively linear stress/strain relationship for all of the materials up to about 2percent strain. The Young's modulus for all of these materials was in the range of 350,000-430,000 psi (2.4-3 GPa). All of the materials underwent a ductile yield at relatively low strains, with the yield strain moving steadily to lower elongation with increasing styrene content. All of the polymers exhibited slight drawing past the yield point up to ultimate failure.
Table IV Microtensile, Fracture Toughness and Hardness Data Ex Wt Yield percentBreak percentYoung's ardnessa #
percentStressStrainStress StrainModulus psi Styrene(psi) at (psi) at (sd) Yield Break 1 54.9 - - - - - 56 2 75.9 - - - - - 86 3 78.1 6,870 2.7 6,720 3.1 -347,000 86 (33,000) 4 80.4 6,950 2.3 6,550 2.9 365,000 89 (48,000) 84.9 7,130 2.1 6,540 4.9 434,000 100 (36,000) 6 91.0 6,320 1.9 6,250 2.5 376,000 99 (68,000) aRockwell scale Fracture toughness was measured using compact tension geometry samples. These experiments were designed to quantify the polymer's resistance to initiation and propagation of the crack with respect to an applied load. The test was performed on a compression-molded square of the polymer, which was notched, and a razor blade was used to produce a crack at the V
of the notch. A tensile load was then applied to the sample in plane stress;
the specimen prepared was ideally thick enough to prevent twisting out the plane of the applied load. The resultant relationship between load and displacement allows for determination of the instantaneous stress required to propagate the crack, known as the stress intensity factor Klc. It was also useful to define the energy required to extend the crack over a given unit area; this quantity was denoted Glc, (the fracture energy or critical strain-energy release rate) and it related to Klc by equation 1:
Gm _ (Knz/E)(1-2) (1) where E was Young's modulus and is Poisson's ratio. Larger values of Klc and Glc mean increased fracture toughness.
Fracture toughness measurements did not show meaningful differences from sample to sample for the materials, which were tested. Table V gives the critical stress intensity factor (K1 C) values for the four samples with the highest styrene content, and data obtained under the same test conditions for a high molecular weight free radically polymerized polystyrene homopolymer. The copolymers show considerably higher K1C and G1C values, and the load to yield and to break were considerably higher for the copolymers than for polystyrene homopolymer.
The improved toughness of these materials with respect to polystyrene may arise from the ability of the ethylene units incorporated to induce a more ductile response to applied stress on the time scale of the fracture test.
Table V Fracture Toughness Data for ES Copolymers Ex # Wt K,~ Maximum Yield Energy G,~"
percent (Mpa Load Point to (J/m2) Styrene m0.5) (lbfj Energy Break (lbf in) (lbf in) Ex 3 78.1 2.9 59.5 0.95 2.9 3,130 Ex 4 80.4 2.8 67.6 1.3 2.8 2,770 Ex 5 84.9 3.4 56.8 0.94 2.1 3,430 Ex 6 91 2.9 46.6 0.97 2.6 2,880 Comp 100B 2.2 28.7 0.34 0.52 1,400 Expt A Calculated using the measured Young's modulus and a Poisson's ratio of 0.33 B Free radical aPS, Mn=114,720, Mw=282,970, Mw/Mn=2.47 C Calculated from Klc using published values for Young's modulus (3.1 GPa) and Poisson's ratio (0.33) for high molecular weight PS (Encyclopedia of Polymer Science and Engineering, Vol. 16, 2 nd Ed., John Wiley & Sons, 1989, pp. 1-246) DMS analysis of the non-crystalline interpolymers was performed to determine the position of the glass transition and to identify other transitions associated with these materials.
The glass transition temperature and room sub-Tg storage modulus increase with increasing styrene content in the copolymer.
In the shear loss modulus (G") response of the non-crystalline ES copolymers , the glass transition temperatures for these materials were clearly observed, and a broad transition was seen between ca. -50°C and room temperature. In polystyrene, this transition has been attributed to backbone relaxation that accompanies phenyl ring dislocation.
The physical properties of the high styrene content interpolymers of the present invention indicate have improved resistance to fracture. This suggests that these interpolymers may provide unique utility in certain applications. The amorphous interpolymers at the highest styrene levels were transparent, so that these polymers may have utility in film applications and may be advantaged with respect to aPS due to their increased toughness. Furthermore, foam sheets of these new polymers may show better resiliency than aPS sheets and may perform better in applications where improved durability was required. These polymers might also be used to toughen aPS while retaining good transparency, if compositions can be found which display compatibility.
Additives such as antioxidants (for example, hindered phenols such as, for example, Irganox~ 1010 a registered trademark of Ciba Geigy), phosphites (for example, Irgafos~ 168 a registered trademark of Ciba Geigy), U.V. stabilizers, cling additives (for example, polyisobutylene), slip agents (such as erucamide and/or stearamide), antiblock additives, colorants, pigments, tackifiers, flame retardants, coupling agents, fillers, plastcizers can also be included in the compositions of the present invention.
Also included as a potential component in the compositions of the present invention are various organic and inorganic fillers. Representative examples of such fillers include organic and inorganic fibers such as those made from asbestos, boron, graphite, ceramic, glass, metals (such as stainless steel) or polymers (such as aramid fibers) talc, carbon black, carbon fibers, calcium carbonate, alumina trihydrate, glass fibers, marble dust, cement dust, clay, feldspar, silica or glass, fumed silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, ammonium polyphosphate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B203, nickel powder or chalk.
Other representative organic or inorganic fiber or mineral fillers include carbonates such as barium, calcium or magnesium carbonate; borates such as magnesium or zinc borate, fluorides such as calcium or sodium aluminum fluoride;
hydroxides such as aluminum hydroxide; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum, antimony, magnesium or zinc oxide, or silicon or titanium dioxide;
silicates _7_ such as asbestos, mica, clay (kaolin or calcined kaolin), calcium silicate, feldspar, glass (ground or flaked glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; sulfates such as barium or calcium sulfate; metal sulfides; cellulose, in forms such as wood or shell flour; calcium terephthalate; and liquid crystals. Mixtures of more than one such filler may be used as well.
The fillers may also be used in conjunction with a coupling agent and/or initiator selected from organic peroxides, silanes, titanates, zirconates,_multi-functional vinyl compounds, organic azides, and mixtures thereof.
Other additives include the hindered amine stabilizers. Such stabilizers include hindered triazines such as substituted triazines and reaction products of triazines. Suitable reaction products include the reaction product of triazine with, for example, diamines and/
or cycloaliphatic compounds such as cyclohexane. A particularly suitable hindered amine stabilizer includes the reaction product of 1, 3-propanediamine, N,N"-1,2-ethanediylbis-, cyclohexane and peroxidized N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine which ismade commercially by Ciba-Geigy and has the name "CG-116 having CAS Reg No. : 191680-81-6.
These additives are employed in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant employed is that amount which prevents the polymer or polymer blend from undergoing oxidation at the temperatures and environment employed during storage and ultimate use of the polymers. Such amount of antioxidants is usually in the range of from 0.01 to 10, preferably from 0.05 to 5, more preferably from 0.1 to 2 percent by weight based upon the weight of the polymer or polymer blend. Similarly, the amounts of any of the other enumerated additives are the functionally equivalent amounts such as the amount to render the polymer or polymer blend antiblocking, to produce the desired result, to provide the desired color from the colorant or pigment. Such additives can suitably be employed in the range of from 0.05 to 50, preferably from 0.1 to 35, more preferably from 0.2 to 20 percent by weight based upon the weight of the interpolymer. Fillers may suitably be employed in the range 1-90 wt.percent.
The polymers of the present invention can be blended with additional polymers including but not limited to; other interpolymers of different molecular weight and/or _g_ vinyl or vinylidene aromatic monomer content, substantially random interpolymers vinyl and vinylidene halide polymers including but not limited to polyvinyl chloride) and poly(vinylidene chloride), polyethylene, and other polyolefins including but not limited to LDPE, and HDPE, PP, homogeneous ethylene/alpha-olefin copolymers produced by metallocene catalysts, including but not limited to the substantially linear ethylene/alpha-olefin copolymers and heterogeneous and heterogeneous ethylene/alpha-olefin copolymers produced by Ziegler catalysts; styrenic polymers including but not limited to polystyrene, SBS copolymers, polyethers, polycarbonates, polyanilines, asphalt, or any combinations thereof.
The interpolymers of the present invention, or blends thereof, can be fabricated into various forms including but not limited to films, fibers, foams, sheets, injection molded articles, membranes, injection-blow molded articles and extruded profiles, and emulsions. Applications for the interpolymers of the present invention, or blends thereof, include, but are not limited to, ignition resistant articles, pressure sensitive filmstock, coating compositions or paints, floor, ceiling and wall coverings, carpet backing, barriers, gaskets, caps and closures, and, with the addition of conductive additives such as carbon black, various conductive applications including electrical devices, conductor shields, insulation shields, and other wire and cable applications. Other applications include as compatibilizers in blends of polystyrene and ethylene and/or alpha-olefin homo-and copolymers. Also included are applications for the sulfonated derivatives including their use in fuel cell membranes, water absorbent applications and HVAC equipment.
Determining the composition of the ethylene/styrene interpolymers of the present invention can be ambiguous using NMR methods of analysis. This ambiguity arises from the fact that the styrene triads and higher order styrene insertions have peaks in both the 'H and'3C spectra that can not be distinguished from peaks of the ubiquitous amorphous atactic polystyrene homopolymer (aPS) which is present in small amounts in the interpolymers. However use of a liquid chromatography (LC) method using gradient solvent polarity allows separation of the interpolymer from the aPS, and the retention time of the interpolymer peak is indicative of its styrene content.
The interpolymer compositions of the present invention comprise from 5 to 85, preferably from 20 to 85, more preferably from 50 to 85 mole percent of at least one vinyl or vinyl or vinylidene aromatic monomer and from 15 to 95, preferably from 15 to 80, more preferably from 15 to 50 mole percent of ethylene and/or at least one aliphatic alpha-olefin having from 3 to 20 carbon atoms.
The melt index (I2) of the interpolymer of the present invention is greater than 0.05, preferably of from 0.5 to 200, more preferably of from 0.5 to 100 g/10 min.
The molecular weight distribution (Mw/Mn) of the interpolymers of the present invention is from 1.5 to 20, preferably of from 1.8 to 10, more preferably of from 2 to 5.
The interpolymer compositions of the present invention contain detectable vinyl aromatic monomer triads. In the case of an ethylene/styrene interpolymer this would correspond to an -SSS- triad. Such triads may also be a part of a longer sequence of vinyl or vinylidene aromatic insertions insertions such as SSSS tetrads, SSSSS
pentads. When any atactic polystyrene impurity is separated out from the polymer, these triads are detectable by the presence of a peak in the'3C NMR which occurs at a chemical shift corresponding to the methine carbons in the polymer backbone of an ethylene/styrene interpolymer at 44.6 ppm (ESSSE).
The following examples are illustrative of the invention, but are not to be construed as to limiting the scope thereof in any manner.
EXAMPLES
Test Methods The molecular weight of the polymer compositions of the present invention is conveniently indicated using Gel Permeation Chromatography using both UV and Refractive Index detectors.
In order to determine the '3C NMR chemical shifts of the interpolymers of the present invention, the following procedures and conditions are employed. A
five to ten weight percent polymer solution is prepared in a mixture consisting of 50 volume percent 1,1,2,2-tetrachloroethane-d2 and 50 volume percent 0.10 molar chromium tris(acetylacetonate) in 1,2,4-trichlorobenzene. NMR spectra are acquired at 130°C using an inverse gated decoupling sequence, a 90°-pulse width and a pulse delay of five seconds or more. The spectra are referenced to the isolated methylene signal of the polymer assigned at 30.000 ppm.
Materials Testing Polymer samples were formed into the shapes required for physical property determination by compression molding at 150°C using a ten minute preheat, 3 minute compression at 10000 pounds force, and immediate cool down.
Differential Scanning Calorimetry (DSC) analysis of this polymer was performed under a nitrogen atmosphere at a heating rate of 5°C/minute using a DuPont Instruments 910 Differential Scanning Calorimeter. All samples were taken through two heating cycles (to remove the effects of previous heat history) and data are reported for the second scan in all cases.
Micro-tensile testing was performed using compression molded micro-tensile bars as per ASTM D638 testing protocol. The samples were pulled using an Instron Series instrument at a cross-head speed of 0.1 inches/minute and a 224.8 lbf load cell at room temperature.
Plain-strain fracture toughness, compact tension single-edge notch geometry samples were compression molded into 1" by 1" by 1/8" squares. These squares were machined to provide a side notch and holes for attachment to the testing apparatus. A pre-crack was formed in each sample by cooling with liquid nitrogen and cracking with a razor blade and hammex. Fracture toughness testing was performed using an Instron 8501 instrument at a cross-head speed of 0.02 in/min with a 224.8 lbf load cell.
Dynamic mechanical spectroscopy was performed on a rectangular bar, which was compression molded at 100°C. Temperature sweeps ranging from -100°C to 150°C were performed at a set frequency of 1 rad/sec with an auto-strain function set by the DMS
instrument.
Density was measured using a helium pycnometer. Rockwell hardness was assessed using ASTM D785-93.
L.C. Analysis.
Between 0.100 and 0.102 grams of polymer were weighed into a 30 ml vial. 10 ml of THF was added. The vial was capped and placed on a heated shaker so as to dissolve the sample. The temperature of the heated shaker was 65° C.
After dissolution, about 1 ml of the solution was transferred to an HP 1090 LC auto-injector vial. A
Hewlett-Packard 1090 LC (serial number 2541A00700) with a diode array detector was used for the collection of all chromatographic data. Signals were collected at 254 nm and 400 nm. The chromatographic data were processed using Grams386 and Excel software.
Two columns were used to determine the styrene contents of the resins by liquid chromatography. Use of either column initially involved determination of the atactic polystyrene content (which peak was clearly discernible). This value was then subtracted from the total styrene content of the sample as determined by 13C N.M.R to give the wtpercent copolymerized styrene. A calibration curve of copolymerized styrene v.
retention time (at the 50'" percentile of the chromatogram peak) was then constructed and the resulting fit was then applied to all new samples. This analysis was performed using two types of column.
The first of these was a C 18 column was obtained from Alltech: Spherisorb ODS
II 5 micron, 250 x 4.60 mm. There was a guard column on the C18 column. It was an RP
8.5 micron. Below are the instrumental conditions used on the HP 1090 with the column).
Solvent A = AcetonitrileAt 24.00 Flow = 1.000 Solvent B = THF At 24.00 percent B =
100.0, C =
Solvent C = 2-Propanol At 25.00 Flow = 1.000 Store Flow 1; At 25.00 percent B =
1.0, C = 0.0 Stop Time=30.00 At 30.00 Flow = 1.000 Post Time = 0.00 At 30.00 percent B =
1.0, C = 0.0 SDS-Config A=1,B=1,C=1 Max Press = 400 Stop time = system Min Press = 8 Post time = 1.00 minute B=1.O,C=0.0 Auto balance = on Injection Volume=10.0 Peak width = 0.100 Oven Temp = 50.0 Spectra Range=240, 600, At 1.00 Flow =1.000 ml/minStore Spectra = peak At 1.00 percent B=1.0,C=0.0Threshold=1.000 At 20.00 Flow =1.000 Signal A=254, 4, 550, At 20.00 percent B=100.0,C=0.0Signal B=400, 4, 550, The second and best column of the two was a nitro column obtained from Phenomenex: Nucleosil 5 N02 250 x 4.60 mm, 5 micron, serial number 243745.
There was a guard column on the nitro column. It was a Phenomenex Nucleosil 5 N02 30 x 4.6 mm, 5 micron 100 angstrom, serial number 2437476. Below are the instrumental conditions used on the HP 1090 with the Nitro2 method (nitro column).
Solvent A = Hexanes At 20.00 Flow=1.000 Solvent B = THF At 20.00 percent B=70.O,C=0.0 Solvent C = 2-propanol At 23.00 Flow=1.000 Store A 1; At 23.00 percent B=70.O,C=0.0 Store B 1; At 24.00 Flow=1.000 Store C 1; At 24.00 percent B=3.O,C=0.0 Store Flow 1; At 30.00 Flow=1.000 Store Temp l; At 30.00 percent B=3.O,C=0.0 Stop Time=30.00 minutes Post Time=0.00 minutes SDS-Config A=1, B=1, Stop Time = System C=1 Flow=1.000 ml/min Post Time=1.00 minute Max Press=400 bar Auto Balance = on Min Press=8 Peakwidth=0.100 percent B=3.O,C=0.0 Spectra Range=240, 600, Inj volum=10.0 1 Store Spectra = peak Oven Temp=30.0 c Threshold=1.000 At 1.00 Flow=1.000 Signal A=254, 4, 550, At 1.00 percent B=3.O,C=0.0Signal B=400, 4, 550, The regression equation used to determine the styrene content on this column was:
[sty] wtpercent = -84.89 + 10.98 * retention time (mins) Preparation of the Examples 1 - 6 of the Inter~olymers of the Present Invention.
1~ Preparation of Catalyst General Syntheses and manipulations were carried out in an inert atmosphere (argon) glove box. Solvents were purchased from Aldrich. Liquid reagents and solvents were first saturated with nitrogen and then dried by passage through activated alumina prior to use as disclosed by Pangborn, A.B.; Giardello, M.A.; Grubbs, R.H.; Rosen, R.K.;
Timmers, F.J. in Organometallics, 1996, I5, 1518- 1520 . Deuterated benzene was dried over sodium/potassium alloy and filtered prior to use. Methylene phenanthrene was purchased from Lancaster. NMR spectra of ligands and metal complexes were recorded on a Varian 300 MHz NMR spectrometer at ambient conditions. '''C NMR spectra of the copolymers were recorded on a Bruker 600 MHz spectrometer.
Synthesis of Lithium Methylenephenanthrenide To 4,5-methylenephenanthrene (0.485 g, 2.55 mmol) in 50 mL of hexanes was added 1.6 M n-BuLi in hexanes ( 1.75 mL, 2.80 mmol). After one day of stirring at ambient conditions the solution appeared darker orange and a small amount of orange precipitated had formed. After 14 days much more precipitate had formed. This was isolated by decanting the supernatant from the solid which stuck to the inside walls of the flask. After drying under reduced pressure, 0.430 g were isolated (86percent yield).
Volatile materials were removed from the supernatant to give an orange solid.
Proton NMR analysis of this material showed it to be the starting methylenephenanthrene.
Synthesis of (4,5-methylenephenanthrenyl)(tert-butylamino)dimethylsilane To (tert-butylamino)dimethylsilyl chloride (0.436 g, 2.63 mmol) in 30 mL THF
was added a cherry red solution of lithium methylenephenanthrenide (0.430 g, 2.19 mmol) in 20 mL THF. The solution was allowed to stir at ambient temperature overnight.
The volatile materials were removed under reduced pressure. The solid residue was slurried in 10 mL hexanes and the volatile materials were removed under reduced pressure. The solid residue was extracted twice with a total of 30 mL hexanes.
The extracts were filtered and the volatile materials were removed from the combined filtrates under reduced pressure to give 0.690 g (99percent yield) of an orange oil.
The'H NMR
spectrum was consistent with the desired product.
Synthesis of [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane]titanium bis(dimethylamide) A solution of the titanium tetrakis amide (0.484 g, 2.16 mmol) and (4,5-methylenephenanthrenyl)(tert-butylamino)dimethylsilane (0.690 g, 2.16 mmol) in 50 mL
n-octane was heated and stirred at reflux. The course of the reaction was monitored by'H
NMR spectroscopy by removing a small aliquot of the solution, removing the volatile materials under reduced pressure, and analyzing the residue in C6D6. Proton NMR
analysis showed clean conversion to the desired product (for example SSpercent conversion after ca. 48 hours reflux.) Several drops of titanium tetrakis amide were added periodically. After seven days at reflux, the reaction appeared not to be progressing past 82percent conversion. The volatile materials were removed from the cooled mixture under reduced pressure. The residue was dissolved in 20 mL of hexanes and the resulting mixture was filtered. The volatile materials were removed from the filtrate under reduced pressure to give a dark powder (0.950 g). Proton NMR analysis of the product showed it to be a mixture of the desired product and the starting ligand, 82/18 mole percent, respectively (87 weight percent of the desired product).
Synthesis of [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane]titanium dichloride To the bis(amide)/ligand mixture isolated above (0.83.g, 1.83 mmol of the bis(amide)) issolved in 40 mL hexanes was added trimethylsilyl chloride (1.33 mL, 10.5 mmol). The solution was stirred at reflux for six hours. A small aliquot of the cooled solution was removed and the volatile materials were removed under reduced pressure.
The residue was dissolved in C6D6 and analyzed by'H NMR spectroscopy. The spectrum showed very clean conversion to the monochloride-monoamide intermediate. An additional 1.3 mL of trimethylsilyl chloride was added and the sealed vessel was stirred at ambient temperature for eight days. The solution was then heated to reflux for six hours.
The cooled solution was placed in the glove box freezer (-25°C). The solids that formed were collected on a glass frit by vacuum filtration. The solid residue was washed once with cold hexanes (ca. 10 mL) and the solid was then dried under reduced pressure to give 0.516 g (65percent yield). Proton NMR analysis showed the material was consistent with very clean desired product.
Synthesis of [(4,5-methylenephenanthrenyl)(tertbutylamido)-dimethylsilane]
dimethyltitanium To the dichloride (0.516 g, 1.18 mmol) in 30 mL of THF was added 3.0 M
methylmagnesium chloride (0.87 mL, 2.6 mmol) which resulted in an immediate color change. After standing overnight, the volatile materials were removed under reduced pressure. The solid residue was slurried in hexanes and the volatile materials were removed under reduced pressure. The residue was extracted several times with hexanes.
The extracts were filtered and the volatile materials were removed from the combined filtrates under reduced pressure to give a bright orange powder, 0.392 g.
Proton and'3C
NMR analysis in C6D6 shows that the desired product was isolated as a 1 to 1 adduct with THF. Assuming a molecular weight was 467.6 g/mol, the isolated yield was 71 percent.
The THF adduct (0.345 g) was dissolved in 50 mL toluene and heated at reflux for six hours. A color change from orange to brown-yellow was observed. The volatile materials were removed under reduced pressure. Proton NMR analysis of the residue showed clean conversion to a new compound.
2.wmerization All transfers of solvents and solutions described below were accomplished using a gaseous pad of dry, purified nitrogen or argon. Gaseous feeds to the reactor were purified by passage through columns of A-204 alumina and QS reactant. Alumina was previously activated at 375°C with nitrogen and QS reactant was activated at 200°C with Spercent hydrogen in nitrogen. Manipulations of catalyst and cocatalyst (tris pentafluorophenyl borane) were carried out in an inert atmosphere glove box.
The semi-batch reactor polymerization was conducted in a two liter Parr reactor with an electrical heating jacket, internal serpentine coil for cooling, and a bottom drain valve. Pressures, temperatures and block valves were computer monitored and controlled.
Isopar E and styrene were measured in a solvent shot tank fitted to a balance.
The resulting solution was then added to the reactor from the solvent shot tank.
The contents of the reactor were stirred at 1200 rpm. Hydrogen was added by differential expansion (ca. 50 psi) from a 75 ml shot tank initially at 300 psig. The contents of the reactor were then heated to the desired run temperature (90°C) under the desired ethylene pressure.
The catalyst, [(4,5-methylenephenanthrenyl)(tert-butylamido)dimethylsilane)-dimethyltitanium and cocatalyst, tris(pentafluorophenyl)borane, were combined in the glove box (as 0.0050 M solutions in toluene)and transferred from the glove box to the catalyst shot tank through 1/16 in (0.16 cm) tubing using toluene to aid in the transfer.
The catalyst tank was then pressurized using nitrogen. After the contents of the reactor had stabilized at the desired run temperature, the catalyst solution was injected into the reactor via a dip tube. The temperature was maintained by allowing cold glycol to pass through the internal cooling coils. The reaction was allowed to proceed for the desired time with ethylene provided on demand. Additional injections of catalyst were prepared and added in the same manner during the course of the run.
The contents of the reactor were then expelled into a 4 liter nitrogen purged vessel and quenched with isopropyl alcohol and 100 mg of Irganox 1010 in toluene was added as an antioxidant. Volatile materials were removed from the polymers in a vacuum oven at 140°C overnight and cooled to 50°C prior to removal from the oven. Reactor conditions and polymerization data were given in Table I.
Table I: Reactor Conditions/Run Data Examp Catalyst CocatalStyren IsoparTEthyleTime Yiel 1e ( mol) yst a (g) M E ne (min) d # (g) ( mol) (psig) (g) 1 18.0 18.0 229 538 S00 30 3.9 2 18.0 18.0 455 358 500 39 56.
3 16.0 16.0 457 360 200 30 51.
4 18.0 27.0 602 - 200 30 56.
18.0 27.0 602 - 100 30 34:
6 18.0 27.0 602 - 50 30 22.
5 Polymer Characterization An LC method using gradient solvent polarity was used to separate the interpolymer from the aPS and the retention time of the interpolymer peak was indicative of its styrene content.
Shown in Table II were composition, apparent molecular weight (polystyrene standards) and density data for the polymers reported herein.
Table II: Polymer Composition, Molecular Weight and Density Data ExamplMole percentWt percentperce Mw Mn Mw/Mn Density a # Styrene Styrene t aPS (g/cm3) 1 24.7 54.9 <1 -- -- -- 0.9979 2 45.8 75.9 <1 -- -- -- 1.028 3 53.8" 81.2" (78.1B)1.7 660,000287,0002.30 1.028 (49.0)B
4 56.6" 82.9" (80.4B10.3 684,000198,0003.45 1.031 (52.5)B ) 63.5~ 86.6" (84.9B)18.3 583,000133,0004.38 1.037 (60.2)B
6 74.6A 91.6A (91.0B)33.5 541,00098,500 5.49 1.038 (73.1)B
A From LC data with nitro column.
B From LC data with C 18 column.
5 C From proton NMR data.
With the information that these copolymers contained aPS, the SSS triad peaks in their '3C NMR spectra could be assigned. A very small EEE triad peak indicated that the interpolymers had very few and short ethylene sequences.
These materials all display either low levels of crystallinity, or were amorphous. As a result, the density of these polymers increases with increasing styrene content and approaches 1.06 g/cc, the density of aPS.
The molecular weight data shows that the catalyst can produce high molecular weight polymers. Since a dual detector was used in the GPC analysis, it was possible to examine the ratio of refractive index divided by UV response across the molecular weight range. This ratio was found not to change much indicating that the composition was relatively uniform across the entire molecular weight range; a slight increase in the styrene content at very low molecular weights was seen in all of the samples. This was consistent with the presence of aPS in these materials.
Materials Properties The thermal transition data as determined by DSC were given in Table III.
Table III Thermal Transitions (DSC) ExamplStyrene Styrene Tg; Tm,C Hf, J/g a # (mol percent)(weight C
percent) 1 24.7 54.9 31.9 123 26.5 2 45.8 75.9 32.5 119 1.7 3 53.8" (49.0)B81.2A (78.139.7 - -- --B ) 4 56.6~ (52.5)B82.9" (80.4B44.2 -- --) 63.5A (60.2)B86.6A (84.9B)55.5 -- --6 74.6" (73.191.6" (91.0B)70.3 -- --)B
A From LC data with nitro column.
B From LC data with C18 column.
5 C From proton NMR data.
As expected, the Tg of these materials was found to increase with increasing styrene content. The last two entries, which were well beyond the composition range of earlier pseudo random materials, show that the Tg rapidly approaches that of aPS (ca.
100°C) as the styrene content approaches near 100 percent. It should also be noted that none of the materials showed a pronounced Tg due to aPS homopolymer. The LC data, however, show aPS in the isolated materials. The polymer with the highest crystallinity (the lowest styrene content 55 wt percent S) displayed a peak melting temperature near 120°C and a Tg near 32°C.
Micro-tensile testing and fracture toughness testing was performed to assess the mechanical properties of these materials, Table IV. Short term tensile analysis showed a relatively glassy response with a high modulus at low tensile stress and a relatively linear stress/strain relationship for all of the materials up to about 2percent strain. The Young's modulus for all of these materials was in the range of 350,000-430,000 psi (2.4-3 GPa). All of the materials underwent a ductile yield at relatively low strains, with the yield strain moving steadily to lower elongation with increasing styrene content. All of the polymers exhibited slight drawing past the yield point up to ultimate failure.
Table IV Microtensile, Fracture Toughness and Hardness Data Ex Wt Yield percentBreak percentYoung's ardnessa #
percentStressStrainStress StrainModulus psi Styrene(psi) at (psi) at (sd) Yield Break 1 54.9 - - - - - 56 2 75.9 - - - - - 86 3 78.1 6,870 2.7 6,720 3.1 -347,000 86 (33,000) 4 80.4 6,950 2.3 6,550 2.9 365,000 89 (48,000) 84.9 7,130 2.1 6,540 4.9 434,000 100 (36,000) 6 91.0 6,320 1.9 6,250 2.5 376,000 99 (68,000) aRockwell scale Fracture toughness was measured using compact tension geometry samples. These experiments were designed to quantify the polymer's resistance to initiation and propagation of the crack with respect to an applied load. The test was performed on a compression-molded square of the polymer, which was notched, and a razor blade was used to produce a crack at the V
of the notch. A tensile load was then applied to the sample in plane stress;
the specimen prepared was ideally thick enough to prevent twisting out the plane of the applied load. The resultant relationship between load and displacement allows for determination of the instantaneous stress required to propagate the crack, known as the stress intensity factor Klc. It was also useful to define the energy required to extend the crack over a given unit area; this quantity was denoted Glc, (the fracture energy or critical strain-energy release rate) and it related to Klc by equation 1:
Gm _ (Knz/E)(1-2) (1) where E was Young's modulus and is Poisson's ratio. Larger values of Klc and Glc mean increased fracture toughness.
Fracture toughness measurements did not show meaningful differences from sample to sample for the materials, which were tested. Table V gives the critical stress intensity factor (K1 C) values for the four samples with the highest styrene content, and data obtained under the same test conditions for a high molecular weight free radically polymerized polystyrene homopolymer. The copolymers show considerably higher K1C and G1C values, and the load to yield and to break were considerably higher for the copolymers than for polystyrene homopolymer.
The improved toughness of these materials with respect to polystyrene may arise from the ability of the ethylene units incorporated to induce a more ductile response to applied stress on the time scale of the fracture test.
Table V Fracture Toughness Data for ES Copolymers Ex # Wt K,~ Maximum Yield Energy G,~"
percent (Mpa Load Point to (J/m2) Styrene m0.5) (lbfj Energy Break (lbf in) (lbf in) Ex 3 78.1 2.9 59.5 0.95 2.9 3,130 Ex 4 80.4 2.8 67.6 1.3 2.8 2,770 Ex 5 84.9 3.4 56.8 0.94 2.1 3,430 Ex 6 91 2.9 46.6 0.97 2.6 2,880 Comp 100B 2.2 28.7 0.34 0.52 1,400 Expt A Calculated using the measured Young's modulus and a Poisson's ratio of 0.33 B Free radical aPS, Mn=114,720, Mw=282,970, Mw/Mn=2.47 C Calculated from Klc using published values for Young's modulus (3.1 GPa) and Poisson's ratio (0.33) for high molecular weight PS (Encyclopedia of Polymer Science and Engineering, Vol. 16, 2 nd Ed., John Wiley & Sons, 1989, pp. 1-246) DMS analysis of the non-crystalline interpolymers was performed to determine the position of the glass transition and to identify other transitions associated with these materials.
The glass transition temperature and room sub-Tg storage modulus increase with increasing styrene content in the copolymer.
In the shear loss modulus (G") response of the non-crystalline ES copolymers , the glass transition temperatures for these materials were clearly observed, and a broad transition was seen between ca. -50°C and room temperature. In polystyrene, this transition has been attributed to backbone relaxation that accompanies phenyl ring dislocation.
The physical properties of the high styrene content interpolymers of the present invention indicate have improved resistance to fracture. This suggests that these interpolymers may provide unique utility in certain applications. The amorphous interpolymers at the highest styrene levels were transparent, so that these polymers may have utility in film applications and may be advantaged with respect to aPS due to their increased toughness. Furthermore, foam sheets of these new polymers may show better resiliency than aPS sheets and may perform better in applications where improved durability was required. These polymers might also be used to toughen aPS while retaining good transparency, if compositions can be found which display compatibility.
Claims (17)
1. An interpolymer comprising;
(1) from 5 to 85 mol percent of polymer units derived from at least one vinyl or vinylidene aromatic monomer, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.
(1) from 5 to 85 mol percent of polymer units derived from at least one vinyl or vinylidene aromatic monomer, (2) from 15 to 95 mol percent of polymer units derived from at least one of ethylene and/or a C3-20 alpha-olefin; and (3) from 0 to 20 mol percent of polymer units derived from one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2); and wherein said interpolymer contains detectable vinyl or vinylidene aromatic monomer triads.
2. The interpolymer of Claim 1; wherein (1) Component (1) comprises from 20 to 85 mol percent of polymer units derived from said vinyl or vinylidene aromatic monomer represented by the following formula;
wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (2) from 15 to 80 mol percent of polymer units derived from ethylene and/or said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-l, hexene-1 or octene-1; and (3) said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) comprises norbornene, or a C1-10 alkyl or C6-10 aryl substituted norbornene.
wherein R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (2) from 15 to 80 mol percent of polymer units derived from ethylene and/or said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-l, hexene-1 or octene-1; and (3) said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) comprises norbornene, or a C1-10 alkyl or C6-10 aryl substituted norbornene.
3. The interpolymer of Claim 1; wherein (1) Component (1) comprises from 50 to 85 mol percent of polymer units derived from said vinyl aromatic monomer which comprises styrene, alpha-methyl styrene, ortho-, meta-, and para-methylstyrene, and the ring halogenated styrenes, or (2) from 15 to 50 mol percent of polymer units derived from ethylene, or ethylene and said alpha-olefin, which comprises ethylene, or ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1; and (3) said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) is norbornene.
4. The interpolymer of Claim 3; wherein Component (1)(a) is styrene; and Component (2) is ethylene.
5. The interpolymer of Claim 3; wherein Component (1)(a) is styrene; and Component (2) is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1.
6. An interpolymer prepared by polymerizing (a) at least one vinyl or vinylidene aromatic monomer, (b) at least one of ethylene and/or a C3-20 alpha-olefin; and (c) optionally one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2);
in the presence of a catalyst comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido)dimethylsilane]dimethyl titanium.
in the presence of a catalyst comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido)dimethylsilane]dimethyl titanium.
7. The interpolymer of Claim 6 wherein;
(a) said vinyl or vinylidene aromatic monomer is represented by the following formula;
R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (b) said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1;
said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) comprises norbornene, or a C1-10 alkyl or C6-10 aryl substituted norbornene.
(a) said vinyl or vinylidene aromatic monomer is represented by the following formula;
R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (b) said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1;
said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) comprises norbornene, or a C1-10 alkyl or C6-10 aryl substituted norbornene.
8. The interpolymer of Claim 7; wherein Component (a) is styrene; and Component (c) is ethylene.
9. The interpolymer of Claim 7; wherein Component (a) is styrene; and Component (c) is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1.
10. A process for preparing an interpolymer by polymerizing (a) at least one vinyl or vinylidene aromatic monomer, or (b) at least one of ethylene and/or a C3-20 alpha-olefin; and (c) optionally one or more of ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2);
in the presence of a catalyst comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium.
in the presence of a catalyst comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane] dimethyl titanium.
11. The process of Claim 10 wherein;
(a) said vinyl or vinylidene aromatic monomer is represented by the following formula;
R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (b) said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1;
(c) said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) if present comprises norbornene, or a C1-10 alkyl or aryl substituted norbornene.
(a) said vinyl or vinylidene aromatic monomer is represented by the following formula;
R1 is selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; each R2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; Ar is a phenyl group or a phenyl group substituted with from 1 to 5 substituents selected from the group consisting of halo, C1-4-alkyl, and C1-4-haloalkyl; and n has a value from zero to 4; or (b) said alpha-olefin which comprises at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1;
(c) said ethylenically unsaturated polymerizable monomers other than those derived from (1) and (2) if present comprises norbornene, or a C1-10 alkyl or aryl substituted norbornene.
12. The process of Claim 11 wherein; wherein Component (a) is styrene; and Component (c) is ethylene.
13. The process of Claim 11 wherein Component (a) is styrene; and Component (c) is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1.
14. A blend comprising;
A) the interpolymer of Claim 1; and B) one or more additional polymer components.
A) the interpolymer of Claim 1; and B) one or more additional polymer components.
15. The blend of claim 15 wherein said additional polymer, Component B, is selected from the group consisting of substantially random interpolymers, vinyl and vinylidene halide, ethylene homopolymers, alpha-olefin homopolymers ethylene/alpha-olefin copolymers, styrenic polymers, polyethers, polycarbonates, polyanilines, asphalt, or any combinations thereof.
16. The transition metal complex, [(4,5-methylene-phenanthrenyl) (tent-butylamido) dimethylsilane]dimethyl titanium.
17. A catalyst composition comprising [(4,5-methylene-phenanthrenyl) (tert-butylamido) dimethylsilane]dimethyl titanium.
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US14019999P | 1999-06-22 | 1999-06-22 | |
US60/140,199 | 1999-06-22 | ||
PCT/US2000/015525 WO2000078831A1 (en) | 1999-06-22 | 2000-06-05 | Ethylene and/or alpha-olefin/vinyl or vinylidene aromatic interpolymer compositions |
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EP (1) | EP1200491A1 (en) |
JP (1) | JP2003503513A (en) |
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CN (1) | CN1357014A (en) |
AR (1) | AR026131A1 (en) |
AU (1) | AU5324300A (en) |
CA (1) | CA2384373A1 (en) |
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US6239242B1 (en) | 1999-08-21 | 2001-05-29 | Nova Chemicals Corporation | Vinylaromatic and olefin pseudoblock polymers |
FR2876222A1 (en) * | 2004-10-06 | 2006-04-07 | Renault Sas | NON-FLUORINATED OR PARTIALLY FLUORINATED MEMBRANE FUEL CELL AND PROCESS FOR THE PREPARATION OF SAID MEMBRANE |
CN113968926B (en) * | 2021-10-29 | 2023-01-13 | 大连理工大学 | Ethylene/alpha-olefin/functionalized styrene derivative terpolymer and preparation method thereof |
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TW473503B (en) * | 1996-09-04 | 2002-01-21 | Dow Chemical Co | Substantially random interpolymer comprising Α-olefin/vinyl aromatic monomer and/or hindered aliphatic or cycloaliphatic vinyl or vinylidene monomers, ethylene/styrene copolymer, and process for preparing Α-olefin/vinyl aromatic monomer interpoly |
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2000
- 2000-06-05 KR KR1020017016398A patent/KR20020013933A/en not_active Application Discontinuation
- 2000-06-05 CA CA002384373A patent/CA2384373A1/en not_active Abandoned
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- 2000-06-05 AU AU53243/00A patent/AU5324300A/en not_active Abandoned
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