TWI322166B - Conjugated diene/monovinylarene block copolymers blends - Google Patents
Conjugated diene/monovinylarene block copolymers blends Download PDFInfo
- Publication number
- TWI322166B TWI322166B TW092113476A TW92113476A TWI322166B TW I322166 B TWI322166 B TW I322166B TW 092113476 A TW092113476 A TW 092113476A TW 92113476 A TW92113476 A TW 92113476A TW I322166 B TWI322166 B TW I322166B
- Authority
- TW
- Taiwan
- Prior art keywords
- styrene
- group
- monovinylarene
- monomer
- conjugated diene
- Prior art date
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims description 63
- 150000001993 dienes Chemical class 0.000 title claims description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 229920002959 polymer blend Polymers 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims description 76
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 40
- 239000003999 initiator Substances 0.000 claims description 28
- -1 methyl methyl Chemical group 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 13
- 239000007822 coupling agent Substances 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- LENBTPHYHQHCSR-UHFFFAOYSA-N 1-phenylethenethiol Chemical compound SC(=C)C1=CC=CC=C1 LENBTPHYHQHCSR-UHFFFAOYSA-N 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 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
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 12
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 claims 7
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 5
- 229910052757 nitrogen Inorganic materials 0.000 claims 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 2
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims 2
- SCXIDQOYDZIEKQ-UHFFFAOYSA-N 3-ethenylbenzenethiol Chemical compound SC1=CC=CC(C=C)=C1 SCXIDQOYDZIEKQ-UHFFFAOYSA-N 0.000 claims 2
- KCCWFTFCEHVSTM-UHFFFAOYSA-N 4-ethenylbenzenethiol Chemical compound SC1=CC=C(C=C)C=C1 KCCWFTFCEHVSTM-UHFFFAOYSA-N 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims 2
- SCZGZDLUGUYLRV-UHFFFAOYSA-N (2-methylphenyl)hydrazine Chemical compound CC1=CC=CC=C1NN SCZGZDLUGUYLRV-UHFFFAOYSA-N 0.000 claims 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims 1
- QOVCUELHTLHMEN-UHFFFAOYSA-N 1-butyl-4-ethenylbenzene Chemical compound CCCCC1=CC=C(C=C)C=C1 QOVCUELHTLHMEN-UHFFFAOYSA-N 0.000 claims 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims 1
- BZUILZIKDIMXBK-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxycarbonyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)OCC1OC1 BZUILZIKDIMXBK-UHFFFAOYSA-N 0.000 claims 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 claims 1
- HDBQZGJWHMCXIL-UHFFFAOYSA-N 3,7-dihydropurine-2-thione Chemical compound SC1=NC=C2NC=NC2=N1 HDBQZGJWHMCXIL-UHFFFAOYSA-N 0.000 claims 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims 1
- JOQJJORTANSCOY-UHFFFAOYSA-N C=CC1=CC=CC=C1.CCCCC=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.CCCCC=CC1=CC=CC=C1 JOQJJORTANSCOY-UHFFFAOYSA-N 0.000 claims 1
- RQALSNXHZSQDQZ-UHFFFAOYSA-N CC=1C=C(C=C)C=CC1.C=C Chemical compound CC=1C=C(C=C)C=CC1.C=C RQALSNXHZSQDQZ-UHFFFAOYSA-N 0.000 claims 1
- FXXQPTWPCMPDSX-UHFFFAOYSA-N CC=CC.CC(=C)C(O)=O Chemical compound CC=CC.CC(=C)C(O)=O FXXQPTWPCMPDSX-UHFFFAOYSA-N 0.000 claims 1
- 229910052691 Erbium Inorganic materials 0.000 claims 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 1
- 241001529936 Murinae Species 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 1
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 claims 1
- 229910052785 arsenic Inorganic materials 0.000 claims 1
- XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical compound CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- LMEDOLJKVASKTP-UHFFFAOYSA-N dibutyl sulfate Chemical compound CCCCOS(=O)(=O)OCCCC LMEDOLJKVASKTP-UHFFFAOYSA-N 0.000 claims 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 claims 1
- 150000005172 methylbenzenes Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 150000002926 oxygen Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- GLVAUDGFNGKCSF-UHFFFAOYSA-N purine-6-thione Natural products S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 claims 1
- ABMSPIUYLYKRLM-UHFFFAOYSA-N styrene hydrobromide Chemical compound Br.C=CC1=CC=CC=C1 ABMSPIUYLYKRLM-UHFFFAOYSA-N 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
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- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
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- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
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- 230000000181 anti-adherent effect Effects 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
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- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000002986 polymer concrete Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- JSUMUQNOVBYHNZ-UHFFFAOYSA-N tris(2-decylphenyl) phosphite Chemical compound CCCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCCC)OC1=CC=CC=C1CCCCCCCCCC JSUMUQNOVBYHNZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
- C08F297/044—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes using a coupling agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
1322166 玖、發明說明: 本申請案係現在核准之第〇9/576,879號之部分接續申"月 案,該部分接續申請案係第08/521,335號,即現行之美國專 利第6,096,8^8號及現在核准之第〇9/576,4〇8號申請案之分 割申請案。 【發明所屬之技術領域】 本發明係關於一種聚合物摻合物,其包含至少一種錐形 共輛二烯-單乙烯芳烴嵌段共聚物及至少一種苯乙烯系聚 合物。 【先前技術】 共軛二烯/單乙烯芳烴之共聚物爲已知且應用於多種目 的。吾人所特別關心的係可形成具有良好物理特性如衝擊 抗性之無色 '透明物品之聚合物。該等物品可應用於製造
玩具、窗口零件、飲料容器及包[譬如,發泡飲料包裝 該等聚合體亦應展示充分熱安定性以適用於習知之注^ 設傷。在很多應用中’需要含有大量笨乙烯之共聚㈣ 物。通常藉由摻合特定之單乙烯芳烴共軛之二烯丘聚物4 ^稀聚:物而製備該等聚合物。但是該等掺合物經心 有非欲之格濁度及藍色色調。因此,需研製結合低藍色Z 、良好透明度、硬度 '剛度心度之聚合物與聚合物⑸ 物。 【發明内容】
本發明之-目的在於提供一種可用於製 透明度之摻合物之聚合物。 民灯尤子 85512-981124.DOC 丄j/ZiOb 丄j/ZiOb 子具有8至18個碳原子之單乙烯芳烴化合物 8至12個碳原子者較佳。該等適當化合物之’分子具有 、α-甲基裟1说、9_田宜世,^ ? &括笨乙烯 烯、4-甲基苯 4-環己基苯乙烯、4_癸基苯乙烯、2乙基^ 、α-曱基苯乙烯、2-甲基苯乙烯、3_甲基笨乙 乙烯、2-乙基苯乙稀、3_乙基笨乙婦、々Ά 正-丙基苯乙烯'4-第三丁基苯:本乙烯、4-< —— 〜甲基笨乙烯、 Μ4-苯基-正-丁基)笨乙烯、i•乙烯基萘、22本^烯、 其混合物。苯乙稀係較佳單乙烯芳煙化合物。#基萘、及 該嵌段共聚物中之共軛二烯與單乙烯芳妗 需具體特性可有报大變化。通常,該財^ :對量視所 嵌段共聚物將含有以最終嵌段共聚物總早乙埽方煙 至⑽重量%範圍之單乙烤芳煙單體,較佳爲="% 約95重量%,更佳爲65重量%至9〇重量%。 里%至 旦=常,存在於該最終嵌段共聚物中之該共^埽單體的 :二該最終嵌段共聚物總重量計約45重量%至約5重量% 範圍中,較佳在約40重量%至約5重量%之範圍中 3 5重量〇/〇至1 〇重量0/〇之範圍中。 至J 一種用於製備本發明之聚合物摻合物的錐形嵌段共 聚物含有至少三個連續共軛二烯/單乙烯芳烴錐形嵌段 被依次併入未插入均聚物嵌段之嵌段共聚物中。 忒錐形嵌段中之各單體的量視所需具體特性可有报大變 化。通常,存在於各錐型嵌段之單乙烯芳烴的量在以該最 終肷段共聚物總重量計約i重量%至約2〇重量%之範圍中, 較佳爲約2重量。/。至約丨5重量%。
85512-981124.DOC =吊,存在於各錐型嵌段中之該共軛二烯的量在以該最 、’:敗奴共聚物總重量計約量%至約15重量%之範圍中, 争4爲4 2重置。/。至約i 2重量。/(^將存在於該最終嵌段共聚 物中之所有共輛二烯單體倂入該錐形嵌段中尤其較佳。 炉錐形肷段中之各單體相對量視所需具體特性亦可有很大 ' 通存在於各錐型嵌段中之該共輛二稀的量在每 伤單乙稀芳;^中約(^份至約1G份範圍之間,較佳爲每份單 乙烯芳烴中約0.2份至約5份。 =垓單體與單體混合物在一引發劑存在下被依次共聚合。 該等引發劑可爲已知用於該等目的之任何有機鹼金屬化合 物車又佳運用式RM之化合物,其中R係含有4至8個碳原子 之烷基、%烷基、或芳基,尺較佳爲一烷基。M係一鹼金屬 ’較佳爲鐘。一較佳引發劑爲正-丁基鋰。 在該技術領域中已知,所運用之引發劑的量依所需聚合 體或增量嵌段分子量而定,且不難決定,從而可獲得原料 流中殘留微量之毒質。通常,存在之該引發劑的量將在約 0.01 phm(按總單體重量計,每百份中之重量份數)至約1〇 phm,較佳爲約0·01 phm至約〇 5 phm,更佳爲〇 〇1 phm至 0.2 phm。 可在烴稀釋劑中運用少量之極性有機化合物,譬如,乙 趟、硫醚、及三級胺’以提高該引發劑的效力,並使在一 混合單體饋入物中之至少部分單乙烯芳烴單體隨機化。較 佳運用四氫呋喃。於運用過程中,所存在之極性有機化合 物的重應可充分提咼該引發劑之效力。舉例而言,當運用 85512-981124.DOC •10- 1322166 四氫呋喃提高該引發劑之效力時,存在之該四氫呋喃量通 常在約0.01至約1.0 phm範圍之内,較佳爲約〇 〇2至約J 〇 phm 〇 該聚合製程在自約-100 C至約i5〇t (較佳爲自約0〇c至 約150°(:)範圍内的任何適當溫度下於—烴稀釋劑中進行, 且該製程中之麼力應可足夠維持該反應混合物大體處於液 相。較佳之烴稀釋劑包含線性或環烷或其混合物。典型實 例包括戊烷、己烷、辛烷、環戊烷、,裒己烷、及A混人物 。本發明中以環己烧爲較佳。該聚合在實質不存在氧與水 下進行,較佳於一惰性氣氛下進行。 饋入物在溶液聚合條件下 混合物饋入物之聚合在饋 使各單體饋入物或單體混合物 水合以使付各早體饋入物或單體 入隨後饋入物之前大體已完成。
典型之引發劑 於以下所述: 模式A 單體與單體混合物饋 入順序包括但 不限 (a) 單乙烯芳烴單體與引發劑, (b) 單乙烯芳烴單體與引發劑, (c) 共軛二烯/單乙烯芳烴單體混合物, (d) 共軛二烯/單乙烯芳烴單體混合物, (e) 共軛二烯/單乙烯芳烴單體混合物,及 ⑴偶合劑;
模式B (a)單乙烯芳烴單體與引發劑,
B5512-981124.DOC 11 1322166 (b) 單乙烯芳烴單體與引發劑, (c) 共輕二稀/單乙烯芳烴單體混合物, (d) 共輛二烯/單乙烯芳烴單體混合物, (e) 共軛二烯/單乙烯芳烴單體混合物, (f) 共軛二烯/單乙烯芳烴單體混合物,及 (g) 偶合劑;
模式C (a) 單乙烯芳烴單體與引發劑, (b) 單乙烯芳烴單體與引發劑, (c) 共軛二烯/單乙烯芳烴單體混合物, (d) 共軛二烯/單乙烯芳烴單體混合物, (e) 共軛二烯/單乙烯芳烴單體混合物, (f) 共軛二烯/單乙烯芳烴單體混合物, (g) 共軛二烯/單乙烯芳烴單體混合物,及 (h) 偶合劑;
模式D (a) 單乙烯芳烴單體與引發劑, (b) 共輛二烯/單乙烯芳烴單體混合物與引發劑, (c) 共軛二烯/單乙烯芳烴單體混合物, (d) 共輛二烯/單乙烯芳烴單體混合物,及 (e) 偶合劑;
模式E (a) 單乙烯芳烴單體與引發劑, (b) 共軛二烯/單乙烯芳烴單體混合物與引發劑, -12-
85512-981124.DOC 1322166 (C)共輛二烯/單乙烯芳烴單體混合物, (d) 共軛二烯/單乙烯芳烴單體混合物, (e) 共軛二烯/單乙烯芳烴單體混合物,及 ⑴偶合劑;
模式F (a) 單乙烯芳烴單體與引發劑, (b) 共軛二烯/單乙烯芳烴單體混合物與引發劑, (c) 共軛二烯/單乙烯芳烴單體混合物, (d) 共軛二烯/單乙烯芳烴單體混合物, (e) 共軛二烯/單乙烯芳烴單體混合物, (f) 共軛二烯/單乙烯芳烴單體混合物,及 (g) 偶合劑。 該單體混合物預先混合並以混合物饋入,亦或該等單體 可同時饋入。於步驟(a)中,可在單乙烯芳烴單體饋入之前 或之後加入該引發劑。在大規模作業中,理想狀況係於步 驟(a)中加入該引發劑之前加入該單乙烯芳烴單體。在含有 引發劑之隨後步驟中,應在於該單體或單體混合物之前加 入該引發劑。 在偶合之前,藉由前述順序聚合製備之典型聚合物鏈包 括下列:
模式A S2-Bi/S3~B2/S4~B3/S5~Li 85512-981124.DOC -13 - 1322166
模式B
Sl_S2_Bi/S3_B2/S4_B3/S5_B4/S6_Li Sz-Bi/Ss-BVSfBVSs-BVScLi 模式C
Sj-SrBj/SyBz/SrBs/Ss-BJSs-Bs/ST-Li S2-Bi/S3-B2/S4-B3/S5_B4/S6 —B5/S7-L1
模式D
S1-Bl/S2-B2/S3-B3/S4-Li B ]/S2-B2/S3~B3/S4-Li 模式E S ] - B 1/S2-B2 /S3-B3/S4-B4/S5-L1 B i/S2-B2/S3-B3/S4_B4/S5-Li
模式F S]-Bj/S2~B2/S3-B3/S4-B4/S5-B5/S6-Li
Bi/S2_B2/S3-B3/S4-B4/S5-B5/S6_Li 其中”S"係單乙烯芳烴嵌段,”B/S"係含有單乙烯芳烴與 共軛二烯”B"之混合物的錐形嵌段,”Li”係來自鹼金屬引發 劑之陽離子殘基。 在聚合完成之後加入該偶合劑。適當之偶合劑包括二-或 多乙烯芳烴化合物,二-或多環氧化物,二-或多異氰酸酯 ,二-或多亞胺,二-或多搭,二-或多酮,烧氧錫化合物, 二-或多鹵化物,尤其係鹵化矽與鹵矽烷,單-、二-、或多 酸酐,二-或多酯,較佳係具有聚羧基酸之單醇之酯,爲單 羥基乙醇與二羧基酸之酯的二酯,爲單鹼酸與如丙三醇及 85512-981124.DOC -14- 其類似物之聚醇之酯的二酯, 、9入1 及兩種或多種該等化合物之 含物。 可用之多官能基偶合劑包括諸如環氧化豆油、環氧化亞 ;籽油及其類似物或其混合物之環氧化植物油。在本發明 偶合劑係環氧化植物油。其中較佳係環氧化豆油。 該偶σ劑可使用任何有效量。儘管相信該量並不重要, 但通常,相對於該活性聚人 名。體鹼金屬之化學計量將會促進 破大限度之偶合。但是,對 十於所而之特定産物,可使用多 !或少於化學計量之量以改變偶合效力。-般地,於聚合
中運用之偶合劑總量在約0.lphmJL 佳爲約一至約5phm,更佳爲一至一。 偶合反應完成後,可以士卷 老如水、酵類、酚類或線性飽和 脂族單二缓基酸之終止劑處理該聚合反應混合物以自該换 段共聚物中移除驗金屬且可達成顏色控制。該較佳終止劑 係水與二氧化碳。 該聚合物混凝物(聚合溶劑中之聚合物)通常含有約10至 40重量%之固體,更通常爲2⑴5重量。/。之固體。可瞬間基 發該聚合物混凝物以蒸發部分該溶劑從而將固體含量增; W 50至約99重$ %之固體濃度,隨後藉由真空供箱或排 氣機筒乾燥以移除殘留溶劑。 可藉由諸如研磨、播屋、或塑料注射成型將該嵌段共聚 物回收及塑成所需形狀。只要含量與類型未妨礙實現本發 月之目的’該錐形嵌段共聚物亦可含有諸如抗氧化劑、抗 黏劑、釋離劑、填料、稀釋劑、與染料,及其類似物。
S5512-981124.DOC -15- 1322166 丙烯酸2_羥乙基酯、(曱基)丙烯酸2-羥丙基酯、(甲基)丙烯 酸3-羥丙基酯、(甲基)丙烯酸羥丁基酯及其類似物之(甲基) 丙烯酸(較佳係甲基丙烯酸)之CM羥基烷基酯;聚醚多醇 (S如I乙一醇、聚丙一醇或聚丁二醇)與不飽和敌基酸 (較佳係甲基丙烯酸)之間之單酯;聚醚多醇(譬如,聚乙二 醇、聚丙二醇或聚丁二醇)與含有羥基之不飽單體(譬如丙 婦iiL 2 -經基g旨)之間之單醚;不飽和缓基酸與單環氧基化入 物之間之加合物;(甲基)丙烯酸縮水甘油基酯(較佳係甲基 丙烯酸酯)與單價酸(譬如’乙酸、丙酸、對-第三_丁基苯曱 酸或脂肪酸)之間之加合物;含有酸酐基之不飽和化合物 (¾如,順丁稀一酸肝或曱叉丁二酸酐)與二醇(鐾如,乙_ 醇、1,6-己二醇或新戊二醇)之間之單酯或二酯;含有氣_ 、溴-、氟-、及羥基之單體,譬如,(甲基)丙烯酸3_氯_2_ 羥丙基酯(較佳係曱基丙烯酸酯)及其類似物;(甲基)丙烯酸 (較佳係甲基丙稀酸)之經取rC1_24烷基酯或環烷基醋,譬 如,甲基丙烯酸曱酯,甲基丙烯酸乙酯’甲基丙烯酸丙酯 ,甲基丙烯酸異丙酯、甲基丙烯酸正-、第二或第=_丁醋 ’甲基丙烯酸己酯’曱基丙烯酸2-乙基己基酯,曱基丙稀 酸辛酯,甲基丙烯酸癸酯’甲基丙烯酸十二烧酿,甲基丙 _酸硬脂龜醋’甲基丙稀酸環己I旨及其類似物;(曱基) 丙烯酸(較佳係甲基丙烯酸)之Cm烷氧烷基酯,譬如,甲基 丙烯酸甲氧基丁酯,甲基丙烯酸曱氧基乙酯,甲基丙烯酸 乙乳基乙自曰,甲基丙烯酸乙氧基丁酯及其類似物;諸如(甲 基)丙烯酿胺,N_甲基(甲基)丙烯醯胺,(甲基)丙稀猜及其 85512-981124.DOC -17- 丄 示=於才父準黑色背景下被測得。正數表示黃色,負數表 二色。當運用15密耳厚之壓出膠片(4〇昨/2〇密耳標稱模 ^隙)時,藍色之絕對值較佳低於15,更佳低於5。 可藉由本技術領域之任何方法(包括溶融摻混及溶解摻 ::仃摻合。較佳係利用任何所需裝置,譬如,班拍裏混 等聚anbury miXer),加熱壓光輥,或擠壓機熔融摻混該 51 σ物。更佳係運用擠壓機摻合技術熔融摻混該等聚合 物。可利用單或雙螺旋擠壓機。可先於該 該等聚合物與任何其它成分或添加劑。 入摻合條件依所用之摻合技術及聚合物而定。若利用該聚 合物^讀乾摻合’則該乾摻合狀態可包括從室溫至恰低 ? /永口物之炼化溫度之溫度,且摻合時間在若干秒至數 小時:譬如’ 2秒至3〇分鐘範圍之内。 一:熔融摻混過程中’肖等聚合物於摻合器中組合之溫度 舨將在所用之該等聚合物之最高熔點與高達高於該熔點 約1 0 0 °c範圍之間。 該^摻合所需時間可有很大變化’且依所運用之摻合 方:而疋。該所需時間係足以徹底混合該等組份之時間。 I吊'^等個別聚合物將摻合約10秒鐘至約丨5分鐘。 量"、頒型未妨礙本發明之目的,該等聚合物摻合
物可含有添加杳丨,辟L 劑言如,穩定劑、抗氧化劑、抗黏劑、脫 模劑、染料、顏劑、及阻燃齊卜及填料及增強劑,譬如, 玻璃纖維。 该等根據本發日月制版 赞月衣備之嵌段共聚物與聚合物摻合物可用
85512-981124.DOC -20- 1322166 。以 0.25 phr(份/100份樹脂)Irganox® 1076及 1 .〇 phr三(壬基 苯基)亞磷酸鹽穩定該等苯乙烯/ 丁二烯嵌段共聚物。 Vikoflex係維京(Viking)化學公司之註冊商標。jrgan〇x係汽 巴嘉基公司(Ciba Geigy Corporation)之註冊商標。 該等嵌段共聚物A1與A2展現7·2與6.5克/1〇分鐘之熔體 流動,分別根據ASTM D-1238,條件G測得。
實例II 藉由混合及摻合製自苯乙烯及丁二烯之至少一種雜形嵌 段共聚物’與製自苯乙烯及甲基丙烯酸甲酯之至少一種苯 乙浠系聚合物而形成聚合物摻合物。Nova 9203及NAS 90 皆爲苯乙烯與曱基丙烯酸曱酯之共聚物,且可自諾華克 (Novacor)塑料分公司獲得,將其以各種重量比率與至少一 種三-錐形苯乙烯/丁二烯嵌段共聚物摻合。 表1概述該等結果。藍色度,即三色激值"b",(藍與黃色 之才曰才示)’係經由HunterLab D25 Μ光學感測器使用1 5密耳 厚之壓出膠片(400°F/20密耳標稱模口間隙)測得。量測於校 準黑色背景下進行。一正數表示黃色,負數表示藍色。霧 濁度百分比係根據ASTM 1003,在15密耳厚之膠片上使用 HunterLab ColorQuest儀器測得。如前所述測得藍色度。藉 由沿用已久之ASTM或標準方法測得其它特性(缺口伊佐德 氏,彎曲屈服值等)。 所使用之該共聚物為所用之苯乙烯/ 丁二烯三錐形嵌段 共聚物。所使用之該苯乙烯系聚合物係苯乙烯及甲基丙烯 酸曱酯之共聚物。 85512-981124.DOC -22- 1322166 表1三錐形嵌段共聚物與苯乙烯-甲基丙烯酸甲酯共聚物 之聚合物摻合物之物理特性 三錐形嵌段 共聚物(wt%) 100 80% 60% 50% 40% 30% 20% 10% 苯乙烯/MMA* 共聚物(wt%) 20% 40% 50% 60% 70% 80% 90% 炫體流動, (g/10min) 10.9 9.1 6.8 5.1 4.8 4.2 3.0 2.4 ASTMD1238 ,條件G 密度(e/cc) 1.0182 1.0279 1.038 1.0431 1.0482 1.0533 1.0581 1.067 ASTM D782 抗張伸展率 (¾破裂(%) 343 238 145 113 76 50 39 8 ASTMD638 2°每分鐘 受拉屈服强 度(psi) 2,203 2,111 3,025 3,651 4,266 5,066 6,620 7,661 ASTMD638 2°每分鐘 彎曲模量(Tan) (psi) 104,991 129,401 182,426 221,981 261,879 332,010 387,423 450,820 ASTM D780 HDT > 66 psi ro 54 55 62 70 71 79 81 81 ASTM D648 HDT,264 psi (°C) 46 48 51 56 63 68 71 72 ASTM D648 維卡氏rc) 60 62 74 80 87 92 93 93 ASTM D1545 蕭氏D硬度 61 65 69 72 75 78 81 85 ASTM D2240 伊佐德氏缺口 衝擊強度, (ft-lb/in) 15.4 17.2 14.3 3.7 0.39 0.27 0.25 0.36 ASTM D256, 1/8"厚度 部分 部分 部分 完全2 部分 完全 完全 完全 完全 伊佐德氏無缺 口衝擊強度, (ft-lb/in) 27.1 4.7 3.1 5.4 ASTM D256 -1/8"厚度 未破裂 未破裂 完成4 未破裂 未破裂 未破裂 完全 完全 完全 Dynatup 衝擊 能量(ln-lb) 296 338 371 395 39.2 31.0 23.8 20.4 0.5忖直徑,Tup ,15磅,30°C 亨特色度,b 3.5 4.7 4.2 3.9 3.3 1.9 1.5 2.7 霧濁度,(%) 14.90 9.2.0 4.80 1.60 1.20 3.80 11.70 26.50 光透射,(%) 89.5 83.7 84.1 85.9 88.3 91.0 91.8 90.0 *錐形共聚物未包含抗黏/衝擊改質添加劑 # Nova NAS 90苯乙烯甲基丙烯酸曱酯共聚物。 -23-
85512-981124.DOC 1322166 表2三錐形嵌段共聚物與苯乙烯-曱基丙烯酸甲酯共聚物 之聚摻合物之塑料注模特性 三錐形嵌段 共聚物(Wt%) 90 70% 60% 50% 40% 30% 20% 15%* 苯乙烯/MMA# 共聚物(wt%) 10 30% 40% 50% 60% 70% 80% 90% 彎曲屈服值(psi) 3394 3826 4538 5847 7610 9407 10466 11172 張力屈服值 2086 2155 3575 4326 5243 6515 6910 抗張强度 2744 2730 2833 3195 3588 4161 4812 5108 缺口伊佐德氏 衝擊強度(ft-lb) - - 2.19 0.46 0.38 0.37 0.35 無缺口伊佐德氏 衝擊強度(ft-lb) - - - 19,9 5.16 3.64 4.05 霧濁度(%) 19.2 21.0 15.6 11.23 5.7 2.37 0.78 0.93 光澤(%) 129 126 126 137 142 143 154 154 亨特色度(b) 4.54 4.70 4.49 4.12 3.44 2.69 1.79 1.48 黃色指數 8.23 8.95 8.51 7.53 5.75 3.98 2.00 1.32 光透射(%) 86.5 84.3 84.0 85.5 87.9 90.2 91.9 92 蕭氏D硬度 63 67 69 72 75 78 81 82 維卡氏°F 143 150 159 175 190 196 199 201 該摻合物含有5重量%2KR03苯乙烯-丁二烯共聚物(雪 佛龍菲利浦化學公司(Chevron Phillips Chemical Company LP)之商品) # 使用 Nova 9203 SMMA。 表1及表2之結果闡明當該三錐形苯乙烯-曱基丙烯酸曱 酯嵌段共聚物的量爲該聚合物摻合物總重量之50重量%或 更多’尤其爲60重量%或更多時,利用含有三個錐形嵌段 85512-981124.DOC • 24· 1322166 之嵌段共聚物之聚合物摻合物展現良好透明度與良好衝擊 韌性之結合。 前述實例僅爲闡述之目的。該等實例並未意欲限制本發 明之範疇。本發明之範疇由所述揭示及申請專利範圍所定 義0 85512-981124.DOC -25 -
Claims (1)
1322166 第092113476號專利申請案 中文申請專利範圍替換本(98年11月) 拾、申請專利範圍: f || 1 · 一種聚合物摻合物,其包括至少一種偶合共軛二烯/單 乙烯芳烴嵌段共聚物與至少一種苯乙烯系聚合物,其中 該偶合共軛二烯/單乙烯芳烴嵌段共聚物係藉由包括 下列之方法製得:於聚合條件下依序使至少一種單乙稀 芳單體、有機鹼金屬引發劑、及至少一種共輕二烯單 體接觸,其後,與多官能基偶合劑偶合以形成該嵌段共 聚物; Μ 提供含有單乙烯芳烴單體與共軛二烯單體的至少三 個連續單體混合物饋入物以在該嵌段共聚物中生成至 少二個連續共概二浠/單乙稀芳烴錐形嵌段; 在饋入之初加入含於各饋入·物之所有單乙烯芳烴單 體及共軛二烯單體,使反應器中存在過量之單體; 該至少一種單乙烯芳烴單體含有8至18個碳原子,而 該至少一種共軛二烯單體含有4至丨 ,笨乙稀系聚合物係選自藉由使至少原」:二系 共單體與至少一種不飽和含氣哎 。 π 災虱或鼠之共早體共聚合所 付之至少-種共聚物’其中該不飽和含氧或氮之共單體 係選自由丙歸酸甲^ ^ 外夂、甲基丙烯酸乙酯、甲基 甲 酯、丙烯酸縮水甘油私 u 油自曰、曱基丙烯酸縮水甘油酯、丙烯 腈、及其混合物組成之群· 其中該聚合物摻合物包括: ⑷5〇重量%或更少之該苯乙烯系聚合物;及 (B) 50重量%或更多之該偶合共軛二烯,單乙烯芳 85512-981124.DOC 1322166 烴嵌段共聚物。 2. 如申請專利範圍第1項之聚合物摻合物,其中 該單乙烯芳烴單體係選自由苯乙烯、2-曱基笨已歸 3 -曱基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4_ _ * 一 « 丁基苯乙烯、α-曱基苯乙烯、及其混合物組成之群;及 該共軛二烯單體係選自丁二烯、異戊二烯、2 基丁二烯。 3. 如申請專利範圍第1項之聚合物摻合物,其中 該苯乙烯系共單體係選自由苯乙烯、2_甲基苯 3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、私堂一 丁基苯乙烯、α-曱基苯乙烯、及其混合物組成之群;及 該不飽和含氧或氮之共單體係選自由丙烯酸甲崎、甲 基丙烯酸乙酯、曱基丙烯酸曱酯、丙烯酸縮水甘油gt 甲基丙烯酸縮水甘油酯、丙烯腈、及其混合物組 〇 4. 如申請專利範圍第1至3項中任一項之聚合物摻合物,其 包括60重量%或更多之該偶合共軛二烯/單乙烯芳烴= 段共聚物。 '^ 5. 如申清專利範圍第4項之聚合物摻合物,其中 該單乙稀芳烴單體係選自由苯乙烤、2_甲基笨 3-甲基苯乙烯、4-甲基苯乙烯、4-乙基苯乙烯、4_第= 丁基苯乙烯、(X-曱基苯乙烯、及其混合物組成之 τ >及 該共軛二烯單體係選自由丁二烯、異戊二烯、2,3、一 甲基丁一稀及其混合物。 85512-981124.DOC 1322166 6. 如申請專利範圍第i項之聚合物摻合物,其中 該單乙烯芳烴單體係選自由苯乙烯、2-甲基苯乙稀、 3-曱基苯乙烯、4_曱基苯乙烯、4_乙基苯乙烯、4第三_ 丁基苯乙烯、α_甲基苯乙烯、及其混合物組成之群; 該共軏一烯單體係選自由丁二浠、異戊二埽、23 -曱基丁二烯及其混合物;及 該笨乙烯系共單體係選自由苯乙烯、2_曱基笨乙稀、 3-曱基苯乙烯、4_曱基苯乙烯、4_乙基苯乙烯、仁第三_ 丁基苯乙烯、α_甲基苯乙烯、及其混合物組成之群。 7. 如申請專利範圍第6項之聚合物摻合物,其包括6〇重量 %或更多之該偶合共軛二烯/單乙烯芳烴嵌段共聚物。 8·如申請專利範圍第6項之聚合物摻合物,其中 該聚合物摻合物包括60重量%或更多之該偶合共輛 二烯/單乙烯芳烴嵌段共聚物; 該單乙烯芳烴單體係選自由笨乙烯、2•甲基笨乙烯 3-甲基苯乙烯、仁甲基苯乙烯、4_乙基苯乙烯、‘第三 丁基苯乙烯、及其混合物組成之群; 該共軛二烯單體係選自由丁二烯、異戊二烯、及立, 合物; ^ ' 該苯乙烯系共單體係選自由苯乙缔、2_甲基苯乙埽 3·甲基苯乙稀、4_甲基苯乙稀、4_乙基苯 丁基苯乙烯、及其混合物組成之群;及 該不飽和含氧或氮之共單體係選自由丙烯酸甲墙、 基丙稀酸乙Sl、甲基丙稀酸甲自旨、及其混合物組成。 85512-98H24.DOC 1322166 9. 一種製造聚合物摻人物 人 物之方法,该方法包括摻合至少一 種偶。共軛二烯/單乙烯芳烴嵌段共聚物盥至少一種苯 乙烯系聚合物,其中: … 。亥偶合共軛二烯/單乙烯芳烴嵌段共聚物係藉由包括 方法製得:於聚合條件下依序使至少一種單乙烯 芳炫單體 '有機鹼金屬引發劑、及至少一種共軛二烯單 體接觸’其後,與多官能基偶合劑偶合以㈣該嵌段共 聚物; 提供含有單乙烯芳烴單體與共軛二烯單體的至少三 個連、戈單體混合物饋入物以在該嵌段共聚物中生成至 >、一個連續共I厄二稀/單乙稀芳烴錐形嵌段; 在饋入之初加入含於各饋入物之所有單乙烯芳烴單 體及共軛二烯單體,而使反應器中存在過量之單體; "亥至夕、種單乙烯芳煙單體含有8至18個碳原子,而 至夕個共扼一稀單體含有4至1 2個碳原子;及 該苯乙烯系聚合物係選自藉由使至少一種苯乙烯系 共單體與至少一種不飽和含氧或氮之共單體製得之 少一種共聚物,其中該不飽和含氧或氮之 至 由丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯峻甲匕、目 烯酸縮水甘油酯、曱基丙烯酸縮水甘油酯、丙軋、丙 其混合物組成之群;其中該聚合物摻合物包括.腈、及 (A) 50重量%或更少之該苯乙烯系聚合物; (B) 5〇重量%或更多之該偶合共軛二烯"。及 I乙烯芳 85512-981124.DOC 丄 烴嵌段共聚物。 10.如申請專利範圍第9項之方法其令: °亥單乙烯芳烴單體係選自由笨乙烯、2-甲基笨乙烯、 苯乙烯、4·甲基苯乙烯、4-乙基苯乙烯、心第三、 丁基苯乙烯、α_甲基苯乙烯、及其混合物組成之群;及 該共軛二烯單體係選自丁二婦、異戊二烯、2卜田 基丁二烯》 ,一甲 11. 如申請專利範圍第9項之方法,其中: 該苯乙烯系共單體係選自由笨乙烯、2_甲基笨乙烯、 3-甲基苯乙烯、各甲基苯乙烯、4_乙基苯乙烯、4_第三'_ 丁基苯乙烯、α-甲基苯乙烯、及其混合物組成之群。 12. 如申請專利範圍第9至"項中任一項之方法,其中該聚 合物摻合物包括60重量%或更多之該偶合共軛二稀^單 乙烯芳烴嵌段共聚物。 13·如申凊專利範圍第丨2項之方法,其中 該單乙烯芳烴單體係選自由苯乙烯、2_曱基笨乙婦 3 -曱基笨乙烯、4-甲基苯乙烯、4_乙基苯乙烯、第二 丁基苯乙烯、α-甲基苯乙烯、及其混合物組成之群;及 δ亥共輕—烯單體係選自丁二稀、異戊二稀、23 一甲 基丁二烯及其混合物。 85512-981124.DOC
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-
2002
- 2002-05-20 US US10/151,443 patent/US6835778B2/en not_active Expired - Lifetime
-
2003
- 2003-05-19 AT AT03755376T patent/ATE369397T1/de not_active IP Right Cessation
- 2003-05-19 AU AU2003247378A patent/AU2003247378A1/en not_active Abandoned
- 2003-05-19 CN CN03814130.2A patent/CN1662600A/zh active Pending
- 2003-05-19 JP JP2004508172A patent/JP2005529992A/ja active Pending
- 2003-05-19 DE DE60315454T patent/DE60315454T2/de not_active Expired - Lifetime
- 2003-05-19 CA CA2486190A patent/CA2486190C/en not_active Expired - Fee Related
- 2003-05-19 WO PCT/US2003/015654 patent/WO2003099925A1/en active IP Right Grant
- 2003-05-19 BR BRPI0311162-8A patent/BR0311162B1/pt not_active IP Right Cessation
- 2003-05-19 MX MXPA04011501A patent/MXPA04011501A/es active IP Right Grant
- 2003-05-19 EP EP03755376A patent/EP1513896B1/en not_active Expired - Lifetime
- 2003-05-19 TW TW092113476A patent/TWI322166B/zh not_active IP Right Cessation
- 2003-05-19 ES ES03755376T patent/ES2287515T3/es not_active Expired - Lifetime
- 2003-08-06 US US10/635,662 patent/US20040059057A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
EP1513896B1 (en) | 2007-08-08 |
EP1513896A1 (en) | 2005-03-16 |
TW200404857A (en) | 2004-04-01 |
CA2486190C (en) | 2011-04-19 |
MXPA04011501A (es) | 2005-02-17 |
BR0311162A (pt) | 2005-03-15 |
ES2287515T3 (es) | 2007-12-16 |
US6835778B2 (en) | 2004-12-28 |
ATE369397T1 (de) | 2007-08-15 |
CA2486190A1 (en) | 2003-12-04 |
BR0311162B1 (pt) | 2013-03-05 |
WO2003099925A1 (en) | 2003-12-04 |
CN1662600A (zh) | 2005-08-31 |
US20040059057A1 (en) | 2004-03-25 |
US20030004267A1 (en) | 2003-01-02 |
JP2005529992A (ja) | 2005-10-06 |
DE60315454T2 (de) | 2008-04-24 |
DE60315454D1 (de) | 2007-09-20 |
AU2003247378A1 (en) | 2003-12-12 |
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