WO2000053649A1 - Styrenic graft copolymer and method of preparing the same - Google Patents
Styrenic graft copolymer and method of preparing the same Download PDFInfo
- Publication number
- WO2000053649A1 WO2000053649A1 PCT/KR2000/000181 KR0000181W WO0053649A1 WO 2000053649 A1 WO2000053649 A1 WO 2000053649A1 KR 0000181 W KR0000181 W KR 0000181W WO 0053649 A1 WO0053649 A1 WO 0053649A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- styrenic
- styrene
- carbon
- group
- syndiotactic
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 21
- 229920000578 graft copolymer Polymers 0.000 title description 2
- 229920001577 copolymer Polymers 0.000 claims abstract description 77
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical group 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 10
- 239000011669 selenium Substances 0.000 claims abstract description 10
- 229910052718 tin Inorganic materials 0.000 claims abstract description 10
- 239000011135 tin Substances 0.000 claims abstract description 10
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 6
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
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- 230000000977 initiatory effect Effects 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 7
- 229940117913 acrylamide Drugs 0.000 claims description 6
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 6
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
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- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 239000000375 suspending agent Substances 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 238000010559 graft polymerization reaction Methods 0.000 claims 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 150000002484 inorganic compounds Chemical class 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 230000008961 swelling Effects 0.000 claims 1
- 239000004677 Nylon Substances 0.000 description 22
- 229920001778 nylon Polymers 0.000 description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000004342 Benzoyl peroxide Chemical group 0.000 description 11
- 235000019400 benzoyl peroxide Nutrition 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 150000003440 styrenes Chemical class 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000013019 agitation Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- AHNYHYYIECFEQY-UHFFFAOYSA-N 2-phenylethenylsilicon Chemical compound [Si]C=CC1=CC=CC=C1 AHNYHYYIECFEQY-UHFFFAOYSA-N 0.000 description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920006249 styrenic copolymer Polymers 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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- 150000002739 metals Chemical class 0.000 description 5
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- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 4
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- 238000004458 analytical method Methods 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
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- 230000003247 decreasing effect Effects 0.000 description 4
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- PPHISMWXPHLFBR-UHFFFAOYSA-N n-isocyanatohydroxylamine Chemical compound ONN=C=O PPHISMWXPHLFBR-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- BPCNEKWROYSOLT-UHFFFAOYSA-N n-phenylprop-2-enamide Chemical compound C=CC(=O)NC1=CC=CC=C1 BPCNEKWROYSOLT-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YFMFSCRSAWIWOP-UHFFFAOYSA-N phenyl(trityl)diazene Chemical compound C1=CC=CC=C1N=NC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 YFMFSCRSAWIWOP-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical group CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
Definitions
- R 10 is an alkyl of C ⁇ . 8
- j is an integer from 2 to 50.
- the acrylonitrile derivative includes: vinylidene cyanate, alpha-methoxy acrylonitrile, alpha-phenyl acrylonitrile, and alpha-acetoxy acrylonitrile.
- the thermoplastic resin which can be used in the resin compositions includes all kinds of resins which are obtained through an add reaction or a condensation reaction.
- the preferable examples include: polyolefin, ethylenevinyl copolymer, amorphous polystyrene, polyester, polyacetal, polycarbonate, polyacrylate, polyamide, polyether, polyphenylene oxide, polyphenylene sulfide, polyoxy methylene, polyimide, polysulfone, polyether sulfone, polyurethane, acrylate resin, and halogenated resin.
- These compounds can be denatured or grafted by the styrenic monomers so as to increase the compatibility with the syndiotactic styrenic polymers. Or they are transformed so as to have a reactive functional group or they originally have it, thereby improving the blending efficiency.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
A styrenic grafted copolymer is disclosed, in which one or more monomers with ethylenically unsaturated bonds are grafted to a syndiotactic polystyrene. The styrenic grafted copolymer is produced through the following steps: (1) preparing a syndiotactic stereogular styrenic polymer having repeating units (A) by polymerizing vinyl aromatic monomers under a catalyst system, the catalyst system consisting of transition metal compounds (I) as main catalyst components and organic aluminum compounds or aluminoxanes (II) as cocatalyst components; and (2) graft-polymerizing monomers of formula (B) having ethylenically unsaturated bonds to the syndiotactic stereoregular styrenic polymer: where R1 is hydrogen, halogen, or a substituent not containing carbon-carbon double bonds but containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; and m is an integer from 1 to 3 (if m is 2 or 3, R1 is same or different); where each of R2-R5 is hydrogen, halogen, or a substituent containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin.
Description
STYRENIC GRAFT COPOLYMER AND METHOD OF PREPARING THE SAME
Field of the Invention
The present invention relates to a styrenic grafted copolymer in which one or more monomers with ethylenically unsaturated bonds are grafted to a syndiotactic polystyrene. More specifically, the present invention relates to a styrenic grafted copolymer in which one or more monomers with ethylenically unsaturated bonds are grafted to a syndiotactic polystyrene not containing unsaturated substituent.
Background of the Invention
Generally, compared with the atactic polystyrene which is manufactured by polymerizing the radicals, the syndiotactic polystyrene (sPS) having the stereoregularity is superior in the heat resistance, in the chemical resistance and in the electrical properties. However, the syndiotactic polystyrene is very low in the impact resistance, in the compatibility with other resins, and in the adhesion to metals, and therefore, its application has been limited. By grafting the monomers with unsaturated radicals to the syndiotactic polystyrene, the present inventors could invent a styrenic grafted copolymer which is superior in the heat resistance, in the chemical resistance, in the compatibility with other resins, in the adhesion and in the coatability, so that the styrenic grafted copolymer can be used as a raw material of resin compositions and as a compatilizing agent. Therefore, the styrenic grafted copolymer according to the present invention and resin compositions containing it can be used to make films, sheets, packing sheets, automobile components, electric or electronic components and the like.
In order to solve the conventional problems of the conventional syndiotactic polystyrene, the random copolymerization and block copolymerization of olefin and
polar monomers were tried.
U.S. Patent 5,260,394 discloses a styrenic copolymer which consists of repeated units of substituted styrene and repeated units of olefin.
U.S. Patent 5,391,671 discloses a styrenic copolymer which consists of repeated units of substituted styrene and repeated units of acrylonitrile.
U.S. Patent 5,262,504 discloses a styrenic copolymer and its manufacturing process, which consists of repeated units of substituted styrene and repeated units of an unsaturated carboxylic acid or its ester.
U.S. Patents 5,475,061 and 5,554,695 disclose a styrenic copolymer which consists of repeated units of substituted styrene and repeated units of another structure.
However, the activity of catalyst was decreased, and the efficiency of the copolymerization was low, while if the content of comonomer was high, then the polystyrene was lead to lose the inherent properties. Thus the problems remained all the same.
In order to solve the problems of the above styrenic copolymers, a grafted copolymerization is being tried.
U.S. Patent 5,250,629 and JP 5-17533 disclose a process for manufacturing a styrenic copolymer. In this manufacturing process, a styrenic monomer having a hydrocarbon radical with an unsaturated bond is copolymerized under a catalyst system which consists of a material formed through contact between a transition metal compound and an organic aluminum compound. Then the unsaturated ethylenic monomers are graft-copolymerized, thereby manufacturing a styrenic grafted copolymer. In the methods of the above mentioned U.S. patent and Japanese Patent, that is, in the method of grafting unsaturated ethylenic monomers to the copolymer of styrene and divinyl benzene, the unreacted vinyl radicals which remain in the copolymer of styrene and divinyl benzene are crosslinked during the grafting process, and therefore, the moldability is deteriorated fatally.
Summary of the Invention
In the present invention, the styrenic polymer or copolymer without containing unsaturated hydrocarbon radicals is synthesized, and is activated by a radical initiating agent. Then it is grafted with olefin or polar monomer, thereby synthesizing a grafted copolymer. The synthesized grafted copolymer is used as a raw material for resin compositions, or used as a compatilizing agent.
Therefore it is an object of the present invention to provide a styrenic grafted copolymer in which one or more of monomers with ethylenically unsaturated bonds are grafted to a syndiotactic polystyrene.
It is another object of the present invention to provide a styrenic grafted copolymer in which diversified functional radicals are grafted to the syndiotactic polystyrene, so that the properties of the syndiotactic polystyrene can be arbitrarily controlled. It is still another object of the present invention to provide a styrenic grafted copolymer which has no residual unreacted vinyl radicals, so that crosslinking would not occur, and that there would be no problem in the moldability.
It is still another object of the present invention to provide a styrenic grafted copolymer in which diversified functional radicals of the syndiotactic polystyrene are introduced, so that the heat resistance and the chemical resistance can be maintained intact, and that the compatibility, the adhesibility and the coatability can be improved, thereby making it possible to use it as a raw material for resin compositions, and as a compatilizer.
It is still another object of the present invention to provide a resin composition in which there are contained one or more components selected from the group consisting of a styrenic grafted copolymer, a syndiotactic polystyrene, a thermoplastic resin, a rubber, and a filler.
Brief Description of the Drawings
The above objects and other advantages of the present invention will become more apparent by describing in detail the preferred embodiment of the present invention with reference to the attached drawings in which:
FIG. 1 is a SEM (scanning electron microscope) photograph showing size of the nylon particles in the syndiotactic polystyrene matrix when the content of the styrenic grafted copolymer is 0%, among the syndiotactic polystyrene/nylon/styrenic grafted copolymers;
FIG. 2 is a SEM photograph showing the decrease of the size of the nylon particles in the syndiotactic polystyrene matrix when the content of the styrenic grafted copolymer is 5%, among the syndiotactic polystyrene/nylon/styrenic grafted copolymers;
FIG. 3 is a SEM photograph showing the decrease of the size of the nylon particles in the syndiotactic polystyrene matrix when the content of the styrenic grafted copolymer is 10%, among the syndiotactic polystyrene/nylon/styrenic grafted copolymers; and
FIG. 4 is a SEM photograph showing the decrease of the size of the nylon particles in the syndiotactic polystyrene matrix when the content of the styrenic grafted copolymer is 20%, among the syndiotactic polystyrene/nylon/styrenic grafted copolymers.
Detailed Description of the Preferred Embodiments
The process for manufacturing the styrenic grafted copolymer according to the present invention includes the steps of: (1) preparing a syndiotactic stereoregular styrenic polymer having repeating units (A) by polymerizing vinylic aromatic monomers under a catalyst system, the catalyst system consisting of a transition metal compound (I) as a main catalyst component and an organic aluminum compound or an aluminoxane (II) as a cocatalyst component; and (2) graft- polymerizing monomers of Formula (B) having an unsaturated radical to the syndiotactic stereoregular styrenic polymer:
where Ri is hydrogen, halogen, or a substituted radical not containing carbon-carbon double bonds but containing one or more components selected from a group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; and m is an integer from 1 to 3 (if m is 2 or 3, Ri is same or different);
where each of R ~R5 is hydrogen, halogen, or a substituted group containing one or more components selected from the group consisting of carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin.
Or any two of R2~R5 are bonded together as following structure:
o o O O
I I I I II I I
■c— o— c or ■C— N— C - rl
where ri is hydrogen, a saturated hydrocarbon of Cι- 0, a hydroxy of Cι. o. a benzyl, a phenyl, or a substituted phenyl.
The styrenic grafted copolymer manufactured according to the present invention contains a polymer having the following repeating units:
where each of Rj, Ri' and Ri" is hydrogen, halogen, or a substituted group not containing carbon-carbon double bonds but containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; m is an integer from 1 to 3 (if m is 2 or 3, Ri is same or different); each of Xi and X2 is a substituted group obtained by radical-polymerizing one or more monomers; n is an integer from 1 to 3 (in a region of 1 <n-H≤3), and i. is an integer from 0 to 2. The vinylic aromatic monomer usable at the step (1) includes: styrene; alkylstyrene; halogenated styrene; vinylbiphenyl; vinylphenylnaphthalene; vinylphenylanthracene; vinylphenylphenanthrene; vinylphenylpyrene; vinylterphenyl; vinylphenylterphenyl; vinylalkylbiphenyl; halogenated vinylbiphenyl; halogen-substituted alkylstyrene; trialkylstannylvinylbiphenyl; trialkylsilylmethylvinylbiphenyl; trialkylstannylmethylvinylbiphenyl; alkylsilylstyrene; alkyl-containing silyl styrene; halogen-containing silylstyrene; silyl-containing silyl styrene; alkoxystyrene; aminostyrene; vinylnaphthalene; vinylbenzoate and their compounds.
The preferable examples of the alkyl-styrene include: p-methylstyrene; m- methylstyrene; o-methylstyrene; 2,4-dimethylstyrene; 2,5-dimethylstyrene; 3,4- dimethyl styrene; 3,5-dimethylstyrene; p-ethylstyrene; m-ethylstyrene; and p- tertiarybutylstyrene.
The preferable examples of the halogenated styrene include: p-chlorostyrene; m-chlorostyrene; o-chlorostyrene; p-bromostyrene; m-bromostyrene; o- bromostyrene; p-fluorostyrene; m-fluorostyrene; o-fluorostyrene; o-methyl-p- fluorostyrene. The preferable examples of the vinyl biphenyl include: 4-vinylbiphenyl; 3- vinylbiphenyl; and 2-vinylbiphenyl.
The preferable examples of the halogenated alkyl styrene include: p-chloro- ethylstyrene; m-chloroethylstyrene; and o-chloroethylstyrene.
The preferable example of the trialkylsilyl vinyl biphenyl includes 4-vinyl-4'- trimethyl silyl biphenyl.
The preferable example of the trialkyl stannyl vinyl biphenyl includes 4-vinyl- 4'-trimethyl stannyl vinyl biphenyl.
The preferable example of the trialkyl silyl methyl vinyl biphenyl includes 4- vinyl-4'-trimethyl silyl methyl vinyl biphenyl. The preferable example of the trialkyl stannyl methyl vinyl biphenyl includes
4-vinyl-4'-trimethyl stannyl methyl vinyl biphenyl.
The preferable example of the alkyl silyl styrene includes p-trimethylsilyl styrene.
The preferable example of the phenyl-containing silyl styrene includes p- dimethylphenylsilylstyrene.
The preferable example of the halogen-containing silyl styrene includes p- dimethylchlorosilylstyrene.
The preferable example of the silyl-containing silyl styrene includes p-(p- trimethyl-silyl) dimethylsilylstyrene. The preferable examples of the alkoxy styrene include: methoxy styrene, and ethoxy styrene.
The preferable example of the amino-styrene includes dimethyl-amino-styrene.
The transition metal compound (I) is expressed by formula (1) as follows:
MR6 aR7 bR8 cR9 4.(a+b+c) or
(1)
where M and M' are transition metals of Groups IV, V and VI of the Periodic Table, and R6~R9 are ligands bondable with metals, such as hydrogen, halogen, hydroxy, alkyl, alkoxy, cycloalkyl, acyloxy, aryloxy, cyclopentadienyl, indenyl, fluorenyl, substituted cyclopentadienyl, substituted indenyl, or substituted fluorenyl.
In the transition metal compound (I), if the ligand has two or more reaction groups which are bondable with metals, then any one of R6~R9 is bonded with one or more different metals to form multi-metal compounds of the following formulas:
*'\ /G\ '
M M'
Cp G Y2
The catalyst components include: organic aluminum compounds and aluminoxane. The examples of the organic aluminum compounds include: trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum. The aluminoxane is a reaction product of the organic aluminum compounds and water, and is expressed by formula (2) as follows:
(2)
where R10 is an alkyl of Cι.8, and j is an integer from 2 to 50.
In the catalyst of the step (1), the mole ratio of aluminum to the transition metal is preferably 1 : 1 - 1 x 106 : 1 , and more preferably 10 : 1 - 1 x 104 : 1.
The polymerization conditions for manufacturing the syndiotactic stereoregular styrenic polymer are as follows. That is, the polymerization temperature is 0 - 120 degrees C; the polymerization time period is 1 second to 24 hours; the polymerization method is a bulk polymerization, a solution polymerization, or a suspension polymerization; and the usable solvent includes aliphatic hydrocarbons, and aromatic hydrocarbons.
The monomers which are grafted at the step (2) include: styrene, vinyl acetate, acrylic acid, acrylic anhydride, methacrylic acid, acrylic acid ester, methacrylic acid ester, acryl amide, acrylonitrile, maleic acid, fumaric acid, maleimide, itaconic acid, itaconic anhydride, diolefin and their derivatives. Further the grafted monomers include: maleic anhydride and a monomer selected from the group consisting of: styrene, vinyl acetate, acrylic acid, acrylic anhydride, methacrylic acid, acrylic acid ester, methacrylic acid ester, acryl amide, acrylonitrile, maleic acid, fumaric acid, maleimide, itonic acid, itaconic anhydride, diolefin and their derivatives.
The styrene derivative includes: all kinds of styrene derivatives used in the step(l).
The vinyl acetate derivative includes: vinyl-alpha-(l-cyclohexenyl) acetate.
The acrylic acid ester includes: aryl acrylate, isopropyl acrylate, ethyl acrylate, 2,3-epoxy propyl acrylate, 2-chloroethyl acrylate, chloroacrylate, cyclododesil acrylate, dibromopropyl acrylate, hydroxy ethyl acrylate, butyl acrylate, benzyl acrylate, 2-hydroxy ethyl acrylate, glycidyl acrylate, and the methacrylic acid ester derivatives corresponding to the acrylic acid ester.
The acryl amide derivative includes: N-methyl acryl amide, N-ethyl acryl amide, N-isopropyl acryl amide, N-butyl acryl amide, N-benzyl acryl amide, N-aryl acryl amide, N-phenyl acryl amide, N-methyl methacryl amide, N-ethyl methacryl amide, N-aryl methacryl amide, N-(methoxy methyl) acryl amide, N-(methoxy ethyl) acryl amide, N,N-bis(2-cianoethyl) acryl amide, N,N'-methylene bisacryl amide, 1 ,2- bis-acryl amide ethane, 1,5-bisacryl amide pentane, N-acryloil glycine amide, and 2- acryl amide propane sulfonic acid.
The acrylonitrile derivative includes: vinylidene cyanate, alpha-methoxy acrylonitrile, alpha-phenyl acrylonitrile, and alpha-acetoxy acrylonitrile.
The derivatives of the maleic acid, fumaric acid and maleic anhydride include: methyl maleic anhydride, phenyl maleic anhydride, chloromaleic anhydride, methyl maleic acid, phenyl maleic acid, chloromaleic acid, dimethyl malate, dibenzyl malate, diethyl fumarate, and fumaronitrile. The maleimide derivative includes: N-butyl maleimide, N-phenyl maleimide,
N-cyclohexyl maleimide, and N-(alpha-naphthyl) maleimide.
The diolefin includes: 1,3-butadiene, isobutadiene, l-ethoxy-l,3-butadiene, and l-chloro-l,3-butadiene.
Besides, unsaturated carboxylic acid, its anhydride, its ester and its amide derivatives can be used.
At the step (2), a radical initiating agent is used, and this initiating agent activates either the chain of the syndiotactic stereoregular styrenic polymer first, or the grafted monomers first, or activates the two simultaneously. In the present invention, the usable radical initiating agent includes: azo compounds, peroxide compounds or compounds capable of forming radicals.
The preferable examples of the azo compounds include: 2,2'-azobis-propane, 2,2'-dichloro-2,2'-azobis-propane, 1,1 '-azo (methylethyl) diacetate, 2,2'-azobis (2- amidinopropane) nitrate, 2,2'-azobis isobutane, 2,2'-azobis isobutyl amide, 2,2'- azobis isobutyl nitrile, 2,2'-azobis-2-methyl butyl nitrile, dimethyl-2,2'-azobis isobutylate, dimethyl 2,2'-azobisisobutylate/ tetrachlorotin (1/19.53), l,l'-azobis (sodium- 1 -methyl butyl nitrile-3 -sulfonate), 2-(4-methyl phenyl azo)-2-methyl malonodinitrile, 4,4'-azobis-4-cianobaleic acid, 3,5-dihydroxy methyl phenyl azo-2- aryl malonodinitrile, 2-(4-bromophenyl azo)-2-aryl malonodinitrile, 2,2'-azobis-2- propyl butyl nitrile, l,l'-azobis cyclohexane nitrile, 2,2'-azobis-2-propyl butyl nitrile, 1,1 '-azobis- 1 -chlorophenyl ethane, 1,1' azobis- 1 -cyclohexane carbonitrile, 1,1'- azobis-cycloheptane nitrile, l,l'-azobis-l -phenyl ethane, 1,1 -azobis cumene, ethyl-4- nitrophenyl azo-benzyl cianoacetate, phenyl-azo-phenyl methane, phenyl azo triphenyl methane, 4-nitrophenyl azo triphenyl methane, 1,1 '-azobis- 1,2-diphenyl ethane, poly (bis phenol A-4,4'-azobis-4-cianopentanoate, and poly (tetraethylene glycol-2,2'-azobis-isobutylate.
The preferable examples of the peroxide compounds include: acetyl peroxide, cumyl peroxide, tertiary butyl peroxide, propionyl peroxide, benzoyl peroxide, 2- chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4- dichlorobenzoyl peroxide, 4-bromomethyl benzoyl peroxide, potassium persulfate, diisopropyl peroxy carbonate, tetrahnhydroperoxide, 1 -phenyl-2-methyl propyl-1 - hydroperoxide, l-phenyl-2 -methyl propyl-1 -hydroperoxide, l-phenyl-2 -methyl propyl-1 -hydroperoxide, tertiary butyl hydroperoxide, tertiary butyl performate, tertiary butyl peracetate, tertiary butyl perbenzoate, tertiary butyl perphenyl acetate, tertiary butyl per-4-methoxy acetate, and tertiary butyl per-N-(3-tolyl)carbamate. The preferable examples of the compounds which are capable of forming the radicals include: 1,4-bis (penta-methylene)-2-tetrazene, 1 ,4-di-methoxy carbonyl- 1 ,4-diphenyl-2-tetrazene, and benzene sulfonyl azide.
At the step (2), the graft reaction is carried out in the following manner. That is, in accordance with the kinds of the grafting monomers and the radical polymerization initiating agent, there is carried out a solution polymerization, a
suspension polymerization or a reaction polymerization (within a reacting mixer or within an extruder), and the reaction is carried out at a temperature of 30 - 320 degrees C for one second to 24 hours. The solvent which can be used in the solution polymerization includes: aliphatic hydrocarbons, and aromatic hydrocarbons. The suspension polymerization is carried out in the following manner. That is, a radical initiating agent and a monomer having one or more unsaturated radicals are sufficiently diffused into a styrenic polymer, and water is used to disperse the particles so as to form a suspension, thereby carrying out a grafting copolymerization. An organic compound and an inorganic salt are used as the suspending agent. The organic compound includes: methyl cellulose, ethyl cellulose, polyacrylic acid, polymethacrylic acid, their salts, polyvinyl alcohol, gelatine, starch, rubber, and protein. The inorganic salt includes: magnesium carbonate, calcium carbonate, calcium phosphate, titanium oxide, aluminum oxide, silicate, clay, and bentonite. And the amount of water used is not particularly limited. The styrenic grafted copolymer manufactured in the above described process is characterized in that the structure of the main chain has a syndiotactic stereoregularity. The syndiotactic stereoregularity is acknowledged if the following conditions are satisfied. That is, the measurements by 13CNMR should show the results that the racemic dyad within the styrenic repeated chains is 75% or more and preferably 85% or more, and the racemic pentad is 30%> or more and preferably 50% or more.
Further, the average molecular weight of the main chain is generally 1,000 - 3,000,000 when it is measured by GPC by dissolving it in 1,2,4-trichlorobenzene at 135 degrees C. In the grafted copolymer, the content of the grafted monomers can be different depending on the kinds of the monomers and the initiating agent. Generally, the content occupies 0.001 to 50 wt% within the total copolymer. and the reduced viscosity is 0.01 to 20 dL/g when it is measured in 1,2,4-trichlorobenzene at 135 degrees C with a concentration of 0.05 g/dL.
The grafted copolymer thus obtained is mixed with one or more ingredients selected from the group consisting of: syndiotactic polystyrene, thermoplastic resin,
rubber, and filler, so as to form various resin compositions of various applications.
The syndiotactic polystyrene which is used in the resin compositions includes: copolymers and their mixtures having the main ingredient of any one of: polystyrene, poly(alkylstyrene), poly(halogenated styrene), poly(halogenated alkyl styrene), poly(alkoxy styrene), and poly(vinyl benzoate).
The thermoplastic resin which can be used in the resin compositions includes all kinds of resins which are obtained through an add reaction or a condensation reaction. The preferable examples include: polyolefin, ethylenevinyl copolymer, amorphous polystyrene, polyester, polyacetal, polycarbonate, polyacrylate, polyamide, polyether, polyphenylene oxide, polyphenylene sulfide, polyoxy methylene, polyimide, polysulfone, polyether sulfone, polyurethane, acrylate resin, and halogenated resin. These compounds can be denatured or grafted by the styrenic monomers so as to increase the compatibility with the syndiotactic styrenic polymers. Or they are transformed so as to have a reactive functional group or they originally have it, thereby improving the blending efficiency.
The preferable examples of the thermoplastic resins having the functional group include: polyethylene terephthalate, polybutylene terephthalate, polyoxy ethoxy benzoate and polyethylene naphthalate having one selected from the group consisting of carbonyl, hydroxy, amino, isocyanate and epoxy; polyester modified by acid; poly aryl sulfide; polyamide-6; polyamide-6,6'; ethylene vinyl alcohol; and ethylene vinyl acetate.
The rubber which can be used in the resin compositions includes: natural rubber, polybutadiene, polyisoprene, polyisobutylene, neoprene, polysulphide rubber, acryl rubber, urethane rubber, silicon rubber, thiocol rubber, epichlorohydrine rubber, styrene/butadiene block copolymer, hydrogenated styrene/butadiene block copolymer, styrene/butadiene/styrene block terpolymer, styrene/butadiene random copolymer, ethylene/propylene copolymer, ethylene/propylene/diene copolymer, core-shelled butadiene/acrylonitrile/styrene terpolymer, methyl methacrylate/butadiene/styrene polymer, alkyl acrylate/butadiene/acrylonitrile/styrene copolymer, butadiene/styrene polymer, rubber transformed so as to have a reactive functional group, and rubber
transformed or grafted to styrenic group.
The fillers which can be used in the resin compositions have no special limitations, and include: silica, boron, alumina, titanium dioxide, magnesium oxide, aluminum hydroxide, aluminum nitride, magnesium carbonate, calcium sulfate, magnesium sulfate, potassium titanate, barium titanate, barium sulfate, talc, clay, glass fiber, boron fiber, silicon bead fiber, metal fiber, carbon black, aluminum powder, and molybdenum sulfide.
Now the present invention will be described based on actual examples. These examples are not for limiting the scope of the appended claims.
Example 1
Preparation of styrene/3(4)-methyl styrene copolymer :
A mixture of 2 L of styrene and 0.077 L of 3(4)-methyl styrene were put into a 10L reaction vessel which had been sufficiently filled with nitrogen. Then 30 mL (0.12 moles) of TIB A was added, and then, an agitation was carried out for 15 minutes. Then 2.5 m moles of MAO was added and then an agitation was carried out for 5 minutes. Then 25 micro moles (Ti) of (Cp*Ti) (OC6H4C(CH3) C H O)3 was added, and then, a pre-polymerization was carried out for one hour. Then a mixture of 10 m moles of MAO and 100 micromoles of a catalyst were added gradually over a time period of 30 minutes, and then a polymerization was carried out for one hour. Then the reaction was terminated by putting methanol. Then a large amount of acetone was put, and NaOH was put to decompose the catalyst. Then a filtering was carried out, the methanol was washed off twice, and then a drying was carried out in a vacuum oven. The synthesized copolymer was 770 g, and the GPC measurements showed that Mn=324,000, Mwe=607,400, and MWD=1.87. The 1H NMR measurement showed a total content of 5.4 mole % of 3(4)-methyl styrene, and a DSC measurement showed that Tg=98.6 degrees C, Tm=257.57 degrees C. The 3(4)- methyl peak of 3(4)-methyl styrene could be confirmed at delta 2.30, 2.36 ppm of Η NMR and at delta 20.8, 21.2 ppm of 13C NMR.
Preparation of (styrene/3(4)-methyl styrene)/glycidyl methacrylate grafted copolymer :
To 50 g of the styrene/3(4)-methyl styrene copolymer which had been prepared in the above described manner, there was added 330 mL of xylene. and then an agitation was carried out for one hour, thereby sufficiently making the polymer swelled. Then a mixture which had been prepared by adding 1 g of benzoyl peroxide to 50 mL of glycidyl methacrylate was added, and then an agitation was carried out for 30 minutes. Then again, an agitation was carried out at a temperature of 110 degrees C for 6 hours. Then the reaction was made to terminate by putting methanol, and then a filtering was carried out. Then the polymer was dissolved in dichlorobenzene, and then the polymer was made to be precipitated by using methyl ethyl ketone. Then a filtering was carried out, and then a thorough wash was carried out by using methyl ethyl ketone, thereby removing the single polymers of glycidyl methacrylate. Then a drying was carried out for 5 hours in a vacuum oven. The polymer thus obtained was analyzed by 1H NMR, and the result showed that the total content of poly glycidyl methacrylate based on the integration ratio of the peak of glycidyl radical (C(C=0)OCH2) at delta 4.464, 4.092 ppm was 10.8 mole%. The GPC measurement result showed that Mn=294,600, Mw=512,400, and MWD=1.74.
Example 2
Preparation of (styrene/3(4)-methyl styrene)/(styrene/maleic anhydride) grafted copolymer : Instead of the glycidyl methacrylate, 10 mL of styrene and 10 g of maleic anhydride were used, and the reaction temperature was not 110 degrees C but 130 degrees C. The benzoyl peroxide was substituted by di-cumyl peroxide. Except the above matters, the manufacture was carried out in the manner same as that of Example 1. The analysis of the obtained polymer by IR showed that the C=O peak was seen at 1779.6 cm"1, and that the total content obtained through the optimum
curve was about 3%. The DSC measurement result showed that Tg=96.4 degrees C, and Tm=255.9 degrees C. The GPC measurement showed that Mn=266,000, Mw=463,800, and MWT 1.74.
Example 3
Preparation of (styrene/3(4)-methyl styrene)/methyl methacrylate grafted copolymer :
A mixture which had been prepared by adding 1 g of benzoyl peroxide to 50 mL of methyl methacrylate was added to 50 g of the styrene/3(4)-methyl styrene copolymer of Example 1. Then an agitation was carried out for 30 minutes, so that the mixture would be sufficiently absorbed into the polymer. Then nitrogen was injected into a distilled water to remove oxygen. Then 1 g of poly vinyl alcohol was added into it, and then an agitation was carried out at 200 rpm. This mixture as a suspension was agitated for 4 hours at a temperature of 95 degrees C. Then the reaction was terminated by putting methanol, a filtering was carried out, and a wash was carried out by using a sufficient amount of water, thereby removing the poly vinyl alcohol. Then this copolymer was completely dissolved in di-chloro-benzene, and it was made to be precipitated by using methyl ethyl ketone. Then a sufficient wash was carried out by using the methyl ethyl ketone, thereby removing the single copolymers of methyl methacrylate. Then a drying was carried out at a temperature of 100 degrees C for 5 hours in a vacuum oven. The copolymer thus obtained was analyzed by Η NMR, and the result showed that the total content of the grafted poly methyl methacrylate was 12.8 mole%. The GPC measurement showed that Mn=286,200, Mw=568,500, and MWD=1.99.
Example 4
Preparation of styrene/4-methyl styrene copolymer : Styrene and 4-methyl styrene were put in respective amounts of 2 L and
0.077 L into a 10L reaction vessel in which nitrogen had been filled. Then the manufacture was carried out in the same manner as that of the styrene/3(4)-methyl styrene copolymer of Example 1. The amount of the synthesized copolymer was 1045 g, and the GPC measurement showed that Mn=233,900, Mw=429,200, and MWD=1.83. At Η NMR delta 2.35 ppm and at 13C NMR delta 20.8 ppm, the 4- methyl peak could be confirmed. The total content of the 4-methyl styrene was 4.5 mole%, and the DSC measurement showed that Tg=99.1 degrees C, and Tm=258.2 degrees C.
Preparation of (styrene/4-methyl styrene)/methyl methacrylate grafted copolymer : As the graft precursor, the styrene/4-methyl styrene copolymer manufactured just above was used instead of the styrene/3(4)-methyl styrene copolymer. Except this matter, the manufacture carried out in the same manner as that of Example 3. The Η NMR analysis on the obtained polymer showed that the total content of the grafted poly methyl methacrylate was 6.1 mole%. The IR analysis showed that the C=O peak was seen at 1730cm"1, the DSC measurement showed that Tg=99.3 degrees C, and Tm=257.4 degrees C. The GPC measurement showed that Mn=219,400, Mw=468,600, and MWD=2.14.
Example 5
Preparation of (styrene/4-methyl styrene)/ethyl acrylate grafted copolymer :
Ethyl acrylate and xylene were used in amounts of 20 mL and 10 mL instead of 50 mL of the methyl methacrylate. Except this matter, the manufacture was carried out in the same manner as that of Example 4. For the obtained polymer, the Η NMR analysis showed that the total content of the grafted poly ethyl acrylate as obtained from the integration ratio of the ethoxy (OCH2CH3) peak at delta 4.298 ppm was 10.6 mole%.
Example 6
Preparation of syndiotactic polystyrene/methyl methacrylate grafted copolymer :
As the graft precursor, a styrene single polymer was used instead of the styrene/3(4)-methyl styrene copolymer. Except this matter, the manufacture was carried out in the same manner as that of Example 3. The 1H NMR analysis on the obtained polymer showed that the total content of the grafted poly methyl methacrylate was 4.7 mole%. The IR analysis showed that the C=O peak was seen at 1730cm"1, and the GPC measurement showed that Mn=l 99,800, Mw=450,600, and MWD=2.26.
Example 7
Preparation of syndiotactic polystyrene/ethyl acrylate grafted copolymer :
Ethyl acrylate and xylene were used in amounts of 20 mL and 10 mL respectively, instead of 50 mL of the methyl methacrylate. Except this matter, the manufacture was carried out in the same manner as that of Example 6. The Η NMR analysis on the obtained polymer showed that the total content of the grafted polyethyl acrylate as obtained from the integration ratio of the ethoxy (OCH?CH3) peak at delta 4.281 ppm was 7.2 mole%.
Example 8
Syndiotactic polystyrene/nylon blending :
Syndiotactic polystyrene and nylon in respective amounts of 36 g and 9g were mixed together. The mixing was carried out at a temperature of 280 degrees C at 50 rpm for 7 minutes by using a Haake mixer. Then a thin sheet with a thickness of 3 mm was formed by a hot pressure. This was cut under nitrogen atmosphere, and the cut edges were plated with gold. Then an observation was carried out by using an SEM (scanning electron microscope). The size of the nylon particles within the syndiotactic polystyrene matrix was 5 - 10 micrometers.
Example 9
Syndiotactic polystyrene/nylon/styrene grafted copolymer blending:
Syndiotactic polystyrene, nylon and the (styrene/maleic anhydride) grafted copolymer of Example 2 in respective amounts of 33.75 g, 9 g, and 2.25 g were mixed together. Then the cut faces were observed in the same manner as that of Example 8. The size of the nylon particles within the syndiotactic polystyrene matrix was 2 - 3 micrometers.
Example 10
Syndiotactic polystyrene/nylon/styrene grafted copolymer blending :
Syndiotactic polystyrene, nylon and styrene/maleic anhydride grafted copolymer of Example 2 in respective amounts of 31.5 g, 9 g, and 4.5 g were mixed together. Then the cut faces were observed in the same manner as that of Example 8. The size of the nylon particles within the syndiotactic polystyrene matrix was less than 1 micrometer.
Example 11
Syndiotactic polystyrene/nylon/styrene grafted copolymer blending :
Syndiotactic polystyrene, nylon and the (styrene/maleic anhydride) grafted copolymer of Example 2 in respective amounts of 27 g, 9 g, and 9 g were mixed together. Then the cut faces were observed in the same manner as that of Example 8. The nylon particles within the syndiotactic polystyrene matrix could not be particularly observed.
The polymerization conditions and results for Examples 1 to 7 are shown in Tabled 1 below. The SEM photographs for the syndiotactic polystyrene/nylon/styrene
grafted copolymer blending of Examples 8 to 11 are shown in FIGs 1 to 4. It can be seen that if the content of the copolymer is increased through 0%, 5%, 10% and 20%, the size of the nylon particles within the syndiotactic polystyrene matrix is decreased.
Example 12
40g of (Styrene/4-methyl styrene)/methyl methacrylate grafted copolymer of Example 4 was carried out at a temperature of 280 degree C at 50 rpm for 5 minutes by Haake mixer. The mixture showed that the value of torque in a solid state was 30. After 1 minute, the copolymer was liquefied and the value of torque was decreased to 10 and maintained. During the reaction, it was observed that the torque was not increased and the moldability by crosslinking was not decreased.
Table 1
Example
Styrenic sP(S-3(4) sP(S-3(4) sP(S-3(4) sP(S-4- sP(S-4- sPS sPS polymer -MS) -MS) -MS) MS) MS)
Monomer GMA SM lOmL MMA MMA EA MMA EA
50mL MAH lOg 50mL 50mL 20mL 50mL 20mL
Radical BPO DCP BPO BPO BPO BPO BPO initiating agent lg lg lg lg lg lg lg
Solvent Xylene Xylene Water Water Water Water Water
200mL 330mL 300mL 300mL 300mL 300mL 300mL
Suspension - - PVA PVA PVA PVA PVA lg lg lg lg ig
Temp. 110T 130°C 95 °C 95 °C 95 °C 95 °C 95 °C
Time 4hr 6hr 4hr 4hr 4hr 4hr 4hr
Graft 10.8 3.0 12.8 6.1 10.6 4.7 7.2 content mole% mole% mole% mole% mole% mole% mole%
IR 1726.3 1779.6 1730.9 1730.1 1734.7 1730.4 1735.1
(cm" 1) (C=0) (MAH) (C=0) (C=0) (C=0) (C=0) (C=0)
NMR 4.464 - 3.721 3.726 4.298 3.726 4.281 delta,ppm 4.092 ~ (OMe) (OMe) (OCH2) (OMe) (OMe) (OCH2)
DSC Tg( TJ ) 94.3 96.4 94.5 99.3 102 100 101
Tm(t) 255.9 255.9 256.1 257.4 258.2 275.1 275.6
Claims
1. A process for producing a styrenic grafted copolymer, comprising the steps of:
(1) preparing a syndiotactic stereoregular styrenic polymer having repeating units (A) by polymerizing vinyl aromatic monomers under a catalyst system, the catalyst system consisting of transition metal compounds (I) as main catalyst components and organic aluminum compounds or aluminoxanes (II) as cocatalyst components; and
(2) graft-polymerizing monomers of Formula (B) having ethylenically unsaturated bonds to the syndiotactic stereoregular styrenic polymer:
where Ri is hydrogen, halogen, or a substituent not containing carbon-carbon double bonds but containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; and m is an integer from 1 to 3 (if m is 2 or 3, Ri is same or different);
where each of R - R5 is hydrogen, halogen, or a substituent containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin.
2. The process as claimed in claim 1 , wherein the grafted monomer is selected from the group consisting of: styrene, vinyl acetate, acrylic acid, acryl anhydride, methacrylic acid, acrylic acid ester, methacrylic acid ester, acryl amide, acrylonitrile, maleic acid, fumaric acid, maleimide, itaconic acid, anhydrous itaconic acid, diolefin and their derivatives.
3. The process as claimed in claim 1 , wherein the grafted monomer comprises: maleic anhydride; and one or more of monomers selected from the group consisting of: styrene, vinyl acetate, acrylic acid, acryl anhydride, methacrylic acid, acrylic acid ester, methacrylic acid ester, acryl amide, acrylonitrile, maleic acid, fumaric acid, maleimide, itaconic acid, anhydrous itaconic acid, diolefin and their derivatives.
4. The process as claimed in claim 1 , wherein to produce the styrenic grafted copolymer, polymerization is carried out at a temperature of 30 - 320 degrees C for 1 second to 24 hours.
5. The process as claimed in claim 1 , wherein the solvent capable of dispersing, swelling or dissolving the syndiotactic stereoregular styrenic polymer is used to carry out the graft polymerization step in a solution of a uniform system or in a suspension of a non-uniform system.
6. The process as claimed in claim 5, wherein the solvent is selected from the group consisting of aliphatic hydrocarbon; alicyclic hydrocarbon; aromatic hydrocarbon; and a hetero hydrocarbon containing halogen, oxygen, nitrogen, or sulfur.
7. The process as claimed in claim 1 , wherein the graft polymerization step is carried out in the suspension system being formed by using water and a suspending agent.
8. The process as claimed in claim 7, wherein the suspending agent comprises organic compounds and inorganic compounds.
9. The process as claimed in claim 1, wherein the graft polymerization step is carried out in a high temperature reactive mixer or extruder, without using a solvent.
10. The process as claimed in claim 1 , wherein the graft polymerization step uses a radical initiating agent.
11. The process as claimed in claim 10, wherein the radical initiating agent is an azo compound, a peroxide compound or other compounds capable of forming radicals.
12. The process as claimed in claim 1 , wherein in the monomer having the ethylenically unsaturated bonds, any two of R - R are bonded together as following structures:
o O O
I I o I I I I I I c— o— c- or C — N — C - 
where T is hydrogen, a saturated hydrocarbon of Cι. 0, a hydroxy of C].2o, a benzyl, a phenyl, or a substituted phenyl.
13. A styrenic grafted copolymer produced based on the steps of: (1) preparing a syndiotactic stereoregular styrenic polymer having repeating units (A) by polymerizing vinyl aromatic monomers under a catalyst system, the catalyst system consisting of transition metal compounds (I) as main catalyst components and organic aluminum compounds or aluminoxanes (II) as cocatalyst components; and (2) graft-polymerizing monomers of Formula (B) having ethylenically unsaturated bonds to the syndiotactic stereoregular styrenic polymer: 
where Ri is hydrogen, halogen, or a substituent not containing carbon-carbon double bonds but containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin; and m is an integer from 1 to 3 (if m is 2 or 3, Ri is same or different);
where each of R ~R5 is hydrogen, halogen, or a substituent containing one or more components selected from the group consisting of: carbon, oxygen, nitrogen, sulfur, phosphorus, selenium, silicon, and tin.
14. The styrenic grafted copolymer as claimed in claim 13, wherein the styrenic grafted copolymer contains a polymer having the following repeating units:
15. The styrenic grafted copolymer as claimed in claim 13, wherein a main chain has a structure of syndiotactic stereoregularity, and a 13CNMR measurement shows racemic dyad of 75% or more within styrenic repeated chains and racemic pentad of 30% or more
16. The styrenic grafted copolymer as claimed in claim 15, wherein the main chain has a structure of syndiotactic stereoregularity, and a 13CNMR measurement shows racemic dyad of 85% or more within styrenic repeated chains and racemic pentad of 50%) or more
17. The styrenic grafted copolymer as claimed in claim 13, wherein an average molecular weight of the main chain is generally 1,000 - 3,000,000 when it is measured by GPC by dissolving it in 1,2,4-trichlorobenzene at 135 degrees C; and a content of the grafted monomer occupies 0.001 to 50 wt% within a total copolymer, and its reduced viscosity is 0.01 to 20 dL/g when it is measured in 1,2,4- trichlorobenzene at 135 degrees C with a concentration of 0.05 g/dL.
18. A resin composition comprising: a styrenic grafted copolymer of claims 13 to 17; and one or more ingredients selected from the group consisting of: syndiotactic polystyrene, thermoplastic resin, rubber, and a filler.
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| KR1999/7544 | 1999-03-08 | ||
| KR10-1999-0007544A KR100369625B1 (en) | 1999-03-08 | 1999-03-08 | Styrenic graft copolymer and method of preparing the same |
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| WO2002048222A1 (en) * | 2000-12-12 | 2002-06-20 | Idemitsu Petrochemical Co., Ltd. | Process for producing polymer composition |
| WO2003082941A1 (en) * | 2002-03-28 | 2003-10-09 | Kometra Kunststoff-Modifikatoren Und -Additiv Ag | Method for the production of functionalized syndiotactic polystyrenes |
| EP1290046A4 (en) * | 2000-06-02 | 2006-09-13 | Samsung Atofina Co Ltd | Method of preparing monomer-grafted syndiotactic polystyrene with polarity |
| WO2008074744A1 (en) * | 2006-12-18 | 2008-06-26 | Akzo Nobel N.V. | Process for the preparation of a cross-linked rubber article |
| CN101573402B (en) * | 2006-12-18 | 2012-03-21 | 阿克佐诺贝尔股份有限公司 | Process for the preparation of a cross-linked rubber article |
| US8277664B2 (en) | 2008-10-03 | 2012-10-02 | California Institute Of Technology | Extraction of anions from solutions and mixtures using hyperbranched macromolecules |
| US8658702B2 (en) | 2009-12-17 | 2014-02-25 | Mamadou Diallo | Soluble anion exchangers from hyperbranched macromolecules |
| US9815712B2 (en) | 2008-10-03 | 2017-11-14 | California Institute Of Technology | High capacity perchlorate-selective resins from hyperbranched macromolecules |
| CN109627665A (en) * | 2018-12-20 | 2019-04-16 | 广州辰东新材料有限公司 | A kind of thermoplastic resin composition and preparation method thereof for laser direct forming |
| CN114456321A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Polymer microsphere with core-shell structure and preparation method and application thereof |
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| KR100340276B1 (en) * | 2000-04-06 | 2002-06-12 | 박호군 | Functionalized Macromonomers and Preparation of Crystalline- Amorphous Graft Copolymers Using Them |
| KR100714658B1 (en) * | 2001-04-16 | 2007-05-07 | 삼성토탈 주식회사 | Syndiotactic Polystyrene Reactor Copolymer |
| CN116425919B (en) * | 2023-03-06 | 2024-01-12 | 湖南工业大学 | Poly(meth)acrylimide foam material and preparation method thereof |
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| JPH05247147A (en) * | 1992-03-03 | 1993-09-24 | Idemitsu Kosan Co Ltd | Graft copolymer and method for producing the same |
| EP0733675A1 (en) * | 1994-10-05 | 1996-09-25 | Idemitsu Kosan Company Limited | High-impact polystyrene resin composition |
| JPH1025382A (en) * | 1997-04-07 | 1998-01-27 | Asahi Chem Ind Co Ltd | Impact-resistant resin composition |
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| EP1290046A4 (en) * | 2000-06-02 | 2006-09-13 | Samsung Atofina Co Ltd | Method of preparing monomer-grafted syndiotactic polystyrene with polarity |
| US6696525B2 (en) | 2000-12-12 | 2004-02-24 | Idemitsu Petrochemical Co., Ltd. | Process for producing polymer composition |
| WO2002048222A1 (en) * | 2000-12-12 | 2002-06-20 | Idemitsu Petrochemical Co., Ltd. | Process for producing polymer composition |
| WO2003082941A1 (en) * | 2002-03-28 | 2003-10-09 | Kometra Kunststoff-Modifikatoren Und -Additiv Ag | Method for the production of functionalized syndiotactic polystyrenes |
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| WO2008074744A1 (en) * | 2006-12-18 | 2008-06-26 | Akzo Nobel N.V. | Process for the preparation of a cross-linked rubber article |
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| US8277664B2 (en) | 2008-10-03 | 2012-10-02 | California Institute Of Technology | Extraction of anions from solutions and mixtures using hyperbranched macromolecules |
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| CN109627665B (en) * | 2018-12-20 | 2021-05-28 | 广州辰东新材料有限公司 | Thermoplastic resin composition for laser direct forming and preparation method thereof |
| CN114456321A (en) * | 2020-10-21 | 2022-05-10 | 中国石油化工股份有限公司 | Polymer microsphere with core-shell structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100369625B1 (en) | 2003-01-30 |
| KR20000059728A (en) | 2000-10-05 |
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