CN1290929C - 具有优异冲击强度的热塑性树脂组合物 - Google Patents
具有优异冲击强度的热塑性树脂组合物 Download PDFInfo
- Publication number
- CN1290929C CN1290929C CNB028031717A CN02803171A CN1290929C CN 1290929 C CN1290929 C CN 1290929C CN B028031717 A CNB028031717 A CN B028031717A CN 02803171 A CN02803171 A CN 02803171A CN 1290929 C CN1290929 C CN 1290929C
- Authority
- CN
- China
- Prior art keywords
- parts
- weight
- graft copolymer
- median size
- butadiene rubber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title claims abstract description 8
- 229920000126 latex Polymers 0.000 claims abstract description 49
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 43
- 239000004816 latex Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 30
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 18
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 10
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims 1
- 238000010559 graft polymerization reaction Methods 0.000 abstract description 10
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 34
- 230000035939 shock Effects 0.000 description 23
- 239000011734 sodium Substances 0.000 description 23
- 229920001971 elastomer Polymers 0.000 description 19
- 239000005060 rubber Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 12
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 12
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 12
- 235000003891 ferrous sulphate Nutrition 0.000 description 12
- 239000011790 ferrous sulphate Substances 0.000 description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- -1 vinyl cyanide compound Chemical class 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 3
- QUPCNWFFTANZPX-UHFFFAOYSA-N hydrogen peroxide;1-methyl-4-propan-2-ylcyclohexane Chemical class OO.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-N 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 3
- 229940093916 potassium phosphate Drugs 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- IHEJEKZAKSNRLY-UHFFFAOYSA-N Acido n-nonacosanoico Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O IHEJEKZAKSNRLY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005399 allylmethacrylate group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- FDIPQOXCCVNUES-UHFFFAOYSA-N octane-1-thiol;tin Chemical compound [Sn].CCCCCCCCS FDIPQOXCCVNUES-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- VNNBZUFJRRODHO-UHFFFAOYSA-N prop-2-enenitrile;prop-1-en-2-ylbenzene Chemical compound C=CC#N.CC(=C)C1=CC=CC=C1 VNNBZUFJRRODHO-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-M ricinoleate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O WBHHMMIMDMUBKC-QJWNTBNXSA-M 0.000 description 1
- 229940066675 ricinoleate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- C08L27/00—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 a halogen; Compositions of derivatives of such polymers
- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
- C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- C08L51/04—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 rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
一种具有优异冲击强度的热塑性树脂组合物,其包含(A)1-30重量份的接枝共聚物和(B)99-70重量份的热塑性树脂,其中所述接枝共聚物是由70-5重量份的单体组分在30-95重量份(按固体计)丁二烯橡胶胶乳存在下通过一步或多步聚合得到的,并且通过使用水溶性电解质凝结粒子和增大粒径,同时使所得接枝共聚物的平均粒径(b)与丁二烯橡胶的平均粒径(a)之比,即(b)/(a),调节到2.9或更高,其中所述的单体组分包含50-100wt%的甲基丙烯酸甲酯和50-0wt%的可与之共聚的其他乙烯基单体。
Description
技术领域
本发明涉及具有优异冲击强度的热塑性树脂组合物。
背景技术
为了提高热塑性树脂的冲击强度,已经提出过各种建议。例如,在氯乙烯树脂作为代表性热塑性树脂的情况下,通过在丁二烯橡胶上接枝-共聚甲基丙烯酸甲酯、苯乙烯等而制得的所谓MBS树脂已被用作抗冲改性剂。公知的是,通过增大丁二烯橡胶的粒径,使MBS树脂增强冲击强度的作用进一步得到提高。因而,现已提出了各种增大粒径的技术。例如,JP-A-42-22541、JP-A-47-49191和JP-A-4-170458公开了几种这样的技术。大多数已知的粒径增大技术均涉及用于可使粒径增大的凝结剂和使用凝结剂的聚合方法。如今在本领域中仍然迫切需要提高冲击强度,并需要进一步改性MBS树脂。
本发明的一个目的是提供一种能够大幅度提高热塑性树脂诸如氯乙烯树脂的冲击强度的抗冲改性剂。
本发明的另一目的是提供一种具有大幅度提高的冲击强度的热塑性树脂组合物。
本发明的又一目的是提供一种制备含有丁二烯橡胶的接枝共聚物的方法,该共聚物具有能大幅度提高冲击强度的作用。
发明公开
本发明人已经发现,当在丁二烯橡胶胶乳存在下,以一步或多步聚合包含50-100wt%甲基丙烯酸甲酯和50-0wt%可与之共聚的其他乙烯基单体的单体组分而制备接枝共聚物时,通过使用凝结剂凝结聚合体系中聚合物粒子的方式来增大粒径,从而使所得胶乳中所得接枝共聚物粒子的平均粒径至少2.9倍于丁二烯橡胶胶乳中橡胶粒子的平均粒径,与具有相同平均粒径的已知接枝共聚物相比,能够大幅度提高含有丁二烯橡胶的接枝共聚物的冲击强度赋予作用。
因此,本发明提供一种热塑性树脂组合物,其包含(A)1-30重量份的接枝共聚物和(B)99-70重量份的热塑性树脂,(A)与(B)的总量是100重量份,其中所述接枝共聚物是通过在30-95重量份(按固体计)丁二烯橡胶胶乳存在下,聚合70-5重量份的单体组分而获得的,该单体组分包含50-100wt%的甲基丙烯酸甲酯和50-0wt%的可与之共聚的其他乙烯基单体,其中通过使用水溶性电解质来凝结聚合体系中的聚合物粒子以增大粒径,使得接枝共聚物的平均粒径“b”与丁二烯橡胶胶乳的平均粒径“a”的b/a比至少为2.9。
本发明还提供一种具有明显提高冲击强度效果的接枝共聚物的制作方法,包括制备丁二烯橡胶胶乳的步骤,和在水溶性电解质和30-95重量份(按固体计)丁二烯橡胶胶乳存在下,70-5重量份的单体组分进行乳液聚合的步骤,其中所述单体组分包含50-100wt%的甲基丙烯酸甲酯和50-0wt%的可与之共聚的其他乙烯基单体,所得接枝共聚物的平均粒径至少2.9倍于所用丁二烯橡胶胶乳的平均粒径,其中单体组分与丁二烯橡胶的总量是100重量份。
本发明的接枝共聚物适用于各种热塑性树脂,特别是含有至少50wt%氯乙烯的氯乙烯树脂。
优选的是,接枝聚合反应中所用的丁二烯橡胶胶乳具有平均粒径“a”不大于0.065μm(不大于65nm),尤其是不大于0.060μm,更尤其是不大于0.055μm,且在接枝聚合反应过程中粒径增大使得b/a比至少是3.5,尤其是至少是4。
另外,优选的是,由接枝聚合反应所得的胶乳中接枝共聚物的平均粒径不小于0.1μm(不小于100nm),尤其是不小于0.12μm。
实现本发明的最佳方式
本发明中所用的丁二烯橡胶由60-100wt%丁二烯、40-0wt%可与丁二烯共聚的乙烯基单体、和0-5wt%交联单体组成。该橡胶胶乳能够通过已知的乳液聚合方法制备。由所用乳化剂和聚合反应引发剂的量控制橡胶胶乳的平均粒径。橡胶胶乳的平均粒径是0.08-0.04μm,尤其是0.07-0.05μm 。
可与丁二烯共聚的乙烯基单体的例子是,芳族化合物诸如苯乙烯,乙烯基氰化合物诸如丙烯腈,具有C1-C5烷基的丙烯酸烷基酯诸如丙烯酸丁酯,和其他乙烯基单体。这些单体均可被单独或以其混合物的形式使用。
丁二烯橡胶可以是交联橡胶或非交联橡胶。作为交联单体,可使用已知为交联剂的分子中具有至少两个可聚合基团的任何化合物。其例子例如是甲基丙烯酸烯丙酯、二乙烯基苯、邻苯二甲酸二烯丙酯、聚乙二醇二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯等等。这些均可被单独或以其混合物的形式使用。交联剂的量是0-5wt%,基于所用单体的总重量。如果该量超过5wt%,橡胶变硬导至冲击强度下降。
本发明的接枝共聚物通过下面获得:在上述胶乳形式的丁二烯橡胶存在下,以一步或多步加入并聚合单体组分,其中该单体组分包含50-100wt%的甲基丙烯酸甲酯和50-0wt%的可与之共聚的其他乙烯基单体,同时通过使用水溶性电解质明显增大粒径。该接枝聚合反应按照常规方法进行。
丁二烯橡胶胶乳按固体计的量是30-95重量份,优选65-85重量份,基于100重量份胶乳(丁二烯橡胶)固体物质和单体组分的总重量。如果橡胶的量少于30重量份,提高氯乙烯树脂冲击强度的作用变小。如果橡胶的量大于95重量份,无法获得粉末状树脂,因为在凝结和从胶乳中回收时,接枝共聚物凝结成大块。
在接枝共聚物的制备中可与所用甲基丙烯酸甲酯共聚的乙烯基单体的例子是,芳族乙烯基单体诸如苯乙烯或苯乙烯衍生物(例如α-甲基苯乙烯和氯苯乙烯);乙烯基氰单体诸如丙烯腈或甲基丙烯腈;具有C1-C12烷基、尤其是C1-C5烷基的丙烯酸烷基酯诸如丙烯酸乙酯或丙烯酸丁酯;除甲基丙烯酸甲酯外的甲基丙烯酸烷基酯;等等。这些单体均可被单独或以其混合物的形式使用。
在接枝聚合反应过程中,用水溶性电解质来凝结橡胶粒子以达到增大粒径的目的。水溶性电解质包括例如离解成诸如Na+、K+、Mg2+、Al3+或H+的离子和诸如Cl-、Br-、SO4 2-、SO3 2-、NO2 -、NO3 -、PO4 3-、CO3 2-或OH-的离子的化合物。从本发明的显著效果可见,中性电解质诸如无机酸盐即使加入到体系中仍能保持聚合反应体系中性是优选的,而诸如无机和有机酸的电解质并不优选。此类电解质的例子是NaCl、KCl、Na2SO4、CaCl2、AlCl3等。电解质的量以每100重量份丁二烯橡胶与接枝单体组分的总重量计,优选是0.5-5重量份。如果电解质的量少于0.5重量份,难以发生增大粒径的凝结作用,而如果该量多于5重量份,胶乳缺乏稳定性导致废料(scale)增加。通常在开始接枝聚合反应之前,将电解质加入到聚合体系中,之后再迅速开始聚合反应。通过这样的步骤,在聚合物粒子凝结以增大粒径的同时进行接枝聚合反应。
在上述条件下进行接枝聚合反应,在接枝聚合的过程中发生聚合物粒子的凝结,由此得到具有增大粒径的接枝共聚物。凝结作用使粒径增大并使b/a比至少为2.9,优选至少为3.5,更优选至少为4,其中“a”是丁二烯橡胶粒子的平均粒径,“b”是接枝共聚物的平均粒径。如果b/a比小于2.9,则冲击强度的提高程度不能超过常规抗冲改性剂的水平。当b/a比是2.9或更高时,接枝共聚物的冲击强度得到大幅度提高。使凝结之前橡胶胶乳的平均粒径“a”小的方法、使制得的接枝共聚物平均粒径“b”大的方法、或将这两者结合,这些方法均能使b/a比达到至少2.9。如果该值“b”增加到0.2μm或更大,则可能出现聚合程度的问题。虽然通过一般方法获得的丁二烯橡胶的平均粒径“a”通常是0.07μm或更大,但优选的是,用诸如增大乳化剂的量或聚合反应引发剂的量的方法,均能将平均粒径“a”降低到不大于0.065μm,尤其是不大于0.060μm,更尤其是不大于0.055μm。丁二烯橡胶和所得接枝共聚物的平均粒径是用动态光散射法以体积平均粒径测试的。
用上述方法获得的接枝共聚物胶乳,通过向其中加入酸和/或盐将其凝结、热处理、洗涤、脱水和干燥,得到粉末状接枝共聚物。通过向99-70重量份热塑性树脂诸如氯乙烯树脂中引入1-30重量份粉末状接枝共聚物(其总重量为100重量份),得到本发明的热塑性树脂组合物,可将其用于模塑等。有需要时,本发明的树脂组合物可含有常规添加剂诸如稳定剂、填料、润滑剂、增塑剂、着色剂等等。
本发明中所用的热塑性树脂包括例如氯乙烯树脂、丙烯酸树脂、苯乙烯树脂、碳酸酯树脂、酰胺树脂、酯类树脂、烯烃树脂等等。乙烯基树脂的例子是聚氯乙烯、至少50wt%氯乙烯与可与之共聚的单体诸如乙酸乙烯酯或乙烯的共聚物、氯化聚氯乙烯等等。丙烯酸树脂的例子是聚甲基丙烯酸甲酯、至少50wt%甲基丙烯酸甲酯与可与之共聚的单体诸如丙烯酸甲酯、丙烯酸丁酯或苯乙烯的共聚物等等。苯乙烯树脂的例子是聚苯乙烯、苯乙烯-丙烯腈共聚物、α-甲基苯乙烯-丙烯腈共聚物、苯乙烯-马来酰亚胺共聚物、苯乙烯-α-甲基苯乙烯-丙烯腈共聚物、苯乙烯-α-甲基苯乙烯-马来酰亚胺-丙烯腈共聚物、苯乙烯-马来酸酐共聚物等等。碳酸酯树脂的例子是双酚型聚碳酸酯、脂族聚碳酸酯等等。酰胺树脂的例子是尼龙6、尼龙66、尼龙12等等。酯类树脂的例子是聚对苯二甲酸乙二醇酯、聚邻苯二甲酸丁二醇酯等等。烯烃树脂的例子是聚丙烯、聚乙烯、环状聚烯烃等等。
以下用实施例更具体地解释本发明,其中所有份数和%都是指重量,除非另有说明。应该理解的是,本发明并不仅限于这些实施例。
实施例1
在混合200份水、1.8份油酸钠、0.4份三代磷酸钾、0.2份β-萘磺酸钠甲醛缩合物和100份丁二烯之后,将温度升高到40℃。向其中加入0.002份硫酸亚铁(FeSO4·7H2O)、0.005份乙二胺四乙酸二钠、0.2份甲醛合次硫酸氢钠和1.0份萜烷过氧化氢,聚合反应进行20小时,得到具有平均粒径为0.07μm的橡胶胶乳(R-1)。
在混合70份(固体物)橡胶胶乳(R-1)与200份水和1.5份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.23μm的接枝共聚物胶乳(G-1)。
将接枝共聚物胶乳(G-1)与盐酸混凝,热处理、脱水并干燥得到粉末状接枝共聚物(A-1)。
然后,将100份聚合度为700的聚氯乙烯(商标为KANE VINYL S1007,由KANEKA CORPORATION生产)与10份粉末状接枝共聚物(A-1)、2.0份辛基硫醇锡、0.5份甘油蓖麻醇酸酯和0.2份二十九酸酯共混。在170℃用轧制机捏和该混合物5分钟,在180℃热压15分钟,得到具有6mm厚的Izod冲击试验试样。按照JIS K 7110测试Izod冲击强度。结果列于表1中。
实施例2
在混合600份水、4.0份油酸钠、0.4份三代磷酸钾、0.2份β-萘磺酸钠甲醛缩合物和100份丁二烯之后,将温度升高到40℃。向其中加入0.002份硫酸亚铁(FeSO4·7H2O)、0.005份乙二胺四乙酸二钠、0.2份甲醛合次硫酸氢钠和1.0份萜烷过氧化氢,聚合反应进行12小时,得到具有平均粒径为0.05μm的橡胶胶乳(R-2)。
在混合70份(固体物)橡胶胶乳(R-2)与200份水和4.8份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.15μm的接枝共聚物胶乳(G-2)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
实施例3
在混合70份(固体物)橡胶胶乳(R-2)与300份水和5.5份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.18μm的接枝共聚物胶乳(G-3)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
实施例4
在混合70份(固体物)橡胶胶乳(R-2)与300份水和6.5份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.21μm的接枝共聚物胶乳(G-4)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
比较例1
在混合70份(固体物)橡胶胶乳(R-1)与200份水和0.8份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.10μm的接枝共聚物胶乳(G-11)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
比较例2
在混合70份(固体物)橡胶胶乳(R-1)与200份水和1.2份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.18μm的接枝共聚物胶乳(G-12)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
比较例3
在混合70份(固体物)橡胶胶乳(R-2)与300份水和2.5份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.09μm的接枝共聚物胶乳(G-13)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
比较例4
在混合70份(固体物)橡胶胶乳(R-2)与300份水和3.8份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.13μm的接枝共聚物胶乳(G-14)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
比较例5
在混合200份水、1.2份油酸钠、0.4份三代磷酸钾、0.2份β-萘磺酸钠甲醛缩合物和100份丁二烯之后,将温度升高到40℃。向其中加入0.002份硫酸亚铁、0.005份乙二胺四乙酸二钠、0.2份甲醛合次硫酸氢钠和1.0份萜烷过氧化氢,聚合反应进行25小时,得到具有平均粒径为0.1μm的橡胶胶乳(R-3)。
在混合70份(固体物)橡胶胶乳(R-3)与200份水和1.5份(固体物)10%的Na2SO4水溶液并升温至60℃之后,向其中加入0.001份硫酸亚铁、0.004份乙二胺四乙酸二钠和0.2份甲醛合次硫酸氢钠。接着在4小时内连续加入20份甲基丙烯酸甲酯、5份苯乙烯、5份丙烯酸丁酯和0.1份氢过氧化枯烯的混合物。聚合反应再持续1小时,得到具有平均粒径为0.18μm的接枝共聚物胶乳(G-15)。以与实施例1中相同的方式评价Izod冲击强度。结果列于表1中。
表1
橡胶的粒径“a”(μm) | 接枝共聚物的粒径“b”(μm) | 电解质 | b/a | Izod冲击强度(J/m) | |
实施例1实施例2实施例3实施例4 | 0.070.050.050.05 | 0.230.150.180.21 | Na2SO4Na2SO4Na2SO4Na2SO4 | 3.293.003.604.20 | 300330410610 |
比较例1比较例2比较例3比较例4比较例5 | 0.070.070.050.050.10 | 0.100.180.090.130.18 | Na2SO4Na2SO4Na2SO4Na2SO4Na2SO4 | 1.422.571.802.601.80 | 100150100140120 |
由实施例3和比较例2的结果应该理解,即使接枝共聚物的平均粒径相同,通过调节b/a比至2.9或更大,也能够大幅度提高接枝共聚物的冲击强度。
工业实用性
与常规抗冲改性剂相比,使用电解质使粒径增大的技术,b/a比被调节到至少2.9的接枝共聚物具有明显增强冲击强度的作用,并且由含此类接枝共聚物和热塑性树脂的本发明树脂组合物制得的模塑制品具有优异冲击强度。
Claims (8)
1.一种热塑性树脂组合物,其包含(A)1-30重量份的接枝共聚物和(B)99-70重量份的热塑性树脂,(A)与(B)的总量是100重量份,其中所述接枝共聚物是由70-5重量份包含50-100wt%的甲基丙烯酸甲酯和50-0wt%的可与之共聚的其他乙烯基单体的单体组分在按固体计为30-95重量份的丁二烯橡胶胶乳存在下通过聚合得到的,其中通过使用水溶性电解质使聚合体系中的聚合物颗粒凝结以增大粒径,由此使所得接枝共聚物的平均粒径“b”与丁二烯橡胶胶乳的平均粒径“a”之比,即b/a,为至少2.9。
2.权利要求1的组合物,其中该热塑性树脂是含有至少50wt%氯乙烯的氯乙烯树脂。
3.权利要求1的组合物,其中b/a比至少是3.5。
4.权利要求1的组合物,其中b/a比至少是4。
5.权利要求1的组合物,其中所述丁二烯橡胶胶乳的平均粒径“a”不大于0.065μm。
6.权利要求1的组合物,其中所述丁二烯橡胶胶乳的平均粒径“a”不大于0.060μm。
7.权利要求1的组合物,其中所述丁二烯橡胶胶乳的平均粒径“a”不大于0.055μm。
8.权利要求1的树脂组合物,其中所述单体组分在65-85重量份丁二烯橡胶胶乳存在下进行聚合。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001315771A JP2003119396A (ja) | 2001-10-12 | 2001-10-12 | 耐衝撃性の優れた熱可塑性樹脂組成物 |
JP315771/2001 | 2001-10-12 | ||
JP315771/01 | 2001-10-12 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1476470A CN1476470A (zh) | 2004-02-18 |
CN1290929C true CN1290929C (zh) | 2006-12-20 |
Family
ID=19133889
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB028031717A Expired - Fee Related CN1290929C (zh) | 2001-10-12 | 2002-10-08 | 具有优异冲击强度的热塑性树脂组合物 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040068034A1 (zh) |
EP (1) | EP1445285A4 (zh) |
JP (1) | JP2003119396A (zh) |
KR (1) | KR20040043104A (zh) |
CN (1) | CN1290929C (zh) |
TW (1) | TWI298344B (zh) |
WO (1) | WO2003033595A1 (zh) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002317094A (ja) * | 2001-04-19 | 2002-10-31 | Kanegafuchi Chem Ind Co Ltd | 熱可塑性樹脂組成物 |
AU2004253557B2 (en) * | 2003-07-02 | 2009-05-07 | Ansell Healthcare Products Llc | Textured surface coating for gloves and method of making |
DE602005022494D1 (de) * | 2004-11-22 | 2010-09-02 | Arkema Inc | Schlagzäh modifizierte thermoplastische harzzusammensetzung |
ATE497995T1 (de) * | 2004-12-27 | 2011-02-15 | Kaneka Corp | Thermoplastharzzusammensetzung |
EP1834989A1 (en) * | 2004-12-27 | 2007-09-19 | Kaneka Corporation | Thermoplastic resin composition |
CN101128518A (zh) * | 2005-02-28 | 2008-02-20 | 株式会社钟化 | 凝固胶乳粒子的制备方法 |
JP5010465B2 (ja) * | 2005-02-28 | 2012-08-29 | 株式会社カネカ | 凝固ラテックス粒子の製造方法 |
WO2007013305A1 (ja) | 2005-07-28 | 2007-02-01 | Kaneka Corporation | 凝固ラテックス粒子の製造方法 |
CN101384668A (zh) | 2006-02-16 | 2009-03-11 | 株式会社钟化 | 热塑性树脂组合物 |
EP1997854A4 (en) * | 2006-03-16 | 2010-04-14 | Kaneka Corp | THERMOPLASTIC RESIN COMPOSITION |
EP2581421A1 (en) | 2011-10-12 | 2013-04-17 | Ineos Europe AG | Additive |
CN114736335A (zh) * | 2022-04-01 | 2022-07-12 | 威海金合思化工有限公司 | 一种高橡胶相内核增韧剂的合成方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1201547A (en) * | 1982-07-13 | 1986-03-04 | Akira Takaki | Graft copolymer useful as reinforcements for vinyl chloride polymers and process for preparing the same |
JPS60235854A (ja) * | 1984-05-08 | 1985-11-22 | Kanegafuchi Chem Ind Co Ltd | 耐溶剤性に優れた塩化ビニル系樹脂組成物 |
JP2634691B2 (ja) * | 1990-11-02 | 1997-07-30 | 鐘淵化学工業株式会社 | 塩化ビニル系樹脂組成物 |
US5534594A (en) * | 1994-12-05 | 1996-07-09 | Rohm And Haas Company | Preparation of butadiene-based impact modifiers |
WO1997002295A1 (fr) * | 1995-07-04 | 1997-01-23 | Mitsubishi Rayon Co., Ltd. | Processus de floculation de latex d'elastomere-caoutchouc de polymere de diene permettant d'augmenter la taille des particules, polymere greffe et composition de resine thermoplastique |
JPH111522A (ja) * | 1997-06-11 | 1999-01-06 | Kanegafuchi Chem Ind Co Ltd | 耐衝撃性に優れた高ゴム含量グラフト共重合体および熱可塑性樹脂組成物 |
-
2001
- 2001-10-12 JP JP2001315771A patent/JP2003119396A/ja not_active Withdrawn
-
2002
- 2002-10-08 KR KR10-2003-7007765A patent/KR20040043104A/ko not_active Application Discontinuation
- 2002-10-08 US US10/399,512 patent/US20040068034A1/en not_active Abandoned
- 2002-10-08 WO PCT/JP2002/010429 patent/WO2003033595A1/ja not_active Application Discontinuation
- 2002-10-08 TW TW091123209A patent/TWI298344B/zh not_active IP Right Cessation
- 2002-10-08 EP EP02801500A patent/EP1445285A4/en not_active Withdrawn
- 2002-10-08 CN CNB028031717A patent/CN1290929C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2003119396A (ja) | 2003-04-23 |
TWI298344B (zh) | 2008-07-01 |
WO2003033595A1 (fr) | 2003-04-24 |
US20040068034A1 (en) | 2004-04-08 |
EP1445285A4 (en) | 2005-08-10 |
KR20040043104A (ko) | 2004-05-22 |
CN1476470A (zh) | 2004-02-18 |
EP1445285A1 (en) | 2004-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1290929C (zh) | 具有优异冲击强度的热塑性树脂组合物 | |
EP0160285B1 (en) | Impact resistant thermoplastic resin composition | |
WO2000004094A1 (fr) | Composition de resine thermoplastique | |
US4508876A (en) | Graft copolymer useful as reinforcements for vinyl chloride polymers and process for preparing the same | |
CN1049229C (zh) | 制备具有改进的抗粘性的合成树脂粉的方法 | |
US4631307A (en) | Heat-resistant high impact styrene resin, process for production thereof, and resin composition comprising said styrene resin | |
CN1163535C (zh) | 热塑性树脂用抗冲击性改性剂 | |
EP0571918B1 (en) | Methacrylate resin composition | |
CN1227269C (zh) | 乳液聚合物的后处理方法 | |
CN1239543C (zh) | 丙烯基抗冲增强剂的制备方法 | |
CA1296823C (en) | Graft copolymer and styrene based resin composition | |
KR100340616B1 (ko) | 염화비닐계 수지 조성물 | |
JPH0331353A (ja) | 軟質シート用重合体混合物 | |
JP3625566B2 (ja) | 熱可塑性樹脂組成物 | |
CN1232581C (zh) | 热塑性树脂组合物 | |
CN1357557A (zh) | 抗冲击耐热共聚树脂的制造方法 | |
GB2315272A (en) | Rubber containing resin composition and styrene resin composition containing the same | |
EP0388943B1 (en) | Vinyl chloride resin composition | |
JP2501015B2 (ja) | 耐衝撃性、耐候性、熱可塑性樹脂組成物 | |
JP2650342B2 (ja) | 熱可塑性樹脂組成物 | |
WO2017104508A1 (ja) | 熱可塑性樹脂組成物 | |
KR960000570B1 (ko) | 충격 보강제용 열가소성 수지 조성물과 그 제조방법 및 이 조성물을 함유한 내충격성 염화비닐계 수지 조성물 | |
CN1068359C (zh) | 一种含有氯乙烯聚合物和接枝共聚物的热塑性树脂组合物 | |
AU2002225400A1 (en) | Impact modifier and amorphous polyester resin compositions containing the same | |
JP2001288327A (ja) | 熱可塑性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061220 Termination date: 20201008 |