CN1068343C - 粒状接枝共聚物和含该共聚物并具有改进的着色能力的热塑模压材料 - Google Patents
粒状接枝共聚物和含该共聚物并具有改进的着色能力的热塑模压材料 Download PDFInfo
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- CN1068343C CN1068343C CN96102567A CN96102567A CN1068343C CN 1068343 C CN1068343 C CN 1068343C CN 96102567 A CN96102567 A CN 96102567A CN 96102567 A CN96102567 A CN 96102567A CN 1068343 C CN1068343 C CN 1068343C
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- acrylate
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- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
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- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 6
- 125000005670 ethenylalkyl group Chemical group 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
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- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
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- 239000004416 thermosoftening plastic Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 2
- 235000019801 trisodium phosphate Nutrition 0.000 description 2
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- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
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- LUECERFWADIZPD-UHFFFAOYSA-N 1-tert-butyl-2-ethenylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1C=C LUECERFWADIZPD-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
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- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 1
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- 241000233855 Orchidaceae Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
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- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 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
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- 239000007924 injection Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 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
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 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
- LFULEKSKNZEWOE-UHFFFAOYSA-N propanil Chemical compound CCC(=O)NC1=CC=C(Cl)C(Cl)=C1 LFULEKSKNZEWOE-UHFFFAOYSA-N 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
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Abstract
本发明涉及一种粒状接枝共聚物，它含有a1)基于该共聚物为5-70%(重量)的，玻璃化温度小于10℃的接枝骨架，a2)基于该共聚物为20-85%(重量)在组分a1存在下的阶段聚合物，和a3)基于该共聚物为10-50%(重量)的制备a2)后所得产物存在下至少另一种阶段聚合物，其中组分a1)，a2)和a3)的组成详见说明书。本发明还涉及含有该粒状接枝共聚物并具有改进的着色能力的热塑模压材料。
Description
本发明涉及粒状接枝共聚物，它含有：
a1)基于A)为5-70％(重量)其玻璃化温度小于10℃的接枝骨架，它包括
a11)基于a1)为50-99.94％(重量)的至少一种丙烯酸烷基酯，其中烷基有1-30个碳原子，
a12)基于a1)为0-49.9％(重量)的可与a11)共聚的另一种单不饱和单体，和
a13)基于a1)为0.01-5％(重量)的多官能交联单体，
a2)基于A)为20-85％(重量)在组分a1)存在下的阶段聚合物，它包括
a21)基于a2)为95-100％(重量)的折射率n20 D大于1.51的至少一种单体，和
a22)基于a2)为0-5％(重量)的多官能交联单体，和
a3)基于A)为10-50％(重量)的制备a2)后所得产物存在下至少另一种阶段聚合物，它包括
a31)基于a3)为50-95％(重量)的乙烯基芳族单体，和
a32)基于a3)为5-50％(重量)的极性的可共聚的共聚用单体，它选自丙烯腈，甲基丙烯腈，烷基有1-20个碳原子的(甲基)丙烯酸酯，马来酐，丙烯酰胺，(甲基)丙烯酰胺和/或烷基有1-8个碳原子的乙烯基烷基醚。
为了得到一种抗冲击、热塑模压材料，将接枝橡胶加到室温下易碎的和形成骨架的聚合物中。由弹性芯，即玻璃化温度小于0℃的聚合物，和玻璃化温度大于25℃的接枝壳体制备粒状接枝聚合物(由DSC法测定玻璃化温度；K.H.Illers,Makromol.Chemie 127(1969),1)，例如通过熟悉的乳液聚合。为此，首先以合适单体的乳液聚合制备接枝骨架。然后，在接枝骨架的存在下，聚合易形成接枝壳体的单体。最外接枝壳体的单体是按照常规选择的，以便它们与要改性的热塑性是相容的或部分相容的。这样的冲击改性物的制备早已为人所知并叙述于例如EP132339中。不过，这些接枝橡胶一般易导致热塑塑料着色能力的退化。确信无疑的是，橡胶粒子越大，骨架的析射率和橡胶粒子的折射率的差别就越大(参见H.J.Biangardi,Angew.Makrom.Chem.183(1990),221-241)。EP3905叙述了通过膨胀小的乳剂粒子制备粗乳剂粒子的方法，尤其以溶剂或以搅拌一定时间后被聚合的单体。由于这些乳剂粒子不含接枝壳体，对于改性热塑塑料它们不太适合。
对于许多应用，为了满足顾客的要求，必须使韧化的热塑模压材料着色。
本发明的目的是改进韧化的热塑模压材料的着色能力和提供制备这种模压材料的组分。
按照本发明，通过本发明的粒状接枝共聚物和热塑模压材料，我们达到了这一目的。
本发明的最佳实施方案下面将叙述。
新颖的接枝共聚物，基于A)含有作为组分a1)玻璃化温度小于10℃的接枝骨架5-70％，较好为10-65％，最好为15-60％(重量)，其组成为：
a11)基于a1)为50-99.94％，较好为55-98％，最好为60-95％(重量)的丙烯酸烷基酯，其中烷基有1-30个碳原子，
a12)基于a1)为0-49.9％，较好为2-45％，最好为4-40％(重量)的可与a11)共聚合的单不饱和单体，和
a13)基于a1)为0.01-5％，较好为0.05-4％，最好为0.1-4％(重量)的多官能交联单体。
优选的单体a11)是丙烯酸烷基酯，其中烷基是2-30个碳原子，特别是丙烯酸乙酯，丙烯酸叔丁酯，丙烯酸异丙酯，丙烯酸正丁酯和丙烯酸2-乙基己酯，其中最后两个最优选。
优选的单体a12)的例子是异戊二烯，丁-二烯，苯乙烯，丙烯腈，甲基丙烯腈和/或乙烯基烷基醚，其中的烷基有1-8个碳原子(例如乙烯基甲基醚，乙烯基丙基醚或乙烯基乙基醚)或其混合物。
交联多官能单体a13)的例子是二乙烯基苯，马来酸二烯丙酯，富马酸二烯丙酯，邻苯二甲酸二烯丙酯和丙烯酸二氢二环戊二烯酯(DCPA，参见DE-A-1260135)，优选最后一个化合物。
另一些例子是氰尿酸三烯丙酯和异氰尿酸三烯丙酯。
利用共聚单体a12)和a13)可以控制聚合物a1)在某些情况下希望的特性，例如交联度。
制备聚合物a1)的方法是熟悉本领域的人已知的并在文献中有记载，例如GB1260135。相应的产品在市场上也可买到。
业已证实，经乳液聚合制备在一些情况下特别有利。
严格的聚合条件，特别是乳化剂的类型和用量被优选，以便至少部分交联的丙烯酸胶乳具有约50-700nm，最好是100-600nm的平均颗粒大小(重量平均d50)。
新的接枝共聚物的阶段聚合物a2)通过相应的单体a21)和如果需要a22)，在阶段聚合物a1)存在下聚合制备。
适合的单体a21)原则上是折射率n20 D大于1.51的所有可聚合单体。乙烯基芳香族单体如苯乙烯或下面通式表示的取代的苯乙烯被优选，特别优选苯乙烯，α-甲基苯乙烯，p-甲基苯乙烯或叔-丁基苯乙烯。
在阶段聚合物a2)制备中，业已证实，如果单体a21)和需要时的a22)在有或无游离基引发剂存在下慢慢加入并在经升温引发聚合反应前一定时间充分地混合所得混合物是有益的。
第三阶段聚合物a3)被接枝到接枝骨架a1)和a2)上，该阶段聚合物a3)由以下共聚而得，
a31)50-95％，较好为60-90％，最好为65-80％(重量)的乙烯基芳香族单体，优选苯乙烯或通式如下的取代苯乙烯，其中R是1-8个碳原子的烷基，氢或卤素，R1是1-8个碳原子的烷基或卤素和n是0,1,2或3，和
a32)5-50％，较好为10-40％，最好为20-35％(重量)的极性共聚单体丙烯腈，甲基丙烯腈，烷基有1-20个碳原子的(甲基)丙烯酸酯，马来酐，(甲基)丙烯酰胺，烷基部分有1-8个碳原子的乙烯基烷基醚和/或苯基马来酰亚胺或其混合物。
接枝壳体a3)可以1步或多步例如2步或3步制备，而整个组合物不受此影响。
接枝壳体优选在乳液中制备，如德国专利1260135和德国公开申请DOS3227555,DOS3149357,DOS3149358和DOS3414118所述。
取决于所选条件，一定比例的苯乙烯和丙烯腈的游离共聚物在接枝共聚中形成。
新的接枝共聚物一般平均颗粒大小为50-1000nm，最好为100-700nm(d50重量平均)。因此，制备高弹体b1)期间和接枝反应期间的条件被优选，以便颗粒大于落入此范围。有关的测定是已知的并叙述于例如德国专利1260135，德国公开申请DOS2826925和J.Appl.polym.Sci.9(1965),2929-2938中。高弹体的胶乳的颗粒大小可以增加，例如通过附聚作用。
在一些情况下，业已证实，许多具有不同颗粒大小的丙烯酸酯聚合物的混合物是有用的。相应的产物叙述于德国公开申请DOS2826925和美国专利5196480中，合并于此作参考。
优选的丙烯酸酯聚合物的混合物是叙述于上述美国专利5196480中的那些，其中第一聚合物的颗粒大小d50为50-150nm和第二聚合物的颗粒大小为200-700nm。
本发明的另一方案涉及热塑模压材料，其中除了新的接枝共聚物(A)外，还含有玻璃化温度大于20℃的热塑性聚合物(B)。一般地A∶B为5∶95至95∶5，较好为10∶90至90∶10，最好为80∶20至20∶80。
优选的聚合物B是基于甲基丙烯酸甲酯特别是聚甲基丙烯酸甲酯的聚合物和50-95％，较好为55-90％，最好为60-85％(重量)乙烯基芳香族单体和5-50％，较好为10-45％，最好为15-40％(重量)极性可共聚单体的共聚物。所说的极性可共聚单体选自丙烯腈，甲基丙烯腈，(甲基)丙烯酸的酯(其中的烷基有1-4个碳原子)，马来酐，(甲基)丙烯酰胺，乙烯基烷基醚(其中的烷基有1-8个碳原子)和/或苯基马来酰亚胺或其混合物。
优选的聚合物B含有组成如下的共聚物：
b1)50-95％(重量)的苯乙烯或α-甲基苯乙烯，
b21)10-50％(重量)的(甲量)丙烯腈或(甲基)丙烯酸甲酯，和
b22)0-40％(重量)的另一种单体b2)。
业已证明，苯乙烯和通式如下的取代的苯乙烯作为乙烯基芳香族单体是有用的，其中R是有1-8个碳原子的烷基氢或卤素，R1是有1-8个碳原子的烷基或卤素和n是0,1,2或3。
制备聚合物B的方法是本领域的人已知的，相应的产物是市场上可以买到的。
新的模压材料可含有作为组分C)的0-50％，较好为5-45％，最好为10-40％(重量)的纤维状或粒状填充料或其混合物。
填充料的例子是碳纤维或织成网的、玻璃板状的、或粗纱状的玻璃纤维，玻璃珠和硅灰石，特别优选玻璃纤维。
当使用玻璃纤维时，为了改进与共混组分的相容性可以加入粘合促进剂。一般地，碳纤维和玻璃纤维的直径为6-20μm。
玻璃纤维可以短玻璃纤维或粗纱形式掺入。玻璃纤维的平均长度为0.05-0.5mm，优选为0.08-0.45mm(在注模件中)。
适合的颗粒填充料是无定型二氧化硅，石棉，碳酸镁(白恶)，粉状石英，云母，滑石，长石和特别是硅酸钙，如硅灰石和高岭土(选煅烧高岭土)。
优选的填充料的结合是，例如20％(重量)的玻璃纤维与15％(重量)硅灰石和15％(重量)玻璃纤维与15％(重量)硅灰石。
新的热塑模压材料可以含有至多30％，优选0.5-10％(重量)的作为组分D的常规添加剂和加工助剂。
常规添加剂是例如稳定剂和抗氧化剂，热稳定剂和UV稳定剂，润滑剂和脱模剂，着色剂如染料和颜色，粉状填充料和增强剂，和增塑剂。这些添加剂以通常的有效量使用。
稳定剂可以在制备热塑性材料的任何阶段加入。优选于早期加入稳定剂以便阻止在材料可以被保护之前开始的分解。
按照本发明可以加到热塑性材料中的抗氧化剂和热稳定剂包括一般加到聚合物中的那些，例如立体受阻酚，氢醌，它们的各种取代物及其结合，其浓度基于混合物重量至多为1％。
另外，一般加到聚合物中的稳定剂的用量，基于混合物至多为2.0％(重量)。
稳定剂的例子是各种取代的间苯二酚，水杨酸盐，苯并三唑，二苯酮，HALS稳定剂等，市场上可以买到的商品名为Topanol,Irganox和Tinuvin的稳定剂。
可以加到热塑性材料中的适合的润滑剂和脱模剂例如是用量至多7％(重量)的硬脂酸，十八烷醇，硬脂酸酯和硬脂酰胺。
另外可能的添加剂是硅油，优选用量为0.05-1％(重量)。
有机染料如苯胺灰和颜料如二氧化钛，硫化镉，硅化硒化镉，酞菁，群青兰或碳黑也可以加入。
组分A)，B)和如果需要的话还有C)和/或D)的混合，以已知的并叙述于文献中的方法，在熔融态最好在挤压机中进行。
由于其性质，新的热塑模压材料特别适合于生产各种着色的成型件，如纤维，膜和模压件。
实施例1-3(橡胶组分的制备)
实施例1接枝共聚物A1的制备
1．橡胶1的制备
1.1接枝骨架a1)的制备
在1500g水中含有3.2g三环癸烯醇的丙烯酸酯和156.8g丙烯酸丁酯的单体混合物，在搅拌下加热至65℃，加入5g C12-C18链烷磺酸的钾盐，3g过氧酸式硫酸钾，3g碳酸氢钠和1.5g焦磷酸钠。聚合反应引发10分钟后，于3小时内加入由另外16.8g三环癸烯醇的丙烯酸酯和823.2g丙烯酰丁酯组成的混合物。单体加完后，乳液于65℃下再保持1小时。
1.2中间体a2)的制备
于30℃下4小时内，将1764g苯乙烯，36g三环癸烯醇的丙烯酸酯和3.6g过氧苯甲酰的混合物加到由450g上述1.1节的接枝骨架，2600g水和3.6g C12-C18链烷磺酸钾盐组成的混合物中，于30℃下搅拌3小时后，升温至65℃直到完成转化。
1.3阶段聚合物a3)的制备
2100g由上述1.2节方法制备的乳液与1150g水和2.7g过氧化酸式硫酸钾混合，在搅拌下加热至65℃。达到反应温度后，含有495g苯乙烯和165g丙烯腈的单体混合物于3小时内加入。加完后，乳液于65℃下再保持2小时。接枝共聚物具有210nm平均颗粒大小。于95℃以氯化钙溶液法从乳液中沉淀出接枝聚合物，水洗和在热空气流中干燥。
实施例2 接枝共聚物A2的制备
2．橡胶2的制备
2.1接枝骨架a1)的制备
12.5g上面1.1节方法制备的乳液与1500g水在搅拌下加热至65℃，再加入3g过氧化酸式硫酸钾，3g碳酸氢钠和1.5g焦磷酸钠。在3小时内加20g三环癸烯基醇的丙烯酸酯和980g丙烯酸丁酯和3gC12-C18链烷磺酸钾盐的混合物。单体加完后，乳液于65℃再保持1小时。
2.2中间体a2)的制备
中间体的制备与上面1.2节所述相同，只是以2.1节方法制备的乳液代替1.1节的乳液。
2.3阶段聚合物a3)的制备
2100g上面2.2节方法制备的乳液与1150g水和2.7g过氧化酸式硫酸钾混合并在搅拌下加热至65℃。达到反应温度后，在1小时内加入含165g苯乙烯和0.1gC12-C18链烷磺酸钾盐的单体混合物。加完后，再加入372g苯乙烯和124g丙烯腈的混合物，然后，乳液在65℃下再保持2小时。接枝聚合物的平均颗粒大小为610nm。在95℃下以氯化钙法从乳液中沉淀出接枝共聚物，水洗并在热空气流中干燥。
实施例3 接枝共聚物A3的制备
按照上面1节所述方法制备橡胶3，只是在制备中间体时用850g苯乙烯。所得接枝共聚物的平均颗粒大小为180nm。
比较试验
在比较试验中不制备中间体，即按照上述1.3,2.3或3节方法，接枝骨架1.1和2.1直接接枝苯乙烯和丙烯腈。相应的接枝橡胶的平均颗粒大小是：
比较接枝橡胶1：105nm
比较接枝橡胶2：480nm
实施例4-7模压材料的制备
为了制备新的模压材料，丙烯腈含量为35％和粘度值为80ml/g(粘度值是在23℃在0.5％DMF溶液中测定)的苯乙烯/丙烯腈共聚物用作组分B。沉淀和干燥后的接枝共聚物与组分B于260℃下在挤压机中混合，以使组分A的含量为50％(重量)。由此混合物生产成型件，并测定该成型件的dE值。
按照DIN6174，由试验样品对白和黑背景色差的改进计算dE值。
与橡胶1-3和比较试验的混合物的dE值如下：
| dE | |
| 与接枝聚合物A1的混合物 | 21 |
| 与接枝聚合物A2的混合物 | 12 |
| 与接枝聚合物A3的混合物 | 17 |
| 与比较接枝橡胶1的混合物 | 7 |
| 与比较接枝橡胶2的混合物 | 2 |
Claims (4)
1．一种粒状接枝共聚物A)，它含有：
a1)基于A)为5-70重量％的其玻璃化温度小于10℃的接枝骨架，它包括，
a11)基于a1)为50-99.94重量％的至少一种丙烯酸烷基酯，其中烷基有1-30个碳原子，
a12)基于a1)为0-49.9重量％的可与a11)共聚的另一种单不饱和单体，和
a13)基于a1)为0.01-5重量％的多官能交联单体，
a2)基于A)为20-85重量％在组分a1)存在下的阶段聚合物，它包括
a21)基于a2)为95-100重量％的折射率n20 D大于1.51的至少一种单体，和
a22)基于a2)为0-5重量％的多官能交联单体，和
a3)基于A)为10-50重量％的制备a2)后所得产物存在下至少另一种阶段聚合物，它包括
a31)基于a3)为50-95重量％的乙烯基芳族单体，和
a32)基于a3)为5-50重量％的极性的可共聚的共聚用单体，它选自丙烯腈，甲基丙烯腈，烷基有1-20个碳原子的丙烯酸酯和甲基丙烯酸酯，马来酐，丙烯酰胺，甲基丙烯酰胺和烷基有1-8个碳原子的乙烯基烷基醚。
2．一种热塑模压材料，它含有：
A)权利要求1的粒状接枝共聚物，和
B)与A不同且玻璃化温度大于20℃的热塑聚合物，其中A∶B为5∶95至95∶5。
3．权利要求2的热塑模压材料，组分B)含有组成如下的共聚物：
b1)50-95重量％的苯乙烯或α-甲基苯乙烯，
b21)10-50重量％丙烯腈、甲基丙烯腈、丙烯酸甲酯或甲基丙烯酸甲酯，和
b22)0-40重量％的马来酐、丙烯酰胺、甲基丙烯酰胺、烷基有1-8个碳原子的乙烯基烷基醚和/或苯基马来酰亚胺或其混合物。
4．权利要求1的接枝共聚物用于改进热塑模压材料的着色能力的用途。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19503545A DE19503545A1 (de) | 1995-02-03 | 1995-02-03 | Teilchenförmige Pfropfcopolymerisate und diese enthaltende thermoplastische Formmassen mit verbesserter Einfärbbarkeit |
| DE19503545.3 | 1995-02-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1133850A CN1133850A (zh) | 1996-10-23 |
| CN1068343C true CN1068343C (zh) | 2001-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96102567A Expired - Fee Related CN1068343C (zh) | 1995-02-03 | 1996-02-02 | 粒状接枝共聚物和含该共聚物并具有改进的着色能力的热塑模压材料 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0725094A3 (zh) |
| JP (1) | JPH08259638A (zh) |
| KR (1) | KR960031496A (zh) |
| CN (1) | CN1068343C (zh) |
| DE (1) | DE19503545A1 (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19623416A1 (de) * | 1996-06-12 | 1997-12-18 | Basf Ag | Teilchenförmige Pfropfcopolymerisate und diese enthaltende thermoplastische Formmassen mit verbesserter Einfärbbarkeit |
| JP3358520B2 (ja) * | 1997-12-09 | 2002-12-24 | 住友化学工業株式会社 | ポリオレフィン改質用微粒子 |
| US6187862B1 (en) * | 1998-05-01 | 2001-02-13 | Bayer Corporation | Weatherable resinous composition having improved opacity and impact strength |
| TWI369379B (en) * | 2007-01-26 | 2012-08-01 | Rohm & Haas | Light-scattering compositions |
| EP2566921B1 (de) * | 2010-05-07 | 2014-04-16 | Styrolution GmbH | Formmasse mit verminderter lichtstreuung |
| KR102329711B1 (ko) | 2014-03-31 | 2021-11-19 | 이네오스 스티롤루션 그룹 게엠베하 | 응집물 형성이 감소된 아크릴레이트 고무의 제조 방법 |
| CN104974310B (zh) * | 2015-06-12 | 2017-09-05 | 长沙市汇华胶粘剂科技有限公司 | 一种水贴纸可剥离膜油用树脂及其制备方法 |
| WO2017055179A1 (de) | 2015-09-30 | 2017-04-06 | Ineos Styrolution Group Gmbh | Verfahren zur herstellung von acrylatkautschuk bei reduzierter emulgatorkonzentration |
| WO2019115420A1 (en) | 2017-12-11 | 2019-06-20 | Ineos Styrolution Group Gmbh | Process for production of impact modified thermoplastic moulding composition with improved processing and impact strength |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206299A (en) * | 1989-03-31 | 1993-04-27 | Takeda Chemical Industries, Ltd. | Core-shell polymer, resin composition and molded articles thereof |
| US5298559A (en) * | 1991-12-05 | 1994-03-29 | Mitsubishi Gas Chemical Company, Inc. | Multi-layered polymers |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3149358A1 (de) * | 1981-12-12 | 1983-06-16 | Basf Ag, 6700 Ludwigshafen | Thermoplastische formmasse |
| IE57758B1 (en) * | 1983-08-31 | 1993-03-24 | Mitsubishi Rayon Co | Impact modifier and thermoplastic resin compositions using the same |
| EP0390144A3 (en) * | 1989-03-31 | 1991-09-04 | Takeda Chemical Industries, Ltd. | Core-shell polymer, resin composition and molded articles thereof |
| CA2013311A1 (en) * | 1989-04-11 | 1990-10-11 | Samuel J. Makower | Thermoplastic acryclic elastomers |
| DE4011162A1 (de) * | 1990-04-06 | 1991-10-10 | Basf Ag | Thermoplastische formmasse |
| DE4131728A1 (de) * | 1991-09-24 | 1993-03-25 | Basf Ag | Teilchenfoermiges pfropfcopolymerisat mit kern/schale-aufbau |
| DE4132497A1 (de) * | 1991-09-30 | 1993-04-01 | Basf Ag | Mehrschaliges pfropfcopolymerisat |
-
1995
- 1995-02-03 DE DE19503545A patent/DE19503545A1/de not_active Withdrawn
-
1996
- 1996-01-26 EP EP96101104A patent/EP0725094A3/de not_active Withdrawn
- 1996-01-31 JP JP8015946A patent/JPH08259638A/ja not_active Withdrawn
- 1996-02-02 CN CN96102567A patent/CN1068343C/zh not_active Expired - Fee Related
- 1996-02-02 KR KR1019960002803A patent/KR960031496A/ko not_active Application Discontinuation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5206299A (en) * | 1989-03-31 | 1993-04-27 | Takeda Chemical Industries, Ltd. | Core-shell polymer, resin composition and molded articles thereof |
| US5298559A (en) * | 1991-12-05 | 1994-03-29 | Mitsubishi Gas Chemical Company, Inc. | Multi-layered polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960031496A (ko) | 1996-09-17 |
| JPH08259638A (ja) | 1996-10-08 |
| EP0725094A2 (de) | 1996-08-07 |
| CN1133850A (zh) | 1996-10-23 |
| DE19503545A1 (de) | 1996-08-08 |
| EP0725094A3 (de) | 1997-08-27 |
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