CN1138064A - 热塑性模塑料 - Google Patents
热塑性模塑料 Download PDFInfo
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- CN1138064A CN1138064A CN96105674A CN96105674A CN1138064A CN 1138064 A CN1138064 A CN 1138064A CN 96105674 A CN96105674 A CN 96105674A CN 96105674 A CN96105674 A CN 96105674A CN 1138064 A CN1138064 A CN 1138064A
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- 239000012778 molding material Substances 0.000 title claims abstract description 10
- 238000009757 thermoplastic moulding Methods 0.000 title claims abstract description 10
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 claims abstract description 31
- 229940087168 alpha tocopherol Drugs 0.000 claims abstract description 14
- 229960000984 tocofersolan Drugs 0.000 claims abstract description 14
- 239000002076 α-tocopherol Substances 0.000 claims abstract description 14
- 235000004835 α-tocopherol Nutrition 0.000 claims abstract description 14
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical group CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000002656 Distearyl thiodipropionate Substances 0.000 claims abstract description 5
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019305 distearyl thiodipropionate Nutrition 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 13
- 239000003381 stabilizer Substances 0.000 claims description 13
- 239000000206 moulding compound Substances 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 9
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 8
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 5
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
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- 238000005457 optimization Methods 0.000 claims description 2
- 229940114930 potassium stearate Drugs 0.000 claims description 2
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 2
- 239000003508 Dilauryl thiodipropionate Substances 0.000 abstract 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 19
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- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 10
- -1 acrylic ester Chemical class 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
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- 229930003799 tocopherol Natural products 0.000 description 4
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- 229960001295 tocopherol Drugs 0.000 description 4
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 3
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 230000018044 dehydration Effects 0.000 description 2
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- 239000002861 polymer material Substances 0.000 description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
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- 229920001169 thermoplastic Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920001617 Vinyon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 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
- 238000012662 bulk polymerization Methods 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005559 polyacrylic rubber Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 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
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1545—Six-membered rings
-
- 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
-
- 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
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- 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
- C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- 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
- C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Graft Or Block Polymers (AREA)
Abstract
由下述成分组成的热塑性模塑料：A)基于A+B计，30-80％(重量)弹性体接枝基底A(详细定义见说明书)；B)基于A+B计，20-70％(重量)接枝到上述接权基底A上的外壳(详细定义见说明书)；C)基于100重量份A+B计，0.001-1重量份α-生育酚，和D)基于C计0.5-10倍量的选自硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯的硫代二丙酸酯。
Description
本发明涉及具有改善的耐热老化性的包括丙烯酸酯接枝橡胶的热塑性模塑料。
人们知道，α-生育酚(维生素E)可以用作天然抗氧化剂来稳定某些聚合物。为了生产光敏性材料的包装材料，EP-A-0384472公开了用维生素E稳定的并含有光稳定剂的热塑性塑料，包括ABS。也特别提及了使用硫代二丙酸二月桂酯和二硬脂酯作为抗氧化剂。JP 40/07053描述了将α-生育酚用作SBR和异戊二烯橡胶的无毒稳定剂。US4489099公开了用来稳定基于SBR橡胶的香口胶材料的维生素E(α-生育酚)与硫代二丙酸二月桂酯的混合物。在JP58/127653中，将生育酚和卵磷脂加到溶液聚合制备的聚丁二烯中，以免在硫化时明显形成亚硝胺。JP 54/034352涉及用来稳定聚烯烃粉末的生育酚(α-，β-或γ-型)与硫代二丙酸酯的混合物。JP 54/074851描述了用MBS橡胶增韧的PVC材料，使MBS胶乳与含有生育酚与硫代二丙酸酯的稳定剂混合物的胶乳接触。
对于含聚乙烯塑料材料的稳定化，EP-A-0542108描述了生育酚化合物例如α-生育酚与含磷或含硫抗氧化剂的混合物，还提及了硫代二丙酸酯，包括硫代二丙酸二硬脂酯。
WO 90/07547公开了包含α-生育酚和甘油与饱和或不饱和脂肪酸的一或二和/或三酯或其混合物的稳定剂混合物，用来稳定热塑性塑料例如聚氯乙烯、苯乙烯聚合物、聚酰胺、聚碳酸酯、聚酯和聚烯烃。除所述稳定剂混合物外，还公开了其它稳定剂例如硬脂酸钙和硫代二丙酸二硬脂酯的添加。
本发明的目的是稳定接枝橡胶，特别是增加耐热老化性。
我们惊讶地发现，这一目的可通过包含接枝橡胶和权利要求1定义的稳定剂混合物的热塑性模塑料来实现，特别是通过将接枝橡胶与由α-生育酚与硫代二丙酸酯的混合物组成的乳液混合获得的热塑性模塑料来实现。
因此，本发明涉及由下述成分组成的热塑性模塑料：A)基于A+B计，30-80％(重量)弹性体接枝基底，基于A计，所述基底包含：
A1)90-99.9％(重量)至少一种烷基部分具有1-8个碳原子的丙烯酸烷基酯，和
A2)0.1-10％(重量)至少一种多官能、交联单体，和B)基于A+B计，20-70％(重量)接枝到上述接枝基底A上的外壳，基于B计，所述外壳包含：
B1)0-100％(重量)乙烯基芳族单体、优选苯乙烯，或者烷基苯乙烯、优选α-甲基苯乙烯，和/或
B2)0-100％(重量)至少一种极性、可共聚不饱和单体，优选丙烯腈、甲基丙烯酸甲酯或苯基马来酰亚胺，
B1与B2之和为100％(重量)，和C)基于100重量份A+B计，0.001-1重量份α-生育酚，和D)基于C计，0.5-10倍量的选自硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯的硫代二丙酸酯，和E)基于100重量份A+B+C+D+E计，0-95％(重量)组成如下(基于E计)的硬质基体：
E1)60-90％(重量)苯乙烯和/或α-甲基苯乙烯和
E2)10-40％(重量)丙烯腈，
E1与E2之和为100％(重量)，和
E3)基于100重量份E计，0-40％(重量)PMMA，必要时，和F)有效量的常规添加剂。
本发明进一步涉及热塑性模塑料的制备方法，特别是稳定剂混合物的制备方法。本发明还涉及模塑料在制备模塑制品中的用途并涉及由它制得的模塑制品。本发明的这些主题被定义在权利要求书中。
弹性体接枝基底A和基于聚丙烯酸烷基酯-g-SAN的接枝的制备被描述于德国专利1260135和US-A-3055859中，在DE-A-3149358和DE-A-3227555中描述了两步接枝的方法。首先通过丙烯酸酯的乳液聚合制备起接枝基底A作用的橡胶状丙烯酸酯聚合物。将乙烯基芳族单体B1与极性、可共聚不饱和单体B2的混合物接枝到所得聚丙烯酸酯胶乳上，该接枝共聚合类似地也优选在乳液中进行。弹性体成分A也可以按照EP132339所述接枝到用A2项所述的单体交联的并且由B项所述单体组成的硬芯上。所述芯优选是Tg＞25℃的硬芯，芯的量为A+B的5-50％(重量)。为获得具有良好机械性能的ASA聚合物，将用作接枝基底的聚丙烯酸酯橡胶交联，即在其制备过程中使丙烯酸酯与少量多官能交联单体A2共聚。
对于丙烯酸酯聚合物的制备，优选烷基基团具有1-8个碳原子、特别优选具有4-8个碳原子的的丙烯酸烷基酯作单体。丙烯酸正丁酯和丙烯酸乙基己酯特别适宜。在用作接枝基底的丙烯酸酯聚合物的制备过程中，可以单独使用丙烯酸酯或者使用其相互之间的混合物。
特别适宜的多官能交联单体A2是能够共聚的并且不是1，3-位共轭的含有两个或更多个烯类双键的单体。适宜的交联单体的例子有二乙烯基苯、马来酸二烯丙酯、富马酸二烯丙酯和邻苯二甲酸二烯丙酯。三环癸烯醇的丙烯酸酯被证明是特别好的交联单体(参见德国专利1260135)。
从A+B成分制备接枝共聚物本身是已知的，并且能够按照例如德国专利1260135所述的方法进行制备。为此，首先通过将丙烯酸酯即丙烯酸酯A1与多官能、交联单体A2在水性乳液中于20-100℃、优选50-80℃以已知的方法聚合制备弹性体聚合物接枝基底A。可以使用常规的乳化剂，例如烷磺酸或烷基芳基磺酸的的碱金属盐、烷基磺酸盐、脂肪醇磺酸盐、具有10-30个碳原子的高级脂肪酸的盐或树脂皂。所用的聚合引发剂具体地是常规过硫酸盐，例如过硫酸钾，但也可使用氧化还原体系。所用的聚合助剂可以是常规的缓冲物质，借助于该缓冲物质最好建立6-9的pH值，例如碳酸氢钠和焦磷酸钠，和0-3％(重量)分子量调节剂，例如硫醇、萜烯醇或二聚α-甲基苯乙烯。
适宜的用来制备接枝到接枝基底A上的外壳B的乙烯基芳族单体B1是苯乙烯、烷基苯乙烯，优选α-甲基苯乙烯和在苯核上烷基化的苯乙烯，例如对甲基苯乙烯和叔丁基苯乙烯。优选的极性、可聚合不饱和单体B2的例子有丙烯腈、烷基基团具有1-4个碳原子的(甲基)丙烯酸烷基酯、丙烯酸、马来酸酐、苯基马来酰亚胺、丙烯酰胺和/或乙烯基甲基醚。特别优选丙烯腈、甲基丙烯酸甲酯和苯基马来酰亚胺。接枝共聚可以在与制备接枝基底A的乳液聚合相同的体系中方便地进行。
在本发明的一个优选的实施方案中，按照德国专利1260135进行一步接枝共聚，将接枝共聚物的乳液与单体B1和B2的混合物最好在水性乳液中聚合。
在本发明的另一优选的实施方案中，接枝分两步进行，首先将乙烯基芳族单体B1在接枝基底A的存在下聚合，这一步骤按照DE-A-3149358或DE-A-3227555进行。在第二步中，随后将至少一种乙烯基芳族单体B1与至少一种极性、可共聚单体B2的混合物进行接枝共聚。应当选择反应条件，使得接枝B含有0-100、优选20-90、特别优选40-85％(重量)单体B1和0-100、优选10-80、特别优选15-60％(重量)单体B2(所有重量份数均以B计)。接枝B的总量占包括A+B的接枝共聚物的20-70、优选25-65、特别优选25-60％(重量)。从而，弹性体接枝基底A的量占A+B的30-80、优选35-75、特别优选40-75％(重量)。
在制备稳定剂乳液的一个优选的实施方案中，成分C和D与具有14-24个碳原子的羧酸(优选硬脂酸)于60-70℃一起熔融。然后在充分搅拌下加入碱，特别是KOH水溶液。在另一实施方案中，将成分C和D一起熔融并分散于含有乳液稳定剂的水溶液中。适宜的乳液稳定剂是硬脂酸钾、烷基磺酸盐或磺基琥珀酸酯。在上述各实施方案中，获得了能数日保持稳定的乳液。
α-生育酚被用作成分C。成分D是选自二月桂酯和二硬脂酯的硫代二丙酸酯。对于稳定化的接枝橡胶乳液的制备，是将未稳定化的接枝橡胶乳液与上述稳定剂的乳液之一混合，使得α-生育酚的量为0.001-1％(重量)、优选0.001-0.8％(重量)、特别是0.005-0.75％(重量)(均基于100重量份A+B计)，成分D的量为C的0.5-10倍，优选0.5-8倍，特别优选0.5-5倍。通过加入盐例如硫酸镁使所得混合物絮凝，然后脱水加工得到新的热塑性模塑料。
在本发明的一个特别优选的实施方案中，模塑料含有至多95％(重量)、优选5-90％(重量)(基于100重量份A+B+C+D+E计)包含苯乙烯和/或α-甲基苯乙烯(成分E1)和丙烯腈(成分E2)和必要时还包含PMMA共聚物的硬质基体E。苯乙烯和/或α-甲基苯乙烯的量为60-90％(重量)，优选62-85％(重量)，特别优选72-84％(重量)(基于E计)，E1与E2之和为100％(重量)。PMMA(成分E3)的量为0-40％(重量)，优选0-35％(重量)，特别优选0-30％(重量)(基于100重量份E计)。
附加的硬质基体E可通过常规的已知方法制得，该方法亦被描述于DE-A-3149358和DE-A-3227555中。从而，苯乙烯和/或α-甲基苯乙烯与丙烯腈的共聚可通过本体聚合、溶液聚合、悬浮聚合或水乳液聚合进行。
在另一个优选的实施方案中，将作为再一种成分F的通常用于ASA聚合物的添加剂加到成分A，B，C，D和可选的E的混合物中。适宜的添加剂的例子是填充剂、其它相容性塑料、抗静电剂、抗氧化剂、耐火剂和润滑剂。添加剂的用量是常规量，基于100重量份混合物(A+B+C+D+E+F)计，添加剂的用量优选0.1-30重量份。
一方面，新的丙烯酸酯接枝橡胶的改进的耐热老化性可以从首先沉淀并干燥的接枝橡胶通过测定在一定条件下直至发生放热反应所需的时间来建立。另一方面，通过将用新的模塑料制得的模塑制品在高温下储存并观察颜色的改变来测定成品的稳定化程度。在上述两种情况下，按照本发明稳定化的接枝橡胶或模塑制品都能比可比的未稳定化的接枝橡胶更长时间地保持稳定。
新的模塑料适合于模塑制品的生产，特别是窗框、园艺设施、小船、信号标志、灯罩和汽车部件的生产。新的模塑料特别适合于要求具有高冲击强度以及良好的耐候性和耐老化性的模塑制品的生产。
用下述实施例说明本发明。
实施例
按照德国专利1,260,135的实施例1制得聚丙烯酸正丁酯-g-SAN接枝橡胶，其固体含量为40％(重量)。为制备稳定剂混合物，将20gα-生育酚和/或硫代二丙酸二月桂酯按照下表所述与2g硬脂酸一起于60-80℃熔融。然后在充分搅拌下向熔体中加入40g浓度为0.1％的KOH。按照下表所述向接枝橡胶的聚合物乳液中加入相应的稳定剂混合物并混合。借助于硫酸镁溶液将如此获得的胶乳沉淀絮凝并脱水。
将如此制得的接枝橡胶粉末在260℃的空气中施加热应力。接枝橡胶受放热氧化损害所需的时间是该混合物的质量的量度。
表
| 实施例号 | α-生育酚的重量份(基于100重量份(A+B)**计) | 硫代二丙酸二月桂酸酯的重量份(基于100重量份(A+B)**计) | t2 *’分钟 |
| (对比) | -- | -- | 208 |
| (对比) | -- | 0.2 | 221 |
| (对比) | 0.2 | -- | 210 |
| (根据本发明) | 0.05 | 0.2 | 262 |
从表中显而易见，新的聚合物材料比不加α-生育酚和硫代二丙酸二月桂酯的聚合物材料在260℃的空气中储存时稳定的时间更长。因此，本发明将导致具有改善的耐热老化性能的接枝橡胶。
Claims (8)
1.由下述成分组成的热塑性模塑料：A)基于A+B计，30-80％(重量)弹性体接枝基底，基于A计，所述基底包含：
A1)90-99.9％(重量)至少一种烷基部分具有1-8个碳原子的丙烯酸烷基酯，和
A2)0.1-10％(重量)至少一种多官能、交联单体，和B)基于A+B计，20-70％(重量)接枝到上述接枝基底A上的外壳，基于B计，所述外壳包含：
B1)0-100％(重量)乙烯基芳族单体、优选苯乙烯，或者烷基苯乙烯、优选α-甲基苯乙烯，或者
B2)0-100％(重量)至少一种极性、可共聚不饱和单体，优选丙烯腈、甲基丙烯酸甲酯或苯基马来酰亚胺，
B1与B2之和为100％(重量)，和C)基于100重量份A+B计，0.001-1重量份α-生育酚，和D)基于C计，0.5-10倍量的选自硫代二丙酸二月桂酯和硫代二丙酸二硬脂酯的硫代二丙酸酯，和E)基于100重量份A+B+C+D+E计，0-95％(重量)组成如下(基于E计)的硬质基体：
E1)60-90％(重量)苯乙烯或α-甲基苯乙烯和
E2)10-40％(重量)丙烯腈，
E1与E2之和为100％(重量)，和
E3)基于100重量份E计，0-40％(重量)PMMA，必要时，和F)有效量的常规添加剂。
2.如权利要求1所述的模塑料，其中成分A接枝到被就A2)所述的单体交联的硬芯K上，其Tg＞25℃，由就B所述的单体组成，芯的量为A+B的5-50％(重量)。
3.如权利要求1和2所述的模塑料，其中成分C是硫代二丙酸二月桂酯。
4制备权利要求1，2或3所述的模塑料的方法，其中在制备了A与B的接枝共聚物后，将由C和D组成的稳定剂混合物乳液加到接枝共聚物乳液中，然后进行沉淀操作。
5.如权利要求4所述的方法，其中稳定剂混合物是这样制备的：将成分C和D混合，将该混合物与硬脂酸一起熔融，然后加入碱，优选KOH。
6.如权利要求4所述的方法，其中稳定剂混合物是这样制备的：将成分C和D混合，然后加入乳化剂水溶液，优选硬脂酸钾、烷基磺酸盐或磺基琥珀酸酯。
7.如权利要求1，2或3所述的模塑料或者通过权利要求4至6中任意一项所述的方法制备的模塑料在生产模塑制品中的用途。
8.用权利要求1，2或3所述的模塑料或者用权利要求4至6中任意一项所述的方法制备的模塑料制得的模塑制品。
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| DE19516283A DE19516283A1 (de) | 1995-05-04 | 1995-05-04 | Thermoplastische Formmasse |
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| CA2221266A1 (en) | 1996-12-10 | 1998-06-10 | Achim Grefenstein | Laminated sheets or films and moldings thereof |
| US6450675B1 (en) * | 1999-01-21 | 2002-09-17 | Kaneka Corp. | Vehicle lamp composition and method of manufacturing |
| JP3943012B2 (ja) * | 2002-12-25 | 2007-07-11 | キヤノンファインテック株式会社 | 被記録媒体 |
| DE102005041402A1 (de) * | 2005-09-01 | 2007-03-08 | Röhm Gmbh | Formkörper mit Lichtstreueigenschaften |
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| NZ711364A (en) | 2010-12-13 | 2017-11-24 | Cytec Tech Corp | Processing additives and uses of same in rotational molding |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH491170A (de) * | 1968-04-08 | 1970-05-31 | Sandoz Ag | Verfahren zur Herstellung von Anthrachinonverbindungen |
| JPS5434352A (en) * | 1977-08-22 | 1979-03-13 | Riken Vitamin Co Ltd | Non-toxically stabilized olefinic polymer composition |
| JPS5474851A (en) * | 1977-11-28 | 1979-06-15 | Kureha Chem Ind Co Ltd | Vinyl chloride resin composition |
| JPS55127454A (en) * | 1979-03-27 | 1980-10-02 | Asahi Chem Ind Co Ltd | Stabilization of vinylidene chloride resin |
| DE3010505A1 (de) * | 1980-03-19 | 1981-10-01 | Basf Ag, 6700 Ludwigshafen | Chromanderivate, verfahren zu ihrer herstellung, ihre verwendung als stabilisatoren von organischen materialien sowie diese stabilisatoren enthaltende organische materialien |
| DE3103707A1 (de) * | 1981-02-04 | 1982-08-19 | Basf Ag, 6700 Ludwigshafen | Chromanderivate |
| JPS58127653A (ja) * | 1982-01-25 | 1983-07-29 | 昭和ゴム株式会社 | 耐老化性乳首の製造法 |
| US4489099A (en) * | 1983-02-28 | 1984-12-18 | The Goodyear Tire & Rubber Company | Vitamin E/DLTDP stabilizer system for chewing gum SBR |
| DE3634531A1 (de) * | 1986-10-10 | 1988-04-14 | Basf Ag | Stabilisatorgemische fuer kunststoffe |
| DE58906177D1 (de) * | 1988-12-23 | 1993-12-16 | Basf Ag | Stabilisatorgemische für kunststoffe. |
| DE69031395T2 (de) * | 1989-02-23 | 1998-01-15 | Fuji Photo Film Co Ltd | Harzzusammensetzung und Verpackungsmaterial für lichtempfindliches Material |
| US5308549A (en) * | 1991-11-12 | 1994-05-03 | Hoffmann-La Roche Inc. | Stabilizers for thermo plastic materials |
-
1995
- 1995-05-04 DE DE19516283A patent/DE19516283A1/de not_active Withdrawn
-
1996
- 1996-04-29 US US08/638,593 patent/US5747568A/en not_active Expired - Fee Related
- 1996-04-29 EP EP96106738A patent/EP0741162A1/de not_active Ceased
- 1996-04-30 JP JP8109803A patent/JPH08302147A/ja not_active Withdrawn
- 1996-05-03 CN CN96105674A patent/CN1138064A/zh active Pending
- 1996-05-03 KR KR1019960014364A patent/KR960041214A/ko not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| KR960041214A (ko) | 1996-12-19 |
| US5747568A (en) | 1998-05-05 |
| DE19516283A1 (de) | 1996-11-07 |
| JPH08302147A (ja) | 1996-11-19 |
| EP0741162A1 (de) | 1996-11-06 |
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