CN109294151A - 经改性的聚合物材料及用于制备聚合物材料的混合物 - Google Patents
经改性的聚合物材料及用于制备聚合物材料的混合物 Download PDFInfo
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- CN109294151A CN109294151A CN201710605167.4A CN201710605167A CN109294151A CN 109294151 A CN109294151 A CN 109294151A CN 201710605167 A CN201710605167 A CN 201710605167A CN 109294151 A CN109294151 A CN 109294151A
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- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 239000002861 polymer material Substances 0.000 title claims abstract description 31
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 49
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 46
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 22
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 21
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 6
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 239000000126 substance Substances 0.000 claims description 44
- -1 dimethyl ethyl Chemical group 0.000 claims description 23
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- 239000001257 hydrogen Substances 0.000 claims description 6
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- BNAOQKULFPHAHL-UHFFFAOYSA-N 3,4-dibutyl-5-(2,4-dimethylphenyl)-3h-1-benzofuran-2-one Chemical compound CCCCC1=C2C(CCCC)C(=O)OC2=CC=C1C1=CC=C(C)C=C1C BNAOQKULFPHAHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 claims description 2
- UVRWBTOHALRHGR-UHFFFAOYSA-N 4-tert-butyl-2-(5-tert-butyl-1-benzofuran-3-yl)phenol Chemical compound CC(C)(C)C1=CC=C(O)C(C=2C3=CC(=CC=C3OC=2)C(C)(C)C)=C1 UVRWBTOHALRHGR-UHFFFAOYSA-N 0.000 claims 1
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- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
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- 238000012545 processing Methods 0.000 abstract description 8
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- 238000012360 testing method Methods 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 12
- 238000000034 method Methods 0.000 description 12
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- 230000001458 anti-acid effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
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- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 3
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- OXWDLAHVJDUQJM-UHFFFAOYSA-N 2-[[2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylamino]-2-oxoacetyl]amino]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCNC(=O)C(=O)NCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OXWDLAHVJDUQJM-UHFFFAOYSA-N 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
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- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
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- CFXCGWWYIDZIMU-UHFFFAOYSA-N Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Chemical compound CCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CFXCGWWYIDZIMU-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- PPZMCRMLNAAHNB-UHFFFAOYSA-N [4-[4-[(2,4-ditert-butylphenoxy)-hydroxyphosphanyl]phenyl]phenyl]phosphonous acid Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(O)C1=CC=C(C=2C=CC(=CC=2)P(O)O)C=C1 PPZMCRMLNAAHNB-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- ZMOXKCINJLBMGB-UHFFFAOYSA-N docosanoic acid;magnesium Chemical compound [Mg].CCCCCCCCCCCCCCCCCCCCCC(O)=O ZMOXKCINJLBMGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000005406 washing Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- 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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- 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
- C08K5/1535—Five-membered rings
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- 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'
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种经改性的聚合物材料,包含共聚物基材及复合式稳定剂组合物。该共聚物基材包括丙烯腈‑丁二烯‑苯乙烯共聚物。该复合式稳定剂组合物包括受阻酚类抗氧剂、选自于含磷有机抗氧剂、含硫有机抗氧剂或其组合的二级抗氧剂及含硫羧酸盐。本发明也提供一种用于制备聚合物材料的混合物,包含丙烯腈、丁二烯、苯乙烯及如上所述的复合式稳定剂组合物。该经改性的聚合物材料在经过多次回收加工后仍能保持其耐冲击强度。
Description
技术领域
本发明涉及一种经改性的聚合物材料,特别是涉及一种包括受阻酚类抗氧剂、二级抗氧剂及特定的含硫羧酸盐的复合式稳定剂组合物的经改性的聚合物材料,及一种用于制备聚合物材料的混合物。
背景技术
丙烯腈-丁二烯-苯乙烯共聚物(acrylonitrile butadiene styrene copolymer,ABS copolymer)具有良好的耐冲击性及耐化学药品性、优良的电器性能,且易于加工、制品尺寸稳定、制造成本低,因而被广泛应用制成各种家电和日常用品的塑料,但ABS在回收加工过程中的热能作用下,容易导致其机械性质下降。
发明内容
本发明的目的在于提供一种经改性的聚合物材料,可以克服上述背景技术的缺点。
本发明的经改性的聚合物材料包含共聚物基材及复合式稳定剂组合物。该共聚物基材包括丙烯腈-丁二烯-苯乙烯(ABS)共聚物。该复合式稳定剂组合物包括受阻酚类抗氧剂、选自于含磷有机抗氧剂、含硫有机抗氧剂或其组合的二级抗氧剂及选自于如以下化学式1至化学式3中至少一种的含硫羧酸盐。
〔化学式1〕
〔化学式2〕
〔化学式3〕
在化学式1中,Mq+表示Ca2+、Ba2+、Mg2+、Zn2+或Al3+,q表示2或3,t表示0至6的整数,R11表示氢或C1至C18烷基,R12表示C1至C30烷基或C6至C18芳烃基。在化学式2中,X21及X22各自独立地表示Ca2+、Ba2+、Mg2+或Zn2+,Y21及Y22各自独立地表示C1至C30烷基或C6至C18芳烃基,a及b各自独立地表示1至6的整数。在化学式3中,X31表示Ca2+、Ba2+、Mg2+或Zn2+,Y31表示C1至C30烷基、C6至C18芳烃基或其中,R33表示C1至C30烷基或C6至C18芳烃基,k表示1至5的整数。
本发明的另一个在于提供一种用于制备聚合物材料的混合物,包含丙烯腈、丁二烯、苯乙烯及如上所述的复合式稳定剂组合物。
本发明的有益效果在于:该经改性的聚合物材料在经过多次回收加工后仍能保持其耐冲击强度。
以下将就本发明内容进行详细说明:
优选地,以该共聚物基材的总重为100重量份,该复合式稳定剂组合物的含量范围为0.01至5.0重量份。
在本发明中,该受阻酚类抗氧剂可为但不限于:四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(以下简称抗氧剂1010)、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯](简称抗氧剂245)、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯(简称抗氧剂1330)、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰尿酸酯(简称抗氧剂3114)、三(丁基甲酚基)丁烷(简称AO-30)、4,4'-亚丁基双(6-叔丁基-3-甲基苯酚)(简称AO-40)、N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼(简称抗氧剂1024)、N,N'-双-[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]己二胺(简称抗氧剂1098)、2,2'-亚甲基双-(4-甲基-6-叔丁基苯酚)(简称抗氧剂2246),以及3,5-二叔丁基-4-羟基苯丙酸异辛酯(简称抗氧剂1135)、3-(3,5-二叔丁基-4-羟基苯基)丙酸正十八烷醇酯(简称抗氧剂1076)、三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰尿酸(简称抗氧剂1790)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷[1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,简称AO-30]、1,1-二(2-甲基-4-羟基-5-叔丁基苯基)丁烷[1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,简称AO-40]、对甲酚与双环戊二烯共聚物(简称Wingstay L或WL,CAS号码为68610-51-5)、2,4-二甲基-6-(1-甲基十五烷基)-酚[2,4-dimethyl-6-(1-methylpentadecyl)-phenol],简称抗氧剂1141,CAS号码为134701-20-5]或其组合。
在本发明中,该含磷有机抗氧剂是选自于如以下化学式4至化学式11中至少一种。
〔化学式4〕
〔化学式5〕
〔化学式6〕
〔化学式7〕
〔化学式8〕
〔化学式9〕
〔化学式10〕
〔化学式11〕
在化学式4至化学式10中,R41至R43、R51至R56、R61至R65、R71至R78、R81至R86、R91至R94,及R101至R108各自独立地表示氢、叔丁基、异丙苯基(isopropylphenyl)或C1至C8直链烷基;T表示C1至C18烃基或其中R95至R97各自独立地表示氢、叔丁基、异丙苯基或C1至C8直链烷基;Z71、Z72、Z81及Z91各自独立地表示O、S、亚甲基或C2至C4亚烷基。
优选地,该含磷有机抗氧剂可为但不限于:3,9-双(2,4-二异丙苯基苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺[5.5]十一烷(简称抗氧剂9228)、三(2,4-二叔丁基)亚磷酸苯酯(以下简称抗氧剂168)、二硬脂基季戊四醇二亚磷酸酯(简称抗氧剂618)、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯(以下简称抗氧剂626)、2,4,8,10-四叔丁基-6-[(2-乙己基)氧]-12H-二苯基[d,g][1,3,2]二氧磷杂八环(简称抗氧剂HP-10)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(简称DOPO)、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯(简称抗氧剂626)、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二磷酸酯(简称PEP-36)、四(2,4-二叔丁基苯基)-4,4'-联苯二亚磷酸酯[tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphonite,简称P-EPQ,CAS号码为119345-01-06]或其组合。
在本发明中,该含硫有机抗氧剂是选自于如以下化学式12至化学式14中至少一种。
〔化学式12〕
〔化学式13〕
〔化学式14〕
〔化学式15〕
在化学式12至化学式15中,R121、R131至R132、R141至R144及R151至R156各自独立地表示叔丁基、异丙苯基或C6至C18直链烷基。
在本发明的具体实施例中,该含硫有机抗氧剂是S(CH2CH2COOC12H25)2(以下简称DL)。
优选地,以该共聚物基材的总重为100重量份,该受阻酚类抗氧剂的含量范围为0.01至2.5重量份,该含磷有机抗氧剂或含硫有机抗氧剂的含量范围为0.01至4.5重量份。
优选地,该复合式稳定剂组合物还包括苯并呋喃酮类抗氧剂、丙烯酸酯类抗氧剂、氧化胺类抗氧剂中至少一种。
在本发明中,该苯并呋喃酮类抗氧剂是如以下化学式16所示。
〔化学式16〕
在化学式16中,R161至R164各自独立地表示氢、C1至C10直链烷基或支链烷基或其中R165至R169各自独立地表示氢、羟基、C1至C10直链烷基或支链烷基。其中R1611至R1613各自独立地表示羟基、C1至C10直链烷基或支链烷基。
优选地,该苯并呋喃酮类抗氧剂是选自于二甲苯基二丁基苯并呋喃酮(xylyldibutylbenzofuranone,以下简称抗氧剂HP-136)、5-叔丁基-3-(5-叔丁基-2-羟基苯基)苯并呋喃-2-(3H)-酮[5-tert-butyl-3-(5-tert-butyl-2-hydroxyphenyl)benzofuran-2-(3H)-one,CAS号码为214354-68-4]、3-[3,5-双(1,1-二甲基乙基)-2-羟基苯基]-5,7-双(1,1-二甲基乙基)-2(3H)-苯并呋喃酮{3-[3,5-bis(1,1-dimethylethyl)-2-hydroxyphenyl]-5,7-bis(1,1-dimethylethyl)-2(3H)-benzofuranone,CAS号码为210709-72-1}或其组合。
在本发明中,该丙烯酸酯类抗氧剂是如以下化学式17所示。
〔化学式17〕
在化学式17中,R171至R175各自独立地表示C1至C10直链烷基或支链烷基。
优选地,该丙烯酸酯类抗氧剂是选自于2-(2-羟基-3-叔丁基-5-甲基苄基)-4-甲基-6-叔丁基苯基丙烯酸酯[2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenylacrylate,简称抗氧剂GM]、2-{1-[2-羟基-3,5-二(2-甲基丁-2-基)苯基]乙基}-4,6-二(2-甲基丁-2-基)苯基丙烯酸酯{2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate,简称抗氧剂GS}或其组合。
在本发明中,该氧化胺类抗氧剂可为但不限于:双(烷基氢化脂肪)氧化胺、双(十八烷基)羟胺(简称抗氧剂FS042)或其组合。
优选地,以该共聚物基材的总重为100重量份,该苯并呋喃酮类抗氧剂的含量范围为0至0.5重量份,该丙烯酸酯类抗氧剂的含量范围为0至0.5重量份,该氧化胺类抗氧剂的含量范围为0至1.0重量份。
优选地,该共聚物基材还包括丙烯腈-苯乙烯共聚物(acrylonitrile-styrenecopolymer,AS)。
优选地,该经改性的聚合物材料还包含制酸剂及金属钝化剂中至少一种。
该制酸剂有助于平衡该经改性的聚合物材料的酸碱值,并能使该含磷有机抗氧剂或含硫有机抗氧剂与该含硫羧酸盐更容易相容。更优选地,该制酸剂是脂肪酸盐。该脂肪酸盐可为但不限于:硬脂酸钙、硬脂酸锌、二十二酸镁、硬脂酸镁、蓖麻油酸钠(sodiumricinoleate)、棕榈酸钾(potassium palmitate)或其组合。
该金属钝化剂能够防止该经改性的聚合物材料产生劣化。更优选地,该金属钝化剂是选自于1,2-二[(3,5-二-叔丁基-4-羟基苯基)丙酰基]肼{1,2-di[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazide}、2,2'-草酰胺基双[乙基3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯]{2,2'-oxamido bis[ethyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]}或其组合。该金属钝化剂的具体商品可为但不限于:MD-1024、Naugard XL-1、Eastman抑制剂OABH。
优选地,以该共聚物基材的总重为100重量份,该制酸剂的含量范围为0至1.5重量份,该金属钝化剂的含量范围为0至1.0重量份。
优选地,该用于制备聚合物材料的混合物还包含分散剂,可包覆在抗氧剂的分子外围,以避免抗氧剂沉降析出。该分散剂可为离子型分散剂或非离子型分散剂。更优选地,该分散剂可为但不限于十二烷基硫酸钠(sodium dodecyl sulfate,SDS)、歧化松香钾皂(disproportionated rosin potassium soap,K-25)、聚乙烯醇(polyvinylalcohol,PVA)、聚乙二醇辛酚醚(octyl phenol ethoxylated,Pannox 8610)、十八烷基醇、聚烷基乙二醇硫酸酯水溶液(2184)。
优选地,该用于制备聚合物材料的混合物还包含水。
优选地,该用于制备聚合物材料的混合物还包含防沉剂,可在抗氧剂的分子间形成支架状的结构,以防止抗氧剂沉降。
本发明经改性的聚合物材料的制备方法并无特别限制,例如但不限于将该复合式稳定剂组合物与ABS共聚物混合(后段加工法),或将该复合式稳定剂组合物加入ABS乳胶液中反应后再经过凝结(coagulation)并干燥生成改性ABS胶粉(前段加工法),后续再加工制成经改性的ABS胶粒,可为不限于押出成型、射出成型等后续加工成型方式。
该前段加工法可为包含以下步骤的乳化加工法:(a)将该复合式稳定剂组合物置于搅拌机的反应槽内并搅拌均匀;(b)加热至100-150℃直到该复合式稳定剂组合物全部熔化后降温至60-95℃,并持续搅拌;(c)再缓慢加入分散剂,并以高转速搅拌,使其均匀混合;(d)再加入去离子水或防沉剂,使其均匀混合后降至室温;(e)将所得产物以筛网滤除加工过程中可能产生的异物;(f)最后将其加入ABS乳胶液中进行聚合反应,再经过凝结并干燥。
在本发明中,前段加工法可为包含以下步骤的研磨加工法:(a)将去离子水、分散剂、抗菌剂、防沉剂和适量玻璃珠置于搅拌机的反应槽内并均匀混合;(b)再加入该复合式稳定剂组合物,于室温水浴下持续搅拌;(c)将所得产物以筛网过滤;(d)最后将其加入ABS乳胶液中进行聚合反应,再经过凝结并干燥。
具体实施方式
本发明将就以下实施例来作进一步说明,但应了解的是,所述实施例仅为例示说明用,而不应被解释为本发明实施的限制。
在以下实施例所使用的化学品中,
1010表示抗氧剂1010;
168表示抗氧剂168;
DL表示S(CH2CH2COOC12H25)2;
S1表示(C12H25─S─CH2CH2COO)2Ca;
S2表示(C12H25─S─CH2CH2COO)3Al;
S3表示
S4表示
HP-136表示抗氧剂HP-136。
[后段加工法]
<实施例1-8及比较例1-6>
依据如下表1所示的复合式稳定剂组合物成分及比例(重量份),将100重量份ABS共聚物(购自于台化公司,品名为AG15A1)分别与复合式稳定剂组合物在25℃中均匀混合,分别得到实施例1-8及比较例1-6的经改性的聚合物材料E1-E8及CE1-CE6。在表1中,“–”表示未添加。
表1
[前段加工法-研磨加工法]
<实施例9-10及比较例7-8>
分别将58g去离子水、2g十二烷基硫酸钠(SDS,分散剂)、0.1g抗菌剂和适量玻璃珠加入1L的搅拌机反应槽内,再利用进行高转速搅拌以均匀混合。再分别依据如下表2所示的复合式稳定剂组合物成分及重量混合配制后加入该反应槽内,于室温水浴下持续搅拌24小时。将所得产物以筛网滤除玻璃珠后分别得到实施例9-10及比较例7-8的均匀分散的研磨液。在表2中,“–”表示未添加。
表2
分别将0.5重量份上述实施例9-10及比较例7-8的研磨液加入100重量份ABS乳胶液(由丙烯腈、丁二烯及苯乙烯所组成,丙烯腈:丁二烯:苯乙烯=20wt%:50wt%:30wt%,固含量为40wt%)均匀搅拌。另将0.4重量份浓硫酸加入2000重量份去离子水,作为凝结剂溶液,并升温至90℃,然后在快速搅拌下,分别将上述含有研磨液的ABS乳胶液缓慢滴入凝结剂溶液中,并保持温度为90℃,待完全加入后升温至95℃并保持15分钟,趁热过滤,并用2000重量份去离子水冲洗过滤,将得到的粉体置于60℃烘箱中干燥20小时,分别得到实施例9-10及比较例7-8的改性ABS胶粉。
将丙烯腈-苯乙烯共聚物(购自于奇美实业,品名为AS127)分别与上述实施例9-10、比较例7-8的改性ABS胶粉以及硬脂酸钙以7:3:0.02的重量比例混合,分别得到实施例9-10及比较例7-8的经改性的聚合物材料E9-E10及CE7-CE8。
[ABS试片制备]
将上述实施例1-10及比较例1-8的经改性的聚合物材料E1-E10以及CE1-CE8分别以双螺杆押出机(中国台湾弘煜机械公司试验机PSM20A)混合押出(温度设定为190至230℃,螺杆转速为200转/分钟,进料速度为6转/分钟),再经过冷却、风干、切粒、干燥,得到经改性的ABS胶粒。
使上述经改性的ABS胶粒充分干燥后,分别以立式射出机于210℃中射出得到尺寸为64mm(长)×12.7mm(厚)×6.4mm(宽)的ABS试片,并放置24小时。
[耐冲击强度测试(Izod impact strength test)]
根据ASTM D256对于ABS试片进行耐冲击强度测试,ABS试片削角后缺口以下厚度约10.2mm,于23℃中进行缺口耐冲击强度测试(耐冲击试验机型号为GOTECH-GT-7045-HML,削角机型号为GOTECH-7016-A3),并将上述经改性的ABS胶粒分别重复进行上述加热押出、冷却、风干、切粒、干燥的加工步骤后射出得到的ABS试片再进行测试,每个实施例及比较例皆测试3片试片,其平均结果分别如下表3所示。
表3
由上表3可以清楚得知,实施例1-10的ABS试片在经过10次重复加工步骤后,仍可维持91.7-98.6%的耐冲击强度(相较于未重复加工),且多数可维持在95.1%以上;而比较例1-8的ABS试片在经过10次重复加工步骤后,仅能维持80.3-84.1%的耐冲击强度,且多数仅在82.4%以下。
综上所述,本发明经改性的聚合物材料在经过多次回收加工后仍能保持其耐冲击强度,所以确实能达成本发明的目的。
以上所述,仅为本发明的实施例而已,当不能以此限定本发明实施的范围,即凡依本发明权利要求书及说明书内容所作的简单的等效变化与修饰,皆仍属本发明的范围。
Claims (10)
1.一种经改性的聚合物材料,其特征在于其包含:
共聚物基材,包括丙烯腈-丁二烯-苯乙烯共聚物;及
复合式稳定剂组合物,包括:
受阻酚类抗氧剂,
选自于含磷有机抗氧剂、含硫有机抗氧剂或其组合的二级抗氧剂,及
选自于如以下化学式1至化学式3中至少一种的含硫羧酸盐,
〔化学式1〕
〔化学式2〕
〔化学式3〕
在化学式1中,Mq+表示Ca2+、Ba2+、Mg2+、Zn2+或Al3+,q表示2或3,t表示0至6的整数,R11表示氢或C1至C18烷基,R12表示C1至C30烷基或C6至C18芳烃基,
在化学式2中,X21及X22各自独立地表示Ca2+、Ba2+、Mg2+或Zn2+,Y21及Y22各自独立地表示C1至C30烷基或C6至C18芳烃基,a及b各自独立地表示1至6的整数,
在化学式3中,X31表示Ca2+、Ba2+、Mg2+或Zn2+,Y31表示C1至C30烷基、C6至C18芳烃基或R33表示C1至C30烷基或C6至C18芳烃基,k表示1至5的整数。
2.根据权利要求1所述的经改性的聚合物材料,其特征在于:该共聚物基材还包括丙烯腈-苯乙烯共聚物。
3.根据权利要求1所述的经改性的聚合物材料,其特征在于:该复合式稳定剂组合物还包括苯并呋喃酮类抗氧剂、丙烯酸酯类抗氧剂、氧化胺类抗氧剂中至少一种。
4.根据权利要求3所述的经改性的聚合物材料,其特征在于:该苯并呋喃酮类抗氧剂是选自于二甲苯基二丁基苯并呋喃酮、5-叔丁基-3-(5-叔丁基-2-羟基苯基)苯并呋喃-2-(3H)-酮、3-[3,5-双(1,1-二甲基乙基)-2-羟基苯基]-5,7-双(1,1-二甲基乙基)-2(3H)-苯并呋喃酮或其组合。
5.根据权利要求3所述的经改性的聚合物材料,其特征在于:该丙烯酸酯类抗氧剂是选自于2-(2-羟基-3-叔丁基-5-甲基苄基)-4-甲基-6-叔丁基苯基丙烯酸酯、2-{1-[2-羟基-3,5-二(2-甲基丁-2-基)苯基]乙基}-4,6-二(2-甲基丁-2-基)苯基丙烯酸酯或其组合。
6.一种用于制备聚合物材料的混合物,其特征在于其包含:
丙烯腈;
丁二烯;
苯乙烯;及
复合式稳定剂组合物,包括:
受阻酚类抗氧剂,
选自于含磷有机抗氧剂、含硫有机抗氧剂或其组合的二级抗氧剂,及
选自于如以下化学式1至化学式3中至少一种的含硫羧酸盐,
〔化学式1〕
〔化学式2〕
〔化学式3〕
在化学式1至化学式3中,Mq+、q、t、R11、R12、X21、X22、Y21、Y22、a、b、X31及Y31的定义是根据权利要求1所述。
7.根据权利要求6所述的用于制备聚合物材料的混合物,其特征在于:还包含分散剂。
8.根据权利要求7所述的用于制备聚合物材料的混合物,其特征在于:该分散剂是十二烷基硫酸钠。
9.根据权利要求6所述的用于制备聚合物材料的混合物,其特征在于:还包含水。
10.根据权利要求6所述的用于制备聚合物材料的混合物,其特征在于:还包含防沉剂。
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Address after: Taipei City, Taiwan, China Applicant after: FDC Lees Chemical Industry Co., Ltd. Address before: Taipei City, Taiwan, China Applicant before: FDC Lees Chemical Industry Co., Ltd. |
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Address after: 18 / F, 102 Roosevelt Road, Zhongzheng District, Taipei, Taiwan, China Applicant after: Yiyi Industry Co.,Ltd. Address before: Taipei City, Taiwan, China Applicant before: FDC,LEES CHEMICAL INDUSTRY Co.,Ltd. |
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