CN100556943C - The thermoplastic resin composition - Google Patents
The thermoplastic resin composition Download PDFInfo
- Publication number
- CN100556943C CN100556943C CNB2004800091876A CN200480009187A CN100556943C CN 100556943 C CN100556943 C CN 100556943C CN B2004800091876 A CNB2004800091876 A CN B2004800091876A CN 200480009187 A CN200480009187 A CN 200480009187A CN 100556943 C CN100556943 C CN 100556943C
- Authority
- CN
- China
- Prior art keywords
- weight parts
- weight
- thermoplastic resin
- weight part
- polymerization
- 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 - Lifetime
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 78
- 239000011342 resin composition Substances 0.000 title claims abstract description 45
- -1 acryl Chemical group 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 66
- 239000000654 additive Substances 0.000 claims abstract description 64
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 42
- 239000011347 resin Substances 0.000 claims abstract description 42
- 230000000996 additive effect Effects 0.000 claims abstract description 41
- 229920000126 latex Polymers 0.000 claims description 76
- 239000004816 latex Substances 0.000 claims description 74
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 71
- 238000006116 polymerization reaction Methods 0.000 claims description 56
- 229920001971 elastomer Polymers 0.000 claims description 48
- 239000000806 elastomer Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 29
- 150000002978 peroxides Chemical class 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 23
- 229920002857 polybutadiene Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 239000000839 emulsion Substances 0.000 claims description 20
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 16
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 16
- 239000011591 potassium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 16
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert-Butyl hydroperoxide Substances CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 13
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 10
- 230000000977 initiatory effect Effects 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 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 5
- 235000019359 magnesium stearate Nutrition 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 5
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 claims description 4
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012190 activator Substances 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- 150000002976 peresters Chemical class 0.000 claims description 3
- 150000004655 tetrazenes Chemical class 0.000 claims description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 75
- 239000011248 coating agent Substances 0.000 abstract description 26
- 238000000576 coating method Methods 0.000 abstract description 26
- 230000008645 cold stress Effects 0.000 abstract description 26
- 238000012545 processing Methods 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 82
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 62
- 230000035939 shock Effects 0.000 description 20
- 238000005452 bending Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 239000003995 emulsifying agent Substances 0.000 description 14
- 239000005060 rubber Substances 0.000 description 13
- 230000008961 swelling Effects 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229920003244 diene elastomer Polymers 0.000 description 11
- 150000002500 ions Chemical group 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 239000007858 starting material Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 238000003466 welding Methods 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000007334 copolymerization reaction Methods 0.000 description 7
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000011790 ferrous sulphate Substances 0.000 description 6
- 235000003891 ferrous sulphate Nutrition 0.000 description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- WRHZVMBBRYBTKZ-UHFFFAOYSA-N pyrrole-2-carboxylic acid Chemical compound OC(=O)C1=CC=CN1 WRHZVMBBRYBTKZ-UHFFFAOYSA-N 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 4
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 3
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 3
- FQEZXNAUMVPGGE-UHFFFAOYSA-N 2,3-dihydro-1h-pyrrole;sodium Chemical compound [Na].C1CC=CN1 FQEZXNAUMVPGGE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 3
- HRKQOINLCJTGBK-UHFFFAOYSA-L dioxidosulfate(2-) Chemical compound [O-]S[O-] HRKQOINLCJTGBK-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical class C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 3
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 2
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 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 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 compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012874 anionic emulsifier Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 2
- 235000019252 potassium sulphite Nutrition 0.000 description 2
- WXZPKGFYANZEQI-UHFFFAOYSA-N prop-2-enenitrile;prop-1-en-2-ylbenzene Chemical compound C=CC#N.C=CC#N.CC(=C)C1=CC=CC=C1 WXZPKGFYANZEQI-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 206010001557 Albinism Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- QUXJSCAOGVQXNK-UHFFFAOYSA-N formaldehyde;sodium;sulfanediol Chemical compound [Na].O=C.OSO QUXJSCAOGVQXNK-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- 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
- C08K5/0016—Plasticisers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The present invention relates to a kind of thermoplastic resin composition.More specifically; the thermoplastic resin of grafted ABS polymkeric substance and heat-resistant copolymerized thing comprises acryl resin, superoxide additive or linking agent; thereby; thermoplastic resin composition of the present invention is effective in the processing of painted thermotolerance ABS resin; because have splendid cold stress albefaction reduction and strength property; and do not reduce other character; and has splendid hot tool weldability, painted and coating ductility; these character are prior in last handling process, and keep mechanical properties and produce splendid thermotolerance and low gloss.
Description
Technical field
The present invention relates to a kind of thermoplastic resin composition.More specifically; the thermoplastic resin of grafted ABS polymkeric substance and heat-resistant copolymerized thing comprises acryl resin, superoxide based additive or crosslinking additives; thereby; the cold stress albefaction (cold stresswhitening) of this thermoplastic resin is lowered, important hot tool weldability (hot-tool weldability) and painted and coating extension characteristics are enhanced and keep splendid thermotolerance and mechanical characteristics in aftertreatment; as tensile strength, bending strength and other characteristic, and make thermoplastic resin itself have low gloss.
Background technology
Recently, with demand to the lightweight automobile, in order to develop the light-weight material inside, carry out many acrylonitrile-butadiene-styrene (ABS) (ABS) resins that efforts be made so that and had stable on heating research, wherein ABS resin has good shock resistance, chemoresistance and workability etc.
As making ABS (acrylonitrile-butadiene-styrene (ABS)) resin have stable on heating method, have the method that good stable on heating multipolymer and grafted ABS polymkeric substance prepare thermotolerance ABS by mixing and be proposed.United States Patent (USP) the 3rd, 010,936 and 4,659, No. 790 the method for preparing the thermotolerance ABS resin is disclosed, wherein, the alpha-methyl styrene that the vinylbenzene of used part or all of amount is had an excellent heat resistance in the preparation of heat-resistant copolymerized thing substitutes.Publication number is Japanese publication and the United States Patent (USP) the 4th of clear 58-206657, clear 63-162708, clear 63-235350, the method etc. that preparation comprises the method for the method of thermotolerance ABS resin of maleimide compound and mixed polycarbonate and ABS and add inorganic substance in ABS is disclosed for 757, No. 109.
These thermotolerance ABS resin are prepared as pellets usually, thereby the preparation of finished product needs the procedure of processing as jet molding or extrusion molding.
Under at low temperatures, especially being lower than 0 ℃ temperature, store or when transportation thermotolerance ABS resin or processing layered product tonal variation that may take place not expect and common albefaction.
If be known as the phenomenon of " cold stress albefaction ", then the priming color of layered product disappears, and this is especially deleterious to painted layered product.
In order to use in thermotolerance ABS resin or processing layered product, the reduction degree of cold stress albinism should be splendid.
Therefore, need increase thermotolerance ABS resin with extremely excellent cold stress albefaction reduction, and, as the method for this thermoplastic resin of preparation, various methods (publication number is Korea S's publication of 2002-0047285) of in thermoplastic polymer, adding the organopolysiloxane of 10～200ppm have been researched and developed.
And procedure of processing and back workability that the thermotolerance ABS resin has behind many jet moldings are important.Especially, the back lampshade of automobile is by injection plexiglass (PMMA), the PMMA sheet is interconnection to be produced for the surface of evenly injection and beautiful outward appearance make with thinner coating, deposition of aluminum and with constant temp and pressure, thereby, the coating stage in preparation process, if the ductility of coating is lowered, then must use thinner extraly, and that thinner can cause the destruction of coating procedure and the deposition appearance in waste and the al deposition process is destroyed.And, because the fusion zone in the generation hot tool welding process, so the reduction of hot tool weldability, and owing to the bonding unevenly evil matter that causes outward appearance.Therefore, the polymethylmethacrylate (PMMA) that uses as the back lampshade of automobile must be splendid aspect hot tool weldability, the painted and coating ductility.
And, along with recent user's organoleptic quality requires the raising of level, to the increase in demand of low gloss resins with more graceful atmosphere.In addition because environmental problem significantly changes, therefore, low gloss resins just towards direct use, avoid low gloss to apply or use the processing of liner to apply direction developing.
Prepare the used cardinal principle of this low gloss resins and be, the slipperiness of control resin surface is to the scope that surpasses visible light, thereby incident light is scattered, therefore, and the performance low gloss effect.Explain method more specifically by following three examples.
The first, as the method that is used to improve acrylonitrile-butadiene-styrene resin, use by what mass polymerization obtained to have a large diameter rubber grain greater than 2 μ m.But by the resin of this method preparation, its low gloss effect is not remarkable, and shock resistance and thermotolerance are relatively poor.
The second, in resin, introduce the method have greater than the low gloss filler of the granularity of 5 μ m.Resin by this method preparation shows splendid formability, still, low gloss characteristic aspect deficiency, and especially, the deterioration of resistance to impact shock is serious.
The 3rd, by using the method for preparing resin as the graft polymerization as the monomer of ethene-unsaturated carboxylic acid and the acrylonitrile-butadiene-styrene (ABS) polymkeric substance by emulsion polymerization prepared of properties-correcting agent.
Resin by the preparation of these methods shows splendid low gloss characteristic and all is being good aspect shock resistance and the various physical properties, therefore is widely used in making resin to have the low gloss effect.
But for use above-mentioned resin in splendid heat-resistant resin, its thermotolerance is relatively poor.And, when above-mentioned resin being applied to the weathering resistance resin that recent its consumption increases, as in the acrylonitrile-butadiene-styrene resin time, the weathering resistance variation.
Summary of the invention
In order to address the above problem, purpose of the present invention has the thermoplastic resin composition that splendid cold stress albefaction reduces for providing.
Another object of the present invention provides splendid thermoplastic resin composition aspect hot tool weldability, painted and coating ductility.
And a further object of the present invention provides to be had splendid thermotolerance and not to reduce physical strength and thermoplastic resin composition that thermoplastic resin self has low gloss.
To achieve these goals, the invention provides a kind of grafted ABS polymkeric substance that comprises 10～50 weight parts; The heat-resistant copolymerized thing of 50～90 weight parts; With the superoxide based additive of 0.01～10 weight part or the thermoplastic resin composition of crosslinking additives.
This thermoplastic resin composition can comprise the grafted ABS polymkeric substance of 20～40 weight parts; The heat-resistant copolymerized thing of 60～80 weight parts; With 0.5～10 weight part superoxide based additive.
This thermoplastic resin composition can comprise the grafted ABS polymkeric substance of 20～40 weight parts; The heat-resistant copolymerized thing of 60～80 weight parts; 0.1 the superoxide based additive of～10 weight parts; Acryl resin with 1.0～10 weight parts.
This thermoplastic resin composition can comprise the grafted ABS polymkeric substance of 10～50 weight parts; The heat-resistant copolymerized thing of 50～90 weight parts; Crosslinking additives with 0.01～10 weight part.
The grafted ABS polymkeric substance can comprise the conjugated diene rubber latex of 40～70 weight parts, the aromatic ethenyl compound of 15～40 weight parts and the acrylonitrile compound of 5～20 weight parts.
The granularity of conjugated diene rubber latex is 2,500～5,000
, its gel content be 70～95% and its swelling index can be 12～30.
Aromatic ethenyl compound is selected from the group that comprises vinylbenzene, alpha-methyl styrene, p-ethyl styrene, Vinyl toluene and derivative thereof.
Acrylonitrile compound is selected from the group that comprises vinyl cyanide (AN), methacrylonitrile, ethyl acrylonitrile and derivative thereof.
Can be by copolymerization 10～40 weight parts have 2,500～3,500
The polybutadiene rubber latex of median size and 70～80% gel contents; 15～30 weight parts have 2,500～3,500
The polybutadiene rubber latex of median size and 80～90% gel contents; The aromatic ethenyl compound of 15～30 weight parts; With the acrylonitrile compound of 10～25 weight parts, thus preparation grafted ABS polymkeric substance.
Prepare the grafted ABS polymkeric substance by the method that may further comprise the steps:
(A) mean particle size of adding 20～30 weight parts is 2,500～3,500
And gel content is that 70～80% the polybutadiene rubber latex and the mean particle size of 20～30 weight parts are 2,500～3,500
And gel content is the mixture of 80～90% polybutadiene rubber latex; The deionized water of the resin acid potassium of the acrylonitrile compound of the aromatic ethenyl compound of 5～10 weight parts, 5～10 weight parts, 0.1～0.5 weight part, the molecular weight regulator of 0.1～1.0 weight part and 50～80 weight parts, the temperature of polymerization reactor is progressively risen to 60 ℃ from 40 ℃, main then by adding peroxide initiator initiated polymerization;
(B) after carrying out 30～60 minutes from above-mentioned polymeric initiation, reach at 50～75% o'clock at monomer conversion, the emulsion of the deionized water of the acrylonitrile compound by adding the aromatic ethenyl compound contain 10～15 weight parts, 10～15 weight parts continuously in 1～2 hour, the resin acid potassium of 0.5～1.5 weight part and 20～30 weight parts is carried out polymerization, lentamente the temperature of polymerization reactor is progressively risen to 70 ℃ by 60 ℃ simultaneously;
(C) in 1～2 hour, add specific peroxide initiator for the second time constantly, add emulsion simultaneously constantly; And
(D) will promote the activator of initiation reaction and for the third time peroxide initiator all add, add above-mentioned emulsion (B) and above-mentioned peroxide initiator (C) then, and in 1～2 hour, the temperature of polymerization reactor is progressively risen to 80 ℃ and finish polymerization by 70 ℃.
Described peroxide initiator is an inorganic peroxide.
Described inorganic peroxide is Potassium Persulphate or Sodium Persulfate.
Can obtain heat-resistant copolymerized thing by the alpha-methyl styrene (AMS) of 50～80 weight parts and vinyl cyanide (AN) polymerization of 20～50 weight parts.
Heat-resistant copolymerized thing is the maleimide base co-polymer.
The superoxide based additive can be selected from and comprise dicumyl peroxide, two-(tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane and 2,5-dimethyl-2, the group of 5-two (tert-butyl hydroperoxide)-3-hexin.
Crosslinking additives can be acyl peroxide, alkyl peroxide, hydrogen peroxide, peresters, azo-compound, disulphide or the tetrazene.
The acryl resin can be for having the polymethylmethacrylate (PMMA) of 50,000～200,000 molecular weight.
The acryl resin can be made of polybutadiene rubber latex, 40～70 parts by weight of acrylic compounds, the aromatic ethenyl compound of 15～30 weight parts and the acrylonitrile compound of 1～20 weight part of 8～25 weight parts.
The thermoplastic resin composition can comprise the slipping agent of 0.1～5 weight part and the antioxidant of 0.1～1.0 weight part.
Lubricant is selected from the group that comprises oxidized polyethlene wax, Magnesium Stearate and composition thereof.
Below describe the present invention in detail.
The invention is characterized in and select the superoxide based additive as forming component, with physical strength that improves the thermoplastic resin for preparing by mixed grafting abs polymer and heat-resistant copolymerized thing and the reduction that improves its cold stress albefaction.
That is to say that prepare the thermoplastic resin composition who has the reduction of splendid cold stress albefaction according to of the present invention by mixed grafting abs polymer, heat-resistant copolymerized thing and superoxide based additive, the preparation method is based on following steps more specifically.
(1) preparation of grafted ABS polymkeric substance
The elastomer latex of small grain size is produced, and afterwards, prepares the elastomer latex of volume particle size by the elastomer latex of the small grain size of condensing, the elastomer latex graft polymerization of aromatic ethenyl compound and acrylonitrile compound and this volume particle size, thereby preparation grafted ABS polymkeric substance.
The granularity of employed conjugated diene rubber latex and gel content have very big influence to the shock strength and the workability of resin in preparation grafted ABS polymkeric substance.Usually, with the particle size reduction of elastomer latex, shock resistance and workability reduce, and, increasing with granularity, shock resistance strengthens.And, reduce with gel content, in elastomer latex, carry out polymerization, and therefore with the increase gradually of apparent particle size, shock strength is enhanced with monomeric solvent swelling state.
When preparation grafted ABS polymkeric substance, percentage of grafting is the character of impact polymer greatly.Therefore, if percentage of grafting reduces, then have the not exposed elastomer latex of grafted, and therefore thermostability is destroyed.And, increasing with the gel content of elastomer latex, and increase with particle diameter, percentage of grafting descends, thereby has limited the raising of thermostability.
Therefore, the method that is used to prepare the conjugated diene rubber latex with suitable particle diameter and gel content is very important, and when aromatic ethenyl compound and acrylonitrile compound in the elastomer latex at volume particle size during grafting, the method that is used to improve percentage of grafting is very important.
By considering that above-mentioned reason prepares the grafted ABS polymkeric substance, at first, preparation has 600～1500
The conjugated diene rubber latex of the minor diameter of particle diameter, 70～95% gel contents and 12～30 swelling indexs, and the graft copolymerization preparation of welding the elastomer latex of small grain size by hot tool has 2,500～5,000
The conjugated diene rubber latex of the volume particle size of particle diameter.If the gel content of the conjugated diene rubber latex of minor diameter is higher than 70～95%, then shock strength reduces, if be lower than 70%, then thermostability reduces.And the granularity with large diameter conjugated diene rubber latex is to make thermoplastic resin have the principal element of high impact-resistant, and therefore, preferably its granularity is 2,500～5,000
, to satisfy physical properties of the present invention.
Below, be divided into the preparation process and the graft copolymerization step of the preparation process of the elastomer latex of small grain size, large diameter elastomer latex by preparation process, and it is carried out detailed explanation the grafted ABS copolymer resin.
(a)
The preparation of the elastomer latex of small grain size
The molecular weight regulator of the polymerization starter of the conjugate diene monomer by disposable adding 100 weight parts in reactor, the emulsifying agent of 1～4 weight part, 0.1～0.6 weight part, the ionogen of 0.1～1.0 weight part, 0.1～0.5 weight part, the ion exchanged water of 90～130 weight parts and 50～60 ℃ of reactions 7～12 hours down; The molecular weight regulator that adds 0.05～1.2 weight part then, and under 55～70 ℃, reacted 5～15 hours, thereby preparation has 600～1500
The conjugated diene rubber latex of the minor diameter of median size, 70～95% gel contents and 12～30 swelling indexs.
Conjugated diene compound can preferably be only the aliphatics conjugated diene compound or be the mixture of aliphatics conjugated diene compound and unsaturated vinyl monomer.
Emulsifying agent is alkaryl sulfuric ester, basic metal alkyl sulfuric ester, sulfonated alkyl ester, fatty acid soaps, alkaline rosinate etc., and these materials can use separately or be used with two or more mixtures.
Polymerization starter is water-based persulphate, redox compound and fat-soluble cpds etc.The water-based persulphate is Sodium Persulfate or potassium etc.Redox compound is superoxide, formaldehyde sodium, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, glucose, pyrroline sodium, sulphite sodium etc.Fat-soluble polymerization starter is cumene hydroperoxide hydrogen, diisopropyl benzene hydrogen peroxide, azo Di-Isobutyl nitrile, tert-butyl hydrogen peroxide, p-methane hydroperoxide, benzoyl peroxide, persulphate etc., and these materials also can be used alone or be used with two or more mixtures.
Ionogen can be independent KCl, NaCl, KHCO that use or that two or more form of mixtures is used
3, NaHCO
3, K
2CO
3, Na
2CO
3, KHSO
3, NaHSO
3, K
4P
2O
7, K
3PO
4, Na
3PO
4, K
2HPO
4And Na
2HPO
4Deng.
Molecular weight regulator can be preferably thio-alcohol, as uncle-lauryl mercaptan, just-lauryl mercaptan etc.
Polymerization temperature is very important for the gel content and the swelling index of control elastomer latex, wherein, should consider the selection of initiator.
B) preparation of volume particle size elastomer latex (elastomer latex of hot tool welding small grain size)
Normally, because the particle diameter of the elastomer latex of volume particle size makes thermoplastic resin have the HI high impact characteristic, therefore, its preparation is very important.In order to satisfy the physical properties among the present invention, required particle diameter is preferably 2,500～5, and 000
In 1 hour, have 600～1500 to 100 weight parts
, 70～95% gel contents and 12～30 swelling indexs the small grain size elastomer latex in add the acetic acid solution of 2.5～4.5 weight parts lentamente, and stir, thereby increase granularity, then, stop to stir, prepare by the hot tool welding and have 2,500～5,000
The elastomer latex of the volume particle size of particle diameter, 70～95% gel contents and 12～30 swelling indexs.
C) graft polymerization
By elastomer latex graft copolymerization with aromatic ethenyl compound and acrylonitrile compound and the volume particle size by method for preparing, thus preparation grafted ABS multipolymer.
That is to say that grafting method is to carry out graft copolymerization by the aromatic ethenyl compound that adds 15～40 weight parts in the conjugated diolefine volume particle size elastomer latex of 40～70 weight parts, the acrylonitrile compound of 5～20 weight parts, the emulsifying agent of 0.2～0.6 weight part, the molecular weight regulator of 0.2～0.6 weight part, the polymerization starter of 0.1～0.5 weight part etc.
Aromatic ethenyl compound is preferably vinylbenzene, alpha-methyl styrene, o-ethyl styrene, p-ethyl styrene, Vinyl toluene and derivative thereof etc., and these materials can be used alone, and perhaps are used with two or more mixtures.
Acrylonitrile compound is preferably vinyl cyanide (AN), methacrylonitrile, ethyl acrylonitrile and derivative thereof etc., and these materials can be used alone, and perhaps are used with two or more mixtures.
Emulsifying agent is preferably alkaryl sulfuric ester, alkaline methyl alkyl sulfuric ester, sulfonated alkyl ester, fatty acid soaps, alkaline rosinate etc., and these materials can be used alone, and perhaps are used with two or more mixtures.
Molecular weight regulator is preferably uncle's lauryl mercaptan.
Polymerization starter is water-based persulphate, redox compound and fat-soluble cpds etc.The water-based persulphate is Sodium Persulfate or Potassium Persulphate etc.
Redox compound is superoxide, formaldehyde sodium, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, glucose, pyrroline sodium, sulphite sodium etc.Fat-soluble polymerization starter is cumene hydroperoxide hydrogen, diisopropyl benzene hydrogen peroxide, azo diisobutyl nitrile, tert-butyl hydrogen peroxide, p-methane hydroperoxide, benzoyl peroxide, persulphate etc., and these materials also can be used alone or be used with two or more mixtures.
When grafting, polymerization temperature is preferably 45～80 ℃, and polymerization time is preferably 3～5 hours.
And in order to improve percentage of grafting and the formation of solid matter to be minimized, the method that adds each component can be used whole addition method, multistep addition method and continuous addition method, preferred multistep addition method and continuous addition method.
After finishing polymerization, the polymerisation conversion of the latex of acquisition is greater than 96%.Antioxidant and stablizer are added in the latex, and by using under 80 ℃ the temperature that aqueous sulfuric acid is cured, dehydration and dry then being higher than, thereby obtain powder.
By as measuring the cured portion (%) of solid type shown in the following formula 1, thus the stability of estimation graft copolymer.
[formula 1]
The cured portion of solid type (%)=(weight of the solid matter that forms in the reactor (g)/total rubber and monomeric weight) * 100
When the cured portion (%) of solid type surpassed 0.7%, the stability of latex was greatly destroyed.In addition, because a large amount of solid matters, thereby be difficult to obtain to be fit to graftomer of the present invention.
In addition, the percentage of grafting of graftomer is measured as follows.By solidifying, clean and the dry graftomer latex that obtains powder type.Then, by the acetone that adds 300ml the 2g powder was stirred 24 hours.By using the ultracentrifuge separation solution, and by separated acetone soln is splashed in the methyl alcohol, thereby obtain not grafting part, then, measure not grafting weight partly by drying.Use observed value, according to measuring percentage of grafting with following formula 2.
[formula 2]
Percentage of grafting (%)=(weight of the weight/rubber of grafted monomer) * 100
In the present invention, the percentage of grafting of grafted ABS polymkeric substance is preferably greater than 26%.If percentage of grafting is lower than 26%, then, thermostability make the grafted ABS polymkeric substance improper because reducing.
(2) preparation of heat-resistant copolymerized thing
By preparing heat-resistant copolymerized thing with suitable proportion polymerization α-Jia Jibenyixidanti and acrylonitrile monemer.As polymerization process, preferred emulsion polymerization and mass polymerization (masspolymerization).Example as preparation, two-the uncle as molecular weight regulator of the toluene as solvent of the vinyl cyanide of the α-Jia Jibenyixidanti of 50～80 weight parts, 20～50 weight parts, 26～30 weight parts, 0.1～1.0 weight part-lauryl mercaptan is mixed, afterwards, its mixture is added in the reactor continuously, and reacts 2～4 hours.At this moment, preferable reaction temperature maintains 140～170 ℃.By comprising that adding the successive processes that feedstock pump, continuously stirring groove, fore-warmer tank and evaporator tank, polymkeric substance transport pump and extrusion processing instrument implements this preparation method.
By using
13The distribution of the alpha-methyl styrene (AMS) that the analysis of CNMR analyser obtains and the molecular chain structure of vinyl cyanide (AN) multipolymer.Analytical procedure is: the spherolite that obtains is dissolved in the deuteriochloroform, and by using tetramethylsilane to measure gained solution as internal standard substance.Recording in the peak value of 140～150ppm, the peak value of the chain structure of alpha-methyl styrene-vinyl cyanide-vinyl cyanide (AMS-AN-AN) appears in the scope of 141～144ppm, the peak value of the chain structure of alpha-methyl styrene-alpha-methyl styrene-vinyl cyanide (AMS-AMS-AN) appears in the scope of 144.5～147ppm, the peak value of the chain structure of alpha-methyl styrene-alpha-methyl styrene-alpha-methyl styrene (AMS-AMS-AMS) appears in the scope of 147.5～150ppm, then, the multipolymer of the areal analysis gained by measuring these peak values.
In the molecular chain structure of multipolymer of the present invention, the chain structure of alpha-methyl styrene-alpha-methyl styrene-alpha-methyl styrene (AMS-AMS-AMS) is preferably lower than 14%.If its chain structure is higher than 14%, then thermostability is owing to the chain structure of alpha-methyl styrene-alpha-methyl styrene-alpha-methyl styrene (AMS-AMS-AMS) is lowered in the pyrolysis that adds man-hour.And the chain structure of alpha-methyl styrene-vinyl cyanide-vinyl cyanide (AMS-AN-AN) is preferably lower than 39%.If its chain structure is greater than 39%, then thermotolerance is relatively poor.
(3) preparation of superoxide based additive
Thermoplastic resin composition's the additive that is suitable for having the cold stress albefaction of reduction is the superoxide based compound, and its form is preferably liquid state or sheet, but is not limited to this.The superoxide based additive can be selected from and comprise dicumyl peroxide, two-(tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane and 2,5-dimethyl-2, the group of 5-two (t-butyl peroxy)-3-hexin.
(4) mixing process
Prepare the thermoplastic resin composition by grafted ABS polymkeric substance, the heat-resistant copolymerized thing of 60～8 α weight parts and the superoxide based additive of 0.5～10 weight part that is blended in 20～40 weight parts of preparation in above-mentioned steps (1)～(3).In order to improve this thermoplastic resin composition's physical properties, can add lubricant and antioxidant.
The consumption of grafted ABS polymkeric substance is preferably 20～40 weight parts, more preferably 25～30 weight parts.
The consumption of heat-resistant copolymerized thing is preferably 60～80 weight parts, more preferably 70～75 weight parts.
The consumption of superoxide based additive is preferably 0.5～10 weight part, more preferably 1.0～5 weight parts.
As lubricant, the consumption of oxidized polyethlene wax, Magnesium Stearate and composition thereof is preferably 0.1～5.0 weight part, more preferably 0.2～1.0 weight part.
The consumption of antioxidant is preferably 0.1～1.0 weight part.
And; the invention is characterized in and use acryl resin and superoxide based additive component as an alternative, thereby improve the physical strength of the thermoplastic resin for preparing by mixed grafting abs polymer and heat-resistant copolymerized thing and improve hot tool weldability, painted and coating ductility.
That is to say that by mixed grafting abs polymer, heat-resistant copolymerized thing, acryl resin and superoxide based additive, thereby preparation is according to the thermoplastic resin composition with good hot tool weldability, painted and coating ductility of the present invention.Preparation method more specifically according to following steps is illustrated as follows.
(1) preparation of grafted ABS polymkeric substance
The method for preparing the grafted ABS polymkeric substance is with identical in the method for preparing the grafted ABS polymkeric substance described in the thermoplastic resin composition of the cold stress albefaction with reduction.
(2) preparation of heat-resistant copolymerized thing
The method for preparing heat-resistant copolymerized thing is with identical in the method for the heat-resistant copolymerized thing of preparation described in the thermoplastic resin composition of the cold stress albefaction with reduction.
(3) preparation of acryl resin
Prepare the acryl resin with polybutadiene rubber latex, acrylic compound, aromatics and acrylonitrile compound.That is to say; mixed 4～7 hours by polybutadiene rubber latex, 40～70 parts by weight of acrylic compounds, the aromatics of 15～30 weight parts, the acrylonitrile compound of 1～20 weight part, the ion exchanged water of 70～110 weight parts, the emulsifying agent of 0.2～0.6 weight part, the molecular weight regulator of 0.2～0.6 weight part and the polymerization initiator of 0.05～0.3 weight part 8～25 weight parts; wherein polymeric reaction temperature is preferably 65～80 ℃, thus preparation acryl resin.
By 1 of disposable adding 100 weight parts, the ion exchanged water of the molecular weight regulator of the ionogen of the polymerization starter of the emulsifying agent of 3-divinyl, 1～4 weight part, 0.2～1.5 weight part, 0.3～0.9 weight part, 0.1～0.5 weight part and 60～100 weight parts, and under 65～85 ℃ temperature, reacting 25～50 hours, thereby preparation polybutadiene rubber latex.The median size of this polybutadiene rubber latex is preferably 2,500～5, and 000
, gel content be preferably 60～95% and swelling index be preferably 12～40.
Acrylic compound can be alkyl methacrylate or alkyl acrylate.
Emulsifying agent is alkaryl sulfuric ester, alkaline methyl alkyl sulfuric ester, sulfonated alkyl ester, fatty acid soaps, alkaline rosinate etc., and these materials can be used alone, and perhaps are used with two or more mixtures.
Molecular weight regulator can be preferably uncle's lauryl mercaptan.
Polymerization starter be with as the reductive agent of formaldehyde sodium, sulfoxylate, sodium ethylenediamine, tetraacetate, ferrous sulfate, glucose, pyrroline sodium, sulphite sodium etc. or as the superoxide blended redox compound of cumene hydroperoxide hydrogen, diisopropyl benzene hydrogen peroxide, persulphate etc., these materials can be used alone, and perhaps are used with two or more mixtures.
(4) preparation of superoxide based additive
Be suitable for having splendid hot tool weldability, the thermoplastic resin composition's of painted and coating extension characteristics additive is the superoxide based compound.The form of this superoxide additive is preferably liquid state or sheet, but is not limited to this.
The example of superoxide additive is dicumyl peroxide, two-(tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane and 2,5-dimethyl-2,5-two (t-butyl peroxy)-3-hexin.
(5) mixing process
By being blended in grafted ABS polymkeric substance, the heat-resistant copolymerized thing of 60～80 weight parts, the acryl resin of 1.0～10 weight parts and the peroxidation based additive of 0.1～10 weight part of 20～40 weight parts of preparation in above-mentioned steps (1)～(4), thus the preparation thermoplastic resin composition.In order to improve this thermoplastic resin composition's physical properties, can add lubricant and antioxidant.
The consumption of grafted ABS polymkeric substance is preferably 20～40 weight parts, 25～30 weight parts more preferably.
The consumption of heat-resistant copolymerized thing is preferably 60～80 weight parts, 70～75 weight parts more preferably.
The consumption of superoxide based additive is preferably 0.1～10 weight part, more preferably 0.5～5 weight part.
The consumption of lubricant is preferably 0.1～5.0 weight part, the more preferably oxidized polyethlene wax, Magnesium Stearate and composition thereof of 0.2～1.0 weight part.
The consumption of antioxidant is preferably 0.1～2.0 weight part.
And, the invention is characterized in and select crosslinking additives component as an alternative, thereby keep the physical properties of the thermoplastic resin for preparing by mixed grafting abs polymer and heat-resistant copolymerized thing, as thermotolerance and physical strength, and the gloss characteristic that it is had.
That is to say, prepare the thermoplastic resin composition who has splendid thermotolerance and low gloss according to of the present invention by mixed grafting abs polymer, heat-resistant copolymerized thing and linking agent.Preparation method more specifically according to following steps is described as follows.
(1) preparation of grafted ABS polymkeric substance
By with aromatic ethenyl compound and acrylonitrile compound and the graft polymerization of conjugated diene rubber latex, and preparation grafted ABS polymkeric substance.
That is to say to have 2,500～3,500 by what mixing comprised 20～30 weight parts
The polybutadiene rubber latex of median size, 70～80% gel contents and 20～30 weight parts have 2,500～3,500
, 80～90% gel contents the elastomer latex mixture of polybutadiene rubber latex; Aromatic ethenyl compound and acrylonitrile compound carry out emulsion graft copolymerization then and close, thus preparation grafted ABS polymkeric substance.As a result, preparation has the grafted ABS polymkeric substance of 10～20% percentage of grafting.
The example for preparing above-mentioned grafted ABS polymkeric substance is as follows.What comprise 20～30 weight parts has 2,500～3,500
The polybutadiene rubber latex of median size, 70～80% gel contents and 20～30 weight parts have 2,500～3,500
, 80～90% gel contents the elastomer latex mixture of polybutadiene rubber latex; The aromatic ethenyl compound of 5～10 weight parts; The acrylonitrile compound of 5～10 weight parts; 0.1 the resin acid potassium of～0.5 weight part; 0.1 the molecular weight regulator of～1.0 weight parts; Be added in the polymerization reactor with the deionized water of 50～80 weight parts, then, the temperature of reactor progressively risen to 60 ℃ by 40 ℃, afterwards, main by adding peroxide initiator initiated polymerization.
Auto-polymerization causes through after 30～60 minutes, when monomer conversion reaches 50～75, in 1～2 hour, the emulsion that adds the deionized water of the resin acid potassium of acrylonitrile compound, 0.5～1.5 weight part of the aromatic ethenyl compound contain 10～15 weight parts, 10～15 weight parts and 20～30 weight parts constantly, and simultaneously the temperature of polymerization reactor is progressively risen to 70 ℃ lentamente by 60 ℃.And, when adding emulsion, in 1～2 hour, add specific peroxide initiator for the second time continuously.After adding emulsion and peroxide initiator, promote the activator of initiation reaction and for the third time peroxide initiator all added, in 1～2 hour, the temperature of polymerization reactor is progressively risen to 80 ℃ lentamente by 70 ℃, and finishes polymerization.
According to the above-mentioned method for preparing the grafted ABS polymkeric substance, the total polymerization time is about 3～7 hours, and polymerisation conversion surpasses 96%.
The conjugated diene rubber latex can be selected from independent aliphatics conjugated diene compound, maybe can be selected from the mixture of aliphatics conjugated diene compound and vinyl unsaturated compound, wherein, and more preferably polybutadiene rubber latex.
Aromatic ethenyl compound can be vinylbenzene, alpha-methyl styrene, p-vinyl toluene, α-ethyl styrene, o-ethyl styrene, p-ethyl styrene, Vinyl toluene and derivative thereof etc., these materials can be used alone, perhaps be used with two or more mixtures, and more preferably vinylbenzene.
Acrylonitrile compound can be vinyl cyanide, methacrylonitrile, ethyl acrylonitrile and derivative thereof etc., and these materials can be used alone, and perhaps is used with two or more mixtures, wherein vinyl cyanide more preferably.
Except that above-mentioned monomer, grafted ABS polymkeric substance of the present invention can with a spot of vinyl monomer, as copolymerizations such as maleimide, N-methyl maleimide, N-ethylomaleimide, N-propyl group maleimide, N-phenyl maleimide, methyl methacrylate, methyl acrylate, butyl acrylate, vinylformic acid, MALEIC ANHYDRIDE.
The emulsifying agent that is used to prepare the emulsion that the grafted ABS multipolymer added can be anionic emulsifier, cationic emulsifier, nonionic emulsifying agent or its mixture.
Anionic emulsifier can be alkaryl sulfuric ester, alkaline methyl alkyl sulfuric ester, sulfonated alkyl ester, fatty acid soaps, alkaline rosinate etc., and its consumption is 0.6～2.0 weight part.
The molecular weight regulator that is used to prepare grafted ABS polymkeric substance of the present invention is preferably mercaptan, more preferably uncle's lauryl mercaptan.
The consumption of molecular weight regulator is preferably 0.1～1.0 weight part.
The peroxide initiator that preparation grafted ABS polymkeric substance is added is preferably inorganic peroxide, as Potassium Persulphate, Sodium Persulfate etc.The consumption of peroxide initiator is preferably 0.05～0.5 weight part, and it is preferably by being divided into three uses.That is to say, preferably, in the polymeric elicitation procedure, 30～50 weight parts in the total amount of use peroxide initiator, carry out in the process at it, 30～50 weight parts in the total amount of use peroxide initiator, and before its terminal procedure, 10～20 weight parts in the total amount of use peroxide initiator.
With the condensing agent of routine, as sulfuric acid, sal epsom (MgSO
4), calcium chloride (CaCl
2), Tai-Ace S 150 (Al
2(SO
4)
3) condense by aforesaid method polymeric grafted ABS polymkeric substance, then, clean, dewater and drying, thereby obtain pulverulence.
(2) preparation of heat-resistant copolymerized thing
Prepare heat-resistant copolymerized thing to prepare the identical method of the method for thermally stable polymer with being used to described in the thermoplastic resin composition of the cold stress albefaction that has reduction in preparation.
And,, can use the heat-resistant copolymerized thing of maleimide base as heat-resistant copolymerized thing of the present invention.
(3) preparation of crosslinking additives
The additive that is suitable for having the thermoplastic resin of good thermotolerance and low gloss is a crosslinking additives.The form of crosslinking additives is not particularly limited, still, and preferred liquid state and sheet.
Crosslinking additives can be selected from acyl peroxide, alkyl peroxide, hydrogen peroxide, peresters, azo-compound, disulphide, the tetrazene etc.
The superoxide based compound can be dicumyl peroxide, two-(tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane and 2,5-dimethyl-2,5-two (tert-butyl peroxide)-3-hexin etc.
By in the preparation of thermoplastic resin, adding these crosslinking additives, in resin treatment, form free radical, advance crosslinking reaction by the free radical that forms, and therefore thermoplastic resin shows low gloss.
(4) mixing process
By mixing through the grafted ABS polymkeric substance of 10～50 prepared weight parts of above-mentioned steps (1)～(3), the heat-resistant copolymerized thing of 50～90 weight parts and the crosslinking additives of 0.05～10 weight part, thus the preparation thermoplastic resin composition.In order to improve the physical properties of thermoplastic resin, can further add lubricant and antioxidant.
The consumption of grafted ABS polymkeric substance is preferably 10～50 weight parts, more preferably 25～30 weight parts.
The consumption of heat-resistant copolymerized thing is preferably 50～90 weight parts, more preferably is 70～75 weight parts.
The containing of crosslinking additives is preferably 0.05～10 weight part, 0.1～1.0 weight part more preferably.
Lubricant can be oxidized polyethlene wax, Magnesium Stearate and composition thereof, wherein, and more preferably distearyl acid magnesium (EBA).The consumption of lubricant is preferably 0.1～5.0 weight part, more preferably 0.1～2.0 weight part.
The consumption of antioxidant is preferably 0.1～1.0 weight part.
Thermoplastic resin by method for preparing have at the miter angle place less than 25 pass through surface gloss that ASTM D-523 measures, and excellent heat resistance.
Embodiment
Hereinafter, by following examples the present invention is described in more detail.Yet scope of the present invention is not limited to following examples.And, estimate by the following method by following examples and the elastomer latex of comparative example's preparation and the physical properties of whole resin.
* gel content and swelling index: with diluted acid or metal-salt curing rubber latex, clean solid then, and in vacuum oven 60 ℃ dry 24 hours down.With scissors the block rubber that obtains is cut into small pieces, and the 1g sheet rubber is joined in the 100g toluene, then, at room temperature, in the darkroom, store 48 hours.The gained material is separated into colloidal sol and gel, then, according to estimating each gel content and swelling indexs with following formula 3 and 4.
[formula 3]
Gel content (%)=(weight/example weight of insoluble part (gel)) * 100
[formula 4]
The weight of the weight/gel of swelling index=swell gel
* particle diameter: use Nicomp (model: 370HPL), measure by dynamic laser scattering method.
* the distribution (Mw/Mn) of weight-average molecular weight (Mw) and molecular weight: when measuring percentage of grafting, add non-solvent to isolating sol-fraction, and extraction and dry, thereby obtain styrene-based copolymers.
Styrene-based copolymers is dissolved in THF weighs, then, measure the distribution (Mw/Mn) of weight-average molecular weight (Mw) and molecular weight by using GPC (gel permeation chromatography).
* percentage of grafting: be the weight percent of the styrene-based copolymers that is grafted to 1g rubber.By adding the acetone of 100ml, the Powdered grafted ABS polymkeric substance of 2g was stirred 24 hours.Not grafted styrene-based copolymers dissolving separates colloidal sol and gel by the use ultracentrifugation then, and estimates the weight of not grafting part.According to calculating percentage of grafting with following formula 5.Rubber content in the formula 5 is the per-cent of the grafted ABS polymkeric substance in the elastomer latex that adds in the polymerization process.
[formula 5]
Percentage of grafting (%)=(weight of gel-(abs polymer * rubber content))/(weight of abs polymer * rubber) * 100
* tensile strength: measure according to ASTM D638.
* bending strength: measure according to ASTM D790.
* shock strength: measure according to ASTM D256.
* cold stress albefaction degree: measure the conventional color coordinate that uses, then, measure cold stress albefaction degree by calculating aberration dE.Serious cold stress albefaction takes place greater than 3 expressions in dE, and it has exceeded the limit that allows usually.
* hot tool weldability: under 320 ℃ temperature,, continue 60 seconds, molten resin, the melting intensity (fusing strength) between estimation resin and the metal covering with the pressure of 5bar.That is to say, at resin with after metal covering contacts, according to the thickness of the band that forms and the degree of dimension estimation hot tool weldability.Under identical hot tool welding conditions, if the bar tape thickness is and many, then the hot tool welding strength descends, if band approaches and do not exist, then the hot tool welding strength is good.The condition that does not have band is the A level, and the condition that forms band everywhere is the C level.According to the number of band and thickness and correspondingly estimate the hot tool weldability.
* coating is painted: measure the conventional color coordinate that uses, then, measure coloring degree by estimation L value.
* coating ductility: coating ductility illustrates in coating procedure, and coating is in the lip-deep degree of stretch of thermotolerance ABS, and it is important in surface and coating wetting, and it is determined by estimating surface energy.
* thermotolerance: measure heat-drawn wire (HDT, Heat DeflectionTemperature) according to ASTM D648.
* low gloss: measure surface gloss according to ASTM D523.
Embodiment 1～9 and comparative example 1: thermoplastic resin with cold stress albefaction of reduction
The preparation of fat
[embodiment 1]
The first step: the preparation of grafted ABS polymkeric substance
(a) preparation of small grain size elastomer latex
Electrolytical yellow soda ash (the Na of conduct of the resin acid potassium as emulsifying agent of the monomeric 1,3-butadiene of the conduct of the ion exchanged water of 100 weight parts, 100 weight parts, 1.2 weight parts, the potassium oleate of 1.5 weight parts, 0.1 weight part
2CO
3), the KHCO of 0.5 weight part
3All joined in the polymerization reactor (autoclave) of nitrogen replacement with the uncle's lauryl mercaptan (TDDM) as molecular weight regulator of 0.3 weight part.Temperature of reaction is risen to 55 ℃, all join in the reactor and initiation reaction by potassium sulfite then, and reacted 10 hours as initiator with 0.3 weight part.Afterwards, uncle's lauryl mercaptan (TDDM) of 0.05 weight part is further joined in the reactant, temperature of reaction is risen to 65 ℃ then, and reacts 8 hours, thereby obtain the elastomer latex of small grain size.The particle diameter of the elastomer latex that obtains is 1,000
, its gel content be 90% and swelling index be 18.
(b) preparation of volume particle size elastomer latex (the hot tool welding process of small grain size elastomer latex)
The small grain size elastomer latex that 100 weight parts prepare in above-mentioned (a) is added in the reactor, and the control stirring velocity is 10rpm, and controlled temperature is 30 ℃, then in 1 hour, the 7wt% acetic acid aqueous solution of 3.0 weight parts is added in the reactor lentamente.Afterwards, stop to stir, and by the gained material is placed 30 minutes, prepare through the hot tool welding of small grain size elastomer latex and to have large diameter conjugated diolefine latex.The particle diameter of this volume particle size elastomer latex is 3,100
Its gel content is 90%, and its swelling index is 17.
(c) grafting step (preparation of grafted ABS multipolymer):
The sulfoxylic acid formaldehyde sodium of the ferrous sulfate of the EDTA sodium of the resin acid potassium as emulsifying agent of the ion exchanged water of the volume particle size elastomer latex of preparation, 65 weight parts, 0.35 weight part, 0.1 weight part, 0.005 weight part and 0.23 weight part is all joined in the polymerization reactor of nitrogen replacement in 50 weight parts above-mentioned (b), and temperature of reaction is risen to 70 ℃.The mixed emulsion that comprises the diisopropylidene hydrogen peroxide of uncle's lauryl mercaptan of vinyl cyanide, 0.4 weight part of vinylbenzene, 15 weight parts of resin acid potassium, 35 weight parts of ion exchanged water, 0.65 weight part of 50 weight parts and 0.4 weight part was added in the reactant in 3 hours continuously, and temperature is risen to 80 ℃, finished reaction in 1 hour by stirring then.
Wherein, polymerisation conversion is 97.5%, and the solid type cured portion is 0.2%, and the grafting ratio is 37%.Solidify this grafted ABS polymkeric substance with aqueous sulfuric acid, and clean, obtain powder afterwards.
Second step: the preparation of heat-resistant copolymerized thing
Two uncles as the molecular weight regulator-lauryl mercaptan as the toluene and 0.15 weight part of solvent of the vinyl cyanide of the alpha-methyl styrene of 70 weight parts, 30 weight parts, 30 weight parts is added in the reactor continuously, wherein the reaction times is set at 3 hours, and temperature of reaction maintains 148 ℃.The polymeric solution that discharges from reactor is heated preheater, and in the evaporation reaction device the unreacted monomer of evaporation, then with the temperature maintenance of polymkeric substance at 210 ℃.Afterwards, by using the transmission pump extrusion molding that heat-resistant copolymerized thing (SAN type multipolymer) is processed as a type.
The 3rd step: mix
Mix the san copolymer by the preparation of second step of the grafted ABS polymkeric substance by the first step preparation, 70 weight parts of 30 weight parts, with respect to (the Perkadox BC of the dicumyl peroxide as the superoxide based additive of rubber content 1.0 weight parts, Perkadox BC-FF, Akzonoble), 1.0 weight parts as the ethene bis-stearamides (EBA) of lubricant and the antioxidant of 0.3 weight part.Then, by using double-shafted extruder to prepare spherolite down at 230 ℃.
The 4th step: the estimation of physical properties
Spherolite by the preparation of the 3rd step is injected once more, then, estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[embodiment 2]
Except that using two-(tert-butyl hydroperoxide sec.-propyl) benzene as the superoxide based additive, prepare the thermoplastic resin composition with the step identical with embodiment 1, and estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[embodiment 3]
Remove and use 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane be as outside the superoxide based additive, prepares the thermoplastic resin composition with the step identical with embodiment 1, and estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[embodiment 4]
Remove with respect to rubber content and use superoxide based additive among the embodiment 2 of 3 weight parts, prepare the thermoplastic resin composition with the step identical with embodiment 1, and estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[embodiment 5]
Remove with respect to rubber content and use superoxide based additive among the embodiment 3 of 5 weight parts, prepare the thermoplastic resin composition with the step identical with embodiment 1, and estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[comparative example 1]
Except that not using the superoxide based additive, prepare the thermoplastic resin composition with the step identical with embodiment 1, and estimation tensile strength, bending strength and cold stress albefaction degree, the result is as shown in table 1.
[table 1]
As shown in table 1, with respect to the comparative example 1 who does not add the superoxide based additive, be splendid in tensile strength, bending strength equal strength properties according to the thermoplastic resin composition of the embodiment 1～9 of the constant composition preparation with grafted ABS polymkeric substance, heat-resistant copolymerized thing and superoxide based additive of the present invention.
And aspect cold stress albefaction degree, the dE value is high more, and the cold stress albefaction is poor more.The dE value of thermoplastic resin composition among the embodiment 1～9 not 1.7～3.8, therefore, the reduction of cold stress albefaction is increased to 70～90% as can be seen.
Embodiment 10～14 and comparative example 2: have extremely excellent hot tool weldability, painted
And the preparation of the thermoplastic resin of coating extension characteristics
[embodiment 10]
The first step: the preparation of grafted ABS polymkeric substance
Prepare the grafted ABS polymkeric substance with the method identical with the first step among the embodiment 1.
Second step: the preparation of heat-resistant copolymerized thing
Prepare heat-resistant copolymerized thing with the method identical with second step among the embodiment 1.
The 3rd step: based on the preparation of the resin of acryl
Electrolytical yellow soda ash (the Na of conduct of the resin acid potassium as emulsifying agent of the ion exchanged water of the 1,3-butadiene of 100 weight parts, 80 weight parts, 1.2 weight parts, 1.5 weight part potassium oleates, 0.7 weight part
2CO
3), the KHCO of 0.8 weight part
3All joined in the polymerization reactor of nitrogen replacement with the uncle-lauryl mercaptan as molecular weight regulator (TTDM) of 0.3 weight part, temperature is controlled to be 65 ℃ then.The Potassium Persulphate that further adds 0.3 weight part as polymerization starter, and temperature risen to 85 ℃ continuously, heat 35 hours, then, finish reaction, thereby prepare the polybutadiene rubber latex.
The polybutadiene rubber latex of the preparation of 10 weight parts, the ion exchanged water of 90 weight parts, 0.2 the sodium oleate as emulsifying agent of weight part, 14.38 the methyl methacrylate as Acrylic Acid Monomer of weight part, 5.62 the vinylbenzene as aromatic vinyl monomers of weight part, 2.5 the vinyl cyanide as acrylonitrile monemer of weight part, 0.2 the uncle-lauryl mercaptan as molecular weight regulator of weight part, 0.048 the minaline sodium as polymerization starter of weight part, 0.012 the glucose of weight part, 0.001 the ferrous sulfate of weight part, 0.04 the isopropyl benzene hydroperoxide of weight part is all added under 50 ℃, and temperature is being risen in 73 ℃, reacting 2 hours.
After the reaction; added continuously in 4 hours by the isopropyl benzene hydroperoxide blended emulsion of the ferrous sulfate of the glucose of the minaline sodium of the uncle-lauryl mercaptan of the vinylbenzene of the methyl methacrylate of the sodium oleate of the ion exchanged water of 70 weight parts, 0.4 weight part, 43.12 weight parts, 16.88 weight parts, 7.5 parts by weight of acrylonitrile, 0.25 weight part, 0.048 weight part, 0.012 weight part, 0.001 weight part and 0.10 weight part; and temperature is risen to 76 ℃ again; with reactant slaking 1 hour; finish reaction then, thus preparation acryl resin.Obtain powder type by condensing with calcium chloride solution, also cleaning.Wherein, polymerisation conversion is 99.5%, and the solid type cured portion is 0.1%.
The 4th step: mix
Mix heat-resistant copolymerized thing, the preparation in the 3rd step of 1 weight part of the grafted ABS multipolymer for preparing in the 30 weight part the first steps, preparation in second step of 70 weight parts the acryl resin, with respect to the dicumyl peroxide as the superoxide based additive (Perkadox BC, Perkadox BC-FF) of 0.1 weight part of rubber content, 1 weight part as the ethene bis-stearamides (EBA) of lubricant and the antioxidant of 0.3 weight part.Then, by using double-shafted extruder to prepare spherolite down at 230 ℃.
[embodiment 11]
Except that the acryl resin that uses 5 weight parts, prepare thermoplastic resin with the method identical with embodiment 10.
[embodiment 12]
The superoxide based additive in the embodiment 10 that uses 1 weight part, prepare thermoplastic resin with the method identical with embodiment 10.
[embodiment 13]
Remove to use the heat-resistant copolymerized beyond the region of objective existence of 80 weight parts, prepare thermoplastic resin with the method identical with embodiment 10.
[embodiment 14]
The superoxide based additive in the embodiment 10 of the acryl resin that uses 3 weight parts, 3 weight parts, prepare thermoplastic resin with the method identical with embodiment 10.And, painted, the surface energy of estimation hot tool weldability, coating, tensile strength, bending strength, the result is as shown in table 2.
[comparative example 2]
Except that not using acryl resin and superoxide based additive, prepare thermoplastic resin with the method identical, and measure painted, surface energy, tensile strength, the bending strength of hot tool weldability, coating with embodiment 10, the result is as shown in table 2.
[table 2]
| Classification | Embodiment 14 | The comparative example 2 |
| The hot tool weldability | A | C |
| Coating painted (45 degree glossy data, L) | 78.2 | 80.1 |
| Surface energy (mN/m) | 56.1 | 50.7 |
| Tensile strength (kg/fcm 2) | 630 | 470 |
| Bending strength (kg/fcm 2) | 1050 | 800 |
As shown in table 2; with respect to the comparative example 1 who does not add acryl resin and superoxide based additive; according to the grafted ABS polymkeric substance with constant composition of the present invention, heat-resistant copolymerized thing, based on the thermoplastic resin composition of the embodiment 5 of acryl resin and peroxide-based additive preparation is being significantly excellent aspect tensile strength, the bending strength, and has extremely excellent hot tool weldability, painted and coating extension characteristics (surface energy).Wherein, the hot tool weldability is the A level that is better than the C level, and aspect coating painted, the L value is more little, and coloring degree is good more, and aspect coating ductility, surface energy is high more, and then coating ductility is good more.
Embodiment 15～21 and comparative example 3～4: have excellent heat resistance and low gloss
The preparation of thermoplastic resin
[embodiment 15]
The first step: the preparation of grafted ABS polymkeric substance
30 weight parts have 3,100
The polybutadiene rubber latex of median size and 75% gel content, 25 weight parts have 3,100
Uncle-the lauryl mercaptan of the vinyl cyanide of the polybutadiene rubber latex of median size and 86% gel content, the ion exchanged water of 145 weight parts, 2.9 weight parts, the vinylbenzene of 9.1 weight parts, 0.5 weight part resin acid potassium and 0.1 weight part is added in the polymerization reactor with heating system.Temperature of reaction rises to 60 ℃, then, by in reactor, add 0.1 weight part as the potassium sulfite of initiator and initiated polymerization.After polyreaction is initiated, temperature is risen to 70 ℃, kept 60 minutes.At this moment, polymerisation conversion is 73%.
Preparation contains the emulsion of the resin acid potassium of the ion exchanged water of vinylbenzene, 25 weight parts of vinyl cyanide, 25.1 weight parts of 7.9 weight parts and 0.9 weight part in isolated mixing device, and is continued to join in the polymerization reactor with 2 hours.And, contain the specific Potassium Persulphate of monomeric emulsion and 0.15 weight part with 2 hours to continue to join in the reactor, wherein, temperature of reaction is maintained 70 ℃.
After adding contained monomeric emulsion, the Potassium Persulphate of 0.05 weight part was all joined in the polymerization reactor, and temperature is elevated to 80 ℃, kept 1 hour, finished polyreaction then.Reaction conversion ratio is 99%.
Antioxidant is added into polyreaction finish after and in the grafted ABS polymkeric substance that obtains, and condense with 10% sulphuric acid soln, clean then and dry, thereby prepare the grafted ABS polymkeric substance of powder type.
Second step: the preparation of heat-resistant copolymerized thing
The mixture as two-uncle as the molecular weight regulator-lauryl mercaptan of the toluene and 0.15 weight part of solvent of the alpha-methyl styrene of 70 weight parts, 30 parts by weight of acrylonitrile, 30 weight parts is added in the reactor continuously, and temperature maintenance is at 148 ℃, and the reaction times is 3 hours.The polymeric solution that discharges from reactor is heated in pre-heaters, the unreacted monomer of evaporation in the evaporation reaction device, and the temperature maintenance of polymkeric substance is at 210 ℃ then.Afterwards, by using the transferpump extrusion molding that heat-resistant copolymerized thing (SAN type multipolymer) is processed as spherolite shape.
The 3rd step: mix
1.0 the antioxidant as the ethene bis-stearamides (EBA) of lubricant and 0.3 weight part of weight part is added into 30 weight parts by in the grafted ABS polymkeric substance of the first step preparation, the 70 weight parts dicumyl peroxide as the superoxide based additive by the SNA multipolymer of second step preparation and 0.1 weight part, and mixes.Then, by using double-shafted extruder to prepare spherolite down at 230 ℃.
The 4th step: the estimation of physical properties
Spherolite by the preparation of the 3rd step is injected once more, and estimation heat-drawn wire (HDF), surface gloss, shock strength, tensile strength and bending strength, and the result is as shown in table 3.
[embodiment 16]
Except that in the initiation step of the first step of preparation grafted ABS polymkeric substance, using the vinyl cyanide of 2.4 weight parts and the vinylbenzene and the preparation of 9.6 weight parts to contain the vinyl cyanide of 6.6 weight parts and containing the monomeric emulsion of 26.4 parts by weight of styrene, prepare thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[embodiment 17]
Remove to use and to comprise the mixed polymerization beyond the region of objective existence of 30 weight parts as the conventional SAN polymkeric substance of the n-phenyl maleimide thermotolerance SAN polymkeric substance of heat-resistant copolymerized thing and 35 weight parts, wherein said n-phenyl maleimide thermotolerance SAN polymkeric substance is the trimer of being made up of the vinyl cyanide of 38wt%n-phenyl maleimide, 53wt% vinylbenzene and 9 weight parts, prepares thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[embodiment 18]
Except that using two (tert-butyl hydroperoxide sec.-propyl) benzene to replace dicumyl peroxide, prepare thermoplastic resin with the method identical with embodiment 15 as the crosslinking additives.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[embodiment 19]
Remove to use 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane replace dicumyl peroxide as outside the crosslinking additives, prepare thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[embodiment 20]
Remove to use 2,5-dimethyl-2,5-two (tert-butyl peroxide)-3-hexin replace dicumyl peroxide as outside the crosslinking additives, prepare thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[embodiment 21]
Except that the dicumyl peroxide that uses 1.0 weight parts as the crosslinking additives, prepare thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[comparative example 3]
Except that the dicumyl peroxide that does not add as crosslinking additives, prepare thermoplastic resin with the method identical with embodiment 15.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[comparative example 4]
Except that the dicumyl peroxide that adds 20 weight parts, prepare thermoplastic resin with the method identical with embodiment 15 as crosslinking additives.Estimation heat-drawn wire (HDT), surface gloss, shock strength, tensile strength and flexural strength, the result is as shown in table 3.
[table 3]
As shown in table 3, when with the comparative example 3 who does not add crosslinking additives, when excessively adding comparative example's 4 contrasts of crosslinking additives, according to of the present invention with the grafted ABS polymkeric substance, heat-resistant copolymerized thing, thermoplastic resin composition among the embodiment 15～21 of the constant composition preparation of crosslinking additives is splendid owing to having height or similar (embodiment 7) heat-drawn wires (HDT) aspect thermotolerance, thereby and because to have the low surface gloss degree be splendid aspect low gloss, in shock strength, tensile strength and bending strength aspect also are splendid.
Industrial applicibility
Thermoplastic resin according to the present invention is effective in the processing of painted thermotolerance ABS resin, because have splendid cold stress albefaction reduction and strength property, and do not reduce other character, and has splendid hot tool weldability, painted and coating ductility, these character are prior in last handling process, and keep mechanical properties and produce splendid thermotolerance and low gloss.
Although described and illustrated specific preferred embodiment of the present invention and comparative example,, should be expressly understood that the present invention is not limited to this, and can in the scope of following claim, carry out various modifications and practice.
Claims (10)
1, a kind of thermoplastic resin composition comprises:
The grafted ABS polymkeric substance of 10～50 weight parts, 50～90 weight parts heat-resistant copolymerized
The crosslinking additives of thing and 0.01～10 weight part,
Wherein, prepare the grafted ABS polymkeric substance by the method that may further comprise the steps:
(A) add the mean particle size comprise 20～30 weight parts be 2,500～
And gel content be the mean particle size of 70～80% polybutadiene rubber latex and 20～30 weight parts be 2,500～
And gel content is the elastomer latex mixture of 80～90% polybutadiene rubber latex; The deionized water of the resin acid potassium of the acrylonitrile compound of the aromatic ethenyl compound of 5～10 weight parts, 5～10 weight parts, 0.1～0.5 weight part, the molecular weight regulator of 0.1～1.0 weight part and 50～80 weight parts, the temperature of polymerization reactor is progressively risen to 60 ℃ from 40 ℃, add peroxide initiator and initiated polymerization by main then;
(B) after carrying out 30～60 minutes from above-mentioned polymerization initiation, reach at 50～75% o'clock at monomer conversion, carry out polymerization by emulsion, lentamente the temperature of polymerization reactor is progressively risen to 70 ℃ by 60 ℃ simultaneously with the deionized water of the resin acid potassium of the acrylonitrile compound that added the aromatic ethenyl compound contain 10～15 weight parts, 10～15 weight parts in 1～2 hour continuously, 0.5～1.5 weight part and 20～30 weight parts;
(C) when adding emulsion constantly, with 1～2 hour, for the second time add specific peroxide initiator constantly; And
(D) will promote the activator of initiation reaction and for the third time peroxide initiator once add, add above-mentioned emulsion (B) and above-mentioned peroxide initiator (C) then, and in 1～2 hour, the temperature of polymerization reactor is progressively risen to 80 ℃ and finish polymerization by 70 ℃;
Obtain heat-resistant copolymerized thing by the alpha-methyl styrene of 50～80 weight parts and the acrylonitrile polymerization of 20～50 weight parts; And
Described crosslinking additives is selected from the group that comprises acyl peroxide, alkyl peroxide, hydrogen peroxide, peresters, azo-compound, disulphide or the tetrazene.
2, a kind of thermoplastic resin composition comprises:
The superoxide based additive of the grafted ABS polymkeric substance of 10～50 weight parts, the heat-resistant copolymerized thing of 50～90 weight parts and 0.01～10 weight part,
Wherein, prepare the grafted ABS polymkeric substance by the method that may further comprise the steps: (A) add the mean particle size comprise 20～30 weight parts and be 2,500～
And gel content be the mean particle size of 70～80% polybutadiene rubber latex and 20～30 weight parts be 2,500～
And gel content is the elastomer latex mixture of 80～90% polybutadiene rubber latex; The deionized water of the resin acid potassium of the acrylonitrile compound of the aromatic ethenyl compound of 5～10 weight parts, 5～10 weight parts, 0.1～0.5 weight part, the molecular weight regulator of 0.1～1.0 weight part and 50～80 weight parts, the temperature of polymerization reactor is progressively risen to 60 ℃ from 40 ℃, add peroxide initiator and initiated polymerization by main then;
(B) after carrying out 30～60 minutes from above-mentioned polymerization initiation, reach at 50～75% o'clock at monomer conversion, carry out polymerization by emulsion, lentamente the temperature of polymerization reactor is progressively risen to 70 ℃ by 60 ℃ simultaneously with the deionized water of the resin acid potassium of the acrylonitrile compound that added the aromatic ethenyl compound contain 10～15 weight parts, 10～15 weight parts in 1～2 hour continuously, 0.5～1.5 weight part and 20～30 weight parts;
(C) when adding emulsion constantly, with 1～2 hour, for the second time add specific peroxide initiator constantly; And
(D) will promote the activator of initiation reaction and for the third time peroxide initiator once add, add above-mentioned emulsion (B) and above-mentioned peroxide initiator (C) then, and in 1～2 hour, the temperature of polymerization reactor is progressively risen to 80 ℃ and finish polymerization by 70 ℃;
Obtain heat-resistant copolymerized thing by the alpha-methyl styrene of 50～80 weight parts and the acrylonitrile polymerization of 20～50 weight parts; And
Described superoxide based additive is selected from and comprises dicumyl peroxide, two-(tert-butyl hydroperoxide sec.-propyl) benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane and 2,5-dimethyl-2, the group of 5-two (tert-butyl hydroperoxide)-3-hexin.
3,, comprise the grafted ABS polymkeric substance of 20～40 weight parts, the heat-resistant copolymerized thing and 0.5～10 weight part superoxide based additive of 60～80 weight parts according to the thermoplastic resin composition of claim 2.
4,, comprise the grafted ABS polymkeric substance of 20～40 weight parts according to the thermoplastic resin composition of claim 2; The acryl resin of the heat-resistant copolymerized thing of 60～80 weight parts, the superoxide based additive of 0.1～10 weight part and 1.0～10 weight parts; Wherein said acryl resin is for having 50; 000～200; the polymethylmethacrylate of 000 molecular weight, perhaps polybutadiene rubber latex, 40～70 parts by weight of acrylic compounds, the aromatic ethenyl compound of 15～30 weight parts and the acrylonitrile compound of 1～20 weight part by 8～25 weight parts constitutes.
5, according to the thermoplastic resin composition of claim 1 or 2, wherein, described aromatic ethenyl compound be selected from comprise vinylbenzene, alpha-methyl styrene, to the group of ethyl styrene and Vinyl toluene.
6, according to the thermoplastic resin composition of claim 1 or 2, wherein, described acrylonitrile compound is selected from the group that comprises vinyl cyanide, methacrylonitrile and ethyl acrylonitrile.
7, according to the thermoplastic resin composition of claim 1 or 2, wherein, described peroxide initiator is an inorganic peroxide.
8, according to the thermoplastic resin composition of claim 7, wherein, described inorganic peroxide is Potassium Persulphate or Sodium Persulfate.
9,, further comprise the lubricant of 0.1～5 weight part and the antioxidant of 0.1～1 weight part according to the thermoplastic resin composition of claim 1 or 2.
10, according to the thermoplastic resin composition of claim 9, wherein, described lubricant is selected from the group that comprises oxidized polyethlene wax, Magnesium Stearate and composition thereof.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20030028214A KR100518891B1 (en) | 2003-05-02 | 2003-05-02 | Thermoplastic Resin Composition with Reduced Cold Stress Whitening |
| KR1020030028214 | 2003-05-02 | ||
| KR1020030034350 | 2003-05-29 | ||
| KR1020030079499 | 2003-11-11 | ||
| KR1020040010900 | 2004-02-19 |
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| Publication Number | Publication Date |
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| CN1768111A CN1768111A (en) | 2006-05-03 |
| CN100556943C true CN100556943C (en) | 2009-11-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800091876A Expired - Lifetime CN100556943C (en) | 2003-05-02 | 2004-04-30 | The thermoplastic resin composition |
Country Status (2)
| Country | Link |
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| KR (1) | KR100518891B1 (en) |
| CN (1) | CN100556943C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100797576B1 (en) * | 2005-06-10 | 2008-01-23 | 주식회사 엘지화학 | Flame retardant thermoplastic resin compositoin comprising organic peroxide, and a method for preparing the same by using organic peroxide |
| KR101020054B1 (en) * | 2008-08-19 | 2011-03-09 | 주식회사 엘지화학 | Thermoplastic abs resin composition having excellent ejectability and colorability |
| CN102516463B (en) * | 2011-11-24 | 2013-12-18 | 华东理工大学 | Method for preparing nano spherical polyelectrolyte brush |
| CN105219012B (en) * | 2015-11-09 | 2017-12-01 | 沈阳化工大学 | A kind of graft modification ABS anti-static materials and preparation method thereof |
| KR101896751B1 (en) | 2015-12-01 | 2018-10-04 | 주식회사 엘지화학 | Thermoplastic resin, method for preparing the resin and thermoplastic resin composition comprising the resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR890003543B1 (en) * | 1986-12-27 | 1989-09-23 | 주식회사 럭키 | Method for preparing lusterless acrylo nitril-butadien-stylene resin |
| JPH093142A (en) * | 1995-06-15 | 1997-01-07 | Japan Synthetic Rubber Co Ltd | Rubber-reinforced vinyl polymer and thermoplastic polymer composition |
| JPH09296015A (en) * | 1996-04-30 | 1997-11-18 | Kao Corp | Manufacture of abs polymer latex |
| KR20020021863A (en) * | 2000-09-18 | 2002-03-23 | 성재갑 | Process for preparing heat resistant thermoplastic resin having superior weatherability and impact resistance |
| KR100385729B1 (en) * | 2000-11-08 | 2003-05-27 | 주식회사 엘지화학 | Thermoplastic resin composition having superior coloring properties |
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- 2003-05-02 KR KR20030028214A patent/KR100518891B1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| KR100518891B1 (en) | 2005-09-30 |
| KR20040094211A (en) | 2004-11-09 |
| CN1768111A (en) | 2006-05-03 |
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