CN106928620A - Weather-resistant ASA/PA alloy and preparation method thereof - Google Patents
Weather-resistant ASA/PA alloy and preparation method thereof Download PDFInfo
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- CN106928620A CN106928620A CN201511026373.7A CN201511026373A CN106928620A CN 106928620 A CN106928620 A CN 106928620A CN 201511026373 A CN201511026373 A CN 201511026373A CN 106928620 A CN106928620 A CN 106928620A
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- 229910001125 Pa alloy Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000002245 particle Substances 0.000 claims abstract description 58
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 4
- 239000000839 emulsion Substances 0.000 claims description 69
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 44
- 239000008367 deionised water Substances 0.000 claims description 41
- 229910021641 deionized water Inorganic materials 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 229920002554 vinyl polymer Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 24
- 238000007306 functionalization reaction Methods 0.000 claims description 24
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 24
- 235000019394 potassium persulphate Nutrition 0.000 claims description 24
- -1 vinyl aromatic compound Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 14
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 10
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229940096992 potassium oleate Drugs 0.000 claims description 10
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical group [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 10
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- PSYGHMBJXWRQFD-UHFFFAOYSA-N 2-(2-sulfanylacetyl)oxyethyl 2-sulfanylacetate Chemical compound SCC(=O)OCCOC(=O)CS PSYGHMBJXWRQFD-UHFFFAOYSA-N 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 8
- 150000008301 phosphite esters Chemical group 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 229920000058 polyacrylate Polymers 0.000 claims description 7
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 229940114930 potassium stearate Drugs 0.000 claims description 6
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- LVDRREOUMKACNJ-BKMJKUGQSA-N N-[(2R,3S)-2-(4-chlorophenyl)-1-(1,4-dimethyl-2-oxoquinolin-7-yl)-6-oxopiperidin-3-yl]-2-methylpropane-1-sulfonamide Chemical compound CC(C)CS(=O)(=O)N[C@H]1CCC(=O)N([C@@H]1c1ccc(Cl)cc1)c1ccc2c(C)cc(=O)n(C)c2c1 LVDRREOUMKACNJ-BKMJKUGQSA-N 0.000 claims description 4
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006152 PA1010 Polymers 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- ITOFPJRDSCGOSA-KZLRUDJFSA-N (2s)-2-[[(4r)-4-[(3r,5r,8r,9s,10s,13r,14s,17r)-3-hydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]pentanoyl]amino]-3-(1h-indol-3-yl)propanoic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H](CC[C@]13C)[C@@H]2[C@@H]3CC[C@@H]1[C@H](C)CCC(=O)N[C@H](C(O)=O)CC1=CNC2=CC=CC=C12 ITOFPJRDSCGOSA-KZLRUDJFSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- OURRXQUGYQRVML-AREMUKBSSA-N [4-[(2s)-3-amino-1-(isoquinolin-6-ylamino)-1-oxopropan-2-yl]phenyl]methyl 2,4-dimethylbenzoate Chemical compound CC1=CC(C)=CC=C1C(=O)OCC1=CC=C([C@@H](CN)C(=O)NC=2C=C3C=CN=CC3=CC=2)C=C1 OURRXQUGYQRVML-AREMUKBSSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 229940125810 compound 20 Drugs 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920000120 polyethyl acrylate Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 3
- 235000011152 sodium sulphate Nutrition 0.000 claims 3
- 239000001301 oxygen Substances 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims 1
- 239000008116 calcium stearate Substances 0.000 claims 1
- 235000013539 calcium stearate Nutrition 0.000 claims 1
- 238000005461 lubrication Methods 0.000 claims 1
- 230000002902 bimodal effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 239000010410 layer Substances 0.000 abstract 3
- 239000012792 core layer Substances 0.000 abstract 1
- 238000010559 graft polymerization reaction Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 22
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 239000012190 activator Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 10
- 235000003891 ferrous sulphate Nutrition 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 7
- 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 6
- 230000000052 comparative effect Effects 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000003607 modifier Substances 0.000 description 4
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000012745 toughening agent Substances 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004067 bulking agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 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 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical class [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- XHIOOWRNEXFQFM-UHFFFAOYSA-N ethyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(=O)C=C XHIOOWRNEXFQFM-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920005621 immiscible polymer blend Polymers 0.000 description 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XNYYNDAEXFUXBD-UHFFFAOYSA-N tert-butylbenzene ethene Chemical compound C=C.C(C)(C)(C)C1=CC=CC=C1 XNYYNDAEXFUXBD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a weather-resistant ASA/PA alloy and a preparation method thereof, wherein the alloy comprises the following components: 30-60 parts of PA; 40-70 parts by weight of a functionalized weather-resistant ASA graft copolymer; 0.1-0.5 parts by weight of a lubricant; 0.1-1 part of antioxidant. In addition, the invention also discloses a preparation method of the weather-resistant ASA/PA alloy, which comprises the steps of (1) preparing a functionalized weather-resistant ASA graft copolymer, wherein the preparation method comprises the preparation of an inner core layer, the preparation of a middle layer and the graft polymerization of an outer layer chain segment, and (2) preparing the weather-resistant ASA/PA alloy. The invention prepares the functionalized ASA graft copolymer with a three-layer structure and bimodal particle size distribution by emulsion polymerization, and mixes the functionalized ASA graft copolymer with PA to prepare the weather-resistant ASA/PA alloy with good impact strength and tensile strength.
Description
Technical field
The present invention relates to a kind of thermoplastic resin with excellent impact resistance energy, tensile property and weather resistance
Resin blends and preparation method thereof.More particularly it relates to a kind of weatherability ASA/PA is closed
Gold.
Background technology
Since DuPont commercially successfully develops super-toughened nylon, researchers exist always
Explore the correlation of chemistry, form and toughness in toughing ways.Wherein, a kind of conventional method is to adopt
With nylon (PA) and various elastomer blended modes, while in order to ensure compatibility therebetween, body
Need to add corresponding bulking agent again in system.As E.I.Du Pont Company is reactive using having in USP4174358
The method of olefin rubber (such as EPDM-MAh) toughened Nylon 6 and nylon66 fiber of group；Such as
CN12353141 patents are compatible as being combined using EVA/PE-g-MAh with PA6, PA66 as base-material
Agent, is blended to prepare ultra-toughness alloy by toughener such as EAA, EVA, PE；And CN1445278
Super-toughened nylon etc. is prepared using dynamic vulcanization maleic anhydride stem grafting polyolefin elastomer.Although the above method
Can improved system to a certain extent toughness, but there is a general character problem：Complex process, matrix with
Poor compatibility between toughener, is separated serious, and the final size of elastomer is largely relied on
It is low to there is poor ductility, notch impact strength in the nylon alloy after processing conditions, and toughness reinforcing, product quality
The defect such as unstable.
Because core-shell modifiers have dimensionally stable, this remarkable advantage not influenceed by processing technology, core
Shell structure modifying agent has turned into another development trend for preparing super-toughened nylon as the toughener of nylon, especially
It is ABS/PA alloys.Such alloy has heat distortion temperature and Vicat softening point higher etc. prominent special
Point, thus as the ideal material of the automobile components such as manufacture body of a motor car coverboard.Additionally, due to its shock resistance
Property, the combination property such as rigidity, chemical proofing it is remarkable, also obtained extensively in common mechanical, daily kind
General application.Yet with undersaturated double bond is contained in ABS, ABS/PA alloys are easily by daylight
Ultraviolet irradiation and change rapidly, be unfavorable in the inferior weatherability requirement of outdoor or photoenvironment environment higher
Lower long-term use.Based on this, we utilize and replace containing in tradition ABS without conjugated double bond rubber type compounds
The butadiene for having unsaturated double-bond prepares weatherability ASA/PA alloys.
Because nylon (PA) is the very low polymer of a kind of crystal type, highly polar, melt viscosity, and
ASA is the polymer of a kind of amorphous, low pole, and the solubility parameters difference of the two is larger, belongs to heating power
Learn Immiscible Polymer Blends, simple blending cannot realize the two effective mixing, so as to cause mechanical property compared with
Difference to the two, it is necessary to carry out Interfacial compatibilization.The technology of preparing of ASA is limited to, at present on ASA
The research of/PA alloys is less.A small amount of research work also just with commodity ASA, PA and with ASA bases
Body phase is held, and carries out increase-volume as bulking agent containing the functional polymer that can be reacted with PA end groups, makes
Standby ASA/PA alloys.As CN101407630A uses maleic anhydride type, carboxylic acid type or metering system
Acid glycidyl ether type compatilizer carries out increase-volume to PA/ASA systems, and it is heat-resisting to improve its using montmorillonite
Performance, but be not described based on change ASA compositions and structure to improve PA/ASA alloy properties
Research.
The content of the invention
It is a primary object of the present invention to provide a kind of weatherability ASA/PA alloys and preparation method thereof,
To overcome ASA/PA alloys impact resistance and tensile strength in the prior art weaker, and prepare work
The complicated defect of skill.
The object of the present invention is achieved like this, and a kind of weatherability ASA/PA alloys, the alloy is included
Following components：
Wherein, the functionalization weatherability ASA graft copolymers be with vinyl aromatic polymers,
One or more in vinyl aromatic-vinyl nitrile copolymer or acrylate polymer is kernel,
It is intermediate layer without conjugated double bond rubber polymer, the vinyl of functional compounds is contained in outer layer grafting end
Aromatic series-vinyl nitrile copolymer.
Weatherability ASA/PA alloys of the present invention, wherein, the PA be preferably PA6,
One or more in PA66 or PA1010, intrinsic viscosity is preferably 1.20dl/g~3.5dl/g, holds carboxylic
Base concentration is preferably 30 μ eq/g~80 μ eq/g, and Amino End Group concentration is preferably 40 μ eq/g~60 μ eq/g.
Weatherability ASA/PA alloys of the present invention, wherein, the vinyl aromatic polymers
Preferably polystyrene, poly alpha methylstyrene and poly- p-tert-butylstyrene constitute in group
Plant or several.
Weatherability ASA/PA alloys of the present invention, wherein, the vinyl aromatic-vinyl
Lonitrile copolymer medium vinyl aromatic compound is preferably styrene, AMS and to tert-butyl benzene
Ethene constitutes one or more in group, second in the vinyl aromatic-vinyl nitrile copolymer
Alkenyl nitrile compound is preferably acrylonitrile or methacrylonitrile, and the acrylate polymer is preferably poly- third
E pioic acid methyl ester, polymethyl methacrylate or polyethyl acrylate.
Weatherability ASA/PA alloys of the present invention, wherein, it is described without the polymerization of conjugated double bond rubber
Thing is preferably butyl polyacrylate, n butyl acrylate styrene or ethyl acrylate-acrylic acid fourth
Ester-vinyl chloroacetate terpolymer.
Weatherability ASA/PA alloys of the present invention, wherein, the functional compounds are preferably
Maleic anhydride, carboxylic acid compound or GMA.
Weatherability ASA/PA alloys of the present invention, wherein, the lubricant is preferably stearic acid
Calcium, magnesium stearate and pentaerythritol stearate constitute one or more in group.
Weatherability ASA/PA alloys of the present invention, wherein, the antioxidant is preferably phosphorous acid
Esters antioxidant, more preferably antioxidant 1010 and/or antioxidant 618.
Present invention also offers the preparation method of weatherability ASA/PA alloys, the method includes as follows
Step：
(1) preparation of functionalization weatherability ASA graft copolymers
The preparation of A, inner nuclear layer
Prepared using emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~400 weight portions, the weight portion of emulsifying agent 2~10, kernel compound, the weight portion of crosslinking agent 0.1~10
With the weight portion of initiator 0.1~1, mixing speed be 100r/min~400r/min, under nitrogen protection in
45 DEG C~85 DEG C reaction 4h~12h, obtain semi-conducting materia emulsion；Wherein, the kernel compound is vinyl
The weight portion of aromatic compound 40~80 and the weight portion of vinyl nitrile compound 20~60, or vinyl aromatic
The weight portion of compounds of group 80~120, or the weight portion of acrylic ester compound 80~120；
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
Prepared using seed emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~300 weight portions, the weight portion of emulsifying agent 2~10, the weight of semi-conducting materia emulsion 40~60 that step A is obtained
Amount part, without the weight portion of conjugated double bond rubber compound 40~60, the weight portion of crosslinking agent 0.1~10, grafting
The weight portion of agent 0.1~10 and the weight portion of initiator 0.1~1, the reaction time are 4~30h, obtain small particle
Intermediate layer emulsion；Wherein, described is butyl acrylate without the weight portion of conjugated double bond rubber compound 40~60
40~60 weight portions, or the weight portion of butyl acrylate 30~55 and the weight portion of styrene 5~10 mixing
Thing, or the weight portion of ethyl acrylate 5~10, the weight portion of butyl acrylate 30~50 and vinyl chloroacetate
The mixture of the weight portion of ester 5~10；
2) prepared by big particle diameter intermediate layer emulsion
Prepared using seed emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~300 weight portions, the weight portion of emulsifying agent 2~10, the weight of semi-conducting materia emulsion 10~30 that step A is obtained
Amount part, without the weight portion of conjugated double bond rubber compound 60~100, the weight portion of crosslinking agent 0.1~10, grafting
The weight portion of agent 0.1~10 and the weight portion of initiator 0.1~1, the reaction time are 4~30h, obtain big particle diameter
Intermediate layer emulsion；Wherein, described is acrylic acid fourth without the weight portion of conjugated double bond rubber compound 60~100
The weight portion of ester 60~100, or the weight portion of butyl acrylate 50~95 and the weight portion of styrene 5~10 mixing
Thing, or the weight portion of ethyl acrylate 5~20, the weight portion of butyl acrylate 50~90 and vinyl chloroacetate
The mixture of the weight portion of ester 5~20.
C, outer layer segment glycerol polymerization
Prepared using emulsion polymerization：In reactor, following material is added by proportioning：Step B is obtained
Small particle intermediate layer emulsion and big particle diameter intermediate layer emulsion the weight portion of mixture 40~80, vinyl aromatic (co)
The weight portion of fragrant compounds of group 15~45, the weight portion of vinyl nitrile compound 5~15, functional compounds
0.4~6 weight portion, the weight portion of lauryl mercaptan 0.05~1, the weight portion of initiator 0.1~1, emulsifying agent
2~10 weight portions and the weight portion of deionized water 80~300, the reaction time are 2h~4h, and cohesion is filtered,
Washing, is dried to obtain three-decker functionalization weatherability ASA graft copolymers；And
(2) by the weight of functionalization weatherability ASA graft copolymers 40~70 obtained in step (1)
Part, the weight portion of lubricant 0.1~0.5, the weight portion of antioxidant 0.1~1 and the weight portions of PA 30~60 in
200 DEG C~240 DEG C, screw speed be 80r/min~160r/min under the conditions of, double screw extruder melting
Blending, prepares weatherability ASA/PA alloys.
The preparation method of weatherability ASA/PA alloys of the present invention, wherein, in the step A
Emulsifying agent is preferably potassium oleate, potassium stearate, disproportionated rosin acid potassium and lauryl sodium sulfate and constitutes group
One or more in group；In the step A initiator be preferably potassium peroxydisulfate or organic hydroperoxide-
Ferrous sulfate composite initiation system；Crosslinking agent is preferably divinylbenzene, dimethyl in the step A
Acrylic acid glycol ester or allyl methacrylate.
The preparation method of weatherability ASA/PA alloys of the present invention, wherein, in the step B
Emulsifying agent is preferably potassium oleate, potassium stearate, disproportionated rosin acid potassium and lauryl sodium sulfate and constitutes group
One or more in group；In the step B initiator be preferably potassium peroxydisulfate or organic hydroperoxide-
Ferrous sulfate composite initiation system；Crosslinking agent is preferably divinylbenzene, dimethyl in the step B
Acrylic acid glycol ester or acrylic acid double cyclopentenyl ester；Grafting agent is preferably allyl in the step B
Esters monomer；The particle size of small particle intermediate layer emulsion is 50nm~150nm in the step B, greatly
The particle size of particle diameter intermediate layer emulsion is 200nm~500nm.
The preparation method of weatherability ASA/PA alloys of the present invention, wherein, in the step C
Emulsifying agent is preferably potassium oleate, potassium stearate, disproportionated rosin acid potassium and lauryl sodium sulfate and constitutes group
One or more in group；In the step C initiator be preferably potassium peroxydisulfate or organic hydroperoxide-
Ferrous sulfate composite initiation system；Functional compounds are preferably maleic anhydride, carboxylic in the step C
Acid compounds or GMA.
The preparation method of weatherability ASA/PA alloys of the present invention, wherein, the vinyl aromatic (co)
Fragrant compounds of group is preferably during styrene, AMS and p-tert-butylstyrene constitute group
One or more, the vinyl nitrile compound is preferably acrylonitrile or methacrylonitrile, the acrylic acid
Ester type compound is preferably methyl acrylate, methyl methacrylate or ethyl acrylate.
The preparation method of weatherability ASA/PA alloys of the present invention, wherein, the organic peroxy
Change hydrogen-ferrous sulfate composite initiation system to be drawn by the redox that organic hydroperoxide and activator are constituted
Hair system, wherein organic hydroperoxide are cumyl hydroperoxide, di-isopropylbenzene hydroperoxide or peroxidating
The tertiary propyl benzene of hydrogen, activator is sub- by complexing agent sodium pyrophosphate or disodium edta, reducing agent sulfuric acid
Iron and reducing agent sodium formaldehyde sulphoxylate or glucose is helped to collectively constitute.
Beneficial effects of the present invention：
1st, it is the official of bimodal distribution that the present invention is prepared with three-decker, particle diameter by emulsion polymerization
ASA graft copolymers can be changed.
2nd, the present invention sets Deformation Mechanisms with molecular structure from core-shell modifiers Molecular Design
Meter is combined, and introduces the different rubber particles of two kinds of Deformation Mechanisms, is allowed to synergy raising blending
The mechanical property of thing, impact strength is up to 1200J/m, tensile strength 47MPa, bending strength
68MPa, bending modulus 1930MPa.Compared with prior art, the present invention is capable of achieving modifying agent
Structure design, process is simple, easily controllable, data redundancy are good, it is easy to industrialized production.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is with technical solution of the present invention as preceding
Put and implemented, give detailed implementation method and process, but protection scope of the present invention is not limited to
Following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part.
PA：
In the present invention, to PA, there is no particular restriction, is typically defined in PA6, PA66 or PA1010
One or more, intrinsic viscosity is 1.2dl/g~3.5dl/g, and carboxylic end group concentration is
30 μ eq/g~80 μ eq/g, Amino End Group concentration is 40 μ eq/g~60 μ eq/g；If carboxylic end group concentration is less than
30 μ eq/g or Amino End Group concentration are less than 40 μ eq/g or intrinsic viscosity less than 1.20dl/g then F-ASA punchings
Hitting modifying agent cannot cause mechanical properties decrease with the abundant increase-volume of matrix resin；If carboxylic end group concentration is more than
80 μ eq/g or Amino End Group concentration are more than 60 μ eq/g or intrinsic viscosity is more than 3.5dl/g then PA matrix trees
The processing characteristics of fat is decreased obviously.
Functionalization weatherability ASA graft copolymers (F-ASA)：
In the present invention, functionalization weatherability ASA graft copolymers are defined to vinyl aromatic polymerization
One or more in thing, vinyl aromatic-vinyl nitrile copolymer or acrylate polymer is interior
Core, is intermediate layer without conjugated double bond rubber polymer, and the second of functional compounds is contained in outer layer grafting end
Alkenyl aroma race-vinyl nitrile copolymer, intermediate layer particle diameter be 50nm~150nm and
The graft copolymer of 200nm~500nm bimodal distributions；The present invention is from core-shell modifiers Molecular Design
Set out, prepare stratum nucleare for composite construction, shell grafted maleic acid anhydride functional group, particle size is for bimodal
ASA core-shell modifiers of distribution, and by it and nylon blending, preparation process is simple and can obtain
To the high impact strength and the ASA/PA alloys of tensile strength of stable performance.
Technical solution of the present invention is described in detail with reference to embodiment.
Embodiment 1：
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
85 DEG C, add the weight portion of deionized water 400 (5kg), the weight portion of lauryl sodium sulfate 10, styrene
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts after the weight portion of GDMA 10
Stirring, stir speed (S.S.) is 100r/min, is cooled to after reaction 4h stand-by after room temperature.
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
75 DEG C, the weight portion of deionized water 300, the weight portion of lauryl sodium sulfate 10, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 60, the weight portion of Butyl Acrylate Monomer 40, ethylene glycol dimethacrylate
The weight portion of ester 0.1, the weight portion of allyl methacrylate 0.2, the weight portion of potassium peroxydisulfate 0.1, reaction
After 8h, particle size range is obtained for 60nm~70nm single dispersing conversion ratios are in the middle of more than 98% small particle
Layer complex emulsions.
2) prepared by big particle diameter intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
75 DEG C, the weight portion of deionized water 100, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 10, the weight portion of Butyl Acrylate Monomer 90, ethylene glycol dimethacrylate
The weight portion of ester 0.25, the weight portion of allyl methacrylate 0.5, the weight portion of potassium peroxydisulfate 1, reaction
After 12h, it is the big particle diameter that 450nm~500nm single dispersing conversion ratios are more than 95% to obtain particle size range
Intermediate layer complex emulsions.
C, outer layer glycerol polymerization
The weight portion of prepared small particle intermediate layer emulsion 20, the weight portion of big particle diameter intermediate layer emulsion 60 are taken,
The weight portion of deionized water 70, the weight portion of cumyl hydroperoxide 0.02 and activator are placed in equipped with stirring
In device, the 20L glass reactors of condensing unit, nitrogen protection is passed through, constant temperature is to 45 DEG C, then incites somebody to action pre-
What is first prepared contains the weight portion of deionized water 10, the weight portion of lauryl sodium sulfate 2, hydrogen peroxide
The weight portion of isopropylbenzene 0.08, the weight portion of p-tert-butylstyrene 15, the weight portion of methacrylonitrile 5, first
The weight portion of base glycidyl acrylate 0.4, the mixed liquor of the weight portion of lauryl mercaptan 0.05 are with continuous
The addition of feeding manner 2h constant speed, continues to be discharged after reaction 1h, condenses, washs, drying, prepared three layers
Structure functionalization weatherability ASA graft copolymers.The activator is constituted：Sodium ethylene diamine tetracetate
The weight portion of salt 0.6, the weight portion of ferrous sulfate 0.008, the weight portion of sodium formaldehyde sulphoxylate 0.4.
2nd, weatherability ASA/PA alloys
Weighing the prepared weight portion of functionalization F-ASA graft copolymers 70, intrinsic viscosity is
1.20dl/g, the μ eq/g of end carboxyl 30, Amino End Group concentration are the weight portion of 40 μ eq/g nylon 630, stearic acid
The weight portion of magnesium 0.3, the weight portion of pentaerythritol stearate 0.2 and the weight of phosphite ester kind antioxidant 1680.5
After amount part mixes through homogenizer, melt blending is carried out in 220 DEG C in double screw extruder, obtained
ASA/PA alloys.Then in test sample is obtained at 220 DEG C in injector, according to ASTM
D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 carry out performance
Test, test result is shown in Table 1.
Embodiment 2：
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 300 (5kg), the disproportionated rosin acid weight portion of potassium 8, styrene 75
Weight portion, the weight portion of acrylonitrile 27, the weight portion of potassium peroxydisulfate 1, after the weight portion of divinylbenzene 0.1
Start stirring, stir speed (S.S.) is 200r/min, be cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, add the weight portion of deionized water 200, disproportionated rosin acid potassium 2 weight portion, obtained in step A
The weight portion of inner nuclear layer emulsion 40, the weight portion of Butyl Acrylate Monomer 40, the weight portion of styrene 5, diethyl
The weight portion of alkenyl benzene 1, the weight portion of allyl methacrylate 2, the weight portion of potassium peroxydisulfate 0.6, reaction
After 8h, obtain during particle size range is more than 98% small particle for 100nm~110nm single dispersing conversion ratios
Interbed complex emulsions.
2) prepared by big particle diameter intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, add the weight portion of deionized water 100, disproportionated rosin acid potassium 5 weight portion, obtained in step A
The weight portion of inner nuclear layer emulsion 10, the weight portion of Butyl Acrylate Monomer 80, the weight portion of styrene 10, two
The weight portion of methacrylic acid glycol ester 2, the weight portion of allyl methacrylate 4, potassium peroxydisulfate 0.7
Weight portion, after reaction 12h, obtains particle size range for 450nm~500nm single dispersings conversion ratio is 95%
Big particle diameter intermediate layer complex emulsions above.
C, outer layer glycerol polymerization
The weight portion of prepared small particle intermediate layer emulsion 40, the weight portion of big particle diameter intermediate layer emulsion 40 are taken,
The weight portion of deionized water 80, the weight portion of cumyl hydroperoxide 0.2 and activator are placed in equipped with stirring
In device, the 20L glass reactors of condensing unit, nitrogen protection is passed through, constant temperature is to 45 DEG C, then incites somebody to action pre-
What is first prepared is different containing the weight portion of deionized water 20, disproportionated rosin acid potassium 2 weight portion, hydrogen peroxide
The weight portion of propyl benzene 0.8, the weight portion of AMS 30, the weight portion of acrylonitrile 10, the weight of acrylic acid 6
Amount part, the mixed liquor of the weight portion of lauryl mercaptan 0.25 are added with continuous feed mode 2h constant speed, after
Discharged after continuous reaction 1h, condense, wash, drying, three-decker functionalization weatherability ASA is obtained and connects
Graft copolymer.The activator is constituted：The weight portion of disodium edta 0.6, ferrous sulfate
0.008 weight portion, the weight portion of glucose 0.4.
2nd, weatherability ASA/PA alloys
Weighing the prepared weight portion of functionalization F-ASA graft copolymers 50, intrinsic viscosity is
1.50dl/g, the μ eq/g of end carboxyl 42.6, Amino End Group concentration are the weight portion of 51.2 μ eq/g nylon66 fibers 50, hard
The weight portion of fatty acid magnesium 0.4, the weight portion of pentaerythritol stearate 0.1 and phosphite ester kind antioxidant 168
After 0.5 weight portion mixes through homogenizer, carry out in 200 DEG C melting altogether in double screw extruder
It is mixed, obtain ASA/PA alloys.Then in injector in obtaining test sample at 200 DEG C, according to
ASTM D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 enter
Row performance test, test result is shown in Table 1.
Embodiment 3：
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 200 (5kg), the weight portion of potassium oleate 6, methyl methacrylate
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts stirring, stirring speed after the weight portion of divinylbenzene 5
Rate is 300r/min, is cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, add the weight portion of deionized water 200, the weight portion of potassium oleate 2, inner nuclear layer obtained in step A
The weight portion of emulsion 40, the weight portion of Butyl Acrylate Monomer 40, the weight portion of ethyl acrylate 5 and chloro vinegar
The weight portion of vinyl acetate 5, the weight portion of divinylbenzene 4, the weight portion of allyl methacrylate 4, mistake
The weight portion of potassium sulfate 0.5, after reaction 8h, obtains particle size range for 140nm~150nm single dispersings are converted
Rate is more than 98% intermediate layer complex emulsions.
2) prepared by big particle diameter intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, add the weight portion of deionized water 100, the weight portion of potassium oleate 2, inner nuclear layer obtained in step A
The weight portion of emulsion 20, the weight portion of Butyl Acrylate Monomer 80, the weight portion of ethyl acrylate 5 and chloro vinegar
The weight portion of vinyl acetate 5, the weight portion of GDMA 10, allyl methacrylate
10 weight portions, the weight portion of potassium peroxydisulfate 0.8, after reaction 12h, obtaining particle size range is
260nm~300nm single dispersing conversion ratios are more than 95% intermediate layer complex emulsions.
C, outer layer glycerol polymerization
The weight portion of prepared small particle intermediate layer emulsion 30, the weight portion of big particle diameter intermediate layer emulsion 50 are taken,
The weight portion of deionized water 250, the weight portion of cumyl hydroperoxide 0.3 and activator are placed in equipped with stirring
In device, the 20L glass reactors of condensing unit, nitrogen protection is passed through, constant temperature is to 45 DEG C, then incites somebody to action pre-
What is first prepared contains the weight portion of deionized water 50, the weight portion of potassium oleate 2, cumyl hydroperoxide 0.7
Weight portion, the weight portion of styrene 30, the weight portion of methacrylonitrile 10, the weight portion of maleic anhydride 4, ten
The mixed liquor of the weight portion of dialkyl group mercaptan 0.25 is added with continuous feed mode 2h constant speed, continues to react 1h
Discharge afterwards, condense, wash, dry, three-decker functionalization weatherability ASA graft copolymerizations are obtained
Thing.The activator is constituted：The weight portion of sodium pyrophosphate 0.5, the weight portion of ferrous sulfate 0.008, first
Aldehyde closes the weight portion of sodium bisulphite 0.5.
2nd, weatherability ASA/PA alloys
Weighing the prepared weight portion of functionalization F-ASA graft copolymers 40, intrinsic viscosity is
2.36dl/g, the μ eq/g of end carboxyl 65, Amino End Group concentration are the weight portion of 52 μ eq/g nylon 1010s 60, hard
The weight portion of fatty acid magnesium 0.2, the weight portion of pentaerythritol stearate 0.4 and phosphite ester kind antioxidant 168
After 0.4 weight portion mixes through homogenizer, carry out in 230 DEG C melting altogether in double screw extruder
It is mixed, obtain ASA/PA alloys.Then in injector in obtaining test sample at 230 DEG C, according to
ASTM D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 enter
Row performance test, test result is shown in Table 1.
Embodiment 4：
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 200 (5kg), the weight portion of lauryl sodium sulfate 6, styrene
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts to stir after the weight portion of GDMA 4
Mix, stir speed (S.S.) is 400r/min, be cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 200, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 40, the weight portion of Butyl Acrylate Monomer 60, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 0.7 after reaction 8h, is obtained
Particle size range is the intermediate layer complex emulsions that 130nm~140nm single dispersing conversion ratios are more than 98%.
2) prepared by big particle diameter intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 100, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 30, the weight portion of Butyl Acrylate Monomer 90, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 1 after reaction 12h, obtains grain
Footpath scope is the intermediate layer complex emulsions that 260nm~300nm single dispersing conversion ratios are more than 95%.
C, outer layer glycerol polymerization
The weight portion of prepared small particle intermediate layer emulsion 20, the weight portion of big particle diameter intermediate layer emulsion 40 are taken,
The weight portion of deionized water 200, the weight portion of cumyl hydroperoxide 0.4 and activator are placed in equipped with stirring
In device, the 20L glass reactors of condensing unit, nitrogen protection is passed through, constant temperature is to 45 DEG C, then incites somebody to action pre-
What is first prepared contains the weight portion of deionized water 50, the weight portion of lauryl sodium sulfate 2, hydrogen peroxide
The weight portion of isopropylbenzene 0.6, the weight portion of styrene 45, the weight portion of acrylonitrile 15, the weight of maleic anhydride 5
Part, the mixed liquor of the weight portion of lauryl mercaptan 0.5 are added with continuous feed mode 2h constant speed, are continued
Discharged after reaction 1h, condensed, washed, dried, three-decker functionalization weatherability ASA is obtained and is grafted
Copolymer.The activator is constituted：The weight portion of sodium pyrophosphate 0.6, the weight of ferrous sulfate 0.008
Part, the weight portion of glucose 0.4.
2nd, weatherability ASA/PA alloys
It is 23.5 to weigh the prepared weight portion of functionalization F-ASA graft copolymers 40, intrinsic viscosity
Dl/g, the μ eq/g of end carboxyl 60, Amino End Group concentration are the weight portion of 80 μ eq/g nylon66 fibers 0, magnesium stearate
0.2 weight portion, the weight portion of pentaerythritol stearate 0.4 and the weight of phosphite ester kind antioxidant 1680.4
After part mixes through homogenizer, melt blending is carried out in 240 DEG C in double screw extruder, obtained
ASA/PA alloys.Then in test sample is obtained at 240 DEG C in injector, according to ASTM
D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 carry out performance
Test, test result is shown in Table 1.
Comparative example 1
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 200 (5kg), the weight portion of lauryl sodium sulfate 6, styrene
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts to stir after the weight portion of GDMA 4
Mix, stir speed (S.S.) is 400r/min, be cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 200, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 40, the weight portion of Butyl Acrylate Monomer 60, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 0.7 after reaction 8h, is obtained
Particle size range is the intermediate layer complex emulsions that 130nm~140nm single dispersing conversion ratios are more than 98%.
C, outer layer glycerol polymerization
Take the prepared weight portion of intermediate layer emulsion 60, the weight portion of deionized water 200, hydrogen peroxide isopropyl
During the weight portion of benzene 0.4 and activator are placed in equipped with agitator, the 20L glass reactors of condensing unit, lead to
Enter nitrogen protection, constant temperature is to 45 DEG C, then will in advance prepare and contain the weight portion of deionized water 50, ten
The weight portion of sodium dialkyl sulfate 2, the weight portion of cumyl hydroperoxide 0.6, the weight portion of styrene 45,
The weight portion of acrylonitrile 15, the weight portion of maleic anhydride 5, the mixed liquor of the weight portion of lauryl mercaptan 0.5
Added with continuous feed mode 2h constant speed, discharging, cohesion, washing, dry, system after 1h are reacted in continuation
Obtain three-decker functionalization weatherability ASA graft copolymers.The activator is constituted：Sodium pyrophosphate
0.6 weight portion, the weight portion of ferrous sulfate 0.008, the weight portion of glucose 0.4.
2nd, weatherability ASA/PA alloys
Weighing the prepared weight portion of functionalization F-ASA graft copolymers 40, intrinsic viscosity is
3.5dl/g, the μ eq/g of end carboxyl 80, Amino End Group concentration are the weight portion of 60 μ eq/g nylon66 fibers 0, stearic acid
The weight portion of magnesium 0.2, the weight portion of pentaerythritol stearate 0.4 and the weight of phosphite ester kind antioxidant 1680.4
After amount part mixes through homogenizer, melt blending is carried out in 220 DEG C in double screw extruder, obtained
ASA/PA alloys.Then in test sample is obtained at 220 DEG C in injector, according to ASTM
D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 carry out performance
Test, test result is shown in Table 1.
Comparative example 2
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 200 (5kg), the weight portion of lauryl sodium sulfate 6, styrene
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts to stir after the weight portion of GDMA 4
Mix, stir speed (S.S.) is 400r/min, be cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 100, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 30, the weight portion of Butyl Acrylate Monomer 90, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 1 after reaction 12h, obtains grain
Footpath scope is the intermediate layer complex emulsions that 260nm~300nm single dispersing conversion ratios are more than 95%.
C, outer layer glycerol polymerization
Take the prepared weight portion of intermediate layer emulsion 60, the weight portion of deionized water 200, hydrogen peroxide isopropyl
During the weight portion of benzene 0.4 and activator are placed in equipped with agitator, the 20L glass reactors of condensing unit, lead to
Enter nitrogen protection, constant temperature is to 45 DEG C, then will in advance prepare and contain the weight portion of deionized water 50, ten
The weight portion of sodium dialkyl sulfate 2, the weight portion of cumyl hydroperoxide 0.6, the weight portion of styrene 45,
The weight portion of acrylonitrile 15, the weight portion of maleic anhydride 5, the mixed liquor of the weight portion of lauryl mercaptan 0.5
Added with continuous feed mode 2h constant speed, discharging, cohesion, washing, dry, system after 1h are reacted in continuation
Obtain three-decker functionalization weatherability ASA graft copolymers.The activator is constituted：Sodium pyrophosphate
0.6 weight portion, the weight portion of ferrous sulfate 0.008, the weight portion of glucose 0.4.
2nd, weatherability ASA/PA alloys
Weighing the prepared weight portion of functionalization F-ASA graft copolymers 40, intrinsic viscosity is
3.5dl/g, the μ eq/g of end carboxyl 80, Amino End Group concentration are the weight portion of 60 μ eq/g nylon66 fibers 0, stearic acid
The weight portion of magnesium 0.2, the weight portion of pentaerythritol stearate 0.4 and the weight of phosphite ester kind antioxidant 1680.4
After amount part mixes through homogenizer, melt blending is carried out in 220 DEG C in double screw extruder, obtained
ASA/PA alloys.Then in test sample is obtained at 220 DEG C in injector, according to ASTM
D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 carry out performance
Test, test result is shown in Table 1.
Comparative example 3：
1st, the preparation of F-ASA graft copolymers：
The preparation of A, inner nuclear layer
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
70 DEG C, add the weight portion of deionized water 200 (5kg), the weight portion of lauryl sodium sulfate 6, styrene
100 weight portions, the weight portion of potassium peroxydisulfate 1 starts to stir after the weight portion of GDMA 4
Mix, stir speed (S.S.) is 400r/min, be cooled to after reaction 6h stand-by after room temperature.
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 200, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 40, the weight portion of Butyl Acrylate Monomer 60, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 0.7 after reaction 8h, is obtained
Particle size range is the intermediate layer complex emulsions that 130nm~140nm single dispersing conversion ratios are more than 98%.
2) prepared by big particle diameter intermediate layer emulsion
In equipped with agitator, the 20L glass reactors of condensing unit, nitrogen protection, constant temperature are passed through
65 DEG C, the weight portion of deionized water 100, the weight portion of lauryl sodium sulfate 2, step A is added to be obtained
The weight portion of inner nuclear layer emulsion 30, the weight portion of Butyl Acrylate Monomer 90, the weight of divinylbenzene 2
Part, the weight portion of allyl methacrylate 4, the weight portion of potassium peroxydisulfate 1 after reaction 12h, obtains grain
Footpath scope is the intermediate layer complex emulsions that 260nm~300nm single dispersing conversion ratios are more than 95%.
C, outer layer glycerol polymerization
The weight portion of prepared small particle intermediate layer emulsion 20, the weight portion of big particle diameter intermediate layer emulsion 40 are taken,
The weight portion of deionized water 200, the weight portion of cumyl hydroperoxide 0.4 and activator are placed in equipped with stirring
In device, the 20L glass reactors of condensing unit, nitrogen protection is passed through, constant temperature is to 45 DEG C, then incites somebody to action pre-
What is first prepared contains the weight portion of deionized water 50, the weight portion of lauryl sodium sulfate 2, hydrogen peroxide
The weight portion of isopropylbenzene 0.6, the weight portion of styrene 45, the weight portion of acrylonitrile 15, lauryl mercaptan
The mixed liquor of 0.5 weight portion is added with continuous feed mode 2h constant speed, is continued to be discharged after reaction 1h, is coagulated
Poly-, washing, dry, prepared three-decker functionalization weatherability ASA graft copolymers.The activation
Agent is constituted：The weight portion of sodium pyrophosphate 0.6, the weight portion of ferrous sulfate 0.008, the weight of glucose 0.4
Part.
2nd, weatherability ASA/PA alloys
It is 23.5 to weigh the prepared weight portion of functionalization F-ASA graft copolymers 40, intrinsic viscosity
Dl/g, the μ eq/g of end carboxyl 60, Amino End Group concentration are the weight portion of 80 μ eq/g nylon66 fibers 0, magnesium stearate
0.2 weight portion, the weight portion of pentaerythritol stearate 0.4 and the weight of phosphite ester kind antioxidant 1680.4
After part mixes through homogenizer, melt blending is carried out in 240 DEG C in double screw extruder, obtained
ASA/PA alloys.Then in test sample is obtained at 240 DEG C in injector, according to ASTM
D256, ASTM D638, ASTM D790, ASTM D1238 and ASTM D648 carry out performance
Test, test result is shown in Table 1.
Table 1ASA/PA the performance test results
Wherein, comparative example 1 and 2 is with a kind of single intermediate layer emulsion preparation ASA, and comparative example 3
It is not add functionalized monomer with the difference of embodiment.Can from above example and comparative example result
Go out, the blending of F-ASA functional groups and different-grain diameter F-ASA is beneficial to the weatherability prepared by raising
The physical and mechanical properties of ASA/PA alloys.
Certainly, the present invention can also have other various embodiments, without departing substantially from spiritual and its essence of the invention
In the case of, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention,
But these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (14)
1. a kind of weatherability ASA/PA alloys, it is characterised in that the alloy includes following components：
Wherein, the functionalization weatherability ASA graft copolymers be with vinyl aromatic polymers,
One or more in vinyl aromatic-vinyl nitrile copolymer or acrylate polymer is kernel,
It is intermediate layer without conjugated double bond rubber polymer, the vinyl of functional compounds is contained in outer layer grafting end
Aromatic series-vinyl nitrile copolymer.
2. weatherability ASA/PA alloys according to claim 1, it is characterised in that the PA
One or more in for PA6, PA66 or PA1010, intrinsic viscosity is 1.20dl/g~3.5dl/g,
Carboxylic end group concentration is 30 μ eq/g~80 μ eq/g, and Amino End Group concentration is 40 μ eq/g~60 μ eq/g.
3. weatherability ASA/PA alloys according to claim 1, it is characterised in that the second
Alkenyl aroma adoption compound is polystyrene, poly alpha methylstyrene and poly- p-tert-butylstyrene institute group
Into one or more in group.
4. weatherability ASA/PA alloys according to claim 1, it is characterised in that the second
Alkenyl aroma race-vinyl nitrile copolymer medium vinyl aromatic compound is styrene, Alpha-Methyl benzene second
Alkene and p-tert-butylstyrene constitute one or more in group, the vinyl aromatic-ethene
Base lonitrile copolymer medium vinyl nitrile compound is acrylonitrile or methacrylonitrile, the acrylate polymer
It is PMA, polymethyl methacrylate or polyethyl acrylate.
5. weatherability ASA/PA alloys according to claim 1, it is characterised in that the nothing
Conjugated double bond rubber polymer is butyl polyacrylate, n butyl acrylate styrene or acrylic acid
Ethylacrylate-acrylic acid butyl ester-vinyl chloroacetate terpolymer.
6. weatherability ASA/PA alloys according to claim 1, it is characterised in that the official
Energy dough compound is maleic anhydride, carboxylic acid compound or GMA.
7. weatherability ASA/PA alloys according to claim 1, it is characterised in that the profit
Lubrication prescription is made up of the one kind or several in group calcium stearate, magnesium stearate and pentaerythritol stearate
Kind.
8. weatherability ASA/PA alloys according to claim 1, it is characterised in that described anti-
Oxygen agent is phosphite ester kind antioxidant.
9. weatherability ASA/PA alloys according to claim 8, it is characterised in that described anti-
Oxygen agent is antioxidant 1010 and/or antioxidant 618.
10. the preparation method of the weatherability ASA/PA alloys any one of claim 1 to 9,
Characterized in that, the method comprises the following steps：
(1) preparation of functionalization weatherability ASA graft copolymers
The preparation of A, inner nuclear layer
Prepared using emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~400 weight portions, the weight portion of emulsifying agent 2~10, kernel compound, the weight portion of crosslinking agent 0.1~10
With the weight portion of initiator 0.1~1, mixing speed be 100r/min~400r/min, under nitrogen protection in
45 DEG C~85 DEG C reaction 4h~12h, obtain semi-conducting materia emulsion；Wherein, the kernel compound is vinyl
The weight portion of aromatic compound 40~80 and the weight portion of vinyl nitrile compound 20~60, or vinyl aromatic
The weight portion of compounds of group 80~120, or the weight portion of acrylic ester compound 80~120；
It is prepared by B, intermediate layer
1) prepared by small particle intermediate layer emulsion
Prepared using seed emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~300 weight portions, the weight portion of emulsifying agent 2~10, the weight of semi-conducting materia emulsion 40~60 that step A is obtained
Amount part, without the weight portion of conjugated double bond rubber compound 40~60, the weight portion of crosslinking agent 0.1~10, grafting
The weight portion of agent 0.1~10 and the weight portion of initiator 0.1~1, the reaction time are 4~30h, obtain small particle
Intermediate layer emulsion；Wherein, described is butyl acrylate without the weight portion of conjugated double bond rubber compound 40~60
40~60 weight portions, or the weight portion of butyl acrylate 30~55 and the weight portion of styrene 5~10 mixing
Thing, or the weight portion of ethyl acrylate 5~10, the weight portion of butyl acrylate 30~50 and vinyl chloroacetate
The mixture of the weight portion of ester 5~10；
2) prepared by big particle diameter intermediate layer emulsion
Prepared using seed emulsion polymerization：In reactor, following material is added by proportioning：Deionized water
100~300 weight portions, the weight portion of emulsifying agent 2~10, the weight of semi-conducting materia emulsion 10~30 that step A is obtained
Amount part, without the weight portion of conjugated double bond rubber compound 60~100, the weight portion of crosslinking agent 0.1~10, grafting
The weight portion of agent 0.1~10 and the weight portion of initiator 0.1~1, the reaction time are 4~30h, obtain big particle diameter
Intermediate layer emulsion；Wherein, described is acrylic acid fourth without the weight portion of conjugated double bond rubber compound 60~100
The weight portion of ester 60~100, or the weight portion of butyl acrylate 50~95 and the weight portion of styrene 5~10 mixing
Thing, or the weight portion of ethyl acrylate 5~20, the weight portion of butyl acrylate 50~90 and vinyl chloroacetate
The mixture of the weight portion of ester 5~20；
C, outer layer segment glycerol polymerization
Prepared using emulsion polymerization：In reactor, following material is added by proportioning：Step B is obtained
Small particle intermediate layer emulsion and big particle diameter intermediate layer emulsion the weight portion of mixture 40~80, vinyl aromatic (co)
The weight portion of fragrant compounds of group 15~45, the weight portion of vinyl nitrile compound 5~15, functional compounds
0.4~6 weight portion, the weight portion of lauryl mercaptan 0.05~1, the weight portion of initiator 0.1~1, emulsifying agent
2~10 weight portions and the weight portion of deionized water 80~300, the reaction time are 2h~4h, and cohesion is filtered,
Washing, is dried to obtain three-decker functionalization weatherability ASA graft copolymers；And
(2) by the weight of functionalization weatherability ASA graft copolymers 40~70 obtained in step (1)
Part, the weight portion of lubricant 0.1~0.5, the weight portion of antioxidant 0.1~1 and the weight portions of PA 30~60 in
200 DEG C~240 DEG C, screw speed be 80r/min~160r/min under the conditions of, double screw extruder melting
Blending, prepares weatherability ASA/PA alloys.
The preparation method of 11. weatherability ASA/PA alloys according to claim 10, its feature
It is that emulsifying agent is potassium oleate, potassium stearate, disproportionated rosin acid potassium and dodecane in the step A
Base sodium sulphate constitutes one or more in group；In the step A initiator be potassium peroxydisulfate or
Organic hydroperoxide-ferrous sulfate composite initiation system；Crosslinking agent is divinyl in the step A
Benzene, GDMA or allyl methacrylate.
The preparation method of 12. weatherability ASA/PA alloys according to claim 10, its feature
It is that emulsifying agent is potassium oleate, potassium stearate, disproportionated rosin acid potassium and dodecane in the step B
Base sodium sulphate constitutes one or more in group；In the step B initiator be potassium peroxydisulfate or
Organic hydroperoxide-ferrous sulfate composite initiation system；Crosslinking agent is divinyl in the step B
Benzene, GDMA or acrylic acid double cyclopentenyl ester；Grafting agent in the step B
It is allyl esters monomer；The particle size of small particle intermediate layer emulsion is in the step B
50nm~150nm, the particle size of big particle diameter intermediate layer emulsion is 200nm~500nm.
The preparation method of 13. weatherability ASA/PA alloys according to claim 10, its feature
It is that emulsifying agent is potassium oleate, potassium stearate, disproportionated rosin acid potassium and dodecane in the step C
Base sodium sulphate constitutes one or more in group；In the step C initiator be potassium peroxydisulfate or
Organic hydroperoxide-ferrous sulfate composite initiation system；Functional compounds are Malaysia in the step C
Acid anhydrides, carboxylic acid compound or GMA.
The preparation method of 14. weatherability ASA/PA alloys according to claim 10, its feature
It is that the vinyl aromatic compounds are styrene, AMS and p-tert-butylstyrene
One or more in constituted group, the vinyl nitrile compound is acrylonitrile or methacrylonitrile,
The acrylic ester compound is methyl acrylate, methyl methacrylate or ethyl acrylate.
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| CN (1) | CN106928620B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136873A (en) * | 2018-09-05 | 2019-01-04 | 合肥久新不锈钢厨具有限公司 | A kind of preparation method of abrasion-proof stainless steel composite board |
| CN111087554A (en) * | 2019-12-24 | 2020-05-01 | 广州熵能创新材料股份有限公司 | High-impact-resistance acrylate-styrene-acrylonitrile graft polymer and preparation method and application thereof |
| CN113136100A (en) * | 2021-05-10 | 2021-07-20 | 会通新材料股份有限公司 | PA6/ASA alloy material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897110A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Styrene resin blend with weather resistance and preparation method thereof |
-
2015
- 2015-12-31 CN CN201511026373.7A patent/CN106928620B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897110A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Styrene resin blend with weather resistance and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 梁惠霞等: "相容剂对ASA/PA6合金力学性能的影响", 《塑料科技》 * |
| 邓云娇等: "马来酸酐官能化ASA对PA6的增韧研究", 《中国塑料》 * |
| 韩业: "ASA树脂及其共混物的制备和性能研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109136873A (en) * | 2018-09-05 | 2019-01-04 | 合肥久新不锈钢厨具有限公司 | A kind of preparation method of abrasion-proof stainless steel composite board |
| CN111087554A (en) * | 2019-12-24 | 2020-05-01 | 广州熵能创新材料股份有限公司 | High-impact-resistance acrylate-styrene-acrylonitrile graft polymer and preparation method and application thereof |
| CN113136100A (en) * | 2021-05-10 | 2021-07-20 | 会通新材料股份有限公司 | PA6/ASA alloy material and preparation method thereof |
| CN113136100B (en) * | 2021-05-10 | 2022-03-22 | 会通新材料股份有限公司 | PA6/ASA alloy material and preparation method thereof |
Also Published As
| Publication number | Publication date |
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| CN106928620B (en) | 2019-06-11 |
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