CN101544727A - An AES colophony with high impact and its preparing method - Google Patents
An AES colophony with high impact and its preparing method Download PDFInfo
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- CN101544727A CN101544727A CN200910115240A CN200910115240A CN101544727A CN 101544727 A CN101544727 A CN 101544727A CN 200910115240 A CN200910115240 A CN 200910115240A CN 200910115240 A CN200910115240 A CN 200910115240A CN 101544727 A CN101544727 A CN 101544727A
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- rubber
- aes
- aes resin
- colophony
- monomer
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- 238000000034 method Methods 0.000 title abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 57
- 239000005060 rubber Substances 0.000 claims abstract description 57
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 150000002825 nitriles Chemical class 0.000 claims abstract description 9
- -1 ethylen-propylene Chemical group 0.000 claims abstract description 7
- 230000002902 bimodal effect Effects 0.000 claims abstract description 6
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 37
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 10
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 239000007858 starting material Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract 6
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 13
- 229920002943 EPDM rubber Polymers 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical group CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 229920002545 silicone oil Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- UOZNXGJVAWDLQK-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC(N2C(C=CC2=O)=O)=C1C UOZNXGJVAWDLQK-UHFFFAOYSA-N 0.000 description 1
- LWFUFCYGHRBLDH-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC(C)=CC=C1N1C(=O)C=CC1=O LWFUFCYGHRBLDH-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- FBPVUBVZRPURIU-UHFFFAOYSA-N 1-hexylpyrrole-2,5-dione Chemical compound CCCCCCN1C(=O)C=CC1=O FBPVUBVZRPURIU-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
- FYZHLRMYDRUDES-UHFFFAOYSA-N 5,7-dimethylocta-1,6-diene Chemical compound CC(C)=CC(C)CCC=C FYZHLRMYDRUDES-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- VFIJBTVGUHVPPW-UHFFFAOYSA-N [Br].C=C Chemical compound [Br].C=C VFIJBTVGUHVPPW-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 229920006335 epoxy glue Polymers 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N perisophthalic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- XKXIQBVKMABYQJ-UHFFFAOYSA-N tert-butyl hydrogen carbonate Chemical compound CC(C)(C)OC(O)=O XKXIQBVKMABYQJ-UHFFFAOYSA-N 0.000 description 1
- OEQJOYQHIGIVTN-UHFFFAOYSA-N tert-butyl nonanoate Chemical compound CCCCCCCCC(=O)OC(C)(C)C OEQJOYQHIGIVTN-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Abstract
The invention relates to an AES colophony with high impact and its preparing method, the colophony is graft copolymer with particle diameter showing bimodal distribution formed by ethylen-propylene rubber, divinyl rubber, uni-alkyl vinyl aromatic hydrocarbons monomer and unsaturated nitrile monomer, and the mass ratio of the aforementioned ethylen-propylene rubber and divinyl rubber is 1:0.05-0.25. The preparing method for the AES colophony includes Material Proportioning, the materials carrying out glycerol polymerization reaction in the catalyst case and the reaction melt prilling through the devolatilization extruder in the end, the glycerol polymerization reaction indicates under the pressure of more than 0.5MPa and the mixing round condition, making the incept materials go through four stages in sequence and obtaining reaction melt, the temperature of the four stages in sequence is 95degrees-105degrees, 110degrees-115degrees, 120degrees-123degrees and 140degrees-150degrees. The AES colophony in this invention not only has good weathering resistance and heat endurance but also has high impulse strength. The method for preparing AES colophony is easy and environmental protecting, and the obtained AES colophony with good comprehensive properties shows the bimodal particle diameter distribution.
Description
Technical field
The present invention relates to a kind of AES resin and preparation method thereof.
Background technology
AES (vinyl cyanide/ethylene-propylene rubber(EPR)/styrol copolymer) is a kind of engineering plastics new variety of developing at ABS weathering resistance difference, EPDM in the AES resin (ethylene-propylene rubber(EPR)) molecular chain double bond content is few, so the weathering resistance of AES is higher 4～8 times than ABS, the thermostability of AES, water-intake rate all are better than ABS resin, and other performances are then similar to ABS.
In the prior art, the single ethylene-propylene rubber(EPR) of the general employing of AES resin, the resin particle diameter is unimodal distribution, and simultaneously, because there is suitable difficulty in the grafting of ethylene-propylene rubber(EPR), the shock strength of the resin that finally makes is not high, can't satisfy more and more higher user demand.
The preparation method of AES resin mainly contains two kinds of direct synthesis technique and blending methods.Direct synthesis technique is by predefined AN (vinyl cyanide)/EPDM/St (vinylbenzene) ratio of components, directly synthetic with solution polymerization, letex polymerization or suspension polymerization, the product that obtains be a kind of be main chain with EPDM, be the novel graft copolymer EPDM-g-SAN of side chain with SAN (St-AN multipolymer).The blend rule is that EPDM and SAN are processed through physical blending under molten state.Present industrialized method has only solution polymerization process, but this method separate out in order to make final polymerisate precipitation, need use a large amount of methyl alcohol, exist solvent load big, complex process, the shortcoming that investment is big, energy consumption is high.
Summary of the invention
Technical problem to be solved by this invention is in order to overcome the deficiencies in the prior art, a kind of AES resin to be provided, this resin high comprehensive performance, particularly its shock strength height.
The present invention also will provide a kind of preparation method of above-mentioned AES resin, and this method is based on solution polymerization process, and technology is simple, compliance with environmental protection requirements.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
A kind of AES resin with high impact, this resin is the graft copolymer that the particle diameter of ethylene-propylene rubber(EPR), divinyl rubber and monoalkyl vinyl aromatic monomer and unsaturated nitrile monomer formation is bimodal distribution, and the mass ratio of described ethylene-propylene rubber(EPR) and divinyl rubber is 1:0.05～0.25.
As further embodiment of the present invention, the ethylene propylene rubber of described ethylene-propylene rubber(EPR) for forming with monoolefine ethene, copolymerization of propylene; Or be the terpolymer EP rubber that monomer copolymerization makes with ethene, propylene and a small amount of non-conjugated dienes; Or both epoxy glues.Wherein the 3rd monomer of terpolymer EP rubber employing has ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, 1,7-octadiene, 6,10-dimethyl-1,5,9-11 triolefins, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 7-methyl isophthalic acid, 6-octadiene etc.The preferred ethylene-propylene diene copolymer that adopts, more preferably ethylidene norbornene is as the 3rd monomeric ethylene-propylene rubber(EPR); The preferred ethylene-propylene rubber(EPR) weight-average molecular weight that adopts is 200,000～350,000, molecular weight distributing index 3～3.5.
Described divinyl rubber is preferably second-order transition temperature smaller or equal to 85 ℃ conjugation 1,3-dience rubber or second-order transition temperature be smaller or equal to 85 ℃ conjugation 1, but 3-dience rubber and the monoene of copolymerization belong to the multipolymer and/or the segmented copolymer of unsaturated monomer.Divinyl rubber most preferably is poly-1, wherein contains the cis-isomeride of weight percentage 30～98% and the trans-isomer(ide) of weight percentage 2～70%; More preferably butylbenzene block rubber or polybutadiene rubber.
Described monoalkyl vinyl aromatic monomer structure is shown below:
Wherein, Ar is preferably one or more in phenyl, halogenophenyl, alkyl phenyl or the halogenated alkyl phenyl; X is preferably hydrogen, methyl or ethyl.The monoalkyl vinyl aromatic monomer is optimal selection with vinylbenzene.
Described unsaturated nitrile monomer is preferably one or more in vinyl cyanide, methacrylonitrile or the ethyl acrylonitrile, most preferably vinyl cyanide.
The described ethylene-propylene rubber(EPR) and the mass ratio of divinyl rubber are preferably 1:0.1～0.2.
The another kind of technical scheme that the present invention takes is: a kind of preparation method of above-mentioned AES resin comprises the steps:
(1), batching: after will dissolving with the monoalkyl vinyl aromatic monomer as ethylene-propylene rubber(EPR), the divinyl rubber of raw material, mix the formation rubber solutions with unsaturated nitrile monomer, this rubber solutions further mixes the starting material that obtains as graft polymerization reaction with auxiliary agent, described auxiliary agent comprises solvent, initiator and chain-transfer agent;
(2), graft polymerization reaction: will be transferred in the reactor by step (1) gained starting material, the controlling reactor internal pressure is more than 0.5MPa, under agitation condition, starting material experience four-stage obtains reaction melt, and the temperature of this four-stage is by being followed successively by 95 ℃～105 ℃, 110 ℃～115 ℃, 120 ℃～125 ℃ and 140 ℃～150 ℃;
(3), step (2) gained reaction melt is through the granulation of devolatilization forcing machine, obtains being fit to the AES resin of injection moulding processing.
In the step (1), described solvent is preferably aromatic hydrocarbons and alkenolic mixture, and the add-on of solvent is 10%～20% of a rubber solutions weight, is preferably 12%～20%.Described aromatic hydrocarbons is to be selected from benzene, ethylbenzene and the toluene one or more, and described aliphatic ketone is to be selected from acetone, methyl ethyl ketone, methyl propyl ketone and the pimelinketone one or more.
Described initiator is preferably one or more of following substances: t-butyl perbenzoate, sec.-propyl percarbonic acid tertiary butyl ester, cross sad tertiary butyl ester, cross different n-nonanoic acid tertiary butyl ester, 2-ethylhexyl list peroxide carbonic acid tertiary butyl ester and cross the neodecanoic acid tertiary butyl ester.Initiator weight is preferably 0.001%～3.0% of rubber solutions weight, and more preferably 0.005～1.0% of rubber solutions weight.
Auxiliary agent also comprises softening agent, oxidation inhibitor, molecular weight adjustment and silicone oil, and wherein, the kind of softening agent and oxidation inhibitor and consumption can be with reference to standards of the prior art; Molecular weight regulator can be mercaptan, halogenide or terpenes; The add-on of silicone oil is 0.05%～0.4% of a rubber solutions weight, and the adding of silicone oil makes and forms the space in the product rubber grain, reduces the stretching yield stress of material, improves toughness and tensile elongation simultaneously, and does not reduce the modulus of material.Suitable silicone oil is the segmented copolymer of siloxane blocks, for example polyether-polysiloxane and the polydialkysiloxane that comprises the viscosity with about 100-1000000 centipoise, preferably polydimethylsiloxane.
Total mass with rubber solutions is a benchmark, and described monoalkyl vinyl aromatic monomer accounts for 50%～55%, and unsaturated nitrile monomer accounts for 15%～20%, and surplus is ethylene-propylene rubber(EPR) and divinyl rubber, and rubber content is no more than 25%, had better not surpass 15%.
As another preferred version of the present invention: in the step (1), also added weight in the starting material and be 1%～5% additional monomer of described rubber solutions gross weight.Additional monomer can be one or more of following substances: vinylformic acid, methyl acrylate, ethyl propenoate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid and corresponding ester, acrylamide, Methacrylamide, vinylchlorid, bromine ethene, inclined to one side sym-dibromoethane, vinyl-acetic ester, vinyl propionate base ester, the toxilic acid dimethyl esters, the toxilic acid diethyl ester, dibutyl maleinate, maleimide, N-methyl maleimide, N-sec.-propyl maleimide, the N-butyl maleimide, N-hexyl maleimide, N-octyl group maleimide, N-dodecyl maleimide, N-cyclohexyl maleimide, N-phenylmaleimide, N-2,3-xylyl maleimide or N-2,4-xylyl maleimide, wherein acrylic ester compound most preferably.
In step (2), reactor is preferably tank reactor, adopts the helical-ribbon type stirring arm, and this stirring arm prevents the reactant back-mixing in reaction early stage, farthest realizes grafting rubbers; When changing, phase obtains enough to shear; Enough shearings are provided, thereby obtain suitable rubber size; The reaction later stage is finished mass-and heat-transfer, smoothly to improve monomeric transformation efficiency under high viscosity systems.
The stirring velocity of four-stage is preferably 200～500rpm, 300～500rpm, 50～100ppm and 30～100rpm successively.
It is to finish in 16～30% o'clock that fs begins to the polymerisate solid content from reaction, and reaction pressure is preferably 5～10atm, and in the fs, graft reaction is fully finished; In subordinate phase, the reaction mixture of finishing graft reaction carries out inversion of phases along with the SAN phase is on the increase in reactor, make rubber become the separation phase, and form rubber particles gradually.Because the existence of two or more rubber, the difference of apparent viscosity under enough stirring shearing conditions, forms bimodal size distribution, and volume average particle size is 0.4～2.5 micron, and solids content is end in 40～45% o'clock to the polymerisate; Form the reaction mixture of rubber particles, continue reaction in third and fourth stage, to promote reaction conversion ratio, stabilising rubber particle simultaneously is to finish in 50～75% o'clock to solids content.
In the step (3), the temperature when devolatilization separates is preferably 190 ℃～220 ℃, and pressure is preferably 2～200mmHg.
Because the utilization of technique scheme, the present invention compared with prior art has following advantage:
AES resin of the present invention is main rubber constituent with ethylene-propylene rubber(EPR), adds few butadiene rubber simultaneously, and resin is two size distribution, not only has good weather resistance and thermostability, also has high impulse strength.
The preparation method of AES of the present invention is based on solution polymerization process, and technology not only simply but also environmental protection; Gained AES resin is bimodal grit and distributes, and the rubber weight average particle diameter is below 2.5 microns, and the high comprehensive performance of resin has particularly obtained the high impulse strength performance.
Description of drawings
Fig. 1 prepares the process flow sheet of AES resin for the present invention;
Wherein: 1, material-compound tank; 2, reactor; 3, forcing machine; 4, dicing machine.
Embodiment
As shown in Figure 1; preparation technology's key step of AES of the present invention is: finish batching in material-compound tank 1; then the material for preparing is got in the reactor 2 with pump; obtain reaction melt behind the reaction specified time, reaction melt obtains being fit to the rosin products of injection moulding processing through forcing machine 3 and dicing machine 4 devolatilization granulations.Below the specific embodiment of the present invention is described, but be not limited to these embodiment.
Embodiment 1
In the rubber dissolving tank, add 0.9kg ethylbenzene and 2.55kg vinylbenzene, start and stir, add Keltan51 EPDM rubber 0.5kg and divinyl glue AE55 rubber 0.1kg by adding Jiao Kou then, normal temperature stirs down and adds 0.9kg vinyl cyanide, 0.05kg mineral oil, 25g oxidation inhibitor after 8 hours, and 15g chain-transfer agent mercaptan and 1.5g cross the neodecanoic acid tertiary butyl ester.Continue dispersed with stirring 30min, batching is finished.
To prepare burden and beat to reactor with pump.Reactor pressure is controlled at more than the 0.5MPa; Temperature of reaction is followed successively by 100 ℃/2h through different steps; 110 ℃/2h; 121 ℃/2h and 145 ℃/2h; The mixing speed of reactor is followed successively by 250/350/100/60rpm through different steps; The reactor volume that is adopted is 6L.
Reaction after finishing in 8 hours, and reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTM standard analysis test products, the results are shown in Table 1.
In the rubber dissolving tank, add 0.7kg toluene, 0.2kg acetone and 2.55kg vinylbenzene, start and stir, then Keltan51 EPDM rubber 0.5kg, divinyl glue AE35 rubber 0.1kg are added in the rubber dissolving tank by adding Jiao Kou, material in the steel basin under the normal temperature, add 0.9kg vinyl cyanide, 0.1kg butyl acrylate, 0.05kg mineral oil, 25g oxidation inhibitor, 15g chain-transfer agent mercaptan and 1.5g t-butyl perbenzoate after 8 hours.Continue dispersed with stirring 30min, batching is finished.
To prepare burden and beat to reactor with pump.Reaction pressure is controlled at more than the 0.5MPa; Temperature of reaction is followed successively by 100 ℃/2h through different steps; 110 ℃/2h; 121 ℃/2h; 145 ℃/2h; The mixing speed of reactor is followed successively by 250/350/100/60rpm through different steps; The reactor volume that is adopted is 6L.
Reaction after finishing in 8 hours, and reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTM standard analysis test products, the results are shown in Table 1.
Embodiment 3
In the rubber dissolving tank, add 0.7kg toluene, 0.2kg acetone and 2.55kg vinylbenzene, start and stir, Keltan51 EPDM rubber 0.5kg and divinyl glue AE55 rubber 0.1kg are added in the above-mentioned rubber dissolving tank by adding Jiao Kou, normal temperature stirred 8 hours down, add 0.9kg vinyl cyanide, 0.05kg mineral oil, 25g oxidation inhibitor then, 15g chain-transfer agent mercaptan and 1.5g cross the neodecanoic acid tertiary butyl ester.Continue dispersed with stirring 30min, batching is finished.
To prepare burden and beat to reactor with pump.Reaction pressure is controlled at more than the 0.8MPa; Temperature of reaction is followed successively by 105 ℃/2h through different steps; 115 ℃/2h; 125 ℃/2h; 150 ℃/2h; The mixing speed of reactor is followed successively by 150/250/120/60rpm through different steps; The reactor volume that is adopted is 6L.
Reaction after finishing in 8 hours, and reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTM standard analysis test products, the results are shown in Table 1.
Embodiment 4
In the rubber dissolving tank, add 0.9kg ethylbenzene and 2.55kg vinylbenzene, start and stir Keltan51EPDM rubber 0.5kg and divinyl glue AE35 rubber 0.1kg, join in the described rubber dissolving tank by adding Jiao Kou, normal temperature stirred 8 hours down, added 0.9kg vinyl cyanide, 0.05kg mineral oil, 25g oxidation inhibitor and 1.5g t-butyl perbenzoate then.Continue dispersed with stirring 30min, batching is finished.
To prepare burden and beat to reactor with pump.Reaction pressure is controlled at more than the 0.5MPa; Temperature of reaction is followed successively by 100 ℃/2h through different steps; 110 ℃/2h; 121 ℃/2h; 145 ℃/2h; The mixing speed of reactor is followed successively by 250/350/100/60rpm through different steps; The reactor volume that is adopted is 6L.
Reaction enters subordinate phase and add 15g chain-transfer agent mercaptan in reactor.Reaction after finishing in 8 hours, and reaction melt obtains a kind of suitable injection moulding product processed through the granulation of devolatilization forcing machine, uses the performance of corresponding ASTM standard analysis test products, the results are shown in Table 1.
The main performance index of the AES resin of table 1 embodiment 1～4
| Performance test methods embodiment 1 |
| Melt mass flow rate (g/10min) ASTM 4.5 4.1 4.7 4.4 D1238 |
| Izod shock strength (kJ/m 2) ASTM 15.0 10.0 13.0 16.0 D256 |
| Tensile yield strength (Mpa) ASTM 44.0 46.0 42.0 43.0 D638 |
| Tensile break strength (Mpa) ASTM 37.2 38.2 37.0 37.0 D638 |
| Elongation at break (%) ASTM 15.0 12.0 15.0 13.0 |
As seen from Table 1, AES resin of the present invention has high impact, and preparation technology is comparatively simple, after graft reaction finishes, need not to use a large amount of organic solvents, directly can obtain to be fit to the rosin products of injection moulding processing, the technology environmental protection by the granulation of devolatilization forcing machine.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (10)
1, a kind of AES resin with high impact, it is characterized in that: this resin is the graft copolymer that the particle diameter of ethylene-propylene rubber(EPR), divinyl rubber and monoalkyl vinyl aromatic monomer and unsaturated nitrile monomer formation is bimodal distribution, and the mass ratio of described ethylene-propylene rubber(EPR) and divinyl rubber is 1:0.05～0.25.
2, the AES resin with high impact according to claim 1, it is characterized in that: described monoalkyl vinyl aromatic monomer is a vinylbenzene, described unsaturated nitrile monomer is the vinyl cyanide that vinyl cyanide or alkyl replace.
3, the AES resin with high impact according to claim 1, it is characterized in that: the mass ratio of described ethylene-propylene rubber(EPR) and divinyl rubber is 1:0.1～0.2.
4, the preparation method of any described AES resin of claim in a kind of claim 1 to 3 is characterized in that: comprise the steps:
(1), batching: after will dissolving with the monoalkyl vinyl aromatic monomer as ethylene-propylene rubber(EPR), the divinyl rubber of raw material, mix the formation rubber solutions with unsaturated nitrile monomer, this rubber solutions further mixes the starting material that obtains as graft polymerization reaction with auxiliary agent, described auxiliary agent comprises solvent, initiator and chain-transfer agent;
(2), graft polymerization reaction: will be transferred in the reactor by step (1) gained starting material, the controlling reactor internal pressure is more than 0.5MPa, under agitation condition, starting material experience four-stage obtains reaction melt, and the temperature of this four-stage is by being followed successively by 95 ℃～105 ℃, 110 ℃～115 ℃, 120 ℃～125 ℃ and 140 ℃～150 ℃;
(3), step (2) gained reaction melt is through the granulation of devolatilization forcing machine, obtains being fit to the AES resin of injection moulding processing.
5, the preparation method of AES resin according to claim 4 is characterized in that: in the step (1), described solvent is aromatic hydrocarbons and alkenolic mixture, and the add-on of solvent is 12%～20% of a described rubber solutions gross weight.
6, the preparation method of AES resin according to claim 5, it is characterized in that: described aromatic hydrocarbons is to be selected from benzene, ethylbenzene and the toluene one or more, and described aliphatic ketone is to be selected from acetone, methyl ethyl ketone, methyl propyl ketone and the pimelinketone one or more.
7, the preparation method of AES resin according to claim 4, it is characterized in that: the total mass with rubber solutions is a benchmark, described monoalkyl vinyl aromatic monomer accounts for 50%～55%, and unsaturated nitrile monomer accounts for 15%～20%, and surplus is ethylene-propylene rubber(EPR) and divinyl rubber.
8, the preparation method of AES resin according to claim 4 is characterized in that: in the step (1), also add 1%～5% additional monomer of described rubber solutions gross weight in the starting material.
9, the preparation method of AES resin according to claim 8 is characterized in that: described additional monomer is an acrylic compound.
10, the preparation method of AES resin according to claim 4 is characterized in that: in the step (2), it is to finish in 16～30% o'clock that the fs begins to the polymerisate solid content from reaction; Subordinate phase solid content to the polymerisate is to finish in 40～45% o'clock, and third and fourth stage solid content to the polymerisate is to finish in 50～70% o'clock.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632867A (en) * | 2016-12-16 | 2017-05-10 | 北方华锦化学工业集团有限公司 | Method for preparing high-impact AES resin by adopting continuous bulk device |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
| CN112339158A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | Super-gravity rotating bed for polymer devolatilization granulation and application method thereof |
-
2009
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632867A (en) * | 2016-12-16 | 2017-05-10 | 北方华锦化学工业集团有限公司 | Method for preparing high-impact AES resin by adopting continuous bulk device |
| CN106632867B (en) * | 2016-12-16 | 2021-02-09 | 北方华锦化学工业股份有限公司 | Method for preparing high-impact AES resin by adopting continuous body device |
| CN112339158A (en) * | 2019-08-09 | 2021-02-09 | 北京化工大学 | Super-gravity rotating bed for polymer devolatilization granulation and application method thereof |
| CN112339158B (en) * | 2019-08-09 | 2022-08-23 | 北京化工大学 | Super-gravity rotating bed for polymer devolatilization granulation and application method thereof |
| CN111499813A (en) * | 2020-04-09 | 2020-08-07 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
| CN111499813B (en) * | 2020-04-09 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
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