CN118290673A - Core-shell ASA copolymer, preparation method thereof and application thereof as impact modifier - Google Patents
Core-shell ASA copolymer, preparation method thereof and application thereof as impact modifier Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000004609 Impact Modifier Substances 0.000 title claims abstract description 27
- 239000011258 core-shell material Substances 0.000 title abstract description 19
- 239000012792 core layer Substances 0.000 claims abstract description 78
- 239000010410 layer Substances 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 229920001971 elastomer Polymers 0.000 claims abstract description 31
- 239000005060 rubber Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 15
- 229920006163 vinyl copolymer Polymers 0.000 claims abstract description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000839 emulsion Substances 0.000 claims description 71
- 239000000178 monomer Substances 0.000 claims description 60
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- -1 siloxane compound Chemical class 0.000 claims description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000002209 hydrophobic effect Effects 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- HSFXEOPJXMFQHG-ONEGZZNKSA-N (e)-4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobut-2-enoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)\C=C\C(O)=O HSFXEOPJXMFQHG-ONEGZZNKSA-N 0.000 claims description 2
- ROZDMUUELHCVQC-ARJAWSKDSA-N (z)-4-oxo-4-(2-prop-2-enoyloxyethoxy)but-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCCOC(=O)C=C ROZDMUUELHCVQC-ARJAWSKDSA-N 0.000 claims description 2
- UCBVELLBUAKUNE-UHFFFAOYSA-N 1,3-bis(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)NC(=O)N(CC=C)C1=O UCBVELLBUAKUNE-UHFFFAOYSA-N 0.000 claims description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004036 acetal group Chemical group 0.000 claims description 2
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000010556 emulsion polymerization method Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 238000009826 distribution Methods 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000008367 deionised water Substances 0.000 description 23
- 229910021641 deionized water Inorganic materials 0.000 description 23
- 239000004816 latex Substances 0.000 description 22
- 229920000126 latex Polymers 0.000 description 22
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 14
- 230000009477 glass transition Effects 0.000 description 12
- 230000009471 action Effects 0.000 description 11
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 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 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Abstract
The invention provides an ASA copolymer with a core-shell structure, a preparation method thereof and application thereof as an impact modifier. The copolymer comprises: a rubber core layer consisting of a seed layer and a core layer; the seed layer is a siloxane polymer or vinyl copolymer; the core layer is an acrylic polymer prepared by emulsion polymerization, and is coated on the surface of the seed layer, and a structure improver is added in the preparation process of the core layer, wherein the structure improver contains at least one vinyl group and at least one hydrophilic group; and the shell layer is coated on the surface of the rubber core layer. The invention provides a copolymer with complete core-shell structure and narrow particle size distribution, which is an impact modifier with an ideal structure, so that the impact resistance of the modified resin is obviously improved.
Description
Technical Field
The invention belongs to the field of polymers, and relates to a core-shell structure copolymer taking polyacrylate rubber as a rubber core, a preparation method thereof, application of the core-shell structure copolymer as an impact modifier, and thermoplastic resin containing the copolymer and taking the copolymer as the impact modifier.
Background
The core-shell structure impact modifier (such as ABS and MBS) taking polybutadiene rubber as a rubber core can effectively improve the impact resistance of thermoplastic resin, but the polybutadiene rubber contains unsaturated double bonds, so that the heat stability and weather resistance of the polybutadiene rubber are poor. The core-shell structure impact modifier (such as ASA and ACR) taking polyacrylate rubber as a rubber core has the unique advantages of good heat stability and weather resistance because of containing no unsaturated double bonds, and is increasingly applied to thermoplastic resin modification. However, since polyacrylate rubber has a higher glass transition temperature than polybutadiene rubber, it is difficult for the impact resistance of the polyacrylate impact modifier to reach the level of the polybutadiene impact modifier. Therefore, how to improve the impact resistance of the polyacrylate impact modifier on the basis of not affecting the heat stability and weather resistance of the material is a key problem to be solved by the material.
The method comprises the steps of using a copolymer of a vinyl monomer and a hydrophilic monomer as a seed for polymerizing polyacrylate rubber, polymerizing the polyacrylate rubber on the basis of a polyorganosiloxane rubber seed in the U.S. Pat. No. 3,182,62, forming a core layer after the polymerization of the polyacrylate rubber is completed, and grafting a resin polymer serving as a shell layer on the core layer to finally obtain the core-shell structure impact modifier. These methods can obtain the effect of improving the impact resistance of the impact modifier to some extent, but because they are not favorable for the growth of the core polymer on a seed basis, it is difficult to obtain a good core composition, structure and particle size distribution, thereby affecting the core-shell structure of the impact modifier, further improving the impact resistance, and negatively affecting the colorability of the thermoplastic resin after the impact modifier is added.
The following problems exist in the prior art: in the synthesis of the polyacrylate impact modifier, in order to improve the impact strength and obtain good processing fluidity, seed emulsion such as copolymer of vinyl monomer and hydrophilic monomer or polyorganosiloxane rubber can be synthesized first, then the polymerization of the polyacrylate rubber is carried out on the basis of the seed emulsion to form a nucleation layer, and finally the resin polymer serving as a shell layer is grafted on the nucleation layer, so that the core-shell structure impact modifier is obtained. However, these methods are not favorable for the growth of the core polymer on the basis of the seeds, and therefore, some seeds cannot be coated with the polyacrylate rubber, or the coating effect is poor, and it is difficult to obtain a good core structure, and at the same time, the particle size distribution is widened, so that the impact strength of the impact modifier and the colorability of the thermoplastic resin after the impact modifier is added are negatively affected.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems, and provides a polyacrylate polymer having high impact strength, which has a narrow distribution of an ideal core-shell structure, has a more remarkable effect of improving impact resistance of a thermoplastic resin when used as an impact modifier, and can maintain excellent colorability of the modified thermoplastic resin, and a method for producing the same.
The present invention also provides a copolymer comprising:
A rubber core layer consisting of a seed layer and a core layer;
the seed layer is a siloxane polymer or vinyl copolymer;
the core layer is an acrylic polymer prepared by emulsion polymerization, and is coated on the surface of the seed layer, and a structure improver is added in the preparation process of the core layer, wherein the structure improver contains at least one vinyl group and at least one hydrophilic group;
And the shell layer is coated on the surface of the rubber core layer.
According to an embodiment of the present invention, the hydrophilic group is selected from at least one of hydroxyl, carboxyl, amino, acetal groups.
According to one embodiment of the invention, the structure-improving agent contains at least two non-conjugated vinyl groups and at least one hydrophilic group; for example, the structure-improving agent is at least one selected from polyethylene glycol diacrylate, 4- (2- (methacryloyloxy) ethoxy) -4-oxobut-2-enoic acid, mono [2 (1-oxo-2-propenyl) oxyethyl ] maleate, monoallyl maleate, 2-hydroxy-1, 3-propanediol bis (2-methyl-2-propenoic acid), diallyl isocyanurate, trimethylolpropane diallyl ether.
According to one embodiment of the invention, the structure-improving agent contains one vinyl group and at least one hydrophilic group and can undergo a condensation reaction, such as N-methylolacrylamide, when the core layer is prepared.
According to an embodiment of the present invention, the core layer is prepared from raw materials including an acrylate monomer and a structure-improving agent; further, the raw materials include a crosslinking agent.
According to an embodiment of the present invention, the weight ratio of the structure improver to the acrylate monomer is (0.1 to 10): 100, for example (0.1-5): 100, also as (0.5-3): 100.
According to an embodiment of the invention, the acrylate monomer is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, preferably n-butyl acrylate.
According to an embodiment of the present invention, the crosslinking agent is at least one selected from divinylbenzene, 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, dicyclopentenyl acrylate, allyl methacrylate.
According to an embodiment of the present invention, the weight ratio of the acrylate monomer to the crosslinking agent is (90-98): (0.1-10).
According to an embodiment of the present invention, the seed layer is prepared from a raw material including a first siloxane compound and a second siloxane compound, or further including a third siloxane compound;
Or the seed layer is prepared from a raw material including a hydrophobic vinyl monomer and a hydrophilic vinyl monomer.
According to an embodiment of the present invention, the shell layer is prepared from a raw material including a vinylbenzene monomer, a vinylcyano monomer, and a divinyl crosslinking agent.
According to an embodiment of the present invention, the seed layer is 0.5 to 50 parts by weight, the core layer is 40 to 89.5 parts by weight, and the shell layer is 10 to 59.5 parts by weight, relative to the copolymer;
for example, the seed layer comprises 1, 5, 10, 15, 20, 30, or 40 parts by weight;
For example, the core layer comprises 50, 60, 70, or 80 parts by weight;
for example, the shell layer may comprise 20, 30, 40 or 50 parts by weight.
According to an embodiment of the invention, the seed layer has a particle size of 50-300nm, such as 60nm, 80nm, 100nm, 150nm, 200nm or 250nm.
According to an embodiment of the invention, the particle size of the rubber core layer is 100-500nm, for example 150nm, 200nm, 250nm, 300nm, 350nm, 400nm or 450nm. Those skilled in the art will recognize that the particle size of the rubber core layer is greater than the particle size of the seed layer.
According to an embodiment of the invention, the polydisperse coefficient PDI of the rubber core layer is < 0.2, preferably PDI < 0.1, and more preferably PDI < 0.05.
According to an embodiment of the invention, the copolymer has a particle size of 200-700nm, such as 250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm or 650nm. Those skilled in the art will recognize that the particle size of the copolymer is greater than the particle size of the rubber layer.
According to an embodiment of the present invention, the cladding ratio of the core layer is not less than 90%; the above coating ratio = surface area of seed layer coated by core layer/surface area of seed layer not coated by core layer 100%. Preferably, the coating ratio is not less than 95%, 96%, 97%, 98%, 99%, or even up to 100%.
The invention also provides a preparation method of the copolymer, which comprises the following steps: sequentially preparing a seed layer, a core layer and a shell layer by an emulsion polymerization method, wherein the structure improver is added in the preparation process of the core layer.
According to an embodiment of the invention, the seed layer, core layer, shell layer have the definitions as indicated above, respectively.
According to an embodiment of the present invention, the method for preparing the copolymer comprises:
(1) Preparing a seed emulsion from the first and second silicone compounds, or further monomers including a third silicone compound, by emulsion polymerization; or alternatively
Preparing seed emulsion from the hydrophobic vinyl monomer and the hydrophilic vinyl monomer through emulsion polymerization;
(2) Mixing acrylate monomers and a structure improver or further mixing the acrylate monomers and a cross-linking agent for pre-emulsification, adding the obtained core layer pre-emulsion into a seed emulsion reaction system, and performing emulsion polymerization to form a core layer to obtain core layer emulsion;
(3) Mixing and pre-emulsifying raw materials comprising vinyl benzene monomer, vinyl cyano monomer and divinyl crosslinking agent, adding the obtained shell pre-emulsion into the core-layer emulsion system, and performing emulsion polymerization to obtain the emulsion of the copolymer.
According to an embodiment of the present invention, the method for preparing the copolymer further comprises a step (4) of mixing the product of the step (3) with a demulsifier and subjecting the demulsified solid to post-treatment (e.g. washing and/or drying).
The invention also provides application of the copolymer as an impact modifier to preparation of thermoplastic resin.
The invention also provides a thermoplastic resin containing the copolymer.
Advantageous effects
The invention provides a copolymer with complete core-shell structure and narrow particle size distribution, which is an impact modifier with an ideal structure, so that the impact resistance of the modified resin is obviously improved.
The preparation method of the copolymer is beneficial to the growth of the core polymer on the basis of seeds, so that the seeds can be completely coated, the particle size distribution of latex particles is controlled, the influence of the glass transition temperature of the seed layer on the impact resistance of the seed layer serving as an impact modifier is improved, namely, the impact resistance of the seed layer with high glass transition temperature or the seed layer with low glass transition temperature can be improved after the structure modifier is introduced.
Detailed Description
[ Seed layer ]
The seed layer has a particle size of 50-300nm and provides sites for the polymer of the rubber core layer to polymerize and grow during the emulsion polymerization process.
[ Low Tg seed layer Polymer ]
According to an embodiment of the present invention, the preparation monomer of the siloxane-based polymer (belonging to the low glass transition temperature seed layer polymer) includes a first siloxane compound and a second siloxane compound, or further includes a third siloxane compound; preferably, the siloxane polymer is prepared from the preparation monomer by emulsion polymerization;
the first siloxane compound is at least one selected from hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane and decamethyl cyclopentasiloxane, and is preferably octamethyl cyclotetrasiloxane;
The second siloxane compound is selected from at least one of gamma-methacryloxypropyl dimethoxy methyl silane, gamma-methacryloxypropyl diethoxy methyl silane, gamma-methacryloxypropyl trimethoxy silane, methyl vinyl dimethoxy silane and methyl vinyl diethoxy silane;
the third siloxane compound is at least one selected from the group consisting of methoxytrimethylsilane, ethoxytrimethylsiloxane, tetraethoxysilane, hexamethyldisiloxane and methylcyclosiloxane.
According to an embodiment of the present invention, the weight ratio of the first silicone compound, the second silicone compound, and the third silicone compound is (85-99): 1-10): 0-10.
[ High Tg seed layer Polymer ]
According to an embodiment of the present invention, the preparation monomers of the vinyl copolymer (belonging to the high glass transition temperature seed layer polymer) include a hydrophobic vinyl monomer and a hydrophilic vinyl monomer; preferably, the vinyl copolymer is prepared from the preparation monomer by emulsion polymerization;
For example, the hydrophobic vinyl monomer may be selected from styrene, butyl acrylate, preferably styrene;
for example, the hydrophilic vinyl monomer is acrylonitrile;
Preferably, the weight ratio of the hydrophobic vinyl monomer to the hydrophilic vinyl monomer is (70-80): 25-35.
According to an embodiment of the present invention, the raw materials for preparing the vinyl copolymer further include a crosslinking agent;
For example, the crosslinking agent may be at least one selected from divinylbenzene, 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, preferably divinylbenzene;
Preferably, the weight ratio of the hydrophobic vinyl monomer, the hydrophilic vinyl monomer and the crosslinking agent is (70-80): 25-35): 1-5.
[ Core layer ]
According to an embodiment of the invention, the core layer is prepared from raw materials comprising acrylate monomers and a structure-improving agent, or further and a crosslinking agent.
The inventors have found that acrylic impact modifiers are typically prepared by a seed emulsion polymerization process, with the impact properties of the impact modifier being affected differently when the seed polymer has a high or low glass transition temperature. On the one hand, the reason for this is that the difference in the glass transition temperature of the seeds causes, on the other hand, that the different polymers, when used as seeds, have a great influence on the core-shell structural integrity of the end product and on the particle size distribution of the latex. Especially when the seed polymer having a high glass transition temperature contains a hydrophilic monomer, or when the core polymer has a higher hydrophobicity than the seed polymer, since the polymer having a higher hydrophobicity tends to be more distant from the aqueous phase, when the core polymer is an acrylic ester-based hydrophobic monomer, it is more prone to form new micelles, resulting in the emulsion finally obtained not being a complete core-shell structure and having a broader particle size distribution, and the impact resistance of the rubber powder is lowered. In order to solve the problem, a structure improver with stronger hydrophilicity is added, so that the core layer polymer has better hydrophilicity and is more beneficial to growth on seeds; on the other hand, the structure improver also has the function of a cross-linking agent, and can be used together with the cross-linking agent or independently; under the combined action of the two effects, the impact strength of the obtained copolymer can be greatly improved, and the copolymer benefits from a more complete core-shell structure, so that the ASA resin modified by taking the copolymer as an impact modifier has better dyeing property.
The effect of the structure-improving agent is more remarkable when the seeds are hydrophobic polymers with low glass transition temperature, and the structure-improving agent has more obvious impact strength increase compared with a copolymer without the structure-improving agent.
When the structure improver containing two vinyl groups with different reactivity is used, the double bond with low reactivity can be used as a grafting site to be more favorable for the grafting reaction of the shell monomer on the surface of the core polymer, so that the formation of a new shell polymer/water interface is promoted, the existence of a rubber core with incomplete coating is reduced, and the formation of a more ideal core-shell structure is facilitated.
[ Shell layer ]
According to an embodiment of the present invention, the shell layer is prepared from a raw material including a vinylbenzene monomer, a vinylcyano monomer, and a divinyl crosslinking agent;
preferably, the weight ratio of the vinyl benzene monomer, the vinyl cyano monomer and the divinyl crosslinking agent is (70-80): 25-35): 0.1-5;
For example, the vinyl benzene monomer may be at least one selected from styrene, α -methylstyrene, and the vinyl cyano monomer is acrylonitrile;
For example, the divinyl crosslinking agent may be at least one selected from divinylbenzene, 1, 4-butanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, preferably divinylbenzene.
[ Method for producing copolymer ]
The preparation method of the copolymer comprises the following steps:
(1) Preparation of copolymer emulsions
The preparation method adopts a seed emulsion polymerization process and comprises three steps:
i) Seed emulsion preparation
A Low glass transition temperature rubber seed Polymer
A four-necked round bottom flask equipped with a stirrer, a thermometer and a condenser was used as a reactor, and the reactor was purged with high-purity nitrogen for 20 to 50 minutes, after which the system was kept under nitrogen atmosphere. Deionized water, emulsifier, catalyst were added to the reactor, the stirrer was turned on, and the temperature was raised to 60-75 ℃. And then uniformly mixing the first siloxane compound and the second siloxane compound or further comprising the third siloxane compound, adding the mixture into a reactor in a uniform manner for 1 to 3 hours, and after the addition, increasing the reaction temperature to 80 to 90 ℃ and preserving the heat for 5 to 10 hours. Or adopting a one-time feeding mode, preserving the temperature at 70-75 ℃ for 1-3 hours after the feeding is finished, then raising the reaction temperature to 80-90 ℃ and preserving the temperature for 5-10 hours. And after the polymerization is completed, cooling to room temperature, and neutralizing the system to pH6-7 by adopting sodium hydroxide to obtain the seed emulsion.
B high glass transition temperature resin seed polymer
A four-necked round bottom flask equipped with a stirrer, thermometer and condenser was used as a reactor, and the reactor was purged with high purity nitrogen for 30 minutes, after which the system was kept under nitrogen atmosphere. Adding deionized water and an emulsifying agent into a reactor, dissolving, heating the reactor to 60-70 ℃, and adding an initiator. After 5 minutes, adding hydrophobic vinyl monomer, hydrophilic vinyl monomer and cross-linking agent, heating the system to 70-75 ℃, controlling the temperature of the reaction system to be 70-75 ℃, and preserving the temperature for 3-5 hours to prepare the styrene-acrylonitrile copolymer seed latex.
Ii) preparation of core layer emulsion
Adding seed latex, deionized water and an initiator into a reactor; and (2) preparing deionized water, an emulsifying agent, an acrylic ester monomer, a cross-linking agent and a structure improver under the action of a high-speed homogenizer to form a pre-emulsion, heating the reactor to 60-70 ℃, slowly adding the pre-emulsion into the reactor at a constant speed for 1.5-2.5 hours, then keeping the temperature in the reactor at 70-75 ℃, and preserving the temperature for 2-6 hours to form a core layer to obtain the core layer latex.
Iii) Shell emulsion preparation
After the nuclear layer emulsion is preserved, the temperature of the reactor is raised to 60-70 ℃ after stirring and dissolving the reducer, the auxiliary reducer and the deionized water in the reactor. And weighing vinyl phenyl monomer, vinyl cyano monomer, divinyl crosslinking agent, molecular weight regulator, oxidant and emulsifier, and preparing into pre-emulsion under the action of a high-speed homogenizer. When the temperature of the reactor reaches 60+/-2 ℃, adding the pre-emulsion into a reaction system at a constant speed, wherein the feeding time is 2-3 hours, then keeping the temperature in the reactor at 60-70 ℃, and preserving the temperature for 2-6 hours to obtain the copolymer emulsion with the core-shell structure.
(2) Preparation of copolymer powders
And mixing the demulsifier aqueous solution with the copolymer emulsion, washing and drying the obtained solid after the emulsion is fully demulsified, so as to obtain copolymer powder. It is also possible to use a method in which the copolymer emulsion is sprayed in a dryer containing hot air to evaporate water to obtain a copolymer powder.
[ Method for producing modified thermoplastic resin ]
The copolymer powder, the thermoplastic resin and the processing aid are mixed in proportion by a double screw extruder to obtain the modified thermoplastic resin.
The term "emulsion" and "latex" in the present application are the same unless otherwise specified.
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Testing the product performance:
measurement of particle size and distribution of latex particles: the test was performed using a 90PLUS nanoparticle size analyzer manufactured by BROOKHAVEN, U.S. A.A., and the samples were diluted to a suitable concentration with water as the dispersed phase and tested 3 times in parallel.
Determination of impact Strength: according to the requirements of GB/T1843-2008, ASA modified resin is injected into a sheet by an injection molding machine, and the notch impact strength of the cantilever beam is tested.
Example 1
Preparation of seed emulsion
A four-necked round bottom flask equipped with a stirrer, thermometer and condenser was used as a reactor, and the reactor was purged with high purity nitrogen for 30 minutes, after which the system was kept under nitrogen atmosphere. 300 parts by weight of deionized water and 1.05 parts by weight of an alkylphenyl sulfo salt were added to the reactor, and after dissolution, the reactor temperature was raised to 65℃and 0.2 parts by weight of potassium persulfate was added. After 5 minutes, 45 parts by weight of styrene, 15 parts by weight of acrylonitrile and 1.5 parts by weight of divinylbenzene were added, the temperature of the system was raised to 70℃and the temperature of the reaction system was kept at 70 to 75℃for 3 hours, thereby preparing a styrene-acrylonitrile copolymer seed latex.
Preparation of core layer emulsion
Adding 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate into a reactor; and (2) weighing 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate and 0.32 part by weight of monoallyl maleate under the action of a high-speed homogenizer to form a pre-emulsion, heating the reactor to 70 ℃, slowly adding the pre-emulsion into the reactor at a constant speed for 2 hours, then keeping the temperature in the reactor at 70-75 ℃, and preserving the temperature for 3 hours to form a core layer to obtain the core layer latex.
Preparation of shell emulsion
After the nuclear layer emulsion is kept warm, 0.35 weight part of white block, 0.35 weight part of ferrous sulfate (1% aqueous solution) and 10 weight parts of deionized water are hung in the reactor, and the temperature of the reactor is raised to 60-70 ℃ after stirring and dissolving. And 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.2 part by weight of divinylbenzene, 0.08 part by weight of n-dodecyl mercaptan, 0.25 part by weight of cumene hydroperoxide, 0.3 part by weight of alkylphenyl sulfonate and 0.2 part by weight of alkylsulfonyl succinate are weighed and prepared under the action of a high-speed homogenizer to form a pre-emulsion. When the temperature of the reactor reaches 60 ℃, adding the pre-emulsion into a reaction system at a constant speed, wherein the feeding time is 2.5h, then keeping the temperature in the reactor at 60-70 ℃, and preserving the temperature for 3 h to obtain the ASA emulsion with a core-shell structure.
Preparation of ASA rubber powder
Adding 393 parts by weight of deionized water and 5.2 parts by weight of magnesium sulfate heptahydrate into a 1L reactor, stirring and dissolving, heating the system to 75 ℃, slowly dripping the ASA emulsion into the reactor, keeping the temperature in the reactor at not lower than 75 ℃, heating the temperature in the reactor to 85 ℃ after the feeding is finished, preserving the heat for 30 minutes, cooling, discharging, filtering and drying to obtain ASA rubber powder.
Preparation of ASA modified resin
Based on 100 parts of total weight of the blended resin, taking 35 parts by weight of ASA impact rubber powder, 65 parts by weight of AS resin (selected from a table NF 2200), 0.2 part by weight of antioxidant 1076 and 0.2 part by weight of antioxidant 168, uniformly mixing in a high-speed mixer, and carrying out blending granulation by adopting a double-screw extruder to obtain the ASA modified resin.
Example 2
The same procedure as in example 1 was followed except that the core layer emulsion was prepared as follows.
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate and 0.64 part by weight of monoallyl maleate are weighed to prepare a pre-emulsion under the action of a high-speed homogenizer, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, then the temperature in the reactor is kept at 70-75 ℃, and the temperature is kept for 3 hours to form a core layer, so that the core layer latex is obtained.
Example 3
The same procedure as in example 1 was followed except that the core layer emulsion was prepared as follows.
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate, 0.32 part by weight of monoallyl maleate and 0.128 part by weight of 1, 4-butanediol diacrylate are additionally weighed and prepared under the action of a high-speed homogenizer to form a pre-emulsion, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, then the temperature in the reactor is kept at 70-75 ℃, and the core layer is formed, so that the core layer latex is obtained.
Example 4
The same procedure as in example 1 was followed except that the core layer emulsion was prepared as follows.
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate, 0.192 part by weight of polyethylene glycol diacrylate (Mw=700) and 0.128 part by weight of 1, 4-butanediol diacrylate are additionally weighed, a pre-emulsion is prepared under the action of a high-speed homogenizer, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, the temperature in the reactor is kept at 70-75 ℃, and the core layer is formed after the temperature is kept for 3 hours, so that the core layer latex is obtained.
Example 5
The same procedure as in example 1 was followed except that the following procedure was used in the preparation of the seed emulsion.
Seed emulsion preparation: a four-necked round bottom flask equipped with a stirrer, thermometer and condenser was used as a reactor, and the reactor was purged with high purity nitrogen for 30 minutes, after which the system was kept under nitrogen atmosphere. 240 parts of deionized water, 0.25 part of alkylphenyl sulfonate, and the stirrer was started and the temperature was raised to 70 ℃. Then, 50 parts by weight of octamethyl cyclotetrasiloxane and 0.5 part of gamma- (methyl) acryloyloxy propyl diethoxymethyl silane are uniformly mixed, the mixture is added into a reactor at a constant speed by a peristaltic pump for 2 hours, and the reaction temperature is increased to 80 ℃ after the addition is completed, and the temperature is kept for 6 hours. And after the polymerization is completed, cooling to room temperature, and neutralizing the system to pH6-7 by adopting sodium hydroxide to obtain the seed emulsion.
Example 6
The same procedure as in example 5 was followed except that the following procedure was used in the preparation of the core layer emulsion
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate, 0.32 part by weight of monoallyl maleate and 0.128 part by weight of 1, 4-butanediol diacrylate are additionally weighed and prepared under the action of a high-speed homogenizer to form a pre-emulsion, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, then the temperature in the reactor is kept at 70-75 ℃, and the core layer is formed, so that the core layer latex is obtained.
Comparative example 1
The same procedure as in example 1 was followed except that the following procedure was used in the preparation of the core layer emulsion
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate and 0.192 part by weight of 1, 4-butanediol diacrylate are weighed to prepare a pre-emulsion under the action of a high-speed homogenizer, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, then the temperature in the reactor is kept at 70-75 ℃, and the temperature is kept for 3 hours to form a core layer, so that the core layer latex is obtained.
Comparative example 2
The same procedure as in example 5 was followed except that the following procedure was used in the preparation of the core layer emulsion
Preparation of core layer emulsion: 48 parts by weight of seed latex, 40 parts by weight of deionized water and 0.2 part by weight of potassium persulfate are added into a reactor, 60 parts by weight of deionized water, 0.27 part by weight of alkylphenyl sulfo salt, 64 parts by weight of butyl acrylate and 0.192 part by weight of 1, 4-butanediol diacrylate are weighed to prepare a pre-emulsion under the action of a high-speed homogenizer, the reactor is heated to 70 ℃, the pre-emulsion is slowly added into the reactor at a constant speed for 2 hours, then the temperature in the reactor is kept at 70-75 ℃, and the temperature is kept for 3 hours to form a core layer, so that the core layer latex is obtained.
TABLE 1
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A copolymer, wherein the copolymer comprises:
A rubber core layer consisting of a seed layer and a core layer;
the seed layer is a siloxane polymer or vinyl copolymer;
the core layer is an acrylic polymer prepared by emulsion polymerization, and is coated on the surface of the seed layer, and a structure improver is added in the preparation process of the core layer, wherein the structure improver contains at least one vinyl group and at least one hydrophilic group;
And the shell layer is coated on the surface of the rubber core layer.
2. The copolymer of claim 1, wherein the hydrophilic group is selected from at least one of hydroxyl, carboxyl, amino, acetal groups.
3. The copolymer according to claim 1 or 2, wherein the structure-improving agent contains at least two non-conjugated vinyl groups and at least one hydrophilic group; for example, the structure-improving agent is at least one selected from polyethylene glycol diacrylate, 4- (2- (methacryloyloxy) ethoxy) -4-oxobut-2-enoic acid, mono [2 (1-oxo-2-propenyl) oxyethyl ] maleate, monoallyl maleate, 2-hydroxy-1, 3-propanediol bis (2-methyl-2-acrylic acid), diallyl isocyanurate, trimethylolpropane diallyl ether;
alternatively, the structure-improving agent contains one vinyl group and at least one hydrophilic group, and may undergo a condensation reaction, such as N-methylolacrylamide, when the core layer is prepared.
4. A copolymer according to any of claims 1 to 3, wherein the core layer is prepared from raw materials comprising acrylate monomers and a structure-improving agent;
preferably, the weight ratio of the structure improver to the acrylate monomer is (0.1-10): 100;
preferably, the acrylate monomer is at least one selected from methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate.
5. The copolymer of any of claims 1-4, wherein the seed layer is prepared from a feedstock comprising a first siloxane compound and a second siloxane compound, or further comprising a third siloxane compound;
or the seed layer is prepared from raw materials comprising a hydrophobic vinyl monomer and a hydrophilic vinyl monomer;
The shell layer is prepared from raw materials including vinyl benzene monomer, vinyl cyano monomer and divinyl crosslinking agent.
6. The copolymer according to any one of claims 1 to 5, wherein the seed layer is 0.5 to 50 parts by weight, the core layer is 40 to 89.5 parts by weight, and the shell layer is 10 to 59.5 parts by weight, relative to the copolymer;
and/or the particle size of the seed layer is 50-300nm; and/or the particle size of the rubber core layer is 100-500nm; and/or the particle size of the copolymer is 200-700nm.
7. A process for the preparation of a copolymer as claimed in any one of claims 1 to 6, comprising: sequentially preparing a seed layer, a core layer and a shell layer by an emulsion polymerization method, wherein the structure improver is added in the preparation process of the core layer.
8. The preparation method according to claim 7, characterized in that the preparation method comprises:
(1) Preparing a seed emulsion from the first and second silicone compounds, or further monomers including a third silicone compound, by emulsion polymerization; or alternatively
Preparing seed emulsion from the hydrophobic vinyl monomer and the hydrophilic vinyl monomer through emulsion polymerization;
(2) Mixing acrylate monomers and a structure improver or further mixing the acrylate monomers and a cross-linking agent for pre-emulsification, adding the obtained core layer pre-emulsion into a seed emulsion reaction system, and performing emulsion polymerization to form a core layer to obtain core layer emulsion;
(3) Mixing and pre-emulsifying raw materials comprising vinyl benzene monomer, vinyl cyano monomer and divinyl crosslinking agent, adding the obtained shell pre-emulsion into the core-layer emulsion system, and performing emulsion polymerization to obtain emulsion of the copolymer;
preferably, the preparation method of the copolymer further comprises a step (4), wherein the product of the step (3) is mixed with a demulsifier, and the solid obtained by demulsification is subjected to post-treatment.
9. Use of the copolymer according to any of claims 1 to 6 as impact modifier for the preparation of thermoplastic resins.
10. A thermoplastic resin comprising the copolymer according to any one of claims 1 to 6.
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