CN1063186C - Process for preparing core-shell particle toughened polystyrene material - Google Patents
Process for preparing core-shell particle toughened polystyrene material Download PDFInfo
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- CN1063186C CN1063186C CN97106350A CN97106350A CN1063186C CN 1063186 C CN1063186 C CN 1063186C CN 97106350 A CN97106350 A CN 97106350A CN 97106350 A CN97106350 A CN 97106350A CN 1063186 C CN1063186 C CN 1063186C
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- shell
- core
- vinylbenzene
- shell particle
- polystyrene material
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- 239000002245 particle Substances 0.000 claims abstract description 65
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011258 core-shell material Substances 0.000 claims abstract description 54
- 239000004793 Polystyrene Substances 0.000 claims abstract description 38
- 229920002223 polystyrene Polymers 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- -1 alkenyl arene Chemical class 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 14
- ADQIFLCRXCDJNL-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(CC)C1=CC=CC=C1 Chemical class C(C(=C)C)(=O)OCCCC(CC)C1=CC=CC=C1 ADQIFLCRXCDJNL-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 235000014380 magnesium carbonate Nutrition 0.000 claims description 3
- 229960001708 magnesium carbonate Drugs 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 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
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000035939 shock Effects 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 3
- 239000004033 plastic Substances 0.000 abstract description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 32
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000000178 monomer Substances 0.000 description 21
- 239000000839 emulsion Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000003995 emulsifying agent Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000007605 air drying Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 239000007859 condensation product Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 208000031639 Chromosome Deletion Diseases 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to technique for preparing toughening and modifying polystyrene material of core-shell particles. In the technique, water and core-shell copolymerizad particulates whose average particle diameter is from 60 to 150 nanometers are first added in styrene; then, dispersing agents selected form polyvinyl alcohol, carboxymethyl cellulose, magnesium carbonate and calcium carbonate and initiator selected from dibenzoyl peroxide or azodiisobutyronitrile are added; the obtained mixture is stirred and polymerize at 85 to 90DEGC; the obtained matter is separated, washed by water and dried to obtain completed products. The toughening and modifying material prepared by the technique has the transparence of pure polystyrene and increases the shock strength by one time than that of the pure polystyrene at the same time; the toughening and modifying material can be used in plastic industry.
Description
The present invention relates to core-shell particle toughened modified polystyrene material preparation technology.Particularly core-shell particle toughened modification transparent polystyrene material preparation process.
Polystyrene is the most facile kind in the transparent plastics, but owing to himself fragility shortcoming, is very limited in the application, only is used for low grade products at present.So far, people have done a large amount of work and have been used for the toughness reinforcing of p-poly-phenyl ethene, as: the terpolymer (ABS resin) of the graft copolymerization of vinylbenzene and polyhutadiene (high-impact polystyrene), vinylbenzene and vinyl cyanide, divinyl and the blend of polystyrene and other polymkeric substance etc., but the general transparency of the material of these method gained is relatively poor.Because the composite emulsion polymerization technology can design the macromolecule emulsion microballoon, regulate copolymer component from microcosmic.The refractive index of nucleocapsid and base material is complementary, changes the composite emulsion polymerization condition simultaneously and make the core-shell particle size be lower than 0.1 μ m, can not influenced the transparent polystyrene of the transparency through physical mixed.Along with going deep into that particulate blending toughening, enhancing are studied, people have been used for how sharp core-shell particle the blending and modifying of plastics.What the usefulness U.S. Rohm and Haas companies such as A.Maazouz.H.Sautereau of France provided among the document Polym.Mater.Sci.Eng.1993.70.13-14 is glue nuclear with butyl polyacrylate or polyhutadiene, is that the core-shell particle (median size 300nm) of shell has been made the research report to TOUGHENING MODIFICATION OF EPOXY RESINS with the crosslinked polymethylmethacrylaparticles.Can improve the toughness of Resins, epoxy greatly and don't reduce its thermal characteristics with this core-shell particle, toughness reinforcing degree can be regulated by the core-shell particle structure.But the particulate mean sizes is the transparency that 300nm obviously can influence base material, the transparent problem of not mentioned material still in this report.
For overcoming the shortcoming that exists in the above-mentioned document, the purpose of this invention is to provide a kind of technology for preparing core-shell particle toughened polystyrene material, make the material that makes both have the transparency of pure polystyrene, have simultaneously than the better shock strength of pure polystyrene.
The objective of the invention is to realize: a kind of preparation core-shell particle toughened polystyrene material technology by following technical scheme, at first in vinylbenzene, add the core-shell particle that entry and median size are 60～150 nanometers, in parts by weight, vinylbenzene: water is 1: 1～3.5, vinylbenzene: core-shell particle is 80～99: 1～20, and then adding is selected from polyvinyl alcohol, carboxymethyl cellulose, magnesiumcarbonate, the dispersion agent of lime carbonate and be selected from dibenzoyl peroxide, the initiator of Diisopropyl azodicarboxylate, wherein by weight percentage, dispersant dosage is 0.5～3% of a vinylbenzene consumption, initiator amount is 0.2～2% of a vinylbenzene consumption, under agitation, polymerization reaction take place under 85～90 ℃ of conditions of temperature is again through separating, washing, the dry toughening material finished product that gets.
In the technique scheme in parts by weight, vinylbenzene: water is 1: 1.5～2.5, vinylbenzene: core-shell particle is 90～97: 3～10, dispersant dosage is 1～2% of a vinylbenzene consumption, initiator amount is 0.3～1% of a vinylbenzene consumption, and core-shell particle median size preferable range is 80～120 nanometers.One of used core-shell particle is examined to containing alkenyl arene segment and linking agent for comprising nuclear, shell, and shell is the segment that contains alkenyl arene, and the segment of shell links by an end and the nuclear phase of linking agent.Used core-shell particle two for comprising nuclear, shell, nuclear contains alkenyl arene segment, acrylate segment and linking agent, shell is the segment that contains alkenyl arene, the segment of shell is by an end and nuclear phase binding of linking agent.
In above-mentioned two kinds of core-shell particles, nuclear is 1: 1.279～1.830 with the weight ratio of shell, and alkenyl arene is vinylbenzene, alpha-methyl styrene, p-methylstyrene, and preferred version is a vinylbenzene.Linking agent is two methacryloxypropyl phenyl-propanes, polyethersulfone diene macromonomer or its mixture.Acrylate is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate, and preferred version is a butyl acrylate.
Above-mentioned cross-linked core-shell copolymerized particle is two kinds of soft nuclear duricrust particulate and stone duricrust particulates.Its preparation method is that soft nuclear duricrust particulate adopts the multi-step emulsion polymerization method synthetic, when the fs forms nuclear, add acrylate and alkenyl arene, with two methacryloxypropyl phenyl-propanes (BVA) or polyethersulfone diene macromonomer (BVPES) linking agent copolymerzation with cross-linking with it, subordinate phase adds vinylbenzene again and forms shell, has the cross-linker molecules chain to be associated between nuclear and the shell.The gained emulsion through breakdown of emulsion, methyl alcohol wash, drying etc. promptly gets soft nuclear duricrust particulate powder.
In the above-mentioned core-shell particle with crosslinked nuclear, double methyl methacrylate class linking agent can be two methacryloxypropyl phenyl-propanes (BVA) or polyethersulfone diene macromonomer (BVPES) consumption account for nuclear partial monosomy gross weight 0.1～20%, preferable range 1～5%.Content of butyl acrylate is 5～50% of nuclear partial monosomy weight in nuclear, preferable range 10～30%.Used initiator can be Potassium Persulphate (K
2S
2O
8), ammonium persulphate [(NH
4)
2S
2O
8] and the redox system of above-mentioned two kinds of initiators and ferrous sulfate, consumption is 0.1～1% of a monomer total amount, preferable range is 0.2～0.5%.The emulsifying agent sodium oleate divides two portions to add in the polyreaction of core-shell particle, when a part is nucleation, be 0.5～10% of monomer weight in the nuclear, decide on want size, generally more suitable about 1～2%: adding sodium oleate during the polymerization of second section shell is about 1% of shell monomers total amount, splashes into simultaneously with initiator.The total amount of water is 1.5～3 times of monomer total amount in the prescription that feeds intake.
Synthesizing when the fs forms nuclear of stone duricrust core-shell particle, is nuclear with two methacryloxypropyl phenyl-propanes (BVA) or polyethersulfone diene macromonomer (BVPES) with the alkenyl arene copolymerzation with cross-linking, subordinate phase adds alkenyl arene again and forms shell, has molecular chain to be associated between nuclear and the shell.The gained emulsion through breakdown of emulsion, methyl alcohol wash, drying etc. promptly gets stone duricrust particulate powder,
In the above-mentioned core-shell particle with crosslinked nuclear, double methyl methacrylate class linking agent can be two methacryloxypropyl phenyl-propanes (BVA) or polyethersulfone diene macromonomer (BVPES) consumption account for nuclear partial monosomy gross weight 0.1～20%, preferable range 1～5%.Used initiator can be Potassium Persulphate (K
2S
2O
8), ammonium persulphate [(NH
4)
2S
2O
8] and the redox system of above-mentioned two kinds of initiators and ferrous sulfate, consumption is 0.1～1% of a monomer total amount, preferable range is 0.2～0.5%.The emulsifying agent sodium oleate divides two portions to add in the polyreaction of core-shell particle, when a part is nucleation, be 0.5～10% of monomer weight in the nuclear, decide on want size, generally more suitable about 1～2%: adding sodium oleate during the polymerization of second section shell is about 1% of shell monomers total amount, splashes into simultaneously with initiator.The total amount of water is 1.5～3 times of monomer total amount in the prescription that feeds intake.
The present invention is owing to adopt the cross-linked core-shell particulate of 60～150 nanometers, with the toughness reinforcing transparent polystyrene of suspension polymerization process on the throne, and rationally control consumption and other processing parameter of core-shell particle, water, vinylbenzene, initiator, dispersion agent, make the toughening material that makes both keep the transparency of pure polystyrene, make the material modified shock strength of polystyrene increase nearly 1 times of fourth simultaneously, obtained effect preferably.
[embodiment 1]
Sodium oleate 1 gram is put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (vinylbenzene 45 grams, butyl acrylate 5 grams, two methacryloxypropyl phenyl-propane 0.82 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue bag, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (65 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.2 gram), H
2The mixture of O (25 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 60 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 2]
Sodium oleate 1 gram is put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (vinylbenzene 30 grams, butyl acrylate 20 grams, two methacryloxypropyl phenyl-propane 0.82 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator (NH
4)
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (65 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), (NH
4)
2S
2O
8(0.2 gram), H
2The mixture of O (25 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 60 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 3]
Sodium oleate 1.5 grams are put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing, add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (vinylbenzene 40 grams, methyl acrylate 5 grams, two methacryloxypropyl phenyl-propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 4]
Sodium oleate 1.5 grams are put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (alpha-methyl styrene 40 grams, methyl acrylate 5 grams, two methacryloxypropyl phenyl-propane 0.8 gram), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.16 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃, and suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 5]
Sodium oleate 1.5 grams are put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (p-methylstyrene 45 grams, butyl acrylate 7 grams, two methacryloxypropyl phenyl-propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.20 gram) reaction 1 hour, this moment, system was blue bag, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 6]
Sodium oleate 1.5 grams are put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (alpha-methyl styrene 40 grams, two methacryloxypropyl phenyl-propane 1.0 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.18 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (75 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours, stops promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 7]
Sodium oleate 1.5 grams are put into there-necked flask, add 1 gram sodium bicarbonate and letting nitrogen in and deoxidizing.Add 140 gram deionized water dissolving and turn on agitator, treat that emulsifying agent sodium oleate and sodium bicarbonate dissolve the back (about 20 minutes) that is uniformly dispersed, add first monomer mixture (vinylbenzene 40 grams, two methacryloxypropyl phenyl-propane 1.5 grams), after continuing to stir 20 minutes abundant dispersions, move in 95 ℃ of water-baths, add initiator K
2S
2O
8(with 20 ml deionized water dissolving, 0.2 gram) reaction 1 hour, this moment, system was blue look, was cooled to 80 ℃.Suction filtration is removed condensation product, adds 0.1 gram sodium oleate again, simultaneously drip styrene (70 gram), acetone (7.5ml) mixture and sodium oleate (0.5 gram), K
2S
2O
8(0.4 gram), H
2The mixture of O (20 gram) continues reaction 2～2.5 hours.Stop promptly to get the cross-linked core-shell copolymerized particle emulsion.
Above-mentioned emulsion is diluted to solid content about 5% through methyl alcohol, with 5% salt naphtenic acid, adds about 580 milliliters altogether, heating is changed 10～20 minutes with fixed attention, and precipitation is through methanol wash centrifugal settling, prior to 70 ℃ of forced air dryings, in 40 ℃ of vacuum-dryings 24 hours, promptly get fine-particle powder again.[embodiment 8]
In 500 milliliters of there-necked flasks, add 200 milliliters of deionized waters, polyethylene of dispersing agent alcohol 2 grams, newly steam core-shell copolymerized particle 10 grams (particle size 129nm) and initiator dibenzoyl peroxide 0.5 gram that monomer styrene 90 grams, embodiment 1 make, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity is in the hope of obtaining suitable particle size in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation.This material in 215 ℃ of injection moldings or in 200 ℃ hot-forming be test bars, be 90% (wavelength 700nm) through surveying light transmission, shock strength is 6.38KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22.03 times.[embodiment 9]
200 milliliters of deionized waters of adding, dispersion agent carboxymethyl cellulose 2 restrain, newly steam core-shell copolymerized particle 5 grams (particle size 129nm) and initiator dibenzoyl peroxide 1 gram that monomer styrene 95 restrains, embodiment 3 makes in 500 milliliters of there-necked flasks, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity is in the hope of obtaining suitable particle size in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation.Behind the processing batten, light transmission is 90% (wavelength 700nm), and shock strength is 6.30KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22.03 times.[embodiment 10]
250 milliliters of deionized waters of adding, dispersion agent magnesiumcarbonate 3 restrain, newly steam core-shell copolymerized particle 5 grams (particle size 105nm) and initiator Diisopropyl azodicarboxylate 1 gram that monomer styrene 95 restrains, embodiment 4 makes in 500 milliliters of there-necked flasks, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity obtains suitable particle size with marrow in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation, and behind the processing batten, light transmission is 89% (wavelength 700nm), and shock strength is 6.27KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22.0 times.[embodiment 11]
150 milliliters of deionized waters of adding, dispersion agent lime carbonate 4 restrain, newly steam core-shell copolymerized particle 3 grams (particle size 90nm) and initiator Diisopropyl azodicarboxylate 2 grams that monomer styrene 97 restrains, implementation column 5 makes in 500 milliliters of there-necked flasks, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity is in the hope of obtaining suitable particle size in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation.Behind the processing batten, light transmission is 88% (wavelength 700nm), and shock strength is 6.0KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
21.9 times.[embodiment 12]
In 500 milliliters of there-necked flasks, add 200 milliliters of deionized waters, polyethylene of dispersing agent alcohol 2 grams, newly steam core-shell copolymerized particle 8 grams (particle size 105nm) and initiator dibenzoyl peroxide 1 gram that monomer styrene 92 grams, embodiment 6 make, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity is in the hope of obtaining suitable particle size in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation.Behind the processing batten, light transmission is 88% (wavelength 700nm), and shock strength is 5.90KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
21.87 times.[embodiment 13]
In 500 milliliters of there-necked flasks, add 200 milliliters of deionized waters, polyethylene of dispersing agent alcohol 3 grams, newly steam core-shell copolymerized particle 5 grams (particle size 129nm) and initiator dibenzoyl peroxide 0.8 gram that monomer styrene 95 grams, embodiment 7 make, stirring and dissolving is uniformly dispersed, letting nitrogen in and deoxidizing, be warming up to 85～90 ℃ of polymerizations 4 hours, the control stirring velocity is in the hope of obtaining suitable particle size in the polymerization process.Product is drying to obtain pearl modification transparent polystyrene through separation.Behind the processing batten, light transmission is 89% (wavelength 700nm), and shock strength is 6.30KJ/m
2, be pure polystyrene shock strength 3.14KJ/m
22 times.[comparative example]
Behind pure polystyrene processing batten, measuring its light transmission is 88～89% (wavelength 700mm), and shock strength is 3.14KJ/m
2
Claims (9)
1. one kind prepares core-shell particle toughened polystyrene material technology, it is characterized in that at first in vinylbenzene, adding the core-shell particle that entry and median size are 60～150 nanometers, in parts by weight, vinylbenzene: water is 1: 1～3.5, vinylbenzene: core-shell particle is 80～99: 1～20, and then adding is selected from polyvinyl alcohol, carboxymethyl cellulose, magnesiumcarbonate, the dispersion agent of lime carbonate and be selected from dibenzoyl peroxide, the initiator of Diisopropyl azodicarboxylate, wherein by weight percentage, dispersant dosage is 0.5～3% of a vinylbenzene consumption, initiator amount is 0.2～2% of a vinylbenzene consumption, core-shell particle comprises nuclear, shell, nuclear is for containing alkenyl arene segment and linking agent, shell is the segment that contains alkenyl arene, the segment of shell links by an end and the nuclear phase of linking agent, and nuclear is 1: 1.279～1.830 with the weight ratio of shell, under agitation, polymerization reaction take place under 85～90 ℃ of conditions of temperature is again through separating, washing, the dry finished product that gets.
2. according to the described preparation core-shell particle toughened polystyrene material of claim 1 technology, it is characterized in that in parts by weight vinylbenzene: water is 1: 1.5～2.5, vinylbenzene: core-shell particle is 90～97: 3～10.
3. according to the described preparation core-shell particle toughened polystyrene material of claim 1 technology, it is characterized in that by weight percentage that dispersant dosage is 1～2% of a vinylbenzene consumption, initiator amount is 0.3～1% of a vinylbenzene consumption.
4. according to the described preparation core-shell particle toughened polystyrene material of claim 1 technology, it is characterized in that core-shell particle comprises nuclear, shell, nuclear contains alkenyl arene segment, acrylate segment and linking agent, shell is the segment that contains alkenyl arene, and the segment of shell links by an end and the nuclear phase of linking agent.
5. according to claim 1 or 4 described preparation core-shell particle toughened polystyrene material technologies, it is characterized in that alkenyl arene is vinylbenzene, alpha-methyl styrene, p-methylstyrene.
6. according to the described preparation core-shell particle toughened polystyrene material of claim 5 technology, it is characterized in that alkenyl arene is a vinylbenzene.
7. according to claim 1 or 4 described preparation core-shell particle toughened polystyrene material technologies, it is characterized in that linking agent is two methacryloxypropyl phenyl-propanes, polyethersulfone diene macromonomer or its mixture.
8. according to the described preparation core-shell particle toughened polystyrene material of claim 4 technology, it is characterized in that acrylate is methyl acrylate, ethyl propenoate, propyl acrylate, butyl acrylate.
9. described according to Claim 8 preparation core-shell particle toughened polystyrene material technology is characterized in that acrylate is a butyl acrylate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106350A CN1063186C (en) | 1997-04-03 | 1997-04-03 | Process for preparing core-shell particle toughened polystyrene material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106350A CN1063186C (en) | 1997-04-03 | 1997-04-03 | Process for preparing core-shell particle toughened polystyrene material |
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| CN1194992A CN1194992A (en) | 1998-10-07 |
| CN1063186C true CN1063186C (en) | 2001-03-14 |
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| CN97106350A Expired - Fee Related CN1063186C (en) | 1997-04-03 | 1997-04-03 | Process for preparing core-shell particle toughened polystyrene material |
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| CN103387717B (en) * | 2012-05-07 | 2015-09-02 | 中国石油化工股份有限公司 | A kind of organic/inorganic composite hollow microballoon and its preparation method and application |
| GB201522691D0 (en) | 2015-12-22 | 2016-02-03 | Lucite Internat Speciality Polymers And Resins Ltd | Additive manufacturing composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684696A (en) * | 1986-03-14 | 1987-08-04 | General Electric Company | Impact modified polyphenylene compositions |
| EP0465792A2 (en) * | 1990-05-11 | 1992-01-15 | Takeda Chemical Industries, Ltd. | Multi-layer polymer, thermoplastic resin composition containing the same, and shaped article produced using the composition |
-
1997
- 1997-04-03 CN CN97106350A patent/CN1063186C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4684696A (en) * | 1986-03-14 | 1987-08-04 | General Electric Company | Impact modified polyphenylene compositions |
| EP0465792A2 (en) * | 1990-05-11 | 1992-01-15 | Takeda Chemical Industries, Ltd. | Multi-layer polymer, thermoplastic resin composition containing the same, and shaped article produced using the composition |
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