CN104910311A - Large-particle-size hollow polymer microsphere, and preparation method thereof - Google Patents
Large-particle-size hollow polymer microsphere, and preparation method thereof Download PDFInfo
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- CN104910311A CN104910311A CN201510273888.0A CN201510273888A CN104910311A CN 104910311 A CN104910311 A CN 104910311A CN 201510273888 A CN201510273888 A CN 201510273888A CN 104910311 A CN104910311 A CN 104910311A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000004005 microsphere Substances 0.000 title abstract description 18
- 229920000642 polymer Polymers 0.000 title abstract description 11
- 239000004793 Polystyrene Substances 0.000 claims abstract description 54
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- 229920002223 polystyrene Polymers 0.000 claims abstract description 54
- 239000006185 dispersion Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 230000008961 swelling Effects 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 28
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 15
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000011859 microparticle Substances 0.000 claims description 37
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 32
- 238000010907 mechanical stirring Methods 0.000 claims description 28
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004575 stone Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 19
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical group CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 12
- 238000005502 peroxidation Methods 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004815 dispersion polymer Substances 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- 239000012986 chain transfer agent Substances 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical class CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 claims description 2
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000012774 insulation material Substances 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000005728 strengthening Methods 0.000 abstract 1
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 30
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000004945 emulsification Methods 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- 229920003081 Povidone K 30 Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 241001411320 Eriogonum inflatum Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000006424 Flood reaction Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a large-particle-size hollow polymer microsphere, and a preparation method thereof. According to the preparation method, a low molecular weight polystyrene seed emulsion and a metal hydroxide which is taken as a dispersant are prepared firstly; an oil phase is prepared via mixing of a vinyl aromatic monomer containing an oil-soluble initiator, methyl acrylate and/or ethyl acrylate, a cross-linking agent, and a pore forming material, and the oil phase, the polystyrene seed emulsion, and the metal hydroxide are subjected to mixing and swelling; high-speed shearing emulsifying dispersion is carried out, an obtained emulsified dispersion liquid is delivered into a reactor for micro-suspension polymerization; and at last the large-particle-size hollow polymer microsphere is obtained, wherein the morphology of the large-particle-size hollow polymer microsphere is nonspherical. The large-particle-size hollow polymer microsphere possesses high decomposition resistance, low apparent density, and excellent organic solvent resistance, and is suitable for preparation of heat-resistant white pigments, thermal insulation materials, lightweight filling materials, sealing rubber-strengthening agents, liquid ingredient gradually releasing agents, and film slipping agents.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of preparation method of Procedure of Polymerized Micro-Particles with Hollow.Specifically, the invention provides a kind of technical matters of Large stone Procedure of Polymerized Micro-Particles with Hollow.
Background technology
Compared to solid microsphere material, after the sub-emulsion drying of hollow minute particle, the water of inside particles disappears and forms single or multiple emptying aperture, low density is shown because inside has cavity structure, high-specific surface area and can the features such as guest molecule be held, therefore at coating, papermaking, electronics, catalysis, be separated, the various fields such as biological medicine have wide application, such as in paper industry, coating significantly lightweight not only can be made for part titanium dioxide with hollow minute particle filial generation, and the organic hollow micropartical of thermoplastically under conditions of heat and pressure, the yielding surface obtaining high smoothness is to realize high blank sheet of paper gloss, organic hollow micropartical internal cavity structures, outer cover height are crosslinked and be easy to dispersed in organic polymer base material, can be used as the important materials of caulking gum lightweight and reinforcement in space industry.In addition, at white ink, heat-sensitive recording material, economize energy heat insulation material material, field hollow minute particle such as optical thin film also have extremely important using value.
No. 2005-206752, Japanese Patent Laid-Open provides a kind of preparation method of the polymeric hollow microsphere used in coated paper manufactures.Under the existence of specific surfactant, unsaturated monomer 20 ~ 60 % by weight containing acid functional group and possible other unsaturated monomer 80 ~ 40 % by weight copolymerization of copolymerization are formed core polymkeric substance, then by the unsaturated monomer 0 ~ 15 % by weight containing acid functional group and possible other unsaturated monomer 100 ~ 85 % by weight of copolymerization, outside core polymer, copolymerization forms embracing layer, by and the aqueous dispersion of Procedure of Polymerized Micro-Particles with Hollow to be formed with space of acid functional group in core polymkeric substance.But the Procedure of Polymerized Micro-Particles with Hollow that this method obtains is double-layer structure, and the polymkeric substance of inner alkali-soluble is easily spread to aqueous phase by embracing layer, thickening can occur during standing storage.
No. 2010-189606, Japanese Patent Laid-Open provides the preparation method of a kind of macroparticle footpath cross-linking type polymeric hollow microsphere.First synthesize low-molecular-weight Non-cross-linked polystyrene microballoon, then with this microballoon for seed; Using the mixture of the monomer containing oil soluble peroxides class initiator, linking agent and pore-creating solvent as oil phase; Then under the existence of emulsifying agent, both are mixed, be warming up to 85 DEG C of polymerizations after stirring placement 24h is swelling, obtain polymer microballoon emulsion, last centrifugation, macroparticle footpath cross-linking type polymeric hollow microsphere can be obtained through vacuum-drying removing pore-creating solvent.Can only obtain spherical hollow particle by the method, and voidage is low, particle footpath is excessive, and polymerization stability is poor.
Summary of the invention
For the defect of prior art, the object of the present invention is to provide a kind of Large stone Procedure of Polymerized Micro-Particles with Hollow, for aspherical, this Procedure of Polymerized Micro-Particles with Hollow has the features such as high voidage, high heat resistance, low apparent density and good organic solvent resistance thereof.
Another object of the present invention is to the preparation method providing a kind of above-mentioned Large stone Procedure of Polymerized Micro-Particles with Hollow, the method is simple to operate, and reaction conditions is gentle, and the Large stone Procedure of Polymerized Micro-Particles with Hollow obtained is separated easily.
The present invention utilizes under polystyrene seed emulsion exists, with metal hydroxides colloid for dispersion agent, adopt microsuspension by methyl acrylate MA or ethyl propenoate EA monomer, carry out being polymerized obtaining polymeric hollow microsphere under oil-soluble initiator with vinyl aromatic monomers.Its formation mechenism is specific as follows: in microsuspension process, first oil-soluble initiator decomposition generation free radical polymerization starts, because in system, the reactive behavior of methacrylate monomer MA and/or acrylic acid ethyl ester monomer EA is higher, and vinyl aromatic monomers is due to the existence of self conjugated structure, its reactive behavior is lower, so methyl acrylate MA and/or ethyl propenoate EA is polymerized sooner than vinyl aromatic monomers, therefore initial reaction stage mainly forms polymethyl acrylate containing a small amount of vinyl aromatic monomers unit and/or polyethyl acrylate (PMA and/or PEA) chain free radical and/segmented copolymer microcell, while polyreaction carries out, the segmented copolymer microcell that MA and/or EA structural unit is rich in is under high-temperature alkaline environment, there is hydrolysis reaction, generate hydrophilic radical COONa/K/Li and COO-, water-swelling, on the other hand because low-molecular-weight polystyrene microballoon part in system is dissolved in polymerization single polymerization monomer and pore-forming material in swelling process, along with the carrying out of polyreaction, the polystyrene microsphere part of dissolving is separated out, and then be separated, water-swelling, therefore in the course of the polymerization process because of the stress difference of these two aspects effect, the aspheric special-shaped hollow structure of final formation.
To achieve these goals, present invention employs following technical scheme:
Large stone Procedure of Polymerized Micro-Particles with Hollow, in aspherical, its median size is 15 ~ 50 μm, and porosity is 10 ~ 50%, 10% weight minimizing temperature is 300 ~ 480 DEG C, and apparent density is 0.1 ~ 0.6g/cm3, pH is 7.2 ~ 11.0.
The preparation method of above-mentioned Large stone Procedure of Polymerized Micro-Particles with Hollow, comprises the following steps:
Step one, the preparation of low-molecular-weight polystyrene seed emulsion;
Step 2, the preparation of metal hydroxides dispersion agent;
Step 3, the oil phase 55 ~ 98wt% vinyl aromatic monomers being dissolved with oil-soluble initiator and 2 ~ 45wt% methyl acrylate and/or ethyl propenoate, linking agent and pore-forming material are mixed to form carries out with polystyrene seed emulsion and metal hydroxides dispersion agent mixing, swelling;
Step 4, the mixed dispersion liquid obtained after swelling is joined in high speed shear dispersion machine and carries out high speed shear emulsion dispersion, after end to be emulsified, emulsified dispersed liquid is added in reactor, be warming up to 50 ~ 95 DEG C, carry out microsuspension under mechanical stirring, obtain the sub-emulsion of Large stone Procedure of Polymerized Micro-Particles with Hollow.
In above-mentioned preparation method, the preparation of described low-molecular-weight polystyrene seed emulsion and metal hydroxides dispersion agent can adopt the preparation method of this area routine when being not particularly illustrated, namely adopt ordinary method by Material synthesis polystyrene seed emulsion and metal hydroxides dispersion agent.
As a kind of optimal way, in described step one, the preparation of described low-molecular-weight polystyrene seed emulsion can adopt dispersion polymerization processes to prepare, when adopting dispersion polymerization processes polymerization, concrete steps are in reactor, add the Organic Alcohol solution being dissolved with high polymer dispersion, under agitation the styrene monomer containing oil-soluble initiator, chain-transfer agent is joined in reactor, be warming up to 50 ~ 80 DEG C, insulation reaction 6 ~ 48h, obtains low-molecular-weight polystyrene micropartical emulsion; Adopt centrifugation precipitation, washing, removing high polymer dispersion, by ps particle from Organic Alcohol mutually transfer to aqueous phase and form water-based polystyrene seed emulsion.
In above-mentioned preparation method, as a kind of optimal way, in described step one, the solid content of described low-molecular-weight polystyrene seed emulsion is 20 ~ 40%, and median size is 2 ~ 8 μm, and number-average molecular weight is 1000 ~ 12000.
In above-mentioned preparation method, as a kind of optimal way, in described step one, described high polymer dispersion is the combination of a kind of in polyvinylpyrrolidone PVP, polyacrylic acid PAA, polymethyl acrylic acid PMAA, polyoxyethylene or at least two kinds; Its usage quantity accounts for 2 ~ 40wt% of styrene monomer.Exemplarily, described usage quantity can be 3wt%, 8wt%, 10wt%, 15wt%, 25wt%, 30wt%, 36wt%.
In above-mentioned preparation method, as a kind of optimal way, in described step one, described Organic Alcohol is one or more combination of methyl alcohol, ethanol, propylene glycol, n-propyl alcohol, Virahol, butanols, butyleneglycol, glycerine.
In above-mentioned preparation method, as a kind of optimal way, in described step one, described oil-soluble initiator is azo and/or peroxidation class, and described peroxide initiator is one or more the combination in dibenzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), hydrogen phosphide cumene, dicumyl peroxide, tertbutyl peroxide; Described azo initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and its usage quantity is 0.05 ~ 5.0wt% of styrene monomer.
In above-mentioned preparation method, as a kind of optimal way, in described step one, described chain-transfer agent is lauryl mercaptan, Thiovanic acid n-octyl, Stearyl mercaptan, alpha-methyl styrene dimer; Its usage quantity is 0.5 ~ 3.0wt% of styrene monomer; Exemplarily, described usage quantity can be 0.6wt%, 1.2wt%, 1.8%.2.4wt％、2.8wt％。
As a kind of optimal way, in described step 2, soluble metallic salt dissolves in deionized water by being prepared as of described metal hydroxides dispersion agent, obtain metal salt solution, under mechanical stirring, in metal salt solution, add strong base solution, obtain metal hydroxides dispersion agent;
Preferably, the D50 of described metal hydroxides dispersion agent is not more than 0.5 μm, and D90 is not more than 1.2 μm; Preferably D50 is 0.05 ~ 0.4 μm further; D90 is 0.5 ~ 1.0 μm; Preferably, the metal ion in described metal-salt and highly basic and the mol ratio of hydroxide ion are 1: 5 ~ 1: 2, more preferably 1: 4 ~ 2: 5;
Preferably, described soluble metallic salt is solubility magnesium salts, soluble calcium salt, the one of soluble ferric iron salt or its combination;
Preferably, described highly basic is one or more the combination of NaOH, KOH or LiOH.
Preferably, described churned mechanically speed setting is 150 ~ 1500pm, and churning time is 5 ~ 100min.
In above-mentioned steps (three), monomer total amount is the gross weight of described vinyl aromatic monomers and methyl acrylate and/or ethyl propenoate.
In above-mentioned preparation method, as a kind of optimal way, in described step 3, described oil-soluble initiator is azo and/or peroxidation class, and described peroxide initiator is one or more the combination in dibenzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), hydrogen phosphide cumene, dicumyl peroxide, tertbutyl peroxide; Described azo initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and its usage quantity is monomer total amount 0.5 ~ 8.0wt%.Exemplarily, described usage quantity can be 1.0wt%, 2.0wt%, 4.0wt%, 6.0wt%, 7.0wt%.
In above-mentioned preparation method, as a kind of optimal way, in described step 3, described vinyl aromatic monomers is vinylbenzene, Vinyl toluene, alpha-methyl styrene, one or more the combination of 2-vinyl naphthalene.
In above-mentioned preparation method, as a kind of optimal way, in described step 3, described linking agent is one or more the combination in divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol double methacrylate, ethylene glycol diacrylate, ethoxylated trimethylolpropane trimethacrylate or trimethylolpropane trimethacrylate, and usage quantity is 10 ~ 100wt% of monomer total amount.Exemplarily, described usage quantity can be 25wt%, 40wt%, 55wt%, 70wt%, 85wt%, 95wt%.
In above-mentioned preparation method, as a kind of optimal way, in described step 3, described pore-forming material is the combination of a kind of in octane, n-Octanol, hexanaphthene, toluene or dimethylbenzene or at least two kinds, its usage quantity is 20 ~ 300wt% of monomer total amount, the property shown ground, described usage quantity can be 50wt%, 100wt%, 150wt%, 220wt%, 280wt%.
In above-mentioned preparation method, as a kind of optimal way, in described step 3, described swelling time is 4 ~ 24h, and swelling temperature is 0 DEG C ~ 40 DEG C.Exemplarily, described swelling time can be 5.5h, 8.5h, 11.5h, 14.5h, 17.5h, 20.5h, 23.5h; Described swelling temperature can be 5 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C.
In above-mentioned preparation method, as a kind of optimal way, in described step 4, the rotating speed 1500 ~ 15000rpm of described high speed shear dispersion machine, shear time is 0.2 ~ 3h; Exemplarily, the described shearing rotating speed time can be 1800rpm, 3000rpm, 5000rpm, 10000rpm, 12000rpm; Described shear time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h.
In above-mentioned preparation method, as a kind of optimal way, in described step 4, described mixing speed is 120 ~ 300rpm, and polymerization reaction time is 4 ~ 16h, polymerization temperature 50 DEG C ~ 95 DEG C.
In above-mentioned preparation method, as a kind of optimal way, in described step 4, the solid content of the sub-emulsion of described Large stone Procedure of Polymerized Micro-Particles with Hollow is 15 ~ 35%.
Compared to prior art, the present invention has following beneficial effect:
(1) Large stone Procedure of Polymerized Micro-Particles with Hollow of the present invention, is aspherical, has the features such as high voidage, high resistance to resolution characteristic, low bulk density and good organic solvent resistance thereof,
(2) the inventive method is simple to operate, and reaction conditions is gentle, and the aspherical Procedure of Polymerized Micro-Particles with Hollow obtained is separated easily.
Accompanying drawing explanation
Fig. 1 is the SEM picture of the sub-emulsion of ps particle that embodiment 1 obtains.
Fig. 2 is the SEM picture of Large stone Procedure of Polymerized Micro-Particles with Hollow that embodiment 1 obtains.
Fig. 3 is the TG curve picture of Large stone Procedure of Polymerized Micro-Particles with Hollow that embodiment 1 obtains.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for the present invention to limit the scope of the invention.Externally should be understood that those skilled in the art make various changes or modifications the present invention after having read content of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Procedure of Polymerized Micro-Particles with Hollow has carried out the mensuration of following performance:
1, the evaluation of the sub-aqueous liquid dispersion of Procedure of Polymerized Micro-Particles with Hollow
(1) stability is polymerized
After polymerization terminates, the sub-emulsion of 500g Procedure of Polymerized Micro-Particles with Hollow is got from reactor, allow it by 325 object wire nettings, on wire netting, residual condensation product is through washing and at 105 DEG C, after 12h drying, on wire netting, the weight of residual dry thing accounts for the percentage of solid content in the sub-emulsion of 500g Procedure of Polymerized Micro-Particles with Hollow.
(2) equal particle footpath is counted
The equal particle footpath of number is in scanning electronic microscope SEM photo, select 100 polymeric microspheres to measure the mean value in particle footpath at random.
The porosity of polymeric hollow microsphere
The porosity of polymer microballoon is drawn by the measurement of Poremaster GT-60 mercury injection apparatus.
(4) pH measures
Get the desk-top pH meter of a certain amount of target product with beaker to measure.
(5) heat-resistant stability measures
TG curve 10% weight reduces temperature, and test condition is: temperature range: room temperature to 700 DEG C, temperature rise rate 2 DEG C/min, nitrogen protection.
(6) mensuration (toluene insoluble component assay) of organic solvent resistance
Sub-for hollow minute particle emulsion is put into centrifuge separator, under the condition of 15000rpm with 30min, makes it be separated, take out the throw out in centrifuge tube, in vacuum drying oven, 25 DEG C of process 48h, obtain dry hollow minute particle (W1) g.With the above-mentioned hollow powder of analytical balance accurate weighing 2g, the toluene putting into 100g floods, then after warming while stirring to 70 DEG C maintains 5h, again be separated with same pelleted by centrifugation, take out a part of upper strata parting liquid, evaporation drying, obtain residual quantity (W2) g of soluble ingredient in hollow minute particle, by the method for calculation in formula 1, calculate the percentage composition of toluene insoluble composition.
Toluene insoluble composition (quality %)=((W1-W2)/W1) × 100 (formula 1)
(7) mensuration of apparent density
A. by division to the sample of about 650g be dry to constant weight in the baking oven of 105 DEG C ± 5 DEG C in temperature, and be cooled to room temperature in moisture eliminator, be divided into two parts for subsequent use;
B. the sample taking oven dry is about 300g (m0), loads and fills in the volumetric flask of half bottle of clean water;
C. rocking-turn volumetric flask, sample is made to be incubated abundant to the water of 23 DEG C ± 1.7 DEG C stirring to get rid of bubble, jam-pack bottle stopper, about 24h is left standstill under constant temperature, then water is added with dropper, make the water surface concordant with bottleneck scale marks, then jam-pack bottle stopper, dry a bottle free surface moisture. claim its total mass (m2);
D. pour out the water in bottle and sample, cleaned by the surfaces externally and internally of bottle, then the clean water (temperature difference is no more than 2 DEG C) injecting same temperature in bottle is to bottleneck scale marks, jam-pack bottle stopper, dries a bottle free surface moisture, claims its total mass (ml).
E. the apparent relative density calculating fine aggregate to be calculated to after radix point 3 by formula (1-1).
γa＝m0/(m0+ml-m2) (1-1)
In formula: γ a---the apparent relative density gathered materials, zero dimension;
M0---the dries quantity (g) gathered materials;
The total mass (g) of m1---water and volumetric flask;
The total mass (g) of m2---sample, water, bottle and volumetric flask
In the polyreaction of all embodiments and comparative example, all complete in nitrogen atmosphere.
Embodiment 1
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 32.5g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 300.8g, 0.57g benzoyl peroxide and 1.20g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.3g lauryl mercaptan), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 25.3%, median size is 5150nm, number-average molecular weight is ps particle of 11000, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.3% polystyrene seed emulsion.
Step 2, takes 50g MgCl26H2O and is dissolved in 775g deionized water and obtains MgCl2 solution; Take 43.60g NaOH to be dissolved in 375g deionized water and to obtain NaOH solution.700rpm under mechanical stirring, slowly adds NaOH solution in MgCl2 solution, and maintains stirring 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 19.38g polystyrene seed emulsion (solid content 22.3%), adds obtained polystyrene seed emulsion in 35.25g deionized water; Take benzoyl peroxide BPO 22.24g successively, vinylbenzene ST 150g, methyl acrylate MA27.00g, divinylbenzene DVB 156.36g, n-Octanol 283.16g, stirring and dissolving obtains oil phase, and Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirred at ambient temperature swelling 12h;
Step 4, swelling good mixed solution is joined in high speed shear dispersion machine, at the emulsified 30min of rotating speed 12000rpm, emulsification terminates rear 300g deionized water rinsing mulser, the liquid that emulsification is good is joined in glass reaction still, is warmed up to 90 DEG C, under the mechanical stirring of 190rpm, react 6h, with 200 order filter-cloth filterings, obtain aspherical polymeric hollow microsphere HP01.Scheme from the SEM of Fig. 1 ps particle, the median size that can obtain ps particle that embodiment 1 obtains is 3 ~ 6 μm, scheme from the SEM of Fig. 2 Procedure of Polymerized Micro-Particles with Hollow, the pattern of Procedure of Polymerized Micro-Particles with Hollow is aspherical, the equal particle footpath of number is 25 ~ 50 μm, from the TG graphic representation of Fig. 3 Procedure of Polymerized Micro-Particles with Hollow, it is 372.6 DEG C that its 10% weight reduces temperature.
Embodiment 2
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 35.1g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 340.8g, 1.7g benzoyl peroxide (is dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.7g lauryl mercaptan), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 23.09%, median size is 4020nm, number-average molecular weight is ps particle of 6000, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 20.06% polystyrene seed emulsion.
Step 2, takes 40g MgCl26H2O and is dissolved in 750g deionized water and obtains MgCl2 solution; Take 38.60g NaOH to be dissolved in 335g deionized water and to obtain NaOH solution.800rpm under mechanical stirring, slowly adds NaOH solution in MgCl2 solution, and maintains stirring 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 22.67g polystyrene seed emulsion (solid content 20.06%), adds obtained polystyrene seed emulsion in 30.25g deionized water; Take benzoyl peroxide BPO 18.24g successively, vinylbenzene ST 140g, methyl acrylate MA5.0g, ethylene glycol dimethacrylate 176.36g, dimethylbenzene 48.4g, stirring and dissolving obtains oil phase, and dispersion agent, oil phase join in reactor by 280rpm successively under mechanical stirring, stirs and swelling 4h at 40 DEG C;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 50min of rotating speed 10000rpm.Emulsification terminates rear 300g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 90 DEG C, under the mechanical stirring of 120rpm, react 16h, with 200 order filter-cloth filterings, obtains aspherical polymeric hollow microsphere HP02.
Embodiment 3
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 28.5g of 20% polyoxyethylene while stirring successively, ethanol 320.6g, 0.76g benzoyl peroxide and 1.50g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and Thiovanic acid n-octyl, and it is obtained to add the mixing of 3.3g Thiovanic acid n-octyl), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 24.4%, median size is 2080nm, number-average molecular weight is ps particle of 1050, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.51% polystyrene seed emulsion.
Step 2, takes 60g MgCl26H2O and is dissolved in 780g deionized water and obtains MgCl2 solution; Take 57g KOH dissolution of solid and obtain KOH solution in 350g deionized water, be under the mechanical stirring of 150rpm at rotating speed, KOH solution slowly added in MgCl2 solution, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 27.5g polystyrene seed emulsion (solid content 22.51%), adds obtained polystyrene seed emulsion in 42.25g deionized water; Take benzoyl peroxide BPO 29.24g successively, alpha-methyl styrene 140g, ethyl propenoate EA 207.40g, divinylbenzene DVB 206.36g, n-Octanol 1382.7g, stirring and dissolving obtains oil phase, and Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirred at ambient temperature swelling 16h;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 12min of rotating speed 15000rpm.Emulsification terminates rear 200g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 90 DEG C, under the mechanical stirring of 220rpm, react 8h, with 200 order filter-cloth filterings, obtains aspherical polymeric hollow microsphere HP03.
Embodiment 4
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the aqueous isopropanol 34.5g of 20% polyoxyethylene while stirring successively, Virahol 310.8g, 0.67g benzoyl peroxide and 1.30g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and Thiovanic acid n-octyl, and it is obtained to add the mixing of 2.1g Thiovanic acid n-octyl), be warming up to 65 DEG C, insulation reaction 24h, namely obtaining solid content is 24.6%, median size is 6190nm, number-average molecular weight is ps particle of 8000, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from Virahol aqueous phase formation solid content is 21.3% polystyrene seed emulsion.
Step 2, takes 55g MgCl26H2O and is dissolved in 785g deionized water and obtains MgCl2 solution; Take 45.60g NaOH to be dissolved in 385g deionized water and to obtain NaOH solution.800rpm under mechanical stirring, slowly adds NaOH solution in MgCl2 solution, and maintains stirring 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 21.43g polystyrene seed emulsion (solid content 21.3%), adds obtained polystyrene seed emulsion in 38.12g deionized water; Take benzoyl peroxide BPO 26.14g successively, vinylbenzene ST 150g, ethyl propenoate MA15.00g, divinylbenzene DVB 170.36g, dimethylbenzene 263.16g, stirring and dissolving obtains oil phase, and Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirs and swelling 24h at 0 DEG C;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, under shearing rotating speed 2000rpm, and emulsion dispersion 1.6h, emulsification terminates rear 300g deionized water rinsing mulser; The mixed dispersion liquid that emulsification is good is joined in the glass reaction still that stirring rake, thermometer, nitrogen inlet valve and reflux condensing tube are housed, be warmed up to 95 DEG C, insulation reaction 4h under the mechanical stirring of 300rpm, be cooled to room temperature, with 200 order filter-cloth filterings, obtain aspherical polymeric hollow microsphere HP04.
Embodiment 5
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 34.5g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 310.8g, 0.67g benzoyl peroxide and 1.30g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.1g lauryl mercaptan), be warming up to 68 DEG C, insulation reaction 24h, namely obtaining solid content is 23.26%, median size is 7950nm, number-average molecular weight is ps particle of 12000, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.1% polystyrene seed emulsion.
Step 2, take 43.4g CaCl22H2O to be dissolved in 600g deionized water and to obtain CaCl2 solution, separately take 59g NaOH dissolution of solid and obtain NaOH solution in 500g deionized water, be under the mechanical stirring of 650rpm at rotating speed, NaOH solution is slowly added in CaCl2 solution, obtained Ca (OH) 2 dispersion agent.
Step 3, takes 25.43g polystyrene seed emulsion (solid content 22.1%), adds obtained polystyrene seed emulsion in 48.12g deionized water; Take Diisopropyl azodicarboxylate 28.14g successively, alpha-methyl styrene 150g, ethyl propenoate EA22.00g, divinylbenzene DVB 170.36g, octane 563.16g, stirring and dissolving obtains oil phase, and Mg (OH) 2 dispersion agent, oil phase join in reactor by 230rpm successively under mechanical stirring, stirred at ambient temperature swelling 12h;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 3h of rotating speed 1500rpm.Emulsification terminates rear 290g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 85 DEG C, under the mechanical stirring of 210rpm, react 7h, with 200 order filter-cloth filterings, obtains aspherical polymeric hollow microsphere HP05.
Comparative example 1
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 32.5g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 300.8g, 0.57g benzoyl peroxide and 1.20g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.3g lauryl mercaptan), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 25.3%, median size is ps particle of 5010nm, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.3% polystyrene seed emulsion.
Step 2, takes 50g MgCl26H2O and is dissolved in 775g deionized water and obtains MgCl2 solution; Take 43.60g NaOH to be dissolved in 375g deionized water and to obtain NaOH solution.700rpm under mechanical stirring, slowly adds NaOH solution in MgCl2 solution, and maintains stirring 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 19.38g polystyrene seed (solid content 22.3%), adds obtained polystyrene seed emulsion in 35.25g deionized water; Take benzoyl peroxide BPO 22.24g successively, vinylbenzene ST 150g, methyl acrylate MA 1.00g, divinylbenzene DVB 156.36g, n-Octanol 1775.16g, stirring and dissolving obtains oil phase, and Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirred at ambient temperature swelling 12h;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 30min of rotating speed 12000rpm.Emulsification terminates rear 300g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 90 DEG C, under the mechanical stirring of 190rpm, react 6h, with 200 order filter-cloth filterings, obtains spherical hollow polymer microballoon D1.
Comparative example 2
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 32.5g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 300.8g, 0.57g benzoyl peroxide and 1.20g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.3g lauryl mercaptan), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 25.3%, median size is ps particle of 5010nm, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.3% polystyrene seed emulsion.
Step 2, takes 50g MgCl26H2O and is dissolved in 775g deionized water and obtains MgCl2 solution; Take 43.60g NaOH to be dissolved in 375g deionized water and to obtain NaOH solution.700rpm under mechanical stirring, slowly adds NaOH solution in MgCl2 solution, and maintains stirring 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 19.38g polystyrene seed (solid content 22.3%), adds obtained polystyrene seed emulsion in 35.25g deionized water; Take benzoyl peroxide BPO 22.24g successively, vinylbenzene ST 150g, divinylbenzene DVB156.36g, n-Octanol 283.16g, stirring and dissolving obtains oil phase, Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirred at ambient temperature swelling 12h;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 30min of rotating speed 12000rpm.Emulsification terminates rear 300g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 90 DEG C, under the mechanical stirring of 190rpm, react 6h, with 200 order filter-cloth filterings, obtains spherical hollow polymer microballoon D2.
Comparative example 3
Step one, to being equipped with reflux condensing tube, thermometer, in four mouthfuls of glass reactors of nitrogen siphunculus, add the ethanolic soln 32.5g of 20% polyvinylpyrrolidone PVP-K30 while stirring successively, ethanol 300.8g, 0.57g benzoyl peroxide and 1.20g Diisopropyl azodicarboxylate (are dissolved in 100g vinylbenzene by the monomer solution containing benzoyl peroxide and Diisopropyl azodicarboxylate mixed initiator and lauryl mercaptan, and it is obtained to add the mixing of 2.3g lauryl mercaptan), be warming up to 70 DEG C, insulation reaction 24h, namely obtaining solid content is 25.3%, median size is ps particle of 5010nm, then precipitate with centrifugation, washing removing macromolecule dispersing agent, polystyrene seed being transferred to from ethanol aqueous phase formation solid content is 22.3% polystyrene seed emulsion.
Step 2, takes 50g MgCl26H2O and is dissolved in 775g deionized water and obtains MgCl2 solution; Take 43.60g NaOH to be dissolved in 375g deionized water and to obtain NaOH solution, 700rpm under mechanical stirring, NaOH solution is slowly added in MgCl2 solution, and maintain and stir 30min, obtained Mg (OH) 2 dispersion agent.
Step 3, takes 19.38g polystyrene seed (solid content 22.3%), adds obtained polystyrene seed emulsion in 35.25g deionized water; Take benzoyl peroxide BPO 22.24g successively, vinylbenzene ST 150g, methyl acrylate MA27.00g, divinylbenzene DVB 156.36g, stirring and dissolving obtains oil phase, Mg (OH) 2 dispersion agent, oil phase join in reactor by 250rpm successively under mechanical stirring, stirred at ambient temperature swelling 12h;
Step 4, joins in high speed shear dispersion machine by swelling good mixed solution, at the emulsified 30min of rotating speed 12000rpm.Emulsification terminates rear 300g deionized water rinsing mulser, is joined in glass reaction still by the liquid that emulsification is good, is warmed up to 90 DEG C, under the mechanical stirring of 190rpm, react 6h, with 200 order filter-cloth filterings, obtains spherical hollow polymer microballoon D3.
The physical index of each embodiment and comparative example gained Procedure of Polymerized Micro-Particles with Hollow thereof is in table 1
Be to be understood that; the purposes of above-described embodiment is only not intended to for illustration of the present invention limit the scope of the invention; in addition; also should understand; after having read technology contents of the present invention; those skilled in the art can do various change, modification, substitute, combine, simplify the present invention, and these all equivalent form of values are included within protection scope of the present invention equally.
Claims (10)
1. a preparation method for Large stone Procedure of Polymerized Micro-Particles with Hollow, is characterized in that, comprises the following steps:
Step one, the preparation of low-molecular-weight polystyrene seed emulsion;
Step 2, the preparation of metal hydroxides dispersion agent;
Step 3, the oil phase 55 ~ 98wt% vinyl aromatic monomers being dissolved with oil-soluble initiator and 2 ~ 45wt% methyl acrylate and/or ethyl propenoate, linking agent and pore-forming material are mixed to form carries out with polystyrene seed emulsion and metal hydroxides dispersion agent mixing, swelling;
Step 4, the mixed dispersion liquid obtained after swelling is joined in high speed shear dispersion machine and carries out high speed shear emulsion dispersion, after end to be emulsified, emulsified dispersed liquid is added in reactor, be warming up to 50 ~ 95 DEG C, carry out microsuspension under mechanical stirring, obtain the sub-emulsion of Large stone Procedure of Polymerized Micro-Particles with Hollow.
2. Large stone Procedure of Polymerized Micro-Particles with Hollow is sub as claimed in claim 1, and in aspherical, median size is 15 ~ 50 μm, and porosity is 10 ~ 50%, 10% weight minimizing temperature is 300 ~ 480 DEG C, and apparent density is 0.1 ~ 0.6g/cm3, pH is 7.2 ~ 11.0.
3. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step one, the preparation of described low-molecular-weight polystyrene seed emulsion, concrete steps are in reactor, add the Organic Alcohol solution being dissolved with high polymer dispersion, under agitation join in reactor by the styrene monomer containing oil-soluble initiator, chain-transfer agent, are warming up to 50 ~ 80 DEG C, insulation reaction 6 ~ 48h, obtains the sub-emulsion of ps particle.
4. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step one, the solid content of described low-molecular-weight polystyrene seed emulsion is 20 ~ 40%, median size is 2 ~ 8 μm, and number-average molecular weight is 1000 ~ 12000.
5. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step one, described high polymer dispersion is the combination of a kind of in polyvinylpyrrolidone PVP, polyacrylic acid PAA, polymethyl acrylic acid PMAA, polyoxyethylene or at least two kinds; Its usage quantity accounts for 2 ~ 40wt% of styrene monomer;
Preferably, described Organic Alcohol is one or more combination of methyl alcohol, ethanol, propylene glycol, n-propyl alcohol, Virahol, butanols, butyleneglycol, glycerine;
Preferably, described oil-soluble initiator is azo and/or peroxidation class, and described peroxide initiator is one or more the combination in dibenzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), hydrogen phosphide cumene, dicumyl peroxide, tertbutyl peroxide; Described azo initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and its usage quantity is 0.05 ~ 5.0wt% of styrene monomer;
Preferably, described chain-transfer agent is lauryl mercaptan, Thiovanic acid n-octyl, Stearyl mercaptan, alpha-methyl styrene dimer; Its usage quantity is 0.5 ~ 3.0wt% of styrene monomer.
6. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, described in step 2, soluble metallic salt dissolves in deionized water by being prepared as of metal hydroxides dispersion agent, obtain metal salt solution, under mechanical stirring, in metal salt solution, add strong base solution, obtain metal hydroxides dispersion agent;
Preferably, the D50 of described metal hydroxides dispersion agent is not more than 0.5 μm, and D90 is not more than 1.2 μm; Preferably D50 is 0.05 ~ 0.4 μm further; D90 is 0.5 ~ 1.0 μm;
Preferably, the metal ion in described metal-salt and highly basic and the mol ratio of hydroxide ion are 1: 5 ~ 1: 2, more preferably 1: 4 ~ 2: 5;
Preferably, described soluble metallic salt is solubility magnesium salts, soluble calcium salt, the one of soluble ferric iron salt or its combination;
Preferably, described highly basic is one or more the combination of NaOH, KOH or LiOH.
Preferably, described churned mechanically speed setting is 150 ~ 1500pm, and churning time is 5 ~ 100min.
7. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step 3, described oil-soluble initiator is azo and/or peroxidation class, and described peroxide initiator is one or more the combination in dibenzoyl peroxide, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), hydrogen phosphide cumene, dicumyl peroxide, tertbutyl peroxide; Described azo initiator is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), and its usage quantity is monomer total amount 0.5 ~ 8.0wt%;
Preferably, described vinyl aromatic monomers is vinylbenzene, Vinyl toluene, alpha-methyl styrene, one or more the combination of 2-vinyl naphthalene;
Preferably, described linking agent is one or more the combination in divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol double methacrylate, ethylene glycol diacrylate, ethoxylated trimethylolpropane trimethacrylate or trimethylolpropane trimethacrylate, and usage quantity is 10 ~ 100wt% of monomer total amount;
Preferably, described pore-forming material is the combination of a kind of in octane, n-Octanol, hexanaphthene, toluene or dimethylbenzene or at least two kinds, and its usage quantity is 20 ~ 300wt% of monomer total amount.
8. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step 3, described polystyrene seed emulsion for by centrifugation precipitation, the high polymer dispersion removing of washing in low-molecular-weight polystyrene seed emulsion that step one is obtained, make polystyrene seed emulsion by Organic Alcohol mutually in transfer to aqueous phase and form water-based polystyrene seed emulsion.
9. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterized in that, in described step 3, described swelling time is 0 ~ 24h, and swelling temperature is 0 DEG C ~ 45 DEG C.
10. the preparation method of Large stone Procedure of Polymerized Micro-Particles with Hollow according to claim 1, is characterized in that, in described step 4, and the rotating speed 1500 ~ 15000rpm of described high speed shear dispersion machine, shear time is 0.1 ~ 3h;
Preferably, in described step 4, described mixing speed is 120 ~ 300rpm, and polymerization reaction time is 4 ~ 16h; Polymerization temperature 50 DEG C ~ 95 DEG C;
Preferably, in described step 4, the solid content of the sub-emulsion of described Large stone Procedure of Polymerized Micro-Particles with Hollow is 15 ~ 35%.
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