CN104910311B - Large-particle-size hollow polymer microparticle and preparation method thereof - Google Patents
Large-particle-size hollow polymer microparticle and preparation method thereof Download PDFInfo
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- CN104910311B CN104910311B CN201510273888.0A CN201510273888A CN104910311B CN 104910311 B CN104910311 B CN 104910311B CN 201510273888 A CN201510273888 A CN 201510273888A CN 104910311 B CN104910311 B CN 104910311B
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- 239000011859 microparticle Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229920000642 polymer Polymers 0.000 title claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 50
- 239000000839 emulsion Substances 0.000 claims abstract description 50
- 229920002223 polystyrene Polymers 0.000 claims abstract description 50
- 239000002270 dispersing agent Substances 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 14
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 230000008961 swelling Effects 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000010008 shearing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000002245 particle Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 43
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 32
- 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 26
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010907 mechanical stirring Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 238000013019 agitation Methods 0.000 claims description 14
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 11
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000004945 emulsification Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 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
- -1 n-octyl Chemical group 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 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 5
- 239000011148 porous material Substances 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
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 4
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004815 dispersion polymer Substances 0.000 claims description 4
- 150000002978 peroxides Chemical class 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
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical class C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-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
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 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
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- UWNNZXDNLPNGQJ-UHFFFAOYSA-N tert-butyl 2-ethylhexanoate Chemical compound CCCCC(CC)C(=O)OC(C)(C)C UWNNZXDNLPNGQJ-UHFFFAOYSA-N 0.000 claims 2
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 229920000265 Polyparaphenylene Polymers 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000006471 dimerization reaction Methods 0.000 claims 1
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical group C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 claims 1
- 229920002627 poly(phosphazenes) Polymers 0.000 claims 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 14
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000011810 insulating material Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- 239000012744 reinforcing agent Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
- 238000010557 suspension polymerization reaction Methods 0.000 abstract 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 28
- 238000003756 stirring Methods 0.000 description 27
- 239000003643 water by type Substances 0.000 description 24
- 239000004342 Benzoyl peroxide Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000011521 glass Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 14
- 229910001629 magnesium chloride Inorganic materials 0.000 description 14
- 239000004005 microsphere Substances 0.000 description 12
- 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229920003081 Povidone K 30 Polymers 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 241001411320 Eriogonum inflatum Species 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 210000000481 breast Anatomy 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
- 230000008859 change Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000012674 dispersion polymerization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004702 methyl esters Chemical class 0.000 description 2
- 150000002829 nitrogen Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- LLSDKQJKOVVTOJ-UHFFFAOYSA-L calcium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ca+2] LLSDKQJKOVVTOJ-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical group CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 description 1
- IRFXVXBSIAKRJM-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS.CCCCCCCCCCCCS IRFXVXBSIAKRJM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007046 ethoxylation reaction Methods 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis 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
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000005837 radical ions Chemical class 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
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 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 microparticle and a preparation method thereof. The preparation method comprises the steps of firstly preparing low-molecular-weight polystyrene seed emulsion and metal hydroxide serving as a dispersing agent, then mixing and swelling an oil phase formed by mixing a vinyl aromatic monomer containing an oil-soluble initiator, methyl acrylate and/or ethyl acrylate, a cross-linking agent and a pore-forming agent with the polystyrene seed emulsion and the metal hydroxide dispersing agent, carrying out high-speed shearing, emulsifying and dispersing, transferring the obtained emulsified dispersion liquid into a reactor for carrying out micro-suspension polymerization, and finally obtaining large-particle-size hollow polymer microparticles with non-spherical shapes. The large-particle-size hollow polymer microparticles have the characteristics of high decomposition resistance, low apparent density, good organic solvent resistance and the like, and are suitable for heat-resistant white pigments, heat-insulating materials, lightweight filling materials, sealing rubber reinforcing agents, liquid component gradual release agents, thin film slipping agents and the like.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of preparation method of Procedure of Polymerized Micro-Particles with Hollow.Specifically
Say that the invention provides a kind of technical matters of big particle diameter Procedure of Polymerized Micro-Particles with Hollow in ground.
Background technology
Compared to solid microsphere material, after the sub- emulsion of hollow minute particle is dried, the water of inside particles disappears to form single one or more
Individual emptying aperture, because inside has cavity structure and shows low-density, high-specific surface area and the features such as can accommodate guest molecule,
Therefore there is wide application in various fields such as coating, papermaking, electronics, catalysis, separation, biological medicines, such as in paper maker
Industry, can not only make coating significantly lightweight, and the organic hollow of thermoplasticity with hollow minute particle filial generation for part titanium dioxide
Under conditions of heat and pressure, the yielding surface for obtaining high flatness is to realize high blank sheet of paper gloss for particulate；In organic
Empty particulate internal cavity structures, outer cover height are crosslinked and are easy to dispersed in organic polymer base material, in aerospace industry
Can as caulking gum lightweight and reinforcement important materials.In addition, in white ink, heat-sensitive recording material, province can break
Hot material, the field such as optical thin film hollow minute particle also has extremely important application value.
It is micro- that Japanese Patent Laid-Open 2005-206752 provides a kind of hollow polymer used in coated sheet manufacture
The preparation method of ball.In the presence of specific surfactant, by the weight % of unsaturated monomer 20~60 containing acid functional group
Form core polymer with the possible other weight % copolymerization of unsaturated monomer 80~40 of copolymerization, then by containing acid functional group not
The weight % of saturation monomer 0~15 and possible other weight % of unsaturated monomer 100~85 of copolymerization, on the outside of core polymer altogether
Combinate form passes through the sub water of the Procedure of Polymerized Micro-Particles with Hollow to be formed with space for neutralizing the acid functional group in core polymer into embracing layer
Property dispersion.But Procedure of Polymerized Micro-Particles with Hollow that the method is obtained is double-layer structure, and the polymer of internal alkali-soluble easily leads to
Cross embracing layer to spread to aqueous phase, can be viscosified during long term storage.
Japanese Patent Laid-Open 2010-189606 provides a kind of system of big particle footpath cross-linking type polymeric hollow microsphere
Preparation Method.The Non-cross-linked polystyrene microballoon of low molecule amount is synthesized first, then using the microballoon as seed；Oil-soluble mistake will be contained
The mixture of the monomer of oxide-based initiator, crosslinking agent and pore-creating solvent is used as oil phase；Then, will in the presence of emulsifying agent
Both mixing, stirring is placed after 24h is swelled and is warming up to 85 DEG C of polymerizations, is obtained polymer microballoon emulsion, is finally centrifuged, through true
It is that can obtain big particle footpath cross-linking type polymeric hollow microsphere that sky, which is dried and removes pore-creating solvent,.With this method can only obtain it is spherical in
Empty particle, and voidage is low, and particle footpath is excessive, and polymerization stability is poor.
The content of the invention
For the defect of prior art, it is an object of the invention to provide a kind of big particle diameter Procedure of Polymerized Micro-Particles with Hollow, it is
Aspherical, Procedure of Polymerized Micro-Particles with Hollow is with high voidage, high-fire resistance, low apparent density and its well resistance to organic molten
The features such as agent performance.
Another object of the present invention is to provide a kind of preparation method of above-mentioned big particle diameter Procedure of Polymerized Micro-Particles with Hollow, the party
Method is simple to operate, and reaction condition is gentle, and obtained big particle diameter Procedure of Polymerized Micro-Particles with Hollow separation is easy.
The present invention is using in the presence of polystyrene seed emulsion, using metal hydroxides colloid as dispersant, using micro-
Suspension polymerisation enters methyl acrylate MA or ethyl acrylate EA monomers with vinyl aromatic monomers under oil-soluble initiator
Row polymerization obtains polymeric hollow microsphere.Its formation mechenism is specific as follows：During microsuspension polymerization, oil-soluble triggers first
Agent is decomposed generation free radical polymerization and started, due to methacrylate monomer MA in system and/or acrylic acid ethyl ester monomer EA
Reactivity it is higher, and vinyl aromatic monomers, due to the presence of itself conjugated structure, its reactivity is relatively low, so third
E pioic acid methyl ester MA and/or ethyl acrylate EA faster polymerize than vinyl aromatic monomers, thus initial reaction stage primarily form containing
The PMA and/or polyethyl acrylate (PMA and/or PEA) chain free radical of a small amount of vinyl aromatic monomers unit
With/block copolymer microcell, while progress with polymerisation, the rich block copolymer of MA and/or EA construction units is micro-
Under high-temperature alkaline environment hydrolysis occurs for area, generation hydrophilic radical COONa/K/Li is COO-, water swelling；It is another
Aspect due in system low-molecular-weight polystyrene microballoon part be dissolved in swelling process in polymerized monomer and pore creating material, with
The progress of polymerisation, the polystyrene microsphere part of dissolving is separated out, and then is separated, water swelling, therefore in polymerization
During the stress that acts on by these two aspects it is different, ultimately form the special-shaped hollow structure of aspherical.
To achieve these goals, present invention employs following technical scheme：
A kind of big particle diameter Procedure of Polymerized Micro-Particles with Hollow, in aspherical, its average grain diameter is 15~50 μm, porosity is 10~
50%, it is 300~480 DEG C that 10% weight, which reduces temperature, and apparent density is 0.1~0.6g/cm3, and pH is 7.2~11.0.
The preparation method of above-mentioned big particle diameter 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 dispersant；
Step 3, by dissolved with the 55~98wt% vinyl aromatic monomers and 2~45wt% propylene of oil-soluble initiator
Oil phase and polystyrene seed emulsion and metallic hydrogen that sour methyl esters and/or ethyl acrylate, crosslinking agent and pore creating material are mixed to form
Oxide dispersant is mixed, is swelled；
Step 4, the mixed dispersion liquid obtained after being swelled, which is added in high speed shear dispersion machine, carries out high speed shearing emulsification
It is scattered, after end to be emulsified, emulsified dispersed liquid is added into reactor, be warming up under 50~95 DEG C, mechanical agitation carry out it is micro-
Suspension polymerisation, obtains the big sub- emulsion of particle diameter Procedure of Polymerized Micro-Particles with Hollow.
In above-mentioned preparation method, the system of the low-molecular-weight polystyrene seed emulsion and metal hydroxides dispersant
It is standby can be using the conventional preparation method in this area, i.e., using conventional method by Material synthesis polystyrene when being not particularly illustrated
Seed emulsion and metal hydroxides dispersant.
As a kind of preferred embodiment, in the step one, the preparation of the low-molecular-weight polystyrene seed emulsion can
With using dispersion polymerization processes prepare, when using dispersion polymerization processes polymerization when, concretely comprise the following steps added into reactor dissolved with
Organic alcoholic solution of high polymer dispersion, under agitation by the styrene list containing oil-soluble initiator, chain-transferring agent
Body is added in reactor, is warming up to 50~80 DEG C, 6~48h of insulation reaction obtains low-molecular-weight polystyrene particulate breast
Liquid；Using precipitation, washing is centrifuged, high polymer dispersion is removed, by ps particle from organic alcohol phase
It is transferred to aqueous phase and forms aqueous polystyrene seed emulsion.
In above-mentioned preparation method, a kind of preferred embodiment, in the step one, the low-molecular-weight polystyrene are used as
The solid content of seed emulsion is 20~40%, and average grain diameter is 2~8 μm, and number-average molecular weight is 1000~12000.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step one, the high molecular polymer disperses
Agent is polyvinylpyrrolidone PVP, polyacrylic acid PAA, polymethylacrylic acid PMAA, one kind in polyethylene glycol oxide or at least two
The combination planted；Its usage amount accounts for 2~40wt% of styrene monomer.Exemplarily, the usage amount can for 3wt%,
8wt%, 10wt%, 15wt%, 25wt%, 30wt%, 36wt%.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step one, the Organic Alcohol is methanol, second
Alcohol, propane diols, normal propyl alcohol, isopropanol, butanol, butanediol, one or more kinds of combinations of glycerine.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step one, the oil-soluble initiator is even
Nitrogen class and/or peroxidating class, the peroxide initiator are dibenzoyl peroxide, peroxidating (2 ethyl hexanoic acid) tertiary fourth
The tertiary own ester of ester, peroxidating neopentanoic acid, cumyl hydroperoxide, cumyl peroxide, one kind in TBHP or
Two or more combinations；The azo initiator is azodiisobutyronitrile, ABVN, and its usage amount is styrene monomer
0.05~5.0wt%.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step one, the chain-transferring agent is dodecane
Base mercaptan, TGA n-octyl, Stearyl mercaptan, α-methylstyrene dimer；Its usage amount is styrene monomer
0.5~3.0wt%；Exemplarily, the usage amount can be 0.6wt%, 1.2wt%, 1.8%.2.4wt%, 2.8wt%.
As a kind of preferred embodiment, in the step 2, being prepared as the metal hydroxides dispersant will be solvable
Property dissolving metal salts in deionized water, obtain metal salt solution, under mechanical stirring, into metal salt solution add highly basic it is molten
Liquid, obtains metal hydroxides dispersant；
Preferably, the D50 of the metal hydroxides dispersant is not more than 0.5 μm, and D90 is not more than 1.2 μm；It is further excellent
It is 0.05~0.4 μm to select D50；D90 is 0.5~1.0 μm；Preferably, the metal ion and hydrogen-oxygen in the metal salt and highly basic
The mol ratio of radical ion is 1: 5~1: 2, more preferably 1: 4~2: 5；
Preferably, the soluble metallic salt is soluble magnesium salt, soluble calcium salt, one kind of soluble ferric iron salt or its group
Close；
Preferably, the highly basic is NaOH, KOH or LiOH one or more kinds of combinations.
Preferably, the churned mechanically speed setting is 150~1500pm, and mixing time is 5~100min.
Monomer total amount is the vinyl aromatic monomers and methyl acrylate and/or acrylic acid second in above-mentioned steps (three)
The gross weight of ester.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 3, the oil-soluble initiator is even
Nitrogen class and/or peroxidating class, the peroxide initiator are dibenzoyl peroxide, peroxidating (2 ethyl hexanoic acid) tertiary fourth
The tertiary own ester of ester, peroxidating neopentanoic acid, cumyl hydroperoxide, cumyl peroxide, one kind in TBHP or
Two or more combinations；The azo initiator is azodiisobutyronitrile, ABVN, and its usage amount is monomer total amount
0.5~8.0wt%.Exemplarily, the usage amount can be 1.0wt%, 2.0wt%, 4.0wt%, 6.0wt%,
7.0wt%.
In above-mentioned preparation method, a kind of preferred embodiment, in the step 3, the vinyl aromatic monomers are used as
For the one or more kinds of combination of styrene, vinyltoluene, α-methylstyrene, 2- vinyl naphthalenes.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 3, the crosslinking agent is divinyl
Benzene, ethylene glycol dimethacrylate, triethylene glycol double methacrylate, ethylene glycol diacrylate, ethoxylation trihydroxy methyl
Combination more than one or both of propane trimethyl acrylic ester or trimethylol-propane trimethacrylate, usage amount
For 10~100wt% of monomer total amount.Exemplarily, the usage amount can be 25wt%, 40wt%, 55wt%, 70wt%,
85wt%, 95wt%.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 3, the pore creating material be normal octane,
One kind or at least two combination in n-octyl alcohol, hexamethylene, toluene or dimethylbenzene, its usage amount for monomer total amount 20~
300wt%, the property shown, the usage amount can be 50wt%, 100wt%, 150wt%, 220wt%, 280wt%.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 3, the swelling time be 4~
24h, swelling temperature is 0 DEG C~40 DEG C.Exemplarily, the swelling time can be 5.5h, 8.5h, 11.5h, 14.5h,
17.5h、20.5h、23.5h；The 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 preferred embodiment, in the step 4, the high speed shear dispersion machine
1500~15000rpm of rotating speed, shear time is 0.2~3h；Exemplarily, the shearing rotating speed time can be 1800rpm,
3000rpm、5000rpm、10000rpm、12000rpm；The shear time can be 0.5h, 1.0h, 1.5h, 2.0h, 2.5h.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 4, the speed of agitator be 120~
300rpm, polymerization reaction time is 4~16h, 50 DEG C~95 DEG C of polymerization temperature.
In above-mentioned preparation method, as a kind of preferred embodiment, in the step 4, the big particle diameter hollow polymer
The solid content of particulate emulsion is 15~35%.
For prior art, the present invention has the advantages that：
(1) big particle diameter Procedure of Polymerized Micro-Particles with Hollow of the present invention, is aspherical, with high voidage, high resistance to resolution characteristic, low
The features such as apparent density and its good organic solvent resistance,
(2) the inventive method is simple to operate, and reaction condition is gentle, and obtained aspherical Procedure of Polymerized Micro-Particles with Hollow separation
Easily.
Brief description of the drawings
Fig. 1 is the SEM pictures for the sub- emulsion of ps particle that embodiment 1 is obtained.
Fig. 2 is the SEM pictures for big particle diameter Procedure of Polymerized Micro-Particles with Hollow that embodiment 1 is obtained.
Fig. 3 is the TG curve pictures for big particle diameter Procedure of Polymerized Micro-Particles with Hollow that embodiment 1 is obtained.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments be only used for the present invention without
For limiting the scope of the present invention.Externally it should be understood that after present disclosure has been read, those skilled in the art are to this hair
Bright to make various changes or modifications, these equivalent form of values equally fall within the application appended claims limited range.
Procedure of Polymerized Micro-Particles with Hollow has carried out the measure of following performance：
1st, the evaluation of the sub- aqueous liquid dispersion of Procedure of Polymerized Micro-Particles with Hollow
(1) it polymerize stability
After polymerization terminates, the sub- emulsion of 500g Procedure of Polymerized Micro-Particles with Hollow is taken from reactor, allows it to pass through the metal of 325 mesh
Condensation product is remained on net, wire netting through washing and at 105 DEG C, after 12h is dried, the weight that dried object is remained on wire netting accounts for 500g
The percentage of solid content in the sub- emulsion of Procedure of Polymerized Micro-Particles with Hollow.
(2) the equal particle footpath of number
The equal particle footpath of number is to select 100 polymeric microspheres to determine particles in SEM SEM photograph at random
The average value in footpath.
The porosity of polymeric hollow microsphere
The porosity of polymer microballoon is drawn by Poremaster GT-60 mercury injection apparatus measurements.
(4) pH is measured
A certain amount of target product is taken to be measured with desk-top pH meter with beaker.
(5) heat-resistant stability is determined
The weight of TG curves 10% reduces temperature, and test condition is：Temperature range：Room temperature to 700 DEG C, 2 DEG C of heating rate/
Min, nitrogen protection.
(6) measure (toluene insoluble component assay) of organic solvent resistance
The sub- emulsion of hollow minute particle is put into whizzer, it is separated under conditions of 15000rpm and 30min, takes
The sediment gone out in centrifuge tube, 25 DEG C of processing 48h, obtain dry hollow minute particle (W1) g in vacuum drying chamber.With analysis
The above-mentioned hollow powders of balance accurate weighing 2g, be put into 100g toluene impregnate, then warming while stirring to 70 DEG C maintenance 5h
Afterwards, separated again with same pelleted by centrifugation, a part of upper strata separating liquid of taking-up, evaporation drying, obtaining can in hollow minute particle
Residual quantity (W2) g of melt into point, by the computational methods in formula 1, calculates the percentage composition of toluene insoluble composition.
Toluene insoluble composition (quality %)=((W1-W2)/W1) × 100 (formula 1)
(7) measure of apparent density
A. the sample of division to 650g or so is dried to constant weight in temperature is 105 DEG C ± 5 DEG C of baking oven, and in drying
Room temperature is cooled in device, is divided into two parts standby；
B. the sample about 300g (m0) of drying is weighed, is fitted into the volumetric flask for filling half bottle of clean water；
C. rocking-turn volumetric flask, makes sample be incubated into 23 DEG C ± 1.7 DEG C of water abundant agitation to exclude bubble, stoppers
Bottle stopper, 24h or so is stood under constant temperature, then adds water with dropper, makes the water surface concordant with bottleneck graduation mark, then stopper bottle
Plug, dries a bottle free surface moisture and claims its gross mass (m2)；
D. the water and sample in bottle are poured out, the surfaces externally and internally of bottle is cleaned, then injects into bottle the clean water of same temperature
(temperature difference is no more than 2 DEG C) stoppers bottle stopper, dries a bottle free surface moisture, claim its gross mass (ml) to bottleneck graduation mark.
E. the apparent relative density for calculating fine aggregate is calculated to 3 after decimal point by formula (1-1).
γ a=m0/ (m0+m1-m2) (1-1)
In formula：γ a --- the apparent relative density gathered materials, dimensionless；
M0 --- the dries quantity (g) gathered materials；
The gross mass (g) of m1 --- water and volumetric flask；
M2 --- sample, water, the gross mass (g) of bottle and volumetric flask
In all embodiments and the polymerisation of comparative example, all completed in nitrogen atmosphere.
Embodiment 1
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 32.5g, ethanol 300.8g, containing benzoyl peroxide and
The monomer solution of azodiisobutyronitrile mixed initiator and lauryl mercaptan is (by 0.57g benzoyl peroxides and 1.20g azos
Bis-isobutyronitrile is dissolved in 100g styrene, and is added 2.3g lauryl mercaptans and be mixed to prepare), 70 DEG C are warming up to, insulation is anti-
24h is answered, that is, obtains solid content for 25.3%, average grain diameter is the ps particle that 5150nm, number-average molecular weight are 11000
Son, then with precipitation, washing removing macromolecule dispersing agent is centrifuged, polystyrene seed is transferred to from ethanol aqueous phase shape
It is 22.3% polystyrene seed emulsion into solid content.
Step 2, weighs 50g MgCl26H2O and is dissolved in 775g deionized waters and obtain MgCl2 solution；Weigh
43.60g NaOH are dissolved in 375g deionized waters and obtain NaOH solution.700rpm, slow by NaOH solution under mechanical stirring
Add in MgCl2 solution, and maintain to stir 30min, Mg (equal 2 dispersants of O are made.
Step 3, weighs 19.38g polystyrene seed emulsions (solid content 22.3%), adds in 35.25g deionized waters
Polystyrene seed emulsion is made；Benzoyl peroxide BPO 22.24g, styrene ST 150g, methyl acrylate are weighed successively
Oil phase is made in MA 27.00g, divinylbenzene DVB 156.36g, n-octyl alcohol 283.16g, stirring and dissolving, under mechanical stirring
The dispersants of Mg (OH) 2, oil phase are added in reactor by 250rpm successively, are stirred at room temperature and are swelled 12h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 12000rpm
30min, emulsification uses 300g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 6h under 190rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains aspherical polymeric hollow microsphere to 90 DEG C
HP01.From the SEM figures of Fig. 1 ps particles, the average grain diameter that can obtain ps particle that embodiment 1 is obtained is 3
~6 μm, it was found from the SEM figures of Fig. 2 Procedure of Polymerized Micro-Particles with Hollow, the pattern of Procedure of Polymerized Micro-Particles with Hollow is aspherical, the equal grain of number
Sub- footpath is 25~50 μm, it was found from the TG curve maps of Fig. 3 Procedure of Polymerized Micro-Particles with Hollow, and it is 372.6 that its 10% weight, which reduces temperature,
℃。
Embodiment 2
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 35.1g, ethanol 340.8g, draw containing benzoyl peroxide
1.7g benzoyl peroxides (are dissolved in 100g styrene, and add 2.7g by the monomer solution of hair agent and lauryl mercaptan
Lauryl mercaptan is mixed to prepare), it is warming up to 70 DEG C, insulation reaction 24h, that is, it is 23.09% to obtain solid content, and average grain diameter is
4020nm, number-average molecular weight are 6000 ps particle, then remove macromolecule with centrifugation precipitation, washing and disperse
Agent, it is 20.06% polystyrene seed emulsion that polystyrene seed is transferred into aqueous phase formation solid content from ethanol.
Step 2, weighs 40g MgCl26H2O and is dissolved in 750g deionized waters and obtain MgCl2 solution；Weigh
38.60g NaOH are dissolved in 335g deionized waters and obtain NaOH solution.800rpm, slow by NaOH solution under mechanical stirring
Add in MgCl2 solution, and maintain to stir 30min, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 22.67g polystyrene seed emulsions (solid content 20.06%), adds in 30.25g deionized waters
Polystyrene seed emulsion is made；Benzoyl peroxide BPO 18.24g, styrene ST 140g, methyl acrylate are weighed successively
Oil phase is made in MA 5.0g, ethylene glycol dimethacrylate 176.36g, dimethylbenzene 48.4g, stirring and dissolving, under mechanical stirring
Dispersant, oil phase are added in reactor by 280rpm successively, are stirred at 40 DEG C and are swelled 4h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 10000rpm
50min.Emulsification uses 300g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 16h under 120rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains aspherical polymeric hollow microsphere to 90 DEG C
HP02。
Embodiment 3
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add the ethanol solution 28.5g of 20% polyethylene glycol oxide, ethanol 320.6g, containing benzoyl peroxide and azodiisobutyronitrile
The monomer solution of mixed initiator and TGA n-octyl is (molten by 0.76g benzoyl peroxides and 1.50g azodiisobutyronitriles
Solution adds 3.3g TGA n-octyls and is mixed to prepare in 100g styrene), it is warming up to 70 DEG C, insulation reaction 24h, i.e.,
Solid content is obtained for 24.4%, average grain diameter is ps particle that 2080nm, number-average molecular weight are 1050, then with from
Heart precipitation and separation, washing remove macromolecule dispersing agent, and polystyrene seed is transferred into aqueous phase formation solid content from ethanol is
22.51% polystyrene seed emulsion.
Step 2, weighs 60g MgCl26H2O and is dissolved in 780g deionized waters and obtain MgCl2 solution；Weigh 57g
KOH solid dissolvings obtain KOH solution in 350g deionized waters, in the case where rotating speed is 150rpm mechanical agitation, KOH solution is slow
Add in MgCl2 solution, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 27.5g polystyrene seed emulsions (solid content 22.51%), adds in 42.25g deionized waters
Polystyrene seed emulsion is made；Benzoyl peroxide BPO 29.24g, α-methylstyrene 140g, acrylic acid second are weighed successively
Oil phase is made in ester EA 207.40g, divinylbenzene DVB 206.36g, n-octyl alcohol 1382.7g, stirring and dissolving, under mechanical stirring
The dispersants of Mg (OH) 2, oil phase are added in reactor by 250rpm successively, are stirred at room temperature and are swelled 16h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 15000rpm
12min.Emulsification uses 200g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 8h under 220rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains aspherical polymeric hollow microsphere to 90 DEG C
HP03。
Embodiment 4
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add the aqueous isopropanol 34.5g of 20% polyethylene glycol oxide, it is isopropanol 310.8g, different containing benzoyl peroxide and azo two
The monomer solution of butyronitrile mixed initiator and TGA n-octyl is (by 0.67g benzoyl peroxides and the isobutyl of 1.30g azos two
Nitrile is dissolved in 100g styrene, and is added 2.1g TGA n-octyls and be mixed to prepare), it is warming up to 65 DEG C, insulation reaction
24h, that is, obtain solid content for 24.6%, and average grain diameter is ps particle that 6190nm, number-average molecular weight are 8000, is connect
With precipitation, washing removing macromolecule dispersing agent is centrifuged, polystyrene seed is transferred to aqueous phase from isopropanol and formed
Solid content is 21.3% polystyrene seed emulsion.
Step 2, weighs 55g MgCl26H2O and is dissolved in 785g deionized waters and obtain MgCl2 solution；Weigh
45.60g NaOH are dissolved in 385g deionized waters and obtain NaOH solution.800rpm, slow by NaOH solution under mechanical stirring
Add in MgCl2 solution, and maintain to stir 30min, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 21.43g polystyrene seed emulsions (solid content 21.3%), adds in 38.12g deionized waters
Polystyrene seed emulsion is made；Benzoyl peroxide BPO 26.14g, styrene ST 150g, ethyl acrylate are weighed successively
Oil phase is made in MA 15.00g, divinylbenzene DVB 170.36g, dimethylbenzene 263.16g, stirring and dissolving, under mechanical stirring
The dispersants of Mg (OH) 2, oil phase are added in reactor by 250rpm successively, are stirred at 0 DEG C and are swelled 24h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, under shearing rotating speed 2000rpm, breast
Change scattered 1.6h, emulsification uses 300g deionized water rinsing mulsers after terminating；The mixed dispersion liquid emulsified is added to and is equipped with
In agitating paddle, thermometer, the glass reaction kettle of nitrogen inlet valve and reflux condensing tube, 95 DEG C are warming up to, in 300rpm machinery
The lower insulation reaction 4h of stirring, is cooled to room temperature, with 200 mesh filter-cloth filterings, obtains aspherical polymeric hollow microsphere HP04.
Embodiment 5
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 34.5g, ethanol 310.8g, containing benzoyl peroxide and
The monomer solution of azodiisobutyronitrile mixed initiator and lauryl mercaptan is (by 0.67g benzoyl peroxides and 1.30g azos
Bis-isobutyronitrile is dissolved in 100g styrene, and is added 2.1g lauryl mercaptans and be mixed to prepare), 68 DEG C are warming up to, insulation is anti-
24h is answered, that is, obtains solid content for 23.26%, average grain diameter is the ps particle that 7950nm, number-average molecular weight are 12000
Son, then with precipitation, washing removing macromolecule dispersing agent is centrifuged, polystyrene seed is transferred to from ethanol aqueous phase shape
It is 22.1% polystyrene seed emulsion into solid content.
Step 2, weighs 43.4g CaCl2.2H2O and is dissolved in 600g deionized waters and obtain CaCl2 solution, separately weighs
59g NaOH solid dissolvings obtain NaOH solution in 500g deionized waters, in the case where rotating speed is 650rpm mechanical agitation, by NaOH
Solution is slowly added in CaCl2 solution, and the dispersants of Ca (OH) 2 are made.
Step 3, weighs 25.43g polystyrene seed emulsions (solid content 22.1%), adds in 48.12g deionized waters
Polystyrene seed emulsion is made；Azodiisobutyronitrile 28.14g, α-methylstyrene 150g, ethyl acrylate EA are weighed successively
Oil phase is made in 22.00g, divinylbenzene DVB 170.36g, normal octane 563.16g, stirring and dissolving, under mechanical stirring 230rpm
The dispersants of Mg (OH) 2, oil phase are added in reactor successively, stirs at room temperature and is swelled 12h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, in the emulsified 3h of rotating speed 1500rpm.
Emulsification uses 290g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, 85 are warming up to
DEG C, 7h is reacted under 210rpm mechanical agitation, with 200 mesh filter-cloth filterings, aspherical polymeric hollow microsphere HP05 is obtained.
Comparative example 1
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 32.5g, ethanol 300.8g, containing benzoyl peroxide and
The monomer solution of azodiisobutyronitrile mixed initiator and lauryl mercaptan is (by 0.57g benzoyl peroxides and 1.20g azos
Bis-isobutyronitrile is dissolved in 100g styrene, and is added 2.3g lauryl mercaptans and be mixed to prepare), 70 DEG C are warming up to, insulation is anti-
24h is answered, that is, it is 25.3% to obtain solid content, average grain diameter is 5010nm ps particle, then uses centrifugation heavy
Form sediment, washing removes macromolecule dispersing agent, polystyrene seed is transferred into aqueous phase formation solid content from ethanol gathers for 22.3%
Styrene seed emulsion.
Step 2, weighs 50g MgCl2.6H2O and is dissolved in 775g deionized waters and obtain MgCl2 solution；Weigh 43.60g
NaOH is dissolved in 375g deionized waters and obtains NaOH solution.700rpm, NaOH solution is slowly added under mechanical stirring
In MgCl2 solution, and maintain to stir 30min, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 19.38g polystyrene seeds (solid content 22.3%), adds in 35.25g deionized waters and is made
Polystyrene seed emulsion；Benzoyl peroxide BPO 22.24g, styrene ST 150g, methyl acrylate MA are weighed successively
Oil phase is made in 1.00g, divinylbenzene DVB 156.36g, n-octyl alcohol 1775.16g, stirring and dissolving, under mechanical stirring 250rpm
The dispersants of Mg (OH) 2, oil phase are added in reactor successively, stirs at room temperature and is swelled 12h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 12000rpm
30min.Emulsification uses 300g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 6h under 190rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains spherical hollow polymer microballoon D1 to 90 DEG C.
Comparative example 2
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 32.5g, ethanol 300.8g, containing benzoyl peroxide and
The monomer solution of azodiisobutyronitrile mixed initiator and lauryl mercaptan is (by 0.57g benzoyl peroxides and 1.20g azos
Bis-isobutyronitrile is dissolved in 100g styrene, and is added 2.3g lauryl mercaptans and be mixed to prepare), 70 DEG C are warming up to, insulation is anti-
24h is answered, that is, it is 25.3% to obtain solid content, average grain diameter is 5010nm ps particle, then uses centrifugation heavy
Form sediment, washing removes macromolecule dispersing agent, polystyrene seed is transferred into aqueous phase formation solid content from ethanol gathers for 22.3%
Styrene seed emulsion.
Step 2, weighs 50g MgCl26H2O and is dissolved in 775g deionized waters and obtain MgCl2 solution；Weigh
43.60g NaOH are dissolved in 375g deionized waters and obtain NaOH solution.700rpm, slow by NaOH solution under mechanical stirring
Add in MgCl2 solution, and maintain to stir 30min, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 19.38g polystyrene seeds (solid content 22.3%), adds in 35.25g deionized waters and is made
Polystyrene seed emulsion；Benzoyl peroxide BPO 22.24g, styrene ST 150g, divinylbenzene DVB are weighed successively
Oil phase is made in 156.36g, n-octyl alcohol 283.16g, stirring and dissolving, under mechanical stirring 250rpm successively by the dispersants of Mg (OH) 2,
Oil phase is added in reactor, is stirred at room temperature and is swelled 12h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 12000rpm
30min.Emulsification uses 300g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 6h under 190rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains spherical hollow polymer microballoon D2 to 90 DEG C.
Comparative example 3
Step one, to being equipped with four mouthfuls of glass reactors of reflux condensing tube, thermometer, nitrogen siphunculus, while stirring
Sequentially add 20% polyvinylpyrrolidone PVP-K30 ethanol solution 32.5g, ethanol 300.8g, containing benzoyl peroxide and
The monomer solution of azodiisobutyronitrile mixed initiator and lauryl mercaptan is (by 0.57g benzoyl peroxides and 1.20g azos
Bis-isobutyronitrile is dissolved in 100g styrene, and is added 2.3g lauryl mercaptans and be mixed to prepare), 70 DEG C are warming up to, insulation is anti-
24h is answered, that is, it is 25.3% to obtain solid content, average grain diameter is 5010nm ps particle, then uses centrifugation heavy
Form sediment, washing removes macromolecule dispersing agent, polystyrene seed is transferred into aqueous phase formation solid content from ethanol gathers for 22.3%
Styrene seed emulsion.
Step 2, weighs 50g MgCl26H2O and is dissolved in 775g deionized waters and obtain MgCl2 solution；Weigh
43.60g NaOH, which are dissolved in 375g deionized waters, obtains NaOH solution, and 700rpm, slow by NaOH solution under mechanical stirring
Add in MgCl2 solution, and maintain to stir 30min, the dispersants of Mg (OH) 2 are made.
Step 3, weighs 19.38g polystyrene seeds (solid content 22.3%), adds in 35.25g deionized waters and is made
Polystyrene seed emulsion；Benzoyl peroxide BPO 22.24g, styrene ST 150g, methyl acrylate MA are weighed successively
Oil phase is made in 27.00g, divinylbenzene DVB 156.36g, stirring and dissolving, and 250rpm is successively by 2 points of Mg (OH) under mechanical stirring
Powder, oil phase are added in reactor, are stirred at room temperature and are swelled 12h；
Step 4, the mixed liquor being swelled is added in high speed shear dispersion machine, emulsified in rotating speed 12000rpm
30min.Emulsification uses 300g deionized water rinsing mulsers after terminating, and the liquid emulsified is added in glass reaction kettle, rises
Temperature reacts 6h under 190rpm mechanical agitation, with 200 mesh filter-cloth filterings, obtains spherical hollow polymer microballoon D3 to 90 DEG C.
The physical index of Procedure of Polymerized Micro-Particles with Hollow is shown in Table 1 obtained by each embodiment and its comparative example
It should be appreciated that the purposes of above-described embodiment is merely to illustrate the present invention and is not intended to limitation protection model of the invention
Enclose, in addition, it will also be appreciated that after the technology contents of the present invention have been read, those skilled in the art can make various to the present invention
Change, modify, substitute, combine, simplify, all these equivalent form of values are also contained within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow, it is characterised in that comprise the following steps：
Step one, the preparation of low-molecular-weight polystyrene seed emulsion；
Step 2, the preparation of metal hydroxides dispersant；
Step 3, by dissolved with 55~98wt% vinyl aromatic monomers of oil-soluble initiator and 2~45wt% acrylic acid first
Oil phase and polystyrene seed emulsion and metal hydroxide that ester and/or ethyl acrylate, crosslinking agent and pore creating material are mixed to form
Thing dispersant is mixed, is swelled；
Step 4, the mixed dispersion liquid obtained after being swelled, which is added in high speed shear dispersion machine, carries out high speed shearing emulsification point
Dissipate, after end to be emulsified, emulsified dispersed liquid is added into reactor, be warming up under 50~95 DEG C, mechanical agitation and carry out micro- hang
Floating polymerization, obtains the big sub- emulsion of particle diameter Procedure of Polymerized Micro-Particles with Hollow.
2. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow, the big particle diameter hollow polymer according to claim 1
Particulate, in aspherical, average grain diameter is 15~50 μm, and porosity is 10~50%, 10% weight reduce temperature be 300~
480 DEG C, apparent density is 0.1~0.6g/cm3, pH is 7.2~11.0.
3. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In one, the preparation of the low-molecular-weight polystyrene seed emulsion is concretely comprised the following steps and added into reactor dissolved with polyphosphazene polymer
Styrene monomer containing oil-soluble initiator, chain-transferring agent, is added to by organic alcoholic solution of compound dispersant under agitation
In reactor, 50~80 DEG C are warming up to, 6~48h of insulation reaction obtains the sub- emulsion of ps particle.
4. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In one, the solid content of the low-molecular-weight polystyrene seed emulsion is 20~40%, and average grain diameter is 2~8 μm, the equal molecule of number
Measure as 1000~12000.
5. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 3, it is characterised in that in the step
In one, the high polymer dispersion be polyvinylpyrrolidone PVP, polyacrylic acid PAA, polymethylacrylic acid PMAA,
One kind or at least two combination in polyethylene glycol oxide；Its usage amount accounts for 2~40wt% of styrene monomer；
The Organic Alcohol be methanol, ethanol, propane diols, normal propyl alcohol, isopropanol, butanol, butanediol, glycerine it is one or two kinds of with
On combination；
The oil-soluble initiator be azo and/or peroxidating class, the peroxide initiator be dibenzoyl peroxide,
Peroxidating (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidating neopentanoic acid, cumyl hydroperoxide, cumyl peroxide, uncle
Combination more than one or both of butylhydroperoxide；The azo initiator is azodiisobutyronitrile, azo two different heptan
Nitrile, its usage amount is 0.05~5.0wt% of styrene monomer；
The chain-transferring agent is lauryl mercaptan, TGA n-octyl, Stearyl mercaptan, α-methylstyrene dimerization
Body；Its usage amount is 0.5~3.0wt% of styrene monomer.
6. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in step 2
The metal hydroxides dispersant be prepared as by soluble metallic salt dissolving in deionized water, obtain metal salt solution,
Under mechanical stirring, strong base solution is added into metal salt solution, metal hydroxides dispersant is obtained；
The D50 of the metal hydroxides dispersant is not more than 0.5 μm, and D90 is not more than 1.2 μm；
The mol ratio of metal ion and hydroxide ion in the metal salt and highly basic is 1: 5~1: 2；
The soluble metallic salt is soluble magnesium salt, soluble calcium salt, one kind of soluble ferric iron salt or its combination；
The highly basic is NaOH, KOH or LiOH one or more kinds of combinations；
The churned mechanically speed setting is 150~1500rpm, and mixing time is 5~100min.
7. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In three, the oil-soluble initiator is azo and/or peroxidating class, and the peroxide initiator is diphenyl peroxide first
Acyl, peroxidating (2 ethyl hexanoic acid) tert-butyl ester, the tertiary own ester of peroxidating neopentanoic acid, cumyl hydroperoxide, cumyl peroxide,
Combination more than one or both of TBHP；The azo initiator is azodiisobutyronitrile, azo two is different
Heptonitrile, its usage amount is 0.5~8.0wt% of monomer total amount；
The vinyl aromatic monomers is styrene, vinyltoluene, α-methylstyrene, 2- vinyl naphthalenes one or two
Combination above；
The crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol double methacrylate, the double propylene of ethylene glycol
Combination more than one or both of acid esters or trimethylol-propane trimethacrylate, usage amount is the 10 of monomer total amount
~100wt%；
The pore creating material be normal octane, n-octyl alcohol, hexamethylene, toluene or dimethylbenzene in one kind or at least two combination, its
Usage amount is 20~300wt% of monomer total amount.
8. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In three, the polystyrene seed emulsion is by centrifuging precipitation, washing the low molecular weight polyphenylene obtained by step one
High polymer dispersion in ethene seed emulsion is removed so that polystyrene seed emulsion is moved on to by organic alcohol phase transfer
Aqueous phase forms aqueous polystyrene seed emulsion.
9. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In three, the swelling time is 4~24h, and swelling temperature is 0~45 DEG C.
10. the preparation method of big particle diameter Procedure of Polymerized Micro-Particles with Hollow according to claim 1, it is characterised in that in the step
In rapid four, 1500~15000rpm of rotating speed of the high speed shear dispersion machine, shear time is 0.1~3h；
In the step 4, the speed of agitator is 120~300rpm, and polymerization reaction time is 4~16h；Polymerization temperature 50
~95 DEG C；
In the step 4, the solid content of the big sub- emulsion of particle diameter Procedure of Polymerized Micro-Particles with Hollow is 15~35%.
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| CN106633057B (en) * | 2016-12-27 | 2018-11-30 | 江南大学 | The preparation of core-shell structure particle with cavity |
| CN108623734A (en) * | 2017-03-24 | 2018-10-09 | 南京工业大学 | Preparation method of hollow polymer microspheres |
| FR3065651B1 (en) * | 2017-04-28 | 2020-05-29 | IFP Energies Nouvelles | PROCESS FOR THE PREPARATION OF A MULTIMODAL POROSITY MONOLITE |
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| CN103204966A (en) * | 2013-04-11 | 2013-07-17 | 江苏大学 | Method for preparing magnetic/hollow double-shell layer print adsorbent by emulsion polymerization |
| CN104043434A (en) * | 2014-07-03 | 2014-09-17 | 江苏大学 | Preparation method for cellulose hollow magnetic imprinted composite microsphere adsorbent |
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| CN103100360A (en) * | 2012-12-30 | 2013-05-15 | 杭州师范大学 | Preparation method of hollow inorganic submicron particle |
| CN103204966A (en) * | 2013-04-11 | 2013-07-17 | 江苏大学 | Method for preparing magnetic/hollow double-shell layer print adsorbent by emulsion polymerization |
| CN104043434A (en) * | 2014-07-03 | 2014-09-17 | 江苏大学 | Preparation method for cellulose hollow magnetic imprinted composite microsphere adsorbent |
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