CN117050374A - Thermal expansion microsphere and preparation method thereof - Google Patents
Thermal expansion microsphere and preparation method thereof Download PDFInfo
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- CN117050374A CN117050374A CN202311058307.2A CN202311058307A CN117050374A CN 117050374 A CN117050374 A CN 117050374A CN 202311058307 A CN202311058307 A CN 202311058307A CN 117050374 A CN117050374 A CN 117050374A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 13
- 239000004088 foaming agent Substances 0.000 claims abstract description 11
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- -1 1-methyl benzyl Chemical group 0.000 claims description 10
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000010008 shearing Methods 0.000 claims description 7
- 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 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000103 Expandable microsphere Polymers 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- HSOOIVBINKDISP-UHFFFAOYSA-N 1-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CCC)OC(=O)C(C)=C HSOOIVBINKDISP-UHFFFAOYSA-N 0.000 claims description 4
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-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 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000001506 calcium phosphate Substances 0.000 claims description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 4
- 235000011010 calcium phosphates Nutrition 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- DHPPBQGPYPPLAE-UHFFFAOYSA-N hexanedioic acid;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OC(=O)CCCCC(O)=O DHPPBQGPYPPLAE-UHFFFAOYSA-N 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 4
- JWFXDAWTXHYWLW-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;methyl 2,3-dimethylbut-2-enoate Chemical compound COC(=O)C(C)=C(C)C.OCC(CO)(CO)CO JWFXDAWTXHYWLW-UHFFFAOYSA-N 0.000 claims description 3
- 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
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 3
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 claims description 3
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920000136 polysorbate Polymers 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 11
- 239000012792 core layer Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 238000009835 boiling Methods 0.000 abstract 1
- 230000003139 buffering effect Effects 0.000 abstract 1
- 238000009413 insulation Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000000565 sealant Substances 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 229920005992 thermoplastic resin Polymers 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 42
- 239000000047 product Substances 0.000 description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 238000005187 foaming Methods 0.000 description 11
- 239000003094 microcapsule Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- NBZANZVJRKXVBH-GYDPHNCVSA-N alpha-Cryptoxanthin Natural products O[C@H]1CC(C)(C)C(/C=C/C(=C\C=C\C(=C/C=C/C=C(\C=C\C=C(/C=C/[C@H]2C(C)=CCCC2(C)C)\C)/C)\C)/C)=C(C)C1 NBZANZVJRKXVBH-GYDPHNCVSA-N 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000011258 core-shell material Substances 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- 239000002775 capsule Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
Abstract
The invention discloses a preparation method of thermal expansion microspheres. The thermal expansion microsphere takes thermoplastic resin as a shell and low-boiling alkane as a core, the core layer is heated and gasified to generate internal pressure, the internal pressure and the external pressure difference enable the shell layer to be stretched outwards, and the core layer gas gradually diffuses outwards along with the reduction of the thickness of the shell layer and the reduction of the barrier property of the shell layer gas, so that the low-density hollow microsphere is finally formed. The microsphere has the characteristics of density reduction, heat insulation, shock resistance, buffering and the like, and is widely used in various fields such as shoe materials, papermaking, detachable sealant, three-dimensional paint and the like. The invention prepares oil phase containing active polymerization regulator, initiator, foaming agent, mono-olefin monomer, cross-linking agent and water phase containing dispersant and assistant separately, and cuts the oil-water two-phase mixture into oil drop suspension; then, heating initiates polymerization. The method introduces an active polymerization regulator innovatively, so that the microsphere has high synthesis efficiency, short reaction time, high expansion rate and good batch stability.
Description
Technical Field
The invention relates to the field of functional microspheres, in particular to a thermal expansion microsphere and a preparation method thereof.
Background
The polymer closed-cell foam is a gas/solid composite material, has the functional characteristics of low density, high specific strength/impact strength and low thermal conductivity, can save a large amount of resources, and has been widely used in the fields of construction, packaging, daily necessities, aerospace and the like. The addition of thermally expandable microspheres to polymeric resins is a common means of obtaining closed cell foams of polymers. Wherein the microsphere expansion properties directly determine the quality of the closed cell foam.
Commercially available thermally expandable microspheres are prepared by suspension polymerization and typically have a particle size of between 5 and 100 microns. Before polymerization, an oil phase containing a polymerization monomer, a foaming agent and an initiator and a water phase containing a dispersing agent and a plurality of auxiliary agents are respectively prepared, and an oil-water mixture is sheared into an oil drop suspension. When polymerization occurs, polymer monomers are gradually polymerized to generate polymer chains, with the improvement of conversion rate, the solution taking the polymer chains as solute and the monomer-foaming agent mixed solution as solvent gradually undergoes phase separation, the polymer chains are precipitated and separated out to form a polymer-rich phase swelling a small amount of monomer/foaming agent, and the monomer-foaming agent mixed solution dissolving a small amount of polymer chains becomes a solvent-rich phase. After phase separation, the polymer-rich phase rapidly coalesces while its swollen monomer continues to polymerize, forming primary particles, which continue to coalesce to form primary particle aggregates. Under thermodynamic driving, primary particles and their aggregates tend to distribute at the oil/water interface and further adhere and form an initially discontinuous shell, eventually evolving into a dense shell as polymerization proceeds; while the solvent-rich phase develops into the core layer in situ.
However, the polymer chains in the center of the oil droplets are sensitive to factors such as chain entanglement, crosslinking, system viscosity and the like, are extremely easy to precipitate in the interior of the micron-sized oil droplets, and are difficult to smoothly diffuse to the oil/water interface. Therefore, in order to obtain an ideal core-shell structure, the polymerization rate is controlled at an extremely low level, resulting in long reaction time and low synthesis efficiency. In addition, when the shell layer is heated to generate plastic deformation, a trace amount of cross-linking agent is usually added to increase the strength of the shell layer in order to ensure the stability of the microsphere structure. However, in the conventional radical crosslinking polymerization, microgels are easily formed in the initial stage of polymerization, so that the crosslinking of the shell layer is uneven, stress concentration is easily induced at the defect position, and the strength of the shell layer cannot be effectively improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a thermal expansion microsphere and a preparation method thereof.
The invention adopts the following specific technical scheme:
a preparation method of thermal expansion microspheres comprises the following operation steps:
mixing 0.1-5 parts by mass of active polymerization regulator, 0.1-2 parts by mass of initiator, 20-100 parts by mass of foaming agent, 100 parts by mass of mono-olefin monomer and 0.01-5 parts by mass of cross-linking agent to form an oil phase;
dispersing or dissolving 1-10 parts by mass of dispersing agent, 0.01-2 parts by mass of emulsifying agent, 1-200 parts by mass of metal salt and 0.01-2 parts by mass of polymerization inhibitor into 150-1000 parts by mass of deionized water to form a water phase;
mixing the oil phase and the water phase, and treating the formed mixture for 5-15 minutes under a shearing field to obtain an oil drop suspension;
heating the suspension to 50-95 ℃ and stopping the reaction after polymerizing for 6-24 hours; and filtering, washing and drying the suspension product to obtain the thermal expansion microsphere.
Further, the structural formula of the active polymerization regulator is as follows:
wherein, the R group is isopropyl, formate, acetate, 1-methyl benzyl, 1-dimethylbenzyl, 2-isobutyronitrile, 3-benzoate, 2-cyanoacetate or 2-amino acetate; the Z group being phenyl, benzyl, alkyl (C) 4 ～C 20 Any length), ethoxy and carbon chain number of C 4 ～C 20 Alkyl mercapto groups of (a).
Further, the initiator is azo initiator with water solubility lower than or equal to 0.5 g/kg water at 25 ℃ and peroxide initiator. The foaming agent has carbon chain number of C 4 ～C 8 A mixture of one or more of the short-chain alkanes in any proportion.
Further, the mono-olefin monomer is one or more mixed monomers of acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, styrene, vinyl toluene, tertiary butyl styrene and N-methylol acrylamide according to any proportion; the cross-linking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylic acid, ethylene glycol diacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, adipic acid dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane and pentaerythritol tetramethyl acrylic acid.
Further, the dispersing agent is one or a mixture of a plurality of common dispersing agents such as polyvinyl alcohol, magnesium hydroxide, calcium carbonate, calcium phosphate, silica sol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, carboxymethyl cellulose and the like according to any proportion. The emulsifier is one or more of common emulsifiers such as sodium dodecyl sulfate, cetyltrimethylammonium bromide, tu phenol polyoxyethylene ether, OP series emulsifier (such as OP-10, OP-30, etc.), MS-1, span, tween, sodium dodecyl benzene sulfonate, etc. in any proportion. The metal salt is sodium chloride; the polymerization inhibitor is one or a mixture of two of nitrite and potassium dichromate according to any proportion.
Further, the shearing field is formed by a high-speed shearing machine, a high-pressure homogenizer, a cell pulverizer or a hypergravity field generating device.
Based on the traditional suspension polymerization method, the high-performance thermal expansion microsphere can be efficiently prepared by only adding an active polymerization regulator into the oil phase. The invention has the beneficial effects that: 1. the microsphere with complete core-shell structure can be prepared at a higher polymerization rate; 2. the problem of uneven crosslinking can be improved, and a high-strength shell layer is obtained, so that the microsphere has more excellent expansion performance.
Drawings
FIG. 1 is an SEM image of the surface morphology of thermally expanded microspheres obtained in example 1 of the present invention;
FIG. 2 is an SEM image of the internal structure of the thermally expanded microspheres obtained in example 1 of the present invention;
FIG. 3 is a graph showing the foaming property of TMA of the heat-expandable microspheres obtained in example 1 of the present invention;
FIG. 4 is an SEM image of the surface morphology of thermally expanded microspheres obtained according to example 2 of the present invention;
FIG. 5 is an SEM image of the internal structure of the thermally expanded microspheres obtained in example 2 of the present invention;
FIG. 6 is a graph showing the foaming property of the heat-expandable microspheres TMA obtained in example 2 of the present invention.
Detailed Description
The invention provides a preparation method of thermal expansion microspheres, which comprises the following operation steps:
(a) Mixing 0.1-5 parts by mass of active polymerization regulator, 0.1-2 parts by mass of initiator, 20-100 parts by mass of foaming agent, 100 parts by mass of mono-olefin monomer and 0.01-0.5 part by mass of cross-linking agent to form an oil phase;
(b) Dispersing or dissolving 1-10 parts by mass of dispersing agent, 0.01-2 parts by mass of emulsifying agent, 1-200 parts by mass of metal salt and 0.01-2 parts by mass of polymerization inhibitor into 150-1000 parts by mass of deionized water to form a water phase;
(c) Mixing the oil phase and the water phase, and treating the formed mixture for 5-15 minutes under a shearing field to obtain an oil drop suspension;
(d) Heating the suspension to 50-95 ℃ and stopping the reaction after polymerizing for 6-24 hours; and filtering, washing and drying the suspension product to obtain the thermal expansion microsphere.
The structural formula of the active polymerization regulator is as follows:
wherein, the R group is isopropyl, formate, acetate, 1-methyl benzyl, 1-dimethylbenzyl, 2-isobutyronitrile, 3-benzoate, 2-cyanoacetate or 2-amino acetate; the Z group being phenyl, benzyl, alkyl (C) 4 ～C 20 Any length), ethoxy, alkylmercapto (C) 4 ～C 20 Arbitrary length).
In the step (a), the initiator is azo initiator and peroxide initiator with water solubility lower than or equal to 0.5 g/kg water at 25 ℃. The foaming agent has carbon chain number of C 4 ～C 8 A mixture of one or more of the short-chain alkanes in any proportion.
The mono-olefin monomer is one or more mixed monomers of acrylic ester, methacrylic ester, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, styrene, vinyl toluene, tertiary butyl styrene and N-methylol acrylamide according to any proportion; the cross-linking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylic acid, ethylene glycol diacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, adipic acid dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane and pentaerythritol tetramethyl acrylic acid.
In the step (b), the dispersing agent is one or a mixture of more of polyvinyl alcohol, magnesium hydroxide, calcium carbonate, calcium phosphate, silica sol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer and carboxymethyl cellulose according to any proportion. The emulsifier is one or more of sodium dodecyl sulfate, cetyltrimethylammonium bromide, tu phenol polyoxyethylene ether, OP series, MS-1, span, tween and sodium dodecyl benzene sulfonate. The metal salt is sodium chloride; the polymerization inhibitor is one or a mixture of two of nitrite and potassium dichromate according to any proportion.
In the step (c), the shearing field is formed by a high-speed shearing machine, a high-pressure homogenizer, a cell pulverizer or a hypergravity field generating device.
Aiming at the fact that the polymer chains almost instantaneously finish growing in the traditional polymerization method, the high molecular weight molecular chains are mutually entangled, and are easy to precipitate and separate out in oil drops before diffusing and migrating to an oil/water interface, so that the shells of the capsules cannot be formed. This is particularly true when cross-linking agents are used, where the linear molecular chains are linked into a three-dimensional network. Therefore, in order to avoid the precipitation of molecular chains in oil drops, the polymerization rate must be controlled at an extremely low level, and the cross-linking agent used in the traditional polymerization has large distribution difference in each chain, so that the cross-linking defect exists, and the problem of limited strength improvement capability is solved, and the preparation method of the thermal expansion microsphere is provided, wherein a polymerization regulator is added to control the simultaneous growth of a plurality of molecular chains, each molecular chain grows slowly, the molecular weight gradually increases, the viscosity in the oil drops is low, and the diffusion coefficient of the molecular chains is high; during most of the diffusion to the oil/water interface, the intertwined precipitates are less likely to separate out. Therefore, the molecular chains can migrate to the interface to form a capsule shell, and the polymerization rate in the whole process is high. Furthermore, under the present method, the crosslinking agent is uniformly distributed in each chain, so-called crosslinking defects are eliminated. Therefore, the microsphere with complete core-shell structure can be prepared at a higher polymerization rate, and the problem of uneven crosslinking can be solved, so that a high-strength shell layer is obtained, and the microsphere has more excellent expansion performance.
The present invention will be further described in detail with reference to the drawings and the detailed description, in order to make the objects, technical solutions and advantages of the present invention more apparent.
In the examples, the structure of the active polymerization modulator (1) is as follows:
the structure of the active polymerization regulator (2) is as follows:
the structure of the active polymerization regulator (3) is as follows:
the structure of the active polymerization regulator (4) is as follows:
the structure of the active polymerization regulator (5) is as follows:
the structure of the active polymerization regulator (6) is as follows:
example 1
The first step: 0 part by mass of the active polymerization controller (1), 0.2 part by mass of azobisisobutyronitrile, 30 parts by mass of isopentane, 100 parts by mass of mono-olefin monomer, and 0.2 part by mass of divinylbenzene were mixed and stirred to form an oil solution.
And a second step of: 10 parts by mass of polyvinyl alcohol, 0.01 part by mass of sodium dodecyl sulfate, 1 part by mass of sodium chloride and 0.01 part by mass of sodium nitrite are dispersed or dissolved in 1000 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated in a shear field of a high speed shear for 15 minutes to give an oil droplet suspension.
Fourth step: the suspension was transferred to a reactor, heated to 60℃and polymerized for 24 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 2
The first step: 2 parts by mass of the active polymerization controller (1), 0.2 part by mass of divinylbenzene, 0.2 part by mass of azobisisobutyronitrile, 30 parts by mass of isopentane, and 100 parts by mass of monoethylene monomer were mixed and stirred to form an oil solution.
And a second step of: 10 parts by mass of polyvinyl alcohol, 0.01 part by mass of sodium dodecyl sulfate, 1 part by mass of sodium chloride and 0.01 part by mass of sodium nitrite are dispersed or dissolved in 1000 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated in a shear field of a high speed shear for 15 minutes to give an oil droplet suspension.
Fourth step: the suspension was transferred to a reactor, heated to 60℃and polymerized for 24 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 3
The first step: 0 parts by mass of the active polymerization controller (4), 0.3 parts by mass of neopentyl glycol dimethacrylate, 1 part by mass of azobisisoheptonitrile, 100 parts by mass of isooctane and 100 parts by mass of monoethylene monomer were mixed and stirred to form an oil solution.
And a second step of: 10 parts by mass of carboxymethyl cellulose, 0.01 part by mass of OP-series emulsifier, 200 parts by mass of sodium chloride and 0.01 part by mass of sodium nitrite are dispersed or dissolved in 300 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 15 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 60℃and polymerized for 24 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 4
The first step: 5 parts by mass of the active polymerization controller (4), 0.3 part by mass of neopentyl glycol dimethacrylate, 1 part by mass of azobisisoheptonitrile, 100 parts by mass of isooctane and 100 parts by mass of monoethylene monomer were mixed and stirred to form an oil solution.
And a second step of: 10 parts by mass of carboxymethyl cellulose, 0.01 part by mass of OP-series emulsifier, 200 parts by mass of sodium chloride and 0.01 part by mass of sodium nitrite are dispersed or dissolved in 300 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 15 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 60℃and polymerized for 6 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 5
The first step: 0.1 part by mass of the active polymerization controller (2), 5 parts by mass of ethylene glycol dimethacrylate, 2 parts by mass of azobisisobutyronitrile, 50 parts by mass of n-hexane, 100 parts by mass of mono-olefin monomer were mixed and stirred to form an oil solution.
And a second step of: 1 part by mass of magnesium hydroxide, 2 parts by mass of cetyltrimethylammonium bromide, 200 parts by mass of sodium chloride and 2 parts by mass of sodium nitrite are dispersed or dissolved in 150 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 5 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 50℃and polymerized for 24 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 6
The first step: 5 parts by mass of the active polymerization controller (3), 0.05 part by mass of butanediol dimethacrylate, 0.1 part by mass of azobisisobutyronitrile, 20 parts by mass of n-heptane, 100 parts by mass of mono-olefin monomer were mixed and stirred to form an oil solution.
And a second step of: 10 parts by mass of calcium phosphate, 1 part by mass of sodium dodecylbenzenesulfonate, 100 parts by mass of sodium chloride, and 0.5 part by mass of potassium dichromate were dispersed or dissolved in 500 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 15 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 95℃and polymerized for 24 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 7
The first step: 0.1 part by mass of the living polymerization regulator (5), 0.05 part by mass of adipic acid dimethacrylate, 0.1 part by mass of azobisisobutyronitrile, 20 parts by mass of n-heptane, 100 parts by mass of the monoethylene monomer were mixed and stirred to form an oil solution.
And a second step of: 1 part by mass of polyvinylpyrrolidone, 2 parts by mass of Span-type emulsifier, 200 parts by mass of sodium chloride, and 0.02 part by mass of sodium nitrite are dispersed or dissolved in 500 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 10 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 95℃and polymerized for 6 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
Example 8
The first step: 5 parts by mass of the active polymerization controller (2), 0.01 part by mass of tetraethyleneglycol dimethacrylate, 2 parts by mass of azobisisobutyronitrile, 100 parts by mass of n-octane, and 100 parts by mass of a monoethylene monomer were mixed and stirred to form an oil solution.
And a second step of: 1 part by mass of silica sol, 1 part by mass of MS-1 type emulsifier, 100 parts by mass of sodium chloride and 0.05 part by mass of potassium dichromate are dispersed or dissolved in 1000 parts by mass of deionized water, and stirred to form an aqueous dispersion.
And a third step of: the oil and water phases were mixed and the mixture was treated under a shear field for 5 minutes to give an oil drop suspension.
Fourth step: the suspension was transferred to a reactor, heated to 65℃and polymerized for 6 hours, and the reaction was stopped. And carrying out suction filtration, water washing and drying on the suspension product to obtain a powdery foaming microcapsule product.
In the above examples, examples 1 to 4 were based on acrylic acid ester or methacrylic acid ester type monoethylene monomers such as acrylic acid ester, examples 5 to 8 were based on acrylonitrile or methacrylic acid nitrile type monoethylene monomers such as acrylonitrile, and the metal salt was sodium chloride.
Referring to fig. 1-6 and table 1, by comparing examples 1-2, it can be found that: when the active polymerization regulator is not added, the surface of the obtained microcapsule is concave, the thickness of the shell layer is uneven, and the in-situ expansion volume of the microcapsule is observed to be small under an optical microscope; when the active polymerization regulator is added, the obtained microcapsule has high sphericity and complete and symmetrical core-shell structure, and the in-situ expansion volume of the capsule is observed under an optical microscope to be large, and the capsule expands to the upper limit of the shell strength and can be broken or retracted. The volume change (i.e. expansion ratio) of the microsphere prepared by the method is large after expansion/before expansion, which indicates that the method can improve the problem of uneven crosslinking and obtain a high-strength shell layer, thereby leading the microsphere to have more excellent expansion performance. Meanwhile, by comparing examples 3 to 4, it can be found that: the addition of the active polymerization regulator shortens the polymerization time from 24 hours to 6 hours. The capsule with close foaming performance can be obtained in a shorter time, which shows that the integral polymerization rate of the invention can be accelerated, and the microsphere with complete core-shell structure can be prepared in a shorter time.
Experiments prove that the microspheres prepared in the examples 3-8 have high sphericity, complete and symmetrical core-shell structure and large thermal expansion volume. In addition, in example 5, the amount of the crosslinking agent used is high, so that the expansion ratio is poor, but the method is still superior to the conventional suspension polymerization method, and the amount of the crosslinking agent can be selected according to actual requirements.
Table 1 shows the values of the expansion times and the dimensions before and after expansion of the thermally expanded microspheres obtained in examples 1 to 8 of the present invention.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary or exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A method of preparing thermally expandable microspheres, comprising:
mixing 0.1-5 parts by mass of active polymerization regulator, 0.1-2 parts by mass of initiator, 20-100 parts by mass of foaming agent, 100 parts by mass of mono-olefin monomer and 0.01-5 parts by mass of cross-linking agent to form an oil phase;
dispersing or dissolving 1-10 parts by mass of dispersing agent, 0.01-2 parts by mass of emulsifying agent, 1-200 parts by mass of metal salt and 0.01-2 parts by mass of polymerization inhibitor into 150-1000 parts by mass of deionized water to form a water phase;
mixing the oil phase and the water phase, and treating the formed mixture under a shearing field to obtain an oil drop suspension;
heating the suspension to 50-95 ℃ and stopping the reaction after polymerizing for 6-24 hours; and filtering, washing and drying the suspension product to obtain the thermal expansion microsphere.
2. The method of claim 1, wherein the active polymerization modulator has the structural formula:
wherein, the R group is isopropyl, formate, acetate, 1-methyl benzyl, 1-dimethylbenzyl, 2-isobutyronitrile, benzoate, 2-cyanoacetate or 2-amino acetate; z groups are phenyl groups, benzyl groups and C carbon chain numbers 4 ～C 20 Alkyl, ethoxy and carbon chain number of C 4 ～C 20 Alkyl mercapto.
3. The process according to claim 1, wherein the initiator is an azo initiator or a peroxide initiator having a water solubility of 0.5 g/kg or less at 25 ℃.
4. The method according to claim 1, wherein the foaming agent has a carbon chain number of C 4 ～C 8 A mixture of one or more of the short-chain alkanes in any proportion.
5. The preparation method according to claim 1, wherein the mono-olefin monomer is a mixed monomer of one or more of acrylic acid ester, methacrylic acid ester, acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, styrene, vinyl toluene, tert-butyl styrene, acrylamide and N-methylolacrylamide in any proportion; the cross-linking agent is one or more of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylic acid, ethylene glycol diacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, adipic acid dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane and pentaerythritol tetramethyl acrylic acid.
6. The preparation method according to claim 1, wherein the dispersing agent is one or more of polyvinyl alcohol, magnesium hydroxide, calcium carbonate, calcium phosphate, silica sol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, and carboxymethyl cellulose.
7. The preparation method according to claim 1, wherein the emulsifier is one or more of sodium dodecyl sulfate, cetyltrimethylammonium bromide, polyoxyethylene Tubased phenol, OP series emulsifier, MS-1, span, tween and sodium dodecyl benzene sulfonate.
8. The method of claim 1, wherein the metal salt is sodium chloride; the polymerization inhibitor is one or a mixture of two of nitrite and potassium dichromate according to any proportion.
9. The method of claim 1, wherein the shear field is generated by a high-speed shear, a high-pressure homogenizer, a cell pulverizer, or a hypergravity field generating device.
10. A thermally expandable microsphere prepared by the method of any one of claims 1 to 9.
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