CN106554446B - A kind of fast preparation method of multifunctionality fluoropolymer microballoon - Google Patents
A kind of fast preparation method of multifunctionality fluoropolymer microballoon Download PDFInfo
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- CN106554446B CN106554446B CN201610962198.0A CN201610962198A CN106554446B CN 106554446 B CN106554446 B CN 106554446B CN 201610962198 A CN201610962198 A CN 201610962198A CN 106554446 B CN106554446 B CN 106554446B
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- fluoropolymer
- microballoon
- necked flask
- reaction
- monomer
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- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 108
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 135
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 110
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000178 monomer Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011259 mixed solution Substances 0.000 claims abstract description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 229920001971 elastomer Polymers 0.000 claims abstract description 31
- 239000005457 ice water Substances 0.000 claims abstract description 31
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 28
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 60
- 229920000642 polymer Polymers 0.000 claims description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 235000019441 ethanol Nutrition 0.000 claims description 36
- 239000012987 RAFT agent Substances 0.000 claims description 32
- 238000001556 precipitation Methods 0.000 claims description 31
- 239000000839 emulsion Substances 0.000 claims description 30
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 30
- -1 glycidyl ester Chemical class 0.000 claims description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 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 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 21
- 230000000977 initiatory effect Effects 0.000 claims description 16
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004090 dissolution Methods 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 6
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 3
- WSTYACAZFNPSBL-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)C1=C(C=CC=C1)P(C1=C(C=CC=C1)C(C1=CC=CC=C1)=O)=O Chemical compound C(C1=CC=CC=C1)(=O)C1=C(C=CC=C1)P(C1=C(C=CC=C1)C(C1=CC=CC=C1)=O)=O WSTYACAZFNPSBL-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 3
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 claims description 3
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims description 2
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- 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 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 claims 1
- FHCANPHHJPWZLM-UHFFFAOYSA-N 5,5,6,7,7,7-hexafluoroheptane-2,3-diol Chemical compound FC(CC(C(C)O)O)(C(C(F)(F)F)F)F FHCANPHHJPWZLM-UHFFFAOYSA-N 0.000 claims 1
- VCGITDXQIPTCIC-UHFFFAOYSA-N FC(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F Chemical group FC(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(C(C(C(C(C(C(C(C(F)(F)F)(F)F)=C(C(F)(F)F)F)(F)F)(F)F)(F)F)(F)F)(F)F)F VCGITDXQIPTCIC-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- XVKKIGYVKWTOKG-UHFFFAOYSA-N diphenylphosphoryl(phenyl)methanone Chemical compound C=1C=CC=CC=1P(=O)(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 XVKKIGYVKWTOKG-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229920001427 mPEG Polymers 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 abstract description 13
- 239000011737 fluorine Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000012429 reaction media Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 abstract description 5
- 238000012674 dispersion polymerization Methods 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- 239000011805 ball Substances 0.000 description 15
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 12
- SLPJGDQJLTYWCI-UHFFFAOYSA-N dimethyl-(4,5,6,7-tetrabromo-1h-benzoimidazol-2-yl)-amine Chemical compound BrC1=C(Br)C(Br)=C2NC(N(C)C)=NC2=C1Br SLPJGDQJLTYWCI-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 6
- 102400000830 Saposin-B Human genes 0.000 description 5
- 101800001697 Saposin-B Proteins 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 1
- 0 C*(C)CC(C)(C)SC(SC(C)(C)CC(CC(C)(C)C(C)(C)C(O)=O)C([N+]([O-])=O)=*)=S Chemical compound C*(C)CC(C)(C)SC(SC(C)(C)CC(CC(C)(C)C(C)(C)C(O)=O)C([N+]([O-])=O)=*)=S 0.000 description 1
- HAHPGQIYPXCFBI-UHFFFAOYSA-N CC(=O)C.N1CCOCC1 Chemical compound CC(=O)C.N1CCOCC1 HAHPGQIYPXCFBI-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000012703 microemulsion polymerization Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/22—Esters containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：After function monomer, RAFT reagents, initiator, organic solvent and stirring and dissolving is added in single-necked flask, single-necked flask is put into ice-water bath and is passed through rubber stopper seal after nitrogen 30min into single-necked flask, single-necked flask, which is then put into the oil bath pan that temperature is 65 90 DEG C, reacts 2h；The present invention is using ethanol/water mixed solution as reaction medium, using light RAFT dispersion polymerization processes, a step, quickly, cryogenically prepare fluoropolymer microballoon.The preparation method is simple, and reaction speed quickly, only needs half an hour that can reach 90% or more monomer conversion, realizes a kind of quick, environmentally protective, energy-efficient fluorine-containing microballoon novel preparation method, and the fluoropolymer microballoon of preparation has good monodispersity；Fluorine-containing microballoon is conducive to microballoon fast transferring to coating surface because of its low surface energy and corrosion resistance so that coating surface has good hydrophobicity and corrosion resistance.
Description
Technical field
The present invention relates to a kind of synthesis field of polymer microballoon, especially a kind of multi-functional fluoropolymer microballoon
Fast preparation method.
Background technology
Polymer microballoon refers to diameter in nanoscale to micron order, and shape is spherical or other spherical solids high scores
Sub- material or polymer composite.Polymer microballoon be widely used in because of its special size and special construction coating and printing ink,
The fields such as electronic information, chromatography, biological medicine, microreactor, derived energy chemical.
Polymer microballoon can by emulsion polymerization, emulsifier-free emulsion polymerization, micro-emulsion polymerization, mini-emulsion polymerization, dispersin polymerization,
The polymerizations means such as suspension polymerisation and precipitation polymerization synthesize to obtain.Wherein, dispersion copolymerization method is to receive because it can prepare particle size range
Meter level becomes to the monodisperse polymer micro-sphere of micron order (0.1~15 μm) and prepares a kind of normal of monodisperse polymer microballoon
Use preparation method.It for fluoropolymer microballoon, is difficult to prepare because of the particularity of its fluorochemical monomer itself, and prepares
Fluorine-containing microballoon particle size distribution range it is very wide, it is difficult to the fluoropolymer microballoon of synthesizing monodisperse.
Patent 201310047973.6 discloses a kind of fluoropolymer microballoon.This method is made with liquid carbon dioxide
Table is prepared using the method for light dispersin polymerization using fluorine-containing and tertiary amine group RAFT macromolecular chains as stabilizer for reaction medium
The polymer microballoon of the fluorine-containing esters of acrylic acid in face or methacrylic acid etc.This method needs to use supercritical carbon dioxide
Technology needs to be reacted in the autoclave of 30~70bar as reaction medium, and to equipment requirement height, operation needs
Hyperbaric environment, complex steps.And the particle diameter distribution of the fluorine-containing microballoon prepared is very wide, and monodispersity is poor.
Patent CN201310680476.X discloses a kind of fluorine-containing microballoon of multifunctionality and the preparation method and application thereof, this is specially
Profit is the inorganic microsphere that is handled using mercaptosilane coupling agents as core, by the hydrophilic monomer, double bond monomer containing epoxy group, fluorine-containing
Monomer is grafted on the fluorine-containing microballoon that inorganic microsphere surface is prepared into multifunctional polymer modification.This method is needed to inorganic particulate table
Face carries out a series of processing, complex steps and limit its extensive industrialization.
In recent years, Light lnduced Free Radicals polymerization is introduced into dispersion polymerization systems, have developed a kind of quick, low
The light-initiated dispersin polymerization of temperature prepares polymer microballoon (Journal of Polymer Science Part A:Polymer
Chemistry, 2008,46 (4)：1329-1338), while in light dispersion polymerization systems reversible addion-fragmentation chain transfer is added
Agent (RAFT) constitutes light-initiated RAFT dispersin polymerizations body (Macromolecules, 2012,45 (21)：8790-8795), it can obtain
Monodispersity polymer microballoon, and polymerization rate is quickly, in 30min monomer conversion can reach 90% with
On.But the microballoon of the monodispersity synthesized at present is only limitted to the monomer of esters of acrylic acid or methyl acrylic ester, for list
The fluorine-containing microballoon of dispersibility, is still a bigger challenge at present.
Therefore, it develops a kind of simple, quick, environmentally protective method and prepares a kind of the multi-functional fluorine-containing micro- of monodispersity
The growing demand in the fields such as ball, referred to as modern coatings, biological medicine.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of quick preparation side of multi-functional fluoropolymer microballoon
Method, it is molten that this method has synthesized the parent that polymer chain terminal contains reversible addion-fragmentation chain transfer agent (RAFT) active group first
Agent Macro RAFT agent, and as stable dispersant, carry out light RAFT dispersin polymerizations under ultraviolet light and be made.
The fluoropolymer microballoon of the present invention can pass through alcohol in the variation of the chemical constitution of Macro RAFT agent and reaction medium
Water quality than variation, you can the grain size for obtaining microballoon changes between nanoscale and micron order；It can be introduced in microsphere surface a variety of
Functional group；And polymerization rate is quickly, and monomer conversion is 90% or more.
The technical scheme is that：A kind of fast preparation method of multifunctionality fluoropolymer microballoon, feature exist
In including the following steps：
It 1), will be single after function monomer, RAFT reagents, initiator, organic solvent and stirring and dissolving, is added in single-necked flask
Mouth flask is put into ice-water bath and uses rubber stopper seal after being passed through nitrogen 30min into single-necked flask, then puts single-necked flask
Enter in the oil bath pan that temperature is 65-90 DEG C and reacts 1h-4h；
2) after the completion of, reaction in oil bath pan, rubber stopper is opened, single-necked flask is placed in ice-water bath, reaction is quenched, so
It is precipitated by ice ether, then is dissolved with tetrahydrofuran (THF) afterwards, after repeating precipitation/dissolving circulation 3 times；In room temperature, vacuum condition
Under be dried to obtain the Macro RAFT agent of yellow；
3), in reaction bulb be added ethanol/water mixed solution, and by Macro RAFT agent, fluoropolymer monomer and
Mixed dissolution in reaction bulb is added in photoinitiator；
4) after, being fully passed through nitrogen 10-18min into reaction bulb after dissolving, reaction bulb is sealed with quartz glass plug, it will be anti-
Answering bottle to be placed in, reaction temperature is 0-90 DEG C, light intensity is 0.2~100mW/cm2, radiation wavelength be 365nm initiation light source under irradiate
1-24h is reacted, white emulsion is obtained；
5) obtained white emulsion, is centrifuged into 2-10min in the case where rotating speed is 6000-12000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
In above-mentioned technical proposal, in step 1), the function monomer is hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate
Ethyl ester (HEMA), acrylic acid, methacrylic acid, acryloyl morpholine (ACMO), n-vinyl pyrrolidone, vinylpyridine
(P4VP), methoxy polyethylene glycol acrylate (OEGA), methoxy polyethylene glycol methacrylate-styrene polymer, acrylamide, isopropyl
Base acrylamide, N, N- dimethacrylamide, acrylic acid N, N- dimethylamino ethyl ester (DMAEA), methacrylic acid N, N-
Dimethylamino ethyl ester, glycidyl methacrylate, hydroxy propyl methacrylate, glycidyl acrylate, acrylic acid
The mixing of one or more of isobutyl ester, isodecyl acrylate, Isooctyl acrylate monomer or above-mentioned monomer it is one or more
The mixing of copolymer.
In above-mentioned technical proposal, in step 1), the initiator be azodiisobutyronitrile (AIBN), azobisisoheptonitrile,
Benzoyl peroxide, tert-butyl hydroperoxide, any one in peroxidized t-butyl perbenzoate, potassium peroxydisulfate, ammonium persulfate
Or several mixing.
In above-mentioned technical proposal, in step 1), the organic solvent is anhydrous dioxane.
In above-mentioned technical proposal, in step 1), the RAFT reagents are dithio formate or three thiocarboxylic classes
Object is closed, chemical constitution formula (I) is：
Wherein, R, R1, R2 are leaving group, and Z is activated group, it is preferable that carboxylic three thiocarboxylics RAFT examinations
Shown in the structural formula such as following formula (II) of agent (RDMAT)：
Wherein, R is the alkane containing 1~16 carbon atom, i.e. saturated aliphatic hydrocarbon, it is preferable that R group be ethyl (correspondingly,
The carboxylic RAFT reagents abbreviation EDMAT), octyl (correspondingly, the carboxylic RAFT reagents abbreviation ODMAT) or
Dodecyl (correspondingly, the carboxylic RAFT reagents abbreviation DDMAT).
In above-mentioned technical proposal, in step 1), the function monomer of addition is 100 with the molar concentration rate of RAFT reagents:1-
500:1, the molar concentration rate of the RAFT reagents and initiator that are added is 20:1-2:1.
In above-mentioned technical proposal, in step 3), the fluoropolymer monomer is 2,2,3,4,4,4- hexafluoro butylacrylic acids
Ester, dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate (HFBMA), 3- (perfluor -5- methylhexyls) -2- hydroxyls
Propyl methacrylate, 1,1,2,2- tetrahydrochysene perfluoro hexyls methacrylate, 1,1,2,2- tetrahydrochysene perfluoro decyl methyl-props
Olefin(e) acid ester, ten difluoro heptyl methacrylates, perfluorooctylethyl group acrylate (PFEA), perfluorododecyl ethylacrylic acid
Ester, perfluoroalkyl propyl methacrylate, 1,1,1,3,3,3- hexafluoro isopropyls methacrylate, 1,1,1,3,3,3- six
Fluorine isopropylacrylic acid ester, perfluorohexyl ethylene, perfluorobutyl ethylene, perfluorododecyl ethylmethyl acrylate, 1,1,
One or more of 2,2- tetrahydrochysene perfluorododecyls methacrylate, trifluoroethyl methacrylate (TFEMA).
In above-mentioned technical proposal, in step 3), the photoinitiator is 2- phenyl -2- dimethylaminos -1- (4- morpholine benzene
Base)-butanone -1,1- hydroxy-cyciohexyls benzophenone, bis- (2,4,6- trimethylbenzoyls) phosphine oxides of phenyl, 2- hydroxyl -2- first
Base -1- phenylacetones -1,2,4,6- trimethylbenzoyls diphenyl phosphine oxide, bis(benzoylphenyl) phosphine oxide, 2- methyl-1s -
Any one in [4- first mercaptophenyl] -2- morpholines acetone -1,
Preferably, the photoinitiator be 2- hydroxy-2-methyl -1- phenylacetones -1,1- hydroxy-cyciohexyls benzophenone, 2,
4,6- trimethylbenzoyls diphenyl phosphine oxide, bis(benzoylphenyl) phosphine oxide, 2- methyl-1s-[4- first mercaptophenyl] -2-
Any one in morpholine acetone -1 or 2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1.
In above-mentioned technical proposal, in step 3), in the ethanol/water mixed solution of addition, the mass parts of ethyl alcohol and water
Number ratio is 60：40~100：0.
In above-mentioned technical proposal, in step 3), the mass fraction of the fluoropolymer monomer of addition mixes for the ethanol/water
The 5-20% of solution quality number, the 0.2- that the mass fraction of Macro RAFT agent is fluoropolymer monomer mass number
20%, the mass fraction of photoinitiator is the 0.5~15% of fluoropolymer monomer mass number.
In above-mentioned technical proposal, in step 4), the initiation light source is medium pressure mercury lamp, ultraviolet light Non-polarized lamp, metal halogen
Any one of lamp or UV-LED light sources.
The functional group of fluoropolymer microsphere surface includes：Carboxyl, hydroxyl, epoxy group, isocyanate group, amido, pyrrole
Piperidinyl, unsaturated double-bond, sulfydryl.
The fluoropolymer microballoon of the preparation, ranging from 0.1-1 microns of change of size.
Beneficial effects of the present invention are：
(1) present invention is using ethanol/water mixed solution as reaction medium, a step, fast using light RAFT dispersion polymerization processes
Speed cryogenically prepares fluoropolymer microballoon.The preparation method is simple, and reaction speed quickly, only needs half an hour that can reach
90% or more monomer conversion realizes a kind of quick, environmentally protective, energy-efficient fluorine-containing microballoon novel preparation method.
(2) fluoropolymer microballoon prepared by the present invention has good monodispersity；Fluorine-containing microballoon is because of its low surface
Energy and corrosion resistance, are conducive to microballoon fast transferring to coating surface so that coating surface has good hydrophobicity and corrosion resistant
Corrosion.
(3) fluoropolymer microballoon prepared by the present invention, surface multiple functions group can be by adjusting macromolecular RAFT
The chemical composition of reagent and obtain, the method is simple and practicable, provides a kind of fluoropolymer microsphere surface functionalization of simplicity
New method.
(4) multi-functional fluoropolymer microballoon prepared by the present invention, grain size can change between nanoscale and micron order,
Can according to actual needs, the mass ratio of simple adjustment reaction medium, so that it may which to realize required grain size, and fluoropolymer is micro-
Ball has good monodispersity always.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 2；
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 3；
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 4；
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 5；
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 6；
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 7；
Fig. 8 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 8；
Fig. 9 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 9；
Figure 10 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 10；
Figure 11 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 11；
Figure 12 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 12；
Figure 13 is the scanning electron microscope (SEM) photograph (SEM) of fluoropolymer microballoon prepared by embodiment 13.
Specific implementation mode
The specific implementation mode of the present invention is described further below in conjunction with the accompanying drawings：
Embodiment 1
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), in single-necked flask be added 400mmol function monomers acrylic acid (AA), 2mmol RAFT reagent Ds DMAT,
After 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
To react 2h in 70 DEG C of oil bath pans；
2) it, reacts and completes in oil bath pan, open rubber stopper, single-necked flask is placed in during ice-water bath carries out, reaction is quenched,
Then it is precipitated by ice ether, is dissolved with tetrahydrofuran (THF), after such precipitation/dissolving circulation 3 times；In room temperature, vacuum condition
Under be dried to obtain the PAA-DDMAT Macro RAFT agents of yellow, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PAA-DDMAT of 0.2g
Macro RAFT agent, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 2.0g and 0.10g photoinitiator 2- hydroxyls
Mixed dissolution in reaction bulb is added in base -2- methyl-1s-phenylacetone -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 2
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) 300mmol function monomers hydroxy-ethyl acrylate (HEA), 2mmol RAFT reagents, are added in single-necked flask
It, will after DDMAT, 0.1mmol initiator azodiisobutyronitrile (AIBN), 340mmol organic solvents dioxane and stirring and dissolving
Single-necked flask is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, then puts single-necked flask
Enter the oil bath pan that temperature is 70 DEG C and reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PHEA-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PHEA- of 0.2g
DDMAT Macro RAFT agents, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 2.0g and 0.1g photoinitiators
Mixed dissolution in reaction bulb is added in 2- hydroxy-2-methyl -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 3
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) 500mmol function monomers vinylpyridine (P4VP), 2mmol RAFT reagents, are added in single-necked flask
It, will be single after DDMAT, 1mmol initiator azodiisobutyronitrile (AIBN), 340mmol organic solvents dioxane and stirring and dissolving
Mouth flask is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, is then put into single-necked flask
The oil bath pan that temperature is 70 DEG C reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The P4VP-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the P4VP- of 0.1g
DDMAT Macro RAFT agents, the fluoropolymer monomer methacrylic acid trifluoro ethyl ester (TFEMA) of 2.0g and 0.10g are light-initiated
Mixed dissolution in reaction bulb is added in agent 2- hydroxy-2-methyl -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Irradiation reaction 1h, obtains white emulsion under the initiation light source that temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength are 365nm；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 4
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), in single-necked flask be added 300mmol function monomer acrylic acid N, N- dimethylamino ethyl esters (DMAEA),
2mmol RAFT reagent Ds DMAT, 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane are simultaneously
After stirring and dissolving, single-necked flask is put into ice-water bath and is passed through rubber stopper seal after nitrogen 30min into single-necked flask, then
Single-necked flask is put into the oil bath pan that temperature is 70 DEG C and reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PDMAEA-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PDMAEA- of 0.1g
DDMAT Macro RAFT agents, the ten difluoro heptyl ester (DFHMA) of fluoropolymer monomer methacrylic acid of 2.0g and 0.10g light draw
It sends out agent 2- hydroxy-2-methyl -1- phenylacetones -1 and mixed dissolution in reaction bulb is added；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 5
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) 200mmol function monomers methoxy polyethylene glycol acrylate (OEGA), 2mmol, are added in single-necked flask
RAFT reagent Ds DMAT, 0.2mmol initiator azodiisobutyronitrile (AIBN), 340mmol organic solvents dioxane simultaneously stir molten
Single-necked flask is put into ice-water bath and is passed through rubber stopper seal after nitrogen 30min into single-necked flask, then by single port by Xie Hou
Flask is put into the oil bath pan that temperature is 70 DEG C and reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The POEGA-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the POEGA- of 0.18g
DDMAT Macro RAFT agents, the fluoropolymer monomer perfluorooctylethyl group acrylate (PFEA) of 0.9g and 0.130g light draw
It sends out agent 2- hydroxy-2-methyl -1- phenylacetones -1 and mixed dissolution in reaction bulb is added；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 5 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 6
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) 400mmol function monomers N-isopropylacrylamide NIPAM, 2mmol RAFT reagents, are added in single-necked flask
It, will after DDMAT, 0.2mmol initiator azodiisobutyronitrile (AIBN), 340mmol organic solvents dioxane and stirring and dissolving
Single-necked flask is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, then puts single-necked flask
Enter the oil bath pan that temperature is 70 DEG C and reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PNIPAM-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PNIPAM- of 0.25g
DDMAT Macro RAFT agents, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 1.5g and 0.20g are light-initiated
Mixed dissolution in reaction bulb is added in agent 2- hydroxy-2-methyl -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 6 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 7
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) 300mmol function monomers acryloyl morpholine (ACMO), 2mmol RAFT reagents, are added in single-necked flask
It, will after DDMAT, 0.2mmol initiator azodiisobutyronitrile (AIBN), 340mmol organic solvents dioxane and stirring and dissolving
Single-necked flask is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, then puts single-necked flask
Enter the oil bath pan that temperature is 70 DEG C and reacts 2h；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PACMO-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the POEGA- of 0.5g
DDMAT Macro RAFT agents, the fluoropolymer monomer methacrylic acid trifluoro ethyl ester (TFEMA) of 2.5g and 0.30g are light-initiated
Mixed dissolution in reaction bulb is added in agent 2- hydroxy-2-methyl -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 7 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 8
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.1mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, ether precipitation, after such precipitation/dissolving circulation 3 times；
The PAA-DDMAT Macro RAFT agents of yellow are dried to obtain under room temperature, vacuum condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PAA-DDMAT of 0.8g
Macro RAFT agent, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 5.0g and 0.70g photoinitiator 2- hydroxyls
Mixed dissolution in reaction bulb is added in base -2- methyl-1s-phenylacetone -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 8 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 9
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.1mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, ether precipitation, after such precipitation/dissolving circulation 3 times；
The PAA-DDMAT Macro RAFT agents of yellow are dried to obtain under room temperature, vacuum condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and the PAA-DDMAT of 1g is big
Molecule RAFT reagents, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 6g and 0.80g photoinitiator 2- hydroxyls-
Mixed dissolution in reaction bulb is added in 2- methyl-1s-phenylacetone -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) after the completion of, centrifuging, clear 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Fig. 9 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 10
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, ether precipitation, after such precipitation/dissolving circulation 3 times；
The PAA-DDMAT Macro RAFT agents of yellow are dried to obtain under room temperature, vacuum condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PAA- of 0.35g
DDMAT Macro RAFT agents, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 7.0g and 1.0g photoinitiators
Mixed dissolution in reaction bulb is added in 2- hydroxy-2-methyl -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Figure 10 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 11
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PAA-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (14.4g/3.6g) ethanol/water, is added in reaction bulb, and by the PAA-DDMAT of 1.8g
Macro RAFT agent, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 9.0g and 1.35g photoinitiator 2- hydroxyls
Mixed dissolution in reaction bulb is added in base -2- methyl-1s-phenylacetone -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Figure 11 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 12
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The PAA-DDMAT Macro RAFT agents of yellow are dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (12.6g/5.4g) ethanol/water, is added in reaction bulb, and by the PAA-DDMAT of 0.2g
Macro RAFT agent, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 2.0g and 0.1g photoinitiator 2- hydroxyls
Mixed dissolution in reaction bulb is added in base -2- methyl-1s-phenylacetone -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Figure 12 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
Embodiment 13
A kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1), be added in single-necked flask 400mmol function monomers acrylic acid AA, 2mmol RAFT reagent Ds DMAT,
After 0.2mmol initiator azodiisobutyronitriles (AIBN), 340mmol organic solvents dioxane and stirring and dissolving, single port is burnt
Bottle is put into ice-water bath and is passed through into single-necked flask rubber stopper seal after nitrogen 30min, and single-necked flask is then put into temperature
2h is reacted for 70 DEG C of oil bath pans；
2), reaction is completed, and is opened rubber stopper, single-necked flask is placed in ice-water bath, reaction is quenched, then pass through ice ether
Precipitation polymers, obtained polymer use tetrahydrofuran (THF) to dissolve again, after such precipitation/dissolving circulation 3 times；In room temperature, very
The Macro RAFT agent of yellow is dried to obtain under empty condition, reactive chemistry structural formula is：
3) mixed solution of 18g (10.8g/7.2g) ethanol/water, is added in reaction bulb, and by the macromolecular of 0.2g
RAFT reagents, the fluoropolymer monomer methacrylic acid hexafluoro butyl ester (HFBMA) of 2.0g and 0.1g photoinitiator 2- hydroxyl -2- first
Mixed dissolution in reaction bulb is added in base -1- phenylacetones -1；
4) after, being passed through nitrogen 15min into reaction bulb, reaction bulb is sealed with quartz glass plug, reaction bulb is placed in reaction
Temperature is 30 DEG C, light intensity 30mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1h, obtain white emulsion；
5) obtained white emulsion, is centrifuged into 3-5min under the conditions of rotating speed is 10000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, it is micro- to obtain fluoropolymer for then vacuum drying
Ball.
Figure 13 is the scanning electron microscope (SEM) photograph (SEM) of the fluoropolymer microballoon of the present embodiment.
The above embodiments and description only illustrate the principle of the present invention and most preferred embodiment, is not departing from this
Under the premise of spirit and range, various changes and improvements may be made to the invention, these changes and improvements both fall within requirement and protect
In the scope of the invention of shield.
Claims (11)
1. a kind of fast preparation method of multifunctionality fluoropolymer microballoon, which is characterized in that include the following steps：
1) after function monomer, RAFT reagents, initiator, organic solvent and stirring and dissolving, is added in single-necked flask, single port is burnt
Bottle is put into ice-water bath and uses rubber stopper seal after being passed through nitrogen 30min into single-necked flask, and single-necked flask is then put into temperature
1h-4h is reacted in the oil bath pan that degree is 65-90 DEG C；
2) after the completion of, reaction in oil bath pan, rubber stopper is opened, single-necked flask is placed in ice-water bath, reaction is quenched, then led to
Ice ether precipitation is crossed, then is dissolved with tetrahydrofuran (THF), repeatedly after precipitation/dissolving 3 times；It is dry under room temperature, vacuum condition
To the Macro RAFT agent of yellow；
3) mixed solution of ethanol/water, is added in reaction bulb, and Macro RAFT agent, fluoropolymer monomer and light are drawn
It sends out agent and mixed dissolution in reaction bulb is added；
4) after, being fully passed through nitrogen 10-18min into reaction bulb after dissolving, reaction bulb is sealed with quartz glass plug, by reaction bulb
It is placed in that temperature is 0-90 DEG C, light intensity is 0.2~100mW/cm2, radiation wavelength be 365nm initiation light source under irradiation reaction 1-
For 24 hours, white emulsion is obtained；
5) obtained white emulsion, is centrifuged into 2-10min in the case where rotating speed is 6000-12000 turns/min；
6) it after the completion of, centrifuging, is cleaned 3 times with ethanol/water mixed solution, then vacuum drying obtains fluoropolymer microballoon.
2. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 1), the function monomer is hydroxy-ethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA), acrylic acid (AA), first
Base acrylic acid, acryloyl morpholine (ACMO), n-vinyl pyrrolidone, vinylpyridine (P4VP), methoxy poly (ethylene glycol) third
Olefin(e) acid ester (OEGA), methoxy polyethylene glycol methacrylate-styrene polymer, acrylamide, N-isopropylacrylamide, N, N- dimethyl propylenes
Acrylamide, acrylic acid N, N- dimethylamino ethyl ester (DMAEA), methacrylic N, N-dimethylamino ethyl ester, metering system
Acid glycidyl ester, hydroxy propyl methacrylate, glycidyl acrylate, isobutyl acrylate, isodecyl acrylate, propylene
The mixing of one or more of the different monooctyl ester of acid or the mixing of one or more copolymers of above-mentioned monomer.
3. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 1), the initiator is azodiisobutyronitrile (AIBN), azobisisoheptonitrile, benzoyl peroxide, t-butyl peroxy
Change hydrogen, any one or a few the mixing in peroxidized t-butyl perbenzoate, potassium peroxydisulfate, ammonium persulfate.
4. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 1), the organic solvent is anhydrous dioxane.
5. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 1), the RAFT reagents are dithio formate or three thiocarboxylic class compounds, chemical constitution formula (I) are：
Wherein, R, R1, R2 are leaving group, and Z is activated group.
6. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 1), the function monomer of addition is 100 with the molar concentration rate of RAFT reagents:1-500:1, be added RAFT reagents with draw
The molar concentration rate for sending out agent is 20:1-2:1.
7. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 3), the fluoropolymer monomer be 2,2,3,4,4,4- hexafluoro butyl propyleneglycol acid esters, dodecafluoroheptyl methacrylate,
Hexafluorobutyl mathacrylate (HFBMA), 3- (perfluor -5- methylhexyls) -2- hydroxy propyl methacrylates, 1,1,2,2-
Tetrahydrochysene perfluoro hexyl methacrylate, 1,1,2,2- tetrahydrochysene perfluoro decyls methacrylate, ten difluoro heptyl methacrylates,
Perfluorooctylethyl group acrylate (PFEA), perfluorododecyl ethyl propylene acid esters, perfluoroalkyl propyl methacrylate,
1,1,1,3,3,3- hexafluoro isopropyls methacrylate, 1,1,1,3,3,3- hexafluoro isopropyls acrylate, perfluoro hexyl second
Alkene, perfluorobutyl ethylene, perfluorododecyl ethylmethyl acrylate, 1,1,2,2- tetrahydrochysene perfluorododecyl metering systems
The mixing of one or more of acid esters, trifluoroethyl methacrylate (TFEMA).
8. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 3), the photoinitiator is 2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1,1- hydroxy-cyciohexyls
Bis- (2,4,6- trimethylbenzoyls) phosphine oxides of benzophenone, phenyl, 2- hydroxy-2-methyl -1- phenylacetones -1,2,4,6- front threes
Base benzoyl diphenyl phosphine oxide, bis(benzoylphenyl) phosphine oxide, 2- methyl-1s-[4- first mercaptophenyl] -2- morpholines acetone -
Any one in 1.
9. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, it is characterised in that：
In step 3), in the ethanol/water mixed solution of addition, the mass fraction ratio of ethyl alcohol and water is 60：40~100：0.
10. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, feature exist
In：In step 3), the mass fraction of the fluoropolymer monomer of addition is the 5- of the ethanol/water mixed solution mass fraction
20%, the mass fraction of Macro RAFT agent is the quality of the 0.2-20% of fluoropolymer monomer mass number, photoinitiator
Number is the 0.5~15% of fluoropolymer monomer mass number.
11. a kind of fast preparation method of multi-functional fluoropolymer microballoon according to claim 1, feature exist
In：In step 4), the light source that causes is appointing in medium pressure mercury lamp, ultraviolet light Non-polarized lamp, metal halid lamp or UV-LED light sources
It is a kind of.
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| CN106967191B (en) * | 2017-04-13 | 2019-11-19 | 佛山科学技术学院 | A kind of environment-friendly preparation method thereof of super-amphiphobic fluoropolymer nano material |
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| CN110330585B (en) * | 2019-07-23 | 2020-07-24 | 淮阴工学院 | Method for preparing monodisperse microspheres by ultrasonic-induced RAFT precipitation polymerization |
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| CN112745705B (en) * | 2020-12-14 | 2022-04-19 | 安徽庆润新材料技术有限公司 | Fluoropolymer nanoparticle modified photocuring fluorocarbon coating and preparation method thereof |
| CN114797512B (en) * | 2021-01-29 | 2023-02-03 | 深圳市碳源生物科技有限公司 | Star-poly (dimethylaminoethyl acrylate) polymer modified PVDF (polyvinylidene fluoride) membrane and application thereof |
| CN113004457A (en) * | 2021-03-02 | 2021-06-22 | 嘉兴昊特新材料科技有限公司 | Polymer nano particle and preparation method and application thereof |
| CN115232253B (en) * | 2022-08-12 | 2024-04-30 | 常州大学 | Monodisperse functional crosslinked polymer microsphere and preparation method thereof |
| CN115433329A (en) * | 2022-09-19 | 2022-12-06 | 山东瑞博龙化工科技股份有限公司 | double-pH response type drug carrier and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702421A (en) * | 2012-06-29 | 2012-10-03 | 北京智生阳光新材料科技发展有限公司 | Method for photochemically preparing monodisperse polymer functional microspheres |
| CN102718894A (en) * | 2012-06-29 | 2012-10-10 | 北京智生阳光新材料科技发展有限公司 | Low temperature synthesis method for monodisperse polymer microsphere |
| CN103130969A (en) * | 2013-02-06 | 2013-06-05 | 上海维凯化学品有限公司 | Fluoropolymer microsphere |
| CN103665280A (en) * | 2013-12-13 | 2014-03-26 | 中科院广州化学有限公司 | Multifunctional fluorine-containing microsphere as well as preparation method and application thereof |
-
2016
- 2016-10-28 CN CN201610962198.0A patent/CN106554446B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702421A (en) * | 2012-06-29 | 2012-10-03 | 北京智生阳光新材料科技发展有限公司 | Method for photochemically preparing monodisperse polymer functional microspheres |
| CN102718894A (en) * | 2012-06-29 | 2012-10-10 | 北京智生阳光新材料科技发展有限公司 | Low temperature synthesis method for monodisperse polymer microsphere |
| CN103130969A (en) * | 2013-02-06 | 2013-06-05 | 上海维凯化学品有限公司 | Fluoropolymer microsphere |
| CN103665280A (en) * | 2013-12-13 | 2014-03-26 | 中科院广州化学有限公司 | Multifunctional fluorine-containing microsphere as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Photoinitiated RAFT Dispersion Polymerization: A Straightforward Approach toward Highly Monodisperse Functional Microspheres;Jianbo Tan等;《Macromolecules》;20121113;第45卷;第8790-8795页 * |
| Synthesis of Highly Monodisperse Surface-Functional Microspheres by Photoinitiated RAFT Dispersion Polymerization Using Macro-RAFT Agents;Jianbo Tan等;《Macromolecules》;20131112;第46卷;第8441-8448页 * |
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