CN106279469B - 一种快速制备干净聚合物微球的方法 - Google Patents
一种快速制备干净聚合物微球的方法 Download PDFInfo
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- CN106279469B CN106279469B CN201610751261.6A CN201610751261A CN106279469B CN 106279469 B CN106279469 B CN 106279469B CN 201610751261 A CN201610751261 A CN 201610751261A CN 106279469 B CN106279469 B CN 106279469B
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- polymer microballoon
- acrylate
- methacrylate
- bifunctionality
- microballoon
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- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 32
- 239000012987 RAFT agent Substances 0.000 claims abstract description 27
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- 102400000830 Saposin-B Human genes 0.000 claims abstract description 14
- 101800001697 Saposin-B Proteins 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 4
- 238000005886 esterification reaction Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 14
- 230000000977 initiatory effect Effects 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 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
- 150000001336 alkenes Chemical class 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000012674 dispersion polymerization Methods 0.000 claims description 3
- 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 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 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 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-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 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- COCLLEMEIJQBAG-UHFFFAOYSA-N 8-methylnonyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C(C)=C COCLLEMEIJQBAG-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
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- -1 isobutyl ester Chemical class 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 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
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-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
- 239000002904 solvent Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 claims 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims 1
- 239000003999 initiator Substances 0.000 claims 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 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
- 238000000926 separation method Methods 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000006185 dispersion Substances 0.000 abstract description 8
- 238000013467 fragmentation Methods 0.000 abstract description 5
- 238000006062 fragmentation reaction Methods 0.000 abstract description 5
- 230000002441 reversible effect Effects 0.000 abstract description 5
- 239000012986 chain transfer agent Substances 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 22
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 12
- 238000002296 dynamic light scattering Methods 0.000 description 12
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 11
- 239000004005 microsphere Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- DZFGVGDQHQHOKZ-UHFFFAOYSA-N 2-dodecylsulfanylcarbothioylsulfanyl-2-methylpropanoic acid Chemical compound CCCCCCCCCCCCSC(=S)SC(C)(C)C(O)=O DZFGVGDQHQHOKZ-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YXYZMHGSOKYZAF-UHFFFAOYSA-M [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C Chemical compound [Cl-].C(C(=C)C)(=O)OCC[N+](C(C)(C)C)(C)C YXYZMHGSOKYZAF-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- 239000012043 crude product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 238000010898 silica gel chromatography Methods 0.000 description 2
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- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- HAHPGQIYPXCFBI-UHFFFAOYSA-N CC(=O)C.N1CCOCC1 Chemical compound CC(=O)C.N1CCOCC1 HAHPGQIYPXCFBI-UHFFFAOYSA-N 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
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- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- 239000012989 trithiocarbonate Substances 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 1
Classifications
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
-
- 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
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
- C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
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Abstract
本发明公开了一种快速制备干净聚合物微球的方法。首先将聚乙二醇的端羟基和含羧基的可逆加成‑断裂链转移剂(RAFT)进行酯化反应合成得到两端含RAFT活性基团的大分子RAFT试剂,并将其作为稳定分散剂用于光分散聚合中。把这种稳定分散剂与聚合单体、光引发剂再氮气气氛下,以乙醇/水混合液作为分散介质,引发光源照射所得混合物0.5~5h,反应结束后即得到稳定的白色乳状分散液,去除分散介质后得到聚合物微球。本发明制制备聚合物微球的方法中,这种稳定分散剂的用量仅需0.2~0.6wt%(相对于单体),即可快速得到单分散性的聚合物微球,所制备得到的聚合物微球表面稳定剂的量非常低。
Description
技术领域
本发明属于聚合物制备技术领域。更具体地,涉及一种快速制备干净聚合物微球的方法。
背景技术
微米级的单分散聚合物微球在电子、涂料、色谱、医药和生物等领域有重要的应用。聚合物微球可通过乳液聚合、沉淀聚合和分散聚合等聚合手段合成得到。
其中,分散聚合法是一种常用的微球制备方法,其主要优势是可以简便地一步合成得到粒径为0.1~15μm的单分散聚合物微球。分散聚合法制备单分散微球的关键是通过加入稳定分散剂对微球进行稳定,从而避免微球之间的聚结而影响单分散性。一般的分散聚合法中,需要加入5~15wt%(相对于单体,下同)的稳定分散剂,才能得到单分散微球,但是这样得到的微球,其表面覆盖了一层稳定分散剂分子链,这在一些应用场合中将受到影响。此外,目前主要采用热引发的分散聚合的方法来进行制备,但是需要比较长的时间(例如24小时)才能达到比较高的单体转化率。
近些年来,将光引发自由基聚合方法和分散聚合结合,开发了快速、低温的光引发分散聚合来制备微米级微球(Journal of Polymer Science Part A:Polymer Chemistry,2008,46(4):1329-1338)。这种方法仅需光照半小时左右就可以得到单分散的聚合物微球,且反应产率达到90%以上,这相对于热引发的分散聚合反应速度快得多,但是得到的微球单分散性较低,并且与传统热引发分散聚合一样,需要加入10wt%左右的稳定分散剂。
另外,在光分散聚合的基础上引入可逆加成-断裂链转移剂(RAFT),构成光引发RAFT分散聚合(Macromolecules,2012,45(21):8790-8795),可以获得单分散性较好的聚合物微球,但是这种方法同样需要加入10wt%左右的稳定分散剂,并且还要加入0.1~1wt%的RAFT试剂,才能得到单分散微球,这样将对所合成的微球造成污染。
杨万泰等采用带正电荷的小分子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)与苯乙烯原位共聚形成稳定剂,利用电荷的作用对微球进行稳定(Macromolecular Chemistryand Physics,2010,211(7):744-751),这种方法的优势是无需外加稳定分散剂,但是需要加入少量的带电荷单体进行共聚使微球稳定;并且该方法是属于热引发的分散聚合,需要较长的反应时间。
发明内容
本发明要解决的技术问题是克服现有技术中聚合物微球制备方法的缺陷和技术不足,合成了两端含可逆加成-断裂链转移剂(RAFT)的直链活性聚合物作为稳定分散剂,在紫外光照射下进行光分散聚合,只需使用0.2wt%的这种稳定分散剂,即可得到单分散聚合物微球,大大减少了稳定剂的用量;而且反应速度很快,得到的微球表面只有极少量的稳定剂分子链。
本发明的目的是提供一种双官能度大分子RAFT试剂。
本发明另一目的是提供一种利用上述双官能度大分子RAFT试剂快速制备干净聚合物微球的方法。
本发明再一目的是提供所述方法制备得到的单分散聚合物微球。
本发明上述目的通过以下技术方案实现:
一种双官能度大分子RAFT试剂,即含双RAFT基团的大分子RAFT试剂,学名为烷基-S’(2-甲基-2-丙酸基)三硫代碳酸酯,是一种两端含可逆加成-断裂链转移剂(RAFT)的直链活性聚合物。
所述双官能度大分子RAFT试剂的结构式如下式(I)所示:
其中,R为含1~16个碳原子的烷烃(饱和链烃),n=20~500。
优选地,R基团为乙基、辛基或十二烷基。
优选地,上述双官能度大分子RAFT试剂的制备方法为:将聚乙二醇和含羧基的RAFT试剂(RDMAT)进行酯化反应合成得到所述双官能度大分子RAFT试剂。
其中,聚乙二醇的端羟基和RDMAT中的羧基进行酯化反应合成,可得到所述双官能度大分子RAFT试剂。
优选地,所述聚乙二醇与DDMAT的摩尔比为1:2~1:2.5。
其中,优选地,所述聚乙二醇的分子量为1000~20000。
所述含羧基的RAFT试剂(RDMAT)的结构式如下式(II)所示:
其中,R为含1~16个碳原子的烷烃,即饱和链烃。
更优选地,R基团为乙基(相对应地,所述含羧基的RAFT试剂简称EDMAT)、辛基(相对应地,所述含羧基的RAFT试剂简称ODMAT)或十二烷基(相对应地,所述含羧基的RAFT试剂简称DDMAT)。
更具体,作为一种优选地可实施方案,所述双官能度大分子RAFT试剂的制备方法如下:
将聚乙二醇、DDMAT、4-二甲氨基吡啶(DMAP)和无水二氯甲烷(CH2Cl2)混合,在冰水浴中搅拌溶解。待温度降到0℃左右时,逐滴滴加含有二环己基碳二亚胺(DCC)的CH2Cl2溶液30min以上,并继续在冰水浴中反应1~1.5h(优选为1h);室温反应45~50h(优选为48h)后,反应液过滤除去生成的不溶物,旋蒸,并用冰乙醚和冰正己烷的混合液(v/v=1:1)沉淀,得到黄色粉末状的粗产物。然后用硅胶层析柱进一步提纯,所有流动相为氯仿和甲醇(v/v=95:5),最终得到双官能度大分子RAFT试剂。
其中,优选地,所述聚乙二醇与DDMAT的摩尔比为1:2~1:2.5。
其中,优选地,所述聚乙二醇的分子量为1000~20000。
优选地,所述DMAP与聚乙二醇的质量比为110~130:1。
更优选地,所述DMAP与聚乙二醇的质量比为120:1。
优选地,所述无水二氯甲烷与聚乙二醇的质量体积比为3~5ml:1g。
更优选地,所述无水二氯甲烷与聚乙二醇的质量体积比为4ml:1g。
优选地,所述含有二环己基碳二亚胺(DCC)的CH2Cl2溶液与无水二氯甲烷的体积比为1:3~5。
更优选地,所述含有二环己基碳二亚胺(DCC)的CH2Cl2溶液与无水二氯甲烷的体积比为1:4。
优选地,所述含有二环己基碳二亚胺(DCC)的CH2Cl2溶液中DCC的浓度为20mmol。
另外,一种快速制备干净聚合物微球的方法,是以上述双官能度大分子RAFT试剂作为稳定分散剂,进行光分散聚合,合成聚合物微球。
具体地,是在氮气氛围下,以乙醇/水混合液作为溶剂,将上述双官能度大分子RAFT试剂、聚合单体和光引发剂在引发光源照射条件下进行分散聚合反应,得到稳定的白色乳状液,离心分离后,用乙醇/水混合液清洗,得到聚合物微球。
所述双官能度大分子RAFT试剂即两端含可逆加成-断裂链转移剂(RAFT)的直链活性聚合物,以其作为稳定分散剂,在紫外光照射下进行光分散聚合,只需使用0.2wt%左右的这种稳定分散剂,即可得到单分散聚合物微球,大大减少了稳定剂的用量;而且快速得到单分散的聚合物微球,得到的微球表面只有极少量的稳定剂分子链。
在所述快速制备干净聚合物微球的方法中,优选地,所述乙醇/水混合液中,乙醇与水的重量比为20:80~80:20。
更优选地,所述乙醇/水混合液中,乙醇与水的重量比为40:60。
优选地,所述聚合单体的浓度为5~20wt%。
优选地,所述双官能度大分子RAFT试剂的用量为聚合单体的0.2~10wt%。
更优选地,所述双官能度大分子RAFT试剂的用量为聚合单体的0.2~5wt%。
更优选地,所述双官能度大分子RAFT试剂的用量为聚合单体的0.2~0.6wt%。
优选地,所述光引发剂的用量为聚合单体的0.5~10wt%。
更优选地,所述光引发剂的用量为聚合单体的1~5wt%。
优选地,所述引发光源的光强为0.2~100mW/cm2。
更优选地,所述引发光源的光强为0.5~20mW/cm2。
优选地,所述引发光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源。
优选地,所述引发光源的辐射波长为365nm。
优选地,所述反应的时间为0.5~5h。
优选地,所述离心是10000转/min离心1~10min。
更优选地,所述离心是10000转/min离心3~5min。
优选地,所述聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺、丙烯腈、丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯、丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种,或上述单体的一种或多种的共聚物。
优选地,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮-1、1-羟基-环己基苯酮、2,4,6-三甲基苯甲酰二苯基氧化膦、双苯甲酰基苯基氧化膦、2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1或2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1中的任意一种。
另外,由本发明所述方法制备得到的聚合物微球及其应用,也应在本发明的保护范围之内。
本发明具有以下有益效果:
本发明利用大分子链末端的RAFT基团的活性/可控聚合特性,在反应过程中现场形成ABA嵌段共聚物。这种嵌段共聚物由于两端含有亲微球的聚合物链(A嵌段),能有效地把亲介质的(B嵌段)锚固在微球表面,从而稳定微球。并且这种在微球表面成弧形的分子链对微球的稳定作用相对于单接点伸展在分散介质中的分子链更有效,因此所需用量很少(低至0.2wt%左右),得到的微球表面的稳定剂含量非常低。
而且,该方法无需像一般的RAFT光分散聚合那样外加RAFT试剂,只需要在大分子链末端接上RAFT连转移基团,在整个分子链中所占的量很少,加上使用的这种大分子链转移剂的量也很少,因此大大降低了RAFT试剂对微球的污染。
此外,本发明的方法采用光引发技术,反应速度很快,甚至比一般的RAFT光分散聚合还快(因为RAFT试剂会延缓聚合反应,而本发明的方法中RAFT基团含量非常低),只需半小时就能达到90%以上的单体转化率。
附图说明
图1为双官能度大分子RAFT稳定剂的不同用量下制备的聚合物微球的扫描电镜图。
图2为实施例3制备的聚合物微球的扫描电镜图(SEM)。
图3为实施例4制备的聚合物微球的扫描电镜图(SEM)。
图4为实施例5制备的聚合物微球的扫描电镜图(SEM)。
图5为实施例6制备的聚合物微球的扫描电镜图(SEM)。
图6为实施例7制备的聚合物微球的扫描电镜图(SEM)。
图7为实施例8制备的聚合物微球的扫描电镜图(SEM)和动态光散射(DLS)。
图8为实施例9制备的聚合物微球的扫描电镜图(SEM)和动态光散射(DLS)。
图9为实施例10制备的聚合物微球的扫描电镜图(SEM)和动态光散射(DLS)。
具体实施方式
以下结合说明书附图和具体实施例来进一步说明本发明,但实施例并不对本发明做任何形式的限定。
除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1制备双官能度大分子RAFT试剂
1、制备方法如下:
(1)在500mL的单口烧瓶中加入HO-PEG(6000)-OH(30.0g,5mmol),DDMAT(7.28g,20mmol),4-二甲氨基吡啶(DMAP)(0.25g,2.0mmol)和无水二氯甲烷(CH2Cl2)(120mL),在冰水浴中搅拌溶解。待温度降到0℃左右时,逐滴滴加含有二环己基碳二亚胺(DCC)(4.12g,20mmol)的CH2Cl2溶液(30mL)30min以上,并继续在冰水浴中反应1h。
(2)室温反应48h后,反应液过滤除去生成的不溶物DCU,旋蒸,并用冰乙醚和冰正己烷的混合液(v/v=1:1)沉淀,得到黄色粉末状的粗产物。
(3)然后用硅胶层析柱进一步提纯,所有流动相为氯仿和甲醇(v/v=95:5),最终得到HO-PEG(6000)-OH大分子RAFT试剂。
2、具体地,其他种类的大分子RAFT试剂的合成与此类似。
合成大分子RART试剂的反应式如下所示:
实施例2双官能度大分子RAFT稳定剂的用量优化
本实施例对制备聚合物微球方法中,双官能度大分子RAFT稳定剂的用量进行优化
1、制备方法
在玻璃反应瓶中,加入甲基丙烯酸甲酯单体(MMA,2.0g,10%固含量),光引发剂D1173(0.06g,3%相对于MMA单体),大分子RAFT试剂(0.2%、0.3、0.4、0.5、0.6、1.0,相对于MMA单体)溶解于乙醇/水(7.2g/10.8g,40/60,w/w)混合溶剂中,通氮气15min后用石英玻璃塞密封。
然后用365nm的UV-LED点光源(光强为2.4mW/cm2)从反应器的顶端光照1h。光照结束后,得到稳定的白色乳液,用10000转/min的离心机离心分离3~5min,并用乙醇/水(40/60,w/w)混合溶液清洗三次,然后放在真空干燥箱中干燥。
2、所得产物扫描电镜图(SEM)如附图1所示。表明,双官能度大分子RAFT稳定剂的优选用量为0.2~0.6wt%(相对于聚合单体)。
以下实施例3~10制备聚合物微球的配方分别如表1所示:
表1不同配方的聚合物微球
*MMA是指甲基丙烯酸甲酯,GMA是指甲基丙烯酸缩水甘油酯,IBOA是指丙烯酸异冰片酯。其中大分子RAFT试剂和光引发剂用量为相对于单体浓度。
实施例3:制备聚合物微球
1、制备方法
在玻璃反应瓶中,加入甲基丙烯酸甲酯单体(MMA,2.0g,10%固含量),光引发剂D1173(0.06g,3%相对于MMA单体),大分子RAFT试剂(0.6%,相对于MMA单体)溶解于乙醇/水(7.2g/10.8g,40/60,w/w)混合溶剂中,通氮气15min后用石英玻璃塞密封。
然后用365nm的UV-LED点光源(光强为2.4mW/cm2)从反应器的顶端光照1h。光照结束后,得到稳定的白色乳液,用10000转/min的离心机离心分离,并用乙醇/水(40/60,w/w)混合溶液清洗三次,然后放在真空干燥箱中干燥。
2、所得产物扫描电镜图(SEM)如附图2所示。
实施例4:制备聚合物微球
本实施例使用大分子RAFT稳定剂DDMAT-PEG(10000)-DDMAT代替实施例3中的DDMAT-PEG(6000)-DDMAT,并且用量改为0.2%(相对于单体),其余试剂种类和用量以及实施过程与实施例3相同。所得产物的扫描电子显微镜照片(SEM)见图3。
实施例5:制备聚合物微球
本实施例使用大分子RAFT稳定剂DDMAT-PEG(20000)-DDMAT代替实施例3中的DDMAT-PEG(6000)-DDMAT,并且用量改为0.2%(相对于单体),其余试剂种类和用量以及实施过程与实施例3相同。所得产物的扫描电子显微镜照片(SEM)见图4。
实施例6:制备聚合物微球
本实施例使用聚合单体为GMA代替实施例5中的MMA,其余试剂种类和用量以及实施过程与实施例5相同。所得产物的扫描电子显微镜照片(SEM)见图5。
实施例7:制备聚合物微球
本实施例使用聚合单体为IBOA代替实施例5中的MMA,其余试剂种类和用量以及实施过程与实施例5相同。所得产物的扫描电子显微镜照片(SEM)见图6。
实施例8:制备聚合物微球
本实施例使用光引发剂用量为1%代替实施例5中的3%,其余试剂种类和用量以及实施过程与实施例5相同。所得产物的扫描电子显微镜照片(SEM)和动态光散射(DLS)见图7。
实施例9:制备聚合物微球
本实施例使用光引发剂用量为6%代替实施例5中的3%,其余试剂种类和用量以及实施过程与实施例5相同。所得产物的扫描电子显微镜照片(SEM)和动态光散射(DLS)见图8。
实施例10:制备聚合物微球
本实施例使用光引发剂用量为9%代替实施例5中的3%,其余试剂种类和用量以及实施过程与实施例5相同。所得产物的扫描电子显微镜照片(SEM)和动态光散射(DLS)见图9。
Claims (10)
1.一种双官能度大分子RAFT试剂,其特征在于,结构式如下式(I)所示:
其中,n=20~500;R基团为乙基、辛基或十二烷基。
2.一种制备权利要求1所述双官能度大分子RAFT试剂的方法,其特征在于,将聚乙二醇和含羧基的RAFT试剂进行酯化反应合成得到所述双官能度大分子RAFT试剂。
3.一种快速制备干净聚合物微球的方法,其特征在于,以权利要求1所述双官能度大分子RAFT试剂作为稳定分散剂,进行光分散聚合,合成聚合物微球。
4.根据权利要求3所述快速制备干净聚合物微球的方法,其特征在于,包括如下步骤:在氮气氛围下,以乙醇/水混合液作为溶剂,将权利要求1所述双官能度大分子RAFT试剂、聚合单体和光引发剂在引发光源照射条件下进行分散聚合反应,得到稳定的白色乳状液,离心分离后,用乙醇/水混合液清洗,得到聚合物微球。
5.根据权利要求4所述快速制备干净聚合物微球的方法,其特征在于,所述聚合单体的浓度为5~20wt%;所述双官能度大分子RAFT试剂的用量为聚合单体的0.2~10wt%;所述光引发剂的用量为聚合单体的0.5~10wt%。
6.根据权利要求4所述快速制备干净聚合物微球的方法,其特征在于,所述引发光源的光强为0.2~100mW/cm2。
7.根据权利要求4所述快速制备干净聚合物微球的方法,其特征在于,所述引发光源为中压汞灯、紫外光无极灯、金属卤素灯或UV-LED光源。
8.根据权利要求4所述快速制备干净聚合物微球的方法,其特征在于,所述聚合单体为乙酸乙烯酯、苯乙烯、丙烯酸、甲基丙烯酸、衣康酸、顺丁烯二酸二丁酯、顺丁烯二酸二辛酯、丙烯酰胺、甲基丙烯酰胺、丙烯腈、丙烯酸甲酯、丙烯酸乙酯、丙烯酸异冰片酯、丙烯酸丁酯、丙烯酸月桂酯、丙烯酸-2-羟乙酯、丙烯酸缩水甘油酯、丙烯酸异丁酯、丙烯酸异癸酯、丙烯酸异辛酯、丙烯酸-2-羟丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸丁酯、甲基丙烯酸月桂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸异丁酯、甲基丙烯酸异癸酯、甲基丙烯酸异辛酯、甲基丙烯酸二甲基氨基乙酯或甲基丙烯酸-2-羟丙酯中的一种或几种,或上述单体的一种或多种的共聚物。
9.根据权利要求4所述快速制备干净聚合物微球的方法,其特征在于,所述光引发剂为2-羟基-2-甲基-1-苯基丙酮-1、1-羟基-环己基苯酮、2,4,6-三甲基苯甲酰二苯基氧化膦、双苯甲酰基苯基氧化膦、2-甲基-1-[4-甲巯基苯基]-2-吗啉丙酮-1或2-苯基-2-二甲氨基-1-(4-吗啉苯基)-丁酮-1。
10.根据权利要求3~9任一所述方法制备得到的聚合物微球。
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