CN106366217B - A kind of polymers function microballoon for cutting off stabilizer and preparation method thereof - Google Patents
A kind of polymers function microballoon for cutting off stabilizer and preparation method thereof Download PDFInfo
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- CN106366217B CN106366217B CN201610751262.0A CN201610751262A CN106366217B CN 106366217 B CN106366217 B CN 106366217B CN 201610751262 A CN201610751262 A CN 201610751262A CN 106366217 B CN106366217 B CN 106366217B
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- microballoon
- preparation
- raft
- acrylate
- methacrylate
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- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000003381 stabilizer Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 41
- 239000012987 RAFT agent Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002270 dispersing agent Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- 102400000830 Saposin-B Human genes 0.000 claims abstract description 13
- 101800001697 Saposin-B Proteins 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- AISZNMCRXZWVAT-UHFFFAOYSA-N 2-ethylsulfanylcarbothioylsulfanyl-2-methylpropanenitrile Chemical compound CCSC(=S)SC(C)(C)C#N AISZNMCRXZWVAT-UHFFFAOYSA-N 0.000 claims description 23
- 239000003153 chemical reaction reagent Substances 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- -1 methyl methacrylate Ester Chemical class 0.000 claims description 3
- 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
- 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
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-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
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 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
- 150000002148 esters Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-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
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 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 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 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 1
- 150000008366 benzophenones Chemical class 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
- 229940119545 isobornyl methacrylate Drugs 0.000 claims 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 11
- 238000005886 esterification reaction Methods 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 230000032050 esterification Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 239000012986 chain transfer agent Substances 0.000 abstract description 2
- 238000013467 fragmentation Methods 0.000 abstract description 2
- 238000006062 fragmentation reaction Methods 0.000 abstract description 2
- 239000004005 microsphere Substances 0.000 description 15
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000002609 medium Substances 0.000 description 7
- 235000019394 potassium persulphate Nutrition 0.000 description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000007970 thio esters Chemical class 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- XIXNSLABECPEMI-VURMDHGXSA-N (z)-2-[2-[(2-methylpropan-2-yl)oxycarbonylamino]-1,3-thiazol-4-yl]pent-2-enoic acid Chemical compound CC\C=C(/C(O)=O)C1=CSC(NC(=O)OC(C)(C)C)=N1 XIXNSLABECPEMI-VURMDHGXSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 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 description 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 1
- 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
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 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 description 1
- DCOSOKFMBGNCQV-UHFFFAOYSA-N CC(C)(C(CCSC(SCc1ccccc1)=S)=O)OCC(C1)C1(C)OC(CCS(CSCc1ccccc1)=S)=O Chemical compound CC(C)(C(CCSC(SCc1ccccc1)=S)=O)OCC(C1)C1(C)OC(CCS(CSCc1ccccc1)=S)=O DCOSOKFMBGNCQV-UHFFFAOYSA-N 0.000 description 1
- 208000031639 Chromosome Deletion Diseases 0.000 description 1
- 239000012988 Dithioester Substances 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical class CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012712 reversible addition−fragmentation chain-transfer polymerization Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 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
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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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- 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
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
- C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Abstract
The invention discloses a kind of polymers function microballoons for cutting off stabilizer and preparation method thereof.First with carboxylic Reversible Addition Fragmentation Chain Transfer agent on the terminal hydroxy group of polyethylene glycol and non-leaving group（RAFT）Esterification is carried out to synthesize to obtain the Z type Macro RAFT agents of both ends active group containing RAFT；Then it is used for light dispersin polymerization as stable dispersant.Specifically this stable dispersant is mixed with polymerized monomer, photoinitiator, function monomer, it is passed through nitrogen, using ethanol/water as decentralized medium, 0.5~5h of illumination, obtain stable white " milky " dispersion liquid, excessive thermal initiator is added in after being diluted with water, leads to nitrogen oil bath heating left and right for 24 hours, the clean polymers function microballoon that surface is free of stable dispersant is obtained after removing decentralized medium.Stable dispersant can be cut off during this method, quickly obtains the polymers function microballoon on surface " clean ", solves the problems, such as that surface-stable dispersant influences functional group.
Description
Technical field
The invention belongs to technical field of polymer preparation.More particularly, to a kind of polymer work(for cutting off stabilizer
Energy microballoon and preparation method thereof.
Background technology
Dispersion copolymerization method is to prepare the most common method of micrograde polymer microsphere at present, the method have it is easy to operate, Gu
The features such as content height and microspherulite diameter are evenly distributed.It is copolymerized by adding in the monomer containing functional group, it can be easily
Obtain various functions copolymerization microsphere.
But dispersion copolymerization method shortcoming is needed in microballoon preparation process using stable dispersant, these are steady
Determine dispersant and be anchored at microsphere surface generally by chemical bonding, it is difficult to remove, obtained microsphere surface is caused to cover
One layer of stable dispersant.When needing that using the functional group of microballoon ontology, this layer of stable dispersant iris action will be played, influence
The using effect of functional group.
At present, one of method for solving the problems, such as this is to reduce the dosage of stable dispersant as far as possible, reduces it to microballoon
Covering, but the nucleation and propagation process of microballoon will be influenced in this way, when stabilizing agent dosage is too low, it is difficult under normal circumstances
To mono-dispersion microballoon.Another method is the mechanism using charge stable, adds in charge-carrying monomers and replaces macromolecular stabilizer dispersant
(Macromolecular Chemistry and Physics, 2010,211 (7)：744-751), the microsphere surface obtained in this way
In addition to containing a small amount of charged group, without other stable dispersants.But a small amount of charge of this use stablizes microballoon
Method be restricted when preparing some function copolymerization microspheres because function comonomer addition interference nucleation process, and
It is possible that influence charge stable effect.It is reported from the document as it can be seen that in order to introduce functional group on microballoon, needs to close in microballoon
Into the rear progress further functionalization of chemical modification.And this method is to belong to the dispersin polymerization of thermal initiation, needs longer reaction
Time.
Invention content
The technical problem to be solved by the present invention is to overcome microsphere surfaces in the prior art to cover stable dispersant, makes microballoon sheet
The problem of application of body function group is somewhat limited has synthesized a kind of special, both ends containing reversible addition-fracture
The straight chain living polymer of chain-transferring agent (RAFT) carries out one step of light dispersin polymerization as stable dispersant under ultraviolet light
Then the stabilizer of microsphere surface is cut off, prepares surface " clean " (not by stable dispersant by complex functionality copolymerization microsphere again
Covering) monodisperse functional polymer microsphere.
The object of the present invention is to provide a kind of Z- types Macro RAFT agents.
Another object of the present invention is to provide a kind of preparation method for the polymer microballoon for cutting off stabilizer.
Another object of the present invention is to provide the polymer microballoon for cutting off stabilizer that the method is prepared.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of Z- types Macro RAFT agent, structural formula are as follows：
Wherein, n=25~500.
As it is a kind of preferably can embodiment, the Z- types Macro RAFT agent is the Z in small molecule RAFT reagents
Macromolecular chain is connected on group to obtain.
Specifically, the Z- types Macro RAFT agent preparation method is：Utilize band on polyethylene glycol (PEG) and Z group
The RAFT reagents for having carboxyl carry out esterification and obtain.The terminal hydroxy group of polyethylene glycol (PEG) and the carboxylic on the Z group of RAFT reagents
Base carries out the Z- type Macro RAFT agents of both ends group containing RAFT that esterification obtains.
Preferably, the RAFT reagents with carboxyl are (but not limited to) benzyl trithiocarbonic acid ester group third on the Z group
Sour (abbreviation BTPA), the esterification reaction product abbreviation BTPA-PEG-BTPA with PEG.
Preferably, the molecular weight of the polyethylene glycol is 1000~20000.
In addition to PEG, in principle all both ends hydroxyls and also be dissolved in reaction medium polymer be adapted to prepare contain
Polyethylene glycol (PEG) Z- type Macro RAFT agents, and for light dispersin polymerization.
In addition, a kind of preparation method for the polymer microballoon for cutting off stabilizer, is tried with above-mentioned Z- types macromolecular RAFT
Agent using ethanol/water mixed liquor as decentralized medium, carries out light dispersin polymerization, synthesis obtains the white of stabilization as stable dispersant
Color emulsion；Then excessive thermal initiator is added in after being diluted with water, leads to 20~28h of nitrogen oil bath heating (preferably for 24 hours), removal point
The clean polymers function microballoon that surface is free of stable dispersant is obtained after dispersion media.
Specifically, as it is a kind of preferably can embodiment, the preparation side of the polymer microballoon for cutting off stabilizer
Method includes the following steps：
S1. the polymer microballoon dispersion liquid that light RAFT dispersin polymerizations obtain：
Z- types Macro RAFT agent and function monomer described in polymerized monomer, photoinitiator, claim 1 are dissolved in second
It in alcohol/water mixed solvent, is sealed after logical nitrogen, is shone with light source light is caused, obtain stable white polymer microballoon dispersion liquid；
S2. polymer microballoon surface RAFT active groups are decomposed, so as to which the stable dispersant strand on surface is cut off.
Wherein it is preferred to polymerized monomer described in step S1 is methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid isobornyl thiocyanoacetate, butyl methacrylate, lauryl methacrylate, Isobutyl methacrylate, isodecyl
Ester, isooctyl methacrylate, methyl acrylate, ethyl acrylate, isobornyl acrylate, butyl acrylate, the acrylic acid moon
Osmanthus ester, isobutyl acrylate, isodecyl acrylate or Isooctyl acrylate monomer any one or a few.
Preferably, photoinitiator described in step S1 is 2,4,6- trimethylbenzoyl diphenyl phosphine oxides, 2- hydroxyl -2- first
Base -1- phenylacetones -1,1- hydroxy-cyciohexyls benzophenone, bis(benzoylphenyl) phosphine oxide, 2- methyl-1s-[4- first sulfydryl benzene
Base] any one in -2- morpholines acetone -1 or 2- phenyl -2- dimethylaminos -1- (4- morpholinyl phenyls)-butanone -1.
Preferably, function monomer described in step S1 for acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate,
Any one of glycidyl methacrylate, acrylic acid -2- hydroxyl ethyl esters or 2-hydroxyethyl methacry-late.
Preferably, the dosage of polymerized monomer described in step S1 is 5~20wt%.
Preferably, the dosage of Z- types Macro RAFT agent described in step S1 is 0.1~15wt% of polymerized monomer.
Preferably, the dosage of photoinitiator described in step S1 is 1~10wt% of polymerized monomer.
Preferably, the dosage of function monomer described in step S1 is 1~10wt% of polymerized monomer.
Preferably, it is UV-LED point light sources to cause light source described in step S1.
Preferably, the light intensity for causing light source described in step S1 is 0.2~20mW/cm2。
Preferably, the radiation wavelength for causing light source described in step S1 is 365nm.
Preferably, the time of illumination described in step S1 is 0.5~5h.
Preferably, the initiation light source is irradiated from the top of reactor.
Preferably, in ethanol/water mixed solvent described in step S1, the weight ratio of ethyl alcohol and water is 20：80~80：20.
It is highly preferred that in ethanol/water mixed solvent described in step S1, the weight ratio of ethyl alcohol and water is 40：60.
Preferably, the time that nitrogen is led to described in step S1 is 10~20min (preferably 15min).
As it is a kind of preferably can embodiment, decompose excision polymer microballoon surface RAFT active groups described in step S2
Specific method be：The polymer microballoon dispersion liquid of S1 is added in into water dilution, excessive thermal initiator is then added in, leads to nitrogen
Afterwards, the oil bath reaction of 60~80 DEG C (preferably 70 DEG C), centrifugation, and wash with ethyl alcohol that for several times, to obtain clean polymers function micro-
Ball.
Preferably, the thermal initiator is potassium peroxydisulfate (KPS) or azodiisobutyronitrile (AIBN).
Preferably, 10~200 times of molal quantity for polymers function microballoon of the dosage of the thermal initiator.
In addition, the polymer microballoon for cutting off stabilizer being prepared by the above method and its application, also all in this hair
Within bright protection domain.
The key problem in technology of the present invention is that design has synthesized a kind of special Z- type Macro RAFT agents, and divide as stablizing
Powder is used for light dispersin polymerization.
RAFT reagents, which are generally dithioesters and three thioesters etc., has the compound of high chain transfer constant, the structure of RAFT reagents
General formula is as follows：
When carrying out RAFT polymerizations, by reversible addition-fracture, chain tra nsfer process, monomer is constantly inserted between S and R, shape
Into macromolecular chain, chain end remains with RAFT active groups.The macromolecular chain of this end group containing RAFT is known as macromolecular
RAFT reagents.When Macro RAFT agent is used for dispersin polymerization, partial monosomy is polymerize on Macro RAFT agent, existing
Field forms block copolymer, and newly-generated macromolecular chain is attached in microballoon ontology, and original parent on Macro RAFT agent
Medium macromolecular chain stretches in the medium, and stable dispersion effect is generated to polymer microballoon, micro- so as to obtain monodisperse polymer
Ball.But the Macro RAFT agent of stable dispersant is typically used for, macromolecular chain is located at the position of R group, forms block
After copolymer, two block molecule chains securely connect, and RAFT groups are always positioned at macromolecular chain least significant end, are embedded in microballoon ontology
Face.Therefore it is difficult that the macromolecular chain of close medium is removed from microsphere surface.
Macro RAFT agent prepared by the present invention is then the Z for the macromolecular chain of close medium being connected to RAFT reagents
Group end, we term it Z- type Macro RAFT agents.When forming block copolymer, new strand is in RAFT reagents
R group end is grown.The block copolymer formed in this way, RAFT groups are between two strands, always with close medium molecule chain
It is connected directly, thus when stablizing polymer microballoon, RAFT reagents are in microsphere surface (as shown in Figure 1).Then pass through one
A little simple methods, RAFT radical decompositions, can just cut off the stable dispersant strand on surface.One is given in the present invention
Kind scheme adds in suitable thermal initiator after microballoon is formed, in the free radical meeting and polymer microballoon that heat resolve generates
RAFT reagents in the C=S keys of three thioesters react the free radical to form transition state, then the free radical of these transition states will continue to
The free radical generated with initiator reacts, thus by the related stable dispersant parent medium molecule chain of three thioester groups on surface
It cuts off to be free of the polymers function microballoon of stabilizer to surface.
The invention has the advantages that：
The present invention utilizes carboxylic reversible addion-fragmentation chain transfer agent on the terminal hydroxy group of polyethylene glycol and non-leaving group
(RAFT) carry out esterification synthesize to obtain the Z- type Macro RAFT agents of both ends active group containing RAFT, then as
Stable dispersant is used in light dispersin polymerization, prepares polymers function microballoon, can removal surface by simple method stabilization
Dispersant quickly obtains the polymers function microballoon on surface " clean ", and solving surface-stable dispersant influences functional group
Problem.
Description of the drawings
Fig. 1 is to carry out light dispersin polymerization thus obtained microsphere structure diagram using Z- types Macro RAFT agent.
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of polymers function microballoon prepared by embodiment 2~4.
Fig. 3 is the scanning electron microscope (SEM) photograph (SEM) of polymers function microballoon prepared by embodiment 5~7.
Fig. 4 is the scanning electron microscope (SEM) photograph (SEM) of polymers function microballoon prepared by embodiment 8~10.
Fig. 5 is that polymers function microballoon product cuts off the X-ray photoelectron spectroscopic analysis (XPS) before stabilizer.
Fig. 6 is that the X-ray photoelectron spectroscopic analysis (XPS) after stabilizer is cut off by thermal initiator of KPS.
Fig. 7 is that the X-ray photoelectron spectroscopic analysis (XPS) after stabilizer is cut off by thermal initiator of AIBN.
Specific embodiment
It is further illustrated the present invention below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the reagent of the invention used, method and apparatus are routinely tried for the art
Agent, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are purchased in market.
Embodiment 1 prepares Z- type Macro RAFT agents
In the single-necked flask of 500mL add in HO-PEG (20000)-OH (30.0g, 1.5mmol), BTPA (1.65g,
6mmol), DMAP (73.7mg, 0.6mmol) and anhydrous CH2Cl2(120mL), the stirring and dissolving in ice-water bath.Treat that temperature drops to 0
DEG C or so when, dropwise be added dropwise DCC (1.24g, 6mmol) CH2Cl2Solution (30mL) more than 30min, and continue in ice-water bath
React 1h.After reacting at room temperature 48h, reaction solution is filtered to remove the insoluble matter DCU of generation, revolving, and with ice ether and ice n-hexane
Mixed liquor (v/v=1:1) it precipitates, obtains the crude product of yellow powder.Then it is further purified, owned with silica gel column chromatography
Mobile phase is chloroform and methanol (v/v=95:5) BTPA-PEG (20000)-BTPA Macro RAFT agents, are finally obtained.
The synthesis of other Macro RAFT agents BTPA-PEG (6000)-BTPA and BTPA-PEG (10000)-BTPA with
BTPA-PEG455-BTPA is similar, and reaction equation is as follows：
The formula difference that example 2 below~10 prepare polymers function microballoon is as shown in table 1：
The polymers function microballoon of 1 different formulations of table
* AA refers to acrylic acid, and GMA refers to glycidyl methacrylate, and HEMA refers to hydroxyethyl methacrylate.Its
Middle Macro RAFT agent and photoinitiator dosage are relative to monomer concentration.
Embodiment 2 prepares polymers function microballoon
1st, in glass reaction bottle, methyl methacrylate monomer (MMA, 2.0g, 10% solid content), photoinitiator are added in
D1173 (0.06g, 3% relative to MMA monomers), Z- types Macro RAFT agent (6% relative to MMA monomers), function monomer AA
(3% relative to MMA monomers) is dissolved in ethanol/water (7.2g/10.8g, 40/60, w/w) in the mixed solvent, after leading to nitrogen 15min
It is sealed with quartz glass plug.Then with UV-LED point light sources (the light intensity 2.4mW/cm of 365nm2) from the top illumination of reactor
1h.After illumination, stable white " milky " dispersion liquid is obtained, and with 10000 turns of centrifuge, and use ethanol/water
(40/60, w/w) mixed solution is cleaned three times to get polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 2.
Embodiment 3 prepares polymers function microballoon
1st, in the embodiment, function monomer acrylic acid AA dosages are changed to 5% (relative to polymerized monomer MMA), remaining reagent
Type and dosage and implementation steps are in the same manner as in Example 2, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 2.
Embodiment 4 prepares polymers function microballoon
1st, in the embodiment, function monomer acrylic acid AA dosages are changed to 10% (relative to polymerized monomer MMA), remaining reagent
Type and dosage and implementation steps are in the same manner as in Example 2, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 2.
Embodiment 5 prepares polymers function microballoon
1st, in the embodiment, Macro RAFT agent dosage is changed to 10% (relative to polymerized monomer MMA), remaining reagent kind
Class and dosage and implementation steps are in the same manner as in Example 4, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 3.
Embodiment 6 prepares polymers function microballoon
1st, in the embodiment, Macro RAFT agent dosage is changed to 15% (relative to polymerized monomer MMA), remaining reagent kind
Class and dosage and implementation steps are in the same manner as in Example 4, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 3.
Embodiment 7 prepares polymers function microballoon
1st, in the embodiment, by Macro RAFT agent BTPA-PEG (20000)-BTPA be changed to BTPA-PEG (6000)-
BTPA, dosage is in 15% (relative to polymerized monomer MMA), remaining reagent type and dosage and implementation steps and embodiment 6
It is identical, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 3.
Embodiment 8 prepares polymers function microballoon
1st, in the embodiment, by Macro RAFT agent BTPA-PEG (20000)-BTPA be changed to BTPA-PEG (10000)-
BTPA, dosage is in 15% (relative to polymerized monomer MMA), remaining reagent type and dosage and implementation steps and embodiment 6
It is identical, obtain polymers function microballoon of the surface with carboxyl.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 4.
Embodiment 9 prepares polymers function microballoon
1st, in the embodiment, function monomer acrylic acid AA is changed to glycidyl methacrylate GMA, dosage 10%
(relative to polymerized monomer MMA), remaining reagent type and dosage and implementation steps are in the same manner as in Example 6, obtain surface band
The polymers function microballoon of epoxy group.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 4.
Embodiment 10 prepares polymers function microballoon
1st, in the embodiment, function monomer acrylic acid AA is changed to hydroxyethyl methacrylate HEMA, dosage is 10% (phase
For polymerized monomer MMA), remaining reagent type and dosage and implementation steps are in the same manner as in Example 6, and it is hydroxyl to obtain surface
Polymers function microballoon.
2nd, products therefrom scanning electron microscope (SEM) photograph (SEM) is shown in Fig. 4.
Embodiment 11 cuts off the stabilizer of polymers function microsphere surface
1st, it is stabilizer based on Macro RAFT agent BTPA-PEG (20000)-BTPA (10wt% of monomer mass)
Light RAFT dispersin polymerizations obtain polymers function microballoon dispersion liquid of the surface with carboxyl, and addition 10.0g water is diluted to 10% and contains admittedly
Amount.Then 100 times or more of thermal initiator potassium peroxydisulfate KPS is added in.After reaction mixture is led to nitrogen 30min, it is placed in 70 DEG C
Oil bath pan in react for 24 hours after, centrifuge and simultaneously wash several times with ethyl alcohol, it is dry, obtain the polymer work(with carboxyl of surface totally
It can microballoon.
2nd, the X-ray photoelectron spectroscopic analysis (XPS) before and after product excision stabilizer is distinguished as shown in Figure 5 and Figure 6.
Embodiment 12 cuts off the stabilizer of polymers function microsphere surface
In the embodiment, thermal initiator AIBN is replaced into the KPS in embodiment 11, remaining reagent type and dosage and reality
It is identical with embodiment 12 to apply step.
X-ray photoelectron spectroscopic analysis (XPS) after product excision stabilizer is as shown in Figure 7.
Claims (10)
1. a kind of Z- types Macro RAFT agent, which is characterized in that its structural formula is as follows：
Wherein, n=25~500；The Z- types Macro RAFT agent is that big point is connected on the Z group of small molecule RAFT reagents
Subchain obtains.
2. a kind of preparation method for the polymer microballoon for cutting off stabilizer, which is characterized in that big with Z- types described in claim 1
Molecule RAFT reagents, using ethanol/water mixed liquor as decentralized medium, carry out light dispersin polymerization, synthesize as stable dispersant
To stable white " milky " dispersion liquid；Then excessive thermal initiator is added in after being diluted with water, leads to nitrogen 20~28h of oil bath heating,
The clean polymers function microballoon that surface is free of stable dispersant is obtained after removal decentralized medium.
3. preparation method according to claim 2, which is characterized in that include the following steps：
S1. the polymer microballoon dispersion liquid that light RAFT dispersin polymerizations obtain：
By Z- types Macro RAFT agent and function monomer described in polymerized monomer, photoinitiator, claim 1 be dissolved in ethyl alcohol/
It in water mixed solvent, is sealed after logical nitrogen, is shone with light source light is caused, obtain stable white polymer microballoon dispersion liquid；
S2. polymer microballoon surface RAFT active groups are decomposed, so as to which the stable dispersant strand on surface is cut off.
4. preparation method according to claim 3, which is characterized in that polymerized monomer described in step S1 is methyl methacrylate
Ester, ethyl methacrylate, isobornyl methacrylate, butyl methacrylate, lauryl methacrylate, metering system
Sour isobutyl ester, isodecyl methacrylate, isooctyl methacrylate, methyl acrylate, ethyl acrylate, isobomyl acrylate
Any one of ester, butyl acrylate, lauryl acrylate, isobutyl acrylate, isodecyl acrylate or Isooctyl acrylate monomer
It is or several.
5. preparation method according to claim 3, which is characterized in that photoinitiator described in step S1 is 2,4,6- trimethyls
Benzoyl diphenyl phosphine oxide, 2- hydroxy-2-methyl -1- phenylacetones -1,1- hydroxy-cyciohexyls benzophenone, double Benzoylbenzenes
Base phosphine oxide, 2- methyl-1s-[4- first mercaptophenyl] -2- morpholines acetone -1 or 2- phenyl -2- dimethylaminos -1-（4- morpholine benzene
Base）Any one in butanone -1.
6. preparation method according to claim 3, which is characterized in that function monomer described in step S1 is acrylic acid, methyl
Acrylic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate, acrylic acid -2- hydroxyl ethyl esters or metering system
Any one of acid -2- hydroxyl ethyl esters.
7. preparation method according to claim 3, which is characterized in that the dosage of polymerized monomer described in step S1 for 5~
20wt%；The dosage of Z- types Macro RAFT agent described in step S1 is 0.1~15wt% of polymerized monomer；Light described in step S1 draws
The dosage for sending out agent is 1~10wt% of polymerized monomer；The dosage of function monomer described in step S1 is 1~10wt% of polymerized monomer.
8. preparation method according to claim 3, which is characterized in that cause light source described in step S1 as medium pressure mercury lamp, purple
Outer smooth Non-polarized lamp, metal halid lamp or UV-LED light sources；The light intensity for causing light source described in step S1 is 0.2~20mW/cm2。
9. preparation method according to claim 3, which is characterized in that the specific method of step S2 is：By the polymer of S1
Microballoon dispersion liquid adds in water dilution, then adds in excessive thermal initiator, after leading to nitrogen, 60~80 DEG C of oil bath reaction, from
The heart, and washed with ethyl alcohol and for several times, obtain clean polymers function microballoon.
10. the polymer microballoon for cutting off stabilizer that any the method for claim 2~9 is prepared.
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