CN114716616B - Active polymer microsphere and preparation method thereof - Google Patents
Active polymer microsphere and preparation method thereof Download PDFInfo
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- CN114716616B CN114716616B CN202210399456.4A CN202210399456A CN114716616B CN 114716616 B CN114716616 B CN 114716616B CN 202210399456 A CN202210399456 A CN 202210399456A CN 114716616 B CN114716616 B CN 114716616B
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- polymer
- monomer
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- microsphere
- poly
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- 229920000642 polymer Polymers 0.000 title claims abstract description 265
- 239000004005 microsphere Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 44
- 125000000129 anionic group Chemical group 0.000 claims abstract description 18
- 230000000977 initiatory effect Effects 0.000 claims abstract description 10
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims description 115
- 239000002904 solvent Substances 0.000 claims description 60
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 46
- 239000003431 cross linking reagent Substances 0.000 claims description 41
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 40
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 31
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 27
- 239000007908 nanoemulsion Substances 0.000 claims description 27
- -1 alkali metal alkoxide Chemical class 0.000 claims description 26
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920000314 poly p-methyl styrene Polymers 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- MLDNIDZCTXRLGC-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]ethyl 2-methylprop-2-enoate Chemical group CC(C(OCCOCC1=CC=C(C=C)C=C1)=O)=C MLDNIDZCTXRLGC-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 230000000694 effects Effects 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
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 4
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical group CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical class O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 3
- 229920013730 reactive polymer Polymers 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 22
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- 239000000835 fiber Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
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- 239000007787 solid Substances 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 238000002296 dynamic light scattering Methods 0.000 description 24
- 238000009826 distribution Methods 0.000 description 20
- 239000004971 Cross linker Substances 0.000 description 16
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 14
- 239000004816 latex Substances 0.000 description 12
- 229920000126 latex Polymers 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 8
- 244000028419 Styrax benzoin Species 0.000 description 7
- 235000000126 Styrax benzoin Nutrition 0.000 description 7
- 235000008411 Sumatra benzointree Nutrition 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 229960002130 benzoin Drugs 0.000 description 7
- 235000019382 gum benzoic Nutrition 0.000 description 7
- 150000003440 styrenes Chemical class 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 238000012650 click reaction Methods 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000003462 sulfoxides Chemical class 0.000 description 4
- NEQQUZIHFXJYLI-UHFFFAOYSA-N 1-ethenyl-4-prop-2-enylbenzene Chemical compound C=CCC1=CC=C(C=C)C=C1 NEQQUZIHFXJYLI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 238000007306 functionalization reaction Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical class C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- UFFNTJZNAAZWHR-UHFFFAOYSA-N C(C(=C)C)(=O)OC.CC1=CC=C(C=C)C=C1 Chemical compound C(C(=C)C)(=O)OC.CC1=CC=C(C=C)C=C1 UFFNTJZNAAZWHR-UHFFFAOYSA-N 0.000 description 2
- PQKZNDJPYVCZNB-UHFFFAOYSA-N Cc1ccc(C=C)cc1.CO[Si](CCCOC(=O)C(C)=C)(OC)OC Chemical compound Cc1ccc(C=C)cc1.CO[Si](CCCOC(=O)C(C)=C)(OC)OC PQKZNDJPYVCZNB-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 239000006087 Silane Coupling Agent Substances 0.000 description 2
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- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
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- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
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- YNQXOOPPJWSXMW-UHFFFAOYSA-N 1-ethenyl-2-fluorobenzene Chemical compound FC1=CC=CC=C1C=C YNQXOOPPJWSXMW-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- VHMFUTNSBRRHKF-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene oxiran-2-ylmethyl 2-methylprop-2-enoate Chemical compound Cc1ccc(C=C)cc1.CC(=C)C(=O)OCC1CO1 VHMFUTNSBRRHKF-UHFFFAOYSA-N 0.000 description 1
- ARJFNIGGXQKXBD-UHFFFAOYSA-N 1-ethenyl-4-methylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CC1=CC=C(C=C)C=C1 ARJFNIGGXQKXBD-UHFFFAOYSA-N 0.000 description 1
- NSGTVMQTRFUUSL-UHFFFAOYSA-N 1-isocyanato-2-propylbenzene Chemical compound CCCC1=CC=CC=C1N=C=O NSGTVMQTRFUUSL-UHFFFAOYSA-N 0.000 description 1
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 1
- XDRLAGOBLZATBG-UHFFFAOYSA-N 1-phenylpenta-1,4-dien-3-one Chemical group C=CC(=O)C=CC1=CC=CC=C1 XDRLAGOBLZATBG-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 description 1
- JEHFRMABGJJCPF-UHFFFAOYSA-N 2-methylprop-2-enoyl isocyanate Chemical compound CC(=C)C(=O)N=C=O JEHFRMABGJJCPF-UHFFFAOYSA-N 0.000 description 1
- JAWKOSRQDZQJMU-UHFFFAOYSA-N 2-methylpropan-2-ol;toluene Chemical compound CC(C)(C)O.CC1=CC=CC=C1 JAWKOSRQDZQJMU-UHFFFAOYSA-N 0.000 description 1
- VAYMIYBJLRRIFR-UHFFFAOYSA-N 2-tolyl isocyanate Chemical compound CC1=CC=CC=C1N=C=O VAYMIYBJLRRIFR-UHFFFAOYSA-N 0.000 description 1
- WPABAKMRZCBXTO-UHFFFAOYSA-N 3-isocyanatopropylbenzene Chemical compound O=C=NCCCC1=CC=CC=C1 WPABAKMRZCBXTO-UHFFFAOYSA-N 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- JISFNYSNQXYXHX-UHFFFAOYSA-N C(=C)C1=CC=C(C)C=C1.C(C(=C)C)(=O)OCCOC(C(=C)C)=O Chemical compound C(=C)C1=CC=C(C)C=C1.C(C(=C)C)(=O)OCCOC(C(=C)C)=O JISFNYSNQXYXHX-UHFFFAOYSA-N 0.000 description 1
- AGJRYHHDBOGLJQ-UHFFFAOYSA-N C1(=CC=CC=C1)C(C[Li])C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)C(C[Li])C1=CC=CC=C1 AGJRYHHDBOGLJQ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- CDKFWIMBZAUBRS-UHFFFAOYSA-M [I-].CC[Mg+] Chemical compound [I-].CC[Mg+] CDKFWIMBZAUBRS-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004171 alkoxy aryl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 229940027564 cytisine Drugs 0.000 description 1
- 229930017327 cytisine Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- NVLHKSGUMYMKRR-UHFFFAOYSA-N dodeca-2,10-dienediamide Chemical compound NC(=O)C=CCCCCCCC=CC(N)=O NVLHKSGUMYMKRR-UHFFFAOYSA-N 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
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- ANJTVLIZGCUXLD-UHFFFAOYSA-N ent-cytisine Natural products C1NCC2CN3C(=O)C=CC=C3C1C2 ANJTVLIZGCUXLD-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CBQKGISIWKPJMB-UHFFFAOYSA-N naphthalene;oxolane;sodium Chemical compound [Na].C1CCOC1.C1=CC=CC2=CC=CC=C21 CBQKGISIWKPJMB-UHFFFAOYSA-N 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- QSGNIZYSOOADSE-UHFFFAOYSA-N penta-1,4-dienylbenzene Chemical compound C=CCC=CC1=CC=CC=C1 QSGNIZYSOOADSE-UHFFFAOYSA-N 0.000 description 1
- 125000005459 perfluorocyclohexyl group Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- QLNOVKKVHFRGMA-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical group [CH2]CC[Si](OC)(OC)OC QLNOVKKVHFRGMA-UHFFFAOYSA-N 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to an active polymer microsphere and a preparation method thereof. The polymer microsphere of the present invention has a core-shell structure, the shell layer comprises a polymer A, the core comprises a polymer B having a cross-linked structure, the molecular chain of the polymer A is connected with the polymer B through a covalent bond, and at least one part of the molecular chain terminal of the polymer B is provided with an anionic active center. The invention ensures that the active center is kept in the microsphere through reasonable design of the microsphere structure, thus being capable of continuously initiating polymerization and providing larger space for subsequent modification. In the preparation method, the composition and the structure of the polymer microsphere are adjustable, the size of the polymer microsphere can be accurately controlled, the solid content is high, the conversion rate is high, the reaction rate is high, and the preparation method has wide application prospects in plastic industry, rubber industry, fiber industry, paint industry and the like.
Description
Technical Field
The invention belongs to the field of polymer materials, and particularly relates to an active polymer microsphere and a preparation method thereof.
Background
The polymer microsphere has wide application in the fields of plastic industry, rubber industry, fiber industry and paint industry. However, the preparation of polymeric microspheres with dimensions in the range of 10-100nm remains a major challenge. The polymer microsphere which is known in the prior art and does not contain a protective chain segment can realize higher monomer conversion rate (> 80%) and narrower size distribution in the living polymerization process, but the prepared polymer microsphere has larger size (micron order) and can not realize the precise control of the structure in the size of 10-100 nm. While the polymerization-induced self-assembly process of the two-block polymerization with the protective chain segment can realize the control of the structure under a smaller size, most of the polymerization-induced self-assembly process adopts a free radical polymerization mode, and therefore the polymerization-induced self-assembly process has the defects of lower monomer conversion rate, slow reaction rate, wider molecular weight distribution and unstable particle structure, and brings larger limitation to industrial application (L.C.Sarah, N.S.Gregory, P.A.Steven, A critical appraisal of raft-mediated polymerization-reduced self-assembly. Macromolecules,2016,49 (6), 1985-2001).
Living anionic polymerization has a wide application space due to its more controllable polymer structure (Mw/Mn can be less than 1.05), faster reaction rate, higher monomer conversion (which can approach 100% conversion). The living anion polymerization can realize the precise regulation and control of different components, molecular weight and structure of the polymer in the polymerization process by means of sectional feeding. Meanwhile, the living anion polymerization does not need additional catalyst and additive, the system is relatively clean, and the post-treatment operation is simple.
The manner of polymerization-induced self-assembly by anionic polymerization reported in the prior art all employs non-polar monomers. Such as styrene, butadiene and homolog systems thereof (X.R.Wang, J.E.Hall, S.Warren, J.Krom, J.M.Magistrelli, M.Rackaitis, G.G.A.Bohm, macromolecules,2007,40 (3), 499-508), which limit subsequent functionalization. In addition, wang et al developed an anionic precipitation polymerization method that could be used for large scale synthesis of nanoparticles and used this method to synthesize a hollow nanoparticle (X.R.Wang et al, U.S. patent 8,821,931[ P ] 2014-9-2).
Disclosure of Invention
Problems to be solved by the invention
The anionic precipitation polymerization method in the prior art only relates to the polymerization of nonpolar monomers, and the active center inside the particles synthesized by the method cannot be kept continuously, cannot be used for subsequent polymerization or functional compounding, and limits the application range.
Solution for solving the problem
Aiming at the problems in the prior art, the invention provides the active polymer microsphere, and the active center is kept in the microsphere through reasonable design of the microsphere structure, so that polymerization can be continuously initiated, and a larger space is provided for subsequent modification.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] An active polymeric microsphere having a core-shell structure, wherein the shell layer comprises a polymer a, the core comprises a polymer B having a cross-linked structure, the molecular chain of the polymer a is linked to the polymer B by a covalent bond, and at least a portion of the molecular chain ends of the polymer B bear an anionic active center.
[2] The active polymer microsphere according to [1], wherein the particle size of the polymer microsphere is 5 to 100nm; wherein the content of the polymer A is 0.1 to 90 weight percent, and the content of the polymer B is 10 to 99.9 weight percent.
[3] The living polymeric microsphere according to [1] or [2], wherein the polymer A is derived from an anionically polymerizable monomer A; the polymer B is derived from an anionically polymerizable crosslinking agent C and optionally an anionically polymerizable monomer B; the monomer A and the monomer B are one or more selected from styrene monomers, conjugated dienes, vinyl pyridine and derivatives thereof, (methyl) acrylic ester monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, substituted halogenated olefins, maleic anhydride, maleimide and acrylonitrile; the cross-linking agent C is one or more selected from styrene, (methyl) acrylic ester, (methyl) acrylamide and isocyanate cross-linking agents;
In the case where the polymer B is derived from an anionically polymerizable crosslinking agent C and an anionically polymerizable monomer B, preferably, monomer a is selected from styrenic monomers and monomer B is selected from (meth) acrylate monomers; or the monomer A is selected from conjugated diene monomers, and the monomer B is selected from styrene monomers and acrylonitrile; or the monomer A is selected from styrene monomer, and the monomer B is selected from vinyl pyridine and derivatives thereof; or the monomer A is selected from alkyl styrene monomer, and the monomer B is styrene;
more preferably, polymer a is poly 4-methylstyrene and polymer B is polyethylene glycol dimethacrylate crosslinked polymethyl methacrylate; or polymer A is polybutadiene and polymer B is divinylbenzene-crosslinked polystyrene; or polymer a is polybutadiene and polymer B is a polymer comprising divinylbenzene-crosslinked polystyrene and polyacrylonitrile; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-methacryloxypropyl trimethoxy silane crosslinked by ethylene glycol dimethacrylate; or polymer A is poly-4-methyl styrene and polymer B is divinylbenzene crosslinked polystyrene; or the polymer A is polyallylstyrene, and the polymer B is polymethyl methacrylate crosslinked by glycol dimethacrylate; or polymer A is poly (4-methyl styrene), and polymer B is poly (2- (4-vinyl benzyloxy) ethanol methacrylate) crosslinked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-isocyanoethyl methacrylate crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is polyethylene glycol dimethacrylate crosslinked poly-glycidyl methacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-2-vinyl pyridine crosslinked by ethylene glycol dimethacrylate;
In the case where the polymer B is derived from an anionically polymerizable cross-linking agent C, preferably the monomer a is selected from styrenic monomers, more preferably 4-methylstyrene, and the cross-linking agent C is selected from (meth) acrylate cross-linking agents.
[4] The living polymer microsphere according to the item [1] or [2], wherein the polymer A and/or the polymer B has a functional segment in a molecular chain thereof or a functional group is attached to the molecular chain of the polymer A and/or the polymer B.
[5] A reactive nanoemulsion comprising the reactive polymer microsphere of any one of [1] to [4] and a solvent, wherein the polymer a is soluble in the solvent, and the monomer and crosslinking agent forming the polymer B are soluble in the solvent.
[6] The reactive nanoemulsion of [5], wherein the solvent is one or more selected from the group consisting of alkane, aromatic hydrocarbon, ether, ester, amide and sulfoxide solvents; the alkane solvent is preferably a linear, branched or cyclic alkane having 5 to 8 carbon atoms; the aromatic hydrocarbon solvent is preferably benzene substituted with 0 to 5 alkyl groups having 1 to 5 carbon atoms; the ether solvent is preferably 1, 4-dioxane or tetrahydrofuran; the ester solvent is preferably ethyl acetate; the amide solvent is preferably N, N-dimethylformamide, and the sulfoxide solvent is preferably dimethyl sulfoxide.
[7] The reactive nanoemulsion according to [5] or [6], wherein the content of the polymer microsphere is 10 to 70wt%, preferably 15 to 50wt%, more preferably 20 to 40wt%.
[8] The reactive nanoemulsion of [5] or [6], wherein the content of the emulsifier is 0 to 1wt%, preferably no emulsifier.
[9] The method for producing an active polymer microsphere according to any one of [1] to [4] or an active nanoemulsion according to any one of [5] to [8], characterized by comprising the steps of:
(a) Dissolving a monomer A in a solvent, adding an anionic polymerization initiator, and initiating the monomer A to carry out anionic polymerization reaction to obtain a polymer A with an anionic active center at the tail end of a molecular chain;
(b) Optionally adding an active center stabilizer;
(c) Adding a cross-linking agent C and an optional monomer B, and continuing to carry out anionic polymerization reaction to form the polymer microsphere.
[10] The process according to [9], wherein the anionic polymerization initiator is one or more selected from the group consisting of an organometallic compound, an alkali metal, an alkaline earth metal, a boron group metal, an alkali metal hydride, an alkali metal hydroxide, an amine, an imine and a derivative thereof, an alkali metal alkoxide, an ether, an alcohol, and an organic phosphide.
[11] The production method according to [9] or [10], characterized in that the polymerization time in the step (a) is 1 to 120 minutes, and the polymerization temperature is-100 to 100 ℃; the polymerization time in the step (c) is 1-180 min, and the polymerization temperature is-100 ℃.
[12] A method for preparing an active nano emulsion, which is characterized by comprising the steps (a) - (c) in claim 9, and further comprising the following steps:
(d) Monomer D is added, and polymerization reaction is continued to form polymer D with active center at the end connected with polymer B through covalent bond.
[13] The process according to [12], wherein the monomer D is one or more selected from the group consisting of a styrene-based monomer, a conjugated diene, a vinyl pyridine and its derivatives, (meth) acrylic acid ester-based monomer, ethylene oxide or propylene oxide and its derivatives, a monoisocyanate-based monomer, a halogenated olefin, maleic anhydride, and maleimide.
[14] The reactive nanoemulsion obtained by the method of any one of [7] to [13 ].
[15] A method for preparing polymer microspheres, characterized in that the active nano latex is prepared according to the preparation method of any one of [9] to [13], and then a chain terminator is added into the active nano latex.
[16] The method according to [15], wherein the chain terminator is one or more selected from the group consisting of an inactive terminator and an active terminator; the inactive terminator is preferably water, alcohol or amine; the activity terminator is preferably a haloalkane.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer microspheres of the present invention have a narrow particle size distribution and retain active centers, and thus can be easily modified later according to actual needs.
The nano-reactive latex of the present invention has a high solid content and is substantially free of emulsifiers, thus eliminating the need for subsequent removal of the emulsifiers.
The preparation method of the polymer microsphere or the nanometer active latex has adjustable composition and structure, can accurately control the size of the polymer microsphere, has high solid content, high conversion rate and high reaction rate, and has wide application prospect in plastic industry, rubber industry, fiber industry, paint industry and the like.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
Terms and definitions
In the present specification, "particle size" means the median particle diameter D of the described particle group 50 Which can be measured by dynamic light scattering as described in the examples section.
In the present specification, the "particle size distribution index" (also simply referred to as "particle size distribution") means a polydispersity index of the particle size of the described particle group, which is defined as
U＝D w /D n
Where Dn is the average particle size of the particles, dw is the defined mathematical average particle size, di is the diameter of the ith particle, k is the sample volume, U is the particle size distribution index, which can be determined by dynamic light scattering as described in the examples section.
In the present specification, "monodisperse" means that the particle size distribution index (PDI) is in the range of 1 to 1.3.
In the present specification, "latex" refers to a dispersion of polymer microspheres in a solvent.
As used herein, "room temperature" refers to a temperature range of 20 to 30 ℃, for example 25 ℃.
In the present specification, "active nanolatex" and "nanoactive latex" have the same meaning, and both may be used interchangeably.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the elements may be combined in any suitable manner in the various embodiments.
Active polymeric microspheres
It is an object of the present invention to provide an active polymer microsphere having a core-shell structure, wherein the shell layer comprises a polymer a, the core comprises a polymer B having a cross-linked structure, a molecular chain of the polymer a is connected to the polymer B through a covalent bond, and at least a part of a molecular chain end of the polymer B has an anionic active center.
In the polymer microsphere, the anionic active center is embedded in the polymer microsphere, so that a reaction site is provided for further polymerization or modification.
In one embodiment, the polymer microspheres have a particle size of 5 to 100nm, preferably 6 to 70nm, more preferably 7 to 40nm, even more preferably 8 to 30nm, and can be well dispersed in a solvent when the particle size of the polymer microspheres is within the above range.
In one embodiment, the polymer microspheres of the present invention have a polymer A content of 0.1 to 90wt%, preferably 20 to 60wt%, and a polymer B content of 10 to 99.9wt%, preferably 40 to 80wt%.
In one embodiment, the polymer a is derived from an anionically polymerizable monomer a; the polymer B is derived from an anionically polymerizable crosslinker C and optionally an anionically polymerizable monomer B.
In one embodiment, the monomers a and B are independently of each other one or more selected from the group consisting of styrenic monomers, conjugated dienes, vinyl pyridines and derivatives thereof, (meth) acrylic monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, substituted haloolefins, maleic anhydride, maleimides.
The styrene monomer includes styrene and its derivative, wherein the derivative of styrene may be C1-10 alkyl substituted styrene, C1-10 alkenyl substituted styrene, C1-10 alkoxy substituted styrene, substituted styrene containing silane coupling agent structure, halogenated styrene, etc. Specific examples of styrenic monomers include, but are not limited to, styrene, 4-methylstyrene, alpha-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, p-styryltrimethoxysilane and derivatives thereof, 4-fluorostyrene, 2-fluorostyrene, 4-chlorostyrene, and the like.
The conjugated diene may be a C4-10 conjugated diene, examples of which include, but are not limited to, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, 2-ethyl-1, 3-butadiene, and the like.
Examples of vinyl pyridine and its derivatives include, but are not limited to, 2-vinyl pyridine, 4-vinyl pyridine, and the like.
The (meth) acrylic monomers include acrylic monomers and methacrylic monomers, which may be alkyl (meth) acrylates, haloalkyl (meth) acrylates, polyol or polyol ether (meth) acrylates, epoxy group-containing (meth) acrylates, vinyl phenyl group-containing (meth) acrylates, orthosilicate substituted (meth) acrylates, isocyanate substituted (meth) acrylates, silane coupling agent structure-containing (meth) acrylic monomers, and the like. Specific examples of (meth) acrylic monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, 1-adamantyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, triethylene glycol monoethyl (meth) acrylate, 2, 3-tetrafluoropropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate and derivatives thereof, (meth) acrylylvinylbenzene, orthosilicate substituted (meth) acrylates (e.g., 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, derivatives thereof, and the like.
The substituent in the derivative of ethylene oxide or propylene oxide may be one or more of alkyl, phenyl, alkylphenyl, specific examples of the derivative of ethylene oxide or propylene oxide include, but are not limited to, glycidyl (meth) acrylate, 1, 2-dimethylethylene oxide, 1, 2-butylene oxide, cyclohexane oxide.
The monoisocyanate monomer is a monomer having one isocyanate group, and may be a compound having the general formula r—nco, wherein the R group may represent an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an alkoxyaryl group, or the like. Specific examples of the monoisocyanate-based monomer include, but are not limited to, methyl isocyanate, ethyl isocyanate, octadecyl isocyanate, propylphenyl isocyanate, 3-phenylpropyl isocyanate, cyclohexyl isocyanate, o-toluene isocyanate, and the like.
The halogenated olefin may be ethylene having 1 to 4 halogen atom substituents, wherein the halogen atom may be a fluorine atom or a chlorine atom. Examples of halogenated olefins include, but are not limited to, vinylidene chloride, vinylidene fluoride, and the like.
The present invention is not particularly limited, and it may be any crosslinking agent capable of anionic polymerization known in the art, and in the case of using the monomer B, the crosslinking agent C may be any crosslinking agent capable of crosslinking reaction with the monomer B known in the art to give the polymer B. The choice of crosslinker C is in accordance with the anionic polymerization sequence, so that the choice of crosslinker C is limited by monomer A. The polymer after polymerization of crosslinker C should have poor solubility in the solvent.
The cross-linking agent C is one or more selected from styrene, (methyl) acrylic ester, (methyl) acrylamide and isocyanate cross-linking agents.
The styrenic crosslinking agent may be an optionally substituted polyvinyl benzene, such as an optionally substituted divinylbenzene, an optionally substituted trivinylbenzene, etc., wherein the substituents may be alkyl groups having 1 to 4 carbon atoms, or oligomers having 3 or more styrene groups in the side chain, such as (meth) acrylate oligomers having a styryl group as a substituent on the side group. Specific examples of styrenic crosslinkers include, but are not limited to, divinylbenzene, trivinylbenzene.
The (meth) acrylic acid ester crosslinking agent may be a polyacrylate of a polyol, specific examples of which include, but are not limited to, diethylene glycol (meth) acrylate (EGDMA), tetraethylene glycol di (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.
The (meth) acrylamide crosslinking agent may be N, N '-methylenebisacrylamide, hexamethylenebisacrylamide, diacetone acrylamide, N' -vinyl bisacrylamide.
The isocyanate-based crosslinking agent may be a polyisocyanate compound such as diisocyanate, triisocyanate, etc., and specific examples thereof include, but are not limited to, 1, 8-diisocyanate, 2, 6-toluene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, etc.
In the present invention, the monomer a and the monomer B are different, preferably at least one of the monomer a and the monomer B is a polar monomer, and preferably the monomer B is a polar monomer.
Herein, "derivative" refers to a product formed by substitution of an atom or group of atoms in a molecule of the described compound with other atoms or groups of atoms.
In a specific embodiment, polymer a is derived from a styrenic monomer and polymer B is derived from a (meth) acrylate monomer and a crosslinking agent. Wherein the styrene monomer is preferably one or more selected from C1-10 alkyl substituted styrenes such as styrene, methyl styrene, etc. and 4-allyl styrene; the (meth) acrylic acid ester monomer is preferably one or more selected from methyl methacrylate, 2- (4-vinylbenzyloxy) ethanol methacrylate, methacryloxypropyl trimethoxysilane, methacryloyl isocyanate, and Glycidyl Methacrylate (GMA).
In a specific embodiment, polymer a is derived from conjugated diene monomer and polymer B is derived from styrene monomer and a crosslinking agent or polymer B further comprises polyacrylonitrile.
In a specific embodiment, polymer a is derived from styrenic monomers and polymer B is derived from vinyl pyridine and its derivatives and a crosslinking agent.
In a specific embodiment, polymer a is derived from an alkylstyrene-based monomer and polymer B is derived from styrene and a crosslinking agent.
In a specific embodiment, polymer A is derived from an alkylstyrene monomer and polymer B is derived from a (meth) acrylate crosslinker, such as ethylene glycol dimethacrylate.
In a more specific embodiment, polymer a is poly 4-methylstyrene and polymer B is polyethylene glycol dimethacrylate crosslinked polymethyl methacrylate; or polymer A is polybutadiene and polymer B is divinylbenzene-crosslinked polystyrene; or polymer a is polybutadiene and polymer B is a polymer comprising divinylbenzene-crosslinked polystyrene and polyacrylonitrile; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-methacryloxypropyl trimethoxy silane crosslinked by ethylene glycol dimethacrylate; or polymer A is poly-4-methyl styrene and polymer B is divinylbenzene crosslinked polystyrene; or the polymer A is polyallylstyrene, and the polymer B is polymethyl methacrylate crosslinked by glycol dimethacrylate; or polymer A is poly (4-methyl styrene), and polymer B is poly (2- (4-vinyl benzyloxy) ethanol methacrylate) crosslinked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-isocyanoethyl methacrylate crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is polyethylene glycol dimethacrylate crosslinked poly-glycidyl methacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-2-vinyl pyridine crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is polyethylene glycol dimethacrylate.
In one embodiment, the polymer a and/or the polymer B has a functional segment in the molecular chain, or the polymer a and/or the polymer B has a functional group attached to the molecular chain. Wherein "functional segment" and "functional group" refer to segments or groups capable of continuing chemical reactions.
In one embodiment, the polymer a and/or the polymer B has carbon-carbon double bonds in the molecular chain. In one aspect of this embodiment, further modification may be achieved by further thiol-vinyl click reaction of the carbon-carbon double bond with a species having a functional segment or functional group. The solvent used in the click reaction can be selected from dichloromethane, alcohols (such as methanol) and dimethylformamide. The catalyst used in click reaction can be amine catalyst (such as n-propylamine) or photocatalyst (such as benzoin dimethyl ether, etc.), and can be used for reaction under ultraviolet irradiation. The mercapto reagent may be selected from mercapto carboxylic acid (e.g. mercaptoacetic acid), alcohol (e.g. mercaptoethanol), amine (e.g. mercaptoethylamine hydrochloride), ketone, and mercapto reagent containing silica coupling agent. The reaction time of the click reaction may be 1 to 120 minutes, preferably 60 to 90 minutes.
The click reaction has high yield, no byproducts and is insensitive to water and oxygen, so the method is a preferable polymer functionalization method. In a preferred embodiment, polymer microspheres may be hydrophilically modified with thioglycolic acid using benzoin dimethyl ether as a catalyst. In this embodiment, the carbon-carbon double bonds in the molecular chain of polymer a and/or polymer B on a molar basis: benzoin dimethyl ether: thioglycollic acid (0.8-1.2): (0.1-0.3): (8-12). The specific proportion can be adjusted according to the required hydrophilicity and hydrophobicity, and the higher the consumption of the thioglycollic acid is, the better the hydrophilicity of the modified polymer microsphere is.
Active nano emulsion
It is an object of the present invention to provide an active nanoemulsion comprising the polymer microspheres of the present invention and a solvent, wherein the polymer a is soluble in the solvent and the monomer B and/or the crosslinker C forming the polymer B is soluble in the solvent.
In one embodiment, the solvent is one or more selected from the group consisting of alkane, aromatic, ether, ester, amide, and sulfoxide solvents. The alkane solvent is preferably a linear, branched or cyclic alkane having 5 to 8 carbon atoms; the aromatic hydrocarbon solvent is preferably benzene substituted with 0 to 5, preferably 1 to 4 alkyl groups having 1 to 5 carbon atoms; the ether solvent is preferably 1, 4-dioxane or tetrahydrofuran; the ester solvent is preferably ethyl acetate; the amide solvent is preferably N, N-dimethylformamide, and the sulfoxide solvent is preferably dimethyl sulfoxide.
These solvents may be used alone or in combination of 2 or 3 or more. In some embodiments, the solvent is a mixed solvent composed of more than 2 solvents, and the combination of different solvents can better adjust the solubility of the polymer A in the solvent, so that the polymer microspheres are more stably dispersed in the solvent. In a preferred embodiment, a mixed solvent of cyclohexane and tetrahydrofuran is used.
In one embodiment, the polymer microspheres are present in an amount of 10 to 70wt%, preferably 15 to 50wt%, more preferably 20 to 40wt%, based on the total weight of the reactive nanoemulsion of the invention. When the solid content is in the above range, the microspheres with monodispersed and controllable particle size can be prepared.
In a preferred embodiment, the nanoreactive latex of the invention is substantially free of emulsifiers, i.e. the amount of emulsifier is from 0 to 1wt%, preferably from 0 to 0.5wt%, more preferably from 0 to 0.1wt%, most preferably completely free of emulsifiers, based on the total weight of the nanoreactive latex.
The active nano emulsion of the invention has the function of stabilizing and emulsifying the cross-linked polymer B which is insoluble in the solvent because the polymer A forming the shell layer of the polymer microsphere is soluble in the solvent, thereby enabling the polymer microsphere to be stably dispersed in the solvent under the condition of basically not containing the emulsifying agent.
Preparation method
It is another object of the present invention to provide a method for preparing the polymer microsphere of the present invention and the active nano latex of the present invention, comprising the steps of:
(a) Dissolving a monomer A in a solvent, adding an anionic polymerization initiator, and initiating the monomer A to carry out anionic polymerization reaction to obtain a polymer A with an anionic active center at the tail end of a molecular chain;
(b) Optionally adding an active center stabilizer;
(c) Adding a cross-linking agent C and an optional monomer B, and continuing to carry out anionic polymerization reaction to form the polymer microsphere.
The preparation method is based on an anionic precipitation polymerization technology, firstly, a chain segment of a polymer A which is soluble in a solvent is formed through anionic polymerization of a monomer A, then, a polymer B which is poor in solubility in the solvent and even insoluble and has a cross-linked structure is further formed on the chain segment of the polymer A, along with the generation of the polymer B, the polymer is self-assembled into polymer microspheres with a core-shell structure, wherein the polymer A is positioned on the outer layer, and the polymer B is positioned inside, and the polymer microspheres are stably dispersed in the solvent by utilizing the solubility of the polymer A.
The respective steps of the production method of the present invention are described below.
Step (a)
In step (a), monomer A is first dissolved in a solvent, and then an anionic polymerization initiator is added to initiate the anionic polymerization of monomer A. After successful initiation, a change in system color can be observed, for example, the system turns orange-yellow, which indicates the formation of anionic active centers.
In one embodiment, the anionic polymerization initiator is one or more selected from the group consisting of organometallic compounds, alkali metals, alkaline earth metals, boron group metals (metals belonging to group IIIA of the periodic Table), alkali metal hydrides, alkali metal hydroxides, amines, imines and derivatives thereof, alkali metal alkoxides, ethers, alcohols, organophosphates.
The organometallic compounds include alkali metal alkyls, alkali metal aryls, formatives, and the like, wherein the alkali metal is lithium, sodium, or potassium. The alkali metal alkyl compound may be alkyl lithium, alkyl sodium, alkyl potassium, alkyl aluminum lithium, alkyl aluminum sodium, etc., specific examples of which include, but are not limited to, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, 1-diphenylhexyl lithium, etc. Specific examples of the alkali metal aryl compound include, but are not limited to, diphenylethyl lithium, sodium naphthalene, potassium naphthalene, lithium naphthalene, and the like. The formative reagent may be alkyl magnesium bromide, alkyl magnesium chloride, alkyl magnesium iodide, wherein alkyl may be methyl, ethyl or propyl, and specific examples of the formative reagent include, but are not limited to, methyl magnesium bromide, methyl magnesium chloride, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium iodide, and the like.
The alkali metal comprises a Li, na, K, rb, cs metal element, the alkaline earth metal comprises a Mg, ca, sr, ba metal element, and the boron group metal comprises a Al, ga, in, tl metal element.
Specific examples of alkali metal hydrides and alkali metal hydroxides include, but are not limited to, sodium hydride, potassium hydroxide, sodium hydroxide, and the like.
Specific examples of amines include, but are not limited to, sodium dialkylamide, ethylamine, n-propylamine, isopropylamine, n-butylamine, and the like.
Specific examples of imines and derivatives thereof include, but are not limited to, cytisine, (CAS: 485-35-8), triethylenediamine (CAS: 88935-43-7).
Specific examples of alkali metal alkoxides include, but are not limited to, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium t-butoxide, sodium t-butoxide, potassium t-butoxide, and the like.
Specific examples of ethers and alcohols include, but are not limited to, t-butanol, diethyl ether, and the like.
Specific examples of the organic phosphorus compound include, but are not limited to, trimethylphosphine, triethylphosphine, and the like.
The above initiators may be used alone or in combination of 2 or more than 3. These initiators may be added as pure substances or in other forms such as solutions. Among these initiators, n-butyllithium, sodium naphthalene and/or t-butanol are preferably used, and may be added to the reaction system, for example, in the form of an n-butyllithium n-hexane solution, a sodium naphthalene tetrahydrofuran solution and/or a t-butanol toluene solution.
In one embodiment, the polymerization temperature of step (a) is from-100℃to 100℃and preferably from-30℃to 60℃and more preferably from-20℃to 60 ℃.
In one embodiment, the polymerization time of step (a) is from 1 to 120 minutes, preferably from 10 to 100 minutes, more preferably from 20 to 60 minutes.
In one embodiment, step (a) is preferably performed under conditions where agitation is applied, which may be performed by mechanical agitation, magnetic agitation or ultrasound.
In one embodiment, in step (a), the amount of monomer A added is from 0.1 to 30% by weight, preferably from 5 to 25% by weight, relative to the amount of solvent used.
In one embodiment, in step (a), the initiator is added in an amount of 0.5 to 100mol% relative to the amount of monomer A; preferably, monomer a: initiator = 30:1 to 100:1.
step (b)
After step (a), depending on the difference in reactivity of monomer A with monomer B and/or crosslinker C, an active center stabilizer may optionally be added to the reaction system to reduce the activity of the anionic active center located at the end of the segment of polymer A, facilitating subsequent polymerization of monomer B and/or crosslinker C.
The active center stabilizer may be any monomer which is less susceptible to growth than the monomer a in the anionic polymerization, for example, when the monomer a is a methacrylate-based monomer, a styrene-based monomer may be used as the active center stabilizer. In addition, the active center stabilizer may also be an active center stabilizer commonly used in the art, such as 1, 1-Diphenylethylene (DPE).
In one embodiment, the active center stabilizer is added in an amount of 100 to 200 mole% relative to the amount of initiator in step (a).
In one embodiment, step (b) is carried out for a time of from 1 to 30 minutes, preferably from 5 to 20 minutes.
A color change, for example, a red color, can be observed upon addition of the active center stabilizer system.
Step (c)
In step (C), the crosslinking agent C and optionally the monomer B may be added stepwise or simultaneously.
In one embodiment, monomer B and crosslinker C are added simultaneously, and under the initiation of the anionic active center at the segment end of polymer a, monomer B and crosslinker C undergo anionic polymerization and crosslink, so that the polymer precipitates from the solvent and self-assembles into the polymeric microspheres of the invention having a core-shell structure. In this embodiment, the reactivity of monomer B and crosslinker C differ little, and the polarity differs little.
In one embodiment, monomer B is added first and after a period of time for polymerization, crosslinker C is added. In this embodiment, after the addition of monomer B, monomer B undergoes anionic polymerization under the initiation of the anionic active center at the segment end of polymer a, and the polymer formed from monomer B is insoluble in the solvent, so that the polymer precipitates from the solvent and self-assembles into polymer microspheres having a core-shell structure. Then adding a cross-linking agent C, wherein the cross-linking agent C enters the core of the polymer microsphere and is polymerized under the initiation of the anionic active center at the tail end of the polymer B, so that the polymer B is cross-linked. In this embodiment, polymer B has a semi-interpenetrating network structure. In this embodiment, the anionic active center stabilizer described above may be optionally added according to the reactivity of the crosslinking agent C before the crosslinking agent C is added.
In one embodiment, only crosslinker C is added, no monomer B is added, and anionically polymerizable crosslinker C undergoes anionic polymerization and forms crosslinked polymer B upon initiation of the anionic active center at the end of the segment of polymer A.
In one embodiment, the polymerization temperature of step (c) is from-100℃to 100℃and preferably from-30℃to 60℃and more preferably from-20℃to 40 ℃.
In one embodiment, the polymerization time of step (c) is from 1 to 180 minutes, preferably from 10 to 150 minutes, more preferably from 20 to 120 minutes.
In one embodiment, step (c) is preferably performed under conditions where agitation is applied, which may be performed by mechanical agitation, magnetic agitation or ultrasound.
In one embodiment, the amount of monomer B added in step (c) is from 0 to 70% by weight, preferably from 5 to 40% by weight, relative to the amount of solvent used in step (a).
In one embodiment, in step (C), the amount of crosslinking agent C is 0.01 to 30wt%, preferably 0.1 to 20wt%, for example 0.1 to 10wt%, relative to the amount of solvent.
After the polymerization of step (c) has been carried out for a period of time, a weak blue light can be observed in the system, indicating that nanoemulsion particles are formed in the system.
Other steps
In one embodiment, the present invention provides a method for preparing an active nanoemulsion, comprising the steps (a) to (c) described above, further comprising the steps of:
(d) Monomer D is added, and polymerization reaction is continued to form polymer D with active center at the end connected with polymer B through covalent bond.
In one embodiment, in step (D), monomer D is further added to the reaction system, and the monomer D undergoes anionic polymerization under the initiation of the active center at the end of polymer B, forming polymer D with an active center attached at one end to the other end of polymer B. Monomer D may be one or more selected from the monomers described above for monomer a.
The invention also relates to a preparation method of the polymer microsphere, firstly, the active nano emulsion is prepared according to the preparation method of the invention, and then, the chain terminator is added into the active nano emulsion. By adding a chain terminator to the reaction system, the active center of the polymer end is deactivated, and thus the polymerization reaction cannot be initiated any more.
In one embodiment, the chain terminator is one or more selected from the group consisting of an inactive terminator and an active terminator; the inactive terminator is preferably water, alcohol or amine; the activity terminator is preferably a haloalkane. By using an active terminator, a functional group can be introduced at the active center in the nano-active latex particle, providing a reactive site for subsequent further functionalization.
The invention also relates to the polymer microspheres and the reactive nanoemulsions produced by the method according to the invention and to the use thereof for producing polymer microspheres in the plastics industry, rubber industry, fiber industry, paint industry.
Examples
The invention is further illustrated by the following examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications of the invention will become apparent to those skilled in the art upon reading the description herein, and such equivalents are intended to fall within the scope of the invention as defined by the appended claims.
In the following examples, the polymer stock solution was diluted to 1% by mass with the same solvent or mixed solvent at 25℃using a dynamic laser light scattering instrument (Malvern Zetasizer Nano ZEN 3700), swept 6 times, and stabilized for 120 seconds to measure the particle diameter.
The anionic polymerization processes referred to in all the examples below were carried out in a glove box. The oxygen value in the glove box is less than 5ppm, and the water value is less than 0.01ppm. The monomer solvent is stirred by calcium hydride overnight and distilled under reduced pressure, and is put into a glove box after 3 times of freezing and pumping operations, and is preserved for no more than 2 weeks in a refrigerator at the temperature of minus 20 ℃.
Molecular weight data given in the examples below are all determined by Gel Permeation Chromatography (GPC), and unless otherwise specified, are number average molecular weights.
The instrumentation and conditions for GPC testing are: eighteen angle laser light scattering detector (Wyatt DAWN HELEOS II), viscosity detector (Wyatt viscoStar II), differential refractive detector (Wyatt Optilab rEX). DMF solution with LiBr in mobile phase 0.5mol/L, column temperature 60℃flow 1ml/min example 1: synthesis of Poly (4-methylstyrene) -methyl methacrylate Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), and after stirring uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and reacted for 30 minutes to give a poly MSt active chain having a polymerization degree of 60, a molecular weight of 7000 and a molecular weight distribution of 1.0.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.15mL of Methyl Methacrylate (MMA) and 0.145mL of Ethylene Glycol Dimethacrylate (EGDMA) serving as a crosslinking agent are mixed and injected into the system for reaction for 1.5 hours, and weak blue light is observed in the reaction system.
The particle size of the polymer microspheres in the system was 25nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution. The molecular weight of the polymer microspheres was 10 ten thousand as measured by Gel Permeation Chromatography (GPC), and the molecular weight distribution was 1.1.
And drying the obtained nano latex system to remove the solvent to obtain the poly 4-methylstyrene-methyl methacrylate polymer microsphere. The prepared polymer microsphere can turn inside and outside in acetone, and a patch-like structure taking polymethyl styrene as a partition can be formed on the surface after a mixed solvent of tetrahydrofuran and acetone is added.
Example 2: synthesis of polybutadiene-styrene Polymer microspheres
1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.2mL of butadiene were added to a polymerization tube (50 mL) at room temperature, the mixture was stirred uniformly, the mixture was capped, and 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added thereto and reacted for 30 minutes to obtain a polybutadiene active chain.
The temperature of the system was lowered to 10℃and 0.2mL of styrene was added after mixing and reacted for 30 minutes. With the formation and growth of the active chain of styrene, the polymer self-assembles into polymer microspheres and precipitates out of the solvent, and the reaction system is observed to appear faintly blue light.
0.2mL of Divinylbenzene (DVB) was added again as a crosslinking agent and reacted for 30min.
The particle size of the polymer microspheres in the system was 27nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
And washing the obtained nano emulsion system through ethanol precipitation for multiple times, centrifuging the final precipitation, and drying to remove the solvent to obtain the polybutadiene-styrene polymer microsphere.
Example 3: synthesis of polybutadiene-polystyrene-Polyacrylonitrile Polymer microspheres
1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.2mL of butadiene were added to a polymerization tube (50 mL) at room temperature, the mixture was stirred uniformly, the mixture was capped, and 16. Mu.L of an n-butyllithium solution (1.6M concentration) was added thereto and reacted for 30 minutes to obtain a polybutadiene active chain.
The temperature of the system is reduced to 5 ℃, 0.2mL of styrene is added after mixing, the reaction is carried out for 30min, the polymer is self-assembled into polymer microspheres along with the formation and growth of active chains of the styrene, and the polymer microspheres are precipitated from a solvent, so that weak blue light is observed in the system.
5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the system turned red.
0.1mL of DVB is added into the system for crosslinking reaction, the polymer microsphere forms an internal environment similar to emulsion drops in emulsion polymerization, and the system does not contain an emulsifier. And continuously adding 0.2mL of acrylonitrile monomer into the system, and gradually swelling the acrylonitrile monomer into the polymer microsphere and polymerizing.
The particle size of the polymer microspheres in the system was 28nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS).
And washing the obtained nano latex system by ethanol precipitation for multiple times, centrifuging the final precipitation, and drying to remove the solvent to obtain the polybutadiene-polystyrene-polyacrylonitrile polymer microsphere.
Example 4: synthesis of Poly 4-methylstyrene-methacryloxypropyl trimethoxysilane Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.30mL of methacryloxypropyl trimethoxysilane (MPS) and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA), a crosslinking agent, were injected into the system to react for 1.5h, and a weak blue light was observed in the reaction system. The particle size of the polymer microspheres in the system was 25nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
The obtained poly (4-methyl styrene-methacryloxypropyl trimethoxy silane) polymer microsphere can turn inside and outside in acetone, and after a system with the turned microsphere is coated on a target surface, a small amount of water is sprayed to induce sol-gel reaction of the methacryloxypropyl trimethoxy silane chain segment, so that a consolidated surface can be formed.
Example 5: synthesis of Poly 4-methylstyrene-styrene Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
After the system was cooled to 6 ℃, 0.30mL of styrene and 0.10mL of Divinylbenzene (DVB), a crosslinking agent, were injected into the system to react for 1.5 hours, and weak blue light was observed in the reaction system. The particle size of the polymer microspheres in the system was measured by Dynamic Light Scattering (DLS) in cyclohexane solution and found to be 26nm with a particle size distribution index of 1.3.
Example 6: synthesis of Poly (allyl styrene) -methyl methacrylate Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-allylstyrene (VSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to obtain a PMSt active chain.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.30mL of Methyl Methacrylate (MMA) and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system to react for 1.5 hours, and the reaction system was observed to generate weak blue light. The particle size of the polymer microspheres in the system was 25nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
After the microsphere is prepared, benzoin dimethyl ether and thioglycollic acid are added into the system, wherein the adding amount of the benzoin dimethyl ether and thioglycollic acid in terms of mole is Vst: benzoin dimethyl ether: thioglycollic acid = 1:0.2: and 10, reacting for 1h under ultraviolet irradiation, and modifying PVSt of the polymer microsphere shell layer to enable the microsphere to be dispersed in water.
Example 7: synthesis of Poly (4-methylstyrene) (2- (4-vinylbenzyloxy) ethanol methacrylate) polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was allowed to proceed for 10 minutes, whereby the reaction system was observed to turn red.
0.30mL of 2- (4-vinylbenzyloxy) ethanol methacrylate and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) serving as a crosslinking agent are injected into the system for reaction for 1.5h, and weak blue light is observed in the reaction system. The particle size of the polymer microspheres in the system was 27nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
After the microsphere is prepared, benzoin dimethyl ether and thioglycollic acid are added into the system, the reaction is carried out for 1h under ultraviolet irradiation, the inner polyacrylate styrene is modified, and the polymer microsphere shell can be changed from hydrophobic to hydrophilic through the click reaction.
Example 8: synthesis of Poly (4-methylstyrene) -isocyanatoethyl methacrylate) Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was allowed to proceed for 10 minutes, whereby the reaction system was observed to turn red.
0.30mL of isocyanoethyl methacrylate and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system to react for 1.5 hours, and the reaction system was observed to appear faintly blue light. The particle size of the polymer microspheres in the system was 27nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
The polymer microsphere prepared in this example has an inner layer containing isocyanate functional groups, and can be foamed internally by adding water.
Example 9: synthesis of Poly (4-methylstyrene) -glycidyl methacrylate Polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.30mL of Glycidyl Methacrylate (GMA) and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system to react for 1.5 hours, and the reaction system was observed to appear faintly blue light. The particle size of the polymer microspheres in the system was 26nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution
The polymer microsphere prepared in this example has an inner layer containing epoxy functional groups, and can be further crosslinked internally by adding isocyanate.
Example 10: synthesis of Poly (4-methylstyrene) -2-vinylpyridine polymer microspheres
At room temperature, 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50 mL), the mixture was stirred uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and the reaction was carried out for 30 minutes to prepare a PMSt active chain.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.30mL of 2-vinylpyridine (2 VP) is added into the reaction system, after about 1h of reaction, 0.10mL of crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) is added for 0.5h of reaction, and weak blue light is observed in the reaction system. The particle size of the polymer microspheres in the system was 28nm and the particle size distribution index was 1.3 as measured by Dynamic Light Scattering (DLS) in cyclohexane solution.
Example 11: synthesis of Poly (4-methylstyrene) -ethylene glycol dimethacrylate Polymer microsphere
To a polymerization tube (50 mL) was added 1.5mL of cyclohexane, 1. Mu.L of tetrahydrofuran and 0.150mL of 4-methylstyrene (MSt) at 8℃and, after stirring uniformly, the mixture was capped, 16. Mu.L of n-butyllithium-n-hexane solution (1.6M concentration) was added, and the reaction system was observed to turn orange, and reacted for 40 minutes to prepare a PMSt active chain.
Then, 5.6. Mu.L of 1, 1-Diphenylethylene (DPE) was added and the reaction was carried out for 10 minutes, and the reaction system was observed to turn red.
0.024mL of crosslinker Ethylene Glycol Dimethacrylate (EGDMA) was added and reacted for 1h. The particle size of the polymer microspheres in the system was measured by Dynamic Light Scattering (DLS) in cyclohexane solution and found to be 9nm with a particle size distribution index of 1.3.
Industrial applicability
The polymer microsphere and the preparation method thereof have wide application in the plastic industry, the rubber industry, the fiber industry and the paint industry.
Claims (19)
1. An active polymeric microsphere having a core-shell structure, wherein the shell layer comprises a polymer a, the core comprises a polymer B having a crosslinked structure, the molecular chain of the polymer a is linked to the polymer B by a covalent bond, and at least a part of the molecular chain ends of the polymer B carry an anionic active center; the particle size of the active polymer microsphere is 5-100 nm;
the polymer a is derived from an anionically polymerizable monomer a; the polymer B is derived from an anionically polymerizable crosslinking agent C and optionally an anionically polymerizable monomer B,
wherein, the polymer A is poly-4-methyl styrene, and the polymer B is polymethyl methacrylate crosslinked by ethylene glycol dimethacrylate; or polymer A is polybutadiene and polymer B is divinylbenzene-crosslinked polystyrene; or polymer a is polybutadiene and polymer B is a polymer comprising divinylbenzene-crosslinked polystyrene and polyacrylonitrile; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-methacryloxypropyl trimethoxy silane crosslinked by ethylene glycol dimethacrylate; or polymer A is poly-4-methyl styrene and polymer B is divinylbenzene crosslinked polystyrene; or the polymer A is polyallylstyrene, and the polymer B is polymethyl methacrylate crosslinked by glycol dimethacrylate; or polymer A is poly (4-methyl styrene), and polymer B is poly (2- (4-vinyl benzyloxy) ethanol methacrylate) crosslinked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-isocyanoethyl methacrylate crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is polyethylene glycol dimethacrylate crosslinked poly-glycidyl methacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly-2-vinyl pyridine crosslinked by ethylene glycol dimethacrylate;
The active polymer microsphere with the core-shell structure is prepared by the following method: firstly, forming a chain segment of a polymer A which is soluble in a solvent through anionic polymerization of a monomer A, then further forming a polymer B which is insoluble in the solvent and has a cross-linked structure on the chain segment of the polymer A, and forming the active polymer microsphere with a core-shell structure, wherein the polymer A is positioned on the outer layer and the polymer B is positioned on the inner layer along with the formation of the polymer B; the solvent is cyclohexane and tetrahydrofuran, wherein the volume ratio of the cyclohexane to the tetrahydrofuran is 1500:1.
2. The active polymer microsphere according to claim 1, wherein the content of polymer a is 0.1 to 90wt% and the content of polymer B is 10 to 99.9wt%.
3. The living polymeric microsphere according to claim 1 or 2, wherein the polymer a and/or the polymer B has a functional segment in the molecular chain or a functional group is attached to the molecular chain of the polymer a and/or the polymer B.
4. A reactive nanoemulsion comprising a reactive polymer microsphere according to any one of claims 1 to 3 and a solvent, wherein the polymer a is soluble in the solvent and the monomers and cross-linking agents forming the polymer B are soluble in the solvent, the solvents being cyclohexane and tetrahydrofuran, wherein the volume ratio of cyclohexane to tetrahydrofuran is 1500:1.
5. The reactive nanoemulsion of claim 4, wherein said polymeric microspheres are present in an amount ranging from 10 to 70wt%.
6. The reactive nanoemulsion of claim 5, wherein said polymeric microspheres are present in an amount ranging from 15-50 wt%.
7. The reactive nanoemulsion of claim 6, wherein said polymeric microspheres are present in an amount ranging from 20-40 wt%.
8. The reactive nanoemulsion of claim 4, wherein the emulsifier is present in an amount of 0-1 wt%.
9. The reactive nanoemulsion of claim 8, wherein no emulsifier is present.
10. A method of preparing the reactive polymer microsphere according to any one of claims 1 to 3 or the reactive nanolatex according to any one of claims 4 to 9, comprising the steps of:
(a) Dissolving a monomer A in a solvent, adding an anionic polymerization initiator, and initiating the monomer A to carry out anionic polymerization reaction to obtain a polymer A with an anionic active center at the tail end of a molecular chain;
(b) Optionally adding an active center stabilizer;
(c) Adding a cross-linking agent C and an optional monomer B, and continuing to carry out anionic polymerization reaction to form the polymer microsphere.
11. The method according to claim 10, wherein the anionic polymerization initiator is one or more selected from the group consisting of an organometallic compound, an alkali metal, an alkaline earth metal, a boron group metal, an alkali metal hydride, an alkali metal hydroxide, an amine, an ether, an alcohol, and an organic phosphide.
12. The method according to claim 11, wherein the organometallic compound is an alkali metal alkoxide, and the amine is an imine or a derivative thereof.
13. The process according to any one of claims 10 to 12, wherein the polymerization time in step (a) is 1 to 120min and the polymerization temperature is-100 to 100 ℃; the polymerization time in the step (c) is 1-180 min, and the polymerization temperature is-100 ℃.
14. A method for preparing an active nano emulsion, which is characterized by comprising the steps (a) - (c) in claim 10, and further comprising the following steps:
(d) Monomer D is added, and polymerization reaction is continued to form polymer D with active center at the end connected with polymer B through covalent bond.
15. The method according to claim 14, wherein the monomer D is one or more selected from the group consisting of styrene monomers, conjugated dienes, vinyl pyridines and derivatives thereof, (meth) acrylic ester monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, halogenated olefins, maleic anhydride, and maleimide.
16. An active nanoemulsion obtainable by the method according to any one of claims 10 to 15.
17. A method for preparing polymer microspheres, characterized in that firstly, active nano emulsion is prepared according to the preparation method of any one of claims 10-15, and then a chain terminator is added into the active nano emulsion.
18. The method of claim 17, wherein the chain terminator is one or more selected from the group consisting of an inactive terminator and an active terminator.
19. The method of claim 18, wherein the non-reactive terminator is water, alcohol or amine; the activity terminator is halogenated alkane.
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