CN114716616A - Active polymer microsphere and preparation method thereof - Google Patents
Active polymer microsphere and preparation method thereof Download PDFInfo
- Publication number
- CN114716616A CN114716616A CN202210399456.4A CN202210399456A CN114716616A CN 114716616 A CN114716616 A CN 114716616A CN 202210399456 A CN202210399456 A CN 202210399456A CN 114716616 A CN114716616 A CN 114716616A
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- Prior art keywords
- polymer
- monomer
- solvent
- poly
- active
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- 229920000642 polymer Polymers 0.000 title claims abstract description 261
- 239000004005 microsphere Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 45
- 239000011258 core-shell material Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 141
- 239000002904 solvent Substances 0.000 claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 60
- 239000003431 cross linking reagent Substances 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 44
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 43
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical group FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 40
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- -1 alkyl styrene Chemical compound 0.000 claims description 28
- 239000004816 latex Substances 0.000 claims description 28
- 229920000126 latex Polymers 0.000 claims description 28
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000004971 Cross linker Substances 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 15
- 125000000129 anionic group Chemical group 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003995 emulsifying agent Substances 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical class C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 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
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 6
- 150000003462 sulfoxides Chemical class 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 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
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002466 imines Chemical class 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
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 150000001555 benzenes Chemical group 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002454 poly(glycidyl methacrylate) polymer Polymers 0.000 claims description 3
- 229920013730 reactive polymer Polymers 0.000 claims description 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 2
- XRIKGOJOMKHZLV-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]ethanol Chemical group OCCOCC1=CC=C(C=C)C=C1 XRIKGOJOMKHZLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007908 nanoemulsion Substances 0.000 claims 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 2
- 238000004132 cross linking Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 5
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000004033 plastic Substances 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 150000001450 anions Chemical class 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 28
- 238000002296 dynamic light scattering Methods 0.000 description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- 238000009826 distribution Methods 0.000 description 20
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 12
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001252 acrylic acid derivatives Chemical class 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
- 244000028419 Styrax benzoin Species 0.000 description 6
- 235000000126 Styrax benzoin Nutrition 0.000 description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 229960002130 benzoin Drugs 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
- 235000019382 gum benzoic Nutrition 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MLDNIDZCTXRLGC-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(C(OCCOCC1=CC=C(C=C)C=C1)=O)=C MLDNIDZCTXRLGC-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 230000009257 reactivity Effects 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
- 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
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012673 precipitation polymerization Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 3
- 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
- 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229920006037 cross link polymer Polymers 0.000 description 2
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- 238000012869 ethanol precipitation Methods 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
- 238000002356 laser light scattering Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- 150000003077 polyols Chemical class 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
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- ANJTVLIZGCUXLD-BDAKNGLRSA-N (-)-Cytisine Natural products C1NC[C@@H]2CN3C(=O)C=CC=C3[C@H]1C2 ANJTVLIZGCUXLD-BDAKNGLRSA-N 0.000 description 1
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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
- 125000000008 (C1-C10) alkyl 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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- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 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
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- BIGOJJYDFLNSGB-UHFFFAOYSA-N 3-isocyanopropyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)CCC[N+]#[C-] BIGOJJYDFLNSGB-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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 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
- 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
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- CDKFWIMBZAUBRS-UHFFFAOYSA-M [I-].CC[Mg+] Chemical compound [I-].CC[Mg+] CDKFWIMBZAUBRS-UHFFFAOYSA-M 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 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
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 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
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 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
- 238000007865 diluting Methods 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
- 230000000694 effects 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
- 150000003947 ethylamines Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 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
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class 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
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 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
- 125000004888 n-propyl amino group Chemical class [H]N(*)C([H])([H])C([H])([H])C([H])([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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-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
- 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
- 239000002244 precipitate Substances 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 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
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010408 sweeping 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
- 229910052716 thallium Inorganic materials 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
- 229920002554 vinyl polymer Polymers 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)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention relates to an active polymer microsphere and a preparation method thereof. The polymer microsphere has a core-shell structure, wherein the shell layer comprises a polymer A, the core comprises a polymer B with a cross-linking 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 ends of the polymer B is provided with an anion active center. According to the invention, through reasonable design of the microsphere structure, the active center is kept in the microsphere, so that polymerization can be continuously initiated, and a larger space is provided 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 the plastic industry, the rubber industry, the fiber industry, the coating 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 coating industry. However, the preparation of polymeric microspheres in the size range of 10-100nm still presents major challenges. The prior art knows that the polymer microspheres without the protective segment can achieve higher monomer conversion rate (> 80%) and narrower size distribution in a living polymerization process, but the sizes of the prepared polymer microspheres are larger (micrometer scale), and the precise control of the structure in the size of 10-100nm cannot be achieved. While the polymerization-induced self-assembly process of the two-block polymerization with the protective segment can realize the control of the structure under smaller size, most of the two-block polymerization adopts a free radical polymerization mode, and therefore, the defects of low monomer conversion rate, slow reaction rate, wide molecular weight distribution and unstable particle structure exist, and great limitation is brought to the industrial application (L.C. Sarah, N.S. Gregory, P.A. Steven, A critical application of raw-processed polymerization-induced selection-assembly, 2016,49(6),1985 and 2001).
Living anionic polymerization has a wide range of applications due to its more controlled polymer structure (Mw/Mn can be less than 1.05), faster reaction rates, higher monomer conversion (approaching 100% conversion). The active anion polymerization can realize the precise regulation and control of different components, molecular weights and structures of the polymer in a sectional feeding mode in the polymerization process. Meanwhile, the active anion polymerization does not need additional catalyst and additive, the system is relatively clean, and the post-treatment operation is simple.
The polymerization-induced self-assembly methods using anionic polymerization reported in the prior art all use non-polar monomers. Such as styrene, butadiene and their homologue systems (x.r. wang, j.e.hall, s.warren, j.krom, j.m.magistrelli, m.rackaitis, g.g.a.bohm, Macromolecules,2007,40(3), 499-. In addition, wang et al developed an anionic precipitation polymerization method that can be used for large-scale synthesis of nanoparticles, and synthesized a hollow nanoparticle using this method (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 non-polar monomers, and the active center in the particle synthesized by the method cannot be continuously maintained and cannot be used for subsequent polymerization or functional recombination, thereby limiting the application range of the method.
Means for solving the problems
Aiming at the problems in the prior art, the invention provides the active polymer microsphere, and through the reasonable design of the microsphere structure, the active center is kept in the microsphere, so that the polymerization can be continuously initiated, and a larger space is provided for the subsequent modification.
Specifically, the present invention solves the problems of the present invention by the following means.
[1] Active polymer microspheres 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 through a covalent bond, and at least a part of the molecular chain ends of the polymer B carry an anionic active center.
[2] The active polymer microsphere according to the item [1], wherein the particle size of the polymer microsphere is 5-100 nm; wherein the content of the polymer A is 0.1-90 wt%, and the content of the polymer B is 10-99.9 wt%.
[3] The reactive polymer 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 crosslinker 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) acrylate monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, substituted halogenated olefins, maleic anhydride, maleimide and acrylonitrile independently; the cross-linking agent C is one or more selected from styrene, (methyl) acrylate, (methyl) acrylamide and isocyanate cross-linking agents;
in the case where the polymer B is derived from an anionically polymerizable cross-linking 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 monomers, and the monomer B is selected from vinylpyridine and derivatives thereof; or the monomer A is selected from alkyl styrene monomers, and the monomer B is styrene;
more preferably, polymer a is poly 4-methylstyrene, polymer B is ethylene glycol dimethacrylate crosslinked polymethylmethacrylate; 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-methylstyrene, polymer B is divinylbenzene-crosslinked polystyrene; or the polymer A is polyallyl styrene, and the polymer B is polymethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly-2- (4-vinyl benzyloxy) ethanol methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly-isocyano ethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly glycidyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, and the polymer B is poly-2-vinylpyridine crosslinked by ethylene glycol dimethacrylate;
in the case where the polymer B is derived from an anionically polymerizable crosslinker C, preferably monomer a is selected from styrenic monomers, more preferably 4-methylstyrene, and crosslinker C is selected from (meth) acrylate crosslinkers.
[4] The active polymer microsphere according to [1] or [2], wherein a functional segment is provided in a molecular chain of the polymer A and/or the polymer B, or a functional group is connected to the molecular chain of the polymer A and/or the polymer B.
[5] An active nano latex, comprising the active 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 the crosslinking agent forming the polymer B are soluble in the solvent.
[6] The reactive nano latex according to [5], wherein the solvent is one or more selected from alkane, aromatic hydrocarbon, ether, ester, amide and sulfoxide solvents; the alkane solvent is preferably straight-chain, branched or cyclic alkane with 5-8 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 active nano latex according to [5] or [6], wherein the content of the polymer microspheres is 10-70 wt%, preferably 15-50 wt%, and more preferably 20-40 wt%.
[8] The reactive nano latex according to [5] or [6], wherein the content of the emulsifier is 0 to 1 wt%, and preferably the emulsifier is not contained.
[9] The method for preparing the active polymer microsphere according to any one of [1] to [4] or the active nano latex according to any one of [5] to [8], 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 molecular chain end;
(b) optionally adding a reactive site stabilizer;
(c) adding a cross-linking agent C and an optional monomer B, and continuing the anionic polymerization reaction to form the polymer microsphere.
[10] The production method according to [9], characterized in that the anionic polymerization initiator is one or more selected from the group consisting of organometallic compounds, alkali metals, alkaline earth metals, boron group metals, alkali metal hydrides, alkali metal hydroxides, amines, imines and derivatives thereof, alkali metal alkoxides, ethers, alcohols, and organophosphates.
[11] The production method according to [9] or [10], characterized in that the polymerization time in the 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 ℃.
[12] A method for preparing an active nano latex, comprising the steps (a) to (c) of claim 9, further comprising the steps of:
(d) adding the monomer D, and continuing the polymerization reaction to form the polymer D with the active center at the tail end connected with the polymer B through a covalent bond.
[13] The production method according to [12], 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 acid ester monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, halogenated olefins, maleic anhydride, and maleimides.
[14] The reactive nano latex obtained by the production method according to any one of [7] to [13 ].
[15] A method for producing polymer microspheres, characterized in that an active nano latex is first produced according to any one of the production methods of [9] to [13], and then a chain terminator is added thereto.
[16] The production method according to [15], wherein the chain terminator is one or more selected from a non-reactive terminator and a reactive terminator; the non-reactive terminator is preferably water, alcohol or amine; the active terminator is preferably a halogenated alkane.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer microsphere has narrow particle size distribution and active center reservation, so that the polymer microsphere can be modified easily according to actual needs.
The nano active latex has high solid content and basically contains no emulsifier, so that the subsequent removal of the emulsifier is not needed.
The preparation method of the polymer microsphere or the nano active latex has the advantages of adjustable composition and structure of the polymer microsphere, accurate control of the size of the polymer microsphere, high solid content, high conversion rate and high reaction rate, and has wide application prospect in the plastic industry, the rubber industry, the fiber industry, the coating industry and the like.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical 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 diameter" means the median diameter D of the described particle group50It 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") refers to a polydispersity index of the particle sizes of the described particle group, which is defined as
U＝Dw/Dn
Where Dn is the average particle size, Dw is the defined mathematical average particle size, Di is the diameter of the ith particle, k is the sample volume, and U is the particle size distribution index, which can be measured 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 this specification, "latex" refers to a dispersion of polymeric microspheres in a solvent.
In the present specification, "room temperature" means a temperature range of 20 to 30 ℃, for example, 25 ℃.
In the present specification, "living nano latex" and "nano living latex" have the same meaning, and they may be used interchangeably.
In the present specification, the numerical range represented by "a numerical value a to B numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the use of "optionally" or "optional" means that certain materials, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
Reference throughout this specification to "a preferred embodiment," "an embodiment," and so forth, 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 described elements may be combined in any suitable manner in the various embodiments.
Active polymer microspheres
An object of the present invention is to provide a reactive polymer 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.
In the polymer microsphere, the anion 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, and even more preferably 8 to 30nm, and when the particle size of the polymer microspheres is within the above range, the polymer microspheres can be well dispersed in the solvent.
In one embodiment, the polymer microspheres of the present invention comprise 0.1 to 90 wt%, preferably 20 to 60 wt% of polymer A, and 10 to 99.9 wt%, preferably 40 to 80 wt% of polymer B.
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 monomer a and the monomer 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) acrylate monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, substituted halogenated olefins, maleic anhydride, maleimide.
The styrene monomer comprises styrene and its derivatives, wherein the styrene derivatives can 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 vinylpyridines and derivatives thereof include, but are not limited to, 2-vinylpyridine, 4-vinylpyridine, and the like.
The (meth) acrylate-based monomer includes acrylate-based monomers and methacrylate-based monomers, which may be alkyl (meth) acrylates, (meth) acrylic acid haloalkyl esters, (meth) acrylates of polyols or polyol ethers, (meth) acrylates having epoxy groups, (meth) acrylates having vinyl phenyl groups, orthosilicate-substituted (meth) acrylates, isocyanate-substituted (meth) acrylates, (meth) acrylate-based monomers containing a silane coupling agent structure, and the like. Specific examples of (meth) acrylate-based 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 ether (meth) acrylate, 2,3, 3-tetrafluoropropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate and derivatives thereof, (meth) acrylate-based vinylbenzene, orthosilicate-substituted (meth) acrylates (e.g., 3- (trimethoxysilyl) methacrylate) Propyl ester, 3- (triethoxysilyl) propyl methacrylate, allyl (meth) acrylate, 3- (trimethoxysilyl) propyl (meth) acrylate, and derivatives thereof.
The substituent in the derivative of ethylene oxide or propylene oxide may be one or more of alkyl, phenyl, alkylphenyl, and 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, and cyclohexene oxide.
The monoisocyanate-based monomer is a monomer having one isocyanate group, which 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, and 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-tolylisocyanate, 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 crosslinking agent C is not particularly limited in the present invention, and may be any crosslinking agent known in the art capable of undergoing anionic polymerization, and in the case of using the monomer B, the crosslinking agent C may be any crosslinking agent known in the art capable of undergoing a crosslinking reaction with the monomer B to give the polymer B. The choice of the crosslinking agent C is in accordance with the anionic polymerization sequence, so the choice of the crosslinking agent C is limited by the monomers A. The polymer after polymerization of the crosslinking agent C should have poor solubility in a solvent.
The cross-linking agent C is one or more selected from styrene, (methyl) acrylate, (methyl) acrylamide and isocyanate cross-linking agents.
The styrenic crosslinker may be an optionally substituted multivinyl benzene, such as an optionally substituted divinylbenzene, an optionally substituted trivinylbenzene, etc., wherein the substituent may be an alkyl group having 1 to 4 carbon atoms, or an oligomer having 3 or more styrene groups on a side chain, such as a (meth) acrylate oligomer having a styrene group as a substituent on a side group. Specific examples of styrenic crosslinkers include, but are not limited to, divinylbenzene, trivinylbenzene.
The (meth) acrylate-based crosslinking agent may be a polyacrylate of a polyol, and specific examples thereof include, but are not limited to, diethylene glycol (meth) acrylate (EGDMA), tetraethylene glycol (meth) acrylate, diethylene glycol (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like.
The (meth) acrylamide-based crosslinking agent may be N, N '-methylenebisacrylamide, hexamethylenebisacrylamide, diacetone acrylamide, N' -vinylbisacrylamide.
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-tolylene 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.
As used herein, a "derivative" refers to a product of a molecule of a described compound in which an atom or group of atoms is replaced with another atom or group of atoms.
In a particular embodiment, polymer a is derived from a styrenic monomer and polymer B is derived from a (meth) acrylate monomer and a crosslinking agent. Among them, the styrenic monomer is preferably one or more selected from the group consisting of C1-10 alkyl-substituted styrenes such as styrene, methyl styrene and the like and 4-allyl styrene; the (meth) acrylate monomer is preferably one or more selected from the group consisting of methyl methacrylate, 2- (4-vinylbenzyloxy) ethanol methacrylate, methacryloxypropyltrimethoxysilane, methacryloyl isocyanate, and Glycidyl Methacrylate (GMA).
In a particular embodiment, polymer a is derived from conjugated diene-based monomers, polymer B is derived from styrenic monomers and a crosslinking agent or polymer B further comprises polyacrylonitrile.
In a particular embodiment, polymer a is derived from a styrenic monomer, polymer B is derived from a vinylpyridine and derivatives thereof and a crosslinking agent.
In a particular embodiment, polymer a is derived from an alkylstyrene monomer and polymer B is derived from styrene and a crosslinking agent.
In a particular embodiment, polymer a is derived from an alkylstyrene monomer and polymer B is derived from a (meth) acrylate based cross-linking agent, such as ethylene glycol dimethacrylate.
In a more specific embodiment, polymer a is poly 4-methylstyrene, polymer B is ethylene glycol dimethacrylate cross-linked polymethylmethacrylate; 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-methylstyrene, polymer B is divinylbenzene-crosslinked polystyrene; or the polymer A is polyallyl styrene, and the polymer B is polymethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly 4-methyl styrene, and the polymer B is poly 2- (4-vinyl benzyloxy) ethanol methacrylate crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly-isocyano ethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly glycidyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, and the polymer B is poly-2-vinylpyridine crosslinked by ethylene glycol dimethacrylate; or the polymer A is poly-4-methyl styrene, and the polymer B is poly (ethylene glycol dimethacrylate).
In one embodiment, the polymer a and/or the polymer B has a functional segment in a molecular chain thereof, or a functional group is bonded to the molecular chain of the polymer a and/or the polymer B. Wherein "functional segment" and "functional group" refer to a segment or group that is capable of continuing chemical reactions.
In one embodiment, the polymer a and/or the polymer B has a carbon-carbon double bond in the molecular chain. In one aspect of this embodiment, further modification can be achieved by further thiol-vinyl click reaction of the carbon-carbon double bond with a substance 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 the click reaction can be amine catalyst (such as n-propylamine) or photocatalyst (such as benzoin dimethyl ether and the like, which react under the irradiation of ultraviolet light). The mercapto reagent can be selected from carboxylic acids containing mercapto (such as thioglycolic acid), alcohols (such as mercaptoethanol), amines (such as mercaptoethylamine hydrochloride), ketones, and mercapto reagents containing silicon-oxygen coupling agent. The reaction time of the click reaction may be 1 to 120min, preferably 60 to 90 min.
The click reaction has high yield, no by-product and is insensitive to water and oxygen, and therefore is a preferred method for functionalizing polymers. In a preferred embodiment, the polymeric 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 are, on a molar basis: benzoin dimethyl ether: thioglycolic acid is (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 dosage of the thioglycolic acid is, the better the hydrophilicity of the modified polymer microsphere is.
Active nano latex
It is an object of the present invention to provide a reactive nanolatex comprising the polymer microspheres of the present invention and a solvent, wherein the polymer a is soluble in the solvent and the monomers B and/or cross-linking agents C forming the polymer B are soluble in the solvent.
In one embodiment, the solvent is one or more selected from the group consisting of alkane, aromatic hydrocarbon, ether, ester, amide and sulfoxide type solvents. The alkane solvent is preferably straight-chain, branched or cyclic alkane with 5-8 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 2 or 3 or more kinds may be used in combination. In some embodiments, the solvent is a mixed solvent consisting of more than 2 of the above solvents, and the solubility of the polymer a in the solvent can be better adjusted by using different solvents in combination, so that the polymer microspheres can be more stably dispersed in the solvent. In a preferred embodiment, a mixed solvent of cyclohexane and tetrahydrofuran is used.
In one embodiment, the content of the polymeric microspheres is 10 to 70 wt%, preferably 15 to 50 wt%, and more preferably 20 to 40 wt% based on the total weight of the reactive nano-latex of the invention. When the solid content is within the above range, monodisperse microspheres with controllable particle size can be prepared.
In a preferred embodiment, the nano-latex of the present invention is substantially free of emulsifier, i.e., the emulsifier is present in an amount of 0 to 1 wt%, preferably 0 to 0.5 wt%, more preferably 0 to 0.1 wt%, and most preferably completely free of emulsifier, based on the total weight of the nano-latex.
The active nano latex can stabilize and emulsify 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 stably dispersing the polymer microsphere in the solvent under the condition of basically not containing an emulsifier.
Preparation method
It is another object of the present invention to provide a method for preparing the polymer microspheres of the present invention and the reactive nanolatex of the present invention, which comprises 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 molecular chain end;
(b) optionally adding a reactive site stabilizer;
(c) adding a cross-linking agent C and an optional monomer B, and continuing the 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 has a cross-linking structure and is poor in solubility or even insoluble in the solvent is further formed on the chain segment of the polymer A, the polymer is self-assembled into polymer microspheres with a core-shell structure, wherein the polymer A is positioned at an outer layer and the polymer B is positioned at an inner part, 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 the step (a), the monomer A is firstly dissolved in a solvent, and then an anionic polymerization initiator is added to initiate the monomer A to carry out anionic polymerization. After successful initiation, a color change of the system can be observed, for example a change of the system to an orange color, 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 (group iiia metals in the periodic table), alkali metal hydrides, alkali metal hydroxides, amines, imines and derivatives thereof, alkali metal alkoxides, ethers, alcohols, and organophosphates.
Organometallic compounds include alkali metal alkyl compounds, alkali metal aryl compounds, Grignard reagents, 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., and specific examples thereof 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, diphenylethyllithium, sodium naphthalene, potassium naphthalene, lithium naphthalene, and the like. The Grignard reagent may be alkyl magnesium bromide, alkyl magnesium chloride, alkyl magnesium iodide, wherein the alkyl group may be methyl, ethyl or propyl, and specific examples of the Grignard 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 Li, Na, K, Rb and Cs simple substances, the alkaline earth metal comprises Mg, Ca, Sr and Ba simple substances, and the boron group metal comprises Al, Ga, In and Tl simple substances.
Specific examples of the alkali metal hydride and the alkali metal hydroxide 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 dialkylamines, ethylamines, n-propylamines, isopropylamines, 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 the alkali metal alkoxide include, but are not limited to, lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-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 organophosphates include, but are not limited to, trimethylphosphine, triethylphosphine, and the like.
The above initiators may be used alone, or 2 or 3 or more of them may be used in combination. These initiators may be added in the form of a pure substance or in the form of a solution or the like. Among these initiators, n-butyllithium, sodium naphthalene and/or t-butanol are preferably used, and may be added to the reaction system in the form of, for example, an n-butyllithium n-hexane solution, a sodium naphthalene tetrahydrofuran solution and/or a t-butanol toluene solution.
In one embodiment, the polymerization temperature in step (a) is from-100 ℃ to 100 ℃, preferably from-30 ℃ to 60 ℃, more preferably from-20 ℃ to 60 ℃.
In one embodiment, the polymerization time in step (a) is 1 to 120min, preferably 10 to 100min, and more preferably 20 to 60 min.
In one embodiment, step (a) is preferably carried out with the application of agitation, which may be carried out by mechanical agitation, magnetic agitation or ultrasound.
In one embodiment, in step (a), the amount of monomer A added is 0.1 to 30 wt%, preferably 5 to 25 wt%, relative to the amount of solvent used.
In one embodiment, in step (a), the amount of initiator added is 0.5 to 100 mol% relative to the amount of monomer A; preferably, the molar ratio of monomer a: initiator 30: 1-100: 1.
step (b)
After step (a), depending on the reactivity difference between monomer A and monomer B and/or crosslinker C, a reactive center stabilizer may optionally be added to the reaction system to reduce the reactivity of the anionic reactive center located at the end of the segment of polymer A, facilitating the subsequent polymerization of monomer B and/or crosslinker C.
The active site stabilizer may be any monomer which is less prone to propagation during anionic polymerization than monomer A, for example, when monomer A is a methacrylate monomer, a styrenic monomer may be used as the active site stabilizer. Furthermore, the active site stabilizer may also be an active site stabilizer commonly used in the art, such as 1, 1-Diphenylethylene (DPE).
In one embodiment, the active site stabilizer is added in an amount of 100 to 200 mol% with respect to the amount of the initiator used in the step (a).
In one embodiment, step (b) is carried out for a period of 1 to 30min, preferably 5 to 20 min.
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 crosslinker C and optionally the monomer B may be added in steps or simultaneously.
In one embodiment, the monomer B and the cross-linking agent C are added simultaneously, and under the initiation of the anion active center at the chain segment end of the polymer A, the monomer B and the cross-linking agent C undergo anion polymerization reaction and cross-linking, so that the polymer is precipitated from the solvent and self-assembled into the polymer microsphere with the core-shell structure. In this embodiment, the reactivity and polarity of monomer B and crosslinker C are not very different.
In one embodiment, monomer B is added first and after the polymerization reaction has proceeded for a period of time, crosslinker C is added. In this embodiment, after the addition of the monomer B, the monomer B undergoes anionic polymerization under the initiation of the anionic active center at the end of the segment of the polymer a, and the polymer formed from the 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. And then adding a cross-linking agent C, wherein the cross-linking agent C enters the core of the polymer microsphere and is subjected to polymerization reaction under the initiation of an 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, an anionic active site stabilizer as described above may optionally be added depending on the reactivity of the crosslinking agent C before the addition of the crosslinking agent C.
In one embodiment, the addition of crosslinker C alone, without addition of monomer B, under initiation of the anionic living centers at the end of the segments of polymer A, anionically polymerizable crosslinker C undergoes anionic polymerization and forms crosslinked polymer B.
In one embodiment, the polymerization temperature in step (c) is from-100 ℃ to 100 ℃, preferably from-30 ℃ to 60 ℃, more preferably from-20 ℃ to 40 ℃.
In one embodiment, the polymerization time in step (c) is 1 to 180min, preferably 10 to 150min, and more preferably 20 to 120 min.
In one embodiment, step (c) is preferably carried out with the application of agitation, which may be carried out by mechanical agitation, magnetic agitation or ultrasound.
In one embodiment, the amount of monomer B added in step (c) is 0 to 70 wt%, preferably 5 to 40 wt%, relative to the amount of solvent used in step (a).
In one embodiment, in step (C), the amount of the crosslinking agent C is 0.01 to 30 wt%, preferably 0.1 to 20 wt%, for example 0.1 to 10 wt%, relative to the amount of the solvent.
After the polymerization in step (c) is carried out for a period of time, the system can be observed to generate weak blue light, which indicates that nano latex particles are formed in the system.
Other steps
In one embodiment, the present invention provides a method for preparing an active nano latex, which comprises the steps (a) to (c) described above, and further comprises the following steps:
(d) adding the monomer D, and continuing the polymerization reaction to form the polymer D with the active center at the tail end connected with the polymer B through a covalent bond.
In one embodiment, in step (D), a monomer D is further added to the reaction system, and the monomer D undergoes anionic polymerization under the initiation of the living center at the end of the polymer B to form a polymer D having one end connected to the polymer B and the other end carrying the living center. 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 preparing the active nano latex according to the preparation method of the invention, and then adding the chain terminator into the active nano latex. By adding a chain terminator to the reaction system, the active center at the polymer terminal is deactivated, and the polymerization cannot be further initiated.
In one embodiment, the chain terminator is one or more selected from the group consisting of a non-reactive terminator and a reactive terminator; the non-reactive terminator is preferably water, alcohol or amine; the active terminator is preferably a halogenated alkane. By using the active terminator, functional groups can be introduced at the active centers in the nano active latex particles to provide reaction sites for further subsequent functionalization.
The invention also relates correspondingly to the polymer microspheres and the reactive nanolatexes prepared by the process of the invention, and to their use for the preparation of polymer microspheres in the plastics industry, the rubber industry, the fiber industry, the coatings industry.
Examples
The present invention will be further described below by way of specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
In the following examples, the particle size was measured by diluting the polymerization solution with the same solvent or mixed solvent to 1% by mass fraction at 25 ℃ using a dynamic laser light scattering apparatus (Malvern Zetasizer Nano ZEN3700), sweeping 6 times for 120 seconds.
All the following examples relate to anionic polymerization processes carried out in a glove box. The oxygen value in the glove box is less than 5ppm, and the water value is less than 0.01 ppm. All the monomer solvents are stirred by calcium hydride overnight, then distilled under reduced pressure, frozen and pumped for 3 times, and then put into a glove box and stored in a refrigerator at the temperature of minus 20 ℃ for no more than 2 weeks.
The molecular weight data given in the following examples are all measured by Gel Permeation Chromatography (GPC), and unless otherwise specified, are number average molecular weights.
The instruments and conditions for the GPC test were: an eighteen-angle laser light scattering detector (Wyatt DAWN HELEOS II), a viscosity detector (Wyatt Viscostar II), a differential refraction detector (Wyatt Optilab rEX). Mobile phase 0.5mol/L LiBr in DMF, column temperature 60 ℃, flow rate 1ml/min example 1: synthesis of poly (4-methylstyrene-methyl methacrylate) polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), after stirring uniformly, the reaction system was sealed, 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added, and it was observed that the reaction system became orange, and reaction was carried out for 30min to obtain 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 thereto and reacted for 10min, and it was observed that the reaction system became red.
0.15mL of Methyl Methacrylate (MMA) and 0.145mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were mixed and injected into the system to react for 1.5h, and the reaction system was observed to emit weak blue light.
In the cyclohexane solution, the particle size of the polymer microspheres in the system is 25nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement. The molecular weight of the polymeric microspheres was 10 million as determined by Gel Permeation Chromatography (GPC), with a molecular weight distribution of 1.1.
And drying the obtained nano latex system to remove the solvent to obtain the poly 4-methylstyrene-methyl methacrylate polymer microspheres. The prepared polymer microspheres can be turned inside and outside in acetone, and a patch-shaped structure with polymethyl styrene as a subarea can be formed on the surface after a mixed solvent of tetrahydrofuran and acetone is added.
Example 2: synthetic polybutadiene-styrene polymer microspheres
Under the condition of room temperature, 1.5mL of cyclohexane, 1 mu L of tetrahydrofuran and 0.2mL of butadiene are added into a polymerization tube (50mL), after the mixture is uniformly stirred, a cover is sealed, 16 mu L of n-butyllithium n-hexane solution (the concentration is 1.6M) is added, and the reaction is carried out for 30min, so as to obtain the polybutadiene active chain.
The temperature of the system is reduced to 10 ℃, 0.2mL of styrene is added after mixing, and the reaction is carried out for 30 min. As the styrene active chain was formed and grown, the polymer self-assembled into polymer microspheres and precipitated from the solvent, and weak blue light was observed in the reaction system.
0.2mL of Divinylbenzene (DVB) was added again as a crosslinking agent and reacted for 30 min.
In the cyclohexane solution, the particle size of the polymer microspheres in the system is 27nm and the particle size distribution index is 1.3 as measured by Dynamic Light Scattering (DLS).
And (3) washing the obtained nano latex system by ethanol precipitation for multiple times, finally precipitating and centrifuging, drying and removing the solvent to obtain the polybutadiene-styrene polymer microsphere.
Example 3: synthetic polybutadiene-polystyrene-polyacrylonitrile polymer microsphere
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.2mL of butadiene were added to a polymerization tube (50mL), the mixture was stirred uniformly and then capped, and 16. mu.L of an n-butyllithium solution (concentration: 1.6M) was added to the mixture to carry out a reaction for 30min, thereby obtaining a polybutadiene active chain.
And (3) reducing the temperature of the system to 5 ℃, mixing, adding 0.2mL of styrene, reacting for 30min, self-assembling the polymer into polymer microspheres along with the formation and growth of a styrene active chain, precipitating from the solvent, and observing that weak blue light appears in the system.
5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added and the system turned red.
0.1mL DVB is added into the system for crosslinking reaction, the polymer microspheres form an internal environment similar to emulsion droplets in emulsion polymerization, and the system does not contain an emulsifier. Continuously adding 0.2mL of acrylonitrile monomer in the system, and gradually swelling the acrylonitrile monomer in the polymer microspheres and polymerizing.
The particle size of the polymer microspheres in the system was measured to be 28nm by Dynamic Light Scattering (DLS), and the particle size distribution index was 1.3.
And (3) washing the obtained nano latex system by ethanol precipitation for multiple times, finally precipitating and centrifuging, drying and removing the solvent to obtain the polybutadiene-polystyrene-polyacrylonitrile polymer microsphere.
Example 4: synthesis of poly 4-methylstyrene-methacryloxypropyltrimethoxysilane polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
Then, 5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added thereto and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of Methacryloxypropyltrimethoxysilane (MPS) and 0.10mL of a crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) were injected into the system and reacted for 1.5 hours, and the reaction system was observed to emit weak blue light. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 25nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement.
The obtained poly 4-methylstyrene-methacryloxypropyltrimethoxysilane polymer microspheres can be turned inside and outside in acetone, a system obtained after the microspheres are turned is coated on the surface of a target, and a small amount of water is sprayed to induce the sol-gel reaction of a methacryloxypropyltrimethoxysilane chain segment, so that a consolidated surface can be formed.
Example 5: synthesis of poly-4-methylstyrene-styrene polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
After the system was cooled to 6 ℃, 0.30mL of styrene and 0.10mL of Divinylbenzene (DVB), which is a crosslinking agent, were injected into the system to react for 1.5 hours, and weak blue light was observed in the reaction system. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 26nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement.
Example 6: synthesis of Polyallylstyrene-methyl methacrylate Polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-allylstyrene (VSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and added with 16. mu.L of n-butyllithium n-hexane solution (concentration: 1.6M), and the reaction system was observed to turn orange, and reacted for 30min to obtain a PMST active chain.
Then, 5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added thereto and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of Methyl Methacrylate (MMA) and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system and reacted for 1.5 hours, and the reaction system was observed to appear weak blue light. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 25nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement.
After the microspheres are prepared, benzoin dimethyl ether and thioglycollic acid are added into the system, and the addition amount in terms of moles is Vst: benzoin dimethyl ether: thioglycolic acid ═ 1: 0.2: 10, reacting for 1 hour under the irradiation of ultraviolet light, and modifying the PVSt of the shell layer of the polymer microsphere so that the microsphere can be dispersed in water.
Example 7: synthesis of poly-4-methylstyrene- (2- (4-vinylbenzyloxy) ethanol methacrylate) polymer microsphere
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of 2- (4-vinylbenzyloxy) ethanol methacrylate and 0.10mL of crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) were injected into the system to react for 1.5h, and weak blue light was observed in the reaction system. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 27nm and the particle size distribution index is 1.3 as measured by Dynamic Light Scattering (DLS).
After the microspheres are prepared, benzoin dimethyl ether and thioglycollic acid are added into the system, the system is reacted for 1 hour under ultraviolet illumination, the inner layer polyacrylate styrene is modified, and the shell of the polymer microsphere can be changed from hydrophobic to hydrophilic through the click reaction.
Example 8: synthesis of poly (4-methylstyrene-isocyanoethyl methacrylate) polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of isocyano ethyl methacrylate and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system and reacted for 1.5h, and the reaction system was observed to produce weak blue light. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 27nm and the particle size distribution index is 1.3 as measured by Dynamic Light Scattering (DLS).
The inner layer of the polymeric microspheres prepared in this example contained isocyanate functional groups and internal foaming was achieved by means of supplemental water.
Example 9: synthesis of poly (4-methylstyrene-glycidyl methacrylate) polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
Then, 5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added thereto and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of Glycidyl Methacrylate (GMA) and 0.10mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent were injected into the system and reacted for 1.5 hours, and the reaction system was observed to show weak blue light. In a cyclohexane solution, the particle size of the polymer microspheres in the system is 26nm and the particle size distribution index is 1.3 measured by Dynamic Light Scattering (DLS)
The polymer microsphere prepared in the embodiment has an inner layer containing epoxy functional groups, and can realize internal further crosslinking by means of supplementing isocyanate.
Example 10: synthesis of poly (4-methylstyrene-2-vinylpyridine) polymer microspheres
Under room temperature conditions, 1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.198mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL), stirred uniformly, capped, and then 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added to observe that the reaction system became orange, and reacted for 30min to obtain a PMST active chain.
Then, 5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added thereto and reacted for 10min, and it was observed that the reaction system became red.
0.30mL of 2-vinylpyridine (2VP) is added into the reaction system, 0.10mL of cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) is added after the reaction is carried out for about 1h, the reaction system is observed to generate weak blue light after the reaction is carried out for 0.5 h. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 28nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement.
Example 11: synthesis of poly (4-methylstyrene-ethylene glycol dimethacrylate) polymer microspheres
1.5mL of cyclohexane, 1. mu.L of tetrahydrofuran and 0.150mL of 4-methylstyrene (MSt) were added to a polymerization tube (50mL) at 8 ℃, stirred uniformly, and then capped, and 16. mu.L of n-butyllithium n-hexane solution (concentration 1.6M) was added thereto, and the reaction was observed to turn orange, followed by reaction for 40min to obtain a PMST active chain.
Then, 5.6. mu.L of 1, 1-Diphenylethylene (DPE) was added thereto and reacted for 10min, and it was observed that the reaction system became red.
0.024mL of Ethylene Glycol Dimethacrylate (EGDMA) as a crosslinking agent was added and reacted for 1 h. In the cyclohexane solution, the particle size of the polymer microspheres in the system is 9nm and the particle size distribution index is 1.3 by Dynamic Light Scattering (DLS) measurement.
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 coating industry.
Claims (16)
1. Active polymer microspheres 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 through a covalent bond, and at least a part of the molecular chain ends of the polymer B carry an anionic active center.
2. The active polymer microsphere according to claim 1, wherein the particle size of the polymer microsphere is 5 to 100 nm; wherein the content of the polymer A is 0.1-90 wt%, and the content of the polymer B is 10-99.9 wt%.
3. Reactive polymeric microspheres according to claim 1 or 2, characterized in that 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; the monomer A and the monomer B are one or more selected from styrene monomers, conjugated dienes, vinyl pyridine and derivatives thereof, (methyl) acrylate monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, substituted halogenated olefins, maleic anhydride, maleimide and acrylonitrile independently; the cross-linking agent C is one or more selected from styrene, (methyl) acrylate, (methyl) acrylamide and isocyanate cross-linking agents;
in the case where the polymer B is derived from an anionically polymerizable cross-linking 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 monomers, and the monomer B is selected from vinylpyridine and derivatives thereof; or the monomer A is selected from alkyl styrene monomers, and the monomer B is styrene;
more preferably, polymer a is poly 4-methylstyrene, polymer B is ethylene glycol dimethacrylate cross-linked polymethylmethacrylate; 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-methylstyrene, polymer B is divinylbenzene crosslinked polystyrene; or the polymer A is polyallyl styrene, and the polymer B is polymethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly-2- (4-vinyl benzyloxy) ethanol methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly-isocyano ethyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, the polymer B is poly glycidyl methacrylate cross-linked with ethylene glycol dimethacrylate; or the polymer A is poly-4-methylstyrene, and the polymer B is poly-2-vinylpyridine crosslinked by ethylene glycol dimethacrylate;
in the case where the polymer B is derived from an anionically polymerizable crosslinker C, preferably monomer a is selected from styrenic monomers, more preferably 4-methylstyrene, and crosslinker C is selected from (meth) acrylate crosslinkers.
4. The active polymer microsphere according to claim 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 connected to the molecular chain of the polymer A and/or the polymer B.
5. A reactive nanolatex comprising the reactive polymer microsphere of any one of claims 1 to 4 and a solvent, wherein the polymer A is soluble in the solvent and the monomers and cross-linking agent forming the polymer B are soluble in the solvent.
6. The reactive nano-emulsion of claim 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 straight-chain, branched or cyclic alkane with 5-8 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 nano-emulsion according to claim 5 or 6, wherein the content of the polymer microspheres is 10 to 70 wt%, preferably 15 to 50 wt%, and more preferably 20 to 40 wt%.
8. The reactive nano-emulsion according to claim 5 or 6, wherein the content of the emulsifier is 0 to 1 wt%, and preferably the emulsifier is not contained.
9. The method for preparing the active polymer microsphere according to any one of claims 1 to 4 or the active nano-emulsion according to any one of claims 5 to 8, comprising the following steps:
(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 molecular chain end;
(b) optionally adding a reactive site stabilizer;
(c) adding a cross-linking agent C and an optional monomer B, and continuing the anionic polymerization reaction to form the polymer microsphere.
10. The method according to claim 9, wherein the anionic polymerization initiator is one or more selected from the group consisting of organometallic compounds, alkali metals, alkaline earth metals, boron group metals, alkali metal hydrides, alkali metal hydroxides, amines, imines and derivatives thereof, alkali metal alkoxides, ethers, alcohols, and organophosphates.
11. The method according to claim 9 or 10, wherein the polymerization time in the 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 ℃.
12. A method for preparing an active nano latex, comprising the steps (a) to (c) of claim 9, further comprising the steps of:
(d) adding the monomer D, and continuing the polymerization reaction to form the polymer D with the active center at the tail end connected with the polymer B through a covalent bond.
13. The method according to claim 12, wherein the monomer D is one or more selected from the group consisting of styrene monomers, conjugated dienes, vinyl pyridines and derivatives thereof, (meth) acrylate monomers, ethylene oxide or propylene oxide and derivatives thereof, monoisocyanate monomers, halogenated olefins, maleic anhydride, and maleimides.
14. The reactive nano-emulsion obtained by the preparation method according to any one of claims 7 to 13.
15. A method for preparing polymer microspheres, wherein the reactive nano latex is prepared according to the preparation method of any one of claims 9 to 13, and then a chain terminator is added.
16. The method according to claim 15, wherein the chain terminator is one or more selected from a non-reactive terminator and a reactive terminator; the non-reactive terminator is preferably water, alcohol or amine; the active terminator is preferably a halogenated alkane.
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