CN114656592A - Water-soluble macromolecular photoinitiator and preparation method and application thereof - Google Patents
Water-soluble macromolecular photoinitiator and preparation method and application thereof Download PDFInfo
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- CN114656592A CN114656592A CN202011544971.4A CN202011544971A CN114656592A CN 114656592 A CN114656592 A CN 114656592A CN 202011544971 A CN202011544971 A CN 202011544971A CN 114656592 A CN114656592 A CN 114656592A
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- Prior art keywords
- water
- photoinitiator
- soluble
- monomer
- polymerization
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 84
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000003254 radicals Chemical class 0.000 claims abstract description 15
- 230000000977 initiatory effect Effects 0.000 claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 26
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 229920002521 macromolecule Polymers 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- -1 (methyl) hydroxyethyl Chemical group 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- 150000003384 small molecules Chemical class 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- 238000012673 precipitation polymerization Methods 0.000 claims description 5
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-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
- 150000003839 salts Chemical class 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 238000007112 amidation reaction Methods 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 239000003759 ester based solvent Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 230000033116 oxidation-reduction process Effects 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 2
- 150000003926 acrylamides Chemical class 0.000 abstract 1
- 229920006397 acrylic thermoplastic Polymers 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 16
- 229920002401 polyacrylamide Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NSGZRMWCXBRSAU-UHFFFAOYSA-N (1-hydroxycyclohexyl)-[4-(2-hydroxyethoxy)phenyl]methanone Chemical compound C1=CC(OCCO)=CC=C1C(=O)C1(O)CCCCC1 NSGZRMWCXBRSAU-UHFFFAOYSA-N 0.000 description 2
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229940117955 isoamyl acetate Drugs 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/12—Esters of phenols or saturated alcohols
- C08F222/20—Esters containing oxygen in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- 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)
Abstract
The invention relates to a water-soluble macromolecular photoinitiator and a preparation method and application thereof. The macromolecular photoinitiator is prepared by the following method: preparing a polymerizable photoinitiator containing unsaturated double bonds by reacting an anhydride monomer with a hydroxyl-terminated or amino-terminated micromolecular photoinitiator; the polymerizable photoinitiator containing unsaturated double bonds is copolymerized with a water-soluble monomer in a free radical copolymerization mode to synthesize the water-soluble macromolecular photoinitiator containing photoinitiating groups in side groups. The synthetic route is simple, and the content of the photoinitiation group in the prepared macromolecular photoinitiator is controllable; and the macromolecular photoinitiator has high dissolution speed in a water phase and high initiation activity, and overcomes the defects of low initiation efficiency, easy migration and the like of the micromolecular photoinitiator. Under the irradiation of ultraviolet light, the water-soluble macromolecular photoinitiator can effectively initiate the polymerization of water-soluble monomers such as acrylamides, acrylics, acrylates and the like, and prepare the water-soluble polymer with a branched structure.
Description
Technical Field
The invention relates to a photoinitiator, in particular to a water-soluble macromolecule photoinitiator and a preparation method thereof.
Background
Photopolymerization technology, as a polymerization means different from the conventional initiator initiation and thermal initiation, has significant advantages and practicality, such as: the polymerization temperature is low (room temperature reaction can be carried out), the initiation efficiency is high, the polymerization speed is high, and the like, a series of photophysical and photochemical reactions are carried out under the action of light and a photosensitive compound (a photosensitizer or a photoinitiator), active substances are generated in a system to initiate the polymerization of monomers, and finally the high molecular weight polymer material is obtained. Compared with the traditional polymerization method, the photopolymerization has the advantages of low energy consumption, simple and convenient operation, high production efficiency, no solvent volatilization, environmental friendliness and the like, and is widely concerned by researchers since the 20 th century and the 60 th era. However, most of the currently commercialized photoinitiators are oil-soluble, insoluble or slightly soluble in water, and need to be dispersed in an aqueous polymerization system by means of an emulsifier and a small amount of monomers, and have a great problem of compatibility with the aqueous system, which affects photoinitiation efficiency and product properties.
In order to overcome the above disadvantages, aqueous photoinitiators have been developed. The common photoinitiator has no water solubility, but the water solubility of the photoinitiator can be greatly improved by introducing hydrophilic groups into the structure of the common photoinitiator, wherein the hydrophilic groups can be-COOH (carboxyl group), -SO3H (sulfo), and the like. However, the conventional small molecule photoinitiator generates a photo-cracking reaction during the photo-polymerization reaction, and the generated free small molecule organic matters have the problems of residue, migration, volatility and the like, so that the application of the small molecule water-soluble photoinitiator is still restricted. For this reason, in recent years, researchers have begun to develop polymerizable or macromolecular photoinitiators that can reduce or eliminate the deficiencies of small molecule photoinitiators by increasing the molecular weight of the photoinitiator, such as: CN101077897A, CN101220106A, CN101333278A and CN102020726A report a series of macromolecular lightsA preparation method of the initiator. Compared with a micromolecular photoinitiator, the macromolecular photoinitiator has the following advantages: high optical activity, no peculiar smell, no migration, good compatibility with polymers and the like, and has good application prospect. Therefore, the development of the macromolecular photoinitiator is an effective way for solving the defects of volatility and mobility of the micromolecular photoinitiator.
The preparation method of the currently known macromolecular photoinitiator mainly comprises the following steps: (1) the small molecular photoinitiator with functional substituent such as hydroxyl or amino is prepared by polycondensation with monomer or polymer containing reactive group such as isocyanate group; (2) the photoinitiating groups are introduced on the side groups of the polymer by means of chemical modification. The two methods can prepare the macromolecular photoinitiator with photoinitiation activity, but the prepared macromolecular photoinitiator is mainly used for the photocuring crosslinking reaction of the oil-soluble monomer; because no hydrophilic group exists, the prepared macromolecular photoinitiator has poor compatibility with a water-based system, and is difficult to be applied to photopolymerization of water-soluble monomers, particularly to the preparation of high-molecular water-soluble polymers with complicated structures such as branched structures, star structures and the like.
On the basis of analyzing the defects of the method, the invention designs a novel water-soluble macromolecular photoinitiator, and the water-soluble macromolecular photoinitiator is simply and efficiently prepared through the free radical copolymerization reaction of a polymerizable photoinitiator and a water-soluble monomer. The related water-soluble macromolecule photoinitiator and the preparation method thereof have the advantages of simple synthetic route and mild reaction conditions, the water-soluble monomers adopted by the prepared water-soluble macromolecule photoinitiator have wide selection range, the molecular weight of the macromolecule photoinitiator can be simply regulated, and the content of the photoinitiation groups in the side groups can be regulated through the molar ratio of the polymerizable photoinitiator to the water-soluble monomers. The used polymerizable photoinitiator can be simply and efficiently synthesized by an organic synthesis method, the water-soluble macromolecular photoinitiator is prepared by solution polymerization or precipitation polymerization, and the prepared water-soluble macromolecular photoinitiator has good water solubility and high photoinitiation group content. In addition, the water-soluble macromolecular photoinitiator prepared by the invention can initiate the polymerization of common water-soluble monomers under the ultraviolet irradiation condition, and is used for preparing water-soluble polymers with specific branched structures. It is noted that the prepared macromolecular photoinitiator has uniformly distributed photoinitiating groups, can effectively control (or overcome) the occurrence of a cross-linking phenomenon when initiating the polymerization of a water-soluble monomer, and can prepare a water-soluble polymer with controllable chemical structure and adjustable molecular weight, in particular a branched water-soluble polymer with ultrahigh molecular weight; compared with the linear structure polymer, the branched structure water-soluble polymer has better solubility, and the formed branched structure water-soluble polymer solution has better shear resistance.
Disclosure of Invention
The invention aims to provide a water-soluble macromolecular photoinitiator which has good water solubility, good photoinitiation performance, no migration and good compatibility with polymers, can effectively initiate the polymerization of water-soluble monomers and prepare branched polymers, and a preparation method thereof. In order to make the prepared macro photoinitiator hydrophilic, the molecular structure of the macro photoinitiator must contain hydrophilic groups and active groups capable of realizing photoinitiation. On the basis of analyzing the preparation method of the conventional macromolecular photoinitiator, the conventional method is improved, and firstly, unsaturated groups with polymerization activity are introduced into the micromolecular photoinitiator to prepare a polymerizable photoinitiator; the prepared polymerizable photoinitiator is further subjected to copolymerization reaction with other water-soluble monomers to prepare the water-soluble macromolecular photoinitiator with the side group containing a photoinitiating group. According to the method, hydrophilic groups are introduced into a molecular chain of the macromolecular photoinitiator, and photoinitiating groups with photoinitiating activity are introduced into a side group of the molecular chain, so that the prepared macromolecular photoinitiator has good photoinitiating performance, has good solubility in an aqueous system, is suitable for replacing a micromolecular photoinitiator, and is used for initiating the photopolymerization of a conventional water-soluble monomer.
It should be pointed out that the photoinitiating groups in the designed and prepared water-soluble macromolecule initiator side group are uniformly distributed, the occurrence of a cross-linking reaction can be effectively inhibited (or overcome) when the water-soluble monomer is initiated to polymerize, and the water-soluble macromolecule initiator side group is suitable for preparing a water-soluble polymer with a branched structure, in particular an ultrahigh molecular weight water-soluble polymer with a branched structure. The branched polymer has better solubility properties and the resulting aqueous branched polymer solution has better shear resistance than conventional linear polymers.
The water-soluble macromolecular photoinitiator prepared by the invention has a structure shown in a general formula (I) or a general formula (II):
wherein, x is 50-800, y is 4-50, and n is 0-10; in order to further improve the photoinitiating performance and water solubility of the water-soluble macromolecular photoinitiator, x is 50-400, y is 4-50, and n is 0-5; more preferably, x is 50 to 200, y is 4 to 50, and n is 0 to 5; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl group or a carboxylate; z is O or NH;
X2selected from any one of the following groups;
PI is a photoinitiating group selected from the group consisting of common cleavage-type photoinitiating groups, preferably any one of the following groups.
The preparation method of the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II) mainly comprises the following two steps: (1) the polymerizable photoinitiator containing unsaturated double bonds is prepared by reacting an anhydride monomer with a hydroxyl-terminated or amino-terminated micromolecular photoinitiator, wherein the anhydride monomer is one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride; (2) the polymerizable photoinitiator containing unsaturated double bonds is copolymerized with a water-soluble monomer A by a free radical copolymerization mode to synthesize the water-soluble macromolecule photoinitiator containing photoinitiating groups in side groups, wherein the water-soluble monomer A is one or more selected from (methyl) acrylamide monomers, (methyl) acrylic acid, (methyl) acrylate, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, hydroxypropyl (methyl) acrylate, dimethylaminoethyl (meth) acrylate and 2-acrylamide-2-methylpropanesulfonic acid (salt), and the water-soluble monomer A is preferably selected from (methyl) acrylamide monomers, (methyl) acrylic acid, (methyl) acrylate, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxypropyl acrylate, N-vinyl pyrrolidone, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, N-vinyl pyrrolidone, and the like, One or more of dimethylaminoethyl (meth) acrylate and 2-acrylamide-2-methylpropanesulfonic acid (salt).
In some specific embodiments, the polymerizable photoinitiator containing an unsaturated double bond is preferably prepared as follows:
firstly, dissolving a hydroxyl-terminated (or amino-terminated) micromolecular photoinitiator with a structure of a general formula (III) and an anhydride monomer (maleic anhydride, citraconic anhydride and/or itaconic anhydride) in a solvent, and mixing to form a uniform reaction system; secondly, adding a catalyst (for the high-activity primary hydroxyl or primary amino, the catalyst can not be added) into the reaction system, mixing uniformly, reacting at the temperature of 0-80 ℃ preferably, further preferably at the temperature of 0-20 ℃, and reacting for 0.5-6 hours preferably, and introducing unsaturated double bonds into the small-molecule photoinitiator through esterification or amidation reaction. Wherein, the selected small molecule photoinitiator containing terminal hydroxyl or terminal amine is preferably n-0-10, more preferably 1-5, and still more preferably 1-3; the mass ratio of the small-molecule photoinitiator to the anhydride monomer is preferably 2:1-1:5, more preferably 1:1-1: 2; the catalyst comprises 4-dimethylamino pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid and sodium acetate, and the amount of the catalyst in the system is preferably 0.05-2 mass percent of the mass of the monomer, more preferably 0.1-1 mass percent;
M-(CH2CH2O)n-PI
general formula (III)
Wherein M is hydroxyl or amine, PI is a photoinitiating group in the macromolecular photoinitiator shown in the general formula (I) or the general formula (II), and n is preferably 0-10, and more preferably 1-5.
Removing the organic solvent by preferably rotary evaporation after the reaction is finished, dissolving the product in dichloromethane, washing, separating, drying, and removing the low-boiling-point organic solvent by preferably rotary evaporation to obtain the polymerizable photoinitiator containing the unsaturated double bond and having the structure shown in the general formula (IV) or the general formula (V);
among them, n is preferably 0 to 10, more preferably 1 to 5; y is1Is H or CH3；Y2Is a carboxyl group or a carboxylate; z is O or NH; PI is a photoinitiation active group of the micromolecule photoinitiator.
In some specific embodiments, the water-soluble macrophotoinitiator is preferably prepared as follows:
the water-soluble macromolecular photoinitiator is prepared by radically copolymerizing a polymerizable photoinitiator with the water-soluble monomer A, more preferably by a polymerization method of solution polymerization or precipitation polymerization.
In some preferred embodiments, the concentration of the monomers in the polymerization system directly affects the molecular weight of the macroinitiator produced, and the total monomer concentration in the reaction system is preferably 5 to 60% by mass, more preferably 10 to 30% by mass. The content of the photoinitiating group in the prepared polymer side group mainly depends on the molar ratio of the polymerizable photoinitiator to the water-soluble monomer in the system, and the molar ratio of the water-soluble monomer to the polymerizable photoinitiator in the reaction system is 1:1-50:1, preferably 2:1-20:1 according to the molecular weight of the polymerizable photoinitiator and the reactivity of the monomer.
The initiators used for the polymerization are the customary free-radical initiators known to the person skilled in the art and may be azo initiators, peroxy initiators or redox initiation systems, the amount of initiator used being from 0.05 to 5.0% by mass, preferably from 0.3 to 1.5% by mass, based on the mass of the monomers. The azo-type initiator includes, but is not limited to: azobisisobutyronitrile, azobisisoheptanide, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisisopropylimidazoline, and the like; the peroxy-based initiator includes, without limitation: dibenzoyl peroxide, dicumyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, diterbutyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like.
In some preferred embodiments, when a solution polymerization method is adopted, the preparation raw materials comprise a polymerizable photoinitiator, a water-soluble monomer A, water and a water-soluble free radical initiator, the water-soluble free radical initiator is adopted to initiate polymerization, the reaction temperature is 40-100 ℃, preferably 60-85 ℃, the reaction is 1-12 hours, so that a water-soluble macromolecular photoinitiator solution can be obtained, the prepared water-soluble macromolecular photoinitiator is precipitated, separated and dried from a polymerization reaction system, so that the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II) can be obtained, and the type and the number of photoinitiating groups in the side groups of the water-soluble macromolecular photoinitiator can be conveniently regulated and controlled.
In other preferred embodiments, when the precipitation polymerization mode is adopted, the operation is simpler and the regulation and control of the product composition, the chemical structure and the molecular weight are convenient. The preparation raw materials comprise a polymerizable photoinitiator, a water-soluble monomer A, a solvent and an initiator; initiating polymerization by adopting an oil-soluble free radical initiator, wherein the reaction temperature is 40-100 ℃, preferably 60-85 ℃, the reaction time is 1-12 hours, and the prepared water-soluble macromolecular photoinitiator gradually precipitates from a polymerization reaction system along with the reaction; separating and drying the prepared water-soluble macromolecular photoinitiator from a polymerization reaction system to obtain the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II).
The solvent used in the preparation of the water-soluble macromolecular photoinitiator includes alcohol solvents such as water, methanol, ethanol, isopropanol, ethylene glycol and glycerol, ketone solvents such as tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone and methyl isopropyl ketone, ester solvents such as ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate and ethyl benzoate, aliphatic hydrocarbon solvents such as n-hexane, cyclohexane, n-heptane, petroleum ether and octane, aromatic hydrocarbon solvents such as toluene, ethylbenzene and xylene, dimethylformamide, dimethylacetamide and dimethylsulfoxide, and may be used alone or in any combination.
The water-soluble macromolecular photoinitiator prepared by the method can initiate the polymerization of common water-soluble monomers B (which can be the same as or different from the water-soluble monomers A) to prepare the water-soluble polymer with a branched structure, the water-soluble macromolecular photoinitiator, the water-soluble monomers and water are added into a reaction vessel to be fully dissolved and uniformly mixed, under the irradiation condition of ultraviolet light, the photoinitiated active groups in the side groups of the water-soluble macromolecular photoinitiator are decomposed to generate free radicals, the water-soluble monomers are initiated to be self-polymerized or copolymerized to form water-soluble polymer side chains, and the water-soluble polymer with the branched structure, particularly the ultra-high molecular weight water-soluble polymer, can be obtained.
In some preferred embodiments, examples of the water-soluble monomer B in the photopolymerization system include, but are not limited to, (meth) acrylamide-based monomers, (meth) acrylic acid, (meth) acrylate salts, (meth) hydroxyethyl acrylate, polyethylene glycol (meth) acrylate, and N-vinyl pyrrolidone; in some preferred embodiments, the water-soluble monomer concentration in the reaction system is from 1 to 40% by weight, preferably from 15 to 30% by weight, and the macrophotoinitiator is used in an amount of from 0.01 to 2% by weight, preferably from 0.02 to 0.5% by weight, based on the mass of the monomers. In some preferred embodiments, the polymerization of the water-soluble monomer is initiated by ultraviolet light irradiation, preferably by low-pressure ultraviolet lamp irradiation with a wavelength of 254nm, and the specific reaction conditions are preferably as follows: the light intensity at the wavelength of 254nm is 0.2-80 mW/cm2The most suitable strength is 2-20 mW/cm2The reaction time is 1 to 12 hours, preferably 2 to 6 hours. In some preferred embodiments, after the reaction is completed, the polymer solution or the gel block is pulverized and dried to obtain the water-soluble graft polymer.
In some more specific embodiments, the synthetic routes of MPI-1 and the corresponding water-soluble macrophotoinitiator poly (AM-co-MPI-1) are shown in mechanism 1 and mechanism 2, respectively, for example, as shown in the following figure for 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone (hereinafter PI-1), polymerizable photoinitiator MPI-1, and the corresponding water-soluble macrophotoinitiator poly (AM-co-MPI-1):
the specific operation steps are as follows:
1. dissolving 2.3g of micromolecular photoinitiator PI-1 and 1g of maleic anhydride in 25mL of Tetrahydrofuran (THF), adding 0.02g of catalyst 4-Dimethylaminopyridine (DMAP), reacting at 50 ℃ for 3 hours, performing rotary evaporation to remove THF after the reaction is finished, dissolving the product in dichloromethane, washing, separating, drying, and performing rotary evaporation to remove a low-boiling-point organic solvent to obtain the polymerizable photoinitiator MPI-1, wherein the yield is about 80%.
2. 0.66g of the polymerizable photoinitiator MPI-1 prepared in the step 1 and 2g of acrylamide are weighed and dissolved in 30mL of ethanol, after uniform mixing, 0.03g of initiator Azobisisobutyronitrile (AIBN) is added, nitrogen is introduced to remove oxygen for 15 minutes, and then reaction is carried out for 6 hours at 75 ℃. After the reaction is finished, centrifugally separating the prepared water-soluble macromolecular photoinitiator from the system, washing the water-soluble macromolecular photoinitiator for three times by using petroleum ether, and then drying the water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) with the side group containing a photoinitiation group in vacuum, wherein the yield is about 87%.
The mass fraction of PI-1 in the prepared macromolecular photoinitiator is 9 percent through ultraviolet characterization, and the molecular weight of the prepared macromolecular photoinitiator is about 2.0 multiplied by 10 through aqueous phase GPC4So that about 8 photoinitiating groups are contained on each molecular chain on average; therefore, the branching degree of the prepared water-soluble polymer is about 8 by using the macromolecular photoinitiator to initiate the polymerization of the water-soluble monomer. Dissolving 10mg of the prepared water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) with the side group containing the photoinitiating group in 20mL of water, adding 30g of water-soluble monomer AM, supplementing 50mL of water, and uniformly mixing the monomers after the monomers are dissolvedIntroducing argon into the reaction system to remove oxygen for 15 minutes, placing the reaction system under a low-pressure ultraviolet lamp with the wavelength of 254nm, and irradiating to initiate AM ultraviolet polymerization, wherein the light intensity of the ultraviolet light is set to be 5mW/cm2And the reaction time is 3 hours, so that the water-soluble PAM polymer with a definite branched structure is obtained, and the molecular weight is measured to be 1.5 multiplied by 10 by adopting a Viscosystem AVS370 full-automatic Ubbelohde viscometer7。
The water-soluble macromolecular photoinitiator prepared by the invention can be used as a substitute of a micromolecular photoinitiator, and can efficiently initiate the polymerization of water-soluble monomers. The type and content of the photoinitiating groups in the molecular chain of the macromolecular photoinitiator can be simply and conveniently controlled by adjusting the type of the polymerizable photoinitiator in a reaction system and the feeding ratio of the polymerizable photoinitiator to the water-soluble monomer, so that the water-soluble macromolecular photoinitiators with different molecular structures and different photoinitiating group contents are prepared. According to the molecular structure of the macromolecular photoinitiator, a photoinitiation group exists in a side chain of a polymer, the photoinitiation group is dissociated under the ultraviolet irradiation condition to form an active free radical in the side chain of the polymer, and the active free radical initiates a water-soluble monomer to grow at the chain end of the free radical in an aqueous phase system to form a water-soluble polymer branched chain. Each photoinitiating group can form a polymer branched chain in a polymer side chain, and the number of the water-soluble polymer branched chains prepared by the polymerization initiated by the prepared macromolecular photoinitiator is correspondingly increased along with the increase of the number of the photoinitiating groups in the side chain. Therefore, the quantity and distribution of the prepared water-soluble polymer branched chains can be conveniently regulated and controlled by controlling the structure of the macroinitiator.
Compared with the prior art, the water-soluble macromolecular photoinitiator and the preparation method thereof have the following advantages:
(1) the water-soluble macromolecular photoinitiator has the advantages of simple preparation process and high conversion rate, and the obtained product is easy to separate;
(2) the composition, structure and molecular weight of the water-soluble macromolecular photoinitiator prepared by the invention and the variety, content and distribution of photoinitiating groups in a polymer molecular chain can be simply and conveniently regulated;
(3) the prepared macromolecular photoinitiator is quickly dissolved in aqueous solution and has the advantages of high photoactivity, no peculiar smell, no migration, good compatibility with polymers and the like;
(4) the prepared water-soluble macromolecule photoinitiator has uniformly distributed photoinitiating groups, can effectively inhibit (or overcome) the occurrence of a crosslinking phenomenon when initiating the polymerization of a water-soluble monomer, and can be used as a substitute of a micromolecular initiator to efficiently initiate the polymerization of an aqueous solution of the water-soluble monomer; more importantly, the prepared water-soluble polymerization product has a definite branched structure and branching degree, and the branched structure can be conveniently regulated and controlled by adjusting the structure of the macromolecular photoinitiator; the molecular weight of the prepared branched water-soluble polymerization product can be effectively regulated and controlled by adjusting the using amount of the macromolecular photoinitiator. Compared with linear water-soluble polymers, the prepared branched water-soluble polymer has better solubility in water, and the branched polymer aqueous solution has better shear resistance.
Drawings
FIG. 1 is an infrared spectrum of a water-soluble macro-photoinitiator poly (AM-co-MPI-1).
FIG. 2 shows UV-visible absorption spectra (a. PI-1; b. Poly (AM-co-MPI-1)) of a small molecule photoinitiator PI-1 and a water-soluble macromolecule photoinitiator poly (AM-co-MPI-1).
Detailed Description
The invention is illustrated below with reference to specific examples, which, however, do not limit the invention.
The chemical composition and structure of the product are measured by a Nexus670 infrared spectrometer and a GBC Cintra-20 ultraviolet spectrometer. Molecular weight of the polymer is ViscosystemR○AVS370 full-automatic Ubbelohde viscometer measurement. The mass percent concentration of the monomer in the polymerization reaction system is a mass fraction based on the total mass of the polymerization reaction system.
Examples
Synthesis of polymerizable photoinitiators
Example 1
The structural formula of the polymerizable photoinitiator MPI-1 is as follows:
2.3g of micromolecule photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methyl propiophenone (PI-1) and 1g of maleic anhydride are dissolved in 25ml of THF, 0.02g of DMAP is added, the mixture is reacted for 3 hours at 50 ℃, THF is removed by rotary evaporation after the reaction is finished, the product is dissolved in dichloromethane, washed with water, separated and dried, and low-boiling-point organic solvent is removed by rotary evaporation, so that the polymerizable photoinitiator MPI-1 is obtained, and the yield is about 80%.
Example 2
The structural formula of the polymerizable photoinitiator MPI-2 is as follows:
dissolving 2.7g of a small-molecular photoinitiator (1-hydroxycyclohexyl) [4- (2-hydroxyethoxy) phenyl ] ketone (PI-2) and 1g of maleic anhydride in 25ml of THF, adding 0.03g of DMAP, reacting at 65 ℃ for 3 hours, performing rotary evaporation to remove THF after the reaction is finished, dissolving the product in dichloromethane, washing the solution, separating and drying the solution, and performing rotary evaporation to remove a low-boiling-point organic solvent to obtain the polymerizable photoinitiator MPI-2, wherein the yield is about 75%.
Example 3
The structural formula of the polymerizable photoinitiator MPI-3 is as follows:
dissolving 2.4g of small-molecular photoinitiator PI-1 and 1g of itaconic anhydride in 25mL of THF, adding 0.02g of DMAP, reacting at 65 ℃ for 3 hours, removing THF through rotary evaporation after the reaction is finished, dissolving the product in dichloromethane, washing, separating, drying, and removing a low-boiling-point organic solvent through rotary evaporation to obtain polymerizable photoinitiator MPI-3, wherein the yield is about 72%.
Example 4
The structural formula of the polymerizable photoinitiator MPI-4 is as follows:
dissolving 2.4g of small-molecule photoinitiator PI-1 and 1g of citraconic anhydride in 25mL of THF, adding 0.02g of DMAP, reacting at 70 ℃ for 6 hours, removing THF through rotary evaporation after the reaction is finished, dissolving the product in dichloromethane, washing, separating, drying, and removing low-boiling-point organic solvent through rotary evaporation to obtain the polymerizable photoinitiator MPI-4, wherein the yield is about 70%.
Preparation of water-soluble macromolecular photoinitiator
Example 5
A macromolecular photoinitiator was synthesized using a polymerizable photoinitiator MPI-1 as an example, and AIBN, MPI-1, AM and butanone as shown in the formulation in Table 1 were added to a 50mL flask in an amount of 1% of the total mass of the monomers. Introducing nitrogen into the reaction system to remove oxygen for 15 minutes, starting stirring, and reacting for 6 hours at the reaction temperature of 75 ℃. After the reaction is finished, the precipitate is centrifugally separated from the system, and the product is washed by petroleum ether for three times and then dried in vacuum, so that the water-soluble macromolecule photoinitiator Poly (AM-co-MPI-1) A #, the infrared spectrogram and the ultraviolet absorption spectrogram of the Poly (AM-co-MPI-1) A #, which are proved to introduce the photoinitiation group into the side chain of the polymer, are obtained. According to the same operation steps, water-soluble macromolecule photoinitiators Poly (AM-co-MPI-2), Poly (AM-co-MPI-3) and Poly (AM-co-MPI-4) with similar structures can be synthesized by changing the types of polymerizable photoinitiators.
FIG. 1 shows an infrared spectrum of a water-soluble macrophotoinitiator poly (AM-co-MPI-1) A #, wherein 1730cm-1The peak at the position is a stretching vibration peak of C ═ O in an ester group formed by the reaction of PI-1 and maleic anhydride, namely, the PI-1 structural unit is proved to be grafted into the polymer. FIG. 2 is an ultraviolet spectrogram of PI-1 and poly (AM-co-MPI-1), wherein characteristic peaks are all 280nm, the content of PI-1 in the macromolecular photoinitiator can be obtained by calculation, and the number of photoinitiating groups on each molecular chain of the water-soluble macromolecular photoinitiator can be obtained by calculation by combining the number average molecular weight of poly (AM-co-MPI-1) A #.
Example 6
AIBN, MPI-1, AM and butanone in the formula shown in Table 1 are added into a 50mL flask, the dosage of AIBN is 1 percent of the total mass of the monomers, the proportion of MPI-1 and AM is changed, and the macromolecular photoinitiator with different photoinitiation group contents is prepared in the same way as in the example 5, namely the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) B #.
Example 7
AIBN, MPI-1, AM and butanone in the formula shown in Table 1 are added into a 50mL flask, the dosage of AIBN is 1 percent of the total mass of the monomers, the proportion of MPI-1 and AM is changed, and the macromolecular photoinitiator with different photoinitiation group contents is prepared in the same way as in the example 5, namely the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) C #.
Example 8
BPO, MPI-1, AM and isoamyl acetate shown in a formula in a table 1 are added into a 50mL flask, the dosage of the BPO is 1 percent of the total mass of the monomers, and macromolecular photoinitiators with different photoinitiating group contents are prepared in the same way as in the example 5, so that the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) D #.
Example 9
BPO, MPI-1, AM and cyclohexanone shown in a formula in a table 1 are added into a 50mL flask, the dosage of the BPO is 1 percent of the total mass of the monomers, and macromolecular photoinitiators with different photoinitiating group contents are prepared in the same way as in the example 5, so that the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) E #.
Example 10
BPO, MPI-1, AM and cyclohexanone shown in the formula of Table 1 are added into a 50mL flask, the dosage of the BPO is 1 percent of the total mass of the monomers, and macromolecular photoinitiators with different photoinitiation group contents are prepared in the same way as in example 5, so that the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) F #.
TABLE 1 Synthesis of Poly (AM-co-MPI-1) formulation
Water-soluble macromolecule photoinitiator for initiating photopolymerization of water-soluble monomer
Example 11
Based on the total mass of the polymerization reaction system, the mass fraction of the AM monomer is 28 percent, and the using amount of the macromolecular photoinitiator poly (AM-co-MPI-1) A # is 0.02 percent of the mass of the AM. Adding the monomer, the macromolecular photoinitiator and water into a reaction container, fully dissolving, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with the wavelength of 254nm to initiate AM ultraviolet polymerization, wherein the light intensity of the ultraviolet light is 5mW/cm2And reacting for 3 hours to obtain the PAM hydrogel. The viscosity-average molecular weight of PAM is as high as 18.7 x 106Because the prepared PAM has a branched structure, the PAM has a high dissolution speed in water, and after drying and crushing, the dissolution time of the PAM dry powder is about 30 minutes and less than 1 hour.
The formulations used in examples 12 to 14 are shown in Table 2, and the procedures for carrying out the same were substantially the same as those of example 11, and branched polyacrylamides of different structures and molecular weights were prepared by varying the kind and content of the water-soluble macrophotoinitiator.
TABLE 2 formula of water-soluble macromolecular photoinitiator for initiating photopolymerization of water-soluble monomer to prepare polyacrylamide with branched structure
Comparative example 1:
the mass fraction of the AM monomer is 28 percent, and the dosage of PI-1 is 0.002 percent of the mass of the monomer. Adding the monomer, the photoinitiator and water into a reaction container for full dissolution, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with the wavelength of 254nm to initiate AM ultraviolet polymerization, wherein the light intensity of the ultraviolet light is 10mW/cm2And reacting for 3 hours to obtain the PAM hydrogel. PAM viscosity average molecular weight of only 7.2X 106Because the prepared PAM is in a linear structure, the PAM has a slow dissolving speed in water, and after drying and crushing, the PAM dry powder has a long dissolving time which is more than 1 hour.
Claims (9)
1. A water-soluble macromolecular photoinitiator, characterized in that the initiator has the structure shown in general formula (I) or general formula (II):
wherein, x is 50-800, y is 4-50, and n is 0-10; x1Is H or CH3；Y1Is H or CH3；Y2Is a carboxyl or carboxylate group; z is O or NH;
X2selected from any one of the following groups;
PI is a photoinitiating group selected from any one of the following groups:
2. a method for preparing the water-soluble macromolecule photoinitiator according to claim 1, wherein the water-soluble macromolecule photoinitiator is synthesized by the following steps: firstly, reacting an anhydride monomer with a small molecular photoinitiator with terminal hydroxyl or amino to prepare a polymerizable photoinitiator containing unsaturated double bonds, wherein the anhydride monomer is one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride; and then, copolymerizing the polymerizable photoinitiator containing the unsaturated double bond with a water-soluble monomer A in a free radical copolymerization mode to synthesize the water-soluble macromolecular photoinitiator containing a photoinitiating group in a side group, wherein the water-soluble monomer A is one or more than two selected from (methyl) acrylamide monomers, (methyl) acrylic acid, (methyl) acrylate, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) dimethylaminoethyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid (salt).
3. The method as claimed in claim 2, wherein the preparation of the unsaturated double bond-containing polymerizable photoinitiator by reacting the anhydride monomer with the hydroxyl-terminated or amine-terminated small molecule photoinitiator comprises the following steps:
dissolving a hydroxyl-terminated or amino-terminated micromolecular photoinitiator with a structure shown in a general formula (III) and an anhydride monomer in a solvent, adding a catalyst, and introducing an unsaturated double bond structure into the micromolecular photoinitiator through esterification or amidation reaction;
wherein M is hydroxyl or amino, PI is photoinitiating group, and n is 0-10;
after the reaction is finished, separating and purifying the product to obtain the polymerizable photoinitiator containing unsaturated double bonds and having the structure shown in the general formula (IV) or the general formula (V);
wherein n is 0-10; y is1Is H or CH3；Y2Is a carboxyl group or a carboxylate; z is O or NH; PI is a photoinitiating group selected from any one of the following groups:
4. the method of claim 2, wherein the preparation of the water-soluble macrophotoinitiator having a structure represented by general formula (i) or general formula (ii) by radical copolymerization of a polymerizable photoinitiator with a water-soluble monomer a by a polymerization method of solution polymerization or precipitation polymerization comprises the steps of:
for solution polymerization, preparing raw materials comprising a polymerizable photoinitiator, a water-soluble monomer A, water and a water-soluble free radical initiator, reacting at 40-100 ℃ for 1-12 hours to obtain a water-soluble macromolecular photoinitiator solution, and precipitating, separating and drying the prepared water-soluble macromolecular photoinitiator from a polymerization reaction system to obtain the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II) and the lateral group containing a photoinitiation group;
for precipitation polymerization, the preparation raw materials comprise a polymerizable photoinitiator, a water-soluble monomer A, a solvent and an initiator; initiating polymerization by adopting an oil-soluble free radical initiator, wherein the reaction temperature is 40-100 ℃, the reaction time is 1-12 hours, and the prepared water-soluble macromolecular photoinitiator is precipitated from a solvent along with the reaction; separating and drying the prepared water-soluble macromolecular photoinitiator from a polymerization reaction system to obtain the water-soluble macromolecular photoinitiator with the structure shown in the general formula (I) or the general formula (II) and the lateral group containing a photoinitiation group.
5. The method according to claim 2 or 3, wherein the mass ratio of the small molecular weight photoinitiator to the anhydride monomer in the preparation process of the polymerizable photoinitiator is 2:1-1:5, the catalyst comprises 4-dimethylaminopyridine, pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid and sodium acetate, and the amount of the catalyst is 0.05-2% by mass of the anhydride monomer.
6. The method according to claim 2 or 4, wherein in the preparation of the water-soluble macromolecular photoinitiator, the total mass percent concentration of the monomers in the reaction system is 5-60% based on the total mass of the polymerization reaction system; the molar ratio of the water-soluble monomer to the polymerizable photoinitiator in the reaction system is 1:1-50: 1.
7. The method according to claim 2 or 4, wherein the solvent used in the preparation of the water-soluble macromolecule photoinitiator comprises water, methanol, ethanol, isopropanol, ethylene glycol, glycerol, tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, dimethylformamide, dimethylacetamide, and dimethyl sulfoxide.
8. The method according to claim 2, wherein the initiator used in the preparation of the water-soluble macrophotoinitiator is a conventional radical initiator, including azo-type initiators, peroxy-type initiators or oxidation-reduction initiation systems, and the amount of the initiator used in the system is 0.05 to 5.0% by mass based on the mass of the monomers.
9. Use of the water-soluble macromolecular photoinitiator according to claim 1 for initiating polymerization of a water-soluble monomer B, which may be the same or different, to prepare a water-soluble polymer having a well-defined branched structure.
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