CN114656592B - 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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- CN114656592B CN114656592B CN202011544971.4A CN202011544971A CN114656592B CN 114656592 B CN114656592 B CN 114656592B CN 202011544971 A CN202011544971 A CN 202011544971A CN 114656592 B CN114656592 B CN 114656592B
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- water
- photoinitiator
- soluble
- monomer
- macromolecular photoinitiator
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- 230000000977 initiatory effect Effects 0.000 claims abstract description 15
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 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
- 150000003384 small molecules Chemical class 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
- 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000012673 precipitation polymerization Methods 0.000 claims description 5
- 230000035484 reaction time Effects 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 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
- 150000007942 carboxylates Chemical group 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
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 229940048053 acrylate Drugs 0.000 claims 3
- YSGXLWIBNRFVMF-UHFFFAOYSA-N C(C=C)(=O)O.C[K] Chemical compound C(C=C)(=O)O.C[K] YSGXLWIBNRFVMF-UHFFFAOYSA-N 0.000 claims 1
- GFDKDHGFNSWQRU-UHFFFAOYSA-N C(C=C)(=O)O.C[Na] Chemical compound C(C=C)(=O)O.C[Na] GFDKDHGFNSWQRU-UHFFFAOYSA-N 0.000 claims 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 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 6
- 230000005012 migration Effects 0.000 abstract description 5
- 238000013508 migration Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 21
- 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 14
- 239000000203 mixture Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000002390 rotary evaporation Methods 0.000 description 12
- 238000009472 formulation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 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
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000003208 petroleum Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000013461 design 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
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- 230000007246 mechanism Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 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 1
- 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
- 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 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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
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- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
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- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
-
- 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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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a water-soluble macromolecular photoinitiator, a preparation method and application thereof. The macromolecular photoinitiator is prepared by the following method: preparing a polymerizable photoinitiator containing unsaturated double bonds through the reaction of an anhydride monomer and a small molecular photoinitiator with hydroxyl or amine ends; 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 invention has simple synthetic route, and the photoinitiation group content in the prepared macromolecular photoinitiator is controllable; and the macromolecular photoinitiator has high dissolution speed in the water phase and high initiation activity, and overcomes the defects of low initiation efficiency, easy migration and the like of the micromolecular photoinitiator. Under ultraviolet irradiation, the water-soluble macromolecular photoinitiator can effectively initiate polymerization of water-soluble monomers such as acrylamide, acrylic acid salts and the like to prepare the water-soluble polymer with a branched structure.
Description
Technical Field
The invention relates to a photoinitiator, in particular to a water-soluble macromolecular photoinitiator and a preparation method thereof, and the prepared water-soluble macromolecular photoinitiator can be used for photopolymerization of water-soluble monomers such as (methyl) acrylamide, (methyl) acrylic acid, (methyl) acrylate and the like, and can be used for preparing water-soluble polymers with branched structures.
Background
The photopolymerization technology, which is a polymerization means different from the traditional initiator initiation and thermal initiation, has remarkable superiority and practicality, such as: the polymerization temperature is low (room temperature reaction can be performed), the initiation efficiency is high, the polymerization speed is high, and the like, and through the action of light and a photosensitive compound (a photosensitizer or a photoinitiator), a series of photophysical and photochemical reactions are performed, active substances are generated in the 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 has been widely paid attention to by researchers since the 60 th century. However, most of the photoinitiators currently commercialized are oil-soluble, insoluble or very low in water, and such photoinitiators are required to be dispersed into aqueous polymerization systems by means of emulsifiers and small amounts of monomers, and have great compatibility problems with aqueous systems, affecting 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) and-SO 3 H (sulfo) and the like. However, the conventional small molecule photoinitiator generates a photocleavage reaction during photopolymerization, and the generated free small molecule organic matters have the problems of residue, migration, easy volatilization and the like, so that the application of the small molecule water-soluble photoinitiator is still restricted. For this reason, researchers have recently begun to develop polymerizable or macromolecular photoinitiators that can reduce or eliminate the disadvantages of small-molecule photoinitiators, such as: CN101077897A, CN101220106A, CN101333278A, CN102020726a reports a series of preparation methods of macromolecular photoinitiators. Compared with a small molecular photoinitiator, the large molecular photoinitiator has the following advantages: high optical activity, no peculiar smell, no migration, good compatibility with polymer, and the like, and has good application prospect. Therefore, developing a macromolecular photoinitiator is an effective way to solve the drawbacks of volatility and mobility of small molecular photoinitiators.
The preparation method of the macromolecule photoinitiator mainly comprises the following steps: (1) A small molecule photoinitiator having a functional substituent such as a hydroxyl group or an amine group, and a monomer or polymer containing a reactive group such as an isocyanate group; (2) Photoinitiating groups are introduced into the pendant 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 of no hydrophilic group, the prepared macromolecular photoinitiator has poor compatibility with an aqueous system, and is difficult to be applied to photopolymerization of water-soluble monomers, in particular to preparation of high molecular weight water-soluble polymers with complex structures such as branching, star-shaped and the like.
On the basis of analyzing the defects of the method, the invention designs a novel water-soluble macromolecular photoinitiator, and prepares the water-soluble macromolecular photoinitiator simply and efficiently through the free radical copolymerization of the polymerizable photoinitiator and the water-soluble monomer. The water-soluble macromolecular photoinitiator and the preparation method thereof have the advantages that the synthesis route is simple, the reaction condition is mild, the selection range of water-soluble monomers adopted by the prepared water-soluble macromolecular photoinitiator is wide, the molecular weight of the macromolecular photoinitiator can be simply regulated and controlled, and the content of photoinitiating 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 adopting an organic synthesis method, the water-soluble macromolecular photoinitiator is prepared by adopting solution polymerization or precipitation polymerization, and the prepared water-soluble macromolecular photoinitiator has good water solubility and high photoinitiating group content. In addition, the water-soluble macromolecular photoinitiator prepared by the invention can initiate common water-soluble monomer polymerization under the ultraviolet irradiation condition, and is used for preparing water-soluble polymers with specific branched structures. The photoinitiation groups in the prepared macromolecular photoinitiator are uniformly distributed, the occurrence of crosslinking phenomenon can be effectively controlled (or overcome) when the polymerization of the water-soluble monomer is initiated, and the water-soluble polymer with controllable chemical structure and adjustable molecular weight, in particular the branched water-soluble polymer with ultrahigh molecular weight, can be prepared; and 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 shearing 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 is used for preparing branched polymers, and a preparation method thereof. In order to make the prepared macromolecular photoinitiator have hydrophilicity, the molecular structure of the macromolecular photoinitiator must contain hydrophilic groups and active groups capable of realizing photoinitiation. The invention improves the prior method based on analyzing the prior known preparation method of the macromolecular photoinitiator, firstly, unsaturated groups with polymerization activity are introduced into the micromolecular photoinitiator to prepare the polymerizable photoinitiator; the prepared polymerizable photoinitiator further performs copolymerization reaction with other water-soluble monomers to prepare the water-soluble macromolecular photoinitiator with the side group containing the photoinitiating group. According to the method, the hydrophilic groups are introduced into the molecular chain of the macromolecular photoinitiator, and the photoinitiating groups with photoinitiating activity are introduced into the side groups of the molecular chain, so that the prepared macromolecular photoinitiator has good photoinitiating performance and good solubility in an aqueous system, is suitable for replacing small molecular photoinitiators, and is used for initiating photopolymerization of conventional water-soluble monomers.
It should be noted that the photoinitiating groups in the side groups of the water-soluble macromolecular initiator prepared by design are uniformly distributed, can effectively inhibit (or overcome) the occurrence of crosslinking reaction when initiating the polymerization of the water-soluble monomer, and is suitable for preparing the water-soluble polymer with a branched structure, in particular to the ultra-high molecular weight water-soluble polymer with a branched structure. Compared with the conventional linear polymer, the branched polymer has better dissolution property, and the formed branched polymer aqueous solution has better shearing resistance.
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=50-800, y=4-50, n=0-10; in order to further improve the photoinitiation performance and water solubility of the water-soluble macromolecular photoinitiator, it is preferable that x=50 to 400, y=4 to 50, and n=0 to 5;further preferred are x=50-200, y=4-50, n=0-5; x is X 1 Is H or CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is carboxyl or carboxylate; z is O or NH;
X 2 any one selected from the following groups;
PI is a photoinitiating group selected from the group consisting of commonly cleaved 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) Preparing a polymerizable photoinitiator containing unsaturated double bonds through the reaction of anhydride monomers and small molecular photoinitiators of hydroxyl-terminated groups or amine groups, wherein the anhydride monomers are one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride; (2) The above-mentioned polymerizable photoinitiator containing an unsaturated double bond is copolymerized with a water-soluble monomer A by means of free radical copolymerization, and the water-soluble macromolecular photoinitiator containing a photoinitiating group in a side group is synthesized, wherein the water-soluble monomer A is one or more selected from the group consisting of (methyl) acrylamide monomers, (methyl) acrylic acid salt, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) dimethylaminoethyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid (salt), and the water-soluble monomer A is preferably one or more selected from the group consisting of (methyl) acrylamide monomers, (methyl) acrylic acid salt, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) dimethylaminoethyl acrylate and 2-acrylamide-2-methylpropanesulfonic acid (salt).
In some specific embodiments, the polymerizable photoinitiator containing unsaturated double bonds is preferably prepared as follows:
firstly, dissolving a hydroxyl-terminated (or amine-terminated) micromolecular photoinitiator with a structure shown in a general formula (III) and anhydride monomers (maleic anhydride, citraconic anhydride and/or itaconic anhydride) in a solvent, and mixing to form a uniform reaction system; secondly, adding a catalyst (for high-activity primary hydroxyl or primary amino, or no catalyst) into the reaction system, uniformly mixing, preferably reacting at 0-80 ℃, further preferably 0-20 ℃, and preferably 0.5-6 hours, and introducing unsaturated double bonds into the small molecule photoinitiator through esterification or amidation reaction. Wherein the selected small molecule photoinitiator with hydroxyl or amine end groups has a structural formula of 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 used comprises 4-dimethylaminopyridine, pyridine, triethylamine, p-toluenesulfonic acid, concentrated sulfuric acid and sodium acetate, and the catalyst dosage in the system is preferably 0.05-2 mass percent, more preferably 0.1-1 mass percent of the monomer mass;
M-(CH 2 CH 2 O) n -PI
general formula (III)
Wherein M is a hydroxyl or amine group and PI is a photoinitiating group in the macrophotoinitiator of formula (i) or formula (ii), preferably n=0 to 10, more preferably 1 to 5.
After the reaction is finished, the organic solvent is preferably removed by rotary evaporation, the product is dissolved in dichloromethane, water washing and liquid separation are carried out, and the low-boiling-point organic solvent is preferably removed by rotary evaporation, so that the polymerizable photoinitiator containing unsaturated double bonds and having the structure shown in the general formula (IV) or the general formula (V) is obtained;
wherein preferably n=0 to 10, more preferably 1 to 5; y is Y 1 Is H or CH 3 ；Y 2 Is carboxyl orA carboxylate salt; z is O or NH; PI is the photoinitiating active group of the small molecule photoinitiator.
In some specific embodiments, the water-soluble macromolecular photoinitiator is preferably prepared as follows:
the water-soluble macromolecular photoinitiator is prepared by copolymerizing a polymerizable photoinitiator with a water-soluble monomer A by a radical polymerization, more preferably by a solution polymerization or a precipitation polymerization method.
In some preferred embodiments, the concentration of monomer in the polymerization reaction system directly affects the molecular weight of the macroinitiator produced, and the total mass percent concentration of monomer in the reaction system is preferably 5 to 60%, more preferably 10 to 30%. The content of photoinitiating groups in the prepared polymer side groups mainly depends on the mole ratio of the polymerizable photoinitiator and the water-soluble monomer in the system, and the mole ratio of the water-soluble monomer and 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 initiator used for the polymerization is a usual radical initiator known to those skilled in the art and may be an azo-type initiator, a peroxy-type initiator or an oxidation-reduction initiation system, and the initiator is used in an amount of 0.05 to 5.0 mass%, preferably 0.3 to 1.5 mass% based on the mass of the monomer. The azo initiator includes but is not limited to: azobisisobutyronitrile, azobisisoheptylcyanogen, azobisisobutylamidine hydrochloride, azobisiso Ding Mi-in hydrochloride, azobiscyano valeric acid, azobisisopropylimidazoline, and the like; the peroxy-based initiator includes, but is not limited to: dibenzoyl peroxide, dicumyl peroxide, bis (2, 4 dichlorobenzoyl) peroxide, ditert-butyl peroxide, lauroyl peroxide, t-butyl perbenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, and the like.
In some preferred embodiments, when a solution polymerization mode 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 carried out for 1-12 hours, a water-soluble macromolecular photoinitiator solution can be obtained, the prepared water-soluble macromolecular photoinitiator is precipitated from a polymerization reaction system, separated and dried, 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 a precipitation polymerization mode is adopted, the operation is simpler and more convenient, and the product composition, chemical structure and molecular weight are convenient to regulate and control. 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 progress of the reaction; and 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 in the preparation process of the water-soluble macromolecular photoinitiator comprises water, methanol, ethanol, isopropanol, alcohol solvents such as glycol and glycerol, ketone solvents such as tetrahydrofuran, dioxane, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone and the like, ester solvents such as ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate, ethyl benzoate and the like, aliphatic hydrocarbon solvents such as normal hexane, cyclohexane, normal heptane, petroleum ether, octane and the like, aromatic hydrocarbon solvents such as toluene, ethylbenzene, xylene and the like, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, and can be used singly or in any combination.
The water-soluble macromolecular photoinitiator prepared by the method can initiate polymerization of a common water-soluble monomer B (which can be the same as or different from the water-soluble monomer A) to prepare a water-soluble polymer with a branched structure, the water-soluble macromolecular photoinitiator, the water-soluble monomer and water are added into a reaction vessel to be fully dissolved and uniformly mixed, and under the condition of ultraviolet irradiation, photoinitiated active groups in the side groups of the water-soluble macromolecular photoinitiator are decomposed to generate free radicals to initiate self-polymerization or copolymerization of the water-soluble monomer to form water-soluble polymer side chains, so that the water-soluble polymer with the branched structure, especially 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 salts, hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, and N-vinylpyrrolidone; in some preferred embodiments, the concentration of water-soluble monomer in the reaction system is 1-40wt%, preferably 15-30wt% of monomer, and the amount of macroinitiator is 0.01-2% of the mass of monomer, preferably 0.02-0.5% of the mass of monomer. In some preferred embodiments, the polymerization of the water-soluble monomer is initiated by ultraviolet irradiation, preferably by irradiation of a low-pressure ultraviolet lamp having a wavelength of 254nm, and the specific reaction conditions are preferably: the light intensity at 254nm wavelength is 0.2-80 mW/cm 2 The most suitable intensity is 2-20 mW/cm 2 The reaction time is 1 to 12 hours, preferably 2 to 6 hours. In some preferred embodiments, the water-soluble graft polymer is obtained by pulverizing the polymer solution or gel block after the reaction is completed and drying.
In some more specific embodiments, taking 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionophenone (hereinafter referred to as PI-1), the polymerizable photoinitiator MPI-1, and the corresponding water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) as shown in the following figures, the synthetic routes of MPI-1 and the corresponding water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) are shown in mechanism 1 and mechanism 2, respectively:
the specific operation steps are as follows:
1. 2.3g of small molecular photoinitiator PI-1 and 1g of maleic anhydride are dissolved in 25mL of Tetrahydrofuran (THF), 0.02g of catalyst 4-Dimethylaminopyridine (DMAP) is added to react for 3 hours at 50 ℃, THF is removed by rotary evaporation after the reaction is finished, the product is dissolved in dichloromethane, water washing and liquid separation are carried out, low-boiling point organic solvent is removed by rotary evaporation, and the polymerizable photoinitiator MPI-1 is obtained with the yield of about 80 percent.
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 being uniformly mixed, 0.03g of initiator Azobisisobutyronitrile (AIBN) is added, nitrogen is introduced to remove oxygen for 15 minutes, and then the mixture is reacted for 6 hours at 75 ℃. After the reaction is finished, the prepared water-soluble macromolecular photoinitiator is centrifugally separated from the system, washed by petroleum ether for three times and then vacuum-dried, and the water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) with the lateral group containing photoinitiating groups is obtained, and the yield is about 87%.
The mass fraction of PI-1 in the prepared macromolecular photoinitiator is 9 percent by ultraviolet characterization, and the molecular weight of the prepared macromolecular photoinitiator is about 2.0x10 by aqueous phase GPC 4 Thus, an average of about 8 photoinitiating groups per molecular chain can be calculated; therefore, the macromolecular photoinitiator is adopted to initiate the polymerization of the water-soluble monomer, and the branching degree of the prepared water-soluble polymer is about 8. 10mg of the prepared water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) with the lateral group containing photoinitiating groups is dissolved in 20mL of water, 30g of water-soluble monomer AM is added, 50mL of water is added, after the monomers are dissolved and uniformly mixed, argon is introduced into a reaction system to deoxidize for 15 minutes, the reaction system is placed under a low-pressure ultraviolet lamp with the wavelength of 254nm, and ultraviolet polymerization reaction of AM is initiated by irradiation, and the ultraviolet light intensity is set to be 5mW/cm 2 The reaction time is 3 hours, and the water-soluble PAM polymer with a definite branched structure is obtained, and the molecular weight is 1.5 multiplied by 10 measured by a viscosimeter of Viscosystem AVS370 7 。
The water-soluble macromolecular photoinitiator prepared by the invention can be used as a substitute of a small molecular photoinitiator to efficiently initiate the polymerization of water-soluble monomers. The types and the contents of photoinitiating groups in the molecular chain of the macromolecular photoinitiator can be simply and conveniently controlled by adjusting the types of the polymerizable photoinitiators in the reaction system and the feeding ratio of the polymerizable photoinitiators to the water-soluble monomers, so that the water-soluble macromolecular photoinitiators with different molecular structures and different photoinitiating group contents can be prepared. From the molecular structure of the macromolecular photoinitiator, the photoinitiating group exists in the side chain of the polymer, the photoinitiating group is dissociated under the ultraviolet irradiation condition, active free radicals are formed in the side chain of the polymer, and the active free radicals trigger the water-soluble monomer to grow at the chain end of the free radicals in the aqueous phase system, so that the water-soluble polymer branched chain is formed. Each photoinitiating group forms a polymer branched chain in a polymer side chain, and the number of water-soluble polymer branched chains prepared by initiating polymerization of the prepared macromolecular photoinitiator correspondingly increases along with the increase of the number of the photoinitiating groups in the side group. Therefore, the quantity and distribution of the branched chains of the prepared water-soluble polymer can be conveniently regulated and controlled by controlling the structure of the macromolecular initiator.
Compared with the prior art, the water-soluble macromolecular photoinitiator and the preparation method thereof have the following advantages:
(1) The preparation process of the water-soluble macromolecular photoinitiator is simple, the conversion rate is high, and the obtained product is easy to separate;
(2) The composition, structure, molecular weight and distribution of the water-soluble macromolecular photoinitiator prepared by the invention can be simply and conveniently regulated and controlled;
(3) The prepared macromolecular photoinitiator is rapidly dissolved in aqueous solution, and has the advantages of high optical activity, no peculiar smell, no migration, good compatibility with polymers and the like;
(4) The photoinitiation groups in the prepared water-soluble macromolecular photoinitiator are uniformly distributed, the occurrence of crosslinking phenomenon can be effectively inhibited (or overcome) when the polymerization of the water-soluble monomer is initiated, and the water-soluble macromolecular photoinitiator can be used as a substitute of a small-molecular initiator to efficiently initiate the aqueous solution polymerization of the water-soluble monomer; more importantly, the prepared water-soluble polymerization product has a definite branching structure and branching degree, and the branching 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 dosage of the macromolecular photoinitiator. Moreover, compared with the linear water-soluble polymer, the prepared branched water-soluble polymer has better solubility in water, and the branched polymer aqueous solution has better shearing resistance.
Drawings
FIG. 1 is an infrared spectrum of a water-soluble macromolecular photoinitiator poly (AM-co-MPI-1).
FIG. 2 is an ultraviolet-visible absorption spectrum of a small molecular photoinitiator PI-1 and a water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) (a.PI-1; b.Poly (AM-co-MPI-1)).
Detailed Description
The invention is illustrated below in connection with specific examples, which, however, do not limit the invention.
The chemical composition and structure of the product are measured by using a Nexus670 infrared spectrometer and a GBC Cintra-20 ultraviolet spectrometer. The molecular weight of the polymer was that of Viscosystem R○ AVS370 fully automated Ubbelohde viscometer measurement. The mass percent concentration of the monomer in the polymerization reaction system is the 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 a small molecular photoinitiator 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionyl benzene (hereinafter abbreviated as PI-1) and 1g of maleic anhydride were dissolved in 25ml of THF, 0.02g of DMAP was added and reacted at 50℃for 3 hours, THF was removed by rotary evaporation after the reaction was completed, the product was dissolved in methylene chloride, and the resultant was separated by water and dried by rotary evaporation to remove a low boiling point organic solvent, thereby obtaining a polymerizable photoinitiator MPI-1 in a yield of about 80%.
Example 2
The structural formula of the polymerizable photoinitiator MPI-2 is as follows:
2.7g of a small molecular photoinitiator (1-hydroxycyclohexyl) [4- (2-hydroxyethoxy) phenyl ] methanone (hereinafter abbreviated as PI-2) and 1g of maleic anhydride were dissolved in 25ml of THF, 0.03g of DMAP was added and reacted at 65℃for 3 hours, THF was removed by rotary evaporation after the completion of the reaction, the product was dissolved in methylene chloride, the water was separated and dried, and the low boiling point organic solvent was removed by rotary evaporation to give a polymerizable photoinitiator MPI-2 in a yield of about 75%.
Example 3
The structural formula of the polymerizable photoinitiator MPI-3 is as follows:
2.4g of small molecule photoinitiator PI-1 and 1g of itaconic anhydride are dissolved in 25mL of THF, 0.02g of DMAP is added for reaction for 3 hours at 65 ℃, THF is removed by rotary evaporation after the reaction is finished, the product is dissolved in dichloromethane, water washing and liquid separation are carried out, low boiling point organic solvent is removed by rotary evaporation, and the polymerizable photoinitiator MPI-3 is obtained with the yield of about 72 percent.
Example 4
The structural formula of the polymerizable photoinitiator MPI-4 is as follows:
2.4g of small molecular photoinitiator PI-1 and 1g of citraconic anhydride are dissolved in 25mL of THF, 0.02g of DMAP is added for reaction at 70 ℃ for 6 hours, THF is removed by rotary evaporation after the reaction is finished, the product is dissolved in dichloromethane, water washing and liquid separation are carried out, low-boiling point organic solvent is removed by rotary evaporation, and the polymerizable photoinitiator MPI-4 is obtained, and the yield is about 70%.
Preparation of water-soluble macromolecular photoinitiator
Example 5
The macromolecular photoinitiator was synthesized using the polymerizable photoinitiator MPI-1 as an example, and AIBN, MPI-1, AM and butanone as shown in the formulation of 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 deoxidize for 15 minutes, and starting stirring, wherein the reaction temperature is 75 ℃, and reacting for 6 hours. After the reaction is finished, centrifugally separating the precipitate from the system, washing the product with petroleum ether for three times, and then drying in vacuum to obtain the water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) A#, wherein the infrared spectrogram and the ultraviolet absorption spectrogram of the Poly (AM-co-MPI-1) A#, and the photoinitiation group is proved to be introduced into a polymer side chain. According to the same operation procedure, the water-soluble macromolecular photoinitiator 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 the polymerizable photoinitiators.
FIG. 1 is an infrared spectrum of a water-soluble macromolecular photoinitiator poly (AM-co-MPI-1) A# of 1730cm -1 The peak at the position is the stretching vibration peak of c=o in the ester group formed by the reaction of PI-1 with maleic anhydride, i.e. it is proved that PI-1 structural units are incorporated in the polymer. FIG. 2 is an ultraviolet spectrum of PI-1 and poly (AM-co-MPI-1), the characteristic peak is 280nm, the content of PI-1 in the macromolecular photoinitiator can be calculated, and the number of photoinitiating groups on each molecular chain of the water-soluble macromolecular photoinitiator can be calculated by combining the number average molecular weight of poly (AM-co-MPI-1) A#.
Example 6
AIBN, MPI-1, AM and butanone as shown in the formulation of Table 1 were added to a 50mL flask, the AIBN amount was 1% of the total mass of the monomers, and the ratio of MPI-1 to AM was changed to prepare a macromolecular photoinitiator having different photoinitiating group contents in the same manner as in example 5, to obtain a water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) B#.
Example 7
AIBN, MPI-1, AM and butanone as shown in the formulation of Table 1 were added to a 50mL flask, the AIBN amount was 1% of the total mass of the monomers, and the ratio of MPI-1 to AM was changed to prepare a macromolecular photoinitiator having different photoinitiating group contents in the same manner as in example 5, to obtain a water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) C#.
Example 8
BPO, MPI-1, AM and isoamyl acetate as shown in the formulation of Table 1 were added to a 50mL flask in an amount of 1% by weight of the total monomer, and a macromolecular photoinitiator having a different photoinitiating group content was prepared in the same manner as in example 5 to obtain a water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) D#.
Example 9
BPO, MPI-1, AM and cyclohexanone as shown in the formulation of Table 1 were added to a 50mL flask in an amount of 1% by weight of the total monomer, and a macromolecular photoinitiator having a different photoinitiating group content was prepared in the same manner as in example 5 to obtain a water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) E#.
Example 10
BPO, MPI-1, AM and cyclohexanone as shown in the formulation of Table 1 were added to a 50mL flask in an amount of 1% by weight of the total monomer, and a macromolecular photoinitiator having a different photoinitiating group content was prepared in the same manner as in example 5 to obtain a water-soluble macromolecular photoinitiator Poly (AM-co-MPI-1) F#.
TABLE 1 Poly (AM-co-MPI-1) formulation
Water-soluble macromolecular photoinitiator for initiating photopolymerization of water-soluble monomer
Example 11
The mass fraction of AM monomer was 28% and the amount of macromolecular photoinitiator poly (AM-co-MPI-1) A# was 0.02% by weight based on the total mass of the polymerization reaction system. Adding monomer, macromolecular photoinitiator and water into a reaction vessel, fully dissolving, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and placing under a low-pressure ultraviolet lamp with wavelength of 254nm to irradiate and initiate ultraviolet polymerization of AM, wherein the ultraviolet light intensity is 5mW/cm 2 The reaction was carried out for 3 hours to obtain PAM hydrogel. PAM viscosity average molecular weight up to 18.7X 10 6 Because the PAM has a branched structure, the dissolution speed of the PAM in water is high, and the dissolution time of the PAM dry powder after drying and crushing is about 30 minutes and less than 1 hour.
The formulations used in examples 12-14 are shown in Table 2, and the procedure is substantially the same as in example 11, except that the type and amount of the water-soluble macromolecular photoinitiator are changed to prepare the branched structure polyacrylamides of different structures and molecular weights.
TABLE 2 formulation for preparing branched polyacrylamide by photopolymerization of water-soluble monomer initiated by water-soluble macromolecular photoinitiator
Comparative example 1:
the mass fraction of the AM monomer is 28%, and the PI-1 dosage is 0.002% of the mass of the monomer. Adding monomer, photoinitiator and water into a reaction vessel, fully dissolving, uniformly mixing, introducing nitrogen to remove oxygen for 15 minutes, and irradiating under a low-pressure ultraviolet lamp with a wavelength of 254nm to initiate ultraviolet polymerization of AM, wherein the ultraviolet light intensity is 10mW/cm 2 The reaction was carried out for 3 hours to obtain PAM hydrogel. PAM viscosity average molecular weight of only 7.2X10 6 As the PAM is of a linear structure, the dissolution speed of the PAM in water is low, and the dissolution time of the PAM dry powder is long and is longer than 1 hour after the PAM is dried and crushed.
Claims (9)
1. A water-soluble macromolecular photoinitiator for initiating the polymerization of water-soluble monomers B for the preparation of water-soluble polymers having a defined branched structure, characterized in that the initiator has a structure of general formula (i) or general formula (ii):
wherein x=50-800, y=greater than 10 and less than 50, n=0-10; x is X 1 Is H or CH 3 ；Y 1 Is H or CH 3 ；Y 2 Is a carboxyl or carboxylate group; z is O or NH;
X 2 any one selected from the following groups;
PI is a photoinitiating group selected from any one of the following groups:
2. a method for preparing the water-soluble macromolecular photoinitiator according to claim 1, wherein the synthetic route of the water-soluble macromolecular photoinitiator is as follows: firstly, preparing a polymerizable photoinitiator containing unsaturated double bonds through the reaction of an anhydride monomer and a small molecular photoinitiator containing hydroxyl or amino, wherein the anhydride monomer is one or more than two selected from maleic anhydride, citraconic anhydride and itaconic anhydride; secondly, the polymerizable photoinitiator containing unsaturated double bonds is copolymerized with a water-soluble monomer A in a free radical copolymerization mode to synthesize a water-soluble macromolecular photoinitiator containing photoinitiating groups in side groups, wherein the water-soluble monomer A is one or more than two selected from (methyl) acrylamide monomers, (methyl) acrylic acid, (methyl) sodium acrylate, (methyl) potassium acrylate, N-vinyl pyrrolidone, (methyl) hydroxyethyl acrylate, (methyl) hydroxypropyl acrylate, (methyl) dimethylaminoethyl acrylate and sodium 2-acrylamide-2-methylpropanesulfonate.
3. The method according to claim 2, wherein the polymerizable photoinitiator containing unsaturated double bonds is prepared by reacting an anhydride-based monomer with a small molecule photoinitiator having a terminal hydroxyl group or an amine group, comprising the steps of:
dissolving a hydroxyl-terminated or amine-terminated small molecular 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 small molecular photoinitiator through esterification or amidation reaction;
wherein M is hydroxyl or amine, PI is a photoinitiating group, n=0-10;
after the reaction is finished, separating and purifying the product to obtain the polymerizable photoinitiator with the structure shown in the general formula (IV) or the general formula (V) and containing unsaturated double bonds;
wherein n=0 to 10; y is Y 1 Is H or CH 3 ；Y 2 Is carboxyl or carboxylate; z is O or NH; PI is a photoinitiating group selected from any one of the following groups:
4. the method according to claim 2, wherein the water-soluble macromolecular photoinitiator having a structure represented by the general formula (i) or the general formula (ii) is prepared by radical copolymerization of a polymerizable photoinitiator with a water-soluble monomer a by a polymerization method of solution polymerization or precipitation polymerization, comprising the steps of:
for solution polymerization, the preparation raw materials comprise a polymerizable photoinitiator, a water-soluble monomer A, water and a water-soluble free radical initiator, the reaction temperature is 40-100 ℃ and the reaction time is 1-12 hours, so as to obtain a water-soluble macromolecular photoinitiator solution, and the prepared water-soluble macromolecular photoinitiator is precipitated, separated and dried from a polymerization reaction system, so that the water-soluble macromolecular photoinitiator with a structure shown as a general formula (I) or a general formula (II) and containing photoinitiating groups on side groups is obtained;
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; and 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), wherein the side group of the water-soluble macromolecular photoinitiator contains a photoinitiating group.
5. A method according to claim 2 or 3, wherein the mass ratio of the small molecular 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 catalyst is 0.05-2 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 percentage concentration of 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 between 1:1 and 50:1.
7. The method according to claim 2 or 4, wherein the solvent used in the preparation of the water-soluble macromolecular 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 dimethylsulfoxide.
8. The method according to claim 2, wherein the initiator used in the preparation of the water-soluble macromolecular photoinitiator is a conventional radical initiator including azo initiator, peroxy initiator or oxidation-reduction initiation system, and the initiator is used in an amount of 0.05 to 5.0 mass% based on the mass of the monomer.
9. Use of a water-soluble macromolecular photoinitiator according to claim 1 for initiating the polymerization of water-soluble monomers B to prepare water-soluble polymers having a well-defined branched structure.
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