CN1844087A - Polymerisable benzophenone photoinitiator and its preparing method - Google Patents

Polymerisable benzophenone photoinitiator and its preparing method Download PDF

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CN1844087A
CN1844087A CN 200610025227 CN200610025227A CN1844087A CN 1844087 A CN1844087 A CN 1844087A CN 200610025227 CN200610025227 CN 200610025227 CN 200610025227 A CN200610025227 A CN 200610025227A CN 1844087 A CN1844087 A CN 1844087A
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benzophenone
thiophenyl
acrylamido
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methyl
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CN100427461C (en
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王洪宇
韦军
印杰
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Shanghai Jiaotong University
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Abstract

The invention discloses a diphenylketone photo-initiator and Method for preparation of polymerisable expressed as follows. Using halogenated diphenylketone and aminophenol or aminobenzenethiol as raw material, producing benzenethiol contains amidol, and then reacting with propenoyl chloride or methyl propenoyl chloride in the existense of triethylamine, producing polymerisable diphenylketone photo-initiator. Because there is phenoxy or benzene sulfenyl in structure, compared with diphenylketone, the ultraviolet absorption has large red shift; the initiation speed has large improvement. The introduction of unsaturated acidamide group improves the compatibility with other initiation system, decresing the surface migration of low-molecule photo-initiator greatly. Because there is unsaturated double bond in structure, it can also be the synthesized monomer of high polymer photo-initiator, hasing wide use in ultraviolet light curing and so on realm.

Description

Polymerisable benzophenone photoinitiator and preparation method thereof
Technical field: the invention belongs to a kind of organic compound and preparation method thereof, particularly a kind of polymerisable benzophenone photoinitiator and preparation method thereof.
Background technology: nineteen forty-six, American I nmont company has delivered unsaturated polyester/vinylbenzene ultraviolet (UV) light-curable ink technical patent in first, and photocuring technology keeps high speed development always since then.Particularly at industrial circles such as photo-cured coating, photoresist material, light-curable ink, electronic package material, tackiness agent, optical media replication, paper glazings, UV-curing technology has shown bright development prospect.In the technical progress process of photocuring system, the research and development of new and effective photoinitiator system occupy crucial position all the time.
Traditional small molecules light trigger, because itself and photocuring system consistency difference and volatilize easily and move, thereby reduced photopolymerisable efficiency of initiation, and cause product smell and toxicity to occur.Therefore research and development efficient, become the focus that people pay close attention to the good polymerisable or polymer light trigger of system consistency.The acrylate chloride group that will contain unsaturated double-bond as (101 pages of nineteen eighty-three periodical Polymer the 24th volumes) such as C.Carlini is incorporated in the 4-dihydroxy benaophenonel structure, has prepared polymerisable diphenyl ketone photo initiator; Du Fusheng etc. (periodical Journal of applied polymer science the 51st volume was 2139 pages in 1994) are incorporated into the methacryloyl cl radical in the 4-dihydroxy benaophenonel molecular structure, make polymerisable light initiation system.The red shift of products therefrom uv-absorbing is little, causes effect and benzophenone and is more or less the same.
Summary of the invention: the present invention is incorporated in the benzophenone structural by oxygen/sulphur atom and the two key of molecular designing with electron rich from Molecular Structure Design, synthesizes a kind of polymerisable benzophenone photoinitiator, has very high efficiency of initiation.Polymerisable benzophenone photoinitiator chemical structural formula of the present invention is as follows:
Figure A20061002522700051
In the formula: R 1～R 8Be selected from hydrogen, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin respectively; R 9Be selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin, diethylin, 3-methacryloyl amido thiophenyl, 3-Methacrylamide phenoxyl, 4-Methacrylamide phenoxyl, 4-methacryloyl amido thiophenyl, 3-acrylamido thiophenyl, 3-acrylamide phenoxyl, 4-acrylamide phenoxyl or 4-acrylamido thiophenyl; R 11Be selected from hydrogen or methyl; X is selected from oxygen or sulphur;
4-[(4-methacryloyl amido is wherein arranged) phenoxy group] benzophenone, 4-[(3-methacryloyl amido) phenoxy group] benzophenone, 4-chloro-4 '-[(4-methacryloyl amido) phenoxy group] benzophenone, 4-chloro-4 '-[(3-methacryloyl amido) phenoxy group] benzophenone, 4,4 '-two [(4-methacryloyl amido) phenoxy group] benzophenone, 4,4 '-two [(3-methacryloyl amido) phenoxy group] benzophenone, the 4-[(4-acrylamido) phenoxy group] benzophenone, the 4-[(3-acrylamido) phenoxy group] benzophenone, 4-chloro-4 '-[(4-acrylamido) phenoxy group] benzophenone, 4-chloro-4 '-[(3-acrylamido) phenoxy group] benzophenone, 4,4 '-two [(4-acrylamido) phenoxy group] benzophenone, 4,4 '-two [(3-acrylamido) phenoxy group] benzophenone, 4-[(4-methacryloyl amido) thiophenyl] benzophenone, 4-[(3-methacryloyl amido) thiophenyl] benzophenone, 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone, 4-chloro-4 '-[(3-methacryloyl amido) thiophenyl] benzophenone, 4,4 '-two [(4-methacryloyl amido) thiophenyl] benzophenone, 4,4 '-two [(3-methacryloyl amido) thiophenyl] benzophenone, the 4-[(4-acrylamido) thiophenyl] benzophenone, the 4-[(3-acrylamido) thiophenyl] benzophenone, 4-chloro-4 '-[(4-acrylamido) thiophenyl] benzophenone, 4-chloro-4 '-[(3-acrylamido) thiophenyl] benzophenone, 4,4 '-two [(4-acrylamido) thiophenyl] benzophenone or 4,4 '-two [(3-acrylamido) thiophenyl] benzophenone.
The preparation method of polymerisable benzophenone photoinitiator is as follows among the present invention: followingly all represent that with mass parts (a) at room temperature is dissolved in 1 part of halogenated benzophenone and 0.3～3 part of amino-phenol or aminothiophenol in 40～150 parts the organic solvent, at potassium hydroxide, salt of wormwood, sodium hydroxide or yellow soda ash exist down, reacted between 100～140 ℃ 1～5 hour, be warming up to then between 140～185 ℃, reacted 1～10 hour, reaction finishes postcooling to room temperature, then reaction solution is poured into to 10～100 parts 5～30% aqueous hydrochloric acid and precipitated, product with solvent recrystallization after, obtain containing the benzophenone hydrochloride of aniline structure; The benzophenone hydrochloride structural formula that wherein contains the aniline structure is as follows:
Figure A20061002522700061
(b) under magnetic agitation and ice bath, the benzophenone hydrochloride that contains the aniline structure of 1 part of porphyrize is slowly joined in 10～50 part of 10～40% ammonia soln or the aqueous sodium acetate solution, vigorous stirring 0.5～5 hour is sloughed hydrochloric acid, obtains containing the benzophenone of aniline structure;
(c) 1 part of benzophenone that contains the aniline structure is dissolved in 5～50 parts the organic solvent; other gets 0.3～2 part 0.3～2 part acrylate chloride or methacrylic chloride and is dissolved in the organic solvent; nitrogen protection and ice bath slowly drip the mixed solution of acrylate chloride or methacrylic chloride down; after stirring reaction 10～20 hours at room temperature; after reaction solution is poured in the frozen water; suction filtration precipitation with the aqueous sodium carbonate washing of 5wt% three times, obtains polymerisable benzophenone photoinitiator after washing three times.
The halogenated benzophenone that the present invention uses is characterized in that its structural formula is as follows:
Figure A20061002522700071
In the formula: R 1～R 8Be selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl group, methylthio group, ethylmercapto group, rosickyite base, nitro, dimethylin or diethylin respectively; R 9Be selected from hydrogen, methyl, ethyl, propyl group, methylthio group, ethylmercapto group, rosickyite base, nitro, dimethylin, diethylin, fluorine, chlorine or bromine; R 10Be selected from fluorine, chlorine or bromine; 4-chlorobenzophenone, 4 is wherein arranged, 4 '-dichloro benzophenone, 4-fluorine benzophenone, 4-bromine benzophenone, 4,4 '-difluoro benzophenone, 4,4 '-dibromo benzophenone, 4-fluoro-4 '-methyldiphenyl ketone, 2-methyl-4 '-bromine benzophenone, 2-methyl-4 '-chlorobenzophenone, 4-chloro-4 '-nitro benzophenone or 4-methyl-4 '-the bromine benzophenone.
Amino-phenol or aminothiophenol that the present invention uses are selected from Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, near amino thiophenols, m-aminothiophenol or p-aminophenyl thiophenol.
The organic solvent that the present invention uses, it is characterized in that being selected from (a) pimelinketone, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-methyl-2-pyridine alkane ketone, (c) organic solvent is selected from acetone, tetrahydrofuran (THF), butanone, N in, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone.
The entire reaction equation that the present invention prepares polymerisable benzophenone photoinitiator can be expressed as:
Figure A20061002522700072
In the above-mentioned reaction equation if R 9When being selected from fluorine, chlorine or bromine, its will experience and above-mentioned shown in R 10Identical reaction mechanism.
Polymerisable benzophenone photoinitiator of the present invention is to be incorporated in the benzophenone molecule by oxygen/sulphur atom and unsaturated double-bond group with electron rich, not only improved the consistency of initiator and initiator system, make benzophenone produce big red shift, can also further generate the polymer light trigger that contains common initiation structure with the tertiary amine copolymerization that contains unsaturated double-bond, significantly reduce its toxicity and migration, simultaneously the sulphur atom generation free radical that self also can rupture under UV-irradiation can use as crack type photoinitiator separately.Measure by photoelectricity differential calorimetric scanner, this type of light initiation system is in the 1,6 hexanediol diacrylate system, and its maximum velocity of initiation significantly improves than benzophenone, has improved the efficient of diphenyl ketone photo initiator greatly and has widened its range of application.So it will have a wide range of applications at the ultraviolet light polymerization industrial circle.
Description of drawings:
Fig. 1 is a 4-[(4-methacryloyl amido) thiophenyl] infrared spectra of diphenyl ketone photo initiator.
Fig. 2 is a 4-[(4-methacryloyl amido) thiophenyl] nucleus magnetic hydrogen spectrum of diphenyl ketone photo initiator.
Fig. 3 is with dimethylaminoethyl methacrylate during as coinitiator, 4-[(4-methacryloyl amido) thiophenyl] benzophenone and benzophenone cause the photoelectricity differential calorimetric comparison diagram of 1,6 hexanediol diacrylate.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; add 1-Methyl-2-Pyrrolidone, 3.60 gram potassium hydroxide, 12.96 4-chlorobenzophenone and the 30mL toluene that restrain of 7.50 gram p-aminophenyl thiophenols, 50mL under the nitrogen protection successively, stirring makes system evenly mixed.Slowly be warmed up to 130～135 ℃ under the oil bath, reacted 3 hours, during moisture in the system go out with methylbenzene azeotropic.Slowly be warmed up to 170～175 ℃ once more, reacted 3 hours.Slowly reduce to suction filtration after the room temperature, remove insolubles.In 1 hour, slowly join in the 100mL concentrated hydrochloric acid and 500mL mixture of ice and water of vigorous stirring considering liquid.Suction filtration, washing, petroleum ether is inserted the vacuum drying oven drying with filter cake, gets 18.35 gram products.The mixing solutions recrystallization of water, concentrated hydrochloric acid and Virahol gets 13.42 gram 4-[(4-amino) thiophenyl] the benzophenone hydrochloride.Fusing point: 101～103 ℃.M/z:305 (removing HCl), FT-IR (KBr): 3460,3368 (NH 2), 1648 (C=O), 1084 (C-S). 1H NMR ([D6] DMSO, 400MHz): δ=7.70-7.63 (5H, phenyl ring), 7.54-7.51 (2H, phenyl ring), 7.49-7.45 (2H, phenyl ring), 7.26-7.23 (2H, phenyl ring), 7.19-7.17 (2H, phenyl ring).C 19H 16ClNOS (341.5gmol -1): ultimate analysis, theoretical value: C 66.75, H 4.72, and N 4.10, and S 9.38; Actual value: C 65.29, H 4.93, and N 3.76, and S 9.02.
(b) under magnetic agitation and ice bath, with the 4-[(4-amino of 13.00 gram porphyrizes) thiophenyl] the benzophenone hydrochloride slowly is added in 10% the ammoniacal liquor of 400mL, stirs after 2 hours suction filtration; Filter cake inserted in 40 ℃ the vacuum drying oven dry 48 hours, 11.4 gram glassy yellow 4-[(4-amino) thiophenyl] benzophenone.
FT-IR(KBr)：3476，3362(NH)，
Figure A20061002522700091
1594(CH＝CH)，1076(C-S)。
1H NMR ([D6] CDCl 3, 400MHz): δ=7.76-7.73 (2H, phenyl ring), 7.66-7.64 (2H, phenyl ring), 7.58-7.54 (1H, phenyl ring), 7.47-7.43 (2H, phenyl ring), 7.37-7.35 (2H, phenyl ring), 7.11-7.09 (2H, phenyl ring), 6.74-6.72 (2H, phenyl ring), 4.01 (2H, NH 2).
(c) under the nitrogen protection in the there-necked flask, with 10.20 gram 4-[(4-amino) thiophenyl] benzophenone and 6mL triethylamine be dissolved in the 30mL dimethyl formamide; Get the 6mL methacrylic chloride and be dissolved in the 10mL dimethyl formamide and place constant pressure funnel, ice bath slowly drips the mixed solution of methacrylic chloride to there-necked flask in following half an hour.Stir after 12 hours under the room temperature, reaction solution is poured in the 300mL icy water, the suction filtration precipitation, filter cake washs three times with 5% aqueous sodium carbonate, deionized water wash three times, 50 ℃ of vacuum-dryings 30 hours, get 11.20 gram xanchromatic 4-[(4-methacryloyl amidos) thiophenyl] benzophenone, with the mixing solutions recrystallization of 1: 3 first alcohol and water.Fusing point: 91～93 ℃, m/z:373.Fig. 1 is a 4-[(4-methacryloyl amido) thiophenyl] infrared spectra of diphenyl ketone photo initiator,
FT-IR(KBr)：3269(NH)，
Figure A20061002522700093
1587(CH＝CH)，1081(C-S)。Fig. 2 is a 4-[(4-methacryloyl amido) thiophenyl] nucleus magnetic hydrogen spectrum of diphenyl ketone photo initiator, 1H NMR (DMSO, 400MHz): δ=7.85-7.82 (2H, phenyl ring), 7.69-7.63 (5H, phenyl ring), 7.54-7.50 (4H, phenyl ring), 7.20-7.18 (2H, phenyl ring), 5.81 (1H, CH), 5.54 (1H, CH), 1.94 (3H, CH 3).Ultimate analysis, theoretical value: C 73.97, H 5.13, and N 3.75, and S 8.59; Measured value: C 73.37, H 5.39, and N 3.96, and S 7.36.Fig. 3 is with dimethylaminoethyl methacrylate during as coinitiator, 4-[(4-methacryloyl amido) thiophenyl] benzophenone and benzophenone cause the photoelectricity differential calorimetric comparison diagram of 1,6 hexanediol diacrylate.Its velocity of initiation approaches the twice of benzophenone as can be seen, has excellent initiation performance.
Embodiment 2:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; the 1-Methyl-2-Pyrrolidone, 2.60 gram potassium hydroxide, 30mL toluene and 8.80 grams 4 that add 8.80 gram p-aminophenyl thiophenols, 40mL under the nitrogen protection successively, 4 '-dichloro benzophenone.Slowly heating up was warmed up between 130～135 ℃ in 30 minutes, reacted 3 hours, during have moisture to go out with methylbenzene azeotropic.Slowly heating up once more rises between 170～175 ℃ system temperature, and toluene is all told, and reacts 3 hours.Naturally cool to room temperature, suction filtration removes insolubles.Filtrate slowly is poured in 140mL concentrated hydrochloric acid and the 400mL mixture of ice and water, stirs, suction filtration, washing.Vacuum-drying gets dark yellow 4,4 '-two [(4-amino) thiophenyl] the benzophenone hydrochloride to light coffee color of 16.01 grams.With the product heating for dissolving at 1: 1: 2: in isopropanol/concentrated hydrochloric acid of 7/ethanol, filtered while hot, remove insolubles, yellow tabular crystal to light coffee color is separated out in cooling, after the pumping rate in 60 ℃ of vacuum drying ovens dry 48 hours, obtain 12.5 grams, 4,4 '-two [(4-amino) thiophenyl] benzophenone hydrochloride.Fusing point: 135～137 ℃.FT-IR(KBr)：3420(NH)，1655(C＝O)，1589(C＝C)，1084(C-S)。 1H NMR ([D6] DMSO, 400MHz): δ=7.66-7.63 (4H, phenyl ring), 7.50-7.47 (4H, phenyl ring), 7.26-7.24 (8H, phenyl ring).C 25H 22Cl 2N 2OS 2(501gmol -1): ultimate analysis, theoretical value: C 59.87, H 4.42, and N 5.59, and S 12.79; Actual value: C 57.69, H 4.68, and N 5.15, and S 12.35.
(b) under magnetic agitation and ice bath, 4,4 '-two [(4-amino) thiophenyl] benzophenone hydrochlorides of 12.5 gram porphyrizes slowly are added in 10% the ammoniacal liquor of 400mL, stir after 2 hours suction filtration; Filter cake inserted in 40 ℃ the vacuum drying oven dry 48 hours, yellow 4,4 '-two [(4-amino) thiophenyl] benzophenone of 10.01 grams.FT-IR(KBr)：3420(NH)，1655(C＝O)，1589(C＝C)，1084(C-S)。 1H NMR (CDCl 3, 400MHz): δ=7.61-7.58 (4H, phenyl ring), 7.35-7.31 (4H, phenyl ring), 7.09-7.06 (4H, phenyl ring), 6.73-6.70 (4H, phenyl ring), 3.90 (NH 2).Mass spectrum, m/z (M+1): 429.
(c) under the nitrogen protection; with 8.56 grams 4; 4 '-two [(4-amino) thiophenyl] benzophenone and 6mL triethylamine are dissolved in the 30mL dimethyl formamide; other gets the 6mL methacrylic chloride and is dissolved in the 10mL dimethyl formamide and places constant pressure funnel; ice bath slowly is added drop-wise in the there-necked flask following half an hour; stirring at room is poured in the cold water of 300mL after 12 hours; suction filtration; 5% aqueous sodium carbonate washing; deionized water wash, after 50 ℃ of following vacuum-dryings 36 hours yellow 4,4 '-two [(the 4-methacryloyl amido) thiophenyl] benzophenone of 10.96 grams; get 6.90 gram pure products behind the chloroform recrystallization, productive rate: 61.2%.Fusing point: 177～179 ℃.Mass spectrum, m/z:565 (M+1).FT-IR(KBr)：3281(NH)，
Figure A20061002522700101
Figure A20061002522700102
1587(CH＝CH)，1081(C-S)。 1H NMR ([D6] DMSO, 400MHz): δ=10.04 (2H, NH), 7.84-7.82 (4H, phenyl ring), 7.61-7.49 (8H, phenyl ring), 7.17-7.15 (4H, phenyl ring), 5.81 (2H, CH), 5.54 (2H, CH), 1.93 (6H, CH 3).
Embodiment 3:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; the 1-Methyl-2-Pyrrolidone, 2.60 gram potassium hydroxide, 30mL toluene and 8.80 grams 4 that add 4.40 gram p-aminophenyl thiophenols, 40mL under the nitrogen protection successively, 4 '-dichloro benzophenone.Slowly heating up was warmed up between 130～135 ℃ in 30 minutes, reacted 3 hours, during have moisture to go out with methylbenzene azeotropic.Slowly heating up once more rises between 170～175 ℃ system temperature, and toluene is all told, and reacts 3 hours.Naturally cool to room temperature, suction filtration removes insolubles.Filtrate slowly is poured in 75mL concentrated hydrochloric acid and the 250mL mixture of ice and water, stirs, suction filtration, washing.Vacuum-drying gets dark yellow 4-chloro-4 '-[(4-amino) thiophenyl] the benzophenone hydrochloride to light coffee color of 12.71 grams, the mixing solutions recrystallization of water, concentrated hydrochloric acid, ethanol and Virahol.Fusing point: 107～109 ℃.FT-IR(KBr)：3406(NH)，1646(C＝O)，1588(C＝C)，1083(C-S)，752(Cl)。 1H NMR ([D6] DMSO, 400MHz): δ=7.73-7.69 (2H, phenyl ring), 7.66-7.58 (4H, phenyl ring), 7.40-7.38 (2H, phenyl ring), 7.20-7.18 (2H, phenyl ring), 7.01-6.99 (2H, phenyl ring), 4.24 (2H, NH 2).C 19H 15Cl 2NOS (376gmol -1): ultimate analysis, theoretical value: C 60.64, H 4.02, and N 3.72, and S 8.52; Actual value: C 60.84, H 4.21, and N 3.43, and S 7.53.
(b) 4-chloro-4 '-[(4-amino) thiophenyl] the benzophenone hydrochlorides with 12.71 gram porphyrizes slowly are added in 10% the ammoniacal liquor of 400mL, stir after 2 hours suction filtration; Filter cake inserted in 40 ℃ the vacuum drying oven dry 48 hours, 10.61 gram yellow 4-chloro-4 '-[(4-amino) thiophenyl] benzophenone.Mass spectrum, m/z:339.FT-IR(KBr)：3465，3380(NH)， 1620，1588(C＝C)，1082(C-S)。 1H NMR (CDCl 3, 400MHz): δ=7.74-7.68 (2H, phenyl ring), 7.62-7.58 (2H, phenyl ring), 7.48-7.42 (2H, phenyl ring), 7.37-7.33 (2H, phenyl ring), 7.11-7.06 (2H, phenyl ring), 6.74-6.71 (2H, phenyl ring), 3.92 (NH 2).
(c) under the nitrogen protection; 12.40 gram 4-chloro-4 '-[(4-amino) thiophenyl] benzophenone and 6mL triethylamine are dissolved in the 30mL dimethyl formamide; other gets the 6mL methacrylic chloride and is dissolved in the 10mL dimethyl formamide and places constant pressure funnel; ice bath slowly is added drop-wise in the there-necked flask following half an hour; stirring at room is poured in the cold water of 300mL after 12 hours; suction filtration; 5% aqueous sodium carbonate washing three times; deionized water wash three times; 50 ℃ of following vacuum-dryings get 14.30 gram yellow 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone after 36 hours; with 1: 3 water and alcohol mixed solution recrystallization, get 12.10 gram pure products after the drying.Fusing point: 105～107 ℃.Mass spectrum, m/z:407.FT-IR(KBr)：3293(NH)， 1587(CH＝CH)，1082(C-S)。 1H NMR (CDCl 3, 400MHz): δ=7.74-7.61 (6H, phenyl ring), 7.52-7.43 (4H, phenyl ring), 7.19-7.14 (2H, phenyl ring), 5.83 (1H, CH), 5.60 (1H, CH), 2.08-2.07 (3H, CH 3).
Embodiment 4:
(a) in the there-necked flask that water trap, prolong and nitrogen protection device are housed; add 1-Methyl-2-Pyrrolidone, 3.60 gram potassium hydroxide, 12.96 4-chlorobenzophenone and the 30mL toluene that restrain of 6.54 gram p-aminophenol, 70mL under the nitrogen protection successively, stirring makes system evenly mixed.Under oil bath, slowly be warmed up to 130～135 ℃, reacted 3 hours, during moisture in the system go out with methylbenzene azeotropic.Slowly be warmed up to 170～175 ℃ once more, reacted 3 hours.Slowly reduce to suction filtration after the room temperature, remove insolubles.In 1 hour, slowly join in the 150mL concentrated hydrochloric acid and 500mL mixture of ice and water of vigorous stirring considering liquid.Suction filtration, washing, petroleum ether is inserted the vacuum drying oven drying with filter cake, gets 17.04 gram products.The mixing solutions recrystallization of water, concentrated hydrochloric acid and Virahol gets 14.31 gram 4-[(4-amino) phenoxy group] the benzophenone hydrochloride.Fusing point: 143～145 ℃.M/z:289 (removing HCl), FT-IR (KBr): 3420 (NH 2), 1648 (C=O), 1258,1167,1147 (C-O). 1H NMR ([D6] DMSO, 400MHz): δ=9.21 (2H, NH 2), 7.78-7.52 (7H, phenyl ring), 7.22-7.05 (6H, phenyl ring).C 19H 16ClNO 2(325.5gmol -1): ultimate analysis, theoretical value: C 70.05, H 5.02, and N 3.91; Actual value: C 71.96, H 4.92, and N 4.30.
(b) with the 4-[(4-amino of 13.02 grams) phenoxy group] benzophenone hydrochloride and 12mL triethylamine be dissolved in the 30mL dimethyl formamide, stirred 10 minutes, slough hydrochloride and get 4-[(4-amino) phenoxy group] benzophenone, because corresponding aminobenzophenone instability is directly carried out next step reaction.
(c) getting the 7mL methacrylic chloride is dissolved in the 10mL dimethyl formamide and places constant pressure funnel, ice bath slowly is added drop-wise in the above-mentioned there-necked flask following half an hour, stirring at room is poured in the cold water of 400mL after 12 hours, suction filtration, 5% aqueous sodium carbonate washing three times, deionized water wash three times, 50 ℃ of following vacuum-dryings get the yellow 4-[(4-methacryloyl amido of 13.60 grams after 36 hours) phenoxy group] benzophenone, product gets 10.60 gram pure products after the recrystallization drying in water/ethanol of 1: 5.Fusing point: 129～131 ℃.Mass spectrum, m/z:357.FT-IR(KBr)：3263(NH)，
Figure A20061002522700123
Figure A20061002522700131
1598(CH＝CH)，1258，1167，1150(C-O)。 1H NMR ([D6] CDCl 3, 400MHz): δ=7.82-7.77 (4H, phenyl ring), 7.63-7.56 (3H, phenyl ring), 7.50-7.46 (2H, phenyl ring), 7.09-7.07 (2H, phenyl ring), 7.02-7.00 (2H, phenyl ring), 2.08-2.07 (3H, CH 3).C 23H 19NO 3(357gmol -1): ultimate analysis, theoretical value: C 77.29, H 5.36, and N 3.92; Actual value: C 76.79, H 5.58, and N 4.18.

Claims (6)

1. polymerisable benzophenone photoinitiator is characterized in that its chemical structural formula is as follows:
In the formula: R 1～R 8Be selected from hydrogen, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin or diethylin respectively; R 9Be selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl group, methoxyl group, oxyethyl group, propoxy-, nitro, dimethylin, diethylin, 3-methacryloyl amido thiophenyl, 3-Methacrylamide phenoxyl, 4-Methacrylamide phenoxyl, 4-methacryloyl amido thiophenyl, 3-acrylamido thiophenyl, 3-acrylamide phenoxyl, 4-acrylamide phenoxyl or 4-acrylamido thiophenyl; R 11Be selected from hydrogen or methyl; X is selected from oxygen or sulphur;
4-[(4-methacryloyl amido is wherein arranged) phenoxy group] benzophenone, 4-[(3-methacryloyl amido) phenoxy group] benzophenone, 4-chloro-4 '-[(4-methacryloyl amido) phenoxy group] benzophenone, 4-chloro-4 '-[(3-methacryloyl amido) phenoxy group] benzophenone, 4,4 '-two [(4-methacryloyl amido) phenoxy group] benzophenone, 4,4 '-two [(3-methacryloyl amido) phenoxy group] benzophenone, the 4-[(4-acrylamido) phenoxy group] benzophenone, the 4-[(3-acrylamido) phenoxy group] benzophenone, 4-chloro-4 '-[(4-acrylamido) phenoxy group] benzophenone, 4-chloro-4 '-[(3-acrylamido) phenoxy group] benzophenone, 4,4 '-two [(4-acrylamido) phenoxy group] benzophenone, 4,4 '-two [(3-acrylamido) phenoxy group] benzophenone, 4-[(4-methacryloyl amido) thiophenyl] benzophenone, 4-[(3-methacryloyl amido) thiophenyl] benzophenone, 4-chloro-4 '-[(4-methacryloyl amido) thiophenyl] benzophenone, 4-chloro-4 '-[(3-methacryloyl amido) thiophenyl] benzophenone, 4,4 '-two [(4-methacryloyl amido) thiophenyl] benzophenone, 4,4 '-two [(3-methacryloyl amido) thiophenyl] benzophenone, the 4-[(4-acrylamido) thiophenyl] benzophenone, the 4-[(3-acrylamido) thiophenyl] benzophenone, 4-chloro-4 '-[(4-acrylamido) thiophenyl] benzophenone, 4-chloro-4 '-[(3-acrylamido) thiophenyl] benzophenone, 4,4 '-two [(4-acrylamido) thiophenyl] benzophenone or 4,4 '-two [(3-acrylamido) thiophenyl] benzophenone.
2. the preparation method of a kind of polymerisable benzophenone photoinitiator as claimed in claim 1 is characterized in that the preparation method is as follows: followingly all represent with mass parts
(a) 1 part of halogenated benzophenone and 0.3～3 part of amino-phenol or aminothiophenol at room temperature are dissolved in 40～150 parts the organic solvent, reacting 1～5 hour in the presence of potassium hydroxide, salt of wormwood, sodium hydroxide or the yellow soda ash, between 100～140 ℃, be warming up to then between 140～185 ℃, reacted 1～10 hour, reaction finishes postcooling to room temperature, then reaction solution is poured into to 10～100 parts 5～30% aqueous hydrochloric acid and precipitated, product with solvent recrystallization after, obtain containing the benzophenone hydrochloride of aniline structure; The benzophenone hydrochloride structural formula that wherein contains the aniline structure is as follows:
(b) under magnetic agitation and ice bath, the benzophenone hydrochloride that contains the aniline structure of 1 part of porphyrize is slowly joined in 10～50 part of 10～40% ammonia soln or the aqueous sodium acetate solution, vigorous stirring 0.5～5 hour is sloughed hydrochloric acid, obtains containing the benzophenone of aniline structure;
(c) 1 part of benzophenone that contains the aniline structure is dissolved in 5～50 parts the organic solvent; other gets 0.3～2 part 0.3～2 part acrylate chloride or methacrylic chloride and is dissolved in the organic solvent; nitrogen protection and ice bath slowly drip the mixed solution of acrylate chloride or methacrylic chloride down; after stirring reaction 10～20 hours at room temperature; after reaction solution is poured in the frozen water; suction filtration precipitation with the aqueous sodium carbonate washing of 5wt% three times, obtains polymerisable benzophenone photoinitiator after washing three times.
3. the preparation method of a kind of polymerisable benzophenone photoinitiator according to claim 2 is characterized in that the halogenated benzophenone structural formula is as follows:
In the formula: R 1～R 8Be selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, propyl group, methylthio group, ethylmercapto group, rosickyite base, nitro, dimethylin or diethylin respectively; R 9Be selected from hydrogen, methyl, ethyl, propyl group, methylthio group, ethylmercapto group, rosickyite base, nitro, dimethylin, diethylin, fluorine, chlorine or bromine; R 10Be selected from fluorine, chlorine or bromine.
4. the preparation method of a kind of polymerisable benzophenone photoinitiator according to claim 2, it is characterized in that halogenated benzophenone is a 4-chlorobenzophenone, 4,4 '-dichloro benzophenone, 4-fluorine benzophenone, 4-bromine benzophenone, 4,4 '-difluoro benzophenone, 4,4 '-dibromo benzophenone, 4-fluoro-4 '-methyldiphenyl ketone, 2-methyl-4 '-bromine benzophenone, 2-methyl-4 '-chlorobenzophenone, 4-chloro-4 '-nitro benzophenone or 4-methyl-4 '-the bromine benzophenone.
5. a kind of polymerisable benzophenone photoinitiator preparation method according to claim 2 is characterized in that amino-phenol or aminothiophenol are Ortho-Aminophenol, Metha Amino Phenon, p-aminophenol, near amino thiophenols, m-aminothiophenol or p-aminophenyl thiophenol.
6. the preparation method of a kind of polymerisable benzophenone photoinitiator according to claim 2 is characterized in that organic solvent is selected from pimelinketone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone in (a); (c) organic solvent is selected from acetone, tetrahydrofuran (THF), butanone, N, dinethylformamide, N,N-dimethylacetamide or N-methyl-2-pyridine alkane ketone in.
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