CN102212151B - Polymerizable benzophenone photoinitiator containing amine used as auxiliary initiator and preparation method thereof - Google Patents
Polymerizable benzophenone photoinitiator containing amine used as auxiliary initiator and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polymerizable benzophenone photoinitiator (shown in the following formula) containing amine used as an auxiliary initiator and a preparation method thereof, which comprises the following steps: carrying out Friedel-Crafts acylation reaction on tertiary amine containing a benzene ring and 4-nitro benzoyl chloride used as raw materials under the catalytic action of anhydrous aluminum chloride used as a catalyst to generate substituted benzophenone containing a nitro group and a tertiary amino group; then reducing the nitro group into a primary amino group in the presence of stannous chloride and concentrated hydrochloric acid; and reacting acryloyl chloride or methacryloyl chloride with the primary amino group to introduce a polymerizable double bond group to the molecular structure, thus acquiring the polymerizable benzophenone photoinitiator containing amine used as the auxiliary initiator. Because the photoinitiator structurally contains the polymerizable group, the problems of toxicity and high mobility existing in the conventional small molecule photoinitiators can be avoided during photocuring; and in addition, the photoinitiator structurally contains the auxiliary initiator group (tertiary amino group), so that the additional auxiliary initiator does not need to be added during photocuring, and the initiation efficiency is high. Thus, the photoinitiator has a wide application prospect in the photocuring field.
Description
Technical field: the invention belongs to a kind of organic compound and preparation method thereof, particularly contain polymerizable diphenyl ketone photo initiator of aided initiating amine and preparation method thereof, it can be used as light trigger and is used for the photocuring field.
Background technology: the Light lnduced Free Radicals polyreaction is widely used in production, such as printed wiring, electronic package material, coating and printing inks etc.Oligopolymer, reactive monomer and various light trigger are the essentially consists of photocuring system.In radical photopolymerization, benzophenone derivates be use the most widely light draw agent, but the uv-absorbing of traditional diphenyl ketone photo initiator is lower, relatively poor (the R.Liska of initiating activity, 2002 term Journal of Polymer Science PartA:Polymer Chemistry, 1504 pages of the 40th volumes).In the technical progress process of photocuring system, the research and development of novel photoinitiator system are all the time in occupation of very important position.With respect to traditional small molecules light trigger, polymerizable photoinitiator can avoid conventional small molecules light trigger problem, the problem includes: toxicity and the problem of high mobility are improved the consistency of light trigger and resin, and can improve the stability of solidifying rear material.The acrylate chloride group that will contain unsaturated double-bond such 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.Wang Hongyu etc. (Chinese invention patent: ZL 200610025227.7 and ZL200510111787.X) utilize the amino reaction on acrylate chloride or maleic anhydride and the benzophenone structural also to be incorporated into undersaturated pair of key group on the benzophenone structural, make polymerisable benzophenone photoinitiator, uv-absorbing is red shift significantly, and light-initiated efficient is far above benzophenone.Diphenyl ketone photo initiator must add aided initiating (usually using tertiary amine) in use, just has very high initiating activity, but micromolecular amine has certain toxicity usually, and easily moves out from solidify rear material, affects the stability of product properties.The polymerizable diphenyl ketone photo initiator that contains at present aided initiating amine there is not yet report at home and abroad.
Summary of the invention: the present invention is from Molecular Structure Design, all be incorporated into polymerizable groups and aided initiating amine groups in the benzophenone structural by molecular designing, because the existence of polymerizable groups, can overcome the toxicity of conventional small molecules light trigger existence and the problem of high mobility, also can improve the stability of material after solidifying; Contain aided initiating group (tertiary amine groups) on this light trigger structure in addition, do not need additionally to add aided initiating again when photocuring, and the process that produces free radical belongs to intramolecular energy and shift, efficiency of initiation is very high.
It is as follows that the present invention contains the chemical structural formula of polymerizable diphenyl ketone photo initiator of aided initiating amine:
R in the formula
1Be selected from H, CH
3R
2Be selected from (CH
2)
n, n=0～2; R
3Be selected from CH
3, C
2H
5
The preparation method of polymerizable diphenyl ketone photo initiator that the present invention contains aided initiating amine is as follows: followingly all represent with mass fraction
(a) 1～1.2 part of tertiary amine that contains phenyl ring slowly is added drop-wise in 1 part of 4-nitrobenzoyl chloride and 1～1.3 part of aluminum trichloride (anhydrous), is being furnished with under the condition of stirring, in ice-water bath, reacted 30～90 minutes; Then reaction solution is moved into the oil bath from ice-water bath, slowly be warmed up between 40～120 ℃, under the condition of vacuum pump negative pressure ventilation, reacted 1～6 hour, reaction is cooled to room temperature after finishing, then reaction solution is poured into 50～100 parts in icing water-cooled hydrochloric acid soln, the precipitating of 10～20wt%, behind suction filtration and recrystallization, obtains containing the substituted benzophenone of nitro and tertiary amine groups;
(b) 1 part of substituted benzophenone that contains nitro and tertiary amine groups at room temperature is dissolved in 40～150 parts the organic solvent, be heated to 60～100 ℃, get in the concentrated hydrochloric acid that 6 parts of tin protochlorides are dissolved in 16 parts, slowly be added drop-wise to the concentrated hydrochloric acid solution of tin protochloride in the reaction system, continue reaction 3～10 hours, behind the cool to room temperature, reaction solution is slowly joined in the dense sodium hydroxide frozen water mixing solutions, behind suction filtration, drying and recrystallization, obtain containing again the substituted benzophenone of primary amine groups and tertiary amine groups;
(c) 1 part of substituted benzophenone that contains primary amine groups and tertiary amine groups is dissolved in 10～60 parts the organic solvent; acrylate chloride or the methacrylic chloride of getting 1～6 part are dissolved in the organic solvent; slowly drip the mixed solution of acrylate chloride or methacrylic chloride under nitrogen protection and the ice bath; at room temperature stirring reaction is 6～24 hours; again reaction solution is poured in the frozen water; the suction filtration precipitation; use respectively the aqueous sodium carbonate of 5wt% and deionized water wash three times, the polymerizable benzophenone of removing to obtain to contain aided initiating amine behind suction filtration, drying and recrystallization is light-initiated.
The tertiary amine that contains phenyl ring among the preparation method of the present invention (a) is selected from DMA, N, N-Diethyl Aniline, N, N-dimethyl benzene methylamine, N, N-phenpromethamine, N, N-diethylbenzene methylamine, N, N-diethylbenzene ethamine.
Organic solvent is pimelinketone, butanone, DMF, N,N-dimethylacetamide or METHYLPYRROLIDONE among the preparation method of the present invention (b); (c) organic solvent is selected from acetone, tetrahydrofuran (THF), butanone, DMF, N,N-dimethylacetamide or METHYLPYRROLIDONE in.
The preparation feedback equation that the present invention contains the polymerizable diphenyl ketone photo initiator of aided initiating amine can be expressed as:
R in the formula
1Be selected from H, CH
3R
2Be selected from (CH
2)
n, n=0～2; R
3Be selected from CH
3, C
2H
5
Among the above-mentioned preparation method (a), it is catalyzer that friedel-crafts acylation adopts aluminum trichloride (anhydrous), and the not extra solvent that uses of reaction, the aniline that contains the tertiary amine structure are not only as reactant but also serve as solvent; Among the preparation method (c), when adopting acrylate chloride or methacrylic chloride, the reaction mechanism that experience is identical.
The preparation method that the present invention contains the polymerizable diphenyl ketone photo initiator of aided initiating amine is incorporated into nitro and tertiary amine groups on the benzophenone molecule by friedel-crafts acylation first, then by reduction reaction nitroreduction is become amino, undersaturated pair of key is incorporated in the molecular structure with amino the reaction by acrylate chloride or methacrylic chloride at last; The polymerizable diphenyl ketone photo initiator that contains aided initiating amine of the present invention's preparation has not only improved the consistency of initiator and resin system, has also greatly reduced toxicity and the transport property of traditional small molecules light trigger.Owing to the aided initiating group, when photocuring, need not add again small molecule amine as aided initiating on the light trigger structure, correspondingly also overcome the defective of small molecules aided initiating.Measure by equation of light scanning calorimeter instrument, this type of light initiation system is causing 1, in the photopolymerization of 6-hexanediyl ester, its peak polymerization rate and resin transformation efficiency significantly improve than benzophenone, so it will have a wide range of applications in the ultraviolet light polymerization field.
Description of drawings:
Fig. 1 is the infrared spectra of 4-methacryloyl amido-4 '-(N, N-dimethyl) aminomethyl benzophenone.
Fig. 2 is that the equation of light of 4-methacryloyl amido-4 '-(N, N-dimethyl) aminomethyl benzophenone and benzophenone initiation 1,6 hexanediol diacrylate is shown the hot comparison diagram of scanning amount.
Concrete embodiment: following embodiment further specifies of the present invention, rather than limits the scope of the invention.
Embodiment 1:
(a) in a 250mL there-necked flask of being furnished with magnetic agitation, add 18.5 gram 4-nitrobenzoyl chlorides and 17.4 gram aluminum trichloride (anhydrous)s, under ice-water bath, in 50 minutes, slowly add 18ml N with constant pressure funnel, N-dimethyl benzene methylamine, continue reaction 60 minutes, then reaction solution is moved into the oil bath from ice-water bath, use the water pump negative pressure ventilation, in 60 minutes, slowly be warmed up to 80 ℃, continue reaction 180 minutes, treat after the reaction that temperature drops to room temperature, reaction solution is poured in the hydrochloric acid soln of 800ml with the water-cooled 3N of ice, stirred, suction filtration, be washed to neutrality, obtain 4-nitro-4 '-(N behind drying and the recrystallization, the N-dimethyl) methylamino-benzophenone 24.4 grams, productive rate 83.6%; Mass spectrum (EIMS): m/e 284; FT-IR (KBr, cm
-1): 1630 (C=O), 2928 (CH
2, CH
3);
1H NMR ([d6] DMSO, 400MHz): δ=8.29-8.28 (2H, phenyl ring), 7.97-7.96 (2H, phenyl ring), 7.68-7.67 (2H, phenyl ring), 7.16-7.15 (2H, phenyl ring), 3.64-3.62 (2H, CH
2), 2.18-2.15 (6H, CH
3);
(b) in a 250mL there-necked flask of being furnished with magnetic agitation; add 28.4 grams to 4-nitro-4 '-(N; the N-dimethyl) methylamino-benzophenone and 60mlTHF; under the high pure nitrogen protection, slowly be heated to backflow, dropwise add the solution of 70 gram (0.4mol) tin protochloride/70mL concentrated hydrochloric acids in one hour.After dripping end, the lower reaction 7 hours that continues refluxes.After reaction system is cooled to room temperature, the reaction solution precipitating in dense sodium hydroxide solution, is obtained amino-4 '-(N, N-dimethyl) the aminomethyl benzophenone of 16.6 gram 4-, productive rate 65.4% behind suction filtration, drying and the recrystallization; Mass spectrum (EIMS): m/e 254; FT-IR (KBr, cm
-1): 3340 (NH
2), 2932 (CH
2, CH
3), 1626 (C=O, Ar-CO-Ar);
1H NMR ([d6] DMSO, 400MHz): δ=7.69-7.67 (2H, phenyl ring), 7.51-7.50 (2H, phenyl ring), 7.17-7.16 (2H, phenyl ring), 6.56-6.55 (2H, phenyl ring), 5.81-5.80 (2H, NH
2), 3.63-3.62 (2H, CH
2), 2.18-2.16 (6H, CH
3);
(c) under the nitrogen protection in the there-necked flask, with 12.70 gram 4-amino-be dissolved in the 40mL dimethyl formamide; Get the 6mL methacrylic chloride and be dissolved in the 10mL dimethyl formamide, and it is moved in the constant pressure funnel, under ice bath, it slowly was added drop-wise to there-necked flask in 1 hour; Stir after 12 hours under the room temperature, reaction solution is poured in the 400mL 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, obtains the yellow 4-methacryloyl amido-4 ' of 14.20 grams-(N through recrystallization, the N-dimethyl) aminomethyl benzophenone, productive rate 88.4%; Mass spectrum (EIMS): m/e254; Fig. 1 is the infrared spectra of 4-methacryloyl amido-4 '-(N, N-dimethyl) aminomethyl benzophenone, FT-IR (KBr, cm
-1): 3338 (NH), 1678 (C=O ,-NH-CO-), 1628 (C=O, Ar-CO-Ar), 1576 (CH=CH);
1H NMR (DMSO, 400MHz): δ=10.50-10.48 (1H, NH), 7.74-7.73 (4H, phenyl ring), (7.67-7.65 2H, phenyl ring), 7.18-7.16 (2H, phenyl ring), (5.79-5.77 2H, C=C), 3.62-3.60 (2H, CH
2), 2.19-2.18 (6H, CH
3), 1.94 (3H, CH
3).Fig. 2 is with 4-methacryloyl amido-4 '-(N, the N-dimethyl) methylamino-benzophenone and benzophenone cause 1, the equation of light of 6-hexanediyl ester is shown the hot comparison diagram of scanning amount, can find out its velocity of initiation close to three times of benzophenone, has excellent initiation performance.
Embodiment 2:
(a) in a 250mL there-necked flask of being furnished with magnetic agitation, add 18.5 gram 4-nitrobenzoyl chlorides and 17.4 gram aluminum trichloride (anhydrous)s, under ice-water bath, in 60 minutes, slowly add 16ml N with constant pressure funnel, accelerine, continue reaction 80 minutes, then reaction solution is moved into the oil bath from ice-water bath, use the water pump negative pressure ventilation, in 60 minutes, slowly be warmed up to 75 ℃, continue reaction 240 minutes, treat after the reaction that temperature drops to room temperature, reaction solution is poured in the hydrochloric acid soln of 800ml with the water-cooled 3N of ice, stir, suction filtration, be washed to neutrality, obtain 4-nitro-4 '-dimethylamino benzophenone 22.1 grams behind drying and the recrystallization, productive rate 82.3%; Mass spectrum (EIMS): m/e 270; FT-IR (KBr, cm
-1): 1636 (C=O), 2930 (CH
2, CH
3);
1H NMR ([d6] DMSO, 400MHz): δ=8.26-8.24 (2H, phenyl ring), 7.95-7.94 (2H, phenyl ring), 7.57-7.56 (2H, phenyl ring), 6.93-6.92 (2H, phenyl ring), 3.02-3.01 (6H, CH
3);
(b) in a 250mL there-necked flask of being furnished with magnetic agitation; add 27.0 grams and compare pyrrolidone to 4-nitro-4 '-dimethylamino benzophenone and 60mlN-methyl-2-; under the high pure nitrogen protection, slowly be heated to backflow, dropwise add the solution of 70 gram (0.4mol) tin protochloride/70mL concentrated hydrochloric acids in one hour.After dripping end, the lower reaction 8 hours that continues refluxes.After reaction system is cooled to room temperature, the reaction solution precipitating in dense sodium hydroxide solution, is obtained amino-the 4 '-dimethylamino benzophenone of 15.9 gram 4-, productive rate 66.5% behind suction filtration, drying and the recrystallization; Mass spectrum (EIMS): m/e 240; FT-IR (KBr, cm
-1): 3342 (NH
2), 2934 (CH
2, CH
3), 1634 (C=O, Ar-CO-Ar);
1H NMR ([d6] DMSO, 400MHz): δ=7.56-7.55 (2H, phenyl ring), 7.50-7.48 (2H, phenyl ring), 6.98-6.96 (2H, phenyl ring), 6.54-6.53 (2H, phenyl ring), 5.86-5.85 (2H, NH
2), 3.02-3.01 (6H, CH
3);
(c) under the nitrogen protection in the there-necked flask, with 12.70 gram 4-amino-be dissolved in the 40mL dimethyl formamide; Get the 5mL acrylate chloride and be dissolved in the 10mL dimethyl formamide, and it is moved in the constant pressure funnel, under ice bath, it slowly was added drop-wise to there-necked flask in 1 hour; Stir after 12 hours under the room temperature, reaction solution is poured in the 400mL 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, obtain the 14.20 4-acrylamido-4 ' that restrains-dimethylamino benzophenone, productive rate 88.4% through recrystallization; Mass spectrum (EIMS): m/e 254; FT-IR (KBr, cm
-1): 3340 (NH), 1660 (C=O ,-NH-CO-), 1620 (C=O, Ar-CO-Ar), 1580 (CH=CH);
1H NMR (DMSO, 400MHz): 5=10.42-10.41 (1H, NH), (7.76-7.74 4H, phenyl ring), 7.58-7.56 (2H, phenyl ring), 6.90-6.88 (2H, phenyl ring), 6.50 (2H, C=C), 6.16-6.15 (1H, C=C), 3.01-2.99 (6H, CH
3).
Claims (4)
1. the polymerizable diphenyl ketone photo initiator that contains aided initiating amine is characterized in that its chemical structural formula is as follows:
R in the formula
1Be selected from H, CH
3R
2Be selected from (CH
2)
n, n=0～2; R
3Be selected from CH
3, C
2H
5
2. the preparation method who contains the polymerizable diphenyl ketone photo initiator of aided initiating amine as claimed in claim 1 below all represents with mass fraction
(a) 1～1.2 part of tertiary amine that contains phenyl ring slowly is added drop-wise in 1 part of 4-nitrobenzoyl chloride and 1～1.3 part of aluminum trichloride (anhydrous), is being furnished with under the condition of stirring, in ice-water bath, reacted 30～90 minutes; Then reaction solution is moved into the oil bath from ice-water bath, slowly be warmed up between 40～120 ℃, under the condition of vacuum pump negative pressure ventilation, reacted 1～6 hour, reaction is cooled to room temperature after finishing, then reaction solution is poured into 50～100 parts in icing water-cooled hydrochloric acid soln, the precipitating of 10～20wt%, behind suction filtration and recrystallization, obtains containing the substituted benzophenone of nitro and tertiary amine groups;
(b) 1 part of substituted benzophenone that contains nitro and tertiary amine groups at room temperature is dissolved in 40～150 parts the organic solvent, be heated to 60～100 ℃, get in the concentrated hydrochloric acid that 6 parts of tin protochlorides are dissolved in 16 parts, slowly be added drop-wise to the concentrated hydrochloric acid solution of tin protochloride in the reaction system, continue reaction 3～10 hours, behind the cool to room temperature, reaction solution is slowly joined in the dense sodium hydroxide frozen water mixing solutions, behind suction filtration, drying and recrystallization, obtain containing again the substituted benzophenone of primary amine groups and tertiary amine groups;
(c) 1 part of substituted benzophenone that contains primary amine groups and tertiary amine groups is dissolved in 10～60 parts the organic solvent; acrylate chloride or the methacrylic chloride of getting 1～6 part are dissolved in the organic solvent; slowly drip the mixed solution of acrylate chloride or methacrylic chloride under nitrogen protection and the ice bath; at room temperature stirring reaction is 6～24 hours; again reaction solution is poured in the frozen water; the suction filtration precipitation; use respectively the aqueous sodium carbonate of 5wt% and deionized water wash three times, behind suction filtration, drying and recrystallization, remove to obtain containing the polymerizable diphenyl ketone photo initiator of aided initiating amine.
3. the preparation method who contains the polymerizable diphenyl ketone photo initiator of aided initiating amine according to claim 2, it is characterized in that the tertiary amine that contains phenyl ring in (a) is selected from N, accelerine, N, N-Diethyl Aniline, N, N-dimethyl benzene methylamine, N, N-phenpromethamine, N, N-diethylbenzene methylamine, N, N-diethylbenzene ethamine.
4. the preparation method who contains the polymerizable diphenyl ketone photo initiator of aided initiating amine according to claim 2, it is characterized in that organic solvent is pimelinketone, butanone, N in (b), dinethylformamide, N,N-dimethylacetamide or METHYLPYRROLIDONE; (c) organic solvent is selected from acetone, tetrahydrofuran (THF), butanone, DMF, N,N-dimethylacetamide or METHYLPYRROLIDONE in.
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| CN103048883B (en) * | 2012-12-05 | 2014-08-13 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing polymerizable photoinitiator |
| CN104119462B (en) * | 2014-07-16 | 2017-06-09 | 长沙新宇高分子科技有限公司 | Diphenyl ketone photo initiator from hydrogen supply and preparation method thereof |
| CN105273108B (en) * | 2015-11-16 | 2017-02-22 | 中山大学 | Benzophenone type hydrogen self-supplying photoinitiator and preparation method and application thereof |
| CN110928139B (en) * | 2018-09-19 | 2023-09-01 | 北京鼎材科技有限公司 | High-efficiency polymerizable photoinitiator for photoresist |
| CN116768742A (en) | 2022-03-07 | 2023-09-19 | 艾坚蒙(安庆)科技发展有限公司 | Benzophenone derivative, preparation method and application thereof |
| CN116813489A (en) * | 2023-06-27 | 2023-09-29 | 深圳清华大学研究院 | Self-hydrogen-supplying polymerizable photoinitiator containing diphenyl ketone structure and preparation method thereof |
| CN118027806B (en) * | 2024-02-01 | 2024-08-09 | 江苏大自然智能家居有限公司 | Water-based UV (ultraviolet) photo-curing coating for wood floor and preparation method thereof |
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| JP2002121307A (en) * | 2000-10-16 | 2002-04-23 | Asahi Glass Co Ltd | Aromatic polyester resin molding with hard coat layer |
| JP2005171028A (en) * | 2003-12-09 | 2005-06-30 | Kyoeisha Chem Co Ltd | Dispersant containing ultraviolet-absorbing copolymer |
| CN1789245A (en) * | 2005-12-22 | 2006-06-21 | 上海交通大学 | Sulfur-containing, polymerizable benzophenone photoinitiator and preparation method thereof |
| CN1844087A (en) * | 2006-03-30 | 2006-10-11 | 上海交通大学 | Polymerisable benzophenone photoinitiator and its preparing method |
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| JP2002121307A (en) * | 2000-10-16 | 2002-04-23 | Asahi Glass Co Ltd | Aromatic polyester resin molding with hard coat layer |
| JP2005171028A (en) * | 2003-12-09 | 2005-06-30 | Kyoeisha Chem Co Ltd | Dispersant containing ultraviolet-absorbing copolymer |
| CN1789245A (en) * | 2005-12-22 | 2006-06-21 | 上海交通大学 | Sulfur-containing, polymerizable benzophenone photoinitiator and preparation method thereof |
| CN1844087A (en) * | 2006-03-30 | 2006-10-11 | 上海交通大学 | Polymerisable benzophenone photoinitiator and its preparing method |
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