CN103709036B - Bifunctional Benzoyl Formic Acid hydroxyketone ester compound and the light trigger containing this compounds - Google Patents

Bifunctional Benzoyl Formic Acid hydroxyketone ester compound and the light trigger containing this compounds Download PDF

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CN103709036B
CN103709036B CN201310648695.XA CN201310648695A CN103709036B CN 103709036 B CN103709036 B CN 103709036B CN 201310648695 A CN201310648695 A CN 201310648695A CN 103709036 B CN103709036 B CN 103709036B
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formic acid
benzoyl
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alpha
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CN103709036A (en
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李钰
武瑞
张齐
马小文
石智铭
毛桂红
杨文杰
赵国锋
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TIANJIN JIURI NEW MATERIALS CO., LTD.
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04—End-capping

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Abstract

The present invention relates to a class novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound and the light trigger containing this compounds, their formula I and II is: wherein: n=0-90, R 1and R 2be selected from hydrogen, C 1-C 12the alkane of straight or branched or aryl, containing C 5-C 12the ring texture of carbocyclic ring; Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl.Compound of the present invention is suitable for the light trigger of light polymerization as alefinically unsaturated compounds or the mixture containing this compounds, and these compounds also can be combined with another light trigger and/or other additive.

Description

Bifunctional Benzoyl Formic Acid hydroxyketone ester compound and the light trigger containing this compounds
Technical field
The present invention describes the preparation method of series of new bifunctional Benzoyl Formic Acid hydroxyl ketone ester class aromatic ketone compounds and this compounds and is used as the light trigger comprising this compounds of alefinically unsaturated compounds system photopolymerization reaction.
Background technology
Benzoyl formate compounds and alpha-hydroxy ketones are the free radical photo-initiations of the known efficient non yellowing of two classes, and there are some compounds to achieve commercialization: methyl benzoylformate (Darocur MBF), hydroxyphenylacetic acids-2-(2-oxygen base-2-phenyl-acetic acid base-oxyethyl group)-ethyl ester and hydroxyphenylacetic acids-2-(2-oxygen base-2-oxyethyl group)-ethyl ester mixture (Irgacure754), 2-hydroxy-2-methyl-1-phenyl-acetone (Darocur1173), 1-hydroxycyclohexyl phenyl ketone (Irgacure184), 2-hydroxyl-4 '-(2-hydroxy ethoxy)-2-methyl phenyl ketone (Irgacure2959).
Irgacure754 be Ciba company on the basis to Benzoyl Formic Acid structural modification, in succession proposing following structure A(CN1157359) and structure B(CN1307207) basis on the light trigger of more excellent performance just released.And the photochemistry study mechanism also comparison system (J.Org.Chem.1997,62:7827, J.Photochem.Photobio.A.Chem.1998,118:75, Macromolecules, 2000,33:4030) to this photoinitiator.
The alpha-hydroxy ketones of simple function group is disclosed (EP0003002) by vapour Bagong department very early, releases again that activity is higher, the better Irgacure127 of performance on this basis.Bifunctional alpha-hydroxy ketones (CN1582267, CN101812142), polyfunctional alpha-alcohol ketone compounds (CN103073658) and macromole class bifunctional alpha-hydroxy ketones (CN102020726), macromole class polyfunctional alpha-alcohol ketone compounds (CN101333263) are also disclosed successively.
Benzoyl formate compounds is obtained two or trifunctional dough Benzoyl Formic Acid hydroxyketone lipoid substance structure C and structure D(CN201010112324.6 by Shenzhen Youwei Chemical Technology Co., Ltd. first together with the structure composite of alpha-hydroxy ketones), this compounds can be used as the light trigger of alefinically unsaturated compounds or the light polymerization containing the mixture of this compounds.
If we find benzoyl formate class chemical combination and alpha-hydroxy ketones to form composite structure; and retain benzoyl formate and the original functional group of alpha-hydroxy ketones in the molecule simultaneously; the compound obtained has good light-cured performance, and this compounds is not also in the news.The shortcoming that this compounds is respective before not only overcoming compound, can also keep after compound even exceeding original activity, and molecular weight obviously increases and overcomes the shortcomings such as small molecule volatile, scent of, transport property after compound, there is the prospect of the light trigger being used as alefinically unsaturated compounds system photopolymerization reaction preferably.
Summary of the invention
The invention provides a kind of novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound and be used as the light trigger comprising this compounds of alefinically unsaturated compounds system photopolymerization reaction, its comprise in following formula I and II compound represented one of at least or the arbitrary composition that forms of following formula I and II compound represented:
Wherein,
n=0-90；
R 1and R 2be selected from hydrogen, C 1-C 12the alkane of straight or branched or aryl, containing C 5-C 12the ring texture of carbocyclic ring;
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl.
Formula I of the present invention novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: n=0-90, R 1and R 2be selected from methyl, cyclohexyl.
Formula I of the present invention novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: n=1-90, R 1and R 2be selected from methyl.
Formula I of the present invention novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: n=1, R 1and R 2be selected from methyl, cyclohexyl.
General formula II of the present invention novel bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: n=0.
Formula I and II provided by the invention can be used as the light trigger of alefinically unsaturated compounds or the mixed light polymerization containing this compounds, and these compounds also can be used in combination with another one or more light trigger.
Formula I and II compound are including, but not limited to following example arrangement:
The invention provides the method for preparation I-II formula compound, can conveniently be prepared by esterification or transesterify, also can be prepared by esterification, acylations, hydrolysis.The many Benzoyl Formic Acid compounds (formula III) that the present invention relates to or benzoyl formate compounds (formula IV) can have been bought from market, also can by the convenient preparation of the method for bibliographical information, as chemical intermediate [J], 2010,04:49-54 disclosed with benzoyl nitrile for raw material, adopt " one kettle way " synthesis, under the vitriol oil and catalyst action, be obtained by reacting intermediate product formula III; Synthesis [J], 2012,44:238-289 disclose with various substituted acetophenone for raw material, react conveniently obtain various benzoyl formate compounds after two bromo-reactions with correspondent alcohol.
Wherein R ' is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl; Ar defines as above-mentioned.
The invention provides the method preparing compound (formula I and II) to obtain with 'alpha '-hydroxylation compound (formula V or VI) esterification or transesterification reaction under acid catalysis with Benzoyl Formic Acid compounds (formula III) or benzoyl formate compounds (formula IV).Compound V part can have been bought from market, also can preparation method disclosed in referenced patent CN201210311169.X.
Wherein n=0-90, Ar, R ', R 1, R 2define as above-mentioned, R ' is preferably methyl, ethyl.
The invention provides the method preparing compound (formula I and II) can also by structure III or IV and hydroxyl; ether (formula VII or VIII) carries out esterification or transesterification reaction obtains ester compound; then react with acyl chlorides (formula Ⅹ) and be then obtained by reacting halobenzoyl carbamate ketone compounds intermediate at carbonyl alpha-position halo or with alpha-halogen acyl chlorides (formula Ⅸ), intermediate is hydrolyzed and can obtains target product.Compound Ⅸ can easily be prepared (Chinese patent CN201110139077.3).
Wherein n=0-90, X=Cl, Br, Ar, R ', R 1, R 2define as above-mentioned, R ' is preferably methyl, ethyl.
The invention provides prepare compound (formula I and II) method can also by structure III or IV and polyoxyethylene glycol (formula Ⅺ) carries out esterification or transesterification reaction obtains ester compound, the hydroxy ester compounds obtained and phosphorus pentachloride or thionyl chloride reacts or to react with methylsulfonyl chloride or react with Tosyl chloride (PTSC) intermediate prepared respectively be E 1, E 2, E 3, be then obtained by reacting ether-ether compounds intermediate with phenol or diphenyl-carbinol, intermediate and alpha-halogen acyl chlorides (formula Ⅸ) are obtained by reacting halobenzoyl carbamate ketone compounds intermediate, and halogenated intermediates is hydrolyzed and can obtains target product.
Wherein n=1-90, Ar, R ', R 1, R 2define as above-mentioned, R ' is preferably methyl, ethyl.As n=0, namely Benzoyl Formic Acid or benzoyl formate and phenol or diphenyl-carbinol carry out esterification or transesterify, obtain ether-ether compounds; Ether-ether compounds reacts with alpha-halogen acyl chlorides (formula Ⅸ) and prepares alpha-halogen midbody compound; Alpha-halogen midbody compound is hydrolyzed in the basic conditions and is obtained by reacting target product.
According to the present invention, at alefinically unsaturated compounds or comprise in the photopolymerization of mixture of this compounds, formula I and II compound can be used as light trigger.Can be used alone one or more to be also combined with other kind of photoinitiator and (or) other additive.
The present invention relates to photopolymerisable compositions, said composition comprises:
The unsaturated photopolymerizable compound of (a) at least one olefinic and,
(b) as light trigger, at least one formula I or II compound,
Except component (b), composition also can comprise other light trigger and (or) other additive.
Specific embodiment:
In order to be illustrated more clearly in the present invention, nonlimiting examples is hereinafter taked to further illustrate.
Embodiment 1:4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl manthanoate (compound 1)
By 2-hydroxy-2-methyl-1-(4-hydroxy phenyl)-1-acetone (22.5g, 0.125mol) be dissolved in 50ml methylene dichloride, add triethylamine (19.0g, 0.188mol), under agitation, be heated to 60 DEG C, drip methyl benzoylformate (20.5g, 0.125mol), drip complete insulation reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be down to room temperature, with equal-volume washing, dry, precipitation, after gained residue from dichloromethane dissolves, be that eluent is purified and obtained light yellow product by petrol ether/ethyl acetate on a silica gel column.
Ultimate analysis: molecular formula C 18h 16o 5
Theoretical content: carbon element content 69.22%; Protium content 5.16%
Actual measurement content: carbon element content 69.11%; Protium content 5.18%
Embodiment 2:4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl manthanoate (compound 1)
1) preparation of benzoyl formyl chloride
Join in reaction vessel by benzoyl formic acid (30.0g, 0.2mol) and 50ml thionyl chloride, stirring and refluxing is reacted, and reclaims excessive thionyl chloride after 2h, and remaining raffinate can be proposed also can not purify directly by underpressure distillation, and next step reacts.
2) preparation of benzoyl formic acid phenyl ester
The above-mentioned benzoyl formyl chloride without purification prepared is dissolved in the methylene dichloride of 120ml, adds phenol (20.6g, 0.22mol) and 30ml triethylamine stirring reaction at ambient temperature, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, add equal-volume water washing, separate organic phase, with anhydrous sodium sulfate drying, precipitation, underpressure distillation (3mmHg), cut when collecting 145 DEG C, obtain 40.7g benzoyl formic acid phenyl ester, yield 90%.
3) 4-(2-chloro-2-methyl propionyl) preparation of phenyl benzoyl manthanoate
100mL methylene dichloride ice-water bath is cooled to 5 DEG C, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 20.6g(0.091mol) benzoyl formic acid phenyl ester (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 DEG C, stir 3h.Reaction solution is cooled to 20 DEG C, joins in the technical hydrochloric acid of 120mL10% and stir 1h.Leave standstill, branch vibration layer, organic phase washed with water is extremely neutral, anhydrous sodium sulfate drying, and precipitation, obtains 4-(2-chloro-2-methyl propionyl) phenyl benzoyl manthanoate 27.2g, yield 90.3%, purity 95.5%.
4) 4-(2-hydroxy-2-methyl propionyl) preparation of phenyl benzoyl manthanoate
By 16.5g(0.05mol) 4-(2-chloro-2-methyl propionyl) phenyl benzoyl manthanoate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep mixture temperature 5 DEG C, 0.2g tertiary butyl brometo de amonio is added again under agitation condition, 9.5g sodium bicarbonate, 60ml water, then 60 DEG C are warmed up to, about insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, room temperature is down to after reacting completely, separate acetonitrile phase, washing precipitation, after gained residue from dichloromethane dissolves, be that eluent is purified and obtained light yellow product by petrol ether/ethyl acetate on a silica gel column.
Ultimate analysis: molecular formula C 18h 16o 5
Theoretical content: carbon element content 69.22%; Protium content 5.16%
Actual measurement content: carbon element content 69.41%; Protium content 5.23%
Embodiment 3:2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate (compound 2)
Methyl benzoylformate (16.4g, 0.1mol) is dissolved in 50ml toluene, adds pyridine (15.8g, 0.2mol), under agitation, 70 DEG C are heated to, add Irgacure2959(22.4g, 0.1mol), drip complete about insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, with equal-volume washing, dry, precipitation, after gained residue from dichloromethane dissolves, be that eluent is purified and obtained light yellow product by petrol ether/ethyl acetate on a silica gel column.
Ultimate analysis: molecular formula C 20h 20o 6
Theoretical content: carbon element content 67.41%; Protium content 5.66%
Actual measurement content: carbon element content 67.23%; Protium content 5.60%
Embodiment 4:2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate (compound 2)
1) preparation of 2-phenoxyethyl alcohol
By phenol (94.0g, 1.0mol), ethylene chlorhydrin (322.0g, 4.0mol), salt of wormwood (276.0g, 2.0mol) join in 2000ml reaction flask with 800ml ethanol, stir and be heated to 70 DEG C, about insulation reaction 16h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, residue 2000ml dchloromethane, 1000ml washes, with anhydrous sodium sulfate drying, precipitation, underpressure distillation is purified, collect 100-105 DEG C (4mmHg), obtain colorless oil 127.0g, yield 92.0%, purity 99.2%.
2) preparation of 2-Phenoxyethyl benzoyl formiate
By methyl benzoylformate (16.4g, 0.1mol), 2-phenoxyethyl alcohol (13.8g, 0.1mol), 0.26g Lithium Acetate and 50ml methylene dichloride join in 250ml reaction flask, be stirred and heated to 60 DEG C, insulation reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, slough the methyl alcohol of solvent and reaction generation, in residue, add 50ml water, extract 2 times with 100ml toluene, merge organic phase, with anhydrous sodium sulfate drying, precipitation both obtained product, confirmed structure by NMR spectrogram and HPLC.
3) 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate
100mL methylene dichloride ice-water bath is cooled to 5 DEG C, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 24.6g(0.091mol) 2-Phenoxyethyl benzoyl formiate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 DEG C, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution be cooled to 20 DEG C, join in the technical hydrochloric acid of 120mL10% and stir 1h.Leave standstill, branch vibration layer, organic phase is with being washed with water to neutrality respectively, and anhydrous sodium sulfate drying, precipitation, obtains 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) ethylbenzoyl manthanoate, by NMR spectrogram and HPLC confirmation structure.
4) 2-(4-(2-hydroxy-2-methyl propionyl) phenoxy group) preparation of ethylbenzoyl manthanoate
By 18.7g(0.05mol) 2-(4-(2-chloro-2-methyl propionyl) phenoxy group) ethylbenzoyl manthanoate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep mixture temperature 5 DEG C, 0.2g tertiary butyl brometo de amonio is added again under agitation condition, 9.5g sodium bicarbonate, 60ml water, then 60 DEG C are warmed up to, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, room temperature is down to after reacting completely, separate acetonitrile phase, washing precipitation, after gained residue from dichloromethane dissolves, be that eluent is purified and obtained light yellow product by petrol ether/ethyl acetate on a silica gel column, structure is confirmed by NMR spectrogram and HPLC.
Ultimate analysis: molecular formula C 20h 20o 6
Theoretical content: carbon element content 67.41%; Protium content 5.66%
Actual measurement content: carbon element content 67.37%; Protium content 5.69%
Embodiment 5:
the preparation of n=2-90
1) be prepared by raw material with Tetraglycol 99
By Tetraglycol 99 (38.8g, 0.2mol) be dissolved in 80ml pyridine, stir and be cooled to 10 DEG C, slowly drip benzoyl formyl chloride (33.8g, 0.2mol), 40min drips complete, and then mixing solutions rises to room temperature, at room temperature stirring reaction about 4h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution is poured in 200g frozen water, use CHCl 3(3*100ml) extract, merge organic phase, wash with the sodium hydrogen carbonate solution that HCl and 100ml of 100ml6mol/L is saturated respectively, organic phase anhydrous sodium sulfate drying, precipitation, after gained residue from dichloromethane dissolves, is that eluent is purified and obtained colorless oil product 43.1g by ethyl acetate on a silica gel column, this product confirms structure by NMR spectrogram and HPLC, and structure is
Get above-mentioned obtained (2-hydroxybenzoyl) manthanoate (16.3g, 0.05mol) be dissolved in 30ml methylene dichloride, drip phosphorus trichloride (2.3g, 0.02mol), 40 DEG C are stirred and heated to, about insulation reaction 3h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, with the extraction of 3*20ml toluene, precipitation obtains chlorobenzoyl manthanoate 16.0g(liquid content 93%).
By phenol (16.9g, 0.18mol), chlorobenzoyl manthanoate (20.3g, 0.046mol), salt of wormwood (49.8g, 0.36mol) join in 250ml reaction flask with 120ml ethanol, stir and be heated to 70 DEG C, about insulation reaction 16h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, residue 120ml dchloromethane, 120ml washes, and with anhydrous sodium sulfate drying, precipitation obtains product 17.6g, this product confirms structure by NMR spectrogram and HPLC, and structure is
120mL methylene dichloride ice-water bath is cooled to 5 DEG C, add 7.6g(0.057mol) aluminum chloride, slowly add 7.3g(0.052mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 17.3g(0.043mol) benzoyl formiate (being dissolved in the 20ml methylene dichloride) 30min of above-mentioned preparation.Be heated to 50 DEG C, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution be cooled to 20 DEG C, join in the technical hydrochloric acid of 100mL10% and stir 1h.Leave standstill, branch vibration layer, organic phase washed with water is to neutral, and anhydrous sodium sulfate drying, precipitation, obtains product 20.7g, and this product confirms structure by NMR spectrogram and HPLC, and structure is
By 19.8g(0.039mol) above-mentioned obtained alpha-chloro product, 5.1g sodium formiate and 60ml acetonitrile join in reaction vessel, keep mixture temperature 5 DEG C, add 0.2g tertiary butyl brometo de amonio, 7.4g sodium bicarbonate, 50ml water under agitation condition again, be then warmed up to 60 DEG C, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, be down to room temperature after reacting completely, separate acetonitrile phase, washing precipitation, obtain light yellow product, structure is that this product confirms structure by NMR spectrogram and HPLC.
Ultimate analysis: molecular formula C 26h 32o 9
Theoretical content: carbon element content 63.92%; Protium content 6.60%
Actual measurement content: carbon element content 63.89%; Protium content 6.63%
Structure is: (compound 3).
2) be prepared by raw material with Polyethylene Glycol-600
By Polyethylene Glycol-600 (60g, 0.1mol) be dissolved in 40ml pyridine, stir and be cooled to 10 DEG C, slowly drip benzoyl formyl chloride (16.9g, 0.1mol), 40min drips complete, and then mixing solutions rises to room temperature, at room temperature stirring reaction about 4h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution is poured in 100g frozen water, use CHCl 3(3*50ml) extract, merge organic phase, wash with the sodium hydrogen carbonate solution that HCl and 50ml of 80ml6mol/L is saturated respectively, organic phase anhydrous sodium sulfate drying, precipitation, obtain colorless oil product 43.9g, the molecular-weight average of this product is 732, and structure is
N(mean value)=13.2
Get above-mentioned obtained (2-hydroxybenzoyl) manthanoate (22.0g, 0.03mol) be dissolved in 30ml methylene dichloride, drip phosphorus trichloride (1.4g, 0.01mol), 40 DEG C are stirred and heated to, about insulation reaction 3h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, with the extraction of 3*20ml toluene, precipitation obtains chlorobenzoyl manthanoate 20.3g.
By phenol (10.3g, 0.11mol), above-mentioned obtained chlorobenzoyl manthanoate (20.3g, 0.027mol), salt of wormwood (30.4g, 0.22mol) join in 250ml reaction flask with 60ml ethanol, stir and be heated to 70 DEG C, about insulation reaction 16h, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, be cooled to room temperature, filter unreacted salt of wormwood, filtrate precipitation, residue 60ml dchloromethane, 60ml washes, and with anhydrous sodium sulfate drying, precipitation obtains product 20.1g, product molecular-weight average is 808, and structure is
N(mean value)=13.2
60mL methylene dichloride ice-water bath is cooled to 5 DEG C, add 4.5g(0.034mol) aluminum chloride, slowly add 4.4g(0.031mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 20.1g(0.025mol) 2-Phenoxyethyl benzoyl formiate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 DEG C, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution be cooled to 20 DEG C, join in the technical hydrochloric acid of 70mL10% and stir 1h.Leave standstill, branch vibration layer, organic phase washed with water is to neutral, and anhydrous sodium sulfate drying, precipitation, obtains product 21.5g, and product molecular-weight average is 912.5, and structure is
N(mean value)=13.2
By 20.1g(0.022mol) above-mentioned obtained alpha-chloro product, 2.9g sodium formiate and 40ml acetonitrile join in reaction vessel, keep mixture temperature 5 DEG C, add 0.2g tertiary butyl brometo de amonio, 4.2g sodium bicarbonate, 35ml water under agitation condition again, be then warmed up to 60 DEG C, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, be down to room temperature after reacting completely, separate acetonitrile phase, washing precipitation, obtain light yellow product, product molecular-weight average is 894, and structure is
N(mean value)=13.2 (compound 4).
Embodiment 6: the preparation of two [4-(2-hydroxy-2-methyl propionyl) phenyl] methylbenzoyl formate (compound 5)
1) preparation of diphenyl methyl benzoyl formiate
Benzoyl formic acid formyl chloride (the 33.7g prepared by embodiment 2 method, 0.2mol) be dissolved in the methylene dichloride of 120ml, add diphenyl-carbinol (40.5g, 0.22mol) and 30ml triethylamine stirring reaction at ambient temperature, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, add equal-volume water washing, separate organic phase, with anhydrous sodium sulfate drying, precipitation both obtained product, confirmed structure by NMR spectrogram and HPLC.
2) preparation of two [4-(2-chloro-2-methyl propionyl) phenyl] methylbenzoyl formate
100mL methylene dichloride ice-water bath is cooled to 5 DEG C, add 16.8g(0.126mol) aluminum chloride, slowly add 16.0g(0.113mol) 2-chloro-2-methyl propionyl chloride 20min, slowly drip 28.8g(0.091mol) diphenyl methyl-2-oxygen base benzoyl formiate (being dissolved in 20ml methylene dichloride) 30min.Be heated to 50 DEG C, stirring reaction, with thin-layer chromatography or liquid phase monitoring reaction, after reacting completely, reaction solution be cooled to 20 DEG C, join in the technical hydrochloric acid of 120mL10% and stir 1h.Leave standstill, branch vibration layer, organic phase washed with water is to neutral, and anhydrous sodium sulfate drying, precipitation, obtains two [4-(2-chloro-2-methyl propionyl) phenyl] methylbenzoyl formate, confirm structure by NMR spectrogram and HPLC.
3) preparation of two [4-(2-hydroxy-2-methyl propionyl) phenyl] methylbenzoyl formate
By 26.3g(0.05mol) two [4-(2-chloro-2-methyl propionyl) phenyl] methylbenzoyl formate, 6.5g sodium formiate and 70ml acetonitrile join in reaction vessel, keep mixture temperature 5 DEG C, 0.2g tertiary butyl brometo de amonio is added again under agitation condition, 9.5g sodium bicarbonate, 60ml water, then 60 DEG C are warmed up to, insulation reaction 20h, with thin-layer chromatography or liquid phase monitoring reaction, room temperature is down to after reacting completely, separate acetonitrile phase, washing precipitation, after gained residue from dichloromethane dissolves, be that eluent is purified and obtained light yellow product by petrol ether/ethyl acetate on a silica gel column, structure is confirmed by NMR spectrogram and HPLC.
Ultimate analysis: molecular formula C 29h 28o 7
Theoretical content: carbon element content 71.30%; Protium content 5.78%
Actual measurement content: carbon element content 71.37%; Protium content 5.70%
Embodiment 7-11:
The following preparation of preparation embodiment 7-11:
The polyacrylic ester of component A:11.38 part hydroxyl is 70% in butylacetate
21.23 parts of pentaerythritol triacrylates are 75% in butylacetate
0.55 part of trolamine
32.03 part methyl alcohol
B component: containing the urethane acrylate (providing with in scale 1) of isocyanate groups
The light trigger will tested with the concentration shown in table 1 under stirring joins component A, then adds B component, after mixing, with squeegee film on a glass, then steams solvent under room temperature, and the solidification of film is irradiated with standard mercury(vapor)lamp.Get 20cm 2above-mentionedly be prepared into sheet glass, put into watch-glass, add 1 gram of gac, put into the baking oven heating 20 minutes of 120 DEG C, cooling, removing sample, extract gac with tetrahydrofuran (THF), the light trigger be prepared into by the quantitative embodiment of high performance liquid chromatography, the results are shown in Table 1.
The volatile research of light trigger prepared by table 1 embodiment
Embodiment 7 8 9 10 11
Component A 65.19 65.19 65.19 65.19 65.19
B component 31.07 31.07 31.07 31.07 31.07
Compound 1 light trigger 3.00
Compound 2 light trigger 1.55
Compound 3 light trigger 2.05
Compound 4 light trigger 2.00
Compound 5 light trigger 1.66
Volatility (mg/m 2） 0.01 0 0 0 0
The result of table 1 shows that all samples light trigger in heat-processed seldom or is not overflowed from preparation.
The light trigger that method prepares above proves through photocuring reaction experiment; all there is excellent Photoinitiation Property; but also there is the advantages such as low volatility, low migration, low smell, non yellowing, can be applied in the industrial production as a class novel bifunctional Benzoyl Formic Acid hydroxyketone ester lightlike initiating agent.

Claims (10)

1. a bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: logical formula I is expressed as:
Wherein:
n＝0，1；
R 1and R 2be selected from hydrogen, C 1-C 12the alkane of straight or branched, C 5-C 12carbocyclic ring structure;
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl;
With following structural compounds
2. a bifunctional Benzoyl Formic Acid hydroxyketone Ester, is characterized in that
3. a bifunctional Benzoyl Formic Acid hydroxyketone ester compound, is characterized in that: logical formula II is expressed as:
Wherein:
n＝0；
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl.
4. bifunctional Benzoyl Formic Acid hydroxyketone ester compound according to claim 1, is characterized in that: n=0, R 1and R 2be selected from methyl, cyclohexyl.
5. bifunctional Benzoyl Formic Acid hydroxyketone ester compound according to claim 1, is characterized in that: n=1, R 1and R 2be selected from methyl, cyclohexyl.
6. bifunctional Benzoyl Formic Acid hydroxyketone ester compound according to claim 1, is characterized in that: n=1, R 1and R 2be selected from methyl.
7. prepare a method for claim 1 or 3 bifunctional Benzoyl Formic Acid hydroxyketone ester compound, the method: directly by Benzoyl Formic Acid or benzoyl formate and formula V or VI carries out esterification or prepared by transesterification reaction,
Wherein:
n＝0，1；
R 1and R 2be selected from hydrogen, C 1-C 12the alkane of straight or branched or aryl, C 5-C 12carbocyclic ring structure;
Or n=4;
R 1and R 2all be selected from methyl;
n＝0；
Ar is selected from phenyl ring, substituted benzene ring, and wherein substituting group is herein one or more R, OR, halogen atom, and R is selected from C 1-C 12the alkyl of straight or branched, phenyl ring or benzyl.
8. prepare a method for claim 1 or 3 bifunctional Benzoyl Formic Acid hydroxyketone ester compound, the method comprises the following steps:
A () is by Benzoyl Formic Acid or benzoyl formate and formula Ⅺ carries out esterification or transesterification reaction prepares hydroxy ester;
B () obtains hydroxy ester and phosphorus trichloride or sulfur oxychloride and reacts, reacts or react with Tosyl chloride prepare chloro ester or sulphonate with methylsulfonyl chloride, then react with phenol or diphenyl-carbinol and prepare ether-ether compounds;
C () ether-ether compounds obtained above reacts with alpha-halogen acyl chlorides (formula Ⅸ) and prepares alpha-halogen midbody compound;
D () alpha-halogen midbody compound is hydrolyzed in the basic conditions and is obtained by reacting target product;
As n=0, carry out esterification or transesterify by Benzoyl Formic Acid or benzoyl formate and phenol or diphenyl-carbinol, obtain ether-ether compounds; Ether-ether compounds reacts with alpha-halogen acyl chlorides (formula Ⅸ) and prepares alpha-halogen midbody compound; Alpha-halogen midbody compound is hydrolyzed in the basic conditions and is obtained by reacting target product.
9. prepare a method for claim 1 or 3 bifunctional Benzoyl Formic Acid hydroxyketone ester compound, the method comprises the following steps:
A () is carried out etherification reaction by phenol or diphenyl-carbinol and formula Ⅺ and is obtained hydroxy ethers compounds;
B () Benzoyl Formic Acid or benzoyl formate and hydroxy ethers compounds carry out esterification or transesterification reaction, obtain ether-ether compounds;
C () ether-ether compounds and alpha-halogen acyl chlorides (formula Ⅸ) react and prepare alpha-halogen midbody compound;
D () alpha-halogen midbody compound is hydrolyzed in the basic conditions and is obtained by reacting target product;
As n=0, directly carry out esterification or transesterify by phenol or diphenyl-carbinol and Benzoyl Formic Acid or benzoyl formate, obtain ether-ether compounds; Ether-ether compounds and alpha-halogen acyl chlorides (formula Ⅸ) react and prepare alpha-halogen midbody compound; Last being hydrolyzed in the basic conditions is obtained by reacting target product;
Its Chinese style Ⅺ, formula Ⅸ such as claim 8 define.
10. a photopolymerisable compositions, comprising:
The unsaturated photopolymerizable compound of (a) at least one olefinic;
(b) as photoinitiator at least one claim 1 described in compound described in compound, material described in claim 2 or claim 3.
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