CN100447127C - Single-component hydrogen-capture-type light initiator and its preparing method and use - Google Patents
Single-component hydrogen-capture-type light initiator and its preparing method and use Download PDFInfo
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- CN100447127C CN100447127C CNB2007100514838A CN200710051483A CN100447127C CN 100447127 C CN100447127 C CN 100447127C CN B2007100514838 A CNB2007100514838 A CN B2007100514838A CN 200710051483 A CN200710051483 A CN 200710051483A CN 100447127 C CN100447127 C CN 100447127C
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Abstract
The invention discloses a compound with general formula as (I) and (II) and making method and application, wherein R and R' can be selected from hydrogen, alkyl and alkoxy; A is -[(CH2)nO]-, -[(CH2)nCOO]- or -[(CH2)nNH]-; n is 0-3; R1 and R2 is C1-18 aklyl, C1-18 hydroxyalkyl, phenyl, benzyl and N, N-dimethyl propyl.
Description
Technical field
The present invention relates to mono-stripped hydrogen light initiating agent and its production and use, belong to field of light-sensitive high molecular materials.
Background technology
UV-curing technology has a wide range of applications at aspects such as coating, tackiness agent, printing-ink, photoengraving and biomaterials as a kind of novel green technology.The ultraviolet light polymerization system generally comprises following three kinds of main ingredients: oligopolymer (or claiming prepolymer, resin), give material with the basic physical chemical property; Monomer claims reactive thinner again, is mainly used in the viscosity of regulation system, but also influential to solidification rate and material property; Light trigger, but be used to produce the free radical or the ion of initiated polymerization.
Light trigger (photoinitiator) is the key components of ultraviolet light polymerization system, and can it be directly connected to formula system oligopolymer and thinner when rayed and be transformed into solid-state rapidly by liquid state.And light trigger requires to possess good solidification rate, and the surface of good curing activity is low smelly, low-yellowing and good characteristics such as solubleness.In addition, along with the human consumer to the responsive day by day of chemical pollution in the food with to the observing of the relevant food processing method that may formulate and optimize future, light trigger is after solidification process is finished, its transport property and the tendency of being captured should reduce as far as possible.
Benzophenone, because it is inexpensive, surface cure is good, is difficult for yellowing and solubility property is good, becomes in the ultraviolet light polymerization system one of the most widely used light trigger.But its molecular weight is low, and smell is strong, and moves to the surface extremely easily from solidifying product, and its Application Areas is restricted, particularly aspect the wrapping material of Food Contact.
Benzophenone migration or tendency of being captured from solidifying product is more serious.Because itself and amine coinitiator generation dimolecular reaction, produce two free radicals, wherein the amine alkyl diradical has higher activity, can be by being attached in the solidifying product with oligopolymer or the reaction of monomeric (methyl) acrylic double bond, and the carbonyl free radical that is produced by benzophenone is lower with the reactive behavior of (methyl) acrylic double bond, in termination reaction, have an effect, perhaps become again to ketone and remain in the solidifying product by oxidation again.Therefore, for having good reaction activity, the surface of good ability to cure is hanged down migration at present, and being difficult for the good benzophenone surrogate of yellowing and solubility property has demand widely.
The present invention is combined in benzophenone and amine in the molecule by chemical process, has made a class mono-stripped hydrogen light initiating agent, can significantly improve its transport property and smell problem.
Summary of the invention
Problem to be solved by this invention provides a kind of compound and its production and use, the gained compound is used for ultraviolet light polymerization as the mono-stripped hydrogen light initiating agent of ultraviolet light polymerization not only to be had good reaction activity, surface of good ability to cure, good solubility energy, is difficult for yellowing, and low migration, low smell.
Technical scheme provided by the invention is: a kind of compound, its structural formula are as (I) or (II):
A represents Shi-[(CH
2)
nO]-,-[(CH
2)
nCOO]-or-[(CH
2)
nNH]-group, wherein n=0～3;
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl, C
1-18Alkoxyl group;
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl, N, N-dimethyl propyl.
The present invention also provides the preparation method of above-mentioned mono-stripped hydrogen light initiating agent:
With 1 molfraction 4-hydroxyalkyl benzophenone, the triethylamine of 4-carboxyalkyl benzophenone or 4-amine alkyl diphenyl ketone and 1-2 molfraction at room temperature is dissolved in and gets solution A in the organic solvent, then solution A is placed ice-water bath, stirring makes its temperature reduce to 0-5 ℃; The acrylate chloride of 1-2 molfraction at room temperature is dissolved in organic solvent gets solution B, with the speed of per second 0.2-0.6mL, solution B is added drop-wise in the solution A of stirring then, after dropwising, continued stirring reaction 4-12 hour; Remove by filter the triethylamine hydrochloride white solid of generation, washing (as the aqueous sodium hydroxide solution of using 5%-10% respectively and deionized water wash reaction soln 1-3 time), dry (as using the anhydrous sodium sulfate drying reaction soln), reduce pressure and remove solvent in the reaction soln, obtain 4-hydroxyalkyl benzophenone, 4-carboxyalkyl benzophenone or the 4-amine alkyl diphenyl ketone of acroleic acid esterification;
4-hydroxyalkyl benzophenone, 4-carboxyalkyl benzophenone or the 4-amine alkyl diphenyl ketone of the acroleic acid esterification that 1 molfraction step a is obtained at room temperature be dissolved in the protonic solvent solution C; At room temperature be dissolved in the secondary amine of 1 molfraction or the primary amine of 0.5 molfraction in the protonic solvent then, and at room temperature be added drop-wise in the solution C of stirring with the speed of per second 0.2-0.6mL, carry out Michael reaction, after dropwising, continued stirring reaction 0.5-5 hour; Protonic solvent is removed in underpressure distillation, handles by column chromatography then, obtains formula (I) or (II) described compound.
The preparation of this photoinitiator is all carried out under with the situation of solvent.For acroleic acid esterification reaction, the character of solvent is not key point to the present invention, as long as it is to reagent or reaction and have no adverse effects.The solvent that this step reaction is fit to use comprises: methylene dichloride, chloroform, benzene, toluene or dimethylbenzene etc.For Michael reaction, need to use protonic solvent, because it has katalysis to reaction, suitable solvent comprises: methyl alcohol or ethanol etc.
The present invention also provides a kind of compositions of ultraviolet curing type, comprising:
(a) polymerisable composition comprises the unsaturated light reactive resin and the reactive thinner that contain at least one ethylenic; Reactive thinner is simple function group, bifunctional or multi-functional acrylate's monomer or methacrylate monomer;
(b) structural formula is as (I) or (II) described compound.
Described unsaturated light reactive resin is epoxy acrylic resin, epoxy methacrylic resin, polyester acrylic resin, polyester methacrylic resin, polyurethane acrylic resin, urethane methacrylic resin, polyacrylic ester acrylic resin, polyacrylic ester methacrylic resin, polyoxyalkylene acrylate resin or polyethers methacrylic resin.
Mono-stripped hydrogen light initiating agent of the present invention is combined in benzophenone and amine in the molecule by chemical process, and the product that obtains is a liquid, and solubility property is good in the ultraviolet light polymerization system.Simultaneously, in the ultraviolet light polymerization process, the amine alkyl diradical has higher activity, can be by being attached in the solidifying product with oligopolymer or the reaction of monomeric (methyl) acrylic double bond, because benzophenone and amine connect into a molecule, so benzophenone also has been incorporated in the solidifying product, thereby reduced the transport property of benzophenone effectively.Its preparation cost is low, easy and simple to handle, the yield height of product, has good reaction activity, surface of good ability to cure, good solubility energy, is difficult for yellowing, and hang down migration, low smell.Can directly replace benzophenone to use, and performance be better than benzophenone, has a wide range of applications in the ultraviolet light polymerization field as light trigger.
Embodiment
Following embodiment describes the present invention in detail, but does not limit the scope of the invention.
Synthetic embodiment:
Embodiment 1:
0.1mol 4-dihydroxy benaophenonel and 0.11mol triethylamine at room temperature are dissolved in the 100mL methylene dichloride, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 10wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-dihydroxy benaophenonel of acroleic acid esterification.
The 4-dihydroxy benaophenonel of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.05mol diethylamine is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the diethylamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-dihydroxy benaophenonel solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product I II.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.33(CH
3)；2.74，3.62(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 2:
0.05mol 4-dihydroxy benaophenonel and 0.055mol triethylamine at room temperature are dissolved in the 50mL toluene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.055mol acrylate chloride at room temperature is dissolved in 30mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.3mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 6wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-dihydroxy benaophenonel of acroleic acid esterification.
The 4-dihydroxy benaophenonel of 0.03mol aforesaid propylene acid estersization at room temperature is dissolved in the 60mL ethanol; Then the 0.03mol diethanolamine is dissolved in 30mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the diethanolamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-dihydroxy benaophenonel solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.4mL.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product I V.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.88，3.64，3.97(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 3:
0.05mol 4-dihydroxy benaophenonel and 0.055mol triethylamine at room temperature are dissolved in the 50mL methylene dichloride, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.055mol acrylate chloride at room temperature is dissolved in the 30mL methylene dichloride, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.6mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 10wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-dihydroxy benaophenonel of acroleic acid esterification.
The 4-dihydroxy benaophenonel of 0.03mol aforesaid propylene acid estersization at room temperature is dissolved in the 60mL methyl alcohol; Then the 0.03mol piperidines is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the piperidine solution in the constant pressure funnel is added drop-wise to slowly in the 4-dihydroxy benaophenonel solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 2 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product V.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.83，2.68，3.64(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 4:
0.05mol 4-methylol benzophenone and 0.055mol triethylamine at room temperature are dissolved in the 50mL methylene dichloride, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.055mol acrylate chloride at room temperature is dissolved in the 30mL methylene dichloride, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 9wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-methylol benzophenone of acroleic acid esterification.
The 4-methylol benzophenone of 0.03mol aforesaid propylene acid estersization at room temperature is dissolved in the 60mL methyl alcohol; Then the 0.03mol morpholine is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the morpholine solution in the constant pressure funnel is added drop-wise to slowly in the 4-methylol benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 2 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product VI.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.70，3.68，4.01，5.67(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 5:
0.1mol 4-hydroxypropyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL methylene dichloride, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.3mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 10wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-hydroxypropyl benzophenone of acroleic acid esterification.
The 4-hydroxypropyl benzophenone of 0.06mol aforesaid propylene acid estersization at room temperature is dissolved in the 100mL methyl alcohol; Then the 0.03mol n-Butyl Amine 99 is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the n-Butyl Amine 99 solution in the constant pressure funnel is added drop-wise to slowly in the 4-hydroxypropyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.3mL.After dropwising, continued stirring reaction 2 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow viscous liquid product VII.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.40(CH
3)；1.67，1.73，2.24，2.69，2.88，3.65，4.43(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 6:
0.1mol 4-amido-4 '-methyldiphenyl ketone and 0.11mol triethylamine at room temperature are dissolved in the 100mL methylene dichloride, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 8wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains 4-amido-the 4 '-methyldiphenyl ketone of acroleic acid esterification.
4-amido-the 4 '-methyldiphenyl ketone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.05mol Diisopropylamine is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the Diisopropylamine solution in the constant pressure funnel is added drop-wise to slowly in 4-amido-the 4 '-methyldiphenyl ketone solution of the acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.3mL.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product VIII.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.38，2.68(CH
3)；3.64(CH
2)；3.31(CH)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 7:
0.1mol 4-amido-4 '-octadecyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.4mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 7wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains 4-amido-the 4 '-octadecyl benzophenone of acroleic acid esterification.
4-amido-the 4 '-octadecyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL methyl alcohol; Then the 0.05mol dicyclohexyl amine is dissolved in 50mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the dicyclohexyl amine solution in the constant pressure funnel is added drop-wise to slowly in 4-amido-the 4 '-octadecyl benzophenone solution of the acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 2 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow viscous liquid product I X.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.66(CH
3)；1.62，1.66，1.71-1.96，2.88，3.83(CH
2)；2.91(CH)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 8:
0.1mol 4-amine ethyl-4 '-ninth of the ten Heavenly Stems oxygen base benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stir and make its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.5mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 8wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-amine ethyl-4 ' of acroleic acid esterification-ninth of the ten Heavenly Stems oxygen base benzophenone.
The 4-amine ethyl-4 ' of 0.05mol aforesaid propylene acid estersization-ninth of the ten Heavenly Stems oxygen base benzophenone at room temperature is dissolved in the 80mL methyl alcohol; Then 0.05mol N-Mono Methyl Ethanol Amine is dissolved in 50mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the N-methyl ethanol amine aqueous solution in the constant pressure funnel is added drop-wise in the 4-amine ethyl-4 ' of the acroleic acid esterification of the stirring-ninth of the ten Heavenly Stems oxygen base benzophenone solution slowly, carries out Michael reaction with the speed of per second 0.5mL.After dropwising, continued stirring reaction 2 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains lurid liquid product X.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.67，2.61(CH
3)；1.62，1.66，1.71-1.96，2.88，3.15，3.58，3.86，3.96(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 9:
0.1mol 4-aminobenzophenone and 0.1lmol triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL benzene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.4mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 7wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-aminobenzophenone of acroleic acid esterification.
The 4-aminobenzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.05mol pentanoic is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the diphenylamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-aminobenzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.3mL.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow viscous liquid product XI.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：4.34(CH
2)；6.43，6.58，7.04，7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 10:
0.1mol 4-aminobenzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL benzene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 12 hours with the speed of per second 0.5mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 9wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-aminobenzophenone of acroleic acid esterification.
The 4-aminobenzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.025mol hexahydroaniline is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the hexahydroaniline solution in the constant pressure funnel is added drop-wise to slowly in the 4-aminobenzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.4mL.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow heavy-gravity liquid product XII.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.72-1.96，3.63(CH
2)；2.91(CH)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 11:
0.1mol 4-carboxyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 6wt% and deionized water wash reaction soln 3 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-carboxyl benzophenone of acroleic acid esterification.
The 4-carboxyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.05mol methylphenylamine is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the methylphenylamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-carboxyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.3mL.After dropwising, continued stirring reaction 3 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains weak yellow liquid product X III.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：3.18(CH
3)；4.63(CH
2)；6.59，6.93，7.25，7.42，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 12:
0.1mol 4-carboxyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL benzene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 6wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-carboxyl benzophenone of acroleic acid esterification.
The 4-carboxyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL methyl alcohol; Then the 0.05mol Pyrrolidine is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the Pyrrolidine solution in the constant pressure funnel is added drop-wise to slowly in the 4-carboxyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 4 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product X IV.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.93，2.58，3.63(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 13:
0.1mol 4-propyloic benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 10 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 9wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-propyloic benzophenone of acroleic acid esterification.
The 4-propyloic benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL methyl alcohol; Then 0.05mol N-ehtylethanolamine is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature,, the N-ethyl hexanol amine aqueous solution in the constant pressure funnel is added drop-wise to slowly in the 4-propyloic benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.6mL.After dropwising, continued stirring reaction 3 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow liquid product XV.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.33(CH
3)；2.73，2.88，2.90，3.16，3.64，3.96(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 14:
0.1mol 4-carboxyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL toluene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.6mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 6wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-carboxyl benzophenone of acroleic acid esterification.
The 4-carboxyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then with 0.025mol N, N-dimethyl-1, the 3-propylene diamine is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the methylphenylamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-carboxyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.4mL.After dropwising, continued stirring reaction 3 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow thick liquid product X VI.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61(CH
3)；1.83，2.69，3.64(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 15:
0.1mol 4-carboxyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL benzene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 8wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-carboxyl benzophenone of acroleic acid esterification.
The 4-carboxyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.025mol cetylamine is dissolved in 80mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the cetylamine solution in the constant pressure funnel is added drop-wise to slowly in the 4-carboxyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.2mL.After dropwising, continued stirring reaction 4 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow thick liquid product X VII.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.29(CH
3)；1.62，1.66，2.88，3.83(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Embodiment 16:
0.1mol 4-carboxyl benzophenone and 0.11mol triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; Then the 0.11mol acrylate chloride at room temperature is dissolved in 50mL benzene, joins in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring, after dropwising, continued stirring reaction 8 hours with the speed of per second 0.2mL; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 8wt% and deionized water wash reaction soln 2 times respectively, use the anhydrous sodium sulfate drying reaction soln then; The solvent in the reaction soln is removed in underpressure distillation, obtains the 4-carboxyl benzophenone of acroleic acid esterification.
The 4-carboxyl benzophenone of 0.05mol aforesaid propylene acid estersization at room temperature is dissolved in the 80mL ethanol; Then the 0.025mol piperazine is dissolved in 60mL ethanol, joins in the constant pressure funnel.Under the room temperature,, the piperazine solution in the constant pressure funnel is added drop-wise to slowly in the 4-carboxyl benzophenone solution of acroleic acid esterification of stirring, carries out Michael reaction with the speed of per second 0.6mL.After dropwising, continued stirring reaction 3 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow solid powder-product XVIII.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.79，3.63(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Application Example:
Application Example 1:
Under the lucifuge condition, in being housed, the Glass Containers of agitator adds the mono-stripped hydrogen light initiating agent that the synthetic embodiment 1 of 3g makes, 23g aliphatic urethane acrylate resin (6000) is 40 ℃ of following stirring and dissolving, add 8g tri-propanediol diacrylate (TPGDA) again, the 8g talcum powder, 42g ground barium sulfate and 16g ground dolomite mix.Can obtain radical photoinitiator solidified coating material.
With coating apparatus the said components for preparing is applied on the substrate coat-thickness 50um.Place illumination 1 minute (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 2:
Aliphatic urethane acrylate resin (6000) 45g
TPGDA 25g
Ground dolomite 25g
The mono-stripped hydrogen light initiating agent 3.5g that synthetic embodiment 4 makes
Oxidation inhibitor 1.5g
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 10um.Place illumination 0.5 minute (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 3
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 27g
The mono-stripped hydrogen light initiating agent 4g that synthetic embodiment 5 makes
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 1um.Place illumination 20 seconds (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 4
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 27g
The mono-stripped hydrogen light initiating agent 4g that synthetic embodiment 6 makes
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 50um.Place illumination 2 minutes (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 5
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 27g
The mono-stripped hydrogen light initiating agent 4g that synthetic embodiment 7 makes
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 1um.Place illumination 1 minute (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 6:
Aliphatic urethane acrylate resin (6000) 45g
TPGDA 25g
Ground dolomite 25g
The mono-stripped hydrogen light initiating agent 3.5g that synthetic embodiment 9 makes
Oxidation inhibitor 1.5g
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 50um.Place illumination 2 minutes (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 7
Aliphatic urethane acrylate resin (6000) 50g
TPGDA 19g
Ground barium sulfate 27g
The mono-stripped hydrogen light initiating agent 4g that synthetic embodiment 12 makes
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 1um.Place illumination 0.5 minute (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Application Example 8:
Aliphatic urethane acrylate resin (6000) 45g
TPGDA 25g
Ground dolomite 25g
The mono-stripped hydrogen light initiating agent 3.5g that synthetic embodiment 16 makes
Oxidation inhibitor 1.5g
Method preparation according to Application Example 1.With coating apparatus the said components for preparing is applied on the substrate coat-thickness 10um.Place illumination 1.5 minutes (luminous range is 10cm) under the 500W high voltage mercury lamp, get photocuring and film.This no any irritating smell of filming does not have obvious xanthochromia.
Claims (6)
1. compound, its structural formula is:
Wherein:
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl, C
1-18Alkoxyl group;
A represents Shi-[(CH
2)
nO]-,-[(CH
2)
nCOO]-or-[(CH
2)
nNH]-group, n=0～3;
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl, N, the N-dimethyl propyl.
2. the preparation method of the described compound of claim 1 is characterized in that reaction divides an a, two steps of b to carry out:
A. with 1 molfraction 4-hydroxyalkyl benzophenone, the triethylamine of 4-carboxyalkyl benzophenone or 4-amine alkyl diphenyl ketone and 1-2 molfraction at room temperature is dissolved in and gets solution A in the organic solvent, then solution A is placed ice-water bath, stirring makes its temperature reduce to 0-5 ℃; The acrylate chloride of 1-2 molfraction at room temperature is dissolved in organic solvent gets solution B, with the speed of per second 0.2-0.6mL, solution B is added drop-wise in the solution A of stirring then, after dropwising, continued stirring reaction 4-12 hour; Remove by filter the triethylamine hydrochloride white solid of generation, washing, drying, underpressure distillation obtain 4-hydroxyalkyl benzophenone, 4-carboxyalkyl benzophenone or the 4-amine alkyl diphenyl ketone of acroleic acid esterification;
B. the 4-hydroxyalkyl benzophenone of the acroleic acid esterification that 1 molfraction step a is obtained, 4-carboxyalkyl benzophenone or 4-amine alkyl diphenyl ketone at room temperature are dissolved in and get solution C in the protonic solvent; At room temperature be dissolved in the secondary amine of 1 molfraction or the primary amine of 0.5 molfraction in the protonic solvent then, and at room temperature be added drop-wise in the solution C of stirring with the speed of per second 0.2-0.6mL, carry out Michael reaction, after dropwising, continued stirring reaction 0.5-5 hour; Protonic solvent is removed in underpressure distillation, handles by column chromatography then, obtains the described compound of claim 1.
3. preparation method according to claim 2 is characterized in that: the organic solvent of a step reaction is methylene dichloride, chloroform, benzene, toluene or dimethylbenzene; The protonic solvent of b step reaction is methyl alcohol or ethanol.
4. the described compound of claim 1 is as the application of mono-stripped hydrogen light initiating agent in field of light-sensitive high molecular materials of ultraviolet light polymerization.
5. compositions of ultraviolet curing type comprises:
(a) polymerisable composition comprises the unsaturated light reactive resin and the reactive thinner that contain at least one ethylenic; Reactive thinner is simple function group, bifunctional or multi-functional acrylate's monomer or methacrylate monomer;
(b) the described compound of claim 1.
6. compositions of ultraviolet curing type according to claim 5 is characterized in that: unsaturated light reactive resin is epoxy acrylic resin, epoxy methacrylic resin, polyester acrylic resin, polyester methacrylic resin, polyurethane acrylic resin, urethane methacrylic resin, polyacrylic ester acrylic resin, polyacrylic ester methacrylic resin, polyoxyalkylene acrylate resin or polyethers methacrylic resin.
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| CN102260358B (en) * | 2010-05-31 | 2012-10-03 | 江苏英力科技发展有限公司 | Use of 2-methoxy-4'-benzoylbiphenyl as photoinitiator |
| CN101941952B (en) * | 2010-07-21 | 2015-04-08 | 深圳市有为化学技术有限公司 | Resin monomer skeleton-derivative ketone compound photoinitiator |
| WO2012062333A1 (en) | 2010-11-12 | 2012-05-18 | Coloplast A/S | Novel polymeric photoinitiators |
| WO2012062334A1 (en) * | 2010-11-12 | 2012-05-18 | Coloplast A/S | New routes to polyacrylates |
| US9353211B2 (en) | 2012-05-16 | 2016-05-31 | Coloplast A/S | Polymeric photoinitiators and photoinitiator monomers |
| CN102863403A (en) * | 2012-08-03 | 2013-01-09 | 北京化工大学常州先进材料研究院 | Benzophenone photoinitiator containing amine serving as promoter and preparation method thereof |
| CN103064251A (en) * | 2012-12-05 | 2013-04-24 | 北京化工大学常州先进材料研究院 | Photosensitive composition containing bifunctional photoinitiator |
| CN103113498A (en) * | 2013-01-31 | 2013-05-22 | 北京化工大学常州先进材料研究院 | Polymeric photoinitiator and preparation method thereof |
| WO2015032069A1 (en) * | 2013-09-06 | 2015-03-12 | 北京英力科技发展有限公司 | Photo-initiator with low mobility |
| CN104327199A (en) * | 2014-11-12 | 2015-02-04 | 长沙新宇高分子科技有限公司 | Self-hydrogen-supply type bifunctional benzophenone photoinitiator |
| CN110467692A (en) | 2018-05-11 | 2019-11-19 | 北京英力科技发展有限公司 | A kind of polyacrylate macromolecular photoinitiator and its synthetic method and application |
| CN114276279B (en) * | 2021-12-29 | 2022-12-30 | 广州鹿山先进材料有限公司 | Hydrogen abstraction type photoinitiator, preparation method and application thereof |
| CN115820144B (en) * | 2022-12-22 | 2023-06-20 | 上海兰庆新材料技术股份有限公司 | Optical temperature-resistant ultraviolet viscosity-reducing composite film and preparation method 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 |
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| WO2006108204A1 (en) * | 2005-04-14 | 2006-10-19 | Technische Universität Wien | Photopolymerisable mixtures comprising photoinitiators based on benzophenone and phenylglycine |
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