CN101029095A - Mono-stripped hydrogen light initiating agent, its production and use - Google Patents
Mono-stripped hydrogen light initiating agent, its production and use Download PDFInfo
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- CN101029095A CN101029095A CN 200710051550 CN200710051550A CN101029095A CN 101029095 A CN101029095 A CN 101029095A CN 200710051550 CN200710051550 CN 200710051550 CN 200710051550 A CN200710051550 A CN 200710051550A CN 101029095 A CN101029095 A CN 101029095A
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Abstract
A mono-component hydrogen-abstraction initiating agent is prepared by reacting dihydroxy-alkyl-benzophenone, dicarboxyl-alkyl-benzophenone or bisamine-alkyl-benzophenone with acryloyl chloride, inducing into acrylate double bond and Michael reacting it with secondary amine or primary amine. It's simple, cheap and efficient, has excellent solubility and mobility. It can be used for coating, binder, printing ink, photo-etching and biological materials.
Description
Technical field
The present invention relates to mono-stripped hydrogen light initiating agent and its production and use, belong to the photosensitive macromolecular material preparation field.
Background technology
UV-curing technology is to utilize UV-light as reaction power, on photosensitive compound, makes it that a series of optical physics take place by light action, photochemical reaction, generate active substance, thus the initiating activity monomer polymerization, and Ye Tai resin is converted into solid-state macromolecular material the most at last.As a kind of novel green technology, it has a wide range of applications at aspects such as coating, tackiness agent, printing-ink, photoengraving and biomaterials.The characteristics of UV-curing technology are to save the energy, environmental friendliness, economical and efficient, photopolymerization device compactness, production efficiency height.In addition, ultraviolet light polymerization compares to traditional curing technology outstanding advantage, and for example self-vulcanizing helps the processing of heat-sensitive substrate material; Curing formula can be regulated by demand, guarantees product performance (as hardness, flexibility, gloss, weathering resistance etc.); Be easy to realize streamline operration, the level of automation height.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.According to the difference of triggering mechanism in the photocuring process, it can be divided into radical photopolymerization and cationic photopolymerization.Use to such an extent that be radical photopolymerization the most widely now, it is fast that it has speed, and the surface properties height is to advantage such as humidity is insensitive.
Benzophenone is a kind of light trigger that is used for radical photopolymerization, 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 a molecule or the macromole by chemical process, has formed a class mono-stripped hydrogen or a macromolecular photoinitiator, 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.
The invention provides the surrogate of a class diphenyl ketone photo initiator, by benzophenone and amine are combined in a molecule or the macromole, can effectively reduce transport property, the general formula of this compounds is shown in (I), (I '), (II), (II '), (III) or (III '):
In the formula: A represents Shi-[(CH
2)
N 'O]-,-[(CH
2)
N 'COO]-or-[(CH
2)
N 'NH]-group, n '=0～3;
n＝2-10000；
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl or C
1-18Alkoxyl group;
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl or N, the N-dimethyl propyl.
The present invention also provides the preparation method of above-claimed cpd: with the triethylamine of 1 molfraction dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or diamines alkyl diphenyl ketone and 2-3 molfraction at room temperature be dissolved in the organic solvent solution A, be placed on then in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; The acrylate chloride of 2-3 molfraction at room temperature is dissolved in organic solvent gets solution B,, solution B is added drop-wise in the above-mentioned solution A of stirring, after dropwising, continued stirring reaction 4-12 hour with the speed of per second 0.2-0.6mL; After removing by filter the triethylamine hydrochloride white solid of generation, washing (as the aqueous sodium hydroxide solution of using 5-10wt% respectively and deionized water wash reaction soln 1-3 time), drying (as using anhydrous sodium sulfate drying), underpressure distillation obtain dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or the diamines alkyl diphenyl ketone of acroleic acid esterification.
With dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or the diamines alkyl diphenyl ketone of 1 molfraction acroleic acid esterification at room temperature be dissolved in the protonic solvent solution C; At room temperature be dissolved in single secondary amine of 2 molfractions or two secondary amine of 1 molfraction or the primary amine of 1 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 2-24 hour; Protonic solvent is removed in underpressure distillation, handles by column chromatography or the precipitator method then, obtains suc as formula the compound shown in (I), (I '), (II), (II '), (III) or (III '); Wherein the structural formula of dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or diamines alkyl diphenyl ketone is:
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl or C
1-18Alkoxyl group; N '=0～3;
Single secondary amine, the structural formula of two secondary amine or primary amine is:
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl or N, the N-dimethyl propyl.
The preparation of above-claimed cpd 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 has been combined in benzophenone and amine in the molecule by chemical process.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 1:
Compound 1 structural formula
With 0.05mol (10.7g) 4,4 '-dihydroxy benaophenonel and 0.11mol (11.1g) triethylamine at room temperature is dissolved in the 60mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.11mol (10.0g) acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.2mL, after dropwising, continued stirring reaction 12 hours; 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 4 of acroleic acid esterification, 4 '-dihydroxy benaophenonel.
With 4 of 0.03mol (9.7g) aforesaid propylene acid estersization, 4 '-dihydroxy benaophenonel at room temperature is dissolved in the 80mL ethanol; Then 0.06mol (4.4g) diethylamine is dissolved in 50mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.2mL, the diethylamine solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-dihydroxy benaophenonel solution, carry out Michael reaction.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 compound 1.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)；7.26，7.87(CH，Ar).
Synthetic embodiment 2:
Compound 2 structural formulas
With 0.05mol (12.1g) 4,4 '-dihydroxymethyl benzophenone and 0.11mol (11.1g) triethylamine at room temperature is dissolved in the 60mL toluene, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.11mol (10.0g) acrylate chloride at room temperature is dissolved in 30mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.6mL, after dropwising, continued stirring reaction 12 hours; 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 4 of acroleic acid esterification, 4 '-dihydroxymethyl benzophenone.
With 4 of 0.03mol (10.5g) aforesaid propylene acid estersization, 4 '-dihydroxymethyl benzophenone at room temperature is dissolved in the 60mL ethanol; Then 0.06mol (6.4g) diethanolamine is dissolved in 60mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.6mL, the diethanolamine solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-dihydroxymethyl benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 2 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow thick liquid compound 2.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.88，3.64，3.97，5.68(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 3:
Compound 3 structural formulas
With 0.1mol (22.7g) 2,4-dihydroxyl-4 '-methyldiphenyl ketone and 0.22mol (22.4g) triethylamine at room temperature are dissolved in the 100mL methylene dichloride, are placed in the ice-water bath, stir to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in the 60mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.3mL, after dropwising, continued stirring reaction 8 hours; 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 2 of acroleic acid esterification, 4-dihydroxyl-4 '-methyldiphenyl ketone.
With 2 of 0.06mol (19.3g) aforesaid propylene acid estersization, 4-dihydroxyl-4 '-methyldiphenyl ketone at room temperature is dissolved in the 80mL methyl alcohol; Then 0.12mol (10.4g) piperidines is dissolved in 60mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.3mL, the piperidine solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 2, in 4-dihydroxyl-4 '-methyldiphenyl ketone solution, carry out Michael reaction.After dropwising, continued stirring reaction 5 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow thick liquid compound 3.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.83，2.57，3.64(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Synthetic embodiment 4:
Compound 4 structural formulas
0.1mol (21.2g) 4,4 '-two amido benzophenone and 0.22mol (22.4g) 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 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 80mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.4mL, after dropwising, continued stirring reaction 6 hours; Remove by filter the triethylamine hydrochloride white solid of generation, use the aqueous sodium hydroxide solution of 8wt% 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 4,4 '-two amido benzophenone of acroleic acid esterification.
4,4 '-two amido benzophenone of 0.06mol (19.2g) aforesaid propylene acid estersization at room temperature are dissolved in the 100mL methyl alcohol; Then 0.12mol (9.1g) 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 to slowly in 4,4 '-two amido 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; Methyl alcohol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains light yellow thick liquid compound 4.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61(CH
3)；2.88，3.63，3.96(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 5:
Compound 5 structural formulas
With 0.1mol (27.0g) 4,4 '-benzophenonedicarboxylic acid and 0.22mol (22.2g) triethylamine at room temperature is dissolved in the 160mL toluene, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 80mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.3mL, after dropwising, continued stirring reaction 8 hours; 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 4 of acroleic acid esterification, 4 '-benzophenonedicarboxylic acid.
With 4 of 0.06mol (22.7g) aforesaid propylene acid estersization, 4 '-benzophenonedicarboxylic acid at room temperature is dissolved in the 100mL ethanol; Then 0.06mol (6.4g) methylphenylamine is dissolved in 60mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.3mL, the methylphenylamine solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-benzophenonedicarboxylic acid solution, carry out Michael reaction.After dropwising, continued stirring reaction 3 hours; Ethanol is removed in underpressure distillation, carries out purification process by column chromatography then, obtains yellow thick liquid compound 5.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：3.18(CH
3)；4.63(CH
2)；6.59，6.93，7.26，7.42，7.87(CH，Ar).
Synthetic embodiment 6:
With 0.1mol (27.0g) 4,4 '-benzophenonedicarboxylic acid and 0.22mol (22.2g) triethylamine at room temperature is dissolved in the 160mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in the 80mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.5mL, after dropwising, continued stirring reaction 8 hours; 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 4 of acroleic acid esterification, 4 '-benzophenonedicarboxylic acid.
With 4 of 0.06mol (22.7g) aforesaid propylene acid estersization, 4 '-benzophenonedicarboxylic acid at room temperature is dissolved in the 100mL methyl alcohol; Then 0.06mol (4.4g) n-Butyl Amine 99 is dissolved in 60mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.3mL, the n-Butyl Amine 99 solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-benzophenonedicarboxylic acid solution, carry out Michael reaction.After dropwising, continued stirring reaction 12 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.29(CH
3)；1.66，2.69，3.96(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 7:
With 0.1mol (46.7g) 2,4-dihydroxyl-4 '-octadecyl benzophenone and 0.22mol (22.4g) triethylamine at room temperature are dissolved in the 100mL toluene, are placed in the ice-water bath, stir to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 60mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.3mL, after dropwising, continued stirring reaction 8 hours; 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 2 of acroleic acid esterification, 4-dihydroxyl-4 '-octadecyl benzophenone.
With 2 of 0.06mol (19.3g) aforesaid propylene acid estersization, 4-dihydroxyl-4 '-octadecyl benzophenone at room temperature is dissolved in the 100mL methyl alcohol; Then with 0.06mol (6.1g) N, N-dimethyl-1, the 3-propylene diamine is dissolved in 60mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.4mL, with the N in the constant pressure funnel, N-dimethyl-1,3-propylene diamine solution be added drop-wise to slowly stirring acroleic acid esterification 2, in 4-dihydroxyl-4 '-octadecyl benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 16 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61(CH
3)；2.69，3.96(CH
2)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Synthetic embodiment 8:
0.1mol (21.2g) 4,4 '-two amido benzophenone and 0.22mol (22.4g) 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 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in the 80mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.5mL, after dropwising, continued stirring reaction 8 hours; 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 4,4 '-two amido benzophenone of acroleic acid esterification.
4,4 '-two amido benzophenone of 0.06mol (19.2g) aforesaid propylene acid estersization at room temperature are dissolved in the 100mL methyl alcohol; Then 0.06mol (5.2g) piperazine is dissolved in 60mL methyl alcohol, 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 4,4 '-two amido 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 20 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61，2.81，3.96(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 9:
With 0.1mol (27.0g) 2,4-benzophenonedicarboxylic acid and 0.22mol (22.2g) triethylamine at room temperature is dissolved in the 160mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in the 80mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.6mL, after dropwising, continued stirring reaction 10 hours; 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 2 of acroleic acid esterification, the 4-benzophenonedicarboxylic acid.
With 2 of 0.06mol (22.7g) aforesaid propylene acid estersization, the 4-benzophenonedicarboxylic acid at room temperature is dissolved in the 100mL ethanol; Then 0.06mol (5.5g) hexahydroaniline is dissolved in 60mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.6mL, the hexahydroaniline solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 2, in the 4-benzophenonedicarboxylic acid solution, carry out Michael reaction.After dropwising, continued stirring reaction 12 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains light yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.72，1.79，1.99，2.61，3.64(CH
2)；2.91(CH)；7.25，7.48，7.59，7.80，7.87(CH，Ar)，
Synthetic embodiment 10:
With 0.05mol (10.7g) 4,4 '-dihydroxy benaophenonel and 0.11mol (11.1g) triethylamine at room temperature is dissolved in the 60mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.11mol (10.0g) acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.4mL, after dropwising, continued stirring reaction 8 hours; 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 4 of acroleic acid esterification, 4 '-dihydroxy benaophenonel.
With 4 of 0.03mol (9.7g) aforesaid propylene acid estersization, 4 '-dihydroxy benaophenonel at room temperature is dissolved in the 80mL ethanol; With 0.03mol (2.6g) N, N '-dimethyl-ethylenediamine is dissolved in 50mL ethanol, joins in the constant pressure funnel then.Under the room temperature, with the speed of per second 0.4mL, with the N in the constant pressure funnel, N '-dimethyl-ethylenediamine solution be added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-dihydroxy benaophenonel solution, carry out Michael reaction.After dropwising, continued stirring reaction 12 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains light yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61(CH
3)；2.79，3.64(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 11:
With 0.1mol (31.5g) 2,4-dihydroxyl-4 '-hexyloxy benzophenone and 0.22mol (22.4g) triethylamine at room temperature are dissolved in the 100mL benzene, are placed in the ice-water bath, stir to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 60mL benzene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.3mL, after dropwising, continued stirring reaction 10 hours; 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 2 of acroleic acid esterification, 4-dihydroxyl-4 '-hexyloxy benzophenone.
With 2 of 0.06mol (19.3g) aforesaid propylene acid estersization, 4-dihydroxyl-4 '-hexyloxy benzophenone at room temperature is dissolved in the 120mL methyl alcohol; With 0.06mol (12.6g) 4,4 '-trimethylammonium, two piperazines are dissolved in 80mL methyl alcohol, join in the constant pressure funnel then.Under the room temperature, with the speed of per second 0.6mL, with 4 in the constant pressure funnel, 4 '-trimethylammonium, two piperazine solution be added drop-wise to slowly stirring acroleic acid esterification 2, in 4-dihydroxyl-4 '-hexyloxy benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 20 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains light yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.58，1.62，1.77-2.62，3.64(CH
2)；2.91(CH)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Synthetic embodiment 12:
With 0.1mol (27.0g) 2,4-benzophenonedicarboxylic acid and 0.22mol (22.2g) triethylamine at room temperature is dissolved in the 160mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in the 80mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.5mL, after dropwising, continued stirring reaction 12 hours; 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 2 of acroleic acid esterification, the 4-benzophenonedicarboxylic acid.
With 2 of 0.06mol (22.7g) aforesaid propylene acid estersization, the 4-benzophenonedicarboxylic acid at room temperature is dissolved in the 100mL ethanol; Then with 0.06mol (8.5g) N, N '-diethyl-2-butylene-1, the 4-diamines is dissolved in 60mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.4mL, with the N in the constant pressure funnel, N '-diethyl-2-butylene-1,4-two amine aqueous solutions be added drop-wise to slowly stirring acroleic acid esterification 2, in the 4-benzophenonedicarboxylic acid solution, carry out Michael reaction.After dropwising, continued stirring reaction 16 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.33(CH
3)；2.73，3.36，(CH
2)；6.06(CH＝)；7.25，7.48，7.59，7.80，7.87(CH，Ar).
Synthetic embodiment 13:
With 0.05mol (12.1g) 4,4 '-dihydroxymethyl benzophenone and 0.11mol (11.1g) triethylamine at room temperature is dissolved in the 60mL toluene, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.11mol (10.0g) acrylate chloride at room temperature is dissolved in 30mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.5mL, after dropwising, continued stirring reaction 12 hours; 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 4 of acroleic acid esterification, 4 '-dihydroxymethyl benzophenone.
With 4 of 0.03mol (10.5g) aforesaid propylene acid estersization, 4 '-dihydroxymethyl benzophenone at room temperature is dissolved in the 60mL ethanol; Then 0.03mol (3.9g) octylame is dissolved in 30mL ethanol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.2mL, the octylame solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-dihydroxymethyl benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 12 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.29(CH
3)；1.62，1.66，2.69，3.65，5.67(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 14:
With 0.1mol (25.4g) 4,4 '-propyloic benzophenone and 0.22mol (22.2g) triethylamine at room temperature is dissolved in the 120mL toluene, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 60mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.3mL, after dropwising, continued stirring reaction 8 hours; 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 4 of acroleic acid esterification, 4 '-propyloic benzophenone.
With 4 of 0.06mol (26.1g) aforesaid propylene acid estersization, 4 '-propyloic benzophenone at room temperature is dissolved in the 120mL methyl alcohol; Then 0.06mol (5.5g) hexahydroaniline is dissolved in 30mL methyl alcohol, joins in the constant pressure funnel.Under the room temperature, with the speed of per second 0.5mL, the hexahydroaniline solution in the constant pressure funnel is added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-propyloic benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 10 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains faint yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.72，1.79，1.99，2.61，3.64(CH
2)；2.91(CH)；7.26，7.87(CH，Ar).
Synthetic embodiment 15:
With 0.05mol (14.9g) 4,4 '-dihydroxypropyl benzophenone and 0.11mol (11.1g) triethylamine at room temperature is dissolved in the 80mL methylene dichloride, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.11mol (10.0g) acrylate chloride at room temperature is dissolved in the 50mL methylene dichloride, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.6mL, after dropwising, continued stirring reaction 10 hours; 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 4 of acroleic acid esterification, 4 '-dihydroxypropyl benzophenone.
With 4 of 0.03mol (12.2g) aforesaid propylene acid estersization, 4 '-dihydroxypropyl benzophenone at room temperature is dissolved in the 80mL ethanol; With 0.03mol (2.6g) N, N '-dimethyl-ethylenediamine is dissolved in 50mL ethanol, joins in the constant pressure funnel then.Under the room temperature, with the speed of per second 0.4mL, with the N in the constant pressure funnel, N '-dimethyl-ethylenediamine solution be added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-dihydroxypropyl benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 18 hours; Ethanol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains light yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：2.61(CH
3)；2.23，2.79，2.88，3.64；4.41(CH
2)；7.26，7.87(CH，Ar).
Synthetic embodiment 16:
With 0.1mol (26.8g) 4,4 '-diamines ethyl benzophenone and 0.22mol (22.4g) triethylamine at room temperature is dissolved in the 100mL toluene, is placed in the ice-water bath, stirs to make its temperature reduce to 0-5 ℃; Then 0.22mol (20.0g) acrylate chloride at room temperature is dissolved in 60mL toluene, join in the constant pressure funnel,, acrylate chloride solution is added drop-wise to slowly in the above-mentioned solution of stirring with the speed of per second 0.2mL, after dropwising, continued stirring reaction 12 hours; 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 4 of acroleic acid esterification, 4 '-diamines ethyl benzophenone.
With 4 of 0.06mol (22.6g) aforesaid propylene acid estersization, 4 '-diamines ethyl benzophenone at room temperature is dissolved in the 120mL methyl alcohol; With 0.06mol (12.6g) 4,4 '-trimethylammonium, two piperazines are dissolved in 80mL methyl alcohol, join in the constant pressure funnel then.Under the room temperature, with the speed of per second 0.2mL, with 4 in the constant pressure funnel, 4 '-trimethylammonium, two piperazine solution be added drop-wise to slowly stirring acroleic acid esterification 4, in 4 '-diamines ethyl benzophenone solution, carry out Michael reaction.After dropwising, continued stirring reaction 20 hours; Methyl alcohol is removed in underpressure distillation, carries out purification process by the precipitator method then, obtains light yellow solid powder mono-stripped hydrogen light initiating agent.Product with
1HNMR carries out structure to be identified.
1H-NMR(CDCl
3，600MHz)：δ(ppm)：1.58，1.62，1.77-2.62，3.15，3.64，3.86(CH
2)；2.91(CH)；7.26，7.87(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 20g
Ground barium sulfate 26g
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) 49g
TPGDA 20g
Ground barium sulfate 28g
The mono-stripped hydrogen light initiating agent 3g 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 26g
Ground barium sulfate 20g
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 30g
Ground dolomite 20g
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) 45g
TPGDA 24g
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 30g
Ground dolomite 20g
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 (7)
1. the compound shown in general formula (I), (I '), (II), (II '), (III) or (III '):
Wherein:
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl or C
1-18Alkoxyl group;
A represents Shi-[(CH
2)
N 'O]-,-[(CH
2)
N 'COO]-or-[(CH
2)
N 'NH]-group, n '=0～3;
n＝2-10000；
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl or N, the N-dimethyl propyl.
2. the preparation method of the described compound of claim 1, it is characterized in that reaction carries out in two steps: a. with the triethylamine of 1 molfraction dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or diamines alkyl diphenyl ketone and 2-3 molfraction at room temperature be dissolved in the organic solvent solution A, be placed on then in the ice-water bath, stirring makes its temperature reduce to 0-5 ℃; The acrylate chloride of 2-3 molfraction at room temperature is dissolved in organic solvent gets solution B,, solution B is added drop-wise in the above-mentioned solution A of stirring, after dropwising, continued stirring reaction 4-12 hour with the speed of per second 0.2-0.6mL; After removing by filter the triethylamine hydrochloride white solid of generation, washing, drying, underpressure distillation obtain dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or the diamines alkyl diphenyl ketone of acroleic acid esterification; B. dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or the diamines alkyl diphenyl ketone of 1 molfraction acroleic acid esterification at room temperature is dissolved in the protonic solvent solution C; At room temperature be dissolved in single secondary amine of 2 molfractions or two secondary amine of 1 molfraction or the primary amine of 1 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 2-24 hour; Protonic solvent is removed in underpressure distillation, handles by the column chromatography or the precipitator method then, obtains the described compound of claim 1; Wherein the structural formula of dihydroxyalkyl benzophenone, dicarboxyl alkyl diphenyl ketone or diamines alkyl diphenyl ketone is:
R and R ' are selected from hydrogen, C respectively alone
1-18Alkyl or C
1-18Alkoxyl group; N '=0～3;
Single secondary amine, the structural formula of two secondary amine or primary amine is:
R
1And R
2Be selected from C respectively alone
1-18Alkyl, C
1-18Hydroxyalkyl, phenyl, benzyl or N, the N-dimethyl propyl.
3. 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, it comprises:
(a) polymerisable composition comprises the unsaturated light reactive resin and the reactive thinner that contain at least one ethylenic;
(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.
7. according to claim 5 or 6 described compositions of ultraviolet curing type, it is characterized in that: reactive thinner is simple function group, bifunctional or multi-functional acrylate's monomer or methacrylate monomer.
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|---|---|---|---|
| CNB2007100515506A CN100551935C (en) | 2007-02-13 | 2007-02-13 | A kind of mono-stripped hydrogen light initiating agent and its production and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100515506A CN100551935C (en) | 2007-02-13 | 2007-02-13 | A kind of mono-stripped hydrogen light initiating agent and its production and use |
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| CN100551935C CN100551935C (en) | 2009-10-21 |
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