CN109896942A - A kind of preparation method of alpha-alcohol ketone photoinitiator - Google Patents
A kind of preparation method of alpha-alcohol ketone photoinitiator Download PDFInfo
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- CN109896942A CN109896942A CN201711285664.7A CN201711285664A CN109896942A CN 109896942 A CN109896942 A CN 109896942A CN 201711285664 A CN201711285664 A CN 201711285664A CN 109896942 A CN109896942 A CN 109896942A
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- alcohol ketone
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention provides a kind of preparation method of alpha-alcohol ketone photoinitiator, the benzene and its derivative for using ketone compounds and trihalomethyl to replace is raw material, a step, which is reacted, under polar solvent and metallic catalyst effect generates halogenated intermediates, obtained product hydrolyzes under the action of alkali metal hydroxide aqueous solution and phase transfer catalyst and obtains alpha-alcohol ketone photoinitiator, it is easy to operate, reaction step is short, lewis acid catalyst is not used in reaction, it pollutes small, catalyst can be with recovery simultaneously, byproduct is few, it is low in cost, Same Way can produce multiple product.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly, to a kind of preparation method of alpha-alcohol ketone photoinitiator.
Background technique
UV is also by the abbreviation as radiation curing, the solidification of UV i.e. UV ultraviolet light, be using in UV ultraviolet light, it is short
Wave (300-800 nanometers) solidifies, under uv radiation, photoinitiator in liquid UV material is stimulated become free radical or sun from
Son, thus cause the process that the high molecular material (resin) containing active function groups aggregates into insoluble/insoluble solid paint film, α-hydroxyl
Base ketone photoinitiator such as 1173/184/2959/180 etc. is widely used in the cured paper of UV, the ink on floor, coating etc.
Industry, whole market usage amount is up to ten thousand tons.
The existing production technology of alpha-alcohol ketone photoinitiator is essentially all to be existed with acyl chlorides and benzene or benzene derivate at present
Friedel-Crafts reaction is carried out under the lewis acidic catalysis such as alchlor, then hydrolyzes to obtain product again by the dangerous technique such as chlorination.
Current technology generates a large amount of waste water, catalyst can not be recycled, reaction step due to largely using alchlor lewis acid
Rapid long, the danger such as chlorine technique also gives production aspect to cause very big hidden danger, with high costs.
Summary of the invention
The problem to be solved in the present invention is to provide it is a kind of it is easy to operate, reaction step is short, do not use lewis acid catalyst,
Catalyst can with recovery, byproduct and pollution less, the preparation method of the alpha-alcohol ketone photoinitiator of low production cost.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of preparation of alpha-alcohol ketone photoinitiator
Method, comprising the following steps:
Step (1): the benzene and its derivative that ketone compounds and trihalomethyl replace is raw material, in polar solvent and metal
A step is reacted under catalyst action and generates halogenated intermediates, wherein the feed ratio of reaction raw materials is ketone compounds: trihalomethyl
Substituted benzene and its derivative: metallic catalyst=0.9-1.5:1:1-10, reaction temperature are as follows: -50-40 DEG C, reaction formula is
General formula (I):
Wherein R1、R2For the alkane or R of C1-C61And R2Merge into cyclohexyl；R3, R4, R5, R6, R7 are hydrogen, C1-C6
The hydroxyalkyl of alkane, the alkoxy of C1-C6 or C1-C6；X is fluorine, chlorine or bromine；
Step (2): halogenated intermediates obtained in step (1) are in alkali metal hydroxide aqueous solution and phase transfer catalyst
Under the action of hydrolysis obtain alpha-alcohol ketone photoinitiator, wherein the feed ratio of reaction raw materials be halogenated intermediates: alkali metal hydrogen-oxygen
Compound: phase transfer catalyst=1:1-5:0.01-0.5, reaction temperature are as follows: 25-80 DEG C, reaction formula is general formula (II):
Further, the reaction temperature of step (1) is -20-10 DEG C.
Further, the feed ratio of reaction raw materials is ketone compounds in step (1): the benzene and its spread out that trihalomethyl replaces
Biology: metallic catalyst=1-1.2:1:1-5.
Further, the metallic catalyst in step (1) includes magnesium, zinc, aluminium, sodium or lithium.
Further, the polar solvent in step (1) includes dimethylformamide or dimethyl sulfoxide.
Further, the reaction temperature of step (2) is 45-60 DEG C.
Further, the feed ratio of reaction raw materials is halogenated intermediates: alkali metal hydroxide: phase transfer in step (2)
Catalyst=1:1-3:0.05-0.1.
Further, the alkali metal hydroxide includes sodium hydroxide, potassium hydroxide, the hydrogen-oxygen that concentration is 10-50%
Change lithium or calcium hydroxide solution.
Further, the concentration of the alkali metal hydroxide is 30-40%.
Further, the phase transfer catalyst includes tetrabutylammonium chloride, tetrabutylammonium bromide, benzyl triethyl ammonium chlorination
Ammonium or benzyl triethyl ammonium bromide.
Compared with prior art, the present invention has the advantage that is with beneficial effect: the present invention uses ketone compounds and three
The benzene and its derivative that halogen methyl replaces is raw material, reacts a step under polar solvent and metallic catalyst effect and generates in halogenated
Mesosome, obtained product hydrolyze under the action of alkali metal hydroxide aqueous solution and phase transfer catalyst and obtain alpha-alcohol ketone light
Initiator, it is easy to operate, reaction step is short, lewis acid catalyst is not used in reaction, pollutes small, while catalyst can return
Receipts are applied, and byproduct is few, low in cost, and Same Way can produce multiple product.
Specific embodiment
It elaborates below to a specific embodiment of the invention.
A kind of preparation method of alpha-alcohol ketone photoinitiator, comprising the following steps:
Step (1): the benzene and its derivative that ketone compounds and trihalomethyl replace is raw material, in polar solvent and metal
A step is reacted under catalyst action and generates halogenated intermediates, wherein the feed ratio of reaction raw materials is ketone compounds: trihalomethyl
Substituted benzene and its derivative: metallic catalyst=0.9-1.5:1:1-10, reaction temperature are as follows: -50-40 DEG C, reaction formula is
General formula (I):
Wherein R1、R2For the alkane or R of C1-C61And R2Merge into cyclohexyl；R3, R4, R5, R6, R7 are hydrogen, C1-C6
The hydroxyalkyl of alkane, the alkoxy of C1-C6 or C1-C6；X is fluorine, chlorine or bromine；
Step (2): halogenated intermediates obtained in step (1) are in alkali metal hydroxide aqueous solution and phase transfer catalyst
Under the action of hydrolysis obtain alpha-alcohol ketone photoinitiator, wherein the feed ratio of reaction raw materials be halogenated intermediates: alkali metal hydrogen-oxygen
Compound: phase transfer catalyst=1:1-5:0.01-0.5, reaction temperature are as follows: 25-80 DEG C, reaction formula is general formula (II):
Further, the reaction temperature of step (1) is -20-10 DEG C.
Further, the feed ratio of reaction raw materials is ketone compounds in step (1): the benzene and its spread out that trihalomethyl replaces
Biology: metallic catalyst=1-1.2:1:1-5.
Further, the metallic catalyst in step (1) includes magnesium, zinc, aluminium, sodium or lithium, preferably magnesium.
Further, the polar solvent in step (1) includes dimethylformamide or dimethyl sulfoxide, preferably diformazan
Base formamide.
Further, the reaction temperature of step (2) is 45-60 DEG C.
Further, the feed ratio of reaction raw materials is halogenated intermediates: alkali metal hydroxide: phase transfer in step (2)
Catalyst=1:1-3:0.05-0.1.
Further, the alkali metal hydroxide includes sodium hydroxide, potassium hydroxide, the hydrogen-oxygen that concentration is 10-50%
Change lithium or calcium hydroxide solution.
Further, the concentration of the alkali metal hydroxide is 30-40%.
Further, the phase transfer catalyst includes tetrabutylammonium chloride, tetrabutylammonium bromide, benzyl triethyl ammonium chlorination
Ammonium or benzyl triethyl ammonium bromide, preferably tetrabutylammonium bromide.
It include with flowering structure according to compound prepared by this method, but the present invention is not by any limit of following compound
System:
Embodiment 1
The synthesis of 1- hydroxycyclohexyl phenyl ketone
The magnesium powder 12g dissolution of 80-100 mesh is suspended in 100mlDMF (dimethylformamide) solvent, under nitrogen protection
Stirring cools to -20 DEG C, and 9.8g cyclohexanone and 23.46g benzenyl trichloride are dissolved in 40mlDMF solvent, are slowly added dropwise
Into the system of the first step, system temperature is maintained to react 2 hours lower than -20--10 DEG C, is warming up to room temperature, filtering, washing naturally
30% NaOH 20g aqueous solution and tetrabutylammonium bromide 0.2g, control reaction temperature to 50 is added with petroleum ether extraction in processing
DEG C reaction two hours, washing, precipitation be recrystallized to give product 16g, purity 99.6%, yield 86%.
Embodiment 2
The synthesis of 2- hydroxy-2-methyl -1- phenylacetone
The magnesium powder 12g dissolution of 80-100 mesh is suspended in 100mlDMF solvent, stirred under nitrogen atmosphere cools to -20
DEG C, 5.8g acetone and 23.46g benzenyl trichloride are dissolved in 40mlDMF solvent, the system of the first step is slowly added drop-wise to
In, it maintains system temperature to react 2 hours lower than -10-0 DEG C, is warming up to room temperature naturally, filtering, washing process are extracted with petroleum ether
It taking, 35% NaOH 17g aqueous solution and tetrabutylammonium bromide 0.15g is added, control reaction temperature is reacted two hours to 50 DEG C,
Washing, precipitation rectifying obtain product 13.3g, purity 99.2%, yield 82%.
Embodiment 3
The synthesis of 2- hydroxyl -4'- (2- hydroxy ethoxy) -2- methyl phenyl ketone
The magnesium powder 12g dissolution of 80-100 mesh is suspended in 100mlDMF solvent, stirred under nitrogen atmosphere cools to -20
DEG C, 9.8g cyclohexanone and 23.46g 4- ethoxy benzenyl trichloride are dissolved in 40mlDMF solvent, are slowly added drop-wise to
In the system of one step, system temperature is maintained to react 2 hours lower than -20~-10 DEG C, be warming up to room temperature naturally, filtered, at washing
30% NaOH 20g aqueous solution and tetrabutylammonium bromide 0.2g is added with petroleum ether extraction in reason, controls reaction temperature to 50 DEG C
Reaction two hours, washing, precipitation are recrystallized to give product 17.5g, purity 98.5%, yield 78%.
In conclusion the preparation method of alpha-alcohol ketone photoinitiator of the invention, reaction step is few, the by-product of generation
It is few, it can react to obtain plurality of target product, meanwhile, the yield and purity of product are higher.
One embodiment of the present invention has been described in detail above, but the content is only preferable implementation of the invention
Example, should not be considered as limiting the scope of the invention.It is all according to all the changes and improvements made by the present patent application range
Deng should still be within the scope of the patent of the present invention.
Claims (10)
1. a kind of preparation method of alpha-alcohol ketone photoinitiator, it is characterised in that: the following steps are included:
Step (1): the benzene and its derivative that ketone compounds and trihalomethyl replace is raw material, in polar solvent and metal catalytic
Agent effect one step of lower reaction generates halogenated intermediates, wherein the feed ratio of reaction raw materials is ketone compounds: trihalomethyl replaces
Benzene and its derivative: metallic catalyst=0.9-1.5:1:1-10, reaction temperature are as follows: -50-40 DEG C, reaction formula is general formula
(I):
Wherein R1、R2For the alkane or R of C1-C61And R2Merge into cyclohexyl；R3, R4, R5, R6, R7 be hydrogen, C1-C6 alkane,
The alkoxy of C1-C6 or the hydroxyalkyl of C1-C6；X is fluorine, chlorine or bromine；
Step (2): work of the halogenated intermediates obtained in step (1) in alkali metal hydroxide aqueous solution and phase transfer catalyst
Alpha-alcohol ketone photoinitiator is obtained with solution is lauched, wherein the feed ratio of reaction raw materials is halogenated intermediates: alkali metal hydroxide
Object: phase transfer catalyst=1:1-5:0.01-0.5, reaction temperature are as follows: 25-80 DEG C, reaction formula is general formula (II):
2. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 1, it is characterised in that: step (1)
Reaction temperature is -20-10 DEG C.
3. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 1, it is characterised in that: in step (1)
The feed ratio of reaction raw materials is ketone compounds: the benzene and its derivative that trihalomethyl replaces: metallic catalyst=1-1.2:1:
1-5。
4. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 1, it is characterised in that: in step (1)
Metallic catalyst include magnesium, zinc, aluminium, sodium or lithium.
5. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 1, it is characterised in that: in step (1)
Polar solvent include dimethylformamide or dimethyl sulfoxide.
6. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 1, it is characterised in that: step (2)
Reaction temperature is 45-60 DEG C.
7. according to right want 1 described in a kind of preparation method of alpha-alcohol ketone photoinitiator, it is characterised in that: it is anti-in step (2)
The feed ratio for answering raw material is halogenated intermediates: alkali metal hydroxide: phase transfer catalyst=1:1-3:0.05-0.1.
8. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 7, it is characterised in that: the alkali metal
Hydroxide includes sodium hydroxide, potassium hydroxide, lithium hydroxide or the calcium hydroxide solution that concentration is 10-50%.
9. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 8, it is characterised in that: the alkali metal
The concentration of hydroxide is 30-40%.
10. a kind of preparation method of alpha-alcohol ketone photoinitiator according to claim 7, it is characterised in that: the phase turns
Shifting catalyst includes tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammoinium chloride or benzyl triethyl ammonium bromide.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493372A (en) * | 2020-04-03 | 2021-10-12 | 常州强力先端电子材料有限公司 | Preparation method of photoinitiator |
| CN113861010A (en) * | 2021-10-13 | 2021-12-31 | 深圳市芯研材料科技有限公司 | Monosubstituted and polysubstituted functional group aromatic ketone compound, preparation method thereof and photopolymerization initiator thereof |
| CN115838327A (en) * | 2022-12-06 | 2023-03-24 | 常州久日化学有限公司 | Alkaline hydrolysis method of photoinitiator 184 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146760A (en) * | 1995-02-03 | 1997-04-02 | 钟渊化学工业株式会社 | Processes for producing 'alpha'-halo ketones, 'alpha'-halohydrine and epoxides |
| CN102267887A (en) * | 2011-07-18 | 2011-12-07 | 连云港升南化学有限公司 | Synthesis process for 1-hydroxycyclohexyl phenyl ketone |
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2017
- 2017-12-07 CN CN201711285664.7A patent/CN109896942A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146760A (en) * | 1995-02-03 | 1997-04-02 | 钟渊化学工业株式会社 | Processes for producing 'alpha'-halo ketones, 'alpha'-halohydrine and epoxides |
| CN102267887A (en) * | 2011-07-18 | 2011-12-07 | 连云港升南化学有限公司 | Synthesis process for 1-hydroxycyclohexyl phenyl ketone |
Non-Patent Citations (1)
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| MICHAEL STEINIGER等: "α，β-unsaturated ketones by cathodic additon of benzotrichloride to ketones", 《ANGEW.CHEM.SUPPL.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113493372A (en) * | 2020-04-03 | 2021-10-12 | 常州强力先端电子材料有限公司 | Preparation method of photoinitiator |
| CN113493372B (en) * | 2020-04-03 | 2023-08-08 | 常州强力先端电子材料有限公司 | Preparation method of photoinitiator |
| CN113861010A (en) * | 2021-10-13 | 2021-12-31 | 深圳市芯研材料科技有限公司 | Monosubstituted and polysubstituted functional group aromatic ketone compound, preparation method thereof and photopolymerization initiator thereof |
| CN115838327A (en) * | 2022-12-06 | 2023-03-24 | 常州久日化学有限公司 | Alkaline hydrolysis method of photoinitiator 184 |
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Application publication date: 20190618 |