CN106518638A - New synthesis technology for photoinitiator1173 - Google Patents
New synthesis technology for photoinitiator1173 Download PDFInfo
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- CN106518638A CN106518638A CN201610942525.6A CN201610942525A CN106518638A CN 106518638 A CN106518638 A CN 106518638A CN 201610942525 A CN201610942525 A CN 201610942525A CN 106518638 A CN106518638 A CN 106518638A
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- Prior art keywords
- isobutyrophenone
- light trigger
- synthesizing
- new technique
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Abstract
The invention relates to a midbody isobutyrophenone of a photoinitiator1173 (2-hydroxy-2-methyl-1-phenyl-1-acetone) and a new synthesis technology for a photoinitiator1173. The new synthesis technology includes the steps that isobutylbenzene serves as a raw material, an oxidizing reaction is carried out with oxygen under the catalytic effect of catalyst cobalt salt or palladium salt, and the isobutyrophenone is obtained; the isobutyrophenone is further chloridized and hydrolyzed with a sodium hydroxide solution, and the photoinitiator1173 is obtained. The influence of the catalyst cobalt salt or palladium salt on isobutyrophenone production in the reaction is inspected, the material ratio in the isobutyrophenone and photoinitiator1173 production is determined, and the new technology is easy to operate and economical.
Description
Technical field
The invention belongs in compound synthesis field a kind of light trigger 1173 preparation method.
Background technology
The nineteen forty-six U.S. Inmot company obtain first ultraviolet light polymerization (UV) in terms of patent.1967, Germany was visitd
Your company industrializes UV curing technologies, so as to draw the concept of light trigger.1970, vapour Ba-Jia Ji companies invented
I -651, it is that the fast development of light trigger lays the foundation, while also established vapour Ba-Jia Ji companies studying in light trigger
With the leadership of production field.Over nearly 10 years, external light trigger consumption annual growth is 8.1%, China's UV cured articles
Annual growth rate is up to 35%.
2- hydroxy-ketones are the new and effective trigger for optical solidification of the class for growing up in recent years, 2- methyl -2- hydroxyls -
1- phenylacetones (1173) are a kind of novel photoinitiators of function admirable, with efficiency of initiation it is high, heat endurance is good, resistance to Huang
The advantages of change, free from extraneous odour, the status in photocuring is especially prominent.
Light trigger 1173 carries out Friedel-Crafts reaction in the presence of alchlor using benzene and isobutyryl chloride and obtains different at present
Butyrophenone, further chlorinated with chlorine, sodium hydroxide solution alkaline hydrolysis obtain light trigger 1173.The technique can produce substantial amounts of hydrogen-oxygen
Change aluminium waste water, while the also high shortcoming of production cost.
The content of the invention
It is an object of the invention in place of overcoming the deficiencies in the prior art, there is provided a kind of preparation side of light trigger 1173
Method, the invention provides new reaction scheme, catalyst, reaction temperature, reacting material ratio, thus provide it is a kind of it is more practical,
The production technology of the lower light trigger 1173 of cost.
The present invention solves its technical problem and takes technical scheme below to realize：
A kind of 1173 new technique for synthesizing of light trigger, the structural formula for being related to intermediate and product is：
Preferably, isobutyl-benzene is adopted for initiation material, obtained with dioxygen oxidation under catalyst cobalt salt or palladium salt effect
Isobutyrophenone, further with chlorinated with chlorine, sodium hydroxide solution hydrolysis obtains light trigger 1173.
Preferably, the catalyst used in the isobutyrophenone is produced is cobalt salt or palladium salt and azodiisobutyronitrile,
Catalyst used in isobutyrophenone chlorination reaction is methyl alcohol, and the catalyst used in chlorination isobutyrophenone Basic fluxing raction is benzyl
Tributyl ammonium bromide.
Preferably, the solvent for adopting in the production process of the isobutyrophenone is acetic acid.
Preferably, the quality of material ratio in the production of the isobutyrophenone is：Isobutylbenzene：Acetic acid：Cobalt salt catalyst：Azo
Bis-isobutyronitrile=1:1:0.02.
Preferably, the reaction temperature in the production of isobutyrophenone is 100-110 DEG C.
Preferably, the product of chlorination reaction directly uses sodium hydroxide solution alkaline hydrolysis in the presence of catalyst without the need for purifying,
Obtain light trigger 1173.
Preferably, the catalyst used in the reaction of isobutyrophenone chlorinated with chlorine is methyl alcohol, and reaction temperature is 50 DEG C.
Preferably, the catalyst that uses of sodium hydroxide hydrolysis reaction is benzyl tributyl ammonium bromide, and naoh concentration is
20%, reaction temperature is 40 DEG C.
Advantages of the present invention and good effect are：
1st, the present invention is initiation material using isobutylbenzene, and, used as catalyst, dioxygen oxidation obtains isobutyl for cobalt salt or palladium salt
Acyl benzene, the reaction are solvent-free reaction, belong to green chemistry.
2nd, by the change to reaction scheme, the isobutyrophenone of synthesis has low price to the present invention, non-environmental-pollution
A little, the industrialized production for light trigger 1173 provides the condition for more optimizing.
Specific embodiment
With reference to specific embodiment, the invention will be further described.With reference to specific embodiment the present invention is made into
One step is described in detail.The synthesis chemical formula that the present invention prepares light trigger 1173 is as follows：
The present invention is described in further detail with reference to embodiment.
Comparative example 1
(1) in 2000 liters of reactor, 400kg isobutylbenzenes, 400kg acetic acid, 8kg cobalt acetates and 30kg brominations are added
Start to warm up under sodium, stirring to more than 100 DEG C, start to be passed through oxygen with the speed of 1Kg/min, kettle temperature is maintained at 100-110 DEG C
Between, after ventilating 20 hours, stop ventilation.Acetic acid is steamed, crude product is obtained, crude product is carried out into rectifying and is obtained isobutyrophenone.
The content of gas chromatographic analysis isobutyrophenone is 99%.
(2) in 1000 liters of reactor, 400kg isobutyrophenones and 4 kilograms of methyl alcohol is added, under stirring, 45-50 is warming up to
DEG C, starting to be passed through chlorine, duration of ventilation is 5 hours.Gas chromatography detects to raw material and is wholly absent, and drives reactant liquor away with nitrogen
Middle excessive chlorine.The reactant liquor for obtaining is reacted for next step.
(3) in 3000 liters of reactor, add 2000 kilograms of 20% sodium hydroxide solution and TBAB 2 public
Jin, is added dropwise 500 kilograms of above-mentioned chlorization products, and keeping temperature is less than 40 degree, continues reaction 6 hours, gas-chromatography inspection after dripping off
Survey raw material to disappear, stop reaction, static layering, the organic phase for taking upper strata carry out vacuum distillation, obtain 420 kilograms of product, content
For 99.3%.
Embodiment 2
(1) in 2000 liters of reactor, 400kg isobutylbenzenes, 500kg acetic acid, 12kg cobalt iso-octoates and 30kg bromines are added
Change sodium, start to warm up under stirring to more than 100 DEG C, start to be passed through oxygen with the speed of 1Kg/min, kettle temperature is maintained at 100-110
Between DEG C, after ventilating 25 hours, stop ventilation.Acetic acid is steamed, crude product is obtained, crude product is carried out into rectifying and is obtained isobutyryl
Benzene.The content of gas chromatographic analysis isobutyrophenone is 99%.
(2) in 1000 liters of reactor, 500kg isobutyrophenones and 5 kilograms of methyl alcohol is added, 50 DEG C under stirring, are warming up to,
Start to be passed through chlorine, duration of ventilation is 5 hours.Gas chromatography is detected to raw material and is wholly absent, driven away in reactant liquor with nitrogen
Excessive chlorine.The reactant liquor for obtaining is reacted for next step.
(3) in 3000 liters of reactor, add 1800 kilograms of 20% sodium hydroxide solution and TBAB 2 public
Jin, is added dropwise 500 kilograms of above-mentioned chlorization products, and keeping temperature is less than 40 degree, continues reaction 6 hours, gas-chromatography inspection after dripping off
Survey raw material to disappear, stop reaction, static layering, the organic phase for taking upper strata carry out vacuum distillation, obtain 420 kilograms of product, content
For 99.2%.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (9)
1. 1173 new technique for synthesizing of a kind of light trigger, it is characterised in that：The structural formula for being related to intermediate and product is：
2. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：Isobutyl-benzene is adopted for starting
Raw material, obtains isobutyrophenone with dioxygen oxidation under catalyst cobalt salt or palladium salt effect, further with chlorinated with chlorine, NaOH
Solution water solution obtains light trigger 1173.
3. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：In the isobutyrophenone production
The catalyst for using is cobalt salt or palladium salt and azodiisobutyronitrile, and the catalyst used in isobutyrophenone chlorination reaction is first
Alcohol, the catalyst used in chlorination isobutyrophenone Basic fluxing raction are benzyl tributyl ammonium bromide.
4. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：The production of the isobutyrophenone
During the solvent that adopts be acetic acid.
5. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：The production of the isobutyrophenone
In quality of material ratio be：Isobutylbenzene：Acetic acid：Cobalt salt catalyst：Azodiisobutyronitrile=1:1:0.02.
6. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：In the production of isobutyrophenone
Reaction temperature is 100-110 DEG C.
7. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：The product of chlorination reaction need not
Purifying, directly uses sodium hydroxide solution alkaline hydrolysis in the presence of catalyst, obtains light trigger 1173.
8. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：Isobutyrophenone chlorinated with chlorine is anti-
Catalyst used in answering is methyl alcohol, and reaction temperature is 50 DEG C.
9. 1173 new technique for synthesizing of light trigger according to claim 1, it is characterised in that：Sodium hydroxide hydrolysis reaction makes
Catalyst is benzyl tributyl ammonium bromide, and naoh concentration is 20%, and reaction temperature is 40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610942525.6A CN106518638A (en) | 2016-11-02 | 2016-11-02 | New synthesis technology for photoinitiator1173 |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610942525.6A CN106518638A (en) | 2016-11-02 | 2016-11-02 | New synthesis technology for photoinitiator1173 |
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| CN106518638A true CN106518638A (en) | 2017-03-22 |
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| CN201610942525.6A Pending CN106518638A (en) | 2016-11-02 | 2016-11-02 | New synthesis technology for photoinitiator1173 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056934A (en) * | 2019-12-31 | 2020-04-24 | 天津久日新材料股份有限公司 | Method for preparing α -hydroxyketone photoinitiator in microreactor |
| 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 |
| CN114835564A (en) * | 2022-04-20 | 2022-08-02 | 宁夏沃凯珑新材料有限公司 | Method for producing photoinitiator UV-1173 by condensation method |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
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| CN102249832A (en) * | 2010-05-19 | 2011-11-23 | 湖北工业大学 | Novel synthesis method of alpha-hydroxyl arone compound |
| CN102304033A (en) * | 2011-07-18 | 2012-01-04 | 连云港升南化学有限公司 | Process for synthesizing 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
| CN103613492A (en) * | 2013-12-10 | 2014-03-05 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
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Patent Citations (3)
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| CN102249832A (en) * | 2010-05-19 | 2011-11-23 | 湖北工业大学 | Novel synthesis method of alpha-hydroxyl arone compound |
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| CN103613492A (en) * | 2013-12-10 | 2014-03-05 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111056934A (en) * | 2019-12-31 | 2020-04-24 | 天津久日新材料股份有限公司 | Method for preparing α -hydroxyketone photoinitiator in microreactor |
| CN111056934B (en) * | 2019-12-31 | 2022-07-12 | 天津久日新材料股份有限公司 | Method for preparing alpha-hydroxy ketone photoinitiator in microreactor |
| 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 |
| CN114835564A (en) * | 2022-04-20 | 2022-08-02 | 宁夏沃凯珑新材料有限公司 | Method for producing photoinitiator UV-1173 by condensation method |
| CN114835564B (en) * | 2022-04-20 | 2024-01-05 | 宁夏沃凯珑新材料有限公司 | Method for producing photoinitiator UV-1173 by condensation method |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
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Application publication date: 20170322 |