CN102532194B - Method for increasing photoinitiator oxidation reaction yield - Google Patents
Method for increasing photoinitiator oxidation reaction yield Download PDFInfo
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- CN102532194B CN102532194B CN201010576916.3A CN201010576916A CN102532194B CN 102532194 B CN102532194 B CN 102532194B CN 201010576916 A CN201010576916 A CN 201010576916A CN 102532194 B CN102532194 B CN 102532194B
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- urea
- organic phase
- mixture
- trimethylbenzoyl
- stratification
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Abstract
The invention discloses a method for increasing photoinitiator oxidation reaction yield. The method comprises the following steps of: feeding xylene and a urea-H2O2 complex into a reaction kettle under the condition of 20-30 DEG C, stirring and dropwise adding a mixed solution of 2,4,6-trimethyl benzoyl diphenyl phosphine and xylene within 80-100 minutes, after dropwise adding is finished, maintaining the temperature and reacting for 4-5 hours, and sampling and analyzing; and washing the reaction liquid obtained in the former step with a saturated saline solution, standing and layering, removing washing water, washing an organic phase with a 5% sodium thiosulfate solution, standing and layering, removing washing water, adjusting pH of the organic phase to 8 with a 5% diluted base solution (such as a sodium hydroxide base solution), standing and layering, taking out the organic phase, removing a xylene solvent under negative pressure, crystallizing with petroleum ether, carrying out suction filtering, and drying to obtain 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.
Description
Technical field
The present invention relates to a kind of synthesis technique of light trigger, specifically the method for the synthetic middle oxidizing reaction of light trigger TPO.
Background technology
TPO(2,4,6-trimethylbenzoyl-diphenyl phosphine oxide) be a kind of efficient radical photoinitiator, be specially adapted to the curing field that pigmented system and rete are thick.The light trigger that curing speed is very fast, because it has very wide absorption region, can be widely used in various coatings, because of its outstanding absorptive character, makes it be specially adapted to ink for screen printing, lithography, flexo ink, wood coatings.TPO is often by organo-peroxide or hydrogen peroxide oxidation 2,4, prepared by 6-trimethylbenzoyl-diphenylphosphine, and the former side reaction is many, and the latter's yield is undesirable, and uses high dense hydrogen peroxide production security poor.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method that improves light trigger oxidizing reaction productive rate, with hydrogen peroxide-urea mixture, makes oxygenant, and oxidation capacity is strong, yield is high, reaction process safety.
The present invention is achieved through the following technical solutions:
A method that improves light trigger oxidizing reaction productive rate, comprises the following steps:
Under 20-30 ℃ of condition, by dimethylbenzene and urea-H
2o
2mixture is added in reactor, drips while stirring the mixing solutions of 2,4,6-trimethylbenzoyl-diphenylphosphine and dimethylbenzene, insulation reaction 4-5 hour after 80-100min dropwises, sampling analysis;
With urea-H
2o
2mixture adds the xylene solvent in reactor together, and its add-on is urea-H
2o
21～2 times of mixture; Drip xylene solvent in the mixing solutions of 2,4,6-trimethylbenzoyl-diphenylphosphine and dimethylbenzene and be 2～5 times of 2,4,6-trimethylbenzoyl-diphenylphosphine weight.
In the reaction solution of above-mentioned steps, add saturated common salt water washing, stratification is removed washing water, and organic phase is washed with 5% hypo solution, then stratification is removed washing water, 5% sig water for organic phase (available sodium hydroxide lye) regulates PH to 8, after stratification, take out organic phase, negative pressure removes xylene solvent, finally with sherwood oil, carries out crystallization, suction filtration, dry 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide;
Described 2,4,6-trimethylbenzoyl-diphenylphosphine and urea-H
2o
2the weight ratio of mixture is 1:1.5～3.
The further improvement project of the present invention is, described urea-H
2o
2in mixture, the weight ratio that urea and 30% superoxol feed intake is: 1:2～3; Its preparation comprises the following steps:, by described weight ratio, below 30 degrees Celsius, hydrogen peroxide to be added in container, then adds urea, under whipped state, reacts 45min～90min, is then cooled to 0 ℃, low temperature crystallization 90～150min, and suction filtration obtains urea-H
2o
2mixture.
The present invention uses urea-hydrogen peroxide complexes as oxygenant in the oxidising process of light trigger TPO, and theoretical active o content can reach 16.0%, is equivalent to H
2o
2content reaches 35.0%, and reaction is carried out in homogeneous phase, improves the relative concentration of active oxygen and 2,4,6-trimethylbenzoyl-diphenylphosphine, and oxidation capacity is strong, the many problems of side reaction when solution hydrogen peroxide oxidation scarce capacity and organo-peroxide are made oxygenant.
Embodiment
embodiment 1
Prepare urea-H
2o
2mixture:
The H that adds 300g30% at 1000ml beaker
2o
2in, then add 120g urea, and low-grade fever to 29 ℃, stirring and dissolving is also reacted 60min, is then cooled to 0 ℃, low temperature crystallization 90min, suction filtration obtains urea-H
2o
2the about 150g of mixture.
Prepare light trigger 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide:
By 300ml dimethylbenzene and 112g urea-H
2o
2mixture adds to 1000ml flask, loads onto mechanical stirring, under room temperature, drips 56g2, the mixing solutions of 4,6-trimethylbenzoyl-diphenylphosphine and 200ml dimethylbenzene, and about 90min dropwises rear insulation reaction approximately 5 hours, and process sampling product LC analyzes.Reaction finishes the rear saturated common salt water washing of using, and stratification is removed washing water, and organic phase is washed with 5% hypo solution; stratification is removed washing water again; organic phase regulates PH to 8 with 5% sig water, and stratification takes out organic phase, and negative pressure removes xylene solvent; finally with sherwood oil, carry out crystallization; suction filtration, dry 2,4; 6-trimethylbenzoyl-diphenyl phosphine oxide 57.5g, yield can reach 98%.
embodiment 2
Prepare urea-H
2o
2mixture:
The H that adds 350g30% at 1000ml beaker
2o
2in, then add 120g urea, and low-grade fever to 30 ℃, stirring and dissolving is also reacted 80min, is then cooled to 0 ℃, low temperature crystallization 90min, suction filtration obtains urea-H
2o
2the about 155g of mixture.
Prepare light trigger 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide:
By 300ml dimethylbenzene and 120g urea-H
2o
2mixture adds to 1000ml flask, loads onto mechanical stirring, under room temperature, drips 56g2, the mixing solutions of 4,6-trimethylbenzoyl-diphenylphosphine and 220ml dimethylbenzene, and about 90min dropwises rear insulation reaction approximately 5 hours, and process sampling product LC analyzes.Reaction finishes the rear saturated common salt water washing of using, and stratification is removed washing water, and organic phase is washed with 5% hypo solution; stratification is removed washing water again; organic phase regulates PH to 7.8 with 5% sig water, and stratification takes out organic phase, and negative pressure removes xylene solvent; finally with sherwood oil, carry out crystallization; suction filtration, dry 2,4; 6-trimethylbenzoyl-diphenyl phosphine oxide 57.7g, yield can reach 98.3%.
embodiment 3
Prepare urea-H
2o
2mixture:
The H that adds 340g30% at 1000ml beaker
2o
2in, then add 120g urea, and low-grade fever to 28 ℃, stirring and dissolving is also reacted 65min, is then cooled to 1 ℃, low temperature crystallization 90min, suction filtration obtains urea-H
2o
2the about 153g of mixture.
Prepare light trigger 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide:
By 300ml dimethylbenzene and 122g urea-H
2o
2mixture adds to 1000ml flask, loads onto mechanical stirring, under room temperature, drips 56g2, the mixing solutions of 4,6-trimethylbenzoyl-diphenylphosphine and 210ml dimethylbenzene, and about 90min dropwises rear insulation reaction approximately 5 hours, and process sampling product LC analyzes.Reaction finishes the rear saturated common salt water washing of using, and stratification is removed washing water, and organic phase is washed with 5% hypo solution; stratification is removed washing water again; organic phase regulates PH to 7.9 with 5% sig water, and stratification takes out organic phase, and negative pressure removes xylene solvent; finally with sherwood oil, carry out crystallization; suction filtration, dry 2,4; 6-trimethylbenzoyl-diphenyl phosphine oxide 57.6g, yield can reach 98.2%.
Claims (3)
1. improve a method for light trigger oxidizing reaction productive rate, it is characterized in that comprising the following steps:
Under 20-30 degrees celsius, by dimethylbenzene and urea-H
2o
2mixture is added in reactor, drips while stirring the mixing solutions of 2,4,6-trimethylbenzoyl-diphenylphosphine and dimethylbenzene, insulation reaction 4-5 hour after 80-100min dropwises, sampling analysis;
In the reaction solution of above-mentioned steps, add saturated common salt water washing, stratification, organic phase is washed with 5% hypo solution, stratification again, organic phase regulates pH to 8 with 5% sig water, and stratification takes out organic phase, negative pressure removes xylene solvent, finally with sherwood oil, carry out crystallization, suction filtration, dry 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide;
Described 2,4,6-trimethylbenzoyl-diphenylphosphine and urea-H
2o
2the weight ratio of mixture is 1:1.5～3.
2. a kind of method that improves light trigger oxidizing reaction productive rate as claimed in claim 1, is characterized in that: described urea-H
2o
2in mixture, the weight ratio that urea and 30% superoxol feed intake is: 1:2～3.
3. a kind of method that improves light trigger oxidizing reaction productive rate as claimed in claim 2, is characterized in that urea-H
2o
2the preparation of mixture comprises the following steps: by weight ratio claimed in claim 2, below 30 degrees Celsius, hydrogen peroxide is added in container, add again urea, under whipped state, react 45min～90min, be then cooled to 0 ℃, low temperature crystallization 90～150min, suction filtration obtains urea-H
2o
2mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010576916.3A CN102532194B (en) | 2010-12-07 | 2010-12-07 | Method for increasing photoinitiator oxidation reaction yield |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010576916.3A CN102532194B (en) | 2010-12-07 | 2010-12-07 | Method for increasing photoinitiator oxidation reaction yield |
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| Publication Number | Publication Date |
|---|---|
| CN102532194A CN102532194A (en) | 2012-07-04 |
| CN102532194B true CN102532194B (en) | 2014-04-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010576916.3A Active CN102532194B (en) | 2010-12-07 | 2010-12-07 | Method for increasing photoinitiator oxidation reaction yield |
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| CN115894561B (en) * | 2023-01-09 | 2023-05-26 | 天津久日新材料股份有限公司 | Method for treating solid waste in production of photo-initiator TPO |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5504236A (en) * | 1992-09-12 | 1996-04-02 | Basf Aktiengesellschaft | Preparation of α-carbonylphosphine oxides |
| CN100532576C (en) * | 2006-11-09 | 2009-08-26 | 宁波工程学院 | Preparation method of urea modified phosphonium salt tanning agent |
| CN101830931A (en) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | Preparation method of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and derivative thereof |
-
2010
- 2010-12-07 CN CN201010576916.3A patent/CN102532194B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5504236A (en) * | 1992-09-12 | 1996-04-02 | Basf Aktiengesellschaft | Preparation of α-carbonylphosphine oxides |
| CN100532576C (en) * | 2006-11-09 | 2009-08-26 | 宁波工程学院 | Preparation method of urea modified phosphonium salt tanning agent |
| CN101830931A (en) * | 2010-04-01 | 2010-09-15 | 天津久日化学工业有限公司 | Preparation method of 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide and derivative thereof |
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| CN102532194A (en) | 2012-07-04 |
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Effective date of registration: 20190226 Address after: 223300 No. 216 East Changjiang Road, Huaiyin District, Huaian City, Jiangsu Province Co-patentee after: Ningxia Wanxiangyuan Biotechnology Co., Ltd. Patentee after: Huaian Wanbang Aromatic Chemicals Co., Ltd. Address before: 223300 No. 216 East Changjiang Road, Huaiyin District, Huaian City, Jiangsu Province Patentee before: Huaian Wanbang Aromatic Chemicals Co., Ltd. |
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Address after: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Co-patentee after: Ningxia Wanxiangyuan Biotechnology Co., Ltd. Patentee after: Wanxiang Technology Co., Ltd. Address before: 223300 No. 216 Changjiang East Road, Huaiyin District, Jiangsu, Huaian Co-patentee before: Ningxia Wanxiangyuan Biotechnology Co., Ltd. Patentee before: Huaian Wanbang Aromatic Chemicals Co., Ltd. |