CN103333206A - Preparation method of TPO photoinitiator - Google Patents
Preparation method of TPO photoinitiator Download PDFInfo
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- CN103333206A CN103333206A CN201310280911XA CN201310280911A CN103333206A CN 103333206 A CN103333206 A CN 103333206A CN 201310280911X A CN201310280911X A CN 201310280911XA CN 201310280911 A CN201310280911 A CN 201310280911A CN 103333206 A CN103333206 A CN 103333206A
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Abstract
The invention relates to the technical field of TPO photoinitiators, specifically to a preparation method of a TPO photoinitiator. The method includes a diphenylethoxy phosphine preparation process and a TPO photoinitiator preparation process. The invention takes diphenylethoxy phosphine as a main raw material, which reacts with toluene and 2, 4, 6-trimethylbenzoyl chloride together, then the reaction product is subjected to heating melting, cooling crystallization, filtration and drying, thus obtaining the product with good stability and high yield. In addition, the method provided in the invention has the advantages of simple production process, low production cost, and less pollution.
Description
Technical field
The present invention relates to TPO light trigger technical field, be specifically related to the preparation method of TPO light trigger.
Background technology
The TPO light trigger is a kind of high efficiency solidifying agent, and it can be used for causing the basic photopolymer of unsaturated polyester, as the pre-polymerization system, and acrylate--as the list of reaction diluent or the compound of multifunctional monomer.Using TPO solidifies in the substitute through complete test back at UV and is used for removing and colored paint at wood, metal, plastics, paper and optical fiber, flexographic ink and tackiness agent.TPO has good solvability in common photocuring reaction reaction system, as based on acrylate and unsaturated polyester system.But complex manufacturing, the production cost of prior art are big, and the pollutent that produces in process of production is more, and the yield of its product is lower.
Summary of the invention
The preparation method of the TPO light trigger that the purpose of this invention is to provide that a kind of production technique is simple, production cost is low, pollute less, the product yield is high.
In order to solve the existing problem of background technology, the present invention is by the following technical solutions: the preparation method of TPO light trigger, comprise phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, and concrete steps are as follows:
(1), phenylbenzene oxyethyl group phosphine preparation section
Drop into toluene 200～300kg, triethylamine 300～400kg, dehydrated alcohol 100～300kg in the reactor in regular turn by weight, earlier with air in the steel cylinder nitrogen replacement still, freezing brine refrigeration is opened in sealing after finishing, and opens stirring then, when temperature of charge is cooled to subzero 2 ℃, begin to drip diphenyl phosphine chloride, the dropping time is about 3～4 hours, and temperature is subzero 2～1 ℃ in the dropping process, after dropwising, be incubated 0.5～1 hour; Close chilled brine then, under agitation, be warming up to normal temperature naturally, continue reaction 1～2 hour, esterification finishes; Carry out suction filtration then, filtration cakes torrefaction reclaims the by-product triethylamine hydrochloride, and mother liquor carries out conventional vacuum distilling, mother liquor is changed in the still kettle, and water circulating vacuum pump distills under than the rough vacuum condition, temperature control is not higher than 110 ℃, reclaim following batch of toluene solution and apply mechanically, after aforesaid operations finishes, open the high vacuum unit, connect and be distilled to receiver, underpressure distillation collect weak yellow liquid, be phenylbenzene oxyethyl group phosphine, remaining distillate outer processing of all entrusting in the still;
(2), TPO light trigger preparation section
By weight with toluene 100～200kg, phenylbenzene oxyethyl group phosphine 300～400kg drops in the synthesis reaction vessel, open stirring, open when being steam heated to 50～60 ℃, begin to drip prepare 2,4,6-tri-methyl chloride, the dropping time is 2～3 hours, temperature is controlled to be 48～52 ℃ in the dropping process, after dropwising, be warmed up to 80 ℃ of heat-preserving condensation reaction 2～3 hours, system has yellow solid to generate gradually, configuration two-stage chilled brine condenser reclaims reaction by-product monochloroethane in the reaction, intensification fusion after reaction finishes, crystallisation by cooling filters again, get yellow solid behind the filter cake drying condensation recovery solvent and be product, mother liquor is distillating recovering solvent toluene separately.
Wherein, main chemical equation is as follows:
The present invention has following beneficial effect: the preparation method of TPO light trigger of the present invention, comprise phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, be main raw material with phenylbenzene oxyethyl group phosphine, with toluene, 2, the common reaction of 4,6-tri-methyl chloride is by getting product after intensification fusion, crystallisation by cooling, filtration, the drying; Its product stability is good, yield is high.In addition, production technique of the present invention is simple, production cost is low, pollution is few.
Embodiment
Below the present invention will be further described in detail.
Embodiment one:
The preparation method of TPO light trigger comprises phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, and concrete steps are as follows:
(1), phenylbenzene oxyethyl group phosphine preparation section
Drop into toluene 200kg, triethylamine 300kg, dehydrated alcohol 100kg in the reactor in regular turn by weight, earlier with air in the steel cylinder nitrogen replacement still, freezing brine refrigeration is opened in sealing after finishing, and opens stirring then, when temperature of charge is cooled to subzero 2 ℃, begin to drip diphenyl phosphine chloride, the dropping time is about 3 hours, and temperature is subzero 2 ℃ in the dropping process, after dropwising, be incubated 0.5 hour; Close chilled brine then, under agitation, be warming up to normal temperature naturally, continue reaction 1 hour, esterification finishes; Carry out suction filtration then, filtration cakes torrefaction reclaims the by-product triethylamine hydrochloride, and mother liquor carries out conventional vacuum distilling, mother liquor is changed in the still kettle, and water circulating vacuum pump distills under than the rough vacuum condition, temperature control is not higher than 110 ℃, reclaim following batch of toluene solution and apply mechanically, after aforesaid operations finishes, open the high vacuum unit, connect and be distilled to receiver, underpressure distillation collect weak yellow liquid, be phenylbenzene oxyethyl group phosphine, remaining distillate outer processing of all entrusting in the still;
(2), TPO light trigger preparation section
By weight with toluene 100kg, phenylbenzene oxyethyl group phosphine 300kg drops in the synthesis reaction vessel, open stirring, open when being steam heated to 50 ℃, begin to drip prepare 2,4,6-tri-methyl chloride, the dropping time is 2 hours, temperature is controlled to be 48 ℃ in the dropping process, after dropwising, be warmed up to 80 ℃ of heat-preserving condensation reaction 2 hours, system has yellow solid to generate gradually, configuration two-stage chilled brine condenser reclaims reaction by-product monochloroethane in the reaction, intensification fusion after reaction finishes, crystallisation by cooling filters again, get yellow solid behind the filter cake drying condensation recovery solvent and be product, mother liquor is distillating recovering solvent toluene separately.
In the present embodiment, the hydrogenchloride of the generation that phenylbenzene oxyethyl group phosphine is produced absorbs salify by the acid binding agent triethylamine, has only a small amount of hydrogenchloride to produce, and the synthetic monochloroethane refrigerated condensation that produces of product reclaims makes by-product, because boiling point is low, the non-condensable gas discharging is arranged; Organic solvent has a small amount of volatilization waste gas to produce when feeding in raw material, distillation is reclaimed has non-condensable gas to produce, and handles outside distillation slag is all entrusted.
Embodiment two:
The preparation method of TPO light trigger comprises phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, and concrete steps are as follows:
(1), phenylbenzene oxyethyl group phosphine preparation section
Drop into toluene 250kg, triethylamine 350kg, dehydrated alcohol 200kg in the reactor in regular turn by weight, earlier with air in the steel cylinder nitrogen replacement still, freezing brine refrigeration is opened in sealing after finishing, and opens stirring then, when temperature of charge is cooled to subzero 2 ℃, begin to drip diphenyl phosphine chloride, the dropping time is about 3.5 hours, and temperature is 0 ℃ in the dropping process, after dropwising, be incubated 0.8 hour; Close chilled brine then, under agitation, be warming up to normal temperature naturally, continue reaction 1.5 hours, esterification finishes; Carry out suction filtration then, filtration cakes torrefaction reclaims the by-product triethylamine hydrochloride, and mother liquor carries out conventional vacuum distilling, mother liquor is changed in the still kettle, and water circulating vacuum pump distills under than the rough vacuum condition, temperature control is not higher than 110 ℃, reclaim following batch of toluene solution and apply mechanically, after aforesaid operations finishes, open the high vacuum unit, connect and be distilled to receiver, underpressure distillation collect weak yellow liquid, be phenylbenzene oxyethyl group phosphine, remaining distillate outer processing of all entrusting in the still;
(2), TPO light trigger preparation section
By weight with toluene 150kg, phenylbenzene oxyethyl group phosphine 350kg drops in the synthesis reaction vessel, open stirring, open when being steam heated to 55 ℃, begin to drip prepare 2,4,6-tri-methyl chloride, the dropping time is 2.5 hours, temperature is controlled to be 50 ℃ in the dropping process, after dropwising, be warmed up to 80 ℃ of heat-preserving condensation reaction 2.5 hours, system has yellow solid to generate gradually, configuration two-stage chilled brine condenser reclaims reaction by-product monochloroethane in the reaction, intensification fusion after reaction finishes, crystallisation by cooling filters again, get yellow solid behind the filter cake drying condensation recovery solvent and be product, mother liquor is distillating recovering solvent toluene separately.
Embodiment three:
The preparation method of TPO light trigger comprises phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, and concrete steps are as follows:
(1), phenylbenzene oxyethyl group phosphine preparation section
Drop into toluene 300kg, triethylamine 400kg, dehydrated alcohol 300kg in the reactor in regular turn by weight, earlier with air in the steel cylinder nitrogen replacement still, freezing brine refrigeration is opened in sealing after finishing, and opens stirring then, when temperature of charge is cooled to subzero 2 ℃, begin to drip diphenyl phosphine chloride, the dropping time is about 4 hours, and temperature is 1 ℃ in the dropping process, after dropwising, be incubated 1 hour; Close chilled brine then, under agitation, be warming up to normal temperature naturally, continue reaction 2 hours, esterification finishes; Carry out suction filtration then, filtration cakes torrefaction reclaims the by-product triethylamine hydrochloride, and mother liquor carries out conventional vacuum distilling, mother liquor is changed in the still kettle, and water circulating vacuum pump distills under than the rough vacuum condition, temperature control is not higher than 110 ℃, reclaim following batch of toluene solution and apply mechanically, after aforesaid operations finishes, open the high vacuum unit, connect and be distilled to receiver, underpressure distillation collect weak yellow liquid, be phenylbenzene oxyethyl group phosphine, remaining distillate outer processing of all entrusting in the still;
(2), TPO light trigger preparation section
By weight with toluene 200kg, phenylbenzene oxyethyl group phosphine 400kg drops in the synthesis reaction vessel, open stirring, open when being steam heated to 60 ℃, begin to drip prepare 2,4,6-tri-methyl chloride, the dropping time is 3 hours, temperature is controlled to be 52 ℃ in the dropping process, after dropwising, be warmed up to 80 ℃ of heat-preserving condensation reaction 3 hours, system has yellow solid to generate gradually, configuration two-stage chilled brine condenser reclaims reaction by-product monochloroethane in the reaction, intensification fusion after reaction finishes, crystallisation by cooling filters again, get yellow solid behind the filter cake drying condensation recovery solvent and be product, mother liquor is distillating recovering solvent toluene separately.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, other modifications that those of ordinary skills make technical scheme of the present invention or be equal to replacement, only otherwise break away from the spirit and scope of technical solution of the present invention, all should be encompassed in the middle of the claim scope of the present invention.
Claims (1)
1.TPO the preparation method of light trigger is characterized in that, comprises phenylbenzene oxyethyl group phosphine preparation section and TPO light trigger preparation section, concrete steps are as follows:
(1), phenylbenzene oxyethyl group phosphine preparation section
Drop into toluene 200～300kg, triethylamine 300～400kg, dehydrated alcohol 100～300kg in the reactor in regular turn by weight, earlier with air in the steel cylinder nitrogen replacement still, freezing brine refrigeration is opened in sealing after finishing, and opens stirring then, when temperature of charge is cooled to subzero 2 ℃, begin to drip diphenyl phosphine chloride, the dropping time is about 3～4 hours, and temperature is subzero 2～1 ℃ in the dropping process, after dropwising, be incubated 0.5～1 hour; Close chilled brine then, under agitation, be warming up to normal temperature naturally, continue reaction 1～2 hour, esterification finishes; Carry out suction filtration then, filtration cakes torrefaction reclaims the by-product triethylamine hydrochloride, and mother liquor carries out conventional vacuum distilling, mother liquor is changed in the still kettle, and water circulating vacuum pump distills under than the rough vacuum condition, temperature control is not higher than 110 ℃, reclaim following batch of toluene solution and apply mechanically, after aforesaid operations finishes, open the high vacuum unit, connect and be distilled to receiver, underpressure distillation collect weak yellow liquid, be phenylbenzene oxyethyl group phosphine, remaining distillate outer processing of all entrusting in the still;
(2), TPO light trigger preparation section
By weight with toluene 100～200kg, phenylbenzene oxyethyl group phosphine 300～400kg drops in the synthesis reaction vessel, open stirring, open when being steam heated to 50～60 ℃, begin to drip prepare 2,4,6-tri-methyl chloride, the dropping time is 2～3 hours, temperature is controlled to be 48～52 ℃ in the dropping process, after dropwising, be warmed up to 80 ℃ of heat-preserving condensation reaction 2～3 hours, system has yellow solid to generate gradually, configuration two-stage chilled brine condenser reclaims reaction by-product monochloroethane in the reaction, intensification fusion after reaction finishes, crystallisation by cooling filters again, get yellow solid behind the filter cake drying condensation recovery solvent and be product, mother liquor is distillating recovering solvent toluene separately.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304220A (en) * | 2016-04-22 | 2017-10-31 | 江苏英力科技发展有限公司 | The method that a kind of " one kettle way " synthesizes 2,4,6- trimethylbenzoy-dipheny phosphine oxides |
| WO2018228041A1 (en) * | 2017-06-16 | 2018-12-20 | 湖北固润科技股份有限公司 | Method for preparing tpo compound and co-producing 3-hydroxyalkyl-substituted oxetane compound |
| CN109336925A (en) * | 2018-11-24 | 2019-02-15 | 绍兴上虞易瑞化工有限公司 | A kind of novel synthesis of photoinitiator 2,4,6- trimethylbenzoy-dipheny phosphine oxide |
| CN109776608A (en) * | 2019-04-02 | 2019-05-21 | 宁波易兮化工科技有限公司 | A kind of novel synthesis of the photoinitiator 2,4,6- trimethylbenzoy-dipheny phosphine oxide of clean and safe |
| CN110818737A (en) * | 2018-08-10 | 2020-02-21 | 天津墨森科技有限公司 | New preparation method of phenylphosphine oxide initiator |
| WO2020113585A1 (en) * | 2018-12-07 | 2020-06-11 | 安庆莱霆光电科技有限公司 | Acylphosphine oxide compound and preparation method therefor |
| CN111925401A (en) * | 2020-08-31 | 2020-11-13 | 怀化市恒渝新材料有限公司 | Method for improving clarity of photoinitiator |
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| DE3139984C2 (en) * | 1981-10-08 | 1989-10-19 | Basf Ag, 6700 Ludwigshafen, De | |
| CN1622948A (en) * | 2002-01-24 | 2005-06-01 | 巴斯福股份公司 | Method for the separation of acids from chemical reaction mixtures by means of ionic fluids |
| CN1777616A (en) * | 2003-04-04 | 2006-05-24 | 巴斯福股份公司 | Method for producing acylphosphine oxide solids |
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Patent Citations (3)
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| DE3139984C2 (en) * | 1981-10-08 | 1989-10-19 | Basf Ag, 6700 Ludwigshafen, De | |
| CN1622948A (en) * | 2002-01-24 | 2005-06-01 | 巴斯福股份公司 | Method for the separation of acids from chemical reaction mixtures by means of ionic fluids |
| CN1777616A (en) * | 2003-04-04 | 2006-05-24 | 巴斯福股份公司 | Method for producing acylphosphine oxide solids |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107304220B (en) * | 2016-04-22 | 2020-03-31 | 江苏英力科技发展有限公司 | Method for synthesizing 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide by one-pot method |
| CN107304220A (en) * | 2016-04-22 | 2017-10-31 | 江苏英力科技发展有限公司 | The method that a kind of " one kettle way " synthesizes 2,4,6- trimethylbenzoy-dipheny phosphine oxides |
| WO2018228041A1 (en) * | 2017-06-16 | 2018-12-20 | 湖北固润科技股份有限公司 | Method for preparing tpo compound and co-producing 3-hydroxyalkyl-substituted oxetane compound |
| CN109134537A (en) * | 2017-06-16 | 2019-01-04 | 湖北固润科技股份有限公司 | The method for preparing the oxetanes based compound of TPO based compound co-production 3- hydroxyalkyl substitution |
| CN109134537B (en) * | 2017-06-16 | 2019-09-06 | 湖北固润科技股份有限公司 | The method for preparing the oxetanes based compound of TPO based compound co-production 3- hydroxyalkyl substitution |
| CN110818737B (en) * | 2018-08-10 | 2022-02-11 | 天津墨森科技有限公司 | New preparation method of phenylphosphine oxide initiator |
| CN110818737A (en) * | 2018-08-10 | 2020-02-21 | 天津墨森科技有限公司 | New preparation method of phenylphosphine oxide initiator |
| CN109336925A (en) * | 2018-11-24 | 2019-02-15 | 绍兴上虞易瑞化工有限公司 | A kind of novel synthesis of photoinitiator 2,4,6- trimethylbenzoy-dipheny phosphine oxide |
| CN109336925B (en) * | 2018-11-24 | 2020-10-09 | 绍兴上虞易瑞化工有限公司 | Synthesis method of photoinitiator 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide |
| WO2020113585A1 (en) * | 2018-12-07 | 2020-06-11 | 安庆莱霆光电科技有限公司 | Acylphosphine oxide compound and preparation method therefor |
| CN113454095A (en) * | 2018-12-07 | 2021-09-28 | 安庆莱霆光电科技有限公司 | Acylphosphinoxide compound and preparation method thereof |
| CN113454095B (en) * | 2018-12-07 | 2023-08-22 | 安庆莱霆光电科技有限公司 | Acylphosphino-oxygen compound and preparation method thereof |
| CN109776608A (en) * | 2019-04-02 | 2019-05-21 | 宁波易兮化工科技有限公司 | A kind of novel synthesis of the photoinitiator 2,4,6- trimethylbenzoy-dipheny phosphine oxide of clean and safe |
| CN111925401A (en) * | 2020-08-31 | 2020-11-13 | 怀化市恒渝新材料有限公司 | Method for improving clarity of photoinitiator |
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Application publication date: 20131002 |