CN108752201A - A kind of green synthesis process of trimethylolpropane trimethacrylate - Google Patents
A kind of green synthesis process of trimethylolpropane trimethacrylate Download PDFInfo
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- CN108752201A CN108752201A CN201810659619.1A CN201810659619A CN108752201A CN 108752201 A CN108752201 A CN 108752201A CN 201810659619 A CN201810659619 A CN 201810659619A CN 108752201 A CN108752201 A CN 108752201A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to a kind of green synthesis process of trimethylolpropane trimethacrylate,（1）Each raw material, temperature rising reflux is added, until no moisture in phegma, is down to room temperature；（2）The washing that last consignment of step (4) obtains mutually is put into reaction kettle washing, obtained Loprazolam water phase concentration, and circulating and recovering next group step（1）；（3）Reaction solution after washing is added sodium hydroxide solution washing, stratification, and sulfuric acid solution, which is added, in obtained alkali cleaning water phase is adjusted, then be evaporated under reduced pressure, rectifying obtains acrylic acid；（4）Water washing is added in material after alkali cleaning, and p-hydroxyanisole, stratification is added, and lower layer's washing is mutually used for next group step (2)；（5）The reaction mass for removing water phase goes to evaporator, vacuumizes, obtains product.The advantage of the invention is that：The present invention enables to catalyst, excessive acrylic raw materials and solvent to be separately recovered and recycle, the discharge of waste water is reduced while having saved production cost by changing post processing mode.
Description
Technical field
The present invention relates to a kind of synthetic method of trimethylolpropane trimethacrylate, more particularly to one kind can will be catalyzed
The green synthesis process for the trimethylolpropane trimethacrylate that agent, raw material propylene acid and solvent recovery cycle utilize.
Background technology
Polyalcohol acrylate has wide in the various fields such as the modification and crosslinking of photocureable coating, ink and polymer
General purposes, wherein trimethylolpropane trimethacrylate (TMPTA) are a kind of important acrylate polyfunctional monomers, it was both
Monomer can be used as synthesizing Special Resin, and be the modifying agent or crosslinking agent of fabulous high molecular polymerization system.Due to three
The double bond content of hydroxymethyl-propane triacrylate is high, and curing rate is fast, this make it in radiation curing field it is most widely used,
The maximum multi-functional acrylate's class reactive diluent of dosage, in addition trimethylolpropane trimethacrylate still manufacture bonding
The raw material of the products such as agent, integrated circuit board, printed wiring board, ink, anaerobic adhesive, therefore trimethylolpropane trimethacrylate is made
There is prodigious application market and important commercial value for new material.
The production method of current trimethylolpropane trimethacrylate is mostly in catalyst, polymerization inhibitor and water entrainer
Under the conditions of existing, direct esterification reaction is carried out by trimethylolpropane and acrylic acid, uses low-concentration alkali liquor after the completion of reaction
Excessive acrylic acid, acidic catalyst in esterifying liquid are neutralized, removing water entrainer is finally vacuumized.In actual production, in order to increase
Esterification degree, usual acrylic acid is excessive 10-20%, and excessive acrylic acid and catalyst must go out, the prior art
Main method is using the technique for neutralizing, washing, and the product for producing 1t about generates the waste water of 1t, and the waste water is seldom seen
Report energy Efficient Cycle processing, majority by the way of direct emission, are lost a large amount of acrylic acid, improve production after sending sewage disposal
Environment is also polluted while cost, is a kind of production technology of pole not environmentally.
Invention content
The technical problem to be solved in the present invention is to provide a kind of green synthesis process of trimethylolpropane trimethacrylate,
The synthesis technology enables to catalyst, excessive acrylic raw materials and solvent to be separately recovered simultaneously by changing post processing mode
It recycles, the discharge of waste water is reduced while having saved production cost.
In order to solve the above technical problems, the technical scheme is that：A kind of trimethylolpropane trimethacrylate it is green
Color synthesis technology, innovative point are：The green synthesis process includes the following steps：
（1）Solvent hexane is put into reaction kettle of the esterification, major ingredient trimethylolpropane and acrylic acid is then added, adds inhibition
Agent p-hydroxyanisole and catalyst methane sulfonic acid after charging, are warming up to 65-75 DEG C of back flow reaction, keep the temperature 6-12h, directly
It is taken out of to no moisture in phegma, starts to be cooled to room temperature；
（2）The washing that last consignment of step (4) obtains mutually is put into reaction kettle to wash, the water phase to obtaining Loprazolam carries out
Concentration, detection Loprazolam content after 50-80% circulating and recovering to next group step（1）Reaction in；
（3）Sodium hydroxide solution washing is added to the reaction solution after washing, the pH for controlling reaction mass is 7-9, and stratification obtains
To the water phase containing sodium acrylate, into obtained alkali cleaning water phase, addition sulfuric acid solution, which is adjusted to after pH=3-5, is directly evaporated under reduced pressure,
The aqueous solution for steaming acrylic acid obtains acrylic acid after purification using rectifying；The kettle liquid sodium hydroxide solution obtained after distillation
It is adjusted to neutrality, by-product sodium sulphate is obtained after concentrated；
（4）Water washing is added to the material after alkali cleaning, and polymerization inhibitor p-hydroxyanisole is added, stands reaction mass layering
Afterwards, the washing that lower layer's washing is mutually used for next group step (2) is collected；
（5）The reaction mass material for removing water phase is transferred in evaporator, is vacuumized, removes solvent and moisture, you can obtain three
Hydroxymethyl-propane triacrylate product, the solvent of removing can be used for step（1）Middle recycled；Wherein, during reaction feeds intake
The weight proportion of each component is：
N-hexane 20-40%
Trimethylolpropane 20-40%
Acrylic acid 35-55%
Step（1）Middle p-hydroxyanisole 100-400ppm
Step（4）Middle p-hydroxyanisole 10-200ppm
Loprazolam 1-5%.
Further, the step（3）The mass concentration of middle sodium hydroxide solution is 1-10%, and the quality of sulfuric acid solution is dense
Degree is 10-50%.
Further, the step（4）In washing water be solvent adding amount 50-150%.
Further, the step（5）Middle vacuum degree < 3000Pa, removal temperature are 60-80 DEG C, and the removing time is 0.5
~1h.
The advantage of the invention is that：The green synthesis process of trimethylolpropane trimethacrylate of the present invention, production technology
Simply, by-product is few, quality is high, mutually handles washing, will recycle respectively with the waste water that alkali cleaning mutually generates in last handling process
To Loprazolam and acrylic acid circulating and recovering to reaction in, greatly reduce production cost；In addition, reaction process almost without
The three wastes are discharged, and environmental protection while creates economic benefit, is a kind of green synthesis process.
Specific implementation mode
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment 1
The green synthesis process of the present embodiment trimethylolpropane trimethacrylate, includes the following steps：
(1) solvent hexane 1352.9g is put into reaction kettle of the esterification, major ingredient trimethylolpropane 1012.6g and acrylic acid is added
1793.3g adds polymerization inhibitor p-hydroxyanisole 0.7g and catalyst methane sulfonic acid 54.5g；69 DEG C of back flow reactions are warming up to,
9h is kept the temperature, until no moisture is taken out of in phegma, starts to be cooled to room temperature；
(2) washing that last consignment of step (4) obtains reaction kettle is mutually put into wash, to obtain the water phase of Loprazolam into
Row concentration detects after its content in circulating and recovering to next batch reaction；
(3) washing of 8% sodium hydroxide solution is added to the reaction solution after washing, the pH for controlling reaction mass is 7.5, stands and divides
Layer, obtains the water phase containing sodium acrylate, is directly concentrated after 35% sulfuric acid solution is adjusted to pH=4.5, and light component is propylene sour water
Solution, using obtaining acrylic acid after rectifying；Heavy constituent is adjusted to neutrality with sodium hydroxide solution, then is concentrated to give by-product sulfuric acid
Sodium；
(4) 1000g water washings are added to the material after alkali cleaning, and polymerization inhibitor p-hydroxyanisole 0.2g is added, stand and wait reacting
After material layering, the washing that lower layer's washing is mutually used for next group step (3) is collected；
(5) the reaction mass material for removing water phase is transferred in evaporator, 80 DEG C of removal temperature, removes time 0.5h, vacuum degree
< 3000Pa remove solvent and moisture, you can obtain product trimethylolpropane trimethacrylate, obtained solvent directly can be with
Recycled.Obtained product is after testing：Ester content 98.2%, acid value<0.05mgKOH/g, color number 15.
Embodiment 2
The green synthesis process of the present embodiment trimethylolpropane trimethacrylate, includes the following steps：
(1) solvent hexane 608kg and recycling n-hexane 744.9kg are put into reaction kettle of the esterification, major ingredient trihydroxy methyl third is added
Alkane 1012.6kg, acrylic acid 1738.9kg and acrylic acid 163.0kg add polymerization inhibitor p-hydroxyanisole 0.8kg, urge
Agent Loprazolam 38.2kg and recycling Loprazolam 43.6kg；69 DEG C of back flow reactions are warming up to, 7h is kept the temperature, until in phegma
No moisture is taken out of, starts to be cooled to room temperature；
(2) the last washing of last consignment of reaction kettle mutually being put into wash, the water phase to obtaining Loprazolam concentrates,
It detects after its content in circulating and recovering to next batch reaction；
(3) washing of 5% sodium hydroxide solution is added to the reaction solution after washing, the pH for controlling reaction mass is 8.0, stands and divides
Layer, obtains the water phase containing sodium acrylate, is directly concentrated after 45% sulfuric acid solution is adjusted to pH=3.5, and light component is propylene sour water
Solution, using obtaining acrylic acid after rectifying；Heavy constituent is adjusted to neutrality with sodium hydroxide solution, then is concentrated to give by-product sulfuric acid
Sodium；
(4) 800kg water washings are added to the material after alkali cleaning, and polymerization inhibitor p-hydroxyanisole 0.2kg is added, standing waits for anti-
After answering material layering, the washing that lower layer's washing is mutually used for next group step (3) is collected；
(5) reaction mass for removing water phase being transferred in evaporator and removes solvent, 60 DEG C of removal temperature removes time 0.8h,
Vacuum degree < 1000Pa.Remove solvent, you can obtain product trimethylolpropane trimethacrylate, obtained solvent directly can be with
Recycled.Obtained product is after testing：Ester content 97.5%, acid value<0.07mgKOH/g, color number 20.
For producing 1t trimethylolpropane trimethacrylate products, the comparison of this method and other methods：
| This method | Other methods | |
| The waste water of generation | Almost without | About 1t |
| Product ester content | >97.0% | >95.0% |
| Product acid value | <0.1mgKOH/g | <0.3mgKOH/g |
| Production cost (ten thousand yuan) | 1.40 | 1.65 |
As can be seen from the above table, simple production process of the present invention, by-product are few, quality is high, in last handling process to washing mutually and
The waste water that alkali cleaning mutually generates is handled respectively, in Loprazolam and acrylic acid circulating and recovering to reaction that recycling is obtained, greatly
Reduce production cost；In addition, reaction process almost no waste discharge, environmental protection while, creates economic benefit, is one
Kind green synthesis process.
The basic principles and main features and advantages of the present invention of the present invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (4)
1. a kind of green synthesis process of trimethylolpropane trimethacrylate, it is characterised in that：The green synthesis process packet
Include following steps：
（1）Solvent hexane is put into reaction kettle of the esterification, major ingredient trimethylolpropane and acrylic acid is then added, adds inhibition
Agent p-hydroxyanisole and catalyst methane sulfonic acid after charging, are warming up to 65-75 DEG C of back flow reaction, keep the temperature 6-12h, directly
It is taken out of to no moisture in phegma, starts to be cooled to room temperature；
（2）The washing that last consignment of step (4) obtains mutually is put into reaction kettle to wash, the water phase to obtaining Loprazolam carries out
Concentration, detection Loprazolam content after 50-80% circulating and recovering to next group step（1）Reaction in；
（3）Sodium hydroxide solution washing is added to the reaction solution after washing, the pH for controlling reaction mass is 7-9, and stratification obtains
To the water phase containing sodium acrylate, into obtained alkali cleaning water phase, addition sulfuric acid solution, which is adjusted to after pH=3-5, is directly evaporated under reduced pressure,
The aqueous solution for steaming acrylic acid obtains acrylic acid after purification using rectifying；The kettle liquid sodium hydroxide solution obtained after distillation
It is adjusted to neutrality, by-product sodium sulphate is obtained after concentrated；
（4）Water washing is added to the material after alkali cleaning, and polymerization inhibitor p-hydroxyanisole is added, stands reaction mass layering
Afterwards, the washing that lower layer's washing is mutually used for next group step (2) is collected；
（5）The reaction mass material for removing water phase is transferred in evaporator, is vacuumized, removes solvent and moisture, you can obtain three
Hydroxymethyl-propane triacrylate product, the solvent of removing can be used for step（1）Middle recycled；Wherein, during reaction feeds intake
The weight proportion of each component is：
N-hexane 20-40%
Trimethylolpropane 20-40%
Acrylic acid 35-55%
Step（1）Middle p-hydroxyanisole 100-400ppm
Step（4）Middle p-hydroxyanisole 10-200ppm
Loprazolam 1-5%.
2. the green synthesis process of trimethylolpropane trimethacrylate according to claim 1, it is characterised in that：It is described
Step（3）The mass concentration of middle sodium hydroxide solution is 1-10%, and the mass concentration of sulfuric acid solution is 10-50%.
3. the green synthesis process of trimethylolpropane trimethacrylate according to claim 1, it is characterised in that：It is described
Step（4）In washing water be solvent adding amount 50-150%.
4. the green synthesis process of trimethylolpropane trimethacrylate according to claim 1, it is characterised in that：It is described
Step（5）Middle vacuum degree < 3000Pa, removal temperature are 60-80 DEG C, and the removing time is 0.5~1h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810659619.1A CN108752201A (en) | 2018-06-25 | 2018-06-25 | A kind of green synthesis process of trimethylolpropane trimethacrylate |
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| CN201810659619.1A CN108752201A (en) | 2018-06-25 | 2018-06-25 | A kind of green synthesis process of trimethylolpropane trimethacrylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110734370A (en) * | 2019-10-21 | 2020-01-31 | 江苏利田科技股份有限公司 | Method and device for recovering acrylic acid from UV (ultraviolet) light curing monomer crude products |
| CN111825550A (en) * | 2019-04-23 | 2020-10-27 | 上海飞凯光电材料股份有限公司 | Preparation method of 4-phenylbenzyl (meth) acrylate |
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| CN102146037A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing 2-methyl-2-propenoic acid 2-ethyl-2-[[(2-methyl-1-oxo-2-propenyl)oxy]methyl]-1,3-propanediyl ester |
| CN105968002A (en) * | 2016-05-06 | 2016-09-28 | 中国环境科学研究院 | Method for producing acrylic acid ester with low pollutant discharge amount |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111825550A (en) * | 2019-04-23 | 2020-10-27 | 上海飞凯光电材料股份有限公司 | Preparation method of 4-phenylbenzyl (meth) acrylate |
| CN110734370A (en) * | 2019-10-21 | 2020-01-31 | 江苏利田科技股份有限公司 | Method and device for recovering acrylic acid from UV (ultraviolet) light curing monomer crude products |
| CN110734370B (en) * | 2019-10-21 | 2022-11-22 | 江苏利田科技有限公司 | Method and device for recovering acrylic acid in UV (ultraviolet) photocuring monomer crude product |
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Application publication date: 20181106 |