CN101003482A - Method for preparing trimethylolpropane trimethyl acrylic ester - Google Patents
Method for preparing trimethylolpropane trimethyl acrylic ester Download PDFInfo
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- CN101003482A CN101003482A CN 200710036705 CN200710036705A CN101003482A CN 101003482 A CN101003482 A CN 101003482A CN 200710036705 CN200710036705 CN 200710036705 CN 200710036705 A CN200710036705 A CN 200710036705A CN 101003482 A CN101003482 A CN 101003482A
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- trimethylolpropane
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Abstract
This invention discloses a method for preparing trihydroxymethyl propane trimethyl acrylate. The method comprises: utilizing trihydroxymethyl propane as the raw material, and esterifying with methyl acrylic acid in the presence of catalyst, polymerization inhibitor water-carrying agent to obtain trihydroxymethyl propane trimethyl acrylate with purity higher than 98%, acid number less than or equal to 0.5 mg/g, and esterification degree higher than 98%. The method has such advantages as mild reaction conditions, easy and safe operation, no apparatus corrosion, and high product purity. The recovered catalyst can be reused.
Description
Technical Field
The invention relates to a preparation method of trimethylolpropane trimethacrylate.
Background
Trimethylolpropane trimethacrylate is an important monomer in acrylate series products, has the characteristics of high double bond content, high curing speed, lowviscosity, high boiling point, low volatility and the like, becomes a multifunctional acrylate active crosslinking diluent which has the widest application and the largest using amount in the radiation curing field, and can be used for ink, coating, adhesive, casting products and the like which can be cured by Ultraviolet (UV), radiation or heat.
In the prior art, trimethylolpropane trimethacrylate is obtained by directly esterifying Trimethylolpropane (TMP) and methacrylic acid (MAA) or is synthesized by ester exchange of the Trimethylolpropane (TMP) and Methyl Methacrylate (MMA) under the action of a catalyst, and the adopted catalyst is sulfuric acid or p-toluenesulfonic acid. The existing method has the disadvantages of complex post-treatment operation, easy corrosion of equipment and high product cost.
A preparation method of trimethylolpropane trimethacrylate is reported in volume 23 and 4 of the 'fine petrochemical industry' in 2006, cerium salt is adopted as a catalyst, and although the adverse factors caused by adopting catalysts such as sulfuric acid and the like are overcome, the cerium salt catalyst is high in price and difficult to recover and is difficult to industrially produce.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of trimethylolpropane trimethacrylate to overcome the defects of complex post-treatment operation, easy corrosion of equipment, high cost of cerium salt catalyst and difficult recovery in the synthesis method in the prior art.
The technical idea of the invention is as follows: trimethylolpropane is used as a raw material and is subjected to esterification reaction with methacrylic acid in the presence of a catalyst, a polymerization inhibitor and a water-carrying agent to obtain thetarget product trimethylolpropane trimethacrylate.
The technical scheme of the invention is as follows:
the reaction formula of the invention is as follows:
reacting trimethylolpropane and methacrylic acid for 3-6 hours at 90-100 ℃ in the presence of a CZ zirconium-based solid acid catalyst, a polymerization inhibitor and a water-carrying agent in the atmosphere of air, and then collecting trimethylolpropane trimethacrylate from reaction products.
According to the invention, the polymerization inhibitor is formed by mixing hydroquinone and phenothiazine, and the water-carrying agent is formed by mixing toluene and cyclohexane. During the reaction, the flow rate of air is kept at 5-7 ml/min.
The mixing ratio of the invention is that the molar ratio of the reactant trimethylolpropane to the methacrylic acid is 1: 3-4, and the mass ratio of the trimethylolpropane to the catalyst is 100: 2-5.
The mass ratio of the trimethylolpropane to the polymerization inhibitor is 100-150: 1, and the polymerization inhibitor is prepared according to the mass ratio of 1-10: 1 of hydroquinone to phenothiazine.
The weight volume ratio of the trimethylolpropane to the water-carrying agent is 40: 100, and the water-carrying agent is prepared according to the volume ratio of toluene to cyclohexane of 30: 70-70: 30.
The collection of trimethylolpropane trimethacrylate from the reaction product according to the present invention comprises the steps of: filtering the reaction solution, adding activated carbon into the reaction mother liquor for decoloring, filtering, and evaporating the solvent from the filtrate under reduced pressure to obtain the target product of the invention.
The trimethylolpropane trimethacrylate prepared by the preparation method has the purity of more than 98 percent, the acid value of less than or equal to 0.5mg/g and the esterification rate of more than 98 percent.
Compared with the prior art, the method uses the catalyst CZ zirconium-based solid acid, has mild reaction process conditions, safe and simple operation, avoids the corrosion problem of equipment, can repeatedly use the catalyst recovered by the preparation method, has low cost and good purity of the obtained product, and is suitable for industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
40.25g (0.3mol) of trimethylolpropane, 90.41g (1.05mol) of methacrylic acid, 0.39g of polymerization inhibitor (prepared according to the mass ratio of hydroquinone to phenothiazine being 2: 1), 1.21g of CZ zirconium-based solid acid catalyst and 100ml of water-carrying agent (prepared according to the volume ratio of toluene to cyclohexane being 45: 55) are respectively added into a reactor provided with a reflux condenser, a water separator, a thermometer, a stirrer and an air sample injection device, the temperature is gradually increased to 85 +/-5 ℃ while stirring, the flow rate of air introduced into the reactor is continuously kept to be 7ml/min, the reaction is carried out for 5 hours at the temperature of 90-100 ℃ (the reaction end point is when no water generated by the reaction of the water-carrying agent is taken out), and filter residue obtained by filtering reaction liquid is the CZ zirconium-based solid acid catalyst (recovered and reused). Adding 2g of activated carbon into the reaction mother liquor, stirring and heating to 45 +/-5 ℃, maintaining for 15 minutes, filtering while the reaction mother liquor is hot, removing the activated carbon, decompressing and distilling off the solvent from the filtrate to obtain 110g of the target product trimethylolpropane trimethacrylate, wherein the purity is 98.2%, the acid value is less than or equal to 0.5mg/g (the acid value detection method is determined according to the method of GB 1668-8), the esterification rate is 98.2%, and the esterification rate detection method is calculated according to the esterification rate (1-the acid value of a system after the reaction/the acid value of a system before the reaction) multiplied by 100).
Example 2
40.25g (0.3mol) of trimethylolpropane, 87.8g (1.02mol) of methacrylic acid, 0.29g of polymerization inhibitor (prepared according to the mass ratio of hydroquinone to phenothiazine being 2: 1), 1.25g of CZ zirconium-based solid acid catalyst and 100ml of water-carrying agent (prepared according to the volume ratio of toluene to cyclohexane being 55: 45) are respectively added into a reactor provided with a reflux condenser, a water separator, a thermometer, a stirrer and an air sample injection device, the temperature is gradually increased to 85 +/-5 ℃ while stirring, the flow rate of air introduced into the reactor is continuously kept to be 7ml/min, the reaction is carried out for 4 hours at the temperature of 90-100 ℃ (the reaction end point is when no water generated by the reaction with the water-carrying agent is taken out), and filter residue obtained by filtering reaction liquid is the CZ zirconium-based solid acid catalyst (recovered and reused). Adding 1g of activated carbon into the reaction mother liquor, stirring and heating to 50 +/-5 ℃, maintaining for 15 minutes, filtering while hot, removing the activated carbon, decompressing and steaming out the solvent from the filtrate to obtain 110g of the target product trimethylolpropane trimethacrylate, wherein the purity is 98.0 percent, the acid value is less than or equal to 0.5mg/g, and the esterification rate is 98.0 percent.
Claims (9)
1. A preparation method of trimethylolpropane trimethacrylate is characterized by comprising the following steps:
reacting trimethylolpropane and methacrylic acid for 3-6 hours at 90-100 ℃ in the presence of a CZ zirconium-based solid acid catalyst, a polymerization inhibitor and a water-carrying agent in the atmosphere of air, and then collecting trimethylolpropane trimethacrylate from reaction products.
2. The method of claim 1, wherein the polymerization inhibitor is a mixture of hydroquinone and phenothiazine.
3. The method of claim 1, wherein the water-carrying agent is a mixture of toluene and cyclohexane.
4. The method of claim 1, wherein the flow rate of air is 5 to 7 ml/min.
5. The method of claim 1, wherein the molar ratio of trimethylolpropane to the methacrylic acid ingredient is 1: 3-4.
6. The method of claim 1, wherein the mass ratio of trimethylolpropane to the catalyst is 100: 2-5.
7. The method according to claim 1, wherein the mass ratio of trimethylolpropane to polymerization inhibitor is 100-150: 1, and the polymerization inhibitor is prepared at a mass ratio of hydroquinone to phenothiazine of 1-10: 1.
8. The method according to claim 1, wherein the weight/volume ratio of trimethylolpropane to water-carrying agent is 40: 100, and the water-carrying agent is prepared according to the volume ratio of toluene to cyclohexane being 30: 70-70: 30.
9. The method of claim 1, wherein the collecting of trimethylolpropane trimethacrylate from the reaction product comprises the steps of: filtering the reaction solution, adding activated carbon into the reaction mother liquor for decoloring, filtering, and evaporating the solvent from the filtrate under reduced pressure to obtain the target product of the invention.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710036705 CN101003482A (en) | 2007-01-22 | 2007-01-22 | Method for preparing trimethylolpropane trimethyl acrylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710036705 CN101003482A (en) | 2007-01-22 | 2007-01-22 | Method for preparing trimethylolpropane trimethyl acrylic ester |
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| CN101003482A true CN101003482A (en) | 2007-07-25 |
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| CN 200710036705 Pending CN101003482A (en) | 2007-01-22 | 2007-01-22 | Method for preparing trimethylolpropane trimethyl acrylic ester |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101450898B (en) * | 2008-12-30 | 2013-12-11 | 江苏利田科技股份有限公司 | UV photo-curing monomer clean production process through coupling reactor and simulated moving bed |
| CN104910014A (en) * | 2015-05-31 | 2015-09-16 | 湖南省金海科技有限公司 | Clean production method for acrylic ester reactive diluent with three functionality degrees |
| CN105732360A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Polymerization inhibitor for acrylic acid monomer refining |
| CN106748761A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN108277393A (en) * | 2018-02-05 | 2018-07-13 | 南通鑫祥锌业有限公司 | A kind of zinc band and preparation method thereof |
-
2007
- 2007-01-22 CN CN 200710036705 patent/CN101003482A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101450898B (en) * | 2008-12-30 | 2013-12-11 | 江苏利田科技股份有限公司 | UV photo-curing monomer clean production process through coupling reactor and simulated moving bed |
| 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 |
| CN105732360A (en) * | 2014-12-08 | 2016-07-06 | 中国石油天然气股份有限公司 | Polymerization inhibitor for acrylic acid monomer refining |
| CN105732360B (en) * | 2014-12-08 | 2018-02-02 | 中国石油天然气股份有限公司 | A kind of polymerization inhibitor refined for acrylic monomers |
| CN104910014A (en) * | 2015-05-31 | 2015-09-16 | 湖南省金海科技有限公司 | Clean production method for acrylic ester reactive diluent with three functionality degrees |
| CN106748761A (en) * | 2016-11-15 | 2017-05-31 | 惠州市长润发涂料有限公司 | A kind of preparation method of trimethylolpropane trimethacrylate |
| CN108277393A (en) * | 2018-02-05 | 2018-07-13 | 南通鑫祥锌业有限公司 | A kind of zinc band and preparation method thereof |
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Application publication date: 20070725 |