CN102229529A - Preparation method of (methyl) crylic acid phenylethanol ester compounds - Google Patents
Preparation method of (methyl) crylic acid phenylethanol ester compounds Download PDFInfo
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- CN102229529A CN102229529A CN2011101209434A CN201110120943A CN102229529A CN 102229529 A CN102229529 A CN 102229529A CN 2011101209434 A CN2011101209434 A CN 2011101209434A CN 201110120943 A CN201110120943 A CN 201110120943A CN 102229529 A CN102229529 A CN 102229529A
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Abstract
The invention relates to a preparation method of (methyl) crylic acid phenylethanol ester compounds. The targeted compounds are prepared by performing esterification reaction or ester exchange reaction on (methyl) crylic acid (ester) and phenylethanol compounds in the presence of an acid catalyst and a polymerization inhibitor. In the method, the used two reaction raw materials are the common chemical reagents, so highly irritant raw materials are avoided; and the targeted products are obtained through the esterification reaction or the ester exchange reaction, so the method is mild in reaction condition, high in yield, simple and convenient in separation and purification, high in purity of the obtained product and applicable to large-scale industrial production.
Description
Technical field
The present invention relates to organic chemistry filed, be specifically related to a kind of method by esterification or transesterification reaction preparation (methyl) vinylformic acid phenylglycollic ester compounds.
Background technology
(methyl) vinylformic acid phenylglycollic ester compounds is the extremely important polymer monomer of a class, and described polymkeric substance is widely used in aspects such as sizing agent, coating, resin, fiber process, rubber industry, medical material.Because its good security and compatibility, by hot research be applied to life medical fields (referring to WO2008/013950A2, WO2009/137525A1 etc.) such as dental material and contact lens.
(methyl) vinylformic acid phenylglycollic ester compounds is monomeric synthetic to respond usually that speed is slow, transformation efficiency is low, raw material and the product easy polymeric characteristics of being heated.The synthetic route of bibliographical information is less, and existing report is the method that the low temperature acyl chlorides becomes ester.
The low temperature acyl chlorides becomes the ester method, as document (J.Org.Chem.2005,70,251-260) described, obtain the methacrylic acid phenylglycollic ester with the reaction of methacrylic chloride and phenylethyl alcohol.The dichloromethane solution of phenylethyl alcohol and triethylamine is cooled to 0 ℃, to wherein dripping methacrylic chloride.Eliminate unnecessary triethylamine with excessive hydrochloric acid solution again, with sodium hydrogen carbonate solution flush away hydrochloric acid.In this method, acyl chlorides price height, instability, pungency is strong, in using and storing personnel and environment is brought danger and problems, and processing unit and working condition are required height, the high enterprise of production cost.
Esterification and transesterification reaction are typical balanced reactions, and speed of response is slow usually, and esterification yield is low, need improve temperature toward contact and promote reaction with the prolongation reaction times.For the esterification or the transesterification reaction of (methyl) acrylic compounds, above-mentioned phenomenon is obvious, also very easily is subjected to thermopolymerization simultaneously.Therefore, seek proper reaction conditions, proper raw material, suitable feed way, promote esterification or transesterification reaction and obtain value product and practical production technique very necessary.
Summary of the invention
For overcoming the defective of (methyl) vinylformic acid phenylglycollic ester compounds preparation method in the prior art, the purpose of this invention is to provide the preparation method of a kind of (methyl) vinylformic acid phenylglycollic ester compounds.
Described preparation method by general formula (I) and (II) compound prepare target compound by esterification or transesterification reaction;
Described general formula (I) compound is:
Wherein, R
1Be H or CH
3R
2Be OH, OCH
3, OCH
2CH
3Or OCH (CH
3)
2
Described general formula (II) compound is:
Wherein, R
3Be H, OH, alkyl or halogen, the preferred C1-C6 alkyl of described alkyl.
Described preparation method further may further comprise the steps:
(1) general formula (II) compound, acid catalyst, stopper are mixed and the adding organic solvent, be warming up to 50～90 ℃;
(2) under the described temperature of step (1), drip general formula (I) compound, and remove the by product that dereaction generates by atmospheric pressure reflux or underpressure distillation;
(3) dropwising the back keeps described temperature to reaction to finish.
Above-mentioned reaction can be adopted the normal experiment means to monitor to raw material reaction then to react end when complete, as thin-layer chromatography, gas-chromatography or high performance liquid chromatography etc.
Described acid catalyst is sulfuric acid, phosphoric acid, Phenylsulfonic acid or tosic acid; Described stopper is Resorcinol, p methoxy phenol, Butylated Hydroxytoluene, 4-tert-butyl catechol or 2-Tert. Butyl Hydroquinone.
The consumption of described acid catalyst of step (1) and general formula (II) compound is a mol ratio 0.02～0.4: 1, preferred 0.1～0.3: 1; The consumption of described stopper and general formula (II) compound is a mass ratio 0.1～3: 1000, preferred 0.1～1: 1000.
Described organic solvent is selected from benzene,toluene,xylene or hexanaphthene; The consumption of described solvent is every gram general formula (II) compound 3～10mL.
The described dropping time of step (2) is 1～10 hour, preferred 2～5 hours.
Described general formula (I) compound and general formula (II) compound amount are mol ratio 1.0～3.0: 1.
Also comprise post-processing step in above-mentioned each technical scheme: after reaction finishes reaction system is reduced to room temperature, adds alkaline solution to water and be neutral, organic phase concentrate target compound.
Described alkaline solution is the aqueous solution of yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus; Concentration is that 0.02g/mL is to saturated.
Described target compound underpressure distillation is purified, and the vacuum tightness of described underpressure distillation is 5-300Pa; Distillation temperature is 50～90 ℃.
Reaction process of the present invention is as follows:
In general formula (I) compound according to R
2Difference, the by product difference that esterification or transesterification reaction produce, carboxylic esterification produces water, transesterification reaction generates corresponding alcohol, isolating mode is according to the boiling point difference decision of by product with the reaction organic solvent, if temperature of reaction is higher than the boiling point of the by-product alcohols that reaction produces, then carries out normal pressure and separate by-product alcohols; If temperature of reaction is lower than the boiling point of by-product alcohols, then adopt underpressure distillation to remove by product, to carry out to the positive reaction direction better for guaranteeing esterification, the rate of addition of general formula (I) compound speed best and that by product is removed is suitable.
In the method for the present invention, raw material (methyl) vinylformic acid (ester) and target compound (methyl) vinylformic acid phenylglycollic ester compounds are owing to contain active double bond structure, therefore, polymerization very easily takes place in conventional esterification or transesterification reaction form complicated polymerization system, make esterification or transesterification reaction be difficult to carry out, do not use esterification or ester-interchange method to prepare (methyl) vinylformic acid phenylglycollic ester compounds in the prior art.Technical scheme of the present invention adds stopper in esterification or transesterification reaction, and adjust a series of technique means such as temperature of reaction, solvent, material dropping mode, separation and purification operation, impel esterification or transesterify when positive dirction is carried out, prevent the generation of polyreaction.That is to say that parameters such as catalyzer of the present invention, stopper, temperature of reaction, time all are that passed through that strict cooperation and control just obtains good becomes the ester effect.
Two kinds of reaction raw materials of preparation method of the present invention all are common chemical reagent, and easy being easy to get avoided use strong and stimulating raw material; Obtain target product by esterification or transesterification reaction, the reaction conditions gentleness, yield is higher, and separation and purification is easy, and products therefrom purity is good, is applicable to large-scale industrial production.
Embodiment
Following examples are used to illustrate the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
The acid esters legal system is equipped with the 2 phenylethyl alcohol acrylate
In the 100L reactor, add the 10.0Kg phenylethyl alcohol, 34.4Kg toluene (4.0mL/g), the 1.62Kg vitriol oil (0.1eq.) and 2.0g p methoxy phenol, stirring obtains light yellow clarification mixed solution, with the mixed solution heat temperature raising to 70-75 ℃.In mixed solution, drip 7.07Kg vinylformic acid (1.3eq.) liquid, begin to vacuumize making refluxing toluene divide water simultaneously.Dropwise addition of acrylic acid 2 hours after finishing, is incubated 70～75 ℃ and continues decompression branch water, to reacting completely.Reaction mixture being cooled to room temperature, dripping saturated aqueous sodium carbonate in mixed solution, is neutral to water; Leave standstill separatory, after organic phase water (20L * 3) washing, use 1.0Kg anhydrous magnesium sulfate drying 4 hours; Suction filtration, filter cake revolves to steam and obtains pale brown look liquid crude product (vacuum tightness is-0.09MPa that bath temperature is 55 ℃) with toluene (1.0L) drip washing, filtrate decompression.At 13-20Pa, underpressure distillation under 70～78 ℃ of conditions obtains colourless liquid product: 10.7Kg, yield: 74.3%, and purity (GC):＞98.5%.
Embodiment 2
The acid esters legal system is equipped with 2 phenylethyl alcohol-2-methacrylic ester
In the 200L reactor, add the 24.0Kg phenylethyl alcohol, 82.6Kg toluene (4.0mL/g) the 1.9Kg vitriol oil (0.1eq.) and 2.4g Resorcinol, stirring obtains light yellow clarification mixed solution.This mixed solution heat temperature raising to 60-65 ℃, is added dropwise to 22.0Kg methacrylic acid (1.3eq.), begins to vacuumize making refluxing toluene divide water simultaneously, Dropwise 5 hour.Dropwise, be incubated 60～65 ℃ of decompressions and divide water, to reacting completely.Be cooled to room temperature, in system, be added dropwise to the 0.04g/mL aqueous sodium carbonate, be neutralized to water for neutral; Leave standstill separatory, organic phase water (24L * 3) washing was used the 2.0Kg anhydrous magnesium sulfate drying 4 hours again; Suction filtration, filter cake revolves to steam and obtains pale brown look liquid crude product (vacuum tightness is-0.09MPa that bath temperature is 55 ℃) with toluene (2.0L) drip washing, filtrate decompression.At 5-10Pa, and underpressure distillation under 62～68 ℃ of conditions (really obtain colourless liquid product: 26.8Kg, yield: 71.8%, purity (GC) 98.6%.
Embodiment 3
Ester-interchange method prepares 2 phenylethyl alcohol-2-methacrylic ester
In the 500mL reaction flask, add the 48.9g phenylethyl alcohol, 100mL toluene (2.0mL/g) the 7.8g vitriol oil (0.2eq.) and 0.024g Resorcinol, stirring obtains light yellow clarification mixed solution.This mixed solution heat temperature raising to 70-75 ℃, slowly is added dropwise to 48.1g methyl methacrylate (1.2eq.), begins to vacuumize slow solvent distillation (maintenance distillates speed and rate of addition basically identical) simultaneously, the dropping process continues 3 hours.Dropwise, be incubated 70～75 ℃ to reacting completely.Benzene feedstock ethanol has residue, mends to be added dropwise to 4.0g methyl methacrylate (0.1eq.), is incubated 70～75 ℃ again and tracks to and react completely.Be cooled to room temperature, in system, add 100mL toluene (2.0mL/g), be added dropwise to the 0.14g/mL aqueous sodium carbonate, be neutralized to water for neutral; Leave standstill separatory, after organic phase water (100mL * 3) washing, use 10g anhydrous magnesium sulfate drying 4h again; Behind the suction filtration, filtrate decompression is revolved steaming (vacuum tightness is-0.09MPa that bath temperature is 55 ℃), obtains liquid product: 56.1g, and yield: 73.8%, purity (GC): 83.4%.
Though above used general explanation, embodiment and experiment, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of (methyl) vinylformic acid phenylglycollic ester compounds is characterized in that, by general formula (I) and (II) compound prepare target compound by esterification or transesterification reaction;
Described general formula (I) compound is:
Wherein, R
1Be H or CH
3R
2Be OH, OCH
3, OCH
2CH
3Or OCH (CH
3)
2
Described general formula (II) compound is:
Wherein, R
3Be H, OH, alkyl or halogen, the preferred C1-C6 alkyl of described alkyl.
2. preparation method according to claim 1 is characterized in that, described preparation method may further comprise the steps:
(1) general formula (II) compound, acid catalyst, stopper are mixed and the adding organic solvent, be warming up to 50～90 ℃;
(2) under the described temperature of step (1), drip general formula (I) compound, and remove the by product that dereaction generates by atmospheric pressure reflux or underpressure distillation;
(3) dropwising the back keeps described temperature to reaction to finish.
3. preparation method according to claim 2 is characterized in that, the described acid catalyst of step (1) is sulfuric acid, phosphoric acid, Phenylsulfonic acid or tosic acid; Described stopper is Resorcinol, p methoxy phenol, Butylated Hydroxytoluene, 4-tert-butyl catechol or 2-Tert. Butyl Hydroquinone.
4. preparation method according to claim 3 is characterized in that, the consumption of described acid catalyst of step (1) and general formula (II) compound is a mol ratio 0.02～0.4: 1, preferred 0.1～0.3: 1; The consumption of described stopper and general formula (II) compound is a mass ratio 0.1～3: 1000, preferred 0.1～1: 1000.
5. preparation method according to claim 2 is characterized in that, the described organic solvent of step (1) is selected from benzene,toluene,xylene or hexanaphthene; The consumption of described organic solvent is every gram general formula (II) compound 3～10mL.
6. preparation method according to claim 2 is characterized in that, the described dropping time of step (2) is 1～10 hour, preferred 2～5 hours.
7. preparation method according to claim 2 is characterized in that, described general formula (I) compound and general formula (II) compound amount are mol ratio 1.0～3.0: 1.
8. according to each described preparation method of claim 2-7, it is characterized in that, also comprise post-processing step: after reaction finishes reaction system is reduced to room temperature, adds alkaline solution to water and be neutral, organic phase concentrate target compound.
9. preparation method according to claim 8 is characterized in that, described alkaline solution is the aqueous solution of yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus; Concentration is that 0.02g/mL is to saturated.
10. preparation method according to claim 8 is characterized in that, described target compound underpressure distillation is purified, and the vacuum tightness of described underpressure distillation is 5-300Pa; Distillation temperature is 50～90 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193911A (en) * | 2013-03-14 | 2013-07-10 | 新发药业有限公司 | Amino arene structure unit-containing polyacrylate functionalized polymer and preparation method thereof |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
| CN110818560A (en) * | 2019-12-02 | 2020-02-21 | 怀化金鑫新材料有限公司 | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate |
| CN112079714A (en) * | 2020-09-22 | 2020-12-15 | 湖北长海新能源科技有限公司 | Preparation method of 2-phenylethyl acrylate |
| CN114315583A (en) * | 2021-12-22 | 2022-04-12 | 红宝丽集团泰兴化学有限公司 | Preparation method and device of acrylate compound |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| US20020156317A1 (en) * | 2001-01-11 | 2002-10-24 | Derks Franciscus J.M. | Process for the preparation of esters of (meth)acrylic acid |
| CN1733687A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A (methyl) higher aliphatic acrylate preparation method |
| JP2010095467A (en) * | 2008-10-16 | 2010-04-30 | Toagosei Co Ltd | Method for continuously producing (meth)acrylate |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
| CN101959838A (en) * | 2008-02-27 | 2011-01-26 | 巴斯夫欧洲公司 | Method for the production of (meth)acrylates of C10 alcohol mixtures |
-
2011
- 2011-05-11 CN CN2011101209434A patent/CN102229529B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| US20020156317A1 (en) * | 2001-01-11 | 2002-10-24 | Derks Franciscus J.M. | Process for the preparation of esters of (meth)acrylic acid |
| CN1733687A (en) * | 2005-08-29 | 2006-02-15 | 上海华谊丙烯酸有限公司 | A (methyl) higher aliphatic acrylate preparation method |
| CN101959838A (en) * | 2008-02-27 | 2011-01-26 | 巴斯夫欧洲公司 | Method for the production of (meth)acrylates of C10 alcohol mixtures |
| JP2010095467A (en) * | 2008-10-16 | 2010-04-30 | Toagosei Co Ltd | Method for continuously producing (meth)acrylate |
| CN101723830A (en) * | 2009-12-04 | 2010-06-09 | 广东工业大学 | Method for synthesizing (methyl) acrylate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193911A (en) * | 2013-03-14 | 2013-07-10 | 新发药业有限公司 | Amino arene structure unit-containing polyacrylate functionalized polymer and preparation method thereof |
| CN103193911B (en) * | 2013-03-14 | 2015-04-08 | 新发药业有限公司 | Amino arene structure unit-containing polyacrylate functionalized polymer and preparation method thereof |
| CN103553920A (en) * | 2013-09-26 | 2014-02-05 | 上海维凯化学品有限公司 | Preparation method of phenoxy benzyl acrylic ester |
| CN110818560A (en) * | 2019-12-02 | 2020-02-21 | 怀化金鑫新材料有限公司 | Preparation method of 4-benzyloxy phenyl ethyl n-decanoate |
| CN112079714A (en) * | 2020-09-22 | 2020-12-15 | 湖北长海新能源科技有限公司 | Preparation method of 2-phenylethyl acrylate |
| CN114315583A (en) * | 2021-12-22 | 2022-04-12 | 红宝丽集团泰兴化学有限公司 | Preparation method and device of acrylate compound |
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