CN100516019C - Method for synthesizing hydroxyalkyl(meth)acrylate - Google Patents
Method for synthesizing hydroxyalkyl(meth)acrylate Download PDFInfo
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- CN100516019C CN100516019C CNB2006100960355A CN200610096035A CN100516019C CN 100516019 C CN100516019 C CN 100516019C CN B2006100960355 A CNB2006100960355 A CN B2006100960355A CN 200610096035 A CN200610096035 A CN 200610096035A CN 100516019 C CN100516019 C CN 100516019C
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Abstract
The invention discloses a synthesizing method of acroleic acid and methacrylate hydroxyalkyl ester, adopting acroleic acid or methacrylate as raw material; proceeding additional reaction for epoxyethane or epoxypropane with molar rate at 1-1.5: 1 to produce (methyl) acroleic hydroxyethyl (hydroxypropyl) ester; setting the reacting temperature at 60-120 deg.c; using the quantity of catalyst at 0.1-1.0% as reactant.
Description
Technical field
The present invention relates to a kind of (methyl) hydroxyalkyl acrylate synthetic method, especially a kind of synthetic method that relates to a kind of (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate chemistry (methyl) senecioate by name-hydroxyl ethyl ester or (methyl) senecioate-hydroxypropyl acrylate, structural formula is: CH
2=CR
1COOCH
2CHR
2OH (R
1, R
2=H, CH
3).Belong to field of chemical technology.
Background technology
(methyl) hydroxyalkyl acrylate mainly contains Hydroxyethyl acrylate, Propylene glycol monoacrylate, four kinds of hydroxyethyl methylacrylate and Rocryl 410s, be a kind of water white liquid, have two active functional groups, carbon-carbon double bond and hydroxyl are a kind of highly active functional monomers, in the acrylic resin paint of synthetic excellent performance, important purposes is arranged, be widely used in aspects such as fiber process, coating, light-cured resin, tackiness agent, sheet processing, rubber industry.
The synthesis route of (methyl) hydroxyalkyl acrylate has following several:
1, direct esterification method, be that ethylene glycol or propylene glycol and (methyl) vinylformic acid directly carry out esterification and obtains (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, this method speed of response at low temperatures is slow, often improves temperature of reaction to improve speed of response; Esterification yied is lower, exists the selective problems of monoesters and dibasic acid esters.
2, ester-interchange method, promptly ethylene glycol or propylene glycol and (methyl) methyl acrylate carry out transesterification reaction and obtain (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate.
3, the reaction of ethylene glycol or propylene glycol and (methyl) acrylate chloride can be made (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, because the cost of acyl chlorides has significant limitation far above corresponding carboxylic acid in industrial application.
4, ethylene glycol or propylene glycol carbonic ether can be made (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate with the reaction of (methyl) vinylformic acid, and this method reaction times is longer, and temperature of reaction is higher, and long-time and high temperature causes side reaction to increase.
5, chlorohydrination, i.e. (methyl) sodium acrylate or (methyl) potassium acrylate and chloroethanol or propylene chlorohydrin reaction can be made (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, and there be filtration problem and the big shortcoming of chloropharin toxicity of by product NaCl in this method.
6, oxyethane or propylene oxide and the direct open loop method of (methyl) vinylformic acid are the universal methods of present preparation (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, and characteristics are that speed of response is fast, the reaction conversion ratio height; Temperature of reaction is low, and side reaction particularly polyreaction reduces; Aftertreatment is simple, is easy to obtain highly purified product by rectifying, is suitable for scale operation; Core is the catalyzer of exploitation high reactivity and highly selective.
Oxyethane or propylene oxide and the direct open loop method of (methyl) vinylformic acid catalyzer mainly contain following a few class:
1, chromium-based catalysts is divided into organic chromium class and inorganic chromium class, and chromium-based catalysts has good active and selectivity, the product yield height.But this class catalyzer environmental pollution is bigger, and the need that have use with extraordinary promotor, stopper coupling, the chromium recycling difficulty in the raffinate of refining back.
2, Fe-series catalyst has catalytic performance (activity and selectivity) preferably, but is that catalytic performance is poor than chromium.
3, amines catalyst, the catalyzer that document is openly reported has aliphatic tertiary amine such as triethylamine etc., aromatic nitrile base such as xylidine etc., acid amides such as N, dinethylformamide, quaternary ammonium hydroxide such as choline etc., quaternary ammonium salt such as trimethyl benzyl ammonia chloride etc., miazines, pyridines; Under this class catalyst action, the ring-opening reaction of oxyethane and methacrylic acid has the selectivity of height, and by product is few with respect to Fe-series catalyst and color and luster thick product is more shallow, is comparatively ideal catalyzer.
(methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate are the unsaturated compounds of two keys of a class band and hydroxyl, and chemical property is very active, the vinyl that has very easily autohemagglutination or with other monomer copolymerizations.Stopper commonly used at present has Resorcinol, MEHQ, methyl and ethyl Resorcinol, p-Nitrosophenol, thiodiphenylamine, copper dibutyldithiocarbamate, copper powder and quinhydrones etc.
Summary of the invention
The objective of the invention is to select for use the catalyzer and the related process parameter thereof of a kind of high reactivity and highly selective, a kind of (methyl) hydroxyalkyl acrylate synthetic method is provided.
The object of the present invention is achieved like this: a kind of (methyl) hydroxyalkyl acrylate synthetic method, be to be raw material with acrylic or methacrylic acid, under hexamethylenetetramine catalyzer and Resorcinol-MEHQ inhibitor action, carry out opening with oxyethane or propylene oxide and make (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, the main reaction formula is as follows:
In the formula: R
1=H, CH
3R
2=H, CH
3
The catalyzer that the present invention uses is a heterocyclic amine catalyzer hexamethylenetetramine, and structural formula is:
The quality consumption of catalyzer is 0.1～1.0% of a reactant, and suitable catalyst quality consumption is 0.3～0.7% of a reactant, and optimum catalyst quality consumption is 0.5～0.6% of a reactant.Hexamethylenetetramine belongs to basic catalyst, and under this class catalyst action, the ring-opening reaction of oxyethane and methacrylic acid has the selectivity of height, and the color and luster of thick product is more shallow, and the raffinate environmental pollution of rectifying is low, is comparatively ideal catalyzer.
The stopper that the present invention uses is Resorcinol and MEHQ composite polymerzation inhibitor system, and the quality consumption of stopper respectively is 0.025%～0.1% of a reactant.
The charge ratio oxyethane of the present invention's preparation (methyl) Hydroxyethyl acrylate or the reaction of (methyl) Propylene glycol monoacrylate or propylene oxide and (methyl) vinylformic acid are 1～1.5: 1 (mol), suitable charge ratio is 1.05～1.2: 1 (mol), and optimum charge ratio is 1.05～1.1: 1 (mol).The excessive amount of by-products that can cause too much of oxyethane or propylene oxide increases; It is too high to cross residual at least acid content, and quality product is defective.
The temperature of reaction of the present invention's preparation (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate is 60～120 ℃, and suitable temperature of reaction is 70～100 ℃, and optimum temperature of reaction is 80～90 ℃.Temperature is low excessively, and speed of reaction is low excessively, and temperature is too high, and the formation amount of unwanted polymkeric substance is too much.
The hexamethylenetetramine catalyzer that the present invention uses separates the hydroxyethyl methylacrylate product gas chromatographic analysis that makes, purity 〉=97.0% by rectification under vacuum with the product hydroxyethyl methylacrylate.
The raw material oxyethane that the present invention uses is technical grade, and Yangzi Petrochemical Co., Ltd produces; Vinylformic acid and methacrylic acid are chemical pure, and Shanghai Ling Feng chemical reagent company limited produces; Hexamethylenetetramine is an analytical pure, and Yixing City Chemical Reagent Plant No.2 produces; Resorcinol is an analytical pure, and Yixing City Chemical Reagent Plant No.2 produces; MEHQ is a chemical pure, and Chemical Reagent Co., Ltd., Sinopharm Group produces.
The present invention is catalyzer with the hexamethylenetetramine, selected suitable charge ratio and temperature of reaction, make the acrylic or methacrylic acid and the ring-opening reaction of oxyethane or propylene oxide have high reactivity and selectivity, by product is less relatively, characteristics such as the color and luster of reactor product is more shallow, and the raffinate environmental pollution of rectifying is low.Can realize cleaner production.
Embodiment
Example 1:
In the 1L autoclave that has mechanical stirrer, add 258g methacrylic acid (MAA), the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 132g oxyethane (EO), 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, after oxyethane 30min adds, and insulation reaction 120min; Reaction finishes, and reaction product is cooled to 40 ℃ with bottom discharge, gets thick product 392g, through gas chromatographic analysis, result following (HEMA---hydroxyethyl methylacrylate, monoesters---methacrylic acid diethylene glycol monoesters, dibasic acid esters---dimethyl ethyl, down together):
| Form | EO | Ethylene glycol | MAA | HEM | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 0.6 | 0.2 | 4.3 | 89.3 | 4.0 | 0.7 | 0.9 |
Example 2:
In the 1L autoclave that has mechanical stirrer, add 258g methacrylic acid, 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feed 138.6g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure are less than 0.5MPa, and oxyethane 30min adds, insulation reaction 120min, reaction finishes.Reaction product is cooled to 40 ℃ with bottom discharge, gets thick product 398.9g, product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 1.0 | 0.2 | 1.3 | 91.7 | 3.9 | 0.9 | 1.0 |
Example 3:
In the 1L autoclave that has mechanical stirrer, add the 258g methacrylic acid, the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 145.2g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 30min adds, and continues insulation reaction 120min; Reaction finishes, and reaction product is cooled to 40 ℃ with bottom discharge, gets thick product 405.3g, and product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 1.5 | 0.4 | 0.5 | 91.4 | 3.8 | 1.7 | 0.7 |
Example 4:
In the 1L autoclave that has magnetic stirring apparatus, add the 258g methacrylic acid, 2.1g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 151.8g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 30min adds, and continues insulation reaction 120min; Reaction finishes, and reaction product is cooled to 40 ℃ with bottom discharge, gets thick product 412.8g, and product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 2.3 | 6.3 | 0.4 | 48.6 | 1.9 | 36.5 | 4.0 |
Example 5:
In the autoclave of the 1L that has magnetic stirring apparatus, add 258g methacrylic acid, 0.4g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feed 138.6g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure are less than 0.5MPa, and oxyethane 35min adds, stop the follow-up continuation of insurance temperature of logical oxyethane reaction 115min, reaction finishes.Reaction product is cooled to 45 ℃ with bottom discharge, gets thick product 394.2g, its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 4.1 | 0.06 | 14.8 | 70.6 | 8.3 | 0.5 | 1.6 |
Example 6:
In the 1L autoclave that has magnetic stirring apparatus, add the 258g methacrylic acid, 1.2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 138.6g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 35min adds, and continues insulation reaction 115min; Reaction finishes, and reaction product is cooled to 40 ℃ of dischargings, gets thick product 396.9g, and its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 1.2 | 0.1 | 3.9 | 87.5 | 5.2 | 0.7 | 1.4 |
Example 7:
In the autoclave of the 1L that has magnetic stirring apparatus, add the 258g methacrylic acid, 2.8g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 138.6g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 35min adds, and continues insulation reaction 115min; Reaction finishes, and reaction product is cooled to 40 ℃ of dischargings, gets thick product 399.5g, and product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEM | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 0.7 | 0.2 | 1.2 | 91.8 | 3.4 | 1.1 | 1.6 |
Example 8:
In the autoclave of the 1L that has magnetic stirring apparatus, add the 258g methacrylic acid, the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 60 ℃, feeds 145.2g oxyethane, 60～70 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 30min adds, and continues insulation reaction 120min; Reaction finishes, and reaction product is cooled to 35 ℃ of dischargings, gets thick product 398.2g, and its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and assorted |
| Content (%) | 6.6 | 0.05 | 18.1 | 70.1 | 3.2 | 0.2 | 1.7 |
Example 9:
In the autoclave of the 1L that has magnetic stirring apparatus, add the 258g methacrylic acid, the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 70 ℃, feeds 145.2g oxyethane, 70～80 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 30min adds, and continues insulation reaction 120min; Reaction finishes, and reaction product is cooled to 45 ℃ of dischargings, gets thick product 405.4g, and its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 2.9 | 0.1 | 4.2 | 86.9 | 3.7 | 0.7 | 1.5 |
Example 10:
In the autoclave of the 1L that has magnetic stirring apparatus, add the 258g methacrylic acid, the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 90 ℃, feeds 145.2g oxyethane, 90～100 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 25min adds, insulation reaction 125min; Reaction finishes, and reaction product is cooled to 40 ℃ of dischargings, gets thick product 405.5g, and its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 1.0 | 3.7 | 0.1 | 70.1 | 3.3 | 20.4 | 1.4 |
Example 11:
In the autoclave of the 1L that has magnetic stirring apparatus, add the 258g methacrylic acid, the 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds 145.2g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure is less than 0.5MPa, and oxyethane 30min adds, insulation reaction 60min; Reaction finishes, and reaction product is cooled to 40 ℃ of dischargings, gets thick product 404.4g, and its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 2.3 | 0.3 | 0.8 | 90.6 | 3.6 | 1.2 | 1.2 |
Example 12:
In the autoclave of the 1L that has magnetic stirring apparatus, add 258g methacrylic acid, 2g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feed 145.2g oxyethane, 80～90 ℃ of control reaction temperature, reaction pressure are less than 0.5MPa, and oxyethane 30min adds, insulation reaction 150min, reaction finishes.Reaction product is cooled to 40 ℃ of dischargings, gets thick product 404.4g, its product is formed through gas chromatographic analysis, the results are shown in following table:
| Form | EO | Ethylene glycol | MAA | HEMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 1.0 | 1.0 | 0.3 | 89.2 | 3.9 | 3.3 | 1.3 |
Example 13
In the autoclave of the 1L that has magnetic stirring apparatus, add 258g methacrylic acid, 2.6g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feed 182.7g propylene oxide (PO), 80～90 ℃ of control reaction temperature, reaction pressure are less than 0.3MPa, and propylene oxide 30min adds, insulation reaction 120min, reaction finishes.Reaction product is cooled to 40 ℃ of dischargings, thick product 440.2g, its product is formed through gas chromatographic analysis, the results are shown in following table (in the table: HPMA---Rocryl 410, monoesters---methacrylic acid dipropylene glycol monoesters, dibasic acid esters---dimethyl allene propyl propionate):
| Form | PO | Propylene glycol | MAA | HPMA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 5.0 | / | 7.4 | 83.7 | 1.7 | 0.5 | / |
Example 14
In the autoclave of the 1L that has magnetic stirring apparatus, add 252g vinylformic acid (AA), 2.8g hexamethylenetetramine, 0.5g Resorcinol, 0.5g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feeds the 215.2g propylene oxide, 80～85 ℃ of control reaction temperature, reaction pressure is less than 0.3MPa, and propylene oxide 30min adds, insulation reaction 120min; Reaction finishes, and reaction product is cooled to 40 ℃ of dischargings, gets thick product 465.3g, its product is formed through gas chromatographic analysis, the results are shown in following table (in the table: HPA---Propylene glycol monoacrylate, monoesters---vinylformic acid dipropylene glycol monoesters, dibasic acid esters---diacrylate propyl ester):
| Form | PO | Propylene glycol | AA | HPA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 10.3 | / | 5.6 | 65.9 | 5.2 | 0.9 | / |
Example 15:
In the autoclave of the 1L that has magnetic stirring apparatus, add 252g vinylformic acid, 2.5g hexamethylenetetramine, 0.4g Resorcinol, 0.4g MEHQ, air in the nitrogen replacement reactor, turn on agitator is warming up to 80 ℃, feed 161.7g oxyethane, 80～85 ℃ of control reaction temperature, reaction pressure are less than 0.3MPa, and oxyethane 30min adds, insulation reaction 120min, reaction finishes.Reaction product is cooled to 40 ℃ of dischargings, thick product 399.4g, its product is formed through gas chromatographic analysis, the results are shown in following table (in the table: HEA---Hydroxyethyl acrylate, monoesters---vinylformic acid Diethylene Glycol monoesters, dibasic acid esters---diacrylate ethyl ester):
| Form | EO | Ethylene glycol | AA | HEA | Monoesters | Dibasic acid esters | Heavy constituent and impurity |
| Content (%) | 2.0 | / | 6.9 | 72.5 | 5.1 | 0.2 | / |
Claims (4)
1, a kind of (methyl) hydroxyalkyl acrylate synthetic method, it is characterized in that it is is raw material with acrylic or methacrylic acid, under hexamethylenetetramine catalyzer and Resorcinol-MEHQ inhibitor action, carry out opening with oxyethane or propylene oxide and make (methyl) Hydroxyethyl acrylate or (methyl) Propylene glycol monoacrylate, the main reaction formula is as follows:
In the formula: R
1=H, CH
3R
2=H, CH
3
2, a kind of (methyl) according to claim 1 hydroxyalkyl acrylate synthetic method, it is characterized in that described oxyethane or propylene oxide and (methyl) vinylformic acid molar ratio are: 1～1.5: 1, temperature of reaction is 60～120 ℃, and the quality consumption of catalyzer hexamethylenetetramine is 0.1～1.0% of a reactant.
3, a kind of (methyl) according to claim 2 hydroxyalkyl acrylate synthetic method, it is characterized in that described oxyethane or propylene oxide and (methyl) vinylformic acid molar ratio are: 1.05～1.2: 1, temperature of reaction is 70～100 ℃, and the quality consumption of catalyzer hexamethylenetetramine is 0.3～0.7% of a reactant.
4, a kind of (methyl) according to claim 3 hydroxyalkyl acrylate synthetic method, it is characterized in that described oxyethane or propylene oxide and (methyl) vinylformic acid molar ratio are: 1.05～1.1: 1, temperature of reaction is 80～90 ℃, and the quality consumption of catalyzer hexamethylenetetramine is 0.5～0.6% of a reactant.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100960355A CN100516019C (en) | 2006-09-14 | 2006-09-14 | Method for synthesizing hydroxyalkyl(meth)acrylate |
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|---|---|---|---|
| CNB2006100960355A CN100516019C (en) | 2006-09-14 | 2006-09-14 | Method for synthesizing hydroxyalkyl(meth)acrylate |
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| CN100516019C true CN100516019C (en) | 2009-07-22 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475475B (en) * | 2009-01-21 | 2011-10-19 | 南京林业大学 | Method for synthesizing acrylic alkoxy ethyl ester or methacrylate alkoxy ethyl ester |
| JP5516090B2 (en) * | 2010-06-02 | 2014-06-11 | 日立化成株式会社 | Method for producing hydroxyalkyl (meth) acrylic acid ester |
| JP2012041310A (en) * | 2010-08-20 | 2012-03-01 | Hitachi Chem Co Ltd | Method of producing hydroxyalkyl (meth)acrylic acid ester |
| CN103599815B (en) * | 2013-11-16 | 2015-08-26 | 南京林业大学 | The immobilized perfluorinated sulfonic resin catalyst of active carbon and for catalyzing and synthesizing (methyl) acrylic acid alkoxyalkyl methacrylate |
| CN105541618A (en) * | 2016-02-05 | 2016-05-04 | 中国海洋石油总公司 | Preparation method of 6-chlorohexyl acrylate |
| CN105646213A (en) * | 2016-02-15 | 2016-06-08 | 南通市东昌化工有限公司 | Preparation method of acrylic acid-4-chlorobutyl ester compounds |
| CN108409568B (en) * | 2018-04-03 | 2020-09-25 | 上海华谊新材料有限公司 | Process for preparing hydroxyalkyl (meth) acrylates |
| CN110551026B (en) * | 2018-06-04 | 2022-02-15 | 永胜光学股份有限公司 | Modified curcumin and preparation method thereof |
| CN113185408B (en) * | 2021-04-15 | 2023-11-17 | 佳化化学科技发展（上海）有限公司 | Ethylene oxide modified acrylic acid, low-viscosity polyurethane acrylic ester, preparation method and application |
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| CN1313273A (en) * | 2000-03-13 | 2001-09-19 | 株式会社日本触媒 | Production of hydroxyalkyl(methyl) acrylic ester |
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|---|---|---|---|---|
| US3280176A (en) * | 1962-12-12 | 1966-10-18 | Basf Ag | Esterification of alpha, beta-unsaturated carboxylic acids with alkylene oxides |
| CN1313273A (en) * | 2000-03-13 | 2001-09-19 | 株式会社日本触媒 | Production of hydroxyalkyl(methyl) acrylic ester |
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| Title |
|---|
| 《（甲基）丙烯酸羟烷基酯合成技术研究进展》. 尹佳子，朱新宝.《化学工业与工程技术》，第26卷第6期. 2005 |
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| CN1919826A (en) | 2007-02-28 |
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