CN102464633A - Synthetic method for (methyl) glycidyl acrylate - Google Patents
Synthetic method for (methyl) glycidyl acrylate Download PDFInfo
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- CN102464633A CN102464633A CN2010105498227A CN201010549822A CN102464633A CN 102464633 A CN102464633 A CN 102464633A CN 2010105498227 A CN2010105498227 A CN 2010105498227A CN 201010549822 A CN201010549822 A CN 201010549822A CN 102464633 A CN102464633 A CN 102464633A
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Abstract
The invention relates to a synthetic method for (methyl) glycidyl acrylate. The method is characterized by using (methyl) acrylic acid and epoxy chloropropane as raw materials, under the action of a catalyst and an inhibitor, reacting the raw materials to generate 3-chloro-2-hydroxyl propyl methacrylate, and introducing aqueous solution of sodium hydroxide to react with the 3-chloro-2-hydroxyl propyl methacrylate to generate the (methyl) glycidyl acrylate, wherein the reactions are performed in a microreactor. By the method, the reaction time can be greatly shortened, a large number of side reactions are avoided, and the (methyl) glycidyl acrylate can be synthesized with high efficiency, high yield (over 97 percent) and high purity.
Description
One, technical field
The present invention relates to the compound method of a kind of (methyl) glycidyl acrylate, belong to field of chemical technology.
Two, background technology
(methyl) glycidyl acrylate chemistry (methyl) senecioate by name-epoxy propyl ester, structural formula is:
(methyl) glycidyl acrylate is a kind of water white liquid; Have two active functional groups; Carbon-carbon double bond and epoxy group(ing); Be a kind of highly active functional monomer, in the acrylic resin paint of synthetic excellent performance, important purposes arranged, be widely used in aspects such as fiber process, coating, light-cured resin, tackiness agent, sheet processing, rubber industry.
Traditional compound method mainly contains single stage method and two-step approach; Single stage method is a raw material with acrylic or methacrylic acid sodium-salt, epoxy chloropropane; One-step synthesis acrylic or methacrylic acid glycidyl ester: the characteristics of this method are the reaction times to lack (2-4h); Productive rate high (generally 92～97%), good product quality is the method that overseas enterprise generally adopts.But this method requires whole reaction system anhydrous, and the sodium salt water cut just can make the ester yield reach more than 92% less than 0.5%, and have epoxy chloropropane consumption many (needing excessive 4-10 times), shortcoming such as reactions step is many, subsequent disposal is numerous and diverse.Two-step approach is a raw material with acrylic or methacrylic acid, epoxy chloropropane, and reaction generates the acrylic or methacrylic acid glycidyl ester with aqueous sodium hydroxide solution again for first synthetic intermediate 3-chloro-2-hydroxy propyl methacrylate (CHPMA), midbody.Two-step approach epoxy chloropropane consumption less (needing excessive 1.3-1.5 doubly), simple to operate, can adopt the method for " treating different things alike "; Second step used water as solvent ratio than environmental protection; Product and raw material mixed when but main drawback was " treating different things alike ", produced a lot of side reactions, had a large amount of by products to generate; Quality product is relatively poor, productive rate lower (referring to another patent CN100545154C of the inventor).
Three, summary of the invention:
To above-mentioned shortcoming, the object of the present invention is to provide a kind of feedstock conversion complete, side reaction is few, and yield is high, and mild condition is easy and simple to handle, is easier to the compound method of (methyl) glycidyl acrylate of industrialized more environmental protection.Compare with method in the past; This method can greatly shorten the reaction times; And the product that each step is constantly generated separates with raw material at any time, thereby has avoided a large amount of side reactions, can be with synthetic (methyl) glycidyl acrylate of high-level efficiency, high yield (more than 97%) and high purity.
Technology contents of the present invention is: the compound method of (methyl) glycidyl acrylate; It is characterized in that: with (methyl) vinylformic acid, epoxy chloropropane is raw material, and under catalyzer and stopper effect, reaction generates 3-chloro-2-hydroxy propyl methacrylate in microreactor earlier; In microreactor, feed aqueous sodium hydroxide solution and 3-chloro-2-hydroxy propyl methacrylate reaction generation (methyl) glycidyl acrylate again; Catalyzer is hexamethylenetetramine, Pottasium Hydroxide, imidazoles or ionic liquid, and consumption is 0.7wt%, and stopper is a MEHQ; Consumption is 0.3wt%; The charge ratio of (methyl) vinylformic acid and epoxy chloropropane is 1: 1-1.3 (mol) or 1.2-1: 1 (mol), and temperature of reaction is 60-100 ℃, the reaction times is 2-30 minute; Sodium hydroxide is 1.2-1 with (methyl) acrylic acid charge ratio: 1 (mol), and the concentration of aqueous sodium hydroxide solution is 18-30%, and temperature of reaction is 18-50 ℃, and the reaction times is 2-10 minute.
The microreactor that uses among the present invention is meant the reactor drum of fluid flowing passage characteristic dimension at hundreds of micrometer ranges.The U.S. mattress of Germany microtechnology institute now is one of research institution that is engaged in the earliest in the world the microreactor technological development, has successfully developed the microreactor assembly that is applicable to various chemical processes, can be used for lab scale research and actual production.In fine chemistry industry and medicine organic synthesis, the microreactor The Application of Technology has obtained the most extensive research.Multiple sophisticated production technique based on the microreactor technology has been arranged in the market.At other field, also obtain increasing application like microreactor technology in bulk chemical and the Polymer Synthesizing.For example, Siemens Company has developed the production technique of utilizing microreactor to prepare polyacrylic ester, and throughput reaches 2000t/a; Uop Inc. has set up the pilot plant of producing hydrogen peroxide with the microreactor technology, and the production equipment of one 150,000 t/a is built in plan; Degussa group has developed the large-scale microreactor that is used for production of propylene oxide based on the microreactor technology.Certainly, the microreactor technology also has the limitation of self, and not all chemical reaction all is adapted at carrying out in the microreactor.At first, the channel size of microreactor is very little, is easy to stopped up by solid particulate; Secondly the volume in the microreactor is very little, and the reactant residence time therein is very short usually.Fewer to the understanding of little chemical industry in view of people, successful story is fewer, and little chemical industry technology is not extensive in current application, and does not find microreactor is used for the production of (methyl) glycidyl acrylate similar substance so far as yet.The inventor is optimized various reaction parameters through a large amount of groping and testing, and finally successfully microreactor is used for the scale operation of (methyl) glycidyl acrylate.
The main reaction formula that relates among the present invention is following:
The first step:
Second step:
In the formula: R
1=H, CH
3
(methyl) vinylformic acid nail base vinylformic acid or vinylformic acid among the present invention; (methyl) glycidyl acrylate nail base glycidyl acrylate or glycidyl acrylate.
The suitable charge ratio of (methyl) vinylformic acid and epoxy chloropropane is 1 among the present invention: 1-1.2 (mol) or 1.2-1: 1 (mol).
The suitable temperature of reaction of the first step generation 3-chloro-2-hydroxy propyl methacrylate is 60-95 ℃ among the present invention, and the suitable reaction times is 3-30 minute.
Among the present invention sodium hydroxide and (methyl) vinylformic acid suitable charge ratio be 1.1-1: 1 (mol).
The concentration of suitable aqueous sodium hydroxide solution is 18-25% among the present invention.
The optimal temperature of aqueous sodium hydroxide solution and 3-chloro-2-hydroxy propyl methacrylate reaction is 20-40 ℃ among the present invention, and the suitable reaction times is 2-6 minute.
The advantage that the present invention compared with prior art has is that feedstock conversion is complete, and side reaction is few, and yield is high, and mild condition is easy and simple to handle, is easier to industriallization, more environmental protection.The present invention can also greatly shorten the reaction times, and the continuous product that generates of each step is separated with raw material at any time, thereby has avoided a large amount of side reactions, can be with synthetic (methyl) glycidyl acrylate of high-level efficiency, high yield and high purity.
Four, specific embodiment
The invention is further illustrated by the following examples, but the present invention is not limited to the embodiment that lifted.
The raw material that the present invention uses is analytical pure, and MEHQ is a CP, is Chemical Reagent Co., Ltd., Sinopharm Group and produces.The typical liquid liquid phase microreactor that microreactor adopts Mainz, Germany microtechnology institute to produce.
The oxirane value of (methyl) glycidyl acrylate detects with hydrochloric acid-acetone method and detects.
Embodiment 1
In methylacrylic acid, add the 2.7g hexamethylenetetramine, the 1.4g MEHQ feeds methylacrylic acid and epoxy chloropropane in microreactor; Throughput ratio is 7.0/8.0 (ml/min); Temperature of reaction is 80 ℃, reacts to obtain 3-chloro-2-hydroxy propyl methacrylate 121g after 4 minutes, and be 3-chloro-2-hydroxy propyl methacrylate and concentration that 20% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 7.0/8.0 (ml/min); Temperature of reaction is 40 ℃, reacts to obtain SY-Monomer G 90.2g after 3 minutes, and oxirane value is 0.691eq/100g.
Embodiment 2
In methylacrylic acid, add the 1.9g hexamethylenetetramine, the 0.4g MEHQ feeds methylacrylic acid and epoxy chloropropane in microreactor; Throughput ratio is 0.6/0.5 (ml/min); Temperature of reaction is 80 ℃, reacts to obtain 3-chloro-2-hydroxy propyl methacrylate 85g after 25 minutes, and be 3-chloro-2-hydroxy propyl methacrylate and concentration that 20% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 7.0/8.0 (ml/min); Temperature is 35 ℃, reacts to obtain SY-Monomer G 47.0g after 4 minutes, and oxirane value is 0.673eq/100g.
Embodiment 3
In vinylformic acid, add the 1.7g imidazoles, the 0.3g MEHQ feeds vinylformic acid and epoxy chloropropane in microreactor; Throughput ratio is 1/1.1 (ml/min); Temperature of reaction is 60 ℃, reacts to obtain 3-chloro-2-hydroxypropyl propenoate 95g after 10 minutes, and be 3-chloro-2-hydroxypropyl propenoate and concentration that 20% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 6.5/7.0 (ml/min); Temperature is 25 ℃, reacts to obtain glycidyl acrylate 70.0g after 2 minutes, and oxirane value is 0.677eq/100g.
Embodiment 4
In methylacrylic acid, add the 1.9g hexamethylenetetramine, the 0.4g MEHQ feeds methylacrylic acid and epoxy chloropropane in microreactor; Throughput ratio is 0.6/0.7 (ml/min); Temperature of reaction is 50 ℃, reacts to obtain 3-chloro-2-hydroxy propyl methacrylate 80g after 30 minutes, and be 3-chloro-2-hydroxy propyl methacrylate and concentration that 20% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 7.0/8.0 (ml/min); Temperature is 30 ℃, reacts to obtain SY-Monomer G 40.0g after 4 minutes, and oxirane value is 0.688eq/100g.
Embodiment 5
In methylacrylic acid, add the 1.9g hexamethylenetetramine, the 0.4g MEHQ feeds methylacrylic acid and epoxy chloropropane in microreactor; Throughput ratio is 15/17.7 (ml/min); Temperature of reaction is 100 ℃, reacts to obtain 3-chloro-2-hydroxy propyl methacrylate 117g after 2 minutes, and be 3-chloro-2-hydroxy propyl methacrylate and concentration that 18% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 3.5/3.8 (ml/min); Temperature is 45-50 ℃, reacts to obtain SY-Monomer G 44.7g after 10 minutes, and oxirane value is 0.700eq/100g.
Embodiment 6
In methylacrylic acid, add 2.0g EMIMF (HF)
2.3(Journal of Fluorine Chemistry, 125 (2004), 1127-1129); 0.4g MEHQ feeds methylacrylic acid and epoxy chloropropane in microreactor, throughput ratio is 14/15 (ml/min); Temperature of reaction is 70-80 ℃, reacts to obtain 3-chloro-2-hydroxy propyl methacrylate 70g after 2 minutes, and be 3-chloro-2-hydroxy propyl methacrylate and concentration that 20% aqueous sodium hydroxide solution feeds in the microreactor again; Throughput ratio is 7.0/8.0 (ml/min); Temperature is 35 ℃, reacts to obtain SY-Monomer G 25.0g after 4 minutes, and oxirane value is 0.695eq/100g.
Comparative Examples 1 (not using microreactor)
In the 500mL four-hole boiling flask that has machine mixer, add 117g methylacrylic acid, 1.7g hexamethylenetetramine, 0.2g MEHQ; Turn on agitator; Be warming up to 80 ℃, drip 132g epoxy chloropropane (ECH), 60 ~ 70 ℃ of control reaction temperature; After epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 190 grams of 32% weight; 35 ~ 45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h; Get SY-Monomer G product 50.6g, oxirane value is 0.503ep/100g.
Comparative Examples 2 (not using microreactor)
In the 500mL four-hole boiling flask that has machine mixer, add 144g vinylformic acid, 2.2g hexamethylenetetramine, 0.4g MEHQ; Turn on agitator is warming up to 80 ℃, drips 222g epoxy chloropropane (ECH); 80 ~ 90 ℃ of control reaction temperature, after epoxy chloropropane 6h drips, insulation reaction 1h; Reaction finishes, and reaction product is cooled to below 40 ℃, begins to drip aqueous sodium hydroxide solution 265 grams of 32% weight; 35 ~ 45 ℃ of control reaction temperature, after 3h drips, insulation reaction 1h; Get glycidyl acrylate product 121g, oxirane value is 0.31eq/100g.
Claims (5)
1. the compound method of (methyl) glycidyl acrylate; It is characterized in that: with (methyl) vinylformic acid, epoxy chloropropane is raw material; Under catalyzer and stopper effect; Reaction generates 3-chloro-2-hydroxy propyl methacrylate in microreactor earlier, and the reaction of feeding aqueous sodium hydroxide solution and 3-chloro-2-hydroxy propyl methacrylate generates (methyl) glycidyl acrylate in microreactor again.
2. the compound method of claim 1, it is characterized in that: said catalyzer is hexamethylenetetramine, Pottasium Hydroxide, imidazoles or ionic liquid, and consumption is 0.7wt%, and stopper is a MEHQ, and consumption is 0.3wt%.
3. claim 1 or 2 compound method, it is characterized in that: the charge ratio of (methyl) vinylformic acid and epoxy chloropropane is 1: 1-1.3 (mol) or 1.2-1: 1 (mol), temperature of reaction is 60-100 ℃, the reaction times is 2-30 minute; Sodium hydroxide is 1.2-1 with (methyl) acrylic acid charge ratio: 1 (mol), and the concentration of aqueous sodium hydroxide solution is 18-30%, and temperature of reaction is 18-50 ℃, and the reaction times is 2-10 minute.
4. the compound method of claim 3, it is characterized in that: the charge ratio of (methyl) vinylformic acid and epoxy chloropropane is 1: 1-1.2 (mol) or 1.2-1: 1 (mol), temperature of reaction is 60-95 ℃, the reaction times is 3-30 minute; Sodium hydroxide is 1.1-1 with (methyl) acrylic acid charge ratio: 1 (mol), and the concentration of aqueous sodium hydroxide solution is 18-25%, and temperature of reaction is 20-40 ℃, and the reaction times is 2-6 minute.
5. the compound method of claim 2, it is characterized in that: said ionic liquid is EMIMF (HF)
2.3
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| CN201010549822.7A CN102464633B (en) | 2010-11-19 | 2010-11-19 | Synthetic method for (methyl) glycidyl acrylate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108299343A (en) * | 2018-02-09 | 2018-07-20 | 江苏泰特尔新材料科技有限公司 | It is a kind of to be prepared with micro passage reaction（Methyl）The method of acrylic acid -3,4- epoxycyclohexanecarboxylates |
| CN109467505A (en) * | 2018-11-16 | 2019-03-15 | 潍坊科麦化工有限公司 | A kind of preparation method of hydroxyethyl methacrylate |
| CN110054601A (en) * | 2019-03-13 | 2019-07-26 | 杭州盛弗泰新材料科技有限公司 | A kind of synthetic method of (methyl) acrylic acid ethers hydroxyl alkane esters |
| CN113443984A (en) * | 2016-06-28 | 2021-09-28 | 清远市柯林达新材料有限公司 | Vinyl fluorine-containing epoxy carboxylate intermediate, water-soluble fluorine modified acrylate, preparation method and acrylate coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0371821A1 (en) * | 1988-11-30 | 1990-06-06 | Rhone-Poulenc Specialty Chemicals Co. | A process for the production of substituted acryloyloxyhydroxypropyltrialkylammonium chloride |
| CN101085764A (en) * | 2007-07-09 | 2007-12-12 | 南京林业大学 | Synthesis method for (methyl)glycidyl acrylate |
-
2010
- 2010-11-19 CN CN201010549822.7A patent/CN102464633B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0371821A1 (en) * | 1988-11-30 | 1990-06-06 | Rhone-Poulenc Specialty Chemicals Co. | A process for the production of substituted acryloyloxyhydroxypropyltrialkylammonium chloride |
| CN101085764A (en) * | 2007-07-09 | 2007-12-12 | 南京林业大学 | Synthesis method for (methyl)glycidyl acrylate |
Non-Patent Citations (1)
| Title |
|---|
| AGNIESZKA BUKOWSKA ET AL.: "Synthesis of glycidyl esters", 《JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY》, vol. 74, 31 December 1999 (1999-12-31), pages 1145 - 1148 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113443984A (en) * | 2016-06-28 | 2021-09-28 | 清远市柯林达新材料有限公司 | Vinyl fluorine-containing epoxy carboxylate intermediate, water-soluble fluorine modified acrylate, preparation method and acrylate coating |
| CN108299343A (en) * | 2018-02-09 | 2018-07-20 | 江苏泰特尔新材料科技有限公司 | It is a kind of to be prepared with micro passage reaction（Methyl）The method of acrylic acid -3,4- epoxycyclohexanecarboxylates |
| CN109467505A (en) * | 2018-11-16 | 2019-03-15 | 潍坊科麦化工有限公司 | A kind of preparation method of hydroxyethyl methacrylate |
| CN110054601A (en) * | 2019-03-13 | 2019-07-26 | 杭州盛弗泰新材料科技有限公司 | A kind of synthetic method of (methyl) acrylic acid ethers hydroxyl alkane esters |
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