阅读说明：本技术 一种丙烯酸缩水甘油酯的合成方法及应用 (Synthesis method and application of glycidyl acrylate ) 是由 张春雨 蓝俊杰 于 2020-12-23 设计创作，主要内容包括：本发明公开了一种丙烯酸缩水甘油酯的合成方法及应用,包括以下步骤：步骤一,反应合成；步骤二,减压精馏；步骤三,低温精馏收集；步骤四,高温精馏收集；步骤五,冷却储存；其中在上述步骤一中,取用适量的环氧氯丙烷和丙烯酸钠投入搅拌釜中,随后将相转移催化剂加入,搅拌均匀后加热保温,反应完成后制成丙烯酸缩水甘油酯粗品；该发明采用相转移催化剂,极大地提高了反应的收率,过程温和,无三废,绿色低碳环保,蒸馏得到前馏分用于下次反应,提高了收率,反应可用釜式反应器间歇操作,有利于扩大生产,同时反应产生的固体氯化钠可用环氧氯丙烷洗涤后,烘干,包装当副产品销售,有利于提高经济效益,增加了收入。(The invention discloses a synthesis method and application of glycidyl acrylate, which comprises the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing; adding a proper amount of epoxy chloropropane and sodium acrylate into a stirring kettle, adding a phase transfer catalyst, uniformly stirring, heating, keeping the temperature, and preparing a crude product of glycidyl acrylate after the reaction is finished; the method adopts the phase transfer catalyst, greatly improves the reaction yield, has mild process, no three wastes, is green, low-carbon and environment-friendly, obtains the front fraction by distillation for the next reaction, improves the yield, can use a kettle type reactor for intermittent operation, is favorable for expanding production, and simultaneously can use solid sodium chloride generated by the reaction to be washed by epoxy chloropropane, dried and packaged as a byproduct for sale, is favorable for improving economic benefit and increases income.)

1. A synthetic method and application of glycidyl acrylate comprise the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing; the method is characterized in that:

adding a proper amount of epoxy chloropropane and sodium acrylate into a stirring kettle, adding a phase transfer catalyst, uniformly stirring, heating, keeping the temperature, and preparing a crude product of glycidyl acrylate after the reaction is finished;

in the second step, the crude glycidyl acrylate product prepared in the first step is rectified under vacuum and reduced pressure to 10mmHg, the mixture is stirred in a tower kettle and heated to reflux, the reflux ratio is adjusted, and then the refluxed product is introduced into a collecting tower to be collected;

in the third step, when the product heated and refluxed in the second step enters a collecting tower, keeping the temperature of the top of the tower at 60-90 ℃, filtering and collecting unreacted epoxy chloropropane as front fraction, and continuously rectifying the filtrate;

in the fourth step, the temperature of the collection tower is raised, the temperature of the top of the tower is kept at 90-120 ℃, the filtrate is rectified at high temperature, the collected product is glycidyl acrylate, and the rectification is finished, so that high-purity glycidyl acrylate is obtained;

in the fifth step, the high-purity glycidyl acrylate obtained by rectification in the fourth step is cooled to room temperature, and then the high-purity glycidyl acrylate is placed in a cool and ventilated place for storage by using a closed container.

2. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the first step, the phase transfer catalyst is one or a mixture of more of PEG400, PEG800 and PEG 1000.

3. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the first step, the ratio of the sodium acrylate to the epichlorohydrin is 1.0: 0.8-3.0 according to the molar ratio, and the phase transfer catalyst is 0.3-4% of the sodium acrylate by mass percent.

4. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the first step, the temperature is raised to 60 ℃ under stirring, and the reaction time is kept at 5 h.

5. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the first step, the solid sodium chloride generated by the reaction can be washed by epoxy chloropropane, dried and packaged to be sold as a byproduct, so that the benefit is obviously improved.

6. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the third step, the filtered and collected epoxy chloropropane can participate in the next reaction, so that the material circulation is realized, the cost is saved, and the yield is improved.

7. The synthesis method and the application of the glycidyl acrylate according to claim 1, wherein the synthesis method comprises the following steps: in the fourth step, the yield of the glycidyl acrylate is 86%, and the purity of the glycidyl acrylate is 99-100%.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to a synthesis method and application of glycidyl acrylate.

Background

Glycidyl acrylate is a monomer with double functional groups, it has relatively higher reactivity than glycidyl methacrylate, have vinyl and epoxy group in its molecular formula at the same time, can carry on different reactions separately, while initiating with the free radical type initiating agent, can make the double bond open and other acrylate monomers copolymerize, produce the linear polymer with epoxy group, and the double functional group structure of glycidyl acrylate itself, make the high polymer of the acrylate can further crosslink into the network structure, its products have fine weather resistance, resist ultraviolet, water-fast and heat-resisting characteristic, etc., therefore, have been applied to the photosensitive material at present extensively, organic synthesis, many fields such as macromolecule synthesis and polymer modification.

Although the glycidyl acrylate has a plurality of uses and a wide application range, the raw materials are expensive, the cost is high, the synthesis method is complex, the price of the synthesized glycidyl acrylate is high, the large-scale popularization is not facilitated, and certain wastes are generated in the synthesis process, so that the environment is not facilitated.

Disclosure of Invention

The invention aims to provide a synthesis method and application of glycidyl acrylate, so as to solve the problems in the background technology.

In order to solve the technical problems, the invention provides the following technical scheme: a synthetic method and application of glycidyl acrylate comprise the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing;

adding a proper amount of epoxy chloropropane and sodium acrylate into a stirring kettle, adding a phase transfer catalyst, uniformly stirring, heating, keeping the temperature, and preparing a crude product of glycidyl acrylate after the reaction is finished;

in the second step, the crude glycidyl acrylate product prepared in the first step is rectified under vacuum and reduced pressure to 10mmHg, the mixture is stirred in a tower kettle and heated to reflux, the reflux ratio is adjusted, and then the refluxed product is introduced into a collecting tower to be collected;

in the third step, when the product heated and refluxed in the second step enters a collecting tower, keeping the temperature of the top of the tower at 60-90 ℃, filtering and collecting unreacted epoxy chloropropane as front fraction, and continuously rectifying the filtrate;

in the fourth step, the temperature of the collection tower is raised, the temperature of the top of the tower is kept at 90-120 ℃, the filtrate is rectified at high temperature, the collected product is glycidyl acrylate, and the rectification is finished, so that high-purity glycidyl acrylate is obtained;

in the fifth step, the high-purity glycidyl acrylate obtained by rectification in the fourth step is cooled to room temperature, and then the high-purity glycidyl acrylate is placed in a cool and ventilated place for storage by using a closed container.

According to the technical scheme, in the first step, the phase transfer catalyst is one or a mixture of more of PEG400, PEG800 and PEG 1000.

According to the technical scheme, in the first step, the ratio of the sodium acrylate to the epichlorohydrin is 1.0: 0.8-3.0 according to the molar ratio, and the phase transfer catalyst is 0.3-4% of the sodium acrylate by mass percent.

According to the technical scheme, in the first step, the temperature is raised to 60 ℃ under stirring, and the reaction time is kept at 5 h.

According to the technical scheme, in the step one, the solid sodium chloride generated by the reaction can be washed by epoxy chloropropane, dried and packaged to be sold as a byproduct, so that the income is obviously improved.

According to the technical scheme, in the third step, the filtered and collected epoxy chloropropane can participate in the next reaction, so that material circulation is realized, the cost is saved, and the yield is improved.

According to the technical scheme, in the fourth step, the yield of the glycidyl acrylate is 86%, and the purity of the glycidyl acrylate is 99-100%.

Compared with the prior art, the invention has the following beneficial effects: the method adopts the phase transfer catalyst, greatly improves the reaction yield, has mild process, no three wastes, is green, low-carbon and environment-friendly, obtains the front fraction by distillation for the next reaction, improves the yield, can use a kettle type reactor for intermittent operation, is favorable for expanding production, and simultaneously can use solid sodium chloride generated by the reaction to be washed by epoxy chloropropane, dried and packaged as a byproduct for sale, is favorable for improving economic benefit and increases income.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a flow chart of the method of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Referring to fig. 1, the present invention provides a technical solution:

example 1:

a synthetic method and application of glycidyl acrylate comprise the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing;

in the first step, sodium acrylate, epichlorohydrin and PEG400 are respectively weighed according to the weight part ratio of 94: 270: 1.5, then the obtained product is put into a 500-liter stirring kettle, the obtained product is uniformly stirred, heated and kept warm, the temperature is raised to 60 ℃ under stirring, the heat-preservation reaction time is 5 hours, a crude glycidyl acrylate product is prepared after the reaction is finished, and solid sodium chloride generated by the reaction can be washed by epichlorohydrin, dried and packaged to serve as a byproduct for sale, so that the income is obviously improved;

in the second step, the crude glycidyl acrylate product prepared in the first step is rectified under vacuum and reduced pressure to 10mmHg, the mixture is stirred in a tower kettle and heated to reflux, the reflux ratio is adjusted, and then the refluxed product is introduced into a collecting tower to be collected;

in the third step, when the product heated and refluxed in the second step enters a collecting tower, the temperature of the top of the tower is kept at 60-90 ℃, unreacted epoxy chloropropane is filtered and collected to be used as front fraction, the filtrate is continuously rectified, and the filtered and collected epoxy chloropropane can participate in the next reaction, so that the material circulation is realized, the cost is saved, and the yield is improved;

in the fourth step, the temperature of the collecting tower is raised, the temperature of the top of the tower is kept at 90-120 ℃, the filtrate is rectified at high temperature, the collected product is glycidyl acrylate until the rectification is finished, and thus the high-purity glycidyl acrylate is obtained, the yield of the glycidyl acrylate is 86%, and the purity of the glycidyl acrylate is 99-100%;

in the fifth step, the high-purity glycidyl acrylate obtained by rectification in the fourth step is cooled to room temperature, and then the high-purity glycidyl acrylate is placed in a cool and ventilated place for storage by using a closed container.

Example 2:

a synthetic method and application of glycidyl acrylate comprise the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing;

in the first step, sodium acrylate, epichlorohydrin and PEG800 are respectively weighed according to the weight part ratio of 94: 270: 1.5, then the obtained product is put into a 500-liter stirring kettle, the obtained product is uniformly stirred, heated and kept warm, the temperature is raised to 60 ℃ under stirring, the heat-preservation reaction time is 5 hours, a crude glycidyl acrylate product is prepared after the reaction is finished, and solid sodium chloride generated by the reaction can be washed by epichlorohydrin, dried and packaged to serve as a byproduct for sale, so that the income is obviously improved;

in the second step, the crude glycidyl acrylate product prepared in the first step is rectified under vacuum and reduced pressure to 10mmHg, the mixture is stirred in a tower kettle and heated to reflux, the reflux ratio is adjusted, and then the refluxed product is introduced into a collecting tower to be collected;

in the third step, when the product heated and refluxed in the second step enters a collecting tower, the temperature of the top of the tower is kept at 60-90 ℃, unreacted epoxy chloropropane is filtered and collected to be used as front fraction, the filtrate is continuously rectified, and the filtered and collected epoxy chloropropane can participate in the next reaction, so that the material circulation is realized, the cost is saved, and the yield is improved;

in the fourth step, the temperature of the collecting tower is raised, the temperature of the top of the tower is kept at 90-120 ℃, the filtrate is rectified at high temperature, the collected product is glycidyl acrylate until the rectification is finished, and thus the high-purity glycidyl acrylate is obtained, the yield of the glycidyl acrylate is 86%, and the purity of the glycidyl acrylate is 99-100%;

in the fifth step, the high-purity glycidyl acrylate obtained by rectification in the fourth step is cooled to room temperature, and then the high-purity glycidyl acrylate is placed in a cool and ventilated place for storage by using a closed container.

Example 3:

a synthetic method and application of glycidyl acrylate comprise the following steps: step one, reaction synthesis; step two, rectification under reduced pressure; step three, low-temperature rectification and collection; step four, high-temperature rectification and collection; step five, cooling and storing;

in the first step, sodium acrylate, epichlorohydrin and PEG1000 are respectively weighed according to the weight part ratio of 94: 270: 1.5, then the mixture is put into a 500-liter stirring kettle, the mixture is heated and insulated after being uniformly stirred, the temperature is raised to 60 ℃ under stirring, the insulation reaction time is 5 hours, a crude glycidyl acrylate product is prepared after the reaction is finished, and the solid sodium chloride generated by the reaction can be washed by epichlorohydrin, dried and packaged to be sold as a byproduct, so that the income is obviously improved;

in the second step, the crude glycidyl acrylate product prepared in the first step is rectified under vacuum and reduced pressure to 10mmHg, the mixture is stirred in a tower kettle and heated to reflux, the reflux ratio is adjusted, and then the refluxed product is introduced into a collecting tower to be collected;

in the third step, when the product heated and refluxed in the second step enters a collecting tower, the temperature of the top of the tower is kept at 60-90 ℃, unreacted epoxy chloropropane is filtered and collected to be used as front fraction, the filtrate is continuously rectified, and the filtered and collected epoxy chloropropane can participate in the next reaction, so that the material circulation is realized, the cost is saved, and the yield is improved;

in the fourth step, the temperature of the collecting tower is raised, the temperature of the top of the tower is kept at 90-120 ℃, the filtrate is rectified at high temperature, the collected product is glycidyl acrylate until the rectification is finished, and thus the high-purity glycidyl acrylate is obtained, the yield of the glycidyl acrylate is 86%, and the purity of the glycidyl acrylate is 99-100%;

in the fifth step, the high-purity glycidyl acrylate obtained by rectification in the fourth step is cooled to room temperature, and then the high-purity glycidyl acrylate is placed in a cool and ventilated place for storage by using a closed container.

The glycidyl acrylates obtained in the above examples were compared and the results obtained are shown in the following table:

	example 1	Example 2	Example 3
				Epichlorohydrin residue	Less residue	A small amount of residue	Substantially has no residue

Based on the above, the method has the advantages that the method adopts the phase transfer catalyst, the reaction yield is greatly improved, the process is mild, three wastes are avoided, the method is green, low-carbon and environment-friendly, the front fraction obtained by distillation is used for the next reaction, the yield is improved, the reaction can be intermittently operated by using a kettle type reactor, the method is favorable for expanding production, and meanwhile, the solid sodium chloride generated by the reaction can be washed by epoxy chloropropane, dried and packaged to be sold as a byproduct, so that the economic benefit is improved, and the income is increased.

It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.