CN102050734A - Method for synthesizing allyl methacrylate - Google Patents
Method for synthesizing allyl methacrylate Download PDFInfo
- Publication number
- CN102050734A CN102050734A CN201010598670XA CN201010598670A CN102050734A CN 102050734 A CN102050734 A CN 102050734A CN 201010598670X A CN201010598670X A CN 201010598670XA CN 201010598670 A CN201010598670 A CN 201010598670A CN 102050734 A CN102050734 A CN 102050734A
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- Prior art keywords
- methacrylate
- allyl methacrylate
- distillation
- chlorallylene
- allyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing allyl methacrylate. The method comprises the following steps of: A, reacting potassium methacrylate or sodium methacrylate and 3-chloropropene serving as raw materials in a solvent in the presence of a catalyst and a polymerization inhibitor with stirring at the temperature of between 40 and 60 DEG C for 2 to 5 hours; and B, recovering excess 3-chloropropene by distillation, and distilling or fractionating to obtain the allyl methacrylate, wherein the molar ratio of the potassium methacrylate or the sodium methacrylate to the 3-chloropropene is 1:1.5-5; the solvent is selected from dimethyl sulfoxide and N,N-dimethylformamide; the catalyst is selected from hexadecyl trimethyl ammonium bromide serving as a quaternary ammonium salt and benzyl triethyl ammonium chloride; and the polymerization inhibitor is selected from p-benzoquinone and hydroquinone. The method is simple and convenient, is easy to operate, has short reaction time and is low in cost; and by the method, the allyl methacrylate can be prepared at a higher yield.
Description
Technical field
The present invention relates to the Synthetic Organic Chemistry technical field, more specifically relate to a kind of method of synthesize methyl acrylic allyl propionate.
Background technology
Allyl methacrylate(AMA) is a kind of high polymer monomer, and it contains the functional group of vinyl and two inequivalences of allyl group simultaneously, can be used as the linking agent of multipolymer, the properties-correcting agent of macromolecular material.The silicon hydrogen addition of it and silane can be used for preparing silane coupling agent.
At present, the method for preparing allyl methacrylate(AMA) mainly contains with vinyl carbinol and methacrylic acid and is the esterification process of raw material and is the ester-interchange method of raw material with vinyl carbinol and methacrylic ester.The prepared in reaction that also has document utilization vinyl carbinol and methacrylic chloride.
Chinese patent CN1410412 is a raw material with vinyl carbinol and methacrylic acid, with the tosic acid is catalyzer, is stopper with the Resorcinol, makes allyl methacrylate(AMA) in 5 hours through back flow reaction, need to add water liquid benzene in the reaction process, remove the water of generation with continuous separation.Reaction is finished after excessive vinyl carbinol is reclaimed in fractionation, and through underpressure distillation purifying methacrylic acid allyl ester, productive rate is 90-92%.
Patent RO89221 is a raw material with vinyl carbinol and methacrylic acid also, adopts an acidic catalyst, makes allyl methacrylate(AMA) by esterification.
Patent CN101337886 is a raw material with vinyl carbinol and methacrylic ester then, and wherein transesterification reaction is carried out catalysis by the methyl ethyl diketone zirconium.
Patent CN101486648 is a raw material with vinyl carbinol and methyl methacrylate equally, uses the mixed catalyst of organic tin and organic titanium class, adopts the reaction of rectifying ester exchange process, needs in the reaction process in time to remove the methyl alcohol that reaction generates by azeotropic distillation.After underpressure distillation removes excessive methyl methacrylate, remove catalyzer and stopper, underpressure distillation obtains allyl methacrylate(AMA).
PL162537B1 also adopts ester exchange process synthesize methyl acrylic allyl propionate, and the catalyzer of use is the alkyl titanium that makes under certain condition by titanium tetrachloride and excessive methanol.
EP 646567 also adopts ester-interchange method, is raw material with methyl methacrylate and vinyl carbinol, generates ester under sodium methylate, p-cresol and the effect of organotin dimethyltin chloride.
Adopt ester-interchange method to prepare Jpn. Kokai Tokkyo Koho JP 01258642, JP 11-222462, JP 2000-169429 and the DE 3423441 etc. in addition of methyl acrylic ester, catalyst system therefor is respectively four isobutyl-titanic acid ester, tetraalkyl titanate, the catalyzer of having born transition metal and lithium chloride/calcium oxide.
In the aforesaid method, its steam of raw material vinyl carbinol that is adopted has the intense stimulus effect to eyes, and price is higher; Most patents need be synthesized organometallics as catalyzer, and cost is higher.In addition, esterification reaction process need dewater, and ester-exchange reaction then needs to remove the methyl alcohol of generation, and the reaction times is generally longer.
Summary of the invention
In order to overcome the shortcoming of above-mentioned currently known methods, the objective of the invention is to be to provide a kind of method of synthesize methyl acrylic allyl propionate, method is easy, processing ease, reaction times is short, and cost is low, and the method according to this invention can prepare to higher yields allyl methacrylate(AMA).
In order to realize above-mentioned task, the present invention adopts following technical measures:
A kind of method of synthesize methyl acrylic allyl propionate comprises the following steps:
A, be raw material, use solvent, in the presence of catalyzer and stopper, in 40-60 ℃ of stirring reaction 2-5 hour with methacrylic acid potassium or sodium methacrylate and chlorallylene.Be cooled to room temperature (20-25 ℃, below identical).
B, reclaim excessive chlorallylene, can obtain allyl methacrylate(AMA) through distillation or fractionation again through distillation.
Raw material of the present invention is methacrylic acid potassium or sodium methacrylate and chlorallylene, and mol ratio is 1:1.5-5; Described solvent is methyl-sulphoxide and N, wherein a kind of of dinethylformamide; Described catalyzer is wherein a kind of of quaternary ammonium salt cetrimonium bromide and benzyltriethylammonium chloride; Described stopper is wherein a kind of of para benzoquinone and Resorcinol.
Compare with reporting literature method, the advantage of the inventive method comprise following some:
1) utilize the lower chlorallylene of price to be raw material synthesize methyl acrylic allyl propionate.
2) because employing methacrylate and chlorallylene are raw material, the reaction times is shorter, and is simple to operate.
3) not adopting organometallics is catalyzer, and adopting quaternary ammonium salt commonly used is catalyzer, and consumption is less, and cost is lower.
4) adopt polar solvent methyl-sulphoxide and N, dinethylformamide, reaction yield is higher.
Embodiment
With reference to following specific embodiment, those skilled in the art can more clearly be understood the inventive method.
Embodiment 1
In the there-necked flask that reflux condensing tube, thermometer are housed, add methyl-sulphoxide 70 ml, methacrylic acid potassium 25 g, chlorallylene 41 ml, para benzoquinone 0.1 g, benzyltriethylammonium chloride 0.75 g, in 40 or 44 or 48 or 50 or 54 or 58 or 60 ℃ of mechanical stirring reactions 3 hours.Be cooled to room temperature, propenyl chloride is reclaimed in distillation.The dress fractional column, fractionation obtains allyl methacrylate(AMA), and yield is greater than 70%.
Embodiment 2
In the there-necked flask that reflux condensing tube, thermometer are housed, add methyl-sulphoxide 70 ml, methacrylic acid potassium 25 g, chlorallylene 41 ml, para benzoquinone 0.1 g, cetrimonium bromide 0.75 g, in 60 ℃ of mechanical stirring reactions 2 or 3 or 4 hours.Be cooled to room temperature, propenyl chloride is reclaimed in distillation.The dress fractional column, fractionation obtains allyl methacrylate(AMA), and yield is greater than 80%.
Embodiment 3
In the there-necked flask that reflux condensing tube, thermometer are housed, add methyl-sulphoxide 70 ml, methacrylic acid potassium 25 g, chlorallylene 41 ml, para benzoquinone 0.1 g, cetrimonium bromide 0.75 g, in 40 or 45 or 50 or 55 or 60 ℃ of mechanical stirring reactions 3 or 5 hours.Be cooled to room temperature, propenyl chloride is reclaimed in distillation.The dress fractional column, fractionation obtains allyl methacrylate(AMA), and yield is greater than 80%.
Embodiment 4
In the there-necked flask that reflux condensing tube, thermometer are housed, add N, dinethylformamide 70 ml, sodium methacrylate 22 g, chlorallylene 41 ml, para benzoquinone 0.1 g, cetrimonium bromide 0.75 g were in 40 or 45 or 50 or 55 or 60 ℃ of mechanical stirring reactions 3 or 4 hours.Be cooled to room temperature, propenyl chloride is reclaimed in distillation.Product is removed N through extracting and washing, dinethylformamide, and drying, distillation obtains allyl methacrylate(AMA), and yield is greater than 80%.
The scope of the invention is not restricted to the described embodiments, and described embodiment only is used for illustrating a method of the present invention, and the embodiment of any equal effect within the scope of the present invention.In fact, according to above description, except that the invention described above embodiment, the various improvement that the present invention is carried out are conspicuous for those skilled in the art.Described improvement is in protection scope of the present invention.All patents and document that the present invention mentions are quoted reference in the present invention as proof.
Claims (1)
1. the method for a synthesize methyl acrylic allyl propionate the steps include:
A, be raw material, use solvent, in the presence of catalyzer and stopper,, be cooled to room temperature in 40-60 ℃ of stirring reaction 2-5 hour with methacrylic acid potassium or sodium methacrylate and chlorallylene;
B, reclaim excessive chlorallylene, obtain allyl methacrylate(AMA) through distillation or fractionation again through distillation;
The mol ratio of described methacrylic acid potassium or sodium methacrylate and chlorallylene is 1:1.5 – 5;
Described solvent is methyl-sulphoxide and N, wherein a kind of of dinethylformamide;
Described catalyzer is wherein a kind of of quaternary ammonium salt cetrimonium bromide and benzyltriethylammonium chloride;
Described stopper is wherein a kind of of para benzoquinone and Resorcinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598670XA CN102050734A (en) | 2010-12-21 | 2010-12-21 | Method for synthesizing allyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010598670XA CN102050734A (en) | 2010-12-21 | 2010-12-21 | Method for synthesizing allyl methacrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102050734A true CN102050734A (en) | 2011-05-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010598670XA Pending CN102050734A (en) | 2010-12-21 | 2010-12-21 | Method for synthesizing allyl methacrylate |
Country Status (1)
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| CN (1) | CN102050734A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542994A (en) * | 2016-10-09 | 2017-03-29 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410412A (en) * | 2001-09-28 | 2003-04-16 | 湖北武大有机硅新材料股份有限公司 | Synthesis of methacrylate allyl propyl ester |
-
2010
- 2010-12-21 CN CN201010598670XA patent/CN102050734A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410412A (en) * | 2001-09-28 | 2003-04-16 | 湖北武大有机硅新材料股份有限公司 | Synthesis of methacrylate allyl propyl ester |
Non-Patent Citations (1)
| Title |
|---|
| 卢言菊 等: "相转移催化法合成松香树脂酸烯丙酯工艺", 《化学进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542994A (en) * | 2016-10-09 | 2017-03-29 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
| CN106542994B (en) * | 2016-10-09 | 2018-11-09 | 烟台德邦先进硅材料有限公司 | A kind of synthetic method of allyl acrylate |
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| PB01 | Publication | ||
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
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Application publication date: 20110511 |