CN108586249A - A kind of synthetic method of 1,4-butanediol dimethylacrylate - Google Patents
A kind of synthetic method of 1,4-butanediol dimethylacrylate Download PDFInfo
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- CN108586249A CN108586249A CN201810522561.6A CN201810522561A CN108586249A CN 108586249 A CN108586249 A CN 108586249A CN 201810522561 A CN201810522561 A CN 201810522561A CN 108586249 A CN108586249 A CN 108586249A
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- butanediol
- synthetic method
- butanediol dimethylacrylate
- dimethylacrylate
- methacrylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to rubber to synthesize field, disclose one kind 1, the synthetic method of 4 butanediol dimethylacrylates, with methacrylic acid and 1,4 butanediols are that raw material is reacted using dicyclohexylcarbodiimide as dehydrating agent at 5 DEG C to 0 DEG C, then Isosorbide-5-Nitrae butanediol dimethylacrylate is made by filtering, concentration, rectifying.The raw material sources that the present invention uses are extensive, cheap, and reaction temperature is relatively low, and without toxic gas in reaction process, post-processing is simple, and products therefrom yield, purity are higher.
Description
Technical field
The present invention relates to rubber synthesis field more particularly to a kind of synthesis sides of 1,4-butanediol dimethylacrylate
Method.
Background technology
Acrylic rubber（ACM）It is a kind of special synthetic rubber of saturation backbone structure, it is by acrylate and to lack
A kind of elastomer made of monomer copolymerization of the amount with the active group for cross-linking reaction.It has excellent heat resistance, resistance to
Oiliness resists cold, resistance to ozone, the performances such as fuel oil resistance, also good processability, prominent with framework material adhesive strength height etc.
Go out advantage, is mainly used for the rubber accessory at each position of auto industry contact deep fat engine, there is the title of " automobile-used rubber ", acrylic acid
Ester rubber is disadvantageous in that difficult vulcanization etc..With the development of technique, according to the requirement of use demand and processing technology, production
The acrylic rubber of different cross-linking monomers and Elastomers with Different Curing Systems, the wherein conduct of 1,4-butanediol dimethylacrylate are gone out
One acrylate monomer bifunctional, it has short vulcanization, low injection, heat safe advantage, for synthesizing sizing coating
With ACM rubber.
In the prior art, as long as the synthetic method of 1,4-butanediol dimethylacrylate has following three kinds：
The first, using alkyd direct esterification：By the polyalcohol of certain mol proportion and acrylic acid in acidic catalyst, polymerization inhibitor
And in the presence of solvent, reacted at a certain temperature.During the reaction, made instead by solvent and by-product water azeotropic
The balance answered moves to right.After reaction, acidic catalyst and unreacted raw material are removed by washing or neutralizing.This preparation
Technique in and generates a large amount of high-salt wastewaters in water-washing process, is unfavorable for friendly process requirement；And often generate monoesters and dibasic acid esters
Mixture, yield is relatively low.
Second, using acid, alkali or metal complex make catalyst and carry out ester exchange reaction：It is anti-in case of heating
Methanol or ethyl alcohol should be generated, collects by-product to keep reaction more thorough.This preparation process generally requires higher temperature,
By-product alcohols need to remove using rectifying column, higher to equipment requirement.
The third, acid anhydrides or acyl chlorides are converted into using acrylic acid, and in the presence of acid binding agent, low temperature generates content
Higher acrylate, such method raw material are converted into the acrylic acid that acid anhydrides needs additional equivalent, do not meet atom economy
Theory, make acyl chlorides its to environment, employee injures larger with it, while acid binding agent faces recycling or neutralisation treatment to cause
High-salt wastewater.
From the foregoing, it will be observed that in the prior art the above-mentioned synthetic method of 1,4-butanediol dimethylacrylate exist it is respective
Disadvantage, it is therefore necessary to develop a new route that can solve above-mentioned technical problem.
Invention content
In order to solve the above technical problem, the present invention provides a kind of synthesis sides of 1,4-butanediol dimethylacrylate
Method, the raw material sources that the present invention uses are extensive, cheap, and reaction temperature is relatively low, without toxic gas, post-processing in reaction process
Simply, and product yield, purity are high.
The specific technical solution of the present invention is：A kind of synthetic method of 1,4-butanediol dimethylacrylate, with methyl
Acrylic acid and 1,4-butanediol are that raw material is reacted at -5 DEG C to 0 DEG C, then passed through using dicyclohexylcarbodiimide as dehydrating agent
1,4-butanediol dimethylacrylate is made in filtering, concentration, rectifying.
Present invention employs N, and N- dicyclohexylcarbodiimides are as dehydrating agent, since there are double bonds for it（N=C=N）Knot
Structure so that be easy to that carbonyl is in connection, generate the reactive intermediate of O- acetyl group ureas, while temperature is excessively high, this reactive intermediate
Thermal decomposition is amide, so entire reaction can carry out at low temperature.
In addition, although the product of the present invention is being also required to carry out rectification process final, referred to background technology the
Two kinds of methods are compared, and do not have by-product alcohols in synthetic method of the present invention in products therefrom, therefore rectifying difficulty is smaller, to equipment
It is required that not high.And contain more by-product alcohols in second method products therefrom, the boiling point more phase with target product
Closely, therefore rectifying requires higher, needs the rectifying device more refined.
Preferably, synthesis detailed process is：Methacrylic acid, 1,4-butanediol are added in solvent and are stirred at room temperature
Dissolving is cooled to -5 DEG C to 0 DEG C, and dicyclohexylcarbodiimide solution is added dropwise, drips off within 4-6 hours, then reacts 20-28h, mistake
Sodium carbonate liquor is added in filter, filtrate, and washing is multiple, is washed with water and washs, and organic phase drying, concentration removes solvent, obtains Isosorbide-5-Nitrae-fourth
Diol dimethacrylate.
Preferably, the methacrylic acid and the mass ratio of 1,4-butanediol are 170-210:90.
Methacrylic acid needs excess relative to 1,4-butanediol in the present invention, the reason is that being on the one hand methacrylic acid
It is cheap relative to 1,4-butanediol；On the other hand processing is washed and can be gone out completely after neutralizing, and the processing of butanediol is difficult
Degree is more than methacrylic acid, and remaining 1.4- butanediols, which need to be evaporated under reduced pressure, to be removed, and the additional finishing time that extends is be easy to cause
Product section polymerize, and reduces product yield.
Preferably, the mass ratio of the methacrylic acid and dicyclohexylcarbodiimide is 170-210:206.
Preferably, the solvent is dichloromethane.
Preferably, the solvent of the dicyclohexylcarbodiimide solution is dichloromethane.
Preferably, a concentration of 40-60wt% of the dicyclohexylcarbodiimide solution.
Preferably, a concentration of 4-6wt% of the sodium carbonate liquor, dosage is 1.5-2.5 times of Isosorbide-5-Nitrae butanediol quality.
It is compared with the prior art, the beneficial effects of the invention are as follows：The raw material sources that the present invention uses are extensive, cheap,
Reaction temperature is relatively low, and without toxic gas in reaction process, post-processing is simple, and product yield, purity are high.
Description of the drawings
Fig. 1 is 1,4-butanediol dimethylacrylate chromatography of gases figure produced by the present invention.
Specific implementation mode
With reference to embodiment, the invention will be further described.
Total embodiment
A kind of synthetic method of 1,4-butanediol dimethylacrylate, at room temperature by the methacrylic acid of 170-210g, 90g
1,4-butanediol be added to stirring and dissolving in 200g dichloromethane, be cooled to -5 DEG C to 0 DEG C, 40-60wt% dicyclohexyls be added dropwise
Carbodiimide solution（Dichloromethane）It drips off within 412g, 4-6 hours, then reacts 20-28h, filter, it is dense that 135-225g is added in filtrate
Degree is the sodium carbonate liquor of 4-6wt%, washs 2 times, is washed with water and washs, and organic phase drying, concentration removes solvent, and rectifying obtains 1,
4- butanediol dimethylacrylates.
Embodiment 1
Methacrylic acid 206.6g (2.4mol) at room temperature, 90g (1mol) 1,4-butanediol, 200g dichloromethane, stirring and dissolving,
- 5 DEG C are cooled to, the dichloromethane solution 412g of 50wt% dicyclohexylcarbodiimide solution is added dropwise, drips off within 5 hours, then low temperature
200g sodium carbonate liquors (5%) are added in reaction 24 hours, filtering, filtrate, wash 2 times, 200g water washings, organic phase drying, concentration
Solvent is removed, rectifying obtains the 1,4-butanediol dimethylacrylate of 169.5g, yield 75%, purity 98.6%（Such as figure
Shown in 1）.
Embodiment 2
Methacrylic acid 189.4g (2.2mol) at room temperature, 90g (1mol) 1,4-butanediol, 200g dichloromethane, stirring and dissolving,
It is cooled to 0 DEG C, the dichloromethane solution 412g of 50wt% dicyclohexylcarbodiimide solution is added dropwise, drips off within 5 hours, then low temperature
200g sodium carbonate liquors (5%) are added in reaction 24 hours, filtering, filtrate, wash 2 times, 200g water washings, organic phase drying, concentration
Solvent is removed, rectifying obtains 160.46g 1,4-butanediol dimethylacrylates, yield 71%, purity 98.8%.
Embodiment 3
Methacrylic acid 172.2g (2mol) at room temperature, 90g (1mol) 1,4-butanediol, 200g dichloromethane, stirring and dissolving,
- 2 DEG C are cooled to, the dichloromethane solution 412g of 50wt% dicyclohexylcarbodiimide solution is added dropwise, drips off within 5 hours, then low temperature
200g sodium carbonate liquors (5%) are added in reaction 24 hours, filtering, filtrate, wash 2 times, 200g water washings, organic phase drying, concentration
Solvent is removed, rectifying obtains 140.12g 1,4-butanediol dimethylacrylates, yield 62%, purity 98.6%.
Embodiment 4
At room temperature by the methacrylic acid of 170g（1.98mol）, 90g (1mol) 1,4-butanediol be added to 200g dichloromethanes
Stirring and dissolving in alkane is cooled to -5 DEG C, and 40wt% dicyclohexylcarbodiimide solution is added dropwise（Dichloromethane）412g(0.8mol),
It drips off within 6 hours, then reacted liquid, filter, the sodium carbonate liquor of a concentration of 4wt% of 225g is added in filtrate, washs 2 times, then use water
Washing, organic phase drying, concentration remove solvent, and rectifying obtains 1,4-butanediol dimethylacrylate 126.71g, and yield is
56%, purity 98.9%.
Embodiment 5
At room temperature by the methacrylic acid of 210g (2.44mol), 90g（1mol）1,4-butanediol be added to 200g dichloromethanes
Stirring and dissolving in alkane is cooled to -5 DEG C, and 60wt% dicyclohexylcarbodiimide solution is added dropwise（Dichloromethane）412 (1.2mol) g, 6
Hour drips off, and then reacts 28h, filters, and the sodium carbonate liquor of a concentration of 4wt% of 225g is added in filtrate, washs 2 times, is washed with water
It washs, organic phase drying, concentration removes solvent, and rectifying obtains 1,4-butanediol dimethylacrylate 174.02g, and yield 77% is pure
Degree is 98.5%.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention, every according to the present invention
Technical spirit still falls within the technology of the present invention side to any simple modification, change and equivalent transformation made by above example
The protection domain of case.
Claims (8)
1. a kind of synthetic method of 1,4-butanediol dimethylacrylate, it is characterised in that：With methacrylic acid and 1,4- fourths
Glycol is raw material, using dicyclohexylcarbodiimide as dehydrating agent, is reacted at -5 DEG C to 0 DEG C, then by filtering, concentration, essence
Evaporate obtained 1,4-butanediol dimethylacrylate.
2. a kind of synthetic method of 1,4-butanediol dimethylacrylate as described in claim 1, it is characterised in that specific
Process is：Methacrylic acid, 1,4-butanediol are added to stirring and dissolving in solvent at room temperature, are cooled to -5 DEG C to 0 DEG C, is added dropwise
Dicyclohexylcarbodiimide solution drips off, then reacts 20-28h for 4-6 hours, filtering, and sodium carbonate liquor, washing is added in filtrate
Repeatedly, it is washed with water and washs, organic phase drying, concentration removes solvent, obtains 1,4-butanediol dimethylacrylate.
3. a kind of synthetic method of 1,4-butanediol dimethylacrylate as claimed in claim 1 or 2, which is characterized in that
The mass ratio of the methacrylic acid and 1,4- butanediols is 170-210:90.
4. a kind of synthetic method of 1,4-butanediol dimethylacrylate as claimed in claim 1 or 2, which is characterized in that
The mass ratio of the methacrylic acid and dicyclohexylcarbodiimide is 170-210:206.
5. a kind of synthetic method of 1,4-butanediol dimethylacrylate as claimed in claim 2, which is characterized in that described
Solvent is dichloromethane.
6. a kind of synthetic method of 1,4-butanediol dimethylacrylate as claimed in claim 2, which is characterized in that described
The solvent of dicyclohexylcarbodiimide solution is dichloromethane.
7. a kind of synthetic method of 1,4-butanediol dimethylacrylate as described in claim 2 or 6, which is characterized in that
A concentration of 40-60wt% of the dicyclohexylcarbodiimide solution.
8. a kind of synthetic method of 1,4-butanediol dimethylacrylate as claimed in claim 2, which is characterized in that described
A concentration of 4-6wt% of sodium carbonate liquor, dosage are 1.5-2.5 times of Isosorbide-5-Nitrae butanediol quality.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810522561.6A CN108586249A (en) | 2018-05-28 | 2018-05-28 | A kind of synthetic method of 1,4-butanediol dimethylacrylate |
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| CN201810522561.6A CN108586249A (en) | 2018-05-28 | 2018-05-28 | A kind of synthetic method of 1,4-butanediol dimethylacrylate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336767A (en) * | 2018-11-26 | 2019-02-15 | 山东永浩新材料科技有限公司 | A kind of dehydration synthetic method of ethyl difluoro |
| CN110668939A (en) * | 2019-11-12 | 2020-01-10 | 江苏正丹化学工业股份有限公司 | Synthesis method of 1, 4-butanediol dimethyl benzene enoate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03264550A (en) * | 1990-03-15 | 1991-11-25 | Sanyo Chem Ind Ltd | Production of unsaturated monomer |
| CN105960419A (en) * | 2014-02-14 | 2016-09-21 | 三菱瓦斯化学株式会社 | (meth)acrylic acid ester compound and production method therefor |
-
2018
- 2018-05-28 CN CN201810522561.6A patent/CN108586249A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03264550A (en) * | 1990-03-15 | 1991-11-25 | Sanyo Chem Ind Ltd | Production of unsaturated monomer |
| CN105960419A (en) * | 2014-02-14 | 2016-09-21 | 三菱瓦斯化学株式会社 | (meth)acrylic acid ester compound and production method therefor |
Non-Patent Citations (1)
| Title |
|---|
| 袁训等: "大位阻叔醇酯化合成的研究 ", 《浙江大学学报(工学版)》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109336767A (en) * | 2018-11-26 | 2019-02-15 | 山东永浩新材料科技有限公司 | A kind of dehydration synthetic method of ethyl difluoro |
| CN110668939A (en) * | 2019-11-12 | 2020-01-10 | 江苏正丹化学工业股份有限公司 | Synthesis method of 1, 4-butanediol dimethyl benzene enoate |
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Application publication date: 20180928 |