CN1127745A - Method for preparing alkyl acrylate (or methylacrylate) - Google Patents
Method for preparing alkyl acrylate (or methylacrylate) Download PDFInfo
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- CN1127745A CN1127745A CN 95101716 CN95101716A CN1127745A CN 1127745 A CN1127745 A CN 1127745A CN 95101716 CN95101716 CN 95101716 CN 95101716 A CN95101716 A CN 95101716A CN 1127745 A CN1127745 A CN 1127745A
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- stopper
- reaction
- ester
- catalyzer
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Abstract
In the presence of organotins catalyst and N-O free radicals polymerization inhibitor, the ester whose formula is CH2=CR1COOR2, where R1 is H or CH3 and R2 is CH3 or C2H5, and the alcohol whose formula is R3OH, where R3 is C4-C14 aliphatic or alicyclic alkyl, or R4(OH)n, where R4 is C2-C6 aliphatic alkyl or (CH2CH2O)mCH2CH2-, where m is 1 or 2, n is an integer from 2 to 4, take part in ester exchange reaction to obtain alkyl acrylate or methylacrylate, whose formula is CH2=CR1COOR3 or (CH2=CR1COO)nR4. After reaction, reduced pressure distillation directly takes place for separation. The residual catalyst may be reused.
Description
The present invention relates to the manufacture method of a kind of acrylic or methacrylic acid [hereinafter to be referred as (methyl) vinylformic acid] alkyl ester.Specifically, relate to acrylic acid low-carbon-ester of a kind of utilization (methyl) and higher alcohols or polyvalent alcohol and carry out transesterification reaction, make the method for (methyl) acrylic acid higher alcohols or polyol ester.
People are known, (methyl) acrylic acid low-carbon-ester and higher alcohols or polyvalent alcohol are carried out transesterification reaction, make the method for (methyl) acrylic acid higher alcohols or polyol ester, usually used catalyzer comprises: the alcoholate of basic metal (or alkaline-earth metal) (U.S. Pat 976304), an acidic catalysts such as titan-alkoxide and sulfuric acid (the clear 48-37011 of U.S. Pat 3686268 and Japanese Patent).Say that from industrial respectively there is its different shortcoming in above-mentioned catalyzer, for example: with the alcoholate of the such basic metal of sodium methylate (or alkaline-earth metal) during as catalyzer, though have higher initial activity, but carry out with reaction, catalyst activity reduction is very fast, so that has to carry out constantly adding in the process catalyzer in reaction.In addition, after reaction finishes, need water that catalyst decomposes is removed, so that be suppressed at the polymerization of product in the fractionation by distillation process or reactant, thereby make technology loaded down with trivial details, complicated, and produce a large amount of waste water.When utilizing titan-alkoxide to make catalyzer, reactive activity and selectivity are all high, catalyzer does not need to add and special aftertreatment etc. in batches yet, but this catalyzer is responsive to water electrode, even contain the moisture content of trace in the reaction system catalyst decomposes was lost efficacy, so the requirement to moisture content in the reaction system is harsh, need give and carry out strict processed earlier.Corresponding with above-mentioned alkali series catalysts, the someone has proposed to utilize the method for an acidic catalysts such as sulfuric acid, though mostly an acidic catalyst is cheap compound, exists speed of response slow, easily produces pair reaction and equipment corrosion problems such as polymerization.For overcoming the shortcoming of above-mentioned catalyzer, the someone proposes to adopt the organic tin compound to obtain preferably as this catalyst for reaction (Japanese clear 54-41814) to imitate tiredly, but do not solve the repetition reuse problem of catalyzer again.Organic tin catalyzer price is expensive, as not solving the repetition reuse problem of catalyzer, does not then have an actual application value industrial.
Purpose of the present invention is exactly in order to solve the repetition reuse problem of above-mentioned catalyzer.Remarkable by adopting a kind of new stopper to reach polymerization inhibition effect, make and do not produce superpolymer in ester-exchange reaction and the fractionation by distillation process substantially, thereby catalyzer can repeatedly repeat reuse, thereby reaches the technology that simplifies the operation that reduces production costs, and reduces the purpose of three-waste pollution.
The general introduction of invention: the present invention uses general formula to be CH
2=CR
1COOR
2(R in the formula
1Expression H or CH
3, R
2Expression CH
3Or C
2H
5) (methyl) vinylformic acid low-carbon-ester and general formula be R
3OH (R in the formula
3Expression C
4-C
14Aliphatic or alicyclic hydrocarbon radical) high alcohol or general formula be R
4(OH) R in the n[formula
4Expression C
2-C
6Aliphatic alkyl or-(CH
2CH
2O) m CH
2CH
2-(m is 1 or 2), n is the integer of 2--4] represented polyvalent alcohol, be in the presence of catalyzer and the specific nitroxyl free radical class high-efficiency polymerization inhibitor at known organo-tin compound, carry out transesterification reaction, the manufacturing general formula is CH
2=CR
1COOR
3(methyl) vinylformic acid high alcohol ester, or general formula is (CH
2=CR
1COO) nR
4The method of (methyl) acrylic acid multielement alcohol ester.
The catalyzer that the present invention adopts can be at least a in the catalyzer of following general formula:
[R represents C in the formula
1-C
8Alkyl or aryl, X represents-OR
1,-OCOR
1,-OCOCH=CHCOOR
1(R
1Be C
1-C
8Alkyl)].
Wherein, the compound of general formula (I) can be the methoxyl group tributyl tin, methoxyl group trioctylphosphine tin, the methoxyl group triphenyltin, oxyethyl group tributyl tin, oxyethyl group trioctylphosphine tin, the oxyethyl group triphenyltin, butoxy tributyl tin, butoxy trioctylphosphine tin, the butoxy triphenyltin, tributyltin acetate, acetate trioctylphosphine tin, triphenyltin acetate, sad tributyl tin, dodecylic acid tributyl tin, dodecylic acid trioctylphosphine tin, the stearic acid tributyl tin, stearic acid trioctylphosphine tin, tributyl tin maleic acid mono alkyl ester, tributyltin hydride, hydrogenation trioctylphosphine tin, triphenyltin hydride, tributyltin chloride, chlorination trioctylphosphine tin, triphenyltin chloride etc.
The compound of general formula (II) comprises the dimethoxy dibutyl tin, the dimethoxy dioctyl tin, the dimethoxy tin diphenyl, the diethoxy dibutyl tin, diethoxy dioctyl tin, diethoxy tin diphenyl, dibutyltin diacetate, the oxalic acid dioctyl tin, two dodecylic acid dibutyl tins, two dodecylic acid dioctyl tins, two stearic acid dibutyl tins, two stearic acid dioctyl tins, two maleic acid mono alkyl ester dibutyl tins, two maleic acid mono alkyl ester dioctyl tins, methoxyl group dibutyl tin maleic acid mono alkyl ester, methoxyl group dioctyl tin maleic acid mono alkyl ester, oxyethyl group dibutyl tin maleic acid mono alkyl ester, oxyethyl group dioctyl tin maleic acid mono alkyl ester etc.
The compound of general formula (III) comprises dibutyltin oxide and di-n-octyltin oxide etc.
Above-mentioned organo-tin compound promptly can be used alone, can also be two or more kinds in combination as catalyst for ester exchange reaction of the present invention.
The stopper that uses in the inventive method is 2.2.6.6-tetramethylpiperidinol nitroxyl free radical, or three (2.2.6.6-tetramethyl piperidine nitrogen oxygen free radical) phosphorous acid ester, or both mixtures.Also can adopt one of these two kinds of stoppers and MEHQ, 4-tert-butyl catechol, the composite polymerzation inhibitor of 2.2-methylene radical-two (4-methyl-6-tert butyl phenol) thrin.
The general formula that uses in the inventive method is CH
2=CR
1COOR
2Ester, can be methyl acrylate, ethyl propenoate, methyl methacrylate and Jia Jibingxisuanyizhi etc.
The general formula that uses in the inventive method is R
3OH or R
4(OH) alcohol of n can be propyl carbinol, isopropylcarbinol, Pentyl alcohol, n-hexyl alcohol, hexalin, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, nonylcarbinol, dodecyl alcohol, tetradecanol, cetyl alcohol, 1.4-butyleneglycol, 1.6-hexylene glycol, 2.5-hexylene glycol, ethylene glycol, triglycol, glycerol, hydroxymethyl-propane and tetramethylolmethane etc.
Below detailed manufacturing processed of the present invention.
At first, to thermometer is housed, add a certain amount of raw material in the reactor of agitator and distillation tower, catalyzer and stopper heat, and begin first total reflux for some time, control a certain amount of reflux ratio then, by-product alcohol is constantly removed by the component distillation mode.In the reaction process, the tower top temperature of distillation tower remains on 60--70 ℃, and along with the carrying out of reaction, temperature of reaction rises gradually, can be by the transformation efficiency of the raw alcohol in the gc analysis reaction solution.Reaction is directly carried out underpressure distillation with reaction solution (when needing, can earlier it be filtered) after finishing, and at first steams (methyl) acrylate raw material that reacts, and steams the purpose product then.The distillation residual solution is mainly catalyzer and stopper, can return repeated use.
Usually, the consumption of raw material (methyl) vinylformic acid low-carbon-ester is 1.2-10 times (mol) of raw alcohol, and preferably 1.5--5 doubly.
The usage quantity of catalyzer is generally the 0.1%--20% (m/m) of reaction solution total mass, preferably 0.5%--10%.
The usage quantity of stopper is generally the 0.01%--5% (m/m) of reaction solution total mass, preferably 0.05%--3%.
In manufacturing processed of the present invention, transesterification reaction can be carried out under normal pressure, distillates from reaction system for quickening by-product alcohol, also can under reduced pressure carry out.
Temperature of reaction is generally 50--l50 ℃, preferably 80--130 ℃.Reaction solvent is not special needs, but can use yet.Employed solvent can be benzene, toluene, normal hexane, hexanaphthene etc.
In order to obtain high reaction conversion ratio, by-product alcohol in time must be removed from reaction system.Specifically be to carry out with reaction, with by-product alcohol from azeotrope (with the ester raw material together) form steams from cat head, thereby reaction is carried out fully.Used reflux ratio is generally 1: 1--20: 1, be preferably 1: 1-10: 1.
Reaction times is by proportioning raw materials, temperature of reaction, and the decision of factors such as catalyst levels and reflux ratio is generally 2--10 hour.
Effect of the present invention:
According to method of the present invention, reaction conversion ratio can reach 99.5-99.8%, product yield can reach 95--98%, product purity 99.3%, the stopper that the present invention uses is compared with stopper in the past, has tangible polymerization inhibition effect, substantially not having superpolymer in ester-exchange reaction and the fractionation by distillation process generates, it is good fluidity that reaction solution carries out underpressure distillation separation back gained catalyzer raffinate, do not glue the transparent liquid of still, catalyzer repeats 10 activity of reuse and does not descend (seeing Table 1), can obviously reduce production costs, simplify the operation, reduce the three wastes.
Table 1.
| Catalyzer repeats the reuse number of times | Reaction conversion ratio | Product yield (%) | Product purity (%) | Reaction times h |
| ????1 | ????99.8 | ????95.5 | ????99.2 | ????4.0 |
| ????2 | ????99.7 | ????97.0 | ????99.4 | ????4.0 |
| ????3 | ????99.6 | ????96.5 | ????99.2 | ????4.2 |
| ????4 | ????99.5 | ????96.0 | ????99.3 | ????3.7 |
| ????5 | ????99.6 | ????96.0 | ????99.5 | ????3.4 |
| ????6 | ????99.7 | ????97.0 | ????99.3 | ????4.0 |
| ????7 | ????99.7 | ????96.5 | ????99.2 | ????4.0 |
| ????8 | ????99.5 | ????96.3 | ????99.4 | ????4.0 |
| ????9 | ????99.7 | ????97.0 | ????99.2 | ????3.7 |
| ???10 | ????99.5 | ????96.8 | ????99.3 | ????4.0 |
Following example is further illustrated technical characterictic of the present invention, the invention is not restricted to following example.
Embodiment 1.
Agitator is being housed, in the flask of thermometer and distillation tower, add 130g (1 mole) 2-Ethylhexyl Alcohol, 300g (3 moles) methyl methacrylate, two dodecylic acid dibutyl tins of 6g catalyzer and 0.5g three (2.2.6.6-four phenylpiperidines nitrogen oxygen freedom are former) phosphorous acid ester stopper are heated to boiling while stirring.After about 30 minutes, is control of reflux ratio about 5: 1 with the azeotrope total reflux of the by-product carbinol that generates and methyl methacrylate, and tower top temperature is remained on 64--70 ℃, and reaction is carried out finishing after 4 hours.Reaction solution is directly carried out underpressure distillation, at first unreacted methyl methacrylate is removed in distillation under the pressure of 2.7KPa, distillation obtains methacrylic acid 2--ethylhexyl 190g under 0.7KPa pressure then, its purity is 99.3%, in the 2-Ethylhexyl Alcohol that is added, yield is 96.5%.
After distillation finished, the vinasse of gained (being mainly catalyzer, stopper and remaining methacrylic acid 2-ethylhexyl) was a good fluidity, and the transparent liquid of sticking still wall not can be used as 10 activity of catalyzer direct reuse and do not descend, and the results are shown in Table 1.
Embodiment 2--6
Equipment therefor is also identical with embodiment 1. manufacture method, only changes the kind of raw alcohol, and gained the results are shown in table 2.
Table 2.
| Embodiment | Raw alcohol | Reaction times (h) | Product yield (%) |
| ????2 | Propyl carbinol | ????4.0 | ????95.0 |
| ????3 | Dodecyl alcohol | ????3.0 | ????97.5 |
| ????4 | Hexalin | ????5.0 | ????87.5 |
| ????5 | N-Octanol | ????3.0 | ????97.0 |
| ????6 | Ethylene glycol | ????6.0 | ????92.5 |
Above-mentioned test, after distillation finished, the gained distillation residue were all good fluidity, and the transparent liquid of sticking wall can directly not repeat reuse as catalyzer, and activity does not descend.
Embodiment 7--10 (changing the stopper simultaneous test),
In embodiment 1 described reaction unit, and method similarly to Example 1, only change the kind of stopper, the stopper consumption is 1g, carries out transesterification reaction, and the result who obtains is listed in the table 3.
Table 3.
| Embodiment | Stopper | Reaction times | Product yield | Catalyzer repeats the reuse test |
| 789 10 | Hydroquinones phenthazine N-phenyl-1-naphthalene 2.2.6.6-tetramethyl phenylpiperidines alcohol NO free radical (the present invention) | 4.0 4.0 4.0 4.0 | 89.0 92.0 91.5 97.2 | Distillation residue are solid catalyst can not direct reuse distillation residue thickness, opaque, can not direct reuse.The same distillation residue good fluidity cannot not be sticking that but the transparent liquid catalyzer direct reuse of still is more than 10 times. |
Embodiment 11--15
Method and apparatus similarly to Example 1 only changes catalyst type, carries out transesterification reaction,
The results are shown in table 4.
Table 4.
| Embodiment | Catalyzer | Reaction times (h) | Product yield (%) |
| ??11 | The methoxyl group tributyl tin | ????4.5 | ????92.0 |
| ??12 | Tributyltin chloride | ????7.5 | ????80.5 |
| ??13 | The dimethoxy dioctyl tin | ????4.0 | ????94.0 |
| ??14 | Dibutyltin oxide | ????4.5 | ????96.5 |
| ??15 | Two monomethyl maleate dibutyl tins | ????4.0 | ????97.0 |
Claims (3)
1. the manufacture method of an acrylic or methacrylic acid alkyl ester is to be CH with the general formula
2=CR
1COOR
2[R in the formula
1Expression H or CH
3, R
2Expression CH
3Or C
2H
5] ester, with general formula be R
3R in the OH[formula
3Expression C
4-C
14Aliphatics or alicyclic alkyl] or R
4(OH) [R4 represents C to n in the formula
2-C
6Aliphatic alkyl or-(CH
2CH
2O) mCH
2CH
2-(m is 1 or 2), n represents the integer of 2-4] alcohol, in the presence of organic tin catalyzer and stopper, carry out transesterification reaction, the preparation general formula is CH
2=CR
1COOR
3Or (CH2=CR
1COO) nR
4The acrylic or methacrylic acid alkyl ester, it is characterized in that:
A. used stopper is a nitroxyl free radical class stopper, and its consumption is the 0.01%--5% (m/m) of reaction solution total mass,
B. after reflection finishes, can directly carry out underpressure distillation and separate, gained catalyzer raffinate can repeatedly repeat reuse after the fractionation by distillation.
2. by the described method of claim 1, it is characterized in that described stopper can be 2.2.6.6-tetramethylpiperidinol nitroxyl free radical or three (2.2.6.6-tetramethyl piperidine nitrogen oxygen free radical) phosphorous acid ester, or both mixtures.
3. by claim 1 or 2 described methods, it is characterized in that the stopper consumption is the 0.05%-3% (m/m) of reaction solution total mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101716A CN1054117C (en) | 1995-01-26 | 1995-01-26 | Method for preparing alkyl acrylate (or methylacrylate) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101716A CN1054117C (en) | 1995-01-26 | 1995-01-26 | Method for preparing alkyl acrylate (or methylacrylate) |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1127745A true CN1127745A (en) | 1996-07-31 |
| CN1054117C CN1054117C (en) | 2000-07-05 |
Family
ID=5074057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95101716A Expired - Fee Related CN1054117C (en) | 1995-01-26 | 1995-01-26 | Method for preparing alkyl acrylate (or methylacrylate) |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1054117C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349851C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
| CN100349854C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
| CN101041618B (en) * | 2006-03-24 | 2011-05-25 | 杭州格林香料化学有限公司 | New production technique of cyclohexyl allyl propionate |
| CN102351693A (en) * | 2011-08-23 | 2012-02-15 | 里光 | Preparation method for methoxyethyl methacrylate |
| CN114195639A (en) * | 2021-12-13 | 2022-03-18 | 抚顺东联安信化学有限公司 | Production process of long carbon chain alkyl methacrylate |
| CN115197062A (en) * | 2022-08-29 | 2022-10-18 | 新乡市瑞丰新材料股份有限公司 | Acrylic acid high-carbon ester or methacrylic acid high-carbon ester and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5365816A (en) * | 1976-11-26 | 1978-06-12 | Nitto Chem Ind Co Ltd | Preparation of dimethylaminoethyl methacrylate |
| JPS63196544A (en) * | 1987-02-10 | 1988-08-15 | Osaka Yuki Kagaku Kogyo Kk | Production of fluorinated alkyl (meth)acrylates |
-
1995
- 1995-01-26 CN CN95101716A patent/CN1054117C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100349851C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
| CN100349854C (en) * | 2001-06-08 | 2007-11-21 | 巴斯福股份公司 | Method for producing (meth) acrylic acid esters |
| CN101041618B (en) * | 2006-03-24 | 2011-05-25 | 杭州格林香料化学有限公司 | New production technique of cyclohexyl allyl propionate |
| CN102351693A (en) * | 2011-08-23 | 2012-02-15 | 里光 | Preparation method for methoxyethyl methacrylate |
| CN114195639A (en) * | 2021-12-13 | 2022-03-18 | 抚顺东联安信化学有限公司 | Production process of long carbon chain alkyl methacrylate |
| CN114195639B (en) * | 2021-12-13 | 2023-09-19 | 抚顺东联安信化学有限公司 | Production process of long carbon chain alkyl methacrylate |
| CN115197062A (en) * | 2022-08-29 | 2022-10-18 | 新乡市瑞丰新材料股份有限公司 | Acrylic acid high-carbon ester or methacrylic acid high-carbon ester and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1054117C (en) | 2000-07-05 |
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