CN1027367C - Preparation method of high-grade ester (methyl) acrylate - Google Patents
Preparation method of high-grade ester (methyl) acrylate Download PDFInfo
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- CN1027367C CN1027367C CN 91108345 CN91108345A CN1027367C CN 1027367 C CN1027367 C CN 1027367C CN 91108345 CN91108345 CN 91108345 CN 91108345 A CN91108345 A CN 91108345A CN 1027367 C CN1027367 C CN 1027367C
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Abstract
The present invention relates to a method for preparing higher (methyl) acrylic acid ester. Excessive (methyl) acrylic acid ester reacts with higher alcohol (ROH, wherein R is straight-chain, branched-chain or annular saturated or unsaturated alkyl, and aryl, epoxy groups or other substituents can be carried on alkyl) for 0.5 to 3h below 140 DGE C by using higher alcohol sodium (R'ON, R'=R) as catalysts, generated lower alcohol is distilled in an azeotropic mode simultaneously, acid is added for neutralization, and higher (methyl) acrylic acid ester is prepared through vacuum fractional distillation. The conversion rate of higher alcohol is more than 85%, and the yield of higher (methyl) acrylic acid ester is more than 80%. The method has the advantages of high catalyst activity, low consumption, easy acquirement, low price, little side reaction, simple operation, high yield of products, etc.
Description
The present invention relates to a kind ofly,, produce the method for (methyl) higher hydrocarbyl acrylate by transesterification reaction by (methyl) acrylate.
Under catalyst action, produce (replacement) acrylic ester compound by the transesterify effect, be method commonly used in the organic synthesis.Preparation (replacement) higher hydrocarbyl acrylate is that the transesterify effect by (replacement) vinylformic acid lower member ester and higher alcohols makes.
Selection of catalysts is very big to the influence of transesterification reaction, is the emphasis of various countries researchist research, and the patent of having delivered is a lot, as titanium isopropoxide (Ger.Offen.DE, 2,319,688), phenyl ester titanium (Fr.2,033,441; US, 3,686,268) etc. make transesterification catalyst higher activity is all arranged.Also have alkoxyl group thallium (Fr.2,088,971), LeCl/CaO(Ger.Offen.DE, 3,423,441) etc., these catalyzer need be used rare metal, are not easy to obtain high price.Magnesium methylate is the custom catalysts that obtains easily, and activity is also higher, and consumption is big, and to the preparation of some ester class, yield is lower, an alkali metal salt of lower alcohol, and as sodium methylate, sodium ethylate etc., though cheap and easy to get, active low.Poorly soluble in reaction system, form colloidal suspensions, easily sticking wall causes reactor to need often to clean.If strengthen consumption, can add fast response, but also help polymerization, condensation reaction.
The objective of the invention is, active high by selecting, inexpensive, the suitable catalyzer that is easy to get, the conditioned reaction condition, make from (replacement) vinylformic acid lower member ester, carry out the method that transesterification reaction is produced (replacement) higher hydrocarbyl acrylate, have row easy and simple to handle, easy, few, the product yield advantages of higher of side reaction with higher alcohols.
The method for making of (replacement) of the present invention higher hydrocarbyl acrylate is to adopt (replacement) acrylate (CH
2=CX-COOR ') carry out transesterification reaction with higher alcohols (ROH) under catalyst action and make, its reactional equation is as follows:
CH
2=CX-COOR '+ROH (catalyzer)/() CH
2X is H or CH in=the CX-COOR+R ' OH formula
3, R ' is an alkyl, R is a carbonatoms greater than one the saturated or unsaturated alkyl of straight chain, side chain or cyclic, also can have aryl on the alkyl, epoxy group(ing) or other substituting group, R carbonatoms＞R '.
With excessive (methyl) acrylate, higher alcohols, stopper and catalyst mix are heated to boiling under normal pressure or vacuum, steam the lower alcohol of continuous generation in the reaction and the azeotrope of (methyl) acrylate simultaneously, reaction does not steam about 0.5～3 hour of time to there being lower alcohol.Reaction is finished, and adds the appropriate amount of acid catalyst neutralisation, makes it to generate the salt crystallization and separates out (but elimination in case of necessity).Gas clean-up is carried out fractionation, steams unreacted (methyl) acrylate and higher alcohols earlier, steam then (methyl) higher hydrocarbyl acrylate.
The higher alcohols (ROH) that the present invention is used can be primary, secondary alcohol or polyvalent alcohol.R is a carbon atom greater than one the saturated or unsaturated alkyl of straight chain, side chain or cyclic; Also can have aryl, epoxy group(ing) or other substituting group on the alkyl.Carbonatoms with 3～10 for well.
(replacement) acrylate that the present invention is used, structural formula is CH
2=CX-COOR ', (wherein X is H or CH
3, R ' is low alkyl group, R ' carbonatoms＜R, R ' is with CH
3Best).Its consumption generally surpasses 50～300mol% of stoichiometric calculation consumption.Excessive (methyl) acrylate is taken the lower alcohol that reaction generates out of in order to azeotropic.
Catalyst system therefor of the present invention is that (R " ONa; R wherein " is a carbonatoms greater than one the saturated or unsaturated alkyl of straight chain, side chain or cyclic to senior sodium alkoxide, can have aryl, epoxy group(ing) or other substituting group on the alkyl), can be primary, the sodium salt of secondary alcohol or polyvalent alcohol.This catalyst activity height, consumption is low, and general consumption is 0.0001～0.05 mole (every mole of higher alcohols), with 0.001～0.01 mole for well, use in the reaction the senior sodium alkoxide identical with higher alcohols (be R "=R) make catalyzer; not only can reduce bringing into of impurity and make side reaction minimizing and separate easily, simultaneously, also because senior sodium alkoxide solvability in identical higher alcohols is better; easily disperse; make in the reaction precipitation tie the wall phenomenon and greatly reduce, easy handling, and frequent cleaning reaction still.The joining day of catalyzer also is influential to some transesterification reaction, adds when reaction solution seethes with excitement, and can improve the solvability of catalyzer, disperses better.Catalyzer can directly add, and also dissolves in once to add in the part higher alcohols or add continuously.
The polymerization of (replacement) esters of acrylic acid when the adding stopper can prevent to react in the reaction.Can adopt (replacement) esters of acrylic acid stopper such as Resorcinol commonly used, p-tert-butylphenol, hydroquinone monomethyl ether, thiodiphenylamine etc., for well, general consumption is 0.01～1.0%(weight with the polymerization inhibition effect of thiodiphenylamine) (based on the amount of (methyl) acrylate), be advisable with 0.05～0.5%.
Reaction can be carried out under normal pressure or decompression, and temperature of reaction is controlled at below 140 ℃, with below 120 ℃ for well, this speed of response is very fast, generally the reaction times is 0.5～3 hour.
React to finish and add the acid neutralization, the crystallization of catalyzer salify is separated out, but elimination in case of necessity, in the time of can preventing fractionation like this because polymerization, condensation reaction or other side reaction that the existence of catalyzer may cause, and reduce precipitation and tie situation generations such as wall, particularly important for mass production especially.In order to the acids of catalyst neutralisation, can be mineral acid such as H
2SO
4, CHl, or H
3PO
4Deng, also can be with various organic acids such as formic acid, acetic acid or vinylformic acid etc.
The yield of the transformation efficiency of higher alcohols and the senior ester of generation is calculated as follows:
The transformation efficiency of higher alcohols=(the higher alcohols amount of adding-unreacted higher alcohols amount)/(the higher alcohols amount of adding) * 100%
The yield of senior ester=(generating the weight of senior ester)/(weight that adds higher alcohols) * (molecular weight of higher alcohols)/(molecular weight of senior ester) * 100%
The higher alcohols sodium catalyst that the present invention adopts is inexpensive, be easy to get.When particularly adopting the sodium alkoxide identical with higher alcohols to be catalyzer, not only reduced bringing into of impurity, catalyzer solvability in reaction solution is improved, catalyzer is scattered, and active high, consumption is little, has shortened the reaction times greatly, and side reaction is few in the reaction.Reaction finish to add sour catalyst neutralisation, can make the gluey catalyzer salify of suspension, and crystallization is separated out, elimination in big production, thus significantly reduce polymerization, condensation and other side reaction in the fractionation process, and the disadvantage of residue knot wall in big the production.The transformation efficiency height of this method higher alcohols, generally more than 85%, the yield of (methyl) higher hydrocarbyl acrylate can reach more than 80%.Below the present invention is further elaborated with embodiment.
Embodiment one
To one adding 300g methyl methacrylate (MMA), 128g propyl carbinol and 0.3g thiodiphenylamine (PTZ) are housed in the 500ml there-necked flask of filler distillation tower of thermometer, the band funnel of equilibration tube and the long 40cm of diameter 2cm.The solution that in funnel, adds 20g propyl carbinol and 1.0g propyl carbinol sodium.Transferring to the system vacuum degree is the 300mmHg post, is heated to boiling, adds butanol sodium solution by funnel, keeps tower top temperature at 44-45 ℃, steams methyl alcohol-MMA azeotrope 100g in 1.5 hours.Add vitriol oil 1g then, (cat head is 32 ℃) steams MMA 60g under the 50mmHg post, and gas clean-up is to 40mmHg post (tower top temperature 77-78 ℃), steam butyl methacrylate 275g, purity is 99.0%, yield is 95.9%.
Embodiment two
Device is with embodiment one, in there-necked flask, add 200g MMA, 70g hexalin and 0.2g PTZ, the solution that in funnel, adds 30g hexalin and 1.2g hexamethylene sodium alkoxide, regulation system vacuum tightness is the 300mmHg post, be heated to boiling, add the hexalin sodium solution in the funnel, steam methyl alcohol-MMA azeotrope 50g at tower top temperature 44-45 ℃.Add the 0.5g vitriol oil, gas clean-up is collected 32 ℃ of cuts to the 50mmHg post then, gets MMA82g, and gas clean-up is collected 48 ℃ of cuts to the 1mmHg post, gets cyclohexyl methacrylate 160g, and purity is 99.4%, and yield is 92.3%.
Embodiment three
Device is with embodiment one, in there-necked flask, add 31g ethylene glycol, 0.3g sodium, be heated to the sodium total overall reaction, add 300g MMA again, 0.3g PTZ, reacting by heating under the 300mmHg post, keep tower top temperature at 44-45 ℃, steam methyl alcohol-MMA azeotrope 35g, add the 1g vitriol oil then, under the 50mmHg post, collect 32 ℃ of cuts, get MMA 185g, gas clean-up gets cut 90g to the 1mmHg post, wherein contain Ethylene glycol dimethacrylate 82.0%, contain hydroxyethyl methylacrylate 18.0%.
Embodiment four
Device adds 300g MMA with embodiment one in there-necked flask, 70g vinyl carbinol and 0.3PTZ, the solution of adding 17g vinyl carbinol and 0.8 allyl sodium alkoxide in the funnel.Under atmospheric boiling, add the vinyl carbinol sodium solution, receive to such an extent that methyl alcohol-MMA is total to thing 60g at 63.5-64 ℃.Add 0.5g concentration H
2SO
4, under the 50mmHg post, steam 32 ℃ of cut 150g, wherein contain vinyl carbinol 2.6%, allyl methacrylate(AMA) 1.2%, all the other are MMA.Collect 67-68 ℃ of cut, get allyl methacrylate(AMA) 169g, purity is 99.3%, and transformation efficiency is 95.5%, and yield is 89.4%.
Comparative Examples one
Device adds 300g MMA with embodiment one in there-necked flask, the 87g vinyl carbinol, and 2.0g sodium methylate and 0.3g PTZ seethe with excitement under normal pressure, and total reflux 2 hours does not almost have transesterification reaction and takes place.
Comparative Examples two
Device and operation are changed to the 4.0g magnesium methylate with Comparative Examples one with sodium methylate, and boiling is 4 hours under normal pressure, receive methyl alcohol-MMA azeotropic cut 45g of 63.5-65 ℃.Under the 50mmHg post, receive to such an extent that 30-34 ℃ of cut 200g wherein contains MMA 80.4%, vinyl carbinol 13.6%, allyl methacrylate(AMA) 6.0%.Under the 50mmHg post, collect 67-68 ℃ of cut 110g, its allyl methacrylate(AMA) purity is 99.5%, transformation efficiency is that 68.7% yield is 58.2%.
Embodiment five
Device adds 200g MMA, 70g phenylcarbinol and 0.2g PTZ with embodiment one in there-necked flask.In funnel, add the solution of 38g phenylcarbinol and 1.5g phenylcarbinol sodium, under the 300mmHg post, be heated to boiling, add the phenylcarbinol sodium solution in the funnel, 44-45 ℃ receive methyl alcohol-MMA azeotropic cut 45g.Reacted and added the dense H of 0.5g
2SO
4, under the 50mmHg post, receive 32 ℃ of cut 74g, gas clean-up is to the 5mmHg post, receive 105-110 ℃ of methacrylic acid benzyl ester cut 143g, purity is 98.4%, yield is 81.3%.
Embodiment six
Device adds 200g ethyl propenoate, 60g propyl carbinol and 0.2g PTZ with embodiment one in there-necked flask.The solution that in funnel, adds propyl carbinol 14g and propyl carbinol sodium 1.0g.Under the 200mmHg post, be heated to boiling, add the butanol sodium solution in the funnel, in 2.5 hours, receive to such an extent that ethanol-ethyl propenoate azeotropic cut 50g of 46-48 ℃ adds the dense H of 0.5g
2SO
4, under the 100mmHg post, collect 46-49 ℃ ethyl propenoate cut 86g, gas clean-up is to the 40mmHg post, steam propyl carbinol 11g, collects 64-66 ℃ of cut, must butyl acrylate 121g, purity is 98.9%, the propyl carbinol transformation efficiency is 85.1%, yield is 85.2%.
Claims (9)
1, (methyl) acrylate and higher alcohols be by the method for transesterify effect preparation (methyl) higher hydrocarbyl acrylate, comprising:
(1) (methyl) acrylate general formula is:
Wherein X is H, CH
3, R ' is an alkyl, consumption surpasses 50～300mol% of stoichiometric quantity,
(2) the higher alcohols general formula is ROH, and wherein R is the saturated or unsaturated alkyl or the phenmethyl of above straight chain, side chain or closed chain of a carbon atom, and R carbonatoms＞R ' can be primary, the second month in a season or polyvalent alcohol,
(3) lower alcohol of Sheng Chenging and excessive (methyl) acrylate azeotropic distillate,
It is characterized in that:
(4) with senior sodium alkoxide R " ONa is a catalyzer, R " being saturated or unsaturated alkyl, phenmethyl or the R of above straight chain, side chain and closed chain of a carbon atom "=R wherein,
(5) the senior sodium alkoxide consumption of catalyzer is that every mole of higher alcohols adds 0.0001～0.05 mole.
2, according to the described method of claim 1, it is characterized in that the senior sodium alkoxide of catalyzer is dissolved in the part higher alcohols, when seething with excitement, reaction solution once or continuously adds.
3,, it is characterized in that catalyst levels is that every mole of higher alcohols adds 0.001～0.01 mole according to the described method of claim 1.
4, according to the described method of claim 1, it is characterized in that reaction solution is added with stopper 0.01～1.0%[based on (methyl) acrylate, weight].
5,, it is characterized in that stopper is a thiodiphenylamine according to claim 1 or 4 described methods.
6,, it is characterized in that being reflected at＜carry out under 140 ℃ the boiling temperature according to the described method of claim 1.
7,, it is characterized in that reacting complete add mineral acid or organic acid neutralization according to the described method of claim 1.
8,, it is characterized in that complete mineral acid sulfuric acid, hydrochloric acid or the phosphoric acid of adding of reaction neutralizes according to claim 1 or 7 described methods.
9,, it is characterized in that complete organic acid formic acid, acetic acid or the vinylformic acid of adding of reaction neutralizes according to claim 1 or 7 described methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108345 CN1027367C (en) | 1991-11-15 | 1991-11-15 | Preparation method of high-grade ester (methyl) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108345 CN1027367C (en) | 1991-11-15 | 1991-11-15 | Preparation method of high-grade ester (methyl) acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061216A CN1061216A (en) | 1992-05-20 |
| CN1027367C true CN1027367C (en) | 1995-01-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108345 Expired - Fee Related CN1027367C (en) | 1991-11-15 | 1991-11-15 | Preparation method of high-grade ester (methyl) acrylate |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10127941A1 (en) * | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters by transesterification comprises recycling by-product alcohol to the production of the starting (meth)acrylate |
| DE10127939A1 (en) * | 2001-06-08 | 2002-05-29 | Basf Ag | Production of (meth)acrylate esters, e.g. dialkylaminoethyl (meth)acrylates, by catalytic transesterification involves four-stage distillation |
| CN100344620C (en) * | 2004-06-14 | 2007-10-24 | 杭州民生药业集团有限公司 | Extraction of aromatic turmeric alcohol |
| TW200617125A (en) * | 2004-09-27 | 2006-06-01 | Hitachi Chemical Co Ltd | Photocurable resin composition |
| CN102731304B (en) * | 2011-04-11 | 2016-05-25 | 天津泰瑞倍药研科技有限公司 | The preparation method of alpha-fluoro acrylic ester |
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1991
- 1991-11-15 CN CN 91108345 patent/CN1027367C/en not_active Expired - Fee Related
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