CN1027367C - Process for producing higher (meth) acrylate - Google Patents
Process for producing higher (meth) 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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- methyl
- acrylate
- acid
- higher alcohols
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- 238000000034 method Methods 0.000 title claims abstract description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 4
- 230000008569 process Effects 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 6
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims abstract description 6
- 150000001298 alcohols Chemical class 0.000 claims description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical group C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- 240000005373 Panax quinquefolius Species 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000002148 esters Chemical class 0.000 abstract description 11
- 238000007086 side reaction Methods 0.000 abstract description 6
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract 4
- 125000001424 substituent group Chemical group 0.000 abstract 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 10
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 10
- 238000005809 transesterification reaction Methods 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- BDFJWKALVSRGSR-UHFFFAOYSA-N butan-1-ol;sodium Chemical compound [Na].CCCCO BDFJWKALVSRGSR-UHFFFAOYSA-N 0.000 description 4
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- FJDPDXXVTZSLJK-UHFFFAOYSA-N phenylmethanol;sodium Chemical compound [Na].OCC1=CC=CC=C1 FJDPDXXVTZSLJK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003333 secondary alcohols Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTHIPJYDYLECII-UHFFFAOYSA-N [Na].OCC=C Chemical compound [Na].OCC=C XTHIPJYDYLECII-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- BCNCKJAYWXWHDQ-UHFFFAOYSA-N ethanol;ethyl prop-2-enoate Chemical compound CCO.CCOC(=O)C=C BCNCKJAYWXWHDQ-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing (methyl) acrylic acid higher ester, which comprises reacting excessive (methyl) acrylic acid ester with higher alcohol (ROH, wherein R is straight chain, branched chain or cyclic saturated or unsaturated alkyl, the alkyl can have aryl, epoxy group or other substituent), using higher sodium alkoxide (R 'ONa, R' ═ R) as catalyst at the temperature of less than 140 ℃ for 0.5-3 h, simultaneously distilling off the generated lower alcohol by azeotropy, then adding acid for neutralization, and vacuum fractionating. The conversion rate of the higher alcohol is more than 85 percent, and the yield of the higher (methyl) acrylate is more than 80 percent. The method has the advantages of high catalyst activity, small using amount, easy obtaining, low price, few side reactions, simple operation, high product yield and the like.
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 | Process for producing higher (meth) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91108345 CN1027367C (en) | 1991-11-15 | 1991-11-15 | Process for producing higher (meth) acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061216A CN1061216A (en) | 1992-05-20 |
| CN1027367C true CN1027367C (en) | 1995-01-11 |
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ID=4909244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108345 Expired - Fee Related CN1027367C (en) | 1991-11-15 | 1991-11-15 | Process for producing higher (meth) acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027367C (en) |
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 |
-
1991
- 1991-11-15 CN CN 91108345 patent/CN1027367C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1061216A (en) | 1992-05-20 |
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