CN1050374A - Vinylformic acid C 4-C 8Ester/methacrylic acid C 4-C 8The ester new process of production - Google Patents
Vinylformic acid C 4-C 8Ester/methacrylic acid C 4-C 8The ester new process of production Download PDFInfo
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- CN1050374A CN1050374A CN 89102446 CN89102446A CN1050374A CN 1050374 A CN1050374 A CN 1050374A CN 89102446 CN89102446 CN 89102446 CN 89102446 A CN89102446 A CN 89102446A CN 1050374 A CN1050374 A CN 1050374A
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Abstract
Vinylformic acid C is produced in a kind of employing one step segmentation liquid-phase catalysis esterification
4-C
8Ester/methacrylic acid C
4-C
8Ester new process of production, this law also adopt new catalyst.This law technology is simple, stable, safety, yield reach 92% (in raw material propylene nitrile/acetone cyanohydrin), and compared with the prior art yield improves 15-25%, and equipment capacity doubles, and raw materials cost reduces 20-30%.
Description
The present invention relates to the preparation method of carboxylicesters, particularly prepare vinylformic acid C with vinyl cyanide/acetone cyanohydrin
4～C
8Ester/methacrylic acid C
4～C
8The method of ester.
Vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8Ester is a colourless liquid, is slightly soluble in water, is soluble in ethers, the alcohols, and easily polymerization for alkene family macromolecule monomer, is used to prepare superpolymer and multipolymer.Main as fiber, rubber, plastics, coating, tackiness agent, textile auxiliary agent, also can be used as the treatment agent of leather and paper, also can be used as the Modification of Plexiglass monomer.
Vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8Two kinds of methods of the general employing of the production of ester.One by vinyl cyanide/acetone cyanohydrin, is a catalyzer with sulfuric acid, generate acrylamide vitriol, methacrylamide sulfate, through hydrolysis distill crude acrylic acid/methacrylic acid solution, carry out esterification with various alcohol again, dewater esters of acrylic acid/methyl acrylic ester product.Its two, by vinylformic acid lower member ester (as methyl esters, ethyl ester) and C
4Above alcohol carries out the transesterify gained.Because economically, a kind of technology before the domestic employing always, so this technical process is long, and facility investment is big, and vinylformic acid, methacrylic acid lose big, and yield generally can only reach 50～60%.
Day disclosure special permission JP62-106049(1987) discloses nitrile, water, acid and alcohol under the catalyzer condition, carried out the gas phase contact reacts, the preparation method of step generation carboxylicesters, the situation of the various carboxylicesterss of listed production from special permission.The transformation efficiency 70.3～93.2% of general nitrile, selectivity 37.3～61.7%, carboxylicesters yield 33～55.9%, being of great use of by-product carboxylic acid and carboxylic acid amide, the low value by product is few.Can obtain highly purified carboxylicesters.This method is produced the employed reactor of carboxylicesters and is generally fixed bed or thermopnore, moving-burden bed reactor, and device structure complexity, temperature of reaction are carried out contact reacts up to 350 ℃ under gas phase condition, and operational condition is relatively harsher.As carboxylicesters production, no matter be transformation efficiency, selectivity and total recovery are not ideal.
With vinyl cyanide/acetone cyanohydrin is raw material, generates acrylamide, methacrylamide sulfate with sulfuric acid reaction, obtains (methyl) vinylformic acid C through the hydrolysis esterification
4～C
8The liquid phase method of ester never interrupts for solving the research work that yield is low, byproduct is many.
The object of the present invention is to provide a kind of yield height, the reliable vinylformic acid C of good economy performance and stable operation
4～C
8Ester/methacrylic acid C
4～C
8The new process of production of ester.
The objective of the invention is to carry out amidate action, generate acrylamide vitriol and monoammonium sulfate, while and C by vinyl cyanide/acetone cyanohydrin and sulfuric acid
4～C
8Alcohol carries out one section esterification (I), separates then, abandons monoammonium sulfate, and methacrylamide sulfate adds the catalyzer that sulfuric acid and other compound are formed, and carries out two sections esterifications (II), simultaneously reflux dewatering.Dehydration is finished, and adds above-mentioned catalyzer again and carries out three sections esterifications (III), steams thing and gets the final purpose thing through washing, rectifying.
Vinyl cyanide/acetone cyanohydrin and 75～100% sulfuric acid carry out amidate action, generate acrylamide vitriol/methacrylamide sulfate:
70～120 ℃ of temperature of reaction, vinyl cyanide/acetone cyanohydrin: sulfuric acid: water (mol ratio) is 1: (1～1.5): (0～1.5); In 3～5 hours reaction times, vinyl cyanide/acetone cyanohydrin transformation efficiency is 98～100%, gained acrylamide vitriol/methacrylamide sulfate and water, C
4～C
8Alcohol reacts, and makes acrylamide vitriol/methacrylamide sulfate hydrolysis generate vinylformic acid/methacrylic acid and monoammonium sulfate.While and C
4～C
8One section esterification (I) takes place:
In the formula: R=C
4～C
8Alkyl is (as follows.）
100～150 ℃ of temperature of reaction, acrylamide vitriol/methacrylamide sulfate: ROH: water (mol ratio) is 1: (1～2): (1～1.5), optimal reaction temperature are 120～130 ℃, optimum mole ratio 1: (1～1.2): (1～1.2).
Reaction times is 3～4 hours, and acid amides vitriol is hydrolyzed into vinylformic acid, methacrylic acid, and transformation efficiency is 98～100%, and vinylformic acid, methacrylated total conversion rate are 85～88%.
Reaction is finished, and isolates monoammonium sulfate solution, and 0.05～1% the catalyzer that adds the mother liquor total amount carries out reflux dewatering, carries out two sections esterifications (II), reflux dewatering 2～4 hours, and to phegma during anhydrous separating out, stopped reaction.The conversion rate of esterification of vinylformic acid/methacrylic acid and ROH is 90～95%.
Two sections esterifications (II) finish, and add 2～10% catalyzer of mother liquor total amount again, and (optimum quantity is 2～3%), distillatory carries out three sections esterifications (III) simultaneously, and collection is got C
4～C
8The distillate of the corresponding boiling range of ester, this moment, vinylformic acid/methacrylic acid and ROH conversion rate of esterification were more than or equal to 98%.Through the chemical capacity analysis, steam fraction and contain vinylformic acid/methacrylic acid 0.3～0.8%, vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8Ester content is 95～97%.This distillate with 1～3% aqueous sodium carbonate and pure water washing, is removed vinylformic acid and other acidic substance, and rectifying gets vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8Ester, product yield is more than or equal to 92%.(in raw material propylene cyanalcohol/vinyl cyanide.）
With vinyl cyanide/acetone cyanohydrin is raw material production vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8The ester catalyst system therefor is made up of sulfuric acid and other compound.Described catalyzer composition roughly can be represented by the formula:
（H
2SO
4）
aM
bM
cR
x
In the formula:
M: be following one or more compound combinations: sulfonic acid ion exchange resin, the positive butyl ester of phthalandione, tosic acid, beta-naphthalenesulfonic-acid.
M: be following one or more compound combinations: the oxide compound of iron, cobalt, nickel, sulphur, manganese, chromium and derivative thereof.
R: be C
2～C
22Organic acid molysite, cobalt salt, nickel salt, or one or more combinations of these salt.
The subfix span is:
5≤a≤10;0≤b≤3;0≤c≤3;0≤x≤3
The present invention adopts a step segmentation liquid-phase catalysis esterification to produce vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8The ester new process of production.
Technology of the present invention is simple, stable, safety, vinylformic acid C
4～C
8Ester/methacrylic acid C
4～C
8The yield of ester (in raw material acetone cyanohydrin or vinyl cyanide) can reach more than 92%.Compared with the prior art, yield improves 15～25%, and equipment capacity (in the unit volume reactor) doubles, the corresponding reduction by 20～30% of raw materials cost.
Below will elaborate to the present invention by embodiment, other advantage of the present invention also can further embody in an embodiment.
Embodiment 1:
In four-hole boiling flask, add 85% sulfuric acid, 560 grams, copper sulfate 1 gram, thiodiphenylamine 0.5 gram under agitation splashes into 212 gram vinyl cyanide, and reaction solution thing temperature is controlled at 80～110 ℃, dropwise at 90 ℃ and be incubated 1 hour down, add 80 gram water then, 370 gram butanols, 1.2 gram Resorcinol, reflux, temperature are controlled at 110～130 ℃.React to leave standstill after 3 hours and tell lower floor's monoammonium sulfate solution, add sulfuric acid 1 gram in the liquid of upper strata, P-TOLUENE SULFO ACID 99's sodium 0.5 gram, the reflux dehydration is after 2 hours, the anhydrous back stopped reaction of separating out adds sulfuric acid 1 gram in the phegma, iron stearate 0.3 gram, add thermal distillation, get 100～160 ℃ of cuts, get 515 gram crude products, butyl acrylate content 93.5%, crude product is washed till PH=6.5～7 with deionized water again with 100 milliliters of washings of 3% aqueous sodium carbonate.Carrying out rectifying then, get 80～82 ℃/70mmHg and obtain 472 gram butyl acrylates, is 92.2% with the raw material propylene nitrile rate of collecting.
Embodiment 2:
Replacing butanols with 370 gram isopropylcarbinols in embodiment 1, test with embodiment 1 same method, obtain isobutyl acrylate 468 grams, is 91.4% with the raw material propylene nitrile rate of collecting.
Embodiment 3:
Replacing butanols with 380 gram primary isoamyl alcohol in embodiment 1, test with embodiment 1 same method, obtain vinylformic acid isopentyl ester 526 grams, is 92.6% with the raw material propylene nitrile rate of collecting.
Embodiment 4:
Replacing butanols with 546 gram 2-Ethylhexyl Alcohols in embodiment 1, test with embodiment 1 same method, obtain 2-EHA 672 grams, is 91.3% with the raw material propylene nitrile rate of collecting.
Embodiment 5:
In the four-hole reaction flask, add 100% sulfuric acid, 441 grams, blue vitriol 1 gram, thiodiphenylamine 0.5 gram stirs and drips acetone cyanohydrin 255 grams down, and temperature is controlled at 80～90 ℃.Dropwise, be warming up to 150 ℃ rapidly, be incubated half an hour, add entry 80 grams, propyl carbinol 265 grams, Resorcinol 1 gram, back flow reaction 3 hours, standing demix, tell lower floor's monoammonium sulfate solution, add sulfuric acid 1 gram in the liquid of upper strata, P-TOLUENE SULFO ACID 99's 0.5 gram, temperature rising reflux dehydration, after 2 hours, when no longer separating out water in the phegma, reaction finishes, and adds sulfuric acid 1 gram in the reaction solution, Cobaltous diacetate 0.5 gram, steam boiling point and be 100～170 ℃ thick ester 480 grams, thick ester is washed once with 1% aqueous sodium carbonate, is washed till neutrality with deionized water again.The thick ester of washing carries out rectifying.Getting 80～82 ℃/45mmHg cut, get butyl methacrylate 398 grams, is 93.4% with the acetone cyanohydrin rate of collecting.
Embodiment 6:
Replace propyl carbinols with 265 gram isopropylcarbinols in embodiment 5, test with quadrat method by embodiment 5, the result obtains isobutyl acrylate 385 grams, is 90.4% with the acetone cyanohydrin rate of collecting.
Embodiment 7:
Replace propyl carbinol with 317 gram primary isoamyl alcohol in embodiment 5, test by embodiment 5 same methods, the result obtains vinylformic acid isopentyl ester 434 grams, is 92.7% with the acetone cyanohydrin rate of collecting.
Claims (8)
1, a kind of preparation method of carboxylicesters specially refers to a kind of vinylformic acid C
4～C
3Ester/methacrylic acid C
4～C
3The preparation method of ester, it comprises that with vinyl cyanide/acetone cyanohydrin be raw material, generates acid amides vitriol with sulfuric acid as catalyzer, through hydrolysis, esterification technique, its technical characterictic is that acid amides vitriol generates vinylformic acid/methacrylic acid and monoammonium sulfate through hydrolysis, while and C
4～C
3Alcohol carries out one section esterification (I), separates monoammonium sulfate thereafter, adds the catalyzer that sulfuric acid and other compound are formed, carry out two sections dehydration esterifications (II), esterification adds above-mentioned catalyzer again and carries out three sections esterifications (III) after finishing, and gets the final purpose thing through washing, rectifying.
2, according to the described method of claim 1, described catalyzer contains sulfuric acid, and its technical characterictic is that this catalyzer also contains other compound, and its composition roughly can be represented by the formula:
In the formula:
M: be following one or more compound combinations: sulfonic acid ion exchange resin, the positive butyl ester of phthalandione, tosic acid, beta-naphthalenesulfonic-acid.
M: be following one or more compound combinations: the oxide compound of iron, cobalt, nickel, sulphur, manganese, chromium and derivative thereof.
R: be C
2～C
22The combination of one or more of organic acid molysite, cobalt salt, nickel salt or these salt.
The subfix span is respectively:
5≤a≤10;0≤b≤3;0≤c≤3;0≤x≤3。
When 3, method according to claim 1, its technical characterictic were one section esterification (I), esterification reaction temperature was controlled at 100～150 ℃, vinyl cyanide/acetone cyanohydrin C
4～C
8Alcohol: the water mol ratio is: 1: 1-2: 1～1.5, and esterification time 3～4 hours.
4, method according to claim 3, its technical characterictic are one section esterification, and the temperature optimum value is 120～130 ℃, and optimum mole ratio is 1: 1～1.2: 1～1.2.
When 5, method according to claim 1, its technical characterictic were two sections dehydration esterifications (II), the reacting middle catalyst consumption was that 0.05～1%(is with respect to the esterification mother liquor total amount).
When 6, method according to claim 5, its technical characterictic were two sections dehydration esterifications (II), reacting middle catalyst consumption optimum value was that 0.1～0.5%(is with respect to the esterification mother liquor total amount).
When 7, method according to claim 1, its technical characterictic were three sections esterifications (III), the reacting middle catalyst consumption was that 2～10%(is with respect to esterification mother liquor total amount).
8, according to the described method of claim 7, when its technical characterictic was three sections esterifications (III), the reacting middle catalyst optimum amount was 3～5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102446 CN1050374A (en) | 1989-09-18 | 1989-09-18 | Vinylformic acid C 4-C 8Ester/methacrylic acid C 4-C 8The ester new process of production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102446 CN1050374A (en) | 1989-09-18 | 1989-09-18 | Vinylformic acid C 4-C 8Ester/methacrylic acid C 4-C 8The ester new process of production |
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| Publication Number | Publication Date |
|---|---|
| CN1050374A true CN1050374A (en) | 1991-04-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89102446 Pending CN1050374A (en) | 1989-09-18 | 1989-09-18 | Vinylformic acid C 4-C 8Ester/methacrylic acid C 4-C 8The ester new process of production |
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|---|---|
| CN (1) | CN1050374A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344825C (en) * | 2005-09-23 | 2007-10-24 | 东华大学 | Coated fabric containing organic metal catalyst, and its preparing method and use |
| CN103130671A (en) * | 2013-03-28 | 2013-06-05 | 重庆紫光化工股份有限公司 | Preparation and purification method of clean methacrylamide |
-
1989
- 1989-09-18 CN CN 89102446 patent/CN1050374A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100344825C (en) * | 2005-09-23 | 2007-10-24 | 东华大学 | Coated fabric containing organic metal catalyst, and its preparing method and use |
| CN103130671A (en) * | 2013-03-28 | 2013-06-05 | 重庆紫光化工股份有限公司 | Preparation and purification method of clean methacrylamide |
| CN103130671B (en) * | 2013-03-28 | 2015-06-17 | 重庆紫光化工股份有限公司 | Preparation and purification method of clean methacrylamide |
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