CN103073426A - Preparation process for catalyzing and synthesizing tert-butyl acrylate by using strong acid cation exchange resin as catalyst - Google Patents
Preparation process for catalyzing and synthesizing tert-butyl acrylate by using strong acid cation exchange resin as catalyst Download PDFInfo
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- CN103073426A CN103073426A CN201310041364XA CN201310041364A CN103073426A CN 103073426 A CN103073426 A CN 103073426A CN 201310041364X A CN201310041364X A CN 201310041364XA CN 201310041364 A CN201310041364 A CN 201310041364A CN 103073426 A CN103073426 A CN 103073426A
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- CN
- China
- Prior art keywords
- exchange resin
- cation exchange
- butyl acrylate
- acid cation
- storng
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000002253 acid Substances 0.000 title claims abstract description 29
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000006227 byproduct Substances 0.000 claims abstract description 5
- 238000009413 insulation Methods 0.000 claims abstract description 5
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005516 engineering process Methods 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- YPFRQZILUODWNI-UHFFFAOYSA-N C=CC.C(C=C)(=O)OC(C)(C)C Chemical compound C=CC.C(C=C)(=O)OC(C)(C)C YPFRQZILUODWNI-UHFFFAOYSA-N 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000006250 specific catalysis Methods 0.000 abstract 1
- -1 (methyl) tert-butyl Chemical group 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a preparation process for catalyzing and synthesizing tert-butyl acrylate by using strong acid cation exchange resin as a catalyst, belonging to the technical field of organic synthesis. The preparation process is characterized by comprising the steps of: adding crylic acid, strong acid cation exchange resin, a polymerization inhibitor A and a polymerization inhibitor B into a closed reaction kettle, dropwise adding liquefied isobutene for carrying out esterification reaction; after dropwise adding is completed, carrying out thermal insulation; after the thermal insulation is finished, releasing the pressure of the closed reaction kettle, filtering, extracting a liquid component to enter a rectifying tower; and sequentially separating byproducts of tertiary butanol and diisobutylene and a target project of the tert-butyl acrylate. The preparation process has the beneficial effects that the liquefied isobutene is adopted to be directly catalyzed together with the crylic acid and the cation exchange resin under the action of the polymerization inhibitor A and the polymerization inhibitor B to form a specific catalysis system, gaseous isobutene is not needed to be dissolved in a solvent containing crylic acid for carrying out esterification reaction under the action of the catalyst, and thus the procedure of absorbing a solvent in subsequent operation is removed, resources are saved and procedures are saved.
Description
Technical field
The invention belongs to technical field of organic synthesis, be specifically related to a kind of preparation technology of tert-butyl acrylate.
Background technology
Tert-butyl acrylate, its structural formula is
Tert-butyl acrylate is a kind of very important Elementary Chemical Industry raw material and intermediate, because it has uniqueness and active strong polar molecule, unsaturated double-bond and carboxylicesters (COOR) structure, so can derive the polymer formulators that many kinds have superperformance, and prepare plasticity, the polymkeric substance such as crosslinked through processing modes such as letex polymerization, solution polymerization, copolymerization.
Application number is the synthetic method of having put down in writing a kind of (methyl) tert-butyl acrylate in 20068001094.7 the PCT application for a patent for invention file, the method is as catalyzer with solid acids such as sulfuric acid, the trimethyl carbinol obtains the iso-butylene of gaseous state through kinetics, the iso-butylene of gaseous state is dissolved into to contain carries out esterification in acrylic acid organic solvent, make product (methyl) tert-butyl acrylate through catalysis.After esterification finishes when separating catalyst, product and surplus stock, thereby catalyzer can be washed out together with water and formed a large amount of spent acid, waste water, contaminate environment; These highly acid homogeneous catalysts are difficult to be neutralized fully, wash out after reaction is finished simultaneously, cause the decomposition that can cause the product tert-butyl acrylate in rectifying.Gas, when catalyzing and synthesizing, can cause liquid the increase of energy consumption and the increase of by product, for the rectifying of later stage target product brings difficulty.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provide a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, can improve the yield of tert-butyl acrylate, protection of the environment.
The technical solution adopted for the present invention to solve the technical problems is: a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that carrying out successively as follows:
1) vinylformic acid, storng-acid cation exchange resin, stopper A, stopper B are joined in the closed reactor, the iso-butylene that dropwise adds liquefaction carries out esterification;
2) be added dropwise to complete after, be incubated;
3) insulation is complete, with the closed reactor release, filters, and the extracting liquid component enters rectifying tower;
4) isolate successively the by product trimethyl carbinol, diisobutylene and target product tert-butyl acrylate;
Described stopper A is the ethers stopper, and stopper B is phenolic inhibitor.
Preferably, described each consumption of raw materials amount (mass fraction): storng-acid cation exchange resin: 20-50 part, vinylformic acid: the iso-butylene of 280-360 part, liquefaction: 300-560 part, stopper A:10-30 part, stopper B:1-10 part.
Preferably, the iso-butylene time for adding that liquefies in the described step 1) is 1.5-4 hour.
Preferably, the temperature of esterification is-20 ~ 40 ℃ in the described step 1).
Preferably, soaking time is 6-8 hour described step 2).
Preferably, the solid ingredient after the extracting liquid component turns back to recycling in the step 1) in the described step 3).
Preferably, the iso-butylene of described liquefaction is to be obtained by the methyl tertiary butyl ether cracking.
The performance and the requirement that prepare consumption raw material of the present invention:
Vinylformic acid: molecular formula C
3H
4O
2, molecular weight 72.06, main component: content 〉=99.0%, outward appearance and proterties: colourless liquid has irritating smell.Fusing point (℃): 14, boiling point (℃): 141.
Iso-butylene: have another name called the 2-methacrylic, molecular formula: C
4H
8, molecular weight: 56.11, outward appearance and proterties: colourless gas.Fusing point (℃) :-140.3, boiling point (℃) :-6.9.
Compared with prior art, advantage of the present invention is:
1) the present invention adopt will liquefaction iso-butylene directly and vinylformic acid under the mating reaction of stopper A and stopper B, carry out catalysis with Zeo-karb, form unique catalyst system, need not iso-butylene with gaseous state is dissolved into to contain in acrylic acid solvent could carries out esterification under the effect of catalyzer, simplified the step of esterification, saved the operation of follow-up lyosorption, economize on resources, save operation.Simultaneously, under this unique catalyst system, can make the yield of tert-butyl acrylate of generation greater than 99.5%.
2) storng-acid cation exchange resin used in the present invention has the exchange capacity height, uniform particles, and the advantage such as wear resisting property is good, and appearance luster is shallow is used as esterifying catalyst, has good low-temperature reactivity and selectivity.Simultaneously, can be recycled, the time that recycles economized on resources greater than 2000 hours.
3) in this preparation technology, stopper A and stopper B must be used, and the yield of tert-butyl acrylate is reached more than 99.5%.If use separately stopper A or stopper B, the yield of tert-butyl acrylate does not reach 60%.
4) technique is simple, and utilization rate of raw materials is high.
5) technique environmental protection does not produce spent acid, waste water, need not to carry out spent acid, wastewater treatment.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment one
A kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, carry out successively as follows:
1) vinylformic acid, storng-acid cation exchange resin, stopper A, stopper B are respectively 280 parts, 20 parts, 10 parts, 1 part with mass fraction and join in the closed reactor, the iso-butylene that dropwise adds mass fraction and be 300 parts of liquefaction carries out esterification, drip 1.5 hours, during temperature remain on-20 ℃; Stopper A is the ethers stopper, and stopper B is phenolic inhibitor;
Reaction formula is:
2) be added dropwise to complete after, under-20 ℃, be incubated, be incubated 6 hours;
3) insulation is complete, with the closed reactor release, filters, and the extracting liquid component enters the rectifying glass tower; Remaining solid ingredient turns back to recycling in the step 1).
4) isolate successively the by product trimethyl carbinol, diisobutylene and tert-butyl acrylate, the mass fraction of the tert-butyl acrylate that makes is 400 parts, and yield is 99.5%.
The iso-butylene of above-mentioned liquefaction is to be obtained by the methyl tertiary butyl ether cracking, has reduced the cost of producing of iso-butylene, and has been mature technology of the prior art, realizes easily.The iso-butylene of liquefaction also can adopt other the mode of producing, and for example produces first the iso-butylene of gaseous state, the iso-butylene of the gaseous state that liquefies again.
Embodiment two
Be from the different of embodiment 1:
The mass fraction of the iso-butylene of vinylformic acid, storng-acid cation exchange resin, stopper A, stopper B, liquefaction is respectively 320 parts, 35 parts, 20 parts, 5 parts, 430 parts;
Time for adding is 3 hours, and esterification reaction temperature remains on 10 ℃;
After being added dropwise to complete, under 10 ℃, be incubated, be incubated 7 hours;
The mass fraction of the tert-butyl acrylate that makes is 450 parts, and yield is 99.7%.
Embodiment three
Be from the different of embodiment 1:
1) mass fraction of the iso-butylene of vinylformic acid, storng-acid cation exchange resin, stopper A, stopper B, liquefaction is respectively 360 parts, 50 parts, 30 parts, 10 parts, 560 parts;
2) time for adding is 4 hours, and esterification reaction temperature remains on 40 ℃;
3) be added dropwise to complete after, under 40 ℃, be incubated, be incubated 8 hours;
The mass fraction of the tert-butyl acrylate that 4) makes is 780 parts, and yield is 99.8%.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed to the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations that above embodiment does, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (7)
1. one kind take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that carrying out successively as follows:
1) vinylformic acid, storng-acid cation exchange resin, stopper A, stopper B are joined in the closed reactor, the iso-butylene that dropwise adds liquefaction carries out esterification;
2) be added dropwise to complete after, be incubated;
3) insulation is complete, with the closed reactor release, filters, and the extracting liquid component enters rectifying tower;
4) isolate successively the by product trimethyl carbinol, diisobutylene and target product tert-butyl acrylate;
Described stopper A is the ethers stopper, and stopper B is phenolic inhibitor.
2. according to claim 1 a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that described each consumption of raw materials amount (mass fraction): storng-acid cation exchange resin: 20-50 part, vinylformic acid: the iso-butylene of 280-360 part, liquefaction: 300-560 part, stopper A:10-30 part, stopper B:1-10 part.
3. according to claim 2 a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that: the iso-butylene time for adding that liquefies in the described step 1) is 1.5-4 hour.
4. according to claim 3 a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that: the temperature of esterification is-20 ~ 40 ℃ in the described step 1).
5. according to claim 4 a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that: soaking time is 6-8 hour described step 2).
6. according to claim 5 a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that: the solid ingredient in the described step 3) after the extracting liquid component turns back to recycling in the step 1).
7. according to claim 1 to 6 arbitrary described a kind of take the preparation technology of storng-acid cation exchange resin as catalyst synthesizing propylene tert-butyl acrylate, it is characterized in that: the iso-butylene of described liquefaction is to be obtained by the methyl tertiary butyl ether cracking.
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| CN201310041364.XA CN103073426B (en) | 2013-02-04 | 2013-02-04 | A kind of take storng-acid cation exchange resin as the preparation technology of catalyst synthesizing propylene tert-butyl acrylate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844455A (en) * | 2015-04-13 | 2015-08-19 | 徐德良 | Method used for catalyzed synthesis of tert-butyl acrylate |
| CN104987288A (en) * | 2015-05-12 | 2015-10-21 | 齐鲁工业大学 | Preparation technology of tert-butyl acrylate |
| CN105601510A (en) * | 2015-12-21 | 2016-05-25 | 山东金城医药化工股份有限公司 | Catalytic synthesis method of tert-butyl alpha-bromoisobutyrate by using cation exchange resin |
| CN106397189A (en) * | 2016-08-30 | 2017-02-15 | 江西盛伟科技股份有限公司 | Synthesis method of tert-butyl chloroacetate |
| CN114507131A (en) * | 2022-01-24 | 2022-05-17 | 华谊合丰特种化学淄博有限公司 | Synthesis method of tert-butyl (meth) acrylate |
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2013
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| US4824998A (en) * | 1986-11-27 | 1989-04-25 | Mitsubishi Rayon Co., Ltd. | Process for producing tau-butyl methacrylate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844455A (en) * | 2015-04-13 | 2015-08-19 | 徐德良 | Method used for catalyzed synthesis of tert-butyl acrylate |
| CN104844455B (en) * | 2015-04-13 | 2016-06-22 | 徐德良 | A kind of technique catalyzing and synthesizing tert-butyl acrylate |
| CN104987288A (en) * | 2015-05-12 | 2015-10-21 | 齐鲁工业大学 | Preparation technology of tert-butyl acrylate |
| CN105601510A (en) * | 2015-12-21 | 2016-05-25 | 山东金城医药化工股份有限公司 | Catalytic synthesis method of tert-butyl alpha-bromoisobutyrate by using cation exchange resin |
| CN106397189A (en) * | 2016-08-30 | 2017-02-15 | 江西盛伟科技股份有限公司 | Synthesis method of tert-butyl chloroacetate |
| CN114507131A (en) * | 2022-01-24 | 2022-05-17 | 华谊合丰特种化学淄博有限公司 | Synthesis method of tert-butyl (meth) acrylate |
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