CN104529770A - Preparation method of isobornyl acrylate or isobornyl methacrylate - Google Patents
Preparation method of isobornyl acrylate or isobornyl methacrylate Download PDFInfo
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- CN104529770A CN104529770A CN201410785367.9A CN201410785367A CN104529770A CN 104529770 A CN104529770 A CN 104529770A CN 201410785367 A CN201410785367 A CN 201410785367A CN 104529770 A CN104529770 A CN 104529770A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Abstract
The invention relates to a preparation method of isobornyl acrylate or isobornyl methacrylate. The preparation method disclosed by the invention is used for mainly solving the problems of environment pollution, high production cost, high labor intensity and difficult continuous product in the prior art. The above problems are solved better by adopting the technical scheme as follows: the preparation method of isobornyl acrylate or isobornyl methacrylate is adopted; a molecular sieve is used as the catalyst; acrylic acid and camphene are converted into isobornyl acrylate or methylacrylic acid and camphene are converted into isobornyl methacrylate continuously in a kettle reactor or a fixed-bed tube reactor; and the preparation method disclosed by the invention can be applied to preparation of isobornyl acrylate or isobornyl methacrylate.
Description
Technical field
The present invention relates to the preparation method of a kind of isobornyl acrylate or isobornyl methacrylate.
Background technology
(methyl) isobornyl acrylate has unique bridged cycloalkyl structure, that a kind of hardness and snappiness of melting is in the excellent functional materials of one, as viscosity is starkly lower than corresponding methyl esters, good glossiness, hardness, scrub resistance, resistance to medium and weathering resistance is shown in multipolymer and homopolymer, and water absorbability is starkly lower than methyl methacrylate, be widely used in manufacturing high-performance acrylic acid resin and acrylic ester emulsion, prepare curable adhesive and water base stick.
(methyl) isobornyl acrylate reacts obtained by (methyl) vinylformic acid and amphene under the effect of catalyzer, usually adopts mineral acid, organic acid, solid super-strong acid, heteropolyacid and Zeo-karb etc. as catalyzer.Chinese patent CN1151395A describes with zirconium the method for solid superacid catalyst synthesis (methyl) isobornyl acrylate being main component, 35 DEG C, the reaction times be the condition of 4.5h under carry out autoclave rhythmic reaction, obtaining amphene transformation efficiency when preparing isobornyl methacrylate is 74.1%, and isobornyl methacrylate selectivity is the result of 98.9%; Obtaining amphene transformation efficiency during preparation isobornyl acrylate is 75.1%, and isobornyl methacrylate selectivity is the result of 98.2%.Chinese patent CN101863763A adopts activated carbon supported tin tetrachloride to be catalyzer synthesis (methyl) isobornyl acrylate, adopt still reaction technique, (methyl) isobornyl acrylate yield is greater than 83%, and (methyl) isobornyl acrylate selectivity reaches more than 92%.Chinese patent CN1151395A and Chinese patent CN101863763A adopts autoclave rhythmic reaction technique, there is the shortcomings such as labour intensity is large, environment is poor, environmental pollution, therefore needs to develop to adopt the continuous reaction technique of new catalyst to replace.Chinese patent CN1133281A proposes the preparation method of one (methyl) isobornyl acrylate, after first raw material being mixed in mixing kettle, with in the separated cylinder of mixing kettle by mixture and catalyst exposure.To be the cylinder of catalyzer by Amberlyst15 resin after 226g (methyl) vinylformic acid and 340g amphene and the mixing of 0.1g thiophene piperazine, and circulate, finally resin outlet temperature is adjusted to 40 DEG C of dischargings.Operating result equilibrium value when preparing isobornyl methacrylate is methacrylic acid transformation efficiency is 78%, and the selectivity of isobornyl methacrylate is 96%; Operating result equilibrium value during preparation isobornyl acrylate is vinylformic acid transformation efficiency is 83%, and the selectivity of isobornyl acrylate is 94%.But the resin catalyst life-span is short, and can not regenerate after inactivation, add production cost, and produce a large amount of organic waste need process, add environmental burden.
Molecular sieve is the material of a kind of structure, stable in properties, and the pore structure of its uniqueness and surface acidity make it have good reactivity worth and regenerability, is used widely in reaction fields such as esterification, isomerization, hydrations.
Summary of the invention
Technical problem to be solved by this invention be exist in prior art contaminate environment, production cost large compared with high, labour intensity, be difficult to quantity-produced problem, the preparation method of a kind of new isobornyl acrylate or isobornyl methacrylate is provided.The method is used in the preparation of isobornyl acrylate or isobornyl methacrylate, have that environmental pollution is little, production cost compared with low, labour intensity is little, can quantity-produced advantage.
For solving the problem, the technical solution used in the present invention is as follows: the preparation method of a kind of isobornyl acrylate or isobornyl methacrylate, take molecular sieve as catalyzer, in tank reactor or fixed-bed tube reactor, continuously vinylformic acid and amphene are converted into isobornyl acrylate or methacrylic acid and amphene are converted into isobornyl methacrylate; At least one of described molecular screening in ZSM-5, ZSM-22, ZSM-35, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite, β zeolite, Y zeolite, SAPO-34, SAPO-11.
In technique scheme, preferably, the at least one of described molecular screening in ZSM-22, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite, β zeolite, SAPO-34, described molecular sieve is Hydrogen or the molecular sieve through modification.
In technique scheme, preferably, the mol ratio of described methacrylic acid and amphene is 0.1 ~ 10:1, and the mol ratio of vinylformic acid and amphene is 0.1 ~ 10:1.
In technique scheme, more preferably, the mol ratio of described methacrylic acid and amphene is 0.5 ~ 3:1, and the mol ratio of vinylformic acid and amphene is 0.5 ~ 3:1.
In technique scheme, preferably, the reaction conditions in fixed-bed tube reactor is: temperature of reaction is 10 ~ 150 DEG C, amphene mass space velocity is 0.03 ~ 10.0h
-1, reaction pressure is normal pressure ~ 1.0MPaG.
In technique scheme, more preferably, described reaction conditions in fixed-bed tube reactor is: temperature of reaction is 30 ~ 120 DEG C, amphene mass space velocity is 0.1 ~ 5.0h
-1, reaction pressure is normal pressure ~ 0.5MPaG.
In technique scheme, preferably, reaction conditions in tank reactor is: the consumption of catalyzer be reaction solution quality 1 ~ 50%, temperature of reaction is 10 ~ 150 DEG C, the reaction times is 1 ~ 15 hour, reaction pressure is normal pressure ~ 1.0MPaG, the mol ratio of methacrylic acid and amphene is 0.3 ~ 5:1, or the mol ratio of vinylformic acid and amphene is 0.3 ~ 5:1.
In technique scheme, more preferably, the reaction conditions in tank reactor is: the consumption of catalyzer be reaction solution quality 2 ~ 15%, temperature of reaction is 20 ~ 120 DEG C, the reaction times is 3 ~ 10 hours, reaction pressure is normal pressure ~ 0.5MPaG.
The present invention adopts molecular sieve to be catalyzer; continuous prodution is realized in tank reactor or fixed-bed tube reactor; reaction conditions is gentle; catalyst activity is high; environmental friendliness; the selectivity of obtained isobornyl methacrylate is up to 95.7%; the selectivity of obtained isobornyl acrylate is up to 95.3%; amphene Transformation efficiency is up to 90 .8%; for synthesis (methyl) isobornyl acrylate provides a kind of new effective way; large-scale production (methyl) isobornyl acrylate can be widely used in, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1 ~ 5]
Synthetic zeolite catalyst 100 grams is respectively charged into fixed-bed tube reactor, with volume pump by a certain percentage by amphene with pump into reactor containing the methacrylic acid raw material of 250ppm thiophene piperazine and react, reaction conditions concrete in embodiment 1 ~ 5 and reaction result are in table 1.
Table 1.
[embodiment 6 ~ 10]
Synthetic zeolite catalyst 100 grams is respectively charged into fixed-bed tube reactor, with volume pump by a certain percentage by amphene with pump into reactor containing the acrylic raw materials of 250ppm thiophene piperazine and react, reaction conditions concrete in embodiment 6 ~ 10 and reaction result are in table 2.
Table 2.
[embodiment 11 ~ 15]
In 500 milliliters of stainless steel stirred autoclaves, the catalyzer of 300 grams of mixing raw materials and a certain amount of (calculating based on reaction raw materials) is added respectively by certain methacrylic acid/amphene mol ratio, then heat up and react, stirring velocity 100 ~ 500 revs/min, reaction conditions concrete in embodiment 11 ~ 15 and reaction result are in table 3.
Table 3.
[embodiment 16 ~ 20]
In 500 milliliters of stainless steel stirred autoclaves, the catalyzer of 300 grams of mixing raw materials and a certain amount of (calculating based on reaction raw materials) is added respectively by certain vinylformic acid/amphene mol ratio, then heat up and react, stirring velocity 100 ~ 500 revs/min, reaction conditions concrete in embodiment 16 ~ 20 and reaction result are in table 4.
Table 4.
As can be seen from above-mentioned table 1, table 3: owing to have selected highly active catalyzer, the selectivity of the isobornyl methacrylate that preparation method of the present invention is obtained up to 95.7%, amphene Transformation efficiency is up to 90 .6%.As can be seen from above-mentioned table 2, table 4: owing to have selected highly active catalyzer, the selectivity of the isobornyl acrylate that preparation method of the present invention is obtained up to 95.3%, amphene Transformation efficiency is up to 90 .8%.And preparation method's reaction conditions is gentle, environmentally friendly, can be widely used in the industrialization synthesis of (methyl) isobornyl acrylate.
Claims (8)
1. the preparation method of an isobornyl acrylate or isobornyl methacrylate, take molecular sieve as catalyzer, in tank reactor or fixed-bed tube reactor, continuously vinylformic acid and amphene are converted into isobornyl acrylate or methacrylic acid and amphene are converted into isobornyl methacrylate; At least one of described molecular screening in ZSM-5, ZSM-22, ZSM-35, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite, β zeolite, Y zeolite, SAPO-34, SAPO-11.
2. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 1, it is characterized in that at least one of described molecular screening in ZSM-22, MCM-49, MCM-22, MCM-56, MCM-36, MCM-41, MCM-48, mordenite, β zeolite, SAPO-34, described molecular sieve is Hydrogen or the molecular sieve through modification.
3. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 1, it is characterized in that the mol ratio of described methacrylic acid and amphene is 0.1 ~ 10:1, the mol ratio of vinylformic acid and amphene is 0.1 ~ 10:1.
4. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 3, it is characterized in that the mol ratio of described methacrylic acid and amphene is 0.5 ~ 3:1, the mol ratio of vinylformic acid and amphene is 0.5 ~ 3:1.
5. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 1, is characterized in that the reaction conditions in fixed-bed tube reactor is: temperature of reaction is 10 ~ 150 DEG C, amphene mass space velocity is 0.03 ~ 10.0h
-1, reaction pressure is normal pressure ~ 1.0MPaG.
6. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 5, is characterized in that described reaction conditions in fixed-bed tube reactor is: temperature of reaction is 30 ~ 120 DEG C, amphene mass space velocity is 0.1 ~ 5.0h
-1, reaction pressure is normal pressure ~ 0.5MPaG.
7. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 1, it is characterized in that the reaction conditions in tank reactor is: the consumption of catalyzer be reaction solution quality 1 ~ 50%, temperature of reaction is 10 ~ 150 DEG C, the reaction times is 1 ~ 15 hour, reaction pressure is normal pressure ~ 1.0MPaG, the mol ratio of methacrylic acid and amphene is 0.3 ~ 5:1, or the mol ratio of vinylformic acid and amphene is 0.3 ~ 5:1.
8. the preparation method of isobornyl acrylate or isobornyl methacrylate according to claim 7, is characterized in that the reaction conditions in tank reactor is: the consumption of catalyzer be reaction solution quality 2 ~ 15%, temperature of reaction is 20 ~ 120 DEG C, the reaction times is 3 ~ 10 hours, reaction pressure is normal pressure ~ 0.5MPaG.
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| CN201410785367.9A CN104529770A (en) | 2014-12-16 | 2014-12-16 | Preparation method of isobornyl acrylate or isobornyl methacrylate |
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| CN201410785367.9A CN104529770A (en) | 2014-12-16 | 2014-12-16 | Preparation method of isobornyl acrylate or isobornyl methacrylate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409562A (en) * | 2018-01-22 | 2018-08-17 | 安徽联化新材料有限公司 | A kind of continuous producing method of isobornyl methacrylate |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN115108907A (en) * | 2022-05-24 | 2022-09-27 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by directly esterifying alpha-pinene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151395A (en) * | 1995-08-18 | 1997-06-11 | 埃勒夫阿托化学有限公司 | Process for preparation of isobornyl (meth) acrylate |
| US5672733A (en) * | 1994-12-22 | 1997-09-30 | Elf Atochem S.A. | Process for the preparation of isobornyl (meth) acrylate |
| CN101921191A (en) * | 2010-09-27 | 2010-12-22 | 上海华谊（集团）公司 | Preparation method for synthesizing isobornyl acetate by esterification of camphene and acetic acid |
-
2014
- 2014-12-16 CN CN201410785367.9A patent/CN104529770A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672733A (en) * | 1994-12-22 | 1997-09-30 | Elf Atochem S.A. | Process for the preparation of isobornyl (meth) acrylate |
| CN1151395A (en) * | 1995-08-18 | 1997-06-11 | 埃勒夫阿托化学有限公司 | Process for preparation of isobornyl (meth) acrylate |
| CN101921191A (en) * | 2010-09-27 | 2010-12-22 | 上海华谊（集团）公司 | Preparation method for synthesizing isobornyl acetate by esterification of camphene and acetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 徐晓维，徐徐，魏柏松，王石发: "甲基丙烯酸异冰片酯的合成及性能研究", 《南京林业大学学报( 自然科学版)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409562A (en) * | 2018-01-22 | 2018-08-17 | 安徽联化新材料有限公司 | A kind of continuous producing method of isobornyl methacrylate |
| CN112142593A (en) * | 2020-08-28 | 2020-12-29 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN112142593B (en) * | 2020-08-28 | 2021-07-06 | 华南农业大学 | Preparation method of isobornyl (meth) acrylate of biological origin |
| CN115108907A (en) * | 2022-05-24 | 2022-09-27 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by directly esterifying alpha-pinene |
| CN115108907B (en) * | 2022-05-24 | 2023-05-26 | 万华化学集团股份有限公司 | Method for synthesizing isobornyl acrylate by direct esterification of alpha-pinene |
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Application publication date: 20150422 |