CN102146032A - Method for preparing methyl methacrylate - Google Patents
Method for preparing methyl methacrylate Download PDFInfo
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- CN102146032A CN102146032A CN2010101076512A CN201010107651A CN102146032A CN 102146032 A CN102146032 A CN 102146032A CN 2010101076512 A CN2010101076512 A CN 2010101076512A CN 201010107651 A CN201010107651 A CN 201010107651A CN 102146032 A CN102146032 A CN 102146032A
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- China
- Prior art keywords
- methyl methacrylate
- methyl
- ionic liquid
- formaldehyde
- preparation
- Prior art date
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Abstract
The invention relates to a method for preparing methyl methacrylate. Methyl propionate and formaldehyde are used as reactants, a molar ratio of the methyl propionate to the formaldehyde is 0.1-2.0, alkaline ionic liquid is adopted as a catalyst, the using amount of the catalyst is 0.01 to 10 weight percent of the total reactants, the reaction temperature is controlled to be 103-213DEG C, the reaction pressure is 0.5-4MPa, and the methyl methacrylate is prepared through catalysis reaction. The method overcomes defects of low selectivity and activity of the catalyst in the prior art, and effectively solves the problems of low selectivity and activity of a doped (heavily-doped) alkali metal catalyst. Because the ionic liquid catalyst is adopted, the vapor pressure is extremely low, loss is avoided theoretically in the reaction process, and the ionic liquid catalyst has good solubility property for the reactants, exists in a liquid form under the reaction condition, and can be separated and recovered in an easier mode.
Description
Technical field
The present invention relates under the situation that ionic liquid exists, chain type alkyl acid (or ester) prepares unsaturated acid (or its ester), the particularly novel method of methyl methacrylate with formaldehyde reaction.
Background technology
Methyl methacrylate is a kind of pure color, volatile liquid, it is important organic intermediate, be mainly used in the products such as industrial coating, building coating, leather facing, cakingagent, paper lustering agent, lubricant, dyeing and printing auxiliary and insulation pouring material of producing synthetic glass, flawless finish, its molecular formula is C
5H
8O
2, structural formula is:
20 th century later, multinomial research is raw material with methyl propionate and formaldehyde, reaction makes methyl methacrylate in the presence of basic catalyst.Its reaction formula is as follows:
Eastman Chemical is at Industrial ﹠amp; Engineering chemistry research, 36, studied the catalyzer that kind surplus in the of 80 has potential catalytic performance among (1997) 4600-4608, prove that V family metal (vanadium, niobium, tantalum) has catalytic activity to this reaction, wherein niobium is active maximum.And made 20% niobium/silicon oxide catalyst, but the catalyst life problem has constituted restriction to producing methyl methacrylate.
Mamoru AI is at Bull Chem Soc Jpn, 63, (1990) replace formaldehyde as raw material and methyl propionate reaction with methylal or trioxymethylene among the 3722-3724, this reaction makes methyl methacrylate as catalyst to adopt vanadium-silicon-phosphorus three-phase oxidation thing.But selectivity and the activity that should react are comparatively limited.
Suitable catalyzer for other these reactions of catalysis comprises alkali doped, especially the silicon oxide catalyst of caesium mixes, will lose activity within a short period of time and selectivity can ascribe two factors to: (1) used alkali metal compound presents bigger volatility under the reaction conditions that is adopted, thereby may lose activity owing to alkali-metal loss; (2) according to the deduction of US4942258, think that carrier should have certain little surface-area for wanting activatory basic metal, the hydrolysis of silicon oxide has caused the loss gradually of silica-gel catalyst processing property under reaction conditions.
US6544924 has introduced and has contained 1-10% (weight) basic metal a kind of comprising, especially the multi-hole type high surface area silicon oxide catalyst of caesium, be selected from the compound of boron, magnesium, aluminium, zirconium and hafnium modifier element, the limited inactivation problem that has solved catalyzer by distribution of at least one in the silicon oxide space.
Summary of the invention
The objective of the invention is to overcome catalyst selectivity and active deficiency in the prior art, a kind of preparation method of methyl methacrylate, the present invention has effectively solved the selectivity and the activity problems of doping (weight) base metal catalysts.Simultaneously because the catalyzer that adopts is an ionic liquid, its vapour pressure is extremely low, does not lose in theory in reaction process, and reactant is had the good solubility energy, under the reaction conditions that is adopted, exist with liquid form, and can be with more or less freely mode Separation and Recovery ionic liquid catalyst.
Reaction formula of the present invention is as follows:
The preparation method of a kind of methyl methacrylate of the present invention, it is characterized in that: use methyl propionate and formaldehyde to be reactant, the mol ratio of methyl propionate and formaldehyde is 0.1-2.0, adopt alkali ionic liquid as catalyzer, the 0.01-10wt% of catalyst levels total reactant, control reaction temperature 103-213 ℃, reaction pressure 0.5MPa-4MPa, catalyzed reaction prepares methyl methacrylate, and wherein the structural formula of alkali ionic liquid is:
R
1Be alkyl, R
2Be selected from itrile group, amido, amide group, alkyl, X
-Be OH
-, HCOO
-, CH
3COO
-, HSO4
-Or H
2PO4
-
The present invention has following beneficial effect:
1, use alkali ionic liquid to make the catalyzer synthesizing methylmethacrylate first.
2, temperature of reaction is lower than prior art, has reduced production energy consumption.
3, Preparation of Catalyst is easy, catalytic activity is high, reaction solution methyl methacrylate height, and by product is few.
4, catalyst levels is few, and minimum is 0.01wt%.
5, the catalyst activity height can be recycled, and has reduced the cost of catalyzer.
6, catalytic erosion is low, and reaction unit is not had special requirement, has reduced equipment cost.
Embodiment
The ionic liquid that uses among the present invention can constitute any ionic compound or the mixture that are in a liquid state by a kind of positively charged ion and a kind of negatively charged ion or several cation and several negatively charged ion under the reaction conditions that is adopted.
Catalyzer is expressed as follows:
A, R
1Be methyl, R
2Be selected from butyronitrile base, X
-Be OH
-, structural formula is:
B, R
1Be ethyl, R
2Be selected from Propylamino, X
-Be HCOO
-, structural formula is:
C, R
1Be propyl group, R
2Be selected from acetamido, X
-Be CH
3COO
-, structural formula is:
D, R1 are methyl, and R2 is selected from butyl, X
-Be OH
-, structural formula is:
E, R
1Be ethyl, R
2Be selected from propyl group, X
-Be HCOO
-, structural formula is
F, R
1Be ethyl, R
2Be selected from butyl, X
-Be CH
3COO
-, structural formula is:
G, R
1Be methyl, R
2Be selected from butyl, X
-Be HSO4
-, structural formula is:
H, R
1Be methyl, R
2Be selected from butyl, X
-Be H
2PO
4 -, structural formula is:
Embodiment 1:
In flow reactor, add 10ml catalyzer a, and methyl propionate and formaldehyde are imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 0.1: 1, control reaction temperature is 103 ℃, reaction pressure 0.5MPa, catalyst levels is the 10wt% of reactant, allows methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate, in methyl propionate, the yield of methyl methacrylate is 12.3%, and selectivity is 93.2%.
Embodiment 2:
In flow reactor, add 10ml catalyzer a, and methyl propionate and formaldehyde are imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 2, control reaction temperature is 213 ℃, reaction pressure 4MPa, catalyst levels is the 0.01wt% of reactant, allows methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate, in methyl propionate, the yield of methyl methacrylate is 16.8%, and selectivity is 97.3%.
Embodiment 3: in flow reactor, add 10ml catalyzer a, and methyl propionate and formaldehyde are imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 0.5: 1, control reaction temperature is 150 ℃, reaction pressure 2MPa, catalyst levels is the 5wt% of reactant, allows methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate, in methyl propionate, the yield of methyl methacrylate is 15.8%, and selectivity is 96.3%.
Embodiment 4:
In flow reactor, add 10ml catalyzer a, and methyl propionate and formaldehyde are imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 2.0: 1, control reaction temperature is 150 ℃, reaction pressure 2MPa, catalyst levels is the 0.01wt% of reactant, allows methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate, in methyl propionate, the yield of methyl methacrylate is 13.2%, and selectivity is 95.2%.
Embodiment 5:
In flow reactor, add 20ml catalyzer b, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.45, control reaction temperature is 160 ℃, and reaction pressure 1MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 15.1%, and selectivity is 96.7%.
Embodiment 6:
In flow reactor, add 30ml catalyzer c, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.2, control reaction temperature is 180 ℃, and reaction pressure 1.5MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 16.6%, and selectivity is 94.3%.
Embodiment 7:
In flow reactor, add 40ml catalyzer d, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.45, control reaction temperature is 200 ℃, and reaction pressure 2MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 14.7%, and selectivity is 96.7%.
Embodiment 8:
In flow reactor, add 50ml catalyzer e, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.2, control reaction temperature is 213 ℃, and reaction pressure 1MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 12.8%, and selectivity is 92.4%.
Embodiment 9:
In flow reactor, add 50ml catalyzer f, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.45, control reaction temperature is 150 ℃, and reaction pressure 2MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 10.3%, and selectivity is 91.2%.
Embodiment 10:
In flow reactor, add 50ml catalyzer g, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.2, control reaction temperature is 150 ℃, and reaction pressure 2MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 7.5%, and selectivity is 93.8%.
Embodiment 11:
In flow reactor, add 50ml catalyzer h, and methyl propionate and formaldehyde imported reactor with certain speed, the mol ratio of methyl propionate and formaldehyde is 1: 1.45, control reaction temperature is 150 ℃, and reaction pressure 2MPa, catalyst levels are the 0.01wt% of reactant, allow methyl propionate and formaldehyde abundant contact reacts in catalyzer, the preparation methyl methacrylate.In methyl propionate, the yield of methyl methacrylate is 8.1%, and selectivity is 92.6%.
Claims (10)
1. the preparation method of a methyl methacrylate, it is characterized in that: use methyl propionate and formaldehyde to be reactant, the mol ratio of methyl propionate and formaldehyde is 0.1-2.0, adopt alkali ionic liquid as catalyzer, the 0.01-10wt% of catalyst levels total reactant, control reaction temperature 103-213 ℃, reaction pressure 0.5MPa-4MPa, catalyzed reaction prepares methyl methacrylate, and wherein the structural formula of alkali ionic liquid is:
R
1Be alkyl, R
2Be selected from itrile group, amido, amide group, alkyl, X
-Be OH
-, HCOO
-, CH
3COO
-, HSO4
-Or H
2PO4
-
2. the preparation method of a kind of methyl methacrylate according to claim 1 is characterized in that: R in the described alkali ion liquid
1Be methyl, ethyl or propyl group, R
2Be butyronitrile base, Propylamino, acetamido or butyl, X
-Be OH
-, HCOO
-, CH
3COO
-, HSO4
-Or H
2PO4
-
3. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be methyl, R
2Be selected from butyronitrile base, X
-Be OH
-
4. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be ethyl, R
2Be selected from Propylamino, X
-Be HCOO
-
5. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be propyl group, R
2Be selected from acetamido, X
-Be CH
3COO
-
6. the preparation method of a kind of methyl methacrylate according to claim 2, it is characterized in that: R1 is a methyl in the described alkali ionic liquid, and R2 is selected from butyl, X
-Be OH
-
7. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be ethyl, R
2Be selected from propyl group, X
-Be HCOO
-
8. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be ethyl, R
2Be selected from butyl, X
-Be CH
3COO
-
9. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be methyl, R
2Be selected from butyl, X
-Be HSO4
-
10. the preparation method of a kind of methyl methacrylate according to claim 2 is characterized in that: R in the described alkali ionic liquid
1Be methyl, R
2Be selected from butyl, X
-Be H
2PO
4 -
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101076512A CN102146032A (en) | 2010-02-10 | 2010-02-10 | Method for preparing methyl methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101076512A CN102146032A (en) | 2010-02-10 | 2010-02-10 | Method for preparing methyl methacrylate |
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|---|---|
| CN102146032A true CN102146032A (en) | 2011-08-10 |
Family
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|---|---|---|---|
| CN2010101076512A Pending CN102146032A (en) | 2010-02-10 | 2010-02-10 | Method for preparing methyl methacrylate |
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|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659579A (en) * | 2012-04-17 | 2012-09-12 | 湖北远成药业有限公司 | preparation method of p-chlorine methyl cinnamate |
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
| CN103242159A (en) * | 2013-04-26 | 2013-08-14 | 珠海飞扬新材料股份有限公司 | Production method of methyl acrylate |
| CN103906581A (en) * | 2011-09-27 | 2014-07-02 | 罗门哈斯公司 | Method for cleaning a (meth) acrylate ester process tank |
| CN108101770A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids or unsaturated acid ester |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405140A (en) * | 2002-11-07 | 2003-03-26 | 华东师范大学 | Method of esterifying in ion liquid [Hmim]+ BF4- |
| CN1544410A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院过程工程研究所 | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence |
-
2010
- 2010-02-10 CN CN2010101076512A patent/CN102146032A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1405140A (en) * | 2002-11-07 | 2003-03-26 | 华东师范大学 | Method of esterifying in ion liquid [Hmim]+ BF4- |
| CN1544410A (en) * | 2003-11-27 | 2004-11-10 | 中国科学院过程工程研究所 | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence |
Non-Patent Citations (4)
| Title |
|---|
| 《精细石油化工》 20051130 李桂花等 "离子液体对甲基丙烯醛催化合成甲基丙烯酸甲酯的影响" 第9-12页 1-10 , 第6期 * |
| 《过程工程学报》 20080229 陈琼等 "甲基丙烯醛、甲醇与[BMIM]BF4二元体系的气液相平衡" 第97-101页 1-10 第8卷, 第1期 * |
| 李桂花等: ""离子液体对甲基丙烯醛催化合成甲基丙烯酸甲酯的影响"", 《精细石油化工》, no. 6, 30 November 2005 (2005-11-30), pages 9 - 12 * |
| 陈琼等: ""甲基丙烯醛、甲醇与[BMIM]BF4二元体系的气液相平衡"", 《过程工程学报》, vol. 8, no. 1, 29 February 2008 (2008-02-29), pages 97 - 101 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103906581A (en) * | 2011-09-27 | 2014-07-02 | 罗门哈斯公司 | Method for cleaning a (meth) acrylate ester process tank |
| CN103906581B (en) * | 2011-09-27 | 2016-03-30 | 罗门哈斯公司 | The method of clean (methyl) acrylate treatment trough |
| CN102659579A (en) * | 2012-04-17 | 2012-09-12 | 湖北远成药业有限公司 | preparation method of p-chlorine methyl cinnamate |
| CN102775302A (en) * | 2012-08-03 | 2012-11-14 | 北京旭阳化工技术研究院有限公司 | Method for preparing methyl methacrylate from methyl propionate and formaldehyde |
| CN102775302B (en) * | 2012-08-03 | 2015-09-02 | 旭阳化学技术研究院有限公司 | A kind of method being prepared methyl methacrylate by methyl propionate and formaldehyde |
| CN103242159A (en) * | 2013-04-26 | 2013-08-14 | 珠海飞扬新材料股份有限公司 | Production method of methyl acrylate |
| CN108101770A (en) * | 2016-11-25 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of method that regeneration prepares the catalyst of unsaturated acids or unsaturated acid ester |
| CN108101770B (en) * | 2016-11-25 | 2020-05-05 | 中国科学院大连化学物理研究所 | Method for regenerating catalyst for preparing unsaturated acid or unsaturated acid ester |
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Application publication date: 20110810 |