CN100361955C - Production of 2,2,4-trimethyl-1,-3-pentadiol mono-isobutyric acid - Google Patents
Production of 2,2,4-trimethyl-1,-3-pentadiol mono-isobutyric acid Download PDFInfo
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- CN100361955C CN100361955C CNB2006100243738A CN200610024373A CN100361955C CN 100361955 C CN100361955 C CN 100361955C CN B2006100243738 A CNB2006100243738 A CN B2006100243738A CN 200610024373 A CN200610024373 A CN 200610024373A CN 100361955 C CN100361955 C CN 100361955C
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- trimethylammonium
- hydrotalcite
- pentanediol mono
- mono isobutyrate
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Abstract
The present invention discloses a method for synthesis 2, 2, 4-trimethyl-1, 3-pentanediol monoester isobutyrate through correspondingly environmental-friendly heterogeneous catalysis. Intramolecular Cannizarro's reaction is carried out to the low-temperature condensed and pretreated products of isobutyraldehyde under the action of hydrotalcite-like compounds (namely solid catalysts), and 2, 2, 4-trimethyl-1, 3-pentanediol monoester isobutyrate is generated. The present invention has the advantages of high single-pass yield (can reach 87%), mild reaction condition, small corrosion to devices, recycle of catalysts, etc.
Description
Technical field
The present invention relates to the organic chemistry synthesis technical field, specifically a kind of is Preparation of Catalyst 2,2 with the houghite, 4-trimethylammonium-1, the method for 3-pentanediol mono isobutyrate.
Background technology
2,2,4-trimethylammonium-1, the 3-pentanediol mono isobutyrate is a kind of water-insoluble high boiling point binary alcohol esters, have its unique advantage when being used for solvent and softening agent, have characteristics such as good resin intermiscibility, viscosity and low pollution when being used for coating and latex, be a kind of safely, be efficiently adapted to the novel furtherance film of all kinds of synthetic resin emulsion coating, being applicable to the desirable auxiliary agent of green coating especially, is a kind of important chemical material.U.S. EASTMAN company releases efficient, safe Texanol alcohol ester as the maximum emulsion paint furtherance film manufacturers in the whole world, occupies the very big market share in China.The not enough 7kt of output in domestic, output and quality product can not satisfy the development need of green coating far away.The synthetic of it all is to be raw material with the isobutyric aldehyde, and under catalyst action, through pure ester condensation reaction, rectification under vacuum generates.Selection of catalysts is the key factor of restriction Texanol alcohol ester production technology.In recent years, especially since nineteen ninety-five very active to the research and development of this product both at home and abroad, research emphasis is to adopt different catalyzer to improve synthesis technique in reaction.They adopt two step synthesis methods mostly, i.e. aldehyde condensation and intramolecularly Cannizzaro reaction, and used catalyzer basic metal (hydrogen) oxide compound and alkaline earth (hydrogen) oxide solution etc., but many with these catalyst byproducts, big to equipment corrosion, react not gentle.(WO9741088; WO98/24752; US6,215,020 B1; EP1027925A1; CN94106092.6; CN00107939.5; ) 2004 years, EASTMAN company has reported with the polynite of sodium hydroxide modification earth, Jiao Lingtu, the kaolin catalyzer for synthetic diol monoester, but the reaction times reaches 200 hours (US6,794,325).Therefore, prior art can't realize simultaneously that by product is few, once through yield is high, cost is low, eco-friendly target.
Summary of the invention
Houghite (LDHs) is a class new catalytic material that is subjected to extensive concern in recent years.The mixed metal hydroxides with hydrotalcite (HT) layered crystal structure that this material is made up of divalence and trivalent metal ion, its composition formula is [M
II 1-xM
III x(OH)
2]
x(A
N-)
X/nMH
2O, wherein M
II=Mg
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+, Ni
2+, Pd
2+, V
2+, Fe
2+, Mn
2+Deng divalent metal; M
III=Al
3+, Fe
3+, Co
3+, Cr
3+, V
3+, Mn
3+, Ni
3+, Rh
3+, Ru
3+, Ga
3+, La
3++Deng trivalent metal cation, A
N-=CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-, PO
4 3-, C
6H (COO
-)
2Etc. inorganic or organic anion.Its main characteristic has: the interchangeability of cationic collocation property, interlayer anion in alkalescence, the laminate.Therefore, it can be designed as basic catalyst, redox catalyst and support of the catalyst.
The object of the present invention is to provide a kind of environmental friendliness and economic heterogeneous catalysis preparation 2,2,4-trimethylammonium-1, the method for 3-pentanediol mono isobutyrate is to solve the existing in prior technology problem.
The object of the present invention is achieved like this:
A kind of preparation 2,2,4-trimethylammonium-1, the method of 3-pentanediol mono isobutyrate, it is with isobutyric aldehyde low temperature condensation pre-treatment product intramolecularly Cannizzaro reaction under the effect of houghite solid catalyst, after reaction finishes, filter, filtrate gets 2,2 through underpressure distillation, 4-trimethylammonium-1, the 3-pentanediol mono isobutyrate, hydrotalcite is reusable, and its activity remains unchanged substantially, and once through yield can reach 87%.Reaction expression of the present invention is as follows:
The condensation of isobutyric aldehyde low temperature:
The intramolecularly Cannizzaro reaction:
The present invention includes following concrete operations step:
The isobutyric aldehyde low temperature condensation pre-treatment of the 1st step
In the three-necked flask that has thermometer, reflux condensing tube and constant pressure funnel, 5% the sodium hydroxide solution that adds 25 parts of weight, magnetic agitation, under nitrogen protection, normal pressure, 20 ℃ of conditions, drip the isobutyric aldehyde of 75 parts of weight in the 1h continuously lentamente, drip the back and continue reaction 4h down at 35 ℃; Stopped reaction, 2-3h is left standstill in washing, layering, lower floor is a water layer, the upper strata is an oil reservoir;
The 2nd step intramolecularly Cannizzaro reaction
The oil reservoir that above-mentioned steps is obtained joins in the 100ml three-necked flask that has thermometer, reflux condensing tube, the houghite solid catalyst that adds 1-5 part weight, use magnetic stirrer, under nitrogen protection, normal pressure, 60 ℃ of conditions, react 1h, be warming up to 65-100 ℃ then, continue reaction 10-18h again;
The 3rd step catalyst separating and processing
Filter to isolate catalyzer, with isolated catalyzer washing 2-3 time, dry in 100 ℃ of following air atmosphere again;
The 4th step was carried out underpressure distillation with filtrate, got 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate.
The houghite solid catalyst of described intramolecularly Cannizzaro reaction is magnesium aluminum-hydrotalcite, zinc-aluminium hydrotalcite, lithium aluminum hydrotalcite.
Compare with background technology, advantage of the present invention is: (1) once through yield height, reach 87%, (2) reaction conditions gentleness is little to equipment corrosion; (3) catalyzer can be recycled.Therefore the present invention is a kind of preparation 2,2 with prospects for commercial application, 4-trimethylammonium-1, the method for 3-pentanediol mono isobutyrate.
Embodiment
Below will the present invention is further elaborated by specific embodiment:
Embodiment 1
The isobutyric aldehyde low temperature condensation pre-treatment of the 1st step
In having the 100ml three-necked flask of thermometer, reflux condensing tube and constant pressure funnel, adding 5g concentration is 5% sodium hydroxide solution, magnetic agitation, under nitrogen protection, normal pressure, 20 ℃ condition, drip the 15g isobutyric aldehyde in the 1h continuously lentamente, drip the back and continue reaction 4h down at 35 ℃; Stopped reaction, washing, standing demix, lower floor is a water layer, the upper strata is an oil reservoir.
The 2nd step intramolecularly Cannizzaro reaction
The oil reservoir that isobutyric aldehyde low temperature condensation pre-treatment is obtained joins in the 100mL three-necked flask that has thermometer, reflux condensing tube, add the 0.2g magnesium aluminum-hydrotalcite, magnetic agitation is reacted 1h under nitrogen protection, normal pressure, 60 ℃ of conditions, be warming up to 60-65 ℃ then, continue reaction 10h again;
The 3rd step catalyst separating and processing
Filter to isolate catalyzer, with isolated catalyzer washing 2-3 time, dry 10h in 100 ℃ of following air atmosphere then;
The 4th step was carried out underpressure distillation with filtrate at 0.096-0.098MPa, collected 144-146 ℃ of cut, got 2,2,4-trimethylammonium-1, and the 3-pentanediol mono isobutyrate, purity=99%, yield are 87%.
Once through yield calculates:
Embodiment 2-4
Except for the following differences, all the other are identical with embodiment 1, and catalyzer is reused 3 times, and its reaction result is as follows:
| Embodiment | The catalyzer access times | Once through yield |
| 2 | 2 | 86 |
| 3 4 | 3 4 | 86 78 |
Embodiment 5-7
Except for the following differences, all the other are identical with embodiment 1, and the 2nd step adopted 1g zinc-aluminium hydrotalcite as catalyzer, and temperature of reaction is 80-85 ℃, and the reaction times is 15h.
| Embodiment | The catalyzer access times | Once through yield |
| 5 6 7 | 1 2 3 | 80 79 68 |
Embodiment 8-10
Except for the following differences, all the other are identical with embodiment 1, and the 2nd step adopted the lithium aluminum hydrotalcite as catalyzer, and temperature of reaction is 95-100 ℃, and the reaction times is 18h.
| Embodiment | The catalyzer access times | Once through yield |
| 8 9 10 | 2 3 4 | 72 70 64 |
Claims (3)
1.-plant and prepare 2,2,4-trimethylammonium-1, the method of 3-pentanediol mono isobutyrate is characterized in that it is that isobutyric aldehyde low temperature condensation pre-treatment product is carried out the intramolecularly Cannizzaro reaction under the effect of houghite solid catalyst, generates 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate, after reaction finishes, filter, filtrate gets 2,2 through underpressure distillation, 4-trimethylammonium-1, the 3-pentanediol mono isobutyrate.
2. method according to claim 1 is characterized in that: it comprises following concrete operations step:
The isobutyric aldehyde low temperature condensation pre-treatment of the 1st step
In the three-necked flask that has thermometer, reflux condensing tube and constant pressure funnel, 5% the sodium hydroxide solution that adds 25 parts of weight, magnetic agitation, under nitrogen protection, normal pressure, 20 ℃ of conditions, drip the isobutyric aldehyde of 75 parts of weight in the 1h continuously lentamente, drip the back and continue reaction 4 h down at 35 ℃; Stopped reaction, 2-3h is left standstill in washing, layering, lower floor is a water layer, the upper strata is an oil reservoir;
The 2nd step intramolecularly Cannizzaro reaction
The oil reservoir that above-mentioned steps is obtained joins in the 100ml three-necked flask that has thermometer, reflux condensing tube, the houghite solid catalyst that adds 1-5 part weight, use magnetic stirrer, under nitrogen protection, normal pressure, 60 ℃ of conditions, react 1h, be warming up to 65-100 ℃ then, continue reaction 10-18h again;
The 3rd step catalyst separating and processing
Filter to isolate catalyzer, with isolated catalyzer washing 2-3 time, dry in 100 ℃ of following air atmosphere again;
The 4th step was carried out underpressure distillation with filtrate, got 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate.
3. method according to claim 1 is characterized in that: the houghite solid catalyst of described intramolecularly Cannizzaro reaction is magnesium aluminum-hydrotalcite, zinc-aluminium hydrotalcite, lithium aluminum hydrotalcite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100243738A CN100361955C (en) | 2006-03-03 | 2006-03-03 | Production of 2,2,4-trimethyl-1,-3-pentadiol mono-isobutyric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100243738A CN100361955C (en) | 2006-03-03 | 2006-03-03 | Production of 2,2,4-trimethyl-1,-3-pentadiol mono-isobutyric acid |
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| CN1817850A CN1817850A (en) | 2006-08-16 |
| CN100361955C true CN100361955C (en) | 2008-01-16 |
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| CNB2006100243738A Expired - Fee Related CN100361955C (en) | 2006-03-03 | 2006-03-03 | Production of 2,2,4-trimethyl-1,-3-pentadiol mono-isobutyric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863762A (en) * | 2010-06-30 | 2010-10-20 | 江苏天音化工有限公司 | Method for preparing 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate |
| CN103143340B (en) * | 2013-02-06 | 2014-08-06 | 江苏润泰化学有限公司 | Catalyst applied to n-dodecanol ester synthesis and preparation method thereof |
| CN107698451A (en) * | 2017-10-24 | 2018-02-16 | 安徽省化工设计院 | A kind of production technology of alcohol ester 12 |
| CN107814718A (en) * | 2017-11-14 | 2018-03-20 | 润泰化学（泰兴）有限公司 | A kind of synthetic method of 2,2,4 TMPD monoesters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098712A (en) * | 1994-05-27 | 1995-02-15 | 吉林化学工业公司江南设计研究院 | 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate |
| CN1429809A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Preparation process of 2,2,4-trimethyl-1,3-pentanediol mono-sio butyrate |
-
2006
- 2006-03-03 CN CNB2006100243738A patent/CN100361955C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098712A (en) * | 1994-05-27 | 1995-02-15 | 吉林化学工业公司江南设计研究院 | 2,2,4-trimethylammonium-1, the preparation method of 3-pentanediol mono isobutyrate |
| CN1429809A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Preparation process of 2,2,4-trimethyl-1,3-pentanediol mono-sio butyrate |
Non-Patent Citations (1)
| Title |
|---|
| 2,2,4-三甲基-1,3-戊二醇单异丁酸酯的合成研究. 菅秀君等.山东化工，第29卷第2期. 2000 * |
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