CN1167103A - Method for preparation of polylol allyl ether - Google Patents
Method for preparation of polylol allyl ether Download PDFInfo
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- CN1167103A CN1167103A CN 96115830 CN96115830A CN1167103A CN 1167103 A CN1167103 A CN 1167103A CN 96115830 CN96115830 CN 96115830 CN 96115830 A CN96115830 A CN 96115830A CN 1167103 A CN1167103 A CN 1167103A
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- allyl ether
- polyvalent alcohol
- ether
- alkali metal
- trimethylolpropane
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Abstract
The preparation method of polyaclohol allyl ether by using polyalcohols (such as glycerine, trimethylolpropane and pentaerythritol, etc.), chlorallylene and alkali methal hydroxide as raw material, and making them react in toluene solvent to produce allyl ether, in particular, monoallyl ether can be implemented by two steps: first step, polyalcohol and alkali metal hydroxide are reacted to produce polyalcohol mono(or bi) alkali salt, and second step, the above-mentioned alkali salt and chlorallylene are reacted to produce polyalcohol mono (or bi) allyl ether. The yield of polyalcohol monoallyl ether and biallyl ether can be controlled by selecting different mixing ratio of raw materials, and the ratio of products monoether and biether is 3:2-11:1 (m/m), and selectivity of total ether can be up to above 95%.
Description
The present invention relates to a kind of method for preparing polylol allyl ether, particularly relating to a kind of is raw material with polyvalent alcohol (as glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.), propenyl chloride and alkali metal hydroxide, reaction generates the method for allyl ethers, especially mono allyl ether in solvent.
Polyvalent alcohol (as glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.) allyl ethers is the important chemical intermediate raw material, can be used in solvent and the unsaturated polyester coating.Trihydroxy methyl-propane-allyl ether can be used as makes high rigidity, the properties-correcting agent of high reflective surface coatings, the clean-out system of automobile etc., and allylin can be used as the raw material of the cocuring agent, antitartar agents, vibrin quick dry agent of urethanes etc.In order to satisfy the demand of chemical industry field to polylol allyl ether, the various countries scholar has carried out extensive studies.German Patent 2,437,789 propose to make solvent with toluene, propenyl chloride are joined in the mixed system of polyvalent alcohol and sodium hydroxide, synthetic continuously polylol allyl ether.Japanese Patent 85-231,625 propose the aqueous solution of propenyl chloride and a kind of alkali metal hydroxide is added drop-wise in the mixture that contains TriMethylolPropane(TMP) and solvent, obtain polylol allyl ether, though these two kinds of methods help precipitation and the caking controlling the productive rate of various ethers and prevent alkoxide, but shortcoming is in the reaction process, hydrolysis easily takes place and generates vinyl carbinol in propenyl chloride, reduced the yield of polylol allyl ether, and mostly the product that generates is to mix ether, generally based on bis ether, the ratio of monoether is no more than 50% in the product, and it is difficult that this explanation control generates the reaction conditions of monoether.The clear 60-252 of Ri Tekai, 440 propose to use polyvalent alcohol and alkali metal hydroxide and propenyl chloride to react in the presence of phase-transfer catalyst (quaternary ammonium salt) produces polylol allyl ether, this method helps improving the speed of reaction of polyvalent alcohol, but the propenyl chloride facile hydrolysis generates vinyl carbinol, reduced the yield of polylol allyl ether, and, must add defoamer and handle because the existence of phase-transfer catalyst causes the product separation difficulty.
The objective of the invention is to overcome the weak point that exists in the prior art, a kind of novel method for preparing polylol allyl ether is provided.Prepare allyl ethers with method of the present invention, can reduce the hydrolysis of propenyl chloride, improve the yield of polylol allyl ether, and need not use phase-transfer catalyst, thereby avoided the problem of product separation difficulty.The present invention controls the yield of polyvalent alcohol mono allyl ether and diene propylene ether by selecting different proportioning raw materials, and wherein the monoether yield can reach more than 80%.
In order to achieve the above object, the technical solution used in the present invention is summarized as follows,
By select suitable solvent in order to the water that carries reaction process and generate to reduce the hydrolysis of propenyl chloride, the azeotropic agent that the present invention adopts is benzene, toluene, vinyl acetic monomer etc.Select different proportioning raw materials to control the yield of polyvalent alcohol mono allyl ether and dual-allyl ether, synthetic in two steps polyvalent alcohol an alkali metal salt and polylol allyl ether are to improve the selectivity and the yield of polyvalent alcohol mono allyl ether.The first step joins polyvalent alcohol, alkali metal hydroxide and azeotropic agent in the reactor according to a certain ratio, reaction generates the polyvalent alcohol an alkali metal salt, second step joined propenyl chloride in the reactor, temperature of reaction remains on 100 ℃～145 ℃, the final polylol allyl ether that generates, the polyvalent alcohol that is fit to the inventive method synthesis of allyl ether is glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.Alkali metal hydroxide is sodium hydroxide, potassium hydroxide etc.The present invention does not use any catalyzer, has avoided the product separation difficulty, and polyvalent alcohol excessive or that unreacted is intact comes out by crystalline method and product separation, thereby has saved big energy, has improved the purity and the yield that reclaim polyvalent alcohol again.
Details are as follows for concrete technical scheme:
1. according to different requirements to single bis ether product ratio, join polyvalent alcohol, alkali metal hydroxide and azeotropic agent in the reactor according to a certain ratio, start stirring behind the heating and melting, under the azeotropic temperature of toluene and water, react, and the azeotropic separation by toluene and water goes out the water that reaction generates, and makes the polyvalent alcohol an alkali metal salt.
2. by the forced feed device, propenyl chloride is joined in the reactor, 100 ℃～145 ℃ following stirring reactions of temperature 1 hour～2 hours, etherification reaction finished.
3. after removing azeotropic agent with vacuum distillation, control blowing temperature is directly carried out centrifugation more than 120 ℃ with material.The centrifugation mother liquor carries out stirred crystallization in crystallizer tank, centrifugation polyvalent alcohol crystal when the control temperature of charge is 40～50 ℃.Characteristics of the present invention are:
1. reaction is carried out in two steps, and the first step generates the polyvalent alcohol an alkali metal salt by polyvalent alcohol and alkali metal hydroxide reaction earlier.Second step added the propenyl chloride reaction again and generates polylol allyl ether.Wherein the water of the first step polyvalent alcohol and alkali metal hydroxide reaction generation is taken out of with the azeotropic agent azeotropic that adds.Thereby avoid and propenyl chloride generation hydrolysis, improved the yield of total ether.
2. reach the purpose of monoether and bis ether ratio in the control product by the control proportioning raw materials, the proportional range of monoether and bis ether is 3: 2～11: 1 (m/m).
3. do not use phase-transfer catalyst, avoided the problem of product separation difficulty.
4 unreacted (being excessive) polyvalent alcohol separates with mother liquor by the crystalline method, can save the isolating energy of product mixture, can improve the purity of the polyvalent alcohol that is reclaimed, and the polyvalent alcohol of recovery can recycle.
For the present invention is described better, we enumerate the following example, but the present invention is not limited to following embodiment.Embodiment 1:
In the reactor of 30L 316L material, add 90mol TriMethylolPropane(TMP), 30mol sodium hydroxide, 39mol toluene, start stirring behind the heating and melting, under the azeotropic temperature of toluene and water, react, and the azeotropic separation by toluene and water goes out the water that reaction generates, and control aquifer yield to sodium alkoxide building-up reactions finishes.Add the 90mol propenyl chloride by the forced feed device, be pressurized to 0.5MPa with nitrogen, 115～135 ℃ of following stirring reactions of temperature 1 hour～2 hours, material in the sampling analysis still, etherification reaction finishes, then by vacuum distillation system recoveries 33mol toluene, blowing while hot, contain 28Mol TriMethylolPropane(TMP) mono allyl ether in the reaction mixture material, selectivity is 95.6%.The reaction mixture material is by centrifugation sodium-chlor, filtrate in crystallizer tank 35～55 ℃ of crystallizations, then by centrifugation, the TriMethylolPropane(TMP) of filter cake for reclaiming, quality 60mol, purity is that 90%, the one step rate of recovery is 90%, contains the TriMethylolPropane(TMP) mono allyl ether of 10% (mass percent) and the mixture of dual-allyl ether in the TriMethylolPropane(TMP) that is reclaimed.Filtrate is collected TriMethylolPropane(TMP) mono allyl ether 26mol, yield 87.8% (in propenyl chloride), TriMethylolPropane(TMP) dual-allyl ether 2.3mol, yield 7.8% (in propenyl chloride) by rectification under vacuum.Embodiment 2:
In reactor, add the 90mol TriMethylolPropane(TMP), 60mol potassium hydroxide, 39mol toluene, the condition of synthesizing trimethylol propane monopotassium salt and operation are with embodiment 1, add the 180mol propenyl chloride by the forced feed device then, the synthesis condition of allyl ethers and operation are with embodiment 1.TriMethylolPropane(TMP) mono allyl ether selectivity is 69.5%, crystallization is reclaimed the condition of TriMethylolPropane(TMP) and is operated with embodiment 1, reclaiming the TriMethylolPropane(TMP) quality is 27mol, purity is 91%, the one step rate of recovery is 88%, contains the TriMethylolPropane(TMP) mono allyl ether of 10% (mass percent) in the TriMethylolPropane(TMP) that is reclaimed.TriMethylolPropane(TMP) mono allyl ether yield 64.2% (in propenyl chloride), TriMethylolPropane(TMP) dual-allyl ether yield 31.7% (in propenyl chloride).Embodiment 3:
Add 90mol TriMethylolPropane(TMP), 45mol sodium hydroxide, 39mol toluene in reactor, the condition of synthesizing trimethylol propane list sodium salt and operation are with embodiment 1.Add the 136mol propenyl chloride by the forced feed device then, the synthesis condition of allyl ethers and operation are 60% with embodiment 1. TriMethylolPropane(TMP) mono allyl ether selectivity, crystallization is reclaimed the condition of TriMethylolPropane(TMP) and is operated with embodiment 1, the purity that reclaims TriMethylolPropane(TMP) is 91%, the one step rate of recovery is 88%, contains the TriMethylolPropane(TMP) mono allyl ether of 10% (mass percent) and the mixture of dual-allyl ether in the TriMethylolPropane(TMP) that is reclaimed.It is 56.1% (in propenyl chloride) that filtrate is collected TriMethylolPropane(TMP) mono allyl ether yield by rectification under vacuum, TriMethylolPropane(TMP) dual-allyl ether 0.08mol, yield 36.0% (in propenyl chloride).Embodiment 4:
In reactor, add 3mol glycerine, 1mol sodium hydroxide, 1.2mol toluene, the condition of synthetic glycerine list sodium salt and operation are with embodiment 1.Add the 1.05mol propenyl chloride by the forced feed device then, the synthesis condition of allylin and operation are with embodiment 1.Reclaim excessive glycerine by distillation operation, the glycerine purity that reclaims is that 93%, the one step rate of recovery is 86%, collects allylin 0.8mol by rectification under vacuum, yield 76.2% (in propenyl chloride), the yield of glycerine dual-allyl ether are 15.2% (in propenyl chloride).
Claims (5)
1, a kind of preparation method of polylol allyl ether, be included in the solvent with polyvalent alcohol and alkali metal hydroxide and the synthetic polylol allyl ether of propenyl chloride, it is characterized in that this reaction carries out in two steps, the first step polyvalent alcohol and alkali metal hydroxide reaction generate the polyvalent alcohol an alkali metal salt, and the second step polyvalent alcohol an alkali metal salt and propenyl chloride reaction generate polylol allyl ether.
2, method according to claim 1 is characterized in that the proportional range of product monoether and bis ether is 3: 2～11: 1 (m/m) by the ratio of monoether and bis ether in the selection proper raw material proportioning may command product.
3, method according to claim 1 is characterized in that the polyvalent alcohol that is adopted is glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.
4, method according to claim 1 is characterized in that the alkali metal hydroxide that is adopted is sodium hydroxide, potassium hydroxide etc.
5, method according to claim 1 is characterized in that unreacted polyvalent alcohol (except the glycerine) separates the polyvalent alcohol reusable edible of recovery by the crystalline method with mother liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115830A CN1052970C (en) | 1996-06-04 | 1996-06-04 | Method for preparation of polylol allyl ether |
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| Application Number | Priority Date | Filing Date | Title |
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| CN96115830A CN1052970C (en) | 1996-06-04 | 1996-06-04 | Method for preparation of polylol allyl ether |
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| CN1167103A true CN1167103A (en) | 1997-12-10 |
| CN1052970C CN1052970C (en) | 2000-05-31 |
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| CN96115830A Expired - Fee Related CN1052970C (en) | 1996-06-04 | 1996-06-04 | Method for preparation of polylol allyl ether |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200413B (en) * | 2006-12-11 | 2010-08-25 | 珠海飞扬化工有限公司 | Method for preparing pentaerythrite allyl ether |
| CN102040486A (en) * | 2010-11-24 | 2011-05-04 | 山东省化工研究院 | Preparation method of trimethylolpropane diallyl ether |
| CN102153452A (en) * | 2011-02-21 | 2011-08-17 | 王海艳 | Synthesis method of trimethylolpropane allyl ether |
| CN102300838A (en) * | 2009-01-28 | 2011-12-28 | 迈图专业化学股份有限公司 | Process for the preparation of an ally alkyl ehter by catalytic allyation |
| CN103881080A (en) * | 2012-12-19 | 2014-06-25 | 辽宁奥克化学股份有限公司 | Alkenyl-terminated polyoxyethylene ether, preparation method and application thereof |
| CN105399610A (en) * | 2015-12-15 | 2016-03-16 | 安陆新景化工有限公司 | Technological method for preparation of allyl ether compounds |
| CN112479833A (en) * | 2020-12-11 | 2021-03-12 | 浙江皇马科技股份有限公司 | Preparation method of pentaerythritol triallyl ether |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100410304C (en) * | 2006-11-01 | 2008-08-13 | 南京威尔化工有限公司 | Synthetic method for crosslinking agent-pentaerythritol allyl ether for high molecular polymerization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2437789C3 (en) * | 1974-08-06 | 1980-03-20 | Bayer Ag, 5090 Leverkusen | Process for the continuous production of trimethylolalkane allyl ethers |
| JPS60231625A (en) * | 1984-05-02 | 1985-11-18 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of allyl ether of trimethylolpropane |
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1996
- 1996-06-04 CN CN96115830A patent/CN1052970C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200413B (en) * | 2006-12-11 | 2010-08-25 | 珠海飞扬化工有限公司 | Method for preparing pentaerythrite allyl ether |
| CN102300838A (en) * | 2009-01-28 | 2011-12-28 | 迈图专业化学股份有限公司 | Process for the preparation of an ally alkyl ehter by catalytic allyation |
| CN102040486A (en) * | 2010-11-24 | 2011-05-04 | 山东省化工研究院 | Preparation method of trimethylolpropane diallyl ether |
| CN102040486B (en) * | 2010-11-24 | 2013-03-13 | 山东省化工研究院 | Preparation method of trimethylolpropane diallyl ether |
| CN102153452A (en) * | 2011-02-21 | 2011-08-17 | 王海艳 | Synthesis method of trimethylolpropane allyl ether |
| CN103881080A (en) * | 2012-12-19 | 2014-06-25 | 辽宁奥克化学股份有限公司 | Alkenyl-terminated polyoxyethylene ether, preparation method and application thereof |
| CN103881080B (en) * | 2012-12-19 | 2015-10-21 | 辽宁奥克化学股份有限公司 | A kind of end thiazolinyl Soxylat A 25-7 and its preparation method and application |
| CN105399610A (en) * | 2015-12-15 | 2016-03-16 | 安陆新景化工有限公司 | Technological method for preparation of allyl ether compounds |
| CN112479833A (en) * | 2020-12-11 | 2021-03-12 | 浙江皇马科技股份有限公司 | Preparation method of pentaerythritol triallyl ether |
| CN112479833B (en) * | 2020-12-11 | 2022-09-27 | 浙江皇马科技股份有限公司 | Preparation method of pentaerythritol triallyl ether |
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| CN1052970C (en) | 2000-05-31 |
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