CN102050943A - Compounding method for glycidyl ether polyether - Google Patents
Compounding method for glycidyl ether polyether Download PDFInfo
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- CN102050943A CN102050943A CN2010105498513A CN201010549851A CN102050943A CN 102050943 A CN102050943 A CN 102050943A CN 2010105498513 A CN2010105498513 A CN 2010105498513A CN 201010549851 A CN201010549851 A CN 201010549851A CN 102050943 A CN102050943 A CN 102050943A
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- polyethers
- polyether
- glycidyl ether
- epoxy chloropropane
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Abstract
The invention discloses a compounding method for glycidyl ether polyether. In the method, polyether and epoxy chloropropane, of which the molar ratio is 1 : 1.10 to 2.0, are taken as raw materials, and are treated through the following steps: A) alkali is added into the polyether, the alkali and the polyether react under the condition with temperature from 70 to 120 DEG C and pressure from -0.09 to -0.1 MPa, an intermediate product A is obtained after 1 to 3 hours of the reaction, the molar ratio of the hydroxy of the polyether and the alkali is 1 : 1.05 to 1.9; B) the epoxy chloropropane is dripped into the intermediate product A, the epoxy chloropropane and the intermediate product A react under the temperature condition from 30 to 80 DEG C, and an intermediate product B is obtained after 3 to 6 hours of the reaction; and C) the product is refined through the following steps: first, distilling the intermediate product B, removing excess epoxy chloropropane, and then filtering to obtain the glycidyl ether polyether product. The compounding method has the characteristics of no water, less side reactions, high reaction efficiency, high yield, and the like in a reaction system.
Description
Technical field
The present invention relates to a kind of synthetic method of glycidyl ether polyethers.Belong to polyether-modified technical field.
Background technology
The glycidyl ether polyethers has following general formula:
Wherein: 0＜m+n＜200; R is C
1～C
20The carbochain group; 0＜x＜10.
Contain epoxide group in the glycidyl ether pfpe molecule, good reactivity is arranged, contain polyether segment in the molecule and make it have low viscosity, characteristics such as flexible good.Being mainly used in epoxy resin diluent, muriate stablizer, fabric finishing agent and modified silicon oil etc., is the important intermediate of synthetic various tensio-active agents, important polymerization single polymerization monomer and organic synthesis intermediate.
At present, the method for synthesizing glycidol ether base product mainly contains single stage method and two step method both at home and abroad, and it is more to be applied to synthesizing allyl alcohol, butanols glycidyl ether etc., is applied to prepare the glycidyl ether polyethers seldom.
Single stage method is a raw material with pure and mild epoxy chloropropane, under the effect of NaOH or KOH, by the addition elimination reaction, directly obtains corresponding glycidyl ether.This reaction equation is as follows:
Wherein: R can be CH
2=CHCH
2-, C
4H
9-etc.;
Because single stage method has water to generate in building-up process, therefore the hydrolysis reaction of epoxy chloropropane very easily takes place, and the ring-opening polymerization side reaction easily takes place in epoxy chloropropane under alkaline condition, cause that by product is more in the product, yield is lower.In order to improve the yield of product, need to strengthen the epoxy chloropropane consumption, certainly will cause raw materials cost to increase, simultaneously environment is also impacted.
Two step method is a catalyzer with Lewis acid such as boron trifluoride or strong acid, solid acid, and the first step makes pure and mild epoxy chloropropane carry out opening earlier, generates intermediate chloropharin ether; Second step closed loop under the effect of NaOH or KOH generates corresponding glycidyl ether.This reaction equation is as follows:
Wherein: R can be CH
2=CHCH
2-, C
4H
9-etc.;
Ring-opening reaction is the key of two step method reaction, but its selectivity is relatively poor, proceeds the addition reaction of epoxy chloropropane easily on intermediate chloropharin ether, form polymkeric substance, cause by product to increase, cause the oxirane value of final product on the low side and chloride content is higher, product yield is lower.
Generally all based on synthetic short chain class glycidyl ether, announced the method for synthesis of allyl glycidyl ether under the sodium hydroxide effect as Japanese Patent Jpn.Kokai Tokkyo Koho 07133269 in more existing patent documentations with vinyl carbinol and epoxy chloropropane; Chinese patent CN1927851 has announced that with vinyl carbinol and epoxy chloropropane be raw material, synthesis of allyl glycidyl ether under the catalysis open loop sodium hydroxide ring closure of acid; Chinese patent CN1927852 has announced that with butanols and epoxy chloropropane be raw material, synthetic butylglycidyl ether under the catalysis open loop sodium hydroxide ring closure of acid.
The synthetic method of existing Racemic glycidol ether product exists problems such as by products such as above-mentioned epoxide group hydrolysis of mentioning and open loop addition are more, yield is lower, and does not have in the patent of being reported about synthesizing the method for the glycidyl ether polyethers that contains polyether segment.The difficult point of synthesizing glycidol ether base polyethers is: 1. the pfpe molecule amount is bigger usually, and reactive behavior is low, is difficult for generating the glycidyl ether polyethers with epoxy chloropropane; 2. be that its reactive behavior of polyethers of secondary hydroxyl is lower for molecule chain end.Therefore, the synthetic method of existing glycidyl ether is not suitable for the synthetic glycidyl ether polyethers that contains certain polyether segment.
Summary of the invention
At the problems referred to above, the object of the present invention is to provide in a kind of reaction system and do not had moisture, side reaction is few, the preparation method of reaction efficiency height, glycidyl ether polyethers that yield is high, the end that particularly solves high molecular weight polyether and PO ending is the problem that the polyethers of secondary hydroxyl is difficult to synthesizing glycidol ether base polyethers.
For achieving the above object, the present invention has adopted following technical scheme: a kind of synthetic method of glycidyl ether polyethers, and it is 1 with mol ratio: the polyethers of 1.10-2.0 and epoxy chloropropane are raw material, are undertaken by following processing step:
A) in described polyethers, add alkali, 70～120 ℃ temperature ,-0.09～-react under the pressure condition of 0.1Mpa, react and obtain intermediate A after 1～3 hour; Contain polyethers sodium or polyethers potassium among the described intermediate A; The hydroxyl of described polyethers and the mol ratio of alkali are 1: 1.05～1.9;
B) in intermediate A, drip epoxy chloropropane, under 30～80 ℃ temperature condition, reacted 3～6 hours, obtain intermediate B; Contain glycidyl ether polyethers, excessive epoxy chloropropane among the described intermediate B;
C) product is refining: at first distill intermediate B, remove excessive epoxy chloropropane; Obtain the glycidyl ether polyether product then after filtering.
Described alkali is any one or more than one mixture in solid sodium methylate, solid methanol potassium, methanol solution of sodium methylate, the potassium methylate methanol solution.Described polyethers is allyl alcohol polyethenoxy ether or polyoxyethylene glycol or glycerine atactic polyether or tetramethylolmethane atactic polyether or allyl alcohol random polyether or vinyl carbinol block polyether.
The present invention has following substantial characteristics:
1. adopt a kind of novel reaction principle, at first make polyethers and alkali generate polyethers sodium (potassium), again with epichlorohydrin reaction synthesizing glycidol ether base polyethers; Do not have moisture in the reaction system, side reaction is few, reaction efficiency height, yield height.
2. alkali is selected from a kind of or its mixture in solid sodium methylate, solid methanol potassium, methanol solution of sodium methylate, the potassium methylate methanol solution, can significantly improve the transformation efficiency of polyethers sodium (potassium), has reduced reacting material ratio, has improved reaction efficiency and yield.Experiment shows, can improve yield more than 10% but adopt method prior art of the present invention to compare.
3. synthetic method almost is applicable to all polyethers, and the end that has particularly solved high molecular weight polyether and PO ending is the problem that the polyethers of secondary hydroxyl is difficult to synthesizing glycidol ether base polyethers.
Embodiment
Reaction efficiency is defined as among the embodiment of the present invention:
Wherein oxirane value is the quality of the oxygen on the epoxide group in the 100 gram samples.
The raw material polyethers that the synthetic method of glycidyl ether polyethers of the present invention is selected for use is that Huangma Chemical Group Co., Zhejiang produces, and all the other raw materials are commercially available.Described polyethers has following general formula (I):
The glycidyl ether polyethers for preparing has following general formula (II):
0＜m+n＜200 wherein; R is C
1～C
20The carbochain group; 0＜x＜10
The processing step that adopts:
1. adding alkali in the polyethers of above-mentioned formula (I) reacts, alkali is taken from a kind of or its mixture in solid sodium methylate, solid methanol potassium, methanol solution of sodium methylate, the potassium methylate methanol solution, in the reaction process under vacuum condition (reaction pressure-0.09～-0.1Mpa.) separating methanol, make raw material (I) generate intermediate A.The mixture that contains polyethers sodium or polyethers potassium or polyethers sodium and polyethers potassium among the described intermediate A; The hydroxyl of polyethers and the mol ratio of alkali are 1: 1.05～1.9, and temperature of reaction is 70～120 ℃, 1～3 hour reaction times.
2. drip epoxy chloropropane and continue reaction, 30～80 ℃ of temperature, 3～6 hours time; The hydroxyl of raw material (I) polyethers and the mol ratio of epoxy chloropropane are 1: 1.10～2.0, generate intermediate B, contain glycidyl ether polyethers, excessive epoxy chloropropane and by product among the described intermediate B; The mixture that contains sodium-chlor or Repone K or sodium-chlor and Repone K in the described by product.
3. product is refining: at first excessive epoxy chloropropane is removed in distillation, and thick then product obtains purified product after filtering.
Reaction equation (used alkali is example with the sodium methylate) as follows:
Present invention is described to divide different embodiment below
Embodiment 1
(R is CH to add allyl alcohol polyethenoxy ether in 2L glass polymeric kettle
2=CHCH
2-, x=1, mx=8, nx=0, molecular weight 410) 1000 grams, solid sodium methylate 138 gram, heat to 70～80 ℃, pressure-0.09～-0.1Mpa under, take off the methyl alcohol that generates in the reaction, reacted 2 hours.Be cooled to 30～40 ℃, slowly drip 248 gram epoxy chloropropane, dropwise reaction 3 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether allyl alcohol polyethenoxy ether product of the present invention behind the solids removed by filtration impurity.
Embodiment 2
(R is-CH to add polyoxyethylene glycol in the 2L reactor
2CH
2-, x=2, mx=20, nx=0, molecular weight 942) 1000 grams, solid methanol potassium 62 gram.Be warming up to 80～90 ℃, pressure-0.09～-0.1Mpa, take off the methyl alcohol that generates in the reaction, reacted 2 hours.Be cooled to 40～50 ℃, slowly drip 113 gram epoxy chloropropane, dropwise reaction 3 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether polyoxyethylene glycol product behind the solids removed by filtration impurity.
Embodiment 3
(R is-CH to add the glycerine atactic polyether in 2L glass polymeric kettle
2-CH-CH
2-, x=3, mx=20, nx=20, molecular weight 2132) 1000 grams, solid methanol potassium and solid sodium methylate mixture 39.8 restrain.Be warming up to 90～100 ℃, pressure-0.09～-0.1Mpa, take off the methyl alcohol that generates in the reaction, reacted 1 hour.Be cooled to 50～60 ℃, slowly Dropwise 54 gram epoxy chloropropane dropwise reaction 4 hours.Slough the unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether base glycerol atactic polyether product behind the solids removed by filtration impurity.
Embodiment 4
(R is C (CH to add the tetramethylolmethane atactic polyether in 2L glass polymeric kettle
2-)
4, x=4, mx=20, nx=20, molecular weight 2176) and 1000 grams, methanol solution of sodium methylate (contain solid sodium methylate 31 gram).Be warming up to 90～100 ℃, pressure-0.09～-0.1Mpa, take off the methyl alcohol that generates in the reaction, reacted 1 hour.Be cooled to 50～60 ℃, slowly Dropwise 55 gram epoxy chloropropane dropwise reaction 4 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether tetramethylolmethane atactic polyether product behind the solids removed by filtration impurity.
Embodiment 5
(R is CH to add allyl alcohol random polyether in 2L glass polymeric kettle
2=CHCH
2-, x=1, mx=60, nx=50, molecular weight 5598) 1000 grams, potassium methylate methanol solution (contain solid methanol potassium 14.4 gram).Be warming up to 100～110 ℃, pressure-0.09～-0.1Mpa, take off the methyl alcohol that generates in the reaction, reacted 3 hours.Be cooled to 60～70 ℃, slowly drip 26.4 gram epoxy chloropropane, dropwise reaction 5 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether allyl alcohol random polyether product behind the solids removed by filtration impurity.
Embodiment 6
(R is CH to add the vinyl carbinol block polyether in 2L glass polymeric kettle
2=CHCH
2-, x=1, mx=60, nx=50, molecular weight 5598, terminal P0 ending) 1000 grams, solid sodium methylate 18.3 grams.Be warming up to 110～120 ℃, pressure-0.09～-0.1Mpa, take off the methyl alcohol that generates in the reaction, reacted 3 hours.Be cooled to 70～80 ℃, slowly drip 33 gram epoxy chloropropane, dropwise reaction 6 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether vinyl carbinol block polyether product behind the solids removed by filtration impurity.
Comparative example 1
(R is CH to add the vinyl carbinol block polyether in the 2L reactor
2=CHCH
2-, x=1, mx=60, nx=50, molecular weight 5598, terminal PO ending) 1000 grams, solid potassium hydroxide 14 grams, stir, temperature rises to 60～70 ℃, slowly drips 25 gram epoxy chloropropane, dropwises reaction 5 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether vinyl carbinol block polyether product behind the solids removed by filtration impurity.
Comparative example 2
(R is CH to add the vinyl carbinol block polyether in the 2L reactor
2=CHCH
2-, x=1, mx=60, nx=50, molecular weight 5598, terminal PO ending) 1000 grams, epoxy chloropropane 25 grams, BF
33 grams, stirring are warming up to 60～70 ℃, react 4 hours.Under 60～70 ℃ temperature, add 40% potassium hydroxide solution, 35 grams again, reacted 5 hours.Slough unreacted epoxy chloropropane by underpressure distillation, obtain glycidyl ether vinyl carbinol block polyether product behind the solids removed by filtration impurity.
Processing parameter and reaction result main in the various embodiments described above and the comparative example are summarized in following table.
Can obtain conclusion thus: adopt present method can prepare reaction efficiency, the higher glycidyl ether polyether product of yield; Be the polyethers of secondary hydroxyl for high molecular weight polyether and end particularly, present method obviously is better than the method for existing document, patent report.
Claims (3)
1. the synthetic method of a glycidyl ether polyethers, it is 1 with mol ratio: the polyethers of 1.10-2.0 and epoxy chloropropane are raw material, it is characterized in that being undertaken by following processing step:
A) in described polyethers, add alkali, 70～120 ℃ temperature ,-0.09～-react under the pressure condition of 0.1Mpa, react and obtain intermediate A after 1～3 hour; Contain polyethers sodium or polyethers potassium among the described intermediate A; The hydroxyl of described polyethers and the mol ratio of alkali are 1: 1.05～1.9;
B) in intermediate A, drip epoxy chloropropane, under 30～80 ℃ temperature condition, reacted 3～6 hours, obtain intermediate B; Contain glycidyl ether polyethers, excessive epoxy chloropropane among the described intermediate B;
C) product is refining: at first distill intermediate B, remove excessive epoxy chloropropane; Obtain the glycidyl ether polyether product then after filtering.
2. the synthetic method of glycidyl ether polyethers according to claim 1 is characterized in that described alkali is any one or more than one mixture in solid sodium methylate, solid methanol potassium, methanol solution of sodium methylate, the potassium methylate methanol solution.
3. the synthetic method of glycidyl ether polyethers according to claim 1 and 2 is characterized in that described polyethers is allyl alcohol polyethenoxy ether or polyoxyethylene glycol or glycerine atactic polyether or tetramethylolmethane atactic polyether or allyl alcohol random polyether or vinyl carbinol block polyether.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105330836A (en) * | 2015-12-10 | 2016-02-17 | 浙江皇马科技股份有限公司 | Method for compounding epoxy-terminated allyl alcohol polyoxyethylene ethers |
| CN107936242A (en) * | 2017-12-01 | 2018-04-20 | 辽宁科隆精细化工股份有限公司 | A kind of epoxy terminated allyl alcohol polyethenoxy propylene ether and preparation method thereof |
| CN110128627A (en) * | 2019-04-29 | 2019-08-16 | 中国航空工业集团公司金城南京机电液压工程研究中心 | A kind of synthetic method of polyether epoxy |
| CN113416593A (en) * | 2021-06-18 | 2021-09-21 | 安徽博洋润滑科技有限公司 | Long-life extreme pressure antiwear hydraulic oil and preparation method thereof |
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| US6583185B2 (en) * | 1997-06-10 | 2003-06-24 | Cognis Corporation | Defoamers for aqueous systems |
| CN101448873A (en) * | 2006-05-19 | 2009-06-03 | 陶氏康宁东丽株式会社 | Polyether and method for producing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105330836A (en) * | 2015-12-10 | 2016-02-17 | 浙江皇马科技股份有限公司 | Method for compounding epoxy-terminated allyl alcohol polyoxyethylene ethers |
| CN105330836B (en) * | 2015-12-10 | 2017-07-21 | 浙江皇马科技股份有限公司 | A kind of synthetic method of epoxy terminated allyl alcohol polyethenoxy ether |
| CN107936242A (en) * | 2017-12-01 | 2018-04-20 | 辽宁科隆精细化工股份有限公司 | A kind of epoxy terminated allyl alcohol polyethenoxy propylene ether and preparation method thereof |
| CN110128627A (en) * | 2019-04-29 | 2019-08-16 | 中国航空工业集团公司金城南京机电液压工程研究中心 | A kind of synthetic method of polyether epoxy |
| CN113416593A (en) * | 2021-06-18 | 2021-09-21 | 安徽博洋润滑科技有限公司 | Long-life extreme pressure antiwear hydraulic oil and preparation method thereof |
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Application publication date: 20110511 |