CN1268667C - Esterifying method for polyether alcohol and alpha, beta-unsaturated carboxylic acid - Google Patents
Esterifying method for polyether alcohol and alpha, beta-unsaturated carboxylic acid Download PDFInfo
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- CN1268667C CN1268667C CN 200410054189 CN200410054189A CN1268667C CN 1268667 C CN1268667 C CN 1268667C CN 200410054189 CN200410054189 CN 200410054189 CN 200410054189 A CN200410054189 A CN 200410054189A CN 1268667 C CN1268667 C CN 1268667C
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Abstract
The present invention relates to the field of organic chemical reaction, and more specifically, the present invention provides an esterification method for polyether alcohol and alpha, beta-unsaturated carboxylic acid. The polyether alcohol ester of the alpha, beta-unsaturated carboxylic acid is mainly used as a monomer of a polymer. A polymer generated by the copolymerization of the polyether alcohol ester can be used as a dispersing agent, a scale remover, a corrosion inhibitor, etc., and the polymer is applied to the industries of dye, a building material, etc.; however, the existing esterification method for polyether alcohol and alpha, beta-unsaturated carboxylic acid often has a low yield and low purity. When the alpha, beta-unsaturated carboxylic acid and the polyether alcohol carry out esterification reaction, strong acid is used as a catalyst; meanwhile, water and the azeotropic organic solvent of the water are added, and water generated by the esterification reaction is eliminated. The catalyst is removed after the esterification reaction, and water is added to eliminate the azeotropic organic solvent in an azeotropic distillation mode. The method not only lowers reaction temperature, shortens reaction time, obviously lowers side reaction, and obviously reduces impurities, but also obviously enhances the quality and the yield of a product.
Description
Technical field
The present invention relates to the organic chemical reactions field, specifically, the invention provides a kind of Aethoxy Sklerol and α, the esterification process of beta-unsaturated carboxylic acid.
Background technology
α, beta-unsaturated carboxylic acid polyethers alcohol ester is mainly used in the monomer as polymkeric substance.The polymkeric substance that is produced by its copolymerization can be used as dispersion agent: as can be used as the agent of dye well dispersing of pigments, the dispersion agent of ink, carbon black and lime carbonate, the dispersion agent of gypsum and water slurry, cement dispersants, dispersion agent of weighting agent and thickening material or the like, it also can be used as scale remover, inhibiter or the like except that making dispersion agent.
Preparation α, the method of beta-unsaturated carboxylic acid alkyl alcohol ester is known, normally with α, beta-unsaturated carboxylic acid is with corresponding pure under appropriate reaction conditions, in liquid phase, finish under the catalysis of strong acid, two keys in the raw molecule and the two key polymerization reaction take places in the product molecule generally all add stopper when carrying out esterification, to stop the generation of polyreaction.
And synthetic α requires to carry out under such reaction conditions during beta-unsaturated carboxylic acid polyethers alcohol ester especially.In existing esterification techniques, there is the problem aspect two:
1, esterification is reacted under the condition of the excessive use of certain raw material often.Unreacted raw alcohol or acid generate the obvious decline that alkoxy ester and these side reactions of unsaturated acyl group oxygen base ester cause the esterification yield because the excessive use of certain aspect is carried out the Michael addition reaction with the two keys that form ester easily.
2, the esterification of carboxylic acid and alcohol is a balanced reaction, and this is well-known, sees formula (1),
Which kind of for the yield that obtains generally all uses the method for excessive alcohol or carboxylic acid, decide on raw material separate easily; Maybe the water that forms is removed,, allowed reaction move to the direction that generates ester with destruction of balance.Simultaneously, often use and water azeotropic organic solvent, still, residual in product also can pollute product organic solvent.
Summary of the invention
The invention provides a kind of Aethoxy Sklerol and α, the esterification process of beta-unsaturated carboxylic acid has obviously improved the productive rate and the purity of esterification.
In order to solve the problem that esterification gets productive rate and purity two aspects, we have carried out deep research work.We find α, when beta-unsaturated carboxylic acid and Aethoxy Sklerol esterification, use solid super-strong acid as catalyzer, add simultaneously and water azeotropic organic solvent, remove the water that esterification generates, and it is very effective to carry out esterification with this method.Its feature is that the superacid catalysis ability is strong, can be under lower temperature catalytic esterification, can finish esterification in the short period of time.Reduced temperature of reaction like this, shortened the reaction times, side reaction is obviously reduced, impurity obviously reduces.The yield of quality product and product also is significantly improved.In addition, we utilize azeotropic organic solvent and water azeotropic principle, and the azeotropic organic solvent can dewater, and water also can take off the azeotropic organic solvent conversely.Remove catalyzer after esterification finishes, add the entry component distillation again, be easy to remove and remain in azeotropic organic solvent in the product, avoided its pollution product.
So just overcome the big shortcoming of two in the existing esterification techniques, promptly need not a certain raw material of excessive use, as long as under the effect of solid super-strong acid, dehydration of organic solvent just can move towards the direction of generation ester; And temperature of reaction is low, and speed is fast, and side reaction is rare.Utilize dehydration of organic solvent earlier, water is taken off organic solvent again then, and method is simple and effective.
The esterification process of a kind of Aethoxy Sklerol and α, beta-unsaturated carboxylic acid is characterized in that, in the reaction mixture of Aethoxy Sklerol and α, beta-unsaturated carboxylic acid, makes catalyzer with strong acid, and temperature of reaction is 30-130 ℃; By distillation organic solvent and water are removed from reaction mixture with form of mixtures in the reaction process, by water-and-oil separator water is separated from mixture simultaneously and organic solvent is recirculated in the esterification technique, esterification is carried out fully; After esterification finishes, an acidic catalyst is removed, add entry and distill once more, organic solvent and the water form with mixture is steamed, the organic solvent in the reaction mixture is removed fully.
Aethoxy Sklerol of the present invention can be represented with following formula (2):
R
1O(R
2O)
nH …… (2)
Wherein, R
1Expression C
1-C
20Hydroxyl, R
2O represents C
2-C
12Oxyalkylene group.As-(CH
2CH
2O)
n-,-[CH (CH
3)-CH
2O]
n-,-[CH (CH
2CH
3)-CH
2O]
n-or the like, can be identical, also can be different, n represents the average addition mole number of olefin oxide, generally between 0～200.
α of the present invention, beta-unsaturated carboxylic acid can use formula (3) expression:
R
3-CH=C (R
4)-CO
2H ... (3) be not limited to concrete α, beta-unsaturated carboxylic acid, α, β-unsaturated monoprotic acid and α, β-unsaturated dibasic acid all is suitable for.
Wherein, R
3Expression H, alkyl and carboxyl.R
4Expression H, alkyl and carboxyl.
The α that the present invention uses, beta-unsaturated carboxylic acid can be a vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid etc.Vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, methylene-succinic acid or the like.
Among the present invention, for Aethoxy Sklerol and α, two kinds of raw materials of beta-unsaturated carboxylic acid, the mol ratio of lower boiling raw material and another kind of raw material add-on is 1: 1-10: 1.
From formula (1),
Material molar ratio used in the present invention can be 1: 1, carry out expeditiously in order to guarantee esterification, not restriction especially, the lower boiling raw material is excessive slightly to be desirable, use α, during β-unsaturated monoprotic acid, can excessively use as the vinylformic acid boiling point is low, can be with the vinylformic acid of 2～10moL to the 1moL Aethoxy Sklerol.Remove reaction back distillation easily.
Esterification of the present invention is to carry out in the presence of stopper.Stopper commonly used has quinhydrones, hydroquinone monomethyl ether, para benzoquinone, thiodiphenylamine, 4-hydroxyl-2,2,6,6-tetramethyl--1-oxygen base-piperidines and cupferron, cupric chloride (II) or the like.The present invention is not subjected to the restriction of specific stopper.Stopper may be used alone, can also be used in combination, and is not particularly limited.The usage quantity of stopper is determined on a case-by-case basis according to routine.
In the present invention, the temperature of reaction general requirement of esterification is being carried out below 130 ℃, is preferably in below 120 ℃ and carries out, and is preferably carrying out below 100 ℃; Require minimumly, be preferably in more than 60 ℃ more than 30 ℃.The too high easy generation side reaction of temperature of reaction, and the fracture of ehter bond takes place produces diester, and product impurity is increased, and yield descends, and other side reaction is more arranged, and product colour is deepened etc.On the contrary, low if reaction temperature is spent, speed of response is slow excessively, spend a large amount of reaction times, and is also uneconomical, is unfavorable for suitability for industrialized production.
Therefore, preferred temperature of reaction is 60-100 ℃ among the present invention.
Spendable strongly acidic catalyst has following several in the esterification: mineral acid, example hydrochloric acid, sulfuric acid, phosphoric acid etc.; Organic acid is as methylsulfonic acid, tosic acid, xylene monosulfonic acid, naphthene sulfonic acid, trifluoromethanesulfonic acid etc.; Reach solid acid such as heteropolyacid, solid super-strong acid, storng-acid cation exchange resin or the like.In these an acidic catalysts, consider temperature of dewatering agent and water azeotropic temperature and esterification or the like, require the boiling point of catalyst acid itself to want high, the catalytic esterification reaction temperature of institute is low.
Therefore, the present invention with solid super-strong acid as α, the first-selected catalyzer of beta-unsaturated carboxylic acid and Aethoxy Sklerol esterification.
Solid super acid catalyst is non-acid catalyst, and it has the characteristics of many preciousnesses, at first is the selectivity height to esterification, and side reaction is few, the quality product height that obtains, and yield is good.Next is the catalyzer separate easily, can reuse.And production unit is not had corrodibility, with catalyzer such as sulfuric acid relatively, the three wastes discharge amount much less.
Solid super acid catalyst has multiple, has adopted (ZrO in an embodiment of the present invention
2/ SO
4 2-).
Solid super-strong acid (ZrO
2/ SO
4 2-) prepare by following known method:
Take by weighing a certain amount of zirconium oxychloride, use the weak ammonia hydrolysis, generate the post precipitation of white, leave standstill, separate, wash no chlorion with water, soaked 24 hours with the sulfuric acid of 1N dry back, drain, and dry under infrared lamp, put into groom's stove then 575 ℃ of activation 3 hours, put cold, pulverize, it is stand-by to put into moisture eliminator.
Solid super acid catalyst (ZrO
2/ SO
4 2-) easy to prepare, catalytic esterification is active high, and etching apparatus has not overcome the shortcoming when using sulfuric acid to carry out esterification as catalyzer: shortcomings such as side reaction many (as oxidation dehydration of alcohols, etherificate and ether scission of links etc.), equipment corrosion are serious, raw materials consumption height.
The method of the esterification that the present invention carried out need with water azeotropic organic solvent in the presence of carry out, when not using when carrying out esterification with water azeotropic organic solvent, promptly do not having to carry out esterification under the situation of solvent, in reaction solution, want the bubbling air bubbling, to remove the water that esterification forms.Because raw material α, beta-unsaturated carboxylic acid and Aethoxy Sklerol are under solvent-free situation, directly heat by thermal source, this type of heating may cause the fracture of raw material Aethoxy Sklerol ehter bond, can produce polyether glycol, and then producing the polyether glycol diester, it can directly have influence on the various performances of its polymkeric substance, descends or the like as the dispersing property as dispersion agent.
The add-on of azeotropic organic solvent and water is determined on a case-by-case basis, as long as azeotropic water removing smoothly when reaching esterification is removed the water that adds behind the catalyzer and can azeotropic the purpose of organic solvent Ex-all be got final product.
The present invention is spendable to have benzene,toluene,xylene, hexanaphthene, dioxane, pentane, hexane, heptane, chlorobenzene and isopropyl ether or the like with water azeotropic organic solvent.These entrainers may be used alone, can also be used in combination.
Adopting cyclohexane give in one embodiment of the invention is the azeotropic organic solvent.Adopted benzene as the azeotropic organic solvent in another embodiment of the present invention.
Method of the present invention has not only reduced temperature of reaction, has shortened the reaction times, and side reaction is obviously reduced, and impurity obviously reduces, and the yield of quality product and product also is significantly improved.Use the raw material that method of the present invention prepares dispersion agent, scale remover and inhibiter etc. in the industries such as dyestuff, building materials, can reduce power consumption greatly, shorten the production cycle, improve the output and the purity of product,, improve profit for suitability for industrialized production reduces cost.
Embodiment
For the present invention is described in further detail, now enumerates following several example and specified the present invention; But the invention is not restricted to these examples.(%) that wherein mention all represents weight percent, temperature be degree centigrade (℃).
Embodiment 1:
Thermometer, agitator are being housed, are having in the reaction vessel of water-and-oil separator of condenser, with 165g methoxy poly (ethylene glycol) (n=10), 50g vinylformic acid, 2.5g ZrO
2/ SO
4 2-, 50mg thiodiphenylamine and 10.5g hexanaphthene are put into reactor, then the gained mixture is 110 ℃ in temperature of reaction and carries out esterification, in esterification, water and hexanaphthene azeotropic that esterification generates are steamed, and fall back in the water-and-oil separator through condensation, hexanaphthene and water stratification, the hexanaphthene on upper strata constantly flows back in the reactor, and water is constantly taken in so continuous circulation out of, in 12 hours, esterification yield reaches 87% greatly.Reaction is cold slightly after finishing, and filters out catalyzer.In reaction solution, add stopper quinhydrones 50mg then once more.Under heating and stirring, in reaction solution, constantly drip entry, owing to azeotropic constantly steams hexanaphthene and superfluous vinylformic acid, till having steamed.To regulate water and join in the residuum, thereby obtain aqueous 70% esterified prod solution.
Embodiment 2:
Thermometer being housed, stirring and take into account in the reactor of the water-and-oil separator that has condenser, add 128.5g methoxy poly (ethylene glycol) (n=30), 34.5g vinylformic acid, 6.5g ZrO
2/ SO
4 2-, 20mg thiodiphenylamine and 14g hexanaphthene.Then the gained mixture is carried out esterification under 100 ℃, in esterification, water and hexanaphthene azeotropic that esterification generates are constantly steamed, constantly be cooled again, fall back in the water-and-oil separator, hexanaphthene and water stratification, hexanaphthene constantly flow back in the reactor, after about 15 hours, detect esterification yield and reach 88%.Reaction is cold slightly after finishing, and filters out catalyzer.In reaction solution, add stopper quinhydrones 20mg then once more.Under heating and stirring, in reaction solution, constantly drip entry, owing to azeotropic constantly steams hexanaphthene and superfluous vinylformic acid, till having steamed.To regulate water and join in the residuum, obtain the aqueous 70% esterified prod aqueous solution.
Embodiment 3:
Other are all identical with example 2, just replace the 14g hexanaphthene with 20g benzene, react after 20 hours, and aftertreatment obtains the aqueous 70% esterified prod aqueous solution with example 2.
Embodiment 4:
Thermometer being housed, stirring and take into account in the reactor of the water-and-oil separator that has reflux exchanger, add 265g methoxy poly (ethylene glycol) (n=50), 80g methacrylic acid, 5g solid super-strong acid ZrO
2/ SO
4 2-, 50mg thiodiphenylamine and 16g hexanaphthene.With the heating when stirring of gained mixture, under 90 ℃, carry out esterification then, in esterification, water and hexanaphthene azeotropic that esterification generates are constantly steamed, fall back in the water-and-oil separator through condensation, layering, flow of cyclohexane is got back in the reactor, approximately, detect esterification yield and reach 98% through after 17 hours.Through the solids removed by filtration super acids, in reaction solution, add the 20mg quinhydrones, then heating, answer water and hexanaphthene azeotropic principle in reaction solution, to add entry, hexanaphthene is all steamed, add and regulate water in residuum, obtain the aqueous 70% esterified prod aqueous solution.
Embodiment 5:
Other are all identical with example 4, just catalyzer 6g solid super-strong acid ZrO
2/ SO
4 2-, 338g methoxy poly (ethylene glycol) (n=70) reacted after 25 hours, obtained the aqueous 70% esterified prod aqueous solution.
Embodiment 6:
Thermometer being housed, stirring and take into account in the reactor of the water-and-oil separator that has reflux condensing tube, add 285g methoxy poly (ethylene glycol) (n=5), 68g toxilic acid, 5g solid super-strong acid ZrO
2/ SO
4 2-, 50mg thiodiphenylamine and 15g hexanaphthene.Be heated to 90 ℃ when then the gained mixture being stirred and carry out esterification, constantly take water out of, approximately through after 25 hours, through detecting, esterification yield has reached 97%, the filtration catalizer solid super-strong acid adds the 15mg quinhydrones, heating in reaction solution, with the method that adds entry, hexanaphthene is all taken out of, regulated the water yield of residuum, obtain the aqueous 70% esterified prod aqueous solution.
Claims (6)
1. the esterification process of Aethoxy Sklerol and α, beta-unsaturated carboxylic acid is characterized in that, in the reaction mixture of Aethoxy Sklerol and α, beta-unsaturated carboxylic acid, makes catalyzer with strong acid, and temperature of reaction is 30-130 ℃; By distillation organic solvent and water are removed from reaction mixture with form of mixtures in the reaction process, by water-and-oil separator water is separated from mixture simultaneously and organic solvent is recirculated in the esterification technique, esterification is carried out fully; After esterification finishes, an acidic catalyst is removed, add entry and distill once more, organic solvent and the water form with mixture is steamed, the organic solvent in the reaction mixture is removed fully.
2. the method for claim 1 is characterized in that the α that uses, and beta-unsaturated carboxylic acid is a vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, fumaric acid, a kind of in the methylene-succinic acid.
3. the method for claim 1 is characterized in that temperature of reaction is 60-100 ℃.
4. the method for claim 1 is characterized in that used strongly acidic catalyst is solid super-strong acid ZrO
2/ SO
4 2-
5. the method for claim 1 is characterized in that used azeotropic organic solvent is one or more in benzene,toluene,xylene, hexanaphthene, dioxane, pentane, hexane, heptane, chlorobenzene and the isopropyl ether.
6. method as claimed in claim 5 is characterized in that used azeotropic organic solvent is benzene or hexanaphthene.
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|---|---|---|---|
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| CN103450376B (en) * | 2013-08-29 | 2016-01-20 | 江西麻山化工有限公司 | A kind of for the synthesis of the distil process in production of resins process |
| CN105061752A (en) * | 2015-08-14 | 2015-11-18 | 中国科学院上海高等研究院 | Method for preparing capped polyether through one-step esterification reaction catalyzed by solid acid |
| CN105885028B (en) * | 2016-06-17 | 2020-09-04 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| CN106631785A (en) * | 2016-12-07 | 2017-05-10 | 衢州学院 | Preparation method of perfluoroheptyl ethyl itaconate |
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