CN1613892A - 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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Abstract
An esterification method of polyether alcohol and alpha, beta-unsaturated carboxylic acid are disclosed. The product from the esterification of polyether alcohol and alpha, beta-unsaturated carboxylic acid can be used as the polymer monomer. The polymer from its copolymerization can be applied into many fields such as the die and building profession as the dispersant agent, detergent, inhibitor and so on. The process includes: taking the strong acid as the accelerating agent and depriving the water generating among the esterification reaction using the azeotropic organic solvent, removing the accelerating agent after the reaction, adding in the water and removing the organic solvent by azeotropic distillation. It features: reducing reaction temperature, shortening reaction time, decreasing the secondary reaction and the extraneous component, having a evident increasing of the quality and the yield of product.
Description
Technical Field
The invention relates to the field of organic chemical reactions, and particularly provides an esterification method of polyether alcohol and α -unsaturated carboxylic acid.
Background
α -unsaturated carboxylic acid polyether alcohol ester is mainly used as monomer of polymer, the polymer produced by copolymerization of it can be used as dispersant, such as dispersant of dye and pigment, dispersant of ink, carbon black and calcium carbonate, dispersant of gypsum and water slurry, cement dispersant, dispersant of weighting agent and thickener, etc., besides dispersant, it can also be used as scale remover, corrosion inhibitor, etc.
Methods for preparing α -unsaturated carboxylic acid alkyl alcohol esters are known, and α -unsaturated carboxylic acids and corresponding alcohols are usually reacted under appropriate reaction conditions and catalysis of strong acid in liquid phase, and in order to avoid polymerization of double bonds in the raw material molecules and double bonds in the product molecules, polymerization inhibitors are generally added during esterification to prevent polymerization.
The synthesis of α -unsaturated carboxylic acid polyether alcohol ester is required to be carried out under the reaction conditions, and the prior esterification technology has two problems:
1. the esterification reaction is often carried out under conditions where some raw material is used in excess. The unreacted starting alcohol or acid, when used in an excessive amount, is liable to undergo Michael addition reaction with the double bond of the already formed ester, and side reactions such as formation of an alkoxy ester and an unsaturated acyloxy ester result in a significant decrease in the yield of the esterification reaction.
2. The esterification of carboxylic acids with alcohols is an equilibrium reaction, which is well known and is described in formula (1),
processes which generally use an excess of alcohol or carboxylic acid in order to obtain good yields depend on which starting material is easily isolated; or the water formed is removed to break the equilibrium and allow the reaction to move in the direction of the ester formed. Meanwhile, an organic solvent azeotropic with water is often used, but the residue of the organic solvent in the product also causes pollution to the product.
Disclosure of Invention
The invention provides an esterification method of polyether alcohol and α -unsaturated carboxylic acid, which obviously improves the yield and purity of esterification reaction.
The method is characterized in that the super acid has strong catalytic capacity, can catalyze the esterification reaction at lower temperature, can complete the esterification reaction in shorter time, thus reducing the reaction temperature, shortening the reaction time, obviously reducing side reactions, obviously reducing impurities, and obviously improving the product quality and the product yield.
Thus, two defects in the prior esterification technology are overcome, namely, one raw material is not used excessively, and the organic solvent can move towards the direction of generating ester only by dehydration under the action of solid superacid; and the reaction temperature is low, the speed is high, and side reactions are seldom generated. The organic solvent is firstly used for dehydration, and then the water is used for removing the organic solvent, so that the method is simple, convenient and effective.
The invention provides a method for esterifying polyether alcohol and α -unsaturated carboxylic acid, which comprises the steps of using strong acid as a catalyst in a reaction mixture, controlling the reaction temperature to be 30-130 ℃, removing an organic solvent and water from the reaction mixture in a mixture form by distillation in the reaction process, simultaneously separating the water from the mixture by an oil-water separator, recycling the organic solvent into an esterification process to complete the esterification reaction, removing the acid catalyst after the esterification reaction is finished, adding water for redistillation, distilling the organic solvent and the water in a mixture form, and completely removing the organic solvent in the reaction mixture.
The polyether alcohols of the present invention can be represented by the following formula (2):
R1O(R2O)nH …… (2)
wherein R is1Is represented by C1-C20Hydroxy of (A), R2O represents C2-C12An oxyalkylene group of (a). Such as- (CH)2CH2O)n-，-[CH(CH3)-CH2O]n-，-[CH(CH2CH3)-CH2O]n-and so on,may be the same, may be different,nthe average molar number of addition of the alkylene oxide is usually 0 to 200.
The α -unsaturated carboxylic acid of the present invention can be represented by formula (3):
R3-CH＝C(R4)-CO2h … … (3) is not limited to the specific α -unsaturated carboxylic acid, but is applicable to both α -unsaturated monobasic and α -unsaturated dibasic acids.
Wherein R is3Represents H, a hydrocarbon group and a carboxyl group. R4Represents H, a hydrocarbon group and a carboxyl group.
The α -unsaturated carboxylic acid used in the present invention may be acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc. acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, etc.
In the present invention, the molar ratio of the low-boiling starting material to the other starting material is from 1: 1 to 10: 1 for both starting materials, polyether alcohol and α -unsaturated carboxylic acid.
In view of the formula (1),
the molar ratio of the raw materials used in the present invention may be 1: 1, and in order to ensure efficient esterification, there is no particular limitation, and it is preferable to use a small excess of the low-boiling raw materials, and in the case of using α -unsaturated monobasic acid, for example, an excess of acrylic acid with a low boiling point may be used, and 2 to 10moL of acrylic acid may be used for 1moL of polyether alcohol, and it is easy to remove by distillation after the reaction.
The esterification reaction of the present invention is carried out in the presence of a polymerization inhibitor. As the polymerization inhibitor, hydroquinone monomethyl ether, p-benzoquinone, phenothiazine, 4-hydroxy-2, 6-tetramethyl-1-oxy-piperidine and cupferron, copper (II) chloride and the like are generally used. The present invention is not limited by a specific polymerization inhibitor. The polymerization inhibitor may be used alone or in combination, and is not particularly limited. The amount of the polymerization inhibitor to be used is conventionally determined as the case may be.
In the present invention, the esterification reaction is carried out at a temperature of usually 130 ℃ or lower, preferably 120 ℃ or lower, more preferably 100 ℃ or lower; it is required to be at least 30 ℃ or higher, preferably at 60 ℃ or higher. When the reaction temperature is too high, side reactions are likely to occur, and the ether bond is cleaved to generate a diester, which increases product impurities, lowers the yield, causes other side reactions, darkens the product, and the like. On the contrary, if the reaction temperature is too low, the reaction rate is too slow, which takes a lot of reaction time, and is not economical, and thus it is not suitable for industrial production.
Therefore, the preferred reaction temperature in the present invention is 60 to 100 ℃.
The following strong acid catalysts can be used in the esterification reaction: inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and the like; strong organic acids such as methanesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, naphthalenesulfonic acid, trifluoromethanesulfonic acid and the like; and solid acids such as heteropolyacids, solid superacids, strongly acidic cation exchange resins and the like. Among these acidic catalysts, the catalyst acid itself is required to have a high boiling point and the esterification reaction to be catalyzed to have a low temperature in view of the temperature at which the dehydrating solvent is azeotroped with water, the esterification reaction temperature, and the like.
Therefore, the present invention uses solid superacid as the first catalyst for the esterification reaction of α -unsaturated carboxylic acid with polyether alcohol.
The solid super acidic catalyst is a non-acid catalyst, and has the valuable characteristics of high selectivity to esterification reaction, less side reaction, high product quality and high yield. Secondly, the catalyst is easy to separate and can be reused. And has no corrosiveness on production equipment, and the discharge amount of three wastes is much less compared with catalysts such as sulfuric acid and the like.
There are various solid superacid catalysts, and (ZrO) is used in the examples of the present invention2/SO4 2-)。
Solid superacid (ZrO)2/SO4 2-) The preparation is carried out by the known method as follows:
weighing a certain amount of zirconium oxychloride, hydrolyzing with dilute ammonia water to generate white precipitate, standing, separating, washing with water until no chloride ion is generated, drying, soaking with 1N sulfuric acid for 24 hours, draining, drying under an infrared lamp, then putting into a muffle furnace, activating at 575 ℃ for 3 hours, cooling, crushing, and putting into a dryer for later use.
Solid super acidic catalyst (ZrO)2/SO4 2-) The preparation is convenient, the catalytic esterification reaction has high activity, the equipment is not corroded, and the defects of the esterification reaction using sulfuric acid as a catalyst are overcome: many side reactions (such as dehydration, etherification, ether bond breaking and the like of the oxidized alcohol), serious corrosion of equipment, high consumption of raw materials and the like.
The esterification reaction method carried out by the invention needs to be carried out in the presence of an organic solvent which is azeotropic with water, when the esterification reaction is carried out without using the organic solvent which is azeotropic with water, namely, the esterification reaction is carried out in the absence of the solvent, air is blown into the reaction liquid for bubbling to remove water formed by the esterification reaction, because the raw material α -unsaturated carboxylic acid and polyether alcohol are directly heated by a heat source under the condition of no solvent, the heating mode can cause the rupture of ether bonds of the raw material polyether alcohol, polyether glycol can be generated, and polyether glycol diester can be generated, and the polyether glycol diester can directly influence various performances of the polymer, such as the reduction of the dispersing performance as a dispersing agent and the like.
The addition amount of the azeotropic organic solvent and water is determined according to specific conditions, and the aim of removing the organic solvent by azeotropic dehydration smoothly during the esterification reaction and removing the water by azeotropy after the catalyst is removed can be achieved.
As the organic solvent azeotropic with water, benzene, toluene, xylene, cyclohexane, dioxane, pentane, hexane, heptane, chlorobenzene, isopropyl ether and the like can be used. These azeotropic agents may be used alone or in combination.
Cyclohexane is employed as the azeotropic organic solvent in one embodiment of the present invention. In another embodiment of the present invention, benzene is used as the azeotropic organic solvent.
The method of the invention not only reduces the reaction temperature, shortens the reaction time, obviously reduces the side reaction and the impurities, but also obviously improves the product quality and the product yield. The method for preparing the raw materials of the dispersing agent, the scale remover, the corrosion inhibitor and the like in the industries of dye, building materials and the like can greatly reduce energy consumption, shorten the production period, improve the yield and the purity of products, reduce the cost for industrial production and improve the profit.
Detailed Description
To illustrate the present invention in more detail, the following examples are given to illustrate the present invention; the present invention is not limited to these examples. Where all references to (%) refer to weight percent, all temperatures are in degrees Celsius (. degree. C.).
Example 1:
in a reaction vessel equipped with a thermometer, a stirrer, and an oil-water separator with a condenser, 165g of methoxypolyethylene glycol (n-10), 50g of acrylic acid, and 2.5g of ZrO2/SO4 2-50mg of phenothiazine and 10.5g of cyclohexane are put into a reactor, then the obtained mixture is subjected to esterification reaction at the reaction temperature of 110 ℃, water generated by esterification and the cyclohexane are azeotropically distilled out at the same time of the esterification reaction, the mixture is condensed and falls into an oil-water separator, the cyclohexane and water are separated into layers, the cyclohexane on the upper layer continuously flows back into the reactor, and the circulation is continuously carried out, so that water is continuously taken, and the esterification rate reaches 87 percent in about 12 hours. After the reaction was complete, the catalyst was filtered off, slightly cooled. Then, 50mg of hydroquinone as a polymerization inhibitor was added again to the reaction solution. Under heating and stirring, water is continuously added dropwise to the reaction solution, cyclohexane and excessive acrylic acid are continuously distilled off due to azeotropy,until the steam is finished. Adjusting water was added to the residue to obtain an aqueous 70% esterified product solution.
Example 2:
128.5g of methoxypolyethylene glycol (n: 30), 34.5g of acrylic acid and 6.5g of ZrO 2 were placed in a reactor equipped with a thermometer, a stirrer and an oil-water separator with a condenser2/SO4 2-20mg of phenothiazine and 14g of cyclohexane. Then the mixture is esterified at 100 deg.C, while the esterification reaction, the water produced by esterification and cyclohexane are distilled out by azeotropy, cooled and dropped back into oil-water separator, the cyclohexane and water are separated, the cyclohexane flows back into the reactor continuously, afterabout 15 hours, the esterification rate is up to 88%. After the reaction was complete, the catalyst was filtered off, slightly cooled. Then, 20mg of hydroquinone as a polymerization inhibitor was added again to the reaction solution. While heating and stirring, water was continuously added dropwise to the reaction solution, and cyclohexane and excess acrylic acid were continuously distilled off by azeotropy until completion of distillation. Adjusting water was added to the residue to give an aqueous 70% esterified product solution.
Example 3:
otherwise the same as in example 2, except that 14g of cyclohexane was replaced with 20g of benzene, and after 20 hours of reaction, the same procedure as in example 2 was followed to obtain an aqueous 70% esterified product solution.
Example 4:
265g of methoxypolyethylene glycol (n-50), 80g of methacrylic acid and 5g of solid superacid ZrO were placed in a reactor equipped with a thermometer, a stirrer and an oil-water separator with reflux condenser2/SO4 2-50mg of phenothiazine and 16g of cyclohexane. Heating the obtained mixture while stirring, then carrying out esterification reaction at 90 ℃, distilling off water generated by esterification and cyclohexane in an azeotropic manner while carrying out the esterification reaction, condensing and falling into an oil-water separator, layering, flowing cyclohexane back into the reactor, and detecting that the esterification rate reaches 98% after about 17 hours. Filtering to remove solid superacid, adding 20mg hydroquinone into the reaction solution, heating, and mixing with water and ringHexane azeotropic principle Water was added to the reaction solution, cyclohexane was distilled off completely, and adjusting water was added to the residue to obtain an aqueous 70% esterified product solution.
Example 5:
the rest was the same as in example 4 except that 6g of solid, superacid ZrO was used as the catalyst2/SO4 2-338g of methoxypolyethylene glycol (n-70) were reacted for 25 hours to give an aqueous 70% esterified product solution.
Example 6:
285g of methoxypolyethylene glycol (n-5), 68g of maleic acid and 5g of solid, super-strong acid ZrO were placed in a reactor equipped with a thermometer, a stirrer and an oil-water separator with a reflux condenser2/SO4 2-50mg of phenothiazine and 15g of cyclohexane. And then heating the obtained mixture to 90 ℃ while stirring for esterification reaction, continuously taking out water, detecting that the esterification rate reaches 97% after about 25 hours, filtering out solid superacid serving as a catalyst, adding 15mg of hydroquinone into the reaction solution, heating, completely taking out cyclohexane by a method of adding water, and adjusting the water amount of the residue to obtain a water solution containing 70% of an esterified product.
Claims (6)
1. A process for esterifying polyether alcohol with α -unsaturated carboxylic acid features that in the reaction mixture, strong acid is used as catalyst, the reaction temp is 30-130 deg.C, the organic solvent and water are removed from the reaction mixture by distillation while the water is separated from the mixture by oil-water separator and the organic solvent is circulated back to the esterifying process for complete esterifying reaction, and after the esterifying reaction is finished, the acidic catalyst is removed, water is added for distillation again, the organic solvent and water are evaporated out in the form of mixture for complete removing of organic solvent.
2. The method of claim 1, wherein the α -unsaturated carboxylic acid is one of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid.
3. The process of claim 1, wherein the reaction temperature is from 60 to 100 ℃.
4. The process as claimed in claim 1, wherein the strongly acidic catalyst used is solid superacid ZrO2/SO4 2-。
5. The method as claimed in claim 1, wherein the azeotropic organic solvent is one or more selected from benzene, toluene, xylene, cyclohexane, dioxane, pentane, hexane, heptane, chlorobenzene and isopropyl ether.
6. A process according to claim 5, wherein the azeotropic organic solvent used is benzene or cyclohexane.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450376A (en) * | 2013-08-29 | 2013-12-18 | 江西麻山化工有限公司 | Distillation process for synthetic resin production 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 |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 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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2004
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103450376A (en) * | 2013-08-29 | 2013-12-18 | 江西麻山化工有限公司 | Distillation process for synthetic resin production process |
| 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 |
| CN105885028A (en) * | 2016-06-17 | 2016-08-24 | 华东理工大学 | Polyether alcohol ester compound and application thereof |
| 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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