阅读说明：本技术 一种植物油改性高分子聚醚消泡剂的制备方法 (Preparation method of vegetable oil modified high-molecular polyether defoaming agent ) 是由 肖龙强 凌坤华 侯琳熙 赵玉来 范阳海 吴建康 李玉珍 纪明智 于 2020-04-30 设计创作，主要内容包括：本发明公开了一种植物油改性高分子聚醚消泡剂的制备方法,以环氧植物油、脂肪醇、环氧乙烷和环氧丙烷为原料,在催化剂的作用下发生开环聚合反应,得到植物油改性高分子聚醚消泡剂；其中：催化剂路易斯酸碱对催化剂,由PR<Sub>3</Sub>和有机硼烷组成；本发明操作简单,且生产成本低,在常温下便可进行环氧化合物的开环聚合反应,完成聚醚类聚合物的制备,大大减少能源的损耗,对环境无害,安全环保。(The invention discloses a preparation method of a vegetable oil modified high polymer polyether defoaming agent, which takes epoxidized vegetable oil, fatty alcohol, ethylene oxide and propylene oxide as raw materials, and the raw materials undergo ring-opening polymerization reaction under the action of a catalyst to obtain the vegetable oil modified high polymer polyether defoaming agent; wherein: catalyst Lewis acid-base pair catalyst consisting of PR 3 And an organoborane; the preparation method is simple to operate and low in production cost, can perform ring-opening polymerization reaction of epoxy compounds at normal temperature to complete preparation of polyether polymers, greatly reduces energy consumption, and is harmless to the environment, safe and environment-friendly.)

1. A preparation method of a vegetable oil modified high polymer polyether defoaming agent is characterized by comprising the following steps: using epoxidized vegetable oil, fatty alcohol, ethylene oxide and propylene oxide as raw materials, and performing ring-opening polymerization reaction under the action of a catalyst to obtain a vegetable oil modified high-molecular polyether defoamer; wherein: catalyst Lewis acid-base pair catalyst consisting of PR₃And organoboranes in which R is dimethylamino, diethylamino, diphenylamino, or R is formed with the N atom to which it is attachedAnd the organoborane is triethylboron.

2. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 1, characterized by comprising the following steps:

(1) adding fatty alcohol and a catalyst into a reactor under the protection of nitrogen, adding epoxy vegetable oil, and carrying out ring-opening synthesis reaction at 10-30 ℃; after the reaction is finished, removing unreacted fatty alcohol to obtain a vegetable oil polyol initiator mixture with a catalyst;

(2) under the protection of nitrogen, sequentially adding 10-30 parts of propylene oxide and ethylene oxide into a reactor filled with the vegetable oil polyalcohol initiator mixture obtained in the step (1)^oC, carrying out ring-opening polymerization reaction, after the reaction is finished, adding acetic acid into the reaction solution, filtering out insoluble substances, and removing unreacted propylene oxide and ethylene oxide to obtain the vegetable oil modified high-molecular polyether defoamer.

3. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 2, characterized in that: the epoxidized vegetable oil is epoxidized soybean oil, epoxidized rapeseed oil or epoxidized castor oil.

4. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 2, characterized in that: in the step (1), the molar ratio of the sample change bond of the epoxy vegetable oil to the fatty alcohol is 1: (1-2).

5. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 2, characterized in that: the epoxy value of the epoxy vegetable oil is 4-9.

6. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 2, characterized in that: the fatty alcohol is a water-soluble alcohol.

7. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 6, characterized in that: the water-soluble alcohol is methanol, isopropanol, propanol, butanol, pentanol, hexanol, heptanol, ethylene glycol, propylene glycol, glycerol, butanediol.

8. The preparation method of the vegetable oil modified high molecular polyether defoaming agent according to claim 2, characterized in that: the PR₃The molar ratio of the organic borane to the fatty alcohol to the epoxidized vegetable oil to the propylene oxide to the ethylene oxide is as follows: 1: (1-5): (10-30): (10-100): (200-800): (100-300).

Technical Field

The invention belongs to the technical field of preparation of nonionic surfactants, and particularly relates to a method for preparing a vegetable oil modified high-molecular polyether defoaming agent by using a Lewis acid-base pair catalyst.

Background

The defoaming agent is an indispensable auxiliary agent in modern chemical industrial production, and is mainly used for eliminating harmful foams generated by surface active substances, stirring and other considered or non-considered factors in industrial production. In many industrial production processes, the existence of a large amount of foam often causes inconvenience in operation, reduction in equipment capacity and waste of raw materials, and even causes product quality problems and huge economic losses. Therefore, how to effectively control and restrain the foam in the production process has very important significance for improving the production efficiency and the product quality.

At present, defoaming agents are widely used in various fields such as sewage treatment, biological fermentation and the like, and the main product categories are non-silicon type, polyether type, organic silicon type and polyether modified organic silicon type. Wherein, the polyether type defoaming agent is a copolymer of ethylene oxide and propylene oxide, and the defoaming effect is achieved by mainly utilizing different characteristics of the solubility of the polyether type defoaming agent expressed at different temperatures. The polyether type defoaming agent has the advantages of strong foam inhibition capability, high temperature resistance and the like, and has the defects of certain toxicity, limited use condition by temperature, low foam breaking rate and narrow use field. If the amount of the foam generated is large, the foam cannot be quickly eliminated, and the defoaming effect can be shown only by adding the defoaming agent into the foam again.

Vegetable oil is a substance widely distributed in nature, is low in price and large in quantity, and has good biodegradability. Vegetable oil has certain defoaming capacity, but the long carbon chain of the vegetable oil structure makes the vegetable oil have poor hydrophilic performance and is difficult to effectively disperse in an aqueous solution. Patent CN 104606926B discloses siloxane modified vegetable oil high molecular polyether defoamer and a preparation method thereof, wherein catalysts used for preparing the defoamer are fluoboric acid and double metal cyanide complex catalysts. The two catalysts are harmful to the environment, the toxic gas is easily decomposed and released when the catalysts are heated to high temperature in the preparation process, and the catalysts can be immediately combusted when the catalysts are contacted with a foaming agent. Once the catalyst remains in the defoamer, it can have some effect on the defoaming process and the product. Therefore, developing a catalyst with high catalytic activity, environmental friendliness, energy conservation and high catalytic activity for preparing the vegetable oil modified polymer polyether defoamer is one of the technical problems to be solved urgently by the technical personnel in the field.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for preparing a degradable vegetable oil modified high-molecular polyether defoaming agent by using Lewis acid-base pair catalyst, which has the advantages of simple operation and low production cost, can perform ring-opening polymerization reaction of epoxy compounds at normal temperature to complete the preparation of polyether polymers, greatly reduces energy consumption, and is harmless to the environment, safe and environment-friendly.

The technical scheme provided by the invention is as follows:

a preparation method of a vegetable oil modified high polymer polyether defoamer takes epoxidized vegetable oil, fatty alcohol, ethylene oxide and propylene oxide as raw materials, and the vegetable oil modified high polymer polyether defoamer is obtained by ring-opening polymerization reaction under the action of a catalyst; wherein: catalyst Lewis acid-base pair catalyst consisting of PR₃And organoboranes in which R is dimethylamino, diethylamino, diphenylamino, or R is formed with the N atom to which it is attachedAnd the organoborane is triethylboron.

Preferably, PR₃A compound of any one of the following structures;

preferably, PR₃And organoborane in a molar ratio of 1: (1-5).

Preferably, the PR₃From phosphorus trichloride andamine compounds are obtained by reaction.

More preferably, the amine compound is dimethylamine, diethylamine, diphenylamine or。

Preferably, the preparation method of the vegetable oil modified high molecular polyether defoaming agent comprises the following steps:

(1) adding fatty alcohol and a catalyst into a reactor under the protection of nitrogen, adding epoxy vegetable oil, and carrying out ring-opening synthesis reaction at 10-30 ℃; after the reaction is finished, removing unreacted fatty alcohol to obtain a vegetable oil polyol initiator mixture with a catalyst;

(2) under the protection of nitrogen, sequentially adding propylene oxide and ethylene oxide into a reactor filled with the vegetable oil polyol initiator mixture obtained in the step (1), carrying out ring-opening polymerization reaction at 10-30 ℃, adding acetic acid into reaction liquid after the reaction is finished, filtering out insoluble substances, and removing unreacted propylene oxide and ethylene oxide to obtain the vegetable oil modified high-molecular polyether defoaming agent.

Preferably, the epoxidized vegetable oil is epoxidized soybean oil, epoxidized rapeseed oil or epoxidized castor oil.

Preferably, in the step (1), the molar ratio of the lofted bond of the epoxidized vegetable oil to the fatty alcohol is 1: (1-2).

Preferably, the epoxy value of the epoxy vegetable oil is 4-9.

Preferably, the fatty alcohol is a water-soluble alcohol.

More preferably, the water-soluble alcohol is methanol, isopropanol, propanol, butanol, pentanol, hexanol, heptanol, ethylene glycol, propylene glycol, glycerol, butylene glycol.

Preferably, the molar ratio of the PR3, the organoborane, the fatty alcohol, the epoxidized vegetable oil, the propylene oxide and the ethylene oxide is as follows: 1: (1-5): (10-30): (10-100): (200-800): (100-300).

Compared with the prior art, the invention has the following advantages:

(1) the vegetable oil modified high polymer polyether defoaming agent prepared by the invention takes vegetable oil alkyl chains as a main chain, polypropylene oxide and polyethylene oxide copolymer as side chains, and the polyether side chains are similar to the polyether defoaming agent, so that good spreading performance and emulsion stability can be provided, and the defoaming agent can be uniformly dispersed into various media. The vegetable oil alkyl chain on the main chain provides hydrophobic property, attracts the hydrophobic end of the surfactant, destroys the stability of foam and achieves the technical effect of effectively inhibiting foam and defoaming;

(2) the catalyst used in the invention is a hindered Lewis acid-base pair, the catalyst is a composite catalyst, Lewis acid and Lewis base can not form a stable addition product due to larger steric hindrance, and zwitterion is formed with a hydroxyl-bearing initiator at normal temperature to catalyze the ring-opening polymerization of ethylene oxide and propylene oxide. During reaction, under the conditions of medium alkalinity and normal temperature, the hydroxyl is activated by the large steric hindrance phosphine compound, the initiator is activated, and the complexation of the triethylborane and the hydroxyl activated by the basic group further reduces the whole alkalinity, so that the deprotonation effect of the epoxide does not exist, and no by-product is generated. Meanwhile, the boron in the triethylborane can promote the complexation of the initiator and form a complex activated monomer with epoxide, the catalyst has good stability and high catalytic capability, in addition, the catalyst has no toxicity, can not react with other substances to generate byproducts, has simple operation, wide vegetable oil sources and low production cost, can carry out the ring-opening polymerization reaction of epoxy compounds at normal temperature to complete the preparation of polyether polymers, and greatly reduces the energy loss; is harmless to the environment, safe and environment-friendly.

Drawings

FIG. 1 shows the reaction formulae of examples 1 to 3 and examples 5 to 6

FIG. 2 is a reaction scheme of example 4.

Detailed Description

The invention will now be further described with reference to specific examples.