WO2020063900A1 - 一种一步法生产聚羧酸减水剂单体聚醚的合成工艺 - Google Patents
一种一步法生产聚羧酸减水剂单体聚醚的合成工艺 Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/22—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the initiator used in polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/50—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing nitrogen, e.g. polyetheramines or Jeffamines(r)
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
Definitions
- the invention belongs to the technical field of polyether synthesis, and particularly relates to a one-step synthesis process for producing a polycarboxylic acid water reducing agent monomer polyether.
- Polycarboxylic acid water reducing agent is a low-molecular comb polymer with amphiphilic properties. Usually, it is initiated by terminal alkenyl alkylene polyoxyethylene ether monomer with unsaturated double bond and small molecule monomer of unsaturated carboxylic acid. It is synthesized by copolymerization under the action of additives, so the monomer polyether is a vital basic raw material for the polycarboxylic acid water reducing agent industry.
- polycarboxylic acid superplasticizer monomer polyether mostly adopt the traditional batch production method, such as Xu Shirui, et al. (Xu Shirui, Zhao Xin, Hao Gang. Research on polycarboxylic acid superplasticizer monomer polyether reaction catalyst [J].
- the experimental steps for synthesizing polycarboxylic acid water reducing agent monomer polyether include: 1) pre-made catalyst, the catalyst and methacryl alcohol in the reaction kettle Mix well; 2) Preparation of intermediates, pass ethylene oxide into the reaction kettle to prepare intermediates; 3) Preparation of monomer polyether, continue to add catalyst to the reaction kettle, and remove the remaining ethylene oxide The whole is passed in, and the polycarboxylic acid water-reducing agent is obtained after decompression and ripening.
- This traditional batch production method cannot achieve one-step synthesis and continuous production.
- the technical problem to be solved by the present invention is to overcome the need to synthesize a prepolymer first and then gradually synthesize a macromonomer polyether in the prior art, and the production efficiency is low, the product quality is unstable, the monomer residue is high, and it cannot be continuous Production issues.
- the present invention provides a one-step synthetic process for producing a polycarboxylic acid superplasticizer monomer polyether, including the following steps:
- the initiator and the catalyst are mixed to form a first material
- the one-step synthetic process for producing a polycarboxylic acid superplasticizer monomer polyether includes the following steps:
- the second material is introduced into the reaction kettle C for aging and degassing to obtain a third material; the third material and the carboxylic acid are introduced into the reaction kettle D for neutralization reaction to obtain a monomer polyether product.
- the initiator is an unsaturated alcohol, an unsaturated alcohol ether or an unsaturated amine.
- the initiator is preferably: acryl alcohol, methacryl alcohol, isopentenyl alcohol, butenol, heptenyl alcohol, acryl alcohol glycol ether, methacryl glycol ether, and Hydroxybutyl vinyl ether, tetrahydroxybutyl methacryl alcohol, allylamine, diallylamine, methallylamine, ethylallylamine and their homologues, including homologues of their homologues Isomers.
- the epoxide is one or more of ethylene oxide, propylene oxide, and butylene oxide.
- the catalyst is one or more of an alkali metal, an alkali metal hydroxide, an alkali metal hydride, an alkaline earth metal hydroxide, an alkali metal alkoxide, an alkaline earth metal oxide, and an organic alkali catalyst. Species.
- the catalyst is preferably: the alkali metal is sodium, potassium; the alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide; the alkali metal hydride is: sodium hydride, potassium hydride;
- the hydroxides are magnesium hydroxide and calcium hydroxide;
- the alkali metal alkoxides are sodium methoxide, sodium ethoxide, potassium methoxide, potassium glycerol potassium oxide;
- the alkaline earth metal oxides are magnesium oxide and calcium oxide;
- the organic base catalyst is ethanolamine, Diethanolamine, triethanolamine, dimethylamine, trimethylamine, diethylamine, triethylamine.
- step 1) the first material is heated to 70 ° C to 100 ° C; preferably, it is heated to 80 ° C.
- step 1) the air in the reaction kettle is replaced by vacuum with high purity N 2 , and N 2 is continuously introduced to make the pressure of the reactor reach 0.2 to 0.5 MPa; preferably, the pressure of the reaction kettle is 0.3 MPa.
- step 2) the reaction temperature is 100 ° C. to 125 ° C., and the reaction pressure is 0 MPa ⁇ P ⁇ 0.4 MPa.
- step 2) the rate at which the first material is injected into the reactor is 30-150 kg / h.
- step 3 the curing and degassing temperature is 100 ⁇ 125 ° C, and the neutralization temperature is 70 ⁇ 100 ° C.
- step 3 the acid used for neutralization is glacial acetic acid.
- the molar ratio of the initiator and the epoxide is 1: 21 ⁇ 112; preferably 1: 50 ⁇ 71.
- the molar ratio of initiator and epoxide in the reaction system will affect the polymerization rate of the entire system, and affect the molecular weight, purity and performance of the product.
- the amount of the catalyst is from 0.02% to 0.08% of the total feeding amount, and preferably, the amount of the catalyst is 0.04%.
- the first material and the epoxide are mixed in the process of being injected into the reaction kettle, and the instant reaction is completed, and the one-step synthesis of the target product is achieved by controlling the ratio and rate of the reactant introduction. Separating the four steps of replacement, polymerization, aging, and neutralization in the traditional monomer polyether production process is conducive to the control of each link and can improve the utilization efficiency of the reaction kettle.
- the pressure of the reaction kettle A is set to positive pressure. One is to ensure the tightness of the reaction kettle; the other is to transfer the materials in the reaction kettle A to the reaction kettle B by pressure, and control the transfer rate.
- the reaction temperature directly affects the ring-opening polymerization speed of the epoxide, and also has a great impact on the product quality.
- the temperature of the reaction kettle B is controlled to 100 ⁇ 125 ° C and the pressure is controlled to 0 MPa ⁇ P ⁇ 0.4 MPa.
- the reaction can be stable and stable. Control, can achieve continuous production in a true sense.
- the amount of catalyst plays a vital role in the reaction process.
- Too much catalyst will cause the reaction to be too fast and the amount of heat to be released will require continuous cooling to control the reaction temperature. It will also cause an increase in by-products. Too little amount of catalyst will reduce the reaction rate, react the reactants incompletely, and increase the process time and cost.
- the amount of catalyst in the present invention is far less than the amount of catalyst in the prior art, which is determined by the process itself. Simultaneous introduction with the epoxide to achieve one-step synthesis, which greatly improves the catalyst utilization and catalytic efficiency.
- the present invention has the following advantages:
- the present invention provides a one-step method for synthesizing monomeric polyethers. First, a starting material and a catalyst are mixed in an oxygen-free environment to obtain a first material, and then the first material and an epoxide are simultaneously injected into a reaction kettle. The most important thing is that to achieve the mixing of the first material and the epoxide during the injection process, a co-current feeding method can be used, while injecting, the mixed reaction of the two is achieved in the co-current process.
- the initiator and the catalyst mixture and the epoxide are simultaneously introduced into the reaction kettle at a certain ratio, and the raw materials are simultaneously reacted during the mixing process, thereby realizing the one-step synthesis of the monomer polyether without first synthesizing the pre-polymerization.
- the macromonomer polyether is gradually synthesized in vivo, which improves the production efficiency, and the process is simple, the prepared product has stable structure and high double bond retention rate.
- the one-step method for synthesizing monomeric polyether according to the present invention can realize continuous production, and the mixture and the epoxide in the reaction kettle A are introduced in proportion in order to make them react simultaneously, and the purpose of continuous reaction can also be achieved.
- a certain amount of an initiator is first input, and then a part of the epoxide is reacted to form an intermediate.
- the epoxide is continued to be reacted, and the product cannot be directly synthesized.
- the present invention simultaneously introduces the initiator and The epoxide makes it react instantaneously, and can directly reach the required molecular weight without intermediates.
- the product is continuously produced and the index is more stable.
- the method for synthesizing monomer polyether according to the present invention can realize the controllable molecular weight of the monomer polyether; mainly, the initiator and the epoxide are simultaneously introduced into the B kettle, and the initiator is adjusted by And the feed rate of epoxide to control the molecular weight, and polyether with corresponding molecular weight can be synthesized directly in one kettle of B kettle, without using multiple kettles.
- the method for synthesizing monomer polyether in one step according to the present invention can realize the controllable adjustment of each step in the reaction; the four steps of substitution, polymerization, maturation, neutralization in the traditional monomer polyether production process can be separately controlled. It is carried out in four reactors A, B, C, and D, and the reactors in different steps are set up separately, which can more effectively control each link, and increase the utilization efficiency of the reactor, without causing too much equipment. Idle conditions, and the number of reactors equipped in each reactor can be different according to the cycle conditions in each reactor, to achieve the purpose of using the least number of kettles to achieve the maximum capacity.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 110-120 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 55 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00.
- Acryl alcohol polyoxyethylene ether Acryl alcohol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the product is white or milky white flake solid, the color of the original liquid is ⁇ 50 # Pt-Co; the water content is ⁇ 0.15%; the hydroxyl value is 22.4 ⁇ 24.4mgKOH / g; the PH value is 6.0 ⁇ 7.0; double The key retention rate is ⁇ 96.5%.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 105-110 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 55 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00. Pentenol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 105-110 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 55 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00. Pentenol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the product is a white solid, the color is ⁇ 50 # Pt-Co; the hydroxyl value is 55.7 ⁇ 57.7mgKOH / g; the PH value is 5.0 ⁇ 7.0, and the retention rate is ⁇ 96.5%.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 110-120 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 55 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00. Allyl alcohol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 110-120 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 92 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was reduced to 80 ° C when the pH was ⁇ 7.00.
- Acryl alcohol polyoxyethylene ether Acryl alcohol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the product is white or milky white flake solid, the color of the original liquid is ⁇ 50 # Pt-Co; the water content is ⁇ 0.15%; the hydroxyl value is 22.4 ⁇ 24.4mgKOH / g; the PH value is 6.0 ⁇ 7.0; double The key retention rate is ⁇ 96.5%.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 110-120 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then passed through 48 kg of glacial acetic acid to conduct a neutralization reaction.
- the reaction time was 30 minutes, the pH of a 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00.
- Propylamine polyoxyethylene ether Propylamine polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the product is white or milky white flake solid, the color of the original liquid is ⁇ 50 # Pt-Co; the water content is ⁇ 0.15%; the hydroxyl value is 22.4 ⁇ 24.4mgKOH / g; the PH value is 6.0 ⁇ 7.0; double The key retention rate is ⁇ 96.5%.
- the feed rate of the first material is 100 kg / h
- the molar ratio of the feed rate of the first material and the epoxide is 1:19
- a total of 41130 kg of epoxide is passed.
- the temperature of the kettle is adjusted to 105-110 ° C, and the pressure of the kettle is adjusted. 0 ⁇ P ⁇ 0.4MPa
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 105-110 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered below 100 ° C, and then 92 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 80 ° C when the pH was ⁇ 7.00. Pentenol polyoxyethylene polyoxypropylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the initiator in the first material is used as the calculation basis.
- the molar ratio of methylallylamine to butylene oxide is 1: 31.5, of which The feed rate of the first material was 30 kg / h, the molar ratio of the feed rate of the first material and the butylene oxide was 1: 31.5, the kettle temperature was adjusted to 100 ° C, and the kettle pressure was 0.2 MPa, and the second material was obtained by the reaction;
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 120 ° C, the reaction time is 1 hour, and the third material is obtained by vacuum degassing after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered to 90 ° C, and then passed through 30kg of glacial acetic acid to conduct a neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 70 ° C when the pH was ⁇ 7.00. Allylamine polyoxybutylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 115 ° C., the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered to 90 ° C, and then 40 kg of glacial acetic acid was passed for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 70 ° C when the pH was ⁇ 7.00. Allylamine polyoxybutylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
- the product is a white or milky white flake solid, the original liquid color is 30 # Pt-Co; water content: 0.10%; hydroxyl value: 23.02mgKOH / g; pH value: 6.8; double bond retention rate is 98.0%.
- the second material is introduced into the reaction kettle C for pressure reduction and aging, the temperature is controlled at 110 ° C., the reaction time is 1 hour, and the third material is obtained by vacuum degassing for 30 minutes after aging.
- the third material was introduced into the reaction kettle D, and the temperature was lowered to 80 ° C, and then 55 kg of glacial acetic acid was passed in for neutralization reaction.
- the reaction time was 30 minutes, the pH value of the 1% aqueous solution was controlled, and the temperature was lowered to 70 ° C when the pH was ⁇ 7.00. Allyl alcohol polyoxyethylene ether.
- the amount of the catalyst in the industrial production is very small, so the amount of the starter in the first material is used as the calculation basis.
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Abstract
本发明提供了一种一步法生产聚羧酸减水剂单体聚醚的合成工艺,通过在温度、压力下,将起始剂和催化剂混合后,与环氧化物按一定比例同时通入反应釜中进行开环聚合,一步法合成单体聚醚。本发明的合成工艺无需先合成预聚体再逐步合成大分子单体聚醚实现了连续化生产,提高了生产效率;本发明将传统单体聚醚生产工艺中的置换、聚合、熟化、中和四个环节分开,更有效地控制各个环节并增加了反应釜的利用效率,工艺控制简单、产品结构稳定、双键保留率高。
Description
本发明属于聚醚合成技术领域,具体涉及一种一步法生产聚羧酸减水剂单体聚醚的合成工艺。
混凝土作为当今不可缺少的建筑材料,已经步入了商品化、高性能化时代。混凝土的商品化、高性能化是依靠混凝土外加剂来实现的,外加剂中最重要和最关键的品种是减水剂,聚羧酸减水剂作为绿色环保的高性能减水剂是当今性能最好、最有发展前景的新一代减水剂;它具有极强的分散能力,反应到工程应用表现为很小的掺量就能呈现出很高的减水效率,使混凝土获得很高的流性,还能改善混凝土孔结构、密实程度,以及控制混凝土的塌落度损失。
聚羧酸减水剂是具有两亲属性的低分子梳型聚合物,通常是以带有末端双键的端烯基烷撑聚氧乙烯醚单体与不饱和羧酸小分子单体在引发剂作用下以共聚合方式合成的,因此单体聚醚是聚羧酸减水剂行业至关重要的基础原料。
目前,聚羧酸减水剂单体聚醚的生产工艺大多采用传统的间歇法生产方式,例如徐仕睿等(徐仕睿,赵鑫,郝刚.聚羧酸减水剂单体聚醚反应催化剂的研究[J].河南化工,2016,33(10):24-26.)合成聚羧酸减水剂单体聚醚的实验步骤包括:1)预制催化剂,将催化剂和甲基丙烯醇在反应釜中混匀;2)中间体的制备,向反应釜中通入环氧乙烷制备中间体;3)单体聚醚的制备,继续向反应釜中加入催化剂,并将剩余的环氧乙烷全部通入,降压熟化后得到聚羧酸减水剂。这种传统的间歇式生产方法无法实现一步合成连续化生产,要先合成一个较低分子量的预聚体,再以预聚体为起始剂重复整个聚合工艺合成大分子量的单体聚醚,生产效率低,同时还伴有产品质量不稳定,单体残留量高等一 系列问题。针对这些问题,部分学者作出改进,例如:中国专利申请CN105273181A公开了一种一步法生产聚羧酸减水剂单体聚醚的连续化工艺,以不饱和醇类、不饱和醇醚或者不饱和胺类为起始剂,在一定温度、压力及催化剂的作用下,通过在多个反应釜分段进行环氧化物聚合,进行连续合成制得产品。虽然这种技术实现了连续化生产方式,但这是在间歇法的基础上通过添加装置来实现连续化,增加了工艺的复杂性,同样未摆脱先生产预聚体再聚合成大分子聚醚单体的方式。
发明内容
因此,本发明要解决的技术问题是克服现有技术中需要先合成预聚体再逐步合成大分子单体聚醚,且生产效率低、产品质量不稳定、单体残留量高、无法连续化生产的问题。
为此,本发明提供了一种一步法生产聚羧酸减水剂单体聚醚的合成工艺,包括以下步骤:
1)在无氧环境中,将起始剂和催化剂混合形成第一物料;
2)继续保持无氧环境,将第一物料和环氧化物同时注入反应釜,并在注入过程中混合,反应生成第二物料。
3)第二物料经熟化、脱气、中和后,即得单体聚醚产品。
进一步地,所述一种生产聚羧酸减水剂单体聚醚的一步法合成工艺,包括以下步骤:
1)向反应釜A中加入起始剂和催化剂,采用高纯度N2真空置换反应釜内空气,得第一物料;
2)继续保持无氧环境,将第一物料和环氧化物按照一定的速率比同时通入反应釜B,并在注入过程中混合,反应生成第二物料;
3)将第二物料导入反应釜C中进行熟化脱气,得第三物料;将第三物料和羧酸通入反应釜D中进行中和反应,得单体聚醚产品。
进一步地,所述的起始剂为不饱和醇类、不饱和醇醚或者不饱和胺类。
更进一步地,所述起始剂优选为:丙烯醇、甲基丙烯醇、异戊烯醇、丁烯醇、庚烯醇、丙烯醇乙二醇醚、甲基丙烯醇乙二醇醚、四羟丁基乙烯基醚、四羟丁基甲基丙烯醇、烯丙基胺、二烯丙基胺、甲基烯丙基胺、乙基烯丙基胺及其同系物,同时包括其同系物的同分异构体。
进一步地,所述的环氧化物为环氧乙烷、环氧丙烷和环氧丁烷中的一种或多种。
进一步地,所述催化剂为碱金属、碱金属氢氧化物、碱金属氢化物、碱土金属的氢氧化物、碱金属的烷氧化物、碱土金属的氧化物和有机碱催化剂中的一种或多种。
更进一步地,所述催化剂优选为:碱金属为钠、钾;碱金属氢氧化物为氢氧化钾、氢氧化钠、氢氧化锂;碱金属氢化物为:氢化钠、氢化钾;碱土金属的氢氧化物为氢氧化镁、氢氧化钙;碱金属的烷氧化物为甲醇钠、乙醇钠、甲醇钾、甘油醇钾;碱土金属的氧化物为氧化镁、氧化钙;有机碱催化剂为乙醇胺、二乙醇胺、三乙醇胺、二甲胺、三甲胺、二乙胺、三乙胺。
进一步地,步骤1)中,加热所述第一物料至70 ̄100℃;优选地,加热至80℃。
进一步地,步骤1)中,采用高纯度N
2真空置换反应釜内空气,继续通入N
2使反应釜压力达到0.2 ̄0.5MPa;优选地,反应釜压为0.3MPa。
进一步地,步骤2)中,反应温度为100 ̄125℃,反应压力0MPa<P≤0.4MPa。
进一步地,步骤2)中,第一物料注入反应釜时的速率为30-150kg/h。
进一步地,步骤3)中,熟化、脱气温度为100 ̄125℃,中和温度为70 ̄100℃。
进一步地,步骤3)中,中和所用酸为冰醋酸。
进一步地,所述起始剂和环氧化物摩尔比为1:21 ̄112;优选1:50 ̄71。 反应体系中起始剂和环氧化物的摩尔比会影响整个体系的聚合速率,影响产物的分子量、纯度和性能。
进一步地,所述催化剂用量为总投料量的0.02%-0.08%,优选地,催化剂量为0.04%。
聚羧酸减水剂作为高性能混凝土的重要组成部分,日益受到关注,因此,如何设计出可以连续化生产高性能、质量稳定、操作难度低的合成工艺对于建材行业的发展具有重要的现实意义;本发明将第一物料与环氧化物在注入反应釜的过程中混合,并完成瞬间反应,通过控制反应物通入的比例和速率实现了目标产物的一步合成。将传统单体聚醚生产工艺中的置换、聚合、熟化、中和四个环节分开,利于对各个环节的控制又能提高反应釜的利用效率。限定反应釜A的温度,,可以使起始剂和催化剂混合更加均匀,并提前预热,使反应更好的进行。将反应釜A的压力定为正压,一是为了保证反应釜的密封性;二是通过压力实现反应釜A中物料向反应釜B中转移,并控制转移速率。反应温度的高低直接影响环氧化物的开环聚合速度,并且对于产品质量也有很大影响,将反应釜B的温度控制100 ̄125℃,压力控制为0MPa<P≤0.4MPa,可以反应稳定可控,能够实现真正意义上的连续化生产。除此之外,催化剂的用量在反应过程中起着至关重要的作用,催化剂用量过多会导致反应过快,放热量过大,需要连续降温以控制反应温度,而且还会导致副产物增多;催化剂用量过少会使得反应速率降低,反应物反应不彻底,增加工艺时间和成本;本发明催化剂用量远远小于现有技术中催化剂的用量,这是由工艺本身确定的,将起始剂和环氧化物按照一定比例同时通入实现一步合成,大大提高了催化剂的利用率和催化效率。
本发明相对现有技术具有如下优点:
1、本发明提供了一种一步法合成单体聚醚的方法,首先将起始剂和催化剂在无氧环境中混合得到第一物料,之后将第一物料和环氧化物同时注入反应釜中,最为重要的是,在注入过程中实现第一物料和环氧化物的混合,可以采用并流的进料方式,一边注入,一边在并流过程中实现二者的混合反应。 本发明通过在反应釜中按一定比例同时通入起始剂与催化剂混合物、环氧化物,原料在混合的过程中同时进行反应,从而实现了单体聚醚的一步合成,无需先合成预聚体再逐步合成大分子单体聚醚,提高了生产效率,而且本发明工艺简单、制备得到的产品结构稳定、双键保留率高。
2、本发明所述的一步法合成单体聚醚的方法可以实现连续化生产,同时按比例通入反应釜A中混合物和环氧化物是为了使其同时反应,还可以实现连续反应的目的,现有技术是先投入一定量的起始剂,再通入部分环氧化物反应生成中间体在继续通入环氧化物进行反应,不能直接合成产品,而本发明同时通入起始剂和环氧化物,使其瞬间反应,可以无需中间体直接达到所需要的分子量了,产品连续化生产,指标更稳定。
3、本发明所述的一步法合成单体聚醚的方法可以实现单体聚醚的分子量可控制备;主要是在B釜中同时通入起始剂和环氧化物,通过调节起始剂和环氧化物的进料速度来控制分子量的大小,而且在B釜1个釜中直接合成相应分子量的聚醚,不用多个釜。
4、本发明所述的一步法合成单体聚醚的方法可以实现对反应中各个步骤的可控调节;将传统单体聚醚生产工艺中的置换、聚合、熟化、中和四个环节分别在A、B、C、D四个反应釜中进行,将不同步骤的反应釜分开设置,既能更有效地控制各个环节,又增加反应釜的利用效率,也不会让设备有太多的闲置情况,而且可以根据在每个反应釜内周期情况的不同各个反应釜配备的反应釜数量也不同,来达到用最少的釜达到最大的产能的目的。
提供下述实施例是为了更好地进一步理解本发明,并不局限于所述最佳实施方式,不对本发明的内容和保护范围构成限制,任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品,均落在本发明的保护范围之内。
实施例中未注明具体实验步骤或条件者,按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者,均为可以通过市购获得的常规试剂产品。
实施例1
甲基丙烯醇聚氧乙烯醚的制备
①向反应釜A中加入甲基丙烯醇1350kg和金属钠20kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是50kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:53,共计通入环氧乙烷43650kg,调节釜温为100-120℃,釜压0<P≤0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在110~120℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸55kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得甲基丙烯醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度≤50#Pt-Co;含水:≤0.15%;羟值:22.4~24.4mgKOH/g;PH值:6.0~7.0;双键保留率≥96.5%。
实施例2
异戊烯醇聚氧乙烯醚的制备
①向反应釜A中加入异戊烯醇1600kg和金属钠20kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在 注入过程中混合,其中第一物料的通入速率是80kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:52.5,共计通入环氧乙烷43000kg,调节釜温为105~110℃,釜压0<P≤0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在105~110℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸55kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得异戊烯醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取其切片样品检测其外观:产品为白色或乳白色片状固体,原液色度≤50#Pt-Co;羟值:22.4~24.4mgKOH/g;含水:≤0.15%;PH值:5.5~7;保留率≥96.5%。
实施例3
异戊烯醇聚氧乙烯醚的制备
①向反应釜A中加入异戊烯醇3870kg和金属钠20kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是150kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:21,共计通入环氧乙烷41130kg,调节釜温为105~110℃,釜压0<P≤0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在105~110℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸55kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得异戊烯醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂 用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片检测其指标:外观:产品为白色固体,色度≤50#Pt-Co;羟值:55.7~57.7mgKOH/g;PH值:5.0~7.0,保留率≥96.5%。
实施例4
甲基烯丙醇聚氧乙烯醚的制备
①向反应釜A中加入甲基烯丙醇1080kg和金属钠20kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是30kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:66,共计通入环氧乙烷43920kg,调节釜温为100~120℃,釜压0<P≤0.35MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在110~120℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸55kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得甲基烯丙醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取其切片检查指标:外观:产品为白色或乳白色片状固体,原液色度≤50#Pt-Co;羟值:17.5-18.7mgKOH/g;含水:≤0.15%;PH值:6~7。
实施例5
甲基丙烯醇聚氧乙烯醚的制备
①向反应釜A中加入甲基丙烯醇1350kg和氢化钠35kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在 注入过程中混合,其中第一物料的通入速率是60kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:53,共计通入环氧乙烷43650kg,调节釜温为100-120℃,釜压0<P≤0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在110~120℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸92kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得甲基丙烯醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度≤50#Pt-Co;含水:≤0.15%;羟值:22.4~24.4mgKOH/g;PH值:6.0~7.0;双键保留率≥96.5%。
实施例6
烯丙基胺聚氧乙烯醚的制备
①向反应釜A中加入烯丙基胺1070kg和金属钠18kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是30kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:53,共计通入环氧乙烷43650kg,调节釜温为100-120℃,釜压0<P≤0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在110~120℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸48kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得烯丙基胺聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂 用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度≤50#Pt-Co;含水:≤0.15%;羟值:22.4~24.4mgKOH/g;PH值:6.0~7.0;双键保留率≥96.5%。
实施例7
异戊烯醇聚氧乙烯聚氧丙烯醚的制备
①向反应釜A中加入异戊烯醇3870kg和金属钠20kg,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.3MPa,并加热至釜温为80℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧化物(环氧化物中环氧乙烷和环氧丙烷的摩尔比为2.86:1)同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是100kg/h,第一物料和环氧化物的通入速率摩尔比为1:19,共计通入环氧化物41130kg,调节釜温为105-110℃,釜压0<P≤0.4MPa,
反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在105-110℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至100℃以下后通入冰醋酸92kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至80℃,得异戊烯醇聚氧乙烯聚氧丙烯醚。
其中,在计算第一物料和环氧化物的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取样品检测其指标:外观:无色至浅黄色透明液体;色度:≤50#Pt-Co;羟值:21~25mgKOH/g;不饱和度:≥0.37mgKOH/g;双键保留率≥90%;PH(1%水溶液):5~7。
实施例8
甲基烯丙基胺聚氧丁烯醚的制备
①向反应釜A中加入甲基烯丙基胺1350g、氢氧化钠5g和氢氧化镁5g, 用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.2MPa,并加热至釜温为70℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧丁烷同时注入反应釜B中,并在注入过程中混合,甲基烯丙基胺与环氧丁烷的摩尔比为1:31.5,其中第一物料的通入速率是30kg/h,第一物料和环氧丁烷的通入速率摩尔比为1:31.5,调节釜温为100℃,釜压为0.2MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在120℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至90℃后通入冰醋酸30kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至70℃,得甲基烯丙基胺聚氧丁烯醚。
其中,在计算第一物料和环氧丁烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度40#Pt-Co;含水:0.08%;羟值:24.2mgKOH/g;PH值:6.5;双键保留率97.5%。
实施例9
丙烯醇乙二醇醚聚氧乙烯醚的制备
①向反应釜A中加入丙烯醇乙二醇醚408g、二乙醇胺10g和金属钾20g,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.4MPa,并加热至釜温为90℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是30kg/h,第一物料和环氧乙烷的通入速率摩尔比为1:53,共计通入环氧乙烷9328g,调节釜温为110℃,釜压为0.1MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在115℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至90℃后通入冰醋酸40kg进行中和反应,反应时间为30min,中控1%水 溶液PH值,PH<7.00时降温至70℃,得甲基烯丙基胺聚氧丁烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度30#Pt-Co;含水:0.10%;羟值:23.02mgKOH/g;PH值:6.8;双键保留率98.0%。
实施例10
甲基丙烯醇聚氧乙烯醚的制备
①向反应釜A中加入甲基丙烯醇1350g和金属钠20g,用高纯N
2置换反应釜A内空气;继续通N
2使釜压为0.5MPa,并加热至釜温为100℃,得到第一物料。
②继续保持无氧环境,将第一物料和环氧乙烷同时注入反应釜B中,并在注入过程中混合,其中第一物料的通入速率是30kg/h,环氧乙烷的通入速率是970kg/h,共计通入环氧乙烷43650g,调节釜温为120℃,釜压为0.4MPa,反应得到第二物料;
③将第二物料导入反应釜C中进行降压熟化,控制温度在110℃,反应时间为1h,熟化后真空脱气30min,得第三物料。将第三物料导入反应釜D中,降温至80℃后通入冰醋酸55kg进行中和反应,反应时间为30min,中控1%水溶液PH值,PH<7.00时降温至70℃,得甲基丙烯醇聚氧乙烯醚。
其中,在计算第一物料和环氧乙烷的速率摩尔比时,因工业生产中催化剂用量极少,所以以第一物料中起始剂的用量为计算依据。
取切片样品检测其外观:产品为白色或乳白色片状固体,原液色度40#Pt-Co;含水:0.13%;羟值:23.4mgKOH/g;PH值:6.3;双键保留率98.0%。
显然,上述实施例仅仅是为清楚地说明所作的举例,而并非对实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (10)
- 一种一步法生产聚羧酸减水剂单体聚醚的合成工艺,其特征在于,包括以下步骤:1)在无氧环境中,将起始剂和催化剂混合形成第一物料;2)继续保持无氧环境,将第一物料和环氧化物同时注入反应釜,并在注入过程中混合,反应生成第二物料。3)第二物料经熟化、脱气、中和后,即得单体聚醚产品。
- 根据权利要求1所述的合成工艺,其特征在于,所述起始剂为不饱和醇类、不饱和醇醚或者不饱和胺类。
- 根据权利要求1或2所述的合成工艺,其特征在于,所述环氧化物为环氧乙烷、环氧丙烷和环氧丁烷中的一种或多种。
- 根据权利要求1~3任一项所述的合成工艺,其特征在于,所述催化剂为碱金属、碱金属氢氧化物、碱金属氢化物、碱土金属的氢氧化物、碱金属的烷氧化物、碱土金属的氧化物和有机碱催化剂中的一种或多种。
- 根据权利要求1~4任一项所述的合成工艺,其特征在于,所述步骤1)中,加热所述第一物料至70~100℃。
- 根据权利要求1~5任一项所述的合成工艺,其特征在于,所述步骤2)中,反应温度为100~125℃,反应压力0MPa<P≤0.4MPa。
- 根据权利要求1~5任一项所述的合成工艺,其特征在于,所述步骤2)中,第一物料注入反应釜时的速率为30-150kg/h。
- 根据权利要求1~7任一项所述的合成工艺,其特征在于,所述步骤3)中,熟化脱气温度为100~125℃,中和温度为70~100℃。
- 根据权利要求1~8任一项所述的合成工艺,其特征在于,所述起始剂和环氧化物摩尔比为1:21~112。
- 根据权利要求1~8任一项所述的合成工艺,其特征在于,所述催化剂用量为总投料量的0.02%~0.08%。
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US11639418B2 (en) | 2018-09-27 | 2023-05-02 | Jiahua Chemicals (Fushun) New Material Co. Ltd. | Synthesis process for one-step production of monomeric polyether for polycarboxylic acid water reducing agents |
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CN114015034A (zh) * | 2021-12-08 | 2022-02-08 | 江苏奥克化学有限公司 | 用于合成减水剂聚醚的醇钠催化剂的制备方法与应用 |
CN113929895A (zh) * | 2021-12-08 | 2022-01-14 | 江苏奥克化学有限公司 | 一种减水剂聚醚合成用的醇钠催化剂的制备方法与应用 |
CN115403757B (zh) * | 2022-08-29 | 2023-09-19 | 万华化学集团股份有限公司 | 一聚羧酸减水剂聚醚单体的连续化生产方法 |
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