TW201605759A - The preparation of novel polycarboxylate superplasticizer for concrete engineering - Google Patents

Abstract

This invention discloses a kind of polycarboxylate superplasticizer (PC), as an anionic surfactant, which containing carboxylate groups in the molecular structure of copolymers. The comb like polycarboxylate based superplasticizer (PC) possess short main chain, long side chain and higher space steric effect in molecules, which provides many advantages as high water-reducing ratio, small impacts on the setting time of concrete, low dosage and free adding sequence. This invention is simple operated and possess mild reaction conditions. PC product is common used in cement based material components, which is indispensable to disperse cement particles and release free water from cement gel. The invention has potential for development of concrete technology and construction.

Description

Preparation of a novel polycarboxylic acid type water reducing agent

The polycarboxylic acid type water reducing agent molecule of the invention has high steric hindrance effect, and has the advantages of high water reduction rate, small influence on concrete setting time, low dosage and no need to be added. Mainly used to improve the dispersion of cement particles, this research has greatly promoted the development of concrete technology and construction. The invention relates to a preparation method of a polycarboxylic acid type water reducing agent (PC), which is a method and application for synthesizing a polycarboxylic acid type water reducing agent based on a "radical polymerization" method.

In the early 1930s, lignin sulfonate was the main water-reducing agent in foreign countries, followed by the development of melamine-based and naphthalene-based superplasticizers. The polycarboxylic acid type water reducing agent is the focus of current research: the third generation polycarboxylic acid type water reducing agent (PC) has the advantages of low dosage, high water reduction rate and high concrete strength, and has been successfully applied to high strength concrete and fair water concrete. And special concrete such as self-compacting concrete, and achieved good results. A typical polycarboxylic acid type water reducing agent is a comb copolymer in which a polyacrylic acid copolymer is a main chain and a polyethylene glycol is a side chain, and a small amount of a functional monomer such as a methyl methacrylate monomer or a olefin is copolymerized. Sodium propyl sulfonate, acrylic acid, and the like. PC type water reducing agent adsorbs to the surface of cement particles through the interaction of carboxylate and sulfonate ions in the cement paste. The negative charge of the molecule and the charge neutralization reaction of the cement and the steric hindrance of the long side chain make the cement The particles are deflocculated to achieve a good dispersion effect. The molecular structure of the PC type water reducing agent is controllable, and the molecular design of the PC can be performed by adjusting parameters such as the length of the main side chain, the proportion of the adsorption group, and the bridging group of the main side chain. Cement hydration process spans dissolution, diffusion, nucleation, growth, adsorption and Complexation and so on. In these processes, temperature, relative humidity, cement resistance, and water grayness all have an effect on cement hydration. Among them, the side chain groups and side chain lengths in the molecular structure of PC are important parameters affecting the hydration process of cement. For example, Liu Jiaping investigated the effects of long side chain amphoteric polycarboxylate superplasticizers with different cation contents on early hydration of cement. PC containing cations can accelerate cement hydration and improve early strength of cement (Liu Jiaping, Dong Siqin, Yu Yuhui. Effect of long side chain amphoteric polycarboxylate superplasticizer on early hydration of cement, functional materials, 2014(45): 95- 98). However, in concrete applications, there are also key problems such as easy bleeding, late strength and durability of concrete, lower than expected, and segregation. The academic community generally believes that the development of a new structure of polycarboxylic acid type water reducer (PC) is a major development goal.

In recent years, many studies have reported the preparation of slow-release polycarboxylic acid type water reducing agents to control concrete slump loss and solve the problem of compatibility of concrete materials. For example, Li Chongzhi et al. pass the reaction monomers such as sodium (meth) propyl sulfonate, (meth) propyl (but) alkenyl polyethylene glycol, methyl (meth) acrylate or hydroxyethyl acrylate, and unsaturated monomers. The polyether macromonomer synthesizes a slow-release polycarboxylic acid type water reducing agent with high dispersibility and moisture retention performance. (Li Chongzhi, Ma Jian, Ge Tinglin. Experimental study on slow release polycarboxylate superplasticizer TP2000, Concrete, 2013(2): 50-53); Lei et al. (Lei L, Johann P. Synthesis and properties Of a vinyl ether-based polycarboxylate superplasticizer for concrete possessing caly tolerance, Ind. Eng. Chem. Res, 2014 (53): 1048-1055) synthesized by maleic anhydride and 4-hydroxybutyl vinyl ether The polycarboxylate type water reducing agent of butyl vinyl ether is analyzed by adsorption test and XRD diffraction. The reaction of the material with montmorillonite only passes the principle of surface adsorption; while the traditional PC material, polyethylene glycol segment Embedded in the aluminum silicate layer.

Sun Zhenping uses a one-step synthesis of allyl polyethylene glycol, maleic anhydride and acrylic acid. The methyl ester is a monomer, and an ammonium sulfate solution is used as an initiator to directly polymerize to prepare an allyl polyethylene: alcohol type polycarboxylic acid type water reducing agent. The optimal synthesis process is: n(APEG): n (maleic anhydride): n (methyl acrylate) = 7:8:7, the amount of initiator is 1.7% (molar fraction), polymerization temperature is 80 ° C, reaction is 8 h, The methyl acrylate and initiator solution was added dropwise for 1 h. However, since methyl methacrylate (MMA) has a high price and high energy consumption; and the esterification process is difficult to control, the production process is complicated, and the esterification product has a great influence on the performance of the final product of the polymerization reaction, which has plagued researchers and producers. Therefore, if a kind of high performance can be prepared, and the ideal water reduction and reinforcement effect can be produced under low dosage, the adaptability of cement and admixture is good, the influence on the setting time is small, and there is no waste in the production process. Liquid discharge and the like are key issues to be considered in the preparation of a class of PC type materials.

Based on the single-color polycarboxylate type water reducing agent, the variety is not enough and can not meet the requirements of different areas of performance concrete. In order to save cost, the invention develops from the aspects of concrete performance, price, environmental protection and sustainable development, and develops toward high performance, multi-functionality and ecologicalization. From the perspective of molecular structure design, combined with the relationship between molecular structure and properties, a class of polycarboxylate type water reducer products has been prepared, which has important practical and economic significance for the development of concrete materials and technology, and the progress of construction engineering.

The object of the invention is to solve the problem that the polycarboxylic acid type water reducing agent has single performance, few varieties and can not meet the performance of concrete in different fields. The invention prepares a kind of problem that can solve the crack problem in the early stage of concrete, has high steric hindrance effect of the molecule, has high water-reducing rate and little influence on concrete setting time, from the viewpoint of enriching high-performance macromonomers and developing new varieties. Low dosage and use without the need for mixing order Point of water reducing agent.

A polycarboxylic acid type water reducing agent characterized by having the structural formula represented by the formula (I): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R ₃ is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit . n, a, b, c, and d may be 0 or an integer greater than zero.

The object of the present invention is specifically carried out by the following technical scheme: the preparation method is obtained by "radical polymerization", specifically by polyethylene glycol or polyethylene glycol monomethyl ether containing carboxyl or hydroxyl group, esterification large single The body, the polyether copolymer type or the acrylic monomer are prepared by reacting the main chain structure.

The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group contains one or more repeating units. The structural formula is as shown in (II): Wherein R ₁ is H, CH ₃ or a fluorenyl group, R ₂ , R ₃ and R ₄ are a carboxyl group, a carbonyl hydroxyethyl ester, a carbonyl hydroxypropyl ester carbonyl hydroxybutyl ester, a polyethylene glycol ether, a polyethylene glycol monomethyl ether Or methoxyethyltrimethylammonium chloride or the like; J is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit. a, b, c, and d can be 0 or an integer greater than zero.

The "active polymerization method" is a radical polymerization reaction, and the reaction conditions are: reaction at 0-130 ° C under the catalysis of ascorbic acid or in the absence of a catalyst, and the reaction medium used is water, dimethyl hydrazine, acetone, Toluene, ethyl acetate, tetrahydrofuran, acetonitrile, N,N -dimethylformamide, hydrogen peroxide, etc.

The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group-containing polycarboxylic acid type water reducing agent is prepared by homopolymerization or copolymerization of one or more monomers, and the structural formula of the monomer is as (III): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R ₃ is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit . n, a, b, c, and d may be 0 or an integer greater than zero.

The method for preparing a polycarboxylic acid type water reducing agent, characterized in that the reaction step is:

(a) Add polyethylene glycol or polyethylene glycol monomethyl ether with an amine group, carboxyl group or hydroxyl group (molecular weight 600/1000/1200/2200) in a suitable organic solvent or ultrapure water at -80 After stirring at ~300 ° C for 6~48 hours, add a certain amount of catalyst and add acrylate. The monomer is continuously stirred and stirred at -80~200 °C for 12-48h. After the reaction is completed, the reaction system is extracted with a certain solvent, washed, dried with anhydrous magnesium sulfate, and diluted with ethyl acetate/hexane as a developing solvent. Chromatographic separation, color reaction showed that the reaction was completed, separated by a gel column, and the solvent was distilled off under reduced pressure to obtain the desired reaction product.

(b) After the reaction is completed, the product obtained by 6(a) and propionic acid or butyric acid are added in an organic solvent at a molar ratio of 3:1 to 1:3, and stirred at -80 to 300 ° C for 6 to 48 hours. After the reaction is completed, the allyl macropolyether macromonomer and the appropriate organic solvent are continuously added, and stirred at -80 to 300 ° C for 6 to 48 hours, filtered with a sand core funnel, and the organic solvent is removed by rotary evaporation, followed by extraction with a suitable solvent. After stratification, the solvent was distilled off under reduced pressure, and then the mixture was cooled to room temperature and an alkali solution was added to obtain a polycarboxylic acid type water reducing agent having a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group.

The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group is prepared by homopolymerization or copolymerization of one or more monomers, characterized in that the polymerization process is: esterification Macromonomer and other monomers (such as acrylic acid, methyl methacrylate, methyl acrylate, 2-methylallyl alcohol, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, isoamyl alcohol polyoxyethylene) Ether or propylene oxime oxyethyltrimethylammonium chloride, etc.) are charged at a molar ratio of 10:0 to 0:10, and respectively, by a suitable amount of a catalyst, by microwave assisted polymerization, hydrothermal method, sol-gel method or The supercritical carbon dioxide fluid is polymerized; the product is purified by dissolution-precipitation to obtain a polycarboxylic acid type water reducing agent containing an amine group, a quaternary ammonium salt, an ester group or a carboxyl group.

The method for preparing a polycarboxylic acid type water reducing agent, characterized in that: The step (1) azo derivative is azobenzene, amino azobenzene, carboxy azobenzene, hydroxyazobenzene, etc., acrylic monomer span: (meth)acrylic acid, sodium propylene sulfonate Methyl (meth) acrylate, methyl 2-(hydroxymethyl) acrylate, methyl 3,3-dimethacrylate, methyl 3-methoxy acrylate, sodium (meth) propyl sulfonate, 2-Propylguanamine-2-methylpropanesulfonic acid, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl acrylate propylene oxyethyl trimethylammonium chloride, (A Base) n-butyl acrylate and the like. The step (2) allyl macropolyether macromonomer is allyl polyoxyethylene ether, methyl alkenyl polyoxyethylene ether or methallyl polyoxyethylene ether (molecular weight 600/1000/2200) The polyethylene glycol monomer includes (meth) polyethylene glycol monovinyl ether (molecular weight: 300/500/750/1000/2000) and the like.

The catalyst for preparing a polycarboxylic acid type water reducing agent is selected from the group consisting of p-toluenesulfonic acid, ammonium persulfate, lithium, sodium, potassium, magnesium, zinc, Grignard reagent, ascorbic acid, isocyanate, hydrogen peroxide and camphor. Co-catalysts such as sulfonic acid, sodium gluconate, and lithium hydroxide.

The propionic acid, butyric acid or caproic acid selected for the preparation method of the polycarboxylic acid type water reducing agent is: n-butyric acid, 2 -hydroxybutyric acid, β-aminopropionic acid, γ-aminobutyric acid, 2 -aminobutyric acid, mercaptopropionic acid, 3 -mercaptobutyric acid, 2 -mercaptobutyric acid, bromopropionic acid, bromobutyric acid, 2 -bromobutyric acid, 2 -bromohexanoic acid, and the like. The mash is: sodium hydride, sodium hydrogencarbonate, sodium hydroxide or sodium hydrogencarbonate.

The organic solvent selected for the preparation method of the polycarboxylic acid type water reducing agent is: chloroform, diethyl ether, toluene, tetrahydrofuran, N,N -dimethylformamide, ultrapure water, dimethylammonium , dimethyl acetamide, acetone, and the like.

The invention relates to a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the selected catalyst is: p-toluenesulfonic acid, phosphorus trioxide, hydrogen peroxide, Zinc oxide, concentrated sulfuric acid, antimony trioxide, ammonium persulfate, phosphorus pentaoxide, stannous octoate, tin lactate, tin octoate, ascorbic acid, 4-dimethylaminopyridine, and the like.

The method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the condition selected by hydrothermal polymerization is: a reaction temperature of 20 to 150 ° C, The reaction time is 6~72h, and the amount of the catalyst is 0.05~ 5w t% of the total amount of the monomer.

The method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the conditions selected by the sol-gel polymerization method are: the reaction temperature is 20 to 150 °C, the reaction time is 6~72h, and the amount of catalyst is 0.05~ 5w t% of the total amount of monomer.

The method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the condition for polymerization in a supercritical carbon dioxide fluid is: the reaction temperature is 30~ 150 ° C, the pressure in the reactor is 10 ~ 50MPa, the reaction time is 6 ~ 72h, the amount of catalyst is 0.05 ~ 10 w t% of the total amount of monomer.

The method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the polymerization is selected in the microwave assisted polymerization method: the reaction temperature is 30~ At 130 ° C, the pressure in the reactor is 1 MPa, the microwave power is 5-200 W, the reaction time is 5 min-1 h, and the amount of the catalyst is 0.05 to 5 w t% of the total amount of the monomer.

Compared with the prior art, the main advantages of the present invention are:

(1) Designing esterification macromonomers with other monomers (such as acrylic acid, methyl acrylate, 2-methylallyl alcohol or methacrylic acid, hydroxyethyl methacrylate) by a simple and easy technical route. A carboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group is synthesized by copolymerization of hydroxyethyl acrylate or propylene oxyethyl trimethyl ammonium chloride. The performance of the water reducing agent is regulated by molecular structure design and changing the formulation.

(2) Make full use of the "radical polymerization method" to prepare a kind of polycarboxylic acid type water reducing agent with high performance, multi-functionality and no environmental pollution by one-step method or two-step method.

(3) In the overall material design process, the reaction conditions are relatively mild, and the operation is simple, which can provide better concrete, increase strength, and save water consumption.

(4) The water reducing agent of the invention can reduce the shrinkage rate and dimensional change of the cement, improve the impermeability, delay the hydration of the cement and delay the curing time of the cement.

(5) Since the present invention relates to the versatile diversity of functional side groups in the main chain of the polycarboxylic acid type water reducing agent, the high performance concrete is used to minimize the concrete water cement ratio and improve the strength and durability of the concrete. It has certain advantages. Therefore, the prepared polycarboxylic acid type reducing agent is expected to be widely used in the development of concrete technology and building construction.

Figure 1 is an infrared spectrum of a sustained release polycarboxylate superplasticizer.

Example 1:

Step (1): adding acrylic acid, polyethylene glycol monomethyl ether and p-toluenesulfonic acid in an acetone solvent at a molar ratio of 1:1.1:0.15, stirring the reaction at 75 ° C for 18 hours, and dialysis with a dialysis bag after the reaction is completed; After extraction with ethyl acetate/water, the organic phase was collected, and then the organic solvent was removed by rotary evaporation to give a pale yellow liquid.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, hydroxybutyric acid and propylene oxiranyl trimethylammonium chloride obtained in the step (1) are added in an acetone ratio of 1.1:1.0:0.8 in acetone. After stirring at 50 ° C for 8 h, after the reaction was completed, it was filtered through a sand funnel and the organic solvent was removed by rotary evaporation to obtain a polycarboxylic acid type precursor compound with a quaternary ammonium salt.

Step (3): Weigh 1.5 mol of the precursor compound in step (2), add 2 wt% of hydrogen peroxide in the monomer, and polymerize under microwave assistance, and continuously add 104 g of acrylic acid: the reaction temperature is set to 100 ° C, and the microwave power is 30 W. The reaction time was 20 min; finally, the reaction was terminated by adding 1.5 mol of an aqueous sodium carbonate solution to obtain a side chain quaternized polycarboxylic acid type precursor compound (yield: 90.1%, number average molecular weight: 2.38*10 ⁴ ).

Example 2:

Step (1): adding methacrylic acid, polyethylene glycol and p-toluenesulfonic acid in a molar ratio of 1:2.1:0.2 in tetrahydrofuran solvent, stirring the reaction at 65 ° C for 18 h, and dialysis with a dialysis bag after completion of the reaction; The organic phase was extracted with ethyl acetate/water, and then the organic solvent was removed by rotary evaporation to give a pale yellow liquid.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, hydroxypropionic acid and propylene oxiranyl trimethylammonium chloride obtained in the step (1) are added in a molar ratio of 1.1:1.0:0.8 in tetrahydrofuran. Stir at 50 ° C for 8 h. After the reaction is completed, filter with a sand core funnel and remove the organic solvent by rotary evaporation. The agent obtains a polycarboxylic acid type precursor compound having a quaternary ammonium salt.

Step (3): Weigh 1.5 mol of the precursor compound in step (2), add 2 wt% of stannous octoate in a monomer amount, and polymerize under microwave assistance, and continuously add 175 g of hydroxyethyl acrylate. The reaction temperature is set to 80 ° C. The microwave power was 30 W and the reaction time was 20 min. Finally, the reaction was terminated by adding 1.5 mol of sodium carbonate aqueous solution to obtain a side chain quaternized and esterified polycarboxylic acid precursor compound (yield: 91.2%, number average molecular weight: 2.55). *10 ⁴ ).

Example 3:

Step (1): adding methyl acrylate, polyethylene glycol and p-toluenesulfonic acid in a molar ratio of 1:2.1:0.2 in tetrahydrofuran solvent, stirring the reaction at 95 ° C for 18 h, and dialysis with a dialysis bag after completion of the reaction; The organic phase was extracted with ethyl acetate/water, and then the organic solvent was removed by rotary evaporation to give a pale yellow liquid.

Step (2): after the completion of the reaction of the step (1), the light yellow product obtained by the step (1), mercapto succinic acid and propylene oxiranyl trimethyl chloride are added in a molar ratio of 1.1:1.0:0.8 in tetrahydrofuran. The ammonium was stirred at 50 ° C for 8 h. After the reaction was completed, it was filtered through a sand funnel and the organic solvent was removed by rotary evaporation to obtain a polycarboxylic acid type precursor compound with a quaternary ammonium salt.

Step (3): Weigh 1.5 mol of the precursor compound in step (2), add 2 wt% of antimony trioxide to the monomer, hydrothermally polymerize, and continuously add 198 g of hydroxyethyl methacrylate. The reaction temperature is set to 60. °C, the reaction time was 18h; finally, the reaction was terminated by adding 1.5 mol of aqueous sodium hydroxide solution to obtain a novel type of polycarboxylic acid type water reducing agent (yield: 81.2%, number average molecular weight: 3.15*10 ⁴ ).

Example 4:

Step (1): adding methyl acrylate at a molar ratio of 1:1.2:0.1 in a tetrahydrofuran solvent. Polyethylene glycol monomethyl ether and concentrated sulfuric acid, stirred at 25 ° C for 8 h, after the reaction is completed, dialysis with a dialysis bag; after extraction with ethyl acetate / water, the organic phase is collected, and finally the organic solvent is removed by rotary evaporation, ie A pale yellow liquid was obtained.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, mercaptopropionic acid and hydroxymethyl methacrylate obtained in the step (1) are added in an ultrapure water at a molar ratio of 1.2:1.0:0.8, and stirred at 50 ° C. After 12 h, after the reaction was completed, it was filtered through a sand core funnel to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weighing 2.1 moles of the precursor compound in step (2), adding 0.5% by weight of 4-dimethylaminopyridine to the monomer, hydrothermal polymerization, and continuously adding 144 g of 2-methylallyl alcohol: The reaction temperature was set to 70 ° C and the reaction time was 24 h. Finally, the reaction was terminated by adding 2.1 mol of an aqueous solution of sodium carbonate to obtain a novel type of polycarboxylic acid type water reducing agent (yield: 81.2%, number average molecular weight: 2.85*10 ⁴ ).

Example 5:

Step (1): adding methacrylic acid, polyethylene glycol monomethyl ether and concentrated sulfuric acid in a molar ratio of 1.1:1.3:0.3 in a tetrahydrofuran solvent, stirring the reaction at 110 ° C for 16 h, and dialysis with a dialysis bag after completion of the reaction; After extraction with toluene/water, the organic phase was collected, and finally the organic solvent was removed by rotary evaporation to give a pale brown liquid.

Step (2): After the reaction of the step (1) is completed, the light brown product obtained in the step (1), bromobutyric acid and acrylic acid are added in an ultrapure water ratio of 1.2:1.1:0.9, and stirred at 40 ° C for 18 hours. After completion of the reaction, it was filtered through a sand core funnel to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weighing 2.1 moles of the precursor compound in step (2), adding campose sulfonic acid in an amount of 0.5 wt% of monomer, polymerizing in a supercritical carbon dioxide fluid, and continuously adding 144 g of 2-methylallyl alcohol. The reaction temperature was 80 ° C and the reaction time was 18 h. Finally, the reaction was terminated by adding 2.1 mol of an aqueous sodium carbonate solution to obtain a novel type of polycarboxylic acid type water reducing agent (yield: 85.4%, number average molecular weight: 2.65*10 ⁴ ).

Example 6

Step (1): adding acrylic acid, polyethylene glycol monomethyl ether and concentrated sulfuric acid in a molar ratio of 1.1:1.1:0.3 in an ultrapure water solvent, stirring the reaction at 105 ° C for 16 h, and dialysis with a dialysis bag after completion of the reaction; After extraction with toluene/water, the organic phase was collected, and finally the organic solvent was removed by rotary evaporation to give a pale brown liquid.

Step (2): After the reaction of the step (1) is completed, the light brown product obtained in the step (1) and acrylic acid are added in an ultrapure water at a molar ratio of 1.2:1.1:0.9, and stirred at 60 ° C for 12 h. After the reaction is completed, Filtration with a sand core funnel gave a polycarboxylic acid type precursor compound with a sustained release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 1 wt% of isocyanate in the monomer, polymerize in supercritical carbon dioxide fluid, and continuously add 140 g of methyl acrylate. The reaction temperature is set to 100 ° C. The time was 6 h; finally, the reaction was terminated by adding 1.7 mol of an aqueous solution of sodium hydrogencarbonate to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 89.5%, number average molecular weight: 3.15*10 ⁴ ).

Example 7

Step (1): adding acrylic acid, acrylamido-2-methylpropanesulfonic acid and hydrogen peroxide in an ultrapure water solvent at a ratio of 1.1:1.1:0.3, and stirring the reaction at 45 ° C for 16 h, after the reaction is completed. The dialysis bag was dialyzed; afterwards it was extracted with toluene/water, the organic phase was collected, and finally the organic solvent was removed by rotary evaporation to give a pale brown liquid.

Step (2): After the reaction of the step (1) is completed, the light brown product obtained in the step (1), polyethylene glycol and acrylic acid are added in an ultrapure water at a molar ratio of 1.2:1.1:0.9, and stirred at 60 ° C for 12 hours. After completion of the reaction, it was filtered through a sand core funnel to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 1 wt% of isocyanate in the amount of monomer, hydrothermally polymerize, and continuously add 330 g of propylene oxyethyl trimethylammonium chloride. The reaction time was 12 h at 60 ° C; the reaction was terminated by adding 1.7 mol of an aqueous sodium hydroxide solution to obtain a slow release type polycarboxylic acid type water reducing agent (yield: 86.1%, number average molecular weight: 3.45*10 ⁴ ).

Example 8

Step (1): using a one-step method to put polyethylene glycol, acrylic acid, propylene oxiranyl trimethylammonium chloride and methacrylic acid in ultrapure water according to a molar ratio of 0.75:2.0:0.5:0.5, at 60 After stirring at a constant temperature of °C for 18 hours, after the reaction was completed, a 3 mol aqueous sodium hydroxide solution was added to adjust the pH to about 5 to 7 to terminate the reaction, thereby obtaining a polycarboxylic acid type water reducing agent with a sustained release type (yield: 88.1%). , number average molecular weight: 2.15 * 10 ⁴ ).

Example 9

Step (1): using a one-step method in a pure water, polyethylene glycol monomethyl ether, hydroxyethyl acrylate, propylene oxiranyl trimethyl ammonium chloride and acrylic acid according to a molar ratio of 0.76: 2.1: 0.5: 0.6 The mixture was stirred at a constant temperature of 50 ° C for 18 h. After the reaction was completed, a 3.2 mol sodium carbonate aqueous solution was finally added to adjust the pH to about 5 to 7 to terminate the reaction, thereby obtaining a polycarboxylate type water reducing agent with a sustained release type. : 83.5%, number average molecular weight: 2.59 * 10 ⁴ ).

Example 10:

Step (1): using a one-step method to carboxylate polyethylene glycol monomethyl ether, 2-methylallyl alcohol, propylene oxiranyl trimethyl ammonium chloride and methyl acrylate in ultrapure water according to a molar ratio 0.76:2.1:0.5:0.4 input, stir at 40 °C for 24h, after the reaction is completed, finally add 3.1 moles of sodium bicarbonate aqueous solution to adjust the pH=5~7 to terminate the reaction, that is, a polyglycan with a slow release type A carboxylic acid type water reducing agent (yield: 82.2%, number average molecular weight: 2.65*10 ⁴ ).

Example 11

Step (1): adding methallyl polyoxyethylene ether, acrylamido-2-methylpropanesulfonic acid and Grignard reagent at a molar ratio of 1.1:1.1:0.3 in an ultrapure water solvent at 0 ° C The reaction was stirred for 16 h, and after completion of the reaction, it was dialyzed against a dialysis bag; after that, it was extracted with ethyl acetate/water, and the organic phase was collected, and finally, the organic solvent was removed by rotary evaporation to obtain a pale brown liquid.

Step (2): After the reaction of the step (1) is completed, the pale brown product, polyethylene glycol and γ-aminobutyric acid obtained in the step (1) are added in an ultrapure water at a molar ratio of 1.2:1.1:1.0. After stirring at ° C for 12 h, after the reaction was completed, it was filtered through a sand core funnel to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 1 wt% of ascorbic acid in the amount of monomer, hydrothermally polymerize, and continuously add 120 g of acrylic acid: set the reaction temperature to 30 ° C, and the reaction time is 12 h; The reaction was terminated by the addition of a 1.7 molar aqueous sodium hydroxide solution to obtain a slow-release type polycarboxylic acid type water reducing agent (yield: 87.3%, number average molecular weight: 3.05*10 ⁴ ).

Example 12

Step (1): adding methallyl polyoxyethylene ether, acrylic acid and aniline diazonium salt in a molar ratio of 1.2:1.2:0.3 in N,N -dimethylformamide solvent, stirring at 0 ° C After 16 h, the reaction was completed and dialyzed against a dialysis bag; ethyl acetate/n-hexane was used as a developing solvent for thin layer chromatography, separated by a gel column, and the solvent was distilled off under reduced pressure to obtain the desired reaction product.

Step (2): after the completion of the reaction of the step (1), the light brown product, n-butyric acid and methyl group obtained in the step (1) are added to the N,N -dimethylformamide in a molar ratio of 1.1:1.1:1.0. The allyl polyoxyethylene ether was stirred at 40 ° C for 12 h, and after completion of the reaction, it was filtered through a sand core funnel to obtain a polycarboxylic acid type precursor compound having a sustained-release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 1 wt% of hydrogen peroxide in the monomer, hydrothermally polymerize, and continuously add 120 g of acrylic acid, wherein the reaction temperature is set to 30 ° C, and the reaction time is 12 h; The reaction was terminated by the addition of a 1.7 molar aqueous sodium hydroxide solution to obtain a slow release type polycarboxylic acid type water reducing agent (yield: 84.2%, number average molecular weight: 2.95*10 ⁴ ).

Example 13

Step (1): adding sodium methacrylate sulfonate, acrylic acid and polyethylene glycol in an ultrapure water ratio of 1.2:1.1:0.6, stirring the reaction at 60 ° C for 16 h, and dialysis against the dialysis bag after completion of the reaction; That is, a desired reaction product of a certain molecular weight is obtained.

Step (2): After the reaction of the step (1) is completed, the light brown product obtained in the step (1), polyethylene glycol and p-toluenesulfonic acid are added in an ultrapure water at a molar ratio of 0.5:1.1:0.1, and stirred at 25 ° C. After 18 h, after the reaction was completed, it was dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 1 wt% of hydrogen peroxide in the monomer, hydrothermally polymerize, and continuously add 130 g of prenol polyoxyethylene ether. The reaction temperature is set to 30 ° C. The reaction time was 12 h; finally, the reaction was terminated by adding 1.7 mol of an aqueous sodium hydroxide solution to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 90.3%, number average molecular weight: 2.42*10 ⁴ ).

Example 14

Step (1): adding hydroxypropyl acrylate, acrylic acid and methyl alkenyl polyoxyethylene ether in a molar ratio of 1.2:1.1:0.6 in ethyl acetate, stirring the reaction at 80 ° C for 16 h, and using a dialysis bag after the reaction is completed. Dialysis; that is, the desired reaction product of a certain molecular weight is obtained.

Step (2): After the reaction of the step (1) is completed, the light brown product obtained in the step (1), polyethylene glycol and ammonium persulfate are added in an ethyl acetate ratio of 1.1:0.5:0.1, and stirred at 25 ° C for 18 hours. After the reaction is completed, it is dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weighing 1.5 moles of the precursor compound in step (2), adding 0.5% by weight of ascorbic acid to the monomer, polymerizing by sol-gel method, and continuously adding 150 g of methyl methacrylate, wherein the reaction temperature is set to 60 ° C. The reaction time was 8 h; finally, the reaction was terminated by adding 1.6 mol of an aqueous sodium hydride solution to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 80.3%, number average molecular weight: 2.63*10 ⁴ ).

Example 15

Step (1): adding hydroxypropyl acrylate, allyl polyoxyethylene ether and carboxylazobenzene to the molar ratio of 1.2:1.1:0.6 in ultrapure water, stirring at 60 ° C for 8 h, after the reaction is completed Dialysis with a dialysis bag; that is, a reaction product of a certain molecular weight is obtained.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, 2-mercaptobutyric acid and lithium hydroxide obtained in the step (1) are added in an ultrapure water by a molar ratio of 1.1:1.2:0.1 at 25 ° C. After stirring for 18 hours, after the reaction was completed, it was dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.6 mol of the precursor compound in step (2), add 0.5 wt% of ascorbic acid to the monomer, polymerize by sol-gel method, and continuously add 150 g of methyl methacrylate, wherein the reaction temperature is set to 60 ° C. The reaction time was 8 h; finally, the reaction was terminated by adding 1.7 mol of an aqueous sodium carbonate solution to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 87.3%, number average molecular weight: 2.95*10 ⁴ ).

Example 16:

Step (1): adding hydroxypropyl acrylate, 2-methylallyl alcohol and acrylic acid in a molar ratio of 1.2:1.1:0.6 in hydrogen peroxide, stirring the reaction at 50 ° C for 8 h, and dialysis with a dialysis bag after completion of the reaction; A desired molecular weight of the desired reaction product.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, 2-bromohexanoic acid and magnesium obtained in the step (1) are added in a hydrogen peroxide ratio of 1.1:1.2:0.1, and stirred at 45 ° C for 12 h. After completion of the reaction, it was dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weighing 1.5 moles of the precursor compound in step (2), adding 0.5% by weight of ascorbic acid to the monomer, polymerizing by sol-gel method, and continuously adding 165 g of methallyl polyoxyethylene ether, wherein: setting reaction temperature The reaction time was 8 h at 40 ° C; the reaction was terminated by the addition of 1.6 mol of an aqueous solution of sodium hydrogencarbonate to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 78.1%, number average molecular weight: 3.11*10 ⁴ ).

Example 17

Step (1): using microwave-assisted polymerization method, the reaction temperature is 50 ° C, the microwave power is 20 W, the reaction time is 20 min, and allyl polyoxyethylene ether, hydroxyethyl acrylate, 3-mercaptobutyl hydride is used in ultrapure water. Acid and methacrylic acid were charged according to a molar ratio of 0.56:1.1:0.5:1.1, and lithium hydroxide and ascorbic acid in a molar ratio of 0.16:0.21 were added, and the reaction was continued at a constant temperature of 50 ° C for 20 min. After the reaction was completed, 2.7 mol of sodium carbonate was finally added. The aqueous solution was adjusted to pH=5~7 to terminate the reaction, thereby obtaining a polycarboxylic acid type water reducing agent with a sustained release type (yield: 81.6%, number average molecular weight: 2.29*10 ⁴ ).

Example 18

Step (1): adding acrylic acid, 2-methylallyl alcohol and methyl alkenyl polyoxyethylene ether in a molar ratio of 1.1:1.2:0.7 in dimethylacetamide, stirring and dissolving at 45 ° C for 8 h, After completion of the reaction, dialysis is carried out with a dialysis bag;

Step (2): After the reaction of the step (1) is completed, the pale yellow product, 2-mercaptobutyric acid and ascorbic acid obtained in the step (1) are added in a hydrogen peroxide ratio of 1.1:1.2:0.1, and stirred at 45 ° C for 12 hours. After completion of the reaction, it was dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.5 mol of the precursor compound in step (2), add 0.5 wt% of lithium hydroxide to the monomer, hydrothermally polymerize, and continuously add 115 g of polyethylene glycol, wherein the reaction temperature is set to 45 ° C. The reaction time was 8 h; finally, the reaction was terminated by adding 1.6 mol of an aqueous solution of sodium hydrogencarbonate to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 78.1%, number average molecular weight: 3.11*10 ⁴ ).

Example 19

Step (1): adding acrylic acid, maleic anhydride and allyl polyoxyethylene ether in an ultrapure aqueous amine at a molar ratio of 1.1:1.2:0.7, stirring and dissolving at 50 ° C for 12 h, and dialysis after completion of the reaction. Bag dialysis; that is, a reaction product of a certain molecular weight is obtained.

Step (2): After the reaction of the step (1) is completed, the pale yellow product, γ-aminobutyric acid and ammonium persulfate obtained in the step (1) are added to the ultra-pure water by a molar ratio of 1.1:1.2:0.1. After stirring at ° C for 12 h, after the reaction was completed, it was dialyzed against a dialysis bag to obtain a polycarboxylic acid type precursor compound having a sustained release type.

Step (3): Weigh 1.5 mol of the precursor compound in step (2), add 0.5 wt% of lithium hydroxide to the monomer, hydrothermally polymerize, and continuously add 2-propenylamine-2-methylpropanesulfonic acid 155 g. Among them: the reaction temperature was set to 50 ° C, the reaction time was 12 h; finally, the reaction was terminated by adding 1.6 mol of aqueous sodium hydroxide solution to obtain a type of slow-release polycarboxylic acid type water reducing agent (yield: 88.2%, number average molecular weight: 2.81*) 10 ⁴ ).

A method for producing a polycarboxylic acid type water reducing agent, which has a structural formula represented by the formula (I): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R3 is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit. n, a, b, c, and d may be 0 or an integer greater than zero.

2. The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group, which comprises one or more repeating units. The structural formula is as shown in (II): Wherein R ₁ is H, CH ₃ or a fluorenyl group, R ₂ , R ₃ and R ₄ are a carboxyl group, a carbonyl hydroxyethyl ester, a carbonyl hydroxypropyl ester carbonyl hydroxybutyl ester, a polyethylene glycol ether, a polyethylene glycol monomethyl ether Or methoxyethyltrimethylammonium chloride or the like; J is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit. a, b, c, and d can be 0 or an integer greater than zero.

3. The polycarboxylic acid type water reducing agent of the polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group is prepared by homopolymerization or copolymerization of one or more monomers, and the structural formula of the monomer As shown in (III): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R ₃ is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit . n, a, b, c, and d may be 0 or an integer greater than zero.

Claims (16)

A method for preparing a polycarboxylic acid type water reducing agent, which has a structural formula represented by the formula (I): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R ₃ is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride or other structural unit . n, a, b, c, and d may be 0 or an integer greater than zero. The polycarboxylic acid type water reducing agent according to claim 1, which is prepared by "living polymerization", specifically, a polyethylene glycol or polyethylene glycol monomethyl ether containing a carboxyl group or a hydroxyl group, and a large esterification ester. The body, the polyether copolymer type or the acrylic monomer are prepared by reacting the main chain structure. The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group according to claim 2, which comprises one or more repeating units. The structural formula is as shown in (II): Wherein R ₁ is H, CH ₃ or a fluorenyl group, R ₂ , R ₃ and R ₄ are a carboxyl group, a carbonyl hydroxyethyl ester, a carbonyl hydroxypropyl ester carbonyl hydroxybutyl ester, a polyethylene glycol ether, a polyethylene glycol monomethyl ether Or methoxyethyltrimethylammonium chloride or the like; J is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride, maleic anhydride or other structural unit. a, b, c, and d can be 0 or an integer greater than zero. The "living polymerization method" according to claim 2 is a radical polymerization reaction under the reaction of ascorbic acid or in the absence of a catalyst at 0 to 130 ° C, and the reaction medium used is water and dimethyl amide. Anthracene, acetone, toluene, ethyl acetate, tetrahydrofuran, acetonitrile, N,N -dimethylformamide, hydrogen peroxide, and the like. The polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, a sulfonic acid group, an ester group or a carboxyl group-containing polycarboxylic acid type water reducing agent according to claim 3, which is prepared by homopolymerization or copolymerization of one or more monomers, a monomeric The structural formula is as shown in (III): Wherein R ₁ is H or CH ₃ , and R ₂ and R ₄ are H or a homolog of CH ₃ and CH ₃ . R ₃ is CH ₂ CH ₂ , M is CH ₂ , CONH, Y is CH ₂ or CO, and Z is acrylamido-2-methylpropanesulfonic acid, maleic anhydride, maleic anhydride, maleic anhydride Or other structural unit. n, a, b, c, and d may be 0 or an integer greater than zero. A method for preparing a polycarboxylic acid type water reducing agent according to claim 3, wherein The reaction step is: (a) adding a polyethylene glycol or polyethylene glycol monomethyl ether having an amine group, a carboxyl group or a hydroxyl group in a suitable organic solvent or ultrapure water (molecular weight: 600/1000/1200/2200) After stirring at -80~300 °C for 6~48h, add a certain amount of catalyst, and add acrylate monomer to continue stirring. Stir at -80~200°C for 12-48h. After the reaction is completed, the reaction system must be used. Solvent extraction, washing, drying with anhydrous magnesium sulfate, ethyl acetate / n-hexane as a developing solvent for thin layer chromatography, color reaction shows that the reaction is complete, separation by gel column chromatography, distillation under reduced pressure to obtain the desired reaction product. (b) After the reaction is completed, the product obtained by 6(a) and propionic acid or butyric acid are added in an organic solvent at a molar ratio of 3:1 to 1:3, and stirred at -80 to 300 ° C for 6 to 48 hours. After the reaction is completed, the allyl macropolyether macromonomer and the appropriate organic solvent are continuously added, and stirred at -80 to 300 ° C for 6 to 48 hours, filtered with a sand core funnel, and the organic solvent is removed by rotary evaporation, followed by extraction with a suitable solvent. After stratification, the solvent was distilled off under reduced pressure, and then the mixture was cooled to room temperature and an alkali solution was added to obtain a polycarboxylic acid type water reducing agent having a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group. According to claim 6, the polycarboxylic acid type water reducing agent containing an amine group, an ester group, a sulfonic acid group or a carboxyl group is prepared by homopolymerization or copolymerization of one or more monomers, characterized in that the polymerization process is: ester Macromonomers and other monomers (such as acrylic acid, methyl methacrylate, methyl acrylate, 2-methylallyl alcohol, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, isoamyl alcohol polyoxyl Vinyl ether or propylene oxime oxyethyl trimethyl ammonium chloride, etc.) are charged at a molar ratio of 10:0 to 0:10, and respectively subjected to microwave assisted polymerization, hydrothermal method, sol-gel method under the action of a suitable amount of catalyst Or supercritical carbon dioxide fluid polymerization; the product is purified by dissolution-precipitation to give an amine A polycarboxylic acid type water reducing agent of a base, a quaternary ammonium salt, an ester group or a carboxyl group. According to claim 6 (a), a method for preparing a polycarboxylic acid type water reducing agent, characterized in that the azo derivative in the step (1) is azobenzene, amino azobenzene or carboxy azobenzene , hydroxy azobenzene, etc., acrylic monomer package span: (meth)acrylic acid, sodium propylene sulfonate, methyl (meth) acrylate, methyl 2-(hydroxymethyl) acrylate, 3,3- two Methyl methacrylate, methyl 3-methoxyacrylate, sodium (meth) propyl sulfonate, 2-propenylamine-2-methylpropane sulfonic acid, hydroxymethyl (meth) acrylate, (A) Base) hydroxyethyl acrylate, hydroxypropyl acrylate propylene oxyethyl trimethyl ammonium chloride, n-butyl (meth) acrylate, and the like. The step (2) allyl macropolyether macromonomer is allyl polyoxyethylene ether, methyl alkenyl polyoxyethylene ether or methallyl polyoxyethylene ether (molecular weight 600/1000/2200) The polyethylene glycol monomer includes (meth) polyethylene glycol monovinyl ether (molecular weight: 300/500/750/1000/2000) and the like. According to the requirements of claim 6 (a), a catalyst for preparing a polycarboxylic acid type water reducing agent is selected from the group consisting of p-toluenesulfonic acid, ammonium persulfate, lithium, sodium, potassium, magnesium, zinc, Grignard reagent, ascorbic acid, Co-catalysts such as isocyanate, hydrogen peroxide, camphorsulfonic acid, sodium gluconate, lithium hydroxide, and the like. According to the requirements of claim 6 (b), a method for preparing a polycarboxylic acid type water reducing agent is selected from the group consisting of propionic acid, butyric acid or caproic acid: n-butyric acid, 2-hydroxybutyric acid, β-aminopropionic acid, Γ-aminobutyric acid, 2-aminobutyric acid, mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptobutyric acid, bromopropionic acid, bromobutyric acid, 2-bromobutyric acid, 2-bromohexanoic acid, Wait. The alkali solution is sodium hydride, sodium carbonate, sodium hydroxide or sodium hydrogencarbonate. According to the requirements of claim 6, the organic solvent selected for the preparation method of the polycarboxylic acid type water reducing agent is: chloroform, diethyl ether, toluene, tetrahydrofuran, N,N -dimethylformamide, ultrapure water, two Methyl hydrazine, dimethyl acetamide, acetone, and the like. According to claim 8, a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the selected catalyst is: p-toluenesulfonic acid, trioxide Phosphorus, hydrogen peroxide, zinc oxide, concentrated sulfuric acid, antimony trioxide, ammonium persulfate, phosphorus pentoxide, stannous octoate, tin lactate, tin octylate, ascorbic acid, 4-dimethylaminopyridine, and the like. According to claim 8, a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group is characterized in that the hydrothermal polymerization is selected under the following conditions: a reaction temperature of 20 ~150 ° C, the reaction time is 6 ~ 72h, the amount of catalyst is 0.05 ~ 5 w t% of the total amount of monomer. According to claim 8, a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the conditions selected by the sol-gel polymerization: reaction temperature The reaction time is 6~72h, the reaction time is 6~72h, and the catalyst dosage is 0.05~ 5w t% of the total monomer dosage. According to claim 8, a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that a condition for polymerization in a supercritical carbon dioxide fluid is selected: a reaction The temperature is 30~150°C, the pressure in the reactor is 10~50MPa, the reaction time is 6~72h, and the amount of catalyst is 0.05~ 10w t% of the total amount of monomer. According to claim 8, a method for preparing a polycarboxylic acid type water reducing agent containing a quaternary ammonium salt, an ester group, a sulfonic acid group, a carboxyl group or an amine group, characterized in that the conditions selected for the polymerization in the microwave assisted polymerization method are: The temperature is 30~130 °C, the pressure inside the reaction bottle is 1 MPa, the microwave power is 5-200 W, the reaction time is 5 min-1 h, and the catalyst dosage is 0.05~5 w t% of the total monomer amount.