WO2017113992A1 - 一种磷酸化缩聚物高效减水剂及其制备方法 - Google Patents

一种磷酸化缩聚物高效减水剂及其制备方法 Download PDF

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WO2017113992A1
WO2017113992A1 PCT/CN2016/104954 CN2016104954W WO2017113992A1 WO 2017113992 A1 WO2017113992 A1 WO 2017113992A1 CN 2016104954 W CN2016104954 W CN 2016104954W WO 2017113992 A1 WO2017113992 A1 WO 2017113992A1
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phosphorylated
polycondensate
acid
monomer
reducing agent
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PCT/CN2016/104954
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English (en)
French (fr)
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刘加平
冉千平
王涛
亓帅
马建峰
范士敏
杨勇
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江苏苏博特新材料股份有限公司
攀枝花博特建材有限公司
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Priority to MYPI2018001174A priority Critical patent/MY189400A/en
Priority to EP16880783.2A priority patent/EP3398916B1/en
Priority to US16/067,018 priority patent/US10745510B2/en
Priority to SG11201805639TA priority patent/SG11201805639TA/en
Publication of WO2017113992A1 publication Critical patent/WO2017113992A1/zh
Priority to ZA2018/05105A priority patent/ZA201805105B/en

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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/46—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C04B24/246—Phosphorus-containing polymers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/30—Condensation polymers of aldehydes or ketones
    • C04B24/305—Melamine-formaldehyde condensation polymers
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • 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
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C08G14/10—Melamines
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0059—Graft (co-)polymers
    • C04B2103/006—Comb polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Definitions

  • the invention belongs to the field of chemical building materials, and particularly relates to a phosphorylated polycondensate high-efficiency water reducing agent with novel structure and a preparation method thereof.
  • Polycarboxylate water reducer known as the third-generation concrete superplasticizer, has a comb-like molecular structure and has a strong steric hindrance effect, breaking through the traditional principle of dispersing cement particles through electrostatic repulsion.
  • the utility model has the advantages of low output, high water-reducing rate, improved concrete pore structure and compactness in the concrete system, and can control the slump loss of the concrete, and the problems of air entrainment, retardation and bleeding of the concrete. Due to its comprehensive performance and high application value, its market share in key projects and commercial concrete has expanded year by year, representing a high performance that is currently at the forefront, with the highest technology content, the best application prospects and the best overall performance. Water reducing agent.
  • Polyester type water reducing agent that is, methoxy polyethylene glycol mono(meth) acrylate formed by methoxy polyethylene glycol and (meth)acrylic acid is used as a polyoxyethylene macromonomer.
  • the water agent has the advantages of high water reduction rate, moisture retention performance and good cement adaptability;
  • Ordinary polyether type water reducing agent that is, water-reducing agent prepared by using allyl polyethylene glycol or its modified product as main polyoxyethylene macromonomer, has the advantages of simple synthesis process, low cost and high polymerization concentration. ;
  • high-performance polyether type water reducing agent that is, water-reducing agent prepared by using methallyl polyethylene glycol or its modified product as main polyoxyethylene macromonomer, and having ordinary polyether type water reducing agent And the advantages of polyester water reducer.
  • the research on the modification or performance improvement of polycarboxylic acid is based on the above three types, the system is relatively fixed, and the adsorption group is mainly composed of carboxyl groups.
  • Patent CN1167739A discloses a method for preparing a polycarboxylate cement dispersant, which firstly performs a transesterification reaction of an alkoxy polyalkylene glycol and a (meth) acrylate under the action of a basic catalyst to prepare an alkoxy group.
  • the alkylene glycol mono(meth)acrylate is mixed with (meth)acrylic acid and copolymerized by ammonium persulfate to obtain a polycarboxylic acid water reducing agent.
  • a large excess of (meth) acrylate is required to prepare the alkoxy polyalkylene glycol mono(meth) acrylate monomer, resulting in complicated post-treatment of the product and increased cost.
  • Patent CN1412175 discloses a preparation method of an allyl ether ester monomer and a method for preparing the water reducing agent of the monomer, which first treats the allyl alcohol polyether with an adsorption material such as alumina and has a peroxide value of 5.0 meq/ Below kg, an esterification reaction with an aliphatic monocarboxylic acid is carried out to produce an allyl ether ester monomer.
  • U.S. Patent No. 5,362,324, U.S. Patent No. 5,661, 062, and Chinese Patent Nos. CN101831037A, CN101066851A disclose a process for the preparation of a transesterification type herbicide which utilizes a transesterification agent to undergo ester hydrolysis cleavage in a cementy alkaline medium to slowly release a low molecular weight polymer.
  • a transesterification agent to undergo ester hydrolysis cleavage in a cementy alkaline medium to slowly release a low molecular weight polymer.
  • the concrete's ability to protect the concrete is improved, but the cross-linking of the cross-linked body is poor in the early stage.
  • the raw material status of modern concrete is becoming more and more serious.
  • the use of industrial by-product gypsum as a cement setting agent leads to high content of SO 4 2- in cementitious materials; extensive application of bulk industrial solid waste such as fly ash, slag powder and coal gangue
  • the composition of the cementitious material is more complicated; especially the high quality sand and stone resources are increasingly scarce, and the aggregate content and water absorption rate of the aggregate increase, which directly affects the adaptability between the concrete admixture and the material, resulting in the initial fluidity of the concrete.
  • the ability to maintain liquidity is greatly reduced, which greatly limits the promotion and application of high-efficiency water reducer, which will gradually affect the development of concrete technology.
  • the present invention provides a comb-shaped polymer using phosphate as an adsorption group, that is, a phosphorylated polycondensate superplasticizer and a preparation method thereof, wherein the superplasticizer has novel molecular structure and excellent comprehensive performance.
  • a comb-shaped polymer using phosphate as an adsorption group that is, a phosphorylated polycondensate superplasticizer and a preparation method thereof, wherein the superplasticizer has novel molecular structure and excellent comprehensive performance.
  • the superplasticizer has strong adaptability to cement, low sensitivity to clay and sulfate, and the preparation process can be industrialized, and the market space is broad.
  • the phosphorylated polycondensate superplasticizer of the present invention replaces a conventional carboxyl group and a sulfonic acid group with a phosphorylated melamine derivative as a main adsorption group.
  • the phosphorylated polycondensate superplasticizer of the present invention uses an aromatic alkoxy polyether as a polymer side chain to provide a strong steric hindrance effect and improve polymer dispersibility and dispersion retention performance.
  • the phosphorylated polycondensate superplasticizer according to the present invention has a molecular structural formula as shown in the following formula I:
  • the molecular structure of the polymer is formed by condensation of three monomers: phosphorylated melamine A, aldehyde B and aromatic alkoxy compound C, and the molecular structure is a comb structure;
  • R 1 H
  • the preparation method of monomer A using melamine, phosphorous acid, corresponding formaldehyde or acetaldehyde or benzaldehyde as key raw materials, in the action of catalyst acid, controlling the molar ratio of materials, the classical Mannich reaction occurs, and can refer to the name reaction or related Technical information, easy for the industry to understand and master, to prepare key intermediates II and III;
  • Monomer C is a polycondensate polyether side chain, which is an aromatic alkenyl polyether having a molecular weight of 1000 to 6000, preferably 2000 to 5000, and R 4 and R 5 are H, OH, NH 2 or phenoxy polyoxyalkyl.
  • Ether or phenylamino polyoxyalkylene ether polyoxyalkylene ether is an aromatic alcohol with an active hydrogen or a ring-opening polymerization of an amine with ethylene oxide/propylene oxide), but R 4 and R 5 cannot simultaneously H, OH or NH 2 , at least one of which is a phenoxy or phenylamino polyoxyalkylene ether;
  • the preparation method of the monomer C can adopt a conventional anionic alkoxylation polymerization method, which is relatively mature in the polyether macromonomer industry, and can be specifically referred to the patents ZL200910027884.9 and ZL200910234991.9;
  • the polymer has a weight average molecular weight of 10,000 to 50,000.
  • the preparation method of the phosphorylated polycondensate superplasticizer according to the present invention is as follows: three kinds of the foregoing monomers, under the action of a catalyst, the pH is 1-3, and the phosphorylated polycondensate superplasticizer is synthesized by polycondensation reaction. ;
  • the reaction temperature is 100-150 ° C, the reaction time is 1-10 h, and the reaction system uses water as a solvent; the device needs to be installed with a condenser (tube) reflux to prevent the loss of water or aldehyde in the system and affect the reaction conditions;
  • the catalyst acid may be selected from a mixture of any one or more of sulfonic acid, sulfuric acid, trifluoroacetic acid (TFAA), 4-toluenesulfonic acid (pTSA), monochloroacetic acid (MCAA), glacial acetic acid, hydrochloric acid, and formic acid;
  • the polymerization step is divided into three steps of preparation, condensation and neutralization of the monomer A.
  • the technical personnel in the art can grasp the preparation method of the traditional melamine, naphthalene or sulfamate water reducing agent by simple improvement. Can be completed by "one-pot method";
  • the pH of the polymer reaction system is adjusted using conventional metal hydroxides such as sodium hydroxide or potassium hydroxide.
  • the molecular structure and synthesis method of the phosphorylated polycondensate superplasticizer of the invention are novel, and the molecular structure has a phosphate and a polyether side chain, and a comb polymer having a polyether side chain is synthesized by a conventional polycondensation method, and the breakthrough is achieved.
  • the traditional water reducing agent research system has achieved the following innovative effects:
  • polymer water reducing agent has high adaptability.
  • the introduction of phosphorylated melamine as an adsorption group breaks through the traditional carboxyl and sulfonic acid system, and the phosphate adsorption capacity is strong.
  • the polycondensate exhibits strong cement and high sulfate environmental adaptability and low clay sensitivity.
  • a characteristic, in today's market environment with poor concrete admixture and aggregate quality, has great performance advantages and can be developed into a core technology.
  • the polymer is a comb structure, similar to the molecular structure of the superplasticizer polycarboxylic acid, has a strong steric hindrance effect, excellent water and sequestration performance, and the basic performance meets or exceeds the high-efficiency polycarboxylate water reducer.
  • the raw material cost selected by the process is low, the synthesis process is simple and feasible, the polycondensation efficiency is high, the production energy consumption is small, and the preparation process has industrialization prospects.
  • the invention provides a polycondensate high-efficiency water reducing agent and a preparation method thereof, and has excellent comprehensive performance, has high adaptability to low-grade raw materials of concrete today, has strong market demand, broad prospect, and advanced preparation technology of the polycondensate. With the characteristics of industrial scale production, it is expected to be the core technology in the field of concrete water reducer, leading the development of the industry.
  • Standard polyethylene glycol GPC standard (Sigma-Aldrich, molecular weights 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
  • the feed ratio in this step is the molar ratio of monomer A, monomer B and monomer C.
  • a high-performance polycondensate water reducing agent with a concentration of about 40% is a light brown transparent viscous liquid, and the weight average molecular weight of the polycondensate is 7500 by aqueous gel chromatography.
  • the cement used is Xiaoyetian 52.5R.P.II cement
  • the gravel having a stone particle size of 5-20 mm is continuously graded.
  • the cement paste fluidity test is carried out according to the GB/T8077-2000 standard.
  • the water content is 87g, and the fluidity of the cement paste is measured on the flat glass after stirring for 3 minutes.
  • the slump and slump loss shall be implemented in accordance with the relevant provisions of JC473-2001 "Concrete Pumping Agent".
  • the data in Table 3 shows that the polycondensate water reducing agent synthesized according to the preparation method provided by the present invention has excellent water reducing and moisture retaining properties, and when the dosage is 0.12%, it is reduced with the commercially available high performance polycarboxylic acid.
  • the initial initial slurry fluidity of the cement is comparable, but the 60min retention performance is obvious, indicating that the polycondensate has excellent cement paste dispersion performance and dispersion retention performance.
  • the novel polycondensate water reducing agent provided by the invention has excellent cement paste dispersing property and dispersion maintaining property, and is initially equivalent to the polycarboxylate water reducing agent, and has obvious advantages in protecting the cockroach, far superior to the traditional naphthalene system. , amino, aliphatic and melamine water reducing agents.
  • the comparative sample is a self-prepared polycondensate water reducing agent and a polycarboxylate water reducing agent (PCA), and the initial pulp flow rate is tested by using a slurry mixer.
  • PCA polycarboxylate water reducing agent
  • the data in Table 5 shows that the polycondensate water reducing agent provided by the invention has the ability of resisting montmorillonite, and when the rubber content of the cement is 0.5% and 1.0% montmorillonite, respectively, the liquidity of the slurry is not mixed.
  • the degree of expansion is basically the same, and there is no obvious decrease; the comparison sample shows a lower initial fluidity due to the difference in the structure of the segment, the molecular weight and the sample, when the corresponding content of montmorillonite is added.
  • the degree of expansion has decreased to varying degrees; with the increase of the amount of montmorillonite, the marketability of commercially available polycarboxylate water reducer (PCA) decreases rapidly, and the decline rate even reaches 50%.
  • PCA polycarboxylate water reducer
  • the data in Table 6 shows that the polycondensate water reducing agent provided by the invention has the ability to resist sulfate ion interference, and the adsorption capacity of the phosphate ion is greater than that of the sulfonate ion.
  • the commercially available polycarboxylate water reducing agent (PCA) is added with sulfate.
  • PCA polycarboxylate water reducing agent
  • the increase of the liquidity of the pulp has a certain degree of decrease, indicating that the sulfate ion and the polycarboxylate superplasticizer have competitive adsorption on the surface of the cement particles.
  • the anti-sulfate performance of the polycondensate water-reducing agent has potential huge application space.
  • the concrete fluidity data in Table 8 shows that the newly synthesized polycondensate water reducer is less than the commercially available polycarboxylic acid under the condition that the 1.8% mudstone and the 0.6% mud are aggregate.
  • the water agent (PCA) showed slump value and moisture retention ability, indicating that the polycondensate water reducer has better adaptability to the sand and stones with higher mud content, and the anti-mud effect is obvious.
  • the polycondensate water reducing agent provided by the invention has novel structure, simple preparation process, low raw material cost, and introduces phosphate to replace the traditional carboxyl group, sulfonate and the like as the main adsorption group of the water reducing agent, and comprehensively improves the traditional water reducing agent.
  • the comprehensive performance shows good cement adaptability, clay resistance and resistance to sulfate ion adsorption.
  • the water reducer has a strong advantage. And market application space.

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  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Polyethers (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

一种磷酸化缩聚物高效减水剂，以磷酸化的三聚氰胺衍生物作为主要吸附基团替换传统的羧基、磺酸基，以芳香烷氧基聚醚作为聚合物侧链，提供强空间位阻效应，提升聚合物分散性和分散保持性能，聚合物分子结构由磷酸化三聚氰胺、醛和芳香烷氧基化合物缩合而成，分子结构为梳形结构。同时提供一种缩聚物高效减水剂的制备方法，聚合步骤分为磷酸化三聚氰胺单体制备、缩合、中和三个步骤，可采用"一锅法"完成，所得的磷酸化缩聚物高效减水剂对混凝土低品位的原材料具有良好的适应性。

Description

一种磷酸化缩聚物高效减水剂及其制备方法 技术领域
本发明属于化学建材领域，具体涉及一种具有新颖结构的磷酸化缩聚物高效减水剂及其制备方法。
背景技术
聚羧酸系减水剂(PCE)，被称为第三代混凝土超塑化剂，其具有梳形分子结构，空间位阻作用极强，突破了传统的通过静电排斥实现水泥粒子分散的原理，应用在混凝土体系中具有产量低、减水率高、可改善混凝土孔结构和密实度等优点，而且可以控制混凝土的坍落度损失，以及混凝土的引气、缓凝、泌水等问题。由于其综合性能突出，推广应用价值很高，其在重点工程和商品混凝土中的市场份额逐年扩大，代表了目前最前沿、科技含量最高、应用前景最好、综合性能最优的一种高性能减水剂。
聚羧酸性能提升研究始终为外加剂技术的研究热点和难点，围绕聚醚大单体分子结构、新型共聚单体、吸附基团类型进行了大量的合成探索、性能测试及应用表征等工作。鉴于聚羧酸减水剂发展历程与分子结构，主要分为如下三种：
①聚酯型减水剂，即以甲氧基聚乙二醇与(甲基)丙烯酸生成的甲氧基聚乙二醇单(甲基)丙烯酸酯作为聚氧乙烯基大单体制备的减水剂，具有减水率高、保坍性能及水泥适应性好的优点；
②普通聚醚型减水剂，即以烯丙基聚乙二醇或其改性产品作为主要聚氧乙烯基大单体制备的减水剂，具有合成工艺简单、成本低、聚合浓度高等优点；
③高性能聚醚型减水剂，即以甲代烯丙基聚乙二醇或其改性产品作为主要聚氧乙烯基大单体制备的减水剂，兼具普通聚醚型减水剂和聚酯型减水剂的优点。
目前关于聚羧酸的改性或性能提升研究均基于以上三个类型，体系相对固定，吸附基团主要以羧基为主。
专利CN1167739A中公开了一种制备聚羧酸水泥分散剂的方法，首先将烷氧基多亚烷基二醇和(甲基)丙烯酸酯在碱性催化剂的作用下进行酯交换反应制备烷氧基多亚烷基二醇单(甲基)丙烯酸酯，再与(甲基)丙烯酸混合，在过硫酸铵的作用下共聚合制得聚羧酸减水剂。但是，制备该烷氧基多亚烷基二醇单(甲基)丙烯酸酯单体时需要大量过量的(甲基)丙烯酸酯，造成产品的后处理复杂，成本增加。
专利CN1412175公开了一种烯丙基醚酯单体的制备方法以及该单体制备减水剂的方法，先用氧化铝等吸附材料处理烯丙醇聚醚并使其过氧化值达到5.0meq/kg以下，再与脂肪族一元羧酸进行酯化反应制造烯丙基醚酯单体。再用这种精制过的烯丙基醚酯单体与马来酸酐在80℃下用偶氮二异丁腈做引发剂下制得重均分子量为13500的共聚物，再将此共聚物和烷基聚亚烷基二醇在100℃下酯化得到一种水泥分散剂。但是，由于烯丙基醚酯单体的反应活性较差，造成得到的水泥分散剂的减水性能和坍落度保持性能都不能令人满意。
美国专利US5362324、US5661206和中国专利CN101831037A、CN101066851A公开了一种酯交换体型保坍剂的制备方法，利用酯交换体在水泥强碱性介质中，发生酯水解断裂，从而缓慢释放出低分子量聚合物，进而提高混凝土的保坍能力，但这种交联体前期的分散性较差。
现代混凝土的原材料状况却日趋严峻，工业副产石膏作为水泥调凝剂的使用导致胶凝材料SO4 2-含量偏高；粉煤灰、矿渣粉、煤矸石等大宗工业固体废弃物的广泛应用，使得胶凝材料的组份更加复杂；特别是优质砂、石资源日益匮乏，骨料含泥量和吸水率增大，直接影响混凝土外加剂与材料之间的适应性，导致混凝土初始流动度和流动度保持能力大幅降低，极大限制了高效减水剂的推广应用，逐步会影响到混凝土技术的发展。
针对当今市场上混凝土骨料和掺合料品质较差的状况，有必要开发高适应性的减水剂，突破传统减水剂的局限，进行减水剂吸附基团和分子骨架创新研究，全面提升性能，为现代混凝土技术的发展提供重要支撑。
发明内容
针对市场上混凝土原材料品质却越来越差的局面，而现有减水剂适应性不强，以及现有减水剂的制备工艺复杂，或者减水性能和坍落度保持性能不佳等问题，本发明提供了一种以磷酸根作为吸附基团的梳形聚合物，即一种磷酸化缩聚物高效减水剂及其制备方法，所述高效减水剂分子结构新颖，综合性能优异，特别是对水泥适应性强、粘土和硫酸盐的敏感性低，制备工艺可工业化，市场空间广阔。
本发明所述磷酸化缩聚物高效减水剂，是以磷酸化的三聚氰胺衍生物作为主要吸附基团，替换传统的羧基、磺酸基。
本发明所述磷酸化缩聚物高效减水剂，以芳香烷氧基聚醚作为聚合物侧链，提供强空间位阻效应，提升聚合物分散性和分散保持性能。
本发明所述磷酸化缩聚物高效减水剂，其分子结构式如下式I所示：
Figure PCTCN2016104954-appb-000001
聚合物分子结构由三种单体：磷酸化三聚氰胺A，醛B和芳香烷氧基化合物C缩合而成，分子结构为梳形结构；
聚合物单体摩尔比：m:n:p＝1.5～4.5:1.8～3.2:1，优选m:n:p＝2.0～3.0:2.4～2.8:1；
单体A为磷酸化三聚氰胺，分为单齿化合物II(R1＝H，
Figure PCTCN2016104954-appb-000002
)和双齿化合物III
Figure PCTCN2016104954-appb-000003
减水剂分子结构I中，需要具有如下的一种或两种结构，具体结构如式II和III所示：
Figure PCTCN2016104954-appb-000004
单体A的制备方法，以三聚氰胺、亚磷酸、相应的甲醛或乙醛或苯甲醛为关键原料，在催化剂酸的作用，控制物料的摩尔比，发生经典的Mannich反应，可参考人名反应或相关的技术资料，业内人员容易理解和掌握，制备关键中间体II和III；
其中物料的摩尔比为：三聚氰胺：亚磷酸：醛：酸(H+)＝1:1.0～1.2:1.1～1.5:0.2～1.2，此物料比对应单个磷酸官能团，酸可以为催化量或化学计量的；
单体B为常规的甲醛、乙醛和苯甲醛化合物一种或一种以上(R3＝H或
Figure PCTCN2016104954-appb-000005
Figure PCTCN2016104954-appb-000006
从工业化原料选择和转化率角度，优选37％甲醛溶液(福尔马林)；
单体C为缩聚物聚醚侧链，为芳香烷烯基聚醚，分子量为1000～6000，优选2000～5000，R4和R5为H、OH、NH2或苯氧基聚氧烷基醚或苯氨基聚氧烷烯醚(聚氧烷烯醚为带有活性氢的芳香醇或胺与环氧乙烷/环氧丙烷开环聚合而成)，但R4和R5不能同时为H、OH或NH2，至少其中之一为苯氧基或苯氨基聚氧烷烯醚；
单体C的制备方法可采用常规的阴离子烷氧基化聚合方法，此方法在聚醚大单体行业较为成熟，具体可参照专利ZL200910027884.9和ZL200910234991.9；
聚合物重均分子量为1～5万。
本发明所述磷酸化缩聚物高效减水剂的制备方法为：三种前述单体，在催化剂的作用下，pH为1～3，经缩聚反应合成得到所述磷酸化缩聚物高效减水剂；
反应温度为100～150℃，反应时间1～10h，反应体系以水为溶剂；装置需要安装冷凝器(管)回流，防止体系中水或醛的散失，影响反应条件；
催化剂酸可选自磺酸、硫酸、三氟乙酸(TFAA)、4-甲苯磺酸(pTSA)、一氯乙酸(MCAA)、冰醋酸、盐酸和甲酸等中任意一种以上任意比例的混合物；
聚合步骤分为单体A制备、缩合、中和三个步骤，业内技术人员通过参考传统的密胺系、萘系、氨基磺酸盐系减水剂的制备方法，通过简单改进即可掌握，可采用“一锅法”完成；
聚合物反应体系PH调节选用常规的金属氢氧化物，如氢氧化钠或氢氧化钾。
本发明所述磷酸化缩聚物高效减水剂分子结构与合成方法新颖，分子结构中具有磷酸根和聚醚侧链，以传统的缩聚方法合成了具有聚醚侧链的梳形聚合物，突破了传统的减水剂研究体系，达到了以下方面的创新效果：
①聚合物减水剂具有高适应性。引入磷酸化三聚氰胺作为吸附基团，突破了传统的羧基、磺酸基体系，磷酸根吸附能力强，该缩聚物表现出了较强的水泥和高硫酸盐环境适应性、粘土敏感性低，这一特性，在当今混凝土掺合料和骨料品质较差的市场环境下，具有极大的性能优势，可发展为核心技术。
②综合性能优异。聚合物为梳形结构，类似于高效减水剂聚羧酸的分子结构，具有极强的空间位阻效应，减水和保坍性能优异，基本性能达到甚至超过高效聚羧酸减水剂。
③制备工艺先进。该工艺选择的原料成本低，合成工艺简单可行，缩聚效率高，生产能耗小，制备工艺具有可工业化前景。
本发明提供的一种缩聚物高效减水剂及其制备方法，综合性能优异，对当今混凝土低品位的原材料具有极高的适应性，市场需求强烈，前景广阔，而且该缩聚物制备工艺先进，具备可工业放大生产的工艺特点，有望打造为混凝土减水剂领域的核心技术，引领行业发展。
具体实施方式
以下实施例更详细的描述了本发明提供的一种高效缩聚物减水剂的分子结构与制备过程，这些实施例以说明的方式给出，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，但这些实施例绝不限制本发明的范围。凡根据本发明精神实质所作的等 效变化或修饰，都应涵盖在本发明的保护范围之内。
分子量测试条件：本发明实施例中所有缩聚物的分子量使用水性凝胶色谱(GPC)进行测定，实验条件如下：
凝胶柱：Shodex SB806+803两根色谱柱串联；
流动相：0.1MNaNO3水溶液；
流动相速度：1.01ml/min；
注射：20μl 0.5％水溶液；
检测器：Shodex RI-71型示差折光检测器；
标准物：聚乙二醇GPC标样(Sigma-Aldrich，分子量1010000、478000、263000、118000、44700、18600、6690、1960、628、232)。
各实施例中单体A的合成参数见表1.
表1单体A的合成参数
Figure PCTCN2016104954-appb-000007
Figure PCTCN2016104954-appb-000008
各实施例中减水剂样品的合成参数见表2.
表2改性减水剂合成参数
Figure PCTCN2016104954-appb-000009
注：该步骤投料比均为单体A、单体B和单体C的摩尔比。
合成实施例1
(1)单体A的制备
将三聚氰胺126.02g(1.0mol)，亚磷酸86.10g(1.05mol)和水100ml置于1000ml反应瓶中，加入硫酸78.4g(0.8mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液97.30g(1.2mol)，安装冷凝管，加热回流3h，冷却之后，待用。
(2)缩合反应
在1000ml圆底烧瓶中，依次加入单体C(苯氧基聚氧乙烯醚)250g(0.1mol)、单体A(单取代磷酸化三聚氰胺)52.8g(0.24mol)，升温至80℃，再滴加37％甲醛水溶液21.08g(0.26mol)，保持120℃反应6h。
(3)中和
加入30％氢氧化钠溶液34.67g(0.26mol)，加入水480g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为25000.
合成实施例2
(1)单体A的制备
将三聚氰胺126.05g(1.0mol)，亚磷酸90.20g(1.1mol)和水100ml置于1000ml反应瓶中，加入硫酸98.0g(1.0mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液85.14g(1.05mol)，安装冷凝管，加热回流3h，冷却之后，待用。
(2)缩合反应
在2000ml圆底烧瓶中，依次加入单体C(苯氧基聚氧乙烯醚)450g(0.1mol)、单体A(单取代磷酸化三聚氰胺)66.0g(0.3mol)，升温至80℃，再滴加37％甲醛水溶液22.70g(0.28mol)，保持110℃反应5h。
(3)中和
加入30％氢氧化钠溶液41.3g(0.31mol)，加入水800g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为24000.
合成实施例3
(1)单体A的制备
将三聚氰胺126.0g(1.0mol)，亚磷酸82.06g(1.0mol)和水100ml置于1000ml反应瓶中，加入硫酸19.6g(0.2mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液121.62g(1.5mol)，安装冷凝管，加热回流3.5h，冷却之后，待用。
(2)缩合反应
在2000ml圆底烧瓶中，依次加入单体C(对羟基苯氧基聚氧乙烯醚)350g(0.1mol)、单体A(单取代磷酸化三聚氰胺)33.0g(0.15mol)，升温至80℃，再滴加37％甲醛水溶液14.60g(0.18mol)，保持130℃反应7h。
(3)中和
加入30％氢氧化钠溶液25.33g(0.15mol)，加入水600g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为12000。
合成实施例4
(1)单体A的制备
将三聚氰胺126.04g(1.0mol)，亚磷酸98.4g(1.2mol)和水100ml置于1000ml反应瓶中，加入硫酸117.6g(1.2mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液81.08g(1.0mol)，安装冷凝管，加热回流3h，冷却之后，待用。
(2)缩合反应
在2000ml圆底烧瓶中，依次加入单体C(对氨基苯氧基聚氧乙烯醚)400g(0.1mol)、单体A(单取代磷酸化三聚氰胺)99.0g(0.45mol)，升温至80℃，再滴加37％甲醛水溶液14.60g(0.18mol)，保持110℃反应6h。
(3)中和
加入30％氢氧化钠溶液38.67g(0.29mol)，加入水775g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为46000。
合成实施例5
(1)单体A的制备
将三聚氰胺126.03g(1.0mol)，亚磷酸180.4g(2.2mol)和水150ml置于1000ml反应瓶中，加入硫酸196g(2.0mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液210.81g(2.6mol)，安装冷凝管，加热回流4h，冷却之后，待用。
(2)缩合反应
在2000ml圆底烧瓶中，依次加入单体C(对羟基苯氨基聚氧乙烯醚)600g(0.1mol)、单体A(双取代磷酸化三聚氰胺)62.8g(0.2mol)，升温至80℃，再滴加40％乙醛水溶液27.5g (0.25mol)，保持120℃反应6h。
(3)中和
加入30％氢氧化钠溶液82.67g(0.62mol)，加入水1010g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为32000。
合成实施例6
(1)单体A的制备
将三聚氰胺126.06g(1.0mol)，亚磷酸164.0g(2.0mol)和水150ml置于1000ml反应瓶中，加入硫酸215.6g(2.2mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液194.59g(2.4mol)，安装冷凝管，加热回流4h，冷却之后，待用。
(2)缩合反应
在1000ml圆底烧瓶中，依次加入单体C(苯氨基聚氧乙烯醚)100g(0.1mol)、单体A(双取代磷酸化三聚氰胺)75.36g(0.24mol)，升温至80℃，再滴加苯甲醛溶液29.68g(0.28mol)，保持120℃反应8h。
(3)中和
加入30％氢氧化钠溶液85.33g(0.64mol)，加入水350g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为38000。
对比实施例1
(1)单体A的制备
将三聚氰胺126.00g(1.0mol)，亚磷酸49.2g(0.6mol)和水100ml置于1000ml反应瓶中，加入硫酸9.8g(0.1mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液64.86g(0.8mol)，安装冷凝管，加热回流3h，冷却之后，待用。
(2)缩合反应
在500ml圆底烧瓶中，依次加入单体C(苯氧基聚氧乙烯醚)75g(0.1mol)、单体A(单取代磷酸化三聚氰胺)17.6g(0.08mol)，升温至80℃，再滴加37％甲醛水溶液9.73g(0.12mol)，保持160℃反应10h。
(3)中和
加入30％氢氧化钠溶液10.67g(0.08mol)，加入水150g，调节体系PH＝8～9，制得重 量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为7500。
对比实施例2
(1)单体A的制备
将三聚氰胺126.01g(1.0mol)，亚磷酸123g(1.5mol)和水100ml置于1000ml反应瓶中，加入硫酸156.8g(1.6mol)，升温至100℃，保持10min，然后滴加37％甲醛水溶液145.95g(1.8mol)，安装冷凝管，加热回流3h，冷却之后，待用。
(2)缩合反应
在2000ml圆底烧瓶中，依次加入单体C(苯氧基聚氧乙烯醚)700g(0.1mol)、单体A(单取代磷酸化三聚氰胺)110g(0.5mol)，升温至80℃，再滴加37％甲醛水溶液30.81g(0.38mol)，保持120℃反应8h。
(3)中和
加入30％氢氧化钠溶液49.33g(0.47mol)，加入水1250g，调节体系PH＝8～9，制得重量浓度为40％左右的高性能缩聚物减水剂，为浅棕色透明粘稠液体，水性凝胶色谱测定缩聚物重均分子量为64500。
应用实例1
为了评价本发明所制备的高性能缩聚物减水剂对水泥净浆的分散性能，按照GB/T8077-2000标准进行了水泥净浆流动度测试，实验结果见表3.
本发明应用实施例中，除特别说明，所采用的水泥均为小野田52.5R.P.II水泥，砂为细度模数Mx＝2.6的中砂，石子粒径为5～20mm连续级配的碎石。水泥净浆流动度测试参照GB/T8077-2000标准进行，加水量87g，搅拌3分钟后在平板玻璃上测定水泥净浆流动度。坍落度及坍落度损失参照JC473-2001《混凝土泵送剂》相关规定执行。
表3样品的水泥净浆流动度
Figure PCTCN2016104954-appb-000010
Figure PCTCN2016104954-appb-000011
表3中的数据表明，根据本发明提供的制备方法合成的缩聚物减水剂合具有优异的减水和保坍性能，当掺量均为0.12％时，与市售高性能聚羧酸减水剂(PCA1和PCA2)相比，水泥初始净浆流动度相当，但是60min的保坍性能优势明显，表明该缩聚物具有优异的水泥净浆分散性能和分散保持性能。
对比样结果表明，当物料的比例偏离建议范围过大时，聚合物分子量偏小或偏大，均导致样品初始水泥净浆流动度变小，损失增大。因此，本发明提供的新型缩聚物减水剂，具有优良的水泥净浆分散性能和分散保持性能，初始与聚羧酸减水剂相当，保坍具有明显优势，远远优于传统的萘系、氨基、脂肪族和密胺系减水剂。
应用实例2
为了评价本发明的缩聚物减水剂对水泥的适应性，按照GB/T8077-2000≤混凝土外加剂匀质性试验方法≥中测定水泥净浆流动度的方法，水泥300g，加水量87g，对比样品为自备和市售聚羧酸减水剂(PCA)，采用净浆搅拌机进行测试初始净浆流动度，试验结果见表4.
表4样品对不同水泥的适应性
Figure PCTCN2016104954-appb-000012
Figure PCTCN2016104954-appb-000013
表4中数据表明，本发明提供的缩聚物减水剂具有良好的水泥适应性，在不同地区生产水泥中表现出了平稳的水泥净浆流动度，
而对比样品虽然表现出了较低的初始水泥净浆流动度，但不同水泥中初始水泥流动度相对平稳，市售聚羧酸减水剂(PCA)在不同水泥中变现了较大的浮动，水泥的适应性较差。
应用实例3
为了评价本发明的缩聚物对黏土的适应性，按照GB/T8077-2000≤混凝土外加剂匀质性试验方法≥中测定水泥净浆流动度的方法，水泥300g(鹤林水泥)，加水量87g，分别添加胶凝材料的0.5％和1％含量的蒙脱土，对比样品为自备缩聚物减水剂和聚羧酸减水剂(PCA)，采用净浆搅拌机进行测试初始净浆流动度，试验结果见表5.
表5样品的抗黏土性能测试
Figure PCTCN2016104954-appb-000014
表5中数据表明，本发明提供的缩聚物减水剂具有抗蒙脱土能力，当分别掺加胶材水泥量的0.5％、1.0％蒙脱土时，其净浆流动度值与不掺蒙脱土时相比，扩展度基本相当，无明显降低现象；对比样由于链段结构、分子量与样品有差异，均表现出了较低的初始流动度，当掺加相应含量蒙脱土时，扩展度值都有不同程度下降；市售聚羧酸减水剂(PCA)随着蒙脱土掺量的增加，其净浆流动度迅速下降，下降幅度甚至达到50％以上。在混凝土 骨料和掺合料品质逐渐变差的市场环境下，该缩聚物减水剂具有广阔的工程应用空间，其抗黏土能力会受逐渐受到市场的认可。
应用实例4
为了评价本发明的缩聚物对硫酸盐的适应性，按照GB/T8077-2000≤混凝土外加剂匀质性试验方法≥中测定水泥净浆流动度的方法，水泥300g(鹤林水泥)，加水量87g，分别添加胶凝材料的0.5％和1％含量的硫酸钠，对比样品为自备和市售密胺系减水剂(SM)，采用净浆搅拌机进行测试初始净浆流动度，试验结果见表6.
表6样品的抗硫酸盐能力测试
Figure PCTCN2016104954-appb-000015
表6中数据表明，本发明提供的缩聚物减水剂具有抗硫酸根离子干扰能力，由于磷酸根离子的吸附能力大于磺酸根离子，在水泥净浆体系中，当分别掺加胶材水泥量的0.5％、1.0％硫酸钠时，其净浆流动度值与不掺硫酸盐时相比，其扩展度无明显降低现象；市售聚羧酸减水剂(PCA)随着硫酸盐掺量的增加，其净浆流动度有一定程度的降低，表明硫酸根离子与聚羧酸减水剂在水泥颗粒表面发生了竞争性吸附。在混凝土掺合料品质较差、高硫酸盐水泥体系中，该缩聚物减水剂具有的抗硫酸盐性能具有潜在的巨大应用空间。
应用实例5
按照GB8076-2008≤混凝土外加剂≥标准中高性能减水剂的测试要求，采用鹤林水泥、含泥量为1.8％细度模数为3.3的机制山砂、含泥量为0.6％的公称粒径5-10mm和10-20mm连续级配碎石为材料，按照表7规定的配合比测试了缩聚物减水剂的减水率、含气量、坍 落度保持能力等指标，测试结果见表8.
表7测试用混凝土配合比
原材料 水泥 粉煤灰 矿粉 机制山砂 5-10mm石子 10-20mm石子 水
配比，Kg/m3 240 85 75 886 380 570 174
表8缩聚物减水剂性能测试结果
Figure PCTCN2016104954-appb-000016
注：/表示混凝土没有坍落度和扩展度值
表8中混凝土流动性数据表明，在含泥量为1.8％机制山砂和含泥量为0.6％的石子为骨料的条件下，新合成的缩聚物减水剂较市售聚羧酸减水剂(PCA)表现出了坍落度值和保坍能力，说明缩聚物减水剂对含泥量较高的机制砂、石子具有较好的适应能力，抗泥效果明显。
本发明提供的缩聚物减水剂，结构新颖，制备工艺简单，原料成本低，引入磷酸根代替传统的羧基、磺酸根等作为减水剂的主要吸附基团，全面提升了传统减水剂的综合性能，表现出了良好的水泥适应性、抗黏土能力及抗硫酸根离子竞争吸附能力，在当今混凝土骨料和掺合料品质较差的市场环境下，该减水剂具有较强的优势和市场应用空间。

Claims (6)

  1. 一种磷酸化缩聚物高效减水剂，其特征在于，其分子结构式如下式I所示：
    Figure PCTCN2016104954-appb-100001
    聚合物分子结构有三种结构单元，是由磷酸化三聚氰胺A，醛B和芳香烷氧基化合物C缩合而成，分子结构为梳形结构；
    前述三种单体的摩尔比：m:n:p＝1.5～4.5:1.8～3.2:1，优选m:n:p＝2.0～3.0:2.4～2.8:1；
    单体A为磷酸化三聚氰胺，其结构为下述单齿化合物II和双齿化合物III中的任意一种；
    Figure PCTCN2016104954-appb-100002
    单体B为甲醛、乙醛和苯甲醛化合物一种或一种以上任意比例的混合；
    单体C为缩聚物聚醚侧链，为芳香烷烯基聚醚，分子量为1000～6000；
    所述磷酸化缩聚物高效减水剂的重均分子量为1～5万。
  2. 根据权利要求1所述磷酸化缩聚物高效减水剂，其特征在于，单体A的制备方法，以三聚氰胺、亚磷酸、相应的甲醛或乙醛或苯甲醛为关键原料，在催化剂酸的作用，发生Mannich反应即得；
    其中物料的摩尔比为：三聚氰胺：亚磷酸：醛：酸(H+)＝1:1.0～1.2:1.1～1.5:0.2～1.2。
  3. 根据权利要求1所述磷酸化缩聚物高效减水剂，其特征在于，单体B甲醛。
  4. 根据权利要求1所述磷酸化缩聚物高效减水剂，其特征在于，单体C的分子量为2000～5000，对应结构式I中，R4和R5为H、OH、NH2或苯氧基聚氧烷基醚或苯氨基聚氧烷烯醚，但R4和R5不能同时为H、OH或NH2，至少其中之一为苯 氧基或苯氨基聚氧烷烯醚；所述聚氧烷烯醚为带有活性氢的芳香醇或胺与环氧乙烷/环氧丙烷开环聚合而成。
  5. 权利要求1-4中的任一项所述磷酸化缩聚物高效减水剂的制备方法，其特征在于，
    三种前述单体，在催化剂酸的作用下，pH为1～3，经缩聚反应合成得到所述磷酸化缩聚物高效减水剂；
    反应温度为100～150℃，反应时间1～10h，反应体系以水为溶剂；装置需要安装冷凝器(管)回流，防止体系中水或醛的散失，影响反应条件；
    催化剂酸选自磺酸、硫酸、三氟乙酸(TFAA)、4-甲苯磺酸(pTSA)、一氯乙酸(MCAA)、冰醋酸、盐酸和甲酸等中任意一种以上任意比例的混合物。
  6. 根据权利要求5所述方法，其特征在于，具体制备步骤，分为单体A制备、缩合、中和三个步骤，中和使用PH调节剂，选自氢氧化钠或氢氧化钾。
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CN113307579A (zh) * 2021-06-25 2021-08-27 天津金隅混凝土有限公司 一种机制砂低收缩高保坍混凝土
CN113307579B (zh) * 2021-06-25 2022-08-05 天津金隅混凝土有限公司 一种机制砂低收缩高保坍混凝土
CN113563556A (zh) * 2021-07-05 2021-10-29 武汉善达化工有限公司 一种用于高硅灰耐火浇注料的抗杂质减水剂及其制备方法
CN113563556B (zh) * 2021-07-05 2022-08-19 武汉善达化工有限公司 一种用于高硅灰耐火浇注料的抗杂质减水剂及其制备方法

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