CN101492518B - Ethers polycarboxylic acid water reducing agent and preparation - Google Patents

Ethers polycarboxylic acid water reducing agent and preparation Download PDF

Info

Publication number
CN101492518B
CN101492518B CN 200910046749 CN200910046749A CN101492518B CN 101492518 B CN101492518 B CN 101492518B CN 200910046749 CN200910046749 CN 200910046749 CN 200910046749 A CN200910046749 A CN 200910046749A CN 101492518 B CN101492518 B CN 101492518B
Authority
CN
China
Prior art keywords
monomer
monomers
ether
added
reducing agent
Prior art date
Application number
CN 200910046749
Other languages
Chinese (zh)
Other versions
CN101492518A (en
Inventor
叶光锐
周南南
张鑫
樊钧
王海宾
Original Assignee
上海市建筑科学研究院(集团)有限公司;上海建研建材科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海市建筑科学研究院(集团)有限公司;上海建研建材科技有限公司 filed Critical 上海市建筑科学研究院(集团)有限公司;上海建研建材科技有限公司
Priority to CN 200910046749 priority Critical patent/CN101492518B/en
Publication of CN101492518A publication Critical patent/CN101492518A/en
Application granted granted Critical
Publication of CN101492518B publication Critical patent/CN101492518B/en

Links

Abstract

The invention discloses an ether polycarboxylic water reducing agent which is obtained through water solution copolymerization of three types of monomers of 10-70 percent of allyl polyxyethylated alcohol ether, 20-70 percent of acrylic acid and 10-30 percent of hydroxy-ethyl acrylate. Due to the introduction of hydroxy-ethyl acrylate, the ether polycarboxylic water reducing agent reduces the self-polymerization proportion of the acrylic acid, improves the copolymerization proportion, and greatly reduces the cost of the raw materials; in addition, the molecular weight of the polymer is controllable, the water reduction rate is high, the loss of slump constant with the time is low, and the prepared concrete has high fluidity, good workability, and enough early strength in the beginning of hardening. Besides, the preparation technique of the ether polycarboxylic water reducing agent is a one-step method, the operation is simple, the reaction conditions are easy to control, the productionperiod is short, and the ether polycarboxylic water reducing agent is green and environment-friendly, has low cost and is applicable to industrial production on large scale.

Description

一种醚类聚羧酸减水剂及其制备工艺 One kind of ether polycarboxylate superplasticizer and its preparation process

技术领域 FIELD

[0001] 本发明是涉及一种醚类聚羧酸减水剂及其制备工艺,属于混凝土外加剂技术领域。 [0001] The present invention relates to a preparation process and the Polycarboxylate ethers, belonging to the technical field of concrete admixtures.

背景技术 Background technique

[0002] 混凝土高效减水剂又称为超塑化剂,在混凝土生产中主要起三种不同作用:①不改变混凝土组分条件下,提高混凝土施工工作性,有利于机械化作业;②在给定条件下,减少拌合水和水灰比,以提高混凝土的强度,改善耐久性;③在给定工作性下,减少水和水泥用量,节约水泥,减少徐变、干缩和水泥水化热引起的热应力。 [0002] concrete superplasticizer, also known as a superplasticizer, mainly from three different roles in the production of concrete: ① conditions without changing the components of concrete, improved concrete construction work, in favor of mechanized operations; ② giving under given conditions, and to reduce the mixing water-cement ratio, to improve the strength of concrete, improvement of durability; ③ at a given work, reducing the amount of water and cement, cement savings, reduced creep, shrinkage and cement hydration due to thermal stresses.

[0003] 传统的萘系、三聚氰胺等缩聚型超塑化剂虽然对新拌混凝土具有较好的工作性, 但掺量高,坍落度经时损失太大,一般通过多次添加法、后掺法、与缓凝剂复合使用法来加以解决,但往往会出现一些操作上或技术的困难,引起混凝土质量和性能的不稳定,而且这一类型的超塑化剂大多采用强刺激性气味的甲醛为原料进行缩聚反应,不可避免的对操作工人和环境产生影响,不利于可持续发展,而且受分子结构本身的制约,坍落度损失问题不能从根本上得到解决,性能也不可能有较大的提高。 [0003] The conventional naphthalene-based, melamine-type superplasticizer after condensation, while having good workability of the fresh concrete, but the high dosage, when Slump loss is too large, generally by repeatedly adding method, mixed method, and the method using Retarter to be addressed, but often some of the operational difficulties or technology will cause instability concrete quality and performance, and this type of superplasticizer they use strong irritating odor the formaldehyde condensation reaction as the raw material, the inevitable impact on the operation of the workers and the environment is not conducive to sustainable development, and is subject to the molecular structure itself, slump loss problem can not be solved fundamentally, there can be no performance greatly improved.

[0004] 随着混凝土技术的发展,人们合成出来聚羧酸高效减水剂,它是通过羧基和长侧链支链作用来达到高减水率的效果,并且很好的解决了坍落度损失问题,它的特点是:①低掺量(0. 2%〜0. 5% ),发挥高的分散性能;②保坍性好,90分钟内混凝土坍落度几乎没有损失;③分子结构自由度大,可控参数多,高性能化的潜力大;④绿色无污染。 [0004] With the development of concrete technology, people synthesized polycarboxylate superplasticizer, and a carboxyl group which is obtained by action of the long branches of side chains to achieve high water reduction and good slump solved loss problems, its features are: ① low dosage (0.2% ~ 0 5%.), exhibit high dispersibility; ② good slump, little concrete slump loss over 90 minutes; ③ molecular structure large degree of freedom, controllable parameters, large high performance potential; ④ green pollution.

[0005] 目前制备聚羧酸高效减水剂的常用方法是:1、首先由甲基丙烯酸与聚乙二醇酯化制备大单体,然后将生成的大单体与甲基丙烯酸聚合,从而获得高效减水剂。 [0005] The commonly used method of producing polycarboxylic acid superplasticizer is: 1, first, and then the resultant macromonomer polymerized from methyl methacrylate and methacrylic acid with polyethylene glycol macromonomer prepared esterifying get superplasticizer. 该方法需要先合成大单体、再聚合,制备工艺复杂,成本较高,而且产品的性能对原料的分子量分布(MPEG)和纯度比较敏感;2、由烯丙基聚氧乙烯醇醚与不饱和羧酸类单体在有机溶剂(如甲苯)中进行自由基聚合反应,制备醚类聚羧酸单体。 The first method requires the synthesis of macromer, and then the polymerization, the preparation process complex and costly, and the performance of the product molecular weight distribution of the feedstock (MPEG) and more sensitive purity; 2, from allyl ethers of polyoxyethylene and not unsaturated carboxylic acid monomer to radical polymerization reaction, ether polycarboxylic acid monomer prepared in an organic solvent (e.g., toluene). 该方法的缺陷是要使用大量有机溶剂,对环境污染大,且对人体有害,溶剂去除困难,增加了工业化生产成本;3、由烯丙基聚乙二醇与不饱和羧酸类单体在水溶液中通过自由基共聚方法制备聚羧酸减水剂,该方法存在聚合物的分子量很难控制,分子量分布较宽,拌制的混凝土减水率较低,坍落度损失大等缺陷。 The disadvantage of this method is to use large amounts of organic solvents, environmental pollution, and harmful, difficult to remove the solvent, increases the cost of industrial production; 3, by an allyl polyethylene glycol and an unsaturated carboxylic acid monomer aqueous solutions of polycarboxylate superplasticizer prepared by free radical copolymerization process, the presence of the polymer molecular weight is difficult to control the process, broad molecular weight distribution, mixing and lower concrete water reducing ratio, a large slump loss defects.

发明内容 SUMMARY

[0006] 本发明的目的是针对上述现有技术所存在的缺陷,提供一种分子量可控、减水率高、且坍落度经时损失低的醚类聚羧酸减水剂,及其一种工艺简单、成本低廉的制备工艺。 [0006] The present invention is directed to the above-described prior art defect is present, there is provided a controlled molecular weight, high water reduction and slump loss over a lower ether polycarboxylate superplasticizer, and a process is simple, low cost manufacturing process.

[0007] 为实现上述发明目的,本发明采用的技术方案如下: [0007] In order to achieve the above object, the present invention employs the following technical solutions:

[0008] 本发明所述的醚类聚羧酸减水剂,其特征在于,由以下单体按以下配比进行水溶液共聚合而成: [0008] The present invention is an ether polycarboxylate superplasticizer, characterized in that, for an aqueous solution obtained by copolymerizing the following monomers in the following ratios:

[0009] 1)单体A :烯丙基聚氧乙烯醚(APEG),其化学结构式如下 [0009] 1) monomer A: polyoxyethylene allyl ether (APEG), the chemical structural formula

3[0010] 3 [0010]

[0011] 单体A占单体总重量10〜70% ;所述单体A的分子量为500〜5000 ; [0011] A monomer based on the total weight of the monomers 10~70%; molecular weight of the monomer A is 500~5000;

[0012] 2)单体B :丙烯酸(AA),其化学结构式如下 [0012] 2) monomer B: acrylic acid (AA), the following chemical structural formula

[0013] [0013]

[0014] 单体B占单体总重量20〜70% ; [0014] monomer B 20~70% total weight of the monomers;

[0015] 3)单体C :丙烯酸羟乙酯,其化学结构式如下 [0015] 3) monomer C: hydroxyethyl acrylate, the following chemical structural formula

[0016] [0016]

[0017] 单体C占单体总重量10〜30% ; [0017] Monomer C 10~30% based on the total weight of the monomers;

[0018] 上述三种单体比例的总和为100%。 The sum of [0018] the ratio of the three monomers is 100%.

[0019] 所述单体A以分子量为2000〜3000最好。 [0019] A molecular weight of the monomer is preferably 2000~3000.

[0020] 本发明所述的醚类聚羧酸减水剂的制备工艺如下: [0020] The preparation process of the present invention Polycarboxylate ethers follows:

[0021] 1)将烯丙基聚氧乙烯醚单体加入反应器内,加入去离子水使其溶解; [0021] 1) allyl polyoxyethylene ether monomer is added to the reaction, deionized water was added to dissolve;

[0022] 2) 一边搅拌升温一边用氮气吹扫反应器,当升温到60〜120°C,同时滴加丙烯酸单体与丙烯酸羟乙酯单体的混合水溶液和10%过硫酸铵水溶液,保证4小时滴加完毕; [0022] 2) heating with stirring while purging the reactor with nitrogen, when heated to 60~120 ° C, added dropwise with a mixed aqueous solution of acrylic monomer is hydroxyethyl acrylate monomer and 10% ammonium persulfate aqueous solution, to ensure addition was completed four hours;

[0023] 3)滴毕保温反应1〜3小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可。 [0023] 3) reaction was incubated dropwise 1~3 hours, cooled to 25~55 ° C, adjusted to pH 6. The base was added 0 ~ 7. 5 to.

[0024] 烯丙基聚氧乙烯醚水溶液的质量百分比浓度优选50〜75%。 [0024] polyoxyethylene allyl ether mass concentration of the aqueous solution is preferably 50~75%.

[0025] 总单体混合水溶液的质量百分比浓度优选35〜45 %。 [0025] mixing an aqueous solution of total monomer concentration is preferably 35~45% by mass percentage.

[0026] 过硫酸铵的加入量为总单体重量的1〜5%。 [0026] The ammonium persulfate was added in an amount of 1 ~ 5% of the total monomer weight.

[0027] 因为丙烯酸双键的活性较高,而烯丙基聚氧乙烯醚的双键活性较低,丙烯酸与烯丙基聚氧乙烯醚直接共聚时,会导致大量丙烯酸自聚,以致参与共聚的比例太低,因此存在聚合物的分子量很难控制、分子量分布较宽等缺陷,从而使拌制的混凝土减水率较低,坍落度损失大。 [0027] Since high activity of the double bond of acrylic acid, and the reactive double bonds is low polyoxyethylene allyl ether, acrylic acid and allyl polyoxyethylene ether direct copolymerization of acrylic acid leads to a large number of self-polymerization, so copolymerized the ratio is too low, and therefore difficult to control the molecular weight of the polymer present, defects such broad molecular weight distribution, so that the concrete mixing and low water-reducing ratio, a large slump loss. 为了解决丙烯酸与烯丙基聚氧乙烯醚直接共聚时存在丙烯酸自身聚合的问题, 本发明人研究发现:丙烯酸羟乙酯的活性介于烯丙基聚氧乙烯醚与丙烯酸之间,引入丙烯酸羟乙酯可以调整烯丙基聚氧乙烯醚与丙烯酸单体的反应活性,可以调整减水剂体系的亲水亲油平衡,提高共聚物的减水率和保坍性能。 To solve the problems themselves polymerized acrylic acid with allyl problem polyoxyethylene ether copolymerized directly, who studies the present inventors found that: hydroxyethyl acrylate activity between allyl polyoxyethylene ether with acrylic acid, hydroxyethyl acrylate is introduced ethyl can be adjusted reactive allyl polyoxyethylene ether with acrylic acid monomer, hydrophilic-lipophilic balance may be adjusted superplasticizer system to improve water reduction and slump properties of the copolymer.

[0028] 与现有技术相比,本发明的有益效果如下:[0029] ①本发明由于引入了不饱和酯丙烯酸羟乙酯,从而改变了反应单体丙烯酸与烯丙基聚氧乙烯醚的活性,减少了丙烯酸自聚比例,提高了共聚的比例,使原材料成本大大降低,且聚合物的分子量可控,减水率高。 [0028] Compared with the prior art, the beneficial effects of the present invention are as follows: [0029] ① of the present invention, since the introduction of the unsaturated ester of hydroxyethyl acrylate, thereby changing the reactive monomer acrylic acid with allyl ethers of polyoxyethylene activity, reducing the proportion of self-polymerization of acrylic acid, the copolymerization ratio increased the cost of raw materials is greatly reduced, and the molecular weight of the polymer controlled, less water is high.

[0030] ②由于烯丙基聚氧乙烯醚(APEG)分子在高温下的碱性环境中比甲基丙烯酸聚乙二醇单甲醚酯(MPEGMA)更为稳定,因此本发明的醚类聚羧酸减水剂提高了对混凝土坍落度保持的性能,坍落度经时损失低,配制的混凝土具有高流动性,良好的和易性,且硬化初期有充分的早期强度。 [0030] ② Since allyl polyoxyethylene ether (APEG) molecule ratio of methacrylic acid polyethylene glycol monomethyl ether acetate (MPEGMA) in a basic environment at high temperature is more stable, and therefore the present invention is poly ethers acid water improved concrete slump retention performance, low loss slump, formulated concrete with high fluidity, good workability, and the initial setting adequate early strength.

[0031] ③本发明的制备工艺为一步法,操作简单,反应条件易于控制,生产周期短,绿色环保,成本低廉,适合工业规模化生产。 [0031] The preparation process is a one-step ③ of the present invention, the operation is simple, easy to control the reaction conditions, short production period, low green, cost, suitable for industrial scale production.

具体实施方式 Detailed ways

[0032] 下面结合实施例对本发明做进一步详细、完整地说明,在如下实施例中所用的单体A、单体B和单体C均从市场购得。 [0032] The following embodiments in conjunction with embodiments of the present invention in further detail, a complete description, in the following examples the monomer used in the A, monomer B and monomer C were commercially available.

[0033] 实施例1 [0033] Example 1

[0034] 一、所用单体组成及配比如下: [0034] First, the monomer composition ratio and with the following:

[0035] 1)单体A :烯丙基聚氧乙烯醚(APEG),分子量为2000,占单体总重量10% ; [0035] 1) monomer A: polyoxyethylene allyl ether (APEG), molecular weight of 2000, 10% of the total weight of the monomers;

[0036] 2)单体B :丙烯酸(AA),占单体总重量70% ; [0036] 2) monomer B: acrylic acid (AA), 70% of the total weight of the monomers;

[0037] 3)单体C :丙烯酸羟乙酯,占单体总重量20%。 [0037] 3) monomer C: hydroxyethyl acrylate, 20% of the total weight of the monomers.

[0038] 二、制备工艺如下: [0038] Second, the preparation process is as follows:

[0039] 1)将IOg烯丙基聚氧乙烯醚单体加入反应器内,加入IOg去离子水使其溶解; [0039] 1) The IOg allyl polyoxyethylene ether monomer is added to the reaction, deionized water was added IOg dissolved;

[0040] 2) 一边搅拌升温一边用氮气吹扫反应器,当升温到60°C,同时滴加由70g丙烯酸单体、20g丙烯酸羟乙酯单体及95g去离子水配成的混合水溶液和50gl0%过硫酸铵水溶液,保证4小时滴加完毕; [0040] 2) heating with stirring while purging the reactor with nitrogen, the mixed aqueous solution when heated to 60 ° C, while the acrylic monomer mixture consisting of 70g, 20g and 95g of hydroxyethyl acrylate monomers and deionized water dubbed 50gl0% ammonium persulfate aqueous solution, four hours to ensure completion of the addition;

[0041] 3)滴毕保温反应1小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可。 [0041] 3) dropwise incubated for 1 hour, cooled to 25~55 ° C, adjusted to pH 6. The base was added 0 ~ 7. 5 to.

[0042] 实施例2 [0042] Example 2

[0043] 一、所用单体组成及配比如下: [0043] First, the monomer composition ratio and with the following:

[0044] 1)单体A :烯丙基聚氧乙烯醚(APEG),分子量为2400,占单体总重量40% ; [0044] 1) monomer A: polyoxyethylene allyl ether (APEG), a molecular weight of 2400, 40% of the total weight of the monomers;

[0045] 2)单体B :丙烯酸(AA),占单体总重量30% ; [0045] 2) monomer B: acrylic acid (AA), 30% of the total weight of the monomers;

[0046] 3)单体C :丙烯酸羟乙酯,占单体总重量30%。 [0046] 3) monomer C: hydroxyethyl acrylate, 30% of the total weight of the monomers.

[0047] 二、制备工艺如下: [0047] Second, the preparation process is as follows:

[0048] 1)将40g烯丙基聚氧乙烯醚单体加入反应器内,加入24g去离子水使其溶解; [0048] 1) 40g of allyl polyoxyethylene ether monomer was added to the reactor, 24g of deionized water was added to dissolve;

[0049] 2) 一边搅拌升温一边用氮气吹扫反应器,当升温到90°C,同时滴加由30g丙烯酸单体、30g丙烯酸羟乙酯单体及99g去离子水配成的混合水溶液和30gl0%过硫酸铵水溶液,保证4小时滴加完毕; [0049] 2) heating with stirring while purging the reactor with nitrogen, the mixed aqueous solution when heated to 90 ° C, while the acrylic monomer mixture consisting of 30g, 30g and 99g of hydroxyethyl acrylate monomers and deionized water dubbed 30gl0% ammonium persulfate aqueous solution, four hours to ensure completion of the addition;

[0050] 3)滴毕保温反应2小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可。 [0050] 3) dropwise incubated for 2 hours, cooled to 25~55 ° C, adjusted to pH 6. The base was added 0 ~ 7. 5 to.

[0051] 实施例3 [0051] Example 3

[0052] 一、所用单体组成及配比如下: [0052] First, the monomer composition ratio and with the following:

[0053] 1)单体A :烯丙基聚氧乙烯醚(APEG),分子量为3000,占单体总重量70% ; [0053] 1) monomer A: polyoxyethylene allyl ether (APEG), molecular weight of 3000, 70% of the total weight of the monomers;

[0054] 2)单体B :丙烯酸(AA),占单体总重量20% ; [0054] 2) monomer B: acrylic acid (AA), 20% of the total weight of the monomers;

5[0055] 3)单体C :丙烯酸羟乙酯,占单体总重量10%。 5 [0055] 3) monomer C: hydroxyethyl acrylate, 10% of the total weight of the monomers.

[0056] 二、制备工艺如下: [0056] Second, the preparation process is as follows:

[0057] 1)将70g烯丙基聚氧乙烯醚单体加入反应器内,加入25g去离子水使其溶解; [0057] 1) 70g of allyl polyoxyethylene ether monomer was added to the reactor, 25g of deionized water was added to dissolve;

[0058] 2) 一边搅拌升温一边用氮气吹扫反应器,当升温到120°C,同时滴加由20g丙烯酸单体、IOg丙烯酸羟乙酯单体及80g去离子水配成的混合水溶液和50g 10%过硫酸铵水溶液,保证4小时滴加完毕; [0058] 2) heating with stirring while purging the reactor with nitrogen, when heated to 120 ° C, while a solution of 20g of acrylic monomers, hydroxyethyl acrylate monomers and IoG 80g deionized water and a mixed aqueous solution dubbed 50g 10% aqueous ammonium persulfate solution, four hours to ensure completion of the addition;

[0059] 3)滴毕保温反应3小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可。 [0059] 3) dropwise incubated for 3 hours, cooled to 25~55 ° C, adjusted to pH 6. The base was added 0 ~ 7. 5 to.

[0060] 对照例 [0060] comparative example

[0061] 一、所用单体组成及配比如下: [0061] First, the monomer composition ratio and with the following:

[0062] 1)单体A :烯丙基聚氧乙烯醚(APEG),分子量为2400,占单体总重量40% ; [0062] 1) monomer A: polyoxyethylene allyl ether (APEG), a molecular weight of 2400, 40% of the total weight of the monomers;

[0063] 2)单体B :丙烯酸(AA),占单体总重量60%。 [0063] 2) monomer B: acrylic acid (AA), 60% of the total weight of the monomers.

[0064] 二、制备工艺如下: [0064] Second, the preparation process is as follows:

[0065] 1)将40g烯丙基聚氧乙烯醚单体加入反应器内,加入24g去离子水使其溶解; [0065] 1) 40g of allyl polyoxyethylene ether monomer was added to the reactor, 24g of deionized water was added to dissolve;

[0066] 2) 一边搅拌升温一边用氮气吹扫反应器,当升温到90°C,同时滴加由60g丙烯酸单体与99g去离子水配成的混合水溶液和30g 10%过硫酸铵水溶液,保证4小时滴加完毕; [0066] 2) heating with stirring while purging the reactor with nitrogen, when heated to 90 ° C, while a solution of the mixed aqueous solution of acrylic monomer and 60g 99g of deionized water and 30g 10% dubbed aqueous solution of ammonium persulfate, 4 hours to ensure completion of the addition;

[0067] 3)滴毕保温反应2小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可。 [0067] 3) dropwise incubated for 2 hours, cooled to 25~55 ° C, adjusted to pH 6. The base was added 0 ~ 7. 5 to.

[0068] 应用实施例 [0068] Application Example

[0069] 按水泥:砂:石=390 : 750 : 961配制混凝土,其中:水泥为联合42. 5P. 0,砂为细度模数2. 6的中砂,石子为粒径5〜25mm连续级配碎石,配比为重量份;出机坍落度在210士IOmm ;混凝土中减水剂的掺量为水泥总重0. 5% ;按JC476—2001《混凝土泵送剂》进行混凝土试验,测试结果见表1所示。 [0069] Press cement: sand: Shi = 390: 750: 961 prepared concrete, wherein: cement joint 42. 5P 0, sand sand fineness modulus of 2.6, a particle size 5~25mm continuous stone. graded gravel, the ratio of parts by weight; an extruder slump in 210 persons IOmm; concrete superplasticizer dosage of 0.5% of the total weight of cement; press JC476-2001 "concrete pumping agent" of concrete test, the test results shown in Table 1.

[0070] 表1应用性能测试结果 [0070] Performance test results of Table 1

[0072] 由表1测试结果可见:对照例中因没有加入丙烯酸羟乙酯,混凝土的坍落度损失大,硬化初期的早期强度低;而本发明的醚类聚羧酸减水剂提高了对混凝土坍落度保持的性能,坍落度经时损失低,且硬化初期有充分的早期强度。 [0072] The test results can be seen from Table 1: comparative example because there is no addition of hydroxyethyl acrylate, concrete slump loss, low early strength of the initial cured; and Polycarboxylate ethers of the present invention improves the the performance of concrete slump retention, when slump loss is low, and the initial setting adequate early strength.

Claims (4)

  1. 一种醚类聚羧酸减水剂,其特征在于,由以下单体按以下配比进行水溶液共聚合而成:1)单体A:烯丙基聚氧乙烯醚(APEG),其化学结构式如下单体A占单体总重量10~70%;所述单体A的分子量为500~5000;2)单体B:丙烯酸(AA),其化学结构式如下单体B占单体总重量20~70%;3)单体C:丙烯酸羟乙酯,其化学结构式如下单体C占单体总重量10~30%;上述三种单体比例的总和为100%。 One kind of ether polycarboxylate superplasticizer, characterized in that, for an aqueous solution obtained by copolymerizing the following monomers in the following ratios: 1) monomer A: polyoxyethylene allyl ether (APEG), the chemical structural formula a total weight of monomers as the monomers 10 to 70%; molecular weight of the monomer a is from 500 to 5,000; 2) monomer B: acrylic acid (AA), the chemical structural formula of a monomer B on the total weight of monomers 20 ~ 70%; 3) monomer C: hydroxyethyl acrylate, the following chemical structural formula based on the total weight of monomers monomer C 10 to 30%; the ratio of the sum of the three monomers is 100%. FSB00000171229600011.tif,FSB00000171229600012.tif,FSB00000171229600013.tif FSB00000171229600011.tif, FSB00000171229600012.tif, FSB00000171229600013.tif
  2. 2.根据权利要求1所述的醚类聚羧酸减水剂,其特征在于,所述单体A的分子量为2000 〜3000。 2. ether polycarboxylate superplasticizer according to claim 1, wherein the molecular weight of the monomer A is 2000 ~3000.
  3. 3. —种权利要求1所述的醚类聚羧酸减水剂的制备工艺,其特征在于,包括如下顺序步骤:1)将烯丙基聚氧乙烯醚单体加入反应器内,加入去离子水使其溶解;2) 一边搅拌升温一边用氮气吹扫反应器,当升温到60〜120°C,同时滴加丙烯酸单体与丙烯酸羟乙酯单体的混合水溶液和10%过硫酸铵水溶液,保证4小时滴加完毕;3)滴毕保温反应1〜3小时,降温到25〜55°C,加入碱调pH值为6. 0〜7. 5即可; 烯丙基聚氧乙烯醚水溶液的质量百分比浓度为50〜75% ;总单体混合水溶液的质量百分比浓度为35〜45%。 3. - Preparation of ether polycarboxylate superplasticizer according to claim 1 kind, characterized in that it comprises the following sequential steps: 1) Allyl polyoxyethylene ether monomer was added to the reactor, was added to deionized water to dissolve; 2) heating while stirring the reactor was purged with nitrogen, when heated to 60~120 ° C, added dropwise with acrylic monomers hydroxyethyl acrylate monomer mix and aqueous 10% ammonium persulfate aqueous solution, four hours to ensure the completion of dropwise addition; 3) dropwise. the reaction incubated 1~3 hours, cooled to 25~55 ° C, adjusted to pH 6. the base is added to 5 0 to 7; allyl polyoxyethylene mass concentration of the ether solution 50~75%; mass percentage of the total concentration of the mixed aqueous solution of monomers 35~45%.
  4. 4.根据权利要求3所述的醚类聚羧酸减水剂的制备工艺,其特征在于,过硫酸铵的加入量为总单体重量的1〜5%。 Preparation process according to claim Polycarboxylate ethers according to claim 3, wherein the amount of ammonium persulfate was added to 1 ~ 5% of the total monomer weight.
CN 200910046749 2009-02-27 2009-02-27 Ethers polycarboxylic acid water reducing agent and preparation CN101492518B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 200910046749 CN101492518B (en) 2009-02-27 2009-02-27 Ethers polycarboxylic acid water reducing agent and preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200910046749 CN101492518B (en) 2009-02-27 2009-02-27 Ethers polycarboxylic acid water reducing agent and preparation

Publications (2)

Publication Number Publication Date
CN101492518A CN101492518A (en) 2009-07-29
CN101492518B true CN101492518B (en) 2010-12-08

Family

ID=40923322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200910046749 CN101492518B (en) 2009-02-27 2009-02-27 Ethers polycarboxylic acid water reducing agent and preparation

Country Status (1)

Country Link
CN (1) CN101492518B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107344988A (en) * 2017-08-24 2017-11-14 重庆三圣实业股份有限公司 A kind of high-adaptability protects the water reducer polycarboxylate water-reducer and preparation method thereof that collapses

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102336845B (en) 2010-07-27 2014-04-30 上海台界化工有限公司 Method for synthesizing polycarboxylic acid water reducer
CN102399068B (en) * 2010-09-13 2013-06-05 北京世纪洪雨科技有限公司 Polycarboxylic acid high performance water reducer and its preparation method
CN101983975B (en) * 2010-10-21 2012-09-19 安徽中铁工程材料科技有限公司 Preparation method of polycarboxylic acid water reducer
CN102382270A (en) * 2011-08-04 2012-03-21 陶梅 Oil well cement slurry drag reducer and preparation method thereof
CN102391435B (en) * 2011-10-09 2013-03-13 浙江五龙新材股份有限公司 Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof
CN102491677B (en) * 2011-11-22 2014-06-25 浙江五龙新材股份有限公司 Nuclear power concrete additive and preparation method thereof
CN102584092A (en) * 2012-02-24 2012-07-18 河北金舵建材科技开发有限公司 Slump loss resistant slow release polycarboxylic acid water reducer and preparation method thereof
CN102603996B (en) * 2012-02-28 2013-12-25 武汉理工大学 Ether type polycarboxylic acid slump retaining agent and preparation method thereof
CN102731730A (en) * 2012-06-21 2012-10-17 马清浩 Hydrogen peroxide auxiliarily-initiated carboxylic acid water reducer and its preparation method
CN103626935B (en) * 2012-08-23 2016-09-07 上海东大化学有限公司 A kind of slow-release type polycarboxylate water reducer, its preparation method and using method
CN103011666A (en) * 2012-11-30 2013-04-03 太原理工大学 Polycarboxylate-type cement water-reducing agent and preparation method thereof
CN103553413B (en) * 2013-09-25 2016-05-04 中国建筑材料科学研究总院 A kind of sticky type polycarboxylate water-reducer and preparation method thereof of adjusting
CN103497285B (en) * 2013-10-23 2015-12-02 中国矿业大学(北京) A kind of method adopting microwave assisting method to prepare the efficient superplasticizer of poly carboxylic acid graft copolymer class
CN103694400B (en) * 2013-11-22 2016-07-06 武汉理工大学 Carboxylic acid vinyl copolymer retarder and preparation method thereof
CN103922637B (en) * 2014-03-14 2016-03-30 石家庄市长安育才建材有限公司 High-performance C80 the reinforcement of concrete water reducer and preparation method thereof and using method
CN103980408B (en) * 2014-05-28 2016-02-10 中国日用化学工业研究院 Polyglycerine type poly carboxylic acid series water reducer and preparation method thereof
CN104261721B (en) * 2014-09-22 2016-06-29 科之杰新材料集团有限公司 A kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof
CN104926183A (en) * 2015-05-27 2015-09-23 中交四航工程研究院有限公司 High-adaptability and high-performance polycarboxylic water-reducing agent and preparation method for same
CN104945634A (en) * 2015-06-02 2015-09-30 江苏奥莱特新材料有限公司 Preparation method of amine-ester slow-setting polycarboxylic acid type water-reducer
CN105801766B (en) * 2016-03-24 2019-03-19 辽宁科隆精细化工股份有限公司 A kind of poly carboxylic acid series water reducer and preparation method thereof
CN106008847A (en) * 2016-05-19 2016-10-12 厦门君科建材科技有限公司 Preparation method of slump retaining ether type polycarboxylic water reducing agent
CN106008854A (en) * 2016-06-29 2016-10-12 武汉市华讯方舟科技有限公司 Preparation method of polycarboxylic acid water reducing agent
CN106397683B (en) * 2016-08-30 2019-03-01 北京东方雨虹防水技术股份有限公司 A kind of polycarboxylate water-reducer and preparation method thereof reducing high-grade concrete viscosity
CN107722194A (en) * 2017-10-18 2018-02-23 江苏苏博特新材料股份有限公司 A kind of high diminishing poly-carboxylic-acid cement dispersant and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107344988A (en) * 2017-08-24 2017-11-14 重庆三圣实业股份有限公司 A kind of high-adaptability protects the water reducer polycarboxylate water-reducer and preparation method thereof that collapses

Also Published As

Publication number Publication date
CN101492518A (en) 2009-07-29

Similar Documents

Publication Publication Date Title
CN1277856C (en) Cement admixture and cement composition
CN101497507B (en) High-early strength antifreezing polycarboxylate high performance water reducing agent and preparation
CN101538134B (en) Polyether polycarboxylate superplasticizer type and preparation method
CN101786824B (en) Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof
CN102124035B (en) Copolymer synthesis process
CN101913793B (en) Polyocarboxylic acid high-performance water reducer
CN100591704C (en) Method for synthesizing allyl polyether-type high-performance water reducing agent
CN105110687B (en) A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof
CN102815882A (en) High-performance water reducer of polycarboxylic acid, and preparation method thereof
CN101333092B (en) Cement concrete superplasticizer and method for preparing same
CN104140503A (en) Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature
CN101041570A (en) Preparation method of graft copolymerization carboxylate high-performance dehydragent
CN102358763B (en) Method for preparing additive for inhibiting side effect of clay
CN101928114A (en) High water reduction high collapse protection type polycarboxylate high-performance water reducer and pyrogen-free preparation method thereof
CN101333091B (en) Method for preparing high-efficiency water-reducing agent of poly-carboxylic acid
CN103408706A (en) High-performance polycarboxylic acid water reducing agent and preparation method thereof
CN102286134A (en) A method for preparing a high-performance water-reducing agent
CN102936109A (en) Polycarboxylic acid water reducing agent, preparation method and application thereof
CN102515618B (en) Slow release slump retaining polycarboxylate water reducer and preparation thereof
US8912299B2 (en) Preparation method of high-performance star-shaped polycarboxylate superplasticizer
CN102120805B (en) Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step
CN101215116A (en) Retardation setting type polycarboxylic acids series water reducing agent
CN102030494A (en) High-performance polycarboxylate water reducing agent and low-temperature one-step preparation method thereof
CN101648783A (en) Method for preparing gypsum-based self-leveling material by using desulfurization gypsum
CN103804610A (en) Method for preparing high-performance polycarboxylate superplasticizer via heat resource-free process

Legal Events

Date Code Title Description
C06 Publication
C10 Entry into substantive examination
C14 Grant of patent or utility model
ASS Succession or assignment of patent right

Owner name: CONSTRUCTION BUILDING MATERIALS INSTITUTE LTD.

Free format text: FORMER OWNER: SHANGHAI INSTITUTE OF BUILDING SCIENCES (GROUP) CO., LTD.

Effective date: 20110105

Free format text: FORMER OWNER: CONSTRUCTION BUILDING MATERIALS INSTITUTE LTD.

COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 200032 NO.75, WANPING SOUTH ROAD, XUHUI DISTRICT, SHANGHAI TO: 201414 NO.758, NANFENG HIGHWAY, QINGCUN TOWN, FENGXIAN DISTRICT, SHANGHAI

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 201414 NO. 758, NANFENG HIGHWAY, QINGCUN TOWN, FENGXIAN DISTRICT, SHANGHAI TO: 310000 WEST OF GAOXIN 7TH ROAD, NORTH OF HONGDA ROAD, QIAONAN AREA, XIAOSHAN ECONOMIC AND TECHNOLOGICAL DEVELOPMENT ZONE, XIAOSHAN DISTRICT, HANGZHOU CITY, ZHEJIANG PROVINCE

ASS Succession or assignment of patent right

Owner name: HANGZHOU TRANSFAR NEW BUILDING MATERIALS CO., LTD.

Free format text: FORMER OWNER: SHANGHAI JIANYAN BUILDING MATERIALS TECHNOLOGY CO., LTD.

Effective date: 20110428

C41 Transfer of patent application or patent right or utility model
EXPY Termination of patent right or utility model