WO2019233215A1 - 一种高减水低敏感聚羧酸减水剂及其制备方法 - Google Patents

一种高减水低敏感聚羧酸减水剂及其制备方法 Download PDF

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WO2019233215A1
WO2019233215A1 PCT/CN2019/084516 CN2019084516W WO2019233215A1 WO 2019233215 A1 WO2019233215 A1 WO 2019233215A1 CN 2019084516 W CN2019084516 W CN 2019084516W WO 2019233215 A1 WO2019233215 A1 WO 2019233215A1
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acid
hydroxynaphthalene
water
reaction
hydroxymethylnaphthalene
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PCT/CN2019/084516
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English (en)
French (fr)
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蒋卓君
郭鑫祺
官梦芹
陈晓彬
李祥河
林添兴
郭元强
麻秀星
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科之杰新材料集团有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/306—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and polyethylene oxide chain in the alcohol moiety
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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 technical field of building admixtures, and particularly relates to a polycarboxylic acid superplasticizer with high water reduction and low sensitivity and a preparation method thereof.
  • Polycarboxylic acid superplasticizer has the characteristics of high water reduction, low content and high slump retention, which can make concrete have good fluidity, thixotropy and long-term slump retention performance. No harmful substances such as formaldehyde and ammonia are produced during the synthetic production process.
  • the synthesis temperature is much lower than that of the naphthalene-based water reducing agent, and the production process is energy-saving and environmentally friendly.
  • it has been widely promoted and applied, and it is widely used in engineering fields such as highways, railways, bridges, nuclear power, dams, tunnels, offshore engineering and high-rise buildings.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and to provide a polycarboxylic acid superplasticizer with high water reduction and low sensitivity.
  • Another object of the present invention is to provide a method for preparing the above-mentioned highly water-reducing and low-sensitivity polycarboxylic acid water-reducing agent.
  • a highly water-reducing and low-sensitivity polycarboxylic acid water-reducing agent having molecular weight is 10,000 to 150,000, and its structural formula is as follows:
  • R 1 is H or CH 3
  • R 2 is an alkyl group of 1 to 4 carbons
  • R 3 is an alkyl group of 1 to 4 carbons
  • R 4 is an alkyl group of 1 to 4 carbons
  • R 5 is H or COOM
  • R 6 is H or CH 3
  • R 7 is H or COOM
  • R 8 is H or CH 3
  • R 9 is an empty or 1 to 4 carbon alkyl group
  • R 10 is an alkyl group having one alkane
  • M is H, Na, K or NH 4 ; the relationship between R 3 and R 4 relative to the benzene ring is ortho, meta or para.
  • the method for preparing the high water-reducing and low-sensitivity polycarboxylic acid water-reducing agent comprises the following steps:
  • the first esterification reaction the unsaturated polyether and the first compound are mixed, and the temperature is increased to 70-90 ° C under the protection of nitrogen, and then a catalyst is added, and the reaction is maintained for 0.5-3.0h, during which a vacuum or nitrogen is passed.
  • the method with water is used to remove water, and after the reaction is completed, the temperature is lowered to room temperature to obtain a first mixture containing an esterified product and an unreacted unsaturated polyether.
  • the unsaturated polyether is an allyl polyethylene with a molecular weight of 600 to 5000. At least one of alcohol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol; the structural formula of the first compound is as follows:
  • the carboxylic acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride;
  • the hydroxynaphthalenecarboxylic acid is 1-hydroxynaphthalene-4 formic acid, 1-hydroxynaphthalene-5 formic acid, 1 -Hydroxynaphthalene-6carboxylic acid, 1-hydroxynaphthalene-7carboxylic acid, 2-hydroxynaphthalene-4carboxylic acid, 2-hydroxynaphthalene-5carboxylic acid, 2-hydroxynaphthalene-6carboxylic acid, 2-hydroxynaphthalene-7carboxylic acid, 1-hydroxynaphthalene Methylnaphthalene-4carboxylic acid, 1-hydroxymethylnaphthalene-5carboxylic acid, 1-hydroxymethylnaphthalene-6carboxylic acid, 1-hydroxymethylnaphthalene-7carboxylic acid, 2-hydroxymethylnaphthalene-4carboxylic acid, 2-
  • the molar ratio of the unsaturated polyether and the first compound is 1 to 1.5: 1, and the amount of the catalyst is the unsaturated polyether and the first compound. 0.05 to 0.3% of the total mass.
  • the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalenecarboxylic acid is 2 to 7: 1, and the amount of the catalyst used is 0.03 to 0.3% of the total mass of unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalenecarboxylic acid; the amount of the polymerization inhibitor is 0.2 to 3.0% of the total mass of unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalenecarboxylic acid %.
  • the total amount of water used in step (3) and step (4) is such that the mass concentration of the copolymerization product is 20 to 70%, and the amount of the initiator is the copolymerization. 0.5 to 3.0% of the total mass of the solute in the monomer mixture solution, and the amount of the molecular weight modifier is 0.2 to 2.0% of the total mass of the solute in the comonomer mixture solution.
  • the catalyst is at least one of pyromellitic acid, nitrogen sulfur acid, and trinitrobenzenesulfonic acid.
  • the polymerization inhibitor is at least one of hydroquinone, phenothiazine, and diphenylamine.
  • the initiator is a water-soluble redox initiator system or a water-soluble azo initiator.
  • the molecular weight modifier is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecanethiol.
  • the present invention uses an esterified product of an unsaturated polyether monomer and compound A for the synthesis of a polycarboxylic acid water reducer.
  • a benzene ring and a carboxyl structure are introduced at the branched end of the polycarboxylic acid water reducer molecule.
  • the ring structure makes the steric hindrance effect of the molecular branches of the polycarboxylic acid water reducing agent enhanced, and the carboxyl structure makes the molecular branches of the polycarboxylic acid water reducing agent not only have a steric hindrance effect, but also have an electrostatic repulsion effect, which makes the prepared polymer
  • the carboxylic acid water reducing agent has a higher water reduction rate.
  • naphthalene carboxyl is introduced into the main chain of the polycarboxylic acid water reducing agent molecule by using an esterified product of an unsaturated carboxylic acid or an unsaturated carboxylic anhydride and a hydroxynaphthalene carboxylic acid for the synthesis of a polycarboxylic acid water reducing agent.
  • the acidic side group changes the adsorption effect of the polycarboxylic acid superplasticizer on cement, mud, and stone powder, so that the prepared polycarboxylic acid superplasticizer has the effect of having low sensitivity to mud and powder content in concrete aggregate.
  • the ester structure in the polycarboxylic acid water reducing agent prepared by the present invention will gradually hydrolyze and release part of the carboxylic acid group with water reducing effect under the alkaline environment of concrete, so that the prepared polycarboxylic acid water reducing agent It also has a certain slump protection effect.
  • the molecular weight of the highly water-reducing and low-sensitivity polycarboxylic acid water-reducing agent prepared in the following examples is 10,000 to 150,000, and its structural formula is as follows:
  • R 1 is H or CH 3
  • R 2 is an alkyl group of 1 to 4 carbons
  • R 3 is an alkyl group of 1 to 4 carbons
  • R 4 is an alkyl group of 1 to 4 carbons
  • R 5 is H or COOM
  • R 6 is H or CH 3
  • R 7 is H or COOM
  • R 8 is H or CH 3
  • R 9 is an empty or 1 to 4 carbon alkyl group
  • R 10 is an alkyl group having one alkane
  • M is H, Na, K or NH 4 ; the relationship between R 3 and R 4 relative to the benzene ring is ortho, meta or para.
  • the first esterification reaction 510.00g of allyl polyethylene glycol with a molecular weight of 1000 and 100.00g of phthalic acid are mixed, and the temperature is increased to 75 ° C under the protection of nitrogen, and then 0.50g of pyromellitic acid is added, and the temperature is maintained. The reaction was carried out for 2.0 hours. During the reaction, water was removed by vacuuming or passing nitrogen through water. After the reaction, the temperature was reduced to room temperature to obtain a first mixture containing an esterified product and unreacted allyl polyethylene glycol.
  • Second esterification reaction 80.00 g of methacrylic acid, 100.00 g of 1-hydroxynaphthalene-5 formic acid and 1.90 g of phenothiazine are mixed, and the temperature is increased to 100 ° C. under the protection of nitrogen, and then 0.18 g of trinitrobenzene is added. Sulfuric acid, holding the reaction for 2.5 hours. During the reaction, water was removed by evacuation or nitrogen gas. After the reaction, the temperature was reduced to room temperature to obtain a second mixture containing the esterified product and unreacted methacrylic acid.
  • (1) First esterification reaction 1450.00g of allyl polyethylene glycol having a molecular weight of 3000 and 100.00g of m-carboxymethylbenzoic acid are mixed, and the temperature is increased to 80 ° C under the protection of nitrogen, and then 4.50g of nitrogen and sulfur formula is added. Acid, keep warm for 2.5h. During the reaction, water is removed by vacuum or nitrogen and water. After the reaction, the temperature is reduced to room temperature to obtain a first mixture containing the esterified product and unreacted allyl polyethylene glycol.
  • the highly water-reducing and low-sensitivity polycarboxylic acid water-reducing agents prepared in Examples 1 to 5 were tested.
  • the solids content was 0.19% (relative to the amount of cement)
  • the water-reduction rate Both were higher than 45%
  • the compressive strength ratios were all greater than 150% at 28 days
  • the shrinkage ratios were less than 110% at 28 days.
  • Minfu PO 42.5 ordinary Portland cement is used.
  • the concrete mix ratio is: cement 300kg / m 3 , fly ash 100kg / m 3 , mineral powder 100kg / m 3 , sand 690kg / m 3 , stone 1050kg / m 3 , water 160kg / m 3 , and adding 3.5% of bentonite (relative to the amount of cement).
  • the performance test of water-based agent (PCE) is based on the solid content of 0.15%. Test the initial slump and spread of the concrete, 2h slump and spread.
  • a highly water-reducing and low-sensitivity polycarboxylic acid water-reducing agent having molecular weight is 10,000 to 150,000, and its structural formula is as follows:
  • R 1 is H or CH 3
  • R 2 is an alkyl group of 1 to 4 carbons
  • R 3 is an alkyl group of 1 to 4 carbons
  • R 4 is an alkyl group of 1 to 4 carbons
  • R 5 is H or COOM
  • R 6 is H or CH 3
  • R 7 is H or COOM
  • R 8 is H or CH 3
  • R 9 is an empty or 1 to 4 carbon alkyl group
  • R 10 is an alkyl group having one alkane
  • M is H, Na, K or NH 4 ; the relationship between R 3 and R 4 relative to the benzene ring is ortho, meta or para
  • the method for preparing the high water-reducing and low-sensitivity polycarboxylic acid water-reducing agent comprises the following steps:
  • the first esterification reaction the unsaturated polyether and the first compound are mixed, and the temperature is increased to 70-90 ° C under the protection of nitrogen, and then a catalyst is added, and the reaction is maintained for 0.5-3.0h, during which a vacuum or nitrogen is passed.
  • the method with water is used to remove water, and after the reaction is completed, the temperature is lowered to room temperature to obtain a first mixture containing an esterified product and an unreacted unsaturated polyether.
  • the unsaturated polyether is an allyl polyethylene with a molecular weight of 600 to 5000. At least one of alcohol, 3-methyl-3-butene-1-polyethylene glycol, and 2-methylallyl polyethylene glycol; the structural formula of the first compound is as follows:
  • the carboxylic acid or unsaturated carboxylic anhydride is at least one of acrylic acid, methacrylic acid, maleic acid, and maleic anhydride;
  • the hydroxynaphthalenecarboxylic acid is 1-hydroxynaphthalene-4 formic acid, 1-hydroxynaphthalene-5 formic acid, 1 -Hydroxynaphthalene-6carboxylic acid, 1-hydroxynaphthalene-7carboxylic acid, 2-hydroxynaphthalene-4carboxylic acid, 2-hydroxynaphthalene-5carboxylic acid, 2-hydroxynaphthalene-6carboxylic acid, 2-hydroxynaphthalene-7carboxylic acid, 1-hydroxynaphthalene Methylnaphthalene-4carboxylic acid, 1-hydroxymethylnaphthalene-5carboxylic acid, 1-hydroxymethylnaphthalene-6carboxylic acid, 1-hydroxymethylnaphthalene-7carboxylic acid, 2-hydroxymethylnaphthalene-4carboxylic acid, 2-
  • the molar ratio of the unsaturated polyether to the first compound is 1 to 1.5: 1, and the amount of the catalyst used is 0.05 to 0.3% of the total mass of the unsaturated polyether and the first compound.
  • the molar ratio of the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride to hydroxynaphthalenecarboxylic acid is 2 to 7: 1, and the amount of the catalyst used is unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and The total mass of hydroxynaphthalenecarboxylic acid is 0.03 to 0.3%; the amount of the polymerization inhibitor is 0.2 to 3.0% of the total mass of unsaturated carboxylic acid or unsaturated carboxylic anhydride and hydroxynaphthalenecarboxylic acid.
  • the total amount of water used in step (3) and step (4) is such that the mass concentration of the copolymerization product is 20 to 70%, and the amount of the initiator is equal to the total mass of the solute in the comonomer mixture solution. 0.5 to 3.0%, and the amount of the molecular weight modifier is 0.2 to 2.0% of the total mass of the solute in the comonomer mixture solution.
  • the catalyst is at least one of pyromellitic acid, nitrogen sulfur acid, and trinitrobenzenesulfonic acid.
  • the polymerization inhibitor is at least one of hydroquinone, phenothiazine, and diphenylamine.
  • the initiator is a water-soluble redox initiator system or a water-soluble azo initiator.
  • the molecular weight modifier is at least one of mercaptoacetic acid, mercaptopropionic acid, mercaptoethanol, isopropanol, sodium hypophosphite, trisodium phosphate, sodium formate, sodium acetate, and dodecyl mercaptan.

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  • Organic Chemistry (AREA)
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Abstract

本发明公开了一种高减水低敏感聚羧酸减水剂及其制备方法，其分子量为10000～150000，且其结构式如下：本发明通过将不饱和聚醚单体和化合物A的酯化产物用于聚羧酸减水剂的合成在聚羧酸减水剂分子的支链末端引入了苯环及羧基结构，苯环结构使得聚羧酸减水剂分子支链的空间位阻效应得到了增强，羧基结构使得聚羧酸减水剂分子支链不仅具有空间位阻效应，还具有静电斥力效应，使得制备的聚羧酸减水剂减水率更高。

Description

一种高减水低敏感聚羧酸减水剂及其制备方法 技术领域
本发明属于建筑外加剂技术领域，具体涉及一种高减水低敏感聚羧酸减水剂及其制备方法。
背景技术
聚羧酸高性能减水剂具有高减水、低掺量、高保坍等特点，能使混凝土具有良好的流动性、触变性和长时间保坍性能，且聚羧酸高性能减水剂在合成生产过程中无甲醛、氨等有害物质产生，合成温度相比萘系减水剂低很多，生产工艺节能环保。近十几年来得到了大力的推广应用，广泛应用于公路、铁路、桥梁、核电、大坝、隧道、海工和高层建筑等工程领域。
近年来由于我国房地产市场和基础设施建设高速发展，大量的工程建设耗费了巨量的水泥、砂石，加剧了砂石资源供应的紧张局面，全国不少地区的天然砂、石资源日益匮乏，砂石材料供不应求，导致砂石材料极不稳定以及砂石含泥量高且不稳定，聚羧酸减水剂应用于混凝土，出现减水率不足，保坍不好，敏感性问题日益突出。因此，开发出一种高减水，高保坍，且对材料含泥量不敏感的减水剂意义重大。
发明内容
本发明的目的在于克服现有技术缺陷，提供一种高减水低敏感聚羧酸减水剂。
本发明的另一目的在于提供上述高减水低敏感聚羧酸减水剂的制备方法。
本发明的技术方案如下：
一种高减水低敏感聚羧酸减水剂，其分子量为10000～150000，且其结构式如下：
Figure PCTCN2019084516-appb-000001
其中，R 1为H或CH 3，R 2为1～4个碳的烷基，R 3为空或1～4个碳的烷基，R 4为空或1～4个碳的烷基，R 5为H或COOM，R 6为H或CH 3，R 7为H或COOM，R 8为H或CH 3，R 9为空或1～4个碳的烷基，R 10为具有一个烷基羧酸盐取代基的萘环，M为H、Na、K或NH 4；R 3与R 4相对所在苯环的关系为邻位、间位或对位。
上述高减水低敏感聚羧酸减水剂制备方法，包括如下步骤：
(1)第一酯化反应：将不饱聚醚和第一化合物混合，在氮气保护下，升温至70～90℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱聚醚的第一混合物；上述不饱聚醚为分子量为600～5000的烯丙基聚乙二醇、3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇中的至少一种；上述第一化合物的结构式如下：
Figure PCTCN2019084516-appb-000002
(2)第二酯化反应：将不饱和羧酸或不饱和羧酸酐、羟基萘羧酸和阻聚剂混合，在氮气保护下，升温至90～120℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱和羧酸或不饱和羧酸酐的第二混合物；上述不饱和羧酸或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸、马来酸酐中的至少一种；上述羟基萘羧酸为1-羟基萘-4甲酸、1-羟基萘-5甲酸、1-羟基萘-6甲酸、1-羟基萘-7甲酸、2-羟基萘-4甲酸、2-羟基萘-5甲酸、2-羟基萘-6甲酸、2-羟基萘-7甲酸、1-羟甲基萘-4甲酸、1-羟甲基萘-5甲酸、1-羟甲基萘-6甲酸、1-羟甲基萘-7甲酸、2-羟甲基萘-4甲酸、2-羟甲基萘-5甲酸、2-羟甲基萘-6甲酸、2-羟甲基萘-7甲酸、1-羟基萘-4乙酸、1-羟基萘-5乙酸、1-羟基萘-6乙酸、1-羟基萘-7乙酸、2-羟基萘-4乙酸、2-羟基萘-5乙酸、2-羟基萘-6乙酸、2-羟基萘-7乙酸、1-羟甲基萘-4乙酸、1-羟甲基萘-5乙酸、1-羟甲基萘-6乙酸、1-羟甲基萘-7乙酸、2-羟甲基萘-4乙酸、2-羟甲基萘-5乙酸、2-羟甲基萘-6乙酸、2-羟甲基萘-7乙酸中的至少一种：
(3)单体共混：将步骤(1)制得的第一混合物和步骤(2)制得的第二混合物以100:6～18的质量比混合，并加入水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、引发剂水溶液及分子量调节剂水溶液滴入水中进行反应，反应温度为10～60℃，滴加时间为0.2～6.0h，滴加完毕后保温0～3.0h，得共聚产物；
(5)中和反应：将步骤(3)制得的共聚产物用碱调节pH至5～7，即得所述一种高减水低敏感聚羧酸减水剂。
在本发明的一个优选实施方案中，所述步骤(1)中，所述不饱聚醚和第一化合物的摩尔比为1～1.5:1，催化剂的用量为不饱聚醚和第一化合物总质量的0.05～0.3％。
在本发明的一个优选实施方案中，所述步骤(2)中，所述不饱和羧酸或不饱和羧酸酐和羟基萘羧酸的摩尔比为2～7:1，所述催化剂的用量为不饱和羧酸或不饱和羧酸酐和羟 基萘羧酸总质量的0.03～0.3％；所述阻聚剂用量为不饱和羧酸或不饱和羧酸酐和羟基萘羧酸总质量的0.2～3.0％％。
在本发明的一个优选实施方案中，所述步骤(3)和步骤(4)所用水的总量使得所述共聚产物的质量浓度为20～70％，所述引发剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.5～3.0％，所述分子量调节剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.2～2.0％。
进一步优选的，所述催化剂为苯六甲酸，氮硫方酸和三硝基苯磺酸中的至少一种。
进一步优选的，所述阻聚剂为对苯二酚、吩噻嗪和二苯胺中的至少一种。
进一步优选的，所述引发剂为水溶性氧化还原引发体系或水溶性偶氮引发剂。
进一步优选的，所述分子量调节剂为巯基乙酸、巯基丙酸、巯基乙醇、异丙醇、次磷酸钠、磷酸三钠、甲酸钠、乙酸钠和十二硫醇中的至少一种。
本发明的有益效果是：
1、本发明通过将不饱和聚醚单体和化合物A的酯化产物用于聚羧酸减水剂的合成在聚羧酸减水剂分子的支链末端引入了苯环及羧基结构，苯环结构使得聚羧酸减水剂分子支链的空间位阻效应得到了增强，羧基结构使得聚羧酸减水剂分子支链不仅具有空间位阻效应，还具有静电斥力效应，使得制备的聚羧酸减水剂减水率更高。
2、本发明通过将不饱和羧酸或不饱和羧酸酐和羟基萘羧酸的酯化产物用于聚羧酸减水剂的合成在聚羧酸减水剂分子的主链上引入了萘羧酸侧基，改变了聚羧酸减水剂在水泥、泥、石粉上的吸附效果，使得制备的聚羧酸减水剂具有对混凝土骨料中含泥和含粉量敏感性低的效果。
3、本发明制备的聚羧酸减水剂中的酯基结构在混凝土的碱性环境下还会逐渐水解释放出部分具有减水效果的羧酸基团，使得制备的聚羧酸减水剂也具有一定的保坍效果。
具体实施方式
以下通过具体实施方式对本发明的技术方案进行进一步的说明和描述。
下述实施例所制得的高减水低敏感聚羧酸减水剂的分子量为10000～150000，且其结构式如下：
Figure PCTCN2019084516-appb-000003
其中，R 1为H或CH 3，R 2为1～4个碳的烷基，R 3为空或1～4个碳的烷基，R 4为空或1～4个碳的烷基，R 5为H或COOM，R 6为H或CH 3，R 7为H或COOM，R 8为H或CH 3，R 9为空或1～4个碳的烷基，R 10为具有一个烷基羧酸盐取代基的萘环，M为H、Na、K或NH 4；R 3与R 4相对所在苯环的关系为邻位、间位或对位。
实施例1
(1)第一酯化反应：将510.00g分子量为1000的烯丙基聚乙二醇和100.00g临苯二甲酸混合，在氮气保护下，升温至75℃，再加入0.50g苯六甲酸，保温反应2.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的烯丙基聚乙二醇的第一混合物。
(2)第二酯化反应：将75.00g丙烯酸、100.00g1-羟基萘-4甲酸和2.00g对苯二酚混合，在氮气保护下，升温至95℃，再加入0.08g苯六甲酸，保温反应2.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的丙烯酸的第二混合物；
(3)单体共混：将100.00g步骤(1)制得的第一混合物、10.00g步骤(2)制得的第二混合物混合，并加入40.00g水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、双氧水水溶液(其中双氧水0.90g，水10.00g)、抗坏血酸水溶液(其中0.30g，水10.00g)及巯基乙酸水溶液(其中巯基乙酸0.70g，水10.00g)滴入40.00g水中进行反应，反应温度为55℃，滴加时间为2.5h，滴加完毕后保温1.5h，得共聚产物；
(5)中和反应：将步骤(4)制得的共聚产物用碱调节pH至5～7，即得所述高减水低敏感聚羧酸减水剂PCE-1。
实施例2
(1)第一酯化反应：将1050.00g分子量为2000的3-甲基-3-丁烯-1-聚乙二醇和100.00g间苯二乙酸混合，在氮气保护下，升温至65℃，再加入2.30g三硝基苯磺酸，保温反应2.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的3-甲基-3-丁烯-1-聚乙二醇的第一混合物。
(2)第二酯化反应：将80.00g甲基丙烯酸、100.00g1-羟基萘-5甲酸和1.90g吩噻嗪混合，在氮气保护下，升温至100℃，再加入0.18g三硝基苯磺酸，保温反应2.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的甲基丙烯酸的第二混合物；
(3)单体共混：将100.00g步骤(1)制得的第一混合物、12.00g步骤(2)制得的第二混合物混合，并加入40.00g水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、偶氮二异丁基脒盐酸盐水溶液(其中偶氮二异丁基脒盐酸盐1.20g，水10.00g)及次磷酸钠水溶液(其中次磷酸钠0.80g，水10.00g)滴入40.00g水中进行反应，反应温度为45℃，滴加时间为2.0h，滴加完毕后保温1.5h，得共聚产物；
(5)中和反应：将步骤(4)制得的共聚产物用碱调节pH至5～7，即得所述高减水低敏感聚羧酸减水剂PCE-2。
实施例3
(1)第一酯化反应：将1145.00g分子量为2400的2-甲基烯丙基聚乙二醇和100.00g对苯二丙酸混合，在氮气保护下，升温至80℃，再加入3.70g氮硫方酸，保温反应2.0h， 期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的2-甲基烯丙基聚乙二醇的第一混合物。
(2)第二酯化反应：将150.00g马来酸、100.00g1-羟基萘-6甲酸和1.80g二苯胺混合，在氮气保护下，升温至95℃，再加入0.50g氮硫方酸，保温反应1.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的马来酸的第二混合物；
(3)单体共混：将100.00g步骤(1)制得的第一混合物、8.00g步骤(2)制得的第二混合物混合，并加入40.00g水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、偶氮二氰基戊酸水溶液(其中偶氮二氰基戊酸1.80g，水10.00g)及磷酸三钠水溶液(其中磷酸三钠1.20g，水10.00g)滴入40.00g水中进行反应，反应温度为50℃，滴加时间为2.0h，滴加完毕后保温1.0h，得共聚产物；
(5)中和反应：将步骤(4)制得的共聚产物用碱调节pH至5～7，即得所述高减水低敏感聚羧酸减水剂PCE-3。
实施例4
(1)第一酯化反应：将1450.00g分子量为3000的烯丙基聚乙二醇和100.00g间羧甲基苯甲酸混合，在氮气保护下，升温至80℃，再加入4.50g氮硫方酸，保温反应2.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的烯丙基聚乙二醇的第一混合物。
(2)第二酯化反应：将185.00g马来酸酐、100.00g1-羟基萘-7甲酸和2.00g对苯二酚混合，在氮气保护下，升温至105℃，再加入0.57g三硝基苯磺酸，保温反应1.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的马来酸酐的第二混合物；
(3)单体共混：将100.00g步骤(1)制得的第一混合物、15.00g步骤(2)制得的第二混合物混合，并加入40.00g水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、双氧水水溶液(其中，双氧水1.00g，水10.00g)、磷酸三钠水溶液(其中，磷酸三钠1.00g，水10.00g)、抗坏血酸水溶液(其中，抗坏血酸0.20，水10.00g)滴入40.00g水中进行反应，反应温度为35℃，滴加时间为2.0h，滴加完毕后保温1.0h，得共聚产物；
(5)中和反应：将步骤(4)制得的共聚产物用碱调节pH至5～7，即得所述高减水低敏感聚羧酸减水剂PCE-4。
实施例5
(1)第一酯化反应：将1860.00g分子量为4000的3-甲基-3-丁烯-1-聚乙二醇和100.00g对羧乙基苯甲酸混合，在氮气保护下，升温至75℃，再加入5.80g三硝基苯磺酸，保温反应2.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的3-甲基-3-丁烯-1-聚乙二醇的第一混合物。
(2)第二酯化反应：将100.00g丙烯酸、100.00g2-羟基萘-4甲酸和3.00g吩噻嗪混合，在氮气保护下，升温至110℃，再加入0.16g苯六甲酸，保温反应2.5h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的丙烯酸的第二混合物；
(3)单体共混：将100.00g步骤(1)制得的第一混合物、12.00g步骤(2)制得的第二混合物混合，并加入40.00g水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、偶氮二氰基戊酸水溶液(其中，偶氮二氰基戊酸1.80g，水10.00g)、次磷酸钠水溶液(其中，次磷酸钠1.20g，水20.00g)滴入40.00g水中进行反应，反应温度为40℃，滴加时间为3.0h，滴加完毕后保温0.5h，得共聚产物；
(5)中和反应：将步骤(4)制得的共聚产物用碱调节pH至5～7，即得所述高减水低敏感聚羧酸减水剂PCE-5。
按照GB/T8076-2008对实施例1到实施例5所制得的高减水低敏感聚羧酸减水剂进行测试，折固掺量为0.19％时(相对于水泥用量)，减水率均高于45％，28d抗压强度比均大于150％，28d收缩率比均小于110％。
采用闽福P.O 42.5普通硅酸盐水泥，混凝土配合比为：水泥300kg/m 3、粉煤灰100kg/m 3、矿粉100kg/m 3、砂690kg/m 3、石子1050kg/m 3、水160kg/m 3，并添加膨润土3.5％(相对于水泥用量)，对实施例1到实施例5所制得的高减水低敏感聚羧酸减水剂和市售高减水聚羧酸减水剂(PCE)按照折固掺量0.15％进行性能测试。测试混凝土初始坍落度和扩展度、2h坍落度和扩展度，不同外加剂的测试结果如表1所示。
表1不同外加剂测试结果
Figure PCTCN2019084516-appb-000004
从表1可以看出，对掺有膨润土的材料，本发明合成的实施例对比市售的高减水聚羧酸减水剂(PCE)，减水率更大，保坍性能更好，由此可见本专利制备的聚羧酸减水剂对含泥量高的材料敏感性比较低。
本领域普通技术人员可知，本发明的技术方案在下述范围内变化时，仍然能够得到与上述实施例相同或相近的技术效果，仍然属于本发明的保护范围：
一种高减水低敏感聚羧酸减水剂，其分子量为10000～150000，且其结构式如下：
Figure PCTCN2019084516-appb-000005
其中，R 1为H或CH 3，R 2为1～4个碳的烷基，R 3为空或1～4个碳的烷基，R 4为空或1～4个碳的烷基，R 5为H或COOM，R 6为H或CH 3，R 7为H或COOM，R 8为H或CH 3，R 9为空或1～4个碳的烷基，R 10为具有一个烷基羧酸盐取代基的萘环，M为H、Na、K或NH 4；R 3与R 4相对所在苯环的关系为邻位、间位或对位。
上述高减水低敏感聚羧酸减水剂制备方法，包括如下步骤：
(1)第一酯化反应：将不饱聚醚和第一化合物混合，在氮气保护下，升温至70～90℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱聚醚的第一混合物；上述不饱聚醚为分子量为600～5000的烯丙基聚乙二醇、3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇中的至少一种；上述第一化合物的结构式如下：
Figure PCTCN2019084516-appb-000006
(2)第二酯化反应：将不饱和羧酸或不饱和羧酸酐、羟基萘羧酸和阻聚剂混合，在氮气保护下，升温至90～120℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱和羧酸或不饱和羧酸酐的第二混合物；上述不饱和羧酸或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸、马来酸酐中的至少一种；上述羟基萘羧酸为1-羟基萘-4甲酸、1-羟基萘-5甲酸、1-羟基萘-6甲酸、1-羟基萘-7甲酸、2-羟基萘-4甲酸、2-羟基萘-5甲酸、2-羟基萘-6甲酸、2-羟基萘-7甲酸、1-羟甲基萘-4甲酸、1-羟甲基萘-5甲酸、1-羟甲基萘-6甲酸、1-羟甲基萘-7甲酸、2-羟甲基萘-4甲酸、2-羟甲基萘-5甲酸、2-羟甲基萘-6甲酸、2-羟甲基萘-7甲酸、1-羟基萘-4乙酸、1-羟基萘-5乙酸、1-羟基萘-6乙酸、1-羟基萘-7乙酸、2-羟基萘-4乙酸、2-羟基萘-5乙酸、2-羟基萘-6乙酸、2-羟基萘-7乙酸、1-羟甲基萘-4乙酸、1-羟甲基萘-5乙酸、1-羟甲基萘-6乙酸、1-羟甲基萘-7乙酸、2-羟甲基萘-4乙酸、2-羟甲基萘-5乙酸、2-羟甲基萘-6乙酸、2-羟甲基萘-7乙酸中的至少一种：
(3)单体共混：将步骤(1)制得的第一混合物和步骤(2)制得的第二混合物以100:6～18的质量比混合，并加入水使得其溶解，得到共聚单体混合物溶液；
(4)共聚反应：将上述共聚单体混合物溶液、引发剂水溶液及分子量调节剂水溶液滴入水中进行反应，反应温度为10～60℃，滴加时间为0.2～6.0h，滴加完毕后保温0～3.0h，得共聚产物；
(5)中和反应：将步骤(3)制得的共聚产物用碱调节pH至5～7，即得所述一种高减水低敏感聚羧酸减水剂。
所述步骤(1)中，所述不饱聚醚和第一化合物的摩尔比为1～1.5:1，催化剂的用量为不饱聚醚和第一化合物总质量的0.05～0.3％。所述步骤(2)中，所述不饱和羧酸或不饱和羧酸酐和羟基萘羧酸的摩尔比为2～7:1，所述催化剂的用量为不饱和羧酸或不饱和羧酸酐和羟基萘羧酸总质量的0.03～0.3％；所述阻聚剂用量为不饱和羧酸或不饱和羧酸酐和 羟基萘羧酸总质量的0.2～3.0％％。所述步骤(3)和步骤(4)所用水的总量使得所述共聚产物的质量浓度为20～70％，所述引发剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.5～3.0％，所述分子量调节剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.2～2.0％。
所述催化剂为苯六甲酸，氮硫方酸和三硝基苯磺酸中的至少一种。所述阻聚剂为对苯二酚、吩噻嗪和二苯胺中的至少一种。所述引发剂为水溶性氧化还原引发体系或水溶性偶氮引发剂。所述分子量调节剂为巯基乙酸、巯基丙酸、巯基乙醇、异丙醇、次磷酸钠、磷酸三钠、甲酸钠、乙酸钠和十二硫醇中的至少一种。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (9)

  1. 一种高减水低敏感聚羧酸减水剂，其特征在于：其分子量为10000～150000，且其结构式如下：
    Figure PCTCN2019084516-appb-100001
    其中，R 1为H或CH 3，R 2为1～4个碳的烷基，R 3为空或1～4个碳的烷基，R 4为空或1～4个碳的烷基，R 5为H或COOM，R 6为H或CH 3，R 7为H或COOM，R 8为H或CH 3，R 9为空或1～4个碳的烷基，R 10为具有一个烷基羧酸盐取代基的萘环，M为H、Na、K或NH 4；R 3与R 4相对所在苯环的关系为邻位、间位或对位。
  2. 权利要求1所述的高减水低敏感聚羧酸减水剂制备方法，其特征在于：包括如下步骤：
    (1)第一酯化反应：将不饱聚醚和第一化合物混合，在氮气保护下，升温至70～90℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱聚醚的第一混合物；上述不饱聚醚为分子量为600～5000的烯丙基聚乙二醇、3-甲基-3-丁烯-1-聚乙二醇、2-甲基烯丙基聚乙二醇中的至少一种；上述第一化合物的结构式如下：
    Figure PCTCN2019084516-appb-100002
    (2)第二酯化反应：将不饱和羧酸或不饱和羧酸酐、羟基萘羧酸和阻聚剂混合，在氮气保护下，升温至90～120℃，再加入催化剂，保温反应0.5～3.0h，期间用抽真空或通氮气带水的方法除去水，反应结束后降至室温，得到含有酯化产物和未反应的不饱和羧酸或不饱和羧酸酐的第二混合物；上述不饱和羧酸或不饱和羧酸酐为丙烯酸、甲基丙烯酸、马来酸、马来酸酐中的至少一种；上述羟基萘羧酸为1-羟基萘-4甲酸、1-羟基萘-5甲酸、1-羟基萘-6甲酸、1-羟基萘-7甲酸、2-羟基萘-4甲酸、2-羟基萘-5甲酸、2-羟基萘-6甲酸、2-羟基萘-7甲酸、1-羟甲基萘-4甲酸、1-羟甲基萘-5甲酸、1-羟甲基萘-6甲酸、1-羟甲基萘-7甲酸、2-羟甲基萘-4甲酸、2-羟甲基萘-5甲酸、2-羟甲基萘-6甲酸、2-羟甲基萘-7甲酸、1-羟基萘-4乙酸、1-羟基萘-5乙酸、1-羟基萘-6乙酸、1-羟基萘-7乙酸、2-羟基萘-4乙酸、2-羟基萘-5乙酸、2-羟基萘-6乙酸、2-羟基萘-7乙酸、1-羟甲基萘-4乙酸、1-羟甲基萘-5乙酸、1-羟甲基萘-6乙酸、1-羟甲基萘-7乙酸、2-羟甲基萘-4乙酸、2-羟甲基萘-5乙酸、2-羟甲基萘-6乙酸、2-羟甲基萘-7乙酸中的至少一种：
    (3)单体共混：将步骤(1)制得的第一混合物和步骤(2)制得的第二混合物以100:6～18的质量比混合，并加入水使得其溶解，得到共聚单体混合物溶液；
    (4)共聚反应：将上述共聚单体混合物溶液、引发剂水溶液及分子量调节剂水溶液滴入水中进行反应，反应温度为10～60℃，滴加时间为0.2～6.0h，滴加完毕后保温0～3.0h，得共聚产物；
    (5)中和反应：将步骤(3)制得的共聚产物用碱调节pH至5～7，即得所述一种高减水低敏感聚羧酸减水剂。
  3. 如权利要求2所述的制备方法，其特征在于：所述步骤(1)中，所述不饱聚醚和第一化合物的摩尔比为1～1.5:1，催化剂的用量为不饱聚醚和第一化合物总质量的0.05～0.3％。
  4. 如权利要求2所述的制备方法，其特征在于：所述步骤(2)中，所述不饱和羧 酸或不饱和羧酸酐和羟基萘羧酸的摩尔比为2～7:1，所述催化剂的用量为不饱和羧酸或不饱和羧酸酐和羟基萘羧酸总质量的0.03～0.3％；所述阻聚剂用量为不饱和羧酸或不饱和羧酸酐和羟基萘羧酸总质量的0.2～3.0％％。
  5. 如权利要求2所述的制备方法，其特征在于：所述步骤(3)和步骤(4)所用水的总量使得所述共聚产物的质量浓度为20～70％，所述引发剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.5～3.0％，所述分子量调节剂的用量为所述共聚单体混合物溶液中溶质的总质量的0.2～2.0％。
  6. 如权利要求2至5中任一权利要求所述的制备方法，其特征在于：所述催化剂为苯六甲酸，氮硫方酸和三硝基苯磺酸中的至少一种。
  7. 如权利要求2至5中任一权利要求所述的制备方法，其特征在于：所述阻聚剂为对苯二酚、吩噻嗪和二苯胺中的至少一种。
  8. 如权利要求2至5中任一权利要求所述的制备方法，其特征在于：所述引发剂为水溶性氧化还原引发体系或水溶性偶氮引发剂。
  9. 如权利要求2至5中任一权利要求所述的制备方法，其特征在于：所述分子量调节剂为巯基乙酸、巯基丙酸、巯基乙醇、异丙醇、次磷酸钠、磷酸三钠、甲酸钠、乙酸钠和十二硫醇中的至少一种。
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