WO2020087866A1 - Long-acting sustained-release polycarboxylic acid set-retarding agent and preparation method therefor - Google Patents

Long-acting sustained-release polycarboxylic acid set-retarding agent and preparation method therefor Download PDF

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WO2020087866A1
WO2020087866A1 PCT/CN2019/081223 CN2019081223W WO2020087866A1 WO 2020087866 A1 WO2020087866 A1 WO 2020087866A1 CN 2019081223 W CN2019081223 W CN 2019081223W WO 2020087866 A1 WO2020087866 A1 WO 2020087866A1
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acid
parts
preparation
unsaturated
solution
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PCT/CN2019/081223
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French (fr)
Chinese (zh)
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赖广兴
方云辉
温庆如
赖华珍
李格丽
柯余良
钟丽娜
张小芳
杜可禄
张秉旺
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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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • 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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups 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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
    • 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

Definitions

  • the invention belongs to the technical field of building materials, and in particular relates to a long-acting slow-release type polycarboxylic acid slump retaining agent and a preparation method thereof.
  • polycarboxylic acid water-reducing agent As a third-generation new type of high-performance water-reducing agent, polycarboxylic acid water-reducing agent has the advantages of high water-reducing rate, designable molecular structure and small air entrainment. It is very suitable for the preparation of high-strength and high-performance concrete. It is recognized that it has been widely used in large-scale infrastructure such as nuclear power, water conservancy, bridges, tunnels and other large-scale projects. However, due to factors such as temperature change, cement change, and high mud content of sand and stone materials, the problem of excessive slump loss in the application of polycarboxylic acid water-reducing agent has affected the construction and quality of the project.
  • the following methods can be used: adding a retarder, using multiple additions of water reducing agent method and adopting the method of adding water reducing agent after.
  • adding a retarder using multiple additions of water reducing agent method and adopting the method of adding water reducing agent after.
  • the addition of retarder will affect the setting time of cement.
  • the amount of water-reducing agent is difficult to control, and it is easy to over-mix, which leads to the segregation of concrete bleeding, which affects the quality of the project.
  • the most important and optimal method on the market is to adopt the method of compounding polycarboxylic acid slump-retaining agent, which can solve the problem of slump loss without negatively affecting the setting time and strength development of concrete.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a long-acting slow-release polycarboxylic acid slump retention agent.
  • Another object of the present invention is to provide a preparation method of the above-mentioned ultra-slow-release polycarboxylic acid slump inhibitor.
  • the cumenyl polyoxyethylene ether has the following general formula:
  • n is the average added mole number of EO, n is 10-29, and (EO) n is a homopolymer structure.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer, both solutions are within 5-6h After the addition is completed, keep warm for 2 ⁇ 3h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 30% -50%.
  • the saturated acid is at least one of propionic acid, butyric acid and valeric acid.
  • the polymerization inhibitor is benzyltributylammonium chloride, tris (N-nitroso-N-phenylhydroxylamine) aluminum and 4-oxo-2,2,6 At least one of 6-tetramethylpiperidine-1-oxyl radicals.
  • the catalyst is at least one of copper chloride, zinc chloride and aluminum trichloride.
  • the water-carrying agent is at least one of chloroform, carbon tetrachloride, and 1,2-dichloroethane.
  • the unsaturated monocarboxylic acid is at least one of acrylic acid and methacrylic acid.
  • the photoinitiator is triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate and tri (4-tolyl) sulfonium trifluoromethane At least one of sulfonates.
  • the chain transfer agent is 3-mercaptoacetic acid-2-methylhexyl ester, 2,4-diphenyl-4-methyl-1-pentene and 4-cyano At least one of -4- (phenylthioformylthio) valeric acid.
  • the unsaturated carboxylic acid ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid At least one of methyl ester, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.
  • DIPSO 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid
  • the slump-preventing agent prepared by the present invention uses cumenyl polyoxyethylene ether as a macromonomer, which introduces an aromatic ring and an isopropyl structure, so that the polycarboxylic acid prepared from the macromonomer is slump-preserving
  • the molecular structure of the agent is more conducive to the adsorption on the surface of the cement particles and improves the stretch of the polyether chain, so as to achieve the purpose of improving the slump retention performance.
  • the slump-preserving agent prepared by the present invention will gradually release carboxylic acid groups that contribute to the water-reducing effect due to the gradual hydrolysis of the ester bond in an alkaline environment, thereby compensating for the loss of water-reducing rate and achieving slump retention Degree effect.
  • DIPSO has three hydroxyl groups. After esterification, unsaturated esterified small monomers with three ester groups can release more carboxylate ions than traditional acrylic acid monoester hydrolysis, and the effect of continuous dispersion is better. .
  • the present invention introduces phosphate groups in the synthesis and releases the phosphate groups during the slow hydrolysis of the phosphate groups. Since the phosphate groups have better adsorption capacity than the sulfate in cement, it can make the polycarboxylic acid The performance of the water reducing agent is not affected by the sulfate, and after slow release, the dispersing ability of the polycarboxylic acid water reducing agent is greatly improved, showing a better slump retention ability.
  • the invention emits ultraviolet photons by ultraviolet light to initiate the polymerization reaction. Compared with the conventional solution polymerization method, it has a faster rate of free radical generation, free radical distribution in the solution, no heating, narrow molecular weight distribution, and low cost It has the advantages of simple operation, easy industrial production and wide application prospects.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 5h When finished, keep warm for 2h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 6h When finished, keep warm for 3h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5 to 7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 40%.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer at the same time, both solutions are added dropwise within 5h When finished, keep warm for 3h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 6h When finished, keep warm for 2h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
  • the polycarboxylate slumping agents synthesized in Examples 1 to 4 and the comparative examples were used to measure the concrete properties.
  • the concrete mixing ratio is shown in Table 1.
  • the concrete added with the polycarboxylic acid slump-preserving agent prepared by the present invention has a slump-preserving effect that is significantly better than that of the comparative slump-preserving agent sample, and has a significant slump-preserving effect over a longer period of time (0-4 h).
  • a long-acting slow-release polycarboxylic acid slump retaining agent and preparation method thereof include the following steps:
  • the cumenyl polyoxyethylene ether has the following general formula:
  • n is the average added mole number of EO, n is 10-29, and (EO) n is a homopolymer structure.
  • the wavelength of ultraviolet light is 350-600mm
  • the irradiation intensity is 50-110W / m 2
  • the first solution and the second solution are added dropwise to the primer, both solutions are within 5-6h After the addition is completed, keep warm for 2 ⁇ 3h after the addition;
  • the obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 30% -50%.
  • the saturated acid is at least one of propionic acid, butyric acid and valeric acid.
  • the polymerization inhibitor is benzyltributylammonium chloride, tris (N-nitroso-N-phenylhydroxylamine) aluminum and 4-oxo-2,2,6 At least one of 6-tetramethylpiperidine-1-oxyl radicals.
  • the catalyst is at least one of copper chloride, zinc chloride and aluminum trichloride.
  • the water-carrying agent is at least one of chloroform, carbon tetrachloride, and 1,2-dichloroethane.
  • the unsaturated monocarboxylic acid is at least one of acrylic acid and methacrylic acid.
  • the photoinitiator is triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate and tri (4-tolyl) sulfonium trifluoromethane At least one of sulfonates.
  • the chain transfer agent is 3-mercaptoacetic acid-2-methylhexyl ester, 2,4-diphenyl-4-methyl-1-pentene and 4-cyano At least one of -4- (phenylthioformylthio) valeric acid.
  • the unsaturated carboxylic acid ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid At least one of methyl ester, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Disclosed are a long-acting sustained-release polycarboxylic acid set-retarding agent and a preparation method therefor, the method comprising the following steps: (1) esterification: reacting methacrylic acid, saturated acid and 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid under the action of a catalyst to obtain unsaturated esterified small monomers; (2) putting cumenyl polyoxyethylene ether, unsaturated monocarboxylic acid, diethyl 3-butenylphosphonate, etc. in a substrate material, and then, separately dropping a photoinitiator (a first solution), a chain transfer agent, an unsaturated monocarboxylic acid, an unsaturated esterified small monomer, and an unsaturated carboxylate (a second solution) dissolved in deionized water to the substrate material for reaction and polymerization; and (3) after the heat preservation is completed, adding a pH adjusting solution for neutralization to obtain the product. The set-retarding agent prepared by the present invention has a good slump constant retention capability over a long period of time.

Description

一种长效缓释型聚羧酸保坍剂及其制备方法Long-acting slow-release polycarboxylic acid slump retaining agent and preparation method thereof 技术领域Technical field
本发明属于建筑材料技术领域，具体涉及一种长效缓释型聚羧酸保坍剂及其制备方法。The invention belongs to the technical field of building materials, and in particular relates to a long-acting slow-release type polycarboxylic acid slump retaining agent and a preparation method thereof.
背景技术Background technique
聚羧酸系减水剂作为第三代新型高性能减水剂，具有减水率高、分子结构可设计、引气量小等优点，非常适用于配制高强、高性能混凝土，已受到市场广泛的认可，目前已经大量应用于核电、水利、桥梁、隧道等大型基础设施和其它大型工程。但由于受到温度变化、水泥变化及砂、石材料含泥量较高等因素的影响，使得聚羧酸减水剂在应用中出现了坍落度损失过快的问题，影响工程施工与质量。As a third-generation new type of high-performance water-reducing agent, polycarboxylic acid water-reducing agent has the advantages of high water-reducing rate, designable molecular structure and small air entrainment. It is very suitable for the preparation of high-strength and high-performance concrete. It is recognized that it has been widely used in large-scale infrastructure such as nuclear power, water conservancy, bridges, tunnels and other large-scale projects. However, due to factors such as temperature change, cement change, and high mud content of sand and stone materials, the problem of excessive slump loss in the application of polycarboxylic acid water-reducing agent has affected the construction and quality of the project.
解决混凝土施工中坍落度损失过快的问题，可以采用如下几种方法：加入缓凝剂，采用多次添加减水剂法和采用后掺减水剂法。采用上述几种方法，虽然一定程度上可以解决坍落度损失的问题，但弊端也较多，如加入缓凝剂，会影响水泥的凝结时间，而采用多次添加和后掺减水剂的方法，对减水剂的掺量较难控制，容易超掺，导致混凝土泌水离析，从而影响工程质量。目前市场上最主要和最优的方法就是采用复配聚羧酸保坍剂的方法，既可以解决坍落度损失问题，又不会对混凝土的凝结时间和强度发展等方面带来负面影响。To solve the problem of excessive slump loss in concrete construction, the following methods can be used: adding a retarder, using multiple additions of water reducing agent method and adopting the method of adding water reducing agent after. Using the above methods, although it can solve the problem of slump loss to a certain extent, there are many disadvantages. For example, the addition of retarder will affect the setting time of cement. Method, the amount of water-reducing agent is difficult to control, and it is easy to over-mix, which leads to the segregation of concrete bleeding, which affects the quality of the project. At present, the most important and optimal method on the market is to adopt the method of compounding polycarboxylic acid slump-retaining agent, which can solve the problem of slump loss without negatively affecting the setting time and strength development of concrete.
目前市场上现有的保坍剂在混凝土应用中，虽然可以改善混凝土保坍效果，但保坍性能不足，提高保坍剂用量，成本又大幅度提升，无法完全满足市场需求，且随着城市拥堵的加剧，混凝土搅拌车运输时间越来越长，因此开发一种长效超缓释高保坍性能的保坍剂显得尤为重要。At present, in the application of existing slump retention agents in concrete, although the slump retention effect of concrete can be improved, the slump retention performance is insufficient, the amount of slump retention agent is increased, and the cost is greatly increased, which cannot fully meet the market demand. As congestion intensifies, the transportation time of concrete mixer trucks is getting longer and longer, so it is particularly important to develop a long-acting ultra-slow release high slump retention agent.
发明内容Summary of the invention
本发明的目的在于克服现有技术缺陷，提供一种长效缓释型聚羧酸保坍剂。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a long-acting slow-release polycarboxylic acid slump retention agent.
本发明的另一目的在于提供上述超缓释型聚羧酸保坍剂的制备方法。Another object of the present invention is to provide a preparation method of the above-mentioned ultra-slow-release polycarboxylic acid slump inhibitor.
本发明的具体技术方案如下：The specific technical solution of the present invention is as follows:
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将反应摩尔比为0.5～1.5:1.0～2:1的甲基丙烯酸、饱和酸、3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入占甲基丙烯酸、饱和酸和DIPSO三种物料总量0.1％～0.2％的催化剂、0.05％～0.2％的阻聚剂和5％～15％的带水剂，进行酯化反应，酯化反应温度为100～130℃，反应时间为3～9小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, add methacrylic acid, saturated acid, 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) with a reaction molar ratio of 0.5 ～ 1.5: 1.0 ～ 2: 1 Into the reactor, simultaneously add 0.1% ～ 0.2% catalyst, 0.05% ～ 0.2% polymerization inhibitor and 5% ～ 15% water-carrying agent of methacrylic acid, saturated acid and DIPSO. In the esterification reaction, the esterification reaction temperature is 100-130 ° C, the reaction time is 3-9 hours, and the temperature is reduced to room temperature after the reaction is completed, that is, the unsaturated esterified small monomer is obtained.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚、1～4份3-丁烯基磷羧酸乙酯及0.5～2份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用1～3份不饱和一元羧酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether, 1 to 4 parts of ethyl 3-butenylphosphonate, and 0.5 to 2 parts of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water As a primer, the pH of the primer is adjusted to 5 to 6 with 1 to 3 parts of unsaturated monocarboxylic acid.
所述枯烯基聚氧乙烯醚，有如下通式所示：The cumenyl polyoxyethylene ether has the following general formula:
Figure PCTCN2019081223-appb-000001
Figure PCTCN2019081223-appb-000001
其中EO为氧化乙烯基单元，n为EO的平均加成摩尔数，n为10-29，(EO)n为均聚物结构。Where EO is an oxyethylene unit, n is the average added mole number of EO, n is 10-29, and (EO) n is a homopolymer structure.
将2～6份光引发剂溶于30重量份去离子水中得到第一溶液；将0.5～1.5份链转移剂、1～4份不饱和一元羧酸、2～10份不饱和酯化小单体、5～10份不饱和羧酸酯溶于25重量份去离子水中，得到第二溶液。Dissolve 2 to 6 parts of photoinitiator in 30 parts by weight of deionized water to obtain the first solution; dissolve 0.5 to 1.5 parts of chain transfer agent, 1 to 4 parts of unsaturated monocarboxylic acid, and 2 to 10 parts of unsaturated esterified monomer 5 to 10 parts of unsaturated carboxylic acid ester is dissolved in 25 parts by weight of deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在5～6h内滴加完毕，滴加结束后保温2～3h； Irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer, both solutions are within 5-6h After the addition is completed, keep warm for 2 ~ 3h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为30％～50％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 30% -50%.
在本发明的一个优选实施方案中，所述饱和酸为丙酸、丁酸和戊酸中的至少一种。In a preferred embodiment of the present invention, the saturated acid is at least one of propionic acid, butyric acid and valeric acid.
在本发明的一个优选实施方案中，所述阻聚剂为苄基三丁基氯化铵、三(N-亚硝基-N-苯基羟胺)铝和4-氧-2,2,6,6-四甲基哌啶-1-氧自由基中的至少一种。In a preferred embodiment of the present invention, the polymerization inhibitor is benzyltributylammonium chloride, tris (N-nitroso-N-phenylhydroxylamine) aluminum and 4-oxo-2,2,6 At least one of 6-tetramethylpiperidine-1-oxyl radicals.
在本发明的一个优选实施方案中，所述催化剂为氯化铜、氯化锌和三氯化铝中的至少一种。In a preferred embodiment of the present invention, the catalyst is at least one of copper chloride, zinc chloride and aluminum trichloride.
在本发明的一个优选实施方案中，所述带水剂为氯仿、四氯化碳和1，2-二氯乙烷中的至少一种。In a preferred embodiment of the present invention, the water-carrying agent is at least one of chloroform, carbon tetrachloride, and 1,2-dichloroethane.
在本发明的一个优选实施方案中，所述不饱和一元羧酸为丙烯酸和甲基丙烯酸中的至少一种。In a preferred embodiment of the present invention, the unsaturated monocarboxylic acid is at least one of acrylic acid and methacrylic acid.
在本发明的一个优选实施方案中，所述光引发剂为三苯基锍四氟硼酸盐、三(4-甲苯基)锍六氟磷酸盐和三(4-甲苯基)锍三氟甲烷磺酸盐中的至少一种。In a preferred embodiment of the present invention, the photoinitiator is triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate and tri (4-tolyl) sulfonium trifluoromethane At least one of sulfonates.
在本发明的一个优选实施方案中，所述链转移剂为3-巯基乙酸-2-甲基己酯、2,4-二苯基-4-甲基-1-戊烯和4-氰基-4-(苯基硫代甲酰硫基)戊酸中的至少一种。In a preferred embodiment of the present invention, the chain transfer agent is 3-mercaptoacetic acid-2-methylhexyl ester, 2,4-diphenyl-4-methyl-1-pentene and 4-cyano At least one of -4- (phenylthioformylthio) valeric acid.
在本发明的一个优选实施方案中，所述不饱和羧酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸丁酯中的至少一种。In a preferred embodiment of the present invention, the unsaturated carboxylic acid ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid At least one of methyl ester, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.
本发明的有益效果是：The beneficial effects of the present invention are:
1)本发明通过3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)与不饱和酸，饱和酸进行酯化，制备不饱和酯化小单体，其中DIPSO中带有磺酸根，可有效的降低混凝土溶液中硫酸根离子对其的影响，达到更好的材料适应性。另外，这种结构对因砂石含泥量高而造成的混凝土坍损大的现象有良好的缓解作用。1) In the present invention, 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) is esterified with unsaturated acid and saturated acid to prepare unsaturated esterified small monomer, in which DIPSO contains With sulfonate, it can effectively reduce the influence of sulfate ion in concrete solution to achieve better material adaptability. In addition, this structure has a good mitigating effect on the concrete collapse caused by the high sand and mud content.
2)本发明制备的保坍剂采用枯烯基聚氧乙烯醚作为大单体，这种大单体引入了芳环及异丙基结构，使得由该大单体制备的聚羧酸保坍剂的分子结构更利于在水泥颗粒表面的吸附及改善聚醚链的舒展，从而达到在保坍性能上提高的目的。2) The slump-preventing agent prepared by the present invention uses cumenyl polyoxyethylene ether as a macromonomer, which introduces an aromatic ring and an isopropyl structure, so that the polycarboxylic acid prepared from the macromonomer is slump-preserving The molecular structure of the agent is more conducive to the adsorption on the surface of the cement particles and improves the stretch of the polyether chain, so as to achieve the purpose of improving the slump retention performance.
3)本发明制备的保坍剂会因为酯键在碱性环境中的逐渐水解而逐渐释放出对减水效果有贡献的羧酸基团，从而补偿了损失的减水率，达到保持坍落度的效果。另外，DIPSO带有三个羟基，酯化后参与聚合的不饱和酯化小单体带有三个酯基，比传统的丙烯酸单酯水解能够释放出更多的羧酸根离子，持续分散的效果更佳。3) The slump-preserving agent prepared by the present invention will gradually release carboxylic acid groups that contribute to the water-reducing effect due to the gradual hydrolysis of the ester bond in an alkaline environment, thereby compensating for the loss of water-reducing rate and achieving slump retention Degree effect. In addition, DIPSO has three hydroxyl groups. After esterification, unsaturated esterified small monomers with three ester groups can release more carboxylate ions than traditional acrylic acid monoester hydrolysis, and the effect of continuous dispersion is better. .
4)本发明在合成中引入了磷酸酯基团，在磷酸酯基团缓慢水解中释放出磷酸基团，由于磷酸基团比水泥中的硫酸盐具有更好的吸附能力，可以使得聚羧酸减水剂性能不受硫酸盐的影响，缓慢释放后大大提高该聚羧酸减水剂的分散能力，显示为更好的保坍能力。4) The present invention introduces phosphate groups in the synthesis and releases the phosphate groups during the slow hydrolysis of the phosphate groups. Since the phosphate groups have better adsorption capacity than the sulfate in cement, it can make the polycarboxylic acid The performance of the water reducing agent is not affected by the sulfate, and after slow release, the dispersing ability of the polycarboxylic acid water reducing agent is greatly improved, showing a better slump retention ability.
5)本发明通过紫外灯光发射紫外光子，从而引发聚合反应，与常规的溶液聚合方法相比，具有产生自由基速度快，自由基在溶液中分布均匀，无需加热，分子量分布窄，成本较低的优点，操作简便，易于工业化生产，有广泛应用前景。5) The invention emits ultraviolet photons by ultraviolet light to initiate the polymerization reaction. Compared with the conventional solution polymerization method, it has a faster rate of free radical generation, free radical distribution in the solution, no heating, narrow molecular weight distribution, and low cost It has the advantages of simple operation, easy industrial production and wide application prospects.
3、具体实施方式3. Specific implementation
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。其中，枯烯基聚氧乙烯醚通式及部分信息如下所示：The following further describes and describes the technical solution of the present invention through specific implementation manners. Among them, the general formula and some information of cumenyl polyoxyethylene ether are as follows:
Figure PCTCN2019081223-appb-000002
Figure PCTCN2019081223-appb-000002
表1枯烯基聚氧乙烯醚部分信息Table 1 Partial information of cumenyl polyoxyethylene ether
编号Numbering nn 分子量Molecular weight
P-1P-1 1010 613613
P-2P-2 1515 833833
P-3P-3 2020 10531053
P-4P-4 2929 14491449
实施例1Example 1
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将41份甲基丙烯酸、71份丙酸、130份3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入0.25份氯化铜、0.13份苄基三丁基氯化铵和13份的氯仿，进行酯化反应，酯化反应温度为100℃，反应时间为3小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, add 41 parts of methacrylic acid, 71 parts of propionic acid, and 130 parts of 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) to the reactor, while adding 0.25 Parts of copper chloride, 0.13 parts of benzyltributylammonium chloride and 13 parts of chloroform, esterification reaction, esterification reaction temperature is 100 ℃, reaction time is 3 hours, after the reaction is reduced to room temperature, that is not Saturated small monomer.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚P-1、1份3-丁烯基磷羧酸乙酯及0.5份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用1份丙烯酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether P-1, 1 part of ethyl 3-butenylphosphonate and 0.5 part of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water as For the primer, adjust the pH of the primer to 5-6 with 1 part of acrylic acid.
将3份三苯基锍四氟硼酸盐溶于30重量份去离子水中得到第一溶液；将0.5份3-巯基乙酸-2-甲基己酯、3份丙烯酸、2份不饱和酯化小单体、10份丙烯酸羟乙酯溶于25重量份去离子水中，得到第二溶液。Dissolve 3 parts of triphenylsulfonium tetrafluoroborate in 30 parts by weight of deionized water to obtain a first solution; 0.5 parts of 3-mercaptoacetic acid-2-methylhexyl ester, 3 parts of acrylic acid, and 2 parts of unsaturated esterification The small monomer and 10 parts of hydroxyethyl acrylate were dissolved in 25 parts by weight of deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在5h内滴加完毕，滴加结束后保温2h； Irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 5h When finished, keep warm for 2h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为40％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
实施例2Example 2
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将60份甲基丙烯酸、162份丁酸、130份3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入0.55份氯化锌、0.45份三(N-亚硝基-N-苯基羟胺)铝和18份的四氯化碳，进行酯化反应，酯化反应温度为110℃，反应时间为4小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, 60 parts of methacrylic acid, 162 parts of butyric acid, and 130 parts of 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) were added to the reactor, while 0.55 Parts of zinc chloride, 0.45 parts of tris (N-nitroso-N-phenylhydroxylamine) aluminum and 18 parts of carbon tetrachloride were subjected to an esterification reaction, the esterification reaction temperature was 110 ° C, and the reaction time was 4 hours, After the reaction is completed, the temperature is lowered to room temperature to obtain the unsaturated esterified small monomer.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚P-2、2份3-丁烯基磷羧酸乙酯及1.5份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用2份丙烯酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether P-2, 2 parts of ethyl 3-butenylphosphonate, and 1.5 parts of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water as For the primer, adjust the pH of the primer to 5 to 6 with 2 parts of acrylic acid.
将6份三(4-甲苯基)锍六氟磷酸盐溶于30重量份去离子水中得到第一溶液；将1份2,4-二苯基-4-甲基-1-戊烯、2份甲基丙烯酸、6份不饱和酯化小单体、8份甲基丙烯酸羟乙酯溶于25重量份去离子水中，得到第二溶液。Dissolve 6 parts of tris (4-tolyl) sulfonium hexafluorophosphate in 30 parts by weight of deionized water to obtain a first solution; dissolve 1 part of 2,4-diphenyl-4-methyl-1-pentene, 2 One part of methacrylic acid, 6 parts of unsaturated esterified small monomers, and 8 parts of hydroxyethyl methacrylate were dissolved in 25 parts by weight of deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在6h内滴加完毕，滴加结束后保温3h； Irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 6h When finished, keep warm for 3h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂， 其含固量为40％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5 to 7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 40%.
实施例3Example 3
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将90份甲基丙烯酸、85份丁酸、130份3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入0.6份氯化铜、0.35份苄基三丁基氯化铵和40份的氯仿，进行酯化反应，酯化反应温度为120℃，反应时间为5小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, 90 parts of methacrylic acid, 85 parts of butyric acid, and 130 parts of 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) were added to the reactor, while adding 0.6 Parts of copper chloride, 0.35 parts of benzyltributylammonium chloride and 40 parts of chloroform, esterification reaction, esterification reaction temperature is 120 ℃, reaction time is 5 hours, after the reaction is reduced to room temperature, that is not Saturated small monomer.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚P-3、3份3-丁烯基磷羧酸乙酯及1份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用3份甲基丙烯酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether P-3, 3 parts of ethyl 3-butenylphosphonate, and 1 part of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water as For the primer, adjust the pH of the primer to 5 to 6 with 3 parts of methacrylic acid.
将2份三苯基锍四氟硼酸盐溶于30重量份去离子水中得到第一溶液；将1.5份3-巯基乙酸-2-甲基己酯、14份丙烯酸、8份不饱和酯化小单体、6份丙烯酸羟丙酯溶于25重量份去离子水中，得到第二溶液。Dissolve 2 parts of triphenylsulfonium tetrafluoroborate in 30 parts by weight of deionized water to obtain the first solution; 1.5 parts of 3-mercaptoacetic acid-2-methylhexyl ester, 14 parts of acrylic acid, and 8 parts of unsaturated esterification The small monomer and 6 parts of hydroxypropyl acrylate were dissolved in 25 parts by weight of deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在5h内滴加完毕，滴加结束后保温3h； It is irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer at the same time, both solutions are added dropwise within 5h When finished, keep warm for 3h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为40％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
实施例4Example 4
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将120份甲基丙烯酸、100份戊酸、130份3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入0.7份三氯化铝、0.6份4-氧-2,2,6,6-四甲基哌啶-1-氧自由基和35份的1，2-二氯乙烷，进行酯化反应，酯化反应温度为130℃，反应时间为9小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, 120 parts of methacrylic acid, 100 parts of valeric acid, and 130 parts of 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) were added to the reactor, while adding 0.7 Parts aluminum trichloride, 0.6 parts 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl radical and 35 parts 1,2-dichloroethane for esterification, ester The reaction temperature is 130 ° C., the reaction time is 9 hours, and the temperature is reduced to room temperature after the reaction is completed, that is, the unsaturated esterified small monomer is obtained.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚P-4、4份3-丁烯基磷羧酸乙酯及2份偶氮二咪 唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用2.5份甲基丙烯酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether P-4, 4 parts of ethyl 3-butenylphosphonate and 2 parts of azobisimidazolinyl propane dihydrochloride in appropriate amount of deionized water as For the primer, use 2.5 parts of methacrylic acid to adjust the pH of the primer to 5-6.
将5份三(4-甲苯基)锍三氟甲烷磺酸盐溶于30重量份去离子水中得到第一溶液；将1份4-氰基-4-(苯基硫代甲酰硫基)戊酸、1份甲基丙烯酸、10份不饱和酯化小单体、5份甲基丙烯酸羟丙酯溶于25重量份去离子水中，得到第二溶液。Dissolve 5 parts of tris (4-tolyl) sulfonium trifluoromethanesulfonate in 30 parts by weight of deionized water to obtain a first solution; dissolve 1 part of 4-cyano-4- (phenylthioformylthio) Valeric acid, 1 part methacrylic acid, 10 parts unsaturated esterified small monomers, and 5 parts hydroxypropyl methacrylate were dissolved in 25 parts by weight deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在6h内滴加完毕，滴加结束后保温2h； Irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer, both solutions are added dropwise within 6h When finished, keep warm for 2h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为40％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent with a solid content of 40%.
将实施例1～4合成得到的聚羧酸保坍剂和比较例(市售性能佳的聚羧酸保坍剂，含固量为40％)进行混凝土性能测定，混凝土配合比见表1。将聚羧酸减水剂和保坍剂进行复配，复配工艺为m 聚羧酸减水剂：m 保坍剂：m 水＝400:600:4000，采用相同的掺量，所得结果如表2所示： The polycarboxylate slumping agents synthesized in Examples 1 to 4 and the comparative examples (commercially available polycarboxylate slumping agents with a solid content of 40%) were used to measure the concrete properties. The concrete mixing ratio is shown in Table 1. The polycarboxylic acid water-reducing agent and slumping agent are compounded, the compounding process is m polycarboxylic acid water-reducing agent : m slumping agent : m water = 400: 600: 4000, using the same dosage, the result is Table 2:
表1混凝土原材料及配合比Table 1 Concrete raw materials and mix ratio
材料品种Material variety 水泥cement 粉煤灰Fly ash 砂sand 石stone 水water
用量kg/m 3 Dosage kg / m 3 270270 8080 800800 10501050 160160
表2实施例性能对比Table 2 Example performance comparison
Figure PCTCN2019081223-appb-000003
Figure PCTCN2019081223-appb-000003
Figure PCTCN2019081223-appb-000004
Figure PCTCN2019081223-appb-000004
从上述结果可知，加入本发明制备的聚羧酸保坍剂的混凝土，保坍效果明显优于对比保坍剂样品，且在较长的时间内(0～4h)保坍效果显著。It can be seen from the above results that the concrete added with the polycarboxylic acid slump-preserving agent prepared by the present invention has a slump-preserving effect that is significantly better than that of the comparative slump-preserving agent sample, and has a significant slump-preserving effect over a longer period of time (0-4 h).
本领域普通技术人员可知，本发明的技术参数和原料组分在下述范围内变化时，仍能够得到与上述实施例相同或相近的技术效果，仍属与本发明的保护范围：It can be known by those of ordinary skill in the art that when the technical parameters and raw material components of the present invention are changed within the following ranges, the same or similar technical effects as the above embodiments can still be obtained, which still fall within the protection scope of the present invention:
一种长效缓释型聚羧酸保坍剂及其制备方法，包括如下步骤：A long-acting slow-release polycarboxylic acid slump retaining agent and preparation method thereof include the following steps:
(1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
在常压条件下，将反应摩尔比为0.5～1.5:1.0～2:1的甲基丙烯酸、饱和酸、3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入占甲基丙烯酸、饱和酸和DIPSO三种物料总量0.1％～0.2％的催化剂、0.05％～0.2％的阻聚剂和5％～15％的带水剂，进行酯化反应，酯化反应温度为100～130℃，反应时间为3～9小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, add methacrylic acid, saturated acid, 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) with a reaction molar ratio of 0.5 ～ 1.5: 1.0 ～ 2: 1 Into the reactor, simultaneously add 0.1% ～ 0.2% catalyst, 0.05% ～ 0.2% polymerization inhibitor and 5% ～ 15% water-carrying agent of methacrylic acid, saturated acid and DIPSO. In the esterification reaction, the esterification reaction temperature is 100-130 ° C, the reaction time is 3-9 hours, and the temperature is reduced to room temperature after the reaction is completed, that is, the unsaturated esterified small monomer is obtained.
(2)共聚反应：(2) Copolymerization reaction:
室温下，将100份枯烯基聚氧乙烯醚、1～4份3-丁烯基磷羧酸乙酯及0.5～2份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用1～3份不饱和一元羧酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether, 1 to 4 parts of ethyl 3-butenylphosphonate, and 0.5 to 2 parts of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water As a primer, the pH of the primer is adjusted to 5 to 6 with 1 to 3 parts of unsaturated monocarboxylic acid.
所述枯烯基聚氧乙烯醚，有如下通式所示：The cumenyl polyoxyethylene ether has the following general formula:
Figure PCTCN2019081223-appb-000005
Figure PCTCN2019081223-appb-000005
其中EO为氧化乙烯基单元，n为EO的平均加成摩尔数，n为10-29，(EO)n为均聚物结构。Where EO is an oxyethylene unit, n is the average added mole number of EO, n is 10-29, and (EO) n is a homopolymer structure.
将2～6份光引发剂溶于30重量份去离子水中得到第一溶液；将0.5～1.5份链转移剂、 1～4份不饱和一元羧酸、2～10份不饱和酯化小单体、5～10份不饱和羧酸酯溶于25重量份去离子水中，得到第二溶液。Dissolve 2 to 6 parts of photoinitiator in 30 parts by weight of deionized water to obtain the first solution; dissolve 0.5 to 1.5 parts of chain transfer agent, 1 to 4 parts of unsaturated monocarboxylic acid, and 2 to 10 parts of unsaturated esterified monomer 5 to 10 parts of unsaturated carboxylic acid ester is dissolved in 25 parts by weight of deionized water to obtain a second solution.
置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在5～6h内滴加完毕，滴加结束后保温2～3h； Irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer, both solutions are within 5-6h After the addition is completed, keep warm for 2 ~ 3h after the addition;
(3)中和反应：(3) Neutralization reaction:
将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为30％～50％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 30% -50%.
在本发明的一个优选实施方案中，所述饱和酸为丙酸、丁酸和戊酸中的至少一种。In a preferred embodiment of the present invention, the saturated acid is at least one of propionic acid, butyric acid and valeric acid.
在本发明的一个优选实施方案中，所述阻聚剂为苄基三丁基氯化铵、三(N-亚硝基-N-苯基羟胺)铝和4-氧-2,2,6,6-四甲基哌啶-1-氧自由基中的至少一种。In a preferred embodiment of the present invention, the polymerization inhibitor is benzyltributylammonium chloride, tris (N-nitroso-N-phenylhydroxylamine) aluminum and 4-oxo-2,2,6 At least one of 6-tetramethylpiperidine-1-oxyl radicals.
在本发明的一个优选实施方案中，所述催化剂为氯化铜、氯化锌和三氯化铝中的至少一种。In a preferred embodiment of the present invention, the catalyst is at least one of copper chloride, zinc chloride and aluminum trichloride.
在本发明的一个优选实施方案中，所述带水剂为氯仿、四氯化碳和1，2-二氯乙烷中的至少一种。In a preferred embodiment of the present invention, the water-carrying agent is at least one of chloroform, carbon tetrachloride, and 1,2-dichloroethane.
在本发明的一个优选实施方案中，所述不饱和一元羧酸为丙烯酸和甲基丙烯酸中的至少一种。In a preferred embodiment of the present invention, the unsaturated monocarboxylic acid is at least one of acrylic acid and methacrylic acid.
在本发明的一个优选实施方案中，所述光引发剂为三苯基锍四氟硼酸盐、三(4-甲苯基)锍六氟磷酸盐和三(4-甲苯基)锍三氟甲烷磺酸盐中的至少一种。In a preferred embodiment of the present invention, the photoinitiator is triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate and tri (4-tolyl) sulfonium trifluoromethane At least one of sulfonates.
在本发明的一个优选实施方案中，所述链转移剂为3-巯基乙酸-2-甲基己酯、2,4-二苯基-4-甲基-1-戊烯和4-氰基-4-(苯基硫代甲酰硫基)戊酸中的至少一种。In a preferred embodiment of the present invention, the chain transfer agent is 3-mercaptoacetic acid-2-methylhexyl ester, 2,4-diphenyl-4-methyl-1-pentene and 4-cyano At least one of -4- (phenylthioformylthio) valeric acid.
在本发明的一个优选实施方案中，所述不饱和羧酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸丁酯中的至少一种。In a preferred embodiment of the present invention, the unsaturated carboxylic acid ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, methacrylic acid At least one of methyl ester, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate.
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。The above are only preferred embodiments of the present invention, so the scope of implementation of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the scope of the patent of the present invention and the content of the description should still be covered by the present invention In the range.

Claims (9)

  1. 一种长效缓释型聚羧酸保坍剂及其制备方法，其特征在于：包括如下步骤：A long-acting slow-release polycarboxylic acid slump retaining agent and its preparation method, characterized in that it includes the following steps:
    (1)不饱和酯化小单体的制备：(1) Preparation of unsaturated esterified small monomers:
    在常压条件下，将反应摩尔比为0.5～1.5:1.0～2:1的甲基丙烯酸、饱和酸、3-双(2-羟乙基)氨基-2-羟基丙磺酸(DIPSO)加入到反应器中，同时加入占甲基丙烯酸、饱和酸和DIPSO三种物料总量0.1％～0.2％的催化剂、0.05％～0.2％的阻聚剂和5％～15％的带水剂，进行酯化反应，酯化反应温度为100～130℃，反应时间为3～9小时，反应结束后降至室温，即得不饱和酯化小单体。Under normal pressure, add methacrylic acid, saturated acid, 3-bis (2-hydroxyethyl) amino-2-hydroxypropanesulfonic acid (DIPSO) with a reaction molar ratio of 0.5 ～ 1.5: 1.0 ～ 2: 1 Into the reactor, simultaneously add 0.1% ～ 0.2% catalyst, 0.05% ～ 0.2% polymerization inhibitor and 5% ～ 15% water-carrying agent of methacrylic acid, saturated acid and DIPSO. In the esterification reaction, the esterification reaction temperature is 100-130 ° C, the reaction time is 3-9 hours, and the temperature is reduced to room temperature after the reaction is completed, that is, the unsaturated esterified small monomer is obtained.
    (2)共聚反应：(2) Copolymerization reaction:
    室温下，将100份枯烯基聚氧乙烯醚、1～4份3-丁烯基磷羧酸乙酯及0.5～2份偶氮二咪唑啉基丙烷二盐酸盐溶于适量去离子水中作为底料，用1～3份不饱和一元羧酸调节底料的pH至5～6。At room temperature, dissolve 100 parts of cumenyl polyoxyethylene ether, 1 to 4 parts of ethyl 3-butenylphosphonate, and 0.5 to 2 parts of azobisimidazolinyl propane dihydrochloride in an appropriate amount of deionized water As a primer, the pH of the primer is adjusted to 5 to 6 with 1 to 3 parts of unsaturated monocarboxylic acid.
    所述枯烯基聚氧乙烯醚，有如下通式所示：The cumenyl polyoxyethylene ether has the following general formula:
    Figure PCTCN2019081223-appb-100001
    Figure PCTCN2019081223-appb-100001
    其中EO为氧化乙烯基单元，n为EO的平均加成摩尔数，n为10-29，(EO)n为均聚物结构。Where EO is an oxyethylene unit, n is the average added mole number of EO, n is 10-29, and (EO) n is a homopolymer structure.
    将2～6份光引发剂溶于30重量份去离子水中得到第一溶液；将0.5～1.5份链转移剂、1～4份不饱和一元羧酸、2～10份不饱和酯化小单体、5～10份不饱和羧酸酯溶于25重量份去离子水中，得到第二溶液。Dissolve 2 to 6 parts of photoinitiator in 30 parts by weight of deionized water to obtain the first solution; dissolve 0.5 to 1.5 parts of chain transfer agent, 1 to 4 parts of unsaturated monocarboxylic acid, and 2 to 10 parts of unsaturated esterified monomer 5 to 10 parts of unsaturated carboxylic acid ester is dissolved in 25 parts by weight of deionized water to obtain a second solution.
    置于紫外光下照射，紫外光的波长为350～600mm，照射强度为50～110W/m 2，同时滴加第一溶液和第二溶液至底料中，两种溶液均在5～6h内滴加完毕，滴加结束后保温2～3h； It is irradiated under ultraviolet light, the wavelength of ultraviolet light is 350-600mm, the irradiation intensity is 50-110W / m 2 , and the first solution and the second solution are added dropwise to the primer at the same time, both solutions are within 5-6h After the addition is completed, keep warm for 2 ~ 3h after the addition;
    (3)中和反应：(3) Neutralization reaction:
    将得到的共聚产物用氢氧化钠溶液中和至pH值为5～7，即得所述的聚羧酸保坍剂，其含固量为30％～50％。The obtained copolymerization product is neutralized with a sodium hydroxide solution to a pH value of 5-7, to obtain the polycarboxylic acid slump-proofing agent, which has a solid content of 30% -50%.
  2. 如权利要求1所述的制备方法，其特征在于：所述饱和酸为丙酸、丁酸和戊酸中 的至少一种。The preparation method according to claim 1, wherein the saturated acid is at least one of propionic acid, butyric acid and valeric acid.
  3. 如权利要求1所述的制备方法，其特征在于：所述阻聚剂为苄基三丁基氯化铵、三(N-亚硝基-N-苯基羟胺)铝和4-氧-2,2,6,6-四甲基哌啶-1-氧自由基中的至少一种。The preparation method according to claim 1, wherein the polymerization inhibitor is benzyltributylammonium chloride, tris (N-nitroso-N-phenylhydroxylamine) aluminum and 4-oxo-2 , At least one of 2,6,6-tetramethylpiperidine-1-oxyl radicals.
  4. 如权利要求1所述的制备方法，其特征在于：所述催化剂为氯化铜、氯化锌和三氯化铝中的至少一种。The preparation method according to claim 1, wherein the catalyst is at least one of copper chloride, zinc chloride and aluminum trichloride.
  5. 如权利要求1所述的制备方法，其特征在于：所述带水剂为氯仿、四氯化碳和1，2-二氯乙烷中的至少一种。The preparation method according to claim 1, wherein the water-carrying agent is at least one of chloroform, carbon tetrachloride, and 1,2-dichloroethane.
  6. 如权利要求1所述的制备方法，其特征在于：所述不饱和一元羧酸为丙烯酸和甲基丙烯酸中的至少一种。The preparation method according to claim 1, wherein the unsaturated monocarboxylic acid is at least one of acrylic acid and methacrylic acid.
  7. 如权利要求1所述的制备方法，其特征在于：所述光引发剂为三苯基锍四氟硼酸盐、三(4-甲苯基)锍六氟磷酸盐和三(4-甲苯基)锍三氟甲烷磺酸盐中的至少一种。The preparation method according to claim 1, wherein the photoinitiator is triphenylsulfonium tetrafluoroborate, tri (4-tolyl) sulfonium hexafluorophosphate and tri (4-tolyl) At least one of sulfonium trifluoromethanesulfonate.
  8. 如权利要求1所述的制备方法，其特征在于：所述链转移剂为3-巯基乙酸-2-甲基己酯、2,4-二苯基-4-甲基-1-戊烯和4-氰基-4-(苯基硫代甲酰硫基)戊酸中的至少一种。The preparation method according to claim 1, wherein the chain transfer agent is 3-mercaptoacetic acid-2-methylhexyl ester, 2,4-diphenyl-4-methyl-1-pentene and At least one of 4-cyano-4- (phenylthioformylthio) valeric acid.
  9. 如权利要求1所述的制备方法，其特征在于：所述不饱和羧酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯和甲基丙烯酸丁酯中的至少一种。The preparation method according to claim 1, wherein the unsaturated carboxylic acid ester is hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate , Methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, at least one of butyl acrylate and butyl methacrylate.
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