WO2021136338A1 - Cement early strength agent composition and preparation method therefor - Google Patents
Cement early strength agent composition and preparation method therefor Download PDFInfo
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- WO2021136338A1 WO2021136338A1 PCT/CN2020/141219 CN2020141219W WO2021136338A1 WO 2021136338 A1 WO2021136338 A1 WO 2021136338A1 CN 2020141219 W CN2020141219 W CN 2020141219W WO 2021136338 A1 WO2021136338 A1 WO 2021136338A1
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- 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
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/405—Organo-inorganic complexes
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- 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
- C04B2103/10—Accelerators; Activators
- C04B2103/14—Hardening accelerators
Definitions
- the invention belongs to the technical field of building materials, and relates to an organic/inorganic hybrid calcium silicate hydrate suspension and a preparation method thereof, in particular to a cement early strength agent.
- Component factories usually use high-temperature autoclave curing and adding early strength agents to improve mold turnover.
- High-temperature autoclave curing has high energy consumption, which is not conducive to energy saving and emission reduction. Screening suitable early-strength agents has become the preferred technical way to improve the production efficiency of prefabricated components and reduce energy consumption.
- the purpose of the present invention is to provide a cement early strength agent and a preparation method thereof.
- the preparation method is simple and easy to operate, and the early-strength performance is excellent.
- a cement early strength agent composition characterized in that: a water-soluble calcium salt solution, a water-soluble iron salt solution, a water-soluble aluminum salt solution and a water-soluble silicate solution are reacted in a polymer dispersant solution to produce organic/ The inorganic hybrid hydrated calcium silicate sol particles are the cement early strength agent composition.
- the polymer dispersant contains the following structural unit derived from unsaturated polyether monomer (1) and the following structural unit derived from unsaturated carboxylic acid monomer (2) polycarboxylic acid polymer, wherein:
- the structural unit (1) is a structural unit
- R 5 represents hydrogen or methyl
- R 6 represents hydrogen, methyl or ethyl
- R 7 represents hydrogen or an alkyl group of 1-6 carbon atoms
- X is a linking group, which is -O-, -CH 2 O-, -CH 2 CH 2 O-, Or -O-CH 2 CH 2 CH 2 CH 2 O-
- n represents the average added mole number of oxyalkylene groups, and is any integer from 1-300.
- the structural unit (2) is
- R 8 represents hydrogen, methyl or COOM group
- R 9 represents hydrogen, methyl or CH 2 COOM group
- M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group.
- the polymer dispersant is characterized by a polycarboxylic acid polymerization containing the following structural unit (3) derived from unsaturated polyether monomer and the following structural unit (5) derived from unsaturated carboxylic acid monomer ⁇ , wherein the structural unit (4) is
- R 10 represents hydrogen or methyl
- R 11 O represents oxyalkylene groups with 2-8 carbon atoms and mixtures thereof
- n represents the average number of moles of oxyalkylene groups added, which is any integer from 1 to 180
- R 12 represents hydrogen or an alkyl group of 1 to 6 carbon atoms.
- the structural unit (4) is
- R 13 represents hydrogen, a methyl group or a group
- R 14 represents a hydrogen, a methyl group or a group
- M represents a hydrogen, a monovalent metal, a 1/2 divalent metal, an ammonium group or an organic amine group.
- the molar ratio of the water-soluble calcium salt to the water-soluble silicate is 1-3:2-1.
- the amount of the dispersant is 5-40% of the total mass of the early strength agent composition.
- the mass ratio of the water-soluble iron salt and the water-soluble calcium salt is 0.005-0.1.
- the mass ratio of the water-soluble aluminum salt and the water-soluble calcium salt is 0.01-0.2.
- the water-soluble calcium salt is one or a mixture of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide.
- the water-soluble iron salt is one of ferric nitrate and ferric chloride or a mixture thereof.
- the water-soluble aluminum salt is one or a mixture of aluminum nitrate, aluminum sulfate and aluminum chloride.
- the water-soluble silicate is one or a mixture of sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, and water glass.
- the preparation method of the cement early strength agent composition includes:
- the cement early strength agent composition provided by the present invention can greatly reduce the crystallization nucleation barrier of calcium silicate hydrate (CSH) gel, promote the rate of cement hydration reaction, and significantly improve the ultra-early strength of cement products within 12 hours .
- CSH calcium silicate hydrate
- Using water-soluble iron salt and water-soluble aluminum salt as doping ions can greatly increase the activity of C-S-H sol particles, and strengthen its inducing effect on the nucleation and growth of C-S-H crystals produced by cement hydration.
- the early-strength agent composition prepared by the present invention can be widely used in cement-based products that require early strength, including pipe segments, pipe piles, PC components, special mortars, etc., and can greatly increase the strength development speed, accelerate mold turnover, and increase productivity. At the same time, it can reduce maintenance energy consumption and save costs.
- the early strength performance of the prepared early strength agent was evaluated by the mortar mix ratio listed in Table 1.
- the experimental raw materials were benchmark cement P ⁇ O42.5, standard sand, and polycarboxylic acid water reducing agent (VIVID-500(D), Commercially available).
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
A cement early strength agent composition and a preparation method therefor. The cement early strength agent composition is prepared by reacting a water-soluble calcium salt solution, a water-soluble iron salt solution, a water-soluble aluminium salt solution, and a water-soluble silicate solution in a polycarboxylic acid polymer dispersant solution. The cement early strength agent composition is widely applied to cement-based products including segments, pipe piles, PC components, special mortar, etc. having special requirements for early strength, can increase the development speed of early strength, accelerating the turnover of molds, improving the productivity, and can reduce the energy consumption for curing, saving costs.
Description
本发明属于建筑材料技术领域，涉及一种有机/无机杂化水化硅酸钙悬浮液及其制备方法，具体地说是一种水泥早强剂。The invention belongs to the technical field of building materials, and relates to an organic/inorganic hybrid calcium silicate hydrate suspension and a preparation method thereof, in particular to a cement early strength agent.
预制构件生产过程中提高强度增长速度，可以加快模具周转，提高生产效率。构件厂通常采用高温蒸压养护和添加早强剂的方法来提高模具周转速度。高温蒸压养护能耗高，不利于节能减排。筛选合适的早强剂成为提高预制构件生产效率，降低能耗的优选技术途径。Increasing the growth rate of strength during the production of prefabricated components can speed up mold turnover and improve production efficiency. Component factories usually use high-temperature autoclave curing and adding early strength agents to improve mold turnover. High-temperature autoclave curing has high energy consumption, which is not conducive to energy saving and emission reduction. Screening suitable early-strength agents has become the preferred technical way to improve the production efficiency of prefabricated components and reduce energy consumption.
以无机类、有机类为主的早强剂多年来应用普遍，但存在诸多弊端，常引起混凝土工作性及耐久性的降低，如三乙醇胺类早强剂用量不易控制，且过掺易造成超缓凝或快凝；含氯早强剂易引起钢筋腐蚀；硫酸盐类早强剂使水泥石中大孔含量提高，导致混凝土的抗渗性和耐腐蚀性降低。Early-strength agents, mainly inorganic and organic, have been widely used for many years, but there are many disadvantages, which often cause the workability and durability of concrete to decrease. For example, the amount of triethanolamine-based early-strength agents is not easy to control, and excessive mixing may cause excessive Retarding or rapid setting; Chlorine-containing early-strength agents can easily cause corrosion of steel bars; sulfate-based early-strength agents increase the content of macropores in the cement stone, resulting in a decrease in the impermeability and corrosion resistance of concrete.
发明内容Summary of the invention
本发明的目的是提供一种水泥早强剂及其制备方法。作为一种新型的晶核类早强剂，制备方法简单易操作，早强性能优异。The purpose of the present invention is to provide a cement early strength agent and a preparation method thereof. As a new type of crystal nucleus early-strength agent, the preparation method is simple and easy to operate, and the early-strength performance is excellent.
实现本发明目的的具体技术方案是：The specific technical solutions to achieve the purpose of the present invention are:
一种水泥早强剂组合物，特点是：将水溶性钙盐溶液、水溶性铁盐溶液、水溶性铝盐溶液与水溶性硅酸盐溶液在聚合物分散剂溶液中发生反应，生成有机/无机杂化的水化硅酸钙溶胶颗粒，即为所述水泥早强剂组合物。A cement early strength agent composition, characterized in that: a water-soluble calcium salt solution, a water-soluble iron salt solution, a water-soluble aluminum salt solution and a water-soluble silicate solution are reacted in a polymer dispersant solution to produce organic/ The inorganic hybrid hydrated calcium silicate sol particles are the cement early strength agent composition.
所述聚合物分散剂含有以下的源自不饱和聚醚单体的结构单元(1)和以下的源自不饱和羧酸单体的结构单元(2)的聚羧酸聚合物，其中：The polymer dispersant contains the following structural unit derived from unsaturated polyether monomer (1) and the following structural unit derived from unsaturated carboxylic acid monomer (2) polycarboxylic acid polymer, wherein:
结构单元(1)是The structural unit (1) is
其中：R
5表示氢或者甲基；R
6表示氢、甲基或者乙基；R
7表示氢或1-6个碳原子的烷基；X为连接基团，为-O-、-CH
2O-、-CH
2CH
2O-、
或-O-CH
2CH
2CH
2CH
2O-；n表示氧化烯基的平均加成摩尔数，为1-300中的任意整数。
Wherein: R 5 represents hydrogen or methyl; R 6 represents hydrogen, methyl or ethyl; R 7 represents hydrogen or an alkyl group of 1-6 carbon atoms; X is a linking group, which is -O-, -CH 2 O-, -CH 2 CH 2 O-, Or -O-CH 2 CH 2 CH 2 CH 2 O-; n represents the average added mole number of oxyalkylene groups, and is any integer from 1-300.
结构单元(2)是The structural unit (2) is
其中：R
8表示氢、甲基或COOM基团，R
9表示氢、甲基或CH
2COOM基团，M表示氢、一价金属、1/2二价金属、铵基或者有机胺基。
Wherein: R 8 represents hydrogen, methyl or COOM group, R 9 represents hydrogen, methyl or CH 2 COOM group, and M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group.
所述的聚合物分散剂，其特征在于含有以下的源自不饱和聚醚单体的结构单元(3)和以下的源自不饱和羧酸单体的结构单元(5)的聚羧酸聚合物，其中结构单元(4)是The polymer dispersant is characterized by a polycarboxylic acid polymerization containing the following structural unit (3) derived from unsaturated polyether monomer and the following structural unit (5) derived from unsaturated carboxylic acid monomer物， wherein the structural unit (4) is
其中：R
10表示氢或者甲基；R
11O表示2-8个碳原子的氧化烯基及其混合物；n表示氧化烯基的平均加成摩尔数，为1-180中的任意整数；R
12表示氢或1-6个碳原子的烷基。
Wherein: R 10 represents hydrogen or methyl; R 11 O represents oxyalkylene groups with 2-8 carbon atoms and mixtures thereof; n represents the average number of moles of oxyalkylene groups added, which is any integer from 1 to 180; R 12 represents hydrogen or an alkyl group of 1 to 6 carbon atoms.
结构单元(4)是The structural unit (4) is
其中：R
13表示氢、甲基或基团，R
14表示氢、甲基或基团，M表示氢、一价金属、1/2二价金属、铵基或者有机胺基。
Wherein: R 13 represents hydrogen, a methyl group or a group, R 14 represents a hydrogen, a methyl group or a group, and M represents a hydrogen, a monovalent metal, a 1/2 divalent metal, an ammonium group or an organic amine group.
所述水溶性钙盐和水溶性硅酸盐的摩尔比为1-3:2-1。The molar ratio of the water-soluble calcium salt to the water-soluble silicate is 1-3:2-1.
所述分散剂用量为早强剂组合物总质量的5-40％。The amount of the dispersant is 5-40% of the total mass of the early strength agent composition.
所述水溶性铁盐和水溶性钙盐的质量比为0.005-0.1。The mass ratio of the water-soluble iron salt and the water-soluble calcium salt is 0.005-0.1.
所述水溶性铝盐和水溶性钙盐的质量比为0.01-0.2。The mass ratio of the water-soluble aluminum salt and the water-soluble calcium salt is 0.01-0.2.
所述水溶性钙盐为氯化钙、硝酸钙、甲酸钙、乙酸钙、柠檬酸钙、氢氧化钙和氧化钙中的一种或其混合物。The water-soluble calcium salt is one or a mixture of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide.
所述水溶性铁盐为硝酸铁和氯化铁中的一种或其混合物。The water-soluble iron salt is one of ferric nitrate and ferric chloride or a mixture thereof.
所述水溶性铝盐为硝酸铝、硫酸铝和氯化铝中的一种或其混合物。The water-soluble aluminum salt is one or a mixture of aluminum nitrate, aluminum sulfate and aluminum chloride.
所述水溶性硅酸盐为硅酸钠、硅酸钾、偏硅酸钠、偏硅酸钾、水玻璃中的一种或其混合物。The water-soluble silicate is one or a mixture of sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, and water glass.
所述水泥早强剂组合物的制备方法包括：The preparation method of the cement early strength agent composition includes:
1)称取水溶性钙盐、水溶性铁盐和水溶性铝盐制得水溶性钙溶液；称取水溶性硅酸盐制得水溶性硅酸盐溶液；称取聚合物分散剂制得分散剂溶液。1) Weigh water-soluble calcium salt, water-soluble iron salt and water-soluble aluminum salt to prepare water-soluble calcium solution; weigh water-soluble silicate to prepare water-soluble silicate solution; weigh polymer dispersant to prepare dispersant Solution.
2)控制温度在10-90℃条件下，将水溶性钙溶液和水溶性硅酸盐溶液按照1-3:2-1的摩尔比向分散剂溶液中滴加，同时保持搅拌，滴加时间设定为1-8小时；滴加结束继续搅拌1-3小时，然后缓慢降至室温，制得水泥早强剂组合物。2) Control the temperature under the condition of 10-90℃, add the water-soluble calcium solution and the water-soluble silicate solution to the dispersant solution in a molar ratio of 1-3:2-1, while keeping stirring, the time for dropping Set it to 1-8 hours; continue to stir for 1-3 hours after the dropping, and then slowly decrease to room temperature to prepare the cement early-strength agent composition.
本发明提供的水泥早强剂组合物，可大幅降低水化硅酸钙(C-S-H)凝胶的结晶成核势垒，促进水泥水化反应速率，显著提高水泥制品在12小时以内的超早期强度。采用水溶性铁盐和水溶性铝盐作为掺杂离子，可以大幅提高C-S-H溶胶颗粒的活性，加强其对水泥水化产生的C-S-H结晶成核长大的诱发作用。本发明制备的早强剂组合物可广泛应用于包括管片、管桩、PC构件、特种砂浆等对早期强度有要求的水泥基制品，可大幅提高强度发展速度，加快模具周转，提高产能，同时可以降低养护能耗，节约成本。The cement early strength agent composition provided by the present invention can greatly reduce the crystallization nucleation barrier of calcium silicate hydrate (CSH) gel, promote the rate of cement hydration reaction, and significantly improve the ultra-early strength of cement products within 12 hours . Using water-soluble iron salt and water-soluble aluminum salt as doping ions can greatly increase the activity of C-S-H sol particles, and strengthen its inducing effect on the nucleation and growth of C-S-H crystals produced by cement hydration. The early-strength agent composition prepared by the present invention can be widely used in cement-based products that require early strength, including pipe segments, pipe piles, PC components, special mortars, etc., and can greatly increase the strength development speed, accelerate mold turnover, and increase productivity. At the same time, it can reduce maintenance energy consumption and save costs.
下面结合具体实施例，进一步阐述本发明，应理解实施例仅用于说明本发明而不用于限制本发明的范围。本领域技术人员对本发明的各种等价形式的修改均落于本申请所 附权利要求所限定的范围。The present invention will be further explained below in conjunction with specific embodiments. It should be understood that the embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. The modifications made by those skilled in the art to various equivalent forms of the present invention fall within the scope defined by the appended claims of this application.
实施例1Example 1
称取38.25g的氯化钙和50.15g水配置氯化钙水溶液，称取43.74g硅酸钾和44.26g水配置硅酸钾溶液，分别称取23.80g分散剂和158.2g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在1h左右。滴加完毕继续搅拌1h，然后缓慢降温至室温，制得早强剂HA-1。Weigh 38.25g of calcium chloride and 50.15g of water to prepare calcium chloride aqueous solution, weigh 43.74g of potassium silicate and 44.26g of water to prepare potassium silicate solution, weigh 23.80g of dispersant and 158.2g of water to prepare composite dispersant, respectively Aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, adjust the dropping speed so that the dropping time is controlled at about 1h. After the addition is complete, continue to stir for 1 hour, and then slowly lower the temperature to room temperature to prepare the early-strength agent HA-1.
实施例2Example 2
称取54.85g的硝酸钙和55.29g水配置硝酸钙水溶液，称取53.74g水玻璃和44.26g水配置水玻璃溶液，分别称取22.72g分散剂和141.5g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在2h左右。滴加完毕继续搅拌4h，然后缓慢降温至室温，制得早强剂HA-2。Weigh 54.85 g of calcium nitrate and 55.29 g of water to prepare a calcium nitrate aqueous solution, weigh 53.74 g of water glass and 44.26 g of water to prepare a water glass solution, respectively weigh 22.72 g of dispersant and 141.5 g of water to prepare a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, and adjust the dropping speed so that the dropping time is controlled at about 2h. After the addition, stirring was continued for 4 hours, and then the temperature was slowly lowered to room temperature to prepare the early strength agent HA-2.
实施例3Example 3
称取44.85g的甲酸钙和53.57g水配置甲酸钙水溶液，称取48.36g偏硅酸钾和43.78g水配置偏硅酸钾溶液，分别称取24.18g分散剂和133.5g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在7h左右。滴加完毕继续搅拌3h，然后缓慢降温至室温，制得早强剂HA-3。Weigh 44.85g of calcium formate and 53.57g of water to prepare a calcium formate aqueous solution, weigh 48.36g of potassium metasilicate and 43.78g of water to prepare a potassium metasilicate solution, respectively weigh 24.18g of dispersant and 133.5g of water to prepare a composite dispersant Aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, adjust the dropping speed so that the dropping time is controlled at about 7h. After the addition, stirring was continued for 3 hours, and then the temperature was slowly lowered to room temperature to prepare the early strength agent HA-3.
实施例4Example 4
称取44.85g的甲酸钙和53.57g水配置甲酸钙水溶液，称取48.36g偏硅酸钾和43.78g水配置偏硅酸钾溶液，分别称取24.18g分散剂和133.5g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在7h左右。滴加完毕继续搅拌3h，然后缓慢降温至室温，制得早强剂HA-4。Weigh 44.85g of calcium formate and 53.57g of water to prepare a calcium formate aqueous solution, weigh 48.36g of potassium metasilicate and 43.78g of water to prepare a potassium metasilicate solution, respectively weigh 24.18g of dispersant and 133.5g of water to prepare a composite dispersant Aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, adjust the dropping speed so that the dropping time is controlled at about 7h. After the addition, stirring was continued for 3 hours, and then the temperature was slowly lowered to room temperature to prepare the early strength agent HA-4.
实施例5Example 5
称取39.64g的硝酸钙和54.20g水配置硝酸钙水溶液，称取54.37g偏硅酸钠和52.68g水配置偏硅酸钠溶液，分别称取19.36g分散剂和145.62g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在2h左右。滴加完毕继续搅拌4，然后缓慢降温至室温，制得早强剂HA-5。Weigh 39.64g calcium nitrate and 54.20g water to prepare calcium nitrate aqueous solution, weigh 54.37g sodium metasilicate and 52.68g water to prepare sodium metasilicate solution, respectively weigh 19.36g dispersant and 145.62g water to prepare composite dispersant Aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, and adjust the dropping speed so that the dropping time is controlled at about 2h. After the addition is complete, continue to stir 4, and then slowly lower the temperature to room temperature to prepare the early strength agent HA-5.
实施例6Example 6
称取39.64g硝酸钙、0.40g硝酸铁、0.20g硝酸铝和54.20g水配置硝酸钙水溶液，称取54.37g偏硅酸钠和52.68g水配置偏硅酸钠溶液，分别称取19.36g分散剂和145.62g水配置复合分散剂水溶液。将复合分散剂溶液导入三口烧瓶，温度设为15℃，将分散剂溶液搅拌均匀。保持搅拌的条件下，同时滴加氯化钙水溶液和硅酸钾水溶液，调节滴加速度使得滴加时间控制在2h左右。滴加完毕继续搅拌4，然后缓慢降温至室温，制得早强剂HA-5。Weigh 39.64g calcium nitrate, 0.40g ferric nitrate, 0.20g aluminum nitrate and 54.20g water to prepare calcium nitrate aqueous solution, weigh 54.37g sodium metasilicate and 52.68g water to prepare sodium metasilicate solution, respectively weigh 19.36g and disperse And 145.62g of water to form a composite dispersant aqueous solution. The composite dispersant solution was introduced into a three-necked flask, the temperature was set to 15°C, and the dispersant solution was stirred uniformly. While keeping stirring, add calcium chloride aqueous solution and potassium silicate aqueous solution dropwise at the same time, and adjust the dropping speed so that the dropping time is controlled at about 2h. After the addition is complete, continue to stir 4, and then slowly lower the temperature to room temperature to prepare the early strength agent HA-5.
应用例Application example
采用表1列示的砂浆配合比评价制得的早强剂的早强性能，实验原材料分别为基准水泥P·O42.5，标准砂，聚羧酸减水剂(VIVID-500(D)，市售)。The early strength performance of the prepared early strength agent was evaluated by the mortar mix ratio listed in Table 1. The experimental raw materials were benchmark cement P·O42.5, standard sand, and polycarboxylic acid water reducing agent (VIVID-500(D), Commercially available).
表1砂浆配合比Table 1 Mixture ratio of mortar
| 水泥cement | 标准砂Standard sand | 早强剂Early Strength Agent | VIVID-500(D)VIVID-500(D) | 水water | 养护条件Maintenance conditions |
| 600g600g | 1350g1350g | 1.0-5.0％1.0-5.0% | 2.5g2.5g | 210g210g | 标养Standard |
表2砂浆强度测试结果Table 2 Mortar strength test results
从表2数据可以看出，实施例1-6中添加早强剂砂浆样块强度有显著提升，尤其是7h抗压强度可达961％(实施例6)，而采用传统的无水亚硫酸钠7h抗压强度比只有261％。同时，28d抗压强度方面，添加早强剂没有倒缩现象，这也是区别于传统早强剂的一大优势。It can be seen from the data in Table 2 that the strength of the mortar sample block with the addition of the early strength agent in Examples 1-6 has been significantly improved, especially the 7h compressive strength can reach 961% (Example 6), while the traditional anhydrous sodium sulfite 7h The compressive strength ratio is only 261%. At the same time, in terms of 28d compressive strength, the addition of early-strength agents has no shrinkage, which is also a major advantage different from traditional early-strength agents.
Claims (3)
- 一种水泥早强剂组合物，其特征在于，将水溶性钙盐溶液、水溶性铁盐溶液、水溶性铝盐溶液与水溶性硅酸盐溶液在聚合物分散剂溶液中发生反应，生成有机/无机杂化的水化硅酸钙溶胶颗粒，即为所述水泥早强剂组合物；A cement early strength agent composition, which is characterized in that a water-soluble calcium salt solution, a water-soluble iron salt solution, a water-soluble aluminum salt solution and a water-soluble silicate solution are reacted in a polymer dispersant solution to produce organic /Inorganic hybrid hydrated calcium silicate sol particles, which is the cement early strength agent composition;所述聚合物分散剂含有以下的源自不饱和聚醚单体的结构单元(1)和以下的源自不饱和羧酸单体的结构单元(2)的聚羧酸聚合物，其中：The polymer dispersant contains the following structural unit derived from unsaturated polyether monomer (1) and the following structural unit derived from unsaturated carboxylic acid monomer (2) polycarboxylic acid polymer, wherein:结构单元(1)是The structural unit (1) is
其中：R 5表示氢或者甲基；R 6表示氢、甲基或者乙基；R 7表示氢或1-6个碳原子的烷基；X为连接基团，为-O-、-CH 2O-、-CH 2CH 2O-、-O-CH 2CH 2CH 2CH 2O-；n表示氧化烯基的平均加成摩尔数，为1-300中的任意整数； Wherein: R 5 represents hydrogen or methyl; R 6 represents hydrogen, methyl or ethyl; R 7 represents hydrogen or an alkyl group of 1-6 carbon atoms; X is a linking group, which is -O-, -CH 2 O-, -CH 2 CH 2 O-,
-O-CH 2 CH 2 CH 2 CH 2 O-; n represents the average added mole number of oxyalkylene groups, which is any integer from 1-300;结构单元(2)是The structural unit (2) is
其中：R 8表示氢、甲基或COOM基团，R 9表示氢、甲基或CH 2COOM基团，M表示氢、一价金属、1/2二价金属、铵基或者有机胺基； Wherein: R 8 represents hydrogen, methyl or COOM group, R 9 represents hydrogen, methyl or CH 2 COOM group, M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group;所述的聚合物分散剂为含有以下的源自不饱和聚醚单体的结构单元(3)和以下的源自不饱和羧酸单体的结构单元(4)的聚羧酸聚合物，其中：The polymer dispersant is a polycarboxylic acid polymer containing the following structural unit (3) derived from an unsaturated polyether monomer and the following structural unit (4) derived from an unsaturated carboxylic acid monomer, wherein :结构单元(3)是The structural unit (3) is
其中：R 10表示氢或者甲基；R 11O表示2-8个碳原子的氧化烯基及其混合物；n表示氧化烯基的平均加成摩尔数，为1-180中的任意整数；R 12表示氢或1-6个碳原子的烷基； Wherein: R 10 represents hydrogen or methyl; R 11 O represents oxyalkylene groups with 2-8 carbon atoms and mixtures thereof; n represents the average number of moles of oxyalkylene groups added, which is any integer from 1 to 180; R 12 represents hydrogen or an alkyl group of 1-6 carbon atoms;结构单元(4)是The structural unit (4) is
其中：R 13表示氢、甲基或基团，R 14表示氢、甲基或基团，M表示氢、一价金属、1/2二价金属、铵基或者有机胺基； Wherein: R 13 represents hydrogen, methyl or group, R 14 represents hydrogen, methyl or group, M represents hydrogen, monovalent metal, 1/2 divalent metal, ammonium group or organic amine group;所述水溶性钙盐和水溶性硅酸盐的摩尔比为1-3:2-1；The molar ratio of the water-soluble calcium salt to the water-soluble silicate is 1-3:2-1;所述分散剂用量为早强剂组合物总质量的5-40％；The amount of the dispersant is 5-40% of the total mass of the early strength agent composition;所述水溶性铁盐和水溶性钙盐的质量比为0.005-0.1；The mass ratio of the water-soluble iron salt and the water-soluble calcium salt is 0.005-0.1;所述水溶性铝盐和水溶性钙盐的质量比为0.01-0.2；The mass ratio of the water-soluble aluminum salt and the water-soluble calcium salt is 0.01-0.2;所述水溶性钙盐为氯化钙、硝酸钙、甲酸钙、乙酸钙、柠檬酸钙、氢氧化钙和氧化钙中的一种或其混合物；The water-soluble calcium salt is one or a mixture of calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide;所述水溶性铁盐为硝酸铁和氯化铁中的一种或其混合物；The water-soluble iron salt is one of ferric nitrate and ferric chloride or a mixture thereof;所述水溶性铝盐为硝酸铝、硫酸铝和氯化铝中的一种或其混合物；The water-soluble aluminum salt is one of aluminum nitrate, aluminum sulfate and aluminum chloride or a mixture thereof;所述水溶性硅酸盐为硅酸钠、硅酸钾、偏硅酸钠、偏硅酸钾、水玻璃中的一种或其混合物；The water-soluble silicate is one or a mixture of sodium silicate, potassium silicate, sodium metasilicate, potassium metasilicate, and water glass;所述水泥早强剂组合物的制备方法，具体包括：The preparation method of the cement early strength agent composition specifically includes:1)称取水溶性钙盐、水溶性铁盐和水溶性铝盐制得水溶性钙溶液；称取水溶性硅酸盐制得水溶性硅酸盐溶液；称取聚合物分散剂制得分散剂溶液；1) Weigh water-soluble calcium salt, water-soluble iron salt and water-soluble aluminum salt to prepare water-soluble calcium solution; weigh water-soluble silicate to prepare water-soluble silicate solution; weigh polymer dispersant to prepare dispersant Solution2)控制温度在10-90℃条件下，将水溶性钙溶液和水溶性硅酸盐溶液按照1-3:2-1的摩尔比向分散剂溶液中滴加，同时保持搅拌，滴加时间设定为1-8小时；滴加结束继续搅拌1-3小时，然后缓慢降至室温，制得水泥早强剂组合物。2) Control the temperature under the condition of 10-90℃, add the water-soluble calcium solution and the water-soluble silicate solution to the dispersant solution in a molar ratio of 1-3:2-1, while keeping stirring, the time for dropping Set it to 1-8 hours; continue to stir for 1-3 hours after the dropping, and then slowly decrease to room temperature to prepare the cement early-strength agent composition. - 根据权利要求1所述的水泥早强剂组合物，其特征在于，所述水泥早强剂组合物的含固量为5％-50％。The cement early-strength agent composition according to claim 1, wherein the solid content of the cement early-strength agent composition is 5%-50%.
- 根据权利要求1所述的水泥早强剂组合物，其特征在于，所述水化硅酸钙溶胶颗粒的粒径为50-250nm。The cement early strength agent composition according to claim 1, wherein the particle size of the hydrated calcium silicate sol particles is 50-250 nm.
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