WO2021103473A1 - 一种减缩型聚羧酸减水剂及其制备方法 - Google Patents
一种减缩型聚羧酸减水剂及其制备方法 Download PDFInfo
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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
- 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
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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
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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
- C04B24/16—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
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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
- C04B24/24—Macromolecular compounds
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Definitions
- the invention relates to the technical field of building admixtures, in particular to a shrinkage-reducing polycarboxylic acid water reducer and a preparation method thereof.
- polycarboxylic acid water-reducing agent As a new type of water-reducing agent, polycarboxylic acid water-reducing agent has the advantages of low dosage, high water-reducing rate, good slump retention, low shrinkage, relatively good adaptability to cement and admixtures, and obvious enhancement effects.
- the outstanding performance of the series has been widely used in various engineering fields. With the construction of large-scale national infrastructure nuclear power, water conservancy, bridges and various large-scale projects, the performance requirements of all aspects of concrete are continuously improved. It also has the effect of reducing the drying shrinkage of hardened concrete.
- This multifunctional polycarboxylic acid water reducing agent has become a research hotspot at home and abroad.
- the first type of shrinkage reducing agent currently in use is mainly alcohols, including diols, triols and their homologs. Such substances have low boiling points, are volatile, and flammable, and are inconvenient to use in engineering practice. Alcohols with large molecular weights have disadvantages such as large dosage and high cost; the second type is alkanolamines which also have a good shrinkage reduction effect, but they are expensive and difficult to promote in engineering. At the same time, shrinkage reducing agents will reduce the strength of concrete, which also has a certain impact on the promotion of shrinkage reducing agents.
- the third type is a polycarboxylic acid water reducer with good shrinkage reduction function. This water reducer introduces shrinkage reducing groups from the molecular structure. It has a high water reduction rate and a good shrinkage reduction function. However, the current market The shrinkage reducing agent not only has a low water reduction rate, but also has a poor shrinkage effect.
- Patent CN 106380554 A published on February 08, 2017, discloses a method for preparing lipid viscosity-reducing polycarboxylic acid water-reducing agent, which uses polyethylene glycol monomethyl ether and methyl methacrylate for esterification
- the esterification monomer is prepared by chemical synthesis, and the esterification monomer is polymerized with unsaturated sulfonic acid, crosslinking monomer, and cationic monomer under the action of emulsifier, initiator, and chain transfer agent.
- the reduction involved in this scheme Although the water agent has good dispersibility, viscosity reduction and mud resistance, it has not been able to reduce the drying shrinkage of concrete and improve the strength of concrete. In summary, it is of great significance to develop a shrinkage-reducing polycarboxylic acid water-reducing agent to reduce the drying shrinkage of concrete.
- the present invention provides a shrinkage-reducing polycarboxylic acid water-reducing agent, which also includes the following components: esterified product , Unsaturated polyoxyethylene ether, emulsifier, initiator solution, chain transfer agent solution, ester macromonomer, acrylic acid, shrink-reducing functional monomer and unsaturated sulfonate mixed solution;
- the esterification product includes monomers with amides and dihydroxy groups and unsaturated esterification products;
- the shrinkage reduction functional monomer is a monomer with double bonds and ethoxy groups.
- the preparation method of the monomer with amide and dihydroxy and the unsaturated esterification product comprises the following steps:
- unsaturated acid and compound A i.e. coconut acid diethanolamide
- catalyst and polymerization inhibitor in a protective gas atmosphere, and adjust the temperature to 80-120°C, and react for 4-6h to obtain Monomers with amides and dihydroxyl groups and unsaturated esterification products;
- the structure of the compound A is:
- R is a C 11 H 23 alkyl group.
- the unsaturated acid is one of acrylic acid, maleic anhydride, and fumaric acid.
- the catalyst includes at least one of cerium sulfate, antimony trioxide, and p-toluenesulfonic acid.
- the polymerization inhibitor includes at least one of 4-hydroxypiperidinol oxygen radical, 4-tert-butylcatechol, and methylhydroquinone.
- the molar ratio of the unsaturated acid and the compound A is 1 to 3.5:1
- the amount of the catalyst is 0.5% to 3.5% of the total mass of the unsaturated acid and the compound A
- the amount of the polymerization inhibitor is 0.3%-2% of the total mass of the unsaturated acid and compound A.
- the shrinkage-reducing functional monomer having a double bond and an ethoxy group is triethylene glycol divinyl ether.
- the unsaturated polyoxyethylene ether is methallyl polyoxyethylene ether, allyl polyoxyethylene polyoxypropylene ether, methallyl polyoxyethylene ether with a molecular weight of 3000 One of polyoxyethylene polyoxypropylene ether or allyl alcohol polyoxyethylene ether.
- ester macromonomers are polyethylene glycol monoacrylate with a molecular weight of 1000-3000, polyethylene glycol monomethacrylate, monomethoxy ether monoacrylic acid Polyethylene glycol ester, one of the monomethoxy ether monomethacrylate polyethylene glycol esters.
- the unsaturated sulfonate is sodium 3-allyloxy-2-hydroxy-1-propane sulfonate, 3-prop-2-enoyloxypropane-1 -One of potassium sulfonates.
- the emulsifier is composed of sodium dodecylbenzene sulfonate and diethylene glycol monolaurate in a mass ratio of 1:2.
- the initiator is one of ammonium persulfate-sodium hypophosphite, hydrogen peroxide-sodium hypophosphite, and hydrogen peroxide-ascorbic acid.
- the chain transfer agent is one of thioglycolic acid, mercaptopropionic acid, and n-butyl mercaptan.
- the mass ratio of the esterification product, unsaturated polyoxyethylene ether, ester macromonomer, acrylic acid, shrinkage-reducing functional monomer and unsaturated sulfonate is 1 to 3: 70:30:8 ⁇ 18:1 ⁇ 5:2 ⁇ 5.
- the amount of the emulsifier is 0.9%-1.8% of the total mass of the unsaturated polyoxyethylene ether and the ester macromonomer
- the amount of the initiator is the unsaturated polyoxyethylene ether.
- 2%-5% of the total mass of the ester macromonomer, and the amount of the chain transfer agent is 0.8%-3% of the total mass of the unsaturated polyoxyethylene ether and the ester macromonomer.
- the present invention also provides a preparation method of any of the above-mentioned shrinkage-reducing polycarboxylic acid water-reducing agents, which comprises the following steps:
- esterification product unsaturated polyoxyethylene ether, and emulsifier into the reaction vessel and mix, and then drop the initiator solution, chain transfer agent solution, ester macromonomers, acrylic acid, shrinkage-reducing functional monomers and unsaturated sulfonic acid.
- the salt mixed solution is reacted at room temperature for 1.5 to 2 hours. After the reaction is completed, the temperature is kept for a period of time, and 32% liquid caustic soda is added to adjust the pH to 6 to 7 to obtain the shrinkage-reducing polycarboxylic acid water reducing agent.
- the shrinkage-reducing polycarboxylic acid water reducer provided by the present invention utilizes the esterification product obtained by esterification containing monohydroxyl or dihydroxyl to participate in the next copolymerization reaction, so that the main chain of the polycarboxylic acid water reducer has amides and hydroxyl groups. And other hydrophilic groups, the prepared polycarboxylate water-reducing agent has lower surface tension. By preparing the esterified product and introducing it into the polycarboxylate water-reducing agent, it can effectively reduce the surface tension of the concrete pore solution, thereby reducing the concrete Dry shrinkage.
- the monomer obtained after partial dihydroxy esterification is a cross-linking monomer, which realizes partial cross-linking during the polymerization process and increases the steric effect of the system. Under the alkaline conditions of cement, the hydrolysis of the cross-linked structure is slower than that of esters.
- the water-reducing agent obtained by copolymerization of monomers of groups such as acid anhydride, etc. gradually hydrolyzes over time and continuously releases carboxylic acid groups that contribute to the water-reducing effect, thereby compensating for the loss of water-reducing rate and achieving maintenance
- the effect of slump; amide is hydrophilic and easy to form intramolecular hydrogen bonds, which helps to ensure the stability of molecular configuration; amide groups will form hydrogen bonds with water and form a solvated water film on the surface of cement particles. Play a lubricating effect, the hydrated gel product is tightly needle-like and intertwined with the surrounding gel product, thus improving the strength of the cement.
- the ester macromonomer used in the present invention participates in the copolymerization reaction, so that the long side chain structure is connected to the molecular chain of the water reducer, and the long side chain structure contains ester groups, which are continuously hydrolyzed and released under the alkaline condition of cement.
- the functional carboxyl group plays a role in slump retention, and the ester macromonomer improves the workability of concrete; the introduction of unsaturated sulfonate can effectively improve the initial dispersibility of concrete.
- the provided shrinkage-reducing polycarboxylate water-reducing agent introduces a shrinkage-reducing functional monomer with two double bonds, so that more ethoxy structures are introduced into the molecular chain of the polycarboxylate water-reducing agent, which can effectively reduce the dryness of concrete.
- Shrinkage, and the introduction of two double-bond shrink-reducing functional monomers enables the water-reducing agent to achieve cross-linking to form a three-dimensional network structure, increasing the steric effect of the system, and making the concrete have better dispersibility and dispersibility retention performance.
- the esterification product is prepared by esterification of coconut acid diethanolamide and unsaturated acid, which has the advantages of low cost and simple operation; in addition, coconut acid diethanolamide is an anionic surfactant, which is prepared by preparing esters.
- the chemical product is introduced into the polycarboxylic acid water reducing agent, which can effectively reduce the surface tension of the concrete pore solution, thereby reducing the drying shrinkage of the concrete.
- the emulsion polymerization method adopted in the present invention is not only simple in production, short in synthesis time, and fast in polymerization rate, and the formed latex film has an effective bridging effect on the formation of microcracks inside the concrete Formation and expansion to form a cross-linked network structure, which improves the internal mechanical properties and strength of the concrete.
- esterified product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide and 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- the first dropping device 0.5 parts of ascorbic acid, 1.5 parts of n-butyl mercaptan and 20 parts of water are mixed uniformly in the second dropping device; 8 parts of acrylic acid, 1 part of triethylene glycol divinyl ether, 4 parts of 3- Sodium allyloxy-2-hydroxy-1-propane sulfonate and 20 parts of water are uniformly mixed in the third dripping device; the first dripping device and the second dripping device are successively added to the second reaction vessel at room temperature.
- the materials in the feeding device and the third dripping device are respectively dripped in the materials in the third dripping device, the second dripping device, and the first dripping device in 1.5h, and the constant temperature reaction is 0.5h;
- esterification product In parts by weight, add 87.8 parts of acrylic acid and 100 parts of coco diethanolamide into the first reaction vessel and mix, under nitrogen conditions, add 2.17 parts of cerium sulfate and 1.16 parts of 4-hydroxyl Piperidinol oxygen radical, adjust the temperature to 120°C, react for 6h, and then obtain monomers with amide and dihydroxy and unsaturated esterification products;
- esterified product In parts by weight, 81 parts of fumaric acid and 100 parts of coco diethanolamide were added to the first reaction vessel and mixed, and under nitrogen conditions, 4 parts of cerium sulfate and 2.4 parts of formaldehyde were added. Hydroquinone, adjust the temperature to 80°C, react for 5 hours, and then obtain monomers with amides and dihydroxy groups and unsaturated esterification products;
- esterified product In parts by weight, add 50 parts of maleic anhydride and 100 parts of coco diethanolamide into the first reaction vessel and mix, under nitrogen conditions, add 6.48 parts of p-toluenesulfonic acid, 3.7 A portion of 4-tert-butylcatechol, and adjust the temperature to 100°C, react for 4 hours to obtain monomers with amides and dihydroxy groups and unsaturated esterification products;
- Copolymerization reaction In parts by weight, first mix 70 parts of allyl polyoxyethylene polyoxypropylene ether with a molecular weight of 3000, 30 parts of polyethylene glycol monoacrylate with a molecular weight of 600, and 0.45 parts of dodecyl benzene sulfonate.
- esterified product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide and 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- the materials in the first dropping device, the second dropping device and the third dropping device are sequentially started to be dropped into the second reaction vessel at room temperature , The materials in the third dripping device, the second dripping device, and the first dripping device were respectively dripped in 1.5h, and reacted at a constant temperature for 0.5h.
- esterified product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide and 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- Copolymerization reaction in parts by weight, first combine 3 parts of the esterified product obtained in step (1), 70 parts of allyl polyoxyethylene polyoxypropylene ether with a molecular weight of 3000, and 30 parts of a molecular weight of 600 Polyethylene glycol monoacrylate and 110 parts of water are added into the second reaction vessel and stirred evenly.
- 1.5 parts of hydrogen peroxide and 20 parts of water are mixed evenly in the first dropping device; 0.5 parts of ascorbic acid, 1.5 parts of n-butyl mercaptan and 20 parts Mix parts of water uniformly in the second dropping device; 8 parts of acrylic acid, 1 part of triethylene glycol divinyl ether, 4 parts of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate and 20 parts of water Mix uniformly in the third dripping device; start dripping the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction vessel at room temperature in turn, and finish the dripping in 1.5h.
- the materials in the third dripping device, the second dripping device, and the first dripping device react at a constant temperature for 0.5h;
- esterified product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide and 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- the first dropping device 0.5 parts of ascorbic acid, 1.5 parts of n-butyl mercaptan and 20 parts of water are mixed uniformly in the second dropping device; 8 parts of acrylic acid, 1 part of diethylene glycol monovinyl ether, 4 parts of 3- Sodium allyloxy-2-hydroxy-1-propane sulfonate and 20 parts of water are uniformly mixed in the third dripping device; the first dripping device and the second dripping device are successively added to the second reaction vessel at room temperature.
- the materials in the feeding device and the third dripping device are respectively dripped in the materials in the third dripping device, the second dripping device, and the first dripping device in 1.5h, and the constant temperature reaction is 0.5h;
- Copolymerization reaction In parts by weight, first mix 70 parts of allyl polyoxyethylene polyoxypropylene ether with a molecular weight of 3000, 30 parts of polyethylene glycol monoacrylate with a molecular weight of 600, and 0.45 parts of dodecyl benzene sulfonate. Sodium and 0.9 parts of diethylene glycol monolaurate and 110 parts of water are added into the second reaction vessel and stirred evenly.
- 1.5 parts of hydrogen peroxide and 20 parts of water are evenly mixed in the first dropping device; 0.5 parts of ascorbic acid, 1.5 parts N-Butanethiol and 20 parts of water are mixed uniformly in the second dropping device; 8 parts of acrylic acid, 4 parts of sodium 3-allyloxy-2-hydroxy-1-propane sulfonate and 20 parts of water are mixed uniformly in the third In the dripping device; at room temperature, the materials in the first dripping device, the second dripping device and the third dripping device are successively started to drip into the second reaction vessel at room temperature, and the third dripping device is completed respectively in 1.5h , The materials in the second dripping device and the first dripping device react at a constant temperature for 0.5h;
- esterification product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide, 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- esterified product add 101 parts of fumaric acid and 100 parts of coconut diethanolamide into the first reaction vessel and mix by weight, and add 0.75 parts of antimony trioxide and 0.45 parts of antimony trioxide and 0.45 parts of antimony trioxide under nitrogen conditions. Part of methylhydroquinone, adjust the temperature to 110°C, react for 5h, and then obtain the monomer with amide and dihydroxy and unsaturated esterification product;
- the first dropping device 0.5 parts of ascorbic acid, 1.5 parts of n-butyl mercaptan and 20 parts of water are mixed uniformly in the second dropping device; 8 parts of acrylic acid, 1 part of triethylene glycol divinyl ether and 20 parts of water are mixed Evenly in the third dripping device; at room temperature, start to drip the materials in the first dripping device, the second dripping device and the third dripping device into the second reaction vessel in sequence, and finish the dripping of the first dripping device in 1.5h.
- the materials in the three dripping devices, the second dripping device, and the first dripping device react at a constant temperature for 0.5h;
- the shrinkage-reducing polycarboxylic acid water-reducing agent synthesized in Examples 1 to 4 and Comparative Samples 1 to 4 were made of standard cement, and the mixing amount was 0.25% by cement mass (converted into solids), according to GB 8076-2008 "Concrete Addition Test the slump, expansion and the strength of concrete at various ages; test the shrinkage rate of concrete according to GBT 50082-2009 "Standard for long-term performance and durability test methods of ordinary concrete”; according to GB/T 8077-2012 "Concrete addition Test Method for Agent Homogeneity "Test the surface tension of shrinkage-type polycarboxylate water-reducer The concrete mix ratio is: cement 360kg/m 3 , sand 803kg/m 3 , stone 982kg/m 3 , and the initial slump is controlled at 190 ⁇ 10mm.
- the concrete test results are shown in Table 1.
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Abstract
涉及建筑外加剂技术领域,特别涉及一种减缩型聚羧酸减水剂及其制备方法。所述减水剂包括:酯化产物、不饱和聚氧乙烯醚、乳化剂、引发剂溶液、链转移剂溶液、酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐混合溶液。其制备方法中包括酯化产物制备;共聚反应;中和反应;利用椰油酸二乙醇酰胺与不饱和酸进行酯化制备酯化产物,具有成本低廉、操作简便的优点,而且所制得的酯化产物与减缩功能单体共聚反应,使聚羧酸减水剂主链上带有酰胺等亲水基团和减缩基团,所制备的聚羧酸减水剂具有较低的表面张力,有效降低混凝土的干燥收缩,有效提高了混凝土内部的力学性能和强度,具有显著的应用价值。
Description
本发明涉及建筑外加剂技术领域,特别涉及一种减缩型聚羧酸减水剂及其制备方法。
聚羧酸减水剂作为新型减水剂,具有掺量低、减水率高、坍落度保持性好、收缩率小、与水泥和掺合料适应性相对较好、增强效果明显等一系列突出的性能,目前已广泛应用于各项工程领域中。随着国家大规模基础设施核电、水利、桥梁和各种大型工程的建设,对混凝土各方面性能要求不断的提高,减缩型聚羧酸减水剂是指既具有较高的减水率,同时又具有减少硬化混凝土干燥收缩的效果,这种多功能聚羧酸系减水剂已成为国内外研究的热点。
目前使用的减缩剂第一种主要有醇类,包括二醇、三醇及其同系物,此类物质沸点较低,易挥发,易燃,在工程实际中使用不方便。分子量大的醇具有掺量大,成本高等缺点;第二种为烷醇胺类物质也有很好的减缩效果,但是价格昂贵,在工程中难以推广。同时减缩剂会降低混凝土的强度,这也给减缩剂的推广带来一定影响。第三种是具有较好减缩功能的聚羧酸减水剂,该减水剂从分子结构引入了减缩基团,在具有高减水率的同时具有很好的减缩功能,但目前市场上的减缩型减水剂不仅减水率低而且减缩效果差。
专利CN 106380554 A,公开日为2017年02月08日,公开了一种脂类降粘型聚羧酸减水剂的制备方法,采用聚乙二醇单甲醚与甲基丙烯酸甲酯进行酯化制备酯化单体,将酯化单体与不饱和磺酸、交联单体、阳离子单体在 乳化剂和引发剂、链转移剂作用下进行聚合反应,然而该方案中所涉及的减水剂虽然具有较好的分散性,降粘、抗泥性能,但并未能降低混凝土干燥收缩以及提高混凝土强度等性能。综上,开发一种减缩型聚羧酸减水剂,降低混凝土的干燥收缩具有重要的意义。
发明内容
为解决上述背景技术中提到的现有减缩型减水剂不仅减水率低而且减缩效果差的问题,本发明提供一种减缩型聚羧酸减水剂,还包括以下成分:酯化产物、不饱和聚氧乙烯醚、乳化剂、引发剂溶液、链转移剂溶液、酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐混合溶液;
其中,所述酯化产物包括具有酰胺、双羟基的单体与不饱和酸酯化产物;所述减缩功能单体为具有双键、乙氧基的单体。
在上述技术方案的基础上,进一步地,所述具有酰胺、双羟基的单体与不饱和酸酯化产物的制备方法包括以下步骤:
将不饱和酸、化合物A(即椰油酸二乙醇酰胺)加入反应容器中混合,在保护气体氛围中,加入催化剂、阻聚剂,并调节温度80~120℃,反应4~6h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
所述化合物A的结构为:
其中,R为C
11H
23烷基。
在上述技术方案的基础上,进一步地,所述不饱和酸为丙烯酸、马来酸酐、富马酸中的一种。
在上述技术方案的基础上,进一步地,所述催化剂包括硫酸铈、三氧化二锑、对甲苯磺酸中的至少一种。
在上述技术方案的基础上,进一步地,所述阻聚剂包括4-羟基哌啶醇氧自由基、4-叔丁基邻苯二酚、甲基对苯二酚中的至少一种。
在上述技术方案的基础上,进一步地,所述不饱和酸和化合物A的摩尔比为1~3.5:1,所述催化剂的用量为不饱和酸和化合物A总质量的0.5%-3.5%,所述阻聚剂的用量为不饱和酸和化合物A总质量的0.3%~2%。
在上述技术方案的基础上,进一步地,所述具有双键、乙氧基的减缩功能单体为三乙二醇二乙烯基醚。
在上述技术方案的基础上,进一步地,所述不饱和聚氧乙烯醚为分子量为3000的甲基烯丙醇聚氧乙烯醚、烯丙基聚氧乙烯聚氧丙烯醚、甲基烯丙基聚氧乙烯聚氧丙烯醚或烯丙醇聚氧乙烯醚中的一种。
在上述技术方案的基础上,进一步地,所述酯类大单体为分子量为1000-3000的单丙烯酸聚乙二醇酯,单甲基丙烯酸聚乙二醇酯,单甲氧基醚单丙烯酸聚乙二醇酯,单甲氧基醚单甲基丙烯酸聚乙二醇酯中的一种。
在上述技术方案的基础上,进一步地,所述不饱和磺酸盐为3-烯丙氧基-2-羟基-1-丙烷磺酸钠、3-丙-2-烯酰氧基丙烷-1-磺酸钾中的一种。
在上述技术方案的基础上,进一步地,所述乳化剂由十二烷基苯磺酸钠和二乙二醇单月桂酸酯按1:2的质量比组成。
在上述技术方案的基础上,进一步地,所述引发剂为过硫酸铵-次磷酸钠、双氧水-次磷酸钠、双氧水-抗坏血酸中的一种。
在上述技术方案的基础上,进一步地,所述链转移剂为巯基乙酸、巯基丙酸、正丁硫醇中的一种。
在上述技术方案的基础上,进一步地,所述酯化产物、不饱和聚氧乙烯醚、酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐的质量比为1~ 3:70:30:8~18:1~5:2~5。
在上述技术方案的基础上,进一步地,所述乳化剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的0.9%-1.8%,所述引发剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的2%-5%,所述链转移剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的0.8%-3%。
本发明还提供一种如上任意所述减缩型聚羧酸减水剂的制备方法,包括以下步骤:
将酯化产物、不饱和聚氧乙烯醚、乳化剂加入反应容器中混合,再分别滴加引发剂溶液,链转移剂溶液,酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐混合溶液,在常温下进行反应1.5~2h,反应结束后,保温一段时间,加入32%液碱调节pH至6~7,即得到减缩型聚羧酸减水剂。
本发明的有益效果是:
本发明提供的减缩型聚羧酸减水剂,利用含有单羟基酯化或双羟基酯化制得酯化产物参与下一步共聚反应,使聚羧酸减水剂主链上带有酰胺、羟基等亲水基团,所制备的聚羧酸减水剂具有较低表面张力,通过制备酯化产物引入到聚羧酸减水剂中,能有效降低混凝土毛细孔溶液的表面张力,从而降低混凝土干燥收缩。对于部分双羟基酯化后得到单体为交联单体,在聚合过程中实现部分交联,增加体系空间位阻效应.在水泥的碱性条件下,交联结构的水解较慢于含有酯基、酸酐等基团的单体共聚得到的减水剂,随着时间的延长逐渐水解而不断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;酰胺具有亲水性,且易于形成分子内氢键,有利于保证分子构型的稳定;酰胺基会与水形成氢键而在水泥颗粒表面形成溶剂化水膜对水泥颗粒起到润滑作用,其水化凝胶产物呈紧密针状与其周围凝胶产物相互交织,因此提高了水泥的强度。本发明采用的酯类大单体参与共聚反应,使得减水剂分子链中接上长侧链结构,长侧链结构中带有 酯基,在水泥碱性条件下不断水解释放出具有减水作用的羧基,起保坍作用,而且酯类大单体使得混凝土和易性提高;不饱和磺酸盐引入,能有效提高混凝土初始分散性性能。
此外,提供的减缩型聚羧酸减水剂通过引入带有两个双键的减缩功能单体,使得聚羧酸减水剂分子链中引入较多的乙氧基结构,能有效降低混凝土干燥收缩,而且两个双键的减缩功能单体的引入使得减水剂实现交联形成三维网状结构,增加体系空间位阻效应,使其混凝土具有较好的分散性和分散性保持性能。
在优选方案中,利用椰油酸二乙醇酰胺与不饱和酸进行酯化制备酯化产物,具有成本低廉、操作简便的优点;此外,椰油酸二乙醇酰胺为阴离子表面活性剂,通过制备酯化产物引入到聚羧酸减水剂中,能有效降低混凝土毛细孔溶液的表面张力,从而降低混凝土干燥收缩。
本发明采用减缩型聚羧酸减水剂制备方法中,采用的乳液聚合方法不仅生产简便,合成时间短,聚合速率快,而形成的乳胶膜对混凝土内部形成桥连作用有效的制微裂纹的形成与扩展,形成交联的网状结构,提高了混凝土内部的力学性能和强度。
为使本发明实施例的目的、技术方案和优点更加清楚,下面将结合本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明还提供如下所示实施例:
实施例1
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和113份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份三乙二醇二乙烯基醚、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
实施例2
(1)酯化产物制备:按重量份计,将87.8份丙烯酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入2.17份硫酸铈、1.16份4-羟基哌啶醇氧自由基,并调节温度120℃,反应6h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将2份步骤(1)制得的酯化产物、70份分子量3000的甲基烯丙基聚氧乙烯聚氧丙烯醚和30份分子量1000的单甲氧基醚单丙烯酸聚乙二醇酯、0.5份十二烷基苯磺酸钠和1份二乙二醇单月桂酸 酯和130份水,加入第二反应容器中搅拌均匀,1.5份过硫酸铵与20份水混合均匀于第一滴加装置中;3份次磷酸钠、2.5份巯基乙酸与20份水混合均匀于第二滴加装置中;15份丙烯酸、3份三乙二醇二乙烯基醚、3.5份3-丙-2-烯酰氧基丙烷-1-磺酸钾与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
实施例3
(1)酯化产物制备:按重量份计,将81份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入4份硫酸铈、2.4份甲基对苯二酚,并调节温度80℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将1份步骤(1)制得的酯化产物、70份分子量3000的烯丙醇聚氧乙烯醚和30份分子量2400的单甲氧基醚单甲基丙烯酸聚乙二醇酯、0.3份十二烷基苯磺酸钠和0.6份二乙二醇单月桂酸酯和119份水,加入第二反应容器中搅拌均匀,2.5份双氧水与20份水混合均匀于第一滴加装置中;2.5份次磷酸钠、2份巯基丙酸与20份水混合均匀于第二滴加装置中;12份丙烯酸、2份三乙二醇二乙烯基醚、2份3-丙-2-烯酰氧基丙烷-1-磺酸钾与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于2h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
实施例4
(1)酯化产物制备:按重量份计,将50份马来酸酐、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入6.48份对甲苯磺酸、3.7份4-叔丁基邻苯二酚,并调节温度100℃,反应4h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将2份步骤(1)制得的酯化产物、70份分子量3000的甲基烯丙醇聚氧乙烯醚和30份分子量3000的单甲基丙烯酸聚乙二醇酯、0.6份十二烷基苯磺酸钠和1.2份二乙二醇单月桂酸酯和136份水,加入第二反应容器中搅拌均匀,1.2份过硫酸铵与20份水混合均匀于第一滴加装置中;2份亚硫酸氢钠、0.8份巯基丙酸与20份水混合均匀于第二滴加装置中;18份丙烯酸、5份三乙二醇二乙烯基醚、5.5份3-丙-2-烯酰氧基丙烷-1-磺酸钾与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于2h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例1
(1)共聚反应:按重量份计,先将70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和113份水,加入第二反应容器中搅拌均 匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份三乙二醇二乙烯基醚、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例2
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和110份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h。
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例3
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯和110份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份三乙二醇二乙烯基醚、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例4
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和113份 水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份二乙二醇单乙烯基醚、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例5
(1)共聚反应:按重量份计,先将70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和110份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例6
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、 0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、100份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和113份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份三乙二醇二乙烯基醚、4份3-烯丙氧基-2-羟基-1-丙烷磺酸钠与20份水混合均匀于第三滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
对比例7
(1)酯化产物制备:按重量份计,将101份富马酸、100份椰油酸二乙醇酰胺加入第一反应容器中混合,在氮气条件下,加入0.75份三氧化二锑、0.45份甲基对苯二酚,并调节温度110℃,反应5h,即得到具有酰胺、双羟基的单体与不饱和酸酯化产物;
(2)共聚反应:按重量份计,先将3份步骤(1)制得的酯化产物、70份分子量3000的烯丙基聚氧乙烯聚氧丙烯醚和30份分子量600的单丙烯酸聚乙二醇酯、0.45份十二烷基苯磺酸钠和0.9份二乙二醇单月桂酸酯和107份水,加入第二反应容器中搅拌均匀,1.5份双氧水与20份水混合均匀于第一滴加装置中;0.5份抗坏血酸、1.5份正丁硫醇与20份水混合均匀于第二滴加装置中;8份丙烯酸、1份三乙二醇二乙烯基醚与20份水混合均匀于第三 滴加装置中;常温下向第二反应容器中依次开始滴加第一滴加装置、第二滴加装置和第三滴加装置中的物料,于1.5h分别滴加完第三滴加装置、第二滴加装置、第一滴加装置中的物料,恒温反应0.5h;
(3)中和反应:加入重量份为15份32%质量浓度的氢氧化钠,即得到浓度为40%的所述减缩型聚羧酸减水剂。
将实施例1~4合成得到的减缩型聚羧酸减水剂与对比样1~4,采用标准水泥,掺量按水泥质量0.25%(折成固体份),根据GB 8076-2008《混凝土外加剂》,测其坍落度、扩展度和混凝土各龄期强度;根据GBT 50082-2009《普通混凝土长期性能和耐久性能试验方法标准》测试混凝土收缩率;根据GB/T 8077-2012《混凝土外加剂匀质性试验方法》测试减缩型聚羧酸减水剂的表面张力。混凝土配合比为:水泥360kg/m
3、砂803kg/m
3、石头982kg/m
3,初始坍落度控制在190±10mm,混凝土测试结果如表1所示。
表1实施例性能对比
从表1结果可以看出,本发明制备的混凝土减缩型聚羧酸减水剂实施例1~4相较于对比例,不仅拌制的混凝土初始分散性能和保坍性能较佳,混凝土强度略有提高,表面张力降低,减水剂混凝土28d收缩率降低。
从表2结果可以看出,掺入对比例1(无酯化产物)的表面张力增大,混凝土收缩率提高,强度略有降低;掺入对比例2(无减缩功能单体)的表面张力增大,混凝土初始分散性能和保坍性能变差,收缩率提高。掺入对比例3(无乳液聚合)的混凝土强度降低;掺入对比例4(常规减缩功能单体)的表面张力增大,混凝土初始分散性能和保坍性能变差,收缩率增大。掺入对比例5(无酯化产物和无减缩功能单体)混凝土初始分散性能和保坍性能变差,表面张力和收缩率明显增大。掺入对比例6(无酯类大单体)混凝土保坍性能变差,和易性变差。掺入对比例7(无不饱和磺酸盐)混凝土初始分散性能变差。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (16)
- 一种减缩型聚羧酸减水剂,其特征在于,还包括以下成分:酯化产物、不饱和聚氧乙烯醚、乳化剂、引发剂溶液、链转移剂溶液、酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐混合溶液;其中,所述酯化产物包括具有酰胺、双羟基的单体与不饱和酸酯化产物;所述减缩功能单体为具有双键、乙氧基的单体。
- 根据权利要求2所述的减缩型聚羧酸减水剂,其特征在于:所述不饱和酸为丙烯酸、马来酸酐、富马酸中的一种。
- 根据权利要求2所述的减缩型聚羧酸减水剂,其特征在于:所述催化剂包括硫酸铈、三氧化二锑、对甲苯磺酸中的至少一种。
- 根据权利要求2所述的减缩型聚羧酸减水剂,其特征在于:所述阻聚剂包括4-羟基哌啶醇氧自由基、4-叔丁基邻苯二酚、甲基对苯二酚中的至少一种。
- 根据权利要求2所述的减缩型聚羧酸减水剂,其特征在于:所述不饱 和酸和化合物A的摩尔比为1~3.5:1,所述催化剂的用量为不饱和酸和化合物A总质量的0.5%-3.5%,所述阻聚剂的用量为不饱和酸和化合物A总质量的0.3%~2%。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述具有双键、乙氧基的减缩功能单体为三乙二醇二乙烯基醚。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述不饱和聚氧乙烯醚为分子量为3000的甲基烯丙醇聚氧乙烯醚、烯丙基聚氧乙烯聚氧丙烯醚、甲基烯丙基聚氧乙烯聚氧丙烯醚或烯丙醇聚氧乙烯醚中的一种。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述酯类大单体为分子量为1000-3000的单丙烯酸聚乙二醇酯,单甲基丙烯酸聚乙二醇酯,单甲氧基醚单丙烯酸聚乙二醇酯,单甲氧基醚单甲基丙烯酸聚乙二醇酯中的一种。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述不饱和磺酸盐为3-烯丙氧基-2-羟基-1-丙烷磺酸钠、3-丙-2-烯酰氧基丙烷-1-磺酸钾中的一种。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述乳化剂由十二烷基苯磺酸钠和二乙二醇单月桂酸酯按1:2的质量比组成。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述引发剂为过硫酸铵-次磷酸钠、双氧水-次磷酸钠、双氧水-抗坏血酸中的一种。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述链转移剂为巯基乙酸、巯基丙酸、正丁硫醇中的一种。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述酯化产物、不饱和聚氧乙烯醚、酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐的质量比为1~3:70:30:8~18:1~5:2~5。
- 根据权利要求1所述的减缩型聚羧酸减水剂,其特征在于:所述乳化剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的0.9%-1.8%,所述引发剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的2%-5%,所述链转移剂用量为不饱和聚氧乙烯醚和酯类大单体总质量的0.8%-3%。
- 根据权利要求1-15任一项所述减缩型聚羧酸减水剂的制备方法,其特在于,包括以下步骤:将酯化产物、不饱和聚氧乙烯醚、乳化剂加入反应容器中混合,再分别滴加引发剂溶液,链转移剂溶液,酯类大单体、丙烯酸、减缩功能单体和不饱和磺酸盐混合溶液,在常温下进行反应1.5~2h,反应结束后,保温一段时间,加入32%液碱调节pH至6~7,即得到减缩型聚羧酸减水剂。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1015399B1 (en) * | 1997-07-09 | 2003-10-08 | ARCO Chemical Technology, L.P. | Method of making a water reducing additive for cement |
CN102351999A (zh) * | 2011-07-15 | 2012-02-15 | 清华大学 | 一种纳米粒子型减水剂的制备方法 |
CN108047388A (zh) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | 一种减缩型混凝土流动性稳定剂的制备方法 |
CN109354654A (zh) * | 2018-08-30 | 2019-02-19 | 济南大学 | 一种早强型聚羧酸减水剂及其制备方法 |
CN109575198A (zh) * | 2018-11-15 | 2019-04-05 | 福建路桥翔通建材科技有限公司 | 一种增强型聚羧酸减水剂及其制备方法 |
CN109627396A (zh) * | 2018-12-24 | 2019-04-16 | 科之杰新材料集团有限公司 | 一种改善流变特性的醚酯共聚型聚羧酸减水剂的制备方法 |
CN109970922A (zh) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | 一种减缩型早强型聚羧酸减水剂母液及制备工艺 |
CN110003402A (zh) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | 一种低收缩高适应性的抗泥保坍型聚羧酸减水剂及其低温制备方法 |
TWI667262B (zh) * | 2017-11-14 | 2019-08-01 | 國立高雄第一科技大學 | 常溫合成之高保塑羧酸型強塑劑及其製備方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5506127B2 (ja) * | 2004-01-06 | 2014-05-28 | 株式会社日本触媒 | セメント混和剤用ポリカルボン酸系ポリマーとその用途および製造方法 |
CN103833282B (zh) * | 2014-02-28 | 2016-04-06 | 北京东方雨虹防水技术股份有限公司 | 一种乳化沥青防水砂浆及其制备方法 |
CN104129943B (zh) * | 2014-08-18 | 2016-03-23 | 四川恒泽建材有限公司 | 湿拌砂浆外加剂及其制备方法和应用 |
RU2593404C1 (ru) * | 2015-06-08 | 2016-08-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Петербургский государственный университет путей сообщения Императора Александра I" | Высокопрочный бетон |
ES2781964T3 (es) * | 2015-07-20 | 2020-09-09 | Evonik Operations Gmbh | Nuevos reductores de la contracción para aglutinantes minerales |
CN106116228A (zh) * | 2016-06-24 | 2016-11-16 | 桂林华越环保科技有限公司 | 一种混凝土防冻泵送剂 |
CN106145745A (zh) * | 2016-06-24 | 2016-11-23 | 桂林华越环保科技有限公司 | 一种混凝土补偿收缩泵送剂 |
CN106380550B (zh) * | 2016-08-27 | 2019-03-15 | 广东红墙新材料股份有限公司 | 一种表面张力调整减缩型聚羧酸减水剂及其制备方法 |
CN106279566B (zh) * | 2016-08-27 | 2020-07-03 | 广东红墙新材料股份有限公司 | 一种保水性减缩型聚羧酸减水剂及其制备方法 |
CN108484841A (zh) * | 2018-03-30 | 2018-09-04 | 湖北工业大学 | 一种本体聚合的固片状聚羧酸减水剂的制备方法 |
CN109608594A (zh) * | 2018-12-13 | 2019-04-12 | 广东奥克化学有限公司 | 一种早强型聚羧酸减水剂及其制备方法 |
CN110358023B (zh) * | 2019-07-31 | 2021-10-08 | 科之杰新材料集团有限公司 | 一种低表面张力减缩型聚羧酸减水剂及其制备方法 |
-
2019
- 2019-11-25 CN CN201911166653.6A patent/CN112708042B/zh active Active
-
2020
- 2020-06-04 WO PCT/CN2020/094400 patent/WO2021103473A1/zh active Application Filing
- 2020-06-04 RU RU2020123974A patent/RU2749269C1/ru active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1015399B1 (en) * | 1997-07-09 | 2003-10-08 | ARCO Chemical Technology, L.P. | Method of making a water reducing additive for cement |
CN102351999A (zh) * | 2011-07-15 | 2012-02-15 | 清华大学 | 一种纳米粒子型减水剂的制备方法 |
TWI667262B (zh) * | 2017-11-14 | 2019-08-01 | 國立高雄第一科技大學 | 常溫合成之高保塑羧酸型強塑劑及其製備方法 |
CN108047388A (zh) * | 2017-12-07 | 2018-05-18 | 科之杰新材料集团有限公司 | 一种减缩型混凝土流动性稳定剂的制备方法 |
CN109354654A (zh) * | 2018-08-30 | 2019-02-19 | 济南大学 | 一种早强型聚羧酸减水剂及其制备方法 |
CN109575198A (zh) * | 2018-11-15 | 2019-04-05 | 福建路桥翔通建材科技有限公司 | 一种增强型聚羧酸减水剂及其制备方法 |
CN109627396A (zh) * | 2018-12-24 | 2019-04-16 | 科之杰新材料集团有限公司 | 一种改善流变特性的醚酯共聚型聚羧酸减水剂的制备方法 |
CN109970922A (zh) * | 2019-01-29 | 2019-07-05 | 武汉苏博新型建材有限公司 | 一种减缩型早强型聚羧酸减水剂母液及制备工艺 |
CN110003402A (zh) * | 2019-04-23 | 2019-07-12 | 四川同舟化工科技有限公司 | 一种低收缩高适应性的抗泥保坍型聚羧酸减水剂及其低温制备方法 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113912791A (zh) * | 2021-10-26 | 2022-01-11 | 贵州石博士科技股份有限公司 | 二氧化硅改性减水剂、磷石膏基自流平砂浆及其制备方法 |
CN113912791B (zh) * | 2021-10-26 | 2024-01-26 | 贵州石博士科技股份有限公司 | 二氧化硅改性减水剂、磷石膏基自流平砂浆及其制备方法 |
CN114455880A (zh) * | 2022-02-24 | 2022-05-10 | 漯河市昊源新材料有限公司 | 一种减缩防冻型聚羧酸系减水剂及其制备方法 |
CN114671639A (zh) * | 2022-04-19 | 2022-06-28 | 安徽省路港工程有限责任公司 | 一种抗桥梁护栏混凝土收缩裂缝的调配剂及其配置方法 |
CN114671639B (zh) * | 2022-04-19 | 2023-03-21 | 安徽省路港工程有限责任公司 | 一种抗桥梁护栏混凝土收缩裂缝的调配剂及其配置方法 |
CN116284603A (zh) * | 2023-03-24 | 2023-06-23 | 辽宁奥克化学股份有限公司 | 适用于粉煤灰、矿渣型混凝土的减水剂及其制备方法 |
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CN116715814A (zh) * | 2023-08-10 | 2023-09-08 | 中交路桥建设有限公司 | 一种减胶型聚羧酸减水剂、混凝土及其生产系统 |
CN116715814B (zh) * | 2023-08-10 | 2023-11-28 | 中交路桥建设有限公司 | 一种减胶型聚羧酸减水剂、混凝土及其生产系统 |
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