CN111057198A - Preparation method of block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic group - Google Patents
Preparation method of block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic group Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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Abstract
The invention relates to a preparation method of a benzene ring sulfonic group-containing block modified polycarboxylic acid slump retaining agent, which is characterized in that a block polymerization method is adopted to prepare the polycarboxylic acid slump retaining agent, benzene ring sulfonic group-containing monomers and sulfonic acid monomers are copolymerized under certain conditions to obtain a benzene ring sulfonic group block polymer i, polyether macromonomers and acrylic acid are copolymerized at normal temperature to obtain a block polymer ii, the proportion of the block polymers i and ii is adjusted, hydroxyethyl acrylate is used as a linking monomer, and double bonds and the block copolymer are opened to prepare the polycarboxylic acid slump retaining agent. The polycarboxylic acid slump retaining agent prepared by the invention is prepared by adopting a block method for modification, the steric hindrance of a short side chain region is increased by a benzene ring, strong anionic groups such as sulfonic groups provide anchoring groups, and unsaturated alkyl ester and acrylic acid are used for linking a block polymer, so that the water reducing agent has strong slump retaining performance and durable slurry fluidity.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a preparation method of a benzene ring sulfonic group-containing block modified polycarboxylic acid slump retaining agent.
Background
The polycarboxylate superplasticizer is one of five indispensable components for forming high-performance concrete, and is known as a third-generation concrete superplasticizer as a macromolecular copolymer formed by copolymerizing a polyether macromonomer with a terminal double bond structure and a micromolecular monomer. The polycarboxylic acid slump retaining agent containing the polyether side chain has the advantages of environmental protection, high slump retaining, wide cement adaptation molecular structure freedom degree and obvious concrete reinforcing effect, and is successfully applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like. In China, the polycarboxylic acid slump retaining agent is successfully applied to large-scale projects such as the three gorges dam, the Sutong bridge, the Jinghushi high-speed rail and the like, and remarkable results are obtained. With the rapid increase of the demand of concrete, but the main raw materials of the concrete, such as cement, fly ash and other cementing materials, have great geographical difference, the sources of sand and stone materials are diversified, the supply of high-quality raw materials is short, the content of impurities is high and the like. Higher requirements are provided for concrete admixtures, especially high-performance slump retaining agents, such as good slump retaining property, wide adaptability and the like.
Patent CN102731736(2012, 10, 17) reports a triblock copolymer and its preparation method and application. The invention is prepared by reacting 2-bromine isobutyryl bromide and polyethylene glycol in triethylamine under dry and anhydrous conditions to obtain a bifunctional bromine polyethylene glycol macromolecular initiator, wherein tert-butyl acrylate, a catalyst and a ligand are subjected to atom transfer radical polymerization in toluene. According to the invention, the tert-butyl acrylate-b-polyethylene glycol-b-tert-butyl polyacrylate block copolymer is obtained through atom transfer radical polymerization, although an acrylate monomer is used for atom transfer radical polymerization, the polycarboxylic acid slump retaining agent structure is not ideal, and because polyethylene glycol compounds and the like are not used as reactants, the steric hindrance effect similar to that of a side chain of a water reducing agent is difficult to realize, so that the application of the polycarboxylic acid slump retaining agent and the concrete slump retaining agent field are limited.
The invention discloses a preparation method of an ether polycarboxylic acid slump retaining agent, wherein an esterification product of aliphatic ester and unsaturated anhydride is used for copolymerization synthesis of the polycarboxylic acid slump retaining agent, a molecular structure with carboxyl and double ester groups is introduced into a polycarboxylic acid molecular chain structure, and the negatively charged carboxylate does not influence the electrostatic repulsion effect of a water reducing agent, and simultaneously the problems of the workability and the sensitivity of concrete can be improved. And the double ester groups are hydrolyzed under the alkaline condition of the cement paste to release more carboxyl groups, so that the slump retaining performance of the concrete can be improved, and meanwhile, the polycarboxylic acid slump retaining agent with the structure can be suitable for various materials and is low in sensitivity.
Patent CN105859979A discloses an anti-mud polycarboxylic slump retaining agent and a preparation method thereof, wherein the slump retaining agent is prepared from the following raw materials in percentage by weight: 50-75% of unsaturated polyoxyethylene ether monomer, 4-8% of acrylic acid, 6-12% of maleic anhydride, 11-20% of hydroxyethyl acrylate or hydroxypropyl acrylate, 0.5-3.0% of chain transfer agent, 0.1-5% of initiator and 0.01-2% of initiation aid; the specific preparation method comprises the following steps: dripping acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate solution and initiation aid for 2-3.5h, keeping the temperature for 1-1.5 h, adding sodium hydroxide solution to adjust the pH value to 6-7, and obtaining the anti-mud polycarboxylic acid slump retaining agent with the solid content of 40-45%.
According to the invention, the traditional free radical polymerization in the aqueous solution is replaced by block polymerization, raw materials are put in time, the phenomenon that monomers with stronger reactivity such as acrylic acid and the like are subjected to auto-polymerization in one time is avoided, the block intermediate is obtained by copolymerization of different monomers under respective conditions by adopting segmental block polymerization, and the block intermediate and the residual acrylic acid are subjected to block polymerization under specific conditions to obtain the benzene ring sulfonic acid group block modified polycarboxylic acid slump retaining agent, so that the slump retaining agent has better slump retaining effect.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method of a benzene ring-containing sulfonic acid group block modified polycarboxylic slump retaining agent.
The invention adopts the technical scheme for solving the technical problems that: the invention adopts a block polymerization method to prepare the polycarboxylic acid slump retaining agent, benzene ring-containing monomers and sulfonic acid monomers are copolymerized under certain conditions to obtain benzene ring sulfonic group block polymers i, polyether macromonomers and acrylic acid are copolymerized at normal temperature to obtain block polymers ii, the proportion of the block polymers i and ii is adjusted, hydroxyethyl acrylate is used as a linking monomer, and double bonds and the block copolymers are opened to prepare the polycarboxylic acid slump retaining agent. The method comprises the following specific steps:
1) preparing a benzene ring sulfonic acid group block: adding 4-12 parts of benzene ring monomers, 6-15 parts of sulfonic acid monomers and 50 parts of deionized water into a first reaction kettle, uniformly stirring, dripping an initiator a at the temperature of 30-40 ℃ for 1.5-2h, and reacting to obtain a benzene ring sulfonic acid group block polymer i; the initiator a is a mixed solution of 0.54-0.76 part of initiator a and 50 parts of deionized water;
2) preparation of Block Polymer ii: under the condition of 30-40 ℃, adding 8-13 parts of acrylic acid, 339-354 parts of polyether macromonomer and 350 parts of deionized water into a second reaction kettle, uniformly stirring, dropwise adding an initiator b for 1.5-2h, and reacting to obtain a block polymer ii; the initiator b is a mixed solution of 1.28-1.84 parts of initiator b and 50 parts of deionized water;
3) placing the block polymers i and ii in a third reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature to be 50-70 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 20-27 parts of alkyl acrylate, 1.25-1.75 parts of chain transfer agent and 50 parts of deionized water, the material B is a mixed solution of 0.6-2.36 parts of initiator c and 50 parts of deionized water, and the dropping time is 2.5-3 h; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Preferably, the benzene ring monomer is one or more of styrene, 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene and 4-methoxy-2-vinylaniline; most preferred is 4-methoxy-2-vinylaniline.
Preferably, the sulfonic acid monomer is one or more of sodium methallyl sulfonate, sodium vinyl sulfonate, sodium propenyl sulfonate, sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid; most preferred is a combination of sodium methallylsulfonate and 2-acrylamido-2-methylpropanesulfonic acid in a mass ratio of 1: 1.
Preferably, the polyether macromonomer is one or two of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether; most preferred is a combination of vinylbutyl ether polyoxyethylene ether and prenol polyoxyethylene ether in a mass ratio of 1: 2.
Preferably, the initiator comprises an initiator a, an initiator b and an initiator c; the initiator a is one or two of lauroyl peroxide and dibenzoyl peroxide; most preferably lauroyl peroxide. The initiator b is one or more of azobisisoheptonitrile, azobisisobutyrimidazoline hydrochloride and dimethyl azobisisobutyrate; most preferred is azobisisoheptonitrile. The initiator c is one or more of azo isobutyl cyano formyl, azo diisobutyronitrile and tert-butyl peroxybenzoate; most preferred is azobisisobutyronitrile.
Preferably, the alkyl acrylate is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate. Hydroxyethyl acrylate is most preferred.
Preferably, the chain transfer agent is one or two of mercaptoethanol and mercaptopropanol; most preferred is mercaptopropanol.
The preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: benzene ring monomers: 4-12 parts; sulfonic acid monomer: 6-15 parts; an initiator a: 0.54-0.76 portion; acrylic acid: 8-13 parts; alkyl acrylate: 20-27 parts; polyether macromonomer: 339 and 354 portions; an initiator b: 1.28-1.84 parts; an initiator c: 0.6-2.36 parts; 1.25-1.75 parts of a chain transfer agent; the balance of water.
The polycarboxylic acid slump retaining agent is prepared through block polymerization, and is different from a conventional polycarboxylic acid slump retaining agent preparation method, a polyether monomer and acrylic acid are initiated to polymerize to prepare a block copolymer intermediate, the block copolymer intermediate is then subjected to free radical copolymerization with an alkyl acrylate monomer, the monomer activity matching in a reaction system can be effectively regulated and controlled, and the polycarboxylic acid slump retaining agent prepared through the method is modified through a benzene ring sulfonic group block copolymer, so that the polycarboxylic acid slump retaining agent is better in adsorption and dispersion capacity and better in fluidity retention. The specific technical effects are as follows:
firstly, the preparation process of the polycarboxylic acid slump retaining agent is simple, the operability is strong, and the reaction rate is easy to control; the polyether monomer and the acrylic acid are copolymerized to prepare the block polymer, the polyether branched chains at the block part have high density, the polyether branched chains are mutually exclusive, the rigidity of the main chain of the block area is reduced, the bending is easy, the polyether branched chains on the block are radial, a thicker water film is easily formed between the branched chains, and the slump retaining capacity is improved. The alkyl acrylate is hydrolyzed to generate carboxyl, and the carboxyl is adsorbed on cement particles, so that the repulsion force between the polyether branched chain with high density and other water reducing agents is increased, the cement particles are prevented from being condensed, stronger dispersing capacity is provided, and the water reducing rate is higher;
secondly, monomers with stronger activity such as acrylic acid and the like are prepared into a copolymer intermediate, different reaction systems select different active initiators and mixing amounts, the dropping speed and time are controlled, and the reaction is fully driven to be carried out. By introducing the benzene ring sulfonic group block polymer into the water reducing agent molecules, the spatial configuration and the extension degree of the concrete admixture in a concrete multiphase system can be regulated and controlled, and stronger water reducing and slump retaining capabilities are provided.
Detailed Description
The invention is further illustrated below:
example 1:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: styrene: 4 parts of a mixture; sodium styrene sulfonate: 12 parts of (1); 0.58 part of lauroyl peroxide; acrylic acid: 11 parts of (1); hydroxyethyl acrylate: 27 parts of (1); 342 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether with the mass ratio of 1: 2; azobisisoheptonitrile: 1.43 parts; azobisisobutyronitrile formyl: 0.73 part; 1.26 parts of mercaptoethanol; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 4 parts of styrene, 12 parts of sodium styrene sulfonate and 50 parts of deionized water into a reaction kettle I, uniformly stirring, and dropwise adding an initiator a at the temperature of 30 ℃ for 2 hours to react to prepare a benzene ring sulfonic group block polymer i; the initiator a is a mixed solution of 0.54-0.76 part of lauroyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: under the condition of 35 ℃, adding 11 parts of acrylic acid, 342 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether with the mass ratio of 1:2 and 350 parts of deionized water into a reaction kettle II, uniformly stirring, dropwise adding an initiator b for 2 hours, and reacting to obtain a block polymer ii; the initiator b is a mixture of 1.43 parts of azobisisoheptonitrile and 50 parts of deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature at 50 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 27 parts of hydroxyethyl acrylate, 1.26 parts of mercaptoethanol and 50 parts of deionized water, the material B is a mixed solution of 0.73 part of azobisisobutyronitrile formyl and 50 parts of deionized water, and the dripping time is 2.5 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Example 2:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene in a mass ratio of 1: 2: 8 parts of a mixture; the composition of sodium methallyl sulfonate and sodium vinyl sulfonate with the mass ratio of 1:1 comprises the following components: 6 parts of (1); dibenzoyl peroxide: 0.56 part; acrylic acid: 13 parts; hydroxypropyl acrylate: 22 parts of (A); vinyl butyl ether polyoxyethylene ether: 346 parts of (b); azobisisobutyrimidazoline hydrochloride: 1.34 parts; tert-butyl peroxybenzoate: 1.44 parts; mercaptoethanol: 1.66 parts; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 8 parts of a composition of 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene in a mass ratio of 1:2, 6 parts of a composition of sodium methallyl sulfonate and sodium vinyl sulfonate in a mass ratio of 1:1 and 50 parts of deionized water into a reaction kettle I, uniformly stirring, dropwise adding an initiator a at 35 ℃ for 1.5 hours, and reacting to obtain a benzene ring sulfonic acid group block polymer i, wherein the initiator a is a mixed solution of 0.56 part of dibenzoyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: adding 13 parts of acrylic acid, 346 parts of vinyl butyl ether polyoxyethylene ether and 350 parts of deionized water into a reaction kettle II at 40 ℃, uniformly stirring, dropwise adding an initiator b for 1.8 hours, and reacting to obtain a block polymer ii; initiator b is a mixture of 1.34 parts azobisisobutyrimidazoline hydrochloride and 50 parts deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature at 60 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 22 parts of hydroxypropyl acrylate, 1.66 parts of mercaptoethanol and 50 parts of deionized water, the material B is a mixed solution of 1.44 parts of tert-butyl peroxybenzoate and 50 parts of deionized water, and the dropping time is 3 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Example 3:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: 4-methoxy-2-vinylaniline: 6 parts of (1); the composition of sodium methallyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid in a mass ratio of 1: 14 parts of (1); 0.71 portion of lauroyl peroxide; acrylic acid: 10 parts of (A); hydroxyethyl acrylate: 23 parts; 342 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether with the mass ratio of 1: 2; azobisisoheptonitrile: 1.66 parts; azobisisobutyronitrile: 1.07 parts of a stabilizer; 1.56 parts of mercaptopropanol; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 6 parts of 4-methoxy-2-vinylaniline, 14 parts of a composition of sodium methallylsulfonate and 2-acrylamide-2-methylpropanesulfonic acid in a mass ratio of 1:1 and 50 parts of deionized water into a reaction kettle I, uniformly stirring, dropwise adding an initiator a at 40 ℃ for 2 hours, and reacting to obtain a benzene ring sulfonic group block polymer i; the initiator a is a mixture of 0.71 parts of lauroyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: adding 10 parts of acrylic acid, 342 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether with the mass ratio of 1:2 and 350 parts of deionized water into a reaction kettle II at 38 ℃, uniformly stirring, dropwise adding an initiator b for 1.8 hours, and reacting to obtain a block polymer ii; the initiator b is a mixture of 1.66 parts of azobisisoheptonitrile and 50 parts of deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature to be 65 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 23 parts of hydroxyethyl acrylate, 1.56 parts of mercaptopropanol and 50 parts of deionized water, the material B is a mixed solution of 1.07 parts of azobisisobutyronitrile and 50 parts of deionized water, and the dripping time is 2.8 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Example 4:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: 1-allyl-2-fluorobenzene and 4-methoxy-2-vinylaniline in a mass ratio of 1: 2: 7 parts; 2-acrylamido-2-methylpropanesulfonic acid: 9 parts of (1); the mass ratio is 1: 0.58 part of the composition of lauroyl peroxide and dibenzoyl peroxide of 1; acrylic acid: 8 parts of a mixture; hydroxyethyl acrylate: 21 parts of (1); 350 parts of isopentenol polyoxyethylene ether; dimethyl azodiisobutyrate: 1.72 parts; azobisisobutyronitrile: 1.25 parts; 1.45 parts of mercaptopropanol; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 7 parts of a composition of 1-allyl-2-fluorobenzene and 4-methoxy-2-vinylaniline, 9 parts of 2-acrylamide-2-methylpropanesulfonic acid and 50 parts of deionized water in a mass ratio of 1:2 into a reaction kettle I, uniformly stirring, dropwise adding an initiator a at 35 ℃ for 1.5 hours, and reacting to obtain a benzene ring sulfonic acid group block polymer i; the initiator a is 0.58 part by mass of 1:1 of a composition of lauroyl peroxide and dibenzoyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: adding 8 parts of acrylic acid, 350 parts of prenyl polyoxyethylene ether and 350 parts of deionized water into a reaction kettle II at 40 ℃, uniformly stirring, dropwise adding an initiator 2 for 1.7 hours, and reacting to obtain a block polymer ii; initiator 2 was a mixture of 1.72 parts dimethyl azodiisobutyrate and 50 parts deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature at 70 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 21 parts of hydroxyethyl acrylate, 1.45 parts of mercaptopropanol and 50 parts of deionized water, the material B is a mixed solution of 1.25 parts of azobisisobutyronitrile and 50 parts of deionized water, and the dripping time is 2.6 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Example 5:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: the composition of 1-allyl-4-fluorobenzene and 4-methoxy-2-vinylaniline with the mass ratio of 2:1 comprises the following components: 8 parts of a mixture; the composition of sodium propenyl sulfonate and sodium styrene sulfonate with the mass ratio of 1:2 comprises the following components: 8 parts of a mixture; 0.62 part of lauroyl peroxide; acrylic acid: 9 parts of (1); hydroxypropyl acrylate: 21 parts of (1); 348 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether in a mass ratio of 2: 1; azobisisobutyrimidazoline hydrochloride: 1.76 parts; the mass ratio is 1:2 of azoisobutyronitrile and azobisisobutyronitrile: 2.16 parts of; 1.46 parts of mercaptoethanol; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 8 parts of a composition of 1-allyl-4-fluorobenzene and 4-methoxy-2-vinyl aniline in a mass ratio of 2:1, 8 parts of a composition of sodium propenyl sulfonate and sodium styrene sulfonate in a mass ratio of 1:2 and 50 parts of deionized water into a reaction kettle I, uniformly stirring, dropwise adding an initiator a at 40 ℃, wherein the dropwise adding time is 1.7 hours, and reacting to obtain a benzene ring sulfonic group block polymer i; the initiator a is a mixture of 0.62 parts of lauroyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: adding 9 parts of acrylic acid, 348 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether in a mass ratio of 2:1 and 350 parts of deionized water into a reaction kettle II at the temperature of 30 ℃, uniformly stirring, dropwise adding an initiator b for 1.8 hours, and reacting to obtain a block polymer ii; initiator b is a mixture of 1.76 parts azobisisobutyrimidazoline hydrochloride and 50 parts deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature at 60 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 21 parts of hydroxypropyl acrylate, 1.46 parts of mercaptoethanol and 50 parts of deionized water, and the material B is a mixed solution of 2.16 parts of materials in a mass ratio of 1:2 and 50 parts of deionized water, wherein the dropping time is 2.5 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
Example 6:
the preparation method of the block modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps of 1000 parts by weight of raw materials, and 40% by weight of the raw materials, wherein the block modified polycarboxylic acid slump retaining agent is mainly prepared from the following components: 1-allyl-4-fluorobenzene: 12 parts of (1); the composition of sodium methallyl sulfonate and sodium styrene sulfonate with the mass ratio of 1:1 comprises the following components: 10 parts of (A); 0.74 portion of dibenzoyl peroxide; acrylic acid: 13 parts; hydroxypropyl acrylate: 20 parts of (1); 339 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether in a mass ratio of 2: 1; azobisisoheptonitrile: 1.61 parts; tert-butyl peroxypivalate: 2.33 parts; 1.32 parts of mercaptopropanol; the balance of water.
Step (1): preparing a benzene ring sulfonic acid group block: adding 12 parts of 1-allyl-4-fluorobenzene, 10 parts of a composition of sodium methallyl sulfonate and sodium styrene sulfonate in a mass ratio of 1:1 and 50 parts of deionized water into a reaction kettle I, uniformly stirring, dropwise adding an initiator a at 30 ℃ for 1.8 hours, and reacting to obtain a benzene ring sulfonic group block polymer i; the initiator a is a mixture of 0.74 parts of dibenzoyl peroxide and 50 parts of deionized water.
Step (2): preparation of Block Polymer ii: adding 13 parts of acrylic acid, 339 parts of a composition of vinyl butyl ether polyoxyethylene ether and prenol polyoxyethylene ether with the mass ratio of 2:1 and 350 parts of deionized water into a reaction kettle II at 40 ℃, uniformly stirring, dropwise adding an initiator b for 1.6 hours, and reacting to obtain a block polymer ii; the initiator b is a mixture of 1.61 parts of azobisisoheptonitrile and 50 parts of deionized water.
And (3): placing the block polymers i and ii in a No. III reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature to be 55 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 20 parts of hydroxypropyl acrylate, 1.32 parts of mercaptopropanol and 50 parts of deionized water, the material B is a mixed solution of 2.33 parts of tert-butyl peroxypivalate and 50 parts of deionized water, and the dropping time is 3 hours; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
A working solution with the concentration of 7% is prepared from the modified polycarboxylic acid slump retaining agent containing benzene ring sulfonic acid groups in the above examples 1-6, and the initial fluidity, the flow with time, the compressive strength and other performances of cement paste of the polycarboxylic acid slump retaining agent prepared in the above examples 1-6 are respectively tested under the same mixing amount with the common slump retaining agent. The cement used in the experiment is Huaxin 42.5 ordinary silica cement, and the test standard GB/8076-.
Cement paste fluidity measurement
Concrete Performance measurement
According to the measurement result of the fluidity of the cement paste, the slump retaining agent with the same concentration, the fluidity of examples 1-6 is better than that of the common slump retaining agent with the elapse of time, and the synthetic raw materials and the preparation process of the slump retaining agent are better than those of the common slump retaining agent; through concrete performance measurement, the slump/slump of the concrete mixtures of examples 1-6 have obvious advantages over the common slump retaining agent under the same concentration, the strength is integrally stronger than that of the common slump retaining agent, example 3 is most preferable, and the early strength and the later strength are obviously better than those of the common slump retaining agent and other examples. The cement paste fluidity, slump/spread and the strength at each age of example 3 are superior to those of the conventional slump retaining agent and other examples.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of a block modified polycarboxylic slump retaining agent containing benzene ring sulfonic acid groups comprises the following steps:
1) preparing a benzene ring sulfonic acid group block: adding 4-12 parts of benzene ring monomers, 6-15 parts of sulfonic acid monomers and 50 parts of deionized water into a first reaction kettle, uniformly stirring, dripping an initiator a at the temperature of 30-40 ℃ for 1.5-2h, and reacting to obtain a benzene ring sulfonic acid group block polymer i; the initiator a is a mixed solution of 0.54-0.76 part of initiator a and 50 parts of deionized water;
2) preparation of Block Polymer ii: under the condition of 30-40 ℃, adding 8-13 parts of acrylic acid, 339-354 parts of polyether macromonomer and 350 parts of deionized water into a second reaction kettle, uniformly stirring, dropwise adding an initiator b for 1.5-2h, and reacting to obtain a block polymer ii; the initiator b is a mixed solution of 1.28-1.84 parts of initiator b and 50 parts of deionized water;
3) placing the block polymers i and ii in a third reaction kettle, uniformly stirring the block polymers at the bottom, controlling the temperature to be 50-70 ℃, and sequentially dropwise adding a material A and a material B; the material A is a mixed solution of 20-27 parts of alkyl acrylate, 1.25-1.75 parts of chain transfer agent and 50 parts of deionized water, the material B is a mixed solution of 0.6-2.36 parts of initiator c and 50 parts of deionized water, and the dropping time is 2.5-3 h; and (3) preserving the heat for 1.5h after the dropwise addition is finished, cooling to room temperature, and removing redundant initiator to obtain the diblock polycarboxylic acid slump retaining agent.
2. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the benzene ring monomer is one or more of styrene, 1-allyl-2-fluorobenzene, 1-allyl-4-fluorobenzene and 4-methoxy-2-vinylaniline.
3. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the sulfonic acid monomer is one or more of sodium methallyl sulfonate, sodium vinyl sulfonate, sodium propenyl sulfonate, sodium styrene sulfonate and 2-acrylamide-2-methylpropanesulfonic acid.
4. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the polyether macromonomer is vinyl butyl ether polyoxyethylene ether.
5. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the initiator a is one or two of lauroyl peroxide and dibenzoyl peroxide; the initiator b is one or more of azobisisoheptonitrile, azobisisobutyrimidazoline hydrochloride and dimethyl azobisisobutyrate; the initiator c is one or more of azo isobutyl cyano formyl, azo diisobutyronitrile and tert-butyl peroxybenzoate.
6. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the alkyl acrylate is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
7. The method for preparing the slump retaining agent containing the benzene ring sulfonic acid group block modified polycarboxylic acid as claimed in claim 1, which is characterized in that: the chain transfer agent is composed of one or two of mercaptoethanol and mercaptopropanol.
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| Title |
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| 冯新德: "《高分子辞典》", 30 June 1998, 中国石化出版社 * |
| 张鹏等: "《丙烯酸树脂防腐蚀涂料及其应用》", 30 September 2003, 化学工业出版社 * |
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| WO2022112190A1 (en) * | 2020-11-30 | 2022-06-02 | Basf Se | Process of producing polymer dispersions |
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