CN111057195A - Cation modified slump-retaining type polycarboxylate superplasticizer and block polymerization method thereof - Google Patents
Cation modified slump-retaining type polycarboxylate superplasticizer and block polymerization method thereof Download PDFInfo
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- CN111057195A CN111057195A CN201911360855.4A CN201911360855A CN111057195A CN 111057195 A CN111057195 A CN 111057195A CN 201911360855 A CN201911360855 A CN 201911360855A CN 111057195 A CN111057195 A CN 111057195A
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F287/00—Macromolecular compounds obtained by polymerising monomers on to block polymers
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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
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Abstract
The invention provides a cation modified slump-retaining type polycarboxylate superplasticizer and a block polymerization method thereof, wherein the slump-retaining type polycarboxylate superplasticizer is mainly prepared by the following operation steps: preparing a phenyl cationic block polymer I by using a benzene ring monomer and a cationic monomer at the temperature of 40-60 ℃; step two: preparing a block polymer II from a polyether macromonomer and alkyl acrylate under a normal temperature condition; step three: adding the block polymer I into the block polymer II, and respectively dropwise adding A, B materials at 40-50 ℃; wherein the material A is a mixed solution of acrylic acid, alkyl acrylate and a chain transfer agent, the material B is an initiator solution c, and the polycarboxylic acid slump retaining agent is prepared by cooling to room temperature. The polycarboxylic slump retaining agent prepared by the invention is prepared in a block polymerization manner, and has the advantages of wide adaptability and long slump retaining duration.
Description
Technical Field
The invention relates to a concrete admixture, in particular to a cation modified slump retaining type polycarboxylic acid water reducing agent and a block polymerization method thereof.
Background
With the high importance of national infrastructure on the performance of concrete for buildings, the slump retentivity of concrete at each large concrete mixing plant is required to be higher and higher, and the research and development of the slow-release functional admixture becomes the central importance. The method mainly realizes the permanent slump by carboxyl protection type, crosslinking type, dissolution control type and other methods, wherein the carboxyl protection type is widely used, mainly by introducing structures such as anhydride, hydroxyalkyl ester, amide and the like into a molecular structure, in the cement hydration process, slurry gradually has strong basicity, and the structures such as the anhydride, the hydroxyalkyl ester and the like are hydrolyzed to release carboxyl, thereby playing a role of dispersion.
The invention prepares the polycarboxylate superplasticizer by a block polymerization method, uses alkyl acrylate to replace partial acrylic acid, introduces monomers with larger steric hindrance capability and hydrophobic property such as phenyl and the like, and uses cationic monomers to modify to prepare the amphoteric slump-retaining polycarboxylate superplasticizer.
Patent CN201710400769.6 discloses a concrete slump retaining agent, relates to the building concrete field, concretely relates to concrete slump retaining agent. The material is prepared from the following components in percentage by weight: HPEG: 30-35%, acrylic acid: 0.1-0.5%, hydrogen peroxide: 0.05-0.1%, mercaptopropionic acid: 0.01-0.03%, ascorbic acid: 0.006-0.008%, hydroxy acrylate: 2-3%, sodium hydroxide: 0.1-0.2%, water: 62 to 67 percent. The invention not only improves the durability of the concrete and the slump retaining capacity of the concrete, but also is environment-friendly.
Patent CN201910436621.7 discloses a concrete slump retaining agent and a preparation method and an application method thereof. The concrete slump retaining agent comprises the following components in parts by weight: 3-7 parts of sodium gluconate, 2-5 parts of white sugar, 0.6-1.2 parts of a synergist, 2-5 parts of epoxy resin, 5-10 parts of a solvent, 1-8 parts of polyphosphate, 3-6 parts of triethanolamine, 1-4 parts of anhydrous sodium sulphate, 3-7 parts of borax, 1-5 parts of hydroxypropyl methyl cellulose and 10-15 parts of water. The application method of the concrete slump retaining agent comprises the following steps: mixing the concrete slump retaining agent and the Point-400S type high-efficiency water reducing agent according to the mass ratio of 1:8-9, and then adding the mixture into cement slurry, wherein the using amount of the concrete slump retaining agent is 0.1-0.4% of that of the cementing material. The concrete slump retaining agent has the advantages of long-time plastic retaining effect on concrete, capability of reducing slump loss of the concrete and better workability of the concrete.
Patent CN201611187370.6 provides a preparation method of a long-acting slump retaining agent, which is characterized in that: adding water and ether into a reaction kettle, heating, stirring and dissolving, introducing nitrogen, sequentially adding sodium methallyl sulfonate and ammonium persulfate, and stirring; and (3) dripping A, B materials, cooling to 50 +/-2 ℃ after dripping is finished, adding 30% liquid caustic soda for neutralization, controlling the pH value between 6 and 7, continuously stirring for 15 minutes, supplementing water, and closing nitrogen gas for discharging. The slump retaining agent obtained by the method is added into concrete, so that the slump retaining time is prolonged, and the strength of the concrete is effectively enhanced.
Different from the patents, the invention adopts a block polymerization method to prepare the polycarboxylic slump retaining agent. The raw materials are put in time under different reaction conditions, the dosage and the reaction temperature of the initiator are reasonably controlled, the block reaction rate is controlled, the block polymer with stable structure is prepared, and the cationic monomer is introduced to modify the slump-retaining type polycarboxylate superplasticizer under specific reaction conditions.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a cation modified slump-retaining type polycarboxylate superplasticizer and a block polymerization method thereof.
The invention adopts the technical scheme for solving the technical problems that: the spare wheel of the bicycle comprises a supporting plate, a swing rod and a roller component, wherein one end of the supporting plate is provided with a fastener fixedly connected with a bicycle frame, and the swing rod is connected to the supporting plate in a swinging mode; the roller assembly is connected at the bottom end of the swing rod. When the bicycle is ridden normally, the swing rod is lifted, so that the roller wheel assembly is suspended in the air, and the normal running is not influenced; after a tire burst happens, a user can quickly and manually straighten the swing rod to enable the swing rod and the supporting plate to be in a straight line in the vertical direction, so that the roller assemblies roll on the ground, the tire burst can be suspended in the air, and the user can easily push the electric bicycle.
The invention adopts a block polymerization method to prepare a polycarboxylic acid slump retaining agent, a block polymer is prepared by phenyl cationic group free radical polymerization, the polycarboxylic acid slump retaining agent is uniformly mixed with a block polymer prepared from a polyether macromonomer and alkyl acrylate, acrylic acid and alkyl acrylate are used as monomer linking agents, the synthesized slump retaining agent is in a polyether block area, the density of a polyether branched chain is higher, a thicker water film is formed, alkyl ester is hydrolyzed to form carboxyl, cations and an anion anchoring group coexist, the cations and the anion anchoring group can be adsorbed on the surface of particles with positive electricity and also can be adsorbed on the surface of particles with negative electricity, water reducing agent molecules have enough anchoring groups to be adsorbed on the surface of cement particles, the water film in a comb-type branched chain is thickened, and the flow retaining time of the slump retaining agent is promoted.
The technical scheme of the invention is as follows: a cation modified slump-retaining type polycarboxylate superplasticizer is mainly prepared from the following components: polyether macromonomer: 355-364 parts of cationic monomer: 6-12 parts of benzene ring monomer: 4-8 parts, acrylic acid: 5-8 parts of alkyl acrylate: 10-18 parts of initiator a: 0.45-0.65 part of initiator b: 1.28-1.68 parts of initiator c: 1.52-1.93 parts of chain transfer agent: 1.35-1.76 parts of water, the balance of 1000 parts of the total mass and 40 percent of solid content.
Preferably, the cationic monomer is one or more of methacryloyloxyethyl trimethyl ammonium chloride (DMC), acryloyloxyethyl trimethyl ammonium chloride (DAC), tetrakis (hydroxymethyl) phosphonium sulfate (THPS) and p-vinylbenzyl tributyl phosphonium chloride (VBTBPC); preferably acryloyloxyethyltrimethylammonium chloride (DAC).
Preferably, the benzene ring monomer is one or more of (4-methyl basic) azomethine, styrene, 2-aminostyrene, 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene; 1-allyl-2-fluorobenzene is preferred.
Preferably, the polyether macromonomer is vinyl butyl ether polyoxyethylene ether.
Preferably, the alkyl acrylate is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate; hydroxypropyl acrylate is preferred.
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; preferably dibenzoyl peroxide; the initiator b is one or more of azobisisoheptonitrile, azobisisobutyrimidazoline hydrochloride and dimethyl azobisisobutyrate; preferably azobisisobutyrimidazoline hydrochloride; the initiator c is one or more of azo isobutyronitrile formyl, azo diisobutyronitrile, diisopropyl peroxydicarbonate and tert-butyl peroxybenzoate; preferably azobisisobutyronitrile.
Preferably, the chain transfer agent is one or two of mercaptoethanol and mercaptopropanol; mercaptoethanol is preferred.
The adhesive is prepared by polymerizing the following components in parts by weight, and the specific steps are as follows:
step (1): preparation of benzene ring cationic block I: adding 6-12 parts of cationic monomer, 4-8 parts of benzene ring monomer and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.45-0.65 part of initiator a and 50 parts of deionized water at the temperature of 40-60 ℃ for 0.5-1h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 355-364 parts of polyether macromonomer, 5-10 parts of alkyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the normal temperature condition, namely 1.28-1.68 parts of initiator b and 50 parts of deionized water are stirred and mixed to obtain the mixture, and the mixture is dripped for 2-2.5 hours to obtain a block polymer II;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 5-8 parts of acrylic acid, 5-8 parts of alkyl acrylate, 1.35-1.76 parts of a chain transfer agent and 50 parts of deionized water; the material B is a mixed solution of 1.52-1.93 parts of initiator c and 50 parts of deionized water; dropping the material A at 40-50 ℃ for 2-3h, preserving heat for 1h after dropping, and cooling to room temperature after complete reaction to obtain the polycarboxylic slump retaining agent.
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 cation 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 cation 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.
And thirdly, introducing cations to the main chain of the polycarboxylate water reducer by using a block structure grafting method, wherein the cations and the anion anchoring groups coexist, so that the cations can be adsorbed on the surfaces of particles with positive electricity and particles with negative electricity, and water reducer molecules have enough anchoring groups to be adsorbed on the surfaces of cement particles, so that the adsorption capacity of the water reducer is increased, and the rich fluidity of the water reducer is further increased.
Detailed Description
The invention is further illustrated below:
example 1:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 355 parts of; methacryloyloxyethyl trimethyl ammonium chloride (DMC): 12 parts of (1); (4-methyl-basic) azomethine: 8 parts of a mixture; acrylic acid: 5 parts of a mixture; hydroxyethyl acrylate: 12 parts of (1); lauroyl peroxide: 0.45 part; azobisisoheptonitrile: 1.56 parts; azo-isobutyryl cyano formyl: 1.93 parts; mercaptopropanol: 1.76 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 12 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 8 parts of (4-methyl basic) methyl imine and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.45 part of lauroyl peroxide and 50 parts of deionized water at the temperature of 40 ℃ for 1h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 355 parts of vinyl butyl ether polyoxyethylene ether, 5 parts of hydroxyethyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the condition of normal temperature, namely 1.56 parts of azobisisoheptonitrile and 50 parts of deionized water are stirred and mixed to form the block polymer II, and the block polymer II is prepared after dripping for 2 hours;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 6 parts of acrylic acid, 7 parts of hydroxyethyl acrylate, 1.76 parts of mercaptopropanol and 50 parts of deionized water; the material B is a mixed solution of 1.93 parts of azo isobutyl cyano formyl and 50 parts of deionized water; and (3) dropwise adding the material A at 40 ℃ for 3h, preserving heat for 1h after dropwise adding is finished, and cooling to room temperature after complete reaction to obtain the polycarboxylic acid slump retaining agent.
Example 2:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 357 parts of a mixture; acryloyloxyethyltrimethyl ammonium chloride (DAC): 8 parts of a mixture; styrene: 6 parts of (1); acrylic acid: 5 parts of a mixture; hydroxypropyl acrylate: 18 parts of a mixture; dibenzoyl peroxide: 0.65 part; azobisisobutyrimidazoline hydrochloride: 1.68 parts; azobisisobutyronitrile: 1.52 parts; mercaptoethanol: 1.35 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 8 parts of acryloyloxyethyl trimethyl ammonium chloride (DAC), 6 parts of styrene and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.65 part of dibenzoyl peroxide and 50 parts of deionized water at the temperature of 55 ℃ for 1h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 357 parts of vinyl butyl ether polyoxyethylene ether, 10 parts of hydroxypropyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the condition of normal temperature, namely 1.68 parts of azobisisobutylimidazoline hydrochloride and 50 parts of deionized water are stirred and mixed to form the block polymer II, and the block polymer II is prepared after dripping for 2 hours;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 5 parts of acrylic acid, 8 parts of hydroxypropyl acrylate, 1.35 parts of mercaptoethanol and 50 parts of deionized water; the material B is a mixed solution of 1.52 parts of azobisisobutyronitrile and 50 parts of deionized water; dropping the material A at 40 ℃ for 2.5h, preserving the heat for 1h after the dropping is finished, and cooling to room temperature after the reaction is completed to obtain the polycarboxylic acid slump retaining agent.
Example 3:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 359 parts of (A); methacryloyloxyethyl trimethyl ammonium chloride (DMC): 11 parts of (1); 2-aminostyrene: 7 parts; acrylic acid: 8 parts of a mixture; hydroxyethyl acrylate: 13 parts; lauroyl peroxide: 0.48 part; azobisisoheptonitrile: 1.28 parts; azo-isobutyryl cyano formyl: 1.58 parts; mercaptopropanol: 1.41 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 11 parts of methacryloyloxyethyl trimethyl ammonium chloride (DMC), 7 parts of 2-aminostyrene and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.48 part of lauroyl peroxide and 50 parts of deionized water at the temperature of 50 ℃ for 1h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 359 parts of vinyl butyl ether polyoxyethylene ether, 7 parts of hydroxyethyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the normal temperature condition, namely 1.28 parts of azobisisoheptonitrile and 50 parts of deionized water are stirred and mixed to form the block polymer II, and the block polymer II is obtained after 2 hours of dripping;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 8 parts of acrylic acid, 6 parts of hydroxyethyl acrylate, 1.41 parts of mercaptopropanol and 50 parts of deionized water; the material B is a mixed solution of 1.58 parts of azo isobutyl cyano formyl and 50 parts of deionized water; and (3) dropwise adding the material A at 50 ℃ for 3h, preserving heat for 1h after dropwise adding is finished, and cooling to room temperature after complete reaction to obtain the polycarboxylic acid slump retaining agent.
Example 4:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 361 parts of; acryloyloxyethyltrimethyl ammonium chloride (DAC): 7 parts; 1-allyl-2-fluorobenzene: 5 parts of a mixture; acrylic acid: 7 parts; hydroxypropyl acrylate: 14 parts of (1); dibenzoyl peroxide: 0.52 part; azobisisobutyrimidazoline hydrochloride: 1.35 parts; azobisisobutyronitrile: 1.64 parts; mercaptoethanol: 1.48 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 7 parts of acryloyloxyethyl trimethyl ammonium chloride (DAC), 5 parts of 1-allyl-2-fluorobenzene and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.52 part of dibenzoyl peroxide and 50 parts of deionized water at the temperature of 45 ℃ for 0.5h to obtain a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: adding 361 parts of vinyl butyl ether polyoxyethylene ether, 9 parts of hydroxypropyl acrylate and 350 parts of deionized water into a second reaction kettle, mixing, dropwise adding an initiator under the normal temperature condition, namely stirring and mixing 1.35 parts of azobisisobutyrimidazoline hydrochloride and 50 parts of deionized water, and dropwise adding for 2.5 hours to prepare a block polymer II;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 7 parts of acrylic acid, 5 parts of hydroxypropyl acrylate, 1.48 parts of mercaptoethanol and 50 parts of deionized water; the material B is a mixed solution of 1.64 parts of azobisisobutyronitrile and 50 parts of deionized water; and (3) dropwise adding the material A at 50 ℃ for 2h, preserving heat for 1h after dropwise adding is finished, and cooling to room temperature after complete reaction to obtain the polycarboxylic acid slump retaining agent.
Example 5:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 362 parts of (B); tetrakis Hydroxymethyl Phosphonium Sulfate (THPS): 9 parts of (1); 1-allyl-4-fluorobenzene: 6 parts of (1); acrylic acid: 6 parts of (1); hydroxyethyl acrylate: 10 parts of (A); lauroyl peroxide: 0.56 part; dimethyl azodiisobutyrate: 1.47 parts; diisopropyl peroxydicarbonate: 1.72 parts; mercaptopropanol: 1.52 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 9 parts of tetrakis (hydroxymethyl) phosphonium sulfate (THPS), 6 parts of 1-allyl-4-fluorobenzene and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.56 part of lauroyl peroxide and 50 parts of deionized water at the temperature of 50 ℃ for 0.5h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 362 parts of vinyl butyl ether polyoxyethylene ether, 5 parts of hydroxyethyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the normal temperature condition, namely 1.47 parts of dimethyl azodiisobutyrate and 50 parts of deionized water are stirred and mixed to obtain the block polymer II, and the block polymer II is obtained after dripping for 2.5 hours;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 6 parts of acrylic acid, 5 parts of hydroxyethyl acrylate, 1.52 parts of mercaptopropanol and 50 parts of deionized water; the material B is a mixed solution of 1.72 parts of diisopropyl peroxydicarbonate and 50 parts of deionized water; and (3) dropwise adding the material A at the temperature of 45 ℃ for 2.5h, preserving the heat for 1h after dropwise adding is finished, and cooling to room temperature after complete reaction to obtain the polycarboxylic acid slump retaining agent.
Example 6:
the cation modified slump-retaining type polycarboxylate superplasticizer comprises 1000 parts of raw materials by mass and 40% of mass fraction, and is mainly prepared from the following components: vinyl butyl ether polyoxyethylene ether: 364 parts of (A); p-vinylbenzyltributylphosphonium chloride (VBTBPC): 6 parts of (1); 1-allyl-4-fluorobenzene: 4 parts of a mixture; acrylic acid: 5 parts of a mixture; hydroxypropyl acrylate: 14 parts of (1); dibenzoyl peroxide: 0.61 part; dimethyl azodiisobutyrate: 1.42 parts; tert-butyl peroxybenzoate: 1.81 parts; mercaptoethanol: 1.63 parts; the balance of water, the total mass is 1000 parts, and the solid content is 40%.
Step (1): preparation of benzene ring cationic block I: adding 6 parts of p-vinylbenzyltributyl phosphorus chloride (VBTBPC), 4 parts of 1-allyl-4-fluorobenzene and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.61 part of dibenzoyl peroxide and 50 parts of deionized water at the temperature of 60 ℃ for 0.5h to prepare a benzene ring hydroxyl block polymer I;
step (2): preparation of Block Polymer II: 364 parts of vinyl butyl ether polyoxyethylene ether, 8 parts of hydroxypropyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the normal temperature condition, namely 1.42 parts of dimethyl azodiisobutyrate and 50 parts of deionized water are stirred and mixed to obtain the block polymer II, and the block polymer II is obtained after dripping for 2.5 hours;
and (3): adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 5 parts of acrylic acid, 6 parts of hydroxypropyl acrylate, 1.63 parts of mercaptoethanol and 50 parts of deionized water; the material B is a mixed solution of 1.81 parts of tert-butyl peroxybenzoate and 50 parts of deionized water; and (3) dropwise adding the material A at 50 ℃ for 2.5h, preserving heat for 1h after dropwise adding is finished, and cooling to room temperature after complete reaction to obtain the polycarboxylic acid slump retaining agent.
The block polymerization modified polycarboxylic slump retaining agents of the examples 1-6 are prepared into working solutions with the concentration of 7%, and the initial fluidity, the flow with time, the compressive strength and other performances of cement paste of the polycarboxylic slump retaining agents prepared in the 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 4 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 4 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 (8)
1. A cation modified slump-retaining type polycarboxylate superplasticizer is mainly prepared from the following components: polyether macromonomer: 355-364 parts of cationic monomer: 6-12 parts of benzene ring monomer: 4-8 parts, acrylic acid: 5-8 parts of alkyl acrylate: 10-18 parts of initiator a: 0.45-0.65 part of initiator b: 1.28-1.68 parts of initiator c: 1.52-1.93 parts of chain transfer agent: 1.35-1.76 parts of water, the balance of 1000 parts of the total mass and 40 percent of solid content.
2. The cation modified slump-retaining type polycarboxylate water reducer as claimed in claim 1, which is characterized in that: the cationic monomer is one or more of methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride, tetrakis (hydroxymethyl) phosphonium sulfate and p-vinylbenzyl tributyl phosphonium chloride.
3. The cation modified slump-retaining type polycarboxylate water reducer as claimed in claim 1, which is characterized in that: the benzene ring monomer is one or more of (4-methyl basic) azomethine, styrene, 2-aminostyrene, 1-allyl-2-fluorobenzene and 1-allyl-4-fluorobenzene.
4. The cation modified slump-retaining type polycarboxylate water reducer as claimed in claim 1, which is characterized in that: the polyether macromonomer is vinyl butyl ether polyoxyethylene ether.
5. The cation modified slump-retaining type polycarboxylate water reducer as claimed in claim 1, which is characterized in that: the alkyl acrylate is one or more of hydroxyethyl acrylate and hydroxypropyl acrylate.
6. The cation modified slump-retaining type polycarboxylate water reducer 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 isobutyryl formyl, azo diisobutyronitrile, diisopropyl peroxydicarbonate and tert-butyl peroxybenzoate.
7. The cation modified slump-retaining type polycarboxylate water reducer as claimed in claim 1, which is characterized in that: the chain transfer agent is one or two of mercaptoethanol and mercaptopropanol.
8. A cationic modified slump-retaining type polycarboxylate superplasticizer block polymerization method comprises the following steps:
1) preparation of benzene ring cationic block I: adding 6-12 parts of cationic monomer, 4-8 parts of benzene ring monomer and 50 parts of deionized water into a first reaction kettle, and uniformly dropwise adding an initiator, namely a mixed solution of 0.45-0.65 part of initiator a and 50 parts of deionized water at the temperature of 40-60 ℃ for 0.5-1h to prepare a benzene ring hydroxyl block polymer I;
2) preparation of Block Polymer II: 355-364 parts of polyether macromonomer, 5-10 parts of alkyl acrylate and 350 parts of deionized water are added into a second reaction kettle to be mixed, an initiator is dripped under the normal temperature condition, namely 1.28-1.68 parts of initiator b and 50 parts of deionized water are stirred and mixed to obtain the mixture, and the mixture is dripped for 2-2.5 hours to obtain a block polymer II;
3) adding the block polymers I and II into a third reaction kettle, mixing and stirring uniformly, and dropwise adding a material A and a material B in sequence, wherein the material A is a mixed solution of 5-8 parts of acrylic acid, 5-8 parts of alkyl acrylate, 1.35-1.76 parts of a chain transfer agent and 50 parts of deionized water; the material B is a mixed solution of 1.52-1.93 parts of initiator c and 50 parts of deionized water; dropping the material A at 40-50 ℃ for 2-3h, preserving heat for 1h after dropping, and cooling to room temperature after complete reaction to obtain the polycarboxylic slump retaining agent.
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| CN112521043A (en) * | 2020-12-15 | 2021-03-19 | 温州鼎玛建筑技术有限公司 | Concrete modified water reducing agent and preparation method thereof |
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Application publication date: 20200424 |