CN108249807B - Polycarboxylate superplasticizer, and preparation method and application thereof - Google Patents
Polycarboxylate superplasticizer, and preparation method and application thereof Download PDFInfo
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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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- 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
- C08F2/02—Polymerisation in bulk
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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
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft 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
Abstract
The invention discloses a novel polycarboxylate superplasticizer and a preparation method thereof. The novel polycarboxylate superplasticizer is prepared from an unsaturated acid monomer and a comb-shaped polyether monomer according to a molar ratio of 1: 3-8, carrying out free radical copolymerization reaction to obtain the product; the comb-shaped polyether monomer is prepared from an unsaturated halogen compound, a catalyst, a ligand and an OEGMA monomer according to a molar ratio of 1: 1: 1-2: 5-25, adding an oxidant and water into the comb-shaped polyether monomer, uniformly mixing to obtain a base solution, and then dropwise adding a dropping liquid composed of an unsaturated acid monomer, a reducing agent, a chain transfer agent and water to perform a polymerization reaction, thereby obtaining the novel polycarboxylic acid water reducer. The novel polycarboxylate superplasticizer disclosed by the invention has the advantages of high water reduction, long slump loss resistance, clay resistance and capability of reducing the viscosity of concrete; the novel polycarboxylate superplasticizer is produced by a one-pot method, the process is simple, no waste is produced, and the production process is green and environment-friendly.
Description
Technical Field
The invention relates to a polycarboxylate superplasticizer, a preparation method and application thereof, belonging to the technical field of concrete additives.
Background
The addition of the chemical admixture can greatly improve the durability, the workability, the applicability, the economy and the strength of the concrete, and provide powerful guarantee for the quality of large-scale engineering, so that the wide application of the chemical admixture is known as the 3 rd major breakthrough of the concrete technology after reinforced concrete and prestressed concrete. The water reducing agent (also called as cement dispersant) is an admixture for concrete which is most widely researched and applied at present, and under the condition that the workability of concrete is unchanged, the addition of the water reducing agent can effectively save the using amount of cement, reduce the using amount of water and improve the working performance and strength of concrete.
The application of the water reducing agent has gone through the history of nearly one hundred years, and the lignosulfonate water reducing agent developed in the 30 th of the 20 th century is considered as a first-generation water reducing agent, and the water reducing rate of the lignosulfonate water reducing agent is probably between 10 and 15 percent; naphthalene sulfonate water reducers, aliphatic sulfonate water reducers, sulfamate water reducers and the like developed in the 60 th of the 20 th century are considered as second-generation water reducers, and the water reducing rate of the naphthalene sulfonate water reducers, the aliphatic sulfonate water reducers, the sulfamate water reducers and the like is probably between 15 and 25 percent; the polycarboxylate water reducer developed in the 80 s of the 20 th century is considered as a third-generation water reducer, and the water reducing rate of the polycarboxylate water reducer is approximately 25-40%. The polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate, good slump retaining property, strong molecular structure adjustability, environmental friendliness and the like, is the most mainstream water reducing agent product at present, and has the market share which is improved year by year and reaches more than 70 percent at present.
The excellent performance of the polycarboxylic acid water reducing agent comes from the unique molecular structure, and the polycarboxylic acid is a water-soluble comb-shaped polymer essentially and consists of a main chain rich in carboxylic acid groups and polyoxyalkylene ether (polyether) side chains. The carboxylic acid groups on the polycarboxylic acid main chain can be directionally adsorbed on the surface of positively charged cement or cement hydrate, and the polyether side chains are stretched in the solution to form a hydration layer to provide a steric repulsive force to prevent the cement from agglomerating, so that the polyether side chains can endow the cement paste with good fluidity. The polycarboxylic acid water reducing agent has taken over 30 years of refulgence course from the concept proposal to the product perfection. With the increasing range of applications of polycarboxylic acids, it also exposes a number of problems. Some of the major compelling requirements that users have at the present time put into practice for polycarboxylic acids are: (1) the water reducing rate of the polycarboxylic acid needs to be continuously improved, and the slump retaining time needs to be prolonged; (2) in high-strength concrete with low water-cement ratio, polycarboxylic acid needs to reduce the viscosity of the concrete and improve the workability of the concrete so as to be beneficial to construction; (3) as sandstone resources tend to be deteriorated in various places, the mud content (mainly clay) of the material is higher, and the tolerance of the polycarboxylic acid water reducing agent to the clay needs to be improved. Around the above requirements, a large amount of literature and patent data have been reported.
Chinese patent document CN 106146765A discloses a preparation method of a multi-branched polycarboxylic acid water reducing agent, wherein a polyhydroxy compound is used as an initiator, and three steps of atom transfer radical polymerization are adopted to carry out stepwise polymerization to obtain an AB type diblock copolymer with a multi-branched structure. The product has high water reducing rate, good slump retaining property, low sensitivity to clay, low cost and no pollution, and can obviously improve the fluidity of concrete. However, the method has complicated steps and complex process, is only stopped at a laboratory stage so far, and cannot be applied industrially.
Chinese patent document CN 103992442A discloses a preparation method of an amphoteric polycarboxylate superplasticizer, which synthesizes a cationic-terminated quaternary ammonium salt polycarboxylate superplasticizer by modifying polyether side chains. The synthesized water reducing agent simultaneously introduces anion and cation charges in a molecular structure, when the water reducing agent is added into cement paste, the anion charges of a main chain are adsorbed on the surfaces of cement particles with positive charges, and the positive charges of side chain end groups are adsorbed on the surfaces of the cement particles with negative charges to disperse the cement particles. The cation can inhibit the expansion of soil, so as to reduce the adsorption of the soil to the additive, and the soil has unique dispersing capacity, high water reducing rate, good slump retentivity and excellent performance due to the unique amphoteric structure. However, the product is rich in anions and cations, so that coagulation is easily caused at high concentration, which greatly limits the application prospect.
Chinese patent document CN 104262550A discloses a preparation method of a viscosity-reducing polycarboxylic acid water reducer, which comprises the steps of firstly synthesizing unsaturated primary amine small monomers from unsaturated anhydride and unsaturated primary amine at a certain temperature, then reacting the unsaturated primary amine small monomers with organic small molecules containing epoxy groups and halogen groups to obtain quaternary ammonium salt unsaturated monomers, and finally introducing the unsaturated quaternary ammonium salt serving as a third monomer into a polycarboxylic acid molecular structure to obtain a product with good functions of reducing the viscosity of concrete, improving slump retentivity and the like. But the product sacrifices the most important water reducing capacity of the water reducing agent, and the market application prospect is great.
Chinese patent document CN 103897116A discloses a preparation method of a mud-resistant polycarboxylic acid water reducer, which is prepared by taking vinyl polyoxyethylene ether, sodium styrene sulfonate, acrylic acid and acrylamide compounds as monomers through free radical copolymerization. The product has better dispersibility in the concrete containing the mud, small slump loss and good adaptability to the types of the cement in various regions. But the product introduces acrylamide and sodium styrene sulfonate as adsorption monomers, and the water reducing performance is also sacrificed.
From the above reports, there is no polycarboxylic acid product which can simultaneously satisfy high water reduction, mud resistance and viscosity reduction in the market. Therefore, a new product with the excellent performance is developed, and the method has great significance for promoting the research of the polycarboxylate superplasticizer and improving the technical level of concrete application.
Disclosure of Invention
The invention aims to provide a preparation method of a polycarboxylate water reducer, which has a water reduction rate higher than that of the existing product, can solve the problems of insufficient water reduction rate, high viscosity and poor workability in high-strength concrete, has excellent clay tolerance and has a wide market application prospect.
The invention also aims to provide application of the polycarboxylate superplasticizer as a cement dispersant.
According to a great amount of experiments, researchers of the invention find that after polycarboxylic acid molecules are adsorbed to the surfaces of cement particles, the size of spatial repulsive force provided by a water film layer formed by polyether side chains of the polycarboxylic acid molecules is a key factor influencing the water reducing capability of the polycarboxylic acid molecules, the topological structure of the polyether side chains contained in the polycarboxylic acid molecules is changed from the traditional linear structure into the comb shape, the thickness of the water film layer can be effectively increased, the spatial repulsive force is improved, the water reducing capability of the polycarboxylic acid can be effectively improved finally, and the comprehensive performance of concrete application can be obviously improved.
The invention provides a polycarboxylate superplasticizer which has the following structural formula:
in the formula, R1is-H or-COOH, R2is-H, -CH3or-CH2COOH，R3is-H or-CH3，R4is-CH2-、-CH2CH2-、-OOCCH2-、-CH2OOCCH2-or a benzene ring, X being a chlorine or bromine atom; p, q, m and n represent the number of the repeating units of each repeating unit, p is 10-280, q is 2-35, m is 5-25, and n is 5-21.
The polycarboxylate superplasticizer is prepared by carrying out free radical copolymerization reaction on an unsaturated acid monomer and a comb-shaped polyether monomer;
the molar ratio of the comb-shaped polyether monomer to the unsaturated acid monomer is 1: 3-8;
the unsaturated acid monomer has a structural formula shown as (I):
in the formula, R1is-H or-COOH, R2is-H, -CH3or-CH2COOH, when R1In the case of-COOH, alternative forms which form anhydrides with other-COOH may be employed. Such anhydride alternatives may be converted to carboxylic acids during manufacture or use and are therefore considered equivalent alternatives, the unsaturated acid monomer being at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride;
the comb-shaped polyether monomer is a macromolecular monomer with a comb-shaped topological structure, the main chain of the comb-shaped polyether monomer is a hydrocarbon molecular chain, the side chain of the comb-shaped polyether monomer is polyoxyethylene ether (polyether), the end group of the main chain contains a carbon-carbon double bond, and the structural formula of the comb-shaped polyether monomer is shown as (II):
the weight average molecular weight M of the comb-shaped polyether monomerwThe molecular weight of the water reducer is 2000-10000, the performance of the polycarboxylate water reducer can be obviously influenced, the steric hindrance of a side chain cannot be obviously improved when the molecular weight is too small, and the polymerization activity of the comb-shaped polyether monomer can be reduced when the molecular weight is too large.
The comb-shaped polyether monomer can be prepared by taking polyethylene glycol methacrylate (OEGMA) as a monomer, adding an unsaturated halogen compound, a catalyst and a ligand according to the prior art and performing an atom transfer radical polymerization method, wherein the related references are as follows:
(1)Matyjaszewski K,Coessens V,Nakagawa Y,et al.Synthesis offunctional polymers by atom transfer radical polymerization[M].ACSSymp.Ser.1998,704,16.
(2)Matyjaszewski K,Beers K L,Kern A,et al.Hydrogels by atom transferradical polymerization.I.Poly(N-vinylpyrrolidinone-g-styrene)via themacromonomer method[J].Journal of Polymer Science Part A:Polymer Chemistry,1998,36(5):823-830.
the preparation method of the polycarboxylate superplasticizer comprises the following steps:
(1) synthesizing comb-shaped polyether monomer: unsaturated halogenThe compound, catalyst, ligand and OEGMA monomer are thoroughly mixed in N2Under protection, heating to 60-120 ℃, carrying out polymerization reaction for 2-6 h, and filtering to remove insoluble copper salt to obtain a comb-shaped polyether monomer;
the reaction in the step (1) is bulk polymerization, and an organic solvent is not required to be added in the reaction, so that the purification step is omitted, and the cost is saved;
the molar ratio of the unsaturated halogen compound, the catalyst, the ligand and the OEGMA monomer is 1: 1: 1-2: 5-25;
(2) preparing a polycarboxylic acid water reducing agent: adding an oxidant and water into the comb-shaped polyether monomer prepared in the step (1), uniformly mixing to obtain a primer solution, heating to 25-60 ℃, then dropwise adding a dropping liquid consisting of an unsaturated acid monomer, a reducing agent, a chain transfer agent and water for polymerization reaction for 1-3 h, after dropwise adding, carrying out heat preservation reaction for 1h, and finally adding a NaOH solution to neutralize the reaction solution to obtain a polycarboxylate superplasticizer, wherein the pH value of the reaction solution is 6-8;
the solid contents of the base liquid and the dropping liquid are both 30-60%.
The OEGMA monomer in the step (1) is a commercial raw material, and the weight average molecular weight M of the OEGMA monomerw300-1000, the structural formula is shown as (III):
the unsaturated halogen compound is used as an initiator in the polymerization of OEGMA, so that the terminal of the synthesized comb-shaped polyether monomer has a carbon-carbon double bond, and the comb-shaped polyether monomer is endowed with the capability of polymerizing again, wherein the unsaturated halogen compound is one of 3-chloropropene, 4-chlorobutene, 2-methyl-3-chloropropene, 2-methyl-4-chlorobutene, 3-bromopropene, 4-bromobutene, 2-methyl-3-bromopropene, 2-methyl-4-bromobutene, vinyl chloroacetate, allyl chloroacetate and 4-chloromethyl styrene;
the catalyst is one of cuprous chloride and cuprous bromide;
the ligand is 2,2 '-bipyridyl (bpy), 4' -dinonyl-2, 2 '-bipyridyl (dNbpy), N, N, N' -pentamethyl diethylene glycolTriamines (PMDETA), tris [2- (dimethylamino) ethyl ]]Amine (Me)6TREN), N, N, N ', N' -tetrakis (2-picolyl) ethylenediamine (TPEN);
in the step (2), an oxidation-reduction initiator and a water-soluble chain transfer agent are adopted in the polymerization reaction; in the oxidation-reduction initiator, the oxidant is one of hydrogen peroxide, ammonium persulfate and potassium persulfate, the dosage of the oxidant is 1% -4% of the total molar weight of the unsaturated acid monomer and the comb-shaped polyether monomer, the reducing agent is one of L-ascorbic acid, sodium sulfite, sodium bisulfite and ferrous sulfate, and the dosage of the reducing agent is 0.5% -1% of the total molar weight of the unsaturated acid monomer and the comb-shaped polyether monomer; the water-soluble chain transfer agent is one of mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid, and the dosage of the water-soluble chain transfer agent is 1.5-4.5 percent of the total molar weight of the unsaturated acid monomer and the comb-shaped polyether monomer.
After the copolymerization reaction in the step (2) is finished, the reaction product can be directly used as a main component of a cement dispersant, and a NaOH solution can be further added to neutralize the pH value of the solution to be 6-8 so as to enhance the storage stability of the product, which is a known technology in the field. After neutralization, the carboxyl groups contained in the above general structural formula can be partially or completely converted into carboxylate. The invention neglects the effect of neutralization on the molecular weight of the mud-resistant polycarboxylate superplasticizer because the effect of neutralization on the molecular weight of the mud-resistant polycarboxylate superplasticizer is small.
The weight average molecular weight M of the polycarboxylate superplasticizer provided by the inventionw20000 to 80000.
The polycarboxylate water reducer provided by the invention is mainly different from a common polycarboxylate water reducer in the prior art in that comb-shaped polyether is introduced to replace linear polyether to serve as a side chain structure in a polycarboxylate molecule, so that the steric hindrance of a side chain adsorption layer can be greatly improved, and the water reducing capacity of a product and the comprehensive performance of concrete application are improved.
In another aspect of the invention, the application of the polycarboxylate superplasticizer as a cement dispersant is also provided.
The application method of the polycarboxylic acid water reducing agent is the same as that of the known cement dispersing agent, and the application method is generally known by the person skilled in the art.
The mixing amount of the polycarboxylic acid water reducing agent is 0.05-0.3% of the total mass of the cementing material, the mixing amount is the pure solid mixing amount, and the percentage is mass percent. Too low a content results in deterioration of the performance, and too high a content results in economic waste and performance is not improved.
The polycarboxylate water reducer can be mixed with other commercially available water reducers, such as lignosulfonate water reducers, naphthalene sulfonate water reducers, polycarboxylate water reducers and the like, and can also be added with air entraining agents, retarders, early strength agents, expanding agents, tackifiers, shrinkage reducers and defoaming agents for use.
Compared with the prior art, the invention has the following advantages:
(1) the polycarboxylate superplasticizer disclosed by the invention has the advantages of high water reduction, long slump loss resistance, clay resistance and capability of reducing the viscosity of concrete.
(2) The polycarboxylate superplasticizer disclosed by the invention is produced by adopting a one-pot method, the process is simple, no waste is produced, and the production process is green and environment-friendly.
Detailed Description
The technical solutions of the present invention will be further described in detail with reference to the following examples, but the present invention is by no means limited thereto, and any equivalent changes or modifications made according to the spirit of the present invention should be covered within the scope of the present invention.
In the examples of the present invention, the polymer molecular weight was measured by miniDAWN Tristar aqueous gel permeation chromatograph (GPC, Huanya stunt Co., Ltd.) equipped with TSK-GELSW (Tosoh Biotechnology Co., Ltd.) chromatography, mobile phase: 0.1M NaNO3Aqueous solution, flow rate: 1.0mL/min, sample mass percent concentration: 0.50 percent.
The raw material OEGMA (> 98%) used in the examples of the present invention was purchased from Nanjing Bott New Material Co., Ltd, and other raw materials were commercially available general chemical pure reagents and purchased from Aladdin chemical Co., Ltd.
The synthesis method in the embodiment is divided into two parts, firstly comb-shaped polyether monomer is synthesized, and then polycarboxylic acid water reducing agent is synthesized by a free radical copolymerization method.
Example 1
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of 3-chloropropene, OEGMA (M)wMolecular weight 300)4mol, CuCl0.2mol and PMDETA 0.2mol, introducing N2Removing O in the solution for 30min2Then the system was closed and stirred to raise the temperature to 60 ℃ and react at this temperature for 2 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCwThe molecular weight distribution coefficient was 1.26 at 5150.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerwCalculated by molecular weight 5150, 515g in total), 0.012mol of hydrogen peroxide and 515g of water, then stirring and heating to 40 ℃, dropwise adding a mixed solution consisting of 0.5mol of acrylic acid, 0.027mol of mercaptoethanol, 0.003mol of L-ascorbic acid and 38g of water at the temperature, dropwise adding for 3h, preserving heat for 1h after dropwise adding, finally neutralizing the pH of the reaction solution with a sodium hydroxide solution to be 7 to obtain a polycarboxylic acid water reducing agent aqueous solution, and measuring GPC (measured by M of the polycarboxylic acid) to obtain the M of the polycarboxylic acid water reducing agent aqueous solutionw20600, and a molecular weight distribution coefficient of 1.68.
Example 2
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of 2-methyl-3-chloropropene, OEGMA (M)wMolecular weight 400), 4mol, CuBr0.2mol, bpy 0.4mol, N is introduced2Removing O in the solution for 30min2Then, the system was closed, stirred and warmed to 80 ℃ to react at this temperature for 4 hours. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw6850, and a molecular weight distribution coefficient of 1.35.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerw685g of total molecular weight, 685g of total), 0.028mol of ammonium persulfate and 690g of water, then stirring and heating to 60 ℃, dropwise adding a mixed solution consisting of 0.6mol of methacrylic acid, 0.0245mol of mercaptoethanol, 0.0035mol of sodium bisulfite and 53g of water at the temperature, and dropwise addingThe time is 1h, the temperature is kept for 1h after the dropwise addition is finished, finally, the pH of the reaction solution is neutralized to 7 by using a sodium hydroxide solution to obtain a polycarboxylic acid water reducing agent aqueous solution, and the M is measured by GPC (GPC)w2450 and a molecular weight distribution coefficient of 1.77.
Example 3
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of 2-methyl-4-bromobutene, OEGMA (M)wMolecular weight 500)3.6mol, CuBr0.2mol, TPEN 0.2mol, N is introduced2Removing O in the solution for 30min2Then the system was closed and stirred to raise the temperature to 100 ℃ and reacted at this temperature for 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw7740 and molecular weight distribution coefficient 1.25.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerwCalculating the molecular weight of 7740, totally 774g), potassium persulfate 0.009mol and water 775g, stirring and heating to 60 ℃, dropwise adding a mixed solution consisting of itaconic acid 0.8mol, mercaptopropionic acid 0.0315mol, sodium bisulfite 0.0045mol and water 105g at the temperature, dropwise adding for 2h, keeping the temperature for 1h after dropwise adding, neutralizing the pH of the reaction solution with sodium hydroxide solution to 7 to obtain a polycarboxylic acid water reducer aqueous solution, and measuring the M by GPC (GPC)wIt was 28700, and the molecular weight distribution coefficient was 1.71.
Example 4
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of vinyl chloroacetate, OEGMA (M)wMolecular weight 500)1.2mol, CuBr0.2mol, dNbpy 0.2mol, N is introduced2Removing O in the solution for 30min2Then the system was closed and stirred to raise the temperature to 100 ℃ and reacted at this temperature for 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw2270, molecular weight distribution coefficient of 1.20.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
adding into a flask equipped with a stirrer0.1mol (as M) of the above-described synthesized comb polyether monomerwCalculated by molecular weight 2270, the total amount is 227g), potassium persulfate is 0.004mol and water is 228g, then the temperature is raised to 60 ℃ by stirring, a mixed solution consisting of 0.2mol of acrylic acid, 0.1mol of maleic anhydride, 0.01mol of mercaptopropionic acid, 0.002mol of ferrous sulfate and 47g of water is dripped at the temperature, the dripping time is 3 hours, the temperature is kept for 1 hour after the dripping is finished, finally, the pH of a reaction solution is neutralized by a sodium hydroxide solution to be 7, the polycarboxylic acid water reducing agent aqueous solution is obtained, and the M measured by GPC is MwIt was 27700, and the molecular weight distribution coefficient was 1.63.
Example 5
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of 4-chlorobutene, OEGMA (M)wMolecular weight is 500)3mol, CuBr0.2mol and PMDETA 0.2mol, N is introduced2Removing O in the solution for 30min2Then the system was closed and stirred to raise the temperature to 100 ℃ and reacted at this temperature for 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw6290 and a molecular weight distribution coefficient of 1.28.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerw6290, totaling 629g), 0.012mol of ammonium persulfate and 630g of water, stirring and heating to 60 ℃, dropwise adding a mixed solution consisting of 0.5mol of maleic acid, 0.012mol of mercaptoethanol, 0.0045mol of L-ascorbic acid and 37g of water at the temperature, dropwise adding for 3h, keeping the temperature for 1h after the dropwise adding is finished, finally neutralizing the pH of the reaction solution with a sodium hydroxide solution to be 7 to obtain a polycarboxylic acid water reducer aqueous solution, and measuring the M by GPC (measured by using the GPC) to obtain the polycarboxylic acid water reducer aqueous solutionw42600, the molecular weight distribution coefficient was 1.81.
Example 6
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer was added 0.2mol of 4-bromobutene, OEGMA (M)wMolecular weight is 750), 1mol, CuCl0.2mol and TPEN 0.2mol, N is introduced2Removing O in the solution for 30min2Then the system is closed, stirred and heated to 100 ℃, and the reaction is carried out at the temperatureAnd 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw3030, the molecular weight distribution coefficient was 1.22.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerwCalculated by the molecular weight of 3030, the total is 303g), 0.02mol of hydrogen peroxide and 303g of water, then stirring and heating to 25 ℃, dropwise adding a mixed solution consisting of 0.4mol of fumaric acid, 0.01mol of mercaptoethanol, 0.005mol of L-ascorbic acid and 35g of water at the temperature for 3h, preserving heat for 1h after dropwise adding, finally neutralizing the pH of the reaction solution with a sodium hydroxide solution to be 7 to obtain a polycarboxylic acid water reducing agent aqueous solution, and measuring the GPC (measured M) to obtain the M of the polycarboxylic acid water reducing agent aqueous solutionw35600 and a molecular weight distribution coefficient of 1.75.
Example 7
(1) Synthesizing comb-shaped polyether monomer:
into a flask equipped with a stirrer were charged 0.2mol of 2-methyl-3-bromopropene, OEGMA (M)wMolecular weight 750)2mol, CuCl0.2mol, ME6TREN 0.2mol, charging N2Removing O in the solution for 30min2Subsequently, the system was closed, stirred and warmed to 120 ℃ and reacted at this temperature for 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCw6740, the molecular weight distribution coefficient is 1.29.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerwThe molecular weight is 6740, calculated to be 674g in total), 0.018mol of hydrogen peroxide and 674g of water, then stirring and heating to 30 ℃, dropwise adding a mixed solution composed of 0.8mol of acrylic acid, 0.0135mol of mercaptoethanol, 0.0045mol of sodium bisulfite and 59g of water at the temperature, dropwise adding for 3h, keeping the temperature for 1h after dropwise adding, finally neutralizing the pH of the reaction solution with sodium hydroxide solution to be 7 to obtain the polycarboxylic acid water reducer aqueous solution, and measuring the M by GPC (measured by the GPC) to obtain the polycarboxylic acid water reducer aqueous solutionwIt was 57900, and the molecular weight distribution coefficient was 1.81.
Example 8
(1) Synthesizing comb-shaped polyether monomer:
to a flask equipped with a stirrer were added 0.2mol of 4-chloromethylstyrene, OEGMA (M)wMolecular weight 1000)2.4mol, CuCl0.2mol, ME6TREN 0.2mol, charging N2Removing O in the solution for 30min2Subsequently, the system was closed, stirred and warmed to 120 ℃ and reacted at this temperature for 6 h. After the reaction is finished, filtering to remove the copper salt to obtain a comb-shaped polyether monomer, and measuring M by GPCwIt was 9870, and the molecular weight distribution coefficient was 1.28.
(2) And (3) synthesis of a polycarboxylic acid water reducing agent:
0.1mol (as M) of the comb-shaped polyether monomer synthesized as described above is added to a flask equipped with a stirrerwCalculated by 9870, the total amount is 987g), 0.018mol of hydrogen peroxide and 987g of water, then stirring and heating to 60 ℃, dropwise adding a mixed solution consisting of 0.6mol of acrylic acid, 0.2mol of maleic anhydride, 0.0135mol of mercaptopropionic acid, 0.0045mol of ferrous sulfate and 64g of water at the temperature, dropwise adding for 3 hours, keeping the temperature for 1 hour after dropwise adding is finished, finally neutralizing the pH of the reaction solution with sodium hydroxide solution to be 7 to obtain a polycarboxylic acid water reducing agent aqueous solution, and measuring the M by GPC (GPC)w78800, the molecular weight distribution coefficient was 1.70.
Comparative example 1:
a commercially available high performance polycarboxylate superplasticizer, available from Aolet, Fe, Inc. in Jiangsu, measured by GPC, as MwIt was 33700 and had a molecular weight distribution coefficient of 1.68.
Comparative example 2:
to a flask equipped with a stirrer was added methallyl polyoxyethylene ether (M)wMolecular weight of 2400), 0.1mol of hydrogen peroxide and 240g of water, then stirring and heating to 45 ℃, dropwise adding a mixed solution consisting of 0.4mol of acrylic acid, 0.0125mol of mercaptopropionic acid, 0.025mol of L-ascorbic acid and 30g of water at the temperature, dropwise adding for 3 hours, preserving heat for 1 hour after dropwise adding, finally neutralizing the pH of the reaction solution to 7 by using a sodium hydroxide solution, and measuring the M by GPC (measured by GPC)wIs 31700 and has a molecular weight distribution coefficient of 1.66, which is a common polycarboxylic acid water reducing agent prepared by a conventional method in a laboratory.
The application example is as follows:
in an application embodiment, the adopted cement is Poi 52.5 of a small wild field, the mineral powder is S95 type mineral powder produced by Jiangnan grinding Limited, the fly ash is I-grade fly ash produced by Jiangsu Huaneng electric power company, the sand is medium sand with fineness modulus M of 2.6, and the stones are basalt with continuous gradation of 5-20 mm in particle size.
Application example 1
Measuring the water reducing rate and the air content of the concrete according to a method specified in GB8076-2008 concrete admixture, measuring the slump and the expansion degree of the concrete according to related regulations of JC473-2001 concrete pumping agent, wherein the mixing amount of the fixed water reducing agent is 0.15%, the water consumption is adjusted to control the initial slump of the concrete to be 21cm +/-1 cm, and the weight mixing ratio of the concrete is as follows: cement 267, mineral powder 53, fly ash 60, sand 767, large stone 800 and small stone 260. The results are shown in Table 1.
TABLE 1 concrete Performance test results
The results in Table 1 show that the water reducing rate of the example can reach 43.6% on average under the condition that the mixing amount and the gas content are the same as those of the comparative example, while the comparative example is only about 36.1%, and the comparative example is 20.8% higher than that of the comparative example, which shows that the polycarboxylic acid water reducing agent of the invention can improve the water reducing performance by more than 20% compared with the existing polycarboxylic acid product and can not cause the gas content to rise. In addition, in the case where the initial slump/spread is similar to that of the comparative example, the slump/spread after 50min is greater than that of the comparative example, which shows that the polycarboxylic acid water-reducing agent of the present invention has excellent slump retaining property.
Application example 2
Montmorillonite is a typical clay, and the adsorption capacity of the montmorillonite to polycarboxylic acid is far greater than that of cement, so in the experiment, the clay content in a sandstone material is simulated by a method of adding montmorillonite into cement, and the tolerance of the polycarboxylic acid water reducing agent disclosed by the invention to the clay is detected. The fluidity of the neat paste is measured according to GB/T8077-2000 'test method for homogeneity of concrete admixture', the cement with corresponding mass is replaced by the montmorillonite with different mass, the water cement ratio is fixed to be 0.29, the mixing amount of the water reducing agent is adjusted to ensure that the initial fluidity of the neat paste is about 270mm, and the results are shown in Table 2.
TABLE 2 test of clay adhesion resistance of samples
Note: "- -" indicates no fluidity.
The data in Table 2 show that the polycarboxylate water reducing agent cement paste fluidity of the present invention decreases by about 7.4% and 18.5% when 0.5% and 1% of montmorillonite are added, respectively, while the comparative example decreases by more than 35% until the fluidity is lost. The polycarboxylate superplasticizer has good tolerance to montmorillonite, and has great competitive advantage in some areas with large sand-gravel aggregate mud content.
Application example 3
Then, detecting the influence of the polycarboxylate water reducer on the high-strength concrete according to a method specified in GB8076-2008, and adjusting the mixing amount of the water reducer to ensure that the initial slump of the concrete is between 24 +/-1 cm and the mass mixing ratio of the concrete: cement 376, mineral powder 105, fly ash 82, silica fume 17, sand 800, stone 980 and water 140. The concrete viscosity is quantified by measuring the initial empty time through an inverted slump cone, and the concrete method comprises the following steps: the slump cone is inverted, the bottom is capped, filled with concrete and trowelled (typically the inverted slump cone is fixed to a support, the bottom is 50cm from the ground), the bottom is quickly slid open, and the concrete flow time is measured with a stopwatch. The concrete test results are shown in Table 3.
TABLE 3 high-Strength concrete Performance test results
The high strength concrete test results of table 3 show: (1) under the condition that the mixing amount of the concrete is about 25 percent lower than that of the comparative example, the initial slump/expansion of the concrete is similar to that of the comparative example, and the slump/expansion of the concrete is larger than that of the comparative example in 50min, which shows that the polycarboxylic acid water reducing agent has excellent performances of high water reduction and high slump retention. (2) Under the condition that the air contents of the embodiment and the comparative example are similar, the initial air flow time is within 10 seconds and is far less than 28-30 seconds of the comparative example, the workability of the embodiment is better, and the turning is very easy, so that the polycarboxylate superplasticizer provided by the invention can effectively reduce the viscosity of high-strength concrete, improve the workability of the concrete, is beneficial to pumping the concrete in construction, and has a wide application prospect in the high-strength concrete market.
Claims (9)
1. The polycarboxylate superplasticizer is characterized by having a structural formula as follows:
in the formula, R1is-H or-COOH, R2is-H, -CH3or-CH2COOH，R3is-H or-CH3，R4is-CH2-、-CH2CH2-、-OOCCH2-、-CH2OOCCH2-or a benzene ring, X being a chlorine or bromine atom; p, q, m and n represent the number of the repeating units of each repeating unit, p is 10-280, q is 2-35, m is 5-25, and n is 5-21.
2. The polycarboxylate water reducer according to claim 1, characterized in that: the weight average molecular weight M of the water reducing agentw20000 to 80000.
3. The polycarboxylate water reducer according to claim 2, characterized in that: the polycarboxylate superplasticizer is prepared by carrying out free radical copolymerization reaction on an unsaturated acid monomer and a comb-shaped polyether monomer;
the molar ratio of the comb-shaped polyether monomer to the unsaturated acid monomer is 1: 3-8;
the unsaturated acid monomer has a structural formula shown as (I):
the comb-shaped polyether monomer is a macromonomer with a comb-shaped topological structure, and the structural formula of the comb-shaped polyether monomer is shown as (II):
4. the polycarboxylate water reducer according to claim 3, wherein the unsaturated acid monomer is at least one of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid or maleic anhydride.
5. The polycarboxylate water reducer according to claim 4, characterized in that the comb polyether monomer has a weight average molecular weight MwIs 2000 to 10000.
6. The preparation method of the polycarboxylic acid water reducing agent according to any one of claims 3 to 5, characterized by comprising the steps of:
(1) synthesizing comb-shaped polyether monomer: mixing unsaturated halogen compound, catalyst, ligand and OEGMA monomer thoroughly, and reacting in N2Under protection, heating to 60-120 ℃, carrying out polymerization reaction for 2-6 h, and filtering to remove insoluble copper salt to obtain a comb-shaped polyether monomer;
the molar ratio of the unsaturated halogen compound, the catalyst, the ligand and the OEGMA monomer is 1: 1: 1-2: 5-25;
(2) preparing a polycarboxylic acid water reducing agent: adding an oxidant and water into the comb-shaped polyether monomer prepared in the step (1), uniformly mixing to obtain a primer solution, heating to 25-60 ℃, then dropwise adding a dropping liquid consisting of an unsaturated acid monomer, a reducing agent, a chain transfer agent and water for polymerization reaction for 1-3 h, after dropwise adding, carrying out heat preservation reaction for 1h, and finally adding a NaOH solution to neutralize the reaction solution to obtain a polycarboxylate superplasticizer, wherein the pH value of the reaction solution is 6-8;
the solid contents of the base liquid and the dropping liquid are both 30-60%;
the OEGMA monomer in the step (1) has a structural formula shown as (III):
the unsaturated halogen compound is one of 3-chloropropene, 4-chlorobutene, 2-methyl-3-chloropropene, 2-methyl-4-chlorobutene, 3-bromopropene, 4-bromobutene, 2-methyl-3-bromopropene, 2-methyl-4-bromobutene, vinyl chloroacetate, allyl chloroacetate and 4-chloromethyl styrene;
the catalyst is one of cuprous chloride and cuprous bromide;
the ligand is 2,2 '-bipyridine (bpy), 4' -dinonyl-2, 2 '-bipyridine (dNbpy), N, N, N' -Pentamethyldiethylenetriamine (PMDETA), tris [2- (dimethylamino) ethyl group]Amine (Me)6TREN), N, N, N ', N' -tetrakis (2-picolyl) ethylenediamine (TPEN).
7. The preparation method of the polycarboxylate water reducer as claimed in claim 6, wherein the OEGMA monomer has a weight average molecular weight MwIs 300 to 1000.
8. The preparation method of the polycarboxylate water reducer according to claim 7, characterized in that in the step (2), the oxidant is one of hydrogen peroxide, ammonium persulfate and potassium persulfate, and the amount of the oxidant is 1% -4% of the total molar amount of the unsaturated acid monomer and the comb-shaped polyether monomer;
the reducing agent is one of L-ascorbic acid, sodium sulfite, sodium bisulfite and ferrous sulfate, and the dosage of the reducing agent is 0.5 to 1 percent of the total molar weight of the unsaturated acid monomer and the comb-shaped polyether monomer;
the chain transfer agent is a water-soluble chain transfer agent, the water-soluble chain transfer agent is one of mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid, and the dosage of the water-soluble chain transfer agent is 1.5% -4.5% of the total molar weight of the unsaturated acid monomer and the comb-shaped polyether monomer.
9. The application method of the polycarboxylate superplasticizer according to any one of claims 1 to 5, wherein the blending amount of the polycarboxylate superplasticizer is 0.05-0.3% of the total mass of the cementing material, the blending amount is the pure solid blending amount, and the percentage is mass percent.
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| CN113072667B (en) * | 2020-01-06 | 2023-01-03 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate superplasticizer |
| CN113072666B (en) * | 2020-01-06 | 2022-05-31 | 江苏苏博特新材料股份有限公司 | Preparation method and application of high-water-reduction type polycarboxylic acid superplasticizer |
| CN112011043A (en) * | 2020-08-20 | 2020-12-01 | 安徽海螺新材料科技有限公司 | High-stability polyether and production method and application thereof |
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