CN114685728B - Carboxylic acid-phosphonic acid oligomer, preparation method thereof and application thereof as water reducer - Google Patents
Carboxylic acid-phosphonic acid oligomer, preparation method thereof and application thereof as water reducer Download PDFInfo
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- CN114685728B CN114685728B CN202011594820.XA CN202011594820A CN114685728B CN 114685728 B CN114685728 B CN 114685728B CN 202011594820 A CN202011594820 A CN 202011594820A CN 114685728 B CN114685728 B CN 114685728B
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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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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
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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 carboxylic acid-phosphonic acid oligomer, a preparation method thereof and application of the carboxylic acid-phosphonic acid oligomer as a water reducer. The carboxylic acid-phosphonic acid oligomer is obtained by ester bond cleavage of a polymer consisting of a main chain rich in ester groups and phosphonic acid groups and polyether side chains, wherein the main chain is rich in two adsorption groups of carboxylic acid and phosphonic acid, and the side chains are conventional polyether chain segments; the preparation method comprises the steps of carrying out free radical heterocyclic copolymerization reaction on a polyether monomer, an ketene acetal monomer, a phosphonic acid monomer and an unsaturated acid monomer under the action of an initiator; the carboxylic acid-phosphonic acid oligomer is used as a water reducing agent. The carboxylic acid-phosphonic acid group oligomer water reducer solves the problem of quickened concrete fluidity loss under poor-quality sandstone aggregate in concrete application; the carboxylic acid-phosphonic acid group oligomer water reducer is applied to high-strength concrete (C80-C150), and has the advantages of low mixing amount and small concrete viscosity compared with the conventional polycarboxylic acid water reducer.
Description
Technical Field
The invention belongs to the technical field of additives for concrete, and particularly relates to a carboxylic acid-phosphonic acid oligomer, a preparation method thereof and application of the carboxylic acid-phosphonic acid oligomer as a concrete water reducer.
Background
The polycarboxylate water reducer is the most widely studied and applied concrete admixture at present, and under the condition of unchanged concrete workability, the polycarboxylate water reducer is doped to effectively save the cement dosage, reduce the water consumption and improve the concrete strength. In terms of molecular structure, polycarboxylic acid is a comb polymer consisting of a main chain rich in carboxylic acid groups and polyether side chains, the carboxylic acid groups on the main chain being capable of being directionally adsorbed on the surface of positively charged cement or cement hydrate, while the polyether side chains extend in solution to form a hydration layer to provide steric repulsion to prevent cement agglomeration, so that the structure imparts a strong ability to disperse cement particles to polycarboxylic acid.
In 1981, japanese catalyst Co.applied for the first patent on polycarboxylate water reducers (JP 842022 (S59-018338)). Since then, various universities and businesses have begun research into polycarboxylic acids, and a large number of patents have been filed worldwide for polycarboxylic acid products. For example, german BASF patent US7855260 reports a novel polycarboxylate water reducer prepared by copolymerization of high molecular weight vinyl polyether and acrylic acid, which has slump retaining performance superior to that of conventional polycarboxylate water reducer and can improve early strength of concrete. Patent EP1061089 of Sika of Switzerland reports a novel polycarboxylic acid water reducer containing amide groups, which is obtained by dehydration reaction of polyacrylic acid and aminopolyether, and the novel polycarboxylic acid water reducer has excellent slump retaining, reinforcing and shrinkage resistance functions in concrete application, and can effectively prevent steel bar corrosion. Since the 21 st century, polycarboxylic acid research in China has been rapidly developed, and a number of polycarboxylic acid products having excellent properties have been invented, for example, patent CN103467671a reports the synthesis of highly water-reducing polycarboxylic acids, patent CN102977263a reports the synthesis of long slump-retaining polycarboxylic acids, and patent CN104861127a reports the synthesis of soil-resistant polycarboxylic acids.
In recent years, with the increasing expansion of the construction scale in China, high-quality sand materials are consumed completely, and a large amount of low-quality sand materials and industrial waste residues enter the concrete production. In practical application, the polycarboxylate water reducer is found to have poor adaptability to poor raw materials, and the outstanding problem is represented by the fact that the concrete fluidity retention time (namely slump retention time) is greatly shortened. In order to overcome the problems, concrete production enterprises can only super-mix the polycarboxylate water reducer during construction, and meanwhile, the use proportion of the slump-retaining water reducer (slump-retaining agent) in the mother solution is improved. In this way, although the slump retention time of the concrete is prolonged, the concrete fluidity in the middle period is extremely easy to be reversely increased, meanwhile, the workability of the concrete is poor, and bleeding, layering, slurry floating, viscosity increase and the like occur, so that the engineering quality is reduced.
In view of the above problems, some students hope to prolong the slump retention time and improve the workability of concrete by developing a novel phosphonic acid based water reducer and utilizing the good tolerance of phosphonic acid groups to poor-quality sandstone aggregates. As reported in the patents CN 107337788A and CN 108033978A, the polybasic phosphonic acid based polymer additive can preliminarily realize the stable slump retention of concrete. However, the existing phosphonic acid water reducer has the defects of large synthesis difficulty and far worse dispersion capability than the polycarboxylic acid water reducer, so that the product cannot be popularized and utilized on a large scale.
In conclusion, the high-performance water reducer which has good adaptability to modern low-quality sandstone aggregate, long slump retention time and can improve workability of concrete is developed, and has great significance for promoting high-tech concrete.
Disclosure of Invention
Aiming at the defects of high synthesis difficulty, heavy pollution, poor water reduction performance compared with polycarboxylic acid and the like of the existing phosphonic acid based water reducer, the development of a high-performance polycarboxylic acid water reducer which can adapt to the sandstone aggregate with poor quality, improve the fluidity stability of concrete for a long time and improve the uniformity of the concrete is needed. The invention provides a carboxylic acid-phosphonic acid oligomer which can be used as a water reducer and a preparation method thereof, wherein the carboxylic acid-phosphonic acid oligomer water reducer can be combined with the advantages of strong dispersion capacity of a polycarboxylic acid water reducer and good adaptability of a phosphoric acid water reducer to low-quality sand stone materials, has excellent initial dispersion capacity in concrete application, and can keep the fluidity of concrete stable for a long time on the premise of not compounding a slump retaining agent. In addition, the modified asphalt is applied to high-strength concrete (C80-C150), and has the characteristics of high water reducing rate and capability of reducing the viscosity of the concrete.
According to a large number of documents and patent reports, the molecular weight of the polycarboxylate water reducer is reduced, and the slump retaining capacity of the product can be improved. Meanwhile, the polycarboxylate water reducer with lower molecular weight has lower bulk viscosity, which is beneficial to improving the viscosity of high-strength concrete and reducing the construction difficulty. In the synthesis of the polycarboxylate water reducer, the molecular weight is regulated and controlled by the use amount of a chain transfer agent (mainly a sulfhydryl compound), and the more the use amount of the chain transfer agent is, the lower the molecular weight is within a certain use amount range. However, even if the amount of the chain transfer agent is large, it is difficult to synthesize the polycarboxylic acid oligomer (molecular weight < 8000). This is because, as the amount of the chain transfer agent increases, the effect of reducing the molecular weight becomes less and less remarkable, it is difficult to reduce the molecular weight to 10000 or less, and too much chain transfer agent also greatly reduces the conversion of the raw polyether of the polycarboxylic acid, which seriously affects the performance of the polycarboxylic acid water reducing agent.
The invention provides a carboxylic acid-phosphonic acid oligomer, which is obtained by ester bond cleavage of a polymer consisting of a main chain rich in ester groups and phosphonic acid groups and a polyether side chain, wherein the main chain is rich in two adsorption groups of carboxylic acid and phosphonic acid, and the side chain is a conventional polyether chain segment;
the polymer is a carboxylic acid-phosphonic acid group polymer and is obtained by free radical heterocyclic copolymerization of polyether monomers, ketene acetal monomers, phosphonic acid monomers and unsaturated acid monomers.
The carboxylic acid-phosphonic acid oligomer has the following molecular structural general formula
Wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 ，R 4 is-H or-COONa, R 5 is-H, -CH 3 or-CH 2 COONa，R 6 is-H or-CH 3 ，R 7 is-CH 2 -、-CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 -，R 8 is-H or-CH 3 M, n, x, y, z, k are integers representing the number of repeating units of each repeating unit, where m=0, 1 or 2, and when m takes 0, CH-R is represented 2 Is absent, CH-R 1 And CH-R 3 The attached carbon atoms are directly connected, n=11 to 68, x=10 to 100, y=3 to 18, z=1 to 15, k=1 to 3;
weight average molecular weight (M) of the Carboxylic acid-phosphonic acid based oligomer of the present invention w ) 3000-8000.
The carboxylic acid-phosphonic acid oligomer is prepared by free radical heterocyclic copolymerization of a polyether monomer A, an ketene acetal monomer B, a phosphonic acid monomer C and an unsaturated acid monomer D under the action of an initiator, and is prepared by adding NaOH to react.
The molar ratio of the polyether monomer A to the ketene acetal monomer B to the phosphonic acid monomer C to the unsaturated acid monomer D is 1 (0.06-0.3): 0.2-0.75): (3-10); the initiator is used in an amount of 0.08-2 wt% of the total mass of the polyether monomer A, the ketene acetal monomer B, the phosphonic acid monomer C and the unsaturated acid monomer D.
The polyether monomer A has a structural general formula shown below and is a raw material polyether macromonomer commonly used for producing the polycarboxylate superplasticizer;
wherein when R is 6 is-H or-CH 3 ，R 7 is-CH 2 -、-CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 -n represents the number of repeating units, and is an integer ranging from 11 to 68;
the weight average molecular weight of the polyether monomer A is 500-3000.
The ketene acetal monomer B has a structural general formula shown in the specification,
wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 M is 0, 1 or 2, and represents CH-R when m is 0 2 Absent, R 1 And R is R 3 The attached carbon atoms are directly attached, in which case monomer B is a five-membered ring.
The phosphonic acid monomer C has a structural general formula shown in the specification;
wherein R is 8 is-H or-CH 3 K represents the number of repeating units and is 1, 2 or 3.
The synthesis method of the phosphonic acid monomer C comprises the following steps: adding (methyl) allyl chloride, polyamine monomer and water into a four-neck flask with a stirrer and a thermometer, reacting at a concentration of 50wt%, then heating to 120 ℃, reacting for 8 hours, and evaporating excessive water and polyamine monomer at a high temperature; then adding concentrated hydrochloric acid, phosphorous acid and 37wt% formaldehyde solution into the product at room temperature, heating to 110 ℃, and stirring for reacting for 12 hours to obtain phosphonic acid monomer C;
the polyamine monomer is selected from any one of ethylenediamine, diethylenetriamine and triethylenetetramine;
the molar ratio of (meth) allyl chloride to polyamine monomer is 1:1 to 3
The number of moles of the concentrated hydrochloric acid, phosphorous acid and formaldehyde is related to the kind of polyamine monomer and is equal to the number of moles of hydrogen atoms to which the N atoms in the polyamine monomer are bonded.
The unsaturated acid monomer D has a structural general formula shown in the specification;
wherein R is 4 is-H or-COOH, R 5 is-H, -CH 3 or-CH 2 COOH。
The unsaturated acid monomer D is selected from any one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid and is mixed in any proportion.
The initiator is any one selected from Azodiisobutyronitrile (AIBN), azodiisoheptonitrile (ABVN), dimethyl Azodiisobutyrate (AIBME), azodicyanovaleric acid (V-501), hydrogen peroxide, cumene hydroperoxide, tert-butyl peroxybenzoate, tert-butyl peroxyvalerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and Benzoyl Peroxide (BPO), and is a common initiator for free radical polymerization reaction;
the method used in the invention is free radical heterocyclic copolymerization, and specific principles can be referred to in the documents Tardy A, nicolas J, gigmes D, et al, radial ring-opening polymerization: scope, limits, and application to (bio) degradable materials [ J ]. Chemical reviews,2017,117 (3): 1319-1406. The aim of this reaction is to introduce ester bonds into the polymer backbone leaving it for the next step to obtain polycarboxylic acid-phosphonic acid oligomers by cleavage of the ester bonds.
The carboxylic acid-phosphonic acid based polymer has a structural formula shown as follows:
wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 ，R 4 is-H or-COOH, R 5 is-H, -CH 3 or-CH 2 COOH，R 6 is-H or-CH 3 ，R 7 is-CH 2 -、 -CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 -，R 8 is-H or-CH 3 M, n, w, x, y, z, k are integers representing the number of repeating units of each repeating unit, where m=0, 1 or 2, and when m takes 0, CH-R is represented 2 Is absent, CH-R 1 And CH-R 3 The attached carbon atoms are directly attached, n=11 to 68, w=2 to 6, x=10 to 100, y=3 to 18, z=1 to 15, k=1 to 3.
The weight average molecular weight (Mw) of the carboxylic acid-phosphonic acid based polymer is 15000 to 100000.
The detailed preparation method of the carboxylic acid-phosphonic acid oligomer comprises the following two steps:
(1) Heating the polyether monomer A to 70-150 ℃ for dissolution, adding the ketene acetal monomer B, the phosphonic acid monomer C and the initiator, uniformly mixing, then slowly dropwise adding the unsaturated acid monomer D for 2-12 h, and carrying out heat preservation reaction for 1h after the dropwise adding is finished to obtain the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups;
(2) Adding water and NaOH into the carboxylic acid-phosphonic acid group polymer prepared in the step (1), heating to 80-100 ℃, and stirring for reacting for 12 hours to obtain the carboxylic acid-phosphonic acid group oligomer;
the adding amount of the water in the step (2) is suitable for ensuring the solid content of the reaction system to be 40-60 wt percent, and the adding amount of the NaOH is suitable for ensuring the pH of the reaction system to be 9-13.
The carboxylic acid-phosphonic acid based polymer which is a reaction product after the step (1) is finished can be directly used as a water reducer and has excellent water reducing capability, but compared with the carboxylic acid-phosphonic acid based oligomer water reducer, the carboxylic acid-phosphonic acid based oligomer water reducer has no long-time slump retaining capability and high-strength concrete viscosity reducing capability;
the reaction product after the end in the step (2) is the carboxylic acid-phosphonic acid oligomer, can be directly used as a water reducing agent, and has the same application method as the known cement dispersing agent, and the application method thereof is generally known to the person skilled in the art.
The mixing amount of the carboxylic acid-phosphonic acid group oligomer water reducer is 0.05-0.3% of the total cementing material, the mixing amount is pure solid mixing amount, and the percentage is mass percentage. Too low an amount of the compound may deteriorate the performance, and too high an amount of the compound may cause economic waste and the performance may not be improved.
The carboxylic acid-phosphonic acid group oligomer water reducer can be mixed with other water reducers sold in the market, such as a woody sulfonate water reducer, a naphthalene sulfonate water reducer, a polycarboxylic acid water reducer and the like, and can be used after an air entraining agent, a retarder, an early strength agent, an expanding agent, a tackifier, a shrinkage reducing agent and a defoaming agent are added.
Compared with the prior art, the invention has the following advantages:
(1) The invention abandons the idea of preparing the polycarboxylic acid oligomer water reducer through excessive chain transfer agent, but adopts heterocyclic copolymerization reaction to obtain the carboxylic acid-phosphonic acid based polymer with high molecular weight and rich ester groups in the main chain, and then the high molecular weight polymer is cracked into the oligomer with small molecular weight through hydrolysis reaction of the ester, so that the negative influence of the dosage of the ultra-high chain transfer agent on the polymerization reaction is avoided.
(2) Although the polycarboxylic acid oligomer water reducer has strong slump retaining capability, too small molecular weight also reduces the adsorption capability of the polymer to cement particles, so that the initial dispersing capability of the polycarboxylic acid oligomer water reducer is insufficient. Thus, the invention also introduces phosphonic acid groups with a higher adsorption capacity into the oligomer, which ensures that very low molecular weight oligomers also have an excellent dispersing capacity.
(3) The carboxylic acid-phosphonic acid group oligomer water reducer can stably keep the fluidity of concrete within a certain range under the premise of not compounding a slump retaining agent in the application of concrete, is beneficial to construction, and solves the problem of quickened fluidity loss of the concrete under poor-quality sandstone aggregate;
(4) The carboxylic acid-phosphonic acid group oligomer water reducer is applied to high-strength concrete (C80-C150), and has the advantages of low mixing amount and small viscosity compared with the conventional polycarboxylic acid water reducer.
Detailed Description
The following detailed preparation method of the carboxylic acid-phosphonic acid based oligomer water reducing agent according to the present invention is provided for the purpose of enabling a person skilled in the art to understand the present invention and to implement it, but these examples should not limit the scope of the present invention in any way, and all equivalent changes or modifications according to the spirit of the present invention should be covered in the protection scope of the present invention.
In the examples of the present invention, the molecular weight of the polymer was measured by using a Gel permeation chromatograph (GPC, water Co., U.S.A.) equipped with a 3Mz-Gel SD plus 10 μm (Agilent Co., U.S.A.) column, and the mobile phase: 0.01M NaNO 3 Is an aqueous solution of (a) a flow rate: 1.0mL/min, and the mass percentage concentration of the sample: 0.50%.
The specific molecular structural formulas of the polyether monomer A, the ketene acetal monomer B and the phosphonic acid monomer C used in the embodiment of the invention are shown in the following formulas.
Polyether monomer A has the structural formula:
the structural formula of the ketene acetal monomer B is as follows:
the structural formula of the phosphonic acid monomer C:
the synthesis method of the phosphonic acid monomer C comprises the following steps: (methyl) allyl chloride (1 mol), polyamine (3 mol, optionally ethylenediamine, diethylenetriamine, triethylenetetramine) and water were added to a four-necked flask equipped with a stirrer and a thermometer, the reaction concentration was 50wt%, then the temperature was raised to 120℃and after 8 hours of reaction, the excess water and polyamine were distilled off at high temperature. Then adding concentrated hydrochloric acid, phosphorous acid and 37% formaldehyde solution (the mole number of the added concentrated hydrochloric acid, the phosphorous acid and the 37% formaldehyde solution is related to the type of polyamine, and the mole number of the added concentrated hydrochloric acid, the phosphorous acid and the 37% formaldehyde solution is equal to the mole number of hydrogen atoms connected with N atoms in the polyamine), heating to 110 ℃, and stirring for reacting for 12 hours to obtain the phosphonic acid monomer C.
Example 1:
1) HPEG-500 (0.6 mol,300g, numeral 500 indicating that the weight average molecular weight of HPEG is 500, the same applies hereinafter) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, and then heated to 130℃and N was introduced 2 Removing O from the flask 2 Adding monomer B-1 (0.09 mol,7.74 g), monomer C-1 (0.12 mol,47.8 g) and initiator AIBN 0.473g, stirring uniformly, slowly dripping acrylic acid (1.8 mol,129.6 g) into the reactor for 2h, keeping the temperature for reaction for 1h after the dripping is finished, and obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 45700;
2) Adding 800g of water and 105g of NaOH into the product prepared in the above way, measuring the pH of the reaction solution to be 9.6, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 3260, and measuring the solid content to be 40.2%;
example 2:
1) Into a 2L four-necked flask equipped with a stirrer and a thermometerVPEG-500 (0.6 mol,300 g) was added followed by warming to 70℃and N-up 2 Removing O from the flask 2 Adding monomer B-2 (0.06 mol,6.84 g), monomer C-1 (0.12 mol,47.8 g) and initiator ABVN 1.03g, stirring uniformly, slowly dripping methacrylic acid (2.4 mol,206.4 g) into the reactor for 2h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 74100;
2) Adding 990g of water and 105g of NaOH into the product prepared in the above way, measuring the pH of the reaction solution to be 11.1, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 3550, and measuring the solid content to be 40.4%;
example 3:
1) HVPEG-1000 (0.5 mol,500 g) was charged into a 5L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 90℃and introducing N 2 Removing O from the flask 2 Adding monomer B-3 (0.15 mol,24.3 g), monomer C-1 (0.15 mol,59.7 g) and initiator AIBME 2.12g, stirring uniformly, slowly dripping acrylic acid (2 mol,144 g) and itaconic acid (0.5 mol,65 g) into a reactor for 4h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 16100;
2) Adding 1030g of water and 280g of NaOH into the product prepared in the above way, measuring the pH of the reaction solution to be 10.5, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 3760, and measuring the solid content to be 49.9%;
example 4:
1) APEG-1000 (0.5 mol,500 g) was charged into a 5L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 90℃and N-charging 2 Removing O from the flask 2 Monomer B-4 (0.05 mol,5.0 g), monomer C-2 (0.1 mol,53.5 g) and initiator V-501.85 g are added, after being stirred uniformly, methacrylic acid (3.7 mol, 318.2 g) and fumaric acid (0.3 mol,34.8 g) are slowly dripped into the reactor for 4 hours,after the dripping is finished, carrying out heat preservation reaction for 1h to obtain a carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, and measuring the weight average molecular weight of the product to be 85300;
2) Adding 830g of water and 385g of NaOH into the product, measuring the pH of the reaction solution to be 9.2, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 4020 and the solid content to be 59.5%;
example 5:
1) APEG-1000 (0.5 mol,500 g) was charged into a 5L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 90℃and N-charging 2 Removing O from the flask 2 Adding monomer B-5 (0.05 mol,5.7 g), monomer C-2 (0.37 mol, 198g) and initiator BPO 5.43g, stirring uniformly, slowly dripping acrylic acid (4 mol, 288 g) and maleic acid (5 mol,116 g) into a reactor for 4h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 38600;
2) Adding 1070g of water and 485g of NaOH into the product prepared in the above way, at the moment, measuring the pH of the reaction solution to be 10.9, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, wherein the weight average molecular weight of the product is 4130, and the solid content is 59.8%;
example 6:
1) APEG-1000 (0.5 mol,500 g) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 80℃and N-charging 2 Removing O from the flask 2 Adding monomer B-6 (0.1 mol,12.8 g), monomer C-2 (0.37 mol, 198g) and initiator tert-butyl hydroperoxide (7.95 g), stirring uniformly, slowly dripping acrylic acid (3 mol,216 g) into the reactor for 6h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, and measuring the weight average molecular weight of the product to be 94100;
2) Adding 1050g of water and 170g of NaOH into the product, measuring the pH of the reaction solution to be 11.6, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 4550, and measuring the solid content to be 50.5%;
example 7:
1) HVPEG-1600 (0.25 mol,400 g) was charged into a 2L four-necked flask equipped with a stirrer, thermometer, followed by heating to 80℃and N-charging 2 Removing O from the flask 2 Adding monomer B-7 (0.0625 mol,9.63 g), monomer C-2 (0.12 mol,64.2 g) and initiator tert-butyl hydroperoxide 5.05g, stirring uniformly, slowly dripping acrylic acid (1.25 mol,90 g) into the reactor for 8h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 37700;
2) Adding 630g of water and 76g of NaOH into the product prepared in the above way, measuring the pH of the reaction solution to be 12.8, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 4920, and measuring the solid content to be 50.6%;
example 8:
1) TPEG-1600 (0.25 mol,400 g) was charged into a 2L four-necked flask equipped with a stirrer, thermometer, followed by warming to 80℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.05 mol,5.7 g), monomer C-2 (0.12 mol,64.2 g) and initiator hydrogen peroxide 4.92g, stirring uniformly, slowly dripping methacrylic acid (1 mol,86 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 65700;
2) Adding 6000g of water and 80g of NaOH into the product, measuring the pH of the reaction solution to be 10.7, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 5070, and measuring the solid content to be 50.3%;
example 9:
1) HVPEG-2400 (0.15 mol,360 g) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 130℃and introducing N 2 Removing O from the flask 2 Adding monomer B-9 (0.027 mol,4.70 g), monomer C-2 (0.03 mol,16.1 g) and initiator AIBN 4.08g, stirring uniformly, slowly dripping acrylic acid (0.6 mol,43.2 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 20700;
2) Adding 450g of water and 38g of NaOH into the product, measuring the pH of the reaction solution to be 10.4, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 6130, and measuring the solid content to be 50.5%;
example 10:
1) TPEG-3000 (0.1 mol,300 g) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 70℃and N-charging 2 Removing O from the flask 2 Adding monomer B-10 (0.015 mol,2.13 g), monomer C-3 (0.02 mol,13.2 g) and initiator AIBN 4.96g, stirring uniformly, slowly dripping acrylic acid (0.4 mol, 28.8 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 52400;
2) Adding 360g of water and 25g of NaOH into the product, measuring the pH of the reaction solution to be 11.5, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 6140, and measuring the solid content to be 49.8%;
example 11:
1) TPEG-3000 (0.1 mol,300 g) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 150℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.015 mol,1.71 g), monomer C-3 (0.02 mol,13.2 g) and initiator AIBN 6.61g, stirring, slowly dripping acrylic acid (0.4 mol, 28.8 g) into the reactor for 12h, maintaining the temperature for 1h after dripping, and obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, and measuring the weight average molecular weight of the product73400;
2) Adding 360g of water and 25g of NaOH into the product, measuring the pH of the reaction solution to be 10.3, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 6220, and measuring the solid content to be 50.0%;
example 12:
1) TPEG-1000 (0.3 mol,300 g) was charged into a 2L four-necked flask equipped with a stirrer, thermometer, followed by heating to 150℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.03 mol,3.42 g), monomer C-1 (0.15 mol,98.7 g) and initiator AIBN 8.23g, stirring uniformly, slowly dripping acrylic acid (1.5 mol, 108 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, and measuring the weight average molecular weight of the product to be 39100;
2) Adding 590g of water and 105g of NaOH into the product, measuring the pH of the reaction solution to be 12.2, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 6530, and the solid content to be 49.9%;
example 13:
1) TPEG-1000 (0.3 mol,300 g) was charged into a 2L four-necked flask equipped with a stirrer, thermometer, followed by heating to 120℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.027 mol,3.08 g), monomer C-4 (0.15 mol,78.2 g) and initiator AIBN 3.68g, stirring uniformly, slowly dripping acrylic acid (0.9 mol, 64.8 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 60700;
2) Adding 485g of water and 65g of NaOH into the product, measuring the pH of the reaction solution to be 12.0, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 6890, and measuring the solid content to be 49.5%;
example 14:
1) TPEG-1000 (0.2 mol,200 g) was charged into a 1L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 120℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.014 mol,1.60 g), monomer C-4 (0.06 mol,29.3 g) and initiator AIBN 2.88g, stirring uniformly, slowly dripping acrylic acid (1.2 mol, 86.4 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 19400;
2) Adding 370g of water and 65g of NaOH into the product, measuring the pH of the reaction solution to be 13.5, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 7450, and measuring the solid content to be 50.2%;
example 15:
1) TPEG-1000 (0.2 mol,200 g) was charged into a 1L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 120℃and N-charging 2 Removing O from the flask 2 Adding monomer B-8 (0.012mol, 1.37 g), monomer C-4 (0.06 mol,29.3 g) and initiator AIBN 3.05g, stirring uniformly, slowly dripping methacrylic acid (1.2 mol,103.2 g) into the reactor for 12h, and reacting for 1h after the dripping is finished, thus obtaining the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups, wherein the weight average molecular weight of the product is 44500;
2) Adding 390g of water and 75g of NaOH into the product prepared in the above way, measuring the pH of the reaction solution to be 10.0, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, measuring the weight average molecular weight of the product to be 7670, and measuring the solid content to be 49.6%;
example 16:
1) HPEG-1000 (0.5 mol,500 g) was charged into a 2L four-necked flask equipped with a stirrer and a thermometer, followed by heating to 120℃and N-charging 2 Removing O from the flask 2 Monomer B-8 (0.03 mol,3.42 g), monomer C-4 (0.2 mol,104.2 g) and initiator AIBN 7.19g were added, and after stirring uniformly, acrylic acid (3 mol,216g) Slowly dripping into a reactor for 12h, and reacting for 1h at a temperature after dripping is finished to obtain a carboxylic acid-phosphonic acid group polymer with high molecular weight and rich in ester groups, wherein the weight average molecular weight of the product is 82900;
2) Adding 980g of water and 185g of NaOH into the product, measuring the pH of the reaction solution to be 10.9, keeping the reaction temperature to be 80-100 ℃, stirring and reacting for 12 hours to obtain the carboxylic acid-phosphonic acid oligomer, wherein the weight average molecular weight of the product is 7900, and the solid content is 50.1%.
Comparative example 1:
the PCA-G type high-performance polycarboxylic acid water reducer sold by Su Bote company has a weight average molecular weight of 32300 measured by GPC and a solid content of 40.5%, and the PCA-E type high-performance polycarboxylic acid slump retaining agent sold by Su Bote company has a weight average molecular weight of 29200 measured by GPC and a solid content of 45.6%. In the application example, the water reducer and the slump retaining agent in the comparative example are prepared into a mother solution according to a certain proportion for use.
Comparative example 2:
example 7 the carboxylic acid-phosphonic acid based polymer prepared in step (1) was diluted with water to a solids content of 40% and then used as a conventional water reducing agent, and the weight average molecular weight 37700 was measured by GPC.
Application examples:
in the application embodiment, the cement adopted is PII 52.5 in the field of the south of the Yangtze river; the mineral powder is S95 type mineral powder produced by Jiangnan grinding Limited company; the fly ash is I-grade fly ash produced by Jiangsu Huacan electric company; silica fume was purchased from Shanghai Tian silica fume materials Co., ltd., specific surface area 17800m2/kg; sand is middle sand with fineness modulus m=2.6; the cobble is crushed stone with the grain diameter of 5-20 mm and continuous grading.
Application example 1
The application effect of the carboxylic acid-phosphonic acid oligomer serving as the concrete water reducer is detected according to a method specified in GB8076-2008, and the polymer doping amount is adjusted to ensure that the initial slump of the concrete is 20+/-0.5 cm. Concrete mass mixing ratio: cement 490, fly ash 60, sand 740,5-10mm crushed stone 666, 10-20mm crushed stone 444 and water 192. The test results are shown in Table 1, and the mass ratio of the water reducer to the slump retaining agent in comparative example 1 is 1:1.
TABLE 1 slump over time test results for concrete
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The data in Table 1 show that, although the initial fluidity of the concrete meets the design requirement by adopting the mode of compounding the water reducing agent and the slump retaining agent, the slump stability is poor within 150min, the slump reversely grows to about 23cm in the middle period of 30-60 min, which is obviously very unfavorable for site construction, and the slump is only 17.0cm in the 150min, which indicates that the slump retaining time of comparative example 1 is insufficient. Clearly, increasing the slump retaining agent ratio of comparative example 1 would result in an improvement in slump for 150 minutes, but would also exacerbate the mid-term counter-growth phenomenon, which is undesirable. In contrast, the concrete slump of the examples, which is significantly less than that of comparative example 1, was maintained substantially within 20.+ -. 1.5cm for 150 minutes. The carboxylic acid-phosphonic acid oligomer water reducer can stably control the concrete slump for a long time in concrete application, solves the problem that the concrete slump of the conventional polycarboxylic acid cement dispersant is easy to reversely increase, and has low mixing amount and greatly saves cost. In addition, comparative example 2 provides concrete with good initial slump, but then slump is rapidly lost, and slump is already less than 10cm at 90 minutes, which indicates that the carboxylic acid-phosphonic acid based polymer without hydrolysis can be used as a general water reducing agent, but does not have the long slump retaining ability described in the present invention.
Application example 2:
the application effect of the carboxylic acid-phosphonic acid based oligomer water reducer in high-strength concrete is detected according to a method specified in GB 8076-2008. Adjusting the mixing amount of the polymer to ensure that the initial slump of the concrete is 23+/-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 air flow time through a slump cone, and the concrete viscosity is specifically obtained by the following steps: the slump cone is inverted, the bottom is capped, filled with concrete and smoothed (the inverted slump cone is generally fixed on a support, the bottom is 50cm away from the ground), the bottom cover is quickly slid off, and the concrete emptying time is tested by a stopwatch. The test results are shown in Table 2, and the water reducer is used in all comparative examples without compounding slump retaining agent.
TABLE 2 high strength concrete Performance test results
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As can be seen from the test results of the high-strength concrete in Table 2, although the mixing amount of the examples is about 20% or more lower than that of comparative example 1, the slump and the expansion degree of the concrete are very similar to those of comparative example 1, which shows that the carboxylic acid-phosphonic acid oligomer water reducer of the invention has a large water reducing rate in the high-strength concrete and can save the mixing amount. Under the condition of similar air content, the air flow time of the embodiment is between 10 and 16 seconds, which is far smaller than 22 seconds of comparative example 1, so that the carboxylic acid-phosphonic acid group oligomer water reducer can effectively reduce the viscosity of high-strength concrete, and is beneficial to pumping the concrete in construction. In addition, comparative example 2, although having similar amounts of incorporation, slump, and fluidity to the examples, has a run-to-air time as long as 20s, indicating that the unhydrolyzed carboxylic acid-phosphonic acid based polymer does not have the ability to reduce the viscosity of the high strength concrete as described in the present invention.
Claims (10)
1. A carboxylic acid-phosphonic acid based oligomer characterized by: the carboxylic acid-phosphonic acid oligomer is obtained by ester bond cleavage of a polymer consisting of a main chain rich in ester groups and phosphonic acid groups and a polyether side chain, wherein the main chain is rich in two adsorption groups of carboxylic acid and phosphonic acid, and the side chain is a conventional polyether chain segment;
the polymer is a carboxylic acid-phosphonic acid group polymer and is obtained by free radical heterocyclic copolymerization of polyether monomers, ketene acetal monomers, phosphonic acid monomers and unsaturated acid monomers.
2. A carboxylic acid-phosphonic acid based oligomer as recited in claim 1, wherein said carboxylic acid-phosphonic acid based oligomer has the general molecular structure shown below
Wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 ，R 4 is-H or-COONa, R 5 is-H, -CH 3 or-CH 2 COONa，R 6 is-H or-CH 3 ，R 7 is-CH 2 -、-CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 -，R 8 is-H or-CH 3 M, n, x, y, z, k are integers representing the number of repeating units of each repeating unit, where m=0, 1 or 2, and when m takes 0, CH-R is represented 2 Is absent, CH-R 1 And CH-R 3 The connected carbon atoms are directly connected, n=11-68, x=10-100, y=3-18, z=1-15, and k=1-3;
weight average molecular weight of the carboxylic acid-phosphonic acid based oligomer [ ]M w ) 3000-8000.
3. The carboxylic acid-phosphonic acid oligomer according to claim 1 or 2, wherein the carboxylic acid-phosphonic acid oligomer is prepared by free radical heterocyclic copolymerization of polyether monomer a, ketene acetal monomer B, phosphonic acid monomer C and unsaturated acid monomer D under the action of an initiator to obtain a carboxylic acid-phosphonic acid polymer with high molecular weight rich in ester groups, and then adding NaOH to react to obtain the carboxylic acid-phosphonic acid oligomer;
the molar ratio of the polyether monomer A to the ketene acetal monomer B to the amount of the phosphonic acid monomer C to the amount of the unsaturated acid monomer D is 1 (0.06-0.3): (0.2-0.75): (3-10); the initiator is used in an amount of 0.08-2wt% of the total mass of the polyether monomer A, the ketene acetal monomer B, the phosphonic acid monomer C and the unsaturated acid monomer D.
4. A carboxylic acid-phosphonic acid based oligomer according to claim 3, characterized in that the polyether monomer a has the general structural formula shown below
Wherein R is 6 is-H or-CH 3 ，R 7 is-CH 2 -、-CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 N represents the number of repeating units and is an integer within 11-68;
the weight average molecular weight of the polyether monomer A is 500-3000;
the ketene acetal monomer B has a structural general formula shown in the specification,
wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 M is 0, 1 or 2, and represents CH-R when m is 0 2 Absent, R 1 And R is R 3 The linked carbon atoms are directly linked, and the monomer B is a five-membered ring;
the phosphonic acid monomer C has a structural general formula shown in the specification;
wherein R is 8 is-H or-CH 3 K represents the number of repeating units and is 1, 2 or 3;
the unsaturated acid monomer D has a structural general formula shown in the specification;
wherein R is 4 is-H or-COOH, R 5 is-H, -CH 3 or-CH 2 COOH。
5. A carboxylic acid-phosphonic acid based oligomer as recited in claim 4, wherein said phosphonic acid monomer C is synthesized by the following method: adding (methyl) allyl chloride, polyamine monomer and water into a four-neck flask with a stirrer and a thermometer, reacting at a concentration of 50wt%, then heating to 120 ℃, reacting for 8 hours, and evaporating excessive water and polyamine monomer at a high temperature; then adding concentrated hydrochloric acid, phosphorous acid and 37wt% formaldehyde solution into the product at room temperature, heating to 110 ℃, and stirring for reacting for 12 hours to obtain phosphonic acid monomer C;
the polyamine monomer is selected from any one of ethylenediamine, diethylenetriamine and triethylenetetramine;
the molar ratio of (meth) allyl chloride to polyamine monomer is 1: 1-3;
the number of moles of the concentrated hydrochloric acid, phosphorous acid and formaldehyde is related to the kind of polyamine monomer and is equal to the number of moles of hydrogen atoms to which the N atoms in the polyamine monomer are bonded.
6. A carboxylic acid-phosphonic acid based oligomer according to claim 3 wherein said unsaturated acid monomer D is selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, mixed in any ratio.
7. A carboxylic acid-phosphonic acid based oligomer according to claim 3, characterized in that the initiator is any one selected from the group consisting of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl Azobisisobutyrate (AIBME), azobiscyanovaleric acid (V-501), hydrogen peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxytert-valerate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, benzoyl Peroxide (BPO), all of which are common initiators for free radical polymerization reactions.
8. A carboxylic acid-phosphonic acid based oligomer as claimed in claim 1 or 2, characterized in that the carboxylic acid-phosphonic acid based polymer has the structural formula:
wherein R is 1 is-H, phenyl or C1-C6 alkyl, R 2 is-H, -CH 3 or-OCH 3 ，R 3 is-H or-CH 3 ，R 4 is-H or-COOH, R 5 is-H, -CH 3 or-CH 2 COOH，R 6 is-H or-CH 3 ，R 7 is-CH 2 -、-CH 2 CH 2 -、-OCH 2 CH 2 -or-OCH 2 CH 2 CH 2 CH 2 -，R 8 is-H or-CH 3 M, n, w, x, y, z, k are integers representing the number of repeating units of each repeating unit, where m=0, 1 or 2, and when m takes 0, CH-R is represented 2 Is absent, CH-R 1 And CH-R 3 The connected carbon atoms are directly connected, n=11-68, w=2-6, x=10-100, y=3-18, z=1-15, k=1-3;
the weight average molecular weight (Mw) of the carboxylic acid-phosphonic acid based polymer is 15000-100000.
9. A process for the preparation of a carboxylic acid-phosphonic acid based oligomer as claimed in any one of claims 1 to 8, characterized by the following two steps:
(1) Heating the polyether monomer A to 70-150 ℃ for dissolution, adding the ketene acetal monomer B, the phosphonic acid monomer C and the initiator, uniformly mixing, then slowly dropwise adding the unsaturated acid monomer D for 2-12 h, and carrying out heat preservation reaction 1h after the dropwise adding is finished to obtain the carboxylic acid-phosphonic acid group polymer with high molecular weight and rich ester groups;
(2) Adding water and NaOH into the carboxylic acid-phosphonic acid group polymer prepared in the step (1), heating to 80-100 ℃, and stirring for reacting 12h to obtain the carboxylic acid-phosphonic acid group oligomer;
and (3) adding water in the step (2) to ensure that the solid content of the reaction system is 40-60wt% and adding NaOH to ensure that the pH of the reaction system is 9-13.
10. The application method of the carboxylic acid-phosphonic acid oligomer according to any one of claims 1 to 8, wherein the carboxylic acid-phosphonic acid oligomer is directly used as a water reducer or is mixed with a commercially available lignosulfonate water reducer, a naphthalene sulfonate water reducer and a polycarboxylic acid water reducer, the mixing amount of the carboxylic acid-phosphonic acid oligomer water reducer is 0.05% -0.3% of the total cementing material, the mixing amount is a pure solid mixing amount, and the percentages are mass percentages.
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| WO2019233215A1 (en) * | 2018-06-08 | 2019-12-12 | 科之杰新材料集团有限公司 | High water-reducing and low sensitivity polycarboxylate superplasticizer and preparation method therefor |
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| WO2019233215A1 (en) * | 2018-06-08 | 2019-12-12 | 科之杰新材料集团有限公司 | High water-reducing and low sensitivity polycarboxylate superplasticizer and preparation method therefor |
| CN111377643A (en) * | 2018-12-31 | 2020-07-07 | 江苏苏博特新材料股份有限公司 | High-adaptability viscosity-reduction type polycarboxylate superplasticizer and preparation method and application thereof |
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