CN107586366B - Modified polycarboxylate superplasticizer and preparation method thereof - Google Patents
Modified polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a modified polycarboxylate water reducer and a preparation method thereof, which takes prenyl alcohol polyoxyethylene ether (TPEG), Acrylic Acid (AA) and a modified monomer X as monomers and directly polymerizes under the action of an initiator and a chain transfer agent to prepare the composite polycarboxylate water reducer with the functions of reducing water and protecting slump. The modified polycarboxylate superplasticizer disclosed by the invention can be used alone or mixed with other superplasticizers, is excellent in slump retaining performance and good in expansibility when used in concrete, can produce a delayed dispersion effect on the concrete within 1 hour, and has comprehensive performance exceeding that of the existing products in the market.
Description
Technical Field
The invention relates to a polycarboxylic acid water reducing agent.
Background
The high water-reducing polycarboxylic acid water reducing agent has the functions of generating adsorption on the surfaces of powder particles such as cement, fly ash and the like at the beginning of concrete mixing so as to generate a dispersing effect and improve the working performance of concrete, and the action time is generally 0-20 min. The high slump loss resistant type polycarboxylate water reducing agent is just opposite, does not generate adsorption under the initial condition, gradually generates adsorption in a slow release mode in the cement hydration process, so that the later working performance of concrete is improved, and the time for the water reducing agent to generate the dispersion action is generally 1-3 hours after the concrete is mixed. In engineering application, the working performance and the workability retention capacity of concrete are generally improved by a method of compounding high water reducing agent and high slump retaining type polycarboxylate superplasticizer, but from the characteristics of the dispersion effect of the two types of water reducing agents, the working performance of concrete is easy to fluctuate within a period of 20-60 min. The concrete working performance difficulty is ensured to be high by adjusting the compounding ratio of the high water reducing agent and the high slump loss resistant polycarboxylate superplasticizer, and the concrete is greatly influenced by the change of gas temperature. In response to this problem, there are many well-developed technical solutions in the prior art.
As early as 1997, Japanese catalyst corporation has begun to patente in the Chinese market and introduced the S-series polycarboxylic acid water reducing agent. China started a larger-scale patent application in 2008.
CN102358768B discloses a modified ether polycarboxylic acid water reducing agent, which is prepared by the free radical initiation copolymerization of 50-95% of methyl allyl polyoxyethylene ether (TPEG), 4-40% of Acrylic Acid (AA) and 1-10% of 2-acrylamide-2-methyl propane sulfonic Acid (AMPS). As the TPEG monomer is introduced into the modified ether polycarboxylic acid water reducing agent, the synthesized water reducing agent product has higher water reducing rate and slump retaining performance compared with the ether polycarboxylic acid water reducing agent, the introduced AMPS further improves the water reducing rate of the product, the prepared concrete has low mixing amount, high fluidity, low slump loss over time, good workability and sufficient early strength, and the adaptability of the product to raw materials of different sources is greatly improved.
CN102503226B discloses a high slump retaining type polycarboxylate superplasticizer with a slow release effect and a preparation method thereof. The method is characterized in that: the slump retaining agent is prepared by the steps of carrying out heat preservation reaction on 5-30 mol% of a monomer A, 30-60 mol% of a monomer B and 20-55 mol% of a monomer C for 1-3h at 60-80 ℃ under the action of an initiator, a chain transfer agent and a polymerization inhibitor, copolymerizing to obtain a polymer with the molecular weight of 30000-100000, and then adding alkali for neutralization, wherein the monomer A + B + C is 100 mol%, the monomer C consists of a slump retaining aid 1 and a slump retaining aid 2 according to the molar ratio of 1: 20-13: 20, the monomer A is isopentenol polyoxyethylene ether with the polymerization degree n of 20-60, allyl polyethylene glycol ether, 1-methyl-2-propenyl polyethylene glycol ether or allyl polypropylene glycol ether, and the monomer B is acrylic acid or methacrylic acid. The slump loss resistant auxiliary agent 1 is one or a mixture of more of acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and sodium salt thereof, and acrylic sulfonic acid and sodium salt thereof, and the slump loss resistant auxiliary agent 2 is one or a mixture of more of 2-hydroxypropyl acrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate. The slump loss preventing agent has excellent slump loss preventing performance, basically does not lose slump within 3h, and has wide applicability.
CN102617065B discloses a multi-branched polycarboxylate superplasticizer with slump retaining property, which is prepared by carrying out aqueous solution polymerization on the following monomers under the action of a polymerization initiator: the monomer A accounts for 3-10% of the total weight of reactants; the monomer B accounts for 80-90% of the total weight of reactants; the monomer C accounts for 3-6% of the total weight of reactants; the monomer D accounts for 0.5-2% of the total amount of the reactants; then add the above four100% deionized water, 200% of the total weight of the monomer reactants. The technical scheme has a good slump retaining effect, and can be mixed with other types of polycarboxylic acid water reducing agents for use, so that the slump retaining performance of other products can be improved. It has the following beneficial effects: (1) the molecular structure is novel, the main chain has anion and cation, the branched chain has the structural characteristic of non-ion, the common sandstone material, especially the sandstone material containing mud has better slump-retaining effect, and if the main chain is used alone, the doping amount is 0.10-0.22%. (2) In the molecular structure, there is no retarding component, and the normal setting time of concrete is not affected in different seasons. The structural formula of the monomer B is as follows: (CH)3)2C＝CHCH2O[CH2CH2O]m[CH2CH(CH3)-O]n-OH, wherein m is 20-60, n is 0-10, and the content of polyethylene glycol in the monomer B is 0.5-2%; r is H or methyl. Monomer C is CH2＝C(R1)COOR2，R1Is H or CH3；R2Is CH3-、CH3CH2-, other alkyl radicals, HO-CH2CH2O-、HOCH2CH(CH3) O-or (CH)2CHO)-CH2O-, or one of the above. The monomer D is one or a mixture of two of cationic monomer, acryloyloxyethyltrimethyl ammonium chloride and methacryloyloxyethyltrimethylammonium chloride.
CN102936112B discloses a polycarboxylic acid water reducing agent suitable for high-strength self-compacting concrete and a preparation method thereof. The method is characterized in that: the catalyst is prepared by 70-90 wt% of isopentenyl polyoxyethylene ether monomer a, 5-25 wt% of dibasic unsaturated carboxylic acid and derivative monomer b, 1-10 wt% of monobasic unsaturated carboxylic acid and derivative monomer c, wherein a + b + c is 100 wt%, and introduced copolymerization reaction auxiliary monomer d, under the action of an initiator and a chain transfer agent, react in an aqueous solution at 60-80 ℃ for 1-3.5h for copolymerization, and then are neutralized by adding alkali. The water reducing agent can be compounded into an additive to be used in common concrete, can also be used in C70-C100 high-strength self-compacting concrete, has high fluidity and low viscosity, can meet the requirement of engineering construction on segregation resistance (the performance grade can reach SR2), has excellent performance and meets the construction application requirement; low cost and convenient popularization. The monomer b of the binary unsaturated carboxylic acid and the derivative thereof is one or a mixture of more of maleic acid, fumaric acid, itaconic acid and monovalent alkali metal salt, divalent alkali metal salt, ammonium salt or maleic anhydride and itaconic anhydride thereof. The monomer c of the monoradical unsaturated carboxylic acid and the derivative thereof is one or a mixture of acrylic acid, methacrylic acid and monovalent alkali metal salt, divalent alkali metal salt and ammonium salt thereof.
CN103183796B discloses an allyl sulfonic glycerol polyoxyethylene polyoxypropylene ether polycarboxylic acid water reducer and a synthesis method thereof, the water reducer is a polymer of allyl sulfonic glycerol polyoxyethylene ether or allyl sulfonic glycerol polyoxypropylene ether (unit A) and unsaturated carboxylic acid and derivatives thereof (unit B), and belongs to the field of concrete admixtures. The synthesis method is to use 500-6000 structural unit A as a polymerization monomer to carry out random free radical copolymerization in an aqueous solution system. The side chain is introduced with the long chain of the allyl sulfonic glycerin, so that the water reducer has an early strength function, and the mode that the early strength effect can only be achieved by compounding the early strength agent is changed. In addition, the process is simple, the compatibility is good, the adaptability is good, and the production efficiency and the production benefit can be greatly improved.
CN103214206B discloses a slow-release type polycarboxylate water reducer, which is a polycarboxylate water reducer solution, and comprises: aqueous polymer solution: is polymerized by three components: A. an aqueous solution of polyoxyethylene ether or polyoxypropylene ether; B. esters of acrylic acid and/or methacrylic acid and/or itaconic acid, and/or the three; C. sodium propylene sulfonate and/or sodium methallyl sulfonate; an aqueous alkaline solution for neutralizing the aqueous polymer solution. The slow-release polycarboxylic acid water reducing agent has low alkali content and excellent slump retentivity, is labor-saving when used for concrete operation, has high fluidity, high slump retention and good workability of cement mixtures, and has the advantages of simple production process, easily controlled reaction conditions and no environmental pollution.
CN103450408B discloses an ether early strength type polycarboxylate water reducer and a preparation method thereof, the water reducer takes unsaturated ester, diethanol monoisopropanolamine (DIEPA), 2-acrylamido-methylpropanesulfonic Acid (AMPS), methyl allyl polyoxyethylene polyoxypropylene ether (TPEG) and the like as main chemical synthesis raw materials, and a high polymer with an amphoteric structure is obtained through amidation and copolymerization processes under certain conditions under the action of a catalyst, an initiator, a chain transfer agent and the like. The molecular structure of the water reducing agent has hydrophilic hydroxyl, carboxyl, amido and sulfonic group, hydrophobic carbon chain and polyoxyethylene polyoxypropylene ether long chain structure with certain steric hindrance effect. The N-containing group can obviously improve the early strength of the concrete, so the product is suitable for the concrete prefabricated part needing to improve the early strength.
CN103803846B discloses a mud-resistant and salt-resistant polycarboxylate superplasticizer which is obtained by copolymerizing a monomer mixture comprising a monomer a, a monomer b and a monomer c; the monomer a is one or a mixture of more than two of unsaturated polyether; the monomer b is unsaturated acid, unsaturated acid anhydride or a mixture thereof; monomer c is represented by the general formula (B), Y (CH)2)kSiX3Wherein Y is vinyl, methylvinyl, acryloxy or methacryloxy; x is chloro, methoxy, ethoxy, methoxyethoxy or acetoxy; k is an integer of 0 to 3. The mud-resistant and salt-resistant polycarboxylate superplasticizer can greatly improve the adaptability of cement in concrete, improves the effect of mud resistance and salt resistance, and has the advantages of low mixing amount, high water reducing rate, low slump loss and the like.
CN103804609B discloses a polycarboxylic acid water reducing agent with a net structure, which is obtained by copolymerizing a monomer mixture comprising a monomer a, a monomer b and a monomer c; the monomer a is one or a mixture of more than two of unsaturated polyether conforming to the general formula (A); the monomer b is unsaturated acid, unsaturated anhydride or a mixture thereof; the monomer c is an unsaturated monomer containing two carbon-carbon terminal group double bonds. The polycarboxylate superplasticizer has the advantages of low mixing amount, high water reducing rate, low slump loss, high compressive strength and the like, and simultaneously, the selected monomer has wide sources, so that the production cost is greatly reduced, and the comprehensive utilization rate is improved. Also provides a method for preparing the polycarboxylate superplasticizer with the net structure.
CN103833940B discloses a phosphine-containing polycarboxylic acid water reducing agent and a preparation method thereof. The catalyst is prepared from the following components in parts by weight by adopting a free radical polymerization process of oxidation reduction: 100 parts of isoprene polyoxyethylene ether, 8-30 parts of component R, 17.5-14.5 parts of component R, 20.25-1 parts of component R and 0.17-1 part of chain transfer agent; 0.6-3.5 parts of initiator and 180 parts of water 106-. The component R is N, N-di (phosphonic acid methyl) amino butyl maleic acid monoester. The component R1 is one or a mixture of two of acrylic acid and methacrylic acid, and the component R2 is one or a mixture of more of ascorbic acid, sodium formaldehyde sulfoxylate, sodium bisulfite and oxalic acid. The phosphonate structure is introduced into the polycarboxylate superplasticizer, so that the slump loss resistance of the polycarboxylate superplasticizer is effectively improved, and a reliable and stable solution is provided for solving the long-acting slump loss resistance problem; the whole process adopts a free radical polymerization process of oxidation reduction, the polymerization temperature is lower, the preparation process is simple, the equipment requirement is low, and the production is easy to enlarge and control; and the cost is low, and the method is safe and environment-friendly.
CN103980432B discloses a polycarboxylate superplasticizer containing modified water-soluble acrylate and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, directly reacting polyhydroxy alcohol carbohydrate with acrylic acid for esterification to prepare a modified water-soluble acrylate small monomer; then adding the polyether macromonomer into deionized water, and fully dissolving to prepare reaction base liquid; dissolving acrylate small monomer, acrylic acid, initiator vitamin C and chain transfer agent thioglycolic acid in deionized water to prepare dropping liquid; adding an initiator hydrogen peroxide into the reaction base solution, dripping the dripping liquid into the reaction base solution at a constant speed, stirring for reaction, and then adjusting the pH value of the solution to 7-8 to obtain the polycarboxylate water reducer.
CN104016615B discloses a slow-release high-efficiency polycarboxylic acid water reducing agent and a preparation method thereof, wherein the slow-release high-efficiency polycarboxylic acid water reducing agent is prepared from the following raw materials: acrylic acid, maleic anhydride, polyoxyethylene ether macromonomer, a high molecular template agent, sodium hydroxide, deionized water, a peroxide initiator and a chain transfer agent. The preparation method comprises the steps of putting sodium hydroxide and deionized water into a stirring kettle to prepare a sodium hydroxide solution; dripping acrylic acid into a sodium hydroxide solution by using a peristaltic pump to obtain a reaction solution A; putting a peroxide initiator and deionized water into a charging basket to obtain a dissolving solution B; putting a chain transfer agent and deionized water into a charging bucket to obtain a dissolving solution C; putting a polyoxyethylene ether macromonomer, maleic anhydride and a high-molecular template agent into a reaction kettle, and pumping deionized water to obtain reaction liquid D; and adding the reaction liquid A, the dissolving liquid B and the dissolving liquid C into the reaction liquid D by using a peristaltic pump to obtain the slow-release high-efficiency polycarboxylic acid water reducing agent. Has slow release, high water reducing efficiency, good water reducing performance and good slump retaining performance.
CN104119482B discloses an anti-mud polycarboxylic acid water reducing agent and a preparation method thereof, the anti-mud polycarboxylic acid water reducing agent is obtained by free radical copolymerization of unsaturated polyalkylene glycol ether monomer a, unsaturated carboxylic acid monomer b, unsaturated acid hydroxyalkyl ester c and ammonium salt cation unsaturated monomer d under the action of an initiator and a chain transfer agent, the molar ratio of the monomer a, the monomer b, the monomer c and the monomer d is 1.0: 2.0-4.2: 0.2-1.0: 0.1-0.5, the unsaturated polyalkylene glycol ether monomer a can be allyl polyoxyethylene ether, methyl allyl polyoxyethylene ether or 3-methyl-3-butylene-1-alcohol polyoxyethylene ether, the molecular weight of the monomer a is 1200-2400, and the unsaturated carboxylic acid monomer b can be acrylic acid, methacrylic acid or maleic acid. The unsaturated acid hydroxyalkyl ester c may be hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate or hydroxypropyl methacrylate. The quaternary ammonium salt cationic monomer d can be allyl trimethyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride or 2- (methacrylamide) ethyl trimethyl ammonium chloride. Under the condition that the aggregate contains mud, the dispersion effect of the mud-resistant polycarboxylate superplasticizer is obviously superior to that of the traditional superplasticizer, the mixing amount is low, and the retention performance is better.
From the technical field of the patents, the improvement and innovation are carried out on the compounding of the polycarboxylic acid water reducing agent and the composition of the composition, the structure and the synthesis process of the polycarboxylic acid water reducing agent are also the main development directions at present, and the technical gold content is higher. Aiming at the problem that the working performance of concrete is easy to fluctuate in a specific time period, the invention develops the compound polycarboxylic acid water reducing agent which can generate the delayed dispersion effect on the concrete within 1h and has practical value.
Disclosure of Invention
The invention takes prenyl alcohol polyoxyethylene ether (TPEG), Acrylic Acid (AA) and a modified monomer X as monomers, and directly polymerizes under the action of an initiator and a chain transfer agent to prepare the composite polycarboxylic acid water reducer which can reduce water and protect slump; wherein the modifying monomer X is
One or more of them.
The amount of TPEG monomer accounts for 50-95% of the total mass of the monomer, the amount of AA monomer accounts for 5-40% of the total mass of the monomer, and the amount of modified monomer X accounts for 1-3% of the total mass of the monomer; AMPS may also be used in amounts of 1-3% as desired.
The invention also relates to a preparation method of the modified polycarboxylate superplasticizer, which is characterized by comprising the following steps:
(1) adding TPEG, modified monomer X, chain transfer agent and deionized water into a reactor with a stirrer, introducing nitrogen, heating to 30-50 ℃, and stirring to completely dissolve a macromonomer; optionally, adding AMPS;
(2) after the temperature is raised to 60-90 ℃, simultaneously dripping AA and an initiator, and preserving the heat for 1-3 h;
(3) and (3) after the reaction product is cooled, neutralizing with an alkali solution to obtain the modified polycarboxylic acid water reducing agent.
Preferably, TPEG has a molecular weight of 1000-2400.
From the viewpoint of effect, the modifying monomer X is preferably
The initiator is a persulfate initiator which comprises one or more of potassium persulfate, sodium persulfate and Ammonium Persulfate (APS); the dosage of the initiator is 0.5-3% of the total weight of the monomers.
The chain transfer agent is one or two selected from mercaptopropionic acid, thioglycolic acid and sodium methallyl sulfonate (SMAS), and the amount of the chain transfer agent is 0.1-3% of the total weight of the monomers.
The alkali solution is one of NaOH, KOH or ethylenediamine solution.
Optionally, an appropriate amount of a polymerization inhibitor, such as hydroquinone or phenothiazine, is added.
Optionally, a (meth) acrylate monomer, such as one or more of methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, may also be added. The dosage is 1-5% of the total weight of the monomers.
Optionally, a cationic monomer, such as one or both of acryloyloxyethyltrimethyl ammonium chloride and methacryloyloxyethyltrimethylammonium chloride, may also be added in an amount of 1-3% by weight based on the total weight of the monomers.
The modified polycarboxylate superplasticizer disclosed by the invention can be used alone or mixed with other superplasticizers, is excellent in slump retaining performance and good in expansibility when used in concrete, can produce a delayed dispersion effect on the concrete within 1 hour, and has comprehensive performance exceeding that of the existing products in the market.
Detailed Description
Neat paste fluidity test
The cement paste fluidity test is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method'. The water-cement ratio is 0.29, and the mixing amount of the water reducing agent is 0.16% (broken solid).
Concrete test
The concrete test is carried out according to GB8076-2008 concrete admixture.
Example 1
Adding a certain amount of TPEG, modified monomer X, chain transfer agent SMAS and deionized water into a 500ml four-neck flask with a stirrer, introducing nitrogen, heating to 50 ℃, and stirring to completely dissolve a macromonomer; after the temperature is raised to 80 ℃, simultaneously dripping AA and an initiator APS for 3h, and keeping the temperature for 2 h; and after the reaction product is cooled, neutralizing with NaOH solution to obtain the modified polycarboxylic acid water reducing agent.
Wherein the modifying monomer X is
The using amount of TPEG is 80g, the using amount of modified monomer X is 2g, and the using amount of AA is 10 g; the amount of APS was 0.8g and the amount of SMAS was 0.3 g.
Example 2
Wherein the modifying monomer X is
Otherwise, the same procedure as in example 1 was repeated.
Example 3
Wherein the modifying monomer X is
Otherwise, the same procedure as in example 1 was repeated.
Example 4
2g of methyl acrylate was added together with TPEG, and the procedure was otherwise the same as in example 1.
Example 5
2g of acryloyloxyethyltrimethylammonium chloride was added together with TPEG, and the procedure was otherwise the same as in example 1.
Example 6
AMPS 2g was added along with TPEG, otherwise the same as in example 1.
Example 7
2g of methyl acrylate and 2g of AMPS were added together with TPEG, and the other examples were the same as those in example 1.
Example 8
The same procedure as in example 1 was repeated except that 2g of AMPS and 2g of acryloyloxyethyltrimethyl ammonium chloride were added together with TPEG.
Example 9
2g of acryloyloxyethyltrimethylammonium chloride, 2g of methyl acrylate, 2g of AMPS and the same procedure as in example 1 were added together with TPEG.
Comparative example 1
The procedure of example 4 was repeated except that the modified monomer X was not added.
Comparative example 2
The procedure of example 5 was otherwise the same as in example 5 except that the modifying monomer X was not added.
Comparative example 3
The procedure of example 6 was repeated except that the modified monomer X was not added.
Comparative example 4
The procedure of example 7 was repeated except that the modified monomer X was not added.
Comparative example 5
The procedure of example 8 was repeated except that the modified monomer X was not added.
Comparative example 6
The procedure of example 9 was repeated except that the modified monomer X was not added.
Test concrete mix proportion (kg/m)3) The concrete admixture is characterized in that m cement, m mineral powder, m fly ash, m sand, m gravel and m water are 230: 50: 100: 780: 1060: 155, and the influence of different polycarboxylate water reducers on the working performance of fresh concrete is shown in Table 1.
TABLE 1 Effect of modified polycarboxylic acid Water reducing Agents on fresh concrete workability
Claims (7)
1. A modified polycarboxylate water reducing agent is characterized in that: the modified polycarboxylate superplasticizer is a composite polycarboxylate superplasticizer which is prepared by directly polymerizing isopentenol polyoxyethylene ether, acrylic acid and a modified monomer X serving as monomers under the action of an initiator and a chain transfer agent and has the functions of reducing water and protecting slump; wherein the modifying monomer X is
One ofOr a plurality of the components; the dosage of the prenyl polyoxyethylene ether monomer accounts for 50-95% of the total mass of the monomers, the dosage of the acrylic monomer accounts for 5-40% of the total mass of the monomers, the dosage of the modified monomer X accounts for 1-3% of the total mass of the monomers, and the total dosage of all the monomers is 100%;
the preparation method of the modified polycarboxylate superplasticizer comprises the following steps: (1) adding prenyl alcohol polyoxyethylene ether, a modified monomer X, a chain transfer agent and deionized water into a reactor provided with a stirrer, introducing nitrogen, heating to 30-50 ℃, and stirring to completely dissolve the prenyl alcohol polyoxyethylene ether;
(2) when the temperature is raised to 60-90 ℃, simultaneously dripping acrylic acid and an initiator, and preserving the heat for 1-3 h;
(3) and (3) after the reaction product is cooled, neutralizing with an alkali solution to obtain the modified polycarboxylic acid water reducing agent.
2. The modified polycarboxylate superplasticizer according to claim 1, wherein 2-acrylamido-2-methylpropanesulfonic acid is further added in step (1), the amount thereof is 1 to 3% of the total mass of the monomers, and the total amount of all the monomers is 100%.
3. The modified polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that: the molecular weight of the prenyl polyoxyethylene ether is 1000-2400.
4. The modified polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that: the modifying monomer X is
5. The modified polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that: the initiator is a persulfate initiator which comprises one or more of potassium persulfate, sodium persulfate and ammonium persulfate; the dosage of the initiator is 0.5-3% of the total weight of the monomers.
6. The modified polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that: the chain transfer agent is one or two of mercaptopropionic acid, thioglycolic acid and sodium methallyl sulfonate, and the dosage of the chain transfer agent is 0.1-3% of the total weight of the monomers.
7. The modified polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that: the alkali solution is one of NaOH, KOH or ethylenediamine solution.
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| CN109133698A (en) * | 2018-08-21 | 2019-01-04 | 马清浩 | A kind of water-reducing agent and preparation method thereof improving strength cement-based grouting material high temperature performance |
| CN111592624B (en) * | 2019-02-21 | 2022-07-05 | 天水师范学院 | Method for preparing general comprehensive polycarboxylate superplasticizer |
| CN110229285B (en) * | 2019-07-22 | 2022-01-07 | 云南森博混凝土外加剂有限公司 | Preparation method of early-strength polycarboxylate superplasticizer |
| CN114644741B (en) * | 2020-12-21 | 2023-10-31 | 博特新材料泰州有限公司 | Amphoteric phosphonate water reducer, preparation method and application thereof |
| CN113772992A (en) * | 2021-10-09 | 2021-12-10 | 亚泰集团沈阳现代建筑工业有限公司 | Normal-temperature synthesized plastic-retaining polycarboxylate superplasticizer |
| CN113845342B (en) * | 2021-10-13 | 2022-08-26 | 太原市尖草坪区荣盛新型建材有限公司 | Concrete water permeable brick and preparation method thereof |
| CN113831464B (en) * | 2021-10-13 | 2023-09-12 | 山西丰业荣盛建材股份有限公司 | Water reducer for water permeable bricks and application thereof |
| CN115806648B (en) * | 2022-12-28 | 2024-02-13 | 科之杰新材料集团有限公司 | Polycarboxylate superplasticizer prepared from viscosity reducing macromonomer and preparation method thereof |
| CN116119976B (en) * | 2023-04-04 | 2023-08-04 | 石家庄市长安育才建材有限公司 | High-adsorption water reducer, preparation method thereof and concrete |
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