CN111087422A - Preparation method of (2-phosphonic acid-propylene) malonic acid - Google Patents
Preparation method of (2-phosphonic acid-propylene) malonic acid Download PDFInfo
- Publication number
- CN111087422A CN111087422A CN201911308979.8A CN201911308979A CN111087422A CN 111087422 A CN111087422 A CN 111087422A CN 201911308979 A CN201911308979 A CN 201911308979A CN 111087422 A CN111087422 A CN 111087422A
- Authority
- CN
- China
- Prior art keywords
- acid
- isopropenylphosphonic
- malonic acid
- propylene
- ippa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
-
- 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
Abstract
The invention discloses a preparation method of (2-phosphonic acid-propylene) malonic acid as a water reducer monomer, which specifically comprises the steps of carrying out Michael addition, chlorination, dehydrochlorination and other reaction steps on isopropenylphosphonic acid and malonic acid to synthesize the (2-phosphonic acid-propylene) malonic acid, so that coexistence of phosphonic acid groups and carboxyl groups in units is realized, and the (2-phosphonic acid-propylene) malonic acid is continuously polymerized with an alkenyl polyoxyethylene ether macromonomer to prepare a polycarboxylic water reducer.
Description
Technical Field
The invention relates to the technical field of fine chemicals, in particular to a preparation method of a water reducing agent monomer (2-phosphonic acid-propylene) malonic acid.
Background
With the continuous progress of the construction technology level in China and the updating of building facilities, the requirement on the performance of the concrete of the infrastructure material is higher and higher, and the concrete with high strength, high fluidity and high durability is favored. The concrete is prepared by mixing cement as cementing material, sand and stone as aggregate and water in certain proportion, and through stirring, forming and curing. The concrete is commonly used with concrete additives, the commonly used additives mainly comprise water reducing agents, retarders, air entraining agents, early strength agents, antifreezing agents, expanding agents and the like, and the water reducing agents are the most important components. The development of water reducing agents is decades, and the water reducing agents are developed from the earliest common lignosulfonate water reducing agents to high-efficiency water reducing agents represented by melamine series, naphthalene series and the like, and then to polycarboxylic acid series high-performance water reducing agents with better performance which are widely applied at present. The performance of the water reducing agent can meet the use requirements of most of traditional concrete. However, because concrete raw material resources such as traditional natural river sand, high-quality fly ash and the like are increasingly exhausted, artificial aggregate, coal gangue, desulfurized ash and other low-activity industrial waste residues are gradually used in modern concrete, so that the adaptability of the traditional water reducing agent in a new concrete component system is increasingly poor. In practical application, the performance of the water reducing agent is influenced by new factors such as cement components and artificial aggregates, so that the defects of poor adaptability, high sensitivity and the like of novel cement concrete are easily caused, and the development of concrete technology is limited. Therefore, there is a need to develop a water reducing agent for new cement concrete to meet the engineering requirements.
The polycarboxylic acid water reducing agent has the advantages of low mixing amount, high water reducing rate, good slump retaining property, strong molecular structure adjustability, environmental protection and the like, and is an important product in the concrete admixture market at present. Besides the advantages, the polycarboxylic acid water reducing agent has a retarding effect which cannot meet the requirements of the existing novel concrete, and has poor adaptability in low-activity admixtures. At present, the modification research of polycarboxylic acid water reducing agents has become a research hotspot for solving the problems. Patent CN106905362B utilizes the reaction of acrylic acid and phosphorus trichloride to generate hydroxyl propylenediphosphonic acid with retarding effect. The patent CN105713150A introduces phosphate groups into a main chain structure of the block polycarboxylic acid with definite sequence structure distribution, so that the adsorption capacity of the block polycarboxylic acid is enhanced, the prepared water reducing agent has obvious sulfate resistance, and the water reducing, slump retaining and cement adaptability are obviously improved. Patent CN105713151A reports that a comb-type water reducing agent using phosphorous acid as an adsorption group and using free radical copolymerization to prepare a kind of water reducing agent using phosphorous acid as an adsorption group effectively improves the fluidity and the working performance retention capability of concrete. The patent CN106008853A discloses a preparation method of a mud-resistant slump-retaining phosphate-containing polycarboxylic acid water reducer, which comprises the steps of firstly carrying out prepolymerization on unsaturated halohydrocarbon, unsaturated polyether and unsaturated carboxylic acid free radicals, and then carrying out Arbuzov reaction on the prepolymerized unsaturated halohydrocarbon and alkyl phosphate to obtain a phosphate-based copolymerization product. The patent CN107337749A provides a ternary polymerization phosphonic acid based concrete retarder and a preparation method thereof, and the retarder is mainly prepared by synthesizing an intermediate from 2-acrylamide-2-methyl propanesulfonic Acid (AMPS), a carboxylic acid or ester group monomer and (methyl) allyl chloride under the action of an initiator and a chain transfer agent, and then performing phosphinite acidification.
According to the modification of the polycarboxylic acid water reducing agent, provided monomers before polymerization are all olefins containing phosphonic acid groups or phosphate groups, and no carboxyl group exists, the synthesized water reducing agent needs to be copolymerized with other olefin monomers containing carboxyl groups to introduce the carboxyl group, so that the content of the effective carboxyl group and phosphorus of the polycarboxylic acid water reducing agent is reduced, the performance of the polycarboxylic acid water reducing agent is reduced, and the adaptability of the polycarboxylic acid water reducing agent in concrete is limited.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of a water reducing agent monomer (2-phosphonic acid-propylene) malonic acid, which mainly comprises the following steps:
(1) adding a certain amount of absolute ethyl alcohol into a reaction container as a solvent, adding isopropenylphosphonic acid (IPPA) and malonic acid according to a certain molar ratio, adding a small amount of sodium ethoxide as a catalyst, starting a stirring and cooling reflux device, heating and refluxing for 2-4 hours, cooling and filtering to obtain a filtrate;
(2) adding a small amount of red phosphorus serving as a catalyst into the filtrate, stirring and heating to a reflux state, starting a tail gas absorption device, introducing a certain amount of chlorine gas below the reaction liquid level at a constant speed, controlling the introduction time of the chlorine gas to be 4-5 hours, and after the introduction is finished, continuously keeping the reflux state of the reaction liquid and keeping the temperature for 30 minutes;
(3) and cooling the reaction liquid to below 40 ℃, slowly adding a certain amount of mixed materials of sodium hydroxide and calcium oxide, heating to a reflux state under stirring, adding a small amount of polymerization inhibitor, reacting for 4-6 hours under the protection of nitrogen, filtering, evaporating ethanol outside the filtrate until the filtrate is dry, adding a certain amount of dilute hydrochloric acid for acidification, concentrating, filtering and drying to obtain the monomer (2-phosphonic acid-propylene) malonic acid.
Wherein the mole ratio of the isopropenylphosphonic acid to the malonic acid in the step 1 is n(IPPA)：n(malonic acid)1, (1.0-1.05), the dosage of the solvent absolute ethyl alcohol is 50-100% of the total feeding mass, preferably 70-80%, and the dosage of the catalyst sodium ethoxide is 0.5-1.0% of the feeding mass of the isopropenylphosphonic acid.
Wherein the dosage of the catalyst red phosphorus in the step 2 is 1.0-2.0% of the feeding mass of the isopropenylphosphonic acid, and the molar ratio of the chlorine to the isopropenylphosphonic acid is n(IPPA)：n(chlorine)=1 (1.0-2.0), preferably n(IPPA)：n(chlorine)=1:（1.2~1.5）。
Wherein the molar ratio of the sodium hydroxide to the isopropenylphosphonic acid in the step 3 is n(IPPA)：n(sodium hydroxide)=1 (5.0-6.0), preferably n(IPPA)：n(sodium hydroxide)=1 (5.1-5.5), the molar ratio of calcium oxide to isopropenylphosphonic acid is n(IPPA)：n(calcium oxide)=1:5, the molar ratio of the dilute hydrochloric acid to the isopropenylphosphonic acid is n(IPPA)：n(HCl)And (4.0-4.3), wherein the mass fraction of the dilute hydrochloric acid is 15-25%.
Wherein the polymerization inhibitor in the step 3 is phenol polymerization inhibitor such as hydroquinone, and the dosage of the polymerization inhibitor is 1-2 per mill of the feeding mass of the isopropenylphosphonic acid.
The related chemical formula of the invention is as follows:
main reaction:
side reaction:
the beneficial effects of the invention are as follows:
according to the invention, (2-phosphonic acid-propylene) malonic acid is synthesized by using isopropenylphosphonic acid and malonic acid through reaction steps of Michael addition, chlorination, dehydrochlorination and the like, coexistence of phosphonic acid groups and carboxyl groups in units is realized, and the polycarboxylic acid water reducer prepared by continuing polymerization of the (2-phosphonic acid-propylene) malonic acid and alkenyl polyoxyethylene ether macromonomer has high dispersibility, high slump retentivity and obvious retardation effect, is suitable for various concretes prepared by using low-activity fillers, and simultaneously effectively reduces unit dosage of the water reducer.
Detailed Description
The present invention is described in detail below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, and one skilled in the art will be able to make variations within the scope of the invention based on the disclosure herein, in reagents, catalysts and reaction process conditions. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
(2-Phosphono-propylene) malonic acid was measured by potentiometric titration.
Example 1
The method comprises the following steps: adding 180g of absolute ethyl alcohol, 122g of isopropenylphosphonic acid, 104g of malonic acid and 0.61g of sodium ethoxide into a 500ml round bottom glass flask in sequence, starting stirring and refluxing condensed water, heating to a reflux state, keeping the reflux state, reacting for 4.06 hours, cooling and filtering to obtain 403.1g of filtrate.
Step two: transferring the filtrate into a 1L three-neck round-bottom glass flask, adding 1.22g of red phosphorus as a catalyst, checking the air tightness of a reaction system, adjusting the reaction system to be qualified, starting a stirring and tail gas absorption device, heating to reflux, slowly introducing 85.2g of chlorine below the liquid level according to the flow of 21.2g/h, introducing the chlorine after 4.02h, continuing reflux reaction for 30min, and cooling to 35 ℃.
Step three: and (2) under stirring, slowly adding a mixed material of 204g of sodium hydroxide and 280g of calcium oxide, starting stirring, heating to a reflux state, carrying out suction filtration to separate calcium hydroxide after reacting for 4.01h, heating filtrate, externally steaming ethanol until the filtrate is dry, adding 100g of water for dissolving, slowly adding 584g of hydrochloric acid with the mass fraction of 25% for acidification, heating and concentrating until sodium chloride is separated out, carrying out suction filtration to separate sodium chloride while the filtrate is hot, and externally steaming and drying the filtrate to obtain 224.7g of (2-phosphonic acid-propylene) malonic acid with the purity of 81.93%, the conversion rate of 83.65% and the chloride ion content of 1.26%.
Example 2
The method comprises the following steps: 162g of absolute ethyl alcohol, 122g of isopropenylphosphonic acid, 109g of malonic acid and 0.61g of sodium ethoxide are sequentially added into a 500ml round bottom glass flask, stirring and refluxing are started, condensed water is heated to a refluxing state, the refluxing state is maintained, reaction is carried out for 4.04h, and then 388.7g of filtrate is obtained through cooling and filtration.
Step two: transferring the filtrate into a 1L three-neck round-bottom glass flask, adding 2.44g of red phosphorus as a catalyst, checking the air tightness of a reaction system, adjusting the reaction system to be qualified, starting a stirring and tail gas absorption device, heating to reflux, slowly introducing 106.5g of chlorine below the liquid level according to the flow of 21.3g/h, introducing the chlorine after 5.0h, continuing reflux reaction for 30min, and cooling to 37 ℃.
Step three: the mixed material of 220g of sodium hydroxide and 280g of calcium oxide is slowly added in turn under stirring, stirring is started, the temperature is raised to a reflux state, calcium hydroxide is separated by suction filtration after 4.09h of reaction, filtrate is heated to evaporate ethanol outside until the ethanol is dried, 110g of water is added for dissolving, 584g of hydrochloric acid with the mass fraction of 25% is slowly added for acidification, the mixture is heated and concentrated until sodium chloride is separated out, the sodium chloride is separated by suction filtration when the mixture is hot, and the filtrate is evaporated and dried to obtain 226.7g of (2-phosphonic acid-propylene) malonic acid with the purity of 81.93%, the conversion rate of 83.65% and the chloride ion content of 1.26%.
Application example 1
A polycarboxylic acid water reducing agent was prepared using (2-phosphonic acid-propylene) malonic acid prepared in example 1 as a small monomer, and its application properties were examined. The method comprises the following specific steps:
preparing (2-phosphonic acid-propylene) malonic acid and deionized water into a mixed monomer solution, wherein the mass ratio of the (2-phosphonic acid-propylene) malonic acid to the deionized water is 1:1, an allyloxy polyoxyethylene ether macromonomer with the molecular weight of 1000 is used as a base material, the molar ratio of the allyloxy polyoxyethylene ether to the (2-phosphonic acid-propylene) malonic acid is 1: 3, a Vc-H2O2 system is adopted as an initiating system, an initiator aqueous solution and a monomer aqueous solution are respectively dropwise added under the condition of normal-temperature polymerization, uniformly stirred and dropwise added for 3-4 hours, the reaction is continued for 2-3 hours after the dropwise addition is finished, and finally a sodium hydroxide solution is used for neutralizing until the pH value is 6-7, so that the polycarboxylic acid high-performance water reducer mother solution is obtained and is marked as A1. The experimental data of the fluidity of the cement paste and the concrete slump are shown in the experimental data tables 1 and 2.
Application example 2
A polycarboxylic acid water reducing agent was prepared using (2-phosphonic acid-propylene) malonic acid prepared in example 2 as a small monomer, and its application properties were examined. The method comprises the following specific steps:
preparing acrylic acid, (2-phosphonic acid-propylene) malonic acid and deionized water into a mixed monomer solution, wherein the molar ratio of phosphonic acid monomer to acrylic acid is 1: 3, the mass ratio of the two monomers to deionized water is 1:1, allyloxy polyoxyethylene ether macromonomer with the molecular weight of 1000 is used as a base material, the molar ratio of allyloxy polyoxyethylene ether to acrylic acid to (2-phosphonic acid-propylene) malonic acid is 1: 2, a Vc-H2O2 system is adopted as an initiating system, an initiator aqueous solution and the mixed monomer solution are respectively dripped under the condition of normal-temperature polymerization, the initiator aqueous solution and the mixed monomer solution are uniformly stirred and dripped for 3-4 hours, the reaction is continued for 2-3 hours after the dripping is finished, and finally, the pH is neutralized to 6-7 by using a sodium hydroxide solution, so that the polycarboxylic acid high-performance water reducing agent mother solution is obtained. The experimental data of the fluidity of the cement paste and the concrete slump are shown in the experimental data tables 1 and 2.
Application example 3
A polycarboxylic acid water reducing agent was prepared using (2-phosphonic acid-propylene) malonic acid prepared in example 2 as a small monomer, and its application properties were examined. The method comprises the following specific steps:
preparing acrylic acid, (2-phosphonic acid-propylene) malonic acid and deionized water into a mixed monomer solution, wherein the molar ratio of phosphonic acid monomer to acrylic acid is 2: 1, the mass ratio of the two monomers to deionized water is 1:1, allyloxy polyoxyethylene ether macromonomer with the molecular weight of 1000 is used as a base material, the molar ratio of allyloxy polyoxyethylene ether to acrylic acid to (2-phosphonic acid-propylene) malonic acid is 1: 2: 1, a Vc-H2O2 system is adopted as an initiating system, an initiator aqueous solution and the mixed monomer solution are respectively dripped under the condition of normal-temperature polymerization, the initiator aqueous solution and the mixed monomer solution are uniformly stirred and dripped for 3-4 hours, the reaction is continued for 2-3 hours after the dripping is finished, and finally, the pH is neutralized to 6-7 by using a sodium hydroxide solution, so that the polycarboxylic acid high-performance water reducing agent mother solution is obtained. The experimental data of the fluidity of the cement paste and the concrete slump are shown in the experimental data tables 1 and 2.
Comparative application example 1
Preparing acrylic acid and deionized water into an aqueous solution with the mass fraction of 50%, taking an allyloxy polyoxyethylene ether macromonomer with the molecular weight of 1000 as a base material, taking the molar ratio of allyloxy polyoxyethylene ether to acrylic acid as 1: 3, adopting a Vc-H2O2 system as an initiation system, respectively dropwise adding an initiator aqueous solution and a monomer aqueous solution under the condition of normal-temperature polymerization, uniformly stirring and dropwise adding for 3-4 hours, continuing to react for 2-3 hours after the dropwise adding is finished, and finally neutralizing with a sodium hydroxide solution until the pH value is 6-7 to obtain the polycarboxylic acid high-performance water reducing agent mother solution marked as B1. The experimental data of the fluidity of the cement paste and the concrete slump are shown in the experimental data tables 1 and 2.
Claims (5)
1. A preparation method of (2-phosphonic acid-propylene) malonic acid is characterized by specifically comprising the following steps:
(1) adding absolute ethyl alcohol into a reaction container as a solvent, adding isopropenylphosphonic acid and malonic acid, adding sodium ethoxide as a catalyst, stirring, heating and refluxing for 2-4 hours, cooling, and filtering to obtain a filtrate;
(2) adding red phosphorus serving as a catalyst into the filtrate, stirring and heating to a reflux state, starting a tail gas absorption device, introducing chlorine gas below the reaction liquid level at a constant speed, controlling the introduction time of the chlorine gas to be 4-5 hours, and continuously keeping the reflux state of the reaction liquid and preserving the heat for 30 minutes after the introduction is finished;
(3) cooling the reaction liquid to below 40 ℃, slowly adding a mixed material of sodium hydroxide and calcium oxide, then heating to a reflux state under stirring, adding a polymerization inhibitor, reacting for 4-6 hours under the protection of nitrogen, filtering, and evaporating ethanol from the filtrate until the ethanol is dry; acidifying, concentrating, filtering and drying to obtain the monomer (2-phosphonic acid-propylene) malonic acid.
2. The process of claim 1 wherein the mole ratio of isopropenylphosphonic acid to malonic acid in step 1 is nIPPA：nMalonic acid1: 1.0-1.05, the dosage of the solvent absolute ethyl alcohol is 50-100% of the total feeding mass, and the dosage of the sodium ethoxide is 0.5-1.0% of the feeding mass of the isopropenylphosphonic acid.
3. The method of claim 1, wherein the amount of red phosphorus used in step (2) is 1.0-2.0 w% of the charged mass of isopropenylphosphonic acid, and the molar ratio of chlorine to isopropenylphosphonic acid is nIPPA：nChlorine gas=1:1.0~2.0。
4. The process of claim 1, wherein the molar ratio of sodium hydroxide to isopropenylphosphonic acid in step (3) is nIPPA：nSodium hydroxide=1: 5.0-6.0, the molar ratio of calcium oxide to isopropenylphosphonic acid is nIPPA：nCalcium oxide=1:5。
5. The method according to claim 1, wherein the polymerization inhibitor in step (3) is a phenol polymerization inhibitor such as hydroquinone, and the dosage of the polymerization inhibitor is 1-2 per mill of the feeding mass of the isopropenylphosphonic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911308979.8A CN111087422B (en) | 2019-12-18 | 2019-12-18 | Preparation method of (2-phosphonic acid-propylene) malonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911308979.8A CN111087422B (en) | 2019-12-18 | 2019-12-18 | Preparation method of (2-phosphonic acid-propylene) malonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111087422A true CN111087422A (en) | 2020-05-01 |
| CN111087422B CN111087422B (en) | 2022-04-08 |
Family
ID=70395172
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911308979.8A Active CN111087422B (en) | 2019-12-18 | 2019-12-18 | Preparation method of (2-phosphonic acid-propylene) malonic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111087422B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457452A (en) * | 2020-12-03 | 2021-03-09 | 山东泰和水处理科技股份有限公司 | Degradable water reducing agent and synthesis method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879498A (en) * | 1971-08-31 | 1975-04-22 | Miltiadis I Iliopulos | Dialkyl 1-acryloyloxy-2-alkenyl-1-phosphonates and dialkyl 1-methacryloxy-2-alkenyl-1-phosphonates |
| CN106832147A (en) * | 2017-03-02 | 2017-06-13 | 太原理工大学 | A kind of preparation method containing phosphonyl group polycarboxylate water-reducer |
| CN107337765A (en) * | 2016-12-29 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | Phosphonic acids based polyalcohol with strong adaptability and function of slump protection and its preparation method and application |
-
2019
- 2019-12-18 CN CN201911308979.8A patent/CN111087422B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879498A (en) * | 1971-08-31 | 1975-04-22 | Miltiadis I Iliopulos | Dialkyl 1-acryloyloxy-2-alkenyl-1-phosphonates and dialkyl 1-methacryloxy-2-alkenyl-1-phosphonates |
| CN107337765A (en) * | 2016-12-29 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | Phosphonic acids based polyalcohol with strong adaptability and function of slump protection and its preparation method and application |
| CN106832147A (en) * | 2017-03-02 | 2017-06-13 | 太原理工大学 | A kind of preparation method containing phosphonyl group polycarboxylate water-reducer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112457452A (en) * | 2020-12-03 | 2021-03-09 | 山东泰和水处理科技股份有限公司 | Degradable water reducing agent and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111087422B (en) | 2022-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109354654B (en) | Early-strength polycarboxylate superplasticizer and preparation method thereof | |
| WO2016026346A1 (en) | Low-temperature method for preparing high-adaptability ether polycarboxylic acid water reducer | |
| WO2017113990A1 (en) | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof | |
| CN105837763B (en) | Silane polycarboxylic acid water reducing agent and preparation method thereof | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| WO2020001169A1 (en) | Preparation method for retarding ether type polycarboxylic acid water reducing agent | |
| CN109957103B (en) | Special bidentate phosphonic acid water reducing agent for medium-low slump concrete and preparation method thereof | |
| CN107043227B (en) | Anti-clay polymer dispersant and preparation method thereof | |
| EP2699527A1 (en) | Accelerator composition | |
| CN108276533B (en) | High-adaptability polycarboxylate superplasticizer and preparation method thereof | |
| CN111378113A (en) | Phosphated polyether, preparation method thereof and application thereof in preparation of high-adaptability phosphonic acid-based water reducing agent | |
| WO2020048083A1 (en) | Preparation method for crosslinked viscosity-reducing polycarboxylic acid water reducer | |
| CN111087422B (en) | Preparation method of (2-phosphonic acid-propylene) malonic acid | |
| CN108975746B (en) | Synthesis method of polycarboxylate superplasticizer containing siloxy | |
| CN109942754B (en) | Method for preparing delayed coagulation type superplasticizer by atom transfer radical polymerization | |
| JP5559192B2 (en) | Process for producing a semi-continuously operated copolymer | |
| CN109320714B (en) | Special small-molecule superplasticizer for medium-low slump concrete and preparation method thereof | |
| CN103723945A (en) | Fast hydrolyzable slow releasing polycarboxylate superplasticizer and preparation method thereof | |
| Yu et al. | Synthesis and rapid cement hardening evaluation of polycarboxylate superplasticizers incorporating ester groups in their backbone chain | |
| CN108997151B (en) | Preparation method of unsaturated ester containing alkylamine group, obtained product and application | |
| CN109180876B (en) | Preparation method of viscosity-reducing polycarboxylate superplasticizer | |
| CN110643003B (en) | Preparation method of retarding type ester polycarboxylate superplasticizer | |
| JP5249138B2 (en) | Dispersant for hydraulic composition | |
| CN107337789B (en) | Preparation method and application of micromolecular phosphate dispersant | |
| CN110862544B (en) | Preparation method of composite adsorption type solid water reducing agent for sulphoaluminate cement |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: 277000 No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |