CN110591015A - Polycarboxylate superplasticizer and method for rapidly synthesizing same at normal temperature - Google Patents
Polycarboxylate superplasticizer and method for rapidly synthesizing same at normal temperature Download PDFInfo
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- CN110591015A CN110591015A CN201910933868.XA CN201910933868A CN110591015A CN 110591015 A CN110591015 A CN 110591015A CN 201910933868 A CN201910933868 A CN 201910933868A CN 110591015 A CN110591015 A CN 110591015A
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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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a polycarboxylate superplasticizer which mainly comprises a GPEG polyether macromonomer, an oxidant, a metal accelerator, a chain transfer agent, an unsaturated carboxylic acid small monomer, a reducing agent and the like. Also discloses a method for rapidly synthesizing the compound at normal temperature. The invention uses a novel polyether (GPEG) with molecular weight of 2000-3000, the monomer belongs to a novel monomer with a 2+2 structure, and the monomer can be polymerized with an unsaturated acid small monomer under the condition of adding a chain transfer agent, an oxidant and a reducing agent; compared with the traditional polyether macromonomer, the double bond structure of the monomer has higher double bond activity, so that the polymerization reaction can be completed at normal temperature, the reaction time is shorter, and the production cost is saved. The metal promoter is added in the polymerization reaction, so that the polymerization reaction is easier to carry out at normal temperature, and the polymerization reaction speed is accelerated. Compared with the water reducing agent sold in the market, the water reducing agent obtained by polymerizing the high-activity polyether and the unsaturated carboxylic acid small monomer has more excellent water reducing and slump retaining performances.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a polycarboxylic acid water reducing agent and a method for quickly synthesizing the same at normal temperature.
Background
The polycarboxylic acid water reducing agent is a third generation high-performance concrete water reducing agent developed after a common water reducing agent represented by lignin and a naphthalene high-performance water reducing agent, and is popular in the concrete engineering industry with high water reducing rate and good slump retentivity. The molecular structure of the polycarboxylate superplasticizer contains carboxylic acid, the polycarboxylate superplasticizer is a graft copolymer, the branched chain structure has obvious characteristics, generally the branched chain formed by polyoxyethylene is a branched chain or a comb-shaped branched chain, and the composition form is favorable for improving the surface activity of molecular functional groups. In recent years, organizations mainly using enterprises actively invest in the innovative research and development of the polycarboxylate superplasticizer, and the polycarboxylate superplasticizer with high water reducing rate and good slump retention is prepared. However, the existing preparation method of the low-temperature/normal-temperature polycarboxylate superplasticizer has long reaction time, and the reaction time of a common polymerization initiation system is at least 2-10 h; the high-temperature method is adopted to synthesize the polycarboxylic acid water reducing agent, although the reaction time can be shortened, the reaction temperature is generally above 40 ℃, and the energy consumption is higher. In addition, with the increasing demand and performance requirements of polycarboxylic acid water reducing agents year by year, it is important to prepare water reducing agents with higher water reducing rate and better slump retaining performance.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a polycarboxylic acid water reducing agent which can be rapidly synthesized at normal temperature and has excellent water reducing and slump retaining performances.
The technical scheme of the invention is as follows:
a polycarboxylate superplasticizer comprises the following components in parts by weight: 90-120 parts of GPEG polyether macromonomer, 0.5-0.7 part of oxidant, 0.5-0.7 part of metal accelerator, 0.4-0.8 part of chain transfer agent, 8-15 parts of unsaturated carboxylic acid small monomer and 0.09-0.15 part of reducing agent.
Further, the oxidant is one or the combination of more than two of ammonium persulfate, hydrogen peroxide with the mass fraction of 27.5% or potassium persulfate.
Further, the metal promoter is FeSO4 solution with the mass fraction of 0.5% -1%.
Further, the chain transfer agent is one or a combination of more than two of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
Further, the unsaturated carboxylic small monomer is one or a combination of more than two of maleic anhydride, acrylic acid, methacrylic acid or fumaric acid.
Further, the reducing agent solution is one or a combination of more than two of sodium formaldehyde sulfoxylate, E51 or vitamin C.
Furthermore, the oxidant is 25-30% of hydrogen peroxide, the metal accelerator is 0.5-1% of FeSO4 solution, the chain transfer agent is mercaptopropionic acid, the unsaturated carboxylic acid small monomer is acrylic acid, and the reducing agent is E51.
The second technical problem to be solved by the invention is to provide a method for quickly synthesizing the polycarboxylate superplasticizer at normal temperature.
The technical scheme of the invention is as follows:
a method for quickly synthesizing a polycarboxylate superplasticizer at normal temperature comprises the following steps:
(1) adding GPEG polyether macromonomer and 60-80 parts of tap water into a reaction kettle according to a proportion, stirring and dissolving the mixture into a uniform and transparent solution, and then adding an oxidant and a metal accelerator;
(2) dissolving unsaturated carboxylic acid small monomer and chain transfer agent in 10-15 parts of tap water to prepare a dropping liquid A material for later use, and dissolving reducing agent in 20-22 parts of tap water to prepare a dropping liquid B material for later use;
(3) simultaneously adding the material A and the material B into the base solution obtained in the step 1 at a constant speed, finishing the dropwise addition within 30-60min, and preserving heat for 1 hour after the dropwise addition is finished to finish the reaction to obtain a polycarboxylic acid water reducing agent solution;
(4) and (4) adjusting the pH value to be neutral by using an alkali solution, and obtaining a transparent liquid, namely the polycarboxylic acid water reducing agent.
The invention has the advantages that:
1. in order to shorten the synthesis time of the polycarboxylic acid water reducing agent, a novel polyether macromonomer (GPEG) with the molecular weight of 2000-3000 is used, belongs to a novel monomer with a 2+2 structure, and can be polymerized with an unsaturated acid small monomer under the condition of adding a chain transfer agent, an oxidant and a reducing agent; the double bond structure of the monomer has higher double bond activity than that of the traditional polyether macromonomer, so that the polymerization reaction can be completed at normal temperature, and the reaction time can be shortened to 30min to 1 h.
2. The metal promoter is added in the polymerization reaction, so that the polymerization reaction is easier to carry out at normal temperature, and the polymerization reaction speed is accelerated.
3. The water reducer obtained by polymerizing the high-activity polyether and the unsaturated carboxylic acid small monomer has excellent water reducing and slump retaining performances.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1:
preparing raw materials: 100 parts of GPEG polyether macromonomer, 0.5 part of oxidant (hydrogen peroxide), 0.58 part of metal accelerator (FeSO4), 0.7 part of chain transfer agent (mercaptopropionic acid), 8 parts of unsaturated carboxylic acid small monomer (acrylic acid) and 0.1 part of reducing agent (E51).
The synthesis steps are as follows:
(1) adding 100 parts of GPEG polyether macromonomer into 67 parts of tap water to be dissolved to obtain a kettle bottom solution, stirring and dissolving the mixture into a uniform and transparent solution, and then adding 0.6 part of hydrogen peroxide with the mass fraction of 25-30%, preferably 27.5% of hydrogen peroxide and 0.58 part of FeSO4 solution with the mass fraction of 0.5-1%.
(2) 8 parts of acrylic acid and 0.7 part of mercaptopropionic acid are dissolved in 10-12 parts of tap water to prepare a dropping liquid A material, and 0.1 part of E51 is dissolved in 20-22 parts of tap water to prepare a dropping liquid B material for later use.
(3) And (3) simultaneously, dropwise adding the material A and the material B into the solution obtained in the step (1), wherein the dropwise adding time lasts for 30-60min, and after the dropwise adding is finished, preserving heat for 1h to finish the reaction.
(4) And (4) supplementing an alkali solution to adjust the pH value to be neutral after the heat preservation is finished, and obtaining a transparent liquid, namely the polycarboxylic acid water reducing agent.
Example 2:
preparing raw materials: 95 parts of GPEG polyether macromonomer, 0.58 part of oxidant (hydrogen peroxide), 0.5 part of metal accelerator (FeSO4), 0.4 part of chain transfer agent (mercaptopropionic acid), 9 parts of unsaturated carboxylic acid small monomer (acrylic acid) and 0.09 part of reducing agent (E51).
The synthesis procedure was identical to example 1.
Example 3:
preparing raw materials: 120 parts of GPEG polyether macromonomer, 0.7 part of oxidant (hydrogen peroxide), 0.7 part of metal accelerator (FeSO4), 0.8 part of chain transfer agent (mercaptopropionic acid), 15 parts of unsaturated carboxylic acid small monomer (acrylic acid) and 0.15 part of reducing agent (E51).
The synthesis procedure was identical to example 1.
Concrete performance tests were performed on the samples synthesized in examples 1 to 3 against a commercially available ordinary polycarboxylic acid water reducing agent. Adopting 42.5 cement of conch; class II fly ash; sand: the machine-made sand has the fineness modulus of 2.60; crushing stone: the grain diameter is 5-30 mm; the concrete mix ratio is shown in table 1.
Table 1: concrete test mixing proportion kg/m3
| Cement | Coal ash | Sand | Crushing stone | Water (W) |
| 280 | 90 | 902 | 977 | 160 |
According to GB-8077-.
Table 2: concrete initial slump/expansion and time change by adding different polycarboxylic acid water reducing agents
As can be seen from the test results in Table 2, the polycarboxylic acid water reducing agent prepared in the embodiments 1, 2 and 3 has more excellent performance, the water reducing rate is higher than that of the current commercial water reducing agent, the slump/expansion loss is less with time under the same doping amount, and the doping reduction effect can be achieved.
It should be added that the given examples are only the best examples, and the best effect can be achieved, wherein one or more of the oxidant, the metal promoter, the chain transfer agent, the unsaturated carboxylic small monomer and the reducing agent can be replaced by other materials in the same class of materials, and the materials are not limited to the materials selected in the examples.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (8)
1. The polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight: 90-120 parts of GPEG polyether macromonomer, 0.5-0.7 part of oxidant, 0.5-0.7 part of metal accelerator, 0.4-0.8 part of chain transfer agent, 8-15 parts of unsaturated carboxylic acid small monomer and 0.09-0.15 part of reducing agent.
2. The polycarboxylate water reducer according to claim 1, characterized in that: the oxidant is one or the combination of more than two of ammonium persulfate, hydrogen peroxide with the mass fraction of 27.5 percent or potassium persulfate.
3. The polycarboxylate water reducer according to claim 1, characterized in that: the metal promoter is FeSO4 solution with the mass fraction of 0.5-1%.
4. The polycarboxylate water reducer according to claim 1, characterized in that: the chain transfer agent is one or the combination of more than two of thioglycolic acid, mercaptopropionic acid or mercaptoethanol.
5. The polycarboxylate water reducer according to claim 1, characterized in that: the unsaturated carboxylic acid small monomer is one or the combination of more than two of maleic anhydride, acrylic acid, methacrylic acid or fumaric acid.
6. The polycarboxylic acid water reducing agent according to claim 1, characterized in that: the reducing agent is one or the combination of more than two of sodium formaldehyde sulfoxylate, E51 or vitamin C.
7. The polycarboxylate water reducer according to claim 1, characterized in that: the oxidant is 25-30% of hydrogen peroxide, the metal accelerator is 0.5-1% of FeSO4 solution, the chain transfer agent is mercaptopropionic acid, the unsaturated carboxylic acid small monomer is acrylic acid, and the reducing agent is E51.
8. A method for rapidly synthesizing the polycarboxylic acid water reducer of any one of claims 1 to 7 at normal temperature is characterized by comprising the following steps:
(1) adding GPEG polyether macromonomer and 60-80 parts of tap water into a reaction kettle according to a proportion, stirring and dissolving the mixture into a uniform and transparent solution, and then adding an oxidant and a metal accelerator;
(2) dissolving unsaturated carboxylic acid small monomer and chain transfer agent in 10-15 parts of tap water to prepare a dropping liquid A material for later use, and dissolving reducing agent in 20-22 parts of tap water to prepare a dropping liquid B material for later use;
(3) simultaneously adding the material A and the material B into the base solution obtained in the step 1 at a constant speed, finishing the dropwise addition within 30-60min, and preserving heat for 1 hour after the dropwise addition is finished to finish the reaction to obtain a polycarboxylic acid water reducing agent solution;
(4) and (4) adjusting the pH value to be neutral by using an alkali solution, and obtaining a transparent liquid, namely the polycarboxylic acid water reducing agent.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154045A (en) * | 2019-12-30 | 2020-05-15 | 四川恒泽建材有限公司 | Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof |
| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN112500534A (en) * | 2020-12-03 | 2021-03-16 | 贵州石博士科技股份有限公司 | Amphoteric polycarboxylate superplasticizer and preparation method thereof |
| CN112625191A (en) * | 2020-12-22 | 2021-04-09 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN112707667A (en) * | 2020-06-22 | 2021-04-27 | 科之杰新材料集团有限公司 | Low-sensitivity water reducing agent and preparation method thereof |
| CN112707672A (en) * | 2020-06-22 | 2021-04-27 | 科之杰新材料集团有限公司 | Layered calcium-aluminum double metal hydroxide and preparation method thereof, early-strength water reducing agent and preparation method thereof |
| CN112708063A (en) * | 2020-12-08 | 2021-04-27 | 科之杰新材料集团有限公司 | Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate |
| CN113045718A (en) * | 2021-04-07 | 2021-06-29 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer, preparation method and application |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154045A (en) * | 2019-12-30 | 2020-05-15 | 四川恒泽建材有限公司 | Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof |
| CN112707667A (en) * | 2020-06-22 | 2021-04-27 | 科之杰新材料集团有限公司 | Low-sensitivity water reducing agent and preparation method thereof |
| CN112707672A (en) * | 2020-06-22 | 2021-04-27 | 科之杰新材料集团有限公司 | Layered calcium-aluminum double metal hydroxide and preparation method thereof, early-strength water reducing agent and preparation method thereof |
| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN112500534A (en) * | 2020-12-03 | 2021-03-16 | 贵州石博士科技股份有限公司 | Amphoteric polycarboxylate superplasticizer and preparation method thereof |
| CN112708063A (en) * | 2020-12-08 | 2021-04-27 | 科之杰新材料集团有限公司 | Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate |
| CN112625191A (en) * | 2020-12-22 | 2021-04-09 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN113045718A (en) * | 2021-04-07 | 2021-06-29 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer, preparation method and application |
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