CN111978484B - Silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether - Google Patents
Silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether Download PDFInfo
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- CN111978484B CN111978484B CN202010942758.2A CN202010942758A CN111978484B CN 111978484 B CN111978484 B CN 111978484B CN 202010942758 A CN202010942758 A CN 202010942758A CN 111978484 B CN111978484 B CN 111978484B
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- polyoxyethylene ether
- silane
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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
- 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
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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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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 belongs to the technical field of building materials, and particularly relates to a silicon-containing magnetic water reducer containing 4-hydroxybutyl polyoxyethylene ether, which is prepared by adding an initiator ammonium persulfate, a chain transfer agent thioglycollic acid and water into polyoxyethylene ether A, polyoxyethylene ether B, acrylic acid and silane C serving as polymerization monomers; and discloses a preparation method of the water reducer. The application of the invention can obviously improve the fluidity of the slurry, the retentivity and the compressive strength of the concrete.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether.
Background
The water reducing agent is an indispensable chemical additive for improving slag-based cementing materials and concrete products, and can obviously improve the comprehensive properties of workability, compactness, strength, durability and the like of the products under the condition of lower water-cement ratio.
The polycarboxylate water reducer is used as a third-generation water reducer product, has strong designability of molecular structure and great potential for high performance, and can be prepared into a multifunctional product by selecting monomers with different functions for copolymerization. However, in recent years, the quality problems of cement, mineral admixture, coarse aggregate, fine aggregate and the like are serious, and in addition, the cement variety in China is various, the engineering mix proportion is various, the polycarboxylic acid water reducer is often not suitable for concrete, and the problems of bleeding, segregation, excessively rapid slump loss and the like of fresh concrete are easy to occur. Therefore, through molecular structure design, synthesis process and action mechanism research, the functionality of the polycarboxylate water reducer is continuously perfected, so that the polycarboxylate water reducer has good adaptability to different cements, mineral admixtures, inferior sand and stone materials and the like, and the polycarboxylate water reducer has become an important point of research at home and abroad.
At present, the research on polycarboxylic acid water reducer at home and abroad mainly focuses on the following aspects: (1) research on polymer synthesis methods and processes; (2) searching the relation between the structure and the performance; (3) Designing polymer molecules based on the existing theoretical basis; (4) The action mechanism of the water reducer is presumed according to the relation between the structure and the performance; (5) Through the guidance of action mechanism and research rule, gradually explore a new process for synthesizing the water reducer with better performance. Because of the diversity of molecular structure designs of the polycarboxylic acid water reducer and the necessary connection between the structure and the performance of the polycarboxylic acid water reducer, the research in the field is very active, and the novel polycarboxylic acid water reducer with high performance is endless.
Typical polycarboxylate water reducers are surface-active graft copolymers, in comb-like structures, generally composed of two basic components, a main chain and a side chain. The main chain of the water reducer generally contains a large number of ionizable carboxyl groups, and after the carboxyl groups are ionized in water, the water reducer molecules are adsorbed and anchored on the surfaces of cement particles through the action of ions, so that electrostatic repulsive force exists among the cement particles; the side chain is usually a hydrophilic polyether long chain such as polyethylene glycol monomethyl ether or polypropylene glycol monomethyl ether with a relative molecular weight of 500-3000, and can be fully stretched in water to provide steric hindrance repulsive force for cement particles and improve the dispersibility of the cement particles. The combined action of the two repulsive forces greatly improves the dispersibility of cement particles, so that the cement product added with the polycarboxylate superplasticizer has excellent comprehensive performance.
Disclosure of Invention
The invention aims to provide a silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether.
The second purpose of the invention is to provide a preparation method of the silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the silicon-containing polycarboxylate water reducer is characterized in that: the catalyst is prepared by taking polyoxyethylene ether A, polyoxyethylene ether B, acrylic acid and silane C as polymerization monomers and adding an initiator ammonium persulfate, a chain transfer agent thioglycollic acid and water, wherein the components are as follows in parts by weight:
10-20 parts of polyoxyethylene ether A
10-20 parts of polyoxyethylene ether B
40-60 parts of acrylic acid
Silane C10-20 parts
Ammonium persulfate 0.3-1 part
0.15 to 0.25 part of 3-mercaptoacetic acid
100-400 parts of deionized water;
the polyoxyethylene ether A structure is as follows:
the polyoxyethylene ether B is 4-hydroxybutyl polyoxyethylene ether, and the polyoxyethylene repeating unit number is 150-300;
the structure of the silane C is as follows:
the silane C can be obtained by reacting silane D with ferroferric oxide, and the silane D has the structure of
Further, silane D is obtained by further adding alkoxysilane for hydrolysis after the reaction of silane monomer with amino and alkoxy and maleic anhydride.
Further, the number of polyoxyethylene repeating units in the polyoxyethylene ether B is 200-250. Researches show that the performance can be better improved by adding polyoxyethylene ether B with larger molecular weight and polyoxyethylene ether A with lower molecular weight.
Further, n=30 to 40 of polyoxyethylene ether a.
The preparation method of the water reducer is characterized by comprising the following steps: and (3) carrying out initiator polymerization reaction on each component under the action of an initiator, and carrying out post-treatment to obtain the water reducer.
Further, the preparation method comprises the following steps: adding polyoxyethylene ether A, polyoxyethylene ether B and deionized water into a reaction kettle, and heating and dissolving completely at 20-80 ℃ to obtain a solution A; respectively and simultaneously dropwise adding a deionized water solution of ammonium persulfate and a deionized water mixed solution of acrylic acid, silane C and a chain transfer agent into the solution A, dropwise adding at 60 ℃ for 3.0h, carrying out heat preservation reaction at 60 ℃ for 1.0h after the dropwise adding is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% liquid alkali by mass percent into the solution B, and regulating the pH value to be 6-8 to obtain the polycarboxylate water reducer.
Further, the application of the water reducer is used in cement to obtain magnetic cement.
Wherein, the polyoxyethylene ether A monomer provides two polyoxyethylene ether side chains on the side chains, the polyoxyethylene ether B provides a longer polyoxyethylene ether side chain, and the hydroxysilane C contains nano ferroferric oxide surface and active hydroxyl condensation, more ferroferric oxide particles are introduced, the steric hindrance effect of inorganic particles is better exerted, the ferroferric oxide provides magnetic effect, and the performance of the water reducer is improved; especially, the fluidity, the retention and the compressive strength of concrete are effectively improved, and small molecular monomers such as acrylamide, sodium methacrylate and the like are not required to be added into the monomer.
The invention has the beneficial effects that:
(1) The invention can effectively improve the fluidity of the slurry, the retentivity and the compressive strength of the concrete.
(2) The invention has simple and feasible process, obvious product effect and good engineering application prospect.
Detailed Description
The following are specific embodiments of the present invention and technical solutions of the present invention will be further described with reference to the embodiments, but the present invention is not limited to these examples.
Example 1
Adding polyoxyethylene ether A, polyoxyethylene ether B and deionized water into a reaction kettle, and heating and dissolving completely at 20-80 ℃ to obtain a solution A; respectively and simultaneously dropwise adding a deionized water solution of ammonium persulfate and a deionized water mixed solution of acrylic acid, silane C and mercaptopropionic acid into the solution A, dropwise adding 3.0h at 60 ℃, carrying out heat preservation reaction at 60 ℃ for 1.0h after the dropwise adding is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% liquid alkali by mass percent into the solution B, and regulating the pH value to be 6-8 to obtain the polycarboxylate water reducer.
The polyoxyethylene ether A has the structure that:
the dosage of each component is as follows:
polyoxyethylene ether A15 parts
Polyoxyethylene ether B15 parts
Acrylic acid 50 parts
Silane C15 part
Ammonium persulfate 0.5 part
3-mercaptoacetic acid 0.2 parts
300 parts of deionized water;
example 2
Except for the difference that n=20 of polyoxyethylene ether a was the same as in example 1.
Example 3
Except for the difference that n=50 of polyoxyethylene ether a was the same as in example 1.
Example 4
Except for the difference that the number of repeating units of only polyoxyethylene ether B was 100 as in example 1.
Example 5
Except for the difference that the number of repeating units of only polyoxyethylene ether B was 250, the same as in example 1.
Example 6
Otherwise, the procedure is as in example 1, except that no silane C is added.
Example 7
Except for the difference that the polyoxyethylene ether A was not added in the same manner as in example 1.
Example 8
Except for the difference that the polyoxyethylene ether B was not added in the same manner as in example 1.
The organic-inorganic hybrid polycarboxylate water reducer of the embodiments 1 to 8 of the invention is used for measuring the fluidity of the clean slurry according to GB/T8077-2012 "method for testing homogeneity of concrete admixture", cement is used as reference cement, the compressive strength of the cement is tested according to GB/T50081-2002 "standard for testing mechanical properties of ordinary concrete", and the mixing ratio of concrete is adopted in the experiment: 360Kg/m of reference cement 3 792Kg/m of sand 3 290Kg/m of small stone 3 (5-10 mm), marble 678Kg/m 3 (10-20 mm) and the water-gel ratio is 0.4. The experimental results are shown in the following table:
from the above table, it can be seen that the water reducer of the present invention has good effects in improving the fluidity of slurry, the retention and the compressive strength of concrete.
Claims (8)
1. The utility model provides a silicon-containing magnetism polycarboxylate water reducing agent which characterized in that: the catalyst is prepared by taking polyoxyethylene ether A, polyoxyethylene ether B, acrylic acid and silane C as polymerization monomers and adding an initiator ammonium persulfate, a chain transfer agent thioglycollic acid and water, wherein the components are as follows in parts by weight:
10-20 parts of polyoxyethylene ether A
10-20 parts of polyoxyethylene ether B
40-60 parts of acrylic acid
Silane C10-20 parts
Ammonium persulfate 0.3-1 part
0.15 to 0.25 part of thioglycollic acid
100-400 parts of deionized water;
the polyoxyethylene ether A structure is as follows:
the polyoxyethylene ether B is 4-hydroxybutyl polyoxyethylene ether, and the polyoxyethylene repeating unit number is 150-300;
the structure of the silane C is as follows:
2. the water reducing agent of claim 1, wherein: the silane C is obtained by the reaction of silane D and nano ferroferric oxide, and the structure of the silane D is
3. The water reducer according to claim 2, wherein silane D is obtained by further adding alkoxysilane for hydrolysis after reacting a silane monomer having an amino group and an alkoxy group with maleic anhydride.
4. A water reducing agent according to any one of claims 1 to 3, wherein the number of polyoxyethylene repeat units in polyoxyethylene ether B is from 200 to 250.
5. The water reducing agent according to claim 4, wherein n=30-40 of polyoxyethylene ether a.
6. A method of preparing the water reducing agent of any one of claims 1 to 5, characterized in that: and (3) initiating polymerization reaction of each component under the action of an initiator, and performing aftertreatment to obtain the water reducer.
7. The method of manufacturing according to claim 6, wherein: adding polyoxyethylene ether A, polyoxyethylene ether B and deionized water into a reaction kettle, and heating and dissolving completely at 20-80 ℃ to obtain a solution A; respectively and simultaneously dropwise adding a deionized water solution of ammonium persulfate and a deionized water mixed solution of acrylic acid, silane C and a chain transfer agent into the solution A, dropwise adding at 60 ℃ for 3.0h, carrying out heat preservation reaction at 60 ℃ for 1.0h after the dropwise adding is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% liquid alkali by mass percent into the solution B, and regulating the pH value to be 6-8 to obtain the polycarboxylate water reducer.
8. Use of a water reducing agent according to claim 1, in cement, to obtain a magnetic cement.
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| CN202010942758.2A CN111978484B (en) | 2020-09-09 | 2020-09-09 | Silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105837763A (en) * | 2016-06-04 | 2016-08-10 | 石家庄市长安育才建材有限公司 | Silane polycarboxylate water-reducing agent and preparation method thereof |
| CN105949402A (en) * | 2016-04-26 | 2016-09-21 | 同济大学 | Anti-sulfate competitive adsorption type silane modified polycarboxylate water reducing agent and preparation method thereof |
| CN110128603A (en) * | 2019-06-11 | 2019-08-16 | 云南建投高分子材料有限公司 | Stablize the method for synthesis polycarboxylate water-reducer under cryogenic conditions |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105949402A (en) * | 2016-04-26 | 2016-09-21 | 同济大学 | Anti-sulfate competitive adsorption type silane modified polycarboxylate water reducing agent and preparation method thereof |
| CN105837763A (en) * | 2016-06-04 | 2016-08-10 | 石家庄市长安育才建材有限公司 | Silane polycarboxylate water-reducing agent and preparation method thereof |
| CN110128603A (en) * | 2019-06-11 | 2019-08-16 | 云南建投高分子材料有限公司 | Stablize the method for synthesis polycarboxylate water-reducer under cryogenic conditions |
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Inventor after: Lei Zhen Inventor after: Pei Fei Inventor after: Shi Yu Inventor before: Lei Zhen Inventor before: Wang Qian Inventor before: Li Shaoyan Inventor before: Zheng Yu |
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Effective date of registration: 20220804 Address after: Room 503, Jixiang building, No. 178, south section of Hanguang Road, Yanta District, Xi'an, Shaanxi 710065 Applicant after: Xi'an Institute of quality and standardization Applicant after: China Standardization magazine Co.,Ltd. Address before: Room 503, Jixiang building, No. 178, south section of Hanguang Road, Yanta District, Xi'an, Shaanxi 710065 Applicant before: Xi'an Institute of quality and standardization |
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