CN111978484A - 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 PDF

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CN111978484A
CN111978484A CN202010942758.2A CN202010942758A CN111978484A CN 111978484 A CN111978484 A CN 111978484A CN 202010942758 A CN202010942758 A CN 202010942758A CN 111978484 A CN111978484 A CN 111978484A
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polyoxyethylene ether
silane
water
reducing agent
solution
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CN111978484B (en
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雷震
王迁
李少岩
郑宇�
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China Standardization Magazine Co ltd
Xi'an Institute Of Quality And Standardization
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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
    • 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
    • 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
    • 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 reducing agent containing 4-hydroxybutyl polyoxyethylene ether, which is prepared by adding initiator ammonium persulfate, chain transfer agent thioglycolic acid and water into polyoxyethylene ether A, polyoxyethylene ether B, acrylic acid and silane C as polymerization monomers; and discloses a preparation method of the water reducing agent. The application of the invention can obviously improve the fluidity of the slurry, the retentivity and the compressive strength of the concrete.

Description

Silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether
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 essential chemical admixture for improving slag-based cementing materials and concrete products, and can obviously improve the comprehensive properties of the products such as workability, compactness, strength, durability and the like under the condition of lower water-cement ratio.
The polycarboxylate superplasticizer is used as a third-generation water reducer product, has strong designability of molecular structure and high potential of high performance, and can be copolymerized by selecting monomers with different functions to prepare a multifunctional product. However, in recent years, the quality problems of cement, mineral admixture, coarse aggregate, fine aggregate and the like are serious, and in addition, the problems that the polycarboxylic acid water reducing agent is not suitable for concrete and fresh concrete is easy to bleed, separate, collapse and damage too fast due to the fact that cement in China is various in varieties and engineering mixing ratios are various are often caused. Therefore, through the research of molecular structure design, synthesis process and action mechanism, the functionality of the polycarboxylate superplasticizer is continuously improved, so that the polycarboxylate superplasticizer has good adaptability to different cements, mineral admixtures, poor-quality sandstone materials and the like, which has become the key point of domestic and foreign research.
At present, the domestic and foreign research on the polycarboxylic acid water reducing agent mainly focuses on the following aspects: (1) research on polymer synthesis methods and processes; (2) exploring the relation between the structure and the performance; (3) designing polymer molecules through the existing theoretical basis; (4) the action mechanism of the water reducing agent is presumed according to the relationship between the structure and the performance; (5) gradually explores a new process for synthesizing the water reducer with better performance through the guidance of action mechanism and research rule. Due to the diversity of molecular structure design of the polycarboxylic acid water-reducing agent and the inevitable relation between the structure and the performance, the research in the field is very active, and the number of novel high-performance polycarboxylic acid water-reducing agents is large.
A typical polycarboxylate water reducing agent is a graft copolymer with surface activity, which has a comb-shaped structure and usually consists of two basic components, namely a main chain and a side chain. The main chain of the water reducing agent generally contains a large number of ionizable carboxyl groups, and after the carboxyl groups are ionized in water, the water reducing agent molecules are adsorbed and anchored on the surfaces of cement particles through the action force among ions, so that electrostatic repulsion 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 the relative molecular weight of 500-3000, and the side chain can be fully extended in water, so that steric hindrance repulsion is provided for cement particles, and the dispersibility of the cement particles is improved. The combined action of the two repulsion 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
One of the purposes of the invention is to provide a silicon-containing magnetic polycarboxylate water reducer containing 4-hydroxybutyl polyoxyethylene ether.
The invention also aims to provide a preparation method of the silicon-containing magnetic polycarboxylate superplasticizer containing 4-hydroxybutyl polyoxyethylene ether.
In order to achieve the purpose, the invention adopts the following technical scheme:
a silicon-containing polycarboxylic acid water reducing agent is characterized in that: the polyether-modified acrylic acid 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 thioglycolic acid and water, and comprises the following components in parts by weight:
10-20 parts of polyoxyethylene ether A
10-20 parts of polyoxyethylene ether B
40-60 parts of acrylic acid
10-20 parts of silane C
0.3 to 1 portion of ammonium persulfate
0.15 to 0.25 portion of 3-mercaptoacetic acid
100 portions of deionized water and 400 portions;
the polyoxyethylene ether A has the structure as follows:
Figure BDA0002674194190000021
wherein n is 20 to 50;
the polyoxyethylene ether B is 4-hydroxybutyl polyoxyethylene ether, and the number of the polyoxyethylene repeating units is 150-300;
the structure of the silane C is as follows:
Figure BDA0002674194190000031
the silane C can be obtained by the reaction of silane D and ferroferric oxide, and the structure of the silane D is
Figure BDA0002674194190000032
Further, silane D is obtained by reacting a silane monomer having an amino group and an alkoxy group with maleic anhydride, and then adding further alkoxysilane for hydrolysis.
Further, the number of the 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 of polyoxyethylene ether a is 30 to 40.
The preparation method of the water reducing agent is characterized by comprising the following steps: all the components are subjected to initiator polymerization reaction under the action of an initiator, and the water reducer is obtained after post-treatment.
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 at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping 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, dripping for 3.0 hours at the temperature of 60 ℃, preserving heat for reaction for 1.0 hour at the temperature of 60 ℃ after dripping is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain the polycarboxylic acid water reducing agent.
Furthermore, the application of the water reducing agent is used in cement to obtain magnetic cement.
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, the hydroxysilane C contains the nano ferroferric oxide surface and active hydroxyl for condensation, more ferroferric oxide particles are introduced, the steric hindrance effect of inorganic particles is better played, the ferroferric oxide provides the magnetic effect, and the performance of the water reducing agent is improved; particularly, the fluidity of the slurry, the retentivity and the compressive strength of the concrete are effectively improved, and small molecular monomers such as acrylamide, sodium methylacrylsulfonate and the like do not need to be added into the monomers.
The invention has the beneficial effects that:
(1) the invention can effectively improve the fluidity and the retentivity of the slurry and the compressive strength of the concrete.
(2) The invention has the advantages of simple and feasible process, obvious product effect and good engineering application prospect.
Detailed Description
The following are specific embodiments of the present invention, and the technical solutions of the present invention are 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 at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping 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, dripping for 3.0 hours at the temperature of 60 ℃, preserving heat at the temperature of 60 ℃ after dripping is finished, reacting for 1.0 hour, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain the polycarboxylic acid water reducing agent.
The polyoxyethylene ether A has the structure that:
Figure BDA0002674194190000041
wherein n is 35, the polyoxyethylene ether B is 4-hydroxybutyl polyoxyethylene ether, and the number of repeating units is 200;
the dosage of each component is as follows:
15 portions of polyoxyethylene ether A
15 portions of polyoxyethylene ether B
Acrylic acid 50 parts
Silane C15 parts
0.5 part of ammonium persulfate
0.2 part of 3-mercaptoacetic acid
300 parts of deionized water;
example 2
The procedure was repeated as in example 1 except that n of polyoxyethylene ether A was 20.
Example 3
The procedure was repeated as in example 1 except that n of polyoxyethylene ether A alone was changed to 50.
Example 4
The other examples were the same as example 1 except that the number of the repeating units of polyoxyethylene ether B alone was 100.
Example 5
The other examples were the same as example 1 except that the number of the repeating units of polyoxyethylene ether B alone was 250.
Example 6
The procedure is as in example 1 except that silane C is not added.
Example 7
The procedure is as in example 1 except that polyoxyethylene ether A is not added.
Example 8
The procedure is as in example 1 except that polyoxyethylene ether B is not added.
The method comprises the steps of measuring the fluidity of the net slurry by using the organic-inorganic hybrid polycarboxylic acid water reducing agent in the embodiments 1-8 according to GB/T8077-: reference cement 360Kg/m3792Kg/m of sand3290Kg/m of small stone3(5-10 mm), 678Kg/m of rubble3(10-20 mm) and the water-to-glue ratio is 0.4. The results of the experiment are shown in the following table:
Figure BDA0002674194190000051
Figure BDA0002674194190000061
as can be seen from the above table, the water reducing agent of the present invention has good effects in improving the fluidity of the slurry and the retentivity and compressive strength of the concrete.

Claims (8)

1. A silicon-containing magnetic polycarboxylate superplasticizer is characterized in that: the polyether-modified acrylic acid 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 thioglycolic acid and water, and comprises the following components in parts by weight:
10-20 parts of polyoxyethylene ether A
10-20 parts of polyoxyethylene ether B
40-60 parts of acrylic acid
10-20 parts of silane C
0.3 to 1 portion of ammonium persulfate
0.15 to 0.25 portion of 3-mercaptoacetic acid
100 portions of deionized water and 400 portions;
the polyoxyethylene ether A has the structure as follows:
Figure FDA0002674194180000011
wherein n is 20 to 50;
the polyoxyethylene ether B is 4-hydroxybutyl polyoxyethylene ether, and the number of the polyoxyethylene repeating units is 150-300;
the structure of the silane C is as follows:
Figure FDA0002674194180000012
2. the water reducing agent according to claim 1, characterized in that: the silane C is obtained by the reaction of silane D and nano ferroferric oxide, and the structure of the silane D is
Figure FDA0002674194180000021
3. The water reducing agent according to claim 2, wherein silane D is prepared by reacting silane monomer with amino and alkoxy with maleic anhydride, and then adding alkoxy silane for hydrolysis.
4. The water-reducing agent according to claim 1 to 3, wherein the number of the polyoxyethylene repeating units in the polyoxyethylene ether B is 200-250.
5. The water reducer according to claims 1 to 4, wherein n-30 to 40 of polyoxyethylene ether A.
6. A preparation method for preparing the water reducing agent of claims 1-5 is characterized by comprising the following steps: all the components are subjected to initiator polymerization reaction under the action of an initiator, and the water reducer is obtained after post-treatment.
7. The method of claim 6, wherein: adding polyoxyethylene ether A, polyoxyethylene ether B and deionized water into a reaction kettle, and heating and dissolving at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping 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, dripping for 3.0 hours at the temperature of 60 ℃, preserving heat for reaction for 1.0 hour at the temperature of 60 ℃ after dripping is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; and adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain the polycarboxylic acid water reducing agent.
8. Use of the water reducer of claim 1 in cement to obtain magnetic cement.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031729A (en) * 2021-12-14 2022-02-11 山西凯迪建材有限公司 Preparation method of high-efficiency powdery water reducing agent with siloxane structure

Citations (3)

* Cited by examiner, † Cited by third party
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114031729A (en) * 2021-12-14 2022-02-11 山西凯迪建材有限公司 Preparation method of high-efficiency powdery water reducing agent with siloxane structure

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