CN117903378A - Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof - Google Patents

Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof Download PDF

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Publication number
CN117903378A
CN117903378A CN202311831896.3A CN202311831896A CN117903378A CN 117903378 A CN117903378 A CN 117903378A CN 202311831896 A CN202311831896 A CN 202311831896A CN 117903378 A CN117903378 A CN 117903378A
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China
Prior art keywords
phosphate group
water reducer
acid
polycarboxylic acid
temperature
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CN202311831896.3A
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Chinese (zh)
Inventor
王怀志
仇培云
李旭杰
徐加兵
成志勇
王禹鸥
李方贤
韦江雄
张凯
张百岳
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China Communications Guangzhou Construction Co ltd
Guangzhou Metro Construction Management Co ltd
South China University of Technology SCUT
Guangzhou Metro Group Co Ltd
China Railway Construction South China Construction Co Ltd
China Railway Guangzhou Investment and Development Co Ltd
Original Assignee
China Communications Guangzhou Construction Co ltd
Guangzhou Metro Construction Management Co ltd
South China University of Technology SCUT
Guangzhou Metro Group Co Ltd
China Railway Construction South China Construction Co Ltd
China Railway Guangzhou Investment and Development Co Ltd
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Application filed by China Communications Guangzhou Construction Co ltd, Guangzhou Metro Construction Management Co ltd, South China University of Technology SCUT, Guangzhou Metro Group Co Ltd, China Railway Construction South China Construction Co Ltd, China Railway Guangzhou Investment and Development Co Ltd filed Critical China Communications Guangzhou Construction Co ltd
Priority to CN202311831896.3A priority Critical patent/CN117903378A/en
Publication of CN117903378A publication Critical patent/CN117903378A/en
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Abstract

The invention discloses a preparation method of a polycarboxylic acid water reducer containing phosphate groups, which comprises the following steps: adding isopentenol polyoxyethylene ether into a reaction kettle, adding deionized water, stirring automatically at normal temperature to dissolve completely, adding an aqueous solution of unsaturated carboxylic acid small monomers, a chain transfer agent, an aqueous solution of an initiator and small monomers containing phosphate groups, regulating the temperature of the reaction kettle to 65-70 ℃, and reacting for 2-2.5h at the temperature; and then the temperature is increased to 70-75 ℃, the temperature is kept for 3-3.5h, and the polycarboxylate superplasticizer containing the phosphate group is obtained after cooling to the room temperature, and the preparation process is simple, the reaction is mild, and the pollution is small. The invention also discloses the polycarboxylic acid water reducer containing the phosphate group and the application thereof, which are prepared by the preparation method, and the water reducer has good adaptability to machine-made sand powder, has advantages in aspects of water reduction, slump loss resistance and clay tolerance, and has good application prospect.

Description

Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof
Technical Field
The invention relates to the field of preparation of concrete additives, in particular to a polycarboxylate water reducer containing phosphate groups, and a preparation method and application thereof.
Background
The polycarboxylate water reducer is used as a third-generation water reducer, has the advantages of strong dispersibility for cement concrete, excellent slump retention performance, excellent strength development, good compactness, environmental friendliness, strong structural designability and the like, is widely used by industries, and becomes a necessary technology for manufacturing concrete in modern times. Along with the rapid development of economy, infrastructure construction is also gradually accelerated, the demand for sand is gradually increased, but along with the enhancement of environmental awareness, natural sand is gradually replaced by machine-made sand, and the machine-made sand has the defect of high stone powder content compared with the natural sand. The polycarboxylic acid water reducer on the market in the present stage has weak adaptability to stone powder, and the water reducing effect of the polycarboxylic acid water reducer can be influenced in the using process.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a polycarboxylic acid water reducer containing phosphate groups, which adopts a one-step method, and has the advantages of simple preparation method, mild reaction and small pollution.
The invention also aims to provide the polycarboxylic acid water reducer containing the phosphate groups, which is prepared by the preparation method, and has excellent water reducing, slump retaining and clay tolerance properties.
The invention also aims to provide the application of the polycarboxylic acid water reducer containing the phosphate groups in the preparation of cement concrete mortar containing machine-made sand, and the mortar with good fluidity can be obtained by adding a small amount of the polycarboxylic acid water reducer.
The aim of the invention is achieved by the following technical scheme:
A preparation method of a polycarboxylate water reducer containing phosphate groups comprises the following steps:
Adding isopentenol polyoxyethylene ether into a reaction kettle, adding deionized water, stirring automatically at normal temperature to dissolve completely, adding an aqueous solution of unsaturated carboxylic acid small monomers, an aqueous solution of a chain transfer agent, an aqueous solution of an initiator and a small monomer containing phosphate groups, regulating the temperature of the reaction kettle to 65-70 ℃, and reacting for 2-2.5h at the temperature; then raising the temperature to 70-75 ℃, preserving heat for 3-3.5h, and cooling to room temperature to obtain the polycarboxylate water reducer containing the phosphate group;
the unsaturated carboxylic acid small monomer is acrylic acid or methacrylic acid;
the chain transfer agent is thioglycollic acid, mercaptopropionic acid or mercaptoethanol.
Preferably, the small monomer containing phosphate groups is 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate.
Preferably, the initiator is hydrogen peroxide-ascorbic acid.
Preferably, in the hydrogen peroxide-ascorbic acid, the hydrogen peroxide is 1-1.5% of the total mass of the isopentenol polyoxyethylene ether, the unsaturated carboxylic acid small monomer and the small monomer containing phosphate groups; the mass of the ascorbic acid is 0.2 to 0.5 percent of the total mass of the isopentenol polyoxyethylene ether, the unsaturated carboxylic acid small monomer and the small monomer containing the phosphate group.
Preferably, the mole ratio of the isopentenyl alcohol polyoxyethylene ether to the unsaturated carboxylic acid small monomer is 1: (1-4).
Preferably, the mass of the small monomer containing the phosphate group is 1-3% of the total mass of the isopentenyl alcohol polyoxyethylene ether and the unsaturated carboxylic acid small monomer.
Preferably, the mass of the chain transfer agent is 0.3-0.6% of the total mass of the isopentenyl alcohol polyoxyethylene ether and the unsaturated carboxylic acid small monomer.
The polycarboxylate water reducer containing the phosphate group is prepared by a preparation method of the polycarboxylate water reducer containing the phosphate group.
Preferably, the average molecular weight of the polycarboxylate water reducer containing the phosphate group is 15000-30000.
The application of the polycarboxylic acid water reducer containing the phosphate group is used for preparing cement concrete mortar containing machine-made sand.
Preferably, in the cement concrete mortar containing the machine-made sand, the folding and fixing mixing amount of the polycarboxylic acid water reducer containing the phosphate group is 0.18-0.22%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The preparation method of the polycarboxylic acid water reducer containing the phosphate group is characterized in that the preparation method is synthesized by adopting a one-step method through the isopentenol polyoxyethylene ether, the unsaturated carboxylic acid small monomer, the chain transfer agent, the initiator and the small monomer containing the phosphate group, and has the advantages of simple preparation process, mild reaction and small pollution.
(2) According to the preparation method of the polycarboxylate superplasticizer containing the phosphate groups, the prepared polycarboxylate superplasticizer containing the phosphate groups can be added in a small amount to obtain the mortar with good fluidity.
(3) According to the preparation method of the polycarboxylic acid water reducer containing the phosphate groups, the adsorption groups such as the carboxyl groups and the phosphate groups in the polymer chain are reacted, so that the adsorption of the viscosity-reducing additive to soil can be improved, the expansion of the soil can be inhibited, and the mud resistance of the viscosity-reducing additive can be further improved.
(4) According to the preparation method of the polycarboxylate superplasticizer containing the phosphate groups, the reaction efficiency is improved and the product performance is better through controlling the reaction conditions.
(5) The polycarboxylic acid water reducer containing the phosphate groups introduces the phosphate groups into the polycarboxylic acid structure, enhances the adaptability of the polycarboxylic acid water reducer to machine-made sand powder, has advantages in the aspects of water reduction, slump loss resistance and clay tolerance, and has a good application prospect.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto.
In the examples of the present invention, the weight average molecular weight of the polymer was measured by gel permeation chromatography. (mobile phase is N, N-dimethylamide solution; detector is Agilent 1260II gel chromatograph).
Example 1
100G of isopentenyl alcohol polyoxyethylene ether (with molecular weight of 2400) is added into a reaction kettle, deionized water is added, and stirring is started to completely dissolve the isopentenyl alcohol polyoxyethylene ether; preparing deionized water solution containing 3g of acrylic acid, and preparing deionized water solution containing 0.5g of thioglycollic acid; a deionized water solution containing 0.3g of ascorbic acid and 1.54g of hydrogen peroxide was prepared, and 0.515g of 2-methyl-2-hydroxyethyl 2-acrylate phosphate was weighed. Adding the substances into a reaction kettle, regulating the temperature of the reaction kettle to 65 ℃, reacting for 75min, then, carrying out heat preservation at the temperature of the reaction kettle to 75 ℃ for 3h, and cooling to room temperature after the reaction is finished to obtain the polycarboxylate water reducer product containing the phosphate groups.
The molecular weight of the sample was 16028 by GPC, and the molecular weight distribution was 1.18.
The polycarboxylic acid water reducer containing the phosphate groups, which is prepared in the embodiment, is applied to the preparation of cement concrete mortar containing machine-made sand, and specifically comprises the following steps:
The cement adopted is standard cement (P.O 42.5.5), and the fine aggregate is machine-made sand of rod mill wet crushing and wet sand washing. Mortar fluidity test is performed according to GB/T2419-2009 standard, wherein the water-gel ratio is selected to be 0.5, and the gel-sand ratio is selected to be 1: and 3, slowly stirring the cement paste for 30s, adding machine-made sand in the 30s, then rapidly stirring for 30s, then suspending for 90s, finally rapidly stirring for 60s, and measuring the fluidity of the paste. The test results are shown in Table 1.
When the machine-made sand is limestone machine-made sand, the test results of the machine-made sand using different stone dust (machine-made sand having a particle diameter of less than 0.075 mm) content are shown in table 1.
When the machine-made sand is sandstone machine-made sand, the test results of the machine-made sand using different levels of stone dust (machine-made sand having a particle size of less than 0.075 mm) are shown in table 2.
Example 2
100G of isopentenyl alcohol polyoxyethylene ether (with molecular weight of 2400) is added into a reaction kettle, deionized water is added, and stirring is started to completely dissolve the isopentenyl alcohol polyoxyethylene ether; preparing a deionized water solution containing 6g of acrylic acid, preparing a deionized water solution containing 0.31g of ascorbic acid and 1.59g of hydrogen peroxide, and preparing a deionized water solution containing 0.5g of thioglycollic acid; 0.53g of 2-methyl-2-hydroxyethyl 2-propenoate phosphate was weighed out. Adding the substances into a reaction kettle, regulating the temperature of the reaction kettle to 65 ℃, reacting for 75min, then, carrying out heat preservation at the temperature of the reaction kettle to 75 ℃ for 3h, and cooling to room temperature after the reaction is finished to obtain the polycarboxylate water reducer product containing the phosphate groups.
The molecular weight of the sample was 18407 by GPC and the molecular weight distribution was 1.16.
The polycarboxylic acid water reducer containing the phosphate groups, which is prepared in the embodiment, is applied to the preparation of cement concrete mortar containing machine-made sand, and specifically comprises the following steps:
The cement adopted is standard cement (P.O 42.5.5), and the fine aggregate is machine-made sand of rod mill wet crushing and wet sand washing. Mortar fluidity test is performed according to GB/T2419-2009 standard, wherein the water-gel ratio is selected to be 0.5, and the gel-sand ratio is selected to be 1: and 3, slowly stirring the cement paste for 30s, adding machine-made sand in the 30s, then rapidly stirring for 30s, then suspending for 90s, finally rapidly stirring for 60s, and measuring the fluidity of the paste.
When the machine-made sand is limestone machine-made sand, the test results of the machine-made sand using different stone dust (machine-made sand having a particle diameter of less than 0.075 mm) content are shown in table 1.
When the machine-made sand is sandstone machine-made sand, the test results of the machine-made sand using different levels of stone dust (machine-made sand having a particle size of less than 0.075 mm) are shown in table 2.
Table 1 results of the limestone machine-made sand mortar fluidity test
As can be seen from the results in table 1, the examples of the present invention have better adaptability to machine-made sand with different limestone powder contents, the fluidity change is slower along with the change of the stone powder content, and the fluidity of mortar is better, and thus the water reducer containing phosphate groups has better adaptability.
Table 2 sand flow test results for sandstone machine-made sand slurry
From the results in table 2, the embodiment of the invention has better adaptability to machine-made sand with different sandstone powder contents, the fluidity change is slower along with the change of the stone powder content, the fluidity of mortar is better, and the water reducer containing phosphate groups has better adaptability.
Comparative example 1
100G of isopentenyl alcohol polyoxyethylene ether (with molecular weight of 2400) is added into a reaction kettle, deionized water is added, and stirring is started to completely dissolve the isopentenyl alcohol polyoxyethylene ether; preparing deionized water solution containing 3g of acrylic acid, and preparing deionized water solution containing 0.5g of thioglycollic acid; a deionized water solution containing 0.3g of ascorbic acid and 1.54g of hydrogen peroxide was prepared, and 0.515g of 2-methyl-2-hydroxyethyl 2-acrylate phosphate was weighed. Adding the substances into a reaction kettle, regulating the temperature of the reaction kettle to 60 ℃, reacting for 75min, then, carrying out heat preservation at the temperature of the reaction kettle to 75 ℃ for 3h, and cooling to room temperature after the reaction is finished to obtain the polycarboxylate water reducer product containing the phosphate groups.
The molecular weight of the sample was 14068 and the molecular weight distribution was 1.10 as measured by GPC.
The polycarboxylic acid water reducer containing the phosphate group prepared in the comparative example is applied to the preparation of cement concrete mortar containing machine-made sand, and specifically comprises the following steps:
The cement adopted is standard cement (P.O 42.5.5), and the fine aggregate is machine-made sand of rod mill wet crushing and wet sand washing. Mortar fluidity test is performed according to GB/T2419-2009 standard, wherein the water-gel ratio is selected to be 0.5, and the gel-sand ratio is selected to be 1: and 3, slowly stirring the cement paste for 30s, adding machine-made sand in the 30s, then rapidly stirring for 30s, then suspending for 90s, finally rapidly stirring for 60s, and measuring the fluidity of the paste.
When the folding and solidifying mixing amount of the polycarboxylate water reducer is 1.5%, and sandstone machine-made sand with 5% of stone powder content is adopted, the flow of the polycarboxylate water reducer is 212.0mm; when the folding and solidifying mixing amount of the polycarboxylate water reducer is 0.15%, and when sandstone machine-made sand with 5% of stone powder content is adopted, the mortar fluidity is 165.2mm.
As a result, it was revealed that when the synthesis temperature of the polycarboxylic acid water reducer containing a phosphate group was 60 ℃, the amount of the polycarboxylic acid water reducer containing a phosphate group in examples 1 and 2 was about 1.5% to be added to the concrete containing the sandstone machine-made sand to achieve a fluidity of about 210, whereas the fluidity was only 0.15%.
In the above embodiments, the unsaturated carboxylic acid-based monomer may also be methacrylic acid;
In the above embodiments, the chain transfer agent may also be mercaptopropionic acid or mercaptoethanol.
The embodiments described above are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principles of the present invention should be made in the equivalent manner, and are included in the scope of the present invention.

Claims (10)

1. The preparation method of the polycarboxylate water reducer containing the phosphate group is characterized by comprising the following steps of:
Adding isopentenol polyoxyethylene ether into a reaction kettle, adding deionized water, stirring automatically at normal temperature to dissolve completely, adding an aqueous solution of unsaturated carboxylic acid small monomers, an aqueous solution of a chain transfer agent, an aqueous solution of an initiator and a small monomer containing phosphate groups, regulating the temperature of the reaction kettle to 65-70 ℃, and reacting for 2-2.5h at the temperature; then raising the temperature to 70-75 ℃, preserving heat for 3-3.5h, and cooling to room temperature to obtain the polycarboxylate water reducer containing the phosphate group;
the unsaturated carboxylic acid small monomer is acrylic acid or methacrylic acid;
the chain transfer agent is thioglycollic acid, mercaptopropionic acid or mercaptoethanol.
2. The method for preparing a polycarboxylic acid water reducer containing a phosphate group according to claim 1, wherein the small monomer containing a phosphate group is 2-methyl-2-acrylic acid-2-hydroxyethyl phosphate.
3. The method for preparing a polycarboxylic acid water reducing agent containing a phosphoric acid group according to claim 1, wherein the initiator is hydrogen peroxide-ascorbic acid.
4. The method for preparing a polycarboxylic acid water reducer containing a phosphate group according to claim 3, wherein the mass of hydrogen peroxide oxide in the hydrogen peroxide-ascorbic acid is 1-1.5% of the total mass of the isopentenyl alcohol polyoxyethylene ether, the unsaturated carboxylic acid small monomer and the phosphate group small monomer; the mass of the ascorbic acid is 0.2 to 0.5 percent of the total mass of the isopentenol polyoxyethylene ether, the unsaturated carboxylic acid small monomer and the small monomer containing the phosphate group.
5. The method for preparing the polycarboxylic acid water reducer containing the phosphate group according to claim 1, wherein the molar ratio of the isopentenyl alcohol polyoxyethylene ether to the unsaturated carboxylic acid small monomer is 1: (1-4).
6. The method for preparing a polycarboxylic acid water reducer containing a phosphate group according to claim 1 or 5, wherein the mass of the small monomer containing the phosphate group is 1% -3% of the total mass of the isopentenyl alcohol polyoxyethylene ether and the small monomer containing the unsaturated carboxylic acid.
7. The method for preparing a polycarboxylic acid water reducer containing a phosphate group according to claim 1, wherein the mass of the chain transfer agent is 0.3-0.6% of the total mass of the isopentenyl alcohol polyoxyethylene ether and the unsaturated carboxylic acid small monomer.
8. A polycarboxylic acid water reducing agent containing a phosphate group, characterized by being prepared by the preparation method of the polycarboxylic acid water reducing agent containing a phosphate group as described in any one of claims 1 to 7.
9. The polycarboxylic acid water reducing agent containing a phosphoric acid group according to claim 8, wherein the medium average molecular weight is 15000 to 30000.
10. Use of the polycarboxylic acid water reducer containing phosphate groups according to claim 8 or 9 for the preparation of cement concrete mortars containing machine-made sand.
CN202311831896.3A 2023-12-28 2023-12-28 Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof Pending CN117903378A (en)

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