CN115894910A - Doped monomer and preparation method and application thereof - Google Patents
Doped monomer and preparation method and application thereof Download PDFInfo
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- CN115894910A CN115894910A CN202211683827.8A CN202211683827A CN115894910A CN 115894910 A CN115894910 A CN 115894910A CN 202211683827 A CN202211683827 A CN 202211683827A CN 115894910 A CN115894910 A CN 115894910A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a sensitivity-doped monomer and a preparation method and application thereof. The preparation raw materials of the doped sensitive monomer comprise the following components in parts by weight: 355-710 parts of 2, 2-dimethyl aziridine; 86-172 parts of a catalyst; and 11-33 parts of methacrylic acid. According to the invention, the doped sensitive monomer is introduced into the side chain of the water reducer, so that the density of the adsorption group of the water reducer can be automatically adjusted along with the change of the doping amount, and the water reducer shows approximate dispersion and dispersion retention capability under different doping amounts, so that the prepared water reducer shows high adaptability to different doping amounts, and the application range of the polycarboxylic acid water reducer is expanded.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a sensitivity-doped monomer and a preparation method and application thereof.
Background
In recent years, the polycarboxylic acid water reducing agent is widely applied, has high water reducing rate, higher cost performance, excellent slump retaining performance and good construction performance of mixtures, and is widely accepted in the application process.
But the dispersing ability of the polycarboxylate superplasticizer is limited by the quality fluctuation of raw materials such as cement, fly ash, sand and stone, the mixing amount of the polycarboxylate superplasticizer changes greatly along with the quality fluctuation, and the polycarboxylate superplasticizer shows high sensitivity, and can only achieve the saturated mixing amount of the polycarboxylate superplasticizer to play a good water reducing effect; on the contrary, too large mixing amount will cause segregation and bleeding to reduce the water reducing and enhancing effects, which is not beneficial to the control of the mixing amount of the water reducing agent in the concrete mixing process.
Disclosure of Invention
Based on the above, a need exists for a doped monomer, a preparation method and an application thereof, aiming at solving the problem that the traditional water reducing agent is sensitive to the doping amount.
In order to achieve the above purpose, the invention provides a technical scheme:
the photosensitive monomer is prepared from the following raw materials in parts by weight:
355-710 parts of 2, 2-dimethyl aziridine;
11-33 parts of a catalyst; and
86-172 parts of methacrylic acid.
Preferably, the structure of the doped monomer is as follows:
wherein n is an integer.
The catalyst comprises p-toluenesulfonic acid.
The invention also provides a preparation method of the photosensitive-doped monomer, which comprises the following steps:
adding the catalyst into the 2, 2-dimethyl aziridine to carry out ring-opening polymerization reaction to obtain a polymerization intermediate;
and carrying out condensation reaction on the polymerization intermediate and the methacrylic acid to obtain the doped sensitive monomer.
Preferably, the reaction temperature of the condensation reaction is 60 to 80 ℃.
Preferably, the reaction time of the condensation reaction is 3 to 5 hours.
The invention also provides an application of the sensitivity-doped monomer in a water reducing agent, and a preparation raw material of the water reducing agent comprises the sensitivity-doped monomer.
Preferably, the water reducing agent is prepared from the following raw materials in parts by weight:
preferably, the structural formula of the water reducing agent is as follows:
wherein a, b, c, m and n are integers, a: b: c: m: n =1: (3-6): (2-6): (60-120): (10-30).
Preferably, the preparation step of the water reducing agent comprises:
mixing the sensitivity-doped monomer and the polyether monomer to obtain a mixed solution;
and (3) dropwise adding an unsaturated acid monomer solution, an initiator solution and a chain transfer solution into the mixed solution, keeping the temperature for reaction for 0.5-1.5 h after the dropwise adding is finished, adding liquid alkali after the reaction is finished, and adjusting the pH value of the solution to 6-8 to obtain the water reducer.
The invention has the beneficial effects that:
according to the invention, the sensitivity-doped monomer is introduced into the side chain of the water reducer, and due to the design of the number of the cationic active groups (containing N groups) on the main chain of the sensitivity-doped monomer, the density of the adsorption groups of the water reducer can be automatically adjusted along with the change of the doping amount, so that the water reducer shows approximate dispersion and dispersion retention capacity under different doping amounts, the prepared water reducer shows high adaptability to different doping amounts, and the application range of the polycarboxylic acid water reducer is expanded.
Detailed Description
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention.
In the examples, the test methods used were conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
A photosensitive monomer is prepared from the following raw materials in parts by weight:
355-710 parts of 2, 2-dimethyl aziridine;
11-33 parts of a catalyst; and
86-172 parts of methacrylic acid.
Preferably, the structure of the doped monomer is as follows:
wherein n is an integer.
Specifically, the catalyst comprises p-toluenesulfonic acid.
The invention also provides a preparation method of the photosensitive-doped monomer, which comprises the following steps:
adding a catalyst into 2, 2-dimethyl aziridine to carry out ring-opening polymerization reaction, wherein the reaction time of the ring-opening polymerization reaction is 3-5 h, and obtaining a polymerization intermediate;
and carrying out condensation reaction on the polymerization intermediate and methacrylic acid, wherein the reaction temperature of the condensation reaction is 60-80 ℃, and the reaction time of the condensation reaction is 3-5 h, so as to obtain the sensitized monomer.
The invention also provides an application of the photosensitive monomer in the water reducing agent, and the raw material for preparing the water reducing agent comprises the photosensitive monomer.
In one embodiment, the water reducing agent is prepared from the following raw materials in parts by weight:
in some embodiments, the polyether monomer comprises at least one of ethylene glycol monovinyl polyethylene glycol ether (EPEG), allyl polyoxyethylene ether, methallyl polyoxyethylene ether, polyethylene glycol monomethyl ether, and prenol polyoxyethylene ether, and more particularly, the polyether monomer has a molecular weight of 3000 to 5000.
The initiator comprises an oxidant and a reducing agent, wherein the oxidant comprises at least one of hydrogen peroxide, ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide. The reducing agent comprises at least one of sodium formaldehyde sulfoxylate, sodium sulfite, sodium metabisulfite and L-sodium ascorbate.
The chain transfer agent comprises at least one of thioglycolic acid, mercaptopropionic acid, and hydroxyethyl acrylate.
Preferably, the water reducing agent has the following structural formula:
wherein a, b, c, m and n are integers, a: b: c: m: n =1: (3-6): (2-6): (60-120): (10-30).
In some embodiments, the step of preparing the water reducer comprises:
mixing a sensitivity-doped monomer and a polyether monomer to obtain a mixed solution;
controlling the initial reaction temperature at 15-20 ℃, dropwise adding the unsaturated acid monomer solution, the initiator solution and the chain transfer solution into the mixed solution for 1-1.5 h, keeping the temperature for reaction for 0.5-1.5 h after dropwise adding, adding liquid alkali after the reaction is finished, and adjusting the pH of the solution to 6-8 to obtain the water reducer.
Example 1
400g of 2, 2-dimethyl aziridine and 15g of p-toluenesulfonic acid are added into a glass flask provided with a thermometer and a stirrer, the mixture reacts for 3 hours under the stirring condition, 90g of methacrylic acid is added, the mixture is heated to 70 ℃, and the reaction is continued for 5 hours to obtain the doping amount sensitive monomer A.
Adding 150g of macromonomer EPEG,6g of the doping amount sensitive monomer A,1.2g of hydrogen peroxide and water into a reaction kettle, controlling the temperature at 15 ℃, then respectively dripping a sodium formaldehyde sulfoxylate aqueous solution, a thioglycolic acid aqueous solution and an acrylic acid aqueous solution within 1h, and preserving heat for 1h after dripping to obtain a reaction product with the concentration of 50%; adjusting the pH of the reaction product to 6.0-7.0 by using sodium hydroxide to obtain a water reducing agent;
wherein 0.4g of sodium formaldehyde sulfoxylate aqueous solution is dissolved in 150g of water, 0.3g of thioglycolic acid aqueous solution is dissolved in 150g of water, and 15g of acrylic acid aqueous solution is dissolved in 180g of water. The molecular weight of EPEG is 5000.
Example 2
500g of 2, 2-dimethyl aziridine and 20g of p-toluenesulfonic acid are added into a glass flask provided with a thermometer and a stirrer, the mixture reacts for 3 hours under the stirring condition, 105g of methacrylic acid is added, the mixture is heated to 80 ℃, and the reaction is continued for 4 hours to obtain the doping amount sensitive monomer A.
Adding 160g of macromonomer EPEG,8g of the doping amount sensitive monomer A,1.5g of hydrogen peroxide and water into a reaction kettle, controlling the temperature at 15 ℃, then respectively dripping a sodium formaldehyde sulfoxylate aqueous solution, a thioglycolic acid aqueous solution and an acrylic acid aqueous solution within 1h, and preserving heat for 1h after dripping to obtain a reaction product with the concentration of 50%; adjusting the pH of the reaction product to 6.0-7.0 by using sodium hydroxide to obtain a water reducing agent;
wherein 0.5g of sodium formaldehyde sulfoxylate aqueous solution is dissolved in 150g of water, 0.5g of thioglycolic acid aqueous solution is dissolved in 150g of water, and 18g of acrylic acid aqueous solution is dissolved in 180g of water. The molecular weight of EPEG is 4000.
Example 3
Adding 700g of 2, 2-dimethyl aziridine and 30g of p-toluenesulfonic acid into a glass flask provided with a thermometer and a stirrer, reacting for 3 hours under the condition of stirring, adding 170g of methacrylic acid, heating to 60 ℃, and continuing to react for 3 hours to obtain the doping amount sensitive monomer A.
Adding 180g of macromonomer EPEG,10g of the doping amount sensitive monomer A,3.0g of hydrogen peroxide and water into a reaction kettle, controlling the temperature at 15 ℃, then respectively dripping a sodium formaldehyde sulfoxylate aqueous solution, a thioglycolic acid aqueous solution and an acrylic acid aqueous solution within 1h, and preserving heat for 1h after dripping to obtain a reaction product with the concentration of 50%; adjusting the pH of the reaction product to 6.0-7.0 by using sodium hydroxide to obtain a polycarboxylic acid water reducing agent;
wherein 0.6g of sodium formaldehyde sulfoxylate aqueous solution is dissolved in 150g of water, 0.7g of thioglycolic acid aqueous solution is dissolved in 150g of water, and 20g of acrylic acid aqueous solution is dissolved in 180g of water. The molecular weight of EPEG is 3000.
Comparative example 1
Adding 150g of macromonomer EPEG,1.2g of hydrogen peroxide and water into a reaction kettle, controlling the temperature at 15 ℃, then respectively dropwise adding a sodium formaldehyde sulfoxylate aqueous solution, a thioglycolic acid aqueous solution and an acrylic acid aqueous solution within 1h, and preserving heat for 1h after dropwise adding is finished to obtain a reaction product with the concentration of 50%; adjusting the pH of the reaction product to 6.0-7.0 by using sodium hydroxide to obtain a polycarboxylic acid water reducing agent;
wherein 0.4g of sodium formaldehyde sulfoxylate aqueous solution is dissolved in 150g of water, 0.3g of thioglycolic acid aqueous solution is dissolved in 150g of water, and 15g of acrylic acid aqueous solution is dissolved in 180g of water. The molecular weight of EPEG is 5000.
A total organic carbon analyzer is adopted to test the adsorption rate of the polycarboxylic acid water reducing agent prepared in the embodiment and the comparative example under different doping amounts, and the specific method is as follows:
weighing 100g of cement, 100g of deionized water and a water reducing agent (folded solids) in a beaker respectively, adding magnetons, starting magnetic stirring, sampling and centrifuging at different time points (5 minutes and 90 minutes) to obtain supernatant, testing the carbon content by using a total organic carbon analyzer, comparing with a blank sample, and obtaining the actual adsorption rate by using a differential method.
Table 1 adsorption performance test results
As can be seen from Table 1, at 5min, after the introduction of the doping monomer, the water absorptions of the water reducers of examples 1 to 3 and comparative example 1 were 21 to 24% under the condition of low doping amount of the water reducer (1.0%), the water absorptions of the water reducers of examples 1 to 3 were slightly increased to about 24% when the doping amount of the water reducer was 1.5%, and the water absorptions of the water reducers of examples 1 to 3 were finally about 26% when the doping amount of the water reducer was further increased to 2.0%.
The difference between the comparative example 1 and the examples 1 to 3 is that no sensitive monomer is doped, and as can be seen from the data in Table 1, the adsorption rate of the common water reducing agent is only 21.8% under the condition that the doping amount of the water reducing agent is 1.0% at 5min, and the adsorption rate is increased to about 39.9% at the doping amount of the water reducing agent is 2.0%.
The data fully show that the adsorption rate of the prepared polycarboxylic acid water reducing agent is only changed by about 3 percent when the mixing amount of the water reducing agent is changed from 1.0 percent to 2.0 percent, while the adsorption rate of the ordinary water reducing agent without adding the sensitive monomer is changed by more than 18 percent when the mixing amount of the water reducing agent is changed from 1.0 percent to 2.0 percent. Therefore, the polycarboxylate water reducer prepared by the invention can dynamically adjust the density of the adsorption group along with the change of the doping amount of the water reducer, so that the influence of the doping amount of the water reducer on the adsorption behavior is compensated, and the change of the adsorption behavior of the water reducer is not too large in a wider doping amount range.
In order to compare the dispersing performance and the dispersion retention performance of the polycarboxylate water reducer prepared by the invention under different mixing amounts, a cement paste fluidity test is carried out according to the GB/T8077 standard, 300g of cement is obtained, the water adding amount is 87g, the folding and fixing mixing amounts of the polycarboxylate water reducer are 0.12% except for special instructions, the cement paste fluidity is measured on the plate glass after stirring, the paste fluidity after different time is tested, and the experimental results are shown in Table 2.
TABLE 2 neat paste fluidity test results
As can be seen from the above table, after the introduction of the monomers, the initial fluidity (5 min) of the water-reducing agent neat cements of examples 1-3 and comparative example 1 was substantially about 200mm at the water-reducing agent addition of 1.0%, gradually increased with the water-reducing agent addition, the initial fluidity of the water-reducing agent neat cements of examples 1-3 was substantially about 210mm when the water-reducing agent addition was 1.5%, whereas the initial fluidity of the water-reducing agent neat cement of comparative example 1 was increased to 240mm, and further increased with the water-reducing agent addition, the fluidity of the water-reducing agent neat cements of examples 1-3 was substantially about 220mm when the water-reducing agent addition was 2.0%, whereas the initial fluidity of the water-reducing agent neat cement of comparative example 1 was increased to 260mm. The difference between the comparative example 1 and the examples 1-3 is that no sensitive monomer is added in the comparative example 1, and the dispersing efficiency of the common water reducing agent without the sensitive monomer is greatly influenced by the addition amount of the water reducing agent.
In addition, as can be seen from the fluidity data of the cement paste at 90min in the table, the fluidity degree of the cement paste at 90min of the water reducing agent in the examples 1 to 3 is reduced to 5 to 20mm relative to the fluidity degree of the cement paste at 5min, which shows that the loss of the fluidity of the water reducing agent in the examples 1 to 3 of the invention with time is small, so that the water reducing agent prepared by the invention has good dispersion retention performance and small fluctuation, the fluidity of the cement paste is not changed greatly along with the increase of the mixing amount of the water reducing agent, and the polycarboxylate water reducing agent has low sensitivity to the mixing amount of the water reducing agent.
It should be noted that the specific parameters or some reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
Claims (10)
1. The sensitivity-doped monomer is characterized in that the sensitivity-doped monomer is prepared from the following raw materials in parts by weight:
355-710 parts of 2, 2-dimethyl aziridine;
11-33 parts of a catalyst; and
86-172 parts of methacrylic acid.
2. The doped monomer of claim 1, wherein the doped monomer has the following structural formula:
wherein n is an integer.
3. The sensitized monomer according to claim 1, wherein said catalyst comprises p-toluenesulfonic acid.
4. A process for the preparation of a doped monomer according to any one of claims 1 to 3, comprising the steps of:
adding the catalyst into the 2, 2-dimethyl aziridine to carry out ring-opening polymerization reaction to obtain a polymerization intermediate;
and carrying out condensation reaction on the polymerization intermediate and the methacrylic acid to obtain the photosensitive monomer.
5. The method for preparing the sensitivity-doped monomer according to claim 4, wherein the reaction temperature of the condensation reaction is 60-80 ℃.
6. The method for preparing the monomer doped with the photosensitizer as claimed in claim 4, wherein the reaction time of the condensation reaction is 3-5 h.
7. The use of the sensitivity-doped monomer in the water reducer according to any one of claims 1 to 3, wherein the water reducer is prepared from raw materials comprising the sensitivity-doped monomer.
8. The application of the sensitivity-doped monomer according to claim 7, wherein the water reducer is prepared from the following raw materials in parts by weight:
9. the use of the monomers according to claim 7, wherein the water reducing agent has the following formula:
wherein a, b, c, m and n are integers, a: b: c: m: n =1: (3-6): (2-6): (60-120): (10-30).
10. The use of the monomer of claim 8, wherein the water reducing agent is prepared by the steps of:
mixing the sensitivity-doped monomer and the polyether monomer to obtain a mixed solution;
and (3) dropwise adding an unsaturated acid monomer solution, an initiator solution and a chain transfer solution into the mixed solution, keeping the temperature for reaction for 0.5-1.5 h after the dropwise adding is finished, adding liquid alkali after the reaction is finished, and adjusting the pH value of the solution to 6-8 to obtain the water reducer.
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| CN114166692A (en) * | 2021-12-01 | 2022-03-11 | 浙江华威混凝土有限公司 | Comprehensive evaluation method for performance of water reducing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114166692A (en) * | 2021-12-01 | 2022-03-11 | 浙江华威混凝土有限公司 | Comprehensive evaluation method for performance of water reducing agent |
| CN114166692B (en) * | 2021-12-01 | 2024-05-28 | 浙江华威混凝土有限公司 | Comprehensive evaluation method for performance of water reducer |
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