Organic polymer as well as preparation method and application thereof
By using an organic polymer in cement mortar, the activity of limestone powder is stimulated, and it participates in the hydration reaction to generate a product with gelling properties, the problem of high content of limestone powder affecting the early strength of cement mortar is solved, the mechanical properties of cement mortar are improved, and energy conservation, emission reduction and resource utilization are achieved.
Patent Information
- Application Number
- CN202510103160.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-22
- Publication Date
- 2025-05-27
AI Technical Summary
In the prior art, the high content of limestone powder will affect the early strength of the silicate cement-based material system, resulting in the cement mortar being prone to water secretion, deterioration of the viscosity, and affecting the working performance and quality of the cement material.
An organic polymer is used, and the preparation raw materials include unsaturated alcohol amine esterified, cationic monomer, chain transfer agent, oxidant and reducing agent. Through the reaction of these raw materials, the potential activity of limestone powder is stimulated, so that it participates in the hydration reaction, and produces products with gelling properties, such as C-S-H gel, C-A-S-H gel and N-A-S-H gel, etc., thereby improving the mechanical properties of cement mortar.
By allowing limestone powder to participate in the hydration reaction, the mechanical properties of cement mortar are improved, the working performance and quality of cement materials are ensured, and the comprehensive cost of cement mortar is reduced, energy conservation and emission reduction and resource utilization of solid waste are achieved.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of building material additives, and particularly relates to an organic polymer, a preparation method thereof, and an application thereof. Background Art
[0002] A large amount of carbon emissions are generated during the cement production process. With the enhancement of environmental awareness and the development of low-carbon economy, while solving the increasingly tense resource problem of natural sand and gravel due to over-exploitation, waste recycling of limestone is carried out, and limestone powder is used as a blended material for portland cement. On the premise of ensuring that the strength and workability of the cement mortar are not affected, by using limestone powder in the cement mortar and reducing the amount of cement used, not only the dual goals of promoting energy conservation, emission reduction and resource utilization of solid waste are promoted, but also the comprehensive cost of the cement mortar can be significantly reduced, achieving a win-win situation of economic benefits and environmental responsibility.
[0003] As an inert blended material, limestone powder does not participate in the hydration reaction. If its content is too high, it will affect the early strength of the portland cement-based material system, resulting in negative problems such as easy bleeding of the cement mortar and poor cohesiveness, which affect the workability and quality of the cement material. Summary of the Invention
[0004] The present invention aims to solve at least one of the technical problems in the prior art to some extent. For this reason, an object of the present invention is to provide an organic polymer, a preparation method thereof, and an application thereof.
[0005] In a first aspect of the present invention, an organic polymer is provided. In terms of parts by weight, the raw materials for preparing the organic polymer include: 20-30 parts of unsaturated alcohol amine ester, 20-30 parts of cationic monomer, 0.2-0.5 part of chain transfer agent, 0.1-0.5 part of oxidizing agent, and 0.1-0.5 part of reducing agent; The raw materials for preparing the unsaturated alcohol amine ester include: unsaturated acid, alcohol amine, polymerization inhibitor, catalyst and water. The molar ratio of the unsaturated acid to the alcohol amine is (0.2-1.2):1. For example, the molar ratio is 0.2:1, 0.4:1, 0.6:1, 0.8:1, 1.0:1, 1.2:1, etc., or the range between any two of the above values.
[0006] According to the above-mentioned organic polymer provided by the present invention, first, unsaturated acid and alkanolamine react under the action of an inhibitor and a catalyst to obtain a modified alkanolamine (unsaturated alkanolamine ester), and then an organic polymer prepared by using the unsaturated alkanolamine ester and cationic monomers can make limestone powder participate in the reaction, stimulate its latent activity, and make it participate in the hydration reaction to generate products with gelling properties, such as C-S-H gel, C-A-S-H gel, and N-A-S-H gel, etc., thereby improving the mechanical properties of the final cement mortar. In particular, the inventors found that by controlling the addition amounts of the unsaturated alkanolamine ester, cationic monomers, etc. within the above ranges, the ability of limestone powder to participate in the reaction can be effectively improved, the gel property and the degree of polymerization can be increased, and thus the excellent mechanical properties of the final cement mortar are ensured.
[0007] According to the organic polymer provided by the present invention, based on the total mass of the raw materials for preparing the unsaturated alkanolamine ester, the mass ratio of water is 5-15%. For example, the mass ratio of water is 5%, 8%, 10%, 12%, 15%, etc., or the range between any two of the above values. By controlling the mass ratio of water within the above range, a more appropriate concentration can be adjusted, which is beneficial to free radical copolymerization.
[0008] According to the organic polymer provided by the present invention, based on the total mass of the raw materials for preparing the unsaturated alkanolamine ester, the mass ratio of the inhibitor is 0.5-2.0%.
[0009] According to the organic polymer provided by the present invention, based on the total mass of the raw materials for preparing the unsaturated alkanolamine ester, the mass ratio of the catalyst is 0.5-2.0%.
[0010] In some embodiments of the present invention, the unsaturated acid is selected from one or more of methacrylic acid, fumaric acid, maleic anhydride, and acrylic acid.
[0011] In some embodiments of the present invention, the alkanolamine is selected from one or more of diethanolamine, triethanolamine, and diethanol monoisopropanolamine.
[0012] In some embodiments of the present invention, the inhibitor is selected from one or more of hydroquinone and 98% concentrated sulfuric acid.
[0013] In some embodiments of the present invention, the catalyst is selected from one or more of 98% concentrated sulfuric acid, sulfamic acid, sodium acetate, and 1,3-dicyclohexylcarbodiimide.
[0014] According to the organic polymer provided by the present invention, the method for preparing the unsaturated alkanolamine ester includes: mixing and dissolving the alkanolamine, the inhibitor, and the water, then slowly adding the mixture of the unsaturated acid and the catalyst, and then reacting at 100-120°C for 4-6 hours.
[0015] In some embodiments of the present invention, based on 100 parts by weight, the raw materials for preparation include: 20 to 30 parts of the unsaturated alcohol amine ester, 20 to 30 parts of the cationic monomer, 0.2 to 0.5 parts of the chain transfer agent, 0.1 to 0.5 parts of the oxidant, 0.1 to 0.5 parts of the reducing agent and the remainder water.
[0016] In some embodiments of the present invention, the cationic monomer is selected from one or more of methylpropionyloxyethyl trimethyl ammonium chloride and dimethyl diallyl ammonium chloride. By selecting the above-mentioned cationic monomers, it is more conducive to improving the reaction degree of limestone powder and cement hydration, thereby improving the overall mechanical strength of cement mortar.
[0017] In some embodiments of the present invention, the chain transfer agent is selected from one or more of thioglycolic acid, mercaptopropionic acid, and mercaptoethanol.
[0018] In some embodiments of the present invention, the oxidant is selected from one or more of hydrogen peroxide, ammonium persulfate, dibenzoyl peroxide, sodium persulfate, potassium persulfate, and potassium permanganate.
[0019] In some embodiments of the present invention, the reducing agent is selected from one or more of ascorbic acid, hydroxymethanesulfinic acid monosodium salt dihydrate, and ferrous sulfate heptahydrate.
[0020] In a second aspect of the present invention, the present invention provides a method for preparing the above-mentioned organic polymer, the method comprising: A first mixed solution obtained by mixing a reducing agent, a chain transfer agent and water is added dropwise to a second mixed solution obtained by mixing an unsaturated alcohol amine ester, a cationic monomer, an oxidant and water to react.
[0021] According to the above-mentioned preparation method of the organic polymer provided by the present invention, a reducing agent, a chain transfer agent and water are first mixed to obtain a first mixed liquid; an unsaturated alcohol amine ester, a cationic monomer, an oxidant and water are mixed to obtain a second mixed liquid; and then the first mixed liquid is added dropwise to the second mixed liquid to react. The step-by-step addition method is advantageous for controlling the progress of the free radical copolymerization reaction, controlling the molecular weight, and more advantageous for controlling the gelling ability of the limestone powder.
[0022] Preferably, when the first mixed liquid is added dropwise to the second mixed liquid, the temperature of the first mixed liquid is controlled to be 25-35°C.
[0023] In the third aspect of the present invention, the present invention proposes the use of the above organic polymer in the preparation of building materials.
[0024] In some embodiments of the present invention, the building material includes cement mortar, and the raw materials for preparing the cement mortar include cement, limestone powder, and the organic polymer.
[0025] Preferably, in the raw materials for preparing the cement mortar, the mass ratio of the cement to the limestone powder is not less than 1, and preferably the mass ratio is (5 - 8):(2 - 5).
[0026] In some embodiments of the present invention, based on the total mass of the cement mortar, the mass proportion of the organic polymer is not more than 1%, preferably 0.1% - 0.5%.
[0027] Preferably, in the raw materials for preparing the cement mortar, the mass ratio of the cement to the limestone powder is (5 - 8):(2 - 5), and the mass proportion of the organic polymer is 0.1% - 0.5%.
[0028] The present invention has at least the following technical effects: (1) The organic polymer provided by the present invention can enable the limestone powder to participate in the reaction, stimulate its latent activity, and make it participate in the hydration reaction to generate products with gelling properties, such as C - S - H gel, C - A - S - H gel, and N - A - S - H gel, etc., thereby improving the mechanical properties of the final cement mortar.
[0029] (2) The organic polymer provided by the present invention does not contain sulfates, does not contain chlorides, and does not contain alkalis, and will not affect the durability of the material.
[0030] (3) Raw materials such as limestone powder are widely available and have low costs. The organic polymer of the present invention can enable the raw material of limestone powder to participate in the reaction, improve the utilization rate of solid waste, reduce the environmental burden of waste, and can increase the added value of these inexpensive raw materials. While ensuring the mechanical strength of the material, it can effectively reduce the cement consumption in the cement mortar, achieving the effects of cost reduction and energy conservation and low - carbon. Detailed embodiments
[0031] Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention. The following describes the present invention with reference to specific embodiments. It should be noted that these embodiments are only descriptive and do not limit the present invention in any way.
[0032] Example 1 This example provides 4 kinds of unsaturated alcohol amide esters, and the specific preparation process is as follows: Add diethanolamine and water to the reaction vessel, add hydroquinone inhibitor, stir and dissolve completely, then add acrylic acid and sulfamic acid, and carry out the esterification reaction at a reaction temperature of 120 °C for 4 hours to obtain modified alkanolamines (saturated alkanolamine esters), namely UA-AE-0.2, UA-AE-0.4, UA-AE-0.6 and UA-AE-1. The addition amounts of each raw material are shown in Table 1.
[0033] Table 1
[0034] Add the above 4 kinds of unsaturated alkanolamine esters to P.I 42.5 cement at 0.5 wt% respectively, and determine the mortar strength according to GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)". The blank test is carried out without adding unsaturated alkanolamine esters. The specific test results of the mechanical strength of the cement mortar are shown in Table 2.
[0035] Table 2
[0036] It can be seen from Table 2 that the 4 kinds of unsaturated alkanolamine esters provided by the present invention have a certain promoting effect on the mechanical strength of the cement mortar at different times, and UA-AE-1 has the best effect.
[0037] Example 2 (1) Preparation of organic polymer 1) Take a four-necked flask, add 26.7% methacryloyloxyethyl trimethyl ammonium chloride, 26.7% UA-AE-1 and 32.9% water, stir until completely mixed evenly, then add 0.1% ammonium persulfate and 0.1% hydrogen peroxide, and stir at room temperature (25 °C) for 15 min until completely mixed evenly to obtain the bottom material; 2) Mix 0.1% hydroxymethanesulfinic acid, 0.2% thioglycolic acid and 13.2% water evenly to obtain the dropping material; Slowly drop the dropping material into the bottom material. After 2 h, the dropping is completed, and continue to stir at 30 °C for 1 h until the reaction is complete to obtain the organic polymer.
[0038] (2) Preparation of cement mortar The raw materials used in the mortar mix ratio are cement, limestone powder, sand and water. The total mass of the cementitious materials is 450 g (cement:limestone powder = 10:0), the sand is 1350 g, and the water addition is fixed at 225 g. Among them, the cement is P.I 42.5 and the sand is medium sand in Zone II. The dosage of the organic polymer is 0.1%, 0.5% of the total mass of the cementitious materials. The blank test is carried out without adding the organic polymer.
[0039] The specific surface area of the above limestone powder is 924.9 m2 / kg, and the main mineral components are shown in Table 3.
[0040] Table 3
[0041] The mechanical strength of the mortar was determined in accordance with GB / T 17671-2021 "Test Method for Strength of Cement Mortar (ISO Method)", and the test results are shown in Table 4.
[0042] Table 4
[0043] As can be seen from Table 4, compared with the cement material without the addition of organic polymer, the organic polymer of the present invention significantly improves the mechanical strength of the cement mortar when the addition amount is 0.1%-0.5%.
[0044] Example 3 The difference between Example 3 and Example 2 is as follows: The raw materials used in the mortar mix ratio are cement, limestone powder, sand and water, and the total mass of the cementitious materials is 450 g (cement:limestone powder = 7:3).
[0045] The test results of the mechanical strength of the cement mortar in Example 3 are shown in Table 5.
[0046] Table 5
[0047] As can be seen from Table 5, compared with the cement material without the addition of organic polymer, the organic polymer of the present invention improves the mechanical strength of the cement mortar when the addition amount is 0.1%-0.5%.
[0048] Example 4 The difference between Example 4 and Example 2 is as follows: The raw materials used in the mortar mix ratio are cement, limestone powder, sand and water, and the total mass of the cementitious materials is 450 g (cement:limestone powder = 5:5).
[0049] The test results of the mechanical strength of the cement mortar in Example 4 are shown in Table 6.
[0050] Table 6
[0051] As can be seen from Table 6, compared with the cement material without the addition of organic polymer, the organic polymer of the present invention significantly improves the mechanical strength of the cement mortar when the addition amount is 0.1%-0.5%.
[0052] Example 5 The difference between Example 5 and Example 2 is as follows: The raw materials used in the mortar mix proportion are cement, limestone powder, sand and water, and the total mass of the cementitious materials is 450 g (cement:limestone powder = 3:7).
[0053] The test results of the mechanical strength of the cement mortar in Example 5 are shown in Table 7.
[0054] Table 7
[0055] It can be seen from Table 7 that compared with the cement materials without added organic polymer, the mechanical strength of the cement mortar is improved when the addition amount of the organic polymer of the present invention is 0.1% - 0.5%.
[0056] Comparative Example 1 (1) Preparation of organic polymer A 1) Take a four-necked flask, add 53.4% UA-AE-1 and 32.9% water and stir until completely mixed evenly, then add 0.1% ammonium persulfate and 0.1% hydrogen peroxide and stir at room temperature (25 °C) for 15 min until completely mixed evenly to obtain the base material; 2) Mix 0.1% hydroxymethanesulfinic acid, 0.2% thioglycolic acid and 13.2% water evenly to obtain the dropping material; Slowly drop the dropping material into the base material, finish dropping after 2 h, and continue to stir at 30 °C for 1 h until the reaction is complete to obtain the organic polymer.
[0057] (2) Preparation of cement mortar The preparation process of the cement mortar is the same as that in Example 4.
[0058] The test results of the mechanical strength of the cement mortar in Comparative Example 1 are shown in Table 8.
[0059] Table 8
[0060] Comparative Example 2 (1) Preparation of organic polymer B 1) Take a four-necked flask, add 26.7% methylacryloyloxyethyltrimethylammonium chloride, 26.7% diethanolamine and 32.9% water and stir until completely mixed evenly, then add 0.1% ammonium persulfate and 0.1% hydrogen peroxide and stir at room temperature (25 °C) for 15 min until completely mixed evenly to obtain the base material; 2) Mix 0.1% hydroxymethanesulfinic acid, 0.2% thioglycolic acid and 13.2% water evenly to obtain the dropping material; Slowly drop the dropping material into the base material, finish dropping after 2 h, and continue to stir at 30 °C for 1 h until the reaction is complete to obtain the organic polymer.
[0061] (2)Preparation of cement mortar The preparation process of the cement mortar is the same as that in Example 4.
[0062] The test results of the mechanical strength of the cement mortar in Comparative Example 2 are shown in Table 9.
[0063] Table 9
[0064] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims
1. An organic polymer, characterized in that The raw materials for preparation include, by weight: 20-30 parts of unsaturated alcohol amine ester, 20-30 parts of cationic monomer, 0.2-0.5 parts of chain transfer agent, 0.1-0.5 parts of oxidant, and 0.1-0.5 parts of reducing agent; The raw materials for preparing the unsaturated alcoholamine ester include: unsaturated acid, alcoholamine, inhibitor, catalyst and water, and the molar ratio of the unsaturated acid to the alcoholamine is (0.2~1.2):
1.
2. The organic polymer according to claim 1, characterized in that Based on the total mass of the raw materials for preparing the unsaturated alcoholamine ester, the mass proportion of water is 5-15%; And / or, based on the total mass of the raw materials for preparing the unsaturated alcoholamine ester, the mass proportion of the inhibitor is 0.5-2.0%; And / or, based on the total mass of the raw materials for preparing the unsaturated alcoholamine ester, the mass proportion of the catalyst is 0.5-2.0%.
3. The organic polymer according to claim 1, characterized in that The unsaturated acid is selected from one or more of methacrylic acid, fumaric acid, maleic anhydride and acrylic acid; And / or, the alcoholamine is selected from one or more of diethanolamine, triethanolamine, and diethanol monoisopropanolamine; And / or, the polymerization inhibitor is selected from one or more of hydroquinone and concentrated sulfuric acid; And / or, the catalyst is selected from one or more of concentrated sulfuric acid, aminosulfonic acid, sodium acetate, and 1,3-dicyclohexylcarbodiimide.
4. The organic polymer according to any one of claims 1 to 3, characterized in that The preparation method of the unsaturated alcohol amine ester comprises: mixing and dissolving the alcohol amine, the polymerization inhibitor and the water, slowly adding a mixture of the unsaturated acid and the catalyst, and then reacting at 100-120° C. for 4-6 hours.
5. The organic polymer according to any one of claims 1 to 3, characterized in that Based on 100 parts by weight, the raw materials for preparation include: 20-30 parts of the unsaturated alcohol amine ester, 20-30 parts of the cationic monomer, 0.2-0.5 parts of the chain transfer agent, 0.1-0.5 parts of the oxidant, 0.1-0.5 parts of the reducing agent and the balance water.
6. The organic polymer according to any one of claims 1 to 3, characterized in that The cationic monomer is selected from one or more of methylpropionyloxyethyltrimethylammonium chloride and dimethyldiallylammonium chloride; And / or, the chain transfer agent is selected from one or more of thioglycolic acid, mercaptopropionic acid, and mercaptoethanol; And / or, the oxidant is selected from one or more of hydrogen peroxide, ammonium persulfate, dibenzoyl peroxide, sodium persulfate, potassium persulfate, and potassium permanganate; And / or, the reducing agent is selected from one or more of ascorbic acid, hydroxymethanesulfinic acid monosodium salt dihydrate, and ferrous sulfate heptahydrate.
7. A method for preparing the organic polymer according to any one of claims 1 to 6, characterized in that: include: A first mixed solution obtained by mixing a reducing agent, a chain transfer agent and water is added dropwise to a second mixed solution obtained by mixing an unsaturated alcohol amine ester, a cationic monomer, an oxidant and water to react; Preferably, when the first mixed liquid is added dropwise to the second mixed liquid, the temperature of the first mixed liquid is controlled to be 25-35°C.
8. Use of the organic polymer according to any one of claims 1 to 6 in the preparation of building materials.
9. The use according to claim 8, characterized in that: The building material includes cement mortar, and the raw materials for preparing the cement mortar include cement, limestone powder and the organic polymer; Preferably, the mass ratio of the cement to the limestone powder is not less than 1, and the preferred mass ratio is (5-8): (2-5).
10. The use according to claim 9, characterized in that: Based on the total mass of the cement mortar, the mass proportion of the organic polymer is no more than 1%, preferably 0.1% to 0.5%.