CN115894814A - Novel polycarboxylic acid slump retaining agent and preparation method thereof - Google Patents
Novel polycarboxylic acid slump retaining agent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel polycarboxylic slump retaining agent and a preparation method thereof, wherein the novel polycarboxylic slump retaining agent is generated by the polymerization reaction of a compound A, a compound B, an unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and unsaturated carboxylic ester under the action of an initiator and a molecular weight regulator; the mass ratio of the unsaturated macromonomer, the compound A, the compound B, the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and unsaturated carboxylic ester is 180 (1-5): (1-10): 5-30): 10-40. According to the invention, a compound A is introduced into a molecular structure of a polycarboxylic acid slump retaining agent through a copolymerization reaction, so that a main chain side group has a benzene ring and a carboxyl group or a sulfonic group, the carboxyl group or the sulfonic group provides electrostatic repulsion, and the initial water reducing effect is enhanced; the benzene ring enables the obtained polycarboxylic acid slump retaining agent molecules to be more stretched after being adsorbed on the surfaces of cement particles, the steric effect is more obvious, and the polycarboxylic acid slump retaining agent molecules are less prone to forming intercalation adsorption with mud, so that the slump retaining and mud resistance of products are more excellent.
Description
Technical Field
The invention relates to the field of additives, in particular to a novel polycarboxylic slump retaining agent and a preparation method thereof.
Background
The polycarboxylic acid slump retaining agent has the characteristics of good slump retaining property, strong designability of performance, convenience in production and the like, and the polycarboxylic acid slump retaining agent does not generate harmful substances such as formaldehyde, ammonia and the like in the synthesis production process, can be synthesized without a heat source, and has an energy-saving and environment-friendly production process. The production process of the polycarboxylic acid slump retaining agent is energy-saving and environment-friendly, and is widely popularized and applied in more than ten years, becomes an important composition component of the polycarboxylic acid admixture, and is widely applied to the engineering fields of highways, railways, bridges, nuclear power, dams, tunnels, maritime works, high-rise buildings and the like.
However, in recent years, due to the fact that the situation of the shortage of the sandstone resources for concrete in China is more and more severe, the natural sand and stone resources in many areas of the country are increasingly deficient, and the supply of the sandstone materials is insufficient, the problems that the supply of the sandstone materials is extremely unstable, and the sandstone has high mud content and is unstable are caused. The polycarboxylic acid slump retaining agent is applied to concrete, and the problem of insufficient slump retaining is increasingly prominent. Therefore, the continuous improvement of the structure of the polycarboxylic slump retaining agent and the higher slump retaining performance are the development direction of the polycarboxylic slump retaining agent industry.
Disclosure of Invention
Aiming at the prior art, the invention develops a novel polycarboxylic acid slump retaining agent and a preparation method thereof, and the high-performance polycarboxylic acid slump retaining agent with excellent slump retaining effect can be prepared by using a relatively convenient process method.
Based on the formula, the invention provides a novel polycarboxylic slump retaining agent which is generated by the polymerization reaction of a compound A, a compound B, an unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and unsaturated carboxylic ester under the action of an initiator and a molecular weight regulator;
the structural formula of the compound A is as follows:
wherein R is 1 Is alkylene of 0 to 4 carbons, R 2 Is COOM or SO 3 M or PO 3 M 2 M is H or C0-C4 alkylene or Na, K, NH 4 ；
The structural formula of the compound B is as follows:
wherein R is 3 Is H or CH 3 ，R 4 Is alkylene of 0 to 4 carbons, X is O or S, R 5 Is alkylene of 0 to 4 carbons, R 6 Is alkylene of 0 to 4 carbons, R 7 Is COOM or SO 3 M or PO 3 M 2 Or SO 2 NH 2 M is H or C0-C4 alkylene or Na, K, NH 4 ；
The unsaturated carboxylic acid ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol 1, 3-diacrylate, pentanediol 1, 5-dimethacrylate, glycerol 1, 3-dimethacrylate, glycidyl acrylate, glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.
Furthermore, the mass ratio of the unsaturated macromonomer, the compound A, the compound B, the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and unsaturated carboxylic ester is 180 (1-5) to (1-10) to (5-30) to (10-40).
Further, the compound A is at least one of (4-vinylphenyl) methanesulfonic acid, (4-vinylphenyl) sodium methanesulfonate, 4-vinylphenylacetic acid, 4-vinylbenzoic acid, 2-methyl-2- (4-vinylphenyl) propionic acid, 4-vinyl-methyl benzoate, 4-vinyl-ethyl benzoate, 4-vinylphenyl ethyl acetate and 4-vinylphenyl diethyl phosphate.
Further, the compound B is at least one of 4-vinyloxybenzenesulfonic acid, 4-vinyloxybenzoic acid, 4-vinyloxybenzenesulfonic acid sodium salt, 4-vinyloxybenzenesulfonic acid potassium salt, 4-vinyloxybenzoic acid methyl ester, 4-vinyloxybenzoic acid ethyl ester, 4- (allyloxy) benzenesulfonamide, 4- (vinyloxy) benzenesulfonamide, 2- (vinyloxy) benzenesulfonamide and 4- (allyloxy) benzoic acid.
Further, the molecular weight of the unsaturated macromonomer is 600-6000, and the unsaturated macromonomer is at least one of 3-methyl-3-butylene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether, 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate and methoxy polyethylene glycol acrylate.
Further, the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid, and maleic anhydride.
Further, the using amount of the initiator is 0.5-3.0% of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of reactants.
Further, the initiator includes a water-soluble redox initiating system or a water-soluble peroxide initiating system agent.
Further, the initiator is at least one of hydrogen peroxide-ascorbic acid, hydrogen peroxide-rongalite, hydrogen peroxide-ascorbic acid-ferrous sulfate, hydrogen peroxide-rongalite-ferrous sulfate, hydrogen peroxide-BRUGGOLITE E51-ferrous sulfate and ammonium persulfate.
Further, the molecular weight regulator comprises at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid and sodium hypophosphite.
Another purpose of the present invention is to provide a preparation method of the above novel polycarboxylic acid slump retaining agent, which at least comprises the following steps:
adding unsaturated macromonomer, a compound A, a compound B and water into a reactor for stirring, after the materials are uniformly mixed, dropwise adding unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, unsaturated carboxylic ester, an initiator and a molecular weight regulator for 0.5-2h, wherein the initial reaction temperature is 10-25 ℃, and the temperature of the materials is controlled to be 10-30 ℃ in the dropwise adding process; keeping the temperature for 0.5-1h after the dropwise addition is finished to obtain a copolymerization product; and adding alkali into the copolymerization product to adjust the pH value of the product to 5-7 or adjusting the pH value without adding alkali to obtain the novel polycarboxylic slump retaining agent.
In conclusion, the invention has the following beneficial effects:
1. according to the invention, the compound A is introduced into a molecular structure of the polycarboxylic acid slump retaining agent through a copolymerization reaction, so that a main chain side group has a benzene ring and a carboxyl group or a sulfonic group, the carboxyl group or the sulfonic group provides electrostatic repulsion, and the initial water reducing effect is enhanced; the benzene ring enables the obtained polycarboxylic acid slump retaining agent molecules to be more stretched after being adsorbed on the surfaces of cement particles, the steric effect is more obvious, and the polycarboxylic acid slump retaining agent molecules are less prone to forming intercalation adsorption with mud, so that the slump retaining and mud resistance of products are more excellent.
2. Ester monomers and unsaturated carboxylic acid ester in the compound A and the compound B are introduced into a molecular structure of the polycarboxylic slump retaining agent through copolymerization, so that after the obtained polycarboxylic slump retaining agent is added into an alkaline concrete system, carboxylic acid, sulfonic acid and phosphate groups can be gradually hydrolyzed, and the product has excellent slump retaining performance.
3. The invention also uses other different types of macromonomers to match different types of small monomers, which is more beneficial to copolymerization reaction and ensures that the performance of the final product is more excellent.
4. The raw materials used in the invention have wide sources and simple preparation process, so that the prepared product more meets the application requirements of the polycarboxylic acid slump retaining agent.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials and reagents used in the following examples, etc., are commercially available unless otherwise specified. In the quantitative tests in the following examples, three replicates were set, and the data are the mean or the mean ± standard deviation of the three replicates.
In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, the technical solutions in the embodiments may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
Example 1
(1) Adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 2.00g of 4-vinyl-methyl benzoate, 4.00g of 4-vinyloxy benzenesulfonic acid, 0.006g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid and hydroxyethyl acrylate (wherein 7.00g of acrylic acid, 20.00g of hydroxyethyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water), a mercaptopropionic acid aqueous solution (wherein 0.70g of mercaptopropionic acid and 20.00g of water), a BRUGGOLITE E51 aqueous solution (wherein BRUGGOLITE E E E51.25 g of water and 20.00g of water), starting reaction temperature is 15 ℃, dropwise adding time is 1.0h, controlling the temperature of the dropwise adding process to be less than or equal to 30 ℃, and preserving heat for 1h after dropwise adding is finished, so as to obtain a copolymerization product;
(2) And (2) adding 3g of a 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain the novel polycarboxylic acid slump retaining agent KZJ-1.
Example 2
(1) Adding 180.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 3000, 2.00g of (4-vinylphenyl) sodium methanesulfonate, 2.00g of 4- (vinyloxy) benzenesulfonamide, 1.00g of ethylene glycol diacrylate, 0.005g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, and after the materials are uniformly mixed, beginning to dropwise add a mixed aqueous solution of acrylic acid, hydroxyethyl acrylate and hydroxypropyl acrylate (wherein 8.00g of acrylic acid, 12.00g of hydroxyethyl acrylate, 10.00g of hydroxypropyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.30g of hydrogen peroxide and 20.00g of water), a thioglycolic acid aqueous solution (wherein 0.90g of thioglycolic acid and 20.00g of water), a rongalite aqueous solution (wherein 0.30 g of rongalite and 20.00g of water), the initial reaction temperature is 13 ℃, the dropwise adding time is 0.75h, the temperature of the materials is controlled to be less than or equal to 25 ℃ in the dropwise adding process, and keeping the temperature for 1h after the materials are finished, so as to obtain a copolymerization product;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain the novel polycarboxylic acid slump retaining agent KZJ-2.
Example 3
(1) Adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 2400, 1.00g of 4-vinylphenyl diethyl phosphate, 1.50g of 2-methyl-2- (4-vinylphenyl) propionic acid, 4.00g of 4- (allyloxy) benzoic acid, 2.50g of sodium hypophosphite, 0.005g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, and after the materials are uniformly mixed, dropwise adding a mixed aqueous solution of acrylic acid, maleic anhydride and hydroxypropyl acrylate (wherein 5.00g of acrylic acid, 2.00g of maleic anhydride, 28.00g of hydroxypropyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water) and an ascorbic acid aqueous solution (wherein 0.40 of ascorbic acid and 20.00g of water), wherein the initial reaction temperature is 12 ℃, the dropwise adding time is 1h, the temperature of the dropwise adding process is controlled to be less than or equal to 30 ℃, and preserving the temperature for 1h after the dropwise adding is finished, so as to obtain a copolymerization product;
(2) And (2) adding 4g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain the novel polycarboxylic acid slump retaining agent KZJ-3.
Example 4
(1) Adding 120.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 60.00g of 2-methylallyl polyethylene glycol with the molecular weight of 2400, 1.50g of (4-vinylphenyl) methanesulfonic acid, 1.50g of 4-vinyl-ethyl benzoate, 2.00g of 4-vinyloxybenzenesulfonic acid, 3.00g of 4- (allyloxy) benzoic acid, 1g of glycidyl acrylate, 3.00g of sodium hypophosphite, 0.004g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device after the materials are uniformly mixed, starting dropwise adding a mixed aqueous solution of acrylic acid and hydroxypropyl acrylate (wherein 5.00g of acrylic acid, 32.00g of hydroxypropyl acrylate, 20.00g of water), a hydrogen peroxide solution (wherein 1.20g of water, 20.00g of water) and a BRUGLITE 51 aqueous solution (wherein, BRUGLITE 51.28 g of water and 20.00g of water), wherein the initial reaction temperature is 18 ℃, the dropwise adding time is 1.5h, controlling the temperature of the material to be less than or equal to 30 ℃, keeping the temperature of the dropwise adding process, and obtaining a copolymerization product after heat preservation;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain the novel polycarboxylic acid slump retaining agent KZJ-4.
Example 5
(1) Adding 100.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 80.00g of 3-methyl-3-butene-1-polyethylene glycol with the molecular weight of 2400, 2.40g of (4-vinylphenyl) methanesulfonic acid, 2.00g of 4- (allyloxy) benzoic acid, 2.00g of 4- (allyloxy) benzenesulfonamide, 1.00g of 4-hydroxybutyl acrylate glycidyl ether, 0.004g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, uniformly mixing the materials, and then, dropwise adding a mixed aqueous solution of acrylic acid, hydroxyethyl acrylate and hydroxypropyl methacrylate (wherein 10.00g of acrylic acid, 18.00g of hydroxyethyl acrylate, 2.00g of hydroxypropyl methacrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water), a mercaptopropionic acid aqueous solution (wherein 0.70g of mercaptoethanol and 20.00g of water), an ascorbic acid aqueous solution (wherein 0.40 of ascorbic acid and 20.00g of water are initially added), controlling the reaction temperature to be less than or equal to 0.15 hours, keeping the temperature for 25 hours, and then, and finally obtaining a copolymerization product after finishing the dropwise adding process;
(2) And (2) adding 4g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain the novel polycarboxylic acid slump retaining agent, and marking as KZJ-5.
Comparative example 1
(1) Adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 4.00g of 4-vinyloxy benzenesulfonic acid, 0.006g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid and hydroxyethyl acrylate (wherein 7.00g of acrylic acid, 20.00g of hydroxyethyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water), a mercaptopropionic acid aqueous solution (wherein 0.70g of mercaptopropionic acid and 20.00g of water), a BRUGGOLITE 51 aqueous solution (wherein 0.25g of BRUGGOLITE E and 20.00g of water), starting reaction temperature of 15 ℃, dropwise adding time of 1.0h, controlling the temperature of the dropwise adding process to be less than or equal to 30 ℃, and keeping the temperature of 1h after dropwise adding, so as to obtain a copolymerization product;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain a comparative sample PCE-1.
Comparative example 2
(1) Adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 2.00g of 4-vinyl-methyl benzoate, 0.006g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting dropwise adding a mixed aqueous solution of acrylic acid and hydroxyethyl acrylate (wherein 7.00g of acrylic acid, 20.00g of hydroxyethyl acrylate and 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water), a mercaptopropionic acid aqueous solution (wherein 0.70g of mercaptopropionic acid and 20.00g of water), a BRUGGOLITE 51 aqueous solution (wherein 0.25g of BRUGGOLITE E and 20.00g of water), starting reaction temperature is 15 ℃, dropwise adding time is 1.0h, dropwise adding the temperature of the dropwise adding process control material is less than or equal to 30 ℃, and keeping the temperature for 1h after dropwise adding, thus obtaining a copolymerization product;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain a specific sample PCE-2.
Comparative example 3
(1) Adding 180.00g of ethylene glycol monovinyl polyglycol ether with the molecular weight of 3000, 0.006g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, after the materials are uniformly mixed, beginning to dropwise add a mixed aqueous solution of acrylic acid and hydroxyethyl acrylate (wherein 7.00g of acrylic acid, 20.00g of hydroxyethyl acrylate, 20.00g of water), a hydrogen peroxide aqueous solution (wherein 1.50g of hydrogen peroxide and 20.00g of water), a mercaptopropionic acid aqueous solution (wherein 0.70g of mercaptopropionic acid and 20.00g of water), a BRUGGOLITE 51 aqueous solution (wherein 0.25g of BRUGGOLITE E and 20.00g of water) at the initial reaction temperature of 15 ℃, the dropwise adding time of 1.0h, controlling the material temperature in the dropwise adding process to be less than or equal to 30 ℃, and preserving heat for 1h after dropwise adding to obtain a copolymerization product;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain a specific sample PCE-3.
Comparative example 4
(1) Adding 180.00g of 4-hydroxybutyl vinyl polyoxyethylene ether with the molecular weight of 3000, 2.00g of (4-vinylphenyl) sodium methanesulfonate, 2.00g of 4- (vinyloxy) benzenesulfonamide, 0.005g of ferrous sulfate and 145.00g of water into a reactor, starting a stirrer and a temperature control device, starting to dropwise add an acrylic acid aqueous solution (8.00 g of acrylic acid and 20.00g of water), a hydrogen peroxide aqueous solution (1.30 g of hydrogen peroxide and 20.00g of water), a thioglycolic acid aqueous solution (0.90 g of thioglycolic acid and 20.00g of water), a rongalite aqueous solution (0.30 g of rongalite and 20.00g of water), starting reaction temperature of 13 ℃, dropwise adding time of 0.75h, controlling the temperature of the materials to be less than or equal to 25 ℃ in the dropwise adding process, and preserving heat for 1h after the dropwise adding is finished, so as to obtain a copolymerization product;
(2) And (2) adding 3g of 32% sodium hydroxide aqueous solution into the copolymerization product prepared in the step (1) to obtain a specific sample PCE-4.
Testing the performance of the concrete:
the concrete raw materials and the mixing ratio shown in Table 1 and the admixture formula shown in Table 2 are adopted to carry out performance tests on the novel polycarboxylic slump retaining agent prepared in the examples 1 to 5 and the comparative samples prepared in the comparative examples 1 to 3, the test environment temperature is 30 +/-2 ℃, and the test results are shown in Table 3:
TABLE 1 concrete mix proportion
TABLE 2 additive formulation
| Slump retaining agent | Water reducing agent | Air entraining agent | Defoaming agent | White sugar | Water (I) |
| 70.00 | 75.00 | 0.40 | 0.05 | 6.00 | 365.00 |
Note: the slump retaining agent is diluted to 20% of solid content, the water reducing agent is the Koje Point-S504 polycarboxylate water reducing agent mother liquor of the family, the solid content is 50%, the air entraining agent is the Koje KZJ-AE30 air entraining agent of the family, and the defoaming agent is the Koje KZJ-X20 defoaming agent of the family.
TABLE 3 concrete performances of different slump retaining agents
Note: in Table 3, "X" indicates that the degree of expansion is small.
As shown in table 1:
the result of comparing KZJ-1 with PCE-1 shows that the fluidity of the concrete is slightly reduced in the initial period of 1h, 2h and 3h after 4-vinyl-methyl benzoate in the KZJ-1 is removed (note: when the concrete has the expansion degree, the fluidity of the concrete is mainly seen as the expansion degree; when the concrete has no expansion degree, the fluidity of the concrete is mainly seen as the slump);
the result of comparing KZJ-1 with PCE-2 shows that the fluidity of the concrete is slightly reduced in the initial period of 1h, 2h and 3h after 4-vinyloxy benzenesulfonic acid in the KZJ-1 is removed;
the result of comparing KZJ-1 with PCE-3 shows that after 4-vinyl-methyl benzoate and 4-vinyloxy benzenesulfonic acid in KZJ-1 are removed, the fluidity of the concrete is obviously reduced in the initial period, 1h, 2h and 3 h;
the result of comparing KZJ-2 with PCE-4 shows that after 1.00g of glycol diacrylate and 12.00g of hydroxyethyl acrylate in KZJ-2 are removed, 10.00g of hydroxypropyl acrylate in KZJ-2 obviously reduces the fluidity of the concrete in the initial period of 1 hour, 2 hours and 3 hours;
the product synthesized according to the technical scheme of the invention enables the concrete to have higher initial and 1h, 2h and 3h fluidity, and shows that the product has better initial water reducing and dispersing effects and 1h, 2h and 3h slump retaining effects.
The concrete raw materials and the mixing ratio shown in Table 4 and the admixture formula shown in Table 2 are adopted to carry out performance tests on the novel polycarboxylic slump retaining agent prepared in the examples 1 to 5 and the comparative samples prepared in the comparative examples 1 to 3, the test environment temperature is 30 +/-2 ℃, and the test results are shown in Table 5:
TABLE 4 concrete mix proportion
TABLE 5 different slump retaining agent concrete Properties
Note: in Table 5, "X" indicates that the degree of expansion is small.
Comparing Table 3 and Table 5, 50kg/m of the mixture ratio 3 After the machine-made sand is changed into the mud obtained by washing and drying in the machine-made sand, KZJ-1 to KZJ-5 are influenced by the mud, and the initial and 1h, 2h and 3h fluidity degradation values of the concrete are obviously smaller than the initial and 1h, 2h and 3h fluidity degradation values of the concrete influenced by the mud of PCE-1 to PCE-4, so that the product synthesized according to the technical scheme of the invention has better mud resistance effect.
All possible combinations of the technical features of the above embodiments may not be described in the above embodiments for the sake of brevity, however, the combination of the technical features should be considered as the scope of the present specification unless there is any conflict between the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A novel polycarboxylic slump retaining agent is characterized in that the novel polycarboxylic slump retaining agent is generated by the polymerization reaction of a compound A, a compound B, an unsaturated macromonomer, unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and unsaturated carboxylic ester under the action of an initiator and a molecular weight regulator;
the structural formula of the compound A is as follows:
wherein R is 1 Is alkylene of 0 to 4 carbons, R 2 Is COOM or SO 3 M or PO 3 M 2 M is H or C0-C4 alkylene or Na, K, NH 4 ；
The structural formula of the compound B is as follows:
wherein R is 3 Is H or CH 3 ，R 4 Is alkylene of 0 to 4 carbons, X is O or S, R 5 Is alkylene of 0 to 4 carbons, R 6 Is alkylene of 0 to 4 carbons, R 7 Is COOM or SO 3 M or PO 3 M 2 Or SO 2 NH 2 M is H or C0-C4 alkylene or Na, K, NH 4 ；
The unsaturated carboxylic acid ester is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol 1, 3-diacrylate, pentanediol 1, 5-dimethacrylate, glycerol 1, 3-dimethacrylate, glycidyl acrylate, glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether.
2. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the mass ratio of the unsaturated macromonomer, the compound A, the compound B, the unsaturated carboxylic acid and/or unsaturated carboxylic anhydride and the unsaturated carboxylic ester is 180 (1-5) to (1-10) to (5-30) to (10-40).
3. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the compound A is at least one of (4-vinyl phenyl) methanesulfonic acid, (4-vinyl phenyl) sodium methanesulfonate, 4-vinyl phenylacetic acid, 4-vinyl benzoic acid, 2-methyl-2- (4-vinyl phenyl) propionic acid, 4-vinyl-methyl benzoate, 4-vinyl-ethyl benzoate, 4-vinyl ethyl phenylacetate and 4-vinyl phenyl diethyl phosphate.
4. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the compound B is at least one of 4-vinyloxy benzene sulfonic acid, 4-vinyloxy benzoic acid, 4-vinyloxy phenylacetic acid, 4-vinyloxy benzene sulfonic acid sodium salt, 4-vinyloxy benzene sulfonic acid potassium salt, 4-vinyloxy benzoic acid methyl ester, 4-vinyloxy benzoic acid ethyl ester, 4-vinyloxy benzene acetic acid methyl ester, 4-vinyloxy benzene acetic acid ethyl ester, 4- (allyloxy) benzene sulfonamide, 4- (vinyloxy) benzene sulfonamide, 2- (vinyloxy) benzene sulfonamide and 4- (allyloxy) benzoic acid.
5. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the molecular weight of the unsaturated macromonomer is 600-6000, and the unsaturated macromonomer is at least one of 3-methyl-3-butylene-1-polyethylene glycol, 2-methylallyl polyethylene glycol, ethylene glycol monovinyl polyethylene glycol ether, 4-hydroxybutyl vinyl polyoxyethylene ether, methoxy polyethylene glycol methacrylate and methoxy polyethylene glycol acrylate.
6. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride is at least one of acrylic acid, methacrylic acid and maleic anhydride.
7. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the dosage of the initiator is 0.5 to 3.0 percent of the total mass of the reactants; the dosage of the molecular weight regulator is 0.2-3.0% of the total mass of reactants.
8. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the initiator includes a water-soluble redox initiation system or a water-soluble peroxide initiation system agent.
9. The novel polycarboxylic acid slump retaining agent as claimed in claim 1, wherein: the molecular weight regulator comprises at least one of thioglycolic acid, mercaptoethanol, mercaptopropionic acid, sulfonated mercaptopropionic acid and sodium hypophosphite.
10. A method for producing the novel polycarboxylic acid slump retaining agent as set forth in any one of claims 1 to 9, characterized in that: at least comprises the following steps:
adding unsaturated macromonomer, a compound A, a compound B and water into a reactor for stirring, after the materials are uniformly mixed, dropwise adding unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, unsaturated carboxylic ester, an initiator and a molecular weight regulator for 0.5-2h, wherein the initial reaction temperature is 10-25 ℃, and the temperature of the materials is controlled to be 10-30 ℃ in the dropwise adding process; after the dripping is finished, preserving the heat for 0.5 to 1 hour to obtain a copolymerization product; and adding alkali into the copolymerization product to adjust the pH value of the product to 5-7 or adjusting the pH value without adding alkali, thus obtaining the novel polycarboxylic acid slump retaining agent.
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