CN109836068B - Slump-retaining type polycarboxylate superplasticizer and preparation method and application thereof - Google Patents

Slump-retaining type polycarboxylate superplasticizer and preparation method and application thereof Download PDF

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CN109836068B
CN109836068B CN201811585123.0A CN201811585123A CN109836068B CN 109836068 B CN109836068 B CN 109836068B CN 201811585123 A CN201811585123 A CN 201811585123A CN 109836068 B CN109836068 B CN 109836068B
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张文龙
杜迎吉
牛峰
朱军成
李方
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Levima Jiangsu New Material Research Institute Co ltd
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Abstract

The invention discloses a slump-retaining type polycarboxylate superplasticizer. The slump-retaining polycarboxylate superplasticizer comprises a structural unit A shown as a formula I, a structural unit B shown as a formula II, a structural unit C shown as a formula III and a structural unit D shown as a formula IV; and based on the total weight of the slump-retaining type polycarboxylate superplasticizer, the weight content of the structural unit A is 71-96%, the weight content of the structural unit B is 0.08-12%, the weight content of the structural unit C is 0.08-12%, and the weight content of the structural unit D is 0.08-5%. The water reducing agent disclosed by the invention has excellent slump retaining performance.

Description

Slump-retaining type polycarboxylate superplasticizer and preparation method and application thereof
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a slump-retaining type polycarboxylate superplasticizer and a preparation method and application thereof.
Background
The polycarboxylate superplasticizer is a novel water reducing agent developed in recent years, has the advantages of low mixing amount, high water reducing rate, high slump retaining property, low alkali, environmental protection, high degree of freedom of molecular design and the like compared with the traditional lignosulfonate, naphthalenesulfonate system, melamine system and sulfamate system, and is widely applied to concrete engineering. However, the use of concrete has long been plagued by the problem of how to effectively control slump loss. The pumping concrete produced from the concrete mixing plant usually needs to be transported for a long distance, and the construction environment is different, so that the slump loss of the concrete is inevitably caused, and the construction of the concrete is influenced.
Chinese patent CN102390950A discloses a slow-release type carboxy-reducing slump retaining agent and a preparation method thereof: the material is prepared by copolymerizing and mixing unsaturated carboxylic acid polyethylene glycol monoester, unsaturated polyoxyalkylene ether monoester, unsaturated monocarboxylic acid and derivative monomer thereof, and unsaturated alkenyl sulfonic acid and sodium salt thereof. The compatibility problem of the sand-stone material with large mud content and the water reducing agent can be effectively solved, but the synthesis process is complex, and the performance is greatly influenced by temperature and pH.
Chinese patent CN102153711A reports that allyl sulfonate monomers, acrylic acid monomers, methacrylic acid polyethylene glycol monomethyl ether ester macromonomers and maleic anhydride grafted beta-cyclodextrin macromonomers are subjected to free radical copolymerization to obtain a retarding polycarboxylic acid water reducer, which has good retarding performance and good flowing performance, but the maleic anhydride and beta-cyclodextrin macromonomers have low grafting rate and are greatly influenced by temperature, so that the retarding polycarboxylic acid water reducer is not beneficial to large-scale production and application.
Chinese patent CN104944827B reports a preparation method of a slump-retaining polycarboxylic acid water reducing agent. The method comprises the steps of carrying out free radical polymerization on a hydroxyl-containing unsaturated small monomer, an amine-containing unsaturated small monomer, an initiator, a reducing agent and a chain transfer agent to obtain an amine-containing polymer, and then reacting the prepared amine-containing polymer with epoxy-group-containing polyethylene glycol monomethyl ether to prepare the slump-retaining polycarboxylic acid water reducer. The water reducing agent has a good slump retaining effect on mud-containing stones, but the synthesis process is complex, and the industrial production is not facilitated.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a slump-retaining type polycarboxylate superplasticizer and a preparation method and application thereof.
The invention provides a slump-retaining polycarboxylic acid water reducing agent, which comprises a structural unit A, a structural unit B, a structural unit C and a structural unit D;
the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, the structural unit C is a structural unit shown as a formula III, and the structural unit D is a structural unit shown as a formula IV;
Figure BDA0001918899500000021
Figure BDA0001918899500000031
wherein R is1、R4And R5Identical or different, R1、R4And R5Represents hydrogen or C1-12An alkyl group; for example, R1、R4And R5Represents hydrogen or C1-4Alkyl, illustratively, R1、R4And R5Represents hydrogen or methyl;
R6represents C1-12An alkylene group; for example, R6Represents C1-6An alkylene group; illustratively, R6Represents an ethylene group
Figure BDA0001918899500000032
Or propylene
Figure BDA0001918899500000033
R2And R3Identical or different, R2And R3Represents CxH2xA substituent, wherein x is a natural number from 2 to 20; for example, x is a natural number of 2 to 10, 2 to 6, 2 to 4. Preferably, R2And R3Represents an alkylene group; illustratively, R2Represents an ethylene group
Figure BDA0001918899500000034
Propylene (-, -CH)2-CH2-CH2-) or butylene (-CH)2-CH2-CH2-CH2-)；R3Represents an ethylene group
Figure BDA0001918899500000035
Propylene radical
Figure BDA0001918899500000036
Wherein m + n is a natural number in the range of 10-250; for example, m + n is a natural number in the range of 20 to 200, a natural number in the range of 40 to 150;
wherein formula II may represent a carboxylic acid or a salt of a carboxylic acid; when formula II is a carboxylic acid, M is H; when formula II is a carboxylic acidIn the case of salts, M may be selected from Na, K, NH4One, two or more.
Wherein M in the formula III1Can be selected from Na or K.
The polycarboxylate superplasticizer of the invention comprises 71-96% of the structural unit A, such as 80-95%, 81-93%, 82-90%, 83-89% and 84-88% by weight based on the total weight of the polycarboxylate superplasticizer.
According to the polycarboxylate water reducer, the weight content of the structural unit B is 0.8-12% based on the total weight of the polycarboxylate water reducer; for example, 0.85 to 11.5%, 0.95 to 11.1%, 1 to 10%, 2 to 9%, 4 to 7%.
According to the polycarboxylate water reducer, the weight content of the structural unit C is 0.8-12% based on the total weight of the polycarboxylate water reducer; for example, 0.85 to 11.5%, 0.95 to 11.1%, 1 to 10%, 2 to 9%, 4 to 7%.
The weight content of the structural unit D is 0.08-5%, such as 0.09-5%, 0.1-4%, 0.1-3.5%, 0.1-3%, 0.5-2% based on the total weight of the polycarboxylate superplasticizer.
According to the polycarboxylate superplasticizer provided by the invention, the number average molecular weight of the superplasticizer can be 10000-50000 g/mol, such as 12000-45000 g/mol, 15000-35000 g/mol and 18000-30000 g/mol.
According to the polycarboxylate superplasticizer disclosed by the invention, the solid content of the polycarboxylate superplasticizer is 35-55%, such as 40-50%.
According to a second aspect of the invention, the invention also provides a preparation method of the slump-retaining type polycarboxylate water reducer, which comprises the following steps: the polycarboxylate superplasticizer is prepared from a monomer mixture containing a monomer E with a structure shown in a formula V, a monomer F with a structure shown in a formula VI, a monomer G with a structure shown in a formula VII and a monomer H with a structure shown in a formula VIII through a polymerization reaction;
Figure BDA0001918899500000041
Figure BDA0001918899500000051
wherein R is1’、R4' and R5' same or different, R1’、R4' and R5' represents hydrogen or C1-12An alkyl group; preferably, R1’、R4' and R5' represents hydrogen or C1-4Alkyl, illustratively, R1’、R4' and R5' represents hydrogen or methyl;
R6' represents C1-12An alkylene group; for example, R6' represents C1-6An alkylene group; illustratively, R6' represents an ethylene group
Figure BDA0001918899500000052
Or propylene
Figure BDA0001918899500000053
R2' and R3' same or different, R2' and R3' represents CxH2xA substituent, wherein x is a natural number from 2 to 20; for example, x is a natural number of 2 to 10, 2 to 6, 2 to 4. Preferably, R2And R3Represents an alkylene group; illustratively, R2' represents an ethylene group
Figure BDA0001918899500000054
Propylene radical
Figure BDA0001918899500000055
Figure BDA0001918899500000056
Or butylene
Figure BDA0001918899500000057
R3' represents aEthyl radical
Figure BDA0001918899500000058
Propylene radical
Figure BDA0001918899500000059
Wherein m + n is a natural number in the range of 10-250; for example, m + n is a natural number in the range of 20 to 200, a natural number in the range of 40 to 150;
wherein formula VI may represent a carboxylic acid or carboxylate salt, when formula VI is a carboxylic acid, M' is H; when formula VI is a carboxylate, M' may be selected from Na, K, NH4One, two or more.
Wherein, M in the formula VII1' may be selected from Na or K.
According to the preparation method of the invention, the preparation method specifically comprises the following steps: and carrying out solution polymerization reaction on the monomer mixture containing the monomer E with the structure shown in the formula V, the monomer F with the structure shown in the formula VI, the monomer G with the structure shown in the formula VII and the monomer H with the structure shown in the formula VIII in water in the presence of an initiator to obtain the polycarboxylic acid water reducer. For example, the polycarboxylic acid water reducer can be obtained by preparing an aqueous solution of the monomer E, then preparing a mixed aqueous solution containing the monomer F, the monomer G, the monomer H and the initiator, dropwise adding the mixed aqueous solution into the aqueous solution of the monomer E, curing after the dropwise adding is completed, and cooling to room temperature.
According to the preparation method, the weight ratio of the monomer E to the monomer F to the monomer G to the monomer H can be 1 to (0.01-0.12) to (0.001-0.04); for example, the weight ratio may be 1: 0.01 to 0.117: 0.001 to 0.0375, 1: 0.02 to 0.1: 0.005 to 0.024; illustratively, the weight ratio may be 1: 0.07: 0.01, 1: 0.02: 0.08: 0.006, 1: 0.11: 0.09: 0.02.
According to the preparation method of the invention, the monomer E can be at least one of 4-hydroxybutyl vinyl ether polyoxyethylene ether and 2-hydroxyethyl vinyl ether polyoxyethylene ether; preferably, the molecular weight of the monomer E can be 1000-; more preferably, the monomer E may be selected from at least one of 4-hydroxybutyl vinyl ether polyoxyethylene ether and 2-hydroxyethyl vinyl ether polyoxyethylene ether having a molecular weight of 1000-6000.
For example, the monomer F may be an acrylic monomer; preferably, R in said formula VI4'is H or methyl, M' is Na or NH4. The solubility effect of the slump-retaining water reducer in water can be further improved by selecting a specific monomer F and the using amount thereof for reaction.
For example, the monomer G may be sodium 3- (diallylamino) -2-hydroxypropyl sulfonate; preferably, the monomer G is prepared according to the synthetic methods in S.Gou, S.Luo, T.Liu, H.Xia, D.Jing, Q.Zhang, S.Li, Z.Li and Q.Guo, RSC adv, 2015,5,85165-85173 literature. The monomer G is added in the polymerization reaction, so that the space protection capability of the prepared slump-retaining water reducer is increased, and the monomer G is cooperatively added into the slump-retaining water reducer according to a proportion, so that the slump-retaining performance of the slump-retaining water reducer is improved.
For example, the monomer H is an acrylate monomer; preferably, R in said formula VII5' is H or methyl, R6' is ethyl or propyl. The monomer H is synergistically added into the slump-retaining water reducer according to a proportion, so that the comprehensive optimization of the slump-retaining performance of the slump-retaining water reducer is facilitated.
According to the production method of the present invention, the solution polymerization reaction conditions of the olefin include: the reaction temperature may be 5 to 70 ℃, for example 10 to 40 ℃, illustratively 10 ℃,20 ℃, 40 ℃; the reaction time may be 1 to 10 hours, for example, 2 to 4 hours.
According to the preparation method of the invention, the initiator is a redox system initiator. For example, the amount of the oxidant in the redox initiator may be 0.05 to 2%, for example 0.1 to 1.0% by weight of the total weight of the monomer mixture; illustratively, 0.099%, 0.45%, 0.99%. Wherein the oxidizing agent may be at least one selected from the group consisting of benzoyl peroxide, hydrogen peroxide, t-butyl hydroperoxide, 2, 5-dimethyl-2, 5 bis (hydroperoxy) hexane, ammonium persulfate, sodium persulfate, and potassium persulfate.
For example, the reducing agent may be used in an amount of 0.01 to 2%, for example 0.02 to 1%, based on the total weight of the monomer mixture; exemplary, 0.02%, 0.3%, 1.0%. Wherein the reducing agent can be selected from at least one of L-ascorbic acid, L-ascorbate, isoascorbic acid, isoascorbate and isoascorbate, ferrous sulfate, ferrous ammonium sulfate, cuprous chloride, potassium sulfite, sodium sulfite, ammonium bisulfite, potassium bisulfite, sodium thiosulfate, potassium thiosulfate, rongalite and sodium bisulfite.
According to the preparation method of the invention, the olefin solution polymerization reaction also comprises a molecular weight regulator. For example, the molecular weight regulator may be one, two or more of mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, n-dodecylmercaptan, octylmercaptan, butyl thioglycolate, isopropanol, sodium hypophosphite, and potassium hypophosphite. For example, the molecular weight regulator may be used in an amount of 0.1 to 1.0%, for example 0.5 to 1.0% by weight of the total monomer mixture; exemplary, 0.1%, 0.8%, 1.0%.
The invention also provides application of the slump-retaining type polycarboxylate superplasticizer in the fields of cement, concrete and the like.
The invention has the beneficial effects that:
the slump-retaining polycarboxylic acid water reducing agent provided by the invention has the advantage that the slump-retaining performance of the polycarboxylic acid water reducing agent is improved by selecting a proper functional monomer and a proper proportion of the monomer. The molecular main chain of the slump-retaining polycarboxylate water reducer provided by the invention is provided with an annular structure, so that the adsorption effect with cement is enhanced, meanwhile, after hydroxyl and sulfonic acid groups simultaneously contained on a functional monomer are introduced into the molecules of the water reducer, a better relative effect is formed with an alkaline cement system, the wetting, permeation and adsorption of the water reducer on the cement surface are enhanced, the thickness of a water film layer can be effectively increased, the repulsion effect among cement particles is enhanced, dispersed particles are smaller, the flocculation structure of the cement particles is destroyed, the cement-water system is in a relatively stable suspension state, and the water reducer also has excellent slump-retaining performance.
Definition of terms:
unless otherwise indicated, the definitions of radicals and terms set forth in the specification and claims of this application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions of particular compounds in the examples, and the like, may be combined with one another in any combination and permutation. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
Where a range of numerical values is recited in the specification and claims herein, and where the range of numerical values is defined as an "integer," it is understood that the two endpoints of the range are recited and each integer within the range is recited. For example, "an integer of 0 to 10" should be understood to describe each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. When a range of values is defined as "a number," it is understood that the two endpoints of the range, each integer within the range, and each decimal within the range are recited. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10, but also to recite at least the sum of each integer and 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
The term "C1-12Alkyl is understood to preferably mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms, preferably C1-6An alkyl group. "C1-6Alkyl "is understood to preferably mean a straight-chain or branched saturated monovalent hydrocarbon radical having 1, 2, 3, 4, 5, 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly the group has 1, 2 or 3 carbon atoms ("C)1-3Alkyl groups) such as methyl, ethyl, n-propyl or isopropyl.
The term "C1-12Alkylene "is understood to mean preferably having 1 to 12A straight-chain or branched saturated divalent hydrocarbon radical of carbon atoms, preferably C1-6An alkylene group. "C1-6Alkylene "is understood to preferably mean a straight-chain or branched saturated divalent hydrocarbon radical having 1, 2, 3, 4, 5, 6 carbon atoms. The alkyl radicals are, for example, methylene, ethylene, propylene, butylene, isopropylene, isobutylene, more particularly the radicals having 1, 2 or 3 carbon atoms ("C)1-3Alkylene) such as methylene, ethylene, n-propylene or isopropylene.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the embodiment of the invention, the number average molecular weight M of the polycarboxylate superplasticizer productnMeasuring by an Agilent technologies HPLC instrument, wherein a chromatographic column is formed by connecting an ultra hydrogel 500+ an ultra hydrogel 250+ an ultra hydrogel 120 in series, a mobile phase is 0.1mol/L sodium nitrate aqueous solution, and the flow rate is 1.0 mL/min; PEG with molecular weights of 202g/mol, 430g/mol, 960g/mol, 4290g/mol, 12600g/mol, 44000g/mol and 152000g/mol are used as standard samples.
Example 1
87g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight of 2400) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, and then a mixed solution of 6g of acrylic acid, 6g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that a slump-retaining polycarboxylic acid water reducing agent product S1 is obtained.
The product S1 is characterized by infrared spectrum, 3441.32cm in the infrared spectrum-1Stretching vibration of O-H; 2871.51cm-1And 2873.65cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.43cm-1、1731.25cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1185.36cm-1is-SO3Stretching vibration of Na, 1103.45cm-1And 1258.89cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S1 by GPC measurement, Mn25325 g/mol.
Example 2
90g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight is 4000) is placed in a kettle and dissolved in 60g of water at 10 ℃, 0.1g of thioglycolic acid and 1.0g L-ascorbic acid are added, and then a mixed solution of 2g of acrylic acid, 7.5g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 0.5g of hydroxypropyl acrylate, 3.3g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 2 hours and cooled to room temperature, so that a slump-retaining polycarboxylic acid water reducer product S2 is obtained.
The product S2 is characterized by infrared spectrum, 3442.08cm in the infrared spectrum-1Stretching vibration of O-H; 2871.28cm-1And 2874.06cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1707.65cm-1、1730.76cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1187.12cm-1is-SO3Stretching vibration of Na, 1104.25cm-1And 1257.26cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S2 by GPC measurement, MnIs 20870 g/mol.
Example 3
82g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight is 5000) is placed in a kettle and dissolved in 60g of water at 40 ℃, 1.0g of thioglycolic acid and 0.02g L-ascorbic acid are added, and then a mixed solution of 9g of sodium acrylate, 7g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 2g of hydroxypropyl acrylate, 0.33g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that the slump-retaining polycarboxylic acid water reducer product S3 is obtained.
The product S3 is characterized by infrared spectrum, 3441.45cm in the infrared spectrum-1Stretching vibration of O-H; 2871.34cm-1And 2873.18m-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.18cm-1、1560.24cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1185.28cm-1is-SO3Stretching vibration of Na, 1104.06cm-1And 1257.83cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S3 by GPC measurement, MnIt was 28780 g/mol.
Example 4
87g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight of 2400) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, and then a mixed solution of 6g of methacrylic acid, 6g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that a slump-retaining polycarboxylic acid water reducing agent product S4 is obtained.
The product S4 is characterized by infrared spectrum, 3441.76cm in the infrared spectrum-1Stretching vibration of O-H; 2871.76cm-1And 2873.68cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.58cm-1、1731.65cm-1cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1186.25cm-1is-SO3Stretching vibration of Na, 1104.55cm-1And 1258.34cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S4 by GPC measurement, Mn23560 g/mol.
Example 5
87g of 2-hydroxyethyl vinyl ether polyoxyethylene ether (molecular weight of 2400) is placed in a kettle and dissolved in 60g of water at the temperature of 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, and then a mixed solution of 6g of methacrylic acid, 6g of 3- (diallyl amino) -2-hydroxypropyl sodium sulfonate, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that a slump-retaining polycarboxylic acid water reducer product S5 is obtained.
The product S5 is characterized by infrared spectrum, 3442.12cm in the infrared spectrum-1Stretching vibration of O-H; 2871.86cm-1And 2874.72cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.68cm-1、1731.55cm-1The strong absorption peak of (2) is a C ═ O vibration peak, 1186.45m-1is-SO3Stretching vibration of Na, 1104.75cm-1And 1256.62cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S5 by GPC measurement, MnIt was 21250 g/mol.
Example 6
87g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight is 1000) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, and then a mixed solution of 6g of methacrylic acid, 6g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that the slump-retaining polycarboxylic acid water reducer product S6 is obtained.
The product S6 is characterized by infrared spectrum, 3441.85m in the infrared spectrogram-1Stretching vibration of O-H; 2871.43cm-1And 2874.52cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.52cm-1、1732.62cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1187.43cm-1is-SO3Stretching vibration of Na, 1104.161cm-1And 1257.36cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product S6 by GPC measurement, MnIs 18860g/mol。
Comparative example 1
87g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight of 2400) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, then a mixed solution of 6g of acrylic acid, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is cured for 1 hour, and the mixture is cooled to room temperature, so that a polycarboxylic acid water reducing agent product P1 is obtained.
The product P1 is characterized by infrared spectrum, 3441.75m in the infrared spectrum-1Stretching vibration of O-H; 2872.63cm-1And 2874.76cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1708.75cm-1、1732.63cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1104.76cm-1And 1257.565cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product P1 by GPC measurement, Mn20080 g/mol.
Comparative example 2
87g of 4-hydroxybutyl vinyl ether polyoxyethylene ether (molecular weight of 2400) is placed in a kettle and dissolved in 60g of water at 20 ℃, 0.8g of thioglycolic acid and 0.3g L-ascorbic acid are added, and then a mixed solution of 11.4g of acrylic acid, 0.6g of 3- (diallylamino) -2-hydroxypropyl sodium sulfonate, 1g of hydroxypropyl acrylate, 1.5g of hydrogen peroxide (30 wt% aqueous solution) and 40g of water is added dropwise for 2 hours, after the dropwise addition is completed, the mixture is aged for 1 hour and cooled to room temperature, so that a slump-retaining polycarboxylic acid water reducer product P2 is obtained.
The product P2 is characterized by infrared spectrum, 3441.56m in the infrared spectrum-1Stretching vibration of O-H; 2872.08cm-1And 2874.45cm-1The strong absorption peak of (A) is-CH2Stretching vibration of-and-CH3Bending vibration; 1731.36cm-1The strong absorption peak of (A) is a C ═ O vibration peak, 1186.28cm-1is-SO3Stretching vibration of Na, 1104.26cm-1And 1257.38cm-1The strong absorption peak is-C-O-C-stretching vibration.
Product P2 by GPC measurement, Mn34250 g/mol.
Test example 1
1. Fluidity of cement paste
And (3) testing the net slurry fluidity: in order to examine the effect of the slump-retaining polycarboxylate superplasticizer synthesized by the invention on the fluidity of the disc-set P. 042.5 cement, the net slurry fluidity of each example and each comparative example on the cement at the same mixing amount is tested.
The products S1-S6 prepared in examples 1-6 and the products P1 and P2 prepared in comparative examples 1 and 2 are subjected to a net slurry fluidity test by referring to GB8077-2012 'test method for homogeneity of concrete admixtures', and the test results are shown in Table 1. Wherein the water cement ratio W/C is 0.29, the bending and fixing mixing amount of the water reducing agent is 0.15 percent of the cement using amount, and the mixing amount is the bending and fixing mixing amount.
TABLE 1 Cement paste flow Performance results
Figure BDA0001918899500000131
As can be seen from Table 1, the slump-retaining type polycarboxylate superplasticizers S1-S6 synthesized by the methods of examples 1-6 have obviously higher retention performance on cement paste fluidity than the products P1 of comparative example 1 and P2 of comparative example 2, and hardly lose 5 h.
2. Concrete slump, expansion and compressive strength
The tests refer to GB/T50080-2016 Standard test method for Performance of common concrete mixture and GB/T50081-2016 Standard test method for mechanical Properties of common concrete to test the slump loss and the concrete strength of the products S1-S6 obtained in examples 1-6 and the polycarboxylic acid water reducing agents P1 and P2 prepared in comparative examples 1-2. The design strength is C30, the solid mixing amount of the water reducing agent product in the cement is 0.28%, the reference cement is selected, and the mass mixing ratio of the concrete is the reference cement: sand: stone: water 360: 812: 1033: 195. the test results are shown in Table 2. As can be seen from the concrete test results in Table 2, the slump retaining polycarboxylic acid water reducing agent prepared in the examples has longer slump retaining time of S1-S6 and higher compressive strength at 1 day, 7 days and 28 days compared with the comparative examples P1 and P2.
TABLE 2 concrete test results
Figure BDA0001918899500000141
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (14)

1. The slump-retaining polycarboxylate water reducer is characterized by comprising a structural unit A, a structural unit B, a structural unit C and a structural unit D;
the structural unit A is a structural unit shown as a formula I, the structural unit B is a structural unit shown as a formula II, the structural unit C is a structural unit shown as a formula III, and the structural unit D is a structural unit shown as a formula IV;
Figure 807871DEST_PATH_IMAGE001
the compound has a structure shown in a formula I,
Figure 475613DEST_PATH_IMAGE002
the compound of the formula II is shown in the specification,
Figure 613333DEST_PATH_IMAGE003
in the formula (III), the reaction is carried out,
Figure 528069DEST_PATH_IMAGE004
a formula IV;
R1、R4and R5Identical or different, R1、R4And R5Represents hydrogen or C1-12An alkyl group;
R6represents C1-12An alkylene group;
R2and R3Identical or different, R2And R3Represents CxH2xA substituent, wherein x is a natural number from 2 to 20;
m + n is a natural number of 10-250;
formula II represents a carboxylic acid or carboxylate; when formula II is a carboxylic acid, M is H; when formula II is carboxylate, M is selected from Na, K, NH4One, two or more of;
in the formula III, M is selected from Na or K;
based on the total weight of the polycarboxylate superplasticizer, the weight content of the structural unit A is 71-96%;
the weight content of the structural unit B is 0.8-12%;
the weight content of the structural unit C is 0.8-12%;
the weight content of the structural unit D is 0.08-5%.
2. The slump-retaining polycarboxylic acid water reducing agent according to claim 1, wherein the molecular weight of the water reducing agent is 10000-50000 g/mol.
3. The slump-retaining polycarboxylic acid water reducing agent according to claim 1 or 2, characterized in that the solid content of the polycarboxylic acid water reducing agent is 35-55%.
4. The preparation method of the slump-retaining polycarboxylic acid water reducing agent as claimed in any one of claims 1 to 3, characterized in that the preparation method comprises the steps of: the polycarboxylate superplasticizer is prepared from a monomer mixture containing a monomer E with a structure shown in a formula V, a monomer F with a structure shown in a formula VI, a monomer G with a structure shown in a formula VII and a monomer H with a structure shown in a formula VIII through a polymerization reaction;
Figure 220081DEST_PATH_IMAGE005
the compound of the formula V is shown in the specification,
Figure 425935DEST_PATH_IMAGE006
in the formula VI, the reaction mixture is shown in the specification,
Figure 664499DEST_PATH_IMAGE007
the compound of the formula VII is shown in the specification,
Figure 563185DEST_PATH_IMAGE008
formula VIII;
R1’、R4' and R5' same or different, R1’、R4' and R5' represents hydrogen or C1-12An alkyl group;
R6' represents C1-12An alkylene group;
R2' and R3' same or different, R2' and R3' represents CxH2xA substituent, wherein x is a natural number from 2 to 20;
m + n is a natural number of 10-250;
formula VI represents a carboxylic acid or carboxylate; when formula VI is a carboxylic acid, M' is H; when formula VI is a carboxylate, M' is selected from Na, K, NH4One, two or more of;
m in the formula VII1' is selected from Na or K;
the weight ratio of the monomer E to the monomer F to the monomer G to the monomer H is 1: 0.01-0.12: 0.001-0.04.
5. The preparation method according to claim 4, comprising the following steps: and carrying out solution polymerization reaction on the monomer mixture containing the monomer E with the structure shown in the formula V, the monomer F with the structure shown in the formula VI, the monomer G with the structure shown in the formula VII and the monomer H with the structure shown in the formula VIII in water in the presence of an initiator to obtain the polycarboxylic acid water reducer.
6. The method according to claim 4 or 5, wherein the monomer E is at least one of 4-hydroxybutyl vinyl ether polyoxyethylene ether and 2-hydroxyethyl vinyl ether polyoxyethylene ether.
7. The process according to claim 4 or 5, wherein the molecular weight of the monomer E is 1000-6000.
8. The production method according to claim 4 or 5, wherein the monomer F is an acrylic monomer.
9. The method according to claim 4 or 5, wherein the monomer G is sodium 3- (diallylamino) -2-hydroxypropyl sulfonate.
10. The method according to claim 4 or 5, wherein the monomer H is an acrylate monomer.
11. The method according to claim 5, wherein the solution polymerization reaction conditions of the olefin comprise: the reaction temperature is 5-70 ℃, and the reaction time is 1-10 h.
12. The method according to claim 5 or 11, wherein the initiator is a redox system initiator.
13. The method according to claim 5, wherein the olefin solution polymerization reaction further comprises a molecular weight modifier.
14. The use of the slump-retaining polycarboxylic acid water reducing agent of any one of claims 1 to 3 in the fields of cement and concrete.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371691A (en) * 2014-10-27 2015-02-25 西南石油大学 Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104371691A (en) * 2014-10-27 2015-02-25 西南石油大学 Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型聚羧酸减水剂分子设计及其性能研究;陈常亮;《万方学位论文》;20180727;第1-2、47-49、51-52页 *

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