CN108373522B - Polycarboxylate superplasticizer with modified cyclodextrin side chain structure and preparation method thereof - Google Patents

Polycarboxylate superplasticizer with modified cyclodextrin side chain structure and preparation method thereof Download PDF

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CN108373522B
CN108373522B CN201810145839.2A CN201810145839A CN108373522B CN 108373522 B CN108373522 B CN 108373522B CN 201810145839 A CN201810145839 A CN 201810145839A CN 108373522 B CN108373522 B CN 108373522B
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cyclodextrin
side chain
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chain structure
allyl
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CN108373522A (en
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高玉军
李顺凯
明阳
王文荣
韦鹏亮
陈雍雍
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Cccc Shec Wuhan Port New Materials Co ltd
CCCC Wuhan Harbour Engineering Design and Research Institute Co Ltd
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CCCC Wuhan Harbour Engineering Design and Research Institute Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention discloses a modified cyclodextrin side chain structure polycarboxylate superplasticizer, which has a general structural formula as follows:

Description

Polycarboxylate superplasticizer with modified cyclodextrin side chain structure and preparation method thereof
Technical Field
The invention relates to the technical field of concrete, in particular to a modified cyclodextrin side chain structure polycarboxylate superplasticizer and a preparation method thereof.
Background
The polycarboxylate superplasticizer is used as a third-generation high-performance water reducing agent, has strong designability of molecular structure and high-performance potential, and can be copolymerized by selecting monomers with different functions to prepare a multifunctional product. The polycarboxylate superplasticizer functionally modified by cyclodextrin has the advantages of high slump retention, high water retention, viscosity increasing and the like, has good adaptability to different cements, mineral admixtures, inferior sandstone materials and the like, has wide market application prospect, and has various products.
In patent CN 103819637A, β -cyclodextrin, lignin and maleic anhydride are used for esterification to obtain a maleic anhydride- β -cyclodextrin-lignin esterification product, and the maleic anhydride- β -cyclodextrin-lignin esterification product is subjected to aqueous solution free radical polymerization with allyl polyethylene glycol, acrylic acid and potassium persulfate at the temperature of 60-100 ℃ to prepare a polycarboxylic acid water reducer containing β -cyclodextrin and lignin.
Patent CN 104817663A provides a β -cyclodextrin-containing functional monomer, which is prepared by using β -cyclodextrin, p-toluenesulfonyl chloride, alcohol amine and glycidyl ester as raw materials and performing selective sulfonylation reaction, alcohol amine substitution reaction and epoxy ring-opening reaction to synthesize a modified β -cyclodextrin functional monomer, and performing free radical polymerization reaction on the monomer, acrylic acid, sodium methallylsulfonate, and isobutylene alcohol polyoxyethylene ether by using an oxidation-reduction initiation system to prepare a polycarboxylic acid water reducer with a side chain containing β -cyclodextrin.
In the patent CN 105778023A, esterification is carried out on a sulfonated product of α -cyclodextrin or β -cyclodextrin and maleic anhydride to obtain sulfonated cyclodextrin maleic acid ester, and the sulfonated cyclodextrin maleic acid ester reacts with polyethylene glycol monomethyl ether methacrylate, 2-methylallyl alcohol polyoxyethylene ether, acrylic acid and ammonium persulfate at the temperature of 85-95 ℃ to prepare the sulfonated cyclodextrin polycarboxylic acid water reducer.
The patents successfully prepare the polycarboxylate superplasticizer with the side chain containing the cyclodextrin structure, wherein the cyclodextrin side chain structures in the molecules are connected with the main chain through ester groups, the ester groups are easy to hydrolyze in the alkaline environment of concrete to release cyclodextrin molecules, the cyclodextrin molecules have a retarding effect, the rate of the cyclodextrin molecules released by hydrolysis is related to the pH and the temperature of the concrete, and the inconsistent hydrolysis rates cause the amount of the released cyclodextrin molecules to be more or less along with the difference of the pH and the temperature, so that the setting time or the length of the concrete is shortened, the formation of the concrete strength is influenced, and the quality of the concrete is difficult to ensure; in addition, the intermolecular hydrogen bonding of polycarboxylic acids is weakened, and the water-retaining thickening effect is lowered.
Disclosure of Invention
The invention aims to provide a polycarboxylate superplasticizer with a modified cyclodextrin side chain structure, which is stable in an alkaline environment and has excellent water retention, slump retaining and tackifying performances; the invention also aims to provide a preparation method of the modified cyclodextrin side chain structure polycarboxylate superplasticizer, which has the advantages of easily controlled preparation conditions and high operability.
In order to achieve the purpose, the invention adopts the technical scheme that: a modified polycarboxylate superplasticizer with a cyclodextrin side chain structure has a general structural formula as follows:
Figure BDA0001578654460000021
wherein a, b, c, d, m and n are positive integers, a is 15-20, b is 1-5, c is 55-90, d is 1-5, m is 45-90, and n is 9-27.
Further, the molecular weight of the polycarboxylic acid water reducer with the modified cyclodextrin side chain structure is 30000-80000.
The invention relates to a preparation method of a modified cyclodextrin side chain structure polycarboxylate superplasticizer, which comprises the following steps:
1) adding prenyl alcohol polyoxyethylene ether, allyl polyethylene glycol and deionized water into a reaction kettle, and heating and dissolving to obtain a solution A;
2) respectively and simultaneously dripping a deionized water solution of persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer in the solution A, carrying out heat preservation reaction, and cooling to room temperature to obtain a solution B;
3) adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain the 40% by mass of modified cyclodextrin side chain structure polycarboxylate superplasticizer.
Furthermore, the mole ratio of the isopentenol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the persulfate is 1.0 to (0.1-0.3) to (3.7-6.0) to (0.1-0.3) to (0.15-0.35).
Specifically, the molecular weight of the prenyl polyoxyethylene ether in the step 1) is 2000-4000, and the molecular weight of the allyl polyethylene glycol is 400-1200.
Specifically, the temperature of the heat preservation reaction in the step 2) is 60-80 ℃, the reaction time is 1.0-2.0 h, and the persulfate is selected from sodium persulfate, potassium persulfate and ammonium persulfate.
The preparation method of the cyclodextrin allyl etherification monomer comprises the following steps of reacting bromopropylene and β -cyclodextrin at a molar ratio of 1:1 at 0-10 ℃ for 24-48 h by using N, N-dimethylformamide or pyridine as a solvent and sodium hydroxide or/and potassium hydroxide as a catalyst, precipitating with acetone or isopropanol, repeatedly washing with absolute ethyl alcohol for several times, carrying out vacuum filtration to remove the solvent, and carrying out vacuum drying to obtain a finished product.
The polycarboxylate superplasticizer of the invention 1) has an etherified cyclodextrin side chain structure on the molecule, and compared with the esterified cyclodextrin side chain structure, the polycarboxylate superplasticizer is more stable in the alkaline environment of concrete, does not generate hydrolysis reaction, and has good stability after being added into the concrete; 2) after the concrete is added, the water retention and slump retention performance is good, the thickening stability is more excellent, and the change of the fluidity of the clear paste is small after 120 min; 3) the side chain contains various long chains, so that more steric hindrance can be provided, the dispersibility and the fluidity of the concrete are increased, the retardation of cyclodextrin molecules released by hydrolysis is not depended on, and the setting time of the concrete is not influenced.
Detailed Description
The present invention will be described in further detail with reference to preferred embodiments for better understanding, but the present invention is not limited to the following embodiments.
The main principle of the invention is that β -cyclodextrin contains active alcoholic hydroxyl, which reacts with sodium hydroxide or/and potassium hydroxide to generate sodium alkoxide, and then reacts with halogenated hydrocarbon (bromopropylene) for nucleophilic substitution to generate an etherified structure, and the etherified cyclodextrin side chain structure is connected with a main chain instead of an esterified cyclodextrin side chain to be connected with the main chain, so that the polycarboxylate superplasticizer is more suitable for being used in the alkaline environment of concrete, is not easy to hydrolyze and has more stable performance.
The invention relates to a modified cyclodextrin side chain structure polycarboxylate superplasticizer, which has the structural general formula:
Figure BDA0001578654460000041
wherein a, b, c, d, m and n are polymerization degrees and are positive integers, a is 15-20, b is 1-5, c is 55-90, d is 1-5, m is 45-90, and n is 9-27; the molecular weight of the modified cyclodextrin side chain structure polycarboxylate superplasticizer is 30000-80000.
The invention relates to a preparation method of a modified cyclodextrin side chain structure polycarboxylate superplasticizer, which comprises the following steps:
1) adding prenyl polyoxyethylene ether, allyl polyethylene glycol and deionized water into a reaction kettle, and heating and dissolving at the temperature of 20-80 ℃ to obtain a solution A;
2) respectively and simultaneously dripping a deionized water solution of persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, carrying out heat preservation reaction for 1.0-2.0 h at the temperature of 60-80 ℃, and cooling to room temperature to obtain a solution B; the persulfate is selected from sodium persulfate, potassium persulfate or ammonium persulfate;
3) adding 30 mass percent of liquid alkali into the solution B, adjusting the pH value to 6-8 to obtain a modified cyclodextrin side chain structure polycarboxylate water reducer with 40 mass percent, wherein the molar ratio of prenyl alcohol polyoxyethylene ether, allyl polyethylene glycol, methacrylic acid, a cyclodextrin allyl etherification monomer to persulfate is 1.0 to (0.1-0.3) to (3.7-6.0) to (0.1-0.3) to (0.15-0.35), the molecular weight of prenyl alcohol polyoxyethylene ether is 2000-4000, the molecular weight of allyl polyethylene glycol is 400-1200, the used cyclodextrin allyl etherification monomer is prepared by using N, N-Dimethylformamide (DMF) or pyridine as a solvent, sodium hydroxide (NaOH) or potassium hydroxide (KOH) as a catalyst, reacting bromopropylene and β -cyclodextrin at 0-10 ℃ for 24-48 hours in a molar ratio of 1 to 1, precipitating with acetone or isopropanol, repeatedly washing in vacuum for several times, removing the solvent, and carrying out vacuum filtration to obtain a finished product, and the final product can be dried at 0-10 ℃ or 10 ℃ under a certain temperature gradient, and the final product can be obtained by controlling the temperature to be 0-10 ℃ and the temperature gradient of 0-10 ℃ at a certain gradient.
Example 1
(1) Taking N, N-Dimethylformamide (DMF) as a solvent, adding β -cyclodextrin into a reaction kettle, heating to dissolve completely, adding sodium hydroxide (NaOH) as a catalyst into the reaction kettle, stirring fully for 1h, slowly adding bromopropylene into the reaction kettle, reacting for 48h in an ice-water bath at 0 ℃, precipitating with acetone, repeatedly washing with absolute ethyl alcohol for several times, carrying out vacuum filtration to remove the solvent, and finally carrying out vacuum drying to obtain a white powdery cyclodextrin allyl etherified monomer, wherein the molar ratio of the bromopropylene to the β -cyclodextrin is 1: 1.
(2) Polymerization reaction: adding prenyl alcohol polyoxyethylene ether with the molecular weight of 2080, allyl polyethylene glycol with the molecular weight of 454 and deionized water into a reaction kettle, and heating and dissolving completely at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at the temperature of 60 ℃, preserving heat and reacting for 2.0 hours at the temperature of 60 ℃ after finishing dripping, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J1, wherein the molecular weight of J1 is 30421; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.3: 3.7: 0.1: 0.15.
Example 2
(1) Synthesizing a cyclodextrin allyl etherification monomer, namely adding β -cyclodextrin into a reaction kettle by taking pyridine as a solvent, heating and dissolving completely, adding potassium hydroxide as a catalyst into the reaction kettle, fully stirring for 1h, slowly adding bromopropylene into the reaction kettle, reacting for 24h at 10 ℃, precipitating by using acetone, repeatedly washing by using absolute ethyl alcohol for several times, carrying out vacuum filtration to remove the solvent, and finally carrying out vacuum drying to obtain a white powdery cyclodextrin allyl etherification monomer, wherein the molar ratio of the bromopropylene to the β -cyclodextrin is 1: 1.
(2) Polymerization reaction: adding prenyl alcohol polyoxyethylene ether with molecular weight of 2432, allyl polyethylene glycol with molecular weight of 586 and deionized water into a reaction kettle, and heating and dissolving completely at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of sodium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 70 ℃, preserving the temperature at 70 ℃ after dripping for reaction for 1.5 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J2, wherein the molecular weight of J2 is 36825; wherein the mol ratio of the prenyl alcohol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.28: 4.0: 0.12: 0.18.
Example 3
(1) Synthesizing a cyclodextrin allyl etherification monomer, namely adding β -cyclodextrin into a reaction kettle by taking pyridine as a solvent, heating and dissolving completely, adding potassium hydroxide and sodium hydroxide as catalysts into the reaction kettle, fully stirring for 1h, slowly adding bromopropylene into the reaction kettle, starting reaction in an ice-water bath, gradually heating to 10 ℃, reacting for 24h, precipitating by using isopropanol, repeatedly washing by using absolute ethyl alcohol for several times, carrying out vacuum filtration to remove the solvent, and finally carrying out vacuum drying to obtain a white powdery cyclodextrin allyl etherification monomer, wherein the molar ratio of the bromopropylene to the β -cyclodextrin is 1: 1.
(2) Polymerization reaction: adding prenyl alcohol polyoxyethylene ether with the molecular weight of 2432, allyl polyethylene glycol with the molecular weight of 630 and deionized water into a reaction kettle, and heating and dissolving at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of potassium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving the temperature at 80 ℃ after dripping for reaction for 1.0 hour, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass fraction into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is marked as J3, wherein the molecular weight of J3 is 43178; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.25: 4.0: 0.15: 0.2.
Example 4
(1) Taking N, N-dimethylformamide as a solvent, adding β -cyclodextrin into a reaction kettle, heating and dissolving completely, adding potassium hydroxide and sodium hydroxide as catalysts into the reaction kettle, fully stirring for 1h, slowly adding bromopropylene into the reaction kettle, reacting for 5h in an ice water bath, quickly heating to 5 ℃ for reacting for 15h, quickly heating to 10 ℃ for reacting for 15h, reacting for 35h, precipitating with isopropanol, repeatedly washing with absolute ethyl alcohol for several times, removing the solvent by vacuum filtration, and finally drying in vacuum to obtain the white powdery cyclodextrin allyl etherified monomer, wherein the molar ratio of the bromopropylene to the β -cyclodextrin is 1: 1.
(2) Polymerization reaction: adding prenyl alcohol polyoxyethylene ether with molecular weight of 2696, allyl polyethylene glycol with molecular weight of 630 and deionized water into a reaction kettle, and heating and dissolving completely at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving heat at 60-80 ℃ after finishing dripping, reacting for 1.0-2.0 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass fraction into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with the mass fraction of 40%, which is marked as J4, wherein the molecular weight of J4 is 51386; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.22: 4.5: 0.18: 0.22.
Example 5
(1) Synthesis of cyclodextrin allyl etherification monomer: the same as example 1;
(2) polymerization reaction: adding prenyl alcohol polyoxyethylene ether with molecular weight of 2696, allyl polyethylene glycol with molecular weight of 806 and deionized water into a reaction kettle, and heating and dissolving at 20-80 ℃ to obtain solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving heat at 60-80 ℃ after finishing dripping, reacting for 1.0-2.0 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J5, wherein the molecular weight of J5 is 57732; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.20: 4.5: 0.2: 0.25. 100: 20: 450:
example 6
(1) Synthesis of cyclodextrin allyl etherification monomer: the same as example 1;
(2) polymerization reaction: adding prenyl alcohol polyoxyethylene ether with molecular weight of 3092, allyl polyethylene glycol with molecular weight of 938 and deionized water into a reaction kettle, and heating and dissolving completely at the temperature of 20-80 ℃ to obtain solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving heat at 60-80 ℃ after finishing dripping, reacting for 1.0-2.0 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J6, wherein the molecular weight of J6 is 63958; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.18: 5.5: 0.24: 0.27.
Example 7
(1) Synthesis of cyclodextrin allyl etherification monomer: the same as example 1;
(2) polymerization reaction: adding prenyl alcohol polyoxyethylene ether with the molecular weight of 3488, allyl polyethylene glycol with the molecular weight of 1026 and deionized water into a reaction kettle, and heating and dissolving at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving heat at 60-80 ℃ after finishing dripping, reacting for 1.0-2.0 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J7, wherein the molecular weight of J7 is 71218; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.15: 5.5: 0.27: 0.3.
Example 8
(1) Synthesis of cyclodextrin allyl etherification monomer: the same as example 1;
(2) polymerization reaction: adding prenyl alcohol polyoxyethylene ether with the molecular weight of 3928, allyl polyethylene glycol with the molecular weight of 1158 and deionized water into a reaction kettle, and heating and dissolving at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer into the solution A, dripping for 3.0 hours at 80 ℃, preserving heat at 60-80 ℃ after finishing dripping, reacting for 1.0-2.0 hours, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% of liquid alkali by mass into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a modified cyclodextrin side chain structure polycarboxylate water reducer with 40% of mass fraction, which is recorded as J8, wherein the molecular weight of J8 is 79476; wherein the mol ratio of the isoamylol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherification monomer and the ammonium persulfate is 1.0: 0.1: 6: 0.3: 0.35.
Comparative example 1
Reference is made to the polymerization process of example 1 except that the cyclodextrin allyl etherified monomer is replaced with the cyclodextrin maleated monomer. The specific polymerization reaction is as follows: adding prenyl alcohol polyoxyethylene ether with the molecular weight of 2080, allyl polyethylene glycol with the molecular weight of 454 and deionized water into a reaction kettle, and heating and dissolving completely at the temperature of 20-80 ℃ to obtain a solution A; respectively and simultaneously dripping a deionized water solution of ammonium persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin maleic acid esterification monomer into the solution A, dripping for 3.0 hours at the temperature of 80 ℃, carrying out heat preservation reaction for 1.0-2.0 hours at the temperature of 60-80 ℃ after dripping is finished, and cooling to room temperature after the reaction is finished to obtain a solution B; adding 30% by mass of liquid caustic soda into the solution B, and adjusting the pH value to 6-8 to obtain a product, namely a polycarboxylic acid water reducing agent with an esterified cyclodextrin side chain structure and with a mass fraction of 40%, and marking as K1; wherein the mol ratio of the prenyl polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin maleated monomer and the ammonium persulfate is 1.0: 0.3: 3.7: 0.1: 0.15.
Comparative example 2
A commercial polycarboxylic acid water reducing agent is marked as K2.
Example 9
And (3) verifying the implementation effect:
the polycarboxylate water reducing agents with modified cyclodextrin side chain structures in examples 1-8 of the invention, the polycarboxylate water reducing agents with esterified cyclodextrin side chain structures in comparative example 1 and the commercially available polycarboxylate water reducing agents in comparative example 2 are used for measuring the net slurry fluidity according to GB/T8077-2012 'test method for homogeneity of concrete admixture', cement is reference cement, and the experimental results are shown in Table 1:
TABLE 1 test results of cement paste fluidity of each sample
Figure BDA0001578654460000101
As can be seen from the results in Table 1, in comparison with comparative example 1 and comparative example 2, examples 1 to 8 of the present invention are significantly superior to comparative example 1 and comparative example 2 in the initial net paste fluidity and the loss with time of net paste fluidity at 60min and 120 min. Therefore, compared with the esterified cyclodextrin side chain structure, the etherified cyclodextrin side chain structure is more beneficial to improving the water reducing rate and slump retention of the polycarboxylic acid water reducing agent, and particularly has more excellent dispersibility and fluidity retention compared with the commercial product in the comparative example 2.
Example 10
And (3) verifying the implementation effect:
the compressive strength of the modified polycarboxylate superplasticizer with cyclodextrin side chain structure of examples 1-8 of the invention, the polycarboxylate superplasticizer with esterified cyclodextrin side chain structure of comparative example 1 and the commercially available polycarboxylate superplasticizer with comparative example 2 are tested according to GB/T50081-2002 Standard test method for mechanical Properties of ordinary concrete, and the concrete mixing ratio adopted in the test is as follows: reference cement 360kg/m3792kg/m of sand3290kg/m of small stone3(5-10 mm) Dashi 678kg/m3(10-20 mm) and the water-to-glue ratio is 0.4. The results are shown in Table 2:
TABLE 2 concrete compressive Strength test results for each sample
Figure BDA0001578654460000111
As can be seen from Table 2, in comparison with comparative example 1 and comparative example 2, the compressive strengths of the concrete of examples 1 to 8 of the present invention are higher than those of comparative example 1 and comparative example 2 in different ages. Therefore, the etherified cyclodextrin side chain structure has stronger hydrophilicity than that of the esterified cyclodextrin side chain structure and good water retention, so that the cement is more fully hydrated, the concrete strength is more favorably increased, and especially compared with the commercial product in the comparative example 2, the early strength is more excellent.
What is not described in detail in this specification is prior art that is well known to those of ordinary skill in the art.
The above-mentioned embodiments are merely illustrative, and the restrictive modification of the technical terms used in the present invention is only for the convenience of description of the present invention, and those skilled in the art can derive many forms without departing from the spirit and scope of the present invention as claimed in the claims of the present invention in light of the present invention and the modified cyclodextrin side chain structure of polycarboxylic acid water reducing agent and the preparation method thereof.

Claims (5)

1. The modified polycarboxylate superplasticizer with the cyclodextrin side chain structure is characterized by comprising the following structural general formula:
Figure FDA0002409470690000011
wherein a, b, c, d, m and n are polymerization degrees and are positive integers, a is 15-20, b is 1-5, c is 55-90, d is 1-5, m is 45-90, and n is 9-27;
the modified cyclodextrin side chain structure polycarboxylate superplasticizer is prepared by the following preparation method, and comprises the following steps:
1) adding prenyl alcohol polyoxyethylene ether, allyl polyethylene glycol and deionized water into a reaction kettle, and heating and dissolving to obtain a solution A;
2) respectively and simultaneously dripping a deionized water solution of persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer in the solution A, carrying out heat preservation reaction, and cooling to room temperature to obtain a solution B;
3) adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain 40% by mass of a modified cyclodextrin side chain structure polycarboxylate superplasticizer;
the mole ratio of the isoamylene alcohol polyoxyethylene ether, the allyl polyethylene glycol, the methacrylic acid, the cyclodextrin allyl etherified monomer and the persulfate is 1.0 (0.1-0.3), 3.7-6.0, (0.1-0.3) and (0.15-0.35).
2. The modified cyclodextrin side chain structure polycarboxylate water reducer of claim 1, characterized in that: the molecular weight of the polycarboxylate superplasticizer with the modified cyclodextrin side chain structure is 30000-80000.
3. The preparation method of the polycarboxylate superplasticizer with the modified cyclodextrin side chain structure as claimed in claim 1 or 2, characterized by comprising the following steps:
1) adding prenyl alcohol polyoxyethylene ether, allyl polyethylene glycol and deionized water into a reaction kettle, and heating and dissolving to obtain a solution A;
2) respectively and simultaneously dripping a deionized water solution of persulfate and a deionized water mixed solution of methacrylic acid and a cyclodextrin allyl etherification monomer in the solution A, carrying out heat preservation reaction, and cooling to room temperature to obtain a solution B;
3) adding 30% by mass of liquid alkali into the solution B, and adjusting the pH value to 6-8 to obtain 40% by mass of a modified cyclodextrin side chain structure polycarboxylate superplasticizer; the molecular weight of the prenyl polyoxyethylene ether in the step 1) is 2000-4000, and the molecular weight of the allyl polyethylene glycol is 400-1200.
4. The preparation method of the modified cyclodextrin side chain structure polycarboxylate superplasticizer according to claim 3, characterized by comprising the following steps: the temperature of the heat preservation reaction in the step 2) is 60-80 ℃, the reaction time is 1.0-2.0 h, and the persulfate is selected from sodium persulfate, potassium persulfate and ammonium persulfate.
5. The preparation method of the modified cyclodextrin side chain structure polycarboxylate water reducer according to claim 3 is characterized in that the cyclodextrin allyl etherification monomer is prepared by the following preparation method, N-dimethylformamide or pyridine is used as a solvent, sodium hydroxide or/and potassium hydroxide are used as catalysts, bromopropylene and β -cyclodextrin are reacted for 24-48 hours at 0-10 ℃ in a molar ratio of 1:1, acetone or isopropanol is used for precipitation, absolute ethyl alcohol is used for repeated washing for several times, the solvent is removed by vacuum filtration, and a finished product is obtained by vacuum drying.
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