CN113372549B - Vinyl-terminated hyperbranched polymer, viscosity-reducing polycarboxylate superplasticizer with hyperbranched structure and preparation method of viscosity-reducing polycarboxylate superplasticizer - Google Patents

Vinyl-terminated hyperbranched polymer, viscosity-reducing polycarboxylate superplasticizer with hyperbranched structure and preparation method of viscosity-reducing polycarboxylate superplasticizer Download PDF

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CN113372549B
CN113372549B CN202110886895.3A CN202110886895A CN113372549B CN 113372549 B CN113372549 B CN 113372549B CN 202110886895 A CN202110886895 A CN 202110886895A CN 113372549 B CN113372549 B CN 113372549B
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percent
viscosity
monomer
hyperbranched
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CN113372549A (en
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高育欣
王福涛
刘明
杨文�
曾超
张磊
叶子
闫松龄
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Building Materials Science Research Institute Co Ltd of China West Construction Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33396—Polymers modified by chemical after-treatment with organic compounds containing nitrogen having oxygen in addition to nitrogen
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The invention discloses a vinyl-terminated hyperbranched polymer, a viscosity-reducing polycarboxylate water reducer with a hyperbranched structure and a preparation method thereof, belonging to the technical field of concrete admixtures and comprising the following raw materials in percentage by mass: 3 to 18 percent of unsaturated carboxylic acid, 1 to 10 percent of unsaturated anhydride, 0 to 1 percent of unsaturated phosphate, 75 to 93 percent of unsaturated polyether, 1 to 6 percent of hyperbranched functional monomer, 0.1 to 1 percent of initiator and 0.2 to 3.0 percent of chain transfer agent. The water reducing agent prepared by the invention has the characteristics of special branched topological molecular structure, low intrinsic viscosity and the like, effectively weakens the intermolecular chain winding effect of the polycarboxylic acid water reducing agent, improves the dispersing performance of the water reducing agent and reduces the using amount of the water reducing agent; the thickness of the adsorption layer on the surface of the gelled material particles is increased, the thickness of the solvation layer on the surface of the particles is weakened, free water is released, and the viscosity of the high-strength concrete is reduced.

Description

Vinyl-terminated hyperbranched polymer, viscosity-reducing polycarboxylate superplasticizer with hyperbranched structure and preparation method of viscosity-reducing polycarboxylate superplasticizer
Technical Field
The invention relates to the technical field of hyperbranched polymers and concrete admixtures, in particular to a vinyl-terminated hyperbranched polymer, a viscosity-reducing polycarboxylate superplasticizer with a hyperbranched structure and a preparation method thereof.
Background
Along with the continuous enlargement of civil engineering scale in China, the technological level is continuously improved, and important buildings with special function requirements of super height, large span, high specific strength, high load and the like continuously appear, such as skyscrapers, super large super span bridges, huge hydro junction engineering construction and the like, and the concrete is required to have higher strength. The concrete strength is improved mainly by increasing a cementing material and reducing a water-cement ratio, but the viscosity of the concrete with the low water-cement ratio is high, the flow rate is low, a series of construction problems such as concrete stirring, transportation, pumping and the like are caused, and the popularization and construction efficiency of high-strength and ultrahigh-strength concrete are limited to a great extent.
Low viscosity and high fluidization are the basic characteristics of modern high-strength and ultrahigh-strength concrete, and how to reduce the viscosity of the concrete becomes a key problem for the development of the high-strength and ultrahigh-strength concrete. The prior viscosity reduction method mainly introduces an inorganic admixture, an organic admixture and an inorganic-organic composite admixture. However, the viscosity of high-grade concrete is increased due to the fact that machine-made sand edges are large in angle, grain shapes are irregular, the amount of water reducing agent in single-side concrete is large, and the like. The long side chain of the polycarboxylate superplasticizer is easy to generate winding effect, and the viscosity of the cement paste pore liquid is further increased. At present, viscosity reduction type polycarboxylate superplasticizers are concerned, special functional groups and side chain lengths are generally introduced to adjust the surface tension and the chain winding effect of the superplasticizer at the present stage, the water reduction rate of the polycarboxylate superplasticizer is reduced after the side chain lengths are adjusted, the dosage of the polycarboxylate superplasticizer is increased in use, and the viscosity of a pore liquid in concrete is further increased.
The hyperbranched polymer has the characteristics of good molecular plasticity, strong dispersing capacity, low intrinsic viscosity and the like, and although the hyperbranched polymer is used as a viscosity reducer and a concrete retarder in the field of oil fields in the prior art, the research and development of the hyperbranched viscosity-reducing polycarboxylic acid water reducer are not carried out. Therefore, the viscosity-reducing polycarboxylic acid water reducer with the hyperbranched structure and the preparation method thereof are very significant.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a vinyl-terminated hyperbranched polymer, a viscosity-reducing polycarboxylate water reducer with a hyperbranched structure and a preparation method thereof, which can effectively solve the problems of large water reducer dosage and high concrete viscosity in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a vinyl-terminated hyperbranched polymer, which has the following structural general formula:
Figure SMS_1
wherein R is 0 Is composed of
Figure SMS_2
R 1 is-H or-CH 3 ；R 2 is-CH 2 -、-CH 2 -CH 2 -and-O-CH 2 -CH 2 -CH 2 -CH 2 -at least one of; n is an integer and the value of n is 4 to 40.
Further, n is 5-20.
The invention also provides a preparation method of the vinyl-terminated hyperbranched polymer, which specifically comprises the following steps:
step (1): adding a monomer containing primary amino, a catalyst and an aprotic polar solvent into a reaction device, stirring and dissolving, heating to 30-150 ℃, starting to dropwise add epoxy chloropropane dissolved in a polar cosolvent, keeping the temperature for reaction for 1.0-5.0 h after dropwise addition is finished, cooling to room temperature, adding solid alkali, reacting for 0.5-2 h, and separating and purifying a reaction product after the reaction is finished to obtain a glycidylamine compound;
step (2): and (2) adding the glycidylamine compound obtained in the step (1), a catalyst, a polymerization inhibitor, unsaturated polyether and an aprotic polar solvent into a reaction vessel, reacting at the temperature of 50-150 ℃ for 2.0-10.0 h, and separating and purifying a reaction product after the reaction is finished to obtain the vinyl-terminated hyperbranched polymer.
Further, the dripping time of the step (1) is 0.2 to 1 hour.
Further, the solid alkali is added in step (1) in four equal batches, and the time interval of each addition is 4-8 minutes.
Further, the molar ratio of the monomer containing a primary amino group, epichlorohydrin and solid base in step (1) is 1.
Further, the molar ratio of the glycidylamine compound to the unsaturated polyether in the step (2) is 1; preferably 1.
Further, the dosage of the catalyst in the step (2) accounts for 0.01-0.1 wt% of the total mass of the reaction raw materials in the step (2), and the dosage of the polymerization inhibitor accounts for 0.001-0.05 wt% of the total mass of the reaction raw materials in the step (2).
Further, the monomer containing primary amine group in the step (1) is at least one of 1,3, 5-triaminobenzene and melamine.
Further, in the step (1), the solid base is a hydroxide, preferably at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride and potassium hydride.
Further, the polar cosolvent in the step (1) is at least one of ethanol, isopropanol, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, diethyl ether, chloroform and trichloroethylene.
Further, the aprotic polar solvent in step (1) and step (2) is at least one of benzene, toluene, xylene, cyclohexane, chloroform, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone and acetonitrile.
Further, the unsaturated polyether in the step (2) is at least one of allyl polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, isoamylol polyoxyethylene ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
Further, the unsaturated polyether has a number average molecular weight of 400 to 4000g/mol.
Further, the unsaturated polyether has a number average molecular weight of 400g/mol, 600g/mol, 1000g/mol, 2000g/mol, 2400g/mol, 3200g/mol or 4000g/mol; preferably, the unsaturated polyether has a number average molecular weight of 400g/mol, 600g/mol or 1000g/mol.
Further, the catalyst in step (1) and step (2) is at least one of triethylbenzylammonium chloride, tetraethylammonium bromide, tetraethylammonium hydroxide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, tetrabutylammonium p-toluenesulfonate, dodecyldimethylbenzylammonium chloride, tetrapropylammonium bromide, benzyltrimethylammonium bromide and tributylmethylammonium bromide.
Further, in the step (2), the polymerization inhibitor is at least one of hydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, phenothiazine, p-hydroxyanisole and methyl hydroquinone.
The invention provides a viscosity-reducing polycarboxylate superplasticizer with a hyperbranched structure, which adopts the vinyl-terminated hyperbranched polymer as a hyperbranched functional monomer.
Further, the viscosity-reducing polycarboxylic acid water reducer with the hyperbranched structure comprises the following raw materials in percentage by mass: 3 to 18 percent of unsaturated carboxylic acid, 1 to 10 percent of unsaturated anhydride, 0 to 1 percent of unsaturated phosphate, 75 to 93 percent of unsaturated polyether, 1 to 6 percent of hyperbranched functional monomer, 0.1 to 1 percent of initiator and 0.2 to 3.0 percent of chain transfer agent.
Further, the viscosity-reducing polycarboxylate superplasticizer with the hyperbranched structure comprises the following raw materials in percentage by mass: 3 to 10 percent of unsaturated carboxylic acid, 1 to 8 percent of unsaturated anhydride, 0.1 to 0.6 percent of unsaturated phosphate, 80 to 90 percent of unsaturated polyether, 1 to 6 percent of hyperbranched functional monomer, 0.1 to 1 percent of initiator and 0.2 to 2.0 percent of chain transfer agent.
Further, the viscosity-reducing polycarboxylate superplasticizer with the hyperbranched structure comprises the following raw materials in percentage by mass: 8% of unsaturated carboxylic acid, 2% of unsaturated anhydride, 0.4% of unsaturated phosphate, 86% of unsaturated polyether, 2.5% of hyperbranched functional monomer, 0.5% of initiator and 0.6% of chain transfer agent.
Further, the unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, metal acrylate, metal methacrylate, metal fumarate and metal itaconate.
Further, the unsaturated acid anhydride monomer is at least one of maleic anhydride, itaconic anhydride, citraconic anhydride, nonylsuccinic anhydride and nonenylsuccinic anhydride.
Further, the unsaturated phosphate ester monomer is at least one of diethylaminoethyl methacrylate phosphate, 2-hydroxyethyl methacrylate phosphate, maleic anhydride polyethylene glycol phosphate and maleic anhydride polypropylene glycol phosphate.
Further, the unsaturated polyether monomer is at least one of allyl polyoxyethylene ether, methallyl alcohol polyoxyethylene ether and isoamylol alcohol polyoxyethylene ether.
Further, the molecular weight of the unsaturated polyether monomer is 1200-5000 g/mol; preferably 2000 to 4000g/mol.
The initiator is an organic peroxide initiator, an inorganic peroxide initiator or an azo initiator, and preferably at least one of ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, azobisisobutylamidine hydrochloride, azobisisobutylimidazoline hydrochloride, azobiscyanovaleric acid, azobisdiisopropylimidazoline, benzoyl peroxide, cyclohexanone peroxide, bis (2-phenylethoxy) peroxydicarbonate.
Further, the amount of the initiator is 0.1 to 1wt%, preferably 0.5 to 1wt%, of the total mass of the unsaturated carboxylic acid monomer, the unsaturated anhydride monomer, the unsaturated phosphate ester monomer, the unsaturated polyether monomer and the hyperbranched functional monomer.
Further, the chain transfer agent is at least one of mercaptoethanol, 2-hydroxypropanethiol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid, dodecyl mercaptan, sodium hypophosphite and sodium formate.
Furthermore, the dosage of the chain transfer agent is 0.2-1 wt% of the total mass of the unsaturated carboxylic acid monomer, the unsaturated anhydride monomer, the unsaturated phosphate ester monomer, the unsaturated polyether monomer and the hyperbranched functional monomer.
The invention also provides a preparation method of the viscosity-reducing polycarboxylate superplasticizer with the hyperbranched structure, which comprises the following steps:
step (1): adding an unsaturated anhydride monomer, an unsaturated polyether monomer, a hyperbranched functional monomer and deionized water into a reactor, and continuously stirring until the unsaturated anhydride monomer, the unsaturated polyether monomer, the hyperbranched functional monomer and the deionized water are dissolved to obtain a base material;
step (2): preparing an unsaturated carboxylic acid monomer, an unsaturated phosphate ester monomer, a chain transfer agent and deionized water into a material A, and preparing an initiator and the deionized water into a material B;
and (3): and (3) simultaneously dripping the material A and the material B obtained in the step (2) into the base material obtained in the step (1) at the temperature of 35-75 ℃, preserving heat for reaction for 1-2 hours after dripping is finished, and adding alkali to adjust the pH value to 6-8 after the reaction is finished, so as to obtain the viscosity-reducing polycarboxylic acid high-efficiency water reducing agent with the hyperbranched structure.
Further, the total amount of the deionized water added in the step (1), the step (2) and the step (3) is adjusted by the solid content of the polycarboxylic acid water reducing agent being 30-50%.
In summary, the invention has the following advantages:
1. the invention provides a vinyl-terminated hyperbranched polymer, which takes a nitrogen-containing rigid structure as a core and unsaturated polyether as an arm, introduces a polyether side chain and an anchoring group to the arm of a branched structure to play an excellent steric hindrance effect, and comprises the following preparation processes: performing epoxy-amine ring opening and ring closing reaction on a primary amino monomer, epoxy chloropropane and solid alkali under the action of a catalyst to prepare glycidylamine, and further reacting the glycidylamine with unsaturated polyether under the conditions of a catalyst and a polymerization inhibitor to obtain a vinyl-terminated hyperbranched polymer; and the hyperbranched polymer is used as a hyperbranched functional monomer to be applied to a polycarboxylate water reducer, so that the dispersing performance of the water reducer is improved, and the using amount of the water reducer in single-side concrete is reduced.
2. The viscosity reduction type polycarboxylate superplasticizer with the hyperbranched structure has the characteristics of special branched topological molecular structure, low intrinsic viscosity, large space volume and the like, effectively weakens the intermolecular chain winding effect of the polycarboxylate superplasticizer, improves the dispersing performance of the polycarboxylate superplasticizer, and reduces the dosage of the polycarboxylate superplasticizer; compared with the common polycarboxylate water reducer, the polycarboxylate water reducer has the advantages that the single molecular shape is changed from a worm shape to an ellipsoid shape, adsorption sites on the surfaces of the gelled material particles, which are not occupied by the polycarboxylate water reducer, are increased, the thickness of the adsorption layer on the surfaces of the gelled material particles is thicker, the surface activity of the gelled material particles is enhanced, the thickness of a solvation layer on the surfaces of the particles is reduced, free water is released, the viscosity of slurry pore liquid is reduced, and low viscosity of concrete is realized.
3. The invention has the advantages of low cost of raw materials, no need of expensive monomers, mild reaction conditions, simple and convenient synthesis process, short production period, environmental friendliness and practical application value.
Drawings
FIG. 1 is a viscosity diagram of viscosity-reducing polycarboxylic acid water reducing agents with hyperbranched structures prepared in examples 1-5 and comparative examples 1-2 of the invention in cement pore fluid.
FIG. 2 is a thickness chart of an adsorption layer of the viscosity-reducing type polycarboxylate water reducer with hyperbranched structure prepared in examples 1-5 and comparative examples 1-2 of the present invention on nanometer calcium silicate hydrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer with a hyperbranched structure, which comprises the following raw materials in percentage by mass: 10% of unsaturated carboxylic acid, 1.3% of unsaturated anhydride, 86.7% of unsaturated polyether, 0.4% of unsaturated phosphate, 1% of hyperbranched functional monomer, 0.2% of initiator and 0.4% of chain transfer agent, wherein the total is 100%. The method comprises the following specific steps:
s1, preparing a vinyl-terminated hyperbranched polymer-functional monomer:
s1.1, adding a monomer (specifically melamine, 0.5 mol) containing a primary amino group, a catalyst (specifically triethylbenzylammonium chloride) and an aprotic polar solvent (specifically toluene) into a reactor, heating to 90 ℃, dropwise adding epoxy chloropropane dissolved in ethanol within 1h, keeping the temperature for reaction for 3 hours after dropwise adding, cooling to room temperature, adding solid alkali in four batches in an equivalent manner, wherein the time interval between each addition is 5 minutes, reacting for 1h, standing, removing generated salt by suction filtration, removing the solvent from the obtained solution by a rotary evaporator, and performing vacuum drying for 24.0h at room temperature to obtain glycidylamine; wherein, the molar ratio of the monomer containing primary amino, epichlorohydrin to solid alkali is 1;
s1.2, adding the obtained glycidylamine (0.1 mmol), unsaturated polyether (specifically allyl polyoxyethylene ether), catalyst (specifically tetraethylammonium bromide), polymerization inhibitor (specifically hydroquinone) and aprotic polar solvent (specifically toluene) into a reactor, continuously stirring, reacting at 80 ℃ for 4.0h, and separating and purifying a reaction product in a Soxhlet extractor after the reaction is finished to obtain the vinyl-terminated hyperbranched polymer-functional monomer; wherein, the mol ratio of the glycidylamine compound to the unsaturated polyether is 1;
the structural formula of the vinyl-terminated hyperbranched polymer-functional monomer prepared in step S1 of this example is shown below:
Figure SMS_3
s2, preparing the viscosity-reducing polycarboxylate superplasticizer with the hyperbranched structure:
s2.1, weighing 303.5g of prenyl alcohol polyoxyethylene ether with the molecular weight of 2400, 4.6g of maleic anhydride, 3.5g of vinyl-terminated hyperbranched functional monomer (prepared in the S1) and 300g of deionized water, adding into a reactor, and stirring for dissolving to obtain a base material;
s2.2, weighing 35g of acrylic acid, 1.4g of 2-hydroxyethyl methacrylate phosphate and 1.4g of chain transfer agent mercaptoethanol, and dissolving in 30g of water to obtain a solution A; weighing 0.7g of ammonium persulfate and dissolving in 20g of water to obtain a solution B;
s2.3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into a reactor of S2.1, dripping the material A for 2.0h, dripping the material B for 2.3h, preserving heat for 1h after finishing dripping the material B, then cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 7, and supplementing water to obtain a polycarboxylic acid high-efficiency water reducing agent with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_4
wherein n and f are 6 and 53, respectively; a. b, c, d, e in a ratio of 7.
In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water-reducing agent prepared in this example was measured by gel chromatography to obtain 36872.
Example 2
The embodiment provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer with a hyperbranched structure, which comprises the following raw materials in percentage by mass: 7% of unsaturated carboxylic acid, 1% of unsaturated anhydride, 88.5% of unsaturated polyether, 0.5% of unsaturated phosphate, 2% of hyperbranched functional monomer, 0.4% of initiator and 0.6% of chain transfer agent, wherein the total is 100%. The method comprises the following specific steps:
s1, weighing 310g of prenol polyoxyethylene ether with the molecular weight of 2400, 3.5g of maleic anhydride, 7.0g of vinyl-terminated hyperbranched functional monomer (prepared in S1 in example 1) and 300g of deionized water, adding into a reactor, and stirring and dissolving to obtain a base material;
s2, weighing 21.5g of acrylic acid, 3g of methacrylic acid, 1.75g of methacrylic acid-2-hydroxyethyl phosphate and 2.1g of chain transfer agent mercaptoethanol, and dissolving in 30g of water to obtain a solution A; weighing 1.4g of ammonium persulfate to dissolve in 20g of water to obtain a solution B;
s3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into the reactor of S1, dripping the material A for 2.0 hours, dripping the material B for 2.3 hours, preserving the temperature for 1 hour after dripping the material B, then cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 7, and supplementing water to obtain a polycarboxylic acid high-efficiency water reducing agent with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_5
wherein n and f are 6 and 53, respectively; a. b, c, d, e, g in a ratio of 5. In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water-reducing agent prepared in this example was measured by gel chromatography to obtain 41520.
Example 3
The embodiment provides a preparation method of a viscosity-reducing polycarboxylate superplasticizer with a hyperbranched structure, which comprises the following raw materials in percentage by mass: 6.0 percent of unsaturated carboxylic acid, 1.3 percent of unsaturated anhydride, 89.3 percent of unsaturated polyether, 0.6 percent of unsaturated phosphate, 1.4 percent of hyperbranched functional monomer, 0.6 percent of initiator and 0.8 percent of chain transfer agent, wherein the total is 100 percent. The method comprises the following specific steps:
s1, 313g of methallyl alcohol polyoxyethylene ether with the molecular weight of 2400, 4.55g of maleic anhydride, 4.9 g of vinyl-terminated hyperbranched functional monomer (prepared in S1 in example 1) and 300g of deionized water are weighed and added into a reactor, and stirred and dissolved to obtain a bottom material;
s2, weighing 21g of acrylic acid, 2.1g of 2-hydroxyethyl methacrylate phosphate and 2.8g of chain transfer agent mercaptoethanol, and dissolving in 30g of water to obtain a solution A; weighing 1.6g of ammonium persulfate and 0.5g of azobisisobutylimidazoline hydrochloride, and dissolving in 20g of water to obtain a solution B;
s3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into the reactor of S1, dripping the material A for 2.0 hours, dripping the material B for 2.3 hours, preserving the temperature for 1 hour after dripping the material B, then cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 7, and supplementing water to obtain a polycarboxylic acid high-efficiency water reducing agent with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_6
wherein n and f are 6 and 53, respectively; a. b, c, d, e in a ratio of 7.
In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water reducing agent was measured to be 35497 by gel chromatography.
Example 4
The embodiment provides a preparation method of a viscosity-reducing polycarboxylic acid water reducer with a hyperbranched structure, which comprises the following raw materials in percentage by mass: 4% of unsaturated carboxylic acid, 2.2% of unsaturated anhydride, 89.2% of unsaturated polyether, 0.5% of unsaturated phosphate, 2.3% of hyperbranched functional monomer, 1% of initiator and 0.8% of chain transfer agent, wherein the total content is 100%. The method comprises the following specific steps:
s1, preparing a vinyl-terminated hyperbranched polymer-functional monomer:
s1.1, adding a monomer (specifically 1,3, 5-triaminobenzene, 0.5 mol) containing a primary amino group, a catalyst (specifically tetraethylammonium hydroxide and hexadecyltrimethylammonium chloride) and an aprotic polar solvent (specifically toluene and N, N-dimethylformamide) into a reactor, heating to 90 ℃, dropwise adding epoxy chloropropane dissolved in ethanol within 1h, carrying out heat preservation reaction for 3 hours after dropwise adding, cooling to room temperature, adding solid alkali in four batches in equal amount, wherein the time interval of each addition is 5 minutes, reacting for 1h, standing, carrying out suction filtration to remove generated salt, removing the solvent from the obtained solution through a rotary evaporator, and carrying out vacuum drying for 24.0h at room temperature to obtain glycidylamine; wherein, the molar ratio of the monomer containing primary amino, epichlorohydrin to solid base is 1;
s1.2, adding the obtained glycidylamine (0.1 mmol), unsaturated polyether (specifically, prenyl polyoxyethylene ether), catalyst (specifically, tetraethylammonium bromide), polymerization inhibitor (specifically, hydroquinone) and aprotic polar solvent (specifically, toluene) into a reactor, continuously stirring, reacting at 80 ℃ for 4.0h, and separating and purifying a reaction product in a Soxhlet extractor after the reaction is finished to obtain a vinyl-terminated hyperbranched polymer-functional monomer; wherein the molar ratio of the glycidylamine compound to the unsaturated polyether is 1;
the structural formula of the vinyl-terminated hyperbranched polymer-functional monomer prepared in step S1 of this example is shown below:
Figure SMS_7
s2, preparing the viscosity-reducing polycarboxylic acid water reducer with the hyperbranched structure:
s2.1, weighing 312.2g of prenyl alcohol polyoxyethylene ether with the molecular weight of 2400, 7.7g of maleic anhydride, 8.05g of vinyl-terminated hyperbranched functional monomer (prepared in the S1) and 300g of deionized water, adding into a reactor, and stirring and dissolving to obtain a base material;
s2.2, weighing 14g of acrylic acid, 1.75g of diethylaminoethyl phosphate methacrylate, 0.5g of chain transfer agent mercaptoethanol and 6.0g of sodium hypophosphite, and dissolving the mixture in 30g of water to obtain a solution A; weighing 3.5g of ammonium persulfate and dissolving in 20g of water to obtain a solution B;
s2.3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into a reactor of S1, dripping the material A for 2.0h, dripping the material B for 2.3h, preserving heat for 1h after finishing dripping the material B, then cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 7, and replenishing water to obtain a polycarboxylic acid high-efficiency water reducing agent with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_8
wherein n and f are 6 and 53, respectively; a. the ratio of b, c, d, e is 9.
In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water reducing agent was determined to be 46951 by gel chromatography.
Example 5
The embodiment provides a preparation method of a viscosity-reducing polycarboxylic acid water reducer with a hyperbranched structure, which comprises the following raw materials in percentage by mass: 6.5 percent of unsaturated carboxylic acid, 1 percent of unsaturated anhydride, 88.7 percent of unsaturated polyether, 0.5 percent of unsaturated phosphate, 1.5 percent of hyperbranched functional monomer, 1 percent of initiator and 0.8 percent of chain transfer agent, which are 100 percent in total. The method comprises the following specific steps:
s1, weighing 311g of prenol polyoxyethylene ether with the molecular weight of 3100, 3.5g of maleic anhydride, 5.25g of vinyl-terminated hyperbranched functional monomer (prepared in S1 in example 1) and 300g of deionized water, adding into a reactor, and stirring and dissolving to obtain a base material;
s2, weighing 22.8g of acrylic acid, 1.75g of maleic anhydride polyethylene glycol phosphate and 2.8g of chain transfer agent mercaptoethanol, and dissolving in 30g of water to obtain a solution A; weighing 3.5g of ammonium persulfate and dissolving in 20g of water to obtain a solution B;
s3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into a reactor of the S1, dripping the material A for 2.0 hours, dripping the material B for 2.3 hours, preserving the heat for 1 hour after finishing dripping the material B, then cooling to room temperature, adding a sodium hydroxide solution with the mass fraction of 30% to adjust the pH value to 7, and replenishing water to obtain a polycarboxylic acid high-efficiency water reducing agent with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_9
wherein n, g and f are 6, 15 and 53, respectively; a. b, c, d, e in a ratio of 57.
In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water reducing agent was found to be 23561 by gel chromatography.
Comparative example 1
The polycarboxylic acid water reducer comprises the following polymerization reaction monomer components in percentage by mass: 8.8 percent of unsaturated acid, 1.65 percent of unsaturated anhydride, 88.3 percent of polyether monomer, 0.4 percent of unsaturated phosphate, 0.68 percent of initiator and 0.17 percent of chain transfer agent, and the total is 100 percent. The preparation method comprises the following steps:
s1, weighing 309g of prenyl alcohol polyoxyethylene ether with the molecular weight of 2400, 5.775g of maleic anhydride and 300g of deionized water, adding into a reactor, and stirring for dissolving to obtain a base material;
s2, 30.8g of acrylic acid, 1.4g of 2-hydroxyethyl methacrylate phosphate and 0.595g of a chain transfer agent mercaptoethanol are weighed out and dissolved in 30g of water to obtain a solution A. Weighing 2.38g of ammonium persulfate and dissolving in 20g of water to obtain a solution B;
s3, controlling the reaction temperature to be 50 ℃, simultaneously dripping the material A and the material B into the reactor, dripping the material A for 2.0 hours, dripping the material B for 2.3 hours, preserving the temperature for 1 hour after finishing dripping the material B, then cooling to room temperature, and adding alkali for neutralization to obtain a polycarboxylic acid high-efficiency water reducer with the solid content of 45%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_10
wherein f is 52; a. the ratio of b, c and d is 50.
In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water reducing agent was 45982 as measured by gel chromatography.
Comparative example 2
The polycarboxylic acid water reducer comprises the following polymerization reaction monomer components in percentage by mass: 8.4 percent of unsaturated acid, 1.27 percent of unsaturated anhydride, 88.9 percent of polyether monomer, 0.6 percent of unsaturated phosphate, 0.68 percent of initiator and 0.15 percent of chain transfer agent, and the total is 100 percent. The preparation method comprises the following steps:
s1, weighing 311.15g of methallyl alcohol polyoxyethylene ether with the molecular weight of 2400, 4.45g of maleic anhydride and 300g of deionized water, adding into a reactor, and stirring and dissolving to obtain a bottom material;
s2. Solution A was prepared by dissolving 26g of acrylic acid, 3.4g of methacrylic acid, 2.1g of 2-hydroxyethyl methacrylate phosphate and 0.53g of the chain transfer agent mercaptoethanol in 30g of water. Weighing 2.38g of ammonium persulfate to dissolve in 20g of water to obtain a solution B;
s3, controlling the reaction temperature to be 55 ℃, simultaneously dripping the material A and the material B into the reactor, dripping the material A for 2.0 hours, dripping the material B for 2.3 hours, preserving the temperature for 1 hour after finishing dripping the material B, then cooling to room temperature, adding alkali for neutralization, and replenishing water to obtain the polycarboxylic acid high-efficiency water reducer with the solid content of 40%; the molecular structural formula of the water reducing agent is as follows:
Figure SMS_11
wherein g is 52; a. the ratio of b, c, d and e is 5. In this example, polyacrylic acid was used as a standard sample, and the weight average molecular weight of the water reducing agent was measured by gel chromatography to find 47959.
Examples of the experiments
In this example, the viscosity reduction type polycarboxylate water reducing agents having hyperbranched structures prepared in examples 1 to 5 and comparative examples 1 to 2 and commercially available concrete viscosity reducers were subjected to tests on the working properties and mechanical properties of concrete. The performance of the concrete mixture is tested by referring to 'standard of performance test method of common concrete mixture' GB/T50080-2002, 'standard of mechanical performance test method of common concrete' GB/T50081-2002 and 'technical specification for self-compacting concrete' JGJ/T283-2012 and CECS 203-2006. The test results are shown in Table 1. The water reducer is compounded according to the following formula that the high water reduction type mother liquor, the viscosity reduction type mother liquor and the slump loss type mother liquor = 5.
The concrete formula is as follows: 520kg of Larducian P.O 42.5 cement, 60kg of I-grade fly ash, 30kg of silica fume, 750kg of machine sand (fineness modulus is 2.9), 1000kg of stones and 0.22 of water-to-gel ratio.
TABLE 1 comparative data on concrete Properties
Figure SMS_12
Comparative example 1 is a commercial viscosity-reducing polycarboxylic acid water reducer, and comparative examples 2 and 3 are polycarboxylic acid water reducers prepared according to the monomer ratios of example 1 and example 2, respectively, but without adding hyperbranched functional monomers.
As can be seen from Table 1, under the same conditions of the initial state of the concrete, the viscosity-reducing polycarboxylic acid water reducers with hyperbranched structures in examples 1 to 5 are lower than the commercial viscosity-reducing polycarboxylic acid water reducers and comparative examples 1 and 2, which shows that the water reducers prepared by the invention have higher dispersibility. The collapse time and the T500 time of the water reducing agent without adding the hyperbranched functional monomer (comparative example 1 and comparative example 2) are both longer than those of the viscosity-reducing water reducing agent with the hyperbranched structure prepared by adding the hyperbranched functional monomer, which shows that the viscosity-reducing polycarboxylic acid water reducing agent with the hyperbranched structure prepared by adding the hyperbranched functional monomer has better viscosity-reducing effect. Compared with the commercial viscosity reduction type water reducer with better viscosity reduction effect, the water reducer obtained by the invention can shorten the slump loss time by 45-71%, shorten the T500 time by 3-10 s, and has obvious viscosity reduction effect.
In this example, the viscosity-reducing polycarboxylic acid water reducing agent obtained in examples 1 to 5 and comparative examples 1 to 2 was placed in a cement pore fluid to perform a viscosity test and an adsorption layer thickness test on nano calcium silicate hydrate. The test method is as follows: (1) viscosity test: at a rate of 1.72g/L CaSO 4 、6.95g/L Na 2 SO 4 、4.757g/L K 2 SO 4 And 7.12g/L KOH simulated cement pore liquid, the viscosity of the polycarboxylate superplasticizer is researched by an Antopa MCR302 rheometer at room temperature and 25 ℃, a CC27-SN30972 system is adopted in the test, and the concentration of PCEs (namely the viscosity reduction type polycarboxylate superplasticizer obtained in the examples 1-5 and the comparative examples 1-2) is 15mg/L. (2) thickness test of the adsorption layer: a multi-angle particle size and high sensitivity Zeta potential analyzer (NanoBrook Omni, bruk Highen, USA) was used with a scattering angle of 90 deg. at a wavelength of 620 nm. And measuring the difference of the particle sizes of the nanometer calcium silicate hydrate before and after the nanometer calcium silicate hydrate adsorbs the polycarboxylate water reducer, calculating the thickness of the adsorption layer of the PCEs, and measuring for 5 times to obtain an average value to obtain the thickness of the adsorption layer of the polycarboxylate water reducer. The specific experimental results are shown in fig. 1 and fig. 2. As can be seen from FIG. 1, the viscosity of the viscosity-reducing polycarboxylic acid water-reducing agent prepared in comparative examples 1-2 is 2.28-2.45 mPas, the viscosity of the viscosity-reducing polycarboxylic acid water-reducing agent prepared in inventive examples 1-5 is 1.25-1.61 mPas, and the viscosity of the viscosity-reducing polycarboxylic acid water-reducing agent with hyperbranched structure prepared in the present invention is lower. As can be seen from FIG. 2, the hyperbranched polymers prepared according to the invention are comparable to the comparative examples 1 to 2The viscosity reduction type polycarboxylate water reducer with the structure has higher adsorption thickness.
In conclusion, the viscosity-reducing polycarboxylate superplasticizer provided by the invention has the hyperbranched structure prepared from the hyperbranched functional monomer, and the molecular weight of the polycarboxylate superplasticizer is limited to 3-8 ten thousand g/mol, so that the dispersing capacity of the polycarboxylate superplasticizer and the coverage rate of the surface of a cementing material are improved, free water is released, and the viscosity of concrete is reduced. The hyperbranched structure weakens the winding tendency of hyperbranched polymer chains, endows the polymer with unique low viscosity, reduces the viscosity of the pore fluid of the gelled material, and further reduces the viscosity of concrete. The raw material cost for preparing the water reducing agent is low, the reaction condition is mild, the synthesis process is simple and convenient, the environment is friendly, and the method is suitable for popularization and application.
The foregoing is merely exemplary and illustrative of the present invention and it is within the purview of one skilled in the art to modify or supplement the embodiments described or to substitute similar ones without the exercise of inventive faculty, and still fall within the scope of the claims.

Claims (9)

1. A vinyl-terminated hyperbranched polymer, characterized in that the structural general formula of the vinyl-terminated hyperbranched polymer is as follows:
Figure QLYQS_1
wherein R is 0 Is composed of
Figure QLYQS_2
Or->
Figure QLYQS_3
；R 1 is-H or-CH 3 ；R 2 is-CH 2 -、-CH 2 -CH 2 -and-CH 2 -CH 2 -CH 2 -CH 2 -at least one of O-; n is an integer, and the value of n is 4 to 40.
2. The method of preparing a vinyl-terminated hyperbranched polymer according to claim 1, comprising the steps of:
step (1): adding a monomer containing a primary amino group, a catalyst and an aprotic polar solvent into a reaction device, stirring and dissolving, heating to 30-150 ℃, starting to dropwise add epoxy chloropropane dissolved in a polar cosolvent, keeping the temperature for reaction for 1.0-5.0 h after dropwise addition, cooling to room temperature, adding solid alkali, reacting for 0.5-2 h, and separating and purifying a reaction product after the reaction is finished to obtain a glycidylamine compound;
step (2): and (2) adding the glycidylamine compound obtained in the step (1), a catalyst, a polymerization inhibitor, unsaturated polyether and an aprotic polar solvent into a reaction vessel, reacting for 2.0-10.0 h at the temperature of 50-150 ℃, and separating and purifying a reaction product after the reaction is finished to obtain the vinyl-terminated hyperbranched polymer.
3. The method for preparing the vinyl-terminated hyperbranched polymer according to claim 2, wherein the molar ratio of the monomer containing a primary amine group, epichlorohydrin and a solid base in the step (1) is 1.
4. The method of claim 2 or 3, wherein the primary amine group-containing monomer in step (1) is at least one of 1,3, 5-triaminobenzene and melamine, and the unsaturated polyether in step (2) is at least one of allyl polyoxyethylene ether, methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether, and 4-hydroxybutyl vinyl polyoxyethylene ether.
5. The method of preparing a vinyl-terminated hyperbranched polymer according to claim 2 or 3, wherein the solid base in step (1) is a hydroxide, the polar co-solvent in step (1) is at least one of ethanol, isopropanol, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol monomethyl ether, diethyl ether, chloroform and trichloroethylene, the polymerization inhibitor in step (2) is at least one of hydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, phenothiazine, p-hydroxyanisole and methylhydroquinone, the aprotic polar solvent in step (1) and step (2) is at least one of toluene, xylene, chloroform, dimethyl sulfoxide, N-dimethylformamide, 1, 3-dimethyl-3, 4,5, 6-tetrahydro-2-pyrimidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, N-methylpyrrolidone and acetonitrile, and the catalyst in step (1) and step (2) is at least one of triethylbenzylammonium bromide, tetraethylammonium hydroxide, hexadecyltrimethylammonium bromide, p-dodecylammonium sulfonate, tetramethylammonium bromide, tetrabutylammonium bromide, trimethylbutylammonium bromide and trimethylbutylammonium bromide.
6. The viscosity reduction type polycarboxylate superplasticizer with a hyperbranched structure is characterized by comprising the following raw materials in percentage by mass: 3 to 18 percent of unsaturated carboxylic acid, 1 to 10 percent of unsaturated anhydride, 0 to 1 percent of unsaturated phosphate, 75 to 93 percent of unsaturated polyether, 1 to 6 percent of hyperbranched functional monomer, 0.1 to 1 percent of initiator and 0.2 to 3.0 percent of chain transfer agent;
the vinyl-terminated hyperbranched polymer of claim 1 is used as a hyperbranched functional monomer.
7. The viscosity-reducing polycarboxylate water reducer with hyperbranched structure as defined in claim 6, wherein said unsaturated carboxylic acid monomer is at least one of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, metal acrylate, metal methacrylate, metal fumarate and metal itaconate, said unsaturated anhydride monomer is at least one of maleic anhydride, itaconic anhydride, citraconic anhydride, nonylsuccinic anhydride and nonenylsuccinic anhydride, said unsaturated phosphate ester monomer is at least one of diethylaminoethyl phosphate methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol phosphate maleic anhydride and polypropylene glycol phosphate maleic anhydride, and said unsaturated polyether monomer is at least one of allyl polyoxyethylene ether, methallyl polyoxyethylene ether and isopentenol polyoxyethylene ether.
8. The viscosity-reduction type polycarboxylate water reducer with hyperbranched structure as defined in claim 6, wherein said initiator is organic peroxide initiator, inorganic peroxide or azo initiator, and said chain transfer agent is at least one of mercaptoethanol, 2-hydroxypropanethiol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptosuccinic acid, dodecylmercaptan, sodium hypophosphite and sodium formate.
9. The preparation method of the viscosity-reducing type polycarboxylate water reducer with the hyperbranched structure as defined in any one of claims 6 to 8, comprising the steps of:
step (1): adding an unsaturated anhydride monomer, an unsaturated polyether monomer, a hyperbranched functional monomer and deionized water into a reactor, and continuously stirring until the unsaturated anhydride monomer, the unsaturated polyether monomer, the hyperbranched functional monomer and the deionized water are dissolved to obtain a bottom material;
step (2): preparing an unsaturated carboxylic acid monomer, an unsaturated phosphate ester monomer, a chain transfer agent and deionized water into a material A, and preparing an initiator and the deionized water into a material B;
and (3): and (3) simultaneously dripping the material A and the material B obtained in the step (2) into the base material obtained in the step (1) at the temperature of 35-75 ℃, preserving heat for reaction for 1-2 h after finishing dripping, and adding alkali to adjust the pH value to 6-8 after the reaction is finished, so as to obtain the viscosity-reducing polycarboxylate water reducer with the hyperbranched structure.
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