CN109134784A - It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser and preparation method thereof - Google Patents

It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser and preparation method thereof Download PDF

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CN109134784A
CN109134784A CN201810844151.3A CN201810844151A CN109134784A CN 109134784 A CN109134784 A CN 109134784A CN 201810844151 A CN201810844151 A CN 201810844151A CN 109134784 A CN109134784 A CN 109134784A
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parts
feed liquid
acid
polyoxyethylene ether
deionized water
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CN109134784B (en
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吴伟
刘昭洋
王进春
董树强
刘旭飞
刘欢
刘翠芬
康静
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SHIJIAZHUANG CHANG'AN YUCAI BUILDING MATERIALS Co.,Ltd.
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刘翠芬
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular 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
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688Copolymers containing at least three different monomers
    • C04B24/2694Copolymers containing at least three different monomers containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/40Redox systems

Abstract

It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser and preparation method thereof, polycarboxylic acid super-plasticizer is made of the raw material of following mass fractions: 70~80 parts of polyoxyethylene ether polymeric monomer, 1~1.5 part of reducing agent, aqueous initiator, and 40~50 parts of deionized water, A feed liquid, B feed liquid;A feed liquid is mixed by 7~9 parts of acrylic acid, i.e. unsaturated 0.1~2 part of the alkanolamine ester of the solidifying early strong monomer of rush, 0.1~1 part of unsaturated amides, 15~25 parts of deionized water;B feed liquid is mixed by 0.08~0.15 part of reducing agent Y, 0.3~0.5 part of chain-transferring agent, 18~28 parts of deionized water.Preparation method: polyoxyethylene ether polymeric monomer, reducing agent and deionized water are put into reaction kettle, are heated up, stirring;Aqueous initiator is added in reaction kettle, A feed liquid and B feed liquid is added dropwise, after being added dropwise to complete, insulation reaction is down to room temperature, and liquid alkaline is added and adjusts pH value to 7.The present invention effectively increases early strength of concrete, shortens concrete coagulating time.

Description

It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser and preparation method thereof
Technical field
It is specifically a kind of to promote to coagulate the present invention relates to a kind of concrete admixture more particularly to a kind of polycarboxylic acid super-plasticizer High-early strength polyocarboxy acid superplasticiser belongs to building material technical field.The invention further relates to a kind of systems of polycarboxylic acid super-plasticizer Preparation Method, specifically a kind of preparation method for promoting solidifying high-early strength polyocarboxy acid superplasticiser.
Background technique
Prefabricated components are because its speed of application is fast, save manpower, improves construction site environment, good in economic efficiency characteristic gradually It is widely applied commercially available.Quick template turnover is often required that in prefabricated components production, this often just needs coagulation Soil has very high early strength.Usual way is: increasing cement consumption, mixes early strong inorganic salts, improve steam curing temperature.Increase water Mud dosage bring is the increase of production cost, and it is very high and can bring under later strength to mix volume that inorganic salts usually require Drop improves temperature and needs higher energy consumption.People begin to focus on the angle from dispersing agent to promote early strength of concrete.
The present invention is synthesized by using the long side chain of high component, can effectively facilitate cement early hydration, is generated more fine and close With tiny hydrated product.Unsaturated hydramine is introduced in main chain, hydramine can be released because the alkaline environment of cement hydrolyzes, It can further speed up aquation and play the role of condensing catalyst, while part carboxyl can also be protected to play holding slump-loss Effect.Main chain is grafted partial amides group, because of the presence of N, it is strong to obtain early stage that early hydration can be promoted effect Degree.Because what is do not introduced is all organo-functional group, it will not influence hydrated product mine and mutually change, under later strength is not in The case where drop.
Inventor retrieves following Patents documents: CN101066853 discloses a kind of polyethers ultra early-strength coagulation Native super plasticizer, is prepared using following steps: 1) water-based free radical copolyreaction: by 84~94% monomer a, 5%~15% is single Free radicals copolymerization reaction occurs in an aqueous medium for body b and 1~3% monomer c;2) neutralization reaction: after copolyreaction, altogether The alkoxy organic amine d as shown in general formula (5) or general formula (6) is added in polymers and carries out neutralization reaction, by the pH value tune of copolymer Whole is 6.0~7.5.CN101085701 discloses a kind of super plasticizer for prefabricated components concrete pumping, by monomer a, list The monomer d free radicals copolymerization reaction of body b, monomer c and modification are made, and the monomer d of the modification is by monomer d and Nano-meter SiO_22Reaction It is made;The viscosity average molecular weigh of the super plasticizer is controlled 30000~80000.CN101357834 discloses a kind of early-strength Polycarboxylic acid super-plasticizer, it be by four kinds of monomers in 60 DEG C~95 DEG C aqueous solutions, radical initiator and chain-transferring agent exist Under conditions of be copolymerized and obtain.New polymerized monomer is introduced on polymer molecular chain, forms new polymer molecular structure, to mention The water-reducing rate and early stage enhancing ability of higher polycarboxylic acid super plasticizer.CN107602773A discloses a kind of for the poly- of oil-well cement Carboxylic dispersants and preparation method thereof, the polycarboxylate dispersant are with acrylic acid, n-vinyl pyrrolidone, itaconic acid, 2- third Acrylamide base -2- methyl propane sulfonic acid, sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium and allyl polyglycol are being total to for monomer Polymers;The weight average molecular weight of allyl polyglycol is 300~2400;It is the matter of acrylic acid in terms of 100% by the gross mass of monomer Measuring percentage is 0.5%~20%, and the mass percent of n-vinyl pyrrolidone is 0.5%~15%, the quality of itaconic acid Percentage is that the mass percent of 0.5%~10%, 2- acrylamide-2-methylpro panesulfonic acid is 5%~60%, vinyl sulphur The mass percent of sour sodium is 0.5%~30%, and the mass percent of vinylbenzenesulfonic acid sodium is 0.5%~30%, allyl The mass percent of polyethylene glycol is 20%~70%;The weight average molecular weight of polycarboxylate dispersant is 5000~250000. CN103406067A discloses a kind of polycarboxylate dispersant and the preparation method and application thereof.The polycarboxylate dispersant by 1.0~ 3.0 parts by weight contain the unsaturated monomer of carboxyl, the sulfonic unsaturated monomer of 1.1~2.2 parts by weight and 0.6~1.2 weight Part other free-radical polymerised unsaturated base monomers, 25~35 parts by weight water, 0.11~0.22 parts by weight initiator, Free radical polymerization occurs under the conditions of 0.03~0.06 parts by weight chain-transferring agent and 1.5~4.0 parts by weight alkali compounds are existing Reaction obtains.CN106519151A discloses amphipathic poly-carboxylic-acid cement dispersant and preparation method thereof.The amphipathic carboxylic Sour water cement dispersant is a kind of dispersion liquid of polycarboxylic acids particle with vermiform micromorphology;It includes amphipathic carboxylic that it, which is formed, Sour nanoparticle and water;The weight average molecular weight of the amphipathic carboxylic acid particle is 15000~40000, and it is poly- which employs RAFT Conjunction method, but RAFT polymerization is with high costs, chain-transferring agent is more difficult to buy.It has difficulties in industrial practical application. United States Patent 4792360 discloses the method by introducing styrene sulfonic acid to make amphipathic carboxylic acid Dispersing agent.But the price of styrene sulfonic acid is very high, has equally existed and has been difficult to the problem of promoting.US Patent 5158996 disclose the method by using acetone as solvent synthesis amphoteric dispersant, but can be made to environment using solvent It must also be removed by distillation at pollution, and in subsequent use, increased costs.
The above technology shortens coagulation for how to enable polycarboxylic acid super-plasticizer effectively improve early strength of concrete Native setting time does not provide specific guidance program.
Summary of the invention
Promote solidifying high-early strength polyocarboxy acid superplasticiser, the polycarboxylic acids the technical problem to be solved by the invention is to provide a kind of Super plasticizer can effectively improve early strength of concrete, shorten concrete coagulating time.
For this purpose, another technical problem to be solved by this invention is to provide, a kind of to promote solidifying early-strength polycarboxylic acids super plasticized The preparation method of agent.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows:
It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser, its technical solution is that it is by the raw material system of following mass fractions At: 70~80 parts of (unsaturation) polyoxyethylene ether polymeric monomer, 1~1.5 part of reducing agent X, aqueous initiator, deionized water 40~ 50 parts, A feed liquid, B feed liquid.Above-mentioned A feed liquid is unsaturated alkanolamine ester 0.1~2 by 7~9 parts of acrylic acid, the solidifying early strong monomer of rush Part, 0.1~1 part of unsaturated amides, 15~25 parts of deionized water mix;B feed liquid is by 0.08~0.15 part of reducing agent Y, chain 0.3~0.5 part of transfer agent, 18~28 parts of deionized water mix.
Wherein, above-mentioned polyoxyethylene ether polymeric monomer (molecular weight can be 4000-10000) improves steric hindrance.Polyoxy Vinethene polymeric monomer be methyl allyl polyoxyethylene ether, allyl polyethenoxy ether, isoamyl alcohol polyoxyethylene ether (TPEG), One of isobutene alcohol polyoxyethylene ether;Unsaturated alkanolamine ester be maleic acid triethanolamine dibasic acid esters, maleic acid diethanol amine ester, Maleic acid alkanolamine ester, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, methacrylic acid diethanol amine ester, methacrylic acid list alkanolamine ester, Acrylic acid diethanol amine ester, acrylic acid list alkanolamine ester, fumaric acid triethanolamine ester, fumaric acid diethanol amine ester, fumaric acid list second (any quality proportioning group is pressed in either two kinds of combination or two or more combinations when combination at least one of alkanolamine ester It closes);Unsaturated amides are acrylamide, Methacrylamide, n-isopropyl acrylamide, methylene-bisacrylamide, N, N- Dimethacrylamide, N, at least one in N- acrylamide (N, N- diethyl -2- acrylamide), 2- acrylamide Kind of (either two kinds of combination or two or more combinations are combined by any quality proportioning when combination);Aqueous initiator is double One of oxygen water, persulfate, azo-bis-isobutyrate hydrochloride or any two kinds of combinations by any quality proportioning;Reduction The mass ratio of agent Y and reducing agent X are 10~11:1.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 70~80 parts of polyoxyethylene ether polymeric monomer, reducing agent X and 40~50 parts of deionized waters investment reaction kettle (500ml's Three-necked flask with magnetic agitation) in, 40~50 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. Aqueous initiator is added in reaction kettle, then using constant flow pump starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid is small 2.5~3 When be added dropwise to complete, B feed liquid was added dropwise to complete at 3~3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5~2 hours, Resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
In above-mentioned technical proposal, currently preferred technical solution be can be, and the reducing agent X is ferrous sulfate, also Former agent Y is L-AA, and the mass ratio of reducing agent Y and reducing agent X are 10:1.Above-mentioned chain-transferring agent is mercaptopropionic acid.
In above-mentioned technical proposal, it is super that currently preferred technical solution is also possible that the rush coagulates early-strength polycarboxylic acids Plasticiser is made of the raw material of following mass fractions: polyoxyethylene ether polymeric monomer i.e. 72 parts of isoamyl alcohol polyoxyethylene ether, 0.009 part of reducing agent ferrous sulfate, 1.2 parts of aqueous initiator, that is, hydrogen peroxide, 45 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by 8.6 parts of acrylic acid, unsaturated alkanolamine ester, that is, 0.4 part of trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, unsaturated amides, that is, propylene 0.5 part of amide, 20 parts of deionized water mix;B feed liquid is by 0.09 part of reducing agent L-AA, chain-transferring agent, that is, sulfydryl third 0.3 part, 20 parts of deionized water of acid mixes.The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush includes as follows Processing step: above-mentioned quality proportioning is 1. pressed by 0.009 part and 45 parts 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionizations Water is put into reaction kettle, is warming up to 40 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. being added in reaction kettle aqueous 1.2 parts of initiator, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid was added dropwise to complete at 3 hours, B Feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, was finally dropped resulting product To room temperature, liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
In above-mentioned technical proposal, it is super that currently preferred technical solution is also possible that the rush coagulates early-strength polycarboxylic acids Plasticiser is made of the raw material of following mass fractions: polyoxyethylene ether polymeric monomer i.e. 76 parts of isoamyl alcohol polyoxyethylene ether, 0.012 part of reducing agent ferrous sulfate, 1.5 parts of aqueous initiator, that is, hydrogen peroxide, 48 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by 9 parts of acrylic acid, 1 part of trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, 0.2 part of Methacrylamide, 22 parts of deionized water mixing It forms;B feed liquid is by 0.12 part of reducing agent L-AA, 0.32 part of chain-transferring agent, that is, mercaptopropionic acid, 25 parts of deionized water mixing It forms.The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. matching by above-mentioned quality Than being warming up to 42 in 0.012 part and 48 parts 76 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1.5 parts of aqueous initiator are added in reaction kettle, then adopt respectively Being started that A feed liquid and B feed liquid are added dropwise simultaneously with constant flow pump, A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
Currently preferred technical solution is referring also to the following examples 3~5.
The present invention is synthesized by using the long side chain of high component, can effectively facilitate cement early hydration, is generated more fine and close With tiny hydrated product.Unsaturated hydramine is introduced in main chain, hydramine can be released because the alkaline environment of cement hydrolyzes, It can further speed up aquation and play the role of condensing catalyst, while part carboxyl can also be protected to play holding slump-loss Effect.Main chain is grafted partial amides group, because of the presence of N, it is strong to obtain early stage that early hydration can be promoted effect Degree.Because what is do not introduced is all organo-functional group, it will not influence hydrated product mine and mutually change, under later strength is not in The case where drop.
Polycarboxylic acid super-plasticizer of the invention is related to polycarboxylate dispersant, by (methyl) acrylic acid, unsaturated alkanolamine ester, Unsaturated amides, polyoxyethylene ether carry out free radical polymerization as monomer, and preparation promotees solidifying early strength water-reducing agent.It has high water reduction, High holding capacity, and can effectively shorten concrete coagulating time, thus between reducing the prefabricated components quiet stopping time, such water-reducing agent energy Accelerate template turnover, save the cost.Can effectively promote 1 day early strength of concrete does not reduce by 28 days intensity of concrete simultaneously, Steam curing temperature can be reduced, stripping rate is accelerated, to save steam-cured energy consumption, while template turnover is improved, reduces building Cost.
Detailed description of the invention
Fig. 1 is different sample concrete initial set time diagrams in test of the invention.
Specific embodiment
Embodiment 1: of the present invention to promote to coagulate high-early strength polyocarboxy acid superplasticiser to be by the raw material system of following mass fractions At: polyoxyethylene ether polymeric monomer, that is, 72 parts of isoamyl alcohol polyoxyethylene ether (TPEG4000), reducing agent ferrous sulfate 0.009 Part, 1.2 parts of aqueous initiator, that is, hydrogen peroxide (30% mass percent concentration, hydrogen peroxide 30%), 45 parts of deionized water, A material Liquid, B feed liquid.Above-mentioned A feed liquid by 8.6 parts of acrylic acid, unsaturated alkanolamine ester, that is, 0.4 part of trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, 0.5 part of unsaturated amides, that is, acrylamide, 20 parts of deionized water mix;B feed liquid by 0.09 part of reducing agent L-AA, 0.3 part of chain-transferring agent, that is, mercaptopropionic acid, 20 parts of deionized water mix.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate 0.009 part and 45 parts deionized waters investment reaction kettles (500ml's Three-necked flask with magnetic agitation) in, 40 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. reacting 1.2 parts of aqueous initiator are added in kettle, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid is small 3 When be added dropwise to complete, B feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, finally will Resulting product is down to room temperature, and liquid alkaline (can be the sodium hydrate aqueous solution that mass percent concentration is 30%) is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
Embodiment 2: of the present invention to promote to coagulate high-early strength polyocarboxy acid superplasticiser to be by the raw material system of following mass fractions At: polyoxyethylene ether polymeric monomer, that is, 76 parts of isoamyl alcohol polyoxyethylene ether (TPEG4000), reducing agent ferrous sulfate 0.012 Part, 1.5 parts of aqueous initiator, that is, hydrogen peroxide (hydrogen peroxide 30%), 48 parts of deionized water, A feed liquid, B feed liquid.Above-mentioned A feed liquid It is mixed by 9 parts of acrylic acid, 1 part of trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, 0.2 part of Methacrylamide, 22 parts of deionized water; B feed liquid is mixed by 0.12 part of reducing agent L-AA, 0.32 part of chain-transferring agent, that is, mercaptopropionic acid, 25 parts of deionized water.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 76 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate 0.012 part and 48 parts deionized waters investment reaction kettles (500ml's Three-necked flask with magnetic agitation) in, 42 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. reacting 1.5 parts of aqueous initiator are added in kettle, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid is small 3 When be added dropwise to complete, B feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, finally will Resulting product is down to room temperature, and liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
Embodiment 3: of the present invention to promote to coagulate high-early strength polyocarboxy acid superplasticiser to be by the raw material system of following mass fractions At: polyoxyethylene ether polymeric monomer, that is, 72 parts of isoamyl alcohol polyoxyethylene ether (TPEG6000), reducing agent ferrous sulfate 0.015 Part, 1.5 parts of aqueous initiator, that is, hydrogen peroxide (hydrogen peroxide 30%), 46 parts of deionized water, A feed liquid, B feed liquid.Above-mentioned A feed liquid It is mixed by 8 parts of acrylic acid, 1 part of maleic acid triethanolamine dibasic acid esters, 0.5 part of acrylamide, 21 parts of deionized water;B feed liquid by 0.15 part of reducing agent L-AA, 0.32 part of chain-transferring agent, that is, mercaptopropionic acid, 22 parts of deionized water mix.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate 0.015 part and 46 parts deionized waters investment reaction kettles (500ml's Three-necked flask with magnetic agitation) in, 45 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. reacting 1.5 parts of aqueous initiator are added in kettle, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid is small 3 When be added dropwise to complete, B feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, finally will Resulting product is down to room temperature, and liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
Embodiment 4: of the present invention to promote to coagulate high-early strength polyocarboxy acid superplasticiser to be by the raw material system of following mass fractions At: polyoxyethylene ether polymeric monomer, that is, 72 parts of methyl allyl polyoxyethylene ether, 0.015 part of reducing agent ferrous sulfate aqueous draw It sends out 1.5 parts of agent, that is, hydrogen peroxide (hydrogen peroxide 30%), 44 parts of deionized water, A feed liquid, B feed liquid.Above-mentioned A feed liquid is by acrylic acid 9 Part, 2 parts of maleic acid triethanolamine dibasic acid esters, 1 part of acrylamide, 23 parts of deionized water mix;B feed liquid is anti-bad by reducing agent L- 0.15 part of hematic acid, 0.45 part of chain-transferring agent, that is, mercaptopropionic acid, 26 parts of deionized water mix.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate 0.015 part and 44 parts deionized waters investment reaction kettles (500ml's Three-necked flask with magnetic agitation) in, 40 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. reacting 1.5 parts of aqueous initiator are added in kettle, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid is small 3 When be added dropwise to complete, B feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, finally will Resulting product is down to room temperature, and liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
Embodiment 5: of the present invention to promote to coagulate high-early strength polyocarboxy acid superplasticiser to be by the raw material system of following mass fractions At: 75 parts of polyoxyethylene ether polymeric monomer, that is, isoamyl alcohol polyoxyethylene ether (TPEG, molecular weight 4000), reducing agent sulfuric acid are sub- 0.012 part of iron, 1 part of aqueous initiator, that is, azo-bis-isobutyrate hydrochloride, 42 parts of deionized water, A feed liquid, B feed liquid.Above-mentioned A Feed liquid is by 8 parts of acrylic acid, unsaturated 0.6 part of alkanolamine ester, 0.8 part of unsaturated amides, that is, N,N-DMAA, deionization 20 parts of water mix;B feed liquid is by 0.12 part of reducing agent L-AA, 0.4 part of chain-transferring agent, that is, mercaptopropionic acid, deionized water 23 parts mix;Unsaturated alkanolamine ester is two kinds of maleic acid triethanolamine dibasic acid esters, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester raw materials Combination, the mass ratio of maleic acid triethanolamine dibasic acid esters and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester is 2:1.
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality Proportion by 75 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate 0.012 part and 42 parts deionized waters investment reaction kettles (500ml's Three-necked flask with magnetic agitation) in, 40 DEG C are warming up to, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. reacting 1 part of aqueous initiator is added in kettle, constant flow pump is then respectively adopted and starts that A feed liquid and B feed liquid are added dropwise simultaneously, A feed liquid was at 3 hours It being added dropwise to complete, B feed liquid was added dropwise to complete at 3.5 hours, after all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, finally by institute The product obtained is down to room temperature, and liquid alkaline is added and adjusts pH value to 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
The following are test portions of the invention:
Test material:
Cement: high victory cement P.O 42.5, density=3.11g/cm3, specific surface area=362m2/ kg, compression strength 3d =24.9Mpa, compression strength 28d=49.7Mpa.
1 cement component of table, is indicated with mass percent
Sand: machine-made sand, water absorption rate 1.2%, content of stone powder 16%, apparent density 2720kg/m3
Stone: artificial rubble 5mm-20mm, water absorption rate 0.3%, elongated particles 6%, apparent density 2720kg/m3
Performance evaluation: flowing degree of net paste of cement is tested according to " the concrete admixture homogeneity test side GB8077-2012 Method " regulation progress, select water-cement ratio 0.29.Admixture dosage is cement quality percentage, and specific test data is as follows:
The quiet slurry test data of table 2
Can be seen that commercially available PCE from net slurry test data has to the good dispersion of cement slurry and retention property, still The dispersion of commercially available early-strength PCE and retention property are weaker than conventional PCE, especially extend and all lose very greatly, extend from initial 200mm Degree loss only 140mm divergence to 1 hour, loss late is up to 30%.And the rush in the present invention coagulates early-strength PCE and routine PCE With similar dispersibility and holding capacity, especially 5 product of example compared with conventional PCE for, have and preferably keep energy Power, 1h loss late are only 2.3%.
Concrete test below, concrete mix is as shown in table 3, concrete slump and divergence test according to GB/T50080-2002 " Standard for test methods of properties of ordinary concrete mixture standard (attached provision explanation) " regulation carries out, experimental temperature 20 degree, humidity 52%.
3 concrete mix of table
Under conditions of guaranteeing that water consumption is constant, adjusts PCE volume (with the mass percent of cement), gone out with reaching concrete The machine slump having the same (the positive and negative 10mm of error).Concrete goes out the machine slump and gradual loss is as follows:
4 concrete slump experimental result of table
As can be seen from the above table, concrete test result and net slurry result are coincide.Commercially available morning strong PCE reaches the identical slump Required volume highest, while half an hour loses to the slump and there was only 20mm, loss late is up to 76%.Rush in the present invention is solidifying early strong Volume needed for type PCE and slump-loss situation are close with routine PCE, and 5 performance of example is also better than commercially available routine PCE.
Fig. 1 is different sample concrete initial set time diagrams in test of the invention.As seen from Figure 1, use is commercially available The concrete initial set time of PCE, commercially available morning strong PCE and example 1 is close, in 250min or so.Using from example 2 to example 5 The concrete initial set time obviously shift to an earlier date, the especially 5 initial condensation time of example shortens 60% compared with commercially available PCE.
Concrete is die-filling, and at 20 DEG C, the laboratory of 52% appropriateness is quiet to stop 4 hours, is then placed in rapid curing case, into 40 DEG C of row 6 hours steam-cured, then takes out test specimen and is placed on 20 DEG C, 14 hours in 52% laboratory, then tests concrete one Its intensity.Intensity data is as follows:
5 concrete strength data of table
As can be seen from the above table, commercially available early-strength PCE is obviously improved compared with 1 day intensity of conventional PCE, 28 days intensity Slightly above routine PCE.Example in the present invention, 1 day and 28 days intensity are above strong PCE of commercially available morning.Especially example 5 is 1 day strong Degree is higher than commercially available PCE 21%, is higher than strong PCE 11% of commercially available morning, has more obvious early strong effect.Intensity is higher than height within 28 days In commercially available PCE7%, it is higher than strong PCE 6% of commercially available morning, also has promotion for late strength of concrete.
Above-mentioned 1~example of example 5 is 1~embodiment of embodiment 5.The present invention mainly improves early strength of concrete, It is not adversely affected simultaneously for later strength.The present invention can be shortened the concrete initial set time simultaneously, to accelerate concrete The turnover of clay model plate, improves economic benefit.And relevant document amphipathic carboxylic dispersants are then mainly by adjusting itself parent Water oleophylic value, which reaches, improves concrete flowability, particularly self-compacting concrete handling capacity under the conditions of reinforcing bar concentration, Concrete workability is promoted, it is wrapped.In contrast, proportion and component of the invention is different from, it is solved the technical issues of It is different from.
In conclusion the present invention effectively increases early strength of concrete, concrete coagulating time is shortened.

Claims (10)

1. a kind of promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is made of the raw material of following mass fractions: 70~80 parts of polyoxyethylene ether polymeric monomer, 1~1.5 part of reducing agent X, aqueous initiator, 40~50 parts of deionized water, A feed liquid, B Feed liquid;
Above-mentioned A feed liquid is unsaturated 0.1~2 part of alkanolamine ester, unsaturated amides by 7~9 parts of acrylic acid, the solidifying early strong monomer of rush 0.1~1 part, 15~25 parts of deionized water mixes;B feed liquid is by reducing agent Y0.08~0.15 part, chain-transferring agent 0.3~0.5 Part, 18~28 parts of deionized water mix;
Wherein, above-mentioned polyoxyethylene ether polymeric monomer is methyl allyl polyoxyethylene ether, allyl polyethenoxy ether, iso-amylene One of alcohol polyoxyethylene ether (TPEG), isobutene alcohol polyoxyethylene ether;Unsaturated alkanolamine ester is that maleic acid triethanolamine is double Ester, maleic acid diethanol amine ester, maleic acid alkanolamine ester, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, methacrylic acid diethanol amine ester, Methacrylic acid list alkanolamine ester, acrylic acid diethanol amine ester, acrylic acid list alkanolamine ester, fumaric acid triethanolamine ester, fumaric acid two At least one of ethanol amine ester, fumaric acid monoethanolamine ester;Unsaturated amides are acrylamide, Methacrylamide, N- different Propylacrylamide, methylene-bisacrylamide, N,N-DMAA, N, N- acrylamide, 2- acryloyl At least one of amine;Aqueous initiator is for one of hydrogen peroxide, persulfate, azo-bis-isobutyrate hydrochloride or arbitrarily Two kinds of combinations by any quality proportioning;The mass ratio of reducing agent Y and reducing agent X are 10~11:1;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning In 70~80 parts of polyoxyethylene ether polymeric monomer, reducing agent X and 40~50 parts of deionized waters investment reaction kettles, 40 will be warming up to~ 50 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. aqueous initiator is added in reaction kettle, constant flow pump is then used Starting while A feed liquid and B feed liquid is added dropwise, A feed liquid was added dropwise to complete at 2.5~3 hours, and B feed liquid was added dropwise to complete at 3~3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5~2 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts PH value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
2. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that above-mentioned reducing agent X is sulfuric acid Ferrous iron, reducing agent Y are L-AA, and the mass ratio of reducing agent Y and reducing agent X are 10:1.
3. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that above-mentioned chain-transferring agent is mercapto Base propionic acid.
4. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is by following mass parts Made of several raw materials: polyoxyethylene ether polymeric monomer, that is, 72 parts of isoamyl alcohol polyoxyethylene ether, reducing agent ferrous sulfate 0.009 Part, 1.2 parts of aqueous initiator, that is, hydrogen peroxide, 45 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid by 8.6 parts of acrylic acid, Unsaturated alkanolamine ester, that is, 0.4 part of trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, 0.5 part of unsaturated amides, that is, acrylamide, deionized water 20 parts mix;B feed liquid is by 0.09 part of reducing agent L-AA, 0.3 part of chain-transferring agent, that is, mercaptopropionic acid, deionized water 20 Part mixes;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning By in 0.009 part and 45 parts 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles, it is warming up to 40 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1.2 parts of aqueous initiator are added in reaction kettle, then adopt respectively Being started that A feed liquid and B feed liquid are added dropwise simultaneously with constant flow pump, A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
5. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is by following mass parts Made of several raw materials: polyoxyethylene ether polymeric monomer, that is, 76 parts of isoamyl alcohol polyoxyethylene ether, reducing agent ferrous sulfate 0.012 Part, 1.5 parts of aqueous initiator, that is, hydrogen peroxide, 48 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by 9 parts of acrylic acid, three 1 part of methacrylic acid triethanolamine ester, 0.2 part of Methacrylamide, 22 parts of deionized water mix;B feed liquid is by reducing agent 0.12 part of L-AA, 0.32 part of chain-transferring agent, that is, mercaptopropionic acid, 25 parts of deionized water mix;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning By in 0.012 part and 48 parts 76 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles, it is warming up to 42 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1.5 parts of aqueous initiator are added in reaction kettle, then adopt respectively Being started that A feed liquid and B feed liquid are added dropwise simultaneously with constant flow pump, A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
6. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is by following mass parts Made of several raw materials: polyoxyethylene ether polymeric monomer, that is, 72 parts of isoamyl alcohol polyoxyethylene ether, reducing agent ferrous sulfate 0.015 Part, 1.5 parts of aqueous initiator, that is, hydrogen peroxide, 46 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by 8 parts of acrylic acid, horse Come 1 part of triethylenetetraminehexaacetic acid hydramine dibasic acid esters, 0.5 part of acrylamide, 21 parts of deionized water mix;B feed liquid is by reducing agent L- Vitamin C Acid 0.15 part, 0.32 part of chain-transferring agent, that is, mercaptopropionic acid, 22 parts of deionized water mix;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning By in 0.015 part and 46 parts 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles, it is warming up to 45 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1.5 parts of aqueous initiator are added in reaction kettle, then adopt respectively Being started that A feed liquid and B feed liquid are added dropwise simultaneously with constant flow pump, A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
7. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is by following mass parts Made of several raw materials: polyoxyethylene ether polymeric monomer, that is, 72 parts of methyl allyl polyoxyethylene ether, reducing agent ferrous sulfate 0.015 Part, 1.5 parts of aqueous initiator, that is, hydrogen peroxide, 44 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by 9 parts of acrylic acid, horse Come 2 parts of triethylenetetraminehexaacetic acid hydramine dibasic acid esters, 1 part of acrylamide, 23 parts of deionized water mix;B feed liquid is by reducing agent L-AA 0.15 part, 0.45 part of chain-transferring agent, that is, mercaptopropionic acid, 26 parts of deionized water mix;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning By in 0.015 part and 44 parts 72 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles, it is warming up to 40 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1.5 parts of aqueous initiator are added in reaction kettle, then adopt respectively Being started that A feed liquid and B feed liquid are added dropwise simultaneously with constant flow pump, A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH Value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
8. according to claim 1 promote solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that it is by following mass parts Made of several raw materials: polyoxyethylene ether polymeric monomer, that is, 75 parts of isoamyl alcohol polyoxyethylene ether, reducing agent ferrous sulfate 0.012 Part, 1 part of aqueous initiator, that is, azo-bis-isobutyrate hydrochloride, 42 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is by third 8 parts of olefin(e) acid, unsaturated 0.6 part of alkanolamine ester, 0.8 part of unsaturated amides, that is, N,N-DMAA, 20 parts of deionized water it is mixed It closes;B feed liquid is by 0.12 part of reducing agent L-AA, 0.4 part of chain-transferring agent, that is, mercaptopropionic acid, 23 parts of deionized water mixing It forms;Unsaturated alkanolamine ester is the combination of maleic acid triethanolamine dibasic acid esters, trimethacrylate triethylenetetraminehexaacetic acid two kinds of raw materials of alkanolamine ester, horse The mass ratio for coming triethylenetetraminehexaacetic acid hydramine dibasic acid esters and trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester is 2:1;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning By in 0.012 part and 42 parts 75 parts of polyoxyethylene ether polymeric monomer, ferrous sulfate deionized water investment reaction kettles, it is warming up to 40 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. 1 part of aqueous initiator is added in reaction kettle, then it is respectively adopted Constant flow pump starts that A feed liquid and B feed liquid are added dropwise simultaneously, and A feed liquid was added dropwise to complete at 3 hours, and B feed liquid was added dropwise to complete at 3.5 hours, when After all feed liquids are added dropwise to complete, insulation reaction 1.5 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts pH value To 7 to get the solidifying high-early strength polyocarboxy acid superplasticiser of rush.
9. a kind of preparation method for promoting solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that the rush coagulates early-strength polycarboxylic acids Super plasticizer is made of the raw material of following mass fractions: 70~80 parts of polyoxyethylene ether polymeric monomer, reducing agent X, aqueous being drawn 1~1.5 part of agent of hair, 40~50 parts of deionized water, A feed liquid, B feed liquid;Above-mentioned A feed liquid is solidifying early strong by 7~9 parts of acrylic acid, rush Monomer be unsaturated 0.1~2 part of alkanolamine ester, 0.1~1 part of unsaturated amides, 15~25 parts of deionized water mix;B feed liquid It is mixed by 0.08~0.15 part of reducing agent Y, 0.3~0.5 part of chain-transferring agent, 18~28 parts of deionized water;Wherein, above-mentioned Polyoxyethylene ether polymeric monomer be methyl allyl polyoxyethylene ether, allyl polyethenoxy ether, isoamyl alcohol polyoxyethylene ether One of TPEG, isobutene alcohol polyoxyethylene ether;Unsaturated alkanolamine ester is maleic acid triethanolamine dibasic acid esters, maleic acid diethanol Amine ester, maleic acid alkanolamine ester, trimethacrylate triethylenetetraminehexaacetic acid alkanolamine ester, methacrylic acid diethanol amine ester, methacrylic acid single methanol Amine ester, acrylic acid diethanol amine ester, acrylic acid list alkanolamine ester, fumaric acid triethanolamine ester, fumaric acid diethanol amine ester, rich horse At least one of sour monoethanolamine ester;Unsaturated amides be acrylamide, Methacrylamide, n-isopropyl acrylamide, Methylene-bisacrylamide, N,N-DMAA, N, at least one in N- acrylamide, 2- acrylamide Kind;Aqueous initiator is that one of hydrogen peroxide, persulfate, azo-bis-isobutyrate hydrochloride or any two kinds press any matter Measure the combination of proportion;The mass ratio of reducing agent Y and reducing agent X are 10~11:1;
The preparation method of the solidifying high-early strength polyocarboxy acid superplasticiser of the rush comprises the technical steps that: 1. by above-mentioned quality proportioning In 70~80 parts of polyoxyethylene ether polymeric monomer, reducing agent X and 40~50 parts of deionized waters investment reaction kettles, 40 will be warming up to~ 50 DEG C, stirring to polyoxyethylene ether polymeric monomer is completely dissolved;2. aqueous initiator is added in reaction kettle, constant flow pump is then used Starting while A feed liquid and B feed liquid is added dropwise, A feed liquid was added dropwise to complete at 2.5~3 hours, and B feed liquid was added dropwise to complete at 3~3.5 hours, After all feed liquids are added dropwise to complete, insulation reaction 1.5~2 hours, resulting product is finally down to room temperature, liquid alkaline is added and adjusts PH value promotees solidifying high-early strength polyocarboxy acid superplasticiser to 7.
10. the preparation method according to claim 1 for promoting solidifying high-early strength polyocarboxy acid superplasticiser, it is characterised in that above-mentioned to go back Former agent X is ferrous sulfate, and reducing agent Y is L-AA, and the mass ratio of reducing agent Y and reducing agent X are 10:1;Above-mentioned chain turns Shifting agent is mercaptopropionic acid.
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