CN106519137A - Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof - Google Patents

Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof Download PDF

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CN106519137A
CN106519137A CN201610885964.8A CN201610885964A CN106519137A CN 106519137 A CN106519137 A CN 106519137A CN 201610885964 A CN201610885964 A CN 201610885964A CN 106519137 A CN106519137 A CN 106519137A
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star
cross
preparation
slow release
water
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廖兵
赵阳阳
庞浩
赵宏伟
王坤
黄福仁
黄健恒
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State Owned Assets Management Co Ltd
Guangzhou Chemical Co Ltd of CAS
Nanxiong Material Production Base of Guangzhou Chemical Co Ltd of CAS
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State Owned Assets Management Co Ltd
Guangzhou Chemical Co Ltd of CAS
Nanxiong Material Production Base of Guangzhou Chemical Co Ltd of CAS
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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
    • C04B24/16Sulfur-containing compounds
    • C04B24/161Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • 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
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302Water reducers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention belongs to the technical field of concrete water-reducing agents, specifically to a cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and a preparation method thereof. The preparation method provided by the invention comprises the following steps: subjecting an unsaturated double bond containing terminated cross-star-shaped structure core, an unsaturated macromonomer, an unsaturated carboxylic acid monomer and water to mixing, then carrying out heating, adding an initiator and a chain transfer agent, carrying out a heat-preserving reaction, and carrying out cooling and neutralizing so as to obtain the cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent. The cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent provided by the invention uses a hyperbranched molecule as a core and a comb-shaped structure as an arm, so properties of the hyperbranched molecule and a comb-shaped polycarboxylic-acid water-reducing agent are obtained, and good slow-release and slump-retaining performances are achieved; the cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent is based on electrostatic interaction and steric hinderance effect, so excellent dispersibility to concrete is obtained; an ester group of the cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent is gradually hydrolyzed, so a slow-release effect is achieved; and the cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent is applied to concrete and construction industry, and has low dosage, high water reducing rate, excellent dispersibility, good slow-release and slump-retaining performances, and extensive application prospects.

Description

Star-like slow release slump retaining polycarboxylate water reducer of a kind of cross and preparation method thereof
Technical field
The invention belongs to cement water reducing agent technical field, the star-like slow release collapse protective poly-carboxylic acid of more particularly to a kind of cross subtracts Water preparation and preparation method thereof.
Background technology
As the continuous development of building industry, requirement of the people to cement, concrete are more and more, water reducer is used as raising Concrete strength, the effective measures for improving the aspects such as performance, saving cement consumption and saving energy consumption, it has also become in concrete not The component that can lack.Polycarboxylate high performance water-reducing agent is a kind of new high performance water-reducing agent developed in recent years, is had Low-dosage, high water reducing rate, strong dispersion force, workability are good, and molecular structure is controllable and green environmental protection, high-rise, it is big across Substantial amounts of popularization and application are obtained in the engineerings such as degree bridge, marine drilling platform, tunnel.
For ready-mixed concrete industry, fresh concrete slump-loss is excessive always to perplex compeling for normal construction Be essential problem to be solved.What slump-loss occurred main reason is that cement is a kind of material with hydration activity, with The carrying out of hydrated cementitious, there is provided the moisture of lubrication is constantly reduced, at the same water reducer by cement granules and hydrated product not Disconnected adsorbing result, makes the valid density of water reducer in liquid phase reduce quickly, and the electric potential of system and peptizaiton are not It is disconnected to decline.When concrete mix must be transported for a long time, especially in hot climate, it should be maintained at initial as far as possible Slump level, to ensure that concrete is smoothed out transporting, pumps and pour work.
At present, the research to sustained-release water reducing agent focuses primarily upon the poly- carboxylic of aliphatic polycarboxylic acid's water reducer, pectinate texture Acid type high-performance water reducing agent.Such as, Zhao Shilin et al. (2000) is by monomers such as maleic anhydride, methacrylic acid, alkenyl sulphonate, With in sodium hydroxide and after under nitrogen protection, by composite initiator copolymerization, introduce with negative charge in water solution system Carboxyl and there is the polymer lateral chain of affinity interaction to water, synthesized the efficient diminishing of aliphatic polycarboxylic acid's salt of low slump loss Agent;Liu Chunyan et al. (2012) designs reference acrylamide in polycarboxylate water-reducer molecule so as to which the amide groups of offer are mixed The alkalescence condition for coagulating soil issues raw hydrolysis, discharges carboxylic hydrolyzate, so as to reach the effect of dispersion slow setting, should Although cement water reducing agent is protected, the retarding effect that collapses is good, and the volume of required water reducer is for needed for 0.8% can be only achieved industry Water-reducing effect, water-reducing rate also need further to be improved.Additionally, CN100545118A discloses one kind with allyl polyglycol being The pectination poly carboxylic acid series water reducer of raw material, which is with allyl polyglycol, maleic anhydride, acrylic acid methyl ester., Ammonium persulfate., sulfur Sour stannous, sodium hydroxide and water are prepared and are obtained by appropriate quality proportioning, under conditions of nitrogen protection is connected with, heated reaction , reaction temperature is 50~100 DEG C, and the response time is 4~10h.Initiator of the method using oxidation-reduction system, significantly Efficiency of initiation is improve, and technical process is simple, but adjust the molecular weight of polymer, product due to not adding chain-transferring agent Molecular weight it is excessive, the water-reducing rate of water reducer is relatively low, initial dispersion is indifferent, the concrete initial slump prepared with which compared with It is little.
The fatty chain reported and pectination polycarboxylate water-reducer single effect, it is difficult to meet required by concrete industry Volume is low, and water-reducing effect is good, and the characteristics of slow release function of slump protection is good, combination property needs further to be improved.
The content of the invention
In order to overcome the shortcoming of above-mentioned prior art pectinate texture polycarboxylate water-reducer with not enough, the primary and foremost purpose of the present invention It is to provide a kind of cross star-like slow release slump retaining polycarboxylate water reducer.
The present invention provide new structure polycarboxylate water-reducer, its with super branched molecule as core, with comb-type structure as arm So as to obtain cross hub-and-spoke configuration, while the property of the property with super branched molecule and pectination polycarboxylate water-reducer, can reach Good slow release function of slump protection.Electrostatic interaction of the water reducer of the present invention based on function carboxyl and combed side chain and cross hub-and-spoke configuration Space steric effect make which that there is excellent dispersive property to concrete;Due to the multi-stratification of structure, deposited with hydrophobic form Ester group gradually hydrolyze in alkaline environment, so as to reach slow release effect;Therefore, in actual application, its volume is low, Water-reducing rate is high, dispersive property is excellent, slow release function of slump protection is good, thus is with a wide range of applications.
Another object of the present invention is to provide a kind of preparation side of the star-like slow release slump retaining polycarboxylate water reducer of above-mentioned cross Method.Preparation method of the present invention is with the hub-and-spoke configuration core containing unsaturated double-bond end-blocking, unsaturated polymeric monomer, unsaturated carboxylic acid monomer Water reducer is obtained by water is mutually free-radical polymerized in the presence of initiator.
The purpose of the present invention is realized by following proposal:
A kind of preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross, comprises the following steps:Unsaturation will be contained The star-like structural core of cross of double bond end-blocking, unsaturated polymeric monomer, unsaturated carboxylic acid monomer and water mixing, heating, addition are drawn Agent and chain-transferring agent is sent out, insulation reaction, cooling, neutralization obtain the star-like slow release slump retaining polycarboxylate water reducer of cross.
Wherein in one embodiment, the described star-like structural core of cross containing unsaturated double-bond end-blocking refers to erythrol third Olefin(e) acid ester, pentaerythritol acrylate (PTEA), Lignum Aquilariae Resinatum tetrol acrylate, oxidation resveratrol acrylate etc..
Wherein in one embodiment, described unsaturated carboxylic acid monomer refers to acrylic acid (AA), methacrylic acid (MA), horse Come anhydride (MAH), itaconic acid (IA) etc..
Wherein in one embodiment, described unsaturated polymeric monomer refers to the polymeric monomer containing unsaturated double-bond.
Wherein in one embodiment, described unsaturated polymeric monomer refers to the poly- second of allyl polyglycol, isobutenyl two Alcohol, isopentene group Polyethylene Glycol etc..
Wherein in one embodiment, described unsaturated polymeric monomer refers to the poly- second of allyl polyglycol, isobutenyl two Alcohol, isopentene group Polyethylene Glycol etc., molecular weight are 400~3000.
Wherein in one embodiment, described chain-transferring agent is primarily referred to as TGA, mercaptopropionic acid, n- dodecyl mereaptan Deng.
Wherein in one embodiment, described initiator refers mainly to inorganic peroxide initiator and oxidoreduction class is drawn Send out at least one in agent.
Wherein in one embodiment, described inorganic peroxide initiator refers mainly to persulfuric acid salt, such as persulfuric acid Ammonium, Ammonium persulfate. potassium and sodium peroxydisulfate etc..
Wherein in one embodiment, described redox type initiators are primarily referred to as benzoyl peroxide/sucrose, uncle Butylhydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, accelerine, Ammonium persulfate ./sodium sulfite, over cure Sour potassium/sodium sulfite, hydrogen peroxide/tartaric acid, Ammonium persulfate ./ferrous sulfate, hydrogen peroxide/sulfuric acid are ferrous, benzoyl peroxide Formyl/N, it is N- diethylanilines, benzoyl peroxide/ferrous pyrophosphate, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, different Cumene hydroperoxide/ferrous chloride, potassium peroxydisulfate/ferrous chloride, hydrogen peroxide/ferrous chloride, isopropyl benzene hydroperoxide/tetrem Alkene imines etc..
Wherein in one embodiment, described initiator is first dissolved in water before adding.
Wherein in one embodiment, described initiator is first dissolved in water before adding, and obtains mass concentration for 1~10% Solution.
Wherein in one embodiment, described initiator is first dissolved in water before adding, then is slowly added dropwise to reaction system In.
Wherein in one embodiment, described initiator is first dissolved in water before adding, then is slowly added dropwise to reaction system In, time for adding is 2 hours.
Wherein in one embodiment, the heating refers to and is heated to 50~100 DEG C.
Wherein in one embodiment, the time of the insulation reaction is 1~6h.
Wherein in one embodiment, the neutralization is referred to and is neutralized using dilute alkaline soln.
Wherein in one embodiment, described dilute alkaline soln refers to NaOH, KOH, hexamethylene diamine, triethanolamine etc..
Wherein in one embodiment, the concentration of polymer solution of the dilute alkaline soln is 10~40%.
The present invention provides the star-like slow release slump retaining polycarboxylate water reducer of cross that said method is prepared.Diminishing of the present invention Agent is colourless or light yellow transparent liquid, and which is cross hub-and-spoke configuration, wherein, is respectively foundation containing carboxylic acid in the every arm of structure The pectinate texture long-chain of group, sulfonate group, one or more feature structure in amide group.
The present invention the star-like slow release slump retaining polycarboxylate water reducer of cross, its with super branched molecule as core, with comb-type structure It is arm so as to obtain cross hub-and-spoke configuration, while the property of the property with super branched molecule and pectination polycarboxylate water-reducer, can Reach good slow release function of slump protection.Electrostatic interaction of the water reducer of the present invention based on function carboxyl and combed side chain and cross are star-like The space steric effect of structure makes which have excellent dispersive property to concrete;Due to the multi-stratification of structure, with hydrophobic shape The ester group that formula is present gradually is hydrolyzed in alkaline environment, so as to reach slow release effect;Therefore, concrete and building work be can be applicable to In industry, and in actual application, its volume is low, water-reducing rate is high, dispersive property is excellent, slow release function of slump protection is good, thus has It is widely applied prospect.
The present invention is had the following advantages and beneficial effect relative to prior art:
1st, the star-like polycarboxylate water-reducer of cross prepared by the present invention, its agent structure are cross hub-and-spoke configuration, and structure Pectination knot on per arm respectively containing one or more feature structure in carboxylate group, sulfonate group, amide group Structure long-chain is water reducer field after the innovation for linearly developing to after pectinate texture.
2nd, the star-like polycarboxylate water-reducer excellent combination property of cross prepared by the present invention, is provided simultaneously with low-dosage, and height subtracts Water rate, polymolecularity, high fluidity.
3rd, the star-like polycarboxylate water-reducer of cross prepared by the present invention has good slow release function of slump protection.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Reagent used in the following example can be obtained from commercial channel.
Embodiment 1
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 60g isopentene group polyoxyethylene ether (TPEG), is warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g Pentaerythritol acrylate (PTEA), 10.81g acrylic acid (AA), 3.04g n- dodecyl mereaptans, then to Deca quality in flask Concentration is 1% ammonium persulfate solution 145g, and time for adding is controlled after 2h, completion of dropping, is warming up to 90 DEG C, insulation reaction 1.5h;After reaction terminates, to 40 DEG C, the product mass concentration for obtaining is that 40% sodium hydroxide solution adjusts pH to slow cooling It is worth to 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylate water-reducer, is labeled as PCE-1.
Embodiment 2
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 60g isopentene group polyoxyethylene ether (TPEG), is warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g Pentaerythritol acrylate (PTEA), 10.81g acrylic acid (AA), 3.04g n- dodecyl mereaptans, then to Deca quality in flask Concentration is 1% ammonium persulfate solution 145g, and time for adding is controlled after 2h, completion of dropping, is warming up to 90 DEG C, insulation reaction 3h;After reaction terminates, to 40 DEG C, the product mass concentration for obtaining is that 10% potassium hydroxide solution adjusts pH value to slow cooling To 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylate water-reducer, is labeled as PCE-2.
Embodiment 3
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 15g allyl polyethenoxy ethers, 40g isopentene group polyoxyethylene ether (TPEG) are warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g pentaerythritol acrylates (PTEA), 10.81g acrylic acid (AA), 3.04g n- dodecyl mereaptans, so In backward flask, Deca mass concentration is 1% ammonium persulfate solution 145g, and time for adding is controlled after 2h, completion of dropping, risen Warm to 90 DEG C, insulation reaction 1.5h;After reaction terminates, to 40 DEG C, the product mass concentration for obtaining is 10% to slow cooling Potassium hydroxide solution adjusts pH value to 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylate water-reducer, is labeled as PCE-3.
Embodiment 4
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 15g allyl polyethenoxy ethers, 40g isopentene group polyoxyethylene ether (TPEG) are warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g pentaerythritol acrylates (PTEA), 0.6g acrylic acid (AA), 4.09g maleic anhydrides, 3.04g n- dodecyl mereaptans, then to the ammonium persulfate solution 145g that Deca mass concentration in flask is 1%, time for adding control After 2h, completion of dropping, 90 DEG C are warming up to, insulation reaction 3h;After reaction terminates, slow cooling to 40 DEG C, use by the product for obtaining Mass concentration is that 10% potassium hydroxide solution adjusts pH value to 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylic acids diminishing Agent, is labeled as PCE-4.
Embodiment 5
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 60g isopentene group polyoxyethylene ether (TPEG), is warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g Pentaerythritol acrylate (PTEA), 5g acrylic acid (AA), 0.66g methylpropene sodium sulfonates (AM), 3.04g n- dodecyl mereaptans, Then to the ammonium persulfate solution 152g that Deca mass concentration in flask is 1%, time for adding is controlled after 2h, completion of dropping, 90 DEG C are warming up to, insulation reaction 1.5h;After reaction terminates, to 40 DEG C, the product mass concentration for obtaining is 10% to slow cooling Potassium hydroxide solution adjust pH value to 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylate water-reducer, is labeled as PCE-5.
Embodiment 6
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 60g isopentene group polyoxyethylene ether (TPEG), is warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g Pentaerythritol acrylate (PTEA), 0.6g acrylic acid (AA), 4.09g maleic anhydrides, 0.66g methylpropene sodium sulfonates (AM), 3.04g n- dodecyl mereaptans, then to the ammonium persulfate solution 152g that Deca mass concentration in flask is 1%, time for adding Control is warming up to 90 DEG C, insulation reaction 3h after 2h, completion of dropping;After reaction terminates, slow cooling to 40 DEG C, the product for obtaining Thing mass concentration is that 10% potassium hydroxide solution adjusts pH value to 7 or so.It is cooled to room temperature and obtains final product hub-and-spoke configuration polycarboxylic acids Water reducer, is labeled as PCE-6.
Embodiment 7
Equipped with thermometer, agitator, Dropping funnel sequentially add 50mL water in the 500mL four-hole boiling flasks of condenser, 15g allyl polyethenoxy ethers, 40g isopentene group polyoxyethylene ether (TPEG) are warming up to 65 DEG C, after stirring 10min, at interval of 5min, is sequentially added into 1g pentaerythritol acrylates (PTEA), 0.6g acrylic acid (AA), 4.09g maleic anhydrides, 0.66g methylpropene sodium sulfonates (AM), 3.04g n- dodecyl mereaptans, then to the persulfuric acid that Deca mass concentration in flask is 1% Potassium solution 164g, time for adding are controlled after 2h, completion of dropping, are warming up to 90 DEG C, insulation reaction 3h;After reaction terminates, slowly 40 DEG C are cooled to, the product mass concentration for obtaining is that 10% sodium hydroxide solution adjusts pH value to 7 or so.It is cooled to room temperature Hub-and-spoke configuration polycarboxylate water-reducer is obtained final product, PCE-7 is labeled as.
Implementation result
1st, paste flowing degree
Using reference cement, according to GB/T8077-2000《Methods for testing uniformity of concrete admixture》Test cement Paste flowing degree, the ratio of mud are 0.35, and the volume (the solid volume 0.16% of folding) of water reducer is on the basis of the quality of cement.Choose comb Shape polycarboxylate water-reducer (PCE-0, commercially available) be reference, test result such as table 1 below.
Compared to commercially available pectination polycarboxylate water-reducer, the net slurry stream of the star-like high performance water reducing agent of polyocarboxy acid of prepared cross Dynamic degree and water-reducing rate increase significantly.Wherein, ratio of mud W/C is 0.35, when the solid volume of folding is only 0.16%, prepared The star-like high performance water reducing agent of polyocarboxy acid water-reducing rate of cross of embodiment 1 to embodiment 7 is respectively increased 28%, 38%, 34%, 39%, 42%, 47%, 57%.
1 paste flowing degree of table is tested
2nd, flow retentivity
Using reference cement, according to GB/T8077-2000《Methods for testing uniformity of concrete admixture》Test cement Paste flowing degree, the ratio of mud are 0.35, and water reducer volume is variable, through 0min, 30min, 60min, 90min, 120min's Fluidity, test result such as table 2 below.
2 mobility retentivity of table is tested
From examples detailed above and test result, ratio of mud W/C is 0.35, the initial flow of the star-like polycarboxylate water-reducer of cross Dynamic degree increases with the increase of the solid volume of folding.After placing 1h and 2h, prepared water reducer PCE-1, PCE-2, PCE-3, The paste flowing degree of PCE-4 only has a little reduction, and fluidity still keeps original net slurry stream during the Jing of PCE-5, PCE-6, PCE-7 Dynamic degree, thus the star-like polycarboxylate water-reducer of prepared cross has good slow release function of slump protection.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention not by above-described embodiment Limit, other any spirit without departing from the present invention and the change, modification, replacement made under principle, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

1. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of a kind of cross, it is characterised in that comprise the following steps:Will The star-like structural core of cross containing unsaturated double-bond end-blocking, unsaturated polymeric monomer, unsaturated carboxylic acid monomer and water mixing, plus Heat, adds initiator and chain-transferring agent, insulation reaction, cooling, neutralization to obtain the star-like slow release collapse protective poly-carboxylic acid diminishing of cross Agent.
2. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: The described star-like structural core of cross containing unsaturated double-bond end-blocking refers to erythrol acrylate, pentaerythritol acrylate, sinks At least one in fragrant tetrol acrylate and oxidation resveratrol acrylate.
3. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: Described unsaturated carboxylic acid monomer refers at least one in acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.
4. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: Described unsaturated polymeric monomer refers to the polymeric monomer containing unsaturated double-bond.
5. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: Described unsaturated polymeric monomer refers in allyl polyglycol, isobutenyl Polyethylene Glycol and isopentene group Polyethylene Glycol at least It is a kind of.
6. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: Described chain-transferring agent refers at least one in TGA, mercaptopropionic acid and n- dodecyl mereaptan.
7. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: Described initiator refers mainly to inorganic peroxide initiator and at least one in redox type initiators.
8. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 7, it is characterised in that: Described inorganic peroxide initiator refers at least one in Ammonium persulfate., Ammonium persulfate. potassium and sodium peroxydisulfate;Described oxygen Change reduction class initiator and refer to benzoyl peroxide/sucrose, tert-butyl hydroperoxide/sodium pyrosulfite, benzoyl peroxide/N, N- Dimethylaniline, Ammonium persulfate ./sodium sulfite, potassium peroxydisulfate/sodium sulfite, hydrogen peroxide/tartaric acid, Ammonium persulfate ./ Ferrous sulfate, hydrogen peroxide/sulfuric acid are ferrous, benzoyl peroxide/N, and N- diethylanilines, benzoyl peroxide/pyrophosphoric acid is sub- Ferrum, potassium peroxydisulfate/silver nitrate, persulfate/mercaptan, isopropyl benzene hydroperoxide/ferrous chloride, potassium peroxydisulfate/ferrous chloride, mistake At least one in hydrogen oxide/ferrous chloride and isopropyl benzene hydroperoxide/tetra- aziridine.
9. the preparation method of the star-like slow release slump retaining polycarboxylate water reducer of cross according to claim 1, it is characterised in that: The heating refers to and is heated to 50~100 DEG C;The time of the insulation reaction is 1~6h.
10. the star-like slow release slump retaining polycarboxylate water reducer of a kind of cross, it is characterised in that according to any one of claim 1~9 institute The preparation method stated is obtained.
CN201610885964.8A 2016-10-10 2016-10-10 Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof Pending CN106519137A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
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CN110643005A (en) * 2018-06-26 2020-01-03 科之杰新材料集团有限公司 Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer
CN110642991A (en) * 2018-06-26 2020-01-03 科之杰新材料集团有限公司 Preparation method of ether viscosity-reducing polycarboxylic acid superplasticizer
CN111574100A (en) * 2020-05-29 2020-08-25 酒泉一品太华建筑外加剂生产有限公司 High-strength self-leveling grouting material
CN111690101A (en) * 2020-07-28 2020-09-22 陕西大开建材有限公司 Strong-adaptability polycarboxylate superplasticizer with star-shaped long branched chain structure and preparation method thereof
CN113149506A (en) * 2021-04-02 2021-07-23 山东交通学院 Concrete aggregate dispersant
CN113278113A (en) * 2021-07-01 2021-08-20 北京金隅水泥节能科技有限公司 Aromatic cross-linking agent, star-shaped polycarboxylate superplasticizer and preparation method of star-shaped polycarboxylate superplasticizer

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CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent

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CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110643005A (en) * 2018-06-26 2020-01-03 科之杰新材料集团有限公司 Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer
CN110642991A (en) * 2018-06-26 2020-01-03 科之杰新材料集团有限公司 Preparation method of ether viscosity-reducing polycarboxylic acid superplasticizer
CN110643005B (en) * 2018-06-26 2022-01-04 科之杰新材料集团有限公司 Preparation method of ester viscosity-reducing polycarboxylic acid superplasticizer
CN110642991B (en) * 2018-06-26 2022-01-04 科之杰新材料集团有限公司 Preparation method of ether viscosity-reducing polycarboxylic acid superplasticizer
CN111574100A (en) * 2020-05-29 2020-08-25 酒泉一品太华建筑外加剂生产有限公司 High-strength self-leveling grouting material
CN111690101A (en) * 2020-07-28 2020-09-22 陕西大开建材有限公司 Strong-adaptability polycarboxylate superplasticizer with star-shaped long branched chain structure and preparation method thereof
CN113149506A (en) * 2021-04-02 2021-07-23 山东交通学院 Concrete aggregate dispersant
CN113278113A (en) * 2021-07-01 2021-08-20 北京金隅水泥节能科技有限公司 Aromatic cross-linking agent, star-shaped polycarboxylate superplasticizer and preparation method of star-shaped polycarboxylate superplasticizer

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