CN104016614A - Polycarboxylate water reducer with defoaming function and preparation method of water reducer - Google Patents

Polycarboxylate water reducer with defoaming function and preparation method of water reducer Download PDF

Info

Publication number
CN104016614A
CN104016614A CN201410262099.2A CN201410262099A CN104016614A CN 104016614 A CN104016614 A CN 104016614A CN 201410262099 A CN201410262099 A CN 201410262099A CN 104016614 A CN104016614 A CN 104016614A
Authority
CN
China
Prior art keywords
reducer
initiator
water
parts
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410262099.2A
Other languages
Chinese (zh)
Other versions
CN104016614B (en
Inventor
王进春
刘昭洋
汪咏梅
叶子
倪涛
万甜明
苏荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHIJIAZHUANG CHANG'AN YUCAI BUILDING MATERIALS Co Ltd
Original Assignee
SHIJIAZHUANG CHANG'AN YUCAI BUILDING MATERIALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHIJIAZHUANG CHANG'AN YUCAI BUILDING MATERIALS Co Ltd filed Critical SHIJIAZHUANG CHANG'AN YUCAI BUILDING MATERIALS Co Ltd
Priority to CN201410262099.2A priority Critical patent/CN104016614B/en
Publication of CN104016614A publication Critical patent/CN104016614A/en
Application granted granted Critical
Publication of CN104016614B publication Critical patent/CN104016614B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a polycarboxylate water reducer with a defoaming function and a preparation method of the water reducer. The water reducer is prepared from the following raw materials: polyoxyethylene ether macromonomers, acrylic acid or derivative monomers of acrylic acid, a chain transfer agent, an initiator, defoaming monomers and de-ionized water, wherein the chain transfer agent is selected from thioglycollic acid, thiohydracrylic acid, sodium methallylsulphonate and sodium allysulfonate; the initiator is selected from hydrogen peroxide, ascorbic acid, sodium persulfate and ammonium persulfate; the defoaming monomers are polyoxyethylene-polyoxypropylene block copolymers. The preparation method comprises the following steps of pouring the polyoxyethylene ether macromonomers and the de-ionized water into a three-mouth flask, and adding the chain transfer agent; dissolving the initiator in the de-ionized water to prepare a solution A; dissolving acrylic acid or the derivative monomers of acrylic acid and the defoaming monomers in the de-ionized water to prepare a solution B; dropwise adding the solution A and the solution B by adopting a constant flow pump at the same time, performing insulation reaction, naturally cooling, and adjusting the pH value to obtain the water reducer. The water reducer has a defoaming function while having a high-performance water reducing effect.

Description

There is polycarboxylate water-reducer of their defoaming function and preparation method thereof
Technical field
The present invention relates to a kind of concrete admixture, be specifically related to a kind of polycarboxylate water-reducer, belong to building material technical field, particularly a kind of polycarboxylate water-reducer with their defoaming function.The invention still further relates to the preparation method of described polycarboxylate water-reducer.
Background technology
Along with the raising of building operation to concrete various requirement, need to provide various functional water reducers.In concrete for hydraulic structure large volume construction process, because poly carboxylic acid itself has certain bleed ability, in the process of constructing in addition, vibrate, be difficult to control, cause interior formwork too much, affect surface quality, weather resistance and erosion resistance are also had a significant impact.
In concrete construction, especially, in mass concrete construction, normally directly use polycarboxylate water-reducer, or composite a certain amount of defoamer carrys out control surface bubble in polycarboxylate water-reducer at present.But defoamer is conventionally water insoluble, cannot in concrete, play good dissemination, destroy larger to concrete workability simultaneously.In concrete admixture formula, according to concrete engineering requirement, except adding water reducer component, also can correspondingly add certain slow setting component, water-retaining component, bleed component, froth breaking component etc., ensure corresponding concrete requirement by these composite means.Defoamer mainly contains organic siloxane class, polyethers and organophosphorus compounds, and these are not soluble in water.In Mass Concrete, use polycarboxylate water-reducer to add after froth breaking component, control the heterogeneity bubble that concrete surface occurs, solve honeycomb and scale phenomenon.Or at template brush one deck releasing agent, ensure concrete quality.The shortcoming of prior art be polycarboxylate water-reducer and defoamer composite after, can greatly reduce concrete workability, also can make slump have certain loss, cause constructional difficulties.Add the polycarboxylate water-reducer of defoamer simultaneously, bad at concrete dispersion effect.Especially in Mass Concrete, defoaming effect is not obvious.The part micro-bubble useful to concrete that can disappear on the contrary in addition, reduces concrete gassiness value and causes destroying its frost resistance.CN103183795A discloses a kind of low gas content amount concrete polycarboxylate water-reducer and preparation method thereof, this water reducer is the polymkeric substance that the weight-average molecular weight that formed by three kinds of monomer random copolymerizations is 10000~30000, preparation method is taking the polyoxyethylene of molecular weight 900~4000, polyethenoxy ether as polymerization single polymerization monomer, the random radical copolymerization of carrying out in water solution system.CN103359972A discloses a kind of polycarboxylate water-reducer of preparing clear-water concrete, it is made up of following substances in percentage by weight: co-poly carboxylic acid 5.00%~60.00%, slow release type defoamer 0.02%~1.00%, defoamer 0.01%~1.00%, air entrapment agent 0.01%~1.00%, the water of retardant 0.00%~10.00% and surplus.These technology, for how making polycarboxylate water-reducer also have their defoaming function in obtaining high-performance water-reducing effect, do not provide concrete guidance program above.
Summary of the invention
Technical problem to be solved by this invention is, a kind of polycarboxylate water-reducer with their defoaming function is provided, and this polycarboxylate water-reducer, in obtaining high-performance water-reducing effect, also has their defoaming function.
For this reason, the present invention also will provide the preparation method of described polycarboxylate water-reducer.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of polycarboxylate water-reducer with their defoaming function, its technical scheme is that it is to be made up of the raw material of following mass fraction (quality proportioning or perhaps parts by weight, weight proportion): 85 ~ 95 parts of the large monomers of polyethenoxy ether class, 8 ~ 9 parts of vinylformic acid or its derivatives monomers, 0.9 ~ 1.0 part of chain-transfer agent, 0.4 ~ 0.6 part of initiator, 0.8 ~ 1.0 part of froth breaking type monomer, 145 ~ 155 parts of deionized waters.Wherein, described chain-transfer agent is the combination (when combination, its quality proportioning is arbitrarily) of one or several (components) in Thiovanic acid, thiohydracrylic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; Described initiator is one or several the combination (when combination, its quality proportioning is arbitrarily) in hydrogen peroxide, xitix, Sodium Persulfate, ammonium persulphate; Described froth breaking type monomer is straight-chain polyether type froth breaking cell cube, and molecule, using unsaturated prenol as initiator, is formed by polyoxypropylene and polyoxyethylene blocks copolymerization.The segmented copolymer that froth breaking type monomer is PULLRONIC F68.The large monomer of above-mentioned polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400.The segmented copolymer of above-mentioned PULLRONIC F68 is the one in Plur0nic type, AP type, AE type.
The described polycarboxylate water-reducer with their defoaming function can be that the raw material of preferred following mass fraction is made: 90 parts of the large monomers of polyethenoxy ether class, 8.65 parts, vinylformic acid, 0.95 part of chain-transfer agent, 0.53 part of initiator, 0.9 part of froth breaking type monomer, 150 parts of deionized waters.Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400; Described chain-transfer agent is methallylsulfonic acid sodium; Described initiator is the combination of two kinds, hydrogen peroxide and xitix, and in 0.53 part of initiator, hydrogen peroxide accounts for 0.38 part, and xitix accounts for 0.15 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AP type, molecular weight 7000.
The described polycarboxylate water-reducer with their defoaming function can also be that the raw material of preferred following mass fraction is made: 88 parts of the large monomers of polyethenoxy ether class, 8 parts of vinylformic acid or its derivatives monomers, 1.0 parts of chain-transfer agents, 0.45 part of initiator, 0.85 part of froth breaking type monomer, 148 parts of deionized waters.Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400; Described chain-transfer agent is the combination of three kinds of thiohydracrylic acids, methallylsulfonic acid sodium, sodium allyl sulfonate, and in 1.0 parts of chain-transfer agents, thiohydracrylic acid accounts for 0.15 part, and methallylsulfonic acid sodium accounts for 0.30 part, and sodium allyl sulfonate accounts for 0.55 part; Described initiator is the combination of two kinds of xitix and ammonium persulphates, and in 0.45 part of initiator, xitix accounts for 0.15 part, and ammonium persulphate accounts for 0.30 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AE type, molecular weight 6000.
The preparation method of the described polycarboxylate water-reducer with their defoaming function, its technical scheme is that described deionized water is divided into deionized water X, deionized water Y, deionized water Z, the mass fraction that is used for the deionized water X that dissolves in the large monomer of polyethenoxy ether class, chain-transfer agent is 59 ~ 62 parts, being 48 ~ 51 parts for the mass fraction of deionized water Y that dissolves in initiator, is 38 ~ 42 parts for the mass fraction of the deionized water Z that dissolves in vinylformic acid or its derivatives monomer, froth breaking type monomer; The preparation method of the described polycarboxylate water-reducer with their defoaming function comprises following processing step: 1. by above-mentioned quality proportioning, large polyethenoxy ether class monomer and deionized water X are poured in there-necked flask, stirring in water bath is heated to 38 ~ 42 DEG C, then in there-necked flask, adds chain-transfer agent; In container (beaker), initiator is dissolved in deionized water Y, make solution A; In another container (another beaker), vinylformic acid or its derivatives monomer, froth breaking type monomer are dissolved in deionized water Z, make solution B; 2. wait for after whole dissolving of solid in there-necked flask, at 38 ~ 42 DEG C of temperature, adopt constant flow pump in there-necked flask, to drip respectively solution A and solution B simultaneously, time for adding is controlled at 2.5 ~ 3.0 hours, then continue insulation (temperature is still 38 ~ 42 DEG C) reaction 1.5 ~ 2.0 hours, naturally cool to after certain temperature, products therefrom regulates left and right, pH value to 6.5 ~ 7.0 with basic solution, obtains having the polycarboxylate water-reducer product of their defoaming function.
In technique scheme, the step temperature that 1. middle stirring in water bath is heated to is preferably 40 DEG C, after step waits for that the solid in there-necked flask all dissolves in 2., be preferably at 40 DEG C of temperature, adopt constant flow pump in there-necked flask, to drip respectively solution A and solution B simultaneously, time for adding is preferably controlled at 2.5 hours, then continuing insulation (temperature is still 40 DEG C) reacts best 1.5 hours, naturally cool to after certain temperature, products therefrom regulates pH value preferably to 7.0 left and right with basic solution, obtains having the polycarboxylate water-reducer product of their defoaming function.The step 2. temperature of middle naturally cooling is preferably 20 DEG C.Step 2. neutral and alkali solution is preferably the sodium hydroxide solution of 30wt%.Initiator used can be the combination of two kinds, hydrogen peroxide and xitix, in the time producing solution A, preferably first initiator xitix is dissolved in deionized water Y; After waiting for that solid in there-necked flask all dissolves, then be 30% hydrogen peroxide solution toward adding mass percent in deionized water Y.
Polycarboxylate water-reducer of the present invention is identical with the using method of conventional polycarboxylate water-reducer, joins in concrete 0.15% ~ 0.2%(mass percent that its volume is gelling material by it).
The present invention is directed in Mass Concrete, interior formwork is difficult to the phenomenon of eliminating, by the redesign of polycarboxylate water-reducer molecule being reached to the open bubble problem of eliminating.The present invention be directed to the molecular structure by redesigning polycarboxylate water-reducer, reduce its surface tension, when making it have high-performance water-reducing effect, also have both concrete defoaming effect, can also ensure that the bubble that original bleed component enters is not destroyed simultaneously.
In hydraulic large-volume concrete construction process, when adopting product of the present invention to guarantee to have high-performance water-reducing effect, also have both defoaming effect, reduce secondary construction processing.Can also guarantee the combination that is not destroyed of bubble that original bleed component enters simultaneously, avoid frost resistance destroyed.In covil construction constructions, adopt aluminum masterplate to there will be equally the too much phenomenon of apparent bubble, equally also can obviously improve apparent honeycomb and scale phenomenon after using product of the present invention.The present invention has introduced the monomer with their defoaming function in poly carboxylic acid copolyreaction.The selection of the monomer of their defoaming function is to adopt under unsaturated double-bond to connect 3-5 carbon atom, and then connects the polyethers of the corresponding polymerization degree.The present invention, in poly carboxylic acid building-up process, introduces with the unsaturated monomer of their defoaming function and participates in polyreaction, reduces the surface tension of poly carboxylic acid own, in the situation that not changing concrete workability, plays and eliminates residual bubble in concrete.
In sum, polycarboxylate water-reducer of the present invention, in obtaining high-performance water-reducing effect, also has their defoaming function.
Embodiment
Embodiment 1: the polycarboxylate water-reducer with their defoaming function is to be made up of the raw material of following mass fraction (quality proportioning): 90 parts of the large monomers of polyethenoxy ether class, 8.65 parts, vinylformic acid, 0.95 part of chain-transfer agent, 0.53 part of initiator, 0.9 part of froth breaking type monomer, 150 parts of deionized waters.Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400.The large monomer of described polyethenoxy ether class also can be TPEG-1200, or is HPEG-2400(methacrylic Soxylat A 25-7).Described chain-transfer agent is methallylsulfonic acid sodium; Described initiator is the combination of two kinds, hydrogen peroxide and xitix, and in 0.53 part of initiator, hydrogen peroxide accounts for 0.38 part, and xitix accounts for 0.15 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AP type, molecular weight 7000.
Described deionized water is divided into deionized water X, deionized water Y, deionized water Z, the mass fraction that is used for the deionized water X that dissolves in the large monomer of polyethenoxy ether class, chain-transfer agent is 60 parts, being 50 parts for the mass fraction of deionized water Y that dissolves in initiator, is 40 parts for the mass fraction of the deionized water Z that dissolves in vinylformic acid or its derivatives monomer, froth breaking type monomer; The preparation method of the described polycarboxylate water-reducer with their defoaming function comprises following processing step: 1. pour in there-necked flask by (the large monomer of polyethenoxy ether class) prenol Soxylat A 25-7 TPEG-3000 or for prenol Soxylat A 25-7 TPEG-2400 and deionized water X by above-mentioned quality proportioning, stirring in water bath is heated to 40 DEG C, then in there-necked flask, adds (chain-transfer agent) methallylsulfonic acid sodium; In container (beaker), initiator is dissolved in deionized water Y, make solution A; In another container (another beaker), the segmented copolymer of vinylformic acid, (froth breaking type monomer) AP type PULLRONIC F68 is dissolved in deionized water Z, make solution B; 2. wait for after whole dissolving of solid in there-necked flask, at 40 DEG C of temperature, adopt constant flow pump in there-necked flask, to drip respectively solution A and solution B simultaneously, time for adding is controlled at 2.5 hours, then continue insulation (temperature is still 40 DEG C) reaction 1.5 hours, naturally cool to after certain temperature (can be 20 DEG C), basic solution for products therefrom (can be the sodium hydroxide solution of 30wt%) regulates pH value to 7.0, obtains (solid content is 42%) and have the polycarboxylate water-reducer product of their defoaming function.Above-mentionedly in the time producing solution A, initiator xitix is dissolved in deionized water Y; After waiting for that solid in there-necked flask all dissolves, then be 30% hydrogen peroxide solution toward adding mass percent in deionized water Y, thereby produce solution A.
Embodiment 2: the polycarboxylate water-reducer with their defoaming function is to be made up of the raw material of following mass fraction (quality proportioning): 88 parts of the large monomers of polyethenoxy ether class, 8 parts, vinylformic acid (or its derivatives monomer), 1.0 parts of chain-transfer agents, 0.45 part of initiator, 0.85 part of froth breaking type monomer, 148 parts of deionized waters.Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-2400 or is prenol Soxylat A 25-7 TPEG-3000, the large monomer of described polyethenoxy ether class also can be TPEG-1200, or is HPEG-2400(methacrylic Soxylat A 25-7).Described chain-transfer agent is the combination of three kinds of thiohydracrylic acids, methallylsulfonic acid sodium, sodium allyl sulfonate, and in 1.0 parts of chain-transfer agents, thiohydracrylic acid accounts for 0.15 part, and methallylsulfonic acid sodium accounts for 0.30 part, and sodium allyl sulfonate accounts for 0.55 part; Described initiator is the combination of two kinds of xitix and ammonium persulphates, and in 0.45 part of initiator, xitix accounts for 0.15 part, and ammonium persulphate accounts for 0.30 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AE type, molecular weight 6000.
Described deionized water is divided into deionized water X, deionized water Y, deionized water Z, the mass fraction that is used for the deionized water X that dissolves in the large monomer of polyethenoxy ether class, chain-transfer agent is 59 parts, being 51 parts for the mass fraction of deionized water Y that dissolves in initiator, is 38 parts for the mass fraction of the deionized water Z that dissolves in vinylformic acid or its derivatives monomer, froth breaking type monomer; The preparation method of the described polycarboxylate water-reducer with their defoaming function comprises following processing step: 1. by above-mentioned quality proportioning by (the large monomer of polyethenoxy ether class) prenol Soxylat A 25-7 TPEG-2400(or prenol Soxylat A 25-7 TPEG-3000) and deionized water X pour in there-necked flask, stirring in water bath is heated to 39 DEG C, then in there-necked flask, adds thiohydracrylic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; In container (beaker), xitix and ammonium persulphate are dissolved in deionized water Y, make solution A; In another container (another beaker), the segmented copolymer of vinylformic acid (or its derivatives monomer), AE type PULLRONIC F68 is dissolved in deionized water Z, make solution B; 2. wait for after whole dissolving of solid in there-necked flask, at 39 DEG C of temperature, adopt constant flow pump to drip solution A and solution B in there-necked flask the inside respectively simultaneously, time for adding is controlled at 3.0 hours, then continue insulation (temperature is still 39 DEG C) reaction 2.0 hours, naturally cool to after 20 DEG C, basic solution for products therefrom (can be the sodium hydroxide solution of 30wt%) regulates pH value to 6.5, obtains having the polycarboxylate water-reducer product of their defoaming function.
Embodiment 3: the polycarboxylate water-reducer with their defoaming function is to be made up of the raw material of following mass fraction (quality proportioning): 95 parts of the large monomers of polyethenoxy ether class (or 85 parts or 90 parts), 8 parts of vinylformic acid or its derivatives monomers (or 8.5 parts or 9 parts), 0.9 part of chain-transfer agent (or 0.95 part or 1.0 parts), 0.5 part of initiator (or 0.4 part or 0.6 part), 1.0 parts of froth breaking type monomers (or 0.8 part or 0.9 part), 155 parts of deionized waters (or 145 parts or 151 parts).Wherein, described chain-transfer agent is one or several the combination (when combination, its quality proportioning is arbitrarily) in Thiovanic acid, thiohydracrylic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; Described initiator is one or several the combination (when combination, its quality proportioning is arbitrarily) in hydrogen peroxide, xitix, Sodium Persulfate, ammonium persulphate; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68.The large monomer of above-mentioned polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400.The large monomer of described polyethenoxy ether class also can be TPEG-1200, or is HPEG-2400(methacrylic Soxylat A 25-7).The segmented copolymer of above-mentioned PULLRONIC F68 is Plur0nic type, molecular weight 5000.The segmented copolymer of PULLRONIC F68 can be AP type or is AE type.
Described deionized water is divided into deionized water X, deionized water Y, deionized water Z, the mass fraction that is used for the deionized water X that dissolves in the large monomer of polyethenoxy ether class, chain-transfer agent is 59 ~ 62 parts, being 48 ~ 51 parts for the mass fraction of deionized water Y that dissolves in initiator, is 38 ~ 42 parts for the mass fraction of the deionized water Z that dissolves in vinylformic acid or its derivatives monomer, froth breaking type monomer; The preparation method of the described polycarboxylate water-reducer with their defoaming function comprises following processing step: 1. by above-mentioned quality proportioning, large polyethenoxy ether class monomer and deionized water X are poured in there-necked flask, stirring in water bath is heated to 40 DEG C (or 42 DEG C or 38 DEG C), then in there-necked flask, adds chain-transfer agent; In container (beaker), initiator is dissolved in deionized water Y, make solution A; In another container (another beaker), vinylformic acid or its derivatives monomer, froth breaking type monomer are dissolved in deionized water Z, make solution B; 2. wait for after whole dissolving of solid in there-necked flask, at 40 DEG C of (or 42 DEG C or 38 DEG C) temperature, adopt constant flow pump in there-necked flask, to drip respectively solution A and solution B simultaneously, time for adding is controlled at 3.0 hours, then continue insulation (temperature is still 40 DEG C) reaction 2.0 hours, naturally cool to after certain temperature (can be 21 DEG C), basic solution for products therefrom (can be the sodium hydroxide solution of 30wt%) regulates pH value to 6.8, obtains having the polycarboxylate water-reducer product of their defoaming function.Data in embodiment 3 brackets are also the experimental datas of doing, and belong to the data of embodiment.
In the time that initiator used is the combination of two kinds, hydrogen peroxide and xitix, in the time producing solution A, initiator xitix is dissolved in deionized water Y; After waiting for that solid in there-necked flask all dissolves, then be 30% hydrogen peroxide solution toward adding mass percent in deionized water Y, thereby produce solution A.
The polycarboxylate water-reducer that various embodiments of the present invention obtain, in obtaining high-performance water-reducing effect, also has their defoaming function.Referring to following experimental data form, table 1 is measurement of surface tension, according to GB/T8077 2012 Methods for testing uniformity of concrete admixture, measures surface tension value by automatic interface tension test instrument.Table 2 is the test of clean slurry degree of mobilization, according to GB/T8077 2012 Methods for testing uniformity of concrete admixture, and water-cement ratio 0.29, volume conversion is effective solid volume.Table 3(1) be concrete experiments proportioning, table 3(2) be concrete experiments data.
 

Claims (10)

1. there is a polycarboxylate water-reducer for their defoaming function, it is characterized in that it is to be made up of the raw material of following mass fraction:
85 ~ 95 parts of the large monomers of polyethenoxy ether class, 8 ~ 9 parts of vinylformic acid or its derivatives monomers, 0.9 ~ 1.0 part of chain-transfer agent, 0.4 ~ 0.6 part of initiator, 0.8 ~ 1.0 part of froth breaking type monomer, 145 ~ 155 parts of deionized waters;
Wherein, described chain-transfer agent is one or several in Thiovanic acid, thiohydracrylic acid, methallylsulfonic acid sodium, sodium allyl sulfonate; Described initiator is one or several in hydrogen peroxide, xitix, Sodium Persulfate, ammonium persulphate; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68.
2. the polycarboxylate water-reducer with their defoaming function according to claim 1, is characterized in that the large monomer of above-mentioned polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400.
3. the polycarboxylate water-reducer with their defoaming function according to claim 1, the segmented copolymer that it is characterized in that above-mentioned PULLRONIC F68 is Plur0nic type, AP type, AE type.
4. the polycarboxylate water-reducer with their defoaming function according to claim 1, is characterized in that it is to be made up of the raw material of following mass fraction:
90 parts of the large monomers of polyethenoxy ether class, 8.65 parts, vinylformic acid, 0.95 part of chain-transfer agent, 0.53 part of initiator, 0.9 part of froth breaking type monomer, 150 parts of deionized waters;
Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400; Described chain-transfer agent is methallylsulfonic acid sodium; Described initiator is the combination of two kinds, hydrogen peroxide and xitix, and in 0.53 part of initiator, hydrogen peroxide accounts for 0.38 part, and xitix accounts for 0.15 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AP type, molecular weight 7000.
5. the polycarboxylate water-reducer with their defoaming function according to claim 1, is characterized in that it is to be made up of the raw material of following mass fraction:
88 parts of the large monomers of polyethenoxy ether class, 8 parts of vinylformic acid or its derivatives monomers, 1.0 parts of chain-transfer agents, 0.45 part of initiator, 0.85 part of froth breaking type monomer, 148 parts of deionized waters;
Wherein, the large monomer of described polyethenoxy ether class is prenol Soxylat A 25-7 TPEG-3000 or is prenol Soxylat A 25-7 TPEG-2400; Described chain-transfer agent is the combination of three kinds of thiohydracrylic acids, methallylsulfonic acid sodium, sodium allyl sulfonate, and in 1.0 parts of chain-transfer agents, thiohydracrylic acid accounts for 0.15 part, and methallylsulfonic acid sodium accounts for 0.30 part, and sodium allyl sulfonate accounts for 0.55 part; Described initiator is the combination of two kinds of xitix and ammonium persulphates, and in 0.45 part of initiator, xitix accounts for 0.15 part, and ammonium persulphate accounts for 0.30 part; The segmented copolymer that described froth breaking type monomer is PULLRONIC F68, the segmented copolymer of PULLRONIC F68 is AE type, molecular weight 6000.
6. the preparation method of a polycarboxylate water-reducer with their defoaming function claimed in claim 1, it is characterized in that described deionized water is divided into deionized water X, deionized water Y, deionized water Z, the mass fraction that is used for the deionized water X that dissolves in the large monomer of polyethenoxy ether class, chain-transfer agent is 59 ~ 62 parts, being 48 ~ 51 parts for the mass fraction of deionized water Y that dissolves in initiator, is 38 ~ 42 parts for the mass fraction of the deionized water Z that dissolves in vinylformic acid or its derivatives monomer, froth breaking type monomer; The preparation method of the described polycarboxylate water-reducer with their defoaming function comprises following processing step:
1. by above-mentioned quality proportioning, large polyethenoxy ether class monomer and deionized water X are poured in there-necked flask, stirring in water bath is heated to 38 ~ 42 DEG C, then in there-necked flask, adds chain-transfer agent; In container, initiator is dissolved in deionized water Y, make solution A; In another container, vinylformic acid or its derivatives monomer, froth breaking type monomer are dissolved in deionized water Z, make solution B; 2. wait for after whole dissolving of solid in there-necked flask, at 38 ~ 42 DEG C of temperature, adopt constant flow pump in there-necked flask, to drip respectively solution A and solution B simultaneously, time for adding is controlled at 2.5 ~ 3.0 hours, then continue insulation reaction 1.5 ~ 2.0 hours, naturally cool to after certain temperature, products therefrom regulates pH value to 6.5 ~ 7.0 with basic solution, obtains having the polycarboxylate water-reducer product of their defoaming function.
7. the preparation method of the polycarboxylate water-reducer with their defoaming function according to claim 6, it is characterized in that the temperature that during step 1., stirring in water bath is heated to is 40 DEG C, after step waits for that the solid in there-necked flask all dissolves in 2., at 40 DEG C of temperature, adopt constant flow pump to drip respectively solution A and solution B simultaneously, time for adding is controlled at 2.5 hours, then continue insulation reaction 1.5 hours, naturally cool to after certain temperature, products therefrom regulates pH value to 7.0 left and right with basic solution, obtains having the polycarboxylate water-reducer product of their defoaming function.
8. the preparation method of the polycarboxylate water-reducer with their defoaming function according to claim 6, is characterized in that during step 2., the temperature of naturally cooling is 20 DEG C.
9. the preparation method of the polycarboxylate water-reducer with their defoaming function according to claim 6, is characterized in that the step sodium hydroxide solution that 2. neutral and alkali solution is 30wt%.
10. the preparation method of the polycarboxylate water-reducer with their defoaming function according to claim 6, is characterized in that initiator used is the combination of two kinds, hydrogen peroxide and xitix, dissolves in initiator xitix in deionized water Y in the time producing solution A; After waiting for that solid in there-necked flask all dissolves, then be 30% hydrogen peroxide solution toward adding mass percent in deionized water Y.
CN201410262099.2A 2014-06-13 2014-06-13 Polycarboxylate water-reducer with their defoaming function and preparation method thereof Active CN104016614B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410262099.2A CN104016614B (en) 2014-06-13 2014-06-13 Polycarboxylate water-reducer with their defoaming function and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410262099.2A CN104016614B (en) 2014-06-13 2014-06-13 Polycarboxylate water-reducer with their defoaming function and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104016614A true CN104016614A (en) 2014-09-03
CN104016614B CN104016614B (en) 2015-11-04

Family

ID=51433673

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410262099.2A Active CN104016614B (en) 2014-06-13 2014-06-13 Polycarboxylate water-reducer with their defoaming function and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104016614B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905493A (en) * 2017-03-20 2017-06-30 江苏苏博特新材料股份有限公司 A kind of froth breaking type poly-carboxylic-acid cement dispersant and preparation method thereof
CN107814886A (en) * 2017-11-16 2018-03-20 科之杰新材料集团有限公司 A kind of defoaming type polycarboxylate water-reducer and preparation method thereof
CN109384413A (en) * 2018-12-24 2019-02-26 科之杰新材料集团有限公司 A kind of preparation method of block defoaming type concrete admixture
CN109928666A (en) * 2019-03-06 2019-06-25 陕西腾强新材料有限公司 A kind of preparation method of reinforcing type polycarboxylic acid high-performance water reducing agent
CN110558314A (en) * 2019-08-20 2019-12-13 南京拓际生物科技有限公司 Polycarboxylate macromolecular aqueous suspending agent dispersant and preparation method thereof
CN113248381A (en) * 2021-07-02 2021-08-13 北京金隅水泥节能科技有限公司 Modified fatty acid, polycarboxylate superplasticizer and preparation method of polycarboxylate superplasticizer
CN113667068A (en) * 2021-08-06 2021-11-19 中交路桥建设有限公司 Glue-reducing type polycarboxylate superplasticizer and preparation method thereof
CN115287115A (en) * 2022-08-05 2022-11-04 中冶武汉冶金建筑研究院有限公司 Water-based concrete release agent and preparation method thereof
CN116751017A (en) * 2023-08-10 2023-09-15 中交路桥建设有限公司 Glue-reducing water-reducing concrete and production system thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1052232A1 (en) * 1998-11-30 2000-11-15 Taiheiyo Cement Corporation Process for producing dispersant for powdery hydraulic composition
CN102030494A (en) * 2010-11-12 2011-04-27 河北金舵建材科技开发有限公司 High-performance polycarboxylate water reducing agent and low-temperature one-step preparation method thereof
CN103408706A (en) * 2013-08-19 2013-11-27 科之杰新材料集团有限公司 High-performance polycarboxylic acid water reducing agent and preparation method thereof
CN103539903A (en) * 2013-09-27 2014-01-29 江苏兆佳建材科技有限公司 Preparation method of powder polycarboxylate superplasticizer with air drafting and defoaming functions
CN103554382A (en) * 2013-09-25 2014-02-05 沈阳建筑大学 Method for solid-phase synthesizing polycarboxylic acid water reducer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1052232A1 (en) * 1998-11-30 2000-11-15 Taiheiyo Cement Corporation Process for producing dispersant for powdery hydraulic composition
CN102030494A (en) * 2010-11-12 2011-04-27 河北金舵建材科技开发有限公司 High-performance polycarboxylate water reducing agent and low-temperature one-step preparation method thereof
CN103408706A (en) * 2013-08-19 2013-11-27 科之杰新材料集团有限公司 High-performance polycarboxylic acid water reducing agent and preparation method thereof
CN103554382A (en) * 2013-09-25 2014-02-05 沈阳建筑大学 Method for solid-phase synthesizing polycarboxylic acid water reducer
CN103539903A (en) * 2013-09-27 2014-01-29 江苏兆佳建材科技有限公司 Preparation method of powder polycarboxylate superplasticizer with air drafting and defoaming functions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
戴乐蓉: "聚氧乙烯-聚氧丙烯嵌段共聚物泡沫性质的研究", 《石油化工》 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106905493B (en) * 2017-03-20 2019-12-27 江苏苏博特新材料股份有限公司 Defoaming polycarboxylic acid cement dispersant and preparation method thereof
CN106905493A (en) * 2017-03-20 2017-06-30 江苏苏博特新材料股份有限公司 A kind of froth breaking type poly-carboxylic-acid cement dispersant and preparation method thereof
CN107814886A (en) * 2017-11-16 2018-03-20 科之杰新材料集团有限公司 A kind of defoaming type polycarboxylate water-reducer and preparation method thereof
CN107814886B (en) * 2017-11-16 2020-03-06 科之杰新材料集团有限公司 Defoaming type polycarboxylate superplasticizer and preparation method thereof
CN109384413A (en) * 2018-12-24 2019-02-26 科之杰新材料集团有限公司 A kind of preparation method of block defoaming type concrete admixture
CN109928666A (en) * 2019-03-06 2019-06-25 陕西腾强新材料有限公司 A kind of preparation method of reinforcing type polycarboxylic acid high-performance water reducing agent
CN110558314A (en) * 2019-08-20 2019-12-13 南京拓际生物科技有限公司 Polycarboxylate macromolecular aqueous suspending agent dispersant and preparation method thereof
CN113248381A (en) * 2021-07-02 2021-08-13 北京金隅水泥节能科技有限公司 Modified fatty acid, polycarboxylate superplasticizer and preparation method of polycarboxylate superplasticizer
CN113667068A (en) * 2021-08-06 2021-11-19 中交路桥建设有限公司 Glue-reducing type polycarboxylate superplasticizer and preparation method thereof
CN115287115A (en) * 2022-08-05 2022-11-04 中冶武汉冶金建筑研究院有限公司 Water-based concrete release agent and preparation method thereof
CN115287115B (en) * 2022-08-05 2023-03-10 中冶武汉冶金建筑研究院有限公司 Water-based concrete release agent and preparation method thereof
CN116751017A (en) * 2023-08-10 2023-09-15 中交路桥建设有限公司 Glue-reducing water-reducing concrete and production system thereof
CN116751017B (en) * 2023-08-10 2023-11-24 中交路桥建设有限公司 Glue-reducing water-reducing concrete and production system thereof

Also Published As

Publication number Publication date
CN104016614B (en) 2015-11-04

Similar Documents

Publication Publication Date Title
CN104016614B (en) Polycarboxylate water-reducer with their defoaming function and preparation method thereof
CN102504126B (en) Slump loss resistant type gather carboxylate water-reducing agent and preparation method thereof
CA2690336C (en) A liquid admixture composition
CN105330193B (en) Nuclear power ultra dense real concrete polycarboxylate water-reducer and preparation method thereof
CN109021181A (en) A kind of poly carboxylic acid series water reducer and preparation method thereof for having both viscosity reduction and protecting function of collapsing
CN102515619B (en) Polyether amine modified polycarboxylic water reducer and preparation method thereof
CN103897116A (en) Mud-resistant polycarboxylic acid water reducer and preparation method thereof
CN107586366B (en) Modified polycarboxylate superplasticizer and preparation method thereof
CN106279561B (en) A kind of viscosity reduction type poly carboxylic acid series water reducer for high performance concrete
CN102432776B (en) Method for preparing early strength type polycarboxylic acid water-reducing agent
CN102093521B (en) Method for preparing polycarboxylic acid high slump retaining agent
CN103865007A (en) Preparation method of viscosity-reduction type polycarboxylate water reducer
CN104292397B (en) A kind of preparation method of PHC pile tube dedicated functionality polycarboxylate water-reducer
CN102951865A (en) Air entraining type poly carboxylic acid high performance water reducing agent and preparation method thereof
CN101817657A (en) Polycarboxylic acid slump retaining agent
CN108794700A (en) A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer
CN102952243B (en) Poly carboxylic acid water reducing agent adopting tartaric acid as chain transfer agent, and preparation method thereof
EP3019540B1 (en) Polymeric dispersant
CN106336485B (en) A kind of low damage poly carboxylic acid series water reducer and preparation method thereof that collapses of anti-chamotte mould
CN109134784A (en) It is a kind of to promote solidifying high-early strength polyocarboxy acid superplasticiser and preparation method thereof
KR102638059B1 (en) Additives for cement, cement admixtures, cement compositions, molded bodies, and methods for improving the strength of molded bodies
CN103613307B (en) Slump type polycarboxylate superplasticizer and preparation method thereof
CN104479082A (en) Slow-release type polycarboxylic acid water reducer and preparation method thereof
CN109400825A (en) A kind of low responsive type polycarboxylate water-reducer and preparation method thereof with anti-mud effect
CN106699984B (en) A kind of lightweight aggregate floating inhibitor and preparation method thereof for lightweight aggregate concrete

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Polycarboxylate water reducer with defoaming function and preparation method of water reducer

Effective date of registration: 20160706

Granted publication date: 20151104

Pledgee: Bank of Hebei, Limited by Share Ltd, Luancheng branch

Pledgor: Shijiazhuang Chang'an Yucai Building Materials Co., Ltd.

Registration number: 2016130000009

PLDC Enforcement, change and cancellation of contracts on pledge of patent right or utility model