CN108794700A - A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer - Google Patents
A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer Download PDFInfo
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- CN108794700A CN108794700A CN201810744013.8A CN201810744013A CN108794700A CN 108794700 A CN108794700 A CN 108794700A CN 201810744013 A CN201810744013 A CN 201810744013A CN 108794700 A CN108794700 A CN 108794700A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The present invention relates to chemical building material fields, and in particular to a kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer.The carboxylic acid group polymer is 1 by the amount ratio of substance：(1-3)：The structural unit of the structural unit derived from unsaturated polyether polymeric monomer of (1-3), the structural unit of derived from carboxylic acid esters monomer and derived from propylene acrylic monomer forms.Sustained-release polycarboxylic water reducer provided by the invention has relatively long slow-release time, can keep the higher slump for a long time, and there is more excellent guarantor to collapse effect.In addition, the preparation method of sustained-release polycarboxylic water reducer provided by the invention is using one pot of change method technique, operability is strong, it is with short production cycle, it can be reacted in wide temperature range, reaction process is easily controllable, and reaction system is low to condition responsives such as initial temperature, stirring dynamics, reaction time, properties of product stability can be kept well, can be effectively improved production efficiency, be easy to industrialized production.
Description
Technical field
The invention belongs to chemical building material fields, and in particular to a kind of carboxylic acid group polymer and preparation method thereof and sustained release
Type polycarboxylate water-reducer.
Background technology
Polycarboxylate water-reducer is widely applied third generation high-performance water reducing agent in modern concrete.In recent years, with work
The universalness of Cheng Yingyong, the complication of application environment and the diversification of production raw material, single high water reducing type polycarboxylate water-reducer
Use far from meeting the needs of engineering concrete is to high diminishing, high-thin arch dam and high retentivity.It is especially long for a long time away from
From in transport, the excessive problem of Slump Time losing of Large shows particularly evident, this, which not only influences construction, can also greatly influence
The performance and quality of concrete.Sustained-release polycarboxylic water reducer is using introducing carboxylic acid derivates in molecule, and the group can be with
Hydrolysis under alkaline environment discharges carboxylic acid ion, and the anchoring group to gradually discharge water-reducing agent reaches slow release effect.By
The sustained-release polycarboxylic water reducer of this synthesis has dispersibility from small to large in concrete application, gradually the characteristics of release, is
Solve ready-mixed concrete long-time transport in slump-loss it is too fast the problems such as provide new departure, so increasingly by
The favor of researcher.
Currently, the production technology of sustained-release polycarboxylic water reducer generally uses thermal initiation mode and monomer solution or chain is added dropwise
The shortcomings of transfer agent solution production, there are the production cycle is long, complex for operation step, energy consumption is big, production capacity is limited.
A kind of sustained-release polycarboxylic water reducer and preparation method thereof is disclosed in CN107090062A, concrete operations are：It will
Polyether macromonomer solution obtains the first mixed solution after being mixed with initiator, then to above-mentioned mixed by way of batch charging
It closes and the second mixed solution (150-200min) being made of reducing agent, chain-transferring agent and water is added dropwise in solution and by unsaturated carboxylic
The third mixed solution (120-180min) of acid, carboxylic acid protection monomer and water composition, the reaction was continued after tear drop 40-
120min, moisturizing adjust concentration.Sustained-release polycarboxylic water reducer made from the technique has relatively long slow-release time,
The higher slump can be kept for a long time, but that there are still processing steps is cumbersome, the problems such as production cycle is long.
Disclosed in CN101735411A a kind of ethers sustained-release polycarboxylic water reducer and its preparation process, copolyreaction
Engineering is to require that the polyoxyethylene ether containing unsaturated double-bond or ester polymeric monomer are configured to solution addition first at 40-55 DEG C
In reaction kettle, by methacrylic acid or acrylic acid, sodium allylsulfonate, hydroxy-ethyl acrylate, two ethanedioic acids after being warming up to 60-85 DEG C
The mixed solution of double methacrylate, which is added dropwise, to be added, and persulfate initiator is individually added dropwise additions, the reaction time up to 8h, technique compared with
Complexity, and reaction temperature is 85 DEG C higher, and energy consumption is higher.
A kind of sustained-release polycarboxylic water reducer and preparation method thereof is disclosed in CN107286298A, concrete operations are：It will
Unsaturated carboxylic acid class minor comonomer carries out partial reaction with diphenyl phosphoryl chloride and obtains the unsaturated minor comonomer of phosphoric acid ester group, then
The amine monomers containing phenyl ring are added into above-mentioned reaction system to be obtained by the reaction containing amide group not with phosphate-based
It is saturated minor comonomer, then 20-60 is maintained under the action of initiator, reducing agent and chain-transferring agent with unsaturated polyether polymeric monomer
DEG C carry out Raolical polymerizable 3-5h obtain copolymerization product, and adjust pH value be 6-7, add water obtain mass concentration be 5-60%
Poly carboxylic acid series water reducer.Although the technique can preferably promote turning for the acid amide type polycarboxylate water-reducer of prior art preparation
Rate ensure that prepared sustained-release polycarboxylic water reducer has slump retaining again under the premise of high diminishing, but there are techniques
The problems such as complex steps, the production cycle is long.
Invention content
The purpose of the invention is to provide a kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic to subtract
Aqua.
Specifically, the present invention provides a kind of carboxylic acid group polymers, wherein the carboxylic acid group polymer is by the amount ratio of substance
1：(1-3)：The structural unit derived from unsaturated polyether polymeric monomer of (1-3), the structural unit of derived from carboxylic acid esters monomer
And the structural unit composition of derived from propylene acrylic monomer, the unsaturated polyether polymeric monomer are selected from prenol polyoxyethylene
At least one of ether, isobutene alcohol polyoxyethylene ether and 4- hydroxy butyl vinyl ether polyoxyethylene ether.
Preferably, the number-average molecular weight Mn of the unsaturated polyether polymeric monomer is 2000-3000.
Preferably, the carboxylic acid esters monomer is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, methacrylic acid hydroxypropyl
At least one of ester, hydroxyethyl methacrylate, methyl methacrylate and dimethyl maleate.
Preferably, the acrylic monomer is acrylic acid and/or methacrylic acid.
Preferably, the number-average molecular weight Mn of the carboxylic acid group polymer is 30000-50000.
The present invention also provides a kind of preparation methods of carboxylic acid group polymer, wherein this method includes by unsaturated polyether
Polymeric monomer, carboxylic acid esters monomer and acrylic monomer use one kettle way in the presence of reducing agent, initiator and chain-transferring agent
Raolical polymerizable is carried out, the unsaturated polyether polymeric monomer is selected from isoamyl alcohol polyoxyethylene ether, isobutene alcohol polyoxy second
At least one of alkene ether and 4- hydroxy butyl vinyl ether polyoxyethylene ether.
Preferably, the preparation method of sustained-release polycarboxylic water reducer provided by the invention includes the following steps：
(1) the unsaturated polyether polymeric monomer is soluble in water, it is added at one time the reducing agent, chain-transferring agent, propylene
Acrylic monomer and carboxylic acid esters monomer are made into the solution that solid content is 40-60wt%；
(2) it is added at one time the initiator in the solution obtained to step (1), carries out Raolical polymerizable, reaction
The pH value of reaction system is adjusted to 6-7 after end.
Preferably, the amount ratio of the substance of the unsaturated polyether polymeric monomer, carboxylic acid esters monomer and acrylic monomer is
1：(1-3)：(1-3)；On the basis of the total weight of the unsaturated polyether polymeric monomer, the dosage of the reducing agent is 0.1-0.3
The dosage of weight %, the initiator are 0.1-1 weight %, and the dosage of the chain-transferring agent is 0.2-1 weight %.
The number-average molecular weight and carboxylic acid esters monomer of the unsaturated polyether polymeric monomer and acrylic monomer it is specific
Type has been described herein above, and therefore not to repeat here.
Preferably, it is sub- to be selected from sodium formaldehyde sulfoxylate, sodium hydrogensulfite, sodium thiosulfate, sodium pyrosulfite, pyrophosphoric acid for the reducing agent
At least one of iron, ferrous sulfate, frerrous chloride, sodium hypophosphite and vitamin C.
Preferably, the initiator is selected from hydrogen peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, ammonium persulfate and over cure
At least one of sour sodium.
Preferably, the chain-transferring agent is in thioacetic acid, mercaptopropionic acid, mercaptoethanol and methylpropenyl sodium sulfonate
At least one.
Preferably, the initiation temperature of the Raolical polymerizable is 15-50 DEG C, reaction time 10-90min.
The present invention also provides the carboxylic acid group polymers being prepared by the above method.
In addition, the present invention also provides a kind of sustained-release polycarboxylic water reducers, wherein the sustained-release polycarboxylic water reducer
Contained in water-reducing agent mother liquor be above-mentioned carboxylic acid group polymer.
Preferably, the solid content of the sustained-release polycarboxylic water reducer is 30-50wt%.
Sustained-release polycarboxylic water reducer provided by the invention has relatively long slow-release time, can keep for a long time
There is the higher slump more excellent guarantor to collapse effect.In addition, the preparation side of sustained-release polycarboxylic water reducer provided by the invention
Method polymerize feature according to active component in system, and using one pot of change method technique, easy to operate, simple and practicable, operability is strong,
It is with short production cycle, it can be reacted in wide temperature range, reaction process is easily controllable.Through verifying repeatedly, the reaction system is to rising
The condition responsives such as beginning temperature, stirring dynamics, reaction time are low, can keep properties of product stability well, can effectively improve
Production efficiency is easy to industrialized production.
Specific implementation mode
The preferred embodiment of the present invention is described in more detail below.Although the following describe the preferred implementations of the present invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without should be limited by embodiments set forth herein.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is for illustrating that carboxylic acid group polymer provided by the invention and preparation method thereof and sustained-release polycarboxylic subtract
Aqua.
(1) the isoamyl alcohol polyoxyethylene ether 400g and deionization that number-average molecular weight is 2400 are added into 1L four-hole boiling flasks
Water 550g is stirred evenly, and after monomer all dissolving, thioacetic acid 2.2g, vitamin C 0.6g, acrylic acid 27g, propylene is added
Sour hydroxyl ethyl ester 20g and hydroxypropyl acrylate 30g is simultaneously uniformly mixed, wherein unsaturated polyether polymeric monomer, carboxylic acid esters monomer and third
The amount ratio of the substance of alkene acrylic monomer is 1:2.42:2.25.
(2) sodium peroxydisulfate 2.4g is added in the solution being uniformly mixed to step (1), and 45min is persistently stirred at 20 DEG C.Polymerization
After reaction, it is 6 with 30wt% sodium hydrate aqueous solution regulation system pH value, and moisturizing dilutes to obtain solid content to be 40wt%
Sustained-release polycarboxylic water reducer, the number-average molecular weight of carboxylic acid group polymer contained therein is 42100.
Embodiment 2
The embodiment is for illustrating that carboxylic acid group polymer provided by the invention and preparation method thereof and sustained-release polycarboxylic subtract
Aqua.
(1) the isoamyl alcohol polyoxyethylene ether 400g and deionization that number-average molecular weight is 2400 are added into 1L four-hole boiling flasks
Water 580g is stirred evenly, and after monomer all dissolving, mercaptopropionic acid 2.5g, vitamin C 0.5g, acrylic acid 26g, propylene is added
Sour hydroxyl ethyl ester 30g and dimethyl maleate 20g is simultaneously uniformly mixed, wherein unsaturated polyether polymeric monomer, carboxylic acid esters monomer and third
The amount ratio of the substance of alkene acrylic monomer is 1:2.38:2.16.
(2) potassium peroxydisulfate 2.4g is added in the solution being uniformly mixed to step (1), and 60min is persistently stirred at 15 DEG C.Polymerization
After reaction, it is 7 with 30wt% sodium hydrate aqueous solution regulation system pH value, and moisturizing dilutes to obtain solid content to be 40wt%
Sustained-release polycarboxylic water reducer, the number-average molecular weight of carboxylic acid group polymer contained therein is 46200.
Embodiment 3
The embodiment is for illustrating that carboxylic acid group polymer provided by the invention and preparation method thereof and sustained-release polycarboxylic subtract
Aqua.
(1) the isoamyl alcohol polyoxyethylene ether 400g and deionization that number-average molecular weight is 2400 are added into 1L four-hole boiling flasks
Water 600g is stirred evenly, and after monomer all dissolving, mercaptoethanol 1.8g, vitamin C 0.6g, acrylic acid 30g, propylene is added
Sour hydroxyl ethyl ester 30g and hydroxypropyl acrylate 30g is simultaneously uniformly mixed, wherein unsaturated polyether polymeric monomer, carboxylic acid esters monomer and third
The amount ratio of the substance of alkene acrylic monomer is 1：2.93：2.50.
(2) potassium peroxydisulfate 2.4g is added in the solution being uniformly mixed to step (1), and 60min is persistently stirred at 20 DEG C.Polymerization
After reaction, with 30wt% sodium hydrate aqueous solution regulation system pH value be 6.5, and moisturizing dilute to obtain solid content be
The number-average molecular weight of the sustained-release polycarboxylic water reducer of 40wt%, carboxylic acid group polymer contained therein is 38900.
Embodiment 4
The embodiment is for illustrating that carboxylic acid group polymer provided by the invention and preparation method thereof and sustained-release polycarboxylic subtract
Aqua.
(1) the isoamyl alcohol polyoxyethylene ether 400g and deionization that number-average molecular weight is 2400 are added into 1L four-hole boiling flasks
Water 545g is stirred evenly, after monomer all dissolving, be added thioacetic acid 1.6g, sodium pyrosulfite C 1.0g, acrylic acid 25g,
Hydroxy-ethyl acrylate 20g and hydroxypropyl acrylate 20g is simultaneously uniformly mixed, wherein unsaturated polyether polymeric monomer, carboxylic acid esters monomer
Amount ratio with the substance of acrylic monomer is 1：1.96：2.08.
(2) tert-butyl hydroperoxide 3.0g is added in the solution being uniformly mixed to step (1), is persistently stirred at 20 DEG C
60min.It is 6 with 30wt% sodium hydroxide solution regulation system pH value, and moisturizing dilutes to obtain solid content after polymerisation
Number-average molecular weight for the sustained-release polycarboxylic water reducer of 40wt%, carboxylic acid group polymer contained therein is 38400.
Embodiment 5
The embodiment is for illustrating that carboxylic acid group polymer provided by the invention and preparation method thereof and sustained-release polycarboxylic subtract
Aqua.
(1) the isoamyl alcohol polyoxyethylene ether 400g and deionization that number-average molecular weight is 2400 are added into 1L four-hole boiling flasks
Water 568g is stirred evenly, and after monomer all dissolving, mercaptopropionic acid 2.4g, vitamin C 0.6g, acrylic acid 23.8g and third is added
Olefin(e) acid hydroxyl ethyl ester 48g is simultaneously uniformly mixed, wherein unsaturated polyether polymeric monomer, carboxylic acid esters monomer and acrylic monomer object
The amount ratio of matter is 1：2.48：1.98.
(2) ammonium persulfate 1.0g, hydrogen peroxide 2.8g is added in the solution being uniformly mixed to step (1), is persistently stirred at 40 DEG C
Mix 15min.It is 6 with 30wt% sodium hydroxide solution regulation system pH value, and moisturizing dilutes and contained admittedly after polymerisation
Amount is the sustained-release polycarboxylic water reducer of 40wt%, and the number-average molecular weight of carboxylic acid group polymer contained therein is 43500.
Application examples
Sustained-release polycarboxylic water reducer obtained by embodiment 1-5 is subtracted with two kinds of commercially available solid contents for the slow-release of 40wt%
Aqua LQ-B1 and LQ-B2 carries out contrast test, measures their paste flowing degree and gradual loss and concrete slump
Loss experiment.Specific test mode is as follows：
1, flowing degree of net paste of cement and gradual loss are with reference to standard GB/T/T8077-2012《Concrete admixture is homogeneous
Property test method》It is tested.In each test sample, the sustained-release polycarboxylic water reducer volume that solid content is 40wt% is water
0.13%, the W/C 0.29 of mud gross mass, test result is as shown in table 1.
2, concrete test is with reference to standard GB/T 8076-2008《Concrete admixture》It is tested.Wherein, cement
For conch PO 42.5, sand is the river sand of fineness modulus 2.8, and stone is 5-31.5mm continuous gradings, and additive uses solid content
It is 40 for the sustained-release polycarboxylic water reducer and the compound ratio of ordinary water-reducing agent of 40wt%:60, volume is cementitious material gross mass
0.45%.It is tested by following match ratio, cement：Flyash：Miberal powder：River sand：Stone：Water：Additive=270：25：25：
800：1080：170：1.44 (unit：kg/m3), test result is as shown in table 2.
The paste flowing degree and gradual loss of the different samples of table 1
Note：In table 1, the numerical value of fluidity can persistently become larger or reduce compared to other product numerical value in the time interval of observation
Rate then shows that sustained release performance is more excellent slowly, otherwise opposite.
As can be seen from Table 1, the sustained-release polycarboxylic water reducer that 1-5 of the embodiment of the present invention is provided is in longer time
It is interior, the fluidity of cement paste can be kept, performance quite or better than comparative sample with commercially available comparative sample performance.It is tied by experiment
Fruit it can be found that acrylic acid dosage is bigger in system, get over by the sustained-release polycarboxylic water reducer cement paste initial flow degree of synthesis
Greatly；Carboxylic acid esters monomer dosage is bigger in system, and slow release effect is better, and the holding effect of fluidity is more apparent.
2 concrete slump of table is tested
As can be seen from Table 2, the sustained-release polycarboxylic water reducer that 1-5 of the embodiment of the present invention is provided is in longer time
It is interior, the slump of concrete can be kept.The slump-loss of more commercially available sustained-release water reducing agent LQ-B1 has a clear superiority, compared with
Commercially available sustained-release water reducing agent LQ-B2 performances are suitable.
In conclusion sustained-release polycarboxylic water reducer provided by the invention has relatively long slow-release time, when energy is long
Between keep the higher slump, there is more excellent guarantor to collapse effect.In addition, sustained-release polycarboxylic water reducer provided by the invention
Preparation method, polymerize feature according to active component in system, it is easy to operate using one pot of change method technique, it is simple and practicable, can grasp
The property made is strong, with short production cycle, can be reacted in wide temperature range, reaction process is easily controllable.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of carboxylic acid group polymer, which is characterized in that the carboxylic acid group polymer is 1 by the amount ratio of substance：(1-3)：(1-3's)
Structural unit and the derived from propylene acid of structural unit, derived from carboxylic acid esters monomer derived from unsaturated polyether polymeric monomer
The structural unit of class monomer forms, and the unsaturated polyether polymeric monomer is selected from isoamyl alcohol polyoxyethylene ether, isobutene alcohol polyoxy
At least one of vinethene and 4- hydroxy butyl vinyl ether polyoxyethylene ether.
2. carboxylic acid group polymer according to claim 1, wherein
The number-average molecular weight Mn of the unsaturated polyether polymeric monomer is 2000-3000；
The carboxylic acid esters monomer is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methacrylic acid
At least one of hydroxyl ethyl ester, methyl methacrylate and dimethyl maleate；
The acrylic monomer is acrylic acid and/or methacrylic acid.
3. carboxylic acid group polymer according to claim 1 or 2, wherein the number-average molecular weight Mn of the carboxylic acid group polymer
For 30000-50000.
4. a kind of preparation method of carboxylic acid group polymer, which is characterized in that this method includes by unsaturated polyether polymeric monomer, carboxylic acid
Esters monomer and acrylic monomer carry out radical polymerization in the presence of reducing agent, initiator and chain-transferring agent using one kettle way
Reaction is closed, the unsaturated polyether polymeric monomer is selected from isoamyl alcohol polyoxyethylene ether, isobutene alcohol polyoxyethylene ether and 4- hydroxyl fourths
At least one of base vinyl ethers polyoxyethylene ether.
5. preparation method according to claim 4, wherein this approach includes the following steps：
(1) the unsaturated polyether polymeric monomer is soluble in water, it is added at one time the reducing agent, chain-transferring agent, acrylic compounds
Monomer and carboxylic acid esters monomer are made into the solution that solid content is 40-60wt%；
(2) it is added at one time the initiator in the solution obtained to step (1), carries out Raolical polymerizable, reaction terminates
The pH value of reaction system is adjusted to 6-7 later.
6. preparation method according to claim 5, wherein the unsaturated polyether polymeric monomer, carboxylic acid esters monomer and third
The amount ratio of the substance of alkene acrylic monomer is 1：(1-3)：(1-3)；On the basis of the total weight of the unsaturated polyether polymeric monomer, institute
The dosage for stating reducing agent is 0.1-0.3 weight %, and the dosage of the initiator is 0.1-1 weight %, the use of the chain-transferring agent
Amount is 0.2-1 weight %.
7. preparation method according to claim 5 or 6, wherein
The number-average molecular weight Mn of the unsaturated polyether polymeric monomer is 2000-3000；
The carboxylic acid esters monomer is selected from hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methacrylic acid
At least one of hydroxyl ethyl ester, methyl methacrylate and dimethyl maleate；
The acrylic monomer is acrylic acid and/or methacrylic acid；
It is sub- that the reducing agent is selected from sodium formaldehyde sulfoxylate, sodium hydrogensulfite, sodium thiosulfate, sodium pyrosulfite, ferrous pyrophosphate, sulfuric acid
At least one of iron, frerrous chloride, sodium hypophosphite and vitamin C；
The initiator in hydrogen peroxide, tert-butyl hydroperoxide, potassium peroxydisulfate, ammonium persulfate and sodium peroxydisulfate at least
It is a kind of；
The chain-transferring agent is selected from least one of thioacetic acid, mercaptopropionic acid, mercaptoethanol and methylpropenyl sodium sulfonate.
8. according to the preparation method described in any one of claim 4-6, wherein the initiation temperature of the Raolical polymerizable
Degree is 15-50 DEG C, reaction time 10-90min.
9. the carboxylic acid group polymer being prepared by the method described in any one of claim 4-8.
10. a kind of sustained-release polycarboxylic water reducer, which is characterized in that water-reducing agent contained in the sustained-release polycarboxylic water reducer
Mother liquor is the carboxylic acid group polymer described in any one of claim 1-3 and 9.
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Cited By (9)
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|---|---|---|---|---|
| CN109534714A (en) * | 2018-12-28 | 2019-03-29 | 巩义市豫源建筑工程材料有限责任公司 | High-performance water reducing agent |
| CN110818856A (en) * | 2019-11-21 | 2020-02-21 | 四川宇砼建材有限公司 | Slow-release polycarboxylate superplasticizer and preparation method thereof |
| CN111100252A (en) * | 2019-12-22 | 2020-05-05 | 同济大学 | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and super slump retaining property |
| CN111320729A (en) * | 2020-04-22 | 2020-06-23 | 广州市建筑科学研究院有限公司 | Polycarboxylate superplasticizer for barite concrete and preparation method and application thereof |
| CN111592263A (en) * | 2019-02-21 | 2020-08-28 | 天水师范学院 | Synthesis process and device of retarding polycarboxylate superplasticizer |
| CN113292687A (en) * | 2021-06-29 | 2021-08-24 | 安徽海螺新材料科技有限公司 | High-performance slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| WO2022095232A1 (en) * | 2020-11-03 | 2022-05-12 | 科之杰新材料集团有限公司 | Ether-type anti-corrosive polycarboxylic acid water reducer and preparation method therefor |
| CN114478938A (en) * | 2022-01-06 | 2022-05-13 | 山西佳维新材料股份有限公司 | Slow-release polycarboxylate superplasticizer, preparation method and application |
| CN116284601A (en) * | 2023-03-16 | 2023-06-23 | 湖州绿色新材股份有限公司 | Staged slow-release polycarboxylate superplasticizer and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356314A (en) * | 2014-10-21 | 2015-02-18 | 福建建工建材科技开发有限公司 | Normal-temperature synthetizing method for slow release type polycarboxylate water-reducer and product produced by same |
-
2018
- 2018-07-09 CN CN201810744013.8A patent/CN108794700B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104356314A (en) * | 2014-10-21 | 2015-02-18 | 福建建工建材科技开发有限公司 | Normal-temperature synthetizing method for slow release type polycarboxylate water-reducer and product produced by same |
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| CN109534714A (en) * | 2018-12-28 | 2019-03-29 | 巩义市豫源建筑工程材料有限责任公司 | High-performance water reducing agent |
| CN111592263A (en) * | 2019-02-21 | 2020-08-28 | 天水师范学院 | Synthesis process and device of retarding polycarboxylate superplasticizer |
| CN110818856A (en) * | 2019-11-21 | 2020-02-21 | 四川宇砼建材有限公司 | Slow-release polycarboxylate superplasticizer and preparation method thereof |
| CN111100252A (en) * | 2019-12-22 | 2020-05-05 | 同济大学 | Synthetic method of polycarboxylic acid water reducer with high water reducing rate and super slump retaining property |
| CN111320729A (en) * | 2020-04-22 | 2020-06-23 | 广州市建筑科学研究院有限公司 | Polycarboxylate superplasticizer for barite concrete and preparation method and application thereof |
| WO2022095232A1 (en) * | 2020-11-03 | 2022-05-12 | 科之杰新材料集团有限公司 | Ether-type anti-corrosive polycarboxylic acid water reducer and preparation method therefor |
| CN113292687A (en) * | 2021-06-29 | 2021-08-24 | 安徽海螺新材料科技有限公司 | High-performance slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| CN114478938A (en) * | 2022-01-06 | 2022-05-13 | 山西佳维新材料股份有限公司 | Slow-release polycarboxylate superplasticizer, preparation method and application |
| CN116284601A (en) * | 2023-03-16 | 2023-06-23 | 湖州绿色新材股份有限公司 | Staged slow-release polycarboxylate superplasticizer and preparation method and application thereof |
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