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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
carboxylic acid
monomer
sustained
acid group
group polymer
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
CN201810744013.8A
Other languages
Chinese (zh)
Other versions
CN108794700B (en
Inventor
郑同林
苏晋升
黄海超
沈小君
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.)
Fujian Luqiao Xiang Tong Building Materials Technology Co Ltd
Original Assignee
Fujian Luqiao Xiang Tong Building Materials Technology 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 Fujian Luqiao Xiang Tong Building Materials Technology Co Ltd filed Critical Fujian Luqiao Xiang Tong Building Materials Technology Co Ltd
Priority to CN201810744013.8A priority Critical patent/CN108794700B/en
Publication of CN108794700A publication Critical patent/CN108794700A/en
Application granted granted Critical
Publication of CN108794700B publication Critical patent/CN108794700B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688Copolymers containing at least three different monomers
    • C04B24/2694Copolymers containing at least three different monomers containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (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)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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

A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer
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.
CN201810744013.8A 2018-07-09 2018-07-09 Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent Active CN108794700B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810744013.8A CN108794700B (en) 2018-07-09 2018-07-09 Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810744013.8A CN108794700B (en) 2018-07-09 2018-07-09 Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent

Publications (2)

Publication Number Publication Date
CN108794700A true CN108794700A (en) 2018-11-13
CN108794700B CN108794700B (en) 2021-01-08

Family

ID=64075709

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810744013.8A Active CN108794700B (en) 2018-07-09 2018-07-09 Carboxylic acid-based polymer, preparation method thereof and slow-release polycarboxylic acid water reducing agent

Country Status (1)

Country Link
CN (1) CN108794700B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN108794700B (en) 2021-01-08

Similar Documents

Publication Publication Date Title
CN108794700A (en) A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer
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
CN105110687B (en) A kind of anti-mud collapse protective poly-carboxylic acid water reducing agent and preparation method thereof
CN105061690B (en) A kind of preparation method of high water reducing type solid high-performance polycarboxylate water-reducer
CN112724329A (en) Viscosity-reducing polycarboxylic acid concrete water reducer and preparation method thereof
CN107586366B (en) Modified polycarboxylate superplasticizer and preparation method thereof
CN105601843B (en) Ethers Early-strength polycarboxylate superplasticizer and preparation method thereof
CN106008784B (en) A kind of concrete thinner and preparation method thereof
CN106432628B (en) A kind of muting sensitive induction reactance mud ether-ether copoly type polycarboxylate water-reducer and preparation method thereof
CN106366257B (en) A kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer and preparation method thereof
CN109880019A (en) A kind of workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof
CN103897116A (en) Mud-resistant polycarboxylic acid water reducer and preparation method thereof
CN103467671B (en) Preparation method of polycarboxylate superplasticizer with high water reducing rate
CN107325236A (en) A kind of non-soil responsive type polycarboxylate water-reducer and preparation method thereof
CN109970922A (en) A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process
CN100509683C (en) Low molecular weight copolymer dispersant and preparing method thereof
CN103467669A (en) Early-strength polycarboxylate water-reducing agent and preparation method thereof
CN106519137A (en) Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof
CN109650762A (en) A kind of phosphate type polycarboxylate water-reducer and preparation method
CN108276533A (en) A kind of high ecad polycarboxylate water-reducer and preparation method thereof
CN102503221B (en) Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
CN109400825A (en) A kind of low responsive type polycarboxylate water-reducer and preparation method thereof with anti-mud effect
CN107200839B (en) Methallyl alcohol random polyether and preparation method thereof
CN112126022A (en) Formula and preparation method of polycarboxylate superplasticizer
CN106380551B (en) A kind of muting sensitive induction reactance chamotte mould polycarboxylate water-reducer and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant