CN108192040A - A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent - Google Patents
A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent Download PDFInfo
- Publication number
- CN108192040A CN108192040A CN201711468820.3A CN201711468820A CN108192040A CN 108192040 A CN108192040 A CN 108192040A CN 201711468820 A CN201711468820 A CN 201711468820A CN 108192040 A CN108192040 A CN 108192040A
- Authority
- CN
- China
- Prior art keywords
- unsaturated acids
- esters
- catalyst
- unsaturated
- reducing agent
- 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
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of low entraining type solid polycarboxylic acid water reducing agent.The present invention introduces the phenyl ring, amide group and the polyethers amine structure with the ethylene oxide/propylene oxide for defoaming structure of rigid structure using amidated method, so that the water-reducing agent finally synthesized has good diminishing, guarantor is collapsed and the effect of low entraining, the durability of concrete is effectively enhanced；Using microwave heating method, heating speed is fast, easy to operate, and automation control precision is high, cleanliness without any pollution.The polycarboxylate water-reducer synthesized using bulk polymerization, the organic solvent without pollution environment, molecular structure controllability is strong, environment friendly and pollution-free.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of system of low entraining type solid polycarboxylic acid water reducing agent
Preparation Method.
Background technology
In recent years, poly carboxylic acid series water reducer is in key projects such as high-speed railway, port and pier, Hydropower Dam, municipal works
In be used widely, these Important Projects are proposed very high requirement to the intensity and durability of concrete.However, poly- carboxylic
Sour based water reducer bleed is stronger, can cause air content higher in engineer application, and the intensity and durability for reducing concrete are commonly used
The method of control air content be to compound water-reducing agent and antifoaming agent, but compatibility is asked in water due to conventional antifoam
Topic so that compounding mixture is unstable.
From the theory of MOLECULE DESIGN, the functional group of defoaming type is introduced in the molecular structure, can effectively reduce poly- carboxylic
The frothing capacity of sour water-reducing agent.To assign product good for the wide in range molecular weight of polyetheramine, ammonia degree of functionality, the structural unit that repeats
The advantages that flexibility, toughness, low color, low-viscosity.Therefore introducing polyetheramine in polycarboxylate water-reducer molecule structure can be effective
Surface tension is reduced, the air content in concrete mix is reduced, so as to improve the intensity of concrete and endurance quality problem.
Invention content
It is an object of the invention to overcome prior art defect, a kind of system of low entraining type solid polycarboxylic acid water reducing agent is provided
Preparation Method.
Technical scheme is as follows：
A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent, includes the following steps：
(1) diethyl toluene diamine, unsaturated acids, polymerization inhibitor and the first catalyst are mixed, leads to nitrogen protection, use is micro-
Wave heating mode is warming up to 90~130 DEG C, 2~4h of insulation reaction, then adds in polyetheramine, continues 2~4h of insulation reaction, leads to nitrogen
The method of gas takes the water of reaction generation out of, cools to room temperature after reaction to get unsaturated acids bisacylation product；Wherein diethyl
Base toluenediamine, unsaturated acids and polyetheramine molar ratio are 1: 1.5~8: 1.0~3, and the dosage of polymerization inhibitor is the total of unsaturated acids
0.2~5wt% of amount, the dosage of the first catalyst are 0.2~5wt% of the total amount of unsaturated acids, and above-mentioned first catalyst is
At least two in solid phosphoric acid, ferric sulfate and antimony oxide；
(2) esters polyether monomer is placed in reaction kettle, is warming up to 50~80 DEG C using microwave heating, reaches melting
State adds in the second catalyst and stirs 8~12min, then disposably adds in unsaturated acids and appropriate liquid caustic soda, second catalysis
Agent in phthalic acid dibutyl tin and/or four aziridines, above-mentioned esters polyether monomer for MPEGMAA, MPEGAA and
At least one of MPEGMAn；Wherein the molar ratio of esters polyether monomer and unsaturated acids is 1: 0.2~2, and the second catalyst is ester
0.1~4wt% of the total amount of class polyether monomer, 0.2~2wt% of the liquid caustic soda for the total amount of esters polyether monomer；
(3) the unsaturated acids bisacylation product into the material obtained by step (2) obtained by a dropping step (1) and initiator
Mixture, while the mixture of unsaturated acids, beta-unsaturated esters and chain-transferring agent is added dropwise, time for adding is 0.5~2h, is added dropwise
Afterwards, initiator is then disposably added, keeps the temperature 0.8~1.2h；Wherein esters polyether monomer, unsaturated acids, beta-unsaturated esters, insatiable hunger
Molar ratio with sour bisacylation product, initiator and company's transfer agent is 1: 1.5~6: 0.2~2: 0.2~2: 0.02~0.2:
0.02~0.2；
(4) keep the temperature after, after cooling to room temperature, add in liquid caustic soda, adjust pH to 5~7, using condensation microtome,
Up to the sustained-release polycarboxylic water reducer；
Above-mentioned unsaturated acids is maleic anhydride and/or fumaric acid, and above-mentioned beta-unsaturated esters are hydroxy-ethyl acrylate and/or propylene
Sour hydroxypropyl acrylate.
In a preferred embodiment of the invention, the polymerization inhibitor be 4- hydroxy piperidine alcohol oxygen radicals and/or 2,
4- dimethyl -6- tert-butyl phenols.
In a preferred embodiment of the invention, the initiator is peroxidating two (2,4- dichloro-benzoyl), mistake
Aoxidize at least one of two decoyls and peroxidating (3,5,5- tri-methyl hexanoic acid).
In a preferred embodiment of the invention, the chain-transferring agent for the n- lauryl mercaptan ester of acetic acid and/or
Isopropanol.
The beneficial effects of the invention are as follows：
1st, the present invention introduces the phenyl ring of rigid structure, amide group and with defoaming structure using amidated method
The polyethers amine structure of ethylene oxide/propylene oxide so that the water-reducing agent finally synthesized has good diminishing, protects and collapses and low entraining
Effect effectively enhances the durability of concrete；
2nd, for the present invention using microwave heating method, heating speed is fast, easy to operate, and automation control precision is high, cleans nothing
Pollution.
3rd, the present invention is using the polycarboxylate water-reducer of bulk polymerization synthesis, the organic solvent without pollution environment, point
Minor structure controllability is strong, environment friendly and pollution-free.
Specific embodiment
Technical scheme of the present invention is further detailed and described below by way of specific embodiment.
Embodiment 1
(1) by 178g diethyl toluene diamines, 294g maleic anhydrides, 4.5g2,4- dimethyl -6- tert-butyl phenols add in
Into reaction kettle, under nitrogen protection, microwave is warming up to 70 DEG C, adds in 2.0g solid phosphoric acids and 1.5g ferric sulfate, is warming up to 120
DEG C, then insulation reaction 2h adds in 400g polyetheramines, continue insulation reaction 2h, during which removes water with logical method of the nitrogen with water,
It is down to room temperature after reaction, obtains unsaturated acids bisacylation product；
(2) 200g esters polyether monomers MPEGMAn is added in reaction kettle, it is adjacent to add in 2.0g to 60 DEG C for microwave heating
It is disposable to add in 5g maleic anhydrides and 1.5 liquid caustic soda after phthalic acid dibutyl tin stirring 10min；
(3) the 10g unsaturated acids bisacylation products and 2.3g into the material obtained by step (2) obtained by a dropping step (1)
The mixture of peroxidating two (2,4- dichloro-benzoyl), while 4g hydroxy-ethyl acrylates, 20g maleic anhydrides and 1.7g acetic acid is added dropwise
The mixture of n- lauryl mercaptan ester, time for adding 1h after being added dropwise, disposably add 0.2g peroxidating two (2,4-
Dichloro-benzoyl), keep the temperature 0.8h；
(4) after keeping the temperature, 6g liquid caustic soda is added in, adjusts pH to 5~7, low is drawn to get described using condensation microtome
Gas type solid polycarboxylic acid water reducing agent.
Embodiment 2
(1) 178g diethyl toluene diamines, 348g fumaric acid, 6g4- hydroxy piperidine alcohol oxygen radicals are added to reaction kettle
Interior, under nitrogen protection, microwave is warming up to 70 DEG C, adds in 3.5g solid phosphoric acids and 1g ferric sulfate, is warming up to 110 DEG C, heat preservation is anti-
1.5h is answered, then adds in 500g polyetheramines, continues insulation reaction 3h, during which removes water, reaction knot with logical method of the nitrogen with water
Room temperature is down to after beam, obtains unsaturated acids bisacylation product；
(2) 200g esters polyether monomers MPEGMAA is added in reaction kettle, to 60 DEG C, 2.8g adds in adjacent for microwave heating
It is disposable to add in 5g fumaric acid and 1.5g liquid caustic soda after phthalic acid dibutyl tin stirring 10min；
(3) the 6g unsaturated acids bisacylation products and 2.5g mistakes into the material obtained by step (2) obtained by a dropping step (1)
The mixture of two decoyls is aoxidized, while the mixture of 2g hydroxypropyl acrylates, 18g fumaric acid and 1.1g isopropanols is added dropwise, is added dropwise
Time is 2h, after being added dropwise, disposably adds 0.2g dioctanoyl peroxides, keeps the temperature 1h；
(4) after keeping the temperature, 6g liquid caustic soda is added in, adjusts pH to 5~7, low is drawn to get described using condensation microtome
Gas type solid polycarboxylic acid water reducing agent.
Embodiment 3
(1) 178g diethyl toluene diamines, 490g maleic anhydrides, 4g4- hydroxy piperidine alcohol oxygen radicals are added to reaction
In kettle, under nitrogen protection, microwave is warming up to 70 DEG C, adds in 4g solid phosphoric acids and 1g antimony oxides, is warming up to 110 DEG C, protects
Temperature reaction 3h, then adds in 600g polyetheramines, continues insulation reaction 1.5h, during which removes water with logical method of the nitrogen with water, instead
Room temperature is down to after answering, obtains unsaturated acids bisacylation product；
(2) 100g esters polyether monomer MPEGMAA, 100g esters polyether monomers MPEGMAn is added in reaction kettle, it is micro-
Wave heating is disposable to add in after adding in 1.5g phthalic acids dibutyl tin and tetra- aziridines of 1.0g stirring 10min to 60 DEG C
4g maleic anhydrides and 1.2g liquid caustic soda；
(3) 10g unsaturated acids bisacylations product, the 1.55g into the material obtained by step (2) obtained by a dropping step (1)
Peroxidating (3,5,5- tri-methyl hexanoic acid) and the mixture of 1.2g dioctanoyl peroxides, while 2g hydroxypropyl acrylates, 1g is added dropwise
The mixture of hydroxypropyl acrylate, 17g maleic anhydrides and 1.0g isopropanols, time for adding 2h are disposable to mend after being added dropwise
Add 0.1g peroxidating (3,5,5- tri-methyl hexanoic acid) and 0.1g dioctanoyl peroxides, keep the temperature 1h；
(4) after keeping the temperature, 6g liquid caustic soda is added in, adjusts pH to 5~7, low is drawn to get described using condensation microtome
Gas type solid polycarboxylic acid water reducing agent.
Embodiment 4
Using P.O42.5 Portland cements, according to GB/T 8077-2012《Concrete admixture homogeneity experiment side
Method》It carries out, water-reducing agent volume is the solid volume of folding, is compared, had using commercially available common low entraining type polycarboxylate water-reducer PC-I
Body test situation is as shown in 1~table of table 2：
1 concrete raw material situation of table and match ratio
2 concrete test result of table
Remarks：The dosage that additive usage is concrete mixing amount when being 15L.
As can be seen from Table 2：The research work of air entrained type solid polycarboxylic acid water reducing agent of synthesis of the embodiment of the present invention, in the solid volume of same folding
Under, initial flow degree is bigger than PC-1, and through when protect that plasticity ratio PC-1 is good, and air content is smaller than PC-1, and concrete strength compares PC-1
It is slightly larger.The low entraining solid polycarboxylic acid water reducing agent of the present invention has good diminishing, guarantor is collapsed and the effect of low entraining, can effectively enhance
The durability of concrete.
Skilled person will appreciate that when component and technical parameter of the invention changes in following ranges, it still is able to
To same as the previously described embodiments or similar technique effect：
A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent, includes the following steps：
(1) diethyl toluene diamine, unsaturated acids, polymerization inhibitor and the first catalyst are mixed, leads to nitrogen protection, use is micro-
Wave heating mode is warming up to 90~130 DEG C, 2~4h of insulation reaction, then adds in polyetheramine, continues 2~4h of insulation reaction, leads to nitrogen
The method of gas takes the water of reaction generation out of, cools to room temperature after reaction to get unsaturated acids bisacylation product；Wherein diethyl
Base toluenediamine, unsaturated acids and polyetheramine molar ratio are 1: 1.5~8: 1.0~3, and the dosage of polymerization inhibitor is the total of unsaturated acids
0.2~5wt% of amount, the dosage of the first catalyst are 0.2~5wt% of the total amount of unsaturated acids, and above-mentioned first catalyst is
At least two in solid phosphoric acid, ferric sulfate and antimony oxide；
(2) esters polyether monomer is placed in reaction kettle, is warming up to 50~80 DEG C using microwave heating, reaches melting
State adds in the second catalyst and stirs 8~12min, then disposably adds in unsaturated acids and appropriate liquid caustic soda, second catalysis
Agent in phthalic acid dibutyl tin and/or four aziridines, above-mentioned esters polyether monomer for MPEGMAA, MPEGAA and
At least one of MPEGMAn；Wherein the molar ratio of esters polyether monomer and unsaturated acids is 1: 0.2~2, and the second catalyst is ester
0.1~4wt% of the total amount of class polyether monomer, 0.2~2wt% of the liquid caustic soda for the total amount of esters polyether monomer；
(3) the unsaturated acids bisacylation product into the material obtained by step (2) obtained by a dropping step (1) and initiator
Mixture, while the mixture of unsaturated acids, beta-unsaturated esters and chain-transferring agent is added dropwise, time for adding is 0.5~2h, is added dropwise
Afterwards, initiator is then disposably added, keeps the temperature 0.8~1.2h；Wherein esters polyether monomer, unsaturated acids, beta-unsaturated esters, insatiable hunger
Molar ratio with sour bisacylation product, initiator and company's transfer agent is 1: 1.5~6: 0.2~2: 0.2~2: 0.02~0.2:
0.02~0.2；
(4) keep the temperature after, after cooling to room temperature, add in liquid caustic soda, adjust pH to 5~7, using condensation microtome,
Up to the sustained-release polycarboxylic water reducer；
Above-mentioned unsaturated acids is maleic anhydride and/or fumaric acid, and above-mentioned beta-unsaturated esters are hydroxy-ethyl acrylate and/or propylene
Sour hydroxypropyl acrylate.
The polymerization inhibitor is 4- hydroxy piperidine alcohol oxygen radicals and/or 2,4- dimethyl -6- tert-butyl phenols.The initiation
Agent is at least the one of peroxidating two (2,4- dichloro-benzoyl), dioctanoyl peroxide and peroxidating (3,5,5- tri-methyl hexanoic acid)
Kind.The chain-transferring agent is the n- lauryl mercaptan ester of acetic acid and/or isopropanol.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the range that the present invention is implemented according to this, i.e.,
According to the equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (4)
1. a kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent, it is characterised in that：Include the following steps：
(1) diethyl toluene diamine, unsaturated acids, polymerization inhibitor and the first catalyst are mixed, lead to nitrogen protection, using microwave plus
Hot mode is warming up to 90~130 DEG C, 2~4h of insulation reaction, then adds in polyetheramine, continues 2~4h of insulation reaction, leads to nitrogen
Method takes the water of reaction generation out of, cools to room temperature after reaction to get unsaturated acids bisacylation product；Wherein diethyl first
Phenylenediamine, unsaturated acids and polyetheramine molar ratio are 1: 1.5~8: 1.0~3, and the dosage of polymerization inhibitor is the total amount of unsaturated acids
0.2~5wt%, the dosage of the first catalyst are 0.2~5wt% of the total amount of unsaturated acids, and above-mentioned first catalyst is solid
At least two in phosphoric acid, ferric sulfate and antimony oxide；
(2) esters polyether monomer is placed in reaction kettle, is warming up to 50~80 DEG C using microwave heating, reaches molten
State adds in the second catalyst and stirs 8~12min, then disposably add in unsaturated acids and appropriate liquid caustic soda, adjusts pH=4~5,
Second catalyst be phthalic acid dibutyl tin and/or four aziridines, above-mentioned esters polyether monomer for MPEGMAA,
At least one of MPEGAA and MPEGMAn；Wherein, the molar ratio of esters polyether monomer and unsaturated acids is 1: 0.2~2, second
0.1~4wt% of the catalyst for the total amount of esters polyether monomer, 0.2~2wt% of the liquid caustic soda for the total amount of esters polyether monomer；
(3) mixing of the unsaturated acids bisacylation product and initiator into the material obtained by step (2) obtained by a dropping step (1)
Object, while the mixture of unsaturated acids, beta-unsaturated esters and chain-transferring agent is added dropwise, time for adding is 0.5~2h, after being added dropwise,
Then initiator is disposably added, keeps the temperature 0.8~1.2h；Wherein esters polyether monomer, unsaturated acids, beta-unsaturated esters, unsaturation
The molar ratio of sour bisacylation product, initiator and company's transfer agent is 1: 1.5~6: 0.2~2: 0.2~2: 0.02~0.2: 0.02
~0.2；
(4) keep the temperature after, after cooling to room temperature, add in liquid caustic soda, adjust pH to 5~7, using condensation microtome to get
The sustained-release polycarboxylic water reducer；
Above-mentioned unsaturated acids is maleic anhydride and/or fumaric acid, and above-mentioned beta-unsaturated esters are hydroxy-ethyl acrylate and/or acrylic acid hydroxyl
Propyl ester.
2. preparation method as described in claim 1, it is characterised in that：The polymerization inhibitor is 4- hydroxy piperidine alcohol oxygen radicals
And/or 2,4- dimethyl -6- tert-butyl phenols.
3. preparation method as described in claim 1, it is characterised in that：The initiator is (2, the 4- dichloro-benzenes first of peroxidating two
Acyl), at least one of dioctanoyl peroxide and peroxidating (3,5,5- tri-methyl hexanoic acid).
4. preparation method as described in claim 1, it is characterised in that：The chain-transferring agent is the n- lauryl mercaptan of acetic acid
Ester and/or isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711468820.3A CN108192040B (en) | 2017-12-28 | 2017-12-28 | Preparation method of low-air-entraining solid polycarboxylate superplasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711468820.3A CN108192040B (en) | 2017-12-28 | 2017-12-28 | Preparation method of low-air-entraining solid polycarboxylate superplasticizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108192040A true CN108192040A (en) | 2018-06-22 |
| CN108192040B CN108192040B (en) | 2020-06-09 |
Family
ID=62585601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711468820.3A Active CN108192040B (en) | 2017-12-28 | 2017-12-28 | Preparation method of low-air-entraining solid polycarboxylate superplasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108192040B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003403A (en) * | 2019-04-23 | 2019-07-12 | 长沙加美乐素化工有限公司 | A kind of anti-mud early-strength water-reducing agent and preparation method thereof |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN113354782A (en) * | 2020-04-27 | 2021-09-07 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106447A (en) * | 1997-10-07 | 1999-04-20 | Asahi Glass Co Ltd | Polymer-dispersed polyol, its production and production of rigid polyurethane foam |
| CN102173642A (en) * | 2011-02-25 | 2011-09-07 | 南京瑞迪高新技术公司 | Polyetheramine carboxylate high-efficiency water-reducing agent |
| CN102515619A (en) * | 2011-12-26 | 2012-06-27 | 上海三瑞高分子材料有限公司 | Polyether amine modified polycarboxylic water reducer and preparation method thereof |
| CN105271903A (en) * | 2015-10-22 | 2016-01-27 | 岳阳东方雨虹防水技术有限责任公司 | Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer |
-
2017
- 2017-12-28 CN CN201711468820.3A patent/CN108192040B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11106447A (en) * | 1997-10-07 | 1999-04-20 | Asahi Glass Co Ltd | Polymer-dispersed polyol, its production and production of rigid polyurethane foam |
| CN102173642A (en) * | 2011-02-25 | 2011-09-07 | 南京瑞迪高新技术公司 | Polyetheramine carboxylate high-efficiency water-reducing agent |
| CN102515619A (en) * | 2011-12-26 | 2012-06-27 | 上海三瑞高分子材料有限公司 | Polyether amine modified polycarboxylic water reducer and preparation method thereof |
| CN105271903A (en) * | 2015-10-22 | 2016-01-27 | 岳阳东方雨虹防水技术有限责任公司 | Polycarboxylate superplasticizer with super high early strength and preparation method of polycarboxylate superplasticizer |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110003403A (en) * | 2019-04-23 | 2019-07-12 | 长沙加美乐素化工有限公司 | A kind of anti-mud early-strength water-reducing agent and preparation method thereof |
| CN112608420A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN112608421A (en) * | 2019-11-25 | 2021-04-06 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112608421B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining ether polycarboxylate superplasticizer |
| CN112608420B (en) * | 2019-11-25 | 2022-02-18 | 科之杰新材料集团有限公司 | Preparation method of air-entraining type ester polycarboxylate superplasticizer |
| CN113354782A (en) * | 2020-04-27 | 2021-09-07 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN113354782B (en) * | 2020-04-27 | 2022-08-02 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108192040B (en) | 2020-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108192040A (en) | A kind of preparation method of low entraining type solid polycarboxylic acid water reducing agent | |
| CN108003301B (en) | Preparation method of viscosity-reducing polycarboxylate superplasticizer | |
| CN1081615C (en) | Cement dispersant, method for producing polycarboxylic acid for cement dispersant and cement composition | |
| WO2021217762A1 (en) | Unsaturated polyether monomer, and polycarboxylate superplasticizer and preparation method therefor | |
| KR101939970B1 (en) | Alkoxylates of s-vinylthioalkanols | |
| CN107652405B (en) | Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof | |
| CN104876468B (en) | A kind of functional poly carboxylic acid water reducer for coordinating silicon ash to use and preparation method thereof | |
| CN106146749A (en) | Meet polycarboxylate water-reducer of 620 meters of super high pump-conveying self-compacting concretes requirements and preparation method thereof | |
| CN108707211A (en) | A kind of collapse protection type solid polycarboxylic acid water reducing agent and preparation method thereof | |
| CN101759833A (en) | Polycarboxylic acid water reducing agent with excellent rust resisting function and preparation method thereof | |
| CN104672401A (en) | Preparation method for slump retaining agent for polycarboxylate superplasticizer | |
| CN109836541A (en) | A method of preparing pure solid polycarboxylic acid slump retaining agent | |
| CN106317402A (en) | Polyether monomer and preparation method and application thereof | |
| CN1802331A (en) | Additive for hydraulic material and concrete composition | |
| CN106243288B (en) | A kind of concrete slump retaining agent and preparation method thereof | |
| DE60318431T2 (en) | Preparation process for an alkylene oxide addition product and cement mixture with this | |
| CN109608082A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer, preparation method and application | |
| CN109503774B (en) | A kind of polycarboxylate water-reducer that temperature sensitivity is small | |
| JP2013053010A (en) | Dispersant | |
| CN112679675B (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| JPH1180288A (en) | Hydrophilic graft polymer-containing composition and use thereof | |
| CN106046238B (en) | A kind of unsaturated polyether monomer and synthesis and the method for preparing poly carboxylic acid series water reducer | |
| CN105778011B (en) | A kind of diminishing, the poly carboxylic acid series water reducer for protecting modeling and preparation method thereof | |
| US10538657B2 (en) | Polymer blends in the form of aqueous dispersions or powders that can be redispersed in water | |
| CN108101404A (en) | A kind of preparation method of sustained-release polycarboxylic water reducer |
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 |