CN109651568A - A kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer - Google Patents
A kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer Download PDFInfo
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- CN109651568A CN109651568A CN201910015072.6A CN201910015072A CN109651568A CN 109651568 A CN109651568 A CN 109651568A CN 201910015072 A CN201910015072 A CN 201910015072A CN 109651568 A CN109651568 A CN 109651568A
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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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of preparation methods of novel polyether synthesis sustained-release polycarboxylic water reducer, the following steps are included: S1: polyether macromonomer and deionized water are added in reaction kettle, stirring dissolves it at normal temperature, by unsaturated acids or anhydride minor comonomer, unsaturated esters minor comonomer obtains A liquid after mixing in water；B liquid is obtained after reducing agent, chain-transferring agent and water are sufficiently mixed, it is spare；S2: a certain amount of A liquid is added into polymeric monomer aqueous solution obtained by step S1, stirs evenly；S3: being added oxidant into mixture obtained by step S2 in advance, and B liquid is then added dropwise, and A liquid is added dropwise after 2-10min is added dropwise, keeps the temperature 0.5h after being added dropwise；S4: lye is added after reaction and neutralizes, product is poured out to get sustained-release polycarboxylic water reducer is arrived.The resulting sustained-release polycarboxylic water reducer of the present invention has slow-release time long, can keep the slump for a long time, protects the features such as result of collapsing is excellent.
Description
Technical field
The present invention relates to technical field of concrete additives more particularly to a kind of novel polyether synthesis sustained-release polycarboxylic to subtract
The preparation method of aqua.
Background technique
Polycarboxylate water-reducer is as third generation concrete admixture, because water-reducing rate with higher, preferable cement adapt to
Property, and the features such as production process is environmentally friendly and popularization energetically has been obtained, so that the polyether macromonomer industry in China also obtains
Significant progress.The yield and production capacity of national polyether macromonomer are all continuing to increase, and have reached all-time high within 2017.Mesh
The common polyethers of preceding synthesis polycarboxylate water-reducer is mostly HPEG and TPEG, and product structure is relatively single, and its initiator is supplying
Aspect is answered still to have partial dependency import, especially 5 carbon alcohol initiators.Compared with existing 4 carbon, 5 carbon polymeric monomers, EPEG type polyethers
Polymeric monomer mainly has following advantage: firstly, can not only shorten the time for adding of acrylic acid using EPEG polymeric monomer, but also reacting
Process is easier to control, and adjustment preferably can be carried out to its reaction process；Secondly, requirement of the EPEG monomer to reaction temperature is very
It is low, when polymerization reaction, reaction can be completed under room temperature higher than 5 DEG C, without being heated.Therefore, big using EPEG
Monomer is that the polyethers synthesis polycarboxylate water-reducer of representative will become the development trend of polycarboxylic acids industry in following a period of time.
Patent CN106883356A refers to a kind of preparation method of sustained-release polycarboxylic water reducer, and this method is by propylene
Acid, hydroxy-ethyl acrylate and water are mixed to get 1# solution, and reducing agent, chain-transferring agent, 30% lye and deionized water are mixed
To 2# solution, TPEG polyether macromonomer is added in maleate and the concentrated sulfuric acid and water mixed solution and is dissolved, oxidant is added, stirs
After mixing 3-6min, 2# solution is added dropwise, 1# solution is added dropwise after 2-10min, keeps reaction at 20-60 DEG C, time for adding is controlled in 90-
240min, keeps the temperature 1h, and addition lye adjusting PH arrives sustained-release polycarboxylic water reducer between 6-7.Although this method meets
Polymerized at normal temperature, and ensure that the releasability of product, but the reaction time is too long, energy consumption is high, the polyether macromonomer that uses
For TPEG type polymeric monomer, initiator largely relies on not enough environmental protection in import and its production process in supply process
Patent CN107325235A discloses a kind of sustained-release polycarboxylic water reducer room temperature synthesis technology, including following step
It is rapid: step 1: in the reaction vessel add water, 10-35 DEG C of water temperature；Methacrylic polyoxyethylene is added into reaction vessel
Ether；Step 2: hydrogen peroxide is added in the reaction vessel of step 1, crosses ammonium, and stirs 35 minutes；Step 3: control reaction is held
Between 10-35 DEG C, A drop adds 2.5-3.0 hours device internal temperature, and B drop adds 3.0-3.5 hours.The invention is relative to biography
Blanket insurance is collapsed, and slow-release is poly- to complete sour water-reducing agent manufacturing process, and production method is simple, easy to operate, but its time for adding is long, reaction
Energy consumption is high, at high cost, and polymeric monomer uses methyl allyl polyoxyethylene ether, is unfavorable for environmental protection.
Patent CN108101404A is by two glue of diethyltoluene, unsaturated acids, polymerization inhibitor and solid phosphoric acid, ferric sulfate and three
At least two mixing in two antimony are aoxidized, leads to nitrogen protection, is warming up to 90-130 DEG C using microwave heating, insulation reaction 4-
8h cools to room temperature after reaction to get acylate.Polyether monomer is placed in reaction kettle, is heated up using microwave heating
To 50~80 DEG C, reach molten condition, be added phthalic acid dibutyl tin and/or four ethylene imonium stirring 8~
Then 12min is added at one time unsaturated acids and appropriate liquid alkaline, adjust PH to 4-5, be added dropwise into step (2) resulting material
The mixture of the resulting esterification products of step (1) and initiator, while unsaturated acids, beta-unsaturated esters and chain-transferring agent mixing is added dropwise
Object, time for adding are after 0.5-2h is added dropwise, disposably to add initiator, keep the temperature 0.8-1.2h, after heat preservation, adjust PH
A kind of sustained-release polycarboxylic water reducer is obtained for 6-7.Although the polycarboxylate water-reducer that this method finally synthesizes has excellent
Diminishing dispersion effect and guarantor are collapsed effect, and show very strong adaptability to the cementitious material of different cultivars.But it produced
Journey is complicated, and energy consumption is larger, is unfavorable for industrialized production.
Summary of the invention
The purpose of the present invention is to solve disadvantages existing in the prior art, and a kind of novel polyether synthesis proposed is slow
Release the preparation method of type polycarboxylate water-reducer.
To achieve the goals above, present invention employs following technical solutions:
A kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer, comprising the following steps:
S1: polyether macromonomer and deionized water are added in reaction kettle, and stirring dissolves it at normal temperature, will be unsaturated
Acid or anhydride minor comonomer, unsaturated esters minor comonomer obtain A liquid after mixing in water；Reducing agent, chain-transferring agent and water are filled
B liquid is obtained after dividing mixing, it is spare；
S2: a certain amount of A liquid is added into polymeric monomer aqueous solution obtained by step S1, stirs evenly；
S3: being added oxidant into mixture obtained by step S2 in advance, and B liquid is then added dropwise, is added dropwise after 2-10min is added dropwise
A liquid keeps the temperature 0.5h after being added dropwise；
S4: lye is added after reaction and neutralizes, product is poured out to get sustained-release polycarboxylic water reducer is arrived.
Preferably, novel polyether synthesis sustained-release polycarboxylic water reducer raw material is as follows by weight: polyether macromonomer
250-300 parts, 200-240 parts of deionized water, 6-10 parts of initiator, 165-305 parts of A liquid, 38.8-46.5 parts of B liquid, lye 10-
15 parts.
Preferably, the polyether macromonomer in the S1 is ethylene glycol mono-vinyl polyglycol ether (EPEG, C4 (2+2)
Type), structural formula are as follows: CH2=CH-O-R-O- (C2H4O) n-H, molecular weight 1200-4000.
Preferably, the reaction in the S1-S4 carries out at normal temperature.
Preferably, A liquid described in S1 is comprised the following components in parts by weight: unsaturated acids or 30-65 parts of anhydride minor comonomer,
Unsaturated esters minor comonomer is 90-210 parts, and 25-30 parts of water, the B liquid comprises the following components in parts by weight: chain-transferring agent 1.8-
2.5 parts, 2-4 parts of reducing agent；35-40 parts of water.
Preferably, the minor comonomer of unsaturation acids described in S1 is acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, richness
Horse acid, styrene sulfonic acid, p styrene sulfonic acid, 2- acrylamide-2-methyl propane sulfonic, 2- acrylamido myristyl sulfonic acid
One of or it is a variety of.
Preferably, reducing agent described in S1 be L-AA, sodium bisulphite formaldehyde, sodium sulfite, Sodium Thiosulfate,
One of sodium thiosulfate, sodium hypophosphite, sodium phosphite and frerrous chloride are a variety of；The chain-transferring agent is sulfydryl second
One of acid, mercaptopropionic acid, mercaptobutyric acid, methylpropene sodium sulfonate, sodium allylsulfonate are a variety of；The unsaturation esters list
Body is one of hydroxy-ethyl acrylate, methyl methacrylate, propenoic acid beta-hydroxy propyl ester, vinylacetate or a variety of.
Preferably, the oxidant being added in advance described in S3 is hydrogen peroxide, dibenzoyl peroxide, the tertiary fourth of peroxidating
One of alcohol, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide are a variety of, and the oxidant parts by weight are 4-6 parts.
Preferably, the time for adding of A liquid described in S3 is 30min, and the time for adding of B liquid is 40-50min.
Preferably, lye described in S4 be potassium hydroxide or its aqueous solution, sodium hydroxide or its aqueous solution, sodium carbonate or its
One of aqueous solution is a variety of.
The resulting sustained-release polycarboxylic water reducer of the present invention has slow-release time long, can keep the slump for a long time, guarantor is collapsed
As a result the features such as excellent.Using new polycarboxylic acid water reducer polymeric monomer ethylene glycol mono-vinyl polyglycol ether (EPEG) as anti-
Polymeric monomer is answered, with reactivity height, synthesized polycarboxylate water-reducer has higher adaptability；The time required to reaction
Short, process is easily controllable；It is low to react required temperature, is being higher than 5 DEG C the advantages that can reacting at room temperature.Institute's spent glycol list second
The initiator of alkenyl polyglycol ether (EPEG) polymeric monomer directly reacts generation with ethylene glycol by acetylene, does not generate by-product, not
React that acetylene is recyclable to be recycled, there is environmental protection, low-carbon, sustainable development the advantages that.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, to this
Invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, not
For limiting the present invention.
Embodiment 1
300g polyether macromonomer and 220g deionized water are added in reaction kettle, stirring dissolves it at normal temperature, will
35g acrylic acid, 101g hydroxy-ethyl acrylate, 25g deionized water are uniformly mixed and are configured to A liquid.By 2g mercaptopropionic acid, 4g Victoria C,
35g water is uniformly mixed and is configured to B liquid.The A liquid by 32g will be added into polymeric monomer aqueous solution obtained by S1, is stirring evenly and then adding into
4g hydrogen peroxide, 2min start that B liquid is added dropwise, and A liquid is added dropwise after 2-10min is added dropwise, and wherein A liquid time for adding is 30min, B drop
It is 40min between added-time.The neutralization of 13g lye is added to get a kind of new sustained release type polycarboxylate water-reducer is arrived after keeping the temperature 20min.
Embodiment 2
300g polyether macromonomer and 220g deionized water are added in reaction kettle, stirring dissolves it at normal temperature, will
50g acrylic acid, 15.5g2- acrylamide-2-methyl propane sulfonic, 101g hydroxy-ethyl acrylate, 25g deionized water, which is uniformly mixed, matches
It is set to A liquid.By 2g mercaptopropionic acid, 4g Victoria C, 35g water is uniformly mixed and is configured to B liquid.It will add into polymeric monomer aqueous solution obtained by S1
Entering the A liquid by 35g, is stirring evenly and then adding into 4g hydrogen peroxide, 2min starts that B liquid is added dropwise, A liquid is added dropwise after 2-10min is added dropwise,
Middle A liquid time for adding is 30min, and B liquid time for adding is 40min.The neutralization of 13g lye is added to get one kind is arrived after keeping the temperature 20min
New sustained release type polycarboxylate water-reducer.
Embodiment 3
300g polyether macromonomer and 220g deionized water are added in reaction kettle, stirring dissolves it at normal temperature, will
35g acrylic acid, 80g hydroxy-ethyl acrylate, 24g methyl methacrylate go 25 ionized waters to be uniformly mixed and are configured to A liquid.By 2g mercapto
Base propionic acid, 4g Victoria C, 35g water are uniformly mixed and are configured to B liquid.The A liquid by 34g will be added into polymeric monomer aqueous solution obtained by S1, stirs
4g hydrogen peroxide is added after mixing uniformly, 2min starts that B liquid is added dropwise, and A liquid is added dropwise after 2-10min is added dropwise, wherein A liquid time for adding is
30min, B liquid time for adding are 40min.The neutralization of 13g lye is added to get a kind of poly- carboxylic of new sustained release type is arrived after keeping the temperature 20min
Sour water-reducing agent.
Commercially available room temperature synthetic fluid superelevation water reducing type polycarboxylate water-reducer.
Performance test
1. flowing degree of net paste of cement
According to GB/T8077-2000 " concrete admixture homogeneity test method ", its net slurry is measured using reference cement
Fluidity, test condition W/C=0.29, it is 0.14% that water-reducing agent, which rolls over solid volume, and concrete performance test is according to GB 8076-
2008 " concrete admixtures " carry out.Select Beijing Jinyu cement (P.O42.5) detection concrete slump/divergence measurement knot
Fruit is as shown in Table 1:
Table one: embodiment 1-3 and the flowing degree of net paste of cement of comparative example and concrete slump/divergence measurement result
As can be seen from Table I, the present invention using novel polyether synthesize sustained-release polycarboxylic water reducer slow-release time with
It is slump-retaining, equally matched with the commercially available liquid slow-release type polycarboxylate water-reducer or even excellent and poly- carboxylic of commercially available slow-release
Sour water-reducing agent.And on raw material, the present invention uses novel polyether polymeric monomer ethylene glycol mono-vinyl polyglycol ether, and EPEG is new
Type polyethers not only has reactivity high, and reaction required time is short, the advantages that being synthesized under higher than 5 DEG C environment, and EPEG
The initiator of type polyethers directly reacts generation by acetylene gas and ethylene glycol, extra after completion of the reaction without extra by-product
Acetylene can be recycled and be utilized again, not will cause environmental pollution, the remarkable advantage with sustainable development.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer, which comprises the following steps:
S1: polyether macromonomer and deionized water are added in reaction kettle, and stirring dissolves it at normal temperature, by unsaturated acids or
Anhydride minor comonomer, unsaturated esters minor comonomer obtain A liquid after mixing in water；Reducing agent, chain-transferring agent and water is sufficiently mixed
B liquid is obtained after conjunction, it is spare；
S2: a certain amount of A liquid is added into polymeric monomer aqueous solution obtained by step S1, stirs evenly；
S3: being added oxidant into mixture obtained by step S2 in advance, and B liquid is then added dropwise, and A liquid is added dropwise after 2-10min is added dropwise,
0.5h is kept the temperature after being added dropwise；
S4: lye is added after reaction and neutralizes, product is poured out to get sustained-release polycarboxylic water reducer is arrived.
2. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: it is as follows by weight that the novel polyether synthesizes sustained-release polycarboxylic water reducer raw material: 250-300 parts of polyether macromonomer is gone
200-240 parts of ionized water, 6-10 parts of initiator, 165-305 parts of A liquid, 38.8-46.5 parts of B liquid, 10-15 parts of lye.
3. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: the polyether macromonomer in the S1 is ethylene glycol mono-vinyl polyglycol ether, structural formula are as follows: CH2=CH-O-R-O-
(C2H4O) n-H, molecular weight 1200-4000.
4. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: the reaction in the S1-S4 carries out at normal temperature.
5. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: A liquid described in S1 is comprised the following components in parts by weight: unsaturated acids or 30-65 parts of anhydride minor comonomer, unsaturated esters
Minor comonomer is 90-210 parts, and 25-30 parts of water, the B liquid comprises the following components in parts by weight: 1.8-2.5 parts of chain-transferring agent, reduction
2-4 parts of agent, 35-40 parts of water.
6. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: the minor comonomer of unsaturation acids described in S1 is acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, fumaric acid, benzene second
One of alkene sulfonic acid, p styrene sulfonic acid, 2- acrylamide-2-methyl propane sulfonic, 2- acrylamido myristyl sulfonic acid
Or it is a variety of.
7. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: reducing agent described in S1 is L-AA, sodium bisulphite formaldehyde, sodium sulfite, Sodium Thiosulfate, thiosulfuric acid
One of sodium, sodium hypophosphite, sodium phosphite and frerrous chloride are a variety of；The chain-transferring agent is thioacetic acid, sulfydryl third
One of acid, mercaptobutyric acid, methylpropene sodium sulfonate, sodium allylsulfonate are a variety of；The unsaturation esters monomer is propylene
One of sour hydroxyl ethyl ester, methyl methacrylate, propenoic acid beta-hydroxy propyl ester, vinylacetate are a variety of.
8. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: the oxidant being added in advance described in S3 is hydrogen peroxide, dibenzoyl peroxide, tertbutanol peroxide, tert-butyl mistake
One of hydrogen oxide, isopropyl benzene hydroperoxide are a variety of, and the oxidant parts by weight are 4-6 parts.
9. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: the time for adding of A liquid described in S3 is 30min, and the time for adding of B liquid is 40-50min.
10. a kind of preparation method of novel polyether synthesis sustained-release polycarboxylic water reducer according to claim 1, feature
Be: lye described in S4 is in potassium hydroxide or its aqueous solution, sodium hydroxide or its aqueous solution, sodium carbonate or its aqueous solution
It is one or more.
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Cited By (15)
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| CN110642995A (en) * | 2019-09-27 | 2020-01-03 | 贵州石博士科技有限公司 | Preparation method of polycarboxylic acid water reducer for low-slump concrete |
| CN110698609A (en) * | 2019-09-18 | 2020-01-17 | 四川琪汇新材料有限责任公司 | High-performance polycarboxylic acid water reducing agent synthesized at normal temperature, preparation method and application thereof |
| CN111635490A (en) * | 2020-06-24 | 2020-09-08 | 安徽海螺新材料科技有限公司 | Branched chain type polycarboxylate superplasticizer mother liquor and preparation method thereof |
| CN111704413A (en) * | 2020-06-24 | 2020-09-25 | 南宁市嘉大混凝土有限公司 | Concrete prepared from waste slurry of concrete mixing plant |
| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN111925490A (en) * | 2020-08-19 | 2020-11-13 | 嘉善华豪建材有限公司 | Production process of water-reducing slump-retaining polycarboxylic acid |
| CN112111041A (en) * | 2020-09-30 | 2020-12-22 | 山东同盛建材有限公司 | Preparation method of anti-mud early-strength polycarboxylate superplasticizer for high-mineral admixture concrete |
| CN112574031A (en) * | 2020-12-03 | 2021-03-30 | 贵州石博士科技股份有限公司 | Preparation method and process of slow-release functional monomer and high slump loss resistant polycarboxylic acid water reducer |
| CN113754841A (en) * | 2021-10-21 | 2021-12-07 | 上海三瑞高分子材料股份有限公司 | Method for synthesizing polycarboxylate superplasticizer from vinyl ether monomer at normal temperature |
| CN113912786A (en) * | 2021-10-21 | 2022-01-11 | 杭州构建新型材料有限公司 | Vinyl glycol ether polycarboxylic acid water reducing agent and preparation method thereof |
| CN114014993A (en) * | 2021-11-16 | 2022-02-08 | 北京化工大学 | Preparation method of low-temperature polymerization high-performance polycarboxylate superplasticizer |
| CN114249866A (en) * | 2021-12-31 | 2022-03-29 | 安徽海螺新材料科技有限公司 | High-efficiency polycarboxylic acid water reducing agent and preparation method and application thereof |
| CN114573765A (en) * | 2022-03-09 | 2022-06-03 | 贵州大学 | Polyether slow-release slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| CN114804699A (en) * | 2021-06-01 | 2022-07-29 | 安徽成弘建新材料有限公司 | Concrete sandstone aggregate regulator and preparation method thereof |
| CN116283033A (en) * | 2022-12-14 | 2023-06-23 | 河北红墙新材料有限公司 | Concrete antifreezer and preparation method thereof |
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| CN110698609A (en) * | 2019-09-18 | 2020-01-17 | 四川琪汇新材料有限责任公司 | High-performance polycarboxylic acid water reducing agent synthesized at normal temperature, preparation method and application thereof |
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Application publication date: 20190419 |