CN101530760A - Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method - Google Patents

Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method Download PDF

Info

Publication number
CN101530760A
CN101530760A CN200910135748A CN200910135748A CN101530760A CN 101530760 A CN101530760 A CN 101530760A CN 200910135748 A CN200910135748 A CN 200910135748A CN 200910135748 A CN200910135748 A CN 200910135748A CN 101530760 A CN101530760 A CN 101530760A
Authority
CN
China
Prior art keywords
dispersant
hyper
monomers
polyether
monomer
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.)
Pending
Application number
CN200910135748A
Other languages
Chinese (zh)
Inventor
马临涛
王少江
鲁一晖
陈改新
纪国晋
刘晨霞
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.)
China Institute of Water Resources and Hydropower Research
Beijing IWHR KHL Co Ltd
Original Assignee
China Institute of Water Resources and Hydropower Research
Beijing IWHR KHL 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 China Institute of Water Resources and Hydropower Research, Beijing IWHR KHL Co Ltd filed Critical China Institute of Water Resources and Hydropower Research
Priority to CN200910135748A priority Critical patent/CN101530760A/en
Publication of CN101530760A publication Critical patent/CN101530760A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B24/28Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32Polyethers, e.g. alkylphenol polyglycolether
    • 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
    • C04B2103/40Surface-active agents, dispersants
    • C04B2103/408Dispersants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a polyether-based polycarboxylic acid series hyper-dispersant which is prepared by copolymerization of polyethlene glycol and unsaturated carboxylic acid or the ramification under the action of redox system catalyst, and a synthesizing method which belongs to the water reducing agent field. The method uses the new type redox catalyst, synthesizes a polyether-based hyper-dispersant with high efficiency. The method has simple processing technique, conquers difficult operation caused by low reaction temperature and energy waste caused by high temperature. The hyper-dispersant and the synthesizing method have advantages of environmental-friendly, low energy consumption and low cost.

Description

A kind of polyether-based polycarboxylic acid series hyper-dispersant and synthetic method thereof
Technical field
The present invention relates to a kind of cement concrete hyper-dispersant and synthetic method thereof, specifically with the copolymerization and a kind of polyether-based polycarboxylic acid series hyper-dispersant and the synthetic method thereof that make belong to the concrete admixture field under the redox system catalyst action of allyl polyglycol and unsaturated carboxylic acid or derivatives thereof.
Background technology
The cement concrete hyper-dispersant claims high efficiency water reducing agent again, is building material product indispensable in the engineering construction process, is called as concrete the 5th component.The development of cement concrete dispersant has long history, and has experienced several stages:
Nineteen thirty-five American E.W. Si Kelipuche (Scopture) at first is developed into the lignosulfonates water reducer.This series water reducer water-reducing rate is lower, but owing to cheaply still has use now.
The sixties in 20th century, Japan and Germany synthesize β-naphthalene sulfonic acid-formaldehyde condensation product (SNF) and these two kinds of high efficiency water reducing agents of sulfonated melamine compound condensation product (SMF).From the sixties to the beginning of the eighties, it is the developing stage of high efficiency water reducing agent, this stage water reducer is main representative with naphthalene, main feature be technical maturity, not bleed, not slow setting, good with cement adaptability, water-reducing rate is higher, but concrete slump loss is very fast, need just can reach different construction requirements by composite, but composite back water reducer is influential to the development of concrete early strength again.This product uses formaldehyde, the concentrated sulfuric acid to synthesize in a large number in addition, and environmental pollution is serious in the production process.
Melamine series water reducer performance slightly is better than naphthalene system, but this product price is higher, difficult storage, big, the concrete adhesion of slump-loss, and practical application is few.
Japan utilizes alkene and unsaturated carboxylic acid copolymerization in nineteen ninety-five, has succeeded in developing polycarboxylate high performance water-reducing agent.This kind poly carboxylic acid series water reducer feature is that main chain and side chain connecting key are ester bonds.Poly carboxylic acid series water reducer since water-reducing rate up to more than 30%, volume is few, slump retentivity is good, amount of air entrainment is moderate, suitable preparation high fluidity, self-compacting concrete, and not using formaldehyde in synthetic, environmental pollution is little, thereby is subjected to the favor of engineering circle.Japan is that research and application poly carboxylic acid series water reducer at most also are the most successful countries, and after nineteen ninety-five, the use amount of poly carboxylic acid series water reducer in the Japanese goods concrete surpassed naphthalene water reducer.In Japan, poly carboxylic acid series water reducer the earliest is the copolymer of alkene and unsaturated carboxylic acid, and a lot of breakthrough improvement are all arranged on improved properties and copolymerization technique thereafter, and performance is gradually improved.
In recent years, the research of concrete admixture was tending towards developing to high-performance, free of contamination direction with production day in the world.The co-poly carboxylic acid series additive is because the water-reducing rate height, and function of slump protection is good, and later strength increases big, and suitable preparation is high-strength, super high strength concrete, high fluidity and super plasticizing concrete, self-compacting concrete etc., thereby is subjected to the extensive concern of domestic and international project circle.
At notification number is to have announced among the CN1734556A that a kind of " with maleic anhydride is the method for raw material preparing cement water reducing agent; earlier carry out esterification with maleic anhydride and methoxy poly (ethylene glycol); be catalyst with the p-methyl benzenesulfonic acid; stannous chloride and hydroquinones are polymerization inhibitor; with the cyclohexane is solvent; reacting more than 10 hours must esterification products, remove the back of desolvating and carry out polymerisation with AMPS, MAS, with the Ammonium Persulfate 98.5 is initator, TGA is a chain-transferring agent, reacts down at 90 ℃ to obtain water reducer solution." this process solvent removes difficulty, energy consumption is big, complex process.
Announced a kind ofly with the esterification 4 hours in 110~130 ℃ of reactors of methoxy poly (ethylene glycol), acrylic acid, acetate, polymerization inhibitor and concentrated sulfuric acid catalyst in United States Patent (USP) 6881818, decompression distillation removes water that dereaction produces and the azeotropic mixture of water and acetate obtains esterification products.Maleic anhydride and esterification products are catalyst with the azo-bis-isobutyl cyanide then, under 80 ℃ of reaction temperature conditions, in 6 hours weight average molecular weight 13500 copolymers.This excellent product performance but complex process, and environment caused bigger pollution.Because the production cycle is long, production cost is higher.
Summary of the invention
Copolymer and synthetic methods thereof such as a kind of allyl polyglycol that the objective of the invention is to provide, acrylic acid at the deficiencies in the prior art, its principal character is to have adopted novel oxidation reduction catalyst, is the synthetic a kind of hyper-dispersant of polyether-based efficiently of solvent with water.Production technology is simple, has overcome former reaction temperature and has spent low being difficult to of causing and operate and the too high energy waste that causes of reaction temperature, has environmental protection, low energy consumption, advantage that cost is low.
Implementation of the present invention: propose a kind of hyper-dispersant that the coagulating cement soil particle disperses that is used for, it is characterized in that it is the polymer of allyl polyglycol/pi-allyl polypropylene glycol (A) and unsaturated carboxylic acid and derivative (B) thereof, with formula (1) expression monomer A, as follows with formula (2) expression monomers B:
Figure A200910135748D00041
Wherein: R 1The alkyl group of-hydrogen atom or C atomicity 1~5
R 2The alkyl group of-hydrogen atom or C atomicity 1~5
N, m-be respectively EO and PO unit weighs plural number, they are 0~500, are preferably 0~100, more preferably 2~50
Figure A200910135748D00042
Wherein: the alkyl group of R3-hydrogen atom or C atomicity 1~5
The ether of R4-hydroxyl, amido or C atomicity 1~5
The method of synthetic above-mentioned hyper-dispersant is with the initator copolymerization of monomer A and monomers B employing redox system and get.
The used redox system of the present invention is to be made of sodium ascorbate, ferrous sulfate and hydrogen peroxide.
Used peroxide can be one or more in potassium peroxide, sodium peroxide, the hydrogen peroxide among the present invention.
Used reducing agent can be one or more in ascorbic acid, sodium ascorbate, the sodium sulfite among the present invention.
The consumption of redox system initator accounts for 0.1%~5% of monomer A and monomers B gross weight among the present invention.
The mol ratio of described monomer A and monomers B is 1:1~1:4.
Described copolymerization temperature is between 50~80 ℃, and the copolymerization time is 3~5 hours.
Described monomers B, Oxidizing and Reducing Agents separately drip, and adjust the molecular structure of product by the change of monomers B rate of addition, thereby optimize properties of product.
The present invention is a kind of allyl polyether and copolymers of unsaturated carboxylic acids, adjusts the distribution of monomer in the polymer molecular structure by the change of monomers B rate of addition, to reach the purpose of optimizing properties of product.Monomers B drips first quick and back slow, gets molecular weight of copolymer and is evenly distributed the water-reducing rate height; Monomers B drips when the back is fast slowly earlier, and range of molecular weight distributions is wide, and copolymer slump retentivity is good.The redox system that the present invention adopts sodium ascorbate, ferrous sulfate and hydrogen peroxide three components to constitute.Oxidizer system formed by ferrous sulfate and hydrogen peroxide and reaction monomers is mixed, and hydrogen peroxide is oxidized to ferric iron with two valency iron, discharges oxygen radical simultaneously, and oxygen radical has very high reactivity, can react at a lower temperature, constantly is consumed; Simultaneously sodium ascorbate is reduced into ferrous iron as reducing agent with ferric iron, regenerates ferrous iron and participates in reaction with hydrogen peroxide once more, and constantly circular response discharges oxygen radical, exhausts up to hydrogen peroxide.Raw material sources of the present invention are easy to get, and production cost is low, the easy application performance effect excellence that is easy to suitability for industrialized production, environmentally safe, final products of technology.
The water reducer method for testing performance is seen GB8076-2008 and GB8077-2000.
Polycarboxylate water-reducer molecular weight detection method be with the gel look general be that solvent detects molecular weight 20000~100000 with water.
The specific embodiment
To be described in monomer A used in the preparation process of copolymer of the present invention below, wherein
Figure A200910135748D00051
Represent polyoxyethylene groups,
Figure A200910135748D00052
Represent the polyoxypropylene base.
A-1: allyl polyglycol ether be (adding
Figure A200910135748D00053
Mean molecule quantity 400);
A-2: allyl polyglycol ether be (adding
Figure A200910135748D00054
Mean molecule quantity 1000);
A-3: allyl polyglycol ether be (adding
Figure A200910135748D00055
Mean molecule quantity 1300);
A-4: allyl polyglycol ether be (adding
Figure A200910135748D00056
Mean molecule quantity 2000);
A-5: allyl polyglycol ether be (adding Mean molecule quantity 2400);
A-6: allyl polyglycol ether be (adding
Figure A200910135748D00062
Mean molecule quantity 5000);
A-7: allyl polyglycol ether be (adding
Figure A200910135748D00063
Mean molecule quantity 2000,
Figure A200910135748D00064
Mean molecule quantity 400);
A-8: allyl polyglycol ether be (adding
Figure A200910135748D00065
Mean molecule quantity 1000, Mean molecule quantity 1400);
Used monomers B is an acrylic acid in describing below.
Embodiment 1
Add 25.4gA-1 in the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, 63.5gA-2 adds the 100g deionized water simultaneously, dissolving heats while stirring, be warming up to 55 ± 2 ℃, treat monomer A dissolving after, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 55 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 48000 after testing, density 1.06g/ml.
Embodiment 2
Add 35.3gA-2 in the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, 53.5gA-4 adds the 100g deionized water simultaneously, dissolving heats while stirring, be warming up to 60 ± 2 ℃, treat monomer A dissolving after, add the hydrogen peroxide of 0.006g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 45000 after testing, density 1.06g/ml.
Embodiment 3
In the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, add 95gA-3, add the 100g deionized water simultaneously, the dissolving that heats while stirring is warming up to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 46000 after testing, density 1.06g/ml.
Embodiment 4
In the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, add 100gA-4, add the 100g deionized water simultaneously, the dissolving that heats while stirring is warming up to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 45000 after testing, density 1.06g/ml.
Embodiment 5
In the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, add 110gA-5, add the 100g deionized water simultaneously, the dissolving that heats while stirring is warming up to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 47000 after testing, density 1.06g/ml.
Embodiment 6
Add 125gA-6 having stirring, temperature controller, raw material to drip in the 500ml four-hole boiling flask for the treatment of device, add the 100g deionized water simultaneously, the dissolving that heats while stirring is warming up to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 43000 after testing, density 1.06g/ml.
Embodiment 7
Add 55.5gA-5 in the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, 36.3gA-7 adds the 100g deionized water simultaneously, dissolving heats while stirring, be warming up to 60 ± 2 ℃, treat monomer A dissolving after, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 47000 after testing, density 1.06g/ml.。
Embodiment 8
Add 55.5gA-5 in the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, 33.2gA-8 adds the 100g deionized water simultaneously, dissolving heats while stirring, be warming up to 60 ± 2 ℃, treat monomer A dissolving after, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, while dropwise addition of acrylic acid solution (20g acrylic acid is dissolved in the 5g water) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 48000 after testing, density 1.06g/ml.
Embodiment 9
In the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, add 150gA-5, add the 100g deionized water simultaneously, the dissolving that heats while stirring, intensification degree to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, (20g acrylic acid is dissolved in the 5g water and drips off in two hours in the front dropwise addition of acrylic acid solution simultaneously; 10g acrylic acid is dissolved in the 15g water and drips off in latter two hour) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 49000 after testing, density 1.06g/ml.
Embodiment 10
In the 500ml four-hole boiling flask that devices such as stirring, temperature controller, raw material dropping are arranged, add 150gA-5, add the 100g deionized water simultaneously, the dissolving that heats while stirring is warming up to 60 ± 2 ℃, after treating the monomer A dissolving, add the hydrogen peroxide of 0.005g ferrous sulfate and 0.3g35%.Under 60 ± 2 ℃, (10g acrylic acid is dissolved in the 15g water and drips off in two hours in the front dropwise addition of acrylic acid solution simultaneously; 20g acrylic acid is dissolved in the 5g water and drips off in latter two hour) and sodium ascorbate solution (the 0.4g sodium ascorbate is dissolved in the 30g deionized water), the dropping time was controlled at 4 hours, and reaction temperature remains unchanged.After dropwising, continue insulation 30 minutes, be cooled to afterwards below 40 ℃, hydro-oxidation sodium is neutralized to pH=6.8, and thin up to 40% gets colourless transparent solution.Mean molecule quantity 44000 after testing, density 1.06g/ml.
Evaluation method of the present invention is with reference to GB8076-2008.
Subordinate list 1 clean slurry fluidity test
Embodiment Solid addition (%) Initial flow degree (mm) 30min fluidity (mm) 60min fluidity (mm)
1 0.25 240 260 255
2 0.20 240 235 230
3 0.20 230 230 225
4 0.15 235 218 210
5 0.15 240 223 218
6 0.28 250 180 140
7 0.15 235 230 232
8 0.15 235 228 220
9 0.15 243 240 240
10 0.15 263 225 213
As can be seen from the table, the present invention has excellent dispersion properties and fluidity hold facility to cement paste.

Claims (10)

1. polyether-based polycarboxylic acid series hyper-dispersant, be used for the hyper-dispersant that the coagulating cement soil particle disperses, it is characterized in that it is the polymer of allyl polyglycol/pi-allyl polypropylene glycol (A) and unsaturated carboxylic acid and derivative (B) thereof, with formula (1) expression monomer A, as follows with formula (2) expression monomers B:
Figure A200910135748C00021
Wherein: R 1The alkyl group of-hydrogen atom or C atomicity 1~5
R 2The alkyl group of-hydrogen atom or C atomicity 1~5
N, m Wei EO and PO unit weighs plural numbers, and they are 0~500 independently,
Figure A200910135748C00022
Wherein: the alkyl group of R3-hydrogen atom or C atomicity 1~5
The ether of R4-hydroxyl, amido or C atomicity 1~5.
2. polyether-based polycarboxylic acid series hyper-dispersant according to claim 1 is characterized in that, n, m are 2~50 independently.
3. according to the described polyether-based polycarboxylic acid series hyper-dispersant of claim 1, its mean molecule quantity is 10000~100000.
4. according to the method for the described polyether-based polycarboxylic acid series hyper-dispersant of a kind of synthetic claim 1, it is characterized in that adopting the redox system initator to get monomer A and monomers B through copolyreaction.
5. method according to claim 4 is characterized in that redox system is made of hydrogen peroxide, sodium ascorbate and ferrous sulfate.
6. method according to claim 5, the percentage by weight that it is characterized in that the effective content of hydrogen peroxide and monomer is 0.05~1%.
7. method according to claim 5, the mol ratio that it is characterized in that sodium ascorbate, ferrous oxide and hydrogen peroxide is 1:0.1~1:0.5~10.
8. method according to claim 4 is characterized in that the consumption of redox system initator accounts for 0.1%~5% of monomer A and monomers B weight total amount, the mol ratio 1:1 of monomer A and monomers B~1:4.
9. method according to claim 4 is characterized in that, copolymerization temperature is at 50~80 ℃, 3~8 hours copolymerization time.
10. according to the described method of claim 4, it is characterized in that monomers B, Oxidizing and Reducing Agents separately drip, and adjust the molecular structure of product by the change of monomers B rate of addition.
CN200910135748A 2009-04-28 2009-04-28 Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method Pending CN101530760A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200910135748A CN101530760A (en) 2009-04-28 2009-04-28 Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200910135748A CN101530760A (en) 2009-04-28 2009-04-28 Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method

Publications (1)

Publication Number Publication Date
CN101530760A true CN101530760A (en) 2009-09-16

Family

ID=41101747

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200910135748A Pending CN101530760A (en) 2009-04-28 2009-04-28 Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method

Country Status (1)

Country Link
CN (1) CN101530760A (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120805A (en) * 2011-01-27 2011-07-13 南京瑞迪高新技术公司 Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step
CN102161733A (en) * 2011-01-27 2011-08-24 南京瑞迪高新技术公司 Green preparation method of slow-release polycarboxylic-acid high-performance water reducing agent
CN105118996A (en) * 2015-09-02 2015-12-02 中南大学 Dispersion method for nanometer silicon
CN106634765A (en) * 2016-12-16 2017-05-10 深圳市华星光电技术有限公司 Black sealing compound and LCD (liquid crystal display) special-shaped screen, and manufacturing method thereof
CN106947238A (en) * 2017-03-15 2017-07-14 东莞市雄林新材料科技股份有限公司 A kind of colour-changing method of TPU film
CN112645630A (en) * 2020-12-19 2021-04-13 厦门宏发先科新型建材有限公司 Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete
CN112940194A (en) * 2021-01-29 2021-06-11 武汉奥克特种化学有限公司 Preparation method and application of inorganic pigment and filler water-based dispersant

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102120805A (en) * 2011-01-27 2011-07-13 南京瑞迪高新技术公司 Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step
CN102161733A (en) * 2011-01-27 2011-08-24 南京瑞迪高新技术公司 Green preparation method of slow-release polycarboxylic-acid high-performance water reducing agent
CN102120805B (en) * 2011-01-27 2013-01-02 南京瑞迪高新技术公司 Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step
CN105118996A (en) * 2015-09-02 2015-12-02 中南大学 Dispersion method for nanometer silicon
CN105118996B (en) * 2015-09-02 2017-09-29 中南大学 A kind of process for dispersing of nano-silicon
CN106634765A (en) * 2016-12-16 2017-05-10 深圳市华星光电技术有限公司 Black sealing compound and LCD (liquid crystal display) special-shaped screen, and manufacturing method thereof
CN106947238A (en) * 2017-03-15 2017-07-14 东莞市雄林新材料科技股份有限公司 A kind of colour-changing method of TPU film
CN112645630A (en) * 2020-12-19 2021-04-13 厦门宏发先科新型建材有限公司 Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete
CN112940194A (en) * 2021-01-29 2021-06-11 武汉奥克特种化学有限公司 Preparation method and application of inorganic pigment and filler water-based dispersant
CN112940194B (en) * 2021-01-29 2022-05-24 武汉奥克特种化学有限公司 Preparation method and application of inorganic pigment and filler water-based dispersant

Similar Documents

Publication Publication Date Title
CN102358768B (en) Modified ether polycarboxylic acid water reducing agent and preparation method thereof
CN101530760A (en) Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method
CN110128603B (en) Method for stably synthesizing polycarboxylate superplasticizer under low-temperature condition
CN101993210B (en) Prenyl polyether polycarboxylate water reducing agent and synthesis method thereof
CN102391435B (en) Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof
CN110642993B (en) Preparation method of retarding ether polycarboxylate superplasticizer
EP2937321A1 (en) Slump retaining polycarboxylic acid superplasticizer
CN105601843B (en) Ethers Early-strength polycarboxylate superplasticizer and preparation method thereof
CN109354654A (en) A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof
CN102660037B (en) Preparation method of super-sustained release ester-ether crosslinking polycarboxylic acid water reducer
CN106277899A (en) A kind of polycarboxylate water-reducer and preparation method thereof
CN102146159A (en) Vinyl polyether and preparation method and application thereof
CN101353397B (en) Water-soluble grafting polycarboxylic acids dehydragent and preparation thereof
CN102140018A (en) Concrete polycarboxylate water reducer and preparation method thereof
CN101817657A (en) Polycarboxylic acid slump retaining agent
CN101830663B (en) Collapse protective poly-carboxylic acid water reducing agent and preparation method thereof
CN108794700A (en) A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer
CN101906193A (en) Method for synthesizing polycarboxylic acid water reducing agent
CN102503221B (en) Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
CN102627744A (en) Preparation method of ether amphoteric polycarboxylic acid water reducing agent
CN102250296B (en) Water reducing agent as well as preparation method and application thereof
CN113372510B (en) Preparation method of viscosity-reducing and mud-resisting polycarboxylate superplasticizer
CN102718427A (en) Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof
CN105037647A (en) Preparing method for polycarboxylic admixture
CN105085821A (en) Heat-energy-free novel integrated efficient polycarboxylic acid water reducer and preparation method therefor

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Open date: 20090916