CN101530760A - Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method - Google Patents
Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method Download PDFInfo
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- 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
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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Abstract
一种以烯丙基聚乙二醇与不饱和羧酸或其衍生物在氧化还原体系催化剂作用下共聚而制得的一种聚醚基聚羧酸系超分散剂及其合成方法，属于减水剂领域。采用了新型的氧化还原催化剂，以水为溶剂合成一种高效的聚醚基超分散剂。生产工艺简单，克服了以前反应温度过低造成的难以操作和反应温度过高造成的能源浪费，具有环保、低能耗、成本低的优点。A polyether-based polycarboxylic acid-based hyperdispersant prepared by copolymerizing allyl polyethylene glycol and unsaturated carboxylic acid or its derivatives under the action of a redox system catalyst and its synthesis method belong to water field. A new type of redox catalyst is used to synthesize a high-efficiency polyether-based hyperdispersant with water as the solvent. The production process is simple, overcomes the difficult operation caused by too low reaction temperature and the energy waste caused by too high reaction temperature in the past, and has the advantages of environmental protection, low energy consumption and low cost.
Description
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:
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
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
Represent polyoxyethylene groups,
Represent the polyoxypropylene base.
A-1: allyl polyglycol ether be (adding
Mean molecule quantity 400);
A-2: allyl polyglycol ether be (adding
Mean molecule quantity 1000);
A-3: allyl polyglycol ether be (adding
Mean molecule quantity 1300);
A-4: allyl polyglycol ether be (adding
Mean molecule quantity 2000);
A-5: allyl polyglycol ether be (adding
Mean molecule quantity 2400);
A-6: allyl polyglycol ether be (adding
Mean molecule quantity 5000);
A-7: allyl polyglycol ether be (adding
Mean molecule quantity 2000,
Mean molecule quantity 400);
A-8: allyl polyglycol ether be (adding
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:
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,
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.
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| 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 |
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2009
- 2009-04-28 CN CN200910135748A patent/CN101530760A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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