CN102093501A - Method for preparing hyper-dispersant used for mixed size - Google Patents
Method for preparing hyper-dispersant used for mixed size Download PDFInfo
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Abstract
The invention provides a method for preparing a hyper-dispersant used for mixed size with a water-phase solution polymerization method. The method comprises the following steps of: (1) preparing materials A, B, C1, C2 and D, wherein the materials A and D comprise unsaturated carboxylic acid monomers, multi-functionality functional monomers, molecular weight regulators, reducing system reductant, deionized water and pH regulators, and the materials B, C1 and C2 comprise oxidation initiation system initiators and deionized water; (2) adding the prepared material D in a reactor, and adding all of the material C1 in the reactor after heating to the reaction temperature of 50-100 DEG C; (3) starting to simultaneously drop the material A and the material B for 2-6h; (4) adding all of the material C2 in the reactor after dropping; (5) regulating the temperature in the reactor to 60-100 DEG C and keeping the temperature for reaction for 0.5-4h; and (6) lowering the temperature below 50DEG C after reaction, regulating pH to 5-9 and discharging to obtain the hyper-dispersant. The method adopts simple technology and is suitable for popularization and application.
Description
Technical field
The present invention relates to the preparation method of a kind of mixed slurry with hyper-dispersant, particularly a kind of aqueous phase solution polymerization prepares the method for novel mixed slurry with the polymer hyper-dispersant.
Background technology
Ultrafine powder is in preparation process and use, because there is grinding ultimate problem in grinding, need carry out classification, during the wet classification ultrafine powder, because the particle diameter of ultrafine powder is little, surface energy is easy to greatly reunite, because the existence of coacervate, the microtexture of powder becomes inhomogeneous, hinders the dispersion of powder greatly.Pulpous state mixed slurry preparation process is that pulp particle is suspended in the water, but particle is owing to Van der Waals force is assembled, so must make it to disperse, require to have characteristics such as higher solids content, stability and rheological are good for suspended nitride, just need to add hyper-dispersant.Dispersion agent plays a part very crucial in pulpous state mixed slurry process of lapping, can make by dispersed substance to reach good dispersion effect and stability.
Along with the demand increase of high-quality pulpous state mixed slurry, the hyper-dispersant demand is also increasing.The additive that oversubscription is loose and must be used as the pulpous state slurry carries out modification for inorganic slurry, reduces the reunion between the pulpous state pulp particle, improves the flowability of the content of slurry, the viscosity that reduces the pulpous state slurry, raising pulpous state slurry.Inorganic dispersant or the small molecules dispersion agent that uses on the market in use has a lot of defectives at present, absorption to particle surface is insecure, cause reassembling or precipitating from surface desorption easily, poor stability when causing disperseing, dispersedly poorly cause slurry denseness height to contain low, facile hydrolysis admittedly causing that the slurry wadding is poly-.Organic dispersing agent then dispersion effect is good, and superior performance can prepare low viscosity and the high product that contains admittedly, can improve the fineness of pulpous state slurry, the stability of dispersion system etc.Conventional organic polyacrylic acid dispersant polyreaction is thermopositive reaction, can produce a large amount of reaction heat, thereby sudden and violent poly-phenomenon easily takes place, therefore reaction process is difficult to control, and conversion rate of products is low, remaining a large amount of monomers, product molecular weight distribution causes dispersion effect poor than broad, influences product performance.
Two kinds of systems of the general employing of organic supermolecular dispersion agent preparation process:
(1) organic solvent system: this system mainly be with benzene, toluene, hexanaphthene, solvent wet goods organic solvent as reaction medium, temperature of reaction be not easy control, cause danger easily, the working condition harshness, the aftertreatment complexity, product contamination is serious.
(2) water solution system: this system mainly is as reaction medium with water.Adopt the hyper-dispersant of this system preparation good for the dispersion effect of aqueous suspension system.
The patent of invention of publication number CN1146371A discloses " a kind of polyester type dispersion agent and preparation method thereof ", its shortcoming is that this method employing toluene or dimethylbenzene are solvent, the toxicity of organic solvent is big, aftertreatment technology is complicated, product production is low, production cost is high, contaminate environment, generally be used for solvent-based system, Application Areas is restricted.
Publication number is that the Chinese invention patent application of CN101302278A discloses a kind of hyper-dispersant for polychloroethylene heat stabilizer.This patent is to adopt two step method to prepare hyper-dispersant, also is to be reaction medium with distilled water, is anchoring group with the ester group, in the reaction process, is initiator with the persulphate.Reaction back product also needs can not directly use complicated process of preparation through aftertreatment.
The method that Japanese Patent is opened the clear 62-270605 proposition of communique is in the presence of the inorganic phosphate (salt) of 0.01～5 (wt) %, adopts the above solvent of ethanol 40 (wt) % to make the vinyl-type monomer polymerization of the following energy of (methyl) vinylformic acid and 10 (wt) % copolymerization.The disclosed technology of this communique solvent for use ethanol when polymerization finishes need distill to be removed, and this not only receives the restriction of producing apparatus device aspect, and causes production cost to rise.
It is that monomer based on (methyl) vinylformic acid adds the alkaline aqueous solution that has heated to the peroxide polymerization starter and carries out polymerization that Japanese Patent is opened the disclosed method of the flat 4-268304 of communique.Can obtain number-average molecular weight with this method is 200～2600 low-molecular weight polymer.The technology of the disclosure is to carry out polymerization under strong alkaline condition, if the solid shape concentration of component height of the polymerization reaction system of this neutral condition, the solution viscosity that carries out reaction system along with polymerization significantly rises, and there is the tendency that increases considerably in the molecular weight of resulting polymers.
Summary of the invention
Problem in view of existing dispersion agent product existence, the present invention proposes a kind of mixed slurry hyper-dispersant preparation method, preparation process need not to adopt organic solvent, need not to adopt nitrogen, preparation technology is simple, transformation efficiency is high, hyper-dispersant narrow molecular weight distribution, pollution-free, easy control, the good water solubility of preparation, in order to reach above purpose, the present invention by the following technical solutions:
The raw material of this hyper-dispersant comprises: unsaturated carboxylic acid monomer, polyfunctionality functional monomer, molecular weight regulator, initiator, deionized water and pH regulator agent, initiator is the compound redox initiation system, by the weight percentage of each ingredients constitute total raw material, preparation process is as follows:
(1) configuration A, B, C1, C2, the D material, wherein, the A material package is drawn together unsaturated carboxylic acid monomer 5～50%, polyfunctionality functional monomer 0～5%, molecular weight regulator 0～5%, reduction system reducing agent 0～5%, deionized water 5～25%, it is 4～8 that the pH value is regulated in the pH regulator agent, the B material package is drawn together oxidation initiator system initiator 0～10%, deionized water 5～25%, the C1 material package is drawn together oxidation initiator system initiator 0～5%, deionized water 0～5%, the C2 material package is drawn together oxidation initiator system initiator 0～5%, deionized water 0～5%, the D material package is drawn together unsaturated carboxylic acid monomer 0～15%, polyfunctionality functional monomer 0～5%, molecular weight regulator 0～5%, reduction system reducing agent 0～5%, deionized water 5～25%, it is 4～8 that the pH value is regulated in the pH regulator agent in right amount, and batch temperature is not higher than 50 ℃;
(2) D material is added in the reactor, be heated to 50～100 ℃ of temperature of reaction after, the disposable C1 material that in still, adds;
(3) drip A material and B material simultaneously, the dropping time is 2～6h;
(4) after dropping finishes, the disposable C2 that in still, adds;
(5) reactor temperature is transferred to 60～100 ℃, insulation reaction 0.5～4h;
(6) after reaction finishes, drop to below 50 ℃, add the pH regulator agent and regulate pH=5～9, discharging.
Above-mentioned unsaturated carboxylic acid monomer is one or more in vinylformic acid, methacrylic acid, methylene-succinic acid, the maleic anhydride.
Above-mentioned polyfunctionality functional monomer is that vinylbenzene, vinyl pyrrolidone, 2-acryloyl ammonium-2-methyl propane sulfonic acid salt, sodium allyl sulfonate, methallylsulfonic acid sodium and chain length are one or more in 4～100 polyethylene glycol acrylate, methoxy poly (ethylene glycol) acrylate, methoxy polyethylene glycol methacrylate-styrene polymer, polyethylene glycol methacrylate-styrene polymer, thiazolinyl polyoxyethylene and the methoxyl group thiazolinyl polyoxyethylene.
Above-mentioned molecular weight regulator is one or more in n-dodecyl mercaptan, uncle's lauryl mercaptan, 2 mercapto ethanol, 3-thiohydracrylic acid, 2-Mercaptobutanol, 4-Mercaptobutanol, 3-thiohydracrylic acid hydroxyl ethyl ester, the sodium hypophosphite.
Above-mentioned oxidation system is ammonium persulphate, Sodium Persulfate, Potassium Persulphate, lauroyl peroxide Potassium Persulphate, H
2O
2The quality percentage composition is one or more in 30～50% hydrogen peroxide, tertbutyl peroxide, the cumyl hydroperoxide; Described reduction system reducing agent is one or more in S-WAT, potassium sulfite, S-WAT lithium, sodium bisulfite, Potassium hydrogen sulfite, bisulfite lithium, Sodium Pyrosulfite, potassium pyrosulfite, pyrosulphite lithium, sodium sulfoxylate formaldehyde, the Sulfothiorine.
Above-mentioned pH regulator agent is one or more among sodium hydroxide, potassium hydroxide, sodium hydroxide solution, potassium hydroxide solution, three ethanol, ammoniacal liquor, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, the AM-95.
The hyper-dispersant of the present invention preparation is mainly used in one or more the mixed slurry that disperses to contain in fine particle calcium carbonate, coarse whiting, kaolin, barium sulfate, titanium dioxide, zinc oxide, aluminum oxide, barium titanate, talcum powder, wollastonite, titanium dioxide, ground barium sulfate, grey calcium powder, the dry powder.
The novel mixed slurry hyper-dispersant that the present invention is prepared is faint yellow transparent liquid, nontoxic, harmless, non-stimulated smell, non-corrosiveness, do not fire, not quick-fried.Its starting material wide material sources, cheap, raw materials cost is low, preparation process is fairly simple, consuming time less, equipment is simple, production cost is low, have environmentally safe, reaction conditions and be easy to control, be easy to realize characteristics such as industrialization, overcome deficiencies such as the dispersion system sedimentation that existing dispersion agent exists is fast, poor stability, flowability is poor, dispersion agent is poor for applicability.And consumption eases down to commonly with disperseing 50%～80% of dosage, just can reach characteristics such as desired slurry viscosity, flowability, homogeneity, suspension.
Novel mixed slurry by the present invention's preparation is low with the hyper-dispersant molecular weight, molecular weight distribution is narrower, have low volume and high dispersiveness, can effectively reduce product viscosity, improve fineness and the rheological of slurry and the stability of dispersion system of slurry, can prepare low viscosity and the high product that contains admittedly, compare the obvious consumption that reduced with the like product of other brands, improve the solid content of mixed slurry, reduced production cost.
Embodiment
Below by embodiment the hyper-dispersant of the present invention's preparation is described further.
Embodiment 1
The configuration material, the A material: vinylformic acid 70g, methallylsulfonic acid sodium 1g, maleic anhydride 0.6g, vinylbenzene 0.2g, deionized water 20g at room temperature mixes; B material: 30 (wt) % hydrogen peroxide 0.5g, ammonium persulphate 8g, deionized water 55g; C1 material: 30 (wt) % hydrogen peroxide 0.5g; C2 material: 30 (wt) % hydrogen peroxide 0.5g; The D material: vinylformic acid 7.7g, methallylsulfonic acid sodium 4g, maleic anhydride 2.4g, 3-thiohydracrylic acid 0.4g, deionized water 90g at room temperature mixes.At the four-hole boiling flask that has condenser, thermometer, constant pressure funnel, stirrer, add the D material earlier, after the thermostat water bath water temperature is heated to 60 ℃, disposable to reactor adding C1 material, begin to drip respectively A material and B material, the dropping time is 3h, after dropping finishes, disposable to reactor adding C2 material, temperature of reaction system is raised to 68 ℃, continues insulation 1h, after reaction finishes, reduce the temperature to below 50 ℃, add 30 (wt) % sodium hydroxide solution in system, the control solution PH is 6.5, and reaction finishes, discharging promptly obtains hyper-dispersant.Adopting gel aqueous phase permeation chromatography (GPC), is moving phase with the 0.1M sodium nitrite solution, and sodium polyacrylate is as standard substance, and the number average relative molecular weight that records hyper-dispersant is 2540.
Embodiment 2
The configuration material, the A material: methacrylic acid 277.2g, 2-acryloyl ammonium-2-methyl propane sulfonic acid sodium 4g, maleic anhydride 2.4g, vinyl pyrrolidone 0.55g, sodium bisulfite 10g, deionized water 80g at room temperature mixes; B material: Potassium Persulphate 33.6g, deionized water 220g; C1 material: ammonium persulphate 2g, deionized water 10g; C2 material: ammonium persulphate 2g, deionized water 10g; The D material: vinylformic acid 30.8g, methallylsulfonic acid sodium 6g, maleic anhydride 9.6g, 2-Mercaptobutanol 1g, sodium bisulfite 3g, deionized water 220g at room temperature mixes.At the four-hole boiling flask that has condenser, thermometer, constant pressure funnel, stirrer, add earlier and mix the D material, after the thermostat water bath water temperature is warmed up to 70 ℃, disposable to reactor adding C1 material, begin to drip respectively A material and B material, the dropping time is 3h, after dropping finishes, disposable to reactor adding C2, temperature of reaction system is raised to 78 ℃, continues insulation 1h, after reaction finishes, reduce the temperature to below 50 ℃, add 30 (wt) % potassium hydroxide solution in system, the control solution PH is 6.5, and reaction finishes, discharging promptly obtains hyper-dispersant.Adopting gel aqueous phase permeation chromatography (GPC), is moving phase with the 0.1M sodium nitrite solution, and sodium polyacrylate is as standard substance, and the number average relative molecular weight that records hyper-dispersant is 3320.
Embodiment 3
The configuration material, the A material: vinylformic acid 550g, methallylsulfonic acid sodium 8g, maleic anhydride 4.8g, methoxy poly (ethylene glycol) (methyl) acrylate (nEO=23) 54g, S-WAT 30g, deionized water 160g at room temperature mixes; B material: Potassium Persulphate 121.6g, deionized water 440g; C1 material: Potassium Persulphate 4g; C2 material: Potassium Persulphate 4g; The D material: vinylformic acid 77g, methallylsulfonic acid sodium 5g, maleic anhydride 3g, S-WAT 10g, deionized water 440g at room temperature mixes.At the four-hole boiling flask that has condenser, thermometer, constant pressure funnel, stirrer, thermostat water bath, add earlier and mix the D material, after being warmed up to 80 ℃, disposable to reactor adding C1 material, begin to drip respectively A material and B material, the dropping time is 3h, after dripping end, disposable to reactor adding C2, temperature of reaction system is raised to 88 ℃, continue insulation 1h, reaction reduces the temperature to below 50 ℃ after finishing, and adds ammoniacal liquor in system, the control solution PH is 6.5, reaction finishes, and discharging promptly obtains hyper-dispersant.Adopting gel aqueous phase permeation chromatography (GPC), is moving phase with the 0.1M sodium nitrite solution, and sodium polyacrylate is as standard substance, and the number average relative molecular weight that records hyper-dispersant is 4560.
Embodiment 4
The configuration material, the A material: vinylformic acid 100g, methallylsulfonic acid sodium 26g, methylene-succinic acid 425g, n-dodecyl mercaptan 0.8g, 30 (wt) % sodium hydroxide 30g, Sodium Pyrosulfite 48g, deionized water 400g at room temperature mixes; B material: lauroyl peroxide Potassium Persulphate 276g, deionized water 1100g; C1 material: ammonium persulphate 10g; C2 material: ammonium persulphate 10g; The D material: vinylformic acid 154g, methallylsulfonic acid sodium 30g, maleic anhydride 48g, 3-thiohydracrylic acid 4.6g, 30 (wt) % sodium hydroxide 20g, Sodium Pyrosulfite 16g, deionized water 750g at room temperature mixes.At the four-hole boiling flask that has condenser, thermometer, constant pressure funnel, stirrer, thermostat water bath, add earlier and mix the D material, after being warmed up to 78 ℃, disposable to reactor adding C1 material, begin to drip respectively A material and B material, the dropping time is 3h, after dripping end, disposable to reactor adding C2, temperature of reaction system is raised to 90 ℃, continue insulation 1h, reaction reduces the temperature to below 50 ℃ after finishing, and adds yellow soda ash in system, the control solution PH is 6.5, reaction finishes, and discharging promptly obtains hyper-dispersant.Adopting gel aqueous phase permeation chromatography (GPC), is moving phase with the 0.1M sodium nitrite solution, and sodium polyacrylate is as standard substance, and the number average relative molecular weight that records hyper-dispersant is 5590.
Embodiment 5
The configuration material, the A material: methacrylic acid 1300g, sodium allyl sulfonate 20g, maleic anhydride 96g, 2 mercapto ethanol 1.0g, 30 (wt) % sodium hydroxide 45g, potassium sulfite 75g, deionized water 400g at room temperature mixes; B material: tertbutyl peroxide 250g, deionized water 550g; C1 material: 30 (wt) % hydrogen peroxide 10g; C2 material: 30 (wt) % hydrogen peroxide 10g; The D material: methacrylic acid 154g, methallylsulfonic acid sodium 80g, maleic anhydride 48g, uncle's lauryl mercaptan 5g, 30 (wt) % sodium hydroxide 30g, potassium sulfite 25g, deionized water 700g at room temperature mixes.At the four-hole boiling flask that has condenser, thermometer, constant pressure funnel, stirrer, thermostat water bath, add earlier and mix the D material, after being warmed up to 93 ℃, disposable to reactor adding C1 material, begin to drip respectively A material and B material, the dropping time is 3h, after dripping end, disposable to reactor adding C2, temperature of reaction system is raised to 98 ℃, continue insulation 1h, reaction reduces the temperature to below 50 ℃ after finishing, and adds PH conditioning agent AM-95 in system, the control solution PH is 6.5, reaction finishes, and discharging promptly obtains hyper-dispersant.Adopting gel aqueous phase permeation chromatography (GPC), is moving phase with the 0.1M sodium nitrite solution, and sodium polyacrylate is as standard substance, and the number average relative molecular weight that records hyper-dispersant is 6980.
Test the effect of hyper-dispersant by experiment, testing method is: at first claim deionized water to be added in the white enamel cylinder, it is an amount of to add defoamer then, add mixed slurry, disperse with dispersion machine, adding dispersion agent (weight percent) successively is 0.05%, 0.09%, 0.11%, 0.13%, 0.16%, 6rpm, 60rpm, in cut under the rotating speed viscosimetric.
Mixed slurry prescription reference table:
The dispersiveness of dispersion agent in mixed slurry compares:
Claims (6)
1. a mixed slurry is with the preparation method of hyper-dispersant, the raw material of this hyper-dispersant comprises: unsaturated carboxylic acid monomer, polyfunctionality functional monomer, molecular weight regulator, initiator, deionized water and pH regulator agent, described initiator is the compound redox initiation system, by the weight percentage of each ingredients constitute total raw material, it is characterized in that preparation process is as follows:
1) configuration A, B, C1, C2, the D material, wherein, the A material package is drawn together unsaturated carboxylic acid monomer 10～50%, polyfunctionality functional monomer 0～5%, molecular weight regulator 0～5%, reduction system reducing agent 0～5%, deionized water 5～25%, it is 4～8 that the pH value is regulated in the pH regulator agent, the B material package is drawn together oxidation initiator system initiator 0～10%, deionized water 5～25%, the C1 material package is drawn together oxidation initiator system initiator 0～5%, deionized water 0～5%, the C2 material package is drawn together oxidation initiator system initiator 0～5%, deionized water 0～5%, the D material package is drawn together unsaturated carboxylic acid monomer 0～15%, polyfunctionality functional monomer 0～5%, molecular weight regulator 0～5%, reduction system reducing agent 0～5%, deionized water 5～25%, it is 4～8 that the pH value is regulated in the pH regulator agent in right amount, and batch temperature is not higher than 50 ℃;
2) D material is added in the reactor, be heated to 50～100 ℃ of temperature of reaction after, the disposable C1 material that in still, adds;
3) drip A material and B material simultaneously, the dropping time is 2～6h;
4) after dropping finishes, the disposable C2 material that in still, adds;
5) reactor temperature is transferred to 60～100 ℃, insulation reaction 0.5～4h;
6) after reaction finishes, drop to below 50 ℃, add the pH regulator agent and regulate pH=5～9, discharging.
2. the compound method of hyper-dispersant as claimed in claim 1, it is characterized in that: described unsaturated carboxylic acid monomer is one or more in vinylformic acid, methacrylic acid, methylene-succinic acid, the maleic anhydride.
3. the compound method of hyper-dispersant as claimed in claim 1 is characterized in that: described polyfunctionality functional monomer is that vinylbenzene, vinyl pyrrolidone, 2-acryloyl ammonium-2-methyl propane sulfonic acid salt, sodium allyl sulfonate, methallylsulfonic acid sodium and chain length are one or more in 4～100 polyethylene glycol acrylate, methoxy poly (ethylene glycol) acrylate, methoxy polyethylene glycol methacrylate-styrene polymer, polyethylene glycol methacrylate-styrene polymer, thiazolinyl polyoxyethylene and the methoxyl group thiazolinyl polyoxyethylene.
4. the compound method of hyper-dispersant as claimed in claim 1, it is characterized in that: described molecular weight regulator is one or more in n-dodecyl mercaptan, uncle's lauryl mercaptan, 2 mercapto ethanol, 3-thiohydracrylic acid, 2-Mercaptobutanol, 4-Mercaptobutanol, 3-thiohydracrylic acid hydroxyl ethyl ester, the sodium hypophosphite.
5. the compound method of hyper-dispersant as claimed in claim 1, it is characterized in that: described oxidation system is ammonium persulphate, Sodium Persulfate, Potassium Persulphate, lauroyl peroxide Potassium Persulphate, H
2O
2The quality percentage composition is one or more in 30～50% hydrogen peroxide, tertbutyl peroxide, the cumyl hydroperoxide; Described reduction system reducing agent is one or more in S-WAT, potassium sulfite, S-WAT lithium, sodium bisulfite, Potassium hydrogen sulfite, bisulfite lithium, Sodium Pyrosulfite, potassium pyrosulfite, pyrosulphite lithium, sodium sulfoxylate formaldehyde, the Sulfothiorine.
6. the compound method of hyper-dispersant as claimed in claim 1, it is characterized in that: described pH regulator agent is one or more among sodium hydroxide, potassium hydroxide, sodium hydroxide solution, potassium hydroxide solution, three ethanol, ammoniacal liquor, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, the AM-95.
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Cited By (9)
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| CN102886227A (en) * | 2012-07-25 | 2013-01-23 | 中南大学 | Application of ethoxy ethyl acrylate polymer and preparation method thereof |
| CN103602134A (en) * | 2013-11-05 | 2014-02-26 | 中国科学院广州化学研究所 | Dispersing agent of crotonic copolymers as well as preparation method and application thereof |
| CN103693688A (en) * | 2013-12-09 | 2014-04-02 | 云南新立有色金属有限公司 | Titanium dioxide slurry pretreatment method |
| CN103897101A (en) * | 2014-04-23 | 2014-07-02 | 郑州大学 | Acrylic polyester-type hyperdispersant and preparation method and application thereof |
| CN104086715A (en) * | 2014-06-25 | 2014-10-08 | 中科院广州化学有限公司南雄材料生产基地 | Dispersing agent for kaolin, and preparation method and application thereof |
| CN105566557A (en) * | 2014-10-13 | 2016-05-11 | 上海东升新材料有限公司 | High efficiency block type papermaking paint dispersing agent and preparation method thereof |
| CN109161219A (en) * | 2018-08-29 | 2019-01-08 | 湖南映宏新材料股份有限公司 | A kind of composite material and preparation method prepared with paper plant's waste |
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Cited By (14)
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| CN102886227B (en) * | 2012-07-25 | 2015-01-21 | 中南大学 | Application of ethoxy ethyl acrylate polymer and preparation method thereof |
| CN102886227A (en) * | 2012-07-25 | 2013-01-23 | 中南大学 | Application of ethoxy ethyl acrylate polymer and preparation method thereof |
| CN103602134A (en) * | 2013-11-05 | 2014-02-26 | 中国科学院广州化学研究所 | Dispersing agent of crotonic copolymers as well as preparation method and application thereof |
| CN103693688A (en) * | 2013-12-09 | 2014-04-02 | 云南新立有色金属有限公司 | Titanium dioxide slurry pretreatment method |
| CN103693688B (en) * | 2013-12-09 | 2015-09-16 | 云南新立有色金属有限公司 | Titanium dioxide slurry pretreatment method |
| CN103897101A (en) * | 2014-04-23 | 2014-07-02 | 郑州大学 | Acrylic polyester-type hyperdispersant and preparation method and application thereof |
| CN103897101B (en) * | 2014-04-23 | 2016-02-24 | 郑州大学 | A kind of acrylic polyester type hyper-dispersant and its preparation method and application |
| CN104086715A (en) * | 2014-06-25 | 2014-10-08 | 中科院广州化学有限公司南雄材料生产基地 | Dispersing agent for kaolin, and preparation method and application thereof |
| CN105566557A (en) * | 2014-10-13 | 2016-05-11 | 上海东升新材料有限公司 | High efficiency block type papermaking paint dispersing agent and preparation method thereof |
| CN105566557B (en) * | 2014-10-13 | 2017-12-01 | 上海东升新材料有限公司 | A kind of efficiently block type coating dispersant for papermaking and preparation method thereof |
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| CN109694445A (en) * | 2018-12-14 | 2019-04-30 | 深圳市瑞成科讯实业有限公司 | A kind of thinner and preparation method thereof and coating for paper |
| CN109694445B (en) * | 2018-12-14 | 2021-11-23 | 深圳市瑞成科讯实业有限公司 | Viscosity reducer, preparation method thereof and paper coating |
| CN110498625A (en) * | 2019-09-16 | 2019-11-26 | 安徽海螺新材料科技有限公司 | A kind of cement hexavalent chrome reduction agent and preparation method thereof |
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