CN106543321A - A kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant and its product and application - Google Patents
A kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant and its product and application Download PDFInfo
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- CN106543321A CN106543321A CN201510604394.6A CN201510604394A CN106543321A CN 106543321 A CN106543321 A CN 106543321A CN 201510604394 A CN201510604394 A CN 201510604394A CN 106543321 A CN106543321 A CN 106543321A
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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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
The invention discloses a kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant, comprises the steps：(1) the addition two thio benzoyloxy valeric acid of pentaerythrite and 4- cyano group -4- toward solvent, add water absorbing agent DCC and catalyst DMAP, after the completion of reaction, concentrated and isolated four arms RAFT agent pentaerythrite, four 4- cyano group -4-, two thio benzoyloxy valerates；(2) vinyl carboxylic acid monomer, four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valerates, initiator are added, and nitrogen bubble certain hour at low temperature, sealing；(3) heating response；(4) reaction is distilled off solvent after terminating；(5) pH for adding one or more neutralization aqueous slkali regulation systems is 5～8, adds water regulation solid content to 20%～50%, you can obtain high-efficiency coarse whiting ground dispersant.Product obtained in the method, counterion effect are low, molecular weight and molecualr weight distribution controllable precise, with excellent dispersive property.
Description
Technical field
The present invention relates to a kind of preparation method of grinding distribution agent, more particularly to a kind of four arms star structure is efficiently weighed
The preparation method of calcium grinding distribution agent, and the application of the product and the product according to the method preparation.
Background technology
Dispersant is widely used in the middle of the wet grinding production of ultrafine heavy calcium, and which can significantly reduce coarse whiting slurry
The stability of slurry is instead glued, is increased in the grinding viscosity of material, reduction after grinding, for reduction wears away and raising product product
Matter suffers from important function.
Current study show that, the dispersion mechanism of coarse whiting ground dispersant is：1 Polymeric polycarboxylate's Molecular Adsorption
On calcium carbonate microparticle surface so as to form electric double layer, which has electrostatic repulsion；2 Polymer adsorptions are in particulate
Surface, plays certain steric hindrance between each particulate.
Most coarse whiting ground dispersants are all the polycarboxylic acids sodium water solutions of straight chain type in the market, are reacted
Initiator is inorganic sodium salt mostly, is used mostly sodium hydrate aqueous solution, so as in above procedure in N-process
In introduce substantial amounts of free counterion sodium ion, the introducing of free counterion can effectively reduce Coulomb repulsion work
With so as to reducing the performance of dispersant.
Compare the polymer dispersant molecule with traditional straight chain type structure, star polymer, due to its structure
Collateralization, the viscosity that its fluid can be effectively reduced, the more envelope-bulk to weight ratio for increasing polymer, high efficiency
Adsorb on the surface of calcium carbonate microparticle, strengthen the steric effect between particulate, so as to improve dispersive property in ground.Together
When calcium hydroxide or magnesium hydroxide are introduced in N-process, due to the polycarboxylate dispersion in calcium and magnesium
In, the free degree of calcium ions and magnesium ions is low, and has extraordinary compatibility with calcium carbonate grinding system, therefore,
Free counterion effect can be reduced so as to improve the dispersive property of dispersant.
The topmost synthetic method of traditional dispersant is traditional solution free radical polymerization.But synthesized by the method
Polymer molecular weight distribution is very wide and poor to molecular weight controlling.According to the literature, the molecular weight of dispersant
And its be distributed for its dispersion effect has a very big impact.J.Loiseau[Macromolecules 2003,36,
3066-3077] result of study show, be close to the monodispersed Sodium Polyacrylate of molecular weight than polydisperse polypropylene
Sour sodium has more preferable peptizaiton, and the former can be adsorbed onto on the surface of calcium carbonate particle with irreversible whole,
So as to reach dispersion calcium carbonate well；And the latter can only partial selective be adsorbed onto calcium carbonate particle surface,
The utilization ratio of dispersant is substantially reduced, or even precipitation occurs.
Reversible-addition-fracture chain tra nsfer (RAFT) polymerization is a kind of excellent activity-control polymerization, should
Method can effectively synthesize the polymer of mesh molecular weight, can be accurately obtained mesh by the regulation to reaction condition
Mark the polymer of molecular weight and while can ensure that very narrow molecular weight distribution.Reactions steps are simple, reaction condition
It is gentleer.Therefore, inventor by analysis and experiment, decision adopt RAFT methods to prepare a kind of efficient coarse whiting
Grinding distribution agent.
The content of the invention
In order to overcome above-mentioned problems of the prior art, a first aspect of the present invention, there is provided a kind of
The preparation method of four arm star structure high-efficiency coarse whiting ground dispersants, the reaction expression of the method key step are as follows
It is shown：
Reaction expression (I)
Methods described comprises the steps：
(1) with 1:4 mol ratio adds two thio benzoyloxy of pentaerythrite and 4- cyano group -4- toward solvent
Valeric acid, adds water absorbing agent DCC and catalyst DMAP, under certain reaction temperature after reaction a period of time,
Concentrated and simple pillar layer separation obtains four arm RAFT agent pentaerythrites, four 4- cyano group -4-, two sulphur
For benzoyloxy valerate；
(2) vinyl carboxylic acid monomer, four 4- cyano group -4- of pentaerythrite, two thio benzoxies are added in a solvent
Base valerate, initiator, and nitrogen bubble certain hour at low temperature, sealing；
(3) it is heated to uniform temperature reaction a period of time；
(4) reaction is distilled off solvent after terminating；
(5) pH for adding one or more neutralization aqueous slkali regulation systems is 5～8, adds water regulation
Solid content is to 20%～50%, you can obtain high-efficiency coarse whiting ground dispersant.
Preferably, in the step (1), the mol ratio of following material is [pentaerythrite]：[4- cyano group -4- two
Thio benzoyloxy valeric acid]：[DCC]：[DMAP]=1:4:0.5:0.1, the solvent be dichloromethane, institute
It is room temperature to state reaction temperature, and the reaction is 6～12 hours for a period of time.
Preferably, in the step (2), the mass fraction of each reactant is as follows：
30～100 parts of vinyl carboxylic acid monomer
0.1～2 part of four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valerates
0.01～2 part of initiator
Also, the consumption of solvent causes the concentration of vinyl carboxylic acid monomer to remain 1～8mol/L.
Preferably, in the step (2), the bubbling certain hour is 15-30 minutes；The step (3)
In, the temperature is 60～80 DEG C, and described reaction a period of time is 8 to 16 hours.
Preferably, in the step (5), the neutralization alkali is calcium hydroxide and magnesium hydroxide, and institute
The addition of calcium hydroxide and magnesium hydroxide is stated according to following mass fraction：
0～100 part of calcium hydroxide
0～100 part of magnesium hydroxide
It is further preferred that the vinyl carboxylic acid monomer is acrylic acid or methacrylic acid.
It is further preferred that the initiator is selected from azodiisobutyronitrile, ABVN, two isobutyl of azo
One or more in base valeric acid, dibenzoyl peroxide, cyclohexanone peroxide, TBHP.
It is further preferred that the solvent is selected from tetrahydrofuran, benzene, toluene, DMF, second
One or more in benzene, dimethylbenzene, 1,4- dioxane.
In addition, above all of mass fraction is 100% calculating according to raw material effective content and indicates, it is real
Actually active content conversion of the border used in amounts according to raw material.
A second aspect of the present invention, there is provided a kind of to adopt the efficient coarse whiting of four arm star structures obtained in said method
Grinding distribution agent.
A third aspect of the present invention, there is provided above-mentioned four arms star structure high-efficiency coarse whiting ground dispersant is ultra-fine heavy
Application in the wet grinding production of calcium.
Certainly, the dispersant for being obtained according to said method, can be not only used for coarse whiting ground, it can also be used to fine particle calcium carbonate point
Dissipate.Gained calcium carbonate superfine powder can be used for papermaking, coating, plastics, rubber, fluid sealant, medicine, food and
The fields such as cosmetics.
The present invention synthesizes four arm star structures using the method that reversible-addition-fracture chain tra nsfer (RAFT) is polymerized
Molecule the polyvinyl carboxylic acid that molecular weight amount is controllable, molecular weight distribution is narrower, then in N-process introduce
Alkali calcium hydroxide/magnesium hydroxide is so as to obtaining polyvinyl carboxylate high-efficiency coarse whiting ground dispersant.The method is closed
Into four arm star structure polymer efficiently can adsorb on calcium carbonate microparticle surface, the steric hindrance produced after absorption
Effect is big, so better than traditional straight chain type polycarboxylic acids on dispersion effect, simultaneously synthesizing method with it is traditional
It is narrower for molecular weight controllable precise, molecular weight distribution that advantage is compared in radical polymerization, is not introduced certainly in elicitation procedure
By counter ion.Used in N-process, calcium hydroxide/magnesium hydroxide, effectively reduces free counterion pair
The impact of calcium carbonate dispersion system, comprehensive above feature, the dispersant that the method is obtained have excellent performance.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following enforcement
Mode.
A kind of a first aspect of the present invention, there is provided preparation side of four arms star structure high-efficiency coarse whiting ground dispersant
Method, comprises the steps：
(1) with 1:4 mol ratio adds two thio benzoyloxy of pentaerythrite and 4- cyano group -4- toward solvent
Valeric acid, adds water absorbing agent DCC and catalyst DMAP, under certain reaction temperature after reaction a period of time,
Concentrated and simple pillar layer separation obtains four arm RAFT agent pentaerythrites, four 4- cyano group -4-, two sulphur
For benzoyloxy valerate；
(2) vinyl carboxylic acid monomer, four 4- cyano group -4- of pentaerythrite, two thio benzoxies are added in a solvent
Base valerate, initiator, and nitrogen bubble certain hour at low temperature, sealing；
(3) it is heated to uniform temperature reaction a period of time；
(4) reaction is distilled off solvent after terminating；
(5) pH for adding one or more neutralization aqueous slkali regulation systems is 5～8, adds water regulation
Solid content is to 20%～50%, you can obtain high-efficiency coarse whiting ground dispersant.
In a preferred embodiment, in the step (1), the mol ratio of following material is [pentaerythrite]：
[two thio benzoyloxy valeric acids of 4- cyano group -4-]：[DCC]：[DMAP]=1:4:0.5:0.1, the solvent is two
Chloromethanes, the reaction temperature are room temperature, and the reaction is 6～12 hours for a period of time.
In a preferred embodiment, in the step (2), the mass fraction of each reactant is as follows：
30～100 parts of vinyl carboxylic acid monomer
0.1～2 part of four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valerates
0.01～2 part of initiator
Also, the consumption of solvent causes the concentration of vinyl carboxylic acid monomer to remain 1～8mol/L.
In a preferred embodiment, in the step (2), the bubbling certain hour is 15-30 point
Clock；In the step (3), the temperature is 60～80 DEG C, and described reaction a period of time is 8 to 16 hours.
In a preferred embodiment, in the step (5), the neutralization alkali is calcium hydroxide and hydrogen
Magnesia, and the addition of the calcium hydroxide and magnesium hydroxide is according to following mass fraction：
0～100 part of calcium hydroxide
0～100 part of magnesium hydroxide
In a further preferred embodiment, the vinyl carboxylic acid monomer is acrylic acid or metering system
Acid.
In a further preferred embodiment, the initiator is selected from azodiisobutyronitrile, two different heptan of azo
In nitrile, azo diisobutyl valeric acid, dibenzoyl peroxide, cyclohexanone peroxide, TBHP
One or more.
In a further preferred embodiment, the solvent is selected from tetrahydrofuran, benzene, toluene, N, N-
One or more in dimethylformamide, ethylbenzene, dimethylbenzene, 1,4- dioxane.
A second aspect of the present invention, there is provided a kind of to adopt the efficient coarse whiting of four arm star structures obtained in said method
Grinding distribution agent.
A third aspect of the present invention, there is provided above-mentioned four arms star structure high-efficiency coarse whiting ground dispersant is ultra-fine heavy
Application in the wet grinding production of calcium.
The preparation of four arm star polyacrylates of 1 low-molecular-weight narrow ditribution of embodiment
Two thio benzoyloxy valeric acids of pentaerythrite 1.36g, 4- cyano group -4- are added in 200g dichloromethane
12.0g, adds 3g water absorbing agent dicyclohexylcarbodiimides (DCC) and 0.54g catalyst 4- dimethylaminos
Pyridine (DMAP).After reacting 8 hours under room temperature, concentrated and simple pillar layer separation obtains four arm RAFT
Four 4- cyano group -4- of chain-transferring agent pentaerythrite, two thio benzoyloxy valerate 12.97g.Hold in reaction again afterwards
Four 4- cyano group -4- of dithioesters chain-transferring agent pentaerythrite, two thio benzoyloxy valerates are added in device
8.07g, initiator azodiisobutyronitrile 1.71g, solvent dioxane 288.0g and monomeric acrylic 172g.
System is sealed with after nitrogen bubble 20 minutes, is reacted 12 hours under the conditions of being warming up to 70 DEG C afterwards.Reaction knot
By resulting solution vacuum distillation after beam, after removing solvent, plus a small amount of water dilution, add mol ratio [hydroxide
Calcium]:[magnesium hydroxide]=2:It is 6.89 that 1 neutralization alkali mixing suspension adjusts pH, and the regulation polymer that adds water
Solution solid content is 25%, obtains final dispersant sample.Gained dispersant number-average molecular weight is 6420,
Molecular weight distributing index is 1.25.
The preparation of four arm star poly-methyl acrylates of 2 low-molecular-weight narrow ditribution of embodiment：
Two thio benzoyloxy valeric acids of pentaerythrite 1.91g, 4- cyano group -4- are added in 250g dichloromethane
16.8.0g, 4.2g water absorbing agent dicyclohexylcarbodiimides (DCC) and 0.76g catalyst 4- diformazans are added
Aminopyridine (DMAP).After reacting 8 hours under room temperature, concentrated and simple pillar layer separation obtains four
Four 4- cyano group -4- of arm RAFT agent pentaerythrite, two thio benzoyloxy valerate 17.81g.Afterwards again
Four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valeric acid 10.45g are added in quartz reaction container, is drawn
Send out agent azodiisobutyronitrile 2.34g, solvents tetrahydrofurane 400.21g and monomer methacrylic acid 215.00g.
System is sealed with after nitrogen bubble 20 minutes, is reacted 8 hours under the conditions of being warming up to 80 DEG C afterwards.Reaction terminates
Afterwards by resulting solution vacuum distillation, after removing solvent, plus a small amount of water dilution, add mol ratio [hydroxide
Calcium]:[magnesium hydroxide]=1:It is 7.11 that 1 neutralization alkali mixing suspension adjusts pH, and the regulation polymer that adds water
Solution solid content is 25%, obtains final dispersant sample.Gained dispersant number-average molecular weight is 5620,
Molecular weight distributing index is 1.21.
The preparation of the four arm stars poly- (PAA-co- methacrylates) of 3 low-molecular-weight narrow ditribution of embodiment
Two thio benzoyloxy valeric acids of pentaerythrite 1.09g, 4- cyano group -4- are added in 200g dichloromethane
10.8g, adds 2.4g water absorbing agent dicyclohexylcarbodiimides (DCC) and 0.43g catalyst 4- diformazan ammonia
Yl pyridines (DMAP).After reacting 8 hours under room temperature, concentrated and simple pillar layer separation obtains four arms
Four 4- cyano group -4- of RAFT agent pentaerythrite, two thio benzoyloxy valerate 10.98g.Exist again afterwards
Four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valeric acid 7.22g, initiator are added in quartz reaction container
ABVN 1.91g, solvent Isosorbide-5-Nitrae-dioxane 322.24g and monomer methacrylic acid 112.0g, third
Olefin(e) acid 90.23g.System is sealed with after nitrogen bubble 20 minutes, reacts 16 under the conditions of being warming up to 65 DEG C afterwards
Hour.React by resulting solution vacuum distillation after terminating, after removing solvent, plus a small amount of water dilution, add and rub
You are than [calcium hydroxide]:[magnesium hydroxide]=1:It is 7.01 that 2 neutralization alkali mixing suspension adjusts pH, and plus
It is 25% that water adjusts polymer solution solid content, obtains final dispersant sample.The equal molecule of gained dispersant number
Measure as 8320, molecular weight distributing index is 1.37.
Grinding effect is detected
(United States Patent (USP) 20020019329A1 will be pressed according to dispersant obtained in embodiment 1～3 and control sample
Dispersant prepared by disclosed method, number-average molecular weight 4400, and molecular weight distributing index is 1.43) at 98 grades
Carry out in coarse whiting ground using (dispersant admittedly containing be 25%).
The water of amount of calculation is added in 15 liters of grinding pots, stirring is opened, the dispersant of amount of calculation, stirring is added
Add the powdered whiting powder of amount of calculation, grinding to discharge after 2 hours after uniform, carry out viscosity and particle size data
The ratio of detection, wherein dispersant dosage and ground slurry other each components is consistent.It is quiet after particle diameter and dispersion
Only 1 hour viscosity data is as follows：
Table 1
Can be seen that from the data result of table 1：The grinding of the dispersant prepared using the embodiment of the present invention 1～3
Effect will be substantially better than control sample dispersant.
Above the specific embodiment of the present invention has been described in detail, but, which is intended only as example, this
It is bright to be not restricted to particular embodiments described above.To those skilled in the art, it is any to the present invention
The equivalent modifications for carrying out and replacement are also all among scope of the invention.Therefore, in the essence without departing from the present invention
The impartial conversion made under god and scope and modification, should all cover within the scope of the invention.
Claims (10)
1. a kind of preparation method of four arms star structure high-efficiency coarse whiting ground dispersant, it is characterised in that comprise the steps:
(1) with 1:4 mol ratio adds two thio benzoyloxy valeric acid of pentaerythrite and 4- cyano group -4- toward solvent, add water absorbing agent DCC and catalyst DMAP, under certain reaction temperature after reaction a period of time, concentrated and simple pillar layer separation obtains four arm RAFT agent pentaerythrites, four 4- cyano group -4-, two thio benzoyloxy valerates；
(2) vinyl carboxylic acid monomer, four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valerates, initiator are added in a solvent, and nitrogen bubble certain hour at low temperature, sealing；
(3) it is heated to uniform temperature reaction a period of time；
(4) reaction is distilled off solvent after terminating；
(5) pH for adding one or more neutralization aqueous slkali regulation systems is 5～8, adds water regulation solid content to 20%～50%, you can obtain high-efficiency coarse whiting ground dispersant.
2. the method according to claims 1, it is characterised in that in the step (1), the mol ratio of following material is [pentaerythrite]：[two thio benzoyloxy valeric acids of 4- cyano group -4-]：[DCC]：[DMAP]=1:4:0.5:0.1, the solvent is dichloromethane, and the reaction temperature is room temperature, and the reaction is 6～12 hours for a period of time.
3. method according to claim 1, it is characterised in that in the step (2), the mass fraction of each reactant is as follows：
30～100 parts of vinyl carboxylic acid monomer
0.1～2 part of four 4- cyano group -4- of pentaerythrite, two thio benzoyloxy valerates
0.01～2 part of initiator
Also, the consumption of solvent causes the concentration of vinyl carboxylic acid monomer to remain 1～8mol/L.
4. method according to claim 1, it is characterised in that in the step (2), the bubbling certain hour are 15-30 minutes；In the step (3), the temperature is 60～80 DEG C, and described reaction a period of time is 8 to 16 hours.
5. method according to claim 1, it is characterised in that in the step (5), the neutralization alkali is calcium hydroxide and magnesium hydroxide, and the addition of the calcium hydroxide and magnesium hydroxide is according to following mass fraction：
0～100 part of calcium hydroxide
0～100 part of magnesium hydroxide.
6. the method according to any one of claim 1-5, it is characterised in that the vinyl carboxylic acid monomer is acrylic acid or methacrylic acid.
7. the method according to any one of claim 1-5, characterized in that, the initiator is selected from one or more in azodiisobutyronitrile, ABVN, azo diisobutyl valeric acid, dibenzoyl peroxide, cyclohexanone peroxide, TBHP.
8. the method according to any one of claim 1-5, it is characterised in that one or more in tetrahydrofuran, benzene, toluene, DMF, ethylbenzene, dimethylbenzene, Isosorbide-5-Nitrae-dioxane of the solvent.
9. the four arm star structure high-efficiency coarse whiting ground dispersants that prepared by the method according to any one of claim 1～8.
10. application of the four arms star structure high-efficiency coarse whiting ground dispersant according to claim 9 in the wet grinding production of ultrafine heavy calcium.
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| CN201510604394.6A CN106543321B (en) | 2015-09-21 | 2015-09-21 | The preparation method and its product of a kind of four arms star structure high-efficiency coarse whiting ground dispersant and application |
| PCT/CN2015/094782 WO2017049750A1 (en) | 2015-09-21 | 2015-11-17 | Method for preparing four-arm star-shaped structure high efficiency heavy calcium carbonate grinding dispersant, product and use thereof |
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| CN201510604394.6A CN106543321B (en) | 2015-09-21 | 2015-09-21 | The preparation method and its product of a kind of four arms star structure high-efficiency coarse whiting ground dispersant and application |
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| CN111440259A (en) * | 2020-04-23 | 2020-07-24 | 济宁明升新材料有限公司 | Multi-branch type dispersing agent and preparation method thereof |
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| CN104017119A (en) * | 2014-06-12 | 2014-09-03 | 东升新材料（山东）有限公司 | Dispersing agent for grinding triple superphosphate with branched structure and preparation method thereof |
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| CN103030729B (en) * | 2012-12-06 | 2015-04-29 | 永港伟方（北京）科技股份有限公司 | Dispersant for grinding heavy calcium carbonate as well as synthetic method and application thereof |
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- 2015-09-21 CN CN201510604394.6A patent/CN106543321B/en active Active
- 2015-11-17 WO PCT/CN2015/094782 patent/WO2017049750A1/en active Application Filing
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| WO2000037168A1 (en) * | 1998-12-18 | 2000-06-29 | 3M Innovative Properties Company | Polyelectrolyte dispersants for hydrophobic particles in water-based systems |
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| EP2657264A1 (en) * | 2010-12-22 | 2013-10-30 | Jiangsu Bote New Materials Co., Ltd | Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant |
| CN103709283A (en) * | 2013-12-17 | 2014-04-09 | 聊城大学 | Honeycomb porous membrane made of four-arm star-shaped polymer and preparation method of honeycomb porous membrane |
| CN104017119A (en) * | 2014-06-12 | 2014-09-03 | 东升新材料（山东）有限公司 | Dispersing agent for grinding triple superphosphate with branched structure and preparation method thereof |
| CN104031190A (en) * | 2014-06-12 | 2014-09-10 | 东升新材料（山东）有限公司 | Preparation of efficient ground calcium carbonate grinding dispersant by photo-initiating room-temperature RAFT (Reversible Additive Fragment Transfer) polymerization |
| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
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| CN111440259A (en) * | 2020-04-23 | 2020-07-24 | 济宁明升新材料有限公司 | Multi-branch type dispersing agent and preparation method thereof |
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| WO2017049750A1 (en) | 2017-03-30 |
| CN106543321B (en) | 2018-11-09 |
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