CN102212161B - Dispersant for wet grinding superfine calcium carbonate and its preparation method and application - Google Patents
Dispersant for wet grinding superfine calcium carbonate and its preparation method and application Download PDFInfo
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- CN102212161B CN102212161B CN2011101075552A CN201110107555A CN102212161B CN 102212161 B CN102212161 B CN 102212161B CN 2011101075552 A CN2011101075552 A CN 2011101075552A CN 201110107555 A CN201110107555 A CN 201110107555A CN 102212161 B CN102212161 B CN 102212161B
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- calcium carbonate
- dispersant
- preparation
- wet grinding
- oxidizing agent
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 74
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 37
- 238000001238 wet grinding Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 239000007800 oxidant agent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 claims abstract 6
- 230000001590 oxidative effect Effects 0.000 claims abstract 5
- 238000010438 heat treatment Methods 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 46
- 239000007788 liquid Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 40
- 239000000843 powder Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008676 import Effects 0.000 description 5
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 235000019394 potassium persulphate Nutrition 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- -1 ZX-I) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001033 granulometry Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a dispersant used for wet grinding of ultrafine calcium carbonate, and a preparation method and application thereof. The preparation method of the dispersant comprises the following steps of: mixing a reducing agent and a monomer mixture, and heating to 65-75 DEG C; dropwise adding an oxidant solution within 0.5-1 hour; simultaneously dropwise adding the oxidant solution and residual monomer mixture within 2-3 hours; heating to 75-85 DEG C, adding residual oxidant solution, and carrying out heat preservation for 0.5-1 hour; and cooling to 20-30 DEG C, and adjusting the pH value to 5-6 to obtain the dispersant used for wet grinding of ultrafine calcium carbonate. The dispersant provided by the invention can improve the dispersion property of ultrafine heavy calcium carbonate, and particularly reduce the viscosity of an dispersion liquid obviously; and the preparation method provided by the invention has simple process and low equipment requirement, saves energy, and facilitates application and popularization.
Description
Technical field
The invention belongs to the papermaking material field, be specifically related to a kind of dispersion agent that is used for the wet grinding calcium carbonate superfine powder and preparation method thereof and application.
Background technology
Along with the develop rapidly of papermaking surface coating technique, to coating pigment require increasingly highly, particularly receive the recipe-imposed of European high carbon acid calcium proportioning; The particle less than 2 μ ms of the granularity of coating level calcium carbonate superfine powder before 10 years accounts for 90% of sum, 98 grades (accounting for 98%) often seeing on the market till now, even 100% all less than 2 μ m; Also require its good fluidity simultaneously; Dispersion liquid viscosity is low, and 2 μ m reach more than 95% like granularity, solid content>=75%; Initial viscosity≤250cp, degree of after-tacking≤350cp (degree of after-tacking is meant and leaves standstill the viscosity that detects behind the 1h).The producer that has, adopting full lime carbonate is pigment, and this just requires more high-quality grinding calcium carbonate, and what require that the size distribution of lime carbonate tries one's best is narrow, reaches more than 90% less than 1 μ m.So high granularity requirements and mobile requirement, calcium carbonate slurry prepare in the process must add suitable dispersion agent.
The action principle of dispersion agent is that behind the adding dispersion agent, particle surface has adsorbed polyelectrolyte.This type of polyelectrolyte is a macromole, is made up of ionogenic group unit.Through absorption dispersion agent (like ZX-I), particle has not only obtained thicker adsorption layer, has improved sterically hindered; And the skeleton heavy ion with electric density higher; Therefore its Effect of Electric Double Layer strengthens, and is used through static, steric hindrance, so viscosity reduces rapidly.Along with the carrying out of grinding; Calcium carbonate granule divides in running foul of each other with grinding medium and becomes more and more thinner; Specific surface area also increases sharply; Produced the increasing section that is not coated by polyelectrolyte, a little less than this part sterically hindered and electrostatic interaction relative thin, the coalescence of wadding a quilt with cotton easily causes viscosity and raises.This just needs constantly to replenish dispersion agent, to guarantee to have enough polyelectrolyte coated caco3 particles.In order to guarantee to grind the covered effect of later stage dispersion agent,, must develop and be different from the novel dispersant that leading portion grinds dispersion agent to the characteristic that back segment grinds to calcium carbonate granule; Characteristics are that relative molecular mass is little; A little less than the adsorptive power, to the tiny coating effect of particle also clearly, wetting action is strong than leading portion also; For the GCC particle section of a large amount of appearance, can bring into play good wetting dissemination.Have certain high-temperature stability simultaneously, along with milling time prolongs, lot of energy converts heat energy into, and the dispersion agent interaction energy was kept when the temperature of GCC slurry was raise.
Commonly used satisfy ZX-I dispersion agent that 90 grades of lime carbonate preparations require and prepare in the process and can not meet the demands, can not meet the demands even increase consumption at fine granularity dispersion liquid more, thereby dispersant special that must exploitation extra-fine grinding calcium carbonate slurry.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of preparation method who is used for the dispersion agent of wet grinding calcium carbonate superfine powder with not enough.
Another object of the present invention is to provide aforesaid method the prepared dispersion agent that obtains.
A purpose more of the present invention is to provide the application of above-mentioned dispersion agent, and it can be used for improving the dispersing property of superfine heavy calcium carbonate, particularly obviously reduces the viscosity of dispersion liquid.
The object of the invention is realized through following technical proposals:
A kind of wet grinding calcium carbonate superfine powder may further comprise the steps with the preparation method of dispersion agent:
(1) it is soluble in water to get oxygenant, is mixed with oxidizing agent solution; Take by weighing total amount again and be oxygenant quality 10-12 monomer mixture doubly, subsequent use;
(2) the preparation reductive agent aqueous solution adds 1/5 of monomer mixture total amount, is heated to 65-75 ℃;
(3) in step (2) reaction system, add 1/5 of oxidizing agent solution total mass, dripped in 0.5-1 hour;
(4) in step (3) reaction system 3/5 of dropping oxidizing agent solution total mass with remaining monomer mixture, drip in 2-3 hour;
(5) with step (4) reaction system heat temperature raising to 75-85 ℃, add remaining oxidizing agent solution, soaking time 0.5-1 hour;
(6) treat that step (5) reaction system is cooled to 20-30 ℃, regulate its pH value to 5～6, promptly get the wet grinding calcium carbonate superfine powder and use dispersion agent;
The mass concentration of oxygenant is 11.1-16.7% in the described oxidizing agent solution;
The mass concentration of reductive agent is 0.5-4% in the described reductive agent aqueous solution;
The consumption of the said reductive agent of step (2) is the 0.2-4% of monomer total mass;
Described oxygenant is a kind of in ydrogen peroxide 50, ammonium persulphate or the Potassium Persulphate;
Described reductive agent is a kind of in ferrous sulfate, sodium sulfite anhy 96, S-WAT or the inferior sodium phosphate;
Described monomer mixture is made up of Acrylic Acid Monomer and function monomer, is preferably Acrylic Acid Monomer and function monomer and obtains by mass ratio 100: 10～25 mixing;
Described function monomer is preferably at least a in acrylic amide, maleic anhydride, fumaric acid, methylene-succinic acid, methylacrylic acid or the USAF RH-1.
Described water is meant deionized water.
A kind of dispersion agent that is used for the wet grinding calcium carbonate superfine powder is prepared from above-mentioned preparation method.
The wet grinding calcium carbonate superfine powder process that is used for dispersion agent of the present invention reduce lime carbonate viscosity, improve its flowability.
The present invention has following advantage and effect with respect to prior art:
(1) dispersion agent of the present invention can improve the dispersing property of superfine heavy calcium carbonate, particularly obviously reduces the viscosity of dispersion liquid.
(2) preparation method of dispersion agent of the present invention is simple, low with equipment requirements, and saves energy consumption, helps applying.
Description of drawings
Fig. 1 is the size-grade distribution of sample A dispersion liquid.
Fig. 2 is the size-grade distribution of sample B dispersion liquid.
Fig. 3 is the size-grade distribution of import dispersion agent dispersion liquid.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described in further detail, but embodiment of the present invention is not limited thereto.
A kind of wet grinding calcium carbonate superfine powder may further comprise the steps with the preparation method of dispersion agent:
(1) gets ydrogen peroxide 50 10 grams and be dissolved in the 80 gram deionized waters, be mixed with oxidizing agent solution;
(2) take by weighing the monomer (wherein acrylic amide 13 gram, maleic anhydride 7 grams, vinylformic acid 100 grams) of 120 grams, mix;
(3) in four-hole bottle, add the deionized water that ferrous sulfate 0.5 gram and 100 restrains, the preparation reductive agent aqueous solution adds 1/5 of monomer total mass again, is heated to 70 ℃;
(4) in four-hole bottle 1/5 of dropping oxidizing agent solution total mass, drip off in the 30min;
(5) in four-hole bottle, add oxidizing agent solution total mass 3/5 and remaining monomer, drip off in the 3h;
(6) be warming up to 75 ℃, add remaining oxidizing agent solution, soaking time is 1h;
(7) be cooled to 25 ℃ after, using mass concentration is 40% sodium hydroxide solution neutralization reaction system pH to 5～6, promptly gets the wet grinding calcium carbonate superfine powder and uses dispersion agent, is sample A.
Embodiment 2
A kind of wet grinding calcium carbonate superfine powder may further comprise the steps with the preparation method of dispersion agent:
(1) gets ammonium persulphate 10 grams and be dissolved in the 50 gram deionized waters, be mixed with oxidizing agent solution;
(2) take by weighing the monomer (vinylformic acid 100 gram, methylene-succinic acid 10 grams) of 110 grams, mix;
(3) in four-hole bottle, add the deionized water that sodium sulfite anhy 96 5 grams and 120 restrain, the preparation reductive agent aqueous solution adds 1/5 of monomer total mass again, is heated to 65 ℃;
(4) in four-hole bottle 1/5 of dropping oxidizing agent solution total mass, drip off in the 1h;
(5) in four-hole bottle, add oxidizing agent solution total mass 3/5 and remaining monomer simultaneously, drip off in the 2h;
(6) be warming up to 85 ℃, add remaining oxidizing agent solution, soaking time is 0.5h;
(7) be cooled to 30 ℃, the use mass concentration is 40% sodium hydroxide solution neutralization reaction system pH to 5～6, promptly gets the wet grinding calcium carbonate superfine powder and uses dispersion agent, is sample B.
Embodiment 3
A kind of wet grinding calcium carbonate superfine powder may further comprise the steps with the preparation method of dispersion agent:
(1) gets Potassium Persulphate 10 grams and be dissolved in the 50 gram deionized waters, be mixed with oxidizing agent solution;
(2) take by weighing the monomer (vinylformic acid 80 gram, USAF RH-1 9 grams, methylacrylic acid 8 grams, fumaric acid 3 grams) of 100 grams, mix;
(3) in four-hole bottle, add the deionized water that inferior sodium phosphate 5 grams and 120 restrain, the preparation reductive agent aqueous solution adds 1/5 of monomer total mass again, is heated to 75 ℃;
(4) in four-hole bottle 1/5 of dropping oxidizing agent solution total mass, drip off in the 30min;
(5) in four-hole bottle, add oxidizing agent solution total mass 3/5 and remaining monomer simultaneously, drip in the 2.5h;
(6) be warming up to 80 ℃, add remaining oxidizing agent solution, soaking time is 1h;
(7) be cooled to 20 ℃ after, using mass concentration is 40% sodium hydroxide solution neutralization reaction system pH to 5～6, promptly gets the wet grinding calcium carbonate superfine powder and uses dispersion agent, is sample C.
Above-mentioned sample is to the dispersion effect of superfine heavy calcium carbonate.The imported product (French DC dispersion agent) that adopts factory to use now compares, and adopts high speed dispersor 5000rpm to disperse 30 minutes, and raw material adopts the industrial extra fine heavy calcium carbonate powder of 1250 orders, and dispersion results is represented as follows.The result shows that the dispersion effect of sample A, B, C is better than import dispersion agent, especially on degree of after-tacking.
Sample A/B/C and import appearance are to 70% solid content ultrafine heavy calcium viscosity and degree of after-tacking contrast (viscosity unit: cp)
Wherein the dispersion liquid granulometry result of sample A and sample B and import dispersion agent is shown in Fig. 1-3.Find out obviously among the figure that sample A and B are thinner than the particle of import dispersion agent gained dispersion liquid, especially sample A.Explain that dispersion agent of the present invention is to disperseing thinner lime carbonate better effects if.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
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| CN2011101075552A CN102212161B (en) | 2011-04-28 | 2011-04-28 | Dispersant for wet grinding superfine calcium carbonate and its preparation method and application |
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| EP2910609B1 (en) * | 2014-02-21 | 2017-08-16 | Omya International AG | Process for the preparation of a calcium carbonate filler product |
| CN106749901A (en) * | 2015-11-20 | 2017-05-31 | 衡阳市银利实业有限公司 | A kind of method for preparing anti-chamotte mould cement water reducing agent |
| CN106746875A (en) * | 2015-11-20 | 2017-05-31 | 衡阳市银利实业有限公司 | Anti- chamotte mould cement water reducing agent |
| CN107540778B (en) * | 2017-08-31 | 2020-12-01 | 湖北工业大学 | Preparation method of low molecular weight anionic polymer dispersant for wet grinding |
| CN107649068B (en) * | 2017-08-31 | 2020-01-14 | 湖北工业大学 | Low-molecular-weight cationic polymer dispersant for wet grinding and preparation method thereof |
| CN108383938A (en) * | 2018-01-31 | 2018-08-10 | 郑州大学 | A kind of titanium dioxide hyper-dispersant preparation method and application |
| CN111206453A (en) * | 2020-02-26 | 2020-05-29 | 济宁明升新材料有限公司 | Efficient composite dispersant and preparation method thereof |
| CN115785324A (en) * | 2023-02-09 | 2023-03-14 | 广东壮丽彩印股份有限公司 | Preparation method of dispersing agent for nano calcium carbonate |
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|---|---|---|---|---|
| CN1563120A (en) * | 2004-03-25 | 2005-01-12 | 陕西科技大学 | Method for preparing dispersant for filling material in papermaking made from copolymer in ethylene group |
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| CN1563120A (en) * | 2004-03-25 | 2005-01-12 | 陕西科技大学 | Method for preparing dispersant for filling material in papermaking made from copolymer in ethylene group |
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| 伦俊文.超细碳酸钙研磨及分散剂的选择.《造纸化学品》.2006,第18卷(第4期),全文. * |
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