CN102775546B - Branched polyacrylic acid dispersant, and preparation method and application thereof - Google Patents
Branched polyacrylic acid dispersant, and preparation method and application thereof Download PDFInfo
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- CN102775546B CN102775546B CN201110119702.8A CN201110119702A CN102775546B CN 102775546 B CN102775546 B CN 102775546B CN 201110119702 A CN201110119702 A CN 201110119702A CN 102775546 B CN102775546 B CN 102775546B
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Abstract
The invention discloses a branched polyacrylic acid dispersant, and a preparation method and application thereof. According to the invention, polyene monomers are introduced into molecular chains of a linear sodium polyacrylate dispersant so as to obtain a branched dispersant structure which allows the branched polyacrylic acid dispersant to better clad cross sections newly occurred after grinding, and therefore, grinding and dispersing efficiency is improved; furthermore, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, sodium methylacrylsulfonate, 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and the like are introduced and can provide monomers with stronger negative charges, improve electrostatic repulsion action of double electric layers, mitigate agglomeration among calcium carbonate particles and reduce the viscosity of ground slurry. The dispersant provided by the invention enables high efficiency in grinding of calcium carbonate to be obtained and the slurry to have the characteristics of low viscosity, good dispersibility and stability.
Description
Technical field
The present invention relates to a kind of synthetic polymer carbonic acid calcium wet grinding dispersing agent, especially a kind of for being coated with branched p 0 lypropylene acids dispersion agent of calcium carbonate grinding and its preparation method and application.
Technical background
Water-ground limestone (GCC) is a kind of non-metallic minerals powder of widespread use, and whiteness is high, opacifying power good, mobility is good, is the main source of papermaking coating.Papermaking coating requires high dense low glutinous, makes ground calcium carbonate dispersing become high density to become extremely important.Water-ground limestone for papermaking paint is a kind of subparticle obtaining after wet-milling calcium carbonate, the fineness rank of particle is because of purposes difference difference, as the primary coat GCC of coating can be slightly thick, face is coated with GCC must be tiny, and fineness reaches more than 95% (< 2 μ m).Grain breakage process surface molecular is in nonequilibrium state, and its inside or surface molecular all have magnetism to a certain degree.Further during refinement, the activated surface area of tool can become very large, and now fine particle surface tension is just extended and caught its material around, and more serious along with granularity super-refinement.From thermodynamic (al) angle, because superfine powder has huge specific surface area, its surface can be quite large, causes system in the unsettled thermodynamic state of antipode.And in the miniaturization process of solid, the internal bond strength of small-particle, lattice are constantly destroyed, and particle surface forms many unsaturated link(age)s, and the surfactivity of particle and the total energy of system are constantly increased, make the surface properties of ultrafine powder become more active, must absorption material around.Therefore to reach good grinding rank, must in medium, add dispersion agent with stable particle.
Summary of the invention
In order to solve the dissatisfactory problem of the stabilization of dispersion agent in prior art, one of object of the present invention is to provide a kind of branched p 0 lypropylene acids dispersion agent grinding for being coated with calcium carbonate, its unique molecular chain structure can better be coated grinding the new cross section producing, grinding distribution can be carried out smoothly efficiently, the electrostatic double layer electrostatic repulsion of while dispersion agent of the present invention, can reduce the agglomeration between calcium carbonate granule, reduce the viscosity of slurry.
In order to achieve the above object, the present invention adopts following technical scheme:
Novel branched polyacrylic dispersion agent of the present invention, to be made by the raw material of following mass fraction: Acrylic Acid Monomer is 18～20 parts, comonomer total amount is 5～7 parts, many vinyl monomers are 3～5 parts, alkaline matter 16-18 part, the oxygenant reductive agent summation of initiator system is 2～3 parts, and water is 47-56 part.
Another object of the present invention is to provide a kind of method of preparing described branched p 0 lypropylene acids dispersion agent, and the technical scheme adopting is:
Take vinylformic acid as principal reaction monomer, add one or more monomers in methacrylic acid, maleic anhydride, fumaric acid, methylene-succinic acid, methylpropene sodium sulfonate, AMPS (2-acrylamide-2-methyl propane sulfonic) as comonomer, add in addition many vinyl monomers, take redox system as initiator system, by aqueous solution polymerization, form, finally with alkaline matter, neutralize.
Concrete, by following operation steps, undertaken:
(1) reductive agent of a certain amount of water and initiator system is added in reactor as bed material to stirring and dissolving;
(2) by Acrylic Acid Monomer, comonomer, many vinyl monomers, a certain amount of water wiring solution-forming, and neutralize with alkaline matter, then add the residue reductive agent of initiator system to be made into dropping liquid A;
(3) oxygenant of initiator system, a certain amount of water are made into dropping liquid B;
(4) solution A, B are taked the mode of dropping join in the described reactor of step (1), then carry out polyreaction, after reaction finishes, cooling, finally with alkaline matter neutralization, blowing.
Wherein, the many vinyl monomers that add described in are a kind of in pentaerythritol triacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, Vinylstyrene, Viscoat 335HP or their combination.
Wherein, described initiator system is one or both compound uses in Sodium Persulfate-inferior sodium phosphate system, ammonium persulfate-sodium bisulfite, hydrogen peroxide-ferrous sulfate system; Oxygenant in described initiator system and the part by weight of reductive agent are 1: 2-1.25: 2.
Wherein, raw materials used mass fraction is: Acrylic Acid Monomer is 18～20 parts, and comonomer total amount is 5～7 parts, and many vinyl monomers are 3～5 parts, alkaline matter 16-18 part, and the oxygenant reductive agent summation of initiator system is 2～3 parts, water is 47-56 part.
Wherein, described alkaline matter is sheet alkali, and the alkaline solution that is made into 40-45% is used; With in it and pH be 4-5.
Wherein, the temperature of described polyreaction is 80-87 ℃; The time of described dropping is 5-5.5h; Described polymerization reaction time is 1-1.5h.
With aforesaid method, can prepare the branched p 0 lypropylene acids dispersion agent grinding for being coated with calcium carbonate of the presently claimed invention.
Prepared dispersion agent can be using it as wet-milling calcium carbonate application of dispersant.
Preparation technology of the present invention, it is owing to adopt dripping synthesis technique, and reaction process heat release is few, reacting balance, temperature of reaction is low, and technological process is simple, and reaction reaches the blowing of lowering the temperature after requirement, industrial can well realization.
Specific implementation method
Below in conjunction with specific embodiment and comparative example, the inventive method and advantage are made to further comparative descriptions.
The preparation of novel branched polyacrylic dispersion agent is carried out according to the following steps:
(1) reductive agent of a certain amount of water and initiator system is added in reactor as bed material to stirring and dissolving;
(2) by Acrylic Acid Monomer, comonomer, many vinyl monomers, a certain amount of water wiring solution-forming, and with alkaline matter, to be neutralized to pH be 4 left and right, then add the residue reductive agent of initiator system to be made into dropping liquid A;
(3) oxygenant of initiator system, a certain amount of water are made into dropping liquid B;
(4) solution A, B are taked at a certain temperature the mode of dropping join within a certain period of time in the described reactor of step (1), react again for some time stopped reaction, be cooled to below 50 ℃, with alkaline matter, being neutralized to pH is 5 left and right, blowing.
Wherein, the time of dropping is 5-5.5h; The temperature of polyreaction is 80-87 ℃; Polymerization reaction time is 1-1.5h.
The consumption of embodiment medicine and the product obtaining are as following table:
The preparation of calcium carbonate slurry:
With the dispersion agent of embodiment of the present invention 1-5 and commercially available sodium polyacrylate dispersion agent grinding distribution under same technique as a comparison case.
Dispersing Technology:
In the steel basin of 100kg, add kg premium on currency, open stirring, add dispersion agent 260g, stir, add 325 order calcium carbonate 75kg to carry out pre-dispersed, after being uniformly dispersed, with being pumped in the shredder of two series connection, grinding medium is zirconium pearl.After grinding 1h, add 240g dispersion agent.Both continue to grind after 6h to obtain heavy calcium carbonate slurry, obtain solid content and be 75% slurry.
Adopt ISO2884-2-2003 standard regulation, with NDJ-1 type rotational viscosimeter, recording slurry viscosity is 231cps.Particle diameter is tested by particle instrument.Each sample data in Table:
Under same grinding condition, use the dispersion agent of embodiment of the present invention 1-5 as can be seen from the above table, slurry viscosity is low, and particle diameter is little, good dispersity and more stable.
The foregoing is only preferred embodiment of the present invention, is only illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and in the spirit and scope that limit, can carry out many changes to it in the claims in the present invention, revise, and even equivalence, but all will fall within the scope of protection of the present invention.
Claims (8)
1. the preparation method of a branched p 0 lypropylene acids dispersion agent, to take vinylformic acid as principal reaction monomer, add one or more monomers in methacrylic acid, maleic anhydride, fumaric acid, methylene-succinic acid, methylpropene sodium sulfonate, AMPS as comonomer, add in addition many vinyl monomers, take redox system as initiator system, by aqueous solution polymerization, form, with alkaline matter, neutralize;
Above-mentioned preparation method's concrete steps are as follows:
(1) reductive agent of a certain amount of water and initiator system is added in reactor as bed material to stirring and dissolving;
(2) by Acrylic Acid Monomer, comonomer, many vinyl monomers, a certain amount of water wiring solution-forming, and neutralize with alkaline matter, then add the residue reductive agent of initiator system to be made into dropping liquid A;
(3) oxygenant of initiator system, a certain amount of water are made into dropping liquid B;
(4) solution A, B are taked the mode of dropping join in the described reactor of step (1), then carry out polyreaction, after reaction finishes, cooling, finally with alkaline matter neutralization, blowing;
Wherein, in above-mentioned preparation method, the mass fraction of each raw material is: Acrylic Acid Monomer is 18～20 parts, and comonomer total amount is 5～7 parts, many vinyl monomers are 3～5 parts, alkaline matter 16-18 part, the oxygenant reductive agent summation of initiator system is 2～3 parts, water is 47-56 part.
2. preparation method according to claim 1, the many vinyl monomers that add described in it is characterized in that are a kind of in pentaerythritol triacrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, Vinylstyrene, Viscoat 335HP or their combination.
3. preparation method according to claim 1, is characterized in that described initiator system is one or both compound uses in Sodium Persulfate-inferior sodium phosphate system, ammonium persulfate-sodium bisulfite, hydrogen peroxide-ferrous sulfate system; Oxygenant in described initiator system and the part by weight of reductive agent are 1:2-1.25:2.
4. preparation method according to claim 1, is characterized in that described alkaline matter is sheet alkali, and the alkaline solution that is made into 40-45% is used.
5. preparation method according to claim 1, is characterized in that by alkaline matter neutralization solution pH value be 4-5.
6. preparation method according to claim 1, is characterized in that the temperature of described polyreaction is 80-87 ℃; The time of described dropping is 5-5.5h; The described reaction times is 1-1.5h.
7. the dispersion agent of preparing according to method described in claim 1-6 any one.
8. the application of dispersion agent according to claim 7 is the dispersion agent using it as wet-milling calcium carbonate.
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| CN201110119702.8A CN102775546B (en) | 2011-05-10 | 2011-05-10 | Branched polyacrylic acid dispersant, and preparation method and application thereof |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN103894108B (en) * | 2012-12-28 | 2016-04-13 | 南通市晗泰化工有限公司 | Block type aqueous high molecular dispersant |
| CN103275264A (en) * | 2013-05-08 | 2013-09-04 | 中科院广州化学有限公司 | Water reducing agent capable of reducing viscosity of slurry as well as preparation method and application thereof |
| CN104017119B (en) * | 2014-06-12 | 2016-08-17 | 东升新材料（山东）有限公司 | Branched structure coarse whiting ground dispersant and preparation method thereof |
| CN105859941A (en) * | 2016-02-26 | 2016-08-17 | 宁波市嘉化新材料科技有限公司 | Dispersion type rheological agent |
| CN105837729A (en) * | 2016-02-26 | 2016-08-10 | 宁波市嘉化新材料科技有限公司 | Dispersing 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 |
| CN112645625B (en) * | 2019-10-12 | 2022-07-05 | 中国石油化工股份有限公司 | Composite oil well cement polycarboxylic acid dispersant, and preparation method and application thereof |
| CN112724308B (en) * | 2020-12-31 | 2023-03-10 | 九洲生物技术（苏州）有限公司 | Dispersant, grinding dispersant and coating for papermaking coating |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1286275A (en) * | 1999-08-31 | 2001-03-07 | 中国石油化工集团公司 | Process for preparing graft copolymerization type non-ash disperser |
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| GB0910722D0 (en) * | 2009-06-22 | 2009-08-05 | Unilever Plc | Branched polymer dispersants |
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| CN1286275A (en) * | 1999-08-31 | 2001-03-07 | 中国石油化工集团公司 | Process for preparing graft copolymerization type non-ash disperser |
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| "丙烯酸类聚合物分散剂的制备";王春晓等;《河北化工》;20041231(第3期);5-9 * |
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Effective date of registration: 20180906 Address after: 225300 Pearl River Road, Yongan Town, Taizhou, Jiangsu Province, 108 Patentee after: Gai Nannan Address before: 100080 Silver Tower 716, Haidian Avenue, Haidian District, Beijing 716 Patentee before: Everfirst Wisefund (Beijing) Technology Co., Ltd. |
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