CN102516449A - Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization - Google Patents
Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization Download PDFInfo
- Publication number
- CN102516449A CN102516449A CN2011103753305A CN201110375330A CN102516449A CN 102516449 A CN102516449 A CN 102516449A CN 2011103753305 A CN2011103753305 A CN 2011103753305A CN 201110375330 A CN201110375330 A CN 201110375330A CN 102516449 A CN102516449 A CN 102516449A
- Authority
- CN
- China
- Prior art keywords
- vinyl
- salt
- dispersing agent
- solvent
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention provides a salt resistance dispersing agent and a preparation method for preparing the same by adopting the light initiated polymerization. The preparation method comprises the following steps of: (1) performing the reaction on transition metal halide, a solvent and 2,2'-dipyridyl in the solvent in the nitrogen atmosphere to obtain complex solution; (2) then adding a mixed monomer and a photoinitiator and irradiating by ultraviolet rays to perform the reaction, wherein the mixed monomer is a mixture of vinylacetate and vinyl carboxylic ester; (3) processing by an alumina column, mixing the obtained solution with caustic soda solution and hydrolyzing to obtain poly (vinyl carboxyl-co-vinyl alcohol) sodium salt; and (4) distilling to remove the solvent, acetic acid and alcohol by-products, adding the NaOH solution to regulate the pH into 4 to 8 and regulating the weight solid content into 41 to 43 percent to obtain the salt resistance dispersing agent. The product provided by the invention is pure, is simple to operate, has narrow molecular weight distribution and has a god dispersing effect and salt resistance in the grinding and dispersing process of calcium carbonate.
Description
Technical field
The present invention relates to a kind of calcium carbonate superfine powder dispersive salt-tolerance dispersing agent and preparation method thereof that is used for.
Background technology
Lime carbonate is widely used in production, processing and the application of papermaking, coating, rubber, plastics, printing ink, medicine, food, feed, makeup etc. as a kind of very important inorganic chemical industry filler.The lime carbonate granularity is thinner, solid content is high more, and viscosity is just high more during grinding, and anti-sticking also more severe after grinding, therefore, the adding dispersion agent is necessary when grinding and disperse lime carbonate.The raising that Along with people's requires quality product is to the also raising day by day of requirement of the solid content of lime carbonate fineness and homogeneity and calcium carbonate slurry.For the production of high-level lime carbonate, it is particularly important that the effect of dispersion agent seems.
The molecular weight of dispersion agent and distribution thereof have very big influence for its dispersion effect.[Macromolecules 2003 for J.Loiseau; 36; 3066-3077] result of study show; Have better dissemination near the monodispersed ZX-I of molecular weight than polydisperse ZX-I, the former can irreversibly all be adsorbed onto the surface of calcium carbonate particles, thereby disperses lime carbonate well; And the latter can only part optionally be adsorbed onto the calcium carbonate particles surface, and the utilising efficiency of dispersion agent reduces greatly.The ZX-I type dispersion agent overwhelming majority all is to be made by general solution free radical polymerization at present.Common radical polymerization institute synthetic molecular weight distribution is very wide.Present commercial dispersants be used to grind often take place when disperseing high-level lime carbonate serious anti-sticking.
Free counterion has remarkably influenced for the effect of dispersion agent.At present general dispersion agent is all more weak for the resistibility of the influence of free ion, therefore is difficult to adapt to the grinding and the decentralized environment of more complicated.In addition; Ground calcium carbonate superfine powder; If use under or the environment that free counterion concentration is higher higher at inorganic salt concentration; Coalescence also can take place with anti-thick, dispersion agent is for the effect of grinding effect that improves lime carbonate and calcium carbonate superfine powder all highly significant preferably therefore to develop anti-salt property.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of salt-tolerance dispersing agent and employing light initiation polymerization is to overcome the above-mentioned defective that prior art exists.
Light initiation polymerization prepares the method for salt-tolerance dispersing agent, comprises the steps:
(1) with transition metal halide, solvent and 2,2 '-bipyridine, in solvent, in the nitrogen atmosphere, 40～60 ℃ of reactions 0.5-1 hour obtain complex solution;
(2) then under 70～120 ℃, add mix monomer and photoinitiator, ultraviolet light irradiation 0.5～1 hour reacted 5～20 hours;
Said mix monomer is the mixture of vinyl acetate and vinyl carboxylate, and weight ratio is:
Vinyl acetate: vinyl carboxylate=1: 5～10;
In said vinyl carboxylate preferred acrylate or the methacrylic ester one or more, carbonatoms is 4～20 in the monomer;
(3) peroxo-aluminium pillar; After removing transition metal; With gained solution and weight concentration is that 20～50% sodium hydroxide solution mixes, and 80～120 ℃ of hydrolysis 3～10 hours make and gather (vinyl carboxylate-co-vinyl acetate) and change into and gather (vinyl carboxylic acid-co-vinyl alcohol) sodium salt;
(4) distillation remove desolvate, acetic acid and pure by product, adding weight concentration again and be 20～50% NaOH solution, to regulate pH be 4～8, and add water and regulate weight solid content to 41～43%, obtains said salt-tolerance dispersing agent;
The raw materials in part by weight proportioning is following:
Transition metal halide is Cu
II, Fe
III, Ni
III, Rh
IIIOr Ru
IIIMuriate or bromide;
2,2 '-bipyridine is to be used for the complexing transition metal to improve its solubleness;
Initiator is a photoinitiator, like UVNUL MS-40, benzophenone derivates st-yrax, st-yrax verivate, methyl vinyl ketone, resorcinolphthalein or eosin etc.
Solvent is an oil-dissolving solvent, as: benzene, toluene, ethylbenzene, YLENE or ETHYLE ACETATE;
Used ultraviolet source is a high voltage mercury lamp, and wavelength is between 100～1000nm.
The dispersion agent that is obtained can be used for coarse whiting and grinds, and also can be used for fine particle calcium carbonate and disperses.The gained calcium carbonate superfine powder can be used for fields such as papermaking, coating, plastics, rubber, sealer, medicine, foods and cosmetics.
The present invention adopts ultraviolet light irradiation to cause the efficient calcium carbonate dispersant that the distribution of method synthetic molecular weight is very narrow and salt resistance is strong of combination reverse atom transfer radical polymerization.The present invention carries out reverse atom transfer radical polymerization with esters monomers such as propenoate and methacrylic ester and vinyl acetate earlier and prepares the very narrow random copolymers of MWD; Use the sodium hydroxide solution hydrolysis then, make at last have very high dispersive efficient and salt resistance gather (vinyl carboxylic acid-co-vinyl alcohol) sodium salt dispersion agent.
Compare ATRP and have following advantage: need not bring the bigger halogenated alkane of toxicity into; Initiator can be common radical initiator; The high price halide salt that adopts transition metal is as catalyzer, and preparation of high price salt and storage are all much easier than low price salt.
Method of the present invention, the product of acquisition is pure, and is simple to operate; Temperature influence is very little; Adopt method of the present invention, obtain MWD than general radical polymerization narrow the multipolymer of Duoing, it has good dispersion effect and anti-salt property in lime carbonate grinds and disperses.
Embodiment
The preparation that gathers (vinylformic acid-co-vinyl alcohol) sodium salt that embodiment 1. low molecular weight narrows distribute:
In reaction kettle, add CuCl
27.2g, after driving oxygen, fully logical nitrogen adds YLENE 300.20g, mix, and continue logical nitrogen and add 16.74g 2,2 '-bipyridine after 30 minutes, be warmed up to 50 ℃ of reactions 1 hour under the nitrogen protection, obtain homogeneous complex solution.Be warmed up to 100 ℃, add through logical nitrogen drive oxygen tert-butyl acrylate monomer 280.10g, vinyl acetate 31g and and UVNUL MS-40 4g, mix.UV-irradiation 0.5 hour, the logical nitrogen reaction of constant temperature is 5 hours again.Cross post through the aluminum oxide pillar and remove behind the transition metal, make and gather (tert-butyl acrylate-co-vinyl acetate) and change into and gather (vinylformic acid-co-vinyl alcohol) sodium salt gained solution and the hydrolysis of sodium hydroxide solution (concentration 32%) 95g mixing post-heating 3 hours.Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.Add 10g NaOH solution (32%) again and regulate pH to 4.5, and add water adjusting solid content to 42%, obtain final dispersion agent sample.Gained dispersion agent weight-average molecular weight is 5600, and molecular weight distributing index is 1.33.
The preparation that gathers (methylacrylic acid-co-vinyl alcohol) sodium salt that embodiment 2. low molecular weight narrows distribute:
In reaction kettle, add CuBr
216.02g, after driving oxygen, fully logical nitrogen adds YLENE 350g, mix, and continue logical nitrogen and add 22.50g 2,2 '-bipyridine after 30 minutes, be warmed up to 50 ℃ of reactions 1 hour under the nitrogen protection, obtain homogeneous complex solution.Be warmed up to 80 ℃, add the vinyl acetate 64.1g, methacrylic tert-butyl acrylate monomer 321.04g and the UVNUL MS-40 6g that drive oxygen through logical nitrogen, mix, UV-irradiation 0.5 hour, the logical nitrogen reaction of constant temperature is 5 hours again.Cross post through the aluminum oxide pillar and remove behind the transition metal, make and gather (methacrylic tert-butyl acrylate-co-vinyl acetate) and change into and gather (methylacrylic acid-co-vinyl alcohol) sodium salt gained solution and the hydrolysis of sodium hydroxide solution (concentration 32%) 70.12g mixing post-heating 4 hours.Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.Add 5.03gNaOH solution (32%) again and regulate pH to 4.1, and add water adjusting solid content to 42%, obtain final dispersion agent sample.Gained dispersion agent weight-average molecular weight is 4700, and molecular weight distributing index is 1.29.The preparation that gathers (vinylformic acid-co-methylacrylic acid-co-vinyl alcohol) sodium salt that embodiment 3. low molecular weight narrows distribute:
In reaction kettle, add CuCl
210.02g, after driving oxygen, fully logical nitrogen adds toluene 350.13g, mix, and continue logical nitrogen and add 23.05g 2,2 '-bipyridine after 30 minutes, be warmed up to 50 ℃ of reactions 1 hour under the nitrogen protection, obtain homogeneous complex solution.Be warmed up to 100 ℃, add the methacrylic tert-butyl acrylate 160.02g, tert-butyl acrylate 144.12g, vinyl acetate 32.05g and the UVNUL MS-40 7g that drive oxygen through logical nitrogen, mix, UV-irradiation 0.5 hour, the logical nitrogen reaction of constant temperature is 5 hours again.Cross post through the aluminum oxide pillar and remove behind the transition metal, make and gather (tert-butyl acrylate-co-methacrylic tert-butyl acrylate-co-vinyl acetate) and change into and gather (vinylformic acid-co-methylacrylic acid-co-vinyl alcohol) sodium salt gained solution and the hydrolysis of sodium hydroxide solution (concentration 32%) 100.52g mixing post-heating 4.5 hours.Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.Add 50.04g NaOH solution (32%) again and regulate pH to 5.0, and add water adjusting solid content to 42%, obtain final dispersion agent sample.Gained dispersion agent weight-average molecular weight is 4250, and polydispersity index is 1.32.
Embodiment 4. embodiment, 1～3 dispersion agent and comparison sample (are pressed the dispersion agent of USP 20020019329A1 disclosed method preparation; Weight-average molecular weight 5791, and molecular weight distributing index 1.41) application example (the dispersion agent solid content is 42%) under the situation that specially adds salt impurity, 98 grades of coarse whitings being ground:
In 15 liters of grinding pots, add 2.5 kg of water, open and stir, add dispersion agent 155 grams; 7.5 kilograms of heavy calcium carbonate material of back adding and 4 gram sodium-chlor stir; Grind discharging after 2 hours, record particle diameter through the particle diameter appearance and reach more than 98%, get calcium carbonate slurry less than 2 μ m calcium carbonate granule weight contents; The weight solid content is slightly larger than 75%, add water be transferred to the weight solid content be carry out kinematic viscosity after 75%, viscosity and leave standstill the test of viscosity after 1 hour.Disperse back 1 hour viscosity data following:
Can find out from above-mentioned application result: use the embodiment of the invention 1～3 preparation dispersion agent grinding effect when the system saltiness is higher will obviously be superior to comparison sample.
Claims (9)
1. light initiation polymerization prepares the method for salt-tolerance dispersing agent, it is characterized in that, comprises the steps:
(1) with transition metal halide, solvent and 2,2 '-bipyridine, in solvent, react in the nitrogen atmosphere, obtain complex solution;
(2) add mix monomer and photoinitiator then, the ultraviolet light irradiation reaction;
Said mix monomer is the mixture of vinyl acetate and vinyl carboxylate;
(3) peroxo-aluminium pillar mixes gained solution and sodium hydroxide solution, and hydrolysis obtains to gather (vinyl carboxylic acid-co-vinyl alcohol) sodium salt;
(4) distillation remove desolvate, acetic acid and pure by product, adding NaOH solution again, to regulate pH be 4～8, and add water and regulate weight solid content to 41～43%, obtains said salt-tolerance dispersing agent.
2. method according to claim 1 is characterized in that, in the step (1), temperature of reaction is 40～60 ℃, and the reaction times is 0.5-1 hour.
3. method according to claim 1 is characterized in that, in the step (2), under 70～120 ℃, adds mix monomer and photoinitiator, and ultraviolet light irradiation 0.5～1 hour reacted 5～20 hours.
4. according to claim 1,2 or 3 described methods, it is characterized in that,
The raw materials in part by weight proportioning is following:
In the said mix monomer, the weight ratio of component is:
Vinyl acetate: vinyl carboxylate=1: 5～10;
Transition metal halide is Cu
II, Fe
III, Ni
III, Rh
IIIOr Ru
IIIMuriate or bromide.
5. method according to claim 4 is characterized in that said vinyl carboxylate is one or more in propenoate or the methacrylic ester, and carbonatoms is 4～20 in the monomer.
6. method according to claim 4 is characterized in that, initiator is UVNUL MS-40, benzophenone derivates st-yrax, st-yrax verivate, methyl vinyl ketone, resorcinolphthalein or eosin.
7. method according to claim 4 is characterized in that, solvent is benzene, toluene, ethylbenzene, YLENE or ETHYLE ACETATE.
8. the salt-tolerance dispersing agent for preparing according to each said method of claim 1～7.
9. the application of salt-tolerance dispersing agent according to claim 8 is characterized in that, is used for the coarse whiting grinding or is used for fine particle calcium carbonate disperseing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103753305A CN102516449A (en) | 2011-11-22 | 2011-11-22 | Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103753305A CN102516449A (en) | 2011-11-22 | 2011-11-22 | Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102516449A true CN102516449A (en) | 2012-06-27 |
Family
ID=46287555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103753305A Pending CN102516449A (en) | 2011-11-22 | 2011-11-22 | Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516449A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702455A (en) * | 2012-06-29 | 2012-10-03 | 上海东升新材料有限公司 | Segmented copolymer type dispersing agent and photo-initiation polymerization preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857657A (en) * | 2010-06-29 | 2010-10-13 | 上海东升新材料有限公司 | Salt resistant calcium carbonate dispersing agent and preparation method thereof |
| CN102219874A (en) * | 2011-03-29 | 2011-10-19 | 上海东升新材料有限公司 | Salt-resistance copolymer type dispersing agent and preparation method thereof |
-
2011
- 2011-11-22 CN CN2011103753305A patent/CN102516449A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857657A (en) * | 2010-06-29 | 2010-10-13 | 上海东升新材料有限公司 | Salt resistant calcium carbonate dispersing agent and preparation method thereof |
| CN102219874A (en) * | 2011-03-29 | 2011-10-19 | 上海东升新材料有限公司 | Salt-resistance copolymer type dispersing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MEHMET ATILLA TASDELEN ET AL.: "Studies on Photoinduced ATRP in the Presence of Photoinitiator", 《MACROMOLECULAR CHEMISTRY AND PHYSICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702455A (en) * | 2012-06-29 | 2012-10-03 | 上海东升新材料有限公司 | Segmented copolymer type dispersing agent and photo-initiation polymerization preparation method thereof |
| CN102702455B (en) * | 2012-06-29 | 2014-06-18 | 上海东升新材料有限公司 | Segmented copolymer type dispersing agent and photo-initiation polymerization preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101857657B (en) | Salt resistant calcium carbonate dispersing agent and preparation method thereof | |
| Li et al. | Novel modified pectin for heavy metal adsorption | |
| CN104031190A (en) | Preparation of efficient ground calcium carbonate grinding dispersant by photo-initiating room-temperature RAFT (Reversible Additive Fragment Transfer) polymerization | |
| CN101862619A (en) | Block type polymer dispersant and preparation method thereof | |
| CN104017119A (en) | Dispersing agent for grinding triple superphosphate with branched structure and preparation method thereof | |
| CN102274702A (en) | Block macromolecular pigment dispersant, preparation method thereof, and pigment dispersion liquid containing dispersant | |
| CN102219874A (en) | Salt-resistance copolymer type dispersing agent and preparation method thereof | |
| CN104119547A (en) | Application of microcrystalline wax in pre-dispersed masterbatch formula, pre-dispersed masterbatch formula and preparation method of formula | |
| CN104045799A (en) | Salt-resistant block type dispersant and room-temperature photo-initiation RAFT (Reversible Additive Fragment Transfer) polymerization preparation method thereof | |
| CN102050903B (en) | Preparation method and application of high-efficiency calcium carbonate dispersing agent | |
| CN102516449A (en) | Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization | |
| CN102040715B (en) | Salt-resistant segmented copolymer type dispersant and preparation method thereof | |
| CN102585556A (en) | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization | |
| CN104449025B (en) | A kind of paint production method | |
| CN101864050B (en) | High-efficiency salt-tolerance dispersing agent and preparation method and application thereof | |
| CN101864014B (en) | Preparation method for efficient calcium carbonate dispersing agent | |
| CN102702455B (en) | Segmented copolymer type dispersing agent and photo-initiation polymerization preparation method thereof | |
| CN102532373B (en) | Efficient heavy calcium grinding dispersant, and photoinitiated polymerization method and application thereof | |
| CN102363639A (en) | High-efficiency heavy calcium grinding dispersant and preparation method thereof | |
| CN103721826A (en) | Preparation method of heavy calcium carbonate with narrow particle size | |
| CN106188354A (en) | A kind of preparation method of the polyvinyl alcohol dispersant with high efficiency dispersion stability | |
| CN110527011A (en) | A kind of water polyacrylic acid emulsion resin and the preparation method and application thereof | |
| CN106543321B (en) | The preparation method and its product of a kind of four arms star structure high-efficiency coarse whiting ground dispersant and application | |
| CN108191998B (en) | Components, preparation method and application of magnesium ethylate particles | |
| CN106543384B (en) | The preparation method and its product of a kind of high-efficiency coarse whiting ground dispersant of comb shaped structure and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120627 |