CN102585556A - Method for preparing salt-resistant dispersing agent by photo-initiated polymerization - Google Patents
Method for preparing salt-resistant dispersing agent by photo-initiated polymerization Download PDFInfo
- Publication number
- CN102585556A CN102585556A CN2011104585190A CN201110458519A CN102585556A CN 102585556 A CN102585556 A CN 102585556A CN 2011104585190 A CN2011104585190 A CN 2011104585190A CN 201110458519 A CN201110458519 A CN 201110458519A CN 102585556 A CN102585556 A CN 102585556A
- Authority
- CN
- China
- Prior art keywords
- salt
- dispersing agent
- vinyl
- parts
- 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
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a method for preparing a salt-resistant dispersing agent by photo-initiated polymerization. The method comprises the following steps of: (1) reacting transition metal halide with 2,2'-bipyridyl; (2) adding a mixed monomer and a photo-initiator, performing ultraviolet irradiation, and reacting; and (3) performing column chromatography, mixing the obtained solution and a sodium hydroxide (NaOH) solution, hydrolyzing, collecting poly(vinyl carboxylic acid-co-vinyl alcohol) sodium salt, adding a NaOH solution to regulate the pH, adding water to regulate solid content (weight percent), and thus obtaining the salt-resistant dispersing agent. The dispersing agent comprises the following raw materials in part by weight: 26 to 46 parts of mixed monomer, 0.05 to 2 parts of transition metal halide, 0.2 to 8 parts of 2,2'-bipyridyl, 0.01 to 0.1 part of photo-initiator, 52 to 72 parts of solvent and 10 to 100 parts of 20 to 50 weight percent NaOH solution. The product is pure, is slightly influenced by temperature and has a good dispersing effect and high salt resistance, and the method is easy to operate.
Description
Technical field
The present invention relates to a kind of dispersion agent that is used for calcium carbonate superfine powder and preparation method thereof.
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
One of the object of the invention provides the method that a kind of light initiation polymerization prepares salt-tolerance dispersing agent, to overcome the above-mentioned defective that prior art exists;
Two of the object of the invention provides the salt-tolerance dispersing agent that adopts said method preparation.
Method of the present invention comprises the steps:
(1) with transition metal halide and 2,2 '-bipyridine, in solvent, under the nitrogen atmosphere, 40～60 ℃ the reaction 0.5-1 hour, obtain uniform complex solution;
(2) then at 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 said vinyl carboxylate is preferably one or more in propenoate or the methacrylic ester, and monomeric carbonatoms is 4～20;
(3) peroxo-aluminium pillar, remove transition metal after, be that 20～50% sodium hydroxide solution mixes with gained solution and weight concentration; 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, collect and gather (vinyl carboxylic acid-co-vinyl alcohol) sodium salt, adding weight concentration again and be 20～50% NaOH solution, to regulate pH be 4～8; Add water and regulate weight solid content to 41～43%, obtain salt-tolerance dispersing agent;
Raw material weight umber proportioning is following:
Transition metal halide is Cu
I, Fe
IIOr Ni
IIMuriate;
2,2 '-bipyridine is to be used for the complexing transition metal to improve its solubleness;
Initiator is a photoinitiator, preferred UVNUL MS-40, benzophenone derivates, st-yrax, st-yrax verivate, methyl vinyl ketone, resorcinolphthalein or eosin etc.;
Solvent for use is 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 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 the efficient calcium carbonate dispersant that the distribution of son amount is very narrow and salt resistance is strong at last; What have very high dispersive efficient and salt resistance gathers (vinyl carboxylic acid-co-vinyl alcohol) sodium salt dispersion agent, need not bring the bigger halogenated alkane of toxicity into; Initiator can be common radical initiator, and product is pure, and is simple to operate, and temperature influence is very little etc., and it has good dispersion effect and anti-salt property in lime carbonate grinds and disperses.
Embodiment
Among the embodiment, if no special instructions, component concentration is weight.
The preparation that gathers (vinylformic acid-co-vinyl alcohol) sodium salt that embodiment 1. low molecular weight narrows distribute:
In reaction kettle, add CuCl 3.6g, add YLENE 300.20g after fully logical nitrogen drives oxygen, mix, 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 FeCl
28.01g, 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 through logical nitrogen drive oxygen vinyl acetate 35.02g, methacrylic tert-butyl acrylate monomer 350.12g and and UVNUL MS-40 6g, 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 NiCl
25.01g, 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 through logical nitrogen drive oxygen methacrylic tert-butyl acrylate 160.02g, tert-butyl acrylate 144.12g, vinyl acetate 32.05g and and UVNUL MS-40 7g, 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 (10)
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 and 2,2 '-bipyridine, in solvent, under the nitrogen atmosphere, the reaction, obtain uniform complex solution;
(2) add mix monomer and photoinitiator then, ultraviolet light irradiation, reaction again;
Said mix monomer is the mixture of vinyl acetate and vinyl carboxylate;
(3) peroxo-aluminium pillar is that 20～50% sodium hydroxide solution mixes hydrolysis with gained solution and weight concentration; Collection gathers (vinyl carboxylic acid-co-vinyl alcohol) sodium salt; Adding NaOH solution adjusting pH again is 4～8, adds water and regulates weight solid content to 41～43%, obtains salt-tolerance dispersing agent;
Transition metal halide is Cu
I, Fe
IIOr Ni
IIMuriate.
2. method according to claim 1 is characterized in that, in the step (1), temperature of reaction is 40～60 ℃ and is 0.5-1 hour between seasonable.
3. method according to claim 1 is characterized in that, in the step (2), at 70～120 ℃, adds mix monomer and photoinitiator, and ultraviolet light irradiation 0.5～1 hour reacted 5～20 hours again.
4. method according to claim 1 is characterized in that, raw material weight umber proportioning is following:
Weight concentration is that 20～50% NaOH solution is the consumption in the step (3).
5. method according to claim 1 is characterized in that initiator is a photoinitiator, is selected from UVNUL MS-40, benzophenone derivates, st-yrax, st-yrax verivate, methyl vinyl ketone, resorcinolphthalein or eosin.
6. method according to claim 1 is characterized in that solvent for use is benzene, toluene, ethylbenzene, YLENE or ETHYLE ACETATE.
7. method according to claim 1 is characterized in that used ultraviolet source is a high voltage mercury lamp, and wavelength is between 100～1000nm.
8. according to each said method of claim 1～7, it is characterized in that said vinyl carboxylate is one or more in propenoate or the methacrylic ester, monomeric carbonatoms is 4～20.
9. the salt-tolerance dispersing agent for preparing according to each said method of claim 1～8.
10. the application of salt-tolerance dispersing agent according to claim 9 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 |
|---|---|---|---|
| CN2011104585190A CN102585556A (en) | 2011-12-31 | 2011-12-31 | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104585190A CN102585556A (en) | 2011-12-31 | 2011-12-31 | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102585556A true CN102585556A (en) | 2012-07-18 |
Family
ID=46474822
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104585190A Pending CN102585556A (en) | 2011-12-31 | 2011-12-31 | Method for preparing salt-resistant dispersing agent by photo-initiated polymerization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585556A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591990A (en) * | 2020-05-12 | 2020-08-28 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05341434A (en) * | 1992-06-11 | 1993-12-24 | Nikon Corp | Silver halide dispersed plastic material |
| EP0633503A1 (en) * | 1993-07-02 | 1995-01-11 | Ciba-Geigy Ag | Photopolymerizable compositions |
| WO2008036864A2 (en) * | 2006-09-22 | 2008-03-27 | Huntsman Petrochemical Corporation | Ostwald ripening inhibition in chemical formulations |
| CN101279215A (en) * | 2008-01-02 | 2008-10-08 | 沈阳化工学院 | Stable low molecular weight dispersing agent |
| US20100086701A1 (en) * | 2008-10-06 | 2010-04-08 | Xerox Corporation | Radiation curable ink containing fluorescent nanoparticles |
| 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 |
| CN101864050A (en) * | 2010-06-29 | 2010-10-20 | 上海东升新材料有限公司 | High-efficiency salt-tolerance dispersing agent and preparation method and application 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
- 2011-12-31 CN CN2011104585190A patent/CN102585556A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05341434A (en) * | 1992-06-11 | 1993-12-24 | Nikon Corp | Silver halide dispersed plastic material |
| EP0633503A1 (en) * | 1993-07-02 | 1995-01-11 | Ciba-Geigy Ag | Photopolymerizable compositions |
| WO2008036864A2 (en) * | 2006-09-22 | 2008-03-27 | Huntsman Petrochemical Corporation | Ostwald ripening inhibition in chemical formulations |
| CN101279215A (en) * | 2008-01-02 | 2008-10-08 | 沈阳化工学院 | Stable low molecular weight dispersing agent |
| US20100086701A1 (en) * | 2008-10-06 | 2010-04-08 | Xerox Corporation | Radiation curable ink containing fluorescent nanoparticles |
| 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 |
| CN101864050A (en) * | 2010-06-29 | 2010-10-20 | 上海东升新材料有限公司 | High-efficiency salt-tolerance dispersing agent and preparation method and application 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111591990A (en) * | 2020-05-12 | 2020-08-28 | 北京福田戴姆勒汽车有限公司 | Activated carbon material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101857657B (en) | Salt resistant calcium carbonate dispersing agent and preparation method thereof | |
| Mishra et al. | Microwave initiated synthesis of polymethylmethacrylate grafted guar (GG-g-PMMA), characterizations and applications | |
| CN101565570B (en) | Composite latex for paints, water paint and preparation method of water paint | |
| CN101880422B (en) | Preparation method of low-mould shrinkage ratio polypropylene alloy material | |
| CN104031190A (en) | Preparation of efficient ground calcium carbonate grinding dispersant by photo-initiating room-temperature RAFT (Reversible Additive Fragment Transfer) polymerization | |
| Panghal et al. | Dissolution improvement of atorvastatin calcium using modified locust bean gum by the solid dispersion technique | |
| CN101862619A (en) | Block type polymer dispersant and preparation method thereof | |
| CN102649826A (en) | Preparation method of particle diameter controllable monodisperse polystyrene microspheres | |
| 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 | |
| JP2006521988A (en) | Use of polyacrylic acid as grinding aid for calcium carbonate | |
| 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 | |
| CN102219874A (en) | Salt-resistance copolymer type dispersing agent and preparation method thereof | |
| CN102050903B (en) | Preparation method and application of high-efficiency calcium carbonate dispersing agent | |
| 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 | |
| CN102516449A (en) | Salt resistance dispersing agent and preparation method for preparing same by adopting light initiated polymerization | |
| CN102702455B (en) | Segmented copolymer type dispersing agent and photo-initiation polymerization preparation method thereof | |
| CN101864014B (en) | Preparation method for efficient calcium carbonate dispersing agent | |
| CN101864050B (en) | High-efficiency salt-tolerance dispersing agent and preparation method and application thereof | |
| CN101712625B (en) | Method for synthesizing amphoteric slow-breaking quick-setting asphalt emulsifier | |
| CN102532373B (en) | Efficient heavy calcium grinding dispersant, and photoinitiated polymerization method and application thereof | |
| CN102363639B (en) | High-efficiency heavy calcium grinding dispersant and preparation method thereof |
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: 20120718 |