CN102040715A - Salt-resistant segmented copolymer type dispersant and preparation method thereof - Google Patents
Salt-resistant segmented copolymer type dispersant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a salt-resistant segmented copolymer type dispersant and a preparation method thereof. The preparation method comprises the following steps of: (1) reacting transition metal halide with 2,2'-bipyridine in a solvent in an inert atmosphere to prepare complex solution; (2) adding an initiator into a mixture of the complex solution and vinyl acetate for reacting; (3) adding a vinyl carboxylic ester monomer into a product obtained in the step (2) for reacting; (4) mixing the obtained solution and sodium hydroxide solution by allowing a product obtained in the step (3) to pass through an aluminum oxide column and hydrolyzing to obtain poly(vinyl carboxylic acid-b-vinyl alcohol) sodium salt; and (5) distilling to remove the solvent, acetic acid and alcohol byproducts, adding NaOH solution to adjust pH, and adding water to adjust the solid content to obtain the dispersant. The product is the salt-resistant poly(vinyl carboxylic acid-b-vinyl alcohol) sodium salt dispersant with extremely high dispersing efficiency.
Description
Technical field
The present invention relates to a kind of calcium carbonate superfine powder dispersion agent and preparation method thereof with anti-salt property.
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 raising that quality product is required along with people also improves day by day to the requirement of the solid content of lime carbonate fineness and homogeneity and calcium carbonate slurry.The lime carbonate granularity is thin more, solid content is high more, and viscosity is just high more during grinding, and anti-sticking also severe more after grinding, therefore, the adding dispersion agent is necessary when grinding and disperse lime carbonate.For the production of high-level lime carbonate, it is particularly important that the effect of dispersion agent seems.
It is one of the most effective dispersion agent during powder lime carbonate is produced that molecular weight is in sodium polyacrylate between 2000～5000.The molecular weight of sodium polyacrylate and distribution thereof have very big influence for its dispersion effect.J.Loiseau[Macromolecules 2003,36,3066-3077] result of study show, has better dissemination near the monodispersed sodium polyacrylate of molecular weight than polydisperse sodium polyacrylate, 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 sodium polyacrylate 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.
Sodium polyacrylate is the macromolecule dispersing agent of an anionoid type, it is very responsive to the free positively charged ion in the slurry, when containing more free positively charged ion (inorganic salt etc.) in the system, the effect of sodium polyacrylate when grinding and disperse lime carbonate be variation greatly.Therefore, in the grinding of lime carbonate and dispersion system, contain other water-soluble salts more for a long time or during calcium carbonate applications in the system under the more situation of free ion, prepare the strong and very narrow dispersion agent of molecular weight distribution of a kind of salt resistance and just seem very important.
Summary of the invention
The objective of the invention is to disclose a kind of salt resistance segmented copolymer type dispersion agent and preparation method thereof, to overcome the above-mentioned defective that prior art exists.
(1) with transition metal halide in solvent, in the inert atmosphere as in the nitrogen with 2,2 '-the bipyridine reaction, temperature of reaction is 45～55 ℃, preferred 50 ℃ of reactions 0.5～2 hour preferred 1 hour, obtain complex solution;
(2) with the mixture of complex solution and vinyl acetate, add initiator, 60～120 ℃ of reactions 2～10 hours; Preferably, adopt the mode that drips, in 2～5 hours, drip initiator, reacted then 2～10 hours;
(3) vinyl carboxylic acid ester monomers is added the product of step (2), reacted 2～10 hours;
(4) with the product of step (3), by the aluminum oxide pillar, after crossing post and removing transition metal, with gained solution and weight concentration is that 20～50% sodium hydroxide solution mixes, 80～120 ℃ of hydrolysis 2～10 hours make di-block copolymer poly-(vinyl carboxylate-b-vinyl acetate) change poly-(vinyl carboxylic acid-b-vinyl alcohol) sodium salt into;
(5) 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 described dispersion agent.
Perhaps:
(2) with the mixture of complex solution and vinyl carboxylic acid ester monomers, add initiator, 60～120 ℃ of reactions 2～10 hours; Preferably, adopt the mode that drips, in 2～5 hours, drip initiator, reacted then 2～10 hours;
(3) vinyl acetate is added the product of step (2), reacted 2～10 hours;
In step (1)～(4), the raw material weight umber is as follows:
2.6～4.6 parts of vinyl acetates
23.4～41.4 parts of vinyl carboxylic acid ester monomers
0.5～2 part of transition metal halide
2,2 '-1～4 part of bipyridine
0.5～2 part of initiator
52～72 parts of solvents
Weight concentration is 10～65 parts of 20～50% sodium hydroxide solutions
Wherein:
Described vinyl carboxylic acid ester monomers is more than one in acrylate or the methacrylic ester, preferably tert-butyl acrylate, methyl acrylate or ethyl propenoate;
Described transition metal halide is transition metal chloride or bromide, preferred CuCl
2, CuBr
2Deng;
Described 2,2 '-bipyridine is to be used for the complexing transition metal to improve its solubleness;
Described initiator is common radical initiator, as Diisopropyl azodicarboxylate etc.;
Described solvent is oil-dissolving solvents such as toluene.
The present invention carries out reverse atom transfer radical polymerization with esters monomers such as acrylate and methacrylic ester and vinyl acetate earlier and prepares the very narrow di-block copolymer of molecular weight distribution, use the sodium hydroxide solution hydrolysis then, make at last and have very poly-(vinyl carboxylic acid-b-vinyl alcohol) sodium salt dispersion agent of high dispersive efficient and salt resistance.
Embodiment
The preparation of poly-(vinylformic acid-b-vinyl alcohol) sodium salt that embodiment 1. low molecular weight narrows distribute:
In reactor, add CuCl
26.04g logical nitrogen adds toluene 300.20g after driving oxygen, mixes, and continues logical nitrogen after 30 minutes, adds 14.04g 2,2 '-bipyridine, is warmed up to 50 ℃ of reactions 1 hour under the nitrogen protection, obtains homogeneous complex solution.
Be warmed up to 120 ℃, add tert-butyl acrylate monomer 288.10g, mix, in 2 hours, drip the toluene solution 100mL that contains the 4.05g Diisopropyl azodicarboxylate, the logical nitrogen reaction of constant temperature 5 hours.
Add vinyl acetate 32.03g, continue reaction 5 hours.
After crossing post and remove transition metal by the aluminum oxide pillar, with gained solution and the hydrolysis of sodium hydroxide solution (weight concentration 32%) 200g mixing post-heating 3 hours, make poly-(tert-butyl acrylate-b-vinyl acetate) change poly-(vinylformic acid-b-vinyl alcohol) sodium salt into.Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.
Adding 80gNaOH solution (weight concentration 32%) adjusting pH again is 8, and adds water adjusting weight solid content to 42%, obtains dispersion agent.Gained dispersion agent weight-average molecular weight is 6490, and molecular weight distributing index is 1.30.
The preparation of poly-(methacrylic acid-b-vinyl alcohol) sodium salt that embodiment 2. low molecular weight narrows distribute:
In reactor, add CuBr
215.02g, after driving oxygen, fully logical nitrogen adds toluene 350g, mix, and continue logical nitrogen and add 20.98g 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 32.02g that drives oxygen through logical nitrogen, mix.In 3 hours, drip the toluene solution 100mL that contains the 6.06g Diisopropyl azodicarboxylate, the logical nitrogen reaction of constant temperature 5 hours.
Add methacrylic tert-butyl acrylate monomer 320.12g, continue reaction 4 hours.After crossing post and remove transition metal by the aluminum oxide pillar, with gained solution and the hydrolysis of sodium hydroxide solution (weight concentration 20%) 100g mixing post-heating 4 hours, make poly-(methacrylic tert-butyl acrylate-b-vinyl acetate) change poly-(methacrylic acid-b-vinyl alcohol) sodium salt into.
Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.Adding 8.03g NaOH solution (weight concentration 20%) adjusting pH again is 4, and adds water adjusting weight solid content to 42%, obtains dispersion agent.
Gained dispersion agent weight-average molecular weight is 4256, and molecular weight distributing index is 1.28.
The preparation of poly-(vinylformic acid-co-methacrylic acid-b-vinyl alcohol) sodium salt that embodiment 3. low molecular weight narrows distribute:
In reactor, add CuCl
29.07g, after driving oxygen, fully logical nitrogen adds toluene 350.13g, mix, and continue logical nitrogen and add 21.08g 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, the tert-butyl acrylate 144.12g that drive oxygen through logical nitrogen, mix, in 2.5 hours, drip the toluene solution 100mL that contains the 6.09g Diisopropyl azodicarboxylate, the logical nitrogen reaction of constant temperature 5 hours.Add vinyl acetate 32.05g, continue reaction 5 hours.
Cross post by the aluminum oxide pillar and remove behind the transition metal, make poly-(tert-butyl acrylate-co-methacrylic tert-butyl acrylate-b-vinyl acetate) change poly-(vinylformic acid-co-methacrylic acid-b-vinyl alcohol) sodium salt into gained solution and the hydrolysis of sodium hydroxide solution (weight concentration 50%) 100g mixing post-heating 4.5 hours.Distillation removes and to desolvate, acetic acid and trimethyl carbinol by product.
Adding 10g NaOH solution (weight concentration 50%) adjusting pH again is 6, and adds water adjusting solid content to 42%, obtains final dispersion agent sample.Gained dispersion agent weight-average molecular weight is 4450, and polydispersity index is 1.34.
Embodiment 4.
Embodiment 1～3 dispersion agent and contrast sample (are pressed the dispersion agent of United States Patent (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:
Add 25 kg of water in 150 liters of steel basins, unlatching is stirred, and adds 20g sodium-chlor, adds dispersion agent 750g, and the back 75 kilogram of 325 order water-ground limestone powder of adding that stir carries out pre-dispersed, and the back that is uniformly dispersed is with being pumped in two series connection shredders.Grinding medium: (zirconium pearl diameter is respectively the zirconium pearl: coarse grain: 1.5～2.0mm; Middle grain: 1～1.5mm; Particulate: 0.8～1.2mm.Proportioning is coarse grain when using: middle grain: particulate=1: 2: 3), in process of lapping, drip dispersion agent 750g continuously, grind after 2 hours, recording particle diameter through the particle diameter instrument reaches more than 98% less than 2 μ m calcium carbonate granule content, get calcium carbonate slurry, solid content is slightly larger than 75%, add water be transferred to 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 as follows:
From above-mentioned application result as can be seen: use the embodiment of the invention 1～3 preparation dispersion agent grinding effect when the system saltiness is higher will obviously be better than contrasting sample.
Claims (10)
1. the preparation method of salt resistance segmented copolymer type dispersion agent is characterized in that, comprises the steps:
(1) with transition metal halide in solvent, in the inert atmosphere with 2,2 '-the bipyridine reaction, obtain complex solution;
(2) with the mixture of complex solution and vinyl acetate, add initiator, reaction;
(3) vinyl carboxylic acid ester monomers is added the product of step (2), reaction;
(4) with the product of step (3),,, obtain poly-(vinyl carboxylic acid-b-vinyl alcohol) sodium salt with gained solution and sodium hydroxide solution mixed hydrolysis by the aluminum oxide pillar;
(5) distillation remove desolvate, acetic acid and pure by product, add NaOH solution again and regulate pH, and add water and regulate the weight solid content, obtain described dispersion agent.
2. method according to claim 1 is characterized in that, in the step (1), temperature of reaction is 45～55 ℃, and the reaction times is 0.5～2 hour.
3. method according to claim 1 is characterized in that, in the step (2), 60～120 ℃ of reactions 2～10 hours.
4. method according to claim 1 is characterized in that, step (3) adds the product of step (2) with vinyl carboxylic acid ester monomers, reacts 2～10 hours.
5. method according to claim 1 is characterized in that, in the step (4), is 20～50% sodium hydroxide solution mixed hydrolysis 2～10 hours with gained solution and weight concentration, obtains poly-(vinyl carboxylic acid-b-vinyl alcohol) sodium salt.
6. method according to claim 1 is characterized in that, in the step (5), distillation removes and to 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 described dispersion agent.
7. the preparation method of salt resistance segmented copolymer type dispersion agent is characterized in that, comprises the steps:
(1) with transition metal halide in solvent, in the inert atmosphere with 2,2 '-the bipyridine reaction, obtain complex solution;
(2) with the mixture of complex solution and vinyl carboxylic acid ester monomers, add initiator, 60～120 ℃ of reactions 2～10 hours; Preferably, adopt the mode that drips, in 2～5 hours, drip initiator, reacted then 2～10 hours;
(3) vinyl acetate is added the product of step (2), reacted 2～10 hours;
(4) with the product of step (3),,, obtain poly-(vinyl carboxylic acid-b-vinyl alcohol) sodium salt with gained solution and sodium hydroxide solution mixed hydrolysis by the aluminum oxide pillar;
(5) distillation remove desolvate, acetic acid and pure by product, add NaOH solution again and regulate pH, and add water and regulate the weight solid content, obtain described dispersion agent.
8. according to each described method of claim 1～7, it is characterized in that in step (1)～(4), the raw material weight umber is as follows:
2.6～4.6 parts of vinyl acetates
23.4～41.4 parts of vinyl carboxylic acid ester monomers
0.5～2 part of transition metal halide
2,2 '-1～4 part of bipyridine
0.5～2 part of initiator
52～72 parts of solvents
Weight concentration is 10～65 parts of 20～50% sodium hydroxide solutions.
9. method according to claim 8 is characterized in that, described vinyl carboxylic acid ester monomers is more than one in acrylate or the methacrylic ester; Described transition metal halide is transition metal chloride or bromide; Described initiator is common radical initiator; Described solvent is a toluene.
10. according to the salt resistance segmented copolymer type dispersion agent of each described method preparation of claim 1～9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532373A (en) * | 2011-11-22 | 2012-07-04 | 上海东升新材料有限公司 | Efficient heavy calcium grinding dispersant, and photoinitiated polymerization method and application thereof |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831040A (en) * | 2010-04-21 | 2010-09-15 | 广东工业大学 | Amphipathilic block copolymer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101831040A (en) * | 2010-04-21 | 2010-09-15 | 广东工业大学 | Amphipathilic block copolymer and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532373A (en) * | 2011-11-22 | 2012-07-04 | 上海东升新材料有限公司 | Efficient heavy calcium grinding dispersant, and photoinitiated polymerization method and application thereof |
| CN102532373B (en) * | 2011-11-22 | 2013-11-06 | 上海东升新材料有限公司 | Efficient heavy calcium grinding dispersant, and photoinitiated polymerization method and application thereof |
| 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 |
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