CN1544533A - Method for preparing polymer type white organic pigments - Google Patents
Method for preparing polymer type white organic pigments Download PDFInfo
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- CN1544533A CN1544533A CNA2003101121560A CN200310112156A CN1544533A CN 1544533 A CN1544533 A CN 1544533A CN A2003101121560 A CNA2003101121560 A CN A2003101121560A CN 200310112156 A CN200310112156 A CN 200310112156A CN 1544533 A CN1544533 A CN 1544533A
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Abstract
The invention discloses a process for preparing polymer type white organic pigment by using phenylethene and acrylic acid as monomer or unsaturated monomer, using high acid value low molecular weight acrylic resin as dispersant resin, using 2-in-1 negative ion and non-ion surface active agent as emulsifying agent, using peroxodisulfate as initiating agent for two steps of seed emulsion polymerization at 60-80 deg. C, thus synthesizing emulsion with particles of core/shell double-layer structure, then at higher temperature, first swelling the emulsion particle with small amount of organic solvent having high boiling point, then further swelling the emulsion particle with alkaline substances, pore-forming, good whiteness can be realized for the polymer particles through further optical actions.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of polymer type organic pigment.
Background technology
The mankind just bring into use pigment very early the time, traditional pigment is divided into mineral dye and macromole pigment dyestuff.Much contain heavy metal in the mineral dye, bigger to the harm of human body; Macromole pigment dyestuff general toxicity is also bigger.The most of price of these conventional pigment is higher relatively, has increased the cost of relevant goods.Along with the continuous enhancing of people's environmental consciousness, products such as water-borne coatings or printing ink are more and more in addition, but the stability in storage of dispersiveness, consistency and the product of conventional pigment in aqueous product is all relatively poor relatively.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of polymer-type white pigment dyestuff, when the polymer-type white pigment dyestuff that this preparation method makes is used for preparing water-borne coatings or water color ink, be easy to disperse, anti-marquis is not easy to change, good with other component compatibility in the product, can significantly improve the stability in storage and the viscosity stability of water-borne coatings or printing ink, and not have toxicity substantially.
The preparation method of a kind of polymer-type white pigment dyestuff provided by the invention may further comprise the steps:
(1) in the there-necked flask that agitator, thermometer, prolong are housed, at first add entry, logical nitrogen stirs, and adds the water soluble acrylic resin's of lower molecular weight, high acid value the aqueous solution again, the tensio-active agent two-in-one with negatively charged ion and nonionic is emulsifying agent, with the persulphate is initiator, is slowly to splash into nuclear layer monomer under 60～80 ℃ of conditions in temperature, carries out the free radical emulsion copolymerization, drip off about 1～2 hour, be incubated 0.5～1 hour to emulsion blueing light and get seed emulsion;
Drip shell monomers under (2) 60～80 ℃ of conditions, the dropping time is 4～7 hours, is incubated 0.5～1 hour;
(3) in emulsion, add high boiling organic solvent, fully stir, be incubated 0.5～1 hour, make the abundant swelling of emulsion particle;
(4) add alkaline matter in emulsion, be warming up to about 90 ℃, be incubated 1～2 hour, make emulsion particle surface further swelling and pore-forming, re-adjustment pH value is 7～10, and the cooling back adds other usual auxiliaries and obtains after filtration.
In the technique scheme, by weight percentage, the consumption of lower molecular weight, high acid value acrylic resin is 5～15%; The monomer total amount is 30～55%, and wherein nuclear layer monomer accounts for 8～12% of monomer total amount, and shell monomers accounts for 88～92% of monomer total amount; The consumption of the tensio-active agent that negatively charged ion and nonionic are two-in-one is 0.5～3%, and initiator persulphate consumption is 0.2～2.5%, and the consumption of water is 30～53%, and the consumption of high boiling organic solvent is 1～2%, and the consumption of alkaline matter is 1～3%.
In the technique scheme, nuclear layer monomer is selected from vinylbenzene, methacrylic acid C
1-C
6In alkyl ester, Vinylstyrene, n-methylolacrylamide, the trimethylene bisacrylamide at least three kinds; Shell monomers is selected from vinylbenzene, vinylformic acid, methacrylic acid, acrylic or methacrylic acid C
1-C
6At least a in alkyl ester, acrylamide, n-methylolacrylamide, glycidyl methacrylate, Vinylstyrene, the trimethylene bisacrylamide; Its molecular weight of the acrylic resin of lower molecular weight, high acid value is 3000～10000, and acid number is 130～230; The two-in-one tensio-active agent of negatively charged ion and nonionic is a sulfo-succinic acid polyoxyethylene octyl phenol sodium salt; The initiator persulphate is ammonium persulphate or Potassium Persulphate; High boiling organic solvent is pure ether solvent; Alkaline matter is thanomin or ammoniacal liquor; The preferable range of regulating the pH value is 8～9.
Synthetic emulsion particle of the present invention has " nuclear/shell " bilayer structure, and there is more hole on visible emulsion particle surface under electron microscope.The nuclear of emulsion particle and shell are all harder, and the second-order transition temperature of emulsion has surpassed 100 ℃.And contain more acrylic or methacrylic acid in the polymerization single polymerization monomer of shell, thereby introduced a large amount of carboxyls.In the later stage of synthetic emulsion, add a small amount of high-boiling point alcohol ether organic solvent earlier, make emulsion particle generation swelling to a certain degree, add a certain amount of alkaline matter again, the carboxyl reaction of alkaline matter and shell, make molecular chain fully stretch, a large amount of holes appear in shell, and the moisture in the emulsion constantly is filled into the hole of shell, also further swelling of emulsion particle and pore-forming, size increases, and at this moment the emulsion particle median size can be than the big several times of generic latex grain.When emulsion film was dry, the moisture in the shell is volatilization thereupon also, thereby makes the emulsion particle shell loose porous, and density is low than stratum nucleare.Since the density difference of each layer of emulsion particle structure, light at atmosphere/shell, shell/two interfaces of nuclear can reflect, and the interface refraction coefficient has nothing in common with each other, form the intensive diffuse scattering thus, make film opaque, outward appearance shows as white, has certain opacifying property.
In the methods of the invention, a kind of lower molecular weight, high acid value acrylic resin soln when the preparation seed emulsion, have been added.This lower molecular weight, high acid value resin are as dispersion resin, and its hydrophilic carboxyl can make emulsion particle stably be scattered in the system, have strengthened the stability of pigment dyestuff emulsion in use and storage process.And what of this resin demand have direct influence to the gloss of pigment dyestuff after the emulsion drying and the gloss of end article; Add this dispersion resin and can also reduce the consumption of negatively charged ion and the two-in-one emulsifying agent of nonionic.If this lower molecular weight, high acid value acrylic resin join system too late, can influence polymerization mechanism, may make the emulsion drying after pigment dyestuff lackluster.
When carrying out the core/shell type letex polymerization, the phenomenon of " phase reversion " appears easily.In nuclear and shell monomers, select some polyene-based unsaturated monomers for use, take place partial cross-linkedly when making polymerization between molecular chain, then can significantly strengthen the force of cohesion of nuclear and shell, reduce interpenetrating between nuclear, the shell two-phase, avoid taking place " phase reversion ".The polyene-based unsaturated monomer of selecting for use is generally Vinylstyrene etc.The stratum nucleare amount ofthe cross-linking monomer is not more than 5% of nuclear monomer total amount usually, is preferably 1%～3%.For fear of because of the excessive swelling that influences emulsion particle of shell-crosslinked density, amount ofthe cross-linking monomer is relatively low in the shell monomers, is generally 0.5%～1%.
The polymer-type white pigment dyestuff of the inventive method preparation is a kind of novel pigment.This polymer type organic pigment is a kind of hard vinylbenzene one acrylic type emulsion, its emulsion particle has the structure of porous surface, polymer particle whiteness height, stable performance is difficult for and other component reaction, and weather resistance is good, not easy to change, cost is also lower, can substitute the more expensive rutile titanium dioxide of price, as a kind of white hiding pigment.When preparing water-borne coatings or water color ink, be easy to disperse, and nontoxic with this polymer-type white pigment dyestuff emulsion, good with other component compatibility in the product, can significantly improve the stability in storage and the viscosity stability of water-borne coatings or printing ink.
The principal feature of the inventive method is: (1) adopts 2 step seeded emulsion polymerization technology; (2) emulsion particle is " nuclear/shell " bilayer structure, and nuclear is harder with shell, and shell is rich in carboxyl; (3) at high temperature make emulsion particle generation swelling to a certain degree with a small amount of high boiling organic solvent earlier, add a certain amount of alkaline matter again, the carboxyl reaction of alkaline matter and shell makes further swelling of emulsion particle and pore-forming, and the emulsion particle median size can enlarge several times after the swelling; (4) when emulsion film was dry, the atmosphere/shell of emulsion particle, shell/two interfaces of nuclear can produce certain optical effect, make film opaque, and outward appearance shows as white, glossy, has covering effect; Introduce lower molecular weight, high acid value acrylic resin when (5) preparing seed emulsion as dispersion resin, can improve the gloss of polymer-type white pigment dyestuff, also can strengthen the stability of pigment dyestuff emulsion in use and storage process.
The invention will be further elaborated below in conjunction with embodiment.
Embodiment 1
In the there-necked flask that has agitator, thermometer, add 62 parts of deionized waters, 8 parts of ammoniacal liquor are warming up to 60 ℃, and adding 30 parts of molecular weight is 6000, acid number is 220 acrylic resin, high-speed stirring, 60 ℃ of insulations 1 hour, solid content is 30% acrylic resin soln, viscosimetric is 20～25 seconds, and the pH value is 8～8.5.
In the there-necked flask that has prolong, Dropping feeder, agitator, thermometer, add 38.2 parts of deionized waters, 12 part 30% acrylic resin soln and 2 parts of sulfo-succinic acid polyoxyethylene octyl phenol sodium salt emulsifiers are heated to 73 ℃, add 0.3 part of Potassium Persulphate, drip following mix monomer: 5.5 parts of vinylbenzene, 1.2 parts of methyl methacrylates, 0.3 part of Vinylstyrene, added in 1 hour, and be incubated half an hour in 73 ℃; Drip the shell mix monomer again: 25 parts of vinylbenzene, 6 parts of methyl methacrylates, 3.4 parts of methacrylic acids, 0.1 part of Vinylstyrene added in 5 hours, in 73 ℃ of insulations 0.5 hour; Drip 4 parts of propylene glycol monomethyl ethers again, added in 10 minutes, be incubated half an hour in 73 ℃; Be cooled to add 3 parts of ammoniacal liquor below 60 ℃, be warming up to 90 ℃ again, be incubated 1 hour.Be cooled to below 45 ℃, add 0.2 part of other auxiliary agent, filter through 120 eye mesh screens, get polymer-type white pigment dyestuff emulsion, solid content is 46.4%.
Embodiment 2
The shell mix monomer is 25.5 parts of vinylbenzene, 6.2 parts of methyl methacrylates, and 3.8 parts in vinylformic acid, 0.1 part of n-methylolacrylamide, other prescription is identical with embodiment 1 with technology, gets polymer-type white pigment dyestuff emulsion, and solid content is 47.5%.
Embodiment 3
Monomer all drips the back in 73 ℃ of insulations 0.5 hour; Drip 4 parts of butyl glycol ethers again, added in 10 minutes, be incubated half an hour in 73 ℃; Be cooled to add 2 parts of Monoethanolamine MEA BASFs below 60 ℃, be warming up to 90 ℃ again, be incubated 1 hour, other prescription is identical with embodiment 1 with technology, gets polymer-type white pigment dyestuff emulsion, and solid content is 47.1%.
Embodiment 4
The high acid value, the low-molecular-weight acrylic resin soln that add 6 part 30%, other prescription is identical with embodiment 1 with technology, gets polymer-type white pigment dyestuff emulsion, and dry back resin is white in color, but matt.
Claims (9)
1, a kind of preparation method of polymer-type white pigment dyestuff may further comprise the steps:
(1) in the there-necked flask that agitator, thermometer, prolong are housed, at first add entry, logical nitrogen stirs, and adds the water soluble acrylic resin's of lower molecular weight, high acid value the aqueous solution again, the tensio-active agent two-in-one with negatively charged ion and nonionic is emulsifying agent, with the persulphate is initiator, is slowly to splash into nuclear layer monomer under 60～80 ℃ of conditions in temperature, carries out the free radical emulsion copolymerization, drip off about 1～2 hour, be incubated 0.5～1 hour to emulsion blueing light and get seed emulsion;
Drip shell monomers under (2) 60～80 ℃ of conditions, the dropping time is 4～7 hours, is incubated 0.5～1 hour;
(3) in emulsion, add high boiling organic solvent, fully stir, be incubated 0.5～1 hour, make the abundant swelling of emulsion particle;
(4) add alkaline matter in emulsion, be warming up to about 90 ℃, be incubated 1～2 hour, make emulsion particle surface further swelling and pore-forming, re-adjustment pH value is 7～10, and the cooling back adds other usual auxiliaries and obtains after filtration.
2, the preparation method of polymer-type white pigment dyestuff according to claim 1, it is characterized in that: by weight percentage, the consumption of lower molecular weight, high acid value acrylic resin is 5～15%; The monomer total amount is 30～55%, and wherein nuclear layer monomer accounts for 8～12% of monomer total amount, and shell monomers accounts for 88～92% of monomer total amount; The consumption of the tensio-active agent that negatively charged ion and nonionic are two-in-one is 0.5～3%, and initiator persulphate consumption is 0.2～2.5%, and the consumption of water is 30～53%, and the consumption of high boiling organic solvent is 1～2%, and the consumption of alkaline matter is 1～3%.
3, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: described nuclear layer monomer is selected from vinylbenzene, methacrylic acid C
1-C
6In alkyl ester, Vinylstyrene, n-methylolacrylamide, the trimethylene bisacrylamide at least three kinds.
4, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2 is characterized in that: described shell monomers is selected from vinylbenzene, vinylformic acid, methacrylic acid, acrylic or methacrylic acid C
1-C
6At least a in alkyl ester, acrylamide, n-methylolacrylamide, glycidyl methacrylate, Vinylstyrene, the trimethylene bisacrylamide.
5, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: its molecular weight of the acrylic resin of described lower molecular weight, high acid value is 3000～10000, acid number is 130～230.
6, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: the two-in-one tensio-active agent of described negatively charged ion and nonionic is a sulfo-succinic acid polyoxyethylene octyl phenol sodium salt.
7, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: described initiator persulphate is ammonium persulphate or Potassium Persulphate.
8, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: described high boiling organic solvent is pure ether solvent.
9, the preparation method of polymer-type white pigment dyestuff according to claim 1 and 2, it is characterized in that: described alkaline matter is thanomin or ammoniacal liquor.
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| CN 200310112156 CN1240782C (en) | 2003-11-17 | 2003-11-17 | Method for preparing polymer type white organic pigments |
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| CN 200310112156 CN1240782C (en) | 2003-11-17 | 2003-11-17 | Method for preparing polymer type white organic pigments |
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| CN1240782C CN1240782C (en) | 2006-02-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486845A (en) * | 2008-01-14 | 2009-07-22 | 深圳市海川实业股份有限公司 | Method for preparing nano colouring matter aqueous dispersions |
| CN101787100A (en) * | 2010-02-10 | 2010-07-28 | 黄山加佳科技有限公司 | Synthesis technology of water-emulsion fluorescent pigment |
| CN102659990A (en) * | 2012-05-02 | 2012-09-12 | 西北工业大学 | Method for preparing stable-dispersibility pigment/polymer core-shell structure composite granules by using by polymer-wrapped pigment particles |
| CN110790982A (en) * | 2019-10-30 | 2020-02-14 | 东莞理工学院 | Polymer material coating of pigment yellow 138 or derivative thereof, preparation method thereof and downstream product thereof |
| CN116102682A (en) * | 2022-11-16 | 2023-05-12 | 南京瑞固聚合物有限公司 | Acrylic ester polymer with hollow structure and synthesis process thereof |
-
2003
- 2003-11-17 CN CN 200310112156 patent/CN1240782C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101486845A (en) * | 2008-01-14 | 2009-07-22 | 深圳市海川实业股份有限公司 | Method for preparing nano colouring matter aqueous dispersions |
| CN101787100A (en) * | 2010-02-10 | 2010-07-28 | 黄山加佳科技有限公司 | Synthesis technology of water-emulsion fluorescent pigment |
| CN102659990A (en) * | 2012-05-02 | 2012-09-12 | 西北工业大学 | Method for preparing stable-dispersibility pigment/polymer core-shell structure composite granules by using by polymer-wrapped pigment particles |
| CN110790982A (en) * | 2019-10-30 | 2020-02-14 | 东莞理工学院 | Polymer material coating of pigment yellow 138 or derivative thereof, preparation method thereof and downstream product thereof |
| CN110790982B (en) * | 2019-10-30 | 2021-02-09 | 东莞理工学院 | Polymer material coating of pigment yellow 138 or derivative thereof, preparation method thereof and downstream product thereof |
| CN116102682A (en) * | 2022-11-16 | 2023-05-12 | 南京瑞固聚合物有限公司 | Acrylic ester polymer with hollow structure and synthesis process thereof |
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| CN1240782C (en) | 2006-02-08 |
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