CN1800224A - Fluorocarbon elastomer latex and its preparation method - Google Patents
Fluorocarbon elastomer latex and its preparation method Download PDFInfo
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- CN1800224A CN1800224A CN 200510036487 CN200510036487A CN1800224A CN 1800224 A CN1800224 A CN 1800224A CN 200510036487 CN200510036487 CN 200510036487 CN 200510036487 A CN200510036487 A CN 200510036487A CN 1800224 A CN1800224 A CN 1800224A
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Abstract
The invention relates to a fluorocarbon elastic solid emulsion and it's preparing method. The method uses fluorocarbon base to quench the acrylate macromole. The formation of the emulsion used base is that the organic fluorine base with the base total amount 10-30%, the olefin unsaturated acid ester base with the base total amount 5-15% and the olefin acrylate base with the base total amount 55-85%.
Description
Technical field:
The present invention relates to a kind of monomer modified acrylic ester elastic emulsion of organic fluorine that is used as building coating and preparation method thereof.A kind of fluorocarbon elastomer latex and preparation method thereof particularly.
Background technology:
Domestic and international widely used elastomeric propylene yogurt liquid adopts acrylic ester monomer as major ingredient usually at present; though this emulsion has good low temperature flexibility and elasticity; but the weathering resistance of latex film is bad; contamination resistance with the elastic exterior coating material of its preparation is very poor; As time goes on; all occur to some extent filming honeycomb cracks or occur varying in size along with body of wall sand-cement slurry ground cracking the crackle of filming, influenced the decoration provide protection of coating.
Summary of the invention:
For overcoming in the prior art, the elastomeric propylene yogurt liquid of use adopts the building coating of acrylic ester monomer as major ingredient usually, and the deficiency of bringing the object of the present invention is to provide a kind of fluorocarbon elastomer latex and preparation method thereof.Utilize F-C key in the organic fluorine to have maximum bond energy, stable to heat, light, be difficult for uviolize and wear out, and it has very low surface tension, have the characteristic of good contamination resistance.Advantages such as organic fluorine modification acrylate elastic emulsion dry film has that temp. variation resistant, low temperature elasticity after-tack well, anti-, anti-contamination, water-tolerant, fabulous weathering resistance and resistance to cracking are to satisfy the requirement of high-performance coating.This method is by copolyreaction that organic fluorine is monomer-grafted on the high polymer main chain of acrylate, thereby improved the weathering resistance of this elastic emulsion, with (methyl) thus isobornyl acrylate grafts on the contamination resistance that improved the elastic emulsion film on the high polymer main chain of acrylate and surface hardness to realize goal of the invention.
A kind of fluorocarbon elastomer latex of the present invention, the organic fluorine modified acrylic ester copolymer that main chain is made of following repeated structural unit, its main chemism and backbone structure unit molecular formula are:
R--organo-functional group or organic chain
The preparation method of fluorocarbon elastomer latex of the present invention may further comprise the steps:
1 mixture in the nonionogenic tenside of the reactive anion surfactant of total monomer weight 0.5-2.5% and 0.25-0.50% is an emulsifying agent, sodium bicarbonate with 0.1-0.5% is a buffer reagent, with water is medium, preparation component one, and it is standby to drop into reactor;
2 will be in the organic fluorine monomer of total monomer weight 10-30% weight, in the ethylenic unsaturated acid ester monomer of monomer total amount 5-15% weight with in the olefinic acrylic ester monomer of monomer total amount weight 55-85% weight, and be emulsifying agent in the mixture of the nonionogenic tenside of the reactive anion surfactant of total monomer weight 0.5-2.5% and 0.25-1.0%, with water is medium, preparation monomer pre-emulsion is component two under the ultrasonic wave effect, and is standby;
3 heat up component one, are initiator in the water-soluble persulphate of total monomer weight 0.2-1.0%, carry out free-radical emulsion polymerization under 60-90 ℃ of condition.
After 4 reactions finish,, regulate the pH value, obtain after filtration to 8-9 with the basic solution neutralization.
The second-order transition temperature of the emulsion polymeric product of step 3 gained is-50--20 ℃.
The organic fluorine monomer that contains unsaturated double-bond is vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester or dodecafluorhe-ptylacrylate, also can be the mixture of vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester or dodecafluorhe-ptylacrylate.
Ethylenic unsaturated acid ester monomer is isobornyl acrylate or isobornyl methacrylate, also can be the mixture of isobornyl acrylate or isobornyl methacrylate.
The olefinic acrylic ester monomer is vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate or N hydroxymethyl acrylamide, also can be the mixture of vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate or N hydroxymethyl acrylamide.
Reactive anion surfactant is selected from Methacrylamide sodium isopropyl xanthate salt or methylpropenyl sulfonate sodium.
Nonionogenic tenside is selected from polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, fatty alcohol-polyoxyethylene ether.
Initiator comprises ammonium persulphate or Potassium Persulphate metal-salt for water-soluble persulphate commonly used.The basic solution of neutralization usefulness adopts KOH.
Embodiment;
Below by embodiment invention preparation method is further set forth.
Embodiment 1
In the four-hole boiling flask that has prolong, Dropping feeder, agitator, thermometer, add deionized water 150 grams, Methacrylamide sec.-propyl sulfonate 3.5 grams, polyoxyethylene nonylphenol ether 1.85 grams, sodium bicarbonate 0.27 gram.Fully be warming up to 75-80 ℃ after the dissolving.Begin after 5 minutes to drip by methyl methacrylate 15.0 grams, methacrylic acid 12.5 grams, butyl acrylate 135.0 grams, isobornyl methacrylate 27.5 grams, vinylformic acid hexafluoro butyl ester 47.5 grams, NP-40 1.5 grams, polyoxyethylene nonylphenol ether 1.5 grams, 2.0 the monomer pre-emulsion of the mixture preparation that gram N hydroxymethyl acrylamide, deionized water 50.0 grams are formed drips the aqueous solution that ammonium persulphate 1.75 restrains (being dissolved in the 50.0 gram deionized waters) simultaneously.2.5-3 hour add, in 80 ℃ of reactions 2 hours.Add tertbutyl peroxide 0.2 gram (being dissolved in the 5 gram deionized waters) aqueous solution, be cooled to 70 ℃ after 30 minutes, drip rongalite 0.2 gram (being dissolved in the 5 gram deionized waters) aqueous solution, and then be incubated 1 hour.Be cooled to below 40 ℃, regulate the pH value to 8-9 with KOH, after filtration must be with the organic fluorine modification acrylate elastomer emulsions of blue light.
Embodiment 2
In the four-hole boiling flask that has prolong, Dropping feeder, agitator, thermometer, add deionized water 150 grams, methylpropenyl sulfonate 3.6 grams, polyoxyethylene octylphenol ether 1.8 grams, sodium bicarbonate 0.45 gram.Fully be warming up to 75-80 ℃ after the dissolving.Begin after 5 minutes to drip by methyl methacrylate 35 grams, vinylformic acid 10.0 grams, butyl acrylate 120 grams, isobornyl acrylate 10.0 grams, dodecafluorhe-ptylacrylate 15 grams, vinylformic acid hexafluoro butyl ester 30.0 grams, 4.0 gram N hydroxymethyl acrylamide, polyoxyethylene octylphenol ether 1.5 grams, methylpropenyl sodium sulfonate 3.0 grams, the monomer pre-emulsion of the mixture preparation that deionized water 50.0 grams are formed drips the aqueous solution that ammonium persulphate 1.5 restrains (being dissolved in the 35 gram deionized waters) simultaneously.2.5-3 hour add, in 80 ℃ of reactions 2 hours.Add tertbutyl peroxide 0.25 gram (being dissolved in the 5 gram deionized waters), be cooled to 70 ℃ after 30 minutes, drip rongalite 0.25 gram (being dissolved in the 5 gram deionized waters), and then be incubated 1 hour.Be cooled to below 40 ℃, regulate the pH value to 8-9 with KOH, after filtration must be with the organic fluorine modification acrylate elastomer emulsions of blue light.
Embodiment 3
In the four-hole boiling flask that has prolong, Dropping feeder, agitator, thermometer, add deionized water 125 grams, Methacrylamide sec.-propyl sulfonate 3.59 grams, fatty alcohol-polyoxyethylene ether 1.915 grams, sodium bicarbonate 0.20 gram.Fully be warming up to 75-80 ℃ after the dissolving.Begin after 5 minutes to drip by methyl methacrylate 52.50 grams, methacrylic acid 12.67 grams, butyl acrylate 100.0 grams, isobornyl methacrylate 22.5 grams, dodecafluorhe-ptylacrylate 47.5 grams, N hydroxymethyl acrylamide 3.0 grams, NP-40 1.5 grams, polyoxyethylene octylphenol ether 1.5 grams, the monomer pre-emulsion of the mixture preparation that deionized water 51.5 grams are formed drips the aqueous solution that ammonium persulphate 1.8 restrains (being dissolved in the 50 gram deionized waters) simultaneously.2.5-3 hour add, in 80 ℃ of reactions 2 hours.Add tertbutyl peroxide 0.2 gram (being dissolved in the 5 gram deionized waters), be cooled to 70 ℃ after 30 minutes, drip rongalite 0.2 gram (being dissolved in the 5 gram deionized waters), and then be incubated 1 hour.Be cooled to below 40 ℃, regulate the pH value to 8-9 with KOH, after filtration must be with the organic fluorine modification acrylate elastomer emulsions of blue light.
The fluorocarbon elastomer latex performance index that the present invention relates to are
| Test item | Performance index |
| The ionic particle diameter solid content of outward appearance (%) | The about 80-90 nanometer 46 ± 2% of the blue translucent emulsion anionic of ruddiness of milky white colour band |
| pH | 7.0-9.0 |
| Tg (second-order transition temperature) | -25℃ |
| (25 ℃ of MFT (minimum film-forming temperature) brookfield viscosities, No. 3 rotors, 30 rev/mins) mechanical stability chemical stability freeze-thaw stability | -20 ℃ of 1000-4000cps 9000r/min (10min does not have breakdown of emulsion) pass through (not having flocculation) by (1: 1) |
Claims (9)
1 one kinds of fluorocarbon elastomer latexes is characterized in that: fluorocarbon elastomer latex is the organic fluorine modified acrylic ester copolymer that a kind of main chain is made of repeated structural unit, and main chain repeated structural unit molecular formula is:
2 one kinds of fluorocarbon elastomer latex preparation methods may further comprise the steps:
(1) mixture in the nonionogenic tenside of the reactive anion surfactant of total monomer weight 0.5-2.5% and 0.25-0.50% is an emulsifying agent, sodium bicarbonate with 0.1-0.5% is a buffer reagent, with water is medium, preparation component one, and it is standby to drop into reactor;
(2) will be in the organic fluorine monomer that contains unsaturated double-bond of total monomer weight 10-30% weight, in the ethylenic unsaturated acid ester monomer of monomer total amount 5-15% weight with in the olefinic acrylic ester monomer of monomer total amount weight 55-85% weight, and be emulsifying agent in the mixture of the nonionogenic tenside of the reactive anion surfactant of total monomer weight 0.5-2.5% and 0.25-1.0%, with water is medium, preparation monomer pre-emulsion is component two under the ultrasonic wave effect, and is standby;
(3) component one being heated up, is initiator in the water-soluble persulphate of total monomer weight 0.2-1.0%, carries out free-radical emulsion polymerization under 60-90 ℃ of condition;
(4) after reaction finishes,, regulate the pH value, obtain after filtration to 8-9 with the basic solution neutralization.
3 a kind of fluorocarbon elastomer latex preparation methods according to claim 2 is characterized in that the second-order transition temperature of the emulsion polymeric product of step (3) gained is-50--20 ℃.
4 a kind of fluorocarbon elastomer latex preparation methods according to claim 2, it is characterized in that the described organic fluorine monomer that contains unsaturated double-bond is vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester or dodecafluorhe-ptylacrylate, also can be vinylformic acid hexafluoro butyl ester, methacrylic acid hexafluoro butyl ester or dodecafluorhe-ptylacrylate mixture.
5 a kind of fluorocarbon elastomer latex preparation methods according to claim 2, it is characterized in that described ethylenic unsaturated acid ester monomer is isobornyl acrylate or isobornyl methacrylate, also can be isobornyl acrylate or isobornyl methacrylate mixture.
6 a kind of fluorocarbon elastomer latex preparation methods according to claim 2, it is characterized in that described olefinic acrylic ester monomer is vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate or N hydroxymethyl acrylamide, also can be vinylformic acid, methacrylic acid, methyl methacrylate, butyl acrylate or N hydroxymethyl acrylamide mixture.
7 a kind of fluorocarbon elastomer latex preparation methods according to claim 2 is characterized in that described reactive anion surfactant is Methacrylamide sodium isopropyl xanthate salt or methylpropenyl sulfonate sodium.
8 a kind of fluorocarbon elastomer latex preparation methods according to claim 2 is characterized in that described nonionogenic tenside is polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether or fatty alcohol-polyoxyethylene ether.
9 a kind of fluorocarbon elastomer latex preparation methods according to claim 2 is characterized in that described initiator is water-soluble persulphate, and the basic solution of neutralization usefulness adopts KOH.
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| CN 200510036487 CN1800224A (en) | 2005-08-15 | 2005-08-15 | Fluorocarbon elastomer latex and its preparation method |
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| CN 200510036487 CN1800224A (en) | 2005-08-15 | 2005-08-15 | Fluorocarbon elastomer latex and its preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845114A (en) * | 2010-05-28 | 2010-09-29 | 北京化工大学 | Preparation method of fluorinated acrylate microemulsion |
| CN102504084A (en) * | 2011-09-29 | 2012-06-20 | 江苏博特新材料有限公司 | Preparation method of high-performance concrete curing agent with hydrophobic property |
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
| CN106566442A (en) * | 2016-10-28 | 2017-04-19 | 天长市永泰密封材料有限公司 | Dustproof stain-resistant container water-based sealant and preparation method thereof |
| CN106893022A (en) * | 2015-12-17 | 2017-06-27 | 中昊晨光化工研究院有限公司 | A kind of aqueous broken emulsion of polymer containing fluorin and preparation method thereof |
-
2005
- 2005-08-15 CN CN 200510036487 patent/CN1800224A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
| CN102712722B (en) * | 2009-12-03 | 2014-12-10 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
| CN101845114A (en) * | 2010-05-28 | 2010-09-29 | 北京化工大学 | Preparation method of fluorinated acrylate microemulsion |
| CN101845114B (en) * | 2010-05-28 | 2012-07-18 | 北京化工大学 | Preparation method of fluorinated acrylate microemulsion |
| CN102504084A (en) * | 2011-09-29 | 2012-06-20 | 江苏博特新材料有限公司 | Preparation method of high-performance concrete curing agent with hydrophobic property |
| CN106893022A (en) * | 2015-12-17 | 2017-06-27 | 中昊晨光化工研究院有限公司 | A kind of aqueous broken emulsion of polymer containing fluorin and preparation method thereof |
| CN106566442A (en) * | 2016-10-28 | 2017-04-19 | 天长市永泰密封材料有限公司 | Dustproof stain-resistant container water-based sealant and preparation method thereof |
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