CN1935892A - Elastic fluororesin emulsion, and its preparing method and use - Google Patents
Elastic fluororesin emulsion, and its preparing method and use Download PDFInfo
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- CN1935892A CN1935892A CN 200610032413 CN200610032413A CN1935892A CN 1935892 A CN1935892 A CN 1935892A CN 200610032413 CN200610032413 CN 200610032413 CN 200610032413 A CN200610032413 A CN 200610032413A CN 1935892 A CN1935892 A CN 1935892A
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- elastic fluororesin
- elastic
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Abstract
The invention discloses elastic fluoro-resin latex and its preparation method and application. The elastic fluoro-resin latex is made up of solving agent type elastic fluoro-resin, emulsifying agent, neutralizer and water with their weight ratio 1:0.02-0.07:0.12-0.21:1.3-3.5, solid content 20-50%, T-4 cup viscosity 10s-60s. The emulsifying agent is selected from nonylphenol polyethenoxy ether series and average adding surface active agent, surfactant series. The preparation method includes neutralizing, emulsifying, distilling solvent, adding neutralizer, and phase inversion emulsifying. The produced elastic fluoro-resin latex has the advantages of simple technology, low cost, good weathering resistance, chemical resistance and mechanical features, good elasticity etc.
Description
Technical field
The present invention relates to a kind of elastic fluororesin emulsion and preparation method thereof and application, especially relate to a kind of elastic fluororesin emulsion and Phase inversion emulsification preparation method and application.
Background technology
Outside the building wall protection and decoration aspect, advantages such as coating is various with its color, cost is low, easy construction, easy renewal are used more and more.Yet external wall generally is to form with concrete, cement pre-fabricated panel or cement sand plaster, and these metopes be full of cracks can occur mostly through spring, summer, autumn and winter temperature variation and Exposure to Sunlight wind and weather, and the crackle width mostly is 1～3 millimeter.These crackles can make the be full of cracks thereupon of generally filming.For solving this difficult problem, more and more come into one's own with addition of the elastic exterior coating material of flexible emulsion.
At present, preparation elastic exterior coating material employed key ingredient elastic emulsion mostly is pure third and organosilicon crylic acid latex, belongs to low and middle-grade products, compares with fluorine resin at aspects such as weathering resistance, chemical-resistants to have certain gap.
Fluoropolymer with the Fluorine containing olefine preparation has good weathering resistance, chemical-resistant and good mechanical property, but fluoroolefin (as trifluorochloroethylene, tetrafluoroethylene, vinyl fluoride, vinylidene etc.) is gaseous state at normal temperatures, be difficult to water-soluble medium, thereby be difficult to form stable aggretion type water-based fluororesin.
Daikin company [JP99-05951] once was emulsifying agent with the ammonium perfluorocaprylate, and cyclohexyl Vinyl Ether, hydroxyl butyl vinyl ether, ethyl vinyl ether and trifluorochloroethylene are that monomer carries out letex polymerization, make the water-based fluororesin emulsion of solid content 48%; [JP04,164,990 (1992)] such as Suzuki of Japan are with fluorine-containing cats product C
16F
17SO
2NH (CH
2)
3NMe
3Cl and not fluorine-containing cats product C
16H
33NM
e 3It is that monomer carries out letex polymerization that Cl compound emulsifying agent, acrylate, N hydroxymethyl acrylamide, vinylformic acid contain fluoroalkyl (for example trifluoroethyl etc.) ester, develops the thermosetting water fluoro-resin of good stability.But costing an arm and a leg of fluorine surfactant, kind is limited, and therefore producing water-based fluororesin is subjected to certain restriction." preparation research of perfluorocarbon coating resin latex " (P3-6) there are following report " organic fluorine industry ", 2003 the 3rd phases: Perfluorocaprylic Acid and SOCl
2Through chlorination reaction, get perfluorooctane chloride (I), (I) react 3h with thanomin down at 30 ℃ again and obtain N-hydroxyethyl perfluor decoylamide (II), product is with the trichloromethane recrystallization, be catalyzer with the dibutyl tin laurate then, earlier with 2,4-toluene diisocynate alcohol (TDI) is in 65 ℃～70 ℃ reaction 3h under the condition of anhydrous and oxygen-free, and then with methacrylic acid-β-hydroxyl ethanol in 75 ℃-80 ℃ the reaction 4h, N-hydroxyethyl perfluor decoylamide vinylformic acid alcohol monomer (III).With disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate and OP-10 is emulsifying agent, tertbutyl peroxide is an initiator, water is medium, above-mentioned monomer and other alcohols monomers carry out letex polymerization and obtain resin latex, this latex stable performance, have good water-fast, anti-solvent and alkaline resistance properties etc., can be used for preparing the good perfluorocarbon coating of weathering resistance, chemical-resistant and mechanical property." the water-borne coatings preliminary study of fluoro-resin " (" coating technology ", the 3rd phase of calendar year 2001, P5-6) report: the method for carrying out emulsion copolymerization with trifluorochloroethylene and ethyl vinyl ether, water-borne coatings is studied with the copolymerization of fluoro-resin, by adjusting two kinds of mol ratios that monomer is different, studied of the influence of factors such as dispersion agent, temperature of reaction, reaction times, and trifluorochloroethylene and two kinds of monomeric reactivity ratios of ethyl vinyl ether have been done preliminary research polyreaction.These documents have proposed the employing different monomers and have carried out polymeric fluoro-resin emulsion preparation method, but product all lacks flexibility.Be used for the coating preparation, prepared coating contamination resistance is also relatively poor.
Summary of the invention
The purpose of this invention is to provide a kind of elastic fluororesin emulsion and preparation method thereof and application, elastic fluororesin emulsion of the present invention is fluorine-containing polynary monomer copolymer; Use the inventive method to prepare described elastic fluororesin emulsion, technology is simple, and preparation cost is low; Elastic fluororesin water-based exterior wall paint with the preparation of this elastic fluororesin emulsion not only has good weathering resistance, chemical-resistant and favorable mechanical performance, can self-vulcanizing, and also the contamination resistance of paint film and elasticity all are far superior to national Specification.
The objective of the invention is to be achieved through the following technical solutions.
The present invention's elastic fluororesin emulsion is made up of solvent-borne type elastic fluororesin, emulsifying agent, neutralizing agent and water, and each components by weight is: solvent-borne type elastic fluororesin: emulsifying agent: neutralizing agent: water=1: 0.02～0.07: 0.12～0.21: 1.3～3.5; Solid content 20%～50%, T-4 cup viscosity 10 seconds～60 seconds;
Described solvent-borne type elastic fluororesin is fluorine-containing polynary monomer copolymer, and solid content is 53～65wt%, and hydroxyl value is 40～70mg KOH/g, and acid number is 10～25mg KOH/g, and T-4 cup viscosity is 60～140 seconds.
Described emulsifying agent can be polyoxyethylene nonylphenol ether series and peregal surfactants, and 1: 0.2～1.0 is composite by weight, or polyoxyethylenated castor oil series or polyether thiourea hydrochlorate;
Described neutralizing agent can be ammoniacal liquor or organic amine, for example: thanomin, trolamine etc.;
Aspects such as comprehensive source, price are considered, preferred ammoniacal liquor of neutralizing agent or thanomin, and preferred polyoxyethylene nonylphenol ether series of emulsifying agent and peregal surfactants, composite by weight 1: 0.2～1.0.
The present invention's elastic fluororesin emulsion preparation method may further comprise the steps: (1) neutralization, emulsification: add the neutralizing agent that is equivalent to 0.02～0.07 times of its weight and be neutralized to pH7～8 in the solvent-borne type elastic fluororesin, add the emulsifying agent that is equivalent to 0.12～0.21 times of its weight again, stirred 0.2～1 hour; (2) solvent distillation: mixed solution is steamed solvent under 80～100 ℃ and 500～760mmHg vacuum, this solvent is capable of circulation to be used for polymerization or to make thinner and use; Above-mentioned (1), (2) step sequencing can be put upside down, promptly also can first solvent distillation, and neutralization, emulsification again; (3) add neutralizing agent: add the neutralizing agent that is equivalent to 0.02～0.05 times of solvent-borne type elastic fluororesin weight in the liquid behind solvent distillation, stirred 0.2～1 hour; (4) Phase inversion emulsification: add the water that is equivalent to 1.3～3.5 times of solvent-borne type elastic fluororesin weight, stir and carried out emulsification in 0.5～2 hour, promptly obtain the present invention's elastic fluororesin emulsion.
Above-mentioned raw materials used solvent-borne type elastic fluororesin of (1) step can prepare with following method:
It prepares raw materials used initiator, fluorochemical monomer, function monomer, elasticity monomer and the solvent of comprising, each composition weight proportioning is: initiator: fluorochemical monomer: function monomer: the elasticity monomer: solvent=1: 15～16: 4.5～5.1: 8.8～9.2: 14.5～15;
Described initiator can be in superoxide (for example, benzoyl peroxide) or the azo compound (for example, Diisopropyl azodicarboxylate) a kind of;
Described fluorochemical monomer can be vinylidene, tetrafluoroethylene or trifluorochloroethylene (F
2C=CClF) a kind of in;
Described function monomer is hydroxyl vinyl ethers compound [H
2C=CH (OCH
2CH
2)
n-CH
2OH n=0-2] (for example: the hydroxyl vinyl-n-butyl ether) and the mixture of olefin(e) acid;
Described elasticity monomer is for being selected from acrylic compounds [R
2CH=CH (CH
2)
nCO
2H R
2=H or alkyl n=5-8] (for example: Isooctyl acrylate monomer), the mixture of one or both in the suitable divinyl;
Described solvent is one or both or the two or more mixture that is selected from N-BUTYL ACETATE, methyl iso-butyl ketone (MIBK), the benzene kind solvent.
This solvent-borne type elastic fluororesin is a multiple copolymer, mainly carries out polymerization by following several monomers:
A:F
2C=CCLF; B:R
1CO
2CH=CH
2R
1=C
1-C
3Normal chain alkyl; C:H
2C=CH (OCH
2CH
2)
n-CH
2OHn=0-2; D:R
2CH=CH (CH
2)
nCO
2H R
2=H or alkyl n=5-8; E:R
3CO
2CH=CH
2R
3=C
4-C
8Positive structure or isomery alkyl; Five kinds of monomer weight ratios are: A: B: C: D: E=1: 15-20: 1.5-2: 2.5-3.5: 8-13;
Preparation manipulation step: in autoclave, add other the four kinds of monomers except that fluorochemical monomer, deflate, be pressed into fluorochemical monomer again,, react under 0.6～1.2MPa condition and got final product in 16～26 hours at 65～75 ℃.
The application of the present invention's elastic fluororesin emulsion in preparation elastic fluororesin water-borne coatings.
The present invention's elastic fluororesin emulsion, can be used for preparing the elastic fluororesin water-borne coatings, be particularly useful for being mixed with and contain following component, press the elastic fluororesin water-borne coatings of column weight amount: elastic fluororesin emulsion 16～22 than preparation, linking agent 0.8～1.4, color stuffing 0～28; Auxiliary agent 1.5～5.0;
Described linking agent can give polymers for polyisocyanates;
Described color stuffing can be the mixture of a kind of in titanium dioxide, water-ground limestone, talcum powder, mica powder, the kaolin etc. or at least two kinds;
Described auxiliary agent comprises known dispersion agent, wetting agent, defoamer, stablizer, biocide mildewcide, film coalescence aid etc., can add as required.
Compound method: elastic fluororesin emulsion of the present invention and color stuffing are mixed, after stirring, add linking agent, add suitable adjuvants in case of necessity, stir, can use.
The present invention's elastic fluororesin emulsion adopts conventional surfactants to make emulsifying agent, greatly reduces cost, and preparation technology is simple; The elastic fluororesin water-borne coatings that contains this elastic fluororesin emulsion, many excellent properties of fluoro-resin have been inherited, for example have good weathering resistance, chemical-resistant and favorable mechanical performance etc., can self-vulcanizing, and the present invention has solved the contradictory problems of ubiquitous contamination resistance of elastic coating and extensibility aspect fruitfully, the contamination resistance of product paint film and elasticity all substantially exceed the national standard requirement, have good environmental benefit and social benefit.
Embodiment
The invention will be further described below in conjunction with embodiment, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
The preparation embodiment of solvent-borne type elastic fluororesin, elastic fluororesin emulsion
(1) preparation of solvent-borne type elastic fluororesin: 24.35g vinyl acetate, 47.5g hydroxyethyl allyl ether, 15.05g undecylenic acid, 16.7g Diisopropyl azodicarboxylate, Isooctyl acrylate monomer 98.65g, butyl acrylate 51.2g and 247g N-BUTYL ACETATE are put into 1.0 liters of stainless steel autoclaves, decompression deflates, be pressed into the 255g trifluorochloroethylene, 65-75 ℃ of reaction 20 hours, get fluoro-resin 726g.Product solid content 61.2wt%, T-4 cup viscosity 148 seconds, hydroxyl value 53mgKOH/g, carboxylic value 13mgKOH/g.
(2) preparation of elastic fluororesin emulsion: the solvent-borne type elastic fluororesin 70g that gets above-mentioned (one) preparation puts into the 250ml there-necked flask, steam solvent 23g, add thanomin and transfer pH to 8.0, add NP-103.9g, OS-15 3.9g and distilled water 70g simultaneously, be stirred to the translucent milky white liquid of appearance and get final product.Gained elastic fluororesin emulsion solid content 42%, T-4 cup viscosity 11 seconds.
Embodiment 2-8: elastic fluororesin emulsion prepares embodiment
Operation steps and reaction conditions are with embodiment 1, and each composition weight proportioning sees Table 1, and gained elastic fluororesin emulsion performance sees Table 2.
Each amounts of components of table 1 embodiment 2-8
| Project name | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 |
| Elastic fluororesin g (61%) | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| Ammoniacal liquor g (25%) | 6.2 | 7.5 | 10.5 | 6.5 | |||
| Thanomin g | 3.2 | 4.5 | |||||
| Trolamine g | 2.2 | ||||||
| NP-10g | 3.6 | 4.5 | 4.5 | ||||
| NP-30g | 4.5 | 4.5 | 3.9 | 3 | |||
| OS-15g | 2.1 | 2.5 | 2 | 2 | 2.6 | 3.9 | 3 |
| Water g | 100 | 70 | 70 | 70 | 80 | 70 | 120 |
Table 2 elastic fluororesin emulsion performance
| The mensuration project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Solid content wt% | 41 | 41 | 42 | 41 | 42 | 41 | 26 |
| T-4 cup viscosity second | 16 | 18 | 15 | 40 | 56 | 15 | 14 |
| The pH value | 7.2 | 7.6 | 8.2 | 8.0 | 7.4 | 7.8 | 7.7 |
| Outward appearance | White is to light yellow translucent liquid | ||||||
| Freeze-thaw stability | By | ||||||
| Calcium ion stability | By | ||||||
| Mechanical stability | By | ||||||
| Thermostability | By | ||||||
Embodiment 9: elastic fluororesin water-borne coatings embodiment
White elastic fluororesin water-borne coatings preparation: with 12g distilled water, 22g titanium dioxide (R902), 0.8g dispersion agent (5040), 0.4g defoamer (F111), 0.2gpH stablizer (306), 0.2g biocide mildewcide (F10) is placed in the shredder and ground 15-20 minute, makes its homodisperse, adds 0.2g defoamer (F111) again, 1.2g thickening material (3116), 1.0g (solid content 42% pH7.5), stirs and got final product in 10 minutes for film coalescence aid (alcohol ester 12) and 54g elastic fluororesin emulsion.The viscosity 85KU of gained elastic fluororesin water-borne coatings.Add 1.25g linking agent (polyisocyanate prepolymers) and stir, can brush.
Embodiment 10: elastic fluororesin water-borne coatings embodiment
Elastic fluororesin water-borne coatings preparation that white is unglazed: 2g water, 40g titanium dioxide slurry (solid content 70%), 1.5g thickening material (3116) and 0.1g biocide mildewcide (F10) are placed on the interior grinding of shredder 15-20 minute, add 0.4g defoamer (NXZ), 1.0 film coalescence aid (alcohol ester 12) and 45g elastic fluororesin emulsion (solid content 42% again, pH7.5), stirring got final product in 10 minutes.Gained elastic fluororesin water-borne coatings viscosity 86KU.Add 1.1g linking agent (polyisocyanates gives polymers) and stir, can brush.Specific performance sees Table 3.
Table 3 elastic fluororesin water-borne coatings performance
| Interventions Requested | Technical indicator | Assay |
| At condition in container | Stir the no lump in back, evenly attitude | Meet the requirements |
| Application property | Brush twice accessible | Meet the requirements |
| Smear outward appearance | Normally | Meet the requirements |
| Time of drying, h | ≤2 | 1 |
| Contrast ratio (white or light color) | ≥0.90 | 0.93 |
| Water tolerance, 96h | No abnormal | 288h is no abnormal |
| Alkali resistance, 48h | No abnormal | 288h is no abnormal |
| Abrasion resistance, inferior | ≥1000 | 5000 times no abnormal |
| The coating freeze-thaw resistance | Never degenerate | Meet the requirements |
| Coating temperature-change resistance (10 times) | No abnormal | No abnormal |
| Contamination resistance | ＜30 | 17.8 |
| Tensile strength | ≥1.0 | 1.9 |
| Elongation at break | ≥200 | 269 |
| Artificial accelerated aging, h | 400 hours non-foaming, and nothing is peeled off | 1000 hours no abnormal |
Claims (4)
1, a kind of elastic fluororesin emulsion, it is characterized in that, be made up of solvent-borne type elastic fluororesin, emulsifying agent, neutralizing agent and water, each components by weight is: solvent-borne type elastic fluororesin: emulsifying agent: neutralizing agent: water=1: 0.02～0.07: 0.12～0.21: 1.3～3.5; Solid content 20%～50%, T-4 cup viscosity 10 seconds～60 seconds;
Described solvent-borne type elastic fluororesin is fluorine-containing polynary monomer copolymer, and solid content is 53～65wt%, and hydroxyl value is 40～70mgKOH/g, and acid number is 10～25mgKOH/g, and T-4 cup viscosity is 60～140 seconds;
Described emulsifying agent is polyoxyethylene nonylphenol ether series and peregal surfactants, and 1: 0.2～1.0 is composite by weight, or polyoxyethylenated castor oil series or polyether thiourea hydrochlorate;
Described neutralizing agent is ammoniacal liquor or organic amine.
2, elastic fluororesin emulsion according to claim 1 is characterized in that, described organic amine is a thanomin.
3, the preparation method of elastic fluororesin emulsion according to claim 1, it is characterized in that, may further comprise the steps: (1) neutralization, emulsification: in the solvent-borne type elastic fluororesin, add the neutralizing agent that is equivalent to 0.02～0.07 times of its weight and be neutralized to pH7～8, add the emulsifying agent that is equivalent to 0.12～0.21 times of its weight again, stirred 0.2～1 hour; (2) solvent distillation: mixed solution is steamed solvent under 80～100 ℃ and 500～760mmHg vacuum, this solvent is capable of circulation to be used for polymerization or to make thinner and use; Described (1), (2) step sequencing can be put upside down; (3) add neutralizing agent: add the neutralizing agent that is equivalent to 0.02～0.05 times of solvent-borne type elastic fluororesin weight in the liquid behind solvent distillation, stirred 0.2～1 hour; (4) Phase inversion emulsification: add the water that is equivalent to 1.3～3.5 times of solvent-borne type elastic fluororesin weight, stir and carried out emulsification in 0.5～2 hour, promptly obtain the present invention's elastic fluororesin emulsion.
4, the application of elastic fluororesin emulsion according to claim 1 in preparation elastic fluororesin water-borne coatings.
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|---|---|---|---|
| CN 200610032413 CN1935892A (en) | 2006-10-17 | 2006-10-17 | Elastic fluororesin emulsion, and its preparing method and use |
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|---|---|---|---|
| CN 200610032413 CN1935892A (en) | 2006-10-17 | 2006-10-17 | Elastic fluororesin emulsion, and its preparing method and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312320A (en) * | 2014-11-14 | 2015-01-28 | 大连理工大学 | High-transparency composite thin film capable of adsorbing ultraviolet rays and preparation method thereof |
| CN110452587A (en) * | 2019-08-27 | 2019-11-15 | 广西科技大学 | A kind of high-weatherability fluorocarbon coating and preparation method |
| CN114836088A (en) * | 2022-05-18 | 2022-08-02 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
-
2006
- 2006-10-17 CN CN 200610032413 patent/CN1935892A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104312320A (en) * | 2014-11-14 | 2015-01-28 | 大连理工大学 | High-transparency composite thin film capable of adsorbing ultraviolet rays and preparation method thereof |
| CN104312320B (en) * | 2014-11-14 | 2017-05-03 | 大连理工大学 | High-transparency composite thin film capable of adsorbing ultraviolet rays and preparation method thereof |
| CN110452587A (en) * | 2019-08-27 | 2019-11-15 | 广西科技大学 | A kind of high-weatherability fluorocarbon coating and preparation method |
| CN114836088A (en) * | 2022-05-18 | 2022-08-02 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
| CN114836088B (en) * | 2022-05-18 | 2023-09-19 | 龙牌涂料(北京)有限公司 | Coating composition and preparation method thereof |
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