CN1493601A - Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method - Google Patents
Aqueous emulsion type fluorine containing water repellent oil repellent agent and its preparation method Download PDFInfo
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- CN1493601A CN1493601A CNA03141771XA CN03141771A CN1493601A CN 1493601 A CN1493601 A CN 1493601A CN A03141771X A CNA03141771X A CN A03141771XA CN 03141771 A CN03141771 A CN 03141771A CN 1493601 A CN1493601 A CN 1493601A
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Abstract
An aqueous emulsion type fluoric hydrophobing-oleophobing agent is prepared from monomer, emulsifier and water through ultrasonic treating and triggered polymerizing. Its advantages are high hydrophobicity and oleophobicity, low cost, low polymerizing temp and high polymerizing speed.
Description
Technical field
The present invention relates to a kind of fluorine-containing water-repellent oil-repellent agent of water-latex type that does not contain organic solvent and preparation method thereof.
Background technology
Fluoro containing polymers has many excellent properties, as the anti-water of brilliance and oil-proofness, ageing-resistant, high temperature resistant, utmost point low surface tension and chemical stability or the like.With the multipolymer of (methyl) vinylformic acid perfluoro alkyl ethyl be used for fabric hydrophobic, to hate the design of oil dressing agent be well-known, from environment and security consideration, this type of finishing composition develops into present aqueous dispersion by initial being dissolved in the organic solvent.
Because it is water-fast containing (methyl) acrylate of perfluoroalkyl (being called for short Rf) group, and in order to obtain good water and oil repellant performance, often need higher fluorine content in the multipolymer, therefore, its good distribution at water medium is technical difficult point always.In order to solve this difficult problem, the general method that adds other relatively large auxiliary agents that all adopts, this analog assistant be in water and fluorine monomer in the organic solvent of high-dissolvability is all arranged, the use of solvent helps monomer to spread from monomer droplet toward polyalcohol emulsion particle, as U.S. Pat 08/048,350 add acetone as the polymerization solubility promoter when polymerization, Japanese Patent JP309562/1999 proposes water miscible high viscosity solvent (25 ℃ time viscosity more than 3cP) as the compound water-medium of composition that is added to the water such as triethylene glycol, dipropylene glycol dme.But the use of solvent can cause the aqueous dispersion burning-point to descend, and perhaps residues in the object being treated, and this is very disadvantageous.No matter use which kind of solvent, all can increase the VOC value (volatile organic matter) that makes system, unfavorable to environment.For stable dispersion and the polymerization that solves fluorine monomer, also can use relatively large fluorochemical surfactant as emulsifying agent, but this can increase the cost of emulsion.
Ultrasonic technology is introduced letex polymerization receives publicity recently, as Wang Qi etc. utilize the ultrasonic wave method of radiating carry out the methyl methacrylate research of microemulsion polymerization (SCI, 1237-1240:2001).But the preparation that ultrasonic technology is applied to the water and oil repellant emulsion of high fluorine content yet there are no report.
The fluorine-containing latex polymerization starter is general to use 2, two (2-amidine propane) dihydrochlorides or 2 of 2 '-azo, two (NSC 18620) dihydrochlorides of 2 '-azo, this type of initiator is water miscible, and can cause at low temperature, but price is high, and decompose easily, require low-temperature storage.
Summary of the invention
The technical issues that need to address of the present invention are to disclose fluorine-containing water-repellent oil-repellent agent of a kind of water-latex type and preparation method thereof, and the fluorine-containing water-repellent oil-repellent agent of this water-latex type does not contain organic solvent, to overcome the above-mentioned defective that prior art exists, satisfies the needs of relevant department.
The fluorine-containing water-repellent oil-repellent agent of water-latex type of the present invention be by monomer, emulsifying agent and water through the pre-emulsification of ultrasonic technology, initiated polymerization and the emulsion of fluorinated copolymer in water medium that obtain under initiator then, its preferred weight percent content comprises:
Fluorinated copolymer 5～40%
Emulsifying agent 0.5～4%
Water surplus
Said monomer is the mixture of monomer A 1 and monomer A 2, wherein:
The percentage ratio that monomer A 1 accounts for the multipolymer gross weight is 35%～90%, if be lower than 35%, so anti-water, refuse oil, antifouling ability is not enough; Simultaneously also should be less than 90%, if too high, the A2 monomer that plays solublization causes dispersive ability to descend with very few.50%～80% content is proper, and so the anti-oily enduring quality of dispersion stabilization and anti-water reaches well balanced;
The percentage ratio that monomer A 2 accounts for the multipolymer gross weight is 10%～65%.
(methyl) vinylformic acid perfluoro alkyl ethyl that the monomer A of being addressed 1 is served as reasons and had the Rf base;
(methyl) vinylformic acid perfluoro alkyl ethyl of the described Rf of having base is meant that perfluoroalkyl is positioned at the compound of the pure residue part of (methyl) acrylate, and its structure is shown below:
Wherein:
The Rf base preferably all hydrogen atoms replaced by fluorine atom, the structure of terminal portions is with-CF
2CF
3For good; The Rf base can be a linear chain structure, also can be branched structure, is good with linear chain structure; The carbonatoms of Rf base is good with 2～20, and 6～16 better;
R is H or CH
3
A is O, S or NR;
R
1It is the alkylidene group that contains 1～15 carbon atom;
Can enumerate example more specifically:
CH
2＝CHCOOCH
2CH
2(CF
2)
3CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
5CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
7CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
9CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
11CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
13CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
15CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
17CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
3CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
5CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
7CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
9CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
11CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
13CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
15CF
3
CH
2＝CHCOOCH
2CH
2NSO
2(CF
2)
5CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
5CF
3
Based on economic and practical reason, two or more monomeric mixtures that monomer A 1 is preferably above-mentioned with different Rf based structures.
According to the present invention, a kind of and composition thereof in other vinyl monomers except that A1 of monomer A 2, monomer A 2 can reduce cost, and provide the adhesion of special lining, hardness, film-forming properties, effect such as bridging property and sticking power, preferred monomer A 2 comprises vinylbenzene, ethene, propylene, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, (methyl) ethyl propenoate, the vinylformic acid laurate, vinylchlorid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinyl pyrrolidone, vinylbenzene, Vinylstyrene, acrylamide, N hydroxymethyl acrylamide, vinyl-acetic ester, propionate, a kind of in (methyl) acrylonitrile or (methyl) glycidyl acrylate etc.;
The emulsifying agent of being addressed comprises a kind of in anionic, the cationic or non-ionic type;
The anion surfactant of being addressed comprises C
7～C
21Carboxylate salt; C
8～C
18The alkylsurfuric acid salt, as sodium lauryl sulphate etc.; Fat sulfonate such as sodium laurylsulfonate etc.; Fat Phenylsulfonic acid salt is as Sodium dodecylbenzene sulfonate etc.; The Rhodafac of phosphoric acid ester such as Rhodia
RE-610 etc.
The cationic C of comprising that is addressed
12～C
18The quaternary ammonium salt, alkyl biguanide hydrochloride etc. of alkyl quaternary ammonium salts, ether structure;
The non-ionic type of being addressed comprises polyoxyethylene carboxylicesters, polynary alkyd acid esters, polyethylene oxide alkyl ethers, polyoxyethylene alkyl aryl ether, polyoxyethylene acid amides or the like.
Emulsifying agent can be above-mentioned one or more combination, the preferably compound use of ionic and non-ionic type.
The preparation method of the fluorine-containing water-repellent oil-repellent agent of water-latex type of the present invention comprises the steps:
(1) monomer mixture, water, emulsifying agent are added in the container, put into Ultrasonic Cleaners and carry out ultrasonic certain hour and obtain stable pre-emulsion, this technology is known feasible, and relevant professional can implement easily.
(2) add initiator, the preferred water-soluble peroxide of initiator, as hydrogen peroxide-iron protochloride, ammonium persulphate-sodium bisulfite, Potassium Persulphate-iron protochloride, Potassium Persulphate-uncle's DDM dodecyl mercaptan etc., the water-soluble mantoquita such as the copper sulfate that can also add catalytic amount in the system are catalyzer;
The consumption of initiator is 0.1～3% of monomer weight part;
Polymeric reaction temperature can change in the scope of broad, promptly 30 ℃～120 ℃.Preferably at 40～60 ℃;
For the control molecular weight, can add chain-transfer agent for example lauryl mercaptan, tetracol phenixin or carbon tetrabromide in the reaction system, the consumption of chain-transfer agent is 0.05～1% of monomer weight part.
The article that are suitable for using water-latex type water-repellent oil-repellent agent of the present invention to handle can be various fibre products, as natural animal-plant fiber or chemical synthetic fibers such as cotton, fiber crops, wool, polymeric amide, polypropylene, polyacrylonitrile, polyester.Aqueous dispersions of the present invention can adopt and soak method stagnant, coating and make on its surface attached to object being treated, adopts the exsiccant method to handle again.The water-repellent oil-repellent agent of the present invention preparation also can be used for some hard surfaces such as interior exterior wall antifouling paint, marine finish, watt, the coating of brick, cement, concrete etc.
Compared with former technology, the fluorine-containing water-repellent oil-repellent agent of water-latex type of the present invention has excellent water and oil repellant, and do not contain the disadvantageous organic solvent of environment, do not adopt simultaneously expensive initiator 2 yet, two (2-amidine propane) dihydrochlorides or 2 of 2 '-azo, two (NSC 18620) dihydrochlorides of 2 '-azo, polymerization temperature is lower, polymerization velocity is very fast, and prospect will be widely used.
Embodiment
More specifically explain the present invention according to embodiment below, but the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
In the 200ml beaker, mix following ingredients: methacrylic acid perfluor alkyl ethide ester 30g, vinylformic acid laurate 10g, butyl methacrylate 8g, N hydroxymethyl acrylamide 1g, Rocryl 410 1g, lauryl mercaptan 0.25g, sodium lauryl sulphate 1.5g, alkylphenol polyoxyethylene-10 0.5g, deionized water 170g, place the pre-emulsification of SK1200H type ultrasonic cleaner 1 hour, obtain stable aqueous dispersions.The pre-emulsion adding is equipped with in the glass reactor of agitator, thermometer and condenser, add sodium bicarbonate 0.3g, Potassium Persulphate 0.3g, sodium bisulfite 0.15g, copper sulfate 0.025g then, logical nitrogen deoxidation, stirring heating, warming-in-water to 50 ℃, opalescence occurs after 3 minutes, continue reaction 5 hours, get the about 223g of latax of solid content 23.5%.
Embodiment 2
Mix following ingredients: vinylformic acid perfluor alkyl ethide ester 35g, octadecyl acrylate 13g, N hydroxymethyl acrylamide 1g, Hydroxyethyl acrylate 1g, lauryl mercaptan 0.25g, octadecyl trimethylammonium ammonia chloride 1.5g, deionized water 160g, place the pre-emulsification of USC-102 type ultrasonic cleaner 0.5 hour, obtain stable aqueous dispersions.The pre-emulsion adding is equipped with in the glass reactor of agitator, thermometer and condenser, add sodium bicarbonate 0.3g, Ammonium Persulfate 98.5 0.3g, sodium bisulfite 0.15g then, logical nitrogen deoxidation is heated with stirring to 45 ℃ of reactions of water-bath 5 hours, gets the about 183g of latax of solid content 28.6%.
Embodiment 3～8
Basically the method according to embodiment 1 or 2 prepares fluorine-containing latex, and the monomer whose compositing formula is listed in the table 1:
Monomer consumption (weight part) among the table 1 embodiment 3-8
Monomer 345678
Vinylformic acid perfluoro alkyl ethyl 70 80 50---
Methacrylic acid perfluoro alkyl ethyl---60 70 60
Vinylformic acid laurate 20-30 25-30
Stearyl acrylate acid esters 20--30-
Vinylidene chloride 10 0 20 15 0 10
Vinylformic acid-2-hydroxyl ethyl ester-2--2
Methacrylic acid-3-hydroxy propyl ester 2--2--
N-hydroxyacrylamide 222222
Embodiment 9
Testing method:
The experiment of water resisting property can be carried out in order to following method:
A series of standard test solutions (listing in the table 2) by water and Virahol (IPA) preparation are added drop-wise on the sample.From low grade (waterproof test label 1) beginning, at least at a distance of on three positions of 2 inches on each one (about 5mm of diameter or volume 0.05ml).Observe 10 seconds of these drops.If after 10 seconds, there are two to seem to remain spherical in three drops to semisphere, then at the test solution that drips 3 high numbers on the contiguous position, and observed for 10 seconds.Continue, in a kind of 3 drops of test solution, have 2 can not keep spherical till hemispherical.The water-repellancy of sample is exactly to have 2 to keep spherical to hemispheric high grade in 3 drops.
Table 2 standard water test solution
The waterproof test label is formed %IPA % water waterproof test label and is formed %IPA % water
1 2 98 7 50 50
2 5 95 8 60 40
3 10 90 9 70 30
4 20 80 10 80 20
5 30 70 11 90 10
6 40 60 12 100 0
Oil-proofness adopts following method to carry out:
Carry out oil resistance test for polymer samples by the AATCC standard test methods No.118 that revises, its method is as follows: a series of organic liquids (listing in the table 3) are added drop-wise on the polymer samples.During beginning at the test solution (oil resistance test label 1) of 1 (about 5mm of diameter or volume 0.05ml) minimum label on each on three positions of 5mm at least.Observe 30 seconds of these drops.If after this time, there are 2 not have the wicking phenomenon around remaining sphere or semisphere and drop in three drops, then drip the test solution of 3 high labels again and observed simultaneously for 30 seconds in contiguous position.In a kind of 3 drops of test solution, have two can not keep spherical to semisphere or till infiltration phenomenon occurring, the oil-proofness of polymer samples be exactly in 30 seconds two in 3 drops keep spherical to semisphere and there is not the high grade test solution of infiltration phenomenon.
Table 3 oil resistance test
Oil resistance test label test solution
1 Nojol
*Purifying mineral oil (
*Plough company trade(brand)name)
2 65/35 Nojol/ n-hexadecanes
3 n-hexadecanes
4 n-tetradecanes
5 n-dodecanes
6 normal heptanes
Adopt aforesaid method, polymer emulsion is applied on the quartz plate of 18mm * 18mm, form uniform film,, measure waterproof, the grease proofness of polymer samples in 130 ℃ of thermal treatment 3-5 minutes.
The anti-water oil-proofness of table 4 embodiment sample
Stoste water resisting property oil-proofness
Embodiment 1 12 5
Embodiment 2 12 6
Embodiment 3 12 6
Embodiment 4 12 6
Embodiment 5 12 5
Embodiment 6 12 6
Embodiment 7 12 6
Embodiment 8 12 6
By above-mentioned test as seen, the water-repellancy of the fluorine-containing water-repellent oil-repellent agent of water-latex type of the present invention all reaches 12#, and grease proofness reaches 5～6#, and emulsion demonstrates good water and oil repellant.
Claims (10)
1. the fluorine-containing water-repellent oil-repellent agent of water-latex type is characterized in that, for by monomer, emulsifying agent and water through pre-emulsification, polymerization and the emulsion of fluorinated copolymer in water medium that obtain then;
Said monomer is the mixture of monomer A 1 and monomer A 2, wherein:
The percentage ratio that monomer A 1 accounts for the multipolymer gross weight is 35%～90%, and the percentage ratio that monomer A 2 accounts for the multipolymer gross weight is 10%～65%;
The monomer A of being addressed 1 serve as reasons and have perfluoroalkyl (methyl) vinylformic acid perfluoro alkyl ethyl of (being called for short Rf), its structure is shown below:
R is H or CH
3
A is O, S or NR;
R
1It is the alkylidene group that contains 1～15 carbon atom;
Monomer A 2 is a kind of and composition thereof in other vinyl monomers beyond the demonomerization A1;
The emulsifying agent of being addressed is a kind of and composition thereof in anionic, the cationic or non-ionic type.
2. the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 1 is characterized in that, Rf is that whole hydrogen atoms are replaced by fluorine atom, and the structure of terminal portions is-CF
2CF
3
3. the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 2 is characterized in that Rf is linear chain structure or branched structure.
4. the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 3 is characterized in that the carbonatoms of Rf is 2～20.
5. described monomer A 1 is following monomeric one or more mixture:
CH
2＝CHCOOCH
2CH
2(CF
2)
5CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
7CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
9CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
11CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
13CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
15CF
3
CH
2＝CHCOOCH
2CH
2(CF
2)
17CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
3CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
5CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
7CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
9CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
11CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
13CF
3
CH
2＝C(CH
3)COOCH
2CH
2(CF
2)
15CF
3。
6. the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 1, it is characterized in that monomer A 2 comprises vinylbenzene, ethene, propylene, (methyl) methyl acrylate, (methyl) butyl acrylate, (methyl) vinylformic acid, (methyl) ethyl propenoate, the vinylformic acid laurate, vinylchlorid, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, vinyl pyrrolidone, vinylbenzene, Vinylstyrene, acrylamide, N hydroxymethyl acrylamide, vinyl-acetic ester, propionate, a kind of and composition thereof in (methyl) acrylonitrile or (methyl) glycidyl acrylate.
7. according to the fluorine-containing water-repellent oil-repellent agent of each described water-latex type of claim 1～6, it is characterized in that weight percent content is:
Fluorinated copolymer 5～40%
Emulsifying agent 0.5～4%
Water surplus.
8. according to the preparation method of the fluorine-containing water-repellent oil-repellent agent of each described water-latex type of claim 1～7, it is characterized in that, comprise the steps:
(1) monomer mixture, water, emulsifying agent are adopted ultrasonic emulsification;
(2) add initiator, polymerization under 30 ℃～120 ℃ condition.
9. the preparation method of the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 8, it is characterized in that, initiator comprises a kind of and composition thereof in hydrogen peroxide-iron protochloride, ammonium persulphate-sodium bisulfite, Potassium Persulphate-iron protochloride or Potassium Persulphate-uncle's DDM dodecyl mercaptan, and the consumption of initiator is 0.1～3% of monomer weight part.
10. the preparation method of the fluorine-containing water-repellent oil-repellent agent of water-latex type according to claim 8, it is characterized in that, add chain-transfer agent during polyreaction, the transfer agent of being addressed comprises lauryl mercaptan, tetracol phenixin or carbon tetrabromide, and the consumption of chain-transfer agent is 0.05～1% of monomer weight part.
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| WO2018027537A1 (en) * | 2016-08-09 | 2018-02-15 | 广州市雷曼兄弟电子科技有限公司 | Fluorine-containing polymer, waterproof and oilproof treatment agent and preparation method thereof, and protective film |
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