CN102660871B - Fluorine containing water repellent oil repellent composition and its preparation method - Google Patents
Fluorine containing water repellent oil repellent composition and its preparation method Download PDFInfo
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- CN102660871B CN102660871B CN201210112313.7A CN201210112313A CN102660871B CN 102660871 B CN102660871 B CN 102660871B CN 201210112313 A CN201210112313 A CN 201210112313A CN 102660871 B CN102660871 B CN 102660871B
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Abstract
The invention discloses a fluorine containing water repellent oil repellent composition and its preparation method. The composition takes a monomer, inorganic silica, an emulsifier, a solvent and water as raw materials, after the emulsification of the raw materials, the composition is obtained by initiating the polymerization under the initiator existence condition. The composition reduces the biology toxicity and permanent accumulation performance, and can substantially enhance the waterproof performance of a fluorine containing fabric waterproof oilproof agent with perfluoro alkyl carbon chain length of less than or equal to 6.
Description
Technical field
The invention belongs to fabric functional finishing technique field, relate to a kind of fluorine-containing water-repellent oil-repellent agent composition and method of making the same.Process while processing when water fluoric resin emulsion, this technology can significantly improve the water resistance that existing perfluoroalkyl carbon chain lengths is less than or equal to 6 fluorine-containing fabric waterproof oil-proofing agent.
Background technology
Fluoro containing polymers has many excellent properties, refuses water and oil repellent energy as brilliance.Well-known by the copolymer of (methyl) acrylic acid perfluoro alkyl ethyl for the design of water-refusing oil-refusing finishing agent.
Related (methyl) perfluoroalkyl acrylate is mainly the perfluor segment (hereinafter to be referred as C8) that contains eight carbon in side chain or the perfluoroalkyl mixture of C8 and other carbon chain lengths in the market, the introducing of this class monomer, has obviously improved the water and oil repellant performance of fabric.But owing to there is biological accumulation and certain bio-toxicity containing the perfluor segment of eight carbon atoms, the issue of associated biomolecule cumulative bad and toxicity report, makes this series products have the risk of forbidding at present.The exploitation of short perfluoroalkyl carbochain product becomes the focus of research, and current short perfluoroalkyl carbochain product exists the defects such as significant water resistance deficiency, and therefore, the water resistance that promotes short perfluoroalkyl product seems particularly urgent.
Summary of the invention
The object of this invention is to provide a kind of fluorochemical repellent water and refuse fluid composition, this fluorochemical repellent water is refused fluid composition and is improved the water resistance that existing perfluoroalkyl carbon chain lengths is less than or equal to 6 fluorine-containing fabric waterproof oil-proofing agent.
It is taking monomer, inorganic silicon dioxide, emulsifying agent, solvent and water as raw material is after emulsification that fluorochemical repellent water of the present invention is refused fluid composition, and under the condition existing at initator, initiated polymerization forms; Monomer is by monomer A
1, A
2and A
3composition: monomer A
1the percentage that accounts for total monomer weight is 10%-61%, monomer A
2the percentage that accounts for total monomer weight is 28%-85%, monomer A
3the percentage that accounts for total monomer weight is 3%-15%, preferred monomers A
1the percentage that accounts for total monomer weight is 40%-61%, monomer A
2the percentage that accounts for total monomer weight is 30%-50%, monomer A
3the percentage that accounts for total monomer weight is 3%-10% (taking monomer gross weight as 100%).Monomer A
1the fluorochemical monomer that is less than or equal to 6 perfluoroalkyl and there is alpha-substituted acrylic for thering is carbon chain lengths, as: methacrylic acid perfluoro hexyl ethyl ester, methacrylic acid perfluoro butyl ethyl ester; Monomer A
2be equal to or greater than 12 straight chained alkyl acrylate for containing carbon chain lengths, as: octadecyl acrylate, acrylic acid Lauryl Ester, Process Conditions of Cetane Acrylate, metering system dodecyl gallate; Monomer A
3for containing the acrylate monomer that can form with hydroxyl reaction chemical bond, as: glycidyl methacrylate, γ-methacryloxypropyl trimethoxy silane, N hydroxymethyl acrylamide.The inorganic silicon dioxide using is that vapor phase method or the precipitation method are produced, and the particle diameter of particle is between 10 nanometers to 1 micron.
Fluorochemical repellent water of the present invention refuse fluid composition for by monomer, inorganic silicon dioxide, emulsifying agent, solvent and water through ultrasonic technology emulsification, initiated polymerization under the condition then existing at initator and the fluorinated copolymer that the obtains emulsion in aqueous medium.Described inorganic silicon dioxide accounts for the 5%-20% of total monomer weight, preferably account for the 8%-16% of total monomer weight, emulsifying agent accounts for the 3%-8% of total monomer weight, preferably account for the 5%-8% of total monomer weight, solvent accounts for the 15%-35% of total monomer weight, preferably account for the 30%-35% of total monomer weight, the 3-6 that water is total monomer weight doubly, is preferably the 3-4.5 of total monomer weight doubly.Described initator can be azo, peroxide or oxidation-reduction type water soluble starter, preferably azo-bis-isobutyrate hydrochloride, and consumption can be the 0.4%-0.5% that monomer is heavy.Emulsifying agent can be cationic emulsifier, nonionic emulsifier, or both compounds, and cationic emulsifier preferably contains the quaternary emulsifying agent of alkyl, preferably octadecyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride; Nonionic emulsifier preferably contains the alkyl polyoxyethylene base ether of alkyl, poly(ethylene oxide) unit, preferably polyoxyethylene (20) base oil ether, dodecyl polyoxyethylene (10) ether.Solvent can be polyalcohol, preferably ethylene glycol, propylene glycol or its both dimer, tripolymer, most preferably propylene glycol, a contracting tripropylene glycol, a contracting tripropylene glycol.In said composition, can also add lauryl mercaptan as chain-transferring agent, consumption can be the 0.2%-0.3% that monomer is heavy.
The preparation method that fluorochemical repellent water of the present invention is refused fluid composition comprises the following steps: by monomer, inorganic silicon dioxide, emulsifying agent, solvent and water after emulsification, under the condition existing at initator, initiated polymerization forms, obtain emulsion oil-in-water, emulsification times is 10-30 minute; Except under the condition of oxygen, in emulsion, add initator at logical nitrogen, be warming up to 50-60 DEG C, reaction 4-6 hour.
Fluorine-containing water-repellent oil-repellent agent composition of the present invention can be used for processing various fibres, as natural animal-plant fiber or chemical synthetic fibers such as cotton, fiber crops, wool, polyamide, polypropylene, polyacrylonitrile, polyester.Fluorochemical repellent water of the present invention is refused fluid composition and can be adopted and soak method stagnant, coating and make its surface that is attached to object being treated, drier.Water-repellent oil-repellent agent prepared by the present invention also can for some hard surfaces as interior exterior wall antifouling paint, marine paint, watt, the coating of brick, cement, concrete etc.
The present invention compared with prior art has following advantages:
1. the present invention utilizes the whole-fluoroalkyl chain segment (C4-C6) of short carbon chain to substitute the whole-fluoroalkyl chain segment (C8-C12) of long carbochain, has reduced its bio-toxicity and permanent accumulation property.
2. by introducing the inorganic silicon dioxide of certain particle diameter, improve the roughness that is organized material surface, and then the water resistance of improving product.
Detailed description of the invention
Further illustrate the present invention by specific embodiment below.But the detail of embodiment only, for explaining the present invention, should not be construed as limited overall technical solution.
Measure characteristic by following mode.
Water proofing property: fabric one soaks one and rolls finishing agent (10-50g/L, pH 5.0-7.0, pick-up 70%) → preliminary drying (120 DEG C, 90S) → bake (150 DEG C, 3min) or (170 DEG C, 1min).
Water repellency test: fluorochemical repellent water is refused after fluid composition (finishing agent) is coated on fabric face to be dried.Use sprinkling test equip, in 25～30 seconds, 250ml water drenched to wine on measured object, observe fabric wetting state, evaluation WATER REPELLENCY:
100 points: surface is nonwetting, and water droplet does not attach;
95 points: surface is nonwetting, but has few little water droplet to attach;
90 points: surface is nonwetting, but has little water droplet to attach;
85 points: surface has only a few drops wetting;
80 points: surface has drops wetting;
70 points: surface has considerable part wetting;
50 points: surface is almost all wetting;
0 point: positive and negative is all wetting.
Embodiment 1
In the beaker of 500ml, add following component: (particle diameter 10nm-1 μ is 10g, N hydroxymethyl acrylamide 5g, lauryl mercaptan 0.25g, polyoxyethylene (20) base oil ether 5g, octadecyl trimethyl ammonium chloride 2g, propylene glycol 40g m) for methacrylic acid perfluoro hexyl ethyl ester 60g, acrylic acid Lauryl Ester 60g, hydrophily aerosil Aerosil 200 (A200), deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 55 DEG C, reacts 5 hours simultaneously.
Water repellency is in table 1.
Embodiment 2
In the beaker of 500ml, add following component: (particle diameter 10nm-1 μ is 15g, glycidyl methacrylate 9g, lauryl mercaptan 0.25g, dodecyl polyoxyethylene (10) ether 5g, Dodecyl trimethyl ammonium chloride 2g, dipropylene glycol 30g m) for methacrylic acid perfluoro hexyl ethyl ester 60g, octadecyl acrylate 30g, hydrophily aerosil Aerosil 300 (A300), deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 55 DEG C, reacts 5 hours simultaneously.
Water repellency is in table 1.
Embodiment 3
In the beaker of 500ml, add following component: methacrylic acid perfluoro butyl ethyl ester 60g, metering system dodecyl gallate 30g, precipitated silica, average grain diameter 50nm, 20g, γ-methacryloxypropyl trimethoxy silane 15g, octadecyl trimethyl ammonium chloride 8g, a contracting tripropylene glycol 25g, deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 60 DEG C, reacts 4 hours simultaneously.
Water resistance and duration performance are in table 1.
Comparative example 1
In the beaker of 500ml, add following component: methacrylic acid perfluoro hexyl ethyl ester 60g, acrylic acid Lauryl Ester 60g, N hydroxymethyl acrylamide 5g, lauryl mercaptan 0.25g, polyoxyethylene (20) base oil ether 5g, octadecyl trimethyl ammonium chloride 2g, deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 55 DEG C, reacts 5 hours simultaneously.
Water repellency is in table 1.
Comparative example 2
In the beaker of 500ml, add following component: methacrylic acid perfluoro hexyl ethyl ester 60g, octadecyl acrylate 30g, 9 grams of glycidyl methacrylate, lauryl mercaptan 0.25g, polyoxyethylene (10) base lauryl ether 5g, Dodecyl trimethyl ammonium chloride 2g, deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 55 DEG C, reacts 5 hours simultaneously.
Water repellency is in table 1.
Comparative example 3
In the beaker of 500ml, add following component: methacrylic acid perfluoro butyl ethyl ester 60g, octadecyl acrylate 30g, γ-methacryloxypropyl trimethoxy silane 15g, octadecyl trimethyl ammonium chloride 8g, deionized water 400g, be placed in high pressure homogenizer emulsification 20 minutes, obtain stable emulsion oil-in-water.Emulsion is added in the glass reactor that agitator, thermometer and reflux condensing tube are housed, pass into nitrogen deoxygenation, then add initator azo-bis-isobutyrate hydrochloride 0.5g, warming-in-water to 55 DEG C, reacts 5 hours simultaneously.
Water repellency is in table 1.
Table 1 embodiment 1-3 and comparative example 1-3 water repellency test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Water repellency a) | 100 points | 100 points | 95 points | 85 points | 85 points | 80 points |
A): concentration 15g/L, the black filament polyester fabric of 20cm*20cm.
Effect: the present composition has outstanding water resistance.
Claims (8)
1. fluorochemical repellent water is refused a fluid composition, it is characterized in that, taking monomer, inorganic silicon dioxide, emulsifying agent, solvent and water as raw material is after emulsification, under the condition existing at initator, initiated polymerization forms;
Wherein, monomer is by monomer A
1, A
2and A
3composition:
Monomer A
1the fluorochemical monomer that is less than or equal to 6 perfluoroalkyl and there is alpha-substituted acrylic for thering is carbon chain lengths, monomer A
1the percentage that accounts for total monomer weight is 10%-61%;
Monomer A
2be equal to or greater than 12 straight chained alkyl acrylate, monomer A for containing carbon chain lengths
2the percentage that accounts for total monomer weight is 28%-85%;
Monomer A
3for containing the acrylate monomer that can form with hydroxyl reaction chemical bond, monomer A
3the percentage that accounts for total monomer weight is 3%-15%,
Described inorganic silicon dioxide accounts for the 5%-20% of total monomer weight, and the particle diameter of inorganic silicon dioxide is between 10 nanometers to 1 micron; Described emulsifying agent accounts for the 3%-8% of total monomer weight, and solvent accounts for the 15%-35% of total monomer weight, and the 3-6 that water is total monomer weight doubly; Initator is azo, peroxide or oxidation-reduction type water soluble starter; Emulsifying agent is cationic emulsifier, nonionic emulsifier or both compounds; Solvent is polyalcohol.
2. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that monomer A
1for methacrylic acid perfluoro hexyl ethyl ester or methacrylic acid perfluoro butyl ethyl ester.
3. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that monomer A
2for octadecyl acrylate, acrylic acid Lauryl Ester, Process Conditions of Cetane Acrylate or metering system dodecyl gallate.
4. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that A
3for glycidyl methacrylate, γ-methacryloxypropyl trimethoxy silane or N hydroxymethyl acrylamide.
5. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described initator is azo-bis-isobutyrate hydrochloride.
6. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described cationic emulsifier is the quaternary emulsifying agent that contains alkyl; Nonionic emulsifier is the alkyl polyoxyethylene base ether that contains alkyl, poly(ethylene oxide) unit.
7. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described solvent is ethylene glycol, propylene glycol or its both dimer, tripolymer.
8. fluorochemical repellent water claimed in claim 1 is refused a preparation method for fluid composition, it is characterized in that the method comprises the following steps:
By monomer, inorganic silicon dioxide, emulsifying agent, solvent and water, after emulsification, under the condition existing at initator, initiated polymerization forms, and obtains emulsion oil-in-water, and emulsification times is 10-30 minute; Except under the condition of oxygen, in emulsion, add initator at logical nitrogen, be warming up to 50-60 DEG C, reaction 4-6 hour.
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| CN102977291A (en) * | 2012-11-01 | 2013-03-20 | 中科院广州化学有限公司 | Cross-linkable fluorine-containing polymer, and its application in preparation of super-amphiphobic surfaces |
| CN102964544B (en) * | 2012-11-02 | 2014-11-05 | 中科院广州化学有限公司 | Water-dispersible crosslinking type fluoropolymer and application of fluoropolymer in preparation of super-amphiphobic surfaces |
| CN102977292B (en) * | 2012-11-07 | 2014-07-30 | 中科院广州化学有限公司 | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface |
| CN104558386B (en) * | 2014-12-12 | 2017-10-27 | 东莞市长安东阳光铝业研发有限公司 | A kind of ice-covering-proof fluorine carbon emulsion and preparation method thereof |
| CN104562684B (en) * | 2015-02-12 | 2017-03-08 | 王俊 | A kind of water and oil repellent agent and preparation method thereof |
| CN105111877B (en) * | 2015-08-05 | 2018-02-16 | 浙江康德新材料有限公司 | A kind of aerosol type surface soiling treatment compositions |
| CN106087420B (en) * | 2016-06-07 | 2019-04-09 | 苏州联胜化学有限公司 | A kind of no fluoro water proofing agent and preparation method thereof |
| CN106480734B (en) * | 2016-10-28 | 2019-02-05 | 黑龙江泰纳科技发展股份有限公司 | A kind of fabric three-proof finishing agent and its preparation method and application |
| CN107602754B (en) * | 2017-09-19 | 2021-01-08 | 绍兴文理学院 | Preparation method and application of polymer containing short fluorocarbon chains |
| CN113089325B (en) * | 2021-06-08 | 2022-06-10 | 广东德美精细化工集团股份有限公司 | Durable short-chain fluorine-containing water and oil repellent agent and preparation method thereof |
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| CN101735381A (en) * | 2008-11-14 | 2010-06-16 | 杨玉生 | Organic fluorine waterproof oilproof finishing agent emulsion and preparation thereof |
| CN102229777A (en) * | 2011-05-17 | 2011-11-02 | 河北工业大学 | Hydrophobic olephobic epoxy paint and its preparation and application method |
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2012
- 2012-04-13 CN CN201210112313.7A patent/CN102660871B/en not_active Expired - Fee Related
Patent Citations (4)
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| US5346949A (en) * | 1992-05-29 | 1994-09-13 | Hoechst Gosei K.K. | Fluorine containing aqueous composition having water repellent and oil repellent properties |
| CN101006149A (en) * | 2004-08-25 | 2007-07-25 | 大金工业株式会社 | Water-repellent/oil-repellent composition |
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