CN102660871A - 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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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 property finishing technique field, relate to a kind of fluorine-containing water-repellent oil-repellent agent composition and method of making the same.When water fluoric resin emulsion carried out processed, present technique 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 ability like brilliance.The design that the copolymer of (methyl) acrylic acid perfluoro alkyl ethyl is used for water-refusing oil-refusing finishing agent has been well-known.
Related in the market (methyl) perfluoroalkyl acrylate mainly is to contain the perfluor segment (hereinafter to be referred as C8) of eight carbon or the perfluoroalkyl mixture of C8 and other carbon chain lengths in the side chain; The introducing of this type monomer has obviously improved the water and oil repellant performance of fabric.But, there are biological accumulation property and certain bio-toxicity owing to contain the perfluor segment of eight carbon atoms, the issue of associated biomolecule cumulative bad and toxicity report at present makes this series products have the risk of forbidding.Short perfluoroalkyl carbochain Products Development becomes the focus of research, and there are defectives such as significant water resistance deficiency in present short perfluoroalkyl carbochain product, and therefore, the water resistance that promotes short perfluoroalkyl product seems particularly urgent.
Summary of the invention
The purpose 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.
Fluorochemical repellent water of the present invention refuse fluid composition for monomer, inorganic silicon dioxide, emulsifying agent, solvent and water be raw material after emulsification, initiated polymerization forms under the condition that initator exists; Monomer is by monomer A
1, A
2And A
3Form: 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% (is 100% in the monomer gross weight).Monomer A
1For having carbon chain lengths smaller or equal to 6 perfluoroalkyl and have the fluorochemical monomer of alpha-substituted acrylic, 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 acrylic acid ester 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 chemical bond with hydroxyl reaction, as: GMA, γ-methacryloxypropyl trimethoxy silane, N hydroxymethyl acrylamide.The inorganic silicon dioxide that uses is vapor phase method or precipitation method production, and particle grain size 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 and the emulsion of fluorinated copolymer in aqueous medium that obtain under the condition that initator exists then.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 accounts 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, water is 3-6 times of total monomer weight, is preferably 3-4.5 times of total monomer weight.Described initator can be azo class, peroxide or oxidation-reduction type water soluble starter, and preferred azo-bis-isobutyrate hydrochloride, consumption can be the heavy 0.4%-0.5% of monomer.Emulsifying agent can be cationic emulsifier, nonionic emulsifier, or both compounds, and cationic emulsifier preferably contains the quaternary emulsifying agent of alkyl, preferred OTAC, DTAC; Nonionic emulsifier preferably contains the alkyl polyoxyethylene base ether of alkyl, PEO unit, preferred polyoxyethylene (20) base oil ether, dodecyl polyoxyethylene (10) ether.Solvent can be polyalcohol, preferred ethylene glycol, propylene glycol or its both dimer, tripolymer, most preferably propylene glycol, a tripropylene glycol, a tripropylene glycol that contracts that contracts.Can also add lauryl mercaptan in the said composition as chain-transferring agent, consumption can be the heavy 0.2%-0.3% of monomer.
The preparation method that fluorochemical repellent water of the present invention is refused fluid composition may further comprise the steps: with monomer, inorganic silicon dioxide, emulsifying agent, solvent and water after emulsification; Initiated polymerization forms under the condition that initator exists; Obtain emulsion oil-in-water, emulsification times is 10-30 minute; Remove under the condition of oxygen at logical nitrogen, in emulsion, add initator, be warming up to 50-60 ℃, reacted 4-6 hour.
Fluorine-containing water-repellent oil-repellent agent composition of the present invention can be used for handling various fibres, like 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 attached to object being treated, and is dry 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 paint, watt, the coating of brick, cement, concrete etc.
The present invention compared with prior art has advantage:
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. through introducing the inorganic silicon dioxide of certain grain size, improve, and then promote the water resistance of product by the roughness on sorted material surface.
The specific embodiment
Below further specify the present invention through specific embodiment.But the detail of embodiment only is used to explain the present invention, should not be construed as the qualification to the total technical scheme of the present invention.
Mode through following is measured characteristic.
Water proofing property: fabric one soak one roll finishing agent (10-50g/L, pH 5.0-7.0, pick-up 70%) → preliminary drying (120 ℃, 90S) → bake (150 ℃, 3min) or (170 ℃, 1min).
Water repellency test: fluorochemical repellent water is refused fluid composition (finishing agent) be coated on behind the fabric face dry.Use sprinkling test equip, in 25～30 seconds, 250ml water drenched wine on measured object, observe the fabric wetting state, the evaluation WATER REPELLENCY:
100 minutes: the surface was nonwetting, and water droplet does not attach;
95 minutes: the surface was nonwetting, but has few little water droplet to attach;
90 minutes: the surface was nonwetting, but has little water droplet to attach;
85 minutes: the surface had the only a few drops wetting;
80 minutes: the surface had drops wetting;
70 minutes: the surface had considerable part wetting;
50 minutes: the surface was almost all wetting;
0 minute: positive and negative was all wetting.
Embodiment 1
In the beaker of 500ml, add following component: methacrylic acid perfluoro hexyl ethyl ester 60g, acrylic acid Lauryl Ester 60g, hydrophily aerosil Aerosil 200 (A200) (particle diameter 10nm-1 μ m) 10g, N hydroxymethyl acrylamide 5g, lauryl mercaptan 0.25g, polyoxyethylene (20) base oil ether 5g, OTAC 2g, propylene glycol 40g; Deionized water 400g; Place high pressure homogenizer emulsification 20 minutes, and obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 55 ℃ was reacted 5 hours simultaneously.
Water repellency is seen table 1.
Embodiment 2
In the beaker of 500ml, add following component: methacrylic acid perfluoro hexyl ethyl ester 60g, octadecyl acrylate 30g, hydrophily aerosil Aerosil 300 (A300) (particle diameter 10nm-1 μ m) 15g, GMA 9g, lauryl mercaptan 0.25g, dodecyl polyoxyethylene (10) ether 5g, DTAC 2g, dipropylene glycol 30g; Deionized water 400g; Place high pressure homogenizer emulsification 20 minutes, and obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 55 ℃ was reacted 5 hours simultaneously.
Water repellency is seen 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, OTAC 8g, the tripropylene glycol 25g that contracts; Deionized water 400g placed high pressure homogenizer emulsification 20 minutes, obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 60 ℃ was reacted 4 hours simultaneously.
Water resistance and duration performance are seen table 1.
Comparative Examples 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, OTAC 2g, deionized water 400g; Place high pressure homogenizer emulsification 20 minutes, and obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 55 ℃ was reacted 5 hours simultaneously.
Water repellency is seen table 1.
Comparative Examples 2
In the beaker of 500ml, add following component: methacrylic acid perfluoro hexyl ethyl ester 60g, octadecyl acrylate 30g, GMA 9 grams, lauryl mercaptan 0.25g, the basic lauryl ether 5g of polyoxyethylene (10), DTAC 2g, deionized water 400g; Place high pressure homogenizer emulsification 20 minutes, and obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 55 ℃ was reacted 5 hours simultaneously.
Water repellency is seen table 1.
Comparative Examples 3
In the beaker of 500ml, add following component: methacrylic acid perfluoro butyl ethyl ester 60g, octadecyl acrylate 30g, γ-methacryloxypropyl trimethoxy silane 15g, OTAC 8g, deionized water 400g; Place high pressure homogenizer emulsification 20 minutes, and obtained stable emulsion oil-in-water.Emulsion added be equipped with in the glass reactor of agitator, thermometer and reflux condensing tube, feed the nitrogen deoxygenation, add initator azo-bis-isobutyrate hydrochloride 0.5g then, warming-in-water to 55 ℃ was reacted 5 hours simultaneously.
Water repellency is seen table 1.
Table 1 embodiment 1-3 and Comparative Examples 1-3 water repellency test result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | |
| Water repellency a) | 100 minutes | 100 minutes | 95 minutes | 85 minutes | 85 minutes | 80 minutes |
A): concentration 15g/L, the black long filament polyester fabric of 20cm*20cm.
Effect: the present composition has outstanding water resistance.
Claims (10)
1. a fluorochemical repellent water is refused fluid composition, it is characterized in that, with monomer, inorganic silicon dioxide, emulsifying agent, solvent and water be raw material after emulsification, initiated polymerization forms under the condition that initator exists;
Wherein, monomer is by monomer A
1, A
2And A
3Form:
Monomer A
1For having carbon chain lengths smaller or equal to 6 perfluoroalkyl and have the fluorochemical monomer of alpha-substituted acrylic, 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 acrylic acid ester, 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 chemical bond, monomer A with hydroxyl reaction
3The percentage that accounts for total monomer weight is 3%-15%.
2. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that monomer A
1Be 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
2Be 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
3Be GMA, γ-methacryloxypropyl trimethoxy silane or N hydroxymethyl acrylamide.
5. the waterproof and oilproof emulsion type dispersion liquid that contains the inorganic silicon dioxide particle according to claim 1; It is characterized in that described inorganic silicon dioxide accounts for the 5%-20% of total monomer weight; Emulsifying agent accounts for the 3%-8% of total monomer weight; Solvent accounts for the 15%-35% of total monomer weight, and water is 3-6 times of total monomer weight.
6. fluorochemical repellent water according to claim 1 is refused fluid composition, and the particle diameter that it is characterized in that described inorganic silicon dioxide is between 10 nanometers to 1 micron.
7. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described initator is azo class, peroxide or oxidation-reduction type water soluble starter, preferred azo-bis-isobutyrate hydrochloride.
8. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described emulsifying agent is cationic emulsifier, nonionic emulsifier, or both compounds, and cationic emulsifier preferably contains the quaternary emulsifying agent of alkyl; Nonionic emulsifier preferably contains the alkyl polyoxyethylene base ether of alkyl, PEO unit.
9. fluorochemical repellent water according to claim 1 is refused fluid composition, it is characterized in that described solvent is a polyalcohol, preferred ethylene glycol, propylene glycol or its both dimer, tripolymer.
10. the described fluorochemical repellent water of claim 1 is refused the preparation method of fluid composition, it is characterized in that this method may further comprise the steps:
After emulsification, initiated polymerization forms under the condition that initator exists, and obtains emulsion oil-in-water with monomer, inorganic silicon dioxide, emulsifying agent, solvent and water, and emulsification times is 10-30 minute; Remove under the condition of oxygen at logical nitrogen, in emulsion, add initator, be warming up to 50-60 ℃, reacted 4-6 hour.
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Cited By (10)
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| CN102964544A (en) * | 2012-11-02 | 2013-03-13 | 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 |
| CN102977292A (en) * | 2012-11-07 | 2013-03-20 | 中科院广州化学有限公司 | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface |
| 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 |
| CN104558386A (en) * | 2014-12-12 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Anti-icing fluorocarbon emulsion and preparation method thereof |
| CN104562684A (en) * | 2015-02-12 | 2015-04-29 | 王俊 | Water and oil proofing agent and preparation method thereof |
| CN105111877A (en) * | 2015-08-05 | 2015-12-02 | 浙江康德新材料有限公司 | Spray-type surface antifouling treatment composition |
| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN106480734A (en) * | 2016-10-28 | 2017-03-08 | 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 |
| CN107602754A (en) * | 2017-09-19 | 2018-01-19 | 绍兴文理学院 | A kind of preparation method and applications of the polymer containing short fluorocarbon chain |
| CN113089325A (en) * | 2021-06-08 | 2021-07-09 | 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN102964544A (en) * | 2012-11-02 | 2013-03-13 | 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 |
| CN102977292A (en) * | 2012-11-07 | 2013-03-20 | 中科院广州化学有限公司 | Amphiphilic cross-linked fluoropolymer and application thereof in preparation of ultra-amphiphobic surface |
| 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 |
| CN104558386A (en) * | 2014-12-12 | 2015-04-29 | 东莞市长安东阳光铝业研发有限公司 | Anti-icing fluorocarbon emulsion and preparation method thereof |
| CN104562684A (en) * | 2015-02-12 | 2015-04-29 | 王俊 | Water and oil proofing 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 |
| CN105111877A (en) * | 2015-08-05 | 2015-12-02 | 浙江康德新材料有限公司 | Spray-type surface antifouling treatment composition |
| CN106087420A (en) * | 2016-06-07 | 2016-11-09 | 苏州联胜化学有限公司 | A kind of without fluoro water proofing agent and preparation method thereof |
| CN106480734A (en) * | 2016-10-28 | 2017-03-08 | 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 |
| 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 |
| CN107602754A (en) * | 2017-09-19 | 2018-01-19 | 绍兴文理学院 | A kind of preparation method and applications of the polymer containing short fluorocarbon chain |
| CN107602754B (en) * | 2017-09-19 | 2021-01-08 | 绍兴文理学院 | Preparation method and application of polymer containing short fluorocarbon chains |
| CN113089325A (en) * | 2021-06-08 | 2021-07-09 | 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 |
| 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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