CN109468847B - Super-amphiphobic textile finishing agent and preparation method and application thereof - Google Patents

Super-amphiphobic textile finishing agent and preparation method and application thereof Download PDF

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CN109468847B
CN109468847B CN201811195988.6A CN201811195988A CN109468847B CN 109468847 B CN109468847 B CN 109468847B CN 201811195988 A CN201811195988 A CN 201811195988A CN 109468847 B CN109468847 B CN 109468847B
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super
amphiphobic
fabric
preparation
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CN109468847A (en
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姜勇
周旋
江鹏飞
张川
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Southeast University
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/256Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01Stain or soil resistance
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/11Oleophobic properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties

Abstract

The invention discloses a super-amphiphobic textile finishing agent and a preparation method and application thereof, the finishing agent comprises silica sol prepared from volatile organic solvent, siloxane and ammonia water, and low surface energy modification solution prepared from volatile organic solvent, fluorine-containing modifying agent and hydrophobic resin, wherein the weight parts of the raw materials are as follows: 40-100 parts of volatile organic solvent, 2-10 parts of siloxane, 2-10 parts of ammonia water, 2-5 parts of hydrophobic resin, 0.1-0.5 part of curing agent and 0.1-1 part of fluorine-containing modifier. The static contact angles of water drops and oil drops on the surface of the fabric prepared by the super-amphiphobic textile finishing agent are all larger than 150 degrees, and the water drops roll easily on the surface of the fabric. After being soaked in strong acid and strong alkali solution for a long time or being washed or rubbed for a long time, the fabric still has excellent super-amphiphobic performance. Meanwhile, the preparation process is simple and easy to implement, the color of the fabric is not changed, the process is easy to control, and the large-scale production is facilitated.

Description

Super-amphiphobic textile finishing agent and preparation method and application thereof
Technical Field
The invention relates to a super-amphiphobic textile finishing agent, a preparation method and application thereof, belonging to the technical field of textile finishing agents.
Background
Super-hydrophobic fabrics are common on the market at present, but common super-hydrophobic fabrics have weaker repellency to liquid with lower surface tension (<35 mN/m). Therefore, the use of superhydrophobic fabrics is limited due to the inability to repel these low surface tension liquids.
A super-amphiphobic surface refers to a surface having a contact angle of greater than 150 ° for both water and fluids with low surface tension. Water and oil droplets can easily roll off these surfaces. Superamphiphobic surfaces have also received attention for their excellent promise in various applications, such as drag reduction prevention, fingerprint sheeting, corrosion protection, protective apparel, and the like. While fabrics with ultra-amphiphobic properties are particularly useful in the manufacture of protective garments, screens for separation of oil and water mixtures, and self-cleaning garments to protect against toxic liquids.
The preparation of the super-amphiphobic fabrics is mainly carried out by preparing micro-and nano-rough structures on different substrates by using nano-particles and then treating with a low surface energy modifier. The poor mechanical stability also greatly limits the industrial application of the existing super-amphiphobic surfaces, so that the super-amphiphobic surfaces are easily damaged when being subjected to severe washing and abrasion or used under severe working conditions, thereby affecting the hydrophobic and oleophobic effects.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems, the invention provides a super-amphiphobic textile finishing agent, a preparation method and application thereof, the preparation method is simple, and the prepared super-amphiphobic finishing agent has the performances of super-hydrophobicity, super-oleophobic property and oil stain resistance, and meanwhile, the finishing agent has the excellent performances of high transparency, friction resistance, ultraviolet irradiation resistance, strong acid and alkali resistance, environmental protection and the like.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the following technical scheme:
a super-amphiphobic textile finishing agent comprises silica sol prepared from volatile organic solvent, siloxane and ammonia water, and low surface energy modification solution prepared from volatile organic solvent, fluorine-containing modifier, curing agent and hydrophobic resin, wherein the weight parts of the raw materials are as follows:
40-100 parts of volatile organic solvent, 2-10 parts of siloxane, 2-10 parts of ammonia water, 2-5 parts of hydrophobic resin, 0.1-0.5 part of curing agent and 0.1-1 part of fluorine-containing modifier.
The volatile organic solvent comprises one or more of methanol, ethanol, isopropanol, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide and dioctyl phthalate.
The siloxane comprises one or more of tetraethyl orthosilicate, methyltrimethoxysilane, vinyl trimethoxysilane, propyl trimethoxysilane, n-octyl trimethoxysilane and trimethylchlorosilane.
The fluorine-containing modifier comprises one or more of perfluorooctyl trichlorosilane, perfluorodecyl trichlorosilane, fluorooctyl dimethylchlorosilane, perfluorooctyl triethoxysilane, perfluorooctanoyl chloride or perfluorodecyl triethoxysilane.
The hydrophobic resin comprises one or more of fluorocarbon resin or organic silicon resin, and the curing agent comprises one or more of diisocyanate, methyltrimethoxysilane, methyltriethoxysilane, vinyl trimethoxysilane, propyl triethoxysilane, gamma-aminopropyl triethoxysilane, octyl trimethoxysilane, gamma- (2, 3-glycidoxy) propyl trimethoxysilane and gamma-methacryloxy trimethoxysilane.
The preparation method of the super-amphiphobic textile finishing agent comprises the following steps:
(1) under the condition of continuous stirring, firstly adding ammonia water into a volatile organic solvent, adjusting the pH to 8-10, then adding siloxane into the mixed solution, and reacting for 4-12 h at the rotating speed of 200-1200 rpm to form transparent silica sol;
(2) adding hydrophobic resin and curing agent into volatile organic solvent containing fluorine-containing modifier under the condition of continuous stirring to obtain the low surface energy modifying liquid.
The application of the super-amphiphobic textile finishing agent in preparing super-amphiphobic fabrics comprises the following steps: soaking a common fabric in silica sol, taking out, drying at room temperature, soaking in a low surface energy modification solution, taking out and drying.
The common fabric is terylene, nylon, cotton, gauze, sponge, blended fabric and the like, and the fabric treated by the method has super-amphiphobic performance.
The technical effects are as follows: compared with the prior art, the technical scheme of the invention has the following technical advantages:
1) the process is simple, the raw materials are easy to obtain, and the cost is low;
2) the super-amphiphobic finishing agent is colorless and transparent, and cannot influence the color of the treated fiber;
3) the super-amphiphobic fabric finishing agent is not limited by the variety of fabric base materials, and is suitable for fabrics such as cotton, nylon, dacron gauze, sponge and blended fabric;
4) the fabric treated by the treating agent prepared by the invention has super-amphiphobic property, oil stain resistance, strong acid and strong alkali resistance, the contact angles of water and oil are both more than 150 degrees, and the rolling angle is less than 10 degrees;
5) the mechanical property is good, and washing, friction, supersound are resisted, have certain selfreparing function, long service life.
Drawings
FIG. 1: the invention discloses a low-power scanning electron microscope picture of a super-amphiphobic fabric.
FIG. 2: the invention discloses a high-power scanning electron microscope picture of a super-amphiphobic fabric.
FIG. 3: contact angle optical photographs of the inventive superamphiphobic fabrics with water droplets (fig. 3a) and oil droplets (fig. 3 b).
FIG. 4: optical photographs of water droplets (methyl blue stain), regular drinks, ethylene glycol and regular edible oil droplets (sudan II stain) on the surface of the super-amphiphobic fabrics of the present invention.
Detailed Description
For a better understanding and application of the present invention, the following examples are included to further illustrate the present invention.
Example 1
(1) Preparation of silica sol: under the condition of continuous stirring, adding ammonia water into 50 parts of methanol solution, adjusting the pH to 8.5, then adding 2 parts of methyltrimethoxysilane into the mixed solution, and reacting for 4 hours at the rotating speed of 800rpm to form transparent silica sol;
(2) low surface energy modification: at the rotating speed of 1200rpm, 0.3 part of perfluorodecyl triethoxysilane, 3 parts of fluorocarbon resin and 0.3 part of hexamethylene diisocyanate curing agent are added into 50 parts of tetrahydrofuran solution;
(3) soaking the polyester fabric in the step (1) for 15min, taking out, drying at room temperature for 15min, soaking in the step (2) for 15min, and finally drying at 120 ℃ for 2 h.
FIG. 1 is a scanning electron microscope image of a super-amphiphobic polyester fabric in an example. The prepared super-amphiphobic polyester fabric still keeps the super-amphiphobic performance after being soaked in a strong acid solution with the pH value of 1 and a strong base solution with the pH value of 14 for 48 hours, and the super-amphiphobic polyester fabric prepared by the method has excellent acid and alkali new performance.
Example 2
(1) Preparation of silica sol: under the condition of continuous stirring, adding ammonia water into 50 parts of ethanol solution, adjusting the pH to 8.0, then adding 2 parts of vinyltriethoxysilane into the mixed solution, and reacting at the rotating speed of 800rpm for 8 hours to form transparent silica sol;
(2) low surface energy modification: at the rotating speed of 1000rpm, adding 0.2 part of perfluorodecyl trichlorosilane, 2 parts of fluorocarbon resin and 0.1 part of hexamethylene diisocyanate curing agent into 50 parts of N, N-dimethylformamide solution;
(3) soaking the polyester fabric in the step (1) for 15min, taking out, drying at room temperature for 15min, soaking in the step (2) for 15min, and finally drying at 120 ℃ for 2 h.
FIG. 2 is a high-power scanning electron microscope picture of the super-amphiphobic polyester fabric in the embodiment. After the prepared super-amphiphobic polyester fabric is polished by loading a 200g weight on 600-mesh sand paper for 200cm, the contact angle of water is kept above 150 degrees, the contact angle of oil drops is still kept above 140 degrees, and good mechanical properties are shown.
Example 3
(1) Preparation of silica sol: under the condition of continuous stirring, adding ammonia water into 50 parts of isopropanol solution, adjusting the pH value to 8.5, then adding 1 part of trimethylchlorosilane and 2 parts of propyltrimethoxysilane into the mixed solution, and reacting for 8 hours at the rotating speed of 800rpm to form transparent silica sol;
(2) low surface energy modification: at the rotating speed of 1200rpm, 0.2 part of perfluorooctyl trichlorosilane, 3 parts of organic silicon resin and 0.3 part of vinyl trimethoxy silane curing agent are added into 50 parts of N, N-dimethylacetamide solution;
(3) soaking the pure cotton fabric in the solution (1) for 15min, taking out, drying at room temperature for 15min, soaking in the solution (2) for 15min, and drying at 90 deg.C for 2 h.
FIG. 3 is an optical photograph of the contact angle of a water drop (FIG. 3a) and an oil drop (FIG. 3b) of the super-amphiphobic cotton fabric of the example.
Example 4
(1) Preparation of silica sol: under the condition of continuous stirring, adding ammonia water into 50 parts of methanol solution, adjusting the pH value to 8.0, then adding 1 part of n-octyl triethoxysilylsilane, 0.5 part of tetraethyl orthosilicate and 1 part of trimethylchlorosilane into the mixed solution, and reacting for 8 hours at the rotating speed of 1000rpm to form transparent silica sol;
(2) low surface energy modification: at the rotating speed of 1000rpm, 0.5 part of perfluorooctyl triethoxysilane, 4 parts of organic silicon resin and 0.2 part of methyltrimethoxysilane curing agent are added into 50 parts of tetrahydrofuran solution;
(3) soaking the pure cotton fabric in (1) for 15min, taking out, drying at room temperature for 15min, soaking in (2) for 15min, and drying at 100 deg.C for 2 h.
Fig. 4 is an optical photograph of water drops (methyl blue stain), regular beverage, ethylene glycol and regular edible oil drops (sudan II stain) on the surface of a super-amphiphobic cotton fabric in the example.
Example 5
The same as example 1, except that:
40 parts of volatile organic solvent, 2 parts of siloxane, 2 parts of ammonia water, 2 parts of hydrophobic resin, 0.1 part of curing agent and 0.1 part of fluorine-containing modifier.
In the preparation of the silica sol, the pH is adjusted to 8, and the reaction is carried out for 12h at the rotating speed of 200.
The results of the performance tests are basically the same as the above examples.
Example 6
The same as example 1, except that:
100 parts of volatile organic solvent, 10 parts of siloxane, 10 parts of ammonia water, 5 parts of hydrophobic resin, 0.5 part of curing agent and 1 part of fluorine-containing modifier.
In the preparation of the silica sol, the pH was adjusted to 10 and the reaction was carried out at 1200rpm for 4 hours.
The results of the performance tests are basically the same as the above examples.

Claims (1)

1. The preparation method of the super-amphiphobic textile finishing agent is characterized by comprising the following steps:
(1) preparation of silica sol: under the condition of continuous stirring, adding ammonia water into 50 parts of ethanol solution, adjusting the pH to 8.0, then adding 2 parts of vinyltriethoxysilane into the mixed solution, and reacting at the rotating speed of 800rpm for 8 hours to form transparent silica sol;
(2) low surface energy modification: at the rotating speed of 1000rpm, adding 0.2 part of perfluorodecyl trichlorosilane, 2 parts of fluorocarbon resin and 0.1 part of hexamethylene diisocyanate curing agent into 50 parts of N, N-dimethylformamide solution;
(3) soaking the polyester fabric in the step (1) for 15min, taking out, drying at room temperature for 15min, soaking in the step (2) for 15min, and finally drying at 120 ℃ for 2 h.
CN201811195988.6A 2018-10-15 2018-10-15 Super-amphiphobic textile finishing agent and preparation method and application thereof Active CN109468847B (en)

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CN110344255A (en) * 2019-08-19 2019-10-18 南京工程学院 One kind super-hydrophobic cotton resistant to bending and preparation method thereof
CN111172548A (en) * 2020-01-19 2020-05-19 成都斯棱德新材料科技有限公司 Preparation method of super-hydrophobic air-permeable window screen and super-hydrophobic air-permeable window screen

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CN1563555A (en) * 2004-03-17 2005-01-12 韦钧千 Nano self cleaning silk broadcloth and products
CN101397754A (en) * 2008-11-03 2009-04-01 东华大学 Method for preparing floride-free super-hydrophobic cotton fabric
CN102953268A (en) * 2012-11-02 2013-03-06 陕西科技大学 Super oleophilic and super hydrophobic oil-water separation terylene textile preparation method
CN103450727A (en) * 2013-09-20 2013-12-18 云南银峰新材料有限公司 Preparation method of fluoroalkyl chain-containing nano super-amphiphobic coating
CN103626403A (en) * 2012-08-27 2014-03-12 中国科学院兰州化学物理研究所 Preparation method of transparent super-amphiphobic coating
CN105499092A (en) * 2015-11-30 2016-04-20 东南大学 Transparent super-amphiphobic surface layer and layer-by-layer in-situ spraying reaction preparation method
CN107384055A (en) * 2017-07-19 2017-11-24 东南大学 A kind of permanent seal cooling super-hydrophobic coat and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1563555A (en) * 2004-03-17 2005-01-12 韦钧千 Nano self cleaning silk broadcloth and products
CN101397754A (en) * 2008-11-03 2009-04-01 东华大学 Method for preparing floride-free super-hydrophobic cotton fabric
CN103626403A (en) * 2012-08-27 2014-03-12 中国科学院兰州化学物理研究所 Preparation method of transparent super-amphiphobic coating
CN102953268A (en) * 2012-11-02 2013-03-06 陕西科技大学 Super oleophilic and super hydrophobic oil-water separation terylene textile preparation method
CN103450727A (en) * 2013-09-20 2013-12-18 云南银峰新材料有限公司 Preparation method of fluoroalkyl chain-containing nano super-amphiphobic coating
CN105499092A (en) * 2015-11-30 2016-04-20 东南大学 Transparent super-amphiphobic surface layer and layer-by-layer in-situ spraying reaction preparation method
CN107384055A (en) * 2017-07-19 2017-11-24 东南大学 A kind of permanent seal cooling super-hydrophobic coat and preparation method thereof

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