WO2022051953A1 - 一种拒水织物及其制备方法 - Google Patents

一种拒水织物及其制备方法 Download PDF

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WO2022051953A1
WO2022051953A1 PCT/CN2020/114291 CN2020114291W WO2022051953A1 WO 2022051953 A1 WO2022051953 A1 WO 2022051953A1 CN 2020114291 W CN2020114291 W CN 2020114291W WO 2022051953 A1 WO2022051953 A1 WO 2022051953A1
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fabric
water
fluoroalkyl
reaction
carbene
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PCT/CN2020/114291
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English (en)
French (fr)
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纵亚坤
李战雄
陈明强
李武龙
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苏州大学
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Priority to US18/025,199 priority Critical patent/US20230323593A1/en
Priority to PCT/CN2020/114291 priority patent/WO2022051953A1/zh
Publication of WO2022051953A1 publication Critical patent/WO2022051953A1/zh

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the invention relates to a water-repellent fabric and a preparation method thereof, in particular to a carbene polymerized covalently grafted fluorine-containing polymer, and a low surface energy roughening structure with geometric morphology is constructed on the surface of the fiber, belonging to special functional textiles and The technical field of its preparation.
  • Fabric fiber is a material with a large specific surface, and the surface modification of fiber material has become the main method for preparing these functional materials, especially in the field of waterproof and oil-repellent textiles.
  • the main methods for preparing water-repellent fabrics include dip coating method, spraying method, sol-gel method and gas/liquid deposition method, etc., but the surface hydrophobic effect of modified fabrics prepared by these methods is easily weakened or lost.
  • Covalent grafting is a fast-developing and effective chemical modification method in recent years. Since low surface energy and a certain roughness are necessary conditions for obtaining a water-repellent surface, covalent grafting generally builds an active site on the fiber surface or uses the functional groups of the fiber itself to pass the low surface energy polymer through the fiber. The covalent bond is grafted to the fabric, or some monomers containing low surface energy elements are directly polymerized at the grafting site on the fiber surface to form a low surface energy polymer.
  • C2 polymers due to the flexibility between the molecular chains of traditional carbene polymers ( C2 polymers), they tend to form a film rather than a uniform roughened structure after grafting on the fabric surface.
  • the present invention adopts the traditional carbene polymerization covalent
  • the problem of grafting a low surface energy polymer on the surface of the fabric by the grafting method cannot produce a roughened geometric structure.
  • a method for preparing a water-repellent fabric by covalently grafting a fluoropolymer by carbene polymerization is disclosed. Taking advantage of the single-carbon repeating characteristics of carbene polymers, that is, when covalently grafting the surface of the fabric, the polymer growth of monomers that only provide one carbon unit in each chain extension link makes the grafted short fluoro-chain fluoroalkyl chains.
  • the segment has a good shielding effect on the polymer backbone.
  • the carbene fluoropolymer grafted on the surface of the fabric formed a low-surface roughness structure with geometric morphology, which effectively improved the water repellency of the fabric.
  • a low surface energy roughening structure with geometrical morphology is constructed on the surface of the fabric through covalent grafting of carbene polymerization in one step, thereby producing a water-repellent fabric, the chemical structural formula of which is shown as follows.
  • R is H or R ⁇ , m and n represent repeating units, which are conventional expressions; the surface of the fiber covalently grafted by carbene polymerization has micro/nano-scale low surface energy polymer crystal roughening with uniform morphology and generally controllable size structure.
  • a water-repellent fabric includes a fabric and a fluoropolymer covalently grafted by carbene polymerization on the surface of the fabric; the structural formula of the fluoropolymer covalently grafted by carbene polymerization is as follows.
  • R f is a fluoroalkyl group; preferably, the number of fluorine atoms in the fluoroalkyl group is 3-15.
  • the invention discloses the application of the above-mentioned water-repellent fabric in the preparation of waterproof material.
  • the preparation method of the above-mentioned water-repellent fabric comprises the following steps: under the action of a catalyst, placing fluoroalkyl diazoacetate and an active fabric in an organic solvent, and covalently grafting fluorine-containing polymer on the fiber surface of the fabric through a carbene polymerization reaction
  • the active fabric is a fabric containing grafting sites.
  • the number of fluorine atoms is 3-15; the grafting site is diazo; the catalyst is palladium salt; the organic solvent is tetrahydrofuran, dichloromethane, ethanol
  • the carbene polymerization reaction is carried out under shaking or stirring.
  • fluoroalkyl alcohol is reacted with bromoacetyl bromide to obtain fluoroalkyl bromoacetate, and then fluoroalkyl bromoacetate is reacted with N,N'-xylenesulfonyl hydrazide to obtain fluoroalkyl group Diazoacetate; react with N,N'-xylenesulfonyl hydrazide after fabric acylation to prepare active fabric; wherein, the reaction between fluoroalkyl alcohol and bromoacetyl bromide is carried out in the presence of alkali; fluoroalkyl The reaction of bromoacetate and N,N'-xylenesulfonylhydrazide is carried out in the presence of an organic acid binding agent; in the fluoroalkyl alcohol, the number of fluorine atoms is 3-15.
  • the preparation method of the above-mentioned water-repellent fabric specifically includes the following steps.
  • bromoacetate fluoroalkyl alcohol is used as the starting agent, anhydrous tetrahydrofuran is used as the reaction medium, and bromoacetyl bromide undergoes a substitution reaction under the action of sodium bicarbonate to generate fluoroalkyl bromoacetate.
  • the fluoroalkyl alcohol is 3, 3, 3-trifluoropropan-1-ol, perfluorobutyl ethanol, perfluorohexyl ethanol, etc.; the substitution reaction The temperature is -5 ⁇ 5°C, preferably 0 ⁇ 5°C; the reaction time of the substitution reaction is 3 ⁇ 5h.
  • step (2) of the above water-repellent fabric preparation method the temperature of the catalytic reaction is -5 ⁇ 5°C, preferably -5 ⁇ 0°C; the reaction time of the catalytic reaction is 3 ⁇ 5h.
  • the acid binding agent is any one of sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
  • the reaction time of the room temperature reaction is 12 ⁇ 24h.
  • the catalyst is palladium chloride, palladium acetate, allylpalladium(II) chloride dimer or bis(acetonitrile) palladium(II) chloride.
  • the organic solvent is any one or several mixed solvents in anhydrous tetrahydrofuran, anhydrous dichloromethane, ethanol, etc.
  • the carbene polymerization reaction is carried out under conditions such as shaking, stirring, and preferably shaking ;
  • the temperature of the carbene polymerization reaction is 25 ⁇ 35°C, preferably 28 ⁇ 32°C; the reaction time of the carbene polymerization reaction is 12 ⁇ 24h. Vibration generally refers to the movement of the fabric with the conical flask; stirring generally refers to the movement of the fabric and the conical flask does not move.
  • the chemical modification method of covalent grafting take the hydrophilic polar groups such as hydroxyl groups on the fiber surface itself as the active grafting sites, and chemically graft the surface modifier with the active groups, which not only reduces the The hydrophilic groups on the surface of the fibers were introduced, and the functional polymers with low surface energy were introduced.
  • the chemical covalent grafting method at room temperature of the present invention not only makes the water repellency of the modified fabric effective and durable, but also reduces the original performance of the fabric material to a minimum.
  • Carbene polymerization a new single-carbon repeating polymerization method, makes the fluorine-containing side chains on the grafted polymer main chain closely stacked, and the use of a small amount of short carbon chain fluoroalkyl monomers can produce significant effects on the polymer main chain.
  • the chain has a good shielding effect.
  • the whole process of the polymerization reaction is carried out at room temperature, which avoids the potential danger caused by heating during the material preparation and processing.
  • the by-product of polymerization is nitrogen, which does not require tail gas treatment and is relatively environmentally friendly.
  • Fig. 1 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 1.
  • Figure 2 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 2 (12 hours).
  • Figure 3 is a microscopic topography of the fabric surface after the carbene polymerization and grafting prepared in Example 2 (24 hours).
  • FIG. 4 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 3.
  • FIG. 4 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 3.
  • FIG. 5 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 4.
  • FIG. 5 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 4.
  • FIG. 6 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 5.
  • FIG. 6 is a microscopic topography diagram of the surface of the fabric after the carbene polymerization and grafting prepared in Example 5.
  • FIG. 7 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 6 (12 hours).
  • Figure 8 is a microscopic topography of the fabric surface after the carbene polymerization and grafting prepared in Example 6 (24 hours).
  • FIG. 9 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 7 (12 hours).
  • Figure 10 is the microscopic topography of the fabric surface after the carbene polymerization and grafting prepared in Example 7 (24 hours).
  • Figure 11 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 8 (12 hours).
  • Figure 12 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 8 (24 hours).
  • Figure 13 shows the element content and distribution on the surface of the fabric after carbene polymerization and grafting prepared in Example 2 (12 hours).
  • Figure 14 shows the adhesion and hydrophobicity of the carbene polymerized and grafted fabric prepared in Example 2 (12 hours).
  • Figure 15 shows the element content and distribution on the surface of the fabric after carbene polymerization and grafting prepared in Example 7 (12 hours).
  • the invention forms a water-repellent fabric by covalently grafting a fluoropolymer on the surface of the fabric through carbene polymerization.
  • the preparation method of the above-mentioned water-repellent fabric includes the following steps.
  • bromoacetate A short carbon chain fluoroalkyl alcohol containing a certain number of fluorine atoms is used as the starting agent, anhydrous tetrahydrofuran is used as the reaction medium, and a substitution reaction occurs with bromoacetyl bromide under the action of sodium bicarbonate to generate short carbon Carboalkane fluoroalkyl bromoacetate.
  • reaction was quenched with deionized water, then saturated sodium bicarbonate solution was added, extracted with chloroform, dried over anhydrous magnesium sulfate, suction filtered, and rotary evaporated to remove the low-boiling solvent to obtain the product.
  • Cotton fabric pretreatment At room temperature, conventional cotton fabrics were immersed in 20% sodium hydroxide solution for 25 min, washed three times with distilled water, then soaked in 5% glacial acetic acid for 30 min, and then washed with deionized water to medium After drying, alkalized cotton fabrics were obtained, which were used in the examples of the present invention.
  • the product was obtained by removing the low boiling point solvent, and the intermediate trifluoropropyl bromoacetate 1.17 g was obtained, with a yield of 89%.
  • the obtained intermediate was put into a three-necked flask equipped with 60 mL of anhydrous tetrahydrofuran, and 3.41 g of N,N'-bis(p-toluenesulfonyl)hydrazine was cooled to 0°C, and 3.82g of 1,8-diazabicycloundec-7-ene was added dropwise to the mixture under nitrogen to react for 3h.
  • the conical flask was transferred to a water bath shaking pot and shaken slowly for 1h, then reacted at 10°C for 1h, 20°C for 1h, and finally reacted at 30°C for 24h. After the reaction, the fabric of the grafted polymer was washed with ethanol and deionized water respectively, and dried at 50°C.
  • the obtained intermediate was dropped into a three-necked flask equipped with 60 mL of anhydrous tetrahydrofuran, then 3.41g of N,N'-bis(p-toluenesulfonyl)hydrazine was added and cooled to 0°C, and 3.82g of 1,82g was added under nitrogen conditions. 8-diazabicycloundec-7-ene was reacted for 3h. After the reaction, it was quenched with deionized water, extracted with dichloromethane three times, dried over anhydrous magnesium sulfate, suction filtered, and rotary-evaporated to remove the low-boiling solvent to obtain 1.64 g of the product with a yield of 76%.
  • the conical flask was transferred to a water bath shaking pot and shaken slowly for 1h, then reacted at 10°C for 1h, 20°C for 1h, and finally reacted at 30°C for 24h.
  • the polymer-cotton fabric of the grafted polymer was washed with ethanol and deionized water, respectively, and dried at 50 °C.
  • Figure 1 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 1.
  • the generated rod-like roughened structure evolves to a local hollow tubular structure with time, and the contact angle to water is less than 100°.
  • Figure 2 is a microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 2 (12 hours).
  • the resulting micron-scale rod-like roughened structure has uniform coverage, high grafting rate, and a water contact angle of 146°.
  • Figure 3 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 2 (24 hours).
  • Example 4 is a microscopic topography diagram of the surface of the fabric prepared in Example 3 after carbene polymerization and grafting, generating a micron-scale spherical/hemispherical roughened structure, and the contact angle to water is 125°.
  • Figure 5 is the microscopic topography of the surface of the carbene polymerized and grafted fabric prepared in Example 4.
  • the structure is more regular, and the cross-section is a micron-scale rod-like roughened structure with an obvious rectangle.
  • the contact angle to water is 132° (12°). hours) and 135° (24 hours).
  • Fig. 6 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 5.
  • the generated rod-like roughened structures will eventually cross-link and aggregate with each other to form a sheet-like structure, and the contact angles to water are respectively 135° (12 hours). ) and 138° (24 hours).
  • Figure 7 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 6 (12 hours).
  • the uniformly dispersed nano-sized particles will gradually aggregate into micron-sized roughened particles, and the contact angle to water is 153° .
  • Figure 8 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 6 (24 hours), the generated uniformly dispersed nano-scale particles will gradually aggregate into micron-scale roughened particles, and further evolve into loose sheets
  • the contact angle to water is 148°.
  • Fig. 9 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 7 (12 hours). 145° respectively.
  • Figure 10 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 7 (24 hours). A rod-like crystal structure with uniform morphology and size, with a water contact angle of 151°, respectively.
  • Figure 11 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 8 (12 hours).
  • the generated nano-scale particles will aggregate into a micro-scale particle roughening structure, and eventually evolve into larger aggregated particles.
  • the water contact angle is 152°.
  • Figure 12 is the microscopic topography of the fabric surface after carbene polymerization and grafting prepared in Example 8 (24 hours).
  • the generated nano-scale particles will aggregate into a micro-scale particle roughening structure, and eventually evolve into larger aggregated particles, and
  • the new nanoparticles were secondary grown on the stacked large-micrometer surface with a contact angle to water of 154°.
  • Figure 13 shows the element content and distribution on the surface of the fabric after carbene polymerization and grafting prepared in Example 2 (12 hours).
  • Figure 14 shows the adhesion and hydrophobicity of the carbene polymerized and grafted fabric prepared in Example 2 (12 hours).
  • the adhesion between the solid surface and the droplet is one of the important parameters to measure the anti-wetting functional fabric.
  • the chemical composition of the solid surface not only affects the static contact angle, but also has a considerable influence on the dynamic adhesion. Hydrophobic or superhydrophobic surfaces have different adhesion to water. In the adhesion curve, the adhesion of the raw cotton fabric surface to water is above 140 uN, and it can be seen from Figure 14 that after the carbene polymerization of nonafluorohexyl diazoacetate grafting, the adhesion of the fabric to water is 64 uN. uN.
  • Figure 15 shows the element content and distribution on the surface of the fabric after carbene polymerization and grafting prepared in Example 7 (12 hours).
  • the invention discloses a water-repellent fabric, which expands the application research of carbene polymerization in the field of functional material preparation.
  • a novel covalent grafting of carbene polymerization can construct a roughened structure with low surface energy on the surface of fabrics in one step, without the need for traditional organic-inorganic hybridization and multi-step reaction process, and obtain a relatively long-lasting hydrophobic effect.
  • Novel carbene polymerization C 1 polymerization
  • C 1 polymerization can graft low-surface-energy polymers based on single-carbon repeating units onto cotton fabrics, and utilize the molecular chain rigidity of densely packed single-carbon units, which is expected to induce carbene from the fiber surface.
  • the polymer crystallizes, and self-assembly is driven by the crystallization to form a polymer crystal structure with a roughened morphology on the surface of the fabric, thereby obtaining the desired protective physical structure.
  • the process of carbene polymerization and grafting is carried out at low/room temperature. Compared with other modification methods that require high temperature/high pressure process or strong acid/base or strong oxidant conditions, it achieves minimal damage to fibers. And the by-product of the polymerization process is nitrogen, which is relatively environmentally friendly.

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  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明公开了一种拒水织物及其制备方法。以不同氟原子数的短碳链氟烷基醇为起始剂，先经酰化试剂处理生成短碳链氟烷基溴乙酸酯，再与N, N'-双(对甲苯磺酰)肼合成短碳链氟烷基重氮乙酸酯单体；织物先后分别经酰化试剂、N, N'-二甲苯磺酰肼处理制得表面含有接枝位点的重氮化织物；最后经卡宾聚合将具有单碳重复单元的含氟聚合物通过共价键接枝到织物表面，制得了具有疏水性的改性织物。整个反应均是在低温/室温下进行，操作简单，工艺环保。基于卡宾聚合物单碳重复、立体规整的特性，在不同条件下通过纤维表面诱导卡宾聚合物结晶驱动自组装一步在织物表面构筑了不同几何形貌与尺寸的含氟聚合物糙化结构，并且在一定程度上做到了形貌均一、尺寸可控。

Description

一种拒水织物及其制备方法 技术领域
本发明涉及一种拒水织物及其制备方法，具体涉及一种卡宾聚合共价接枝含氟聚合物，在纤维表面构筑具有几何形貌的低表面能糙化结构，属于特种功能性纺织品及其制备技术领域。
 背景技术
随着复合材料的不断发展，我国的功能性纺织品材料虽然还处于开发的初始阶段，但发展空间很大且附加价值也相当高使之成为了近些年材料开发的一个热点。织物纤维是一种比表面很大的材料，而纤维材料的表面改性成为了制备这些功能材料的主要方法，特别是在防水拒油纺织品制备领域。目前制备拒水织物的 主要方法有浸渍涂层法、喷涂法、溶胶凝胶法和气/液相沉积法等，但利用这些方法制得的改性织物表面疏水效果很容易减弱或丧失。
共价接枝是近些年发展比较快且行之有效的化学改性方法。由于较低的表面能和一定的粗糙度是获取拒水表面的必备条件，所以共价接枝一般是在纤维表面构建一个活性位点或者是利用纤维本身的官能团将低表面能聚合物通过共价键接枝到织物上，或者是一些含低表面能元素的单体直接在纤维表面上的接枝位点出发生聚合反应生成了低表面能聚合物。但是由于传统的碳烯聚合物(C 2聚合物)分子链间的柔顺性，使得其在织物表面接枝后往往成膜而不是形貌均一的糙化结构。
技术问题
本发明针对目前采用浸渍涂层法制备拒水功能性织物存在牢度差、对纤维本身产生一定的损伤和大多需要多步的有机-无机杂化的弊端，而采用传统的碳烯聚合共价接枝法在织物表面接枝低表面能聚合物又无法产生几何形貌糙化结构的问题，公开了一种采用卡宾聚合共价接枝含氟聚合物制备拒水织物的方法。利用卡宾聚合物单碳重复的特性即对织物表面共价接枝时，在每个链增长环节中只提供一个碳单元的单体的聚合物生长，使得接枝的短氟链氟烷基链段对聚合物主链具有很好屏蔽效果。在纤维表面的诱导下，在织物表面接枝的卡宾含氟聚合物生成了几何形貌的低表面糙化结构，有效地提高了织物拒水性。
 技术解决方案
本发明通过卡宾聚合共价接枝一步在织物表面构造几何形貌的低表面能糙化结构，进而生产了一种拒水织物，其化学结构式示意如下。
Figure 353083dest_path_image001
。
R为H或者R`，m、n表示重复单元，为常规表示；卡宾聚合共价接枝的纤维表面具有形貌均一、尺寸大体可控的微/纳米级的低表面能聚合物晶体糙化结构。
实现本发明目的的技术方案是。
一种拒水织物，包括织物以及织物表面卡宾聚合共价接枝的含氟聚合物；所述卡宾聚合共价接枝的含氟聚合物结构式如下。
Figure 20825dest_path_image002
。
R f为氟烷基；优选的，氟烷基中的氟原子数为3～15。
本发明公开了上述拒水织物在制备防水材料中的应用。
上述拒水织物的制备方法包括如下步骤：在催化剂作用下，将氟烷基重氮乙酸酯与活性织物置于有机溶剂中，通过卡宾聚合反应在织物的纤维表面共价接枝含氟聚合物，得到拒水织物；所述活性织物为含接枝位点的织物。
本发明中，氟烷基重氮乙酸酯中，氟原子数为3～15；接枝位点为重氮；所述催化剂为钯盐；所述有机溶剂为四氢呋喃、二氯甲烷、乙醇中的一种或几种；卡宾聚合反应在震荡或者搅拌下进行。
本发明中，将氟烷基醇与溴乙酰溴反应，得到氟烷基溴乙酸酯，再将氟烷基溴乙酸酯与N,N’-二甲苯磺酰肼反应，得到氟烷基重氮乙酸酯；将织物酰化后再与N,N’-二甲苯磺酰肼反应，制备活性织物；其中，氟烷基醇与溴乙酰溴的反应在碱存在下进行；氟烷基溴乙酸酯与N,N’-二甲苯磺酰肼的反应在有机缚酸剂存在下进行；氟烷基醇中，氟原子数为3～15。
上述拒水织物的制备方法具体包括如下步骤。
（1）溴乙酸盐制备：以氟烷基醇为起始剂，无水四氢呋喃为反应介质，在碳酸氢钠作用下与溴乙酰溴发生取代反应生成氟烷基溴乙酸酯。
（2）重氮酸盐制备：将氟烷基溴乙酸酯和重氮基前体N,N’-二甲苯磺酰肼溶于无水四氢呋喃溶剂中，在1,8-二氮杂二环十一碳-7-烯下催化反应生成氟烷基重氮乙酸酯。
（3）纤维表面接枝位点制备：以四氢呋喃为溶剂，在缚酸剂作用下，织物的纤维表面基团先经酰化试剂酰化，再与重氮基前体N,N’-二甲苯磺酰肼室温反应制备含接枝位点的活性织物。
（4）卡宾聚合共价接枝反应：在催化剂作用下，将氟烷基重氮乙酸酯与活性织物置于有机溶剂中，在不同条件下通过卡宾聚合反应在纤维表面制得具有几何形貌与尺寸的聚合物晶体糙化结构。
上述拒水织物的制备方法步骤（1）中，所述氟烷基醇为3, 3, 3-三氟丙-1-醇、全氟丁基乙醇、全氟己基乙醇等；所述取代反应的温度为-5~5℃，最好为0~5℃；取代反应的反应时间为3~5h。
上述拒水织物的制备方法步骤（2）中，催化反应的温度为-5~5℃，最好为-5~0℃；催化反应的反应时间为3~5h。
上述拒水织物的制备方法步骤（3）中，所述缚酸剂为碳酸钠，碳酸钾，碳酸氢钠或碳酸氢钾中的任意一种。所述室温反应的反应时间为12~24h。
上述拒水织物的制备方法步骤（4）中，所述的催化剂为氯化钯，醋酸钯，氯化烯丙基钯(II)二聚物或双(乙腈)氯化钯(II)中的任意一种；所述的有机溶剂为无水四氢呋喃，无水二氯甲烷，乙醇等中的任意一种或几种混合型溶剂；所述卡宾聚合反应在震荡、搅拌等条件下进行，优选震荡；所述卡宾聚合反应的温度为25~35℃，最好为28~32℃；卡宾聚合反应的反应时间为12~24h。震荡一般指织物随着锥形瓶一起运动；搅拌一般指织物运动，锥形瓶不动。
 有益效果
与现有技术相比，本发明提供的技术方案其有益效果在于。
1、采用共价接枝的化学改性方法：以纤维表面本身的亲水极性基团如羟基为活性接枝位点，将表面改性剂与活性基团发生化学接枝反应，不仅减少了纤维表面的亲水基团，而且引入了低表面能功能性聚合物。相比传统方法，本发明常温下的化学共价接枝方法不仅使得改性织物拒水性有效、持久，而且能使织物材料的原始性能降低到最低。
2、卡宾聚合这一全新的单碳重复的聚合方式使得接枝的聚合物主链上的含氟侧链密切堆积，使用小量的短碳链氟烷基单体便可产生对聚合物主链很好的屏蔽效果。聚合反应全程均是在常温下进行的，避免了材料制备处理过程中因加热而产生的潜在危险。并且聚合的副产物是氮气，不需要尾气处理且相对环保。
3、利用卡宾聚合物单碳重复、立体规整的特性，一步在织物表面构筑具有低表面能的聚合物糙化结构克服了传统的有机-无机杂化多步改性的繁琐。这种“自下而上（Bottom-up）”的改性方式可以通过设计前体分子结构与改变工艺以达到所需要的几何糙化形貌结构，并且能够做到形貌均一、尺寸可控，克服了无机微/纳米粒子糙化形貌的单一性缺陷。
 附图说明
图1是实施例一制备的卡宾聚合接枝后的织物表面微观形貌图。
图2是实施例二制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图。
图3是实施例二制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图。
图4是实施例三制备的卡宾聚合接枝后的织物表面微观形貌图。
图5是实施例四制备的卡宾聚合接枝后的织物表面微观形貌图。
图6是实施例五制备的卡宾聚合接枝后的织物表面微观形貌图。
图7是实施例六制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图。
图8是实施例六制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图。
图9是实施例七制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图。
图10是实施例七制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图。
图11是实施例八制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图。
图12是实施例八制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图。
图13为实施例二制备（12小时）的卡宾聚合接枝后的织物表面元素含量及其分布。
图14为实施例二制备（12小时）的卡宾聚合接枝后的织物粘附力及其疏水性。
图15为实施例七制备（12小时）的卡宾聚合接枝后的织物表面元素含量及其分布。
 本发明的实施方式
本发明在织物表面通过卡宾聚合共价接枝含氟聚合物组成拒水织物。
上述拒水织物的制备方法，包括如下步骤。
（1）溴乙酸盐制备：以含一定氟原子数的短碳链氟烷基醇为起始剂，无水四氢呋喃为反应介质，在碳酸氢钠作用下与溴乙酰溴发生取代反应生成短碳链氟烷基溴乙酸酯。
（2）重氮酸盐制备：将短碳链氟烷基溴乙酸酯和重氮基前体N, N’-二甲苯磺酰肼溶于无水四氢呋喃溶剂中，在缚酸剂1,8-二氮杂二环十一碳-7-烯催化下反应生成短碳链氟烷基重氮乙酸酯。
（3）纤维表面接枝位点制备：以四氢呋喃为溶剂，在缚酸剂作用下，纤维表面羟基先经酰化试剂酰化，再与重氮基前体N, N’-二甲苯磺酰肼反应制备含接枝位点的活性纤维。
（4）卡宾聚合共价接枝反应：在催化剂作用下，将短碳链氟烷基重氮乙酸酯与活性纤维置于有机溶剂中，在不同条件下通过卡宾聚合反应在纤维表面制得不同形貌与尺寸的聚合物晶体糙化结构。
具体步骤为。
（1）合成短碳链氟烷基溴乙酸酯。
Figure 283179dest_path_image003
。
氮气保护下，以除水四氢呋喃为反应介质。三口烧瓶中投入短碳链氟烷基醇与碳酸氢钠，低温下将溴乙酰溴逐滴缓慢加入混合液中（三者按1:1.5:3mol投料）反应。反应结束后用去离子水淬灭反应，然后加入饱和碳酸氢钠溶液，二氯甲烷萃取，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得产物。
（2）合成短碳链氟烷基重氮乙酸酯。
Figure 604439dest_path_image004
。
以除水四氢呋喃为反应介质，氮气保护下三口烧瓶中投入短碳链氟烷基溴乙酸酯和与N, N'-双(对甲苯磺酰)肼，低温下逐滴将1,8-二氮杂二环十一碳-7-烯（DBU）加入混合液中恒温反应一定时间（三者按1:2:5mol投料）。反应结束后用去离子水淬灭反应，然后加入饱和碳酸氢钠溶液，三氯甲烷萃取，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得产物。
（3）纤维表面接枝位点生成。
Figure 562031dest_path_image005
。
氮气保护下，以除水四氢呋喃为反应介质，锥形瓶中加入碳酸氢纳和棉织物，低温下逐滴加入溴乙酰溴，后置于常温下反应。停止反应后，分别用四氢呋喃和去离子水将织物清洗干净，低温下烘干。然后将烘干后的织物和N, N'-双(对甲苯磺酰)肼投入到反应器中，低温下逐滴将1,8-二氮杂二环十一碳-7-烯（DBU）加入混合液中恒温反应。反应结束后分别用四氢呋喃和去离子水将织物清洗干净，低温下烘干备用。
（4）纤维表面卡宾聚合共价接枝含氟聚合物。
Figure 892518dest_path_image006
。
氮气保护下，分别以除水四氢呋喃、二氯甲烷、甲苯、除水四氢呋喃与无水乙醇的混合液等为反应介质。室温下将单体、活性纤维和NaBPh 4置于装有反应介质的锥形瓶中，低温下加入(π-allylPdCl) 2，后置于稳定的动力模式下恒温反应。反应结束后分别用四氢呋喃和去离子水将棉织物清洗干净，低温下烘干，得到拒水织物。
所涉及的原料都是市售常规产品，织物为常规棉织物，经过常规碱化处理；具体操作方法以及测试方法为常规技术。下面结合附图和实施例对本发明技术方案作进一步描述。棉织物预处理：室温下，常规棉织物浸入质量分数为20%的氢氧化钠溶液处理25 min，蒸馏水洗涤三次，再在5%的冰醋酸中浸泡30 min，然后用去离子水水洗至中性，干燥得到碱化棉织物，用于本发明实施例。
实施例一。
（1）合成三氟丙基重氮乙酸酯：三口烧瓶中加入50mL无水四氢呋喃，0.57g 3, 3, 3-三氟丙-1-醇和1.26g碳酸氢钠并降温至0℃，氮气条件下滴加1.54g溴代乙酰溴，恒温反应3h，反应结束后用去离子水淬灭反应，然后加入饱和碳酸氢钠溶液，二氯甲烷萃取，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得产物，制得中间体三氟丙基溴乙酸酯1.17g，收率89%。将制得的中间体投入装有60mL无水四氢呋喃的三口烧瓶中，再加入3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃，氮气条件下逐滴将3.82g 1,8-二氮杂二环十一碳-7-烯加入混合液中反应3h。反应结束后用去离子水淬灭，然后加入饱和碳酸氢钠溶液，二氯甲烷萃取3次，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得0.68g产物，收率75%。
（2）在纤维表面生成接枝位点：将0.815g棉织物投入装有50mL无水四氢呋喃和1.68g碳酸氢钠的锥形瓶中，降温至0℃，氮气下滴加1.68g溴乙酰溴恒温反应30min，然后置于水浴震荡锅中自然升温至30℃恒温反应15小时，再分别用四氢呋喃和去离子水清洗干净，烘干，得到溴化织物。将溴化织物浸入在装有无水四氢呋喃的锥形瓶中，加入5.11g N, N'-双(对甲苯磺酰)肼后降温至0℃，氮气下滴加4.57g 1, 8-二氮杂二环十一碳-7-烯于0℃下反应30min，最后置于水浴震荡锅中自然升温至30℃，恒温振荡反应20小时。反应结束后，将拥有接枝位点的织物分别用四氢呋喃和去离子水清洗干净，烘干用于步骤（3）。
（3）制备疏水织物：将合成的三氟丙基重氮乙酸酯5mmol加入装有60mL无水四氢呋喃的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，然后降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中振荡反应1h，再依次升温至10℃反应1h、20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干，得到拒水织物。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例二。
（1） 合成九氟己基重氮乙酸酯：三口烧瓶中加入50mL无水四氢呋喃，1.32g全氟丁基乙醇和1.26g碳酸氢钠并降温至0℃，氮气条件下滴加1.54g溴代乙酰溴，恒温反应3h提纯制得中间体九氟己基溴乙酸酯1.75g。然后将制得的中间体投入装有60mL无水四氢呋喃的三口烧瓶中，再加入3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃，氮气条件下逐滴将3.82g 1,8-二氮杂二环十一碳-7-烯加入混合液中反应3h。反应结束后用去离子水淬灭液，二氯甲烷萃取3次，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得1.29g产物，78%。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的九氟己基重氮乙酸酯5mmol加入装有60mL无水四氢呋喃的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，然后置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例三。
（1）合成九氟己基重氮乙酸酯：与实施例二一致。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的九氟己基重氮乙酸酯5mmol加入装有60mL无水四氢呋喃的圆底烧瓶中，将拥有接枝位点的织物固定在搅拌桨底端浸入瓶中，再加入9.15mg (π-allylPdCl) 2，然后置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4；在0℃下搅拌动态（织物旋转，强度与实施例二近似）下反应1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应12h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例四。
（1）合成九氟己基重氮乙酸酯：与实施例二一致。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的九氟己基重氮乙酸酯5mmol加入装有60mL无水甲苯的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，然后置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例五。
（1）合成九氟己基重氮乙酸酯：与实施例二一致。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的九氟己基重氮乙酸酯5mmol加入装有60mL无水二氯甲烷的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，然后置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例六。
（1）合成九氟己基重氮乙酸酯：与实施例二一致。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的九氟己基重氮乙酸酯5mmol加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例七。
（1）合成十三氟辛基重氮乙酸酯：三口烧瓶中加入50mL无水四氢呋喃，1.82g全氟己基乙醇和1.26g碳酸氢钠并降温至0℃，氮气条件下滴加1.54g溴代乙酰溴，恒温反应3h制得中间体十三氟辛基溴乙酸酯2.09g。将制得的中间体投入装有60 mL无水四氢呋喃的三口烧瓶中，再加入3.41g N, N'-双(对甲苯磺酰)肼并降温至0℃，氮气条件下加入3.82g 1,8-二氮杂二环十一碳-7-烯反应3h。反应结束后用去离子水淬灭，二氯甲烷萃取3次，无水硫酸镁干燥，抽滤、旋蒸除去低沸点溶剂得1.64g产物，76%收率。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的十三氟辛基重氮乙酸酯5mmol加入装有60mL无水四氢呋喃的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h、20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
实施例八。
（1）合成十三氟辛基重氮乙酸酯：与实施例七一致。
（2）在纤维表面生成接枝位点：与实施例一一致。
（3）制备疏水织物：将(1)中合成的十三氟辛基重氮乙酸酯5mmol加入装有50mL无水四氢呋喃和10mL无水乙醇混合液的锥形瓶中，将拥有接枝位点的织物浸入瓶中，再加入9.15mg (π-allylPdCl) 2，置于低温反应釜中并降温至-10℃，加入32.5mg NaBPh 4。在0℃下将锥形瓶移置水浴震荡锅中缓慢振荡1h，然后依次10℃反应1h，20℃反应1h，最后30℃下反应24h。反应结束后，将接枝聚合物的织物Polymer-cotton分别用乙醇和去离子水清洗干净，50℃下烘干。
将上述最后30℃下反应24h调整为最后30℃下反应12h，其余不变，得到拒水织物。
（4）接触角测试：采用美国Dataphysics公司的OCAH200型微观液滴润湿性测量仪对接枝后的功能织物进行润湿性能测试，选取水作为测试液滴，液滴体积为5μL，分别测试五次取其平均值。
图1是实施例一制备的卡宾聚合接枝后的织物表面微观形貌图，生成的棒状糙化结构随时间的延长向局部中空管状结构演变，对水接触角小于100°。
图2是实施例二制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的微米级棒状糙化结构覆盖均匀，接枝率较高，对水接触角为146°。
图3是实施例二制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的微米级管状糙化结构覆盖均匀，接枝率较高，对水接触角为152°。
图4是实施例三制备的卡宾聚合接枝后的织物表面微观形貌图，生成微米级球/半球状糙化结构，对水接触角为125°。
图5是实施例四制备的卡宾聚合接枝后的织物表面微观形貌图，结构规整性更强，横截面呈明显矩形的微米级棒状糙化结构，对水接触角分别为132°（12小时）和135°（24小时）。
图6是实施例五制备的卡宾聚合接枝后的织物表面微观形貌图，生成的棒状糙化结构最终会彼此交联聚集，形成片状结构，对水接触角分别为135°（12小时）和138°（24小时）。
图7是实施例六制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的分散均匀的纳米级粒子会逐渐聚集为微米级糙化颗粒，对水接触角为153°。
图8是实施例六制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的分散均匀的纳米级粒子会逐渐聚集为微米级糙化颗粒，并进一步演变为松散的片状，对水接触角为148°。
图9是实施例七制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的覆盖均匀且接枝率较高的棒状糙化结构未演变为管状结构，对水接触角分别为145°。
图10是实施例七制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的覆盖均匀且接枝率较高的棒状糙化结构，清晰可见纤维表面覆盖着一层形貌和尺寸均一的杆状晶体结构，对水接触角分别为151°。
图11是实施例八制备（12小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的纳米级粒子会聚集成微米尺度颗粒糙化结构，最终演变为更大的聚集性颗粒，对水接触角为152°。
图12是实施例八制备（24小时）的卡宾聚合接枝后的织物表面微观形貌图，生成的纳米级粒子会聚集成微米尺度颗粒糙化结构，最终演变为更大的聚集性颗粒，且新的纳米粒子在堆积的大微米表面二次生长，对水接触角为154°。
图13为实施例二制备（12小时）的卡宾聚合接枝后的织物表面元素含量及其分布。
图14为实施例二制备（12小时）的卡宾聚合接枝后的织物粘附力及其疏水性。
固体表面与液滴之间的粘附力是衡量抗浸润功能织物的重要参数之一，固体表面的化学成分不仅影响静态接触角大小，对动态粘附力大小也有着相当大的影响，不管高疏水性还是超疏水性表面，其表面对水的粘附力大小都是不同的。粘附力曲线中，原棉织物表面对水粘附力大小在140 uN 以上，而由图14可知，经九氟己基重氮乙酸酯的卡宾聚合接枝后，织物对水粘附力为64 uN。
图15为实施例七制备（12小时）的卡宾聚合接枝后的织物表面元素含量及其分布。
本发明公开一种拒水织物，拓展了卡宾聚合在功能材料制备领域的应用研究。基于卡宾聚合物单碳重复、立体规整的特性，通过新颖的卡宾聚合共价接枝可一步在织物表面构筑具有低表面能的糙化结构，而不需要传统的有机-无机杂化和多步反应过程，并且获得相对持久的疏水效果。新颖的卡宾聚合(C 1聚合)可将基于单碳重复单元的低表面能聚合物接枝到棉织物上，并且利用单碳单元密集堆砌所具有的分子链刚性，可望由纤维表面诱导卡宾聚合物结晶，由结晶驱动自组装在织物表面形成糙化形貌的聚合物晶体结构，由此获得所需的防护物理结构。卡宾聚合接枝的过程是在低/室温下进行的，相比于其它需要在高温/高压工艺下或强酸/碱或强氧化剂条件下的改性方法相比做到了对纤维最小程度的损伤，并且聚合过程产生的副产物是氮气，相对环保。

Claims (10)

  1. 一种拒水织物，其特征在于，所述拒水织物包括织物以及织物表面卡宾聚合共价接枝的含氟聚合物。
  2. 根据权利要求1所述拒水织物，其特征在于，所述卡宾聚合共价接枝的含氟聚合物结构式如下：
    Figure 858055dest_path_image001
    R f为氟烷基。
  3. 根据权利要求2所述拒水织物，其特征在于，氟烷基中的氟原子数为3～15。
  4. 权利要求1所述拒水织物在制备防水材料中的应用。
  5. 权利要求1所述拒水织物的制备方法，其特征在于，包括如下步骤：在催化剂作用下，将氟烷基重氮乙酸酯与活性织物置于有机溶剂中，通过卡宾聚合反应在织物的纤维表面共价接枝含氟聚合物，得到拒水织物；所述活性织物为含接枝位点的织物。
  6. 根据权利要求5所述拒水织物的制备方法，其特征在于，氟烷基重氮乙酸酯中，氟原子数为3～15；接枝位点为重氮。
  7. 根据权利要求5所述拒水织物的制备方法，其特征在于，所述催化剂为钯盐；所述有机溶剂为四氢呋喃、二氯甲烷、乙醇中的一种或几种；卡宾聚合反应在震荡或者搅拌下进行。
  8. 根据权利要求5所述拒水织物的制备方法，其特征在于，将氟烷基醇与溴乙酰溴反应，得到氟烷基溴乙酸酯，再将氟烷基溴乙酸酯与N,N’-二甲苯磺酰肼反应，得到氟烷基重氮乙酸酯；将织物酰化后再与N,N’-二甲苯磺酰肼反应，制备活性织物。
  9. 根据权利要求8所述拒水织物的制备方法，其特征在于，氟烷基醇与溴乙酰溴的反应在碱存在下进行；氟烷基溴乙酸酯与N,N’-二甲苯磺酰肼的反应在有机缚酸剂存在下进行。
  10. 根据权利要求8所述拒水织物的制备方法，其特征在于，氟烷基醇中，氟原子数为3～15。
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