CN107964734A - 聚偏氟乙烯自清洁薄膜及其制备方法 - Google Patents

聚偏氟乙烯自清洁薄膜及其制备方法 Download PDF

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CN107964734A
CN107964734A CN201610911095.1A CN201610911095A CN107964734A CN 107964734 A CN107964734 A CN 107964734A CN 201610911095 A CN201610911095 A CN 201610911095A CN 107964734 A CN107964734 A CN 107964734A
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徐伟
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    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4318—Fluorine series

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Abstract

本申请公开了一种聚偏氟乙烯自清洁薄膜，包括聚偏氟乙烯薄膜，以及镶嵌在聚偏氟乙烯薄膜表面的环氧改性硅油修饰的二氧化硅纳米粒子。本申请还公开了一种聚偏氟乙烯自清洁薄膜的制备方法，包括步骤：s1、将二氧化硅复合纳米粒子分散在聚偏氟乙烯、N，N‑二甲基乙酰胺和丙酮的混合溶液中，制得纺丝溶液；s2、通过静电纺丝方法将纺丝溶液电纺在铝箔表面；s3、烘干后，在120～150℃条件下热压8～10s。本发明中，环氧改性硅油修饰的二氧化硅纳米粒子与聚偏氟乙烯之间结合的比较牢固，不容易被水浸泡冲蚀掉，其表面具有高疏水角(162°)、低滚动角(1°)，材料使用寿命长。

Description

聚偏氟乙烯自清洁薄膜及其制备方法
技术领域
本申请涉及超疏水材料技术领域，特别是涉及一种聚偏氟乙烯自清洁薄膜，及其制备方法。
背景技术
润湿是一种常见的界面现象，也是固体表面的重要特征之一，通常用液体在固体表面的接触角来表征。超疏水是指表面对水的接触角大于150°，超亲水是指对水的接触角小于5°的现象。一般来说，润湿性由固体表面的化学组成和微观几何结构决定，合适的表面微细结构及高表面自由能或低表面自由能的固体表面及合适的表面微细结构是产生超亲水和超疏水的两个前提条件。这类材料在自清洁材料、微流体装置以及生物等领域得到广泛应用。
目前超疏水及超亲水表面的制备工艺主要有模板法、溶胶-凝胶法、层层自组装法、气相沉积法等。这些制备工艺均有不足之处，模板法受模板限制较大，难以实现大面积表面的制备；溶胶-凝胶法一般需要紫外光照射等方式才能获取超亲水性，且不适用于制备高分子材料的超亲水表面，存在一定的局限性；层层自组装法存在效率低和工艺复杂的问题；化学气相沉淀法缺点是需要高温操作，过程较为复杂，会产生有毒和腐蚀性的气体。物理气相沉淀设备昂贵，操作技术要求高，效率低，条件较为苛刻。
静电纺丝是通过给聚合物溶液施加外加电场来制造聚合物纤维的纺丝技术，其纤维直径在微米和纳米之间。它是能够连续制备纳米纤维的最重要的方法之一。静电纺丝制得的无纺布，具有孔隙率高、比表面积大、纤维精细程度与均一性高等特点，这些特性使其在过滤材料、生物医药工程、纳米导体、膜技术应用等领域有很大的应用前景。
发明内容
本发明的目的在于提供一种聚偏氟乙烯自清洁薄膜及其制备方法，以克服现有技术中的不足。
为实现上述目的，本发明提供如下技术方案：
本申请实施例公开一种聚偏氟乙烯自清洁薄膜，包括聚偏氟乙烯薄膜，以及镶嵌在聚偏氟乙烯薄膜表面的环氧改性硅油修饰的二氧化硅纳米粒子。
相应的，本申请还公开了一种聚偏氟乙烯自清洁薄膜的制备方法，包括步骤：
s1、将二氧化硅复合纳米粒子分散在聚偏氟乙烯、N，N-二甲基乙酰胺和丙酮的混合溶液中，制得纺丝溶液；
s2、通过静电纺丝方法将纺丝溶液电纺在铝箔表面；
s3、烘干后，在120～150℃条件下热压8～10s。
优选的，在上述的聚偏氟乙烯自清洁薄膜的制备方法中，所述步骤s1中，纺丝溶液的浓度为14～20wt.％。
优选的，在上述的聚偏氟乙烯自清洁薄膜的制备方法中，所述步骤s1中，二氧化硅复合纳米粒子与聚偏氟乙烯的质量比为(2～3):1。
优选的，在上述的聚偏氟乙烯自清洁薄膜的制备方法中，所述步骤s2中，静电纺丝电压8～14KV，注射器与铝箔之间的距离控制在10～17cm。
与现有技术相比，本发明的优点在于：本发明中，环氧改性硅油修饰的二氧化硅纳米粒子与聚偏氟乙烯之间结合的比较牢固，不容易被水浸泡冲蚀掉，其表面具有高疏水角(162°)、低滚动角(1°)，材料使用寿命长。
具体实施方式
本发明通过下列实施例作进一步说明：根据下述实施例，可以更好地理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
实施例1
(1)、环氧改性硅油的制备
s1、将八甲基环四氧硅烷和含氢硅油按照比例3:1混合，加入氢氧化钾催化剂和六甲基二硅氧烷封端剂，在120℃温度反应5小时；
s2、离心去除催化剂；
s3、对上清液减压获得低含氢硅油；
s4、将甲苯溶解于乙烯基环氧环乙烷中，加入低含氢硅油，在氮气保护下，加热至50℃反应6小时，升温至80℃反应1小时；
s5、减压除去甲苯，获得环氧改性硅油。
(2)、二氧化硅复合纳米粒子的制备方法
s1、水解正硅酸乙酯，合成分布均匀尺寸在100nm左右的二氧化硅纳米粒子；
s2、将原硅酸四乙酯、氨水和乙醇混合反应6小时；
s3、加入甲氧基硅烷，在氮气保护下反应12小时；
s4、反应物离心、洗涤，干燥后获得氨基改性的二氧化硅纳米粒子；
s5、将二氧化硅纳米粒子分散在乙醇、引发剂和四氢呋喃的混合溶液中，加入环氧改性硅油，在氮气保护下回流10小时；
s6、反应物离心、洗涤，干燥后获得环氧改性硅油修饰的二氧化硅复合纳米粒子。
本实施例改性二氧化硅纳米粒子尺寸小，制备工艺简单。
(3)、聚偏氟乙烯自清洁薄膜的制备方法
s1、将二氧化硅复合纳米粒子分散在聚偏氟乙烯、N，N-二甲基乙酰胺和丙酮的混合溶液中，制得18wt％浓度的纺丝溶液，其中二氧化硅复合纳米粒子与聚偏氟乙烯的质量比为3:1；
s2、通过静电纺丝方法将纺丝溶液电纺在铝箔表面，静电纺丝电压14KV，注射器与铝箔之间的距离控制在15cm；
s3、烘干后，在150℃条件下热压8s。
本实施例中，环氧改性硅油修饰的二氧化硅纳米粒子与聚偏氟乙烯之间结合的比较牢固，不容易被水浸泡冲蚀掉，其表面具有高疏水角(162°)、低滚动角(1°)，材料使用寿命长。
实施例2
(1)、环氧改性硅油的制备
s1、将八甲基环四氧硅烷和含氢硅油按照比例3:1混合，加入氢氧化钾催化剂和六甲基二硅氧烷封端剂，在110℃温度反应4小时；
s2、离心去除催化剂；
s3、对上清液减压获得低含氢硅油；
s4、将甲苯溶解于乙烯基环氧环乙烷中，加入低含氢硅油，在氮气保护下，加热至40℃反应6小时，升温至80℃反应1.5小时；
s5、减压除去甲苯，获得环氧改性硅油。
(2)、二氧化硅复合纳米粒子的制备方法
s1、水解正硅酸乙酯，合成分布均匀尺寸在100nm左右的二氧化硅纳米粒子；
s2、将原硅酸四乙酯、氨水和乙醇混合反应6小时；
s3、加入甲氧基硅烷，在氮气保护下反应12小时；
s4、反应物离心、洗涤，干燥后获得氨基改性的二氧化硅纳米粒子；
s5、将二氧化硅纳米粒子分散在乙醇、引发剂和四氢呋喃的混合溶液中，加入环氧改性硅油，在氮气保护下回流10小时；
s6、反应物离心、洗涤，干燥后获得环氧改性硅油修饰的二氧化硅复合纳米粒子。
本实施例改性二氧化硅纳米粒子尺寸小，制备工艺简单。
(3)、聚偏氟乙烯自清洁薄膜的制备方法
s1、将二氧化硅复合纳米粒子分散在聚偏氟乙烯、N，N-二甲基乙酰胺和丙酮的混合溶液中，制得20wt％浓度的纺丝溶液，其中二氧化硅复合纳米粒子与聚偏氟乙烯的质量比为2:1；
s2、通过静电纺丝方法将纺丝溶液电纺在铝箔表面，静电纺丝电压13KV，注射器与铝箔之间的距离控制在17cm；
s3、烘干后，在130℃条件下热压8s。
最后，还需要说明的是，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。

Claims (5)

1.一种聚偏氟乙烯自清洁薄膜，其特征在于：包括聚偏氟乙烯薄膜，以及镶嵌在聚偏氟乙烯薄膜表面的环氧改性硅油修饰的二氧化硅纳米粒子。
2.权利要求1所述聚偏氟乙烯自清洁薄膜的制备方法，其特征在于，包括步骤：
s1、将二氧化硅复合纳米粒子分散在聚偏氟乙烯、N，N-二甲基乙酰胺和丙酮的混合溶液中，制得纺丝溶液；
s2、通过静电纺丝方法将纺丝溶液电纺在铝箔表面；
s3、烘干后，在120～150℃条件下热压8～10s。
3.根据权利要求2所述的聚偏氟乙烯自清洁薄膜的制备方法，其特征在于：所述步骤s1中，纺丝溶液的浓度为14～20wt.％。
4.根据权利要求2所述的聚偏氟乙烯自清洁薄膜的制备方法，其特征在于：所述步骤s1中，二氧化硅复合纳米粒子与聚偏氟乙烯的质量比为(2～3):1。
5.根据权利要求2所述的聚偏氟乙烯自清洁薄膜的制备方法，其特征在于：所述步骤s2中，静电纺丝电压8～14KV，注射器与铝箔之间的距离控制在10～17cm。
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