CN108396552B - 一种超疏水阻燃材料的制备方法 - Google Patents

一种超疏水阻燃材料的制备方法 Download PDF

Info

Publication number
CN108396552B
CN108396552B CN201810045772.5A CN201810045772A CN108396552B CN 108396552 B CN108396552 B CN 108396552B CN 201810045772 A CN201810045772 A CN 201810045772A CN 108396552 B CN108396552 B CN 108396552B
Authority
CN
China
Prior art keywords
solution
super
parts
drying
tannin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201810045772.5A
Other languages
English (en)
Other versions
CN108396552A (zh
Inventor
黄鑫
叶晓霞
石碧
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sichuan University
Original Assignee
Sichuan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sichuan University filed Critical Sichuan University
Priority to CN201810045772.5A priority Critical patent/CN108396552B/zh
Publication of CN108396552A publication Critical patent/CN108396552A/zh
Application granted granted Critical
Publication of CN108396552B publication Critical patent/CN108396552B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • D06M11/00—Treating 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
    • D06M11/73—Treating 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 carbon or compounds thereof
    • D06M11/74—Treating 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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • 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
    • D06M11/00—Treating 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
    • D06M11/07—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/20—Halides of elements of Groups 4 or 14 of the Periodic Table, e.g. zirconyl chloride
    • 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
    • D06M11/00—Treating 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
    • D06M11/07—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/28—Halides of elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • D06M11/00—Treating 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
    • D06M11/51—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/56—Sulfates or thiosulfates other than of elements of Groups 3 or 13 of the Periodic Table
    • 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
    • D06M11/00—Treating 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
    • D06M11/51—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating 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 sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D06M11/57—Sulfates or thiosulfates of elements of Groups 3 or 13 of the Periodic Table, e.g. alums
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08J2361/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08J2361/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • 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
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

本发明公开的一种超疏水阻燃材料的制备方法是先配制含有碳材料、植物单宁和金属化合物并呈不同pH的混合溶液，然后利用该混合溶液对基底材料进行修饰，构造微‑纳粗糙结构，再用低表面能物质对具有微‑纳粗糙结构的基底材料进行表面处理，即可获得超疏水阻燃材料。本发明通过改变植物单宁‑金属离子配合物溶液的pH值来调控所形成的配合物纳米颗粒形态，不仅作为粘结剂将碳材料稳定包覆在基底材料表面，还能与碳材料共同构建超疏水材料所需微‑纳粗糙结构，再通过低表面能物质的修饰，同时赋予了基底材料优良的超疏水性能及阻燃性能。本发明所用工艺简单，原料价格低廉、易得，且长效节能，可以用于多种多样的织物，适用面广，易于实现大规模工业生产。

Description

一种超疏水阻燃材料的制备方法
技术领域
本发明属于超疏水材料的制备技术领域，具体涉及一种利用纳米技术和表面修饰技术对基底材料进行修饰来制备超疏水阻燃材料的方法。
背景技术
超疏水材料，是指材料表面与水滴的静态接触角大于150°的疏水材料。由于超疏水材料独特的表面润湿特性，使其可广泛应用于防水、防污、自清洁、流体减阻、抑菌等领域(Zhang X,Shi F,Niu J,et al.Superhydrophobic surfaces:from structural controlto functional application[J].Journal of Materials Chemistry,2008,18(6):621-633.Bixler G D,Bhushan B.Fluid drag reduction and efficient self-cleaningwith rice leaf and butterfly wing bioinspired surfaces[J].Nanoscale,2013,5(17):7685-710.)。作为目前功能材料的研究热点之一，超疏水材料的研究已有了一些重大性进展，这些已有的研究结果表明制备超疏水材料方法一般都需要经过两个步骤：一是要让材料表面具有低表面能；二是要让材料表面具有微-纳粗糙结构(Recentadvances indesigning superhydrophobic surfaces[J].Journal of Colloid&Interface Science,2013,402(2):1-18.)。
纳米粒子因具有粒径小﹑比表面积大的特点，因而利用纳米粒子在基底材料表面构建粗糙结构是目前制备超疏水材料的主要方法。采用这种方法所制备的超疏水材料表面由于存在纳米粗糙结构构建的空气囊，因而能有效阻隔水与基底材料表面直接接触，提高其疏水性能，实现超疏水。然而，这种方法的缺点在于纳米粒子与基底材料之间的作用力较弱，纳米粗糙结构难以持久(Verho T,Bower C,Andrew P,et al.Mechanically durablesuperhydrophobic surfaces[J].Advanced Materials,2011,23(5):673.Milionis A,Loth E,Bayer I S.Recent advances in the mechanical durability ofsuperhydrophobic materials[J].Advances in Colloid&Interface Science,2016,229(3):57-59.)。使用粘结剂来提高纳米粒子和基材之间的作用是解决上述问题的有效方法，然而目前已报道方法中用粘接剂来提高纳米粒子和基材之间作用的主要是多巴胺类物质。而多巴胺类物质因是一种脑内分泌物，虽然其粘接性不错，但是成本高昂，难以大规模使用(Wang Y,Shang B,Hu X,et al.Temperature Control of Mussel‐Inspired Chemistrytoward Hierarchical Superhydrophobic Surfaces for Oil/Water Separation[J].Advanced Materials Interfaces,2017,4(2):727.)，这无疑会阻碍利用上述方法来制备超疏水材料。
发明内容
本发明的目的是针对现有技术的缺陷，提供一种利用新的、成本低廉的粘接剂来制备超疏水阻燃材料的方法。
为实现上述目的，本发明所提供的技术方案如下：
一种超疏水阻燃材料的制备方法，其特征在于该方法的工艺步骤和条件如下：
(1)以质量份计，按以下配方于室温下配制混合溶液：
Figure BDA0001550858730000021
并将该混合溶液的pH值调至3.0-10.0；
(2)先将基底材料依次用去离子水、无水乙醇润洗并干燥，然后将其放入上述混合溶液中进行浸泡处理至少5min，干燥后即得具有微-纳粗糙结构的基底材料；
(3)将具有微-纳粗糙结构的基底材料用低表面能物质进行表面处理，即得超疏水阻燃材料。
以上方法中所述的碳材料为单壁碳纳米管、多壁碳纳米管、石墨烯或活性碳粉末中的任一种；其配比优选1.0-6.0份。
以上方法中所述的植物单宁为缩合类单宁或水解类单宁，具体为荆树皮栲胶、杨梅单宁、坚木单宁、橡椀单宁、塔拉单宁或单宁酸中的任一种。
以上方法中所述的金属化合物为六水氯化铁、四水氯化亚铁、硫酸钛、四氯化钛、二水钼酸钠或硫酸铝中的任一种；其配比优选0.5-2.0份。
以上方法中所述的低表面能物质为聚二甲基硅氧烷溶液(PDMS)、乙烯基三乙氧基硅烷溶液(VTEO)或十二硫醇溶液(DT)中的任一种。其中所述的聚二甲基硅氧烷溶液由以下制备方法制得：按质量份计，将0.1-20.0份聚二甲基硅氧烷溶解在80.0-99.9份的溶剂中即可，聚二甲基硅氧烷可优选0.1-10.0份；所述的乙烯基三乙氧基硅烷溶液由以下制备方法制得：按质量份计，将至少0.95份的乙烯基三乙氧基硅烷分散在甲苯中即可；所述的十二硫醇溶液由以下制备方法制得：按质量份计，将至少0.2份的十二硫醇分散在无水乙醇中即可。
以上制备聚二甲基硅氧烷溶液所述的溶剂为异丙醇、十二烷、正庚烷、正己烷或正辛烷中的任一种。
以上方法中所述的基底材料为混纺布料、纯棉布料、再生纤维、三聚氰胺泡沫或聚氨酯泡沫中的任一种，但不局限于这些。
以上方法中所述的混合溶液是将含碳材料、植物单宁和金属离子加入无水乙醇和去离子水中经超声处理分散溶解即可。
以上方法中所述的基底材料放入混合溶液中进行浸泡处理的时间优选2-30min。
以上方法中所述的将具有微-纳粗糙结构的基底材料用低表面能物质进行表面处理的方式是：直接浸泡在聚二甲基硅氧烷溶液中至少2min，优选2-30min后取出并干燥，或直接浸泡在乙烯基三乙氧基硅烷溶液中至少20h，优选20-23h后取出并干燥，或直接浸泡在十二硫醇溶液中至少20h，优选20-22h后取出并干燥。
以上方法中所述的对所述混合溶液pH值的调控可采用不同浓度的NaOH溶液或HCl溶液等常规无机酸碱进行。
通过改变pH值来调控植物单宁与金属离子配位所形成纳米颗粒的形态，使其作为粘结剂将碳材料稳定包覆在基底材料表面，并起到增强纳米粗糙结构的作用，与碳材料共同构建超疏水材料所需微-纳粗糙结构，再通过表面修饰技术来降低基底材料的表面能，从而同时赋予基底材料超疏水性能及阻燃性能。
本发明与现有技术相比，具有以下优点：
1、由于本发明提供的方法是采用来源广泛、价格低廉的植物单宁来作为粘接剂的基料，因而可大大降低成本，大规模推广，弥补了现有采用多巴胺类物质作为粘接剂的缺陷。
2、由于本发明提供的方法在采用来源广泛、价格低廉的植物单宁来作为粘接剂基料的同时，还添加了金属化合物，因而使植物单宁能与金属化合物中的金属离子形成配合物，增大粘接剂的粘度，可将碳材料稳定包覆固定在基底材料表面。
3、由于本发明提供的方法还通过改变植物单宁-金属离子配合物溶液的pH值来调控所形成配合物纳米颗粒的形态，因而不仅使其作为粘结剂能将碳材料稳定包覆在基底材料表面，且同时还能起到增强纳米粗糙结构的作用，与碳材料共同构建超疏水材料所需微-纳粗糙结构。
4、用本发明提供的方法制备超疏水阻燃材料，其不仅工艺简单，原料价廉易得，而且除干燥(也可常温干燥)外，因制备基本都是在常温条件下进行，还是一种长效节能的方法，加之还可以用于处理多种多样的织物，适用面广，易于实现大规模工业生产。
附图说明
图1为本发明实施例1制备的超疏水阻燃泡沫与5.0μL去离子水的接触角照片。
图2为本发明实施例4制备的超疏水阻燃纯棉布料与5.0μL去离子水的接触角照片。
图3为本发明实施例5制备的超疏水阻燃再生纤维与5.0μL去离子水的接触角照片。
图4为本发明实施例8制备的超疏水阻燃混纺布料与5.0μL去离子水的接触角照片。
图5为对比例1的三聚氰胺泡沫与5.0μL去离子水的接触角照片。
图6为对比例3的纯棉布料与5.0μL去离子水的接触角照片。
图7为本发明实施例2制备的植物单宁-金属离子配合物于pH＝3时的形态扫描电镜图，可以作为粘结剂将碳材料稳定包覆在基底材料表面，并起到增强纳米粗糙结构的作用，与碳材料共同构建超疏水材料所需微-纳粗糙结构。
图8为本发明实施例7制备的植物单宁-金属离子配合物于pH＝10时的形态扫描电镜图，可以作为粘结剂将碳材料稳定包覆在基底材料表面，并起到增强纳米粗糙结构的作用，与碳材料共同构建超疏水材料所需微-纳粗糙结构。
具体实施方式
下面通过实施例对本发明进行具体的描述，且本发明技术方案不局限于以下所列举的具体实施方式。有必要在此指出的是，本实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，对于本领域的技术人员根据上述发明内容所做的一些非本质的改进与调整，也视为落在本发明的保护范围内。需要强调的是，此处所描述的具体实施例中的基材尺寸仅仅用以详细叙述本发明内容，并不用于限定本发明。
另外，值得说明的是，1)以下实施例和对比例中所用物料的份数均为质量份；2)以下实施例所得材料和对比例材料的表面润湿性能是在DSA100接触角测量仪上用5.0μL去离子水进行测试，所得接触角的数据是分别在每个样品上随机取10个不同位置测定后的平均值；3)以下实施例所得材料和对比例材料的极限氧指数是按GB 5454-85标准测试的。
实施例1
将0.01份的单壁碳纳米管、0.1份的荆树皮单宁和0.03份的六水三氯化铁溶液加入由49.86份无水乙醇和50份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至7；将10.0cm×10.0cm×2.0cm的三聚氰胺泡沫用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载单壁碳纳米管的三聚氰胺泡沫(SWCNTs/MA-Foam)；先将0.1份的PDMS溶解在99.9份异丙醇中，然后将SWCNTs/MA-Foam浸泡在PDMS溶液中30min，取出并干燥，即可获得超疏水阻燃三聚氰胺泡沫材料(PDMS/SWCNTs/MA-Foam)。
所得PDMS/SWCNTs/MA-Foam的接触角为157.5°；其极限氧指数为34.4％。
实施例2
将0.1份的活性碳粉末、3.8份的杨梅单宁和1.9份的四氯化钛溶液加入由47.1份无水乙醇和47.1份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至3；将10.0cm×10.0cm×2.0cm的聚氨酯泡沫用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中8min，经干燥即可制得负载活性碳粉末的聚氨酯泡沫(PAC/PU-Foam)；先将0.95份的VTEO溶解在99.05份的甲苯溶液中，然后将PAC/PU-Foam浸泡在VTEO溶液中20h，取出并干燥，即可获得超疏水阻燃聚氨酯泡沫材料(VTEO/PAC/PU-Foam)。
所得VTEO/PAC/PU-Foam的接触角为156.5°；其极限氧指数为20.1％。
实施例3
将0.05份的石墨烯、5.0份的塔拉单宁和1.7份的硫酸钛加入由46.6份无水乙醇和46.65份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至5；将10.0cm×10.0cm×2.0cm的三聚氰胺泡沫用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载石墨烯的三聚氰胺泡沫(Gr/MA-Foam)；先将0.2份DT溶解在99.8份的无水乙醇溶液中，然后将Gr/MA-Foam浸泡在DT溶液中20h，取出并干燥，即可获得超疏水阻燃三聚氰胺泡沫材料(DT/Gr/MA-Foam)。
所得DT/Gr/MA-Foam的接触角为155°；其极限氧指数为35.5％。
实施例4
将0.04份的多壁碳纳米管、4.2份的落叶松单宁和1.4份的四氯化钛加入由47.18份无水乙醇和47.18份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至4；将10.0cm×10.0cm的纯棉布料用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中10min，经干燥即可制得负载多壁碳纳米管的纯棉布料(MWCNTs/Textile)；先将10份PDMS溶解在90份的十二烷溶液中，然后将MWCNTs/Textile浸泡在PDMS溶液中30min取出并干燥，即可获得超疏水阻燃纯棉布料材料(PDMS/MWCNTs/Textile)。
所得DT/Gr/MA-Foam的接触角为153.2°；其极限氧指数为21.7％。
实施例5
将0.06份的石墨烯、6.0份的塔拉单宁和2.0份的二水钼酸钠加入由45份无水乙醇和46.94份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至8；将10.0cm×10.0cm的混纺布料(40％棉和60％聚酯纤维)用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载石墨烯的混纺布料(Gr/Textile)；先将2份DT溶解在98份的无水乙醇中，然后将Gr/Textile浸泡在DT溶液中22h取出并干燥，即可获得超疏水阻燃混纺布料材料(DT/Gr/Textile)。
所得DT/Gr/MA-Textile的接触角为152°；其极限氧指数为20.7％。
实施例6
将0.02份的多壁碳纳米管、6.0份的荆树皮单宁和1.5份的硫酸铝加入由46.24份无水乙醇和46.24份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至6；将10.0cm×10.0cm的混纺布料(65％涤纶和35％棉)用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载碳纳米管的混纺布料(MWCNTs/Textile)；先将3份的PDMS溶解在97份的正庚烷中，然后将MWCNTs/Textile浸泡在PDMS溶液中20min取出并干燥，即可获得超疏水阻燃混纺布料材料(PDMS/MWCNTs/Textile)。
所得PDMS/MWCNTs/Textile的接触角为154.5°；其极限氧指数为20.3％。
实施例7
将0.03份的多壁碳纳米管、8.0份的单宁酸和2.0份的四水二氯化铁加入由44.97份无水乙醇和45份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至5；将10.0cm×10.0cm的混纺布料(40％棉和60％聚酯纤维)用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中15min，经干燥即可制得负载多壁碳纳米管的混纺布料(MWCNTs/Textile)；先将20份的PDMS溶解在80份的正己烷中，然后将MWCNTs/Textile浸泡在PDMS溶液中2min取出并干燥，即可获得超疏水阻燃混纺布料(PDMS/MWCNTs/Textile)。
所得PDMS/MWCNTs/Textile的接触角为153°；其极限氧指数为20.1％。
实施例8
将0.02份的单壁碳纳米管、4.0份的杨梅单宁和2.0份的六水三氯化铁加入由46.99份无水乙醇和46.99份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至9；将10.0cm×10.0cm的纯棉布料用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载单壁碳纳米管的纯棉布料(SWCNTs/Textile)；先将5份的PDMS溶解在95份的正辛烷中，然后将SWCNTs/Textile浸泡在PDMS溶液中6min取出并干燥，即可获得超疏水阻燃纯棉布料(PDMS/SWCNTs/Textile)。
所得PDMS/SWCNTs/Textile的接触角为155.3°；其极限氧指数为21.3％。
实施例9
将0.05份的单壁碳纳米管、1.0份的杨梅单宁和0.5份的六水三氯化铁加入由50份无水乙醇和48.45份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至7；将10.0cm×10.0cm的再生纤维用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载单壁碳纳米管的再生纤维(SWCNTs/Textile)；先将5份的PDMS溶解在95份的正辛烷中，然后将SWCNTs/Textile浸泡在PDMS溶液中6min取出并干燥，即可获得超疏水阻燃纯棉布料(PDMS/SWCNTs/Textile)。
所得PDMS/SWCNTs/Textile的接触角为154.6°；其极限氧指数为30.3％。
实施例10
将0.03份的单壁碳纳米管、6.7份的坚木单宁和2.0份的四氯化钛溶液加入由45份无水乙醇和46.2份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至6；将10.0cm×10.0cm的再生纤维用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中30min，经干燥即可制得负载单壁碳纳米管的再生纤维(SWCNTs/Textile)；先将3份的VTEO溶解在97份的甲苯溶液中，然后将SWCNTs/Textile浸泡在VTEO溶液中20h取出并干燥，即可获得超疏水阻燃再生纤维(VTEO/SWCNTs/Textile)。
所得VTEO/SWCNTs/Textile的接触角为153.7°；其极限氧指数为29.1％。
实施例11
将0.09份的活性碳粉末、0.8份的橡椀单宁和0.6份的硫酸钛溶液加入由49.3份无水乙醇和49.21份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至8；将10.0cm×10.0cm×2.0cm的聚氨酯泡沫用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载活性碳粉末的聚氨酯泡沫(PAC/PU-Foam)；先将5份的VTEO溶解在95份的甲苯溶液中，然后将PAC/PU-Foam浸泡在VTEO溶液中20h取出并干燥，即可获得超疏水阻燃聚氨酯泡沫(VTEO/PAC/PU-Foam)。
所得VTEO/PAC/PU-Foam的接触角为152.9°；其极限氧指数为20.6％。
实施例12
将0.05份的石墨烯、2.0份的坚木单宁和1.0份的六水三氯化铁加入由48.47份无水乙醇和48.48份去离子水组成的溶液中，经超声处理分散溶解，并调节该混合溶液的pH至7；将10.0cm×10.0cm×2.0cm的三聚氰胺泡沫用去离子水、无水乙醇依次润洗并干燥，然后将其浸泡在混合溶液中5min，经干燥即可制得负载石墨烯的三聚氰胺泡沫(Gr/MA-Foam)；先将5份的DT溶解在95份无水乙醇中，然后将Gr/MA-Foam浸泡在DT溶液中23h取出并干燥，即可获得超疏水阻燃三聚氰胺泡沫(DT/Gr/MA-Foam)。
所得DT/Gr/MA-Foam的接触角为155.8°；其极限氧指数为35.2％。
对比例1
将10.0cm×10.0cm×2.0cm的三聚氰胺泡沫用去离子水、无水乙醇依次润洗并干燥。
所得三聚氰胺泡沫的接触角为36°；其极限氧指数为34.0％。
对比例2
将10.0cm×10.0cm×2.0cm的聚氨酯泡沫用去离子水、无水乙醇依次润洗并干燥。
所得聚氨酯泡沫的接触角为45°；其极限氧指数为17.9％。
对比例3
将10.0cm×10.0cm的纯棉布料用去离子水、无水乙醇依次润洗并干燥。
所得纯棉布料的接触角为116°；其极限氧指数为18.8％。
对比例4
将10.0cm×10.0cm的混纺布料(40％棉和60％聚酯纤维)用去离子水、无水乙醇依次润洗并干燥。
所得混纺布料的接触角为123°；其极限氧指数为18.2％。
对比例5
将10.0cm×10.0cm的混纺布料(65％涤纶和35％棉)用去离子水、无水乙醇依次润洗并干燥。
所得混纺布料的接触角为118°；其极限氧指数为19.2％。
对比例6
将10.0cm×10.0cm的再生纤维用去离子水、无水乙醇依次润洗并干燥。
所得再生纤维的接触角为130°；其极限氧指数为27.4％。

Claims (6)

1.一种超疏水阻燃材料的制备方法，其特征在于该方法的工艺步骤和条件如下：
（1）以质量份计，按以下配方于室温下配制混合溶液：
碳材料 0.01-0.1 份
植物单宁 0.1-8.0 份
金属化合物 0.03-2.0 份
无水乙醇 45-50 份
去离子水 45-50 份，
并将该混合溶液的pH值调至3.0-10.0；
（2）先将基底材料依次用去离子水、无水乙醇润洗并干燥，然后将其放入上述混合溶液中进行浸泡处理至少5 min，干燥后即得具有微-纳粗糙结构的基底材料；
（3）将具有微-纳粗糙结构的基底材料用低表面能物质进行表面处理，即得超疏水阻燃材料，
其中所述的金属化合物为六水氯化铁、四水氯化亚铁、硫酸钛、四氯化钛、二水钼酸钠或硫酸铝中的任一种；所述的低表面能物质为聚二甲基硅氧烷溶液、乙烯基三乙氧基硅烷溶液或十二硫醇溶液中的任一种。
2.根据权利要求1所述的超疏水阻燃材料的制备方法，其特征在于该方法中所述的碳材料为单壁碳纳米管、多壁碳纳米管、石墨烯或活性碳粉末中的任一种。
3.根据权利要求1或2所述的超疏水阻燃材料的制备方法，其特征在于该方法中所述的植物单宁为缩合类单宁或水解类单宁中的任一种。
4.根据权利要求3所述的超疏水阻燃材料的制备方法，其特征在于该方法中所述的植物单宁为荆树皮栲胶、杨梅单宁、坚木单宁、橡椀单宁、塔拉单宁或单宁酸中的任一种。
5.根据权利要求1或2所述的超疏水阻燃材料的制备方法，其特征在于该方法中所述的将具有微-纳粗糙结构的基底材料用低表面能物质进行表面处理的方式是：直接浸泡在聚二甲基硅氧烷溶液中至少2 min后取出并干燥，或直接浸泡在乙烯基三乙氧基硅烷溶液中至少20 h后取出并干燥，或直接浸泡在十二硫醇溶液中至少20 h后取出并干燥。
6.根据权利要求3所述的超疏水阻燃材料的制备方法，其特征在于该方法中所述的将具有微-纳粗糙结构的基底材料用低表面能物质进行表面处理的方式是：直接浸泡在聚二甲基硅氧烷溶液中至少2 min后取出并干燥，或直接浸泡在乙烯基三乙氧基硅烷溶液中至少20 h后取出并干燥，或直接浸泡在十二硫醇溶液中至少20 h后取出并干燥。
CN201810045772.5A 2018-01-17 2018-01-17 一种超疏水阻燃材料的制备方法 Active CN108396552B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810045772.5A CN108396552B (zh) 2018-01-17 2018-01-17 一种超疏水阻燃材料的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810045772.5A CN108396552B (zh) 2018-01-17 2018-01-17 一种超疏水阻燃材料的制备方法

Publications (2)

Publication Number Publication Date
CN108396552A CN108396552A (zh) 2018-08-14
CN108396552B true CN108396552B (zh) 2020-11-13

Family

ID=63094592

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810045772.5A Active CN108396552B (zh) 2018-01-17 2018-01-17 一种超疏水阻燃材料的制备方法

Country Status (1)

Country Link
CN (1) CN108396552B (zh)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109457470A (zh) * 2018-11-16 2019-03-12 南通纺织丝绸产业技术研究院 利用黄酮和金属盐制备的阻燃蚕丝及其制备方法和应用
CN109734377B (zh) * 2019-01-31 2020-02-11 商丘市睢阳区水务局 一种节能环保型建筑材料及其制备方法
CN111270514B (zh) * 2020-03-03 2022-06-10 江苏理工学院 一种基于戊二醛交联的稳定超疏水抗菌棉织物的制备方法
CN111925555A (zh) * 2020-08-10 2020-11-13 南通大学 一种基于金属协同配合物构建超疏水涂层的方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104562709B (zh) * 2015-01-27 2017-06-13 南昌航空大学 一种耐用超疏水织物的制备方法
CN105949499A (zh) * 2016-07-11 2016-09-21 四川大学 一种超疏水材料的制备方法
CN107059412A (zh) * 2017-06-20 2017-08-18 四川大学 一种耐磨超疏水皮胶原纤维的制备方法

Also Published As

Publication number Publication date
CN108396552A (zh) 2018-08-14

Similar Documents

Publication Publication Date Title
CN108396552B (zh) 一种超疏水阻燃材料的制备方法
Yang et al. Facile construction of robust superhydrophobic cotton textiles for effective UV protection, self-cleaning and oil-water separation
Yin et al. Self-cleaning, underwater writable, heat-insulated and photocatalytic cellulose membrane for high-efficient oil/water separation and removal of hazardous organic pollutants
Zhu et al. Rational design of multi-layered superhydrophobic coating on cotton fabrics for UV shielding, self-cleaning and oil-water separation
Zhao et al. Environmentally benign and durable superhydrophobic coatings based on SiO2 nanoparticles and silanes
Liang et al. Super-hydrophobic self-cleaning bead-like SiO2@ PTFE nanofiber membranes for waterproof-breathable applications
Liu et al. A superhydrophobic TPU/CNTs@ SiO2 coating with excellent mechanical durability and chemical stability for sustainable anti-fouling and anti-corrosion
Pan et al. Fabrication of stable superhydrophobic coating on fabric with mechanical durability, UV resistance and high oil-water separation efficiency
Yan et al. A superhydrophobic bionic coating on silk fabric with flame retardancy and UV shielding ability
Foorginezhad et al. Fabrication of superhydrophobic coatings with self-cleaning properties on cotton fabric based on Octa vinyl polyhedral oligomeric silsesquioxane/polydimethylsiloxane (OV-POSS/PDMS) nanocomposite
Zhang et al. Fabrication of superhydrophobic cotton textiles for water–oil separation based on drop-coating route
Xu et al. One-pot preparation of robust, ultraviolet-proof superhydrophobic cotton fabrics for self-cleaning and oil/water separation
Li et al. Durable, self-cleaning and superhydrophobic bamboo timber surfaces based on TiO2 films combined with fluoroalkylsilane
Jeyasubramanian et al. Fabrication of water repellent cotton fabric by coating nano particle impregnated hydrophobic additives and its characterization
Chen et al. Low cost and facile preparation of robust multifunctional coatings with self-healing superhydrophobicity and high conductivity
CN114855442A (zh) 一种电磁屏蔽用MXene基导电自清洁复合织物及其制备方法
Wang et al. A durable and sustainable superhydrophobic surface with intertwined cellulose/SiO2 blends for anti-icing and self-cleaning applications
Xue et al. Fabrication of superhydrophobic textiles with high water pressure resistance
Teng et al. Robust superhydrophobic surface fabrication by fluorine-free method on filter paper for oil/water separation
CN110499073B (zh) 一种以纳米纤维素和纳米颗粒为原料在水溶液中无氟改性剂改性制备超疏水涂料的方法
Jiang et al. Robust superhydrophobic tungsten oxide coatings with photochromism and UV durability properties
Ji et al. Mg (OH) 2 and PDMS-coated cotton fabrics for excellent oil/water separation and flame retardancy
CN108003710A (zh) 一种超疏水可见光光催化自清洁涂层及其制备方法
CN108441588B (zh) 一种耐磨超疏水阻燃皮革的制备方法
Dan et al. Preparation and characterization of wear-resistant superhydrophobic cotton fabrics

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant