WO2016095370A1 - 一种管道内衬用高阻隔性tpu薄膜及其制备方法 - Google Patents

一种管道内衬用高阻隔性tpu薄膜及其制备方法 Download PDF

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WO2016095370A1
WO2016095370A1 PCT/CN2015/076134 CN2015076134W WO2016095370A1 WO 2016095370 A1 WO2016095370 A1 WO 2016095370A1 CN 2015076134 W CN2015076134 W CN 2015076134W WO 2016095370 A1 WO2016095370 A1 WO 2016095370A1
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tpu
gonrs
film
cnts
mwcnts
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French (fr)
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郑玉婴
曹宁宁
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福州大学
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    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/008—Additives improving gas barrier properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • the invention belongs to the technical field of preparation of polymer composite films, and particularly relates to a high barrier TPU film for pipeline lining and a preparation method thereof.
  • Thermoplastic polyurethane is a kind of versatile elastic block copolymer composed of soft and hard segments. This special structure makes TPU maintain good elasticity and better in a wide range of hardness. Abrasion resistance, ductility and processability. At the same time, compared with traditional plastic materials such as PVC, EVA and butyl rubber (IIR), TPU is a mature environmentally friendly material with high tensile strength, toughness and aging resistance. At present, TPU has been widely used in medical devices, automotive industry, construction industry and sports products, and has become a promising functional material in the new era.
  • TPU medical mattresses such as TPU medical mattresses, TPU biogas storage bags, shale gas and other unconventional gaseous energy transmission pipelines, TPU membranes, TPU wading products, etc.
  • Small molecules such as oxygen and water vapor easily penetrate through the TPU film, greatly limiting the use of TPU films in barriers.
  • TPU is used as a functional material matrix because of its low modulus, its mechanical properties cannot be fully exerted. Therefore, it is necessary to compound with other inorganic or organic materials to prepare multi-component composite materials, so as to improve the barrier properties and mechanical properties of TPU materials.
  • Such composite materials currently available are generally only improved by adding a single dimension of fillers, such as organoclay, nano-microfibers, nano-calcium carbonate, nano-boron nitride, or by melt blending with other high-barrier polymers.
  • fillers such as organoclay, nano-microfibers, nano-calcium carbonate, nano-boron nitride, or by melt blending with other high-barrier polymers.
  • TPU film barrier and mechanical properties but to achieve the required modification effect, there are problems such as large addition amount, incomplete dispersion of filler in the matrix, and easy stress concentration, which limits its wide application.
  • Multi-walled carbon nanotubes have large aspect ratio, excellent mechanical properties, good chemical stability and thermal stability, and have great development prospects in composite materials applications.
  • the performance of functionalized composites mainly depends on the interfacial interaction between the filler and the matrix, the dispersibility and orientation of the filler in the matrix, and the MWCNTs are prone to agglomeration of carbon nanotubes and poor dispersion in the polymer matrix.
  • the application of single dimension MWCNTs in the field of polymer composites is limited.
  • Graphene oxide nanobelts are thin strip-shaped structural materials mainly composed of carbon atoms. The preparation method is simple, the mechanical properties are excellent, and the surface is rich in oxygen-containing functional groups.
  • GONRs have a larger specific surface area, which is more favorable for high barrier and high strength modification of the polymer.
  • GONRs have problems such as easy accumulation and poor dispersibility in some organic solvents, which limits their use in composite materials to some extent.
  • a new structural material combining MWCNTs and GONRs in different dimensions was sought to perform functions on TPU. Processing is a very meaningful job.
  • the invention proposes the idea of simultaneously compounding nanomaterials of different dimensions, and adopts the oxidative longitudinal cutting MWCNTs method to obtain a graphene oxide nanobelt-carbon nanotube (GONRs-CNTs) nanocomposite composite, in order to pass long and entangled CNTs.
  • Grid to prevent the accumulation of GONRs give full play to their comprehensive performance in polymer applications; and then use TPU as the matrix to obtain GONRs-CNTs/TPU composite film by solution casting process, and its barrier properties and mechanical properties The measurement was carried out.
  • the modification of TPU composites with new structural materials combined with different dimensions of GONRs-CNTs has rarely been reported.
  • the present invention successfully provides a new way for the preparation of new comprehensive TPU nanocomposites. It also provides new ideas and exploration for the development of new high-performance polymer nanocomposites in the future, which makes the invention have innovative research value in academics, and has extensive social and economic benefits and strategic value in practical applications.
  • the object of the present invention is to provide a high barrier TPU film for pipe liner and a preparation method thereof in view of the deficiencies and defects in the prior art.
  • the film material prepared by the method of the invention has excellent barrier performance, and is safe, environmentally friendly and mechanically improved, and is especially suitable for preparing an unconventional gaseous energy transportation pipeline lining such as shale gas, and has wide social and economic benefits and strategies. value.
  • the present invention adopts the following technical solutions:
  • a high-barrier TPU film for pipe lining is prepared by using oxidative longitudinal cutting MWCNTs method to obtain graphene oxide nanobelts-carbon nanotubes by controlling the mass ratio of MWCNTs to KMnO 4 in the reaction system (GONRs- CNTs) nanocomposite composites, and then TPU resin as the matrix, using the solution coating film forming process to obtain GONRs-CNTs/TPU composite film.
  • the MWCNTs have a tube diameter of 40 to 80 nm, preferably 40 to 60 nm.
  • the preparation method specifically comprises the following steps:
  • the mixed solution is transferred to an oil bath at 45-50 ° C for 20-24 hours, and the resulting mixed system is slowly poured into a 500 mL ice water mixture, and after condensing for 1 to 2 hours, 10-15 mL of mass fraction is added.
  • Stir for 30 ⁇ H 2 O 2 for 1 ⁇ 2h then disperse the obtained mixed system in a 100W ultrasonic cleaner for 0.5 ⁇ 1h, filter and wash with HCl and deionized water on the polytetrafluoroethylene filter. Multiple times to remove trace impurities in the system and adjust the system to neutral, and finally freeze-dry the obtained GONRs-CNTs nanocomposite composite;
  • Coating film The glass plate with the clean surface is placed on the coating machine to coat the film, and the thickness of the film is controlled to be 0.06-0.08 mm. After the solvent is sufficiently volatilized, the GONRs-CNTs/TPU composite film is obtained.
  • GONRs-CNTs complex obtained by the present invention
  • GONRs are linked by CNTs, and there is a strong ⁇ - ⁇ bond between the two, which makes the binding form stronger and tight, and the existence of CNTs also supports
  • the role of the skeleton prevents the slip and agglomeration of GONRs, and is more conducive to its uniform dispersion in the polymer matrix.
  • a GONRs-CNTs composite is added to a TPU matrix, and a GONRs-CNTs/TPU composite film is obtained by a solution casting molding process. It was found that the GONRs-CNTs in the composite film have good compatibility with the TPU matrix, and the GONRs-CNTs achieve good dispersion in the matrix.
  • This multi-layered, stable and evenly distributed special structure and the tight bond between the GONRs-CNTs intercalation and the TPU matrix reduces the solubility of the gas in the polymer and on the other hand the diffusion and permeation path of the gas
  • the twists and turns are prolonged, the diffusion path is prolonged, and the penetration of small molecules such as gas is improved, so that the barrier property of the material is greatly improved, and the mechanical properties are further improved.
  • the TPU composite film prepared by the invention is safe and environmentally friendly, and is especially suitable for preparing an unconventional gaseous energy transportation pipeline lining such as shale gas; meanwhile, the invention is suitable for the needs of the market today, and the preparation method is scientific and reasonable, the process is simple, and the operation is simple. Strong, greatly increasing the added value of TPU products, and expanding its application range, with broad market prospects and significant social benefits.
  • Figure 1 shows the XRD spectra of MWCNTs and GONRs-CNTs nanocomposites with different content ratios.
  • Figure 2 is a TEM spectrum of MWCNTs and GONRs-CNTs nanocomposites with different content ratios.
  • Figure 3 is a schematic diagram showing the oxygen transmission rate of a pure TPU film and a TPU composite film when different nanofillers are added, wherein 1 is pure TPU, 2 is MWCNTs-TPU, 3 is 1:2-TPU, and 4 is 1:3- TPU, 5 is 1:4-TPU, 6 is 1:5-TPU, and 7 is 1:6-TPU.
  • a high-barrier TPU film for pipeline lining is prepared by using oxidative longitudinal cutting MWCNTs method, and by controlling the mass ratio of MWCNTs to KMnO 4 in the reaction system, different ratios of graphene oxide nanobelts-carbon nanometers are obtained.
  • the GONRs-CNTs/TPU composite film was prepared by using a TPU resin as the matrix and a solution coating film formation process.
  • the diameter of the MWCNTs was 60 nm.
  • the preparation method specifically comprises the following steps:
  • Coating film The glass plate with neat surface is placed on the coating machine for coating film, and the film thickness is controlled to be 0.08 mm. When the coating is completed, the glass piece is allowed to stand at room temperature for 24 hours to fully evaporate the solvent to obtain 0.075 g content.
  • a 1:2 GONRs-CNTs/TPU composite film (labeled 1:2-TPU).
  • the amount of KMnO 4 added in step 1) was 3 g, and other conditions were the same as in Example 2, and finally 0.075 g of a GONRs-CNTs/TPU composite film (labeled as 1:3-TPU) having a 1:3 content was obtained.
  • the amount of KMnO 4 added in step 1) was 4 g, and other conditions were the same as in Example 2, and finally 0.075 g of a GORs-CNTs/TPU composite film (labeled as 1:4-TPU) having a 1:4 content was obtained.
  • the amount of KMnO 4 added in step 1) was 5 g, and other conditions were the same as in Example 2, and finally 0.075 g of a GONRs-CNTs/TPU composite film (labeled as 1:5-TPU) having a 1:5 content was obtained.
  • the amount of KMnO 4 added in step 1) was 6 g, and other conditions were the same as in Example 2, and finally 0.075 g of a GONRs-CNTs/TPU composite film (labeled as 1:6-TPU) having a 1:6 content was obtained.
  • Figure 1 shows the XRD spectra of MWCNTs and GONRs-CNTs nanocomposites with different content ratios.
  • Figure 2 shows the TEM spectra of MWCNTs and GONRs-CNTs nanocomposites with different content ratios.
  • Figure 3 is a schematic diagram showing the oxygen transmission rate of a pure TPU film and a TPU composite film when different nanofillers are added, wherein 1 is pure TPU, 2 is MWCNTs-TPU, 3 is 1:2-TPU, and 4 is 1:3- TPU, 5 is 1:4-TPU, 6 is 1:5-TPU, and 7 is 1:6-TPU.
  • the pure TPU film prepared in Example 1 has an oxygen permeability of 460.335 cm 3 /m 2 ⁇ d.Pa, which is significantly higher than the composite prepared by the GONRs-CNTs complex obtained in Examples 2-6.
  • TPU film when the ratio of MWCNTs to KMnO 4 in the reaction system is 1:4, the oxygen transmission rate reaches a minimum value of 224.172 cm 3 /m 2 .d.Pa, Compared with pure TPU, its oxygen transmission rate decreased by 51.3%, and the barrier performance was significantly improved.
  • the composite material film provided by the invention is suitable for preparing TPU medical mattress, TPU biogas storage bag, shale gas and other unconventional gaseous energy transmission pipeline lining TPU membrane material, TPU wading product, etc. A higher demand area.

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Abstract

.本发明公开了一种管道内衬用高阻隔性TPU薄膜及其制备方法，以MWCNTs、TPU为原料，采用氧化纵向切割MWCNTs法，通过控制MWCNTs与KMn04质量比，制得GONRs-CNTs纳米复合材料综合体，再以TPU树脂为基体，采用溶液涂覆成膜工艺制得GONRs-CNTs/TPU复合材料薄膜。本发明制得的复合材料薄膜，一方面降低了气体在聚合物中的可溶性，另一方面也使得气体的扩散渗透通路变得曲折迂回，延长了扩散路径，提高了气体等小分子物质的穿透难度，从而使得材料的阻隔性能得到了极大程度的提高，尤其适用于制备页岩气等非常规气态能源输送管道内衬，具有广泛的社会及经济效益。

Description

一种管道内衬用高阻隔性TPU薄膜及其制备方法 技术领域
本发明属于高分子复合薄膜制备技术领域，具体涉及一种管道内衬用高阻隔性TPU薄膜及其制备方法。
背景技术
热塑性聚氨酯(TPU)是一类用途广泛的弹性嵌段共聚物，由软段和硬段共同组成，这种特殊的结构使得TPU在较宽的硬度范围内仍能保持良好的弹性及较好的耐磨性、延展性和加工性。同时，与PVC、EVA、丁基橡胶(IIR)等传统塑胶材料相比，TPU具有高张力、强韧和耐老化等特性，是一种成熟的环保型材料。目前TPU已广泛应用于医疗器件、汽车行业、建筑行业及体育制品等领域，成为了新时期极具发展前景的功能性材料。
但一些特定领域对材料的阻隔性能有很高的要求，如TPU医疗床垫、TPU沼气储存袋、页岩气等非常规气态能源输送管道内衬用TPU膜材、TPU涉水类产品等，而氧气和水蒸气等小分子物质很容易渗透通过TPU薄膜，从而极大地限制了TPU薄膜在阻隔方面的应用。同时TPU因为模量低，用作功能材料基体时，其力学性能无法得到充分发挥，因此需要与其他无机或有机材料复合，制备多元复合材料，达到提高TPU材料阻隔性能以及力学性能的目的。目前已有的此类复合材料一般只是通过添加单一维度的填料，如有机粘土、纳米微纤、纳米碳酸钙、纳米氮化硼，或者采用与其他高阻隔聚合物熔融共混的方法来达到提高TPU薄膜阻隔和力学性能的目的，但要达到所要求的改性效果，存在添加量大、填料在基体中无法完全分散、易造成应力集中等问题，限制了其的广泛应用。
多壁碳纳米管(MWCNTs)具有较大的长径比、优异的力学特性、良好的化学稳定性和热稳定性，在复合材料应用领域有着很大的发展前景。功能化复合材料的性能主要取决于填料与基体间的界面作用、填料在基体中的分散性和取向等关键因素，而MWCNTs存在碳管易发生团聚、在聚合物基体中分散性差等缺陷，因此局限了单一维度MWCNTs在聚合物复合材料领域中的应用。氧化石墨烯纳米带(GONRs)是一种主要由碳原子构成的薄条状结构材料，其制备方法简便、力学性能优良、表面具有丰富的含氧官能团。反应活性高，同时，相比于MWCNTs，GONRs具有更大的比表面积，更有利于对聚合物进行高阻隔、高强度改性。然而同MWCNTs一样，GONRs存在易聚积、在部分有机溶剂中分散性差等问题，在一定程度上限制了其在复合材料中的使用。为了充分发挥二者在聚合物改性方面的综合性能，寻找一种MWCNTs与GONRs不同维度相结合的新型结构材料，对TPU进行功能 化处理是一项很有意义的工作。
本发明提出了将不同维度的纳米材料同时复合的思想，采用氧化纵向切割MWCNTs法制得氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)纳米复合材料综合体，以期通过长且纠结缠绕的CNTs网格来阻止GONRs的聚积，充分发挥二者在聚合物应用领域的综合性能；再以TPU为基体，通过溶液浇注成型工艺获得GONRs-CNTs/TPU复合材料薄膜，并对其阻隔性能和力学性能进行了测定。在目前国内外文献中，以GONRs-CNTs不同维度相结合的新型结构材料对TPU复合材料进行修饰还鲜有报道，本发明成功的为制备新型综合性TPU纳米复合材料提供了新的途径，同时也为今后开发新型高性能聚合物纳米复合材料提供了新的思路与探索，使得本发明在学术上具有创新研究价值，在实际应用中具有广泛的社会经济效益和战略价值。
发明内容
本发明的目的在于针对现有技术中的不足与缺陷，提供一种管道内衬用高阻隔性TPU薄膜及其制备方法。经本发明方法制备的薄膜材料具有优异的阻隔性能，其安全环保且力学性能得到了进一步提高，尤其适用于制备页岩气等非常规气态能源输送管道内衬，具有广泛的社会经济效益以及战略价值。
为实现上述目的，本发明采用如下技术方案：
一种管道内衬用高阻隔性TPU薄膜，其制备方法是采用氧化纵向切割MWCNTs法，通过控制反应体系中MWCNTs与KMnO4的质量比，制得氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)纳米复合材料综合体，再以TPU树脂为基体，采用溶液涂覆成膜工艺制得GONRs-CNTs/TPU复合材料薄膜。
所述MWCNTs的管径为40～80nm，优选范围为40～60nm。
其制备方法具体包括如下步骤：
1)GONRs-CNTs纳米复合材料综合体的制备：将180mL质量分数为98％的浓H2SO4倒入250mL的圆底烧瓶中，随后缓慢加入20mL质量分数为85.5％的H3PO4，在100～120r/min的转速下搅拌均匀；接着加入1g MWCNTs，搅拌1～2h，待MWCNTs分散均匀后，缓慢加入KMnO4(KMnO4的加入速度控制在1g/h)，搅拌1～2h得到混合液；将搅拌均匀的混合液移至45～50℃的油浴锅中反应20～24h，再将所得混合体系缓慢倒入500mL冰水混合物中，凝结1～2h后加入10～15mL质量分数为30％的H2O2搅拌1～2h，然后将所得混合体系置于100W的超声波清洗器中超声分散0.5～1h，在聚四氟乙烯滤膜上，用HCl与去离子水过滤、洗涤多次，以除去体系中的微量杂质并调节体系至中性，最后将所得GONRs-CNTs纳米复 合材料综合体冷冻干燥；
2)混合糊状液体的制备：将步骤1)制备的GONRs-CNTs纳米复合材料综合体，加入到60～90mL DMF溶液中，并置于100W的超声波清洗器中超声分散1～2h，待其稳定后加入10～15g预先烘干的TPU颗粒，然后放入60～80℃鼓风干燥箱中溶胀6～8h，再在机械搅拌机上搅拌3～5h，直至TPU完全溶解后，置于100W的超声波清洗器中超声分散1～2h，随后将混合糊状液体倒进带有吸管的小容量瓶中，在抽滤机上抽出糊状液体里的空气并静置1～2h；
3)涂膜：将表面整洁的玻璃板放置于涂膜机上进行涂膜，控制膜厚度0.06～0.08mm，待溶剂充分挥发后得到GONRs-CNTs/TPU复合材料薄膜。
本发明的有益效果在于：
(1)本发明所得GONRs-CNTs综合体中，GONRs之间通过CNTs链接，二者间存在强有力的π-π键，可使这种结合形态更加牢固紧密，同时CNTs的存在也起到了支撑骨架的作用，防止了GONRs的滑移与团聚，更有利于其在聚合物基体中的均匀分散。
(2)本发明将GONRs-CNTs综合体加入到TPU基体中，通过溶液浇注成型工艺获得GONRs-CNTs/TPU复合材料薄膜。经研究发现，复合材料薄膜中GONRs-CNTs与TPU基体相容性很好，且GONRs-CNTs在基体中实现了良好的分散。这种多层、稳固而又均匀分布的特殊结构以及GONRs-CNTs插层与TPU基体间的紧密结合，一方面降低了气体在聚合物中的可溶性，另一方面也使得气体的扩散渗透通路变得曲折迂回，延长了扩散路径，提高了气体等小分子物质的穿透难度，从而使得材料的阻隔性能得到了极大程度的提高，也使其力学性能得到了进一步提高。
(3)本发明制备的TPU复合材料薄膜安全环保，尤其适用于制备页岩气等非常规气态能源输送管道内衬；同时，本发明适应当今市场的需求，制备方法科学合理、工序简单、操作性强，极大地提高了TPU产品的附加值，并扩展了其的应用范围，具有广泛的市场前景和显著的社会效益。
附图说明
图1为MWCNTs和不同含量比的GONRs-CNTs纳米复合材料的XRD谱图。
图2为MWCNTs和不同含量比的GONRs-CNTs纳米复合材料的TEM谱图。
图3为纯TPU薄膜以及添加不同纳米填料时TPU复合材料薄膜的氧气透过率示意图，其中，1为纯TPU，2为MWCNTs-TPU，3为1:2-TPU，4为1:3-TPU，5为1:4-TPU，6为1:5-TPU，7为1:6-TPU。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
将15g预先烘干的TPU颗粒缓慢倒入80mL DMF溶液中，置于80℃的鼓风干燥箱中溶胀1h，紧接着将该混合体系在机械搅拌机上搅拌3.5h，直至TPU完全溶解后，置于100W的超声波清洗器中超声分散2h，随后将混合糊状液体倒进带有吸管的小容量瓶中，在抽滤机上抽出糊状液体里的空气并静置1.5h。将表面整洁的玻璃板放置于涂膜机上进行涂膜，控制膜厚度0.08mm，当涂敷完成后，将玻璃片在室温下晾置24h以充分挥发溶剂，得到纯TPU材料薄膜。
实施例2
一种管道内衬用高阻隔性TPU薄膜，其制备方法是采用氧化纵向切割MWCNTs法，通过控制反应体系中MWCNTs与KMnO4的质量比，制得不同含量比的氧化石墨烯纳米带-碳纳米管(GONRs-CNTs)纳米复合材料综合体，再以TPU树脂为基体，采用溶液涂覆成膜工艺制得GONRs-CNTs/TPU复合材料薄膜。
所述MWCNTs的管径为60nm。
其制备方法具体包括如下步骤：
1)GONRs-CNTs纳米复合材料综合体的制备：将180mL质量分数为98％的浓H2SO4倒入250mL的圆底烧瓶中，随后缓慢加入20mL质量分数为85.5％的H3PO4，在100r/min的转速下搅拌均匀；接着加入1g MWCNTs，搅拌1.5h，待MWCNTs分散均匀后，缓慢加入2g KMnO4(KMnO4的加入速度控制在1g/h)，搅拌1h，得到含量比为1:2的混合液；将搅拌均匀的混合液移至50℃的油浴锅中反应20h，再将所得混合体系缓慢倒入500mL冰水混合物中，凝结2h后加入10mL质量分数为30％的H2O2，搅拌1.5h，然后将所得混合体系置于100W的超声波清洗器中超声分散30min，在聚四氟乙烯滤膜上，用HCl与去离子水过滤、洗涤多次，以除去体系中的微量杂质并调节体系至中性，最后将所得GONRs-CNTs纳米复合材料综合体经冷冻干燥，所得产物简记为1:2；
2)混合糊状液体的制备：将0.075g步骤1)制备的1:2含量的GONRs-CNTs纳米复合材料综合体加入到80mL DMF溶液中，并在100W的超声波清洗器中超声分散6h，待其稳定后加入15g预先烘干的TPU颗粒，然后放入80℃鼓风干燥箱中溶胀1h，再在机械搅拌机上搅拌3.5h，直至TPU完全溶解后，置于100W的超声波清洗器中超声分散2h，随后将混合糊 状液体倒进带有吸管的小容量瓶中，在抽滤机上抽出糊状液体里的空气并静置1.5h；
3)涂膜：将表面整洁的玻璃板放置于涂膜机上进行涂膜，控制膜厚度0.08mm，当涂敷完成后，将玻璃片在室温下晾置24h以充分挥发溶剂，得到0.075g含量为1:2的GONRs-CNTs/TPU复合材料薄膜(标记为1:2-TPU)。
实施例3
步骤1)中KMnO4的加入量为3g，其他条件参数与实施例2相同，最终得到0.075g含量为1:3的GONRs-CNTs/TPU复合材料薄膜(标记为1:3-TPU)。
实施例4
步骤1)中KMnO4的加入量为4g，其他条件参数与实施例2相同，最终得到0.075g含量为1:4的GONRs-CNTs/TPU复合材料薄膜(标记为1:4-TPU)。
实施例5
步骤1)中KMnO4的加入量为5g，其他条件参数与实施例2相同，最终得到0.075g含量为1:5的GONRs-CNTs/TPU复合材料薄膜(标记为1:5-TPU)。
实施例6
步骤1)中KMnO4的加入量为6g，其他条件参数与实施例2相同，最终得到0.075g含量为1:6的GONRs-CNTs/TPU复合材料薄膜(标记为1:6-TPU)。
图1为MWCNTs和不同含量比的GONRs-CNTs纳米复合材料的XRD谱图，图2为MWCNTs和不同含量比的GONRs-CNTs纳米复合材料的TEM谱图。
通过图1和图2可以清晰地看到，随着反应体系中MWCNTs与KMnO4含量比由1:2变化至1:6的过程中，所得GONRs-CNTs综合体中GONRs含量越来越多，并且当MWCNTs与KMnO4含量比为1:6时，所得综合体中已基本观察不到CNTs的存在，此时体系中MWCNTs已基本完全被氧化纵向切割为GONRs；同时通过图2(d)可以清楚地看到，带状结构的GONRs其宽度约为160nm，然而从图中也可看到GONRs明显的团聚现象，限制了其的进一步应用。需要特别指出的是，如图2(b)和图2(c)所示，当MWCNTs与KMnO4含量比为1:2和1:4时，所得GONRs-CNTs综合体中，GONRs之间通过CNTs链接，二者间存在强有力的π-π键，可使这种结合形态更加牢固紧密，同时CNTs的存在也起到了支撑骨架的作用，防止了GONRs的滑移与团聚，更有利于其在聚合物基体中的均匀分散。
图3为纯TPU薄膜以及添加不同纳米填料时TPU复合材料薄膜的氧气透过率示意图，其中，1为纯TPU，2为MWCNTs-TPU，3为1:2-TPU，4为1:3-TPU，5为1:4-TPU，6为1:5-TPU，7为1:6-TPU。
通过图3可以看出，实施例1制得的纯TPU薄膜的氧气透过率为460.335cm3/m2.d.Pa，明显高于实施例2-6所得GONRs-CNTs综合体制备的复合TPU薄膜；同时需要指出的是，如图5所示，当反应体系中MWCNTs与KMnO4含量比为1:4时，其氧气透过率达到最低值224.172cm3/m2.d.Pa，相比纯TPU其氧气透过率下降了51.3％，阻隔性能得到明显提高。
本发明所提供的复合材料薄膜适用于制备TPU医疗床垫、TPU沼气储存袋、页岩气等非常规气态能源输送管道内衬用TPU膜材、TPU涉水类产品等对材料的阻隔性能有较高要求的领域。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (6)

  1. 一种管道内衬用高阻隔性TPU薄膜的制备方法，其特征在于：采用氧化纵向切割MWCNTs法，通过控制反应体系中MWCNTs与KMnO4的质量比，制得GONRs-CNTs纳米复合材料综合体，再以TPU树脂为基体，采用溶液涂覆成膜工艺制得GONRs-CNTs/TPU复合材料薄膜。
  2. 根据权利要求1所述管道内衬用高阻隔性TPU薄膜的制备方法，其特征在于：所述MWCNTs的管径为40～80nm。
  3. 根据权利要求1所述管道内衬用高阻隔性TPU薄膜的制备方法，其特征在于：具体包括如下步骤：
    1)GONRs-CNTs纳米复合材料综合体的制备：将质量分数为85.5％的H3PO4缓慢加入到质量分数为98％的浓H2SO4中，在100～120r/min的转速下搅拌均匀；接着加入MWCNTs搅拌1～2h，待MWCNTs分散均匀后，缓慢加入KMnO4，搅拌1～2h得到的混合液；将搅拌均匀后的混合液移至45～50℃的油浴锅中反应20～24h，再将所得混合体系缓慢倒入冰水混合物中，凝结1～2h后加入质量分数为30％的H2O2搅拌1～2h，然后将混合体系于100W超声下分散0.5～1h，在聚四氟乙烯滤膜上用HCl与去离子水过滤、洗涤多次，以除去体系中的微量杂质并调节体系至中性，最后将所得GONRs-CNTs纳米复合材料综合体冷冻干燥；
    2)混合糊状液体的制备：将步骤1)制备的GONRs-CNTs纳米复合材料综合体加入到DMF溶液中，并在100W下超声分散1～2h，待其稳定后加入预先烘干的TPU颗粒，然后放入60～80℃干燥箱中溶胀6～8h，再搅拌3～5h，直至TPU完全溶解后，于100W下超声分散1～2h，随后将混合糊状液体倒进带有吸管的小容量瓶中，在抽滤机上抽出糊状液体里的空气并静置1～2h；
    3)涂膜：将表面整洁的玻璃板放置于涂膜机上进行涂膜，控制膜厚度0.06～0.08mm，待溶剂充分挥发后得到GONRs-CNTs/TPU复合材料薄膜。
  4. 根据权利要求1所述管道内衬用高阻隔性TPU薄膜的制备方法，其特征在于：步骤1)中KMnO4的加入速度控制在1g/h。
  5. 根据权利要求1所述管道内衬用高阻隔性TPU薄膜的制备方法，其特征在于：步骤2)所用TPU颗粒与DMF溶液的质量体积比为1:6。
  6. 一种如权利要求1或3所述制备方法制得的管道内衬用高阻隔性GONRs-CNTs/TPU薄膜。
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