CN102596534A - 多层复合材料 - Google Patents

多层复合材料 Download PDF

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Publication number
CN102596534A
CN102596534A CN2010800348931A CN201080034893A CN102596534A CN 102596534 A CN102596534 A CN 102596534A CN 2010800348931 A CN2010800348931 A CN 2010800348931A CN 201080034893 A CN201080034893 A CN 201080034893A CN 102596534 A CN102596534 A CN 102596534A
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CN
China
Prior art keywords
dispersion
ptfe
spinning
nanofiber
structure body
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Granted
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CN2010800348931A
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English (en)
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CN102596534B (zh
Inventor
B·L·阿诺
R·L·巴拉德
D·P·加纳
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Zeus Ltd
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Zeus Inc
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Publication of CN102596534B publication Critical patent/CN102596534B/zh
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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    • B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
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Abstract

根据本公开内容的某些实施方案，本发明提供了用于形成多层电纺丝复合材料的方法。该方法包括形成聚合物纳米纤维、纤维化聚合物和溶剂的分散体。该分散体具有至少大约50,000cPs的粘度。在第一ePTFE层上电纺丝来自该分散体的纳米纤维。在纳米纤维上应用第二ePTFE层以形成复合结构体。加热该复合结构体。

Description

多层复合材料
交叉引用的相关申请
本申请基于并且要求了美国在先申请系列号61/232,252，其具有2009年8月7日的提交日期，通过参考将其引入本发明。
背景技术
聚四氟乙烯(PTFE)电纺丝为连续的纤维允许具有用于多重其他应用和形式的潜力的无纺薄片、管和涂层的形成。电纺丝的方法是US专利Nos.2,158,416；4,432,916；4,287,139；4,143,196；4,043,331；4,689,186和6,641,773为代表的文献和专利中公知的，其中的每一篇都通过参考引入本发明。虽然这些专利中的大部分都是关于可溶性聚合物或热塑性塑料的，都不直接与实质上来自于不溶性聚合物的纤维或毡垫或在加热到升高的温度下并不易于流动的那些的形成有关。文献和专利的综述显示出其对这样的方法只有有限的涉及，由该方法可以使一旦加热就易于流动的满足有限的溶解性和不溶性的性质的聚合物，例如PTFE形成适用于电纺丝以形成多种结构体的纤维。二者都通过参考引入本发明的US专利Nos.4,323,525和4,044,404提供了与来自含水或其他分散体的PTFE的加工和电纺丝有关的信息。
但是这种常规的方法具有多种缺点。这种方法描述了其不会导致均一的或一致的纤维的形成的低粘度(15000厘泊)PTFE分散体的使用。此外，这种方法还描述了接地纺丝头和带电标的的使用。观察显示在制备的样品中通过反极性有不同的降解水平。在烧结期间常规的方法也不能提供毡垫的收缩。
因此，存在着对克服以上描述的缺陷的方法的需要。由这种方法制备的材料也将是特别有益的。
发明内容
根据本公开内容的某些实施方案，其提供了一种用于形成多层电纺丝复合材料的方法。该方法包括形成聚合物纳米纤维、纤维化聚合物和溶剂的分散体，该分散体具有至少大约50,000cPs的粘度。将来自该分散体的纳米纤维在第一ePTFE层上电纺丝。在纳米纤维上应用第二ePTFE层以形成复合结构体。加热该复合结构体。
在本公开内容的另一些实施方案中还公开了用于形成多层电纺丝复合结构体的方法。该方法包括在ePTFE层的第一侧面上将具有至少大约50,000cPs的粘度且包括聚合物纳米纤维、纤维化聚合物和溶剂的分散体电纺丝。该方法还进一步包括在ePTFE层的第二侧面上电纺丝具有至少大约50,000cPs的粘度且包括聚合物纳米纤维、纤维化聚合物和溶剂的分散体以形成复合结构体。加热该复合结构体。
还在本公开内容的其他实施方案中描述了用于形成多层电纺丝复合结构体的方法。该方法包括形成聚合物纳米纤维、纤维化聚合物和溶剂的分散体，该分散体具有至少大约50,000cPs的粘度。将来自该分散体的纳米纤维在第一ePTFE层上电纺丝。在纳米纤维上应用基底以形成复合结构体。加热该复合结构体。
通过深入的研究，发明人确定当将电纺丝材料、例如PTFE应用于ePTFE膜时，其建立起电纺丝材料的额外应用、形成和用途。此外，发明人还确定当将宽范围内的电纺丝材料与ePTFE膜和/或其他基底一起合并到层中时，其可以建立具有新的和独特性质的复合材料膜结构体。
以下对本公开内容其他的特征和方面进行更详细的讨论。
附图说明
参考附图更特别地在说明书的其他部分对于本领域技术人员给出包括最佳模式的完整和可行的公开，其中：
图1图解说明了根据本公开内容的多层复合构造的SEM图；以及
图2-5图解说明了根据本公开内容的不同多层复合材料的剖面图。
具体实施方式
现在更详细地参考本公开内容的不同实施方案，以下给出一个或多个实施方案的实例。通过公开内容的解释说明的方法提供每一个实例，而并不是对于该公开的内容的限制。事实上，对本领域技术人员显而易见的是在本公开内容中可以进行不同的改进和变形而并不悖离本公开内容的范围或精神。例如，说明或描述的特征作为一个实施方案的部分可以用于另一个实施方案以获得其他的实施方案。因此其含义是本公开内容覆盖了这些从属权利保护要求和其他等同形式范围内的改进和变形。
本发明涉及包含一种或多种附着于一个或多个延展的聚四氟乙烯(本发明中称为“ePTFE”)膜的电纺丝(本发明也称为“带电纺丝”和/或“电纺”)膜的多层复合材料。在某些实施方案中，电纺丝膜可以包括聚四氟乙烯(本发明中也称为“电纺丝PTFE”)，但是，许多其他合适的材料可以进行电纺丝以及除此外地被使用或与这种电纺丝PTFE相结合使用。例如，根据本公开内容可以电纺丝的其他合适的材料包括尼龙，聚氨酯(PU)，聚酯，氟化乙烯丙烯(FEP)或类似的物质。可以放置在溶液中的聚合物具有进行电纺丝的潜力。可以制成分散体(例如PTFE、FEP以及类似物)的聚合物颗粒也具有进行电纺丝的潜力。该分散体(电纺丝PTFE)必须烧结以开发出所期望的性质，但是许多从溶液进行电纺丝的聚合物在纺丝和干燥期间开发出它们的性质。在烧结期间可能发生电纺丝层的粘附。
例如，在某些实施方案中，存在于电纺丝PTFE层和ePTFE层中的高分子量聚四氟乙烯在烧结温度下熔融，但是其并不流动。因此，存在于每一层中的PTFE在相邻的层之间具有形成物理粘接的机会。其优点在于层的压缩以加强更紧密的接触。该多层复合材料特别用于医药、工业、过滤、军事和消费者应用。
特别优选的ePTFE是透气性延展膜。US专利No.4,902,423中描述了一种用于说明本发明的示例性的膜，通过参考将该文献引入本发明。US专利No.3,962,152中描述了另一个示例性的膜，通过参考将该文献引入本发明。
根据本公开内容预期了大量的构造。例如，该构造可以是本发明描述的材料的两层或多层复合材料。
参见图2，其图解说明了根据本公开内容的多层复合材料的剖面。该复合材料包括ePTFE层1和电纺丝层2。图1图解说明了这种多层复合材料的SEM图，其中电纺丝层是电纺丝PTFE。这种构造的优点包括由于孔尺寸可以控制而导致的不对称的流动结构。此外，电纺丝材料的存在可以导致复合材料对后续层的改进的粘合作用。重要的是，电纺丝材料也可导致ePTFE表面性质的改进。
转向图3，其图解说明了根据本公开内容的多层复合材料的另一个剖面。该复合材料包括ePTFE层1、电纺丝层2和ePTFE层1。电纺丝层2夹在ePTFE层1之间。正如所期望的那样，这种构造允许复合材料的机械性质得以改进。例如，在压缩后可以增加材料的回收。电纺丝材料的选择可以进行调节以改进层之间的粘接性质。在这一点上，任何具有粘合潜力的电纺丝材料都可以用于将层粘合在一起。电纺丝PTFE可以用于将ePTFE层粘合在一起。电纺丝PU也可以用于将ePTFE层粘合在一起。在某些实施方案中，电纺丝PTFE必须加热到385℃以开发出其粘合特性，而例如PU等的材料可以在更低得多的温度下产生粘合的情况。
还在本公开内容的另一个实施方案中，电纺丝层2、ePTFE层1和电纺丝层2的剖面图如图4所示。ePTFE层1夹在电纺丝层2之间。这种构造的优点包括通过电纺丝层调节其表面性质，包括a)如果期望的话，对复合材料的构造的更好的粘合性，b)改变复合材料的表面功能性，c)微孔内生长和响应的控制以及d)增加孔隙度用于增强其他材料的进入。
图5图解说明了根据本公开内容的多层复合材料构造剖面的另一个实施方案。该复合材料包括基底层3、电纺丝层2和ePTFE层1。基底层可以包括天然或人造纤维的织造织物和无纺织物，塑料或陶瓷膜，金属，陶瓷和塑料筛网或类似物。例如，金属stents是一类金属筛网。这种构造允许结构具有增强的坚固性和耐久性，同时保持孔隙度、透气性和其他多孔材料的期望性质。该复合材料可以热或粘合性地与其他织造或无纺多孔基底粘合。这种复合材料还导致改进的孔尺寸分布和改进的耐久性，这可能对于其中碎片和微粒以高速与介质表面接触的过滤应用是非常有利的。此外，整体的过滤效率可能因为电纺丝纤维缠绕的微结构的结果而有所改进。
电纺丝层优选通过本领域技术人员理解的电纺丝的方法直接应用于膜；但是，它还可以使用机械捏合或层压来应用。这些最近的技术包括在第二材料层上压制电纺丝层并且加热到令人赞同的温度。压制技术可以使用平板压机或机械压料辊压机。
性能和特性是无纺织物和膜的汇集。复合材料可以用可控纤维、结点和原纤维尺寸制备并且调节机械值，例如粘接强度、伸长性能和抗拉强度。
复合材料的性能和特性可以是基底层、电纺丝层和ePTFE层的各单独性能的汇集。该复合材料可以用可控纤维、结点和原纤维尺寸制备并且进行机械性调节，例如在最后的复合材料中改进粘接强度、伸长性能和抗拉强度。
多层的典型构造在大约0.032英寸到大约80英寸的宽度下可以产生大约0.0001英寸到大约0.25英寸整体厚度范围内的厚度。各单独的层可以具有从大约0.0001英寸到大约0.25英寸之间变换的厚度。最后的材料尺寸可以有显著的变化，因为复合材料可以制备成有连续卷绕长度的片或管。复合材料的节点间距(IND)可以是大约0.1到大约200μm，且孔隙度范围为大约20到90％。根据通过参考引入本发明的ASTMF316定义的孔结构可以在大约0.05到大约50μm的范围内。由于复合材料的构造，取决于其构造，IND、孔尺寸和孔隙度可以在复合材料的剖面中层层变化。其一个实例是不对称的构造，其中经过介质从表面到表面基于层的评价，孔尺寸由大变小。
在本公开内容的某些实施方案中，该方法可以要求大约10到85％重量之间的PTFE固体的分散体或悬浮液以便帮助收集的纤维毡垫加工为具有足够原始强度的形式。但是，正如以上所述，其他合适的聚合物可以用于电纺丝分散体。如果分散体中的固体含量太低，得到的材料就不会有或者有很差的机械完整性。其次，用于增加用于纺丝的溶液、悬浮液或分散体粘度的聚合物的选择必须小心选择。
此外，当烧结或粘合电纺丝层时，需要保证温度选择为适合烧结材料，使得最终的产品具有良好的机械完整性。
为了制备无纺电纺丝PTFE材料，在水性分散体中提供了窄颗粒尺寸分布的PTFE粉末。颗粒尺寸将优选为大约0.05到0.8μ。将大约1到10wt％重量的纤维化聚合物添加到PTFE水性分散体的体积中。纤维化聚合物在水中应具有高的溶解性，溶解性超过大约0.5wt％是优选的。当在约400℃下烧结时，优选纤维化聚合物具有小于大约5wt％的灰分含量，甚至更优选更低。没有其他的限制，特别优选纤维化聚合物可以包括葡聚糖、藻酸盐、壳聚糖、瓜耳胶化合物、淀粉、聚乙烯基吡啶化合物、纤维素类化合物、纤维素醚、水解的聚丙烯酰胺、聚丙烯酸酯、聚羧酸酯、聚乙烯醇、聚氧化乙烯、聚乙二醇、聚乙烯亚胺、聚乙烯基吡咯烷酮、聚乳酸、聚甲基丙烯酸、聚衣康酸、聚丙烯酸2-羟基乙酯、聚甲基丙烯酸2-二甲基氨基乙基酯共聚丙烯酰胺，聚n-异丙基丙烯酰胺，聚2-丙烯酰胺-2-甲基-1-丙磺酸，聚(甲氧基乙烯)，聚(乙烯醇)，12％酰基的聚(乙烯醇)，聚(2，4-二甲基-6-三嗪基乙烯)，聚(3-吗啉基乙烯)，聚(N-1，2，4-三氮乙烯)，聚(乙烯基亚砜)，聚(乙烯基胺)，聚(N-乙烯基吡咯烷酮共聚乙酸乙烯酯)，聚(g-谷氨酸)，聚(N-丙酰基亚氨基乙烯)，聚(4-氨基-硫-苯胺)，聚[N-(对硫代苯基)氨基-3-羟甲基-1，4-亚苯基亚氨基-1，4-亚苯基]，异丙基纤维素，羟乙基、羟丙基纤维素，乙酸纤维素，硝酸纤维素，藻酸铵盐，i-角叉菜胶，N-[(3′-羟基-2′，3′-二羧基)乙基]壳聚糖，魔芋胶甘露聚糖，支链淀粉，黄原胶，聚(烯丙基氯化铵)，聚(烯丙基磷酸铵)，聚(二烯丙基二甲基氯化铵)，聚(苄基三甲基氯化铵)，聚(二甲基十二烷基(2-丙烯酰胺乙基)溴化铵)，聚(4-N-丁基吡啶鎓碘乙烯)，聚(2-N-甲基吡啶鎓亚甲基碘)，聚(N-甲基吡啶鎓-2，5-二基亚乙烯基)，聚乙二醇聚合物和共聚物，纤维素乙基醚，纤维素乙基羟乙基醚，纤维素甲基羟乙基醚，聚(甲基丙烯酸1-甘油酯)，聚(2-乙基-2-
Figure BDA0000134213490000071
唑啉)，90∶10的聚(甲基丙烯酸2-羟乙基酯/甲基丙烯酸)，聚(甲基丙烯酸2-羟丙基酯)，聚(2-甲基丙烯酰氧基乙基三甲基溴化铵)，聚(2-乙烯基-1-甲基溴化吡啶鎓)，聚(2-乙烯基吡啶-N-氧)，聚(2-乙烯基吡啶)，聚(3-氯代-2-羟丙基-2-甲基丙烯酰氧基乙基二甲基氯化铵)，聚(4-乙烯基吡啶-N-氧)，聚(4-乙烯基吡啶)，80∶20的聚(丙烯酰胺/2-甲基丙烯酰氧基乙基三甲基溴化铵)，聚(丙烯酰胺/丙烯酸)，聚(烯丙基盐酸胺)，聚(丁二烯/马来酸)，聚(二烯丙基二甲基氯化铵)，聚(丙烯酸乙酯/丙烯酸)，聚(乙二醇)二(2-氨基乙基)，聚(乙二醇)单甲基醚，聚(乙二醇)-双酚A二缩水甘油醚加合物，聚(氧化乙烯-b-氧化丙烯)，92∶8的聚(乙烯/丙烯酸)，聚(1-赖氨酸氢溴酸盐)，聚(1-赖氨酸氢溴酸盐)，聚(马来酸)，聚(丙烯酸正丁酯/2-甲基丙烯酰氧基乙基三甲基溴化铵)，聚(N-异丙基丙烯酰胺)，聚(N-乙烯基吡咯烷酮/甲基丙烯酸2-二甲基氨基乙酯)，二甲基四硫酸盐(dimethyl sulfatequaternary)，聚(N-乙烯基吡咯烷酮/乙酸乙烯酯)，聚(氧化乙烯)山梨聚糖单月桂酸酯(Tween)，聚(磺酸苯乙烯)，聚(乙烯醇)，N-甲基-4(4′-甲酰基苯乙烯基)吡啶鎓，甲硫酸乙缩醛，聚(乙烯基甲基醚)，聚(乙烯基胺)盐酸盐，聚(乙烯基膦酸)，聚(乙烯基磺酸)钠盐，聚苯胺以及它们的组合。但是再一次地，还预期该纤维化聚合物与其他聚合物电纺丝分散体一起使用。
特别优选的纤维化聚合物是具有大约50000到4000000amu聚氧化乙烯分子量的聚氧化乙烯。混合后，PTFE和纤维化聚合物分散体优选允许进行均化。在特别优选的方法中允许缓慢形成聚合物溶液而不搅拌，之后转移到以恒定速率运转几天的缸式辊压机(jar roller)中。本公开内容预期使用大于50,000cPs的分散体以提供更均一性和一致的纤维配方以及更快的达成方法。优选产生在得到的高粘度混合物中捕获极少到没有空气的均一的溶液。一旦分散体有均一的一致性，优选过滤以除去任何小块或凝胶。然后在具有用作带电源的固定传导元件的受控泵送装置中装载具有所期望粘度的过滤的分散体。
特别优选的传导元件是一个或几个孔口。孔尺寸优选但不限于直径为大约0.01到3.0mm。来自泵送装置的喷射体积量设定为预定的速率，这取决于制备的形式和所期望的纤维直径。带电源优选与精密DC供电器的正极相连。供电器的负极优选与收集表面或标的相连。该极性可以逆反，但是这不是优选的。
该表面可以是鼓状、图案或片状。该表面可以是金属、陶瓷或聚合材料，且特别优选的材料选自不锈钢、钴铬、镍钛(镍钛诺)以及镁合金。供电器上的电压增加到所期望的电压以便供给均匀地牵拉的聚合物/PTFE溶液。
应用的电压典型地为大约2000到80000伏特。通过连接供电器引入的电量抵消了离开带电源并且使它们粘附在收集表面上的已荷电的聚合物。
收集标的优选与泵和孔口体系垂直放置并且在至少一个方向上移动以便随着纤维向标的牵拉，整个表面被均匀覆盖。一旦收集表面被充分覆盖，该材料优选或者在适当的位置上通过将整个收集表面放置在烘箱中或者通过使片管或其他形式从收集表面处移动并且在烘箱中对它进行烧结而固化、烧结和干燥(其可以同时或在一系列的步骤中发生)。
本领域技术人员公知的是电纺丝织物在烧结时发生收缩。虽然不受任何理论的限制，相信这种收缩发生在两个步骤中。首先，纤维和织物由于纺丝包含了水分和先前描述的纤维化聚合物。纺丝完成时样品干燥并且经受较小程度的纤维重整。在后面的时间里，样品通过使纤维和织物暴露在大约35℃到大约485℃的温度下加热一段时间。
为了与收缩相适应，纤维和织物可以在延展的结构上纺丝。这种结构之后可以除去或缩小。电纺丝层收缩期间，织物皱缩到较小的尺寸而不会破裂。另一种方法包括在之后可以延展和/或在烧结前或烧结期间缩小的结构上对纤维和织物进行纺丝。缩小或延展和缩小的范围在大约3到100％的级别上并且取决于电沉积织物的厚度和尺寸。可替代地，电纺丝层可以放置在烧结期间也缩小的表面上。
对于织物的片，如果沉积的方向是按垂直于织物的平面给出，那么缩小或延展/缩小必须在织物平面中的至少一个或多个方向上发生。对于沉积在圆柱形表面上的织物，该织物必须径向和/或纵向缩小或缩小/延展。对于球形表面，织物必须径向缩小或缩小/延展。缩小和/或延展/缩小的这些基本的概念可以应用于任何电纺丝织物，而不取决于它在其上进行纺丝的表面的形状。因此，在电纺丝织物上为基础的非常复杂的织物形状成为可能。
电纺丝层优选是纤维状的。特别优选的电纺丝纤维具有至少0.1μ的直径。在特别优选的实施方案中，产品烧结后，具有能使以接触点之间0.1到50μ的间距范围的密度沉积的纤维。
参考以下实施例可以更好地理解本公开内容。
实施例
以下通用的指导方针用于本发明描述的不同ePTFE和电纺丝复合构造的方法实施例。
1.在电纺丝PTFE实施方案中，分散体的粘度可以通过从分散体中添加或除去水而改变但是不改变PEO与PTFE的比例。
2.径向延展的ePTFE管或双轴取向的片放置在圆的或平板的基板上以形成所期望的几何形状。
3.在ePTFE或之后与ePTFE膜匹配的表面上，将电纺丝聚合物层以所期望的厚度进行施加从而产生复合结构体，该厚度典型地为大约0.5到1000μm。
4.如果电纺丝涂层以湿态应用于ePTFE，则允许它在移动到下一工艺处理之前进行干燥。但是，如果它作为单独的电纺丝片加工并且干燥，它将与取向的多孔ePTFE层匹配。这种材料之间的匹配加工可以重复多次直至产生所期望的多层复合结构体。
5.之后用不粘性释放箔片覆盖ePTFE/电纺丝复合材料。
6.一旦将复合材料相对于基础工具定位，将压力应用于箔片的表面，由此辅助该粘合工艺。
7.将复合构造放置在温度大约35℃到大约485℃的烘箱中以便允许所有的材料粘合在一起。粘接温度基于材料的选择而选择。
8.一旦从烘箱中取出该部件并且以大约15到25度每分钟的速率冷却，它是未覆盖的并且用于规定性能的测试。
实施例1
类型I构造：ePTFE/电纺丝PTFE：
46cm×36cm的80μ厚不锈钢(SS)片材围着转鼓卷绕。将该转鼓组件放置在回转卡盘上以至其定位以允许沿着转鼓组件的整个长度电纺丝。
将基于4.2％的(PEO/PTFE)、300,000amu的聚氧化乙烯和允许均质化并且之后旋转和过滤以获得平滑一致性的Daikin D210 60％的PTFE分散体的混合物的大约80,500cPs的电纺丝分散体放置于配有21号标准针的10ml的塑料注射器中。将注射器放置在KD ScientificModel 780200L注射泵中并且设定0.5ml/小时的泵送速率。将针头定位在距离转鼓组件大约13cm处。转鼓组件的转速为大约30rpm。梁架用于沿着鼓的长度以3.0mm/sec的行进速率移动电纺丝针。梁架的折返点设定在SS片材的末端。使用10.0kV的电压。在这些条件下PTFE在鼓上电纺丝60分钟以获得大约40μ(当烧结后沉积时)厚的PTFE纤维的覆盖物。从鼓上除去包含PTFE膜的片材并且干燥过夜。
将具有10-30μ模间距(IND)、34μ厚度且起泡点＜3μ的双轴(Bi ax)延展的大约35cm×40cm的ePTFE片材放置在46cm×36cm的不锈钢片材上并且居中。
然后将保留有干燥的电纺丝PTFE膜的SS片材直接定位在保留有ePTFE膜的SS片材上，并且使两个片材在一起以使ePTFE和电纺丝PTFE膜紧密接触。然后在3″ID的不锈钢管上包卷SS箔/ePTFE/电纺丝PTFE/SS箔结构体以产生该组件。然后在未烧结的40μ厚的ePTFE膜中用紧密地围绕整个组件施加的5个包卷包卷整个装置。然后将其放置于385℃的烘箱中15.5分钟。烧结温度和时间可以根据复合材料的厚度和基础重量而变化。烧结后，从烘箱中移出该组件并且将其放置于冷却空气盒中以便冷却30-60分钟。冷却后，ePTFE膜卸卷并且从电纺丝/ePTFE复合材料的中心处取下22cm×28cm的部分。
实施例2-6：
类型I构造：ePTFE/电纺丝PTFE：
用来自实施例1的改进形式类似地进行实施例2-6并且其在表I中显示。通常，平均孔尺寸直径的主要预测是ePTFE膜IND。但是，与实施例1和4的复合材料厚度相对比显示，该孔尺寸还受到烧结期间应用在复合材料上的压力的影响，且具有更高压力的实施例获得更小的孔尺寸。电纺丝PTFE层的厚度还具有如实施例1、2和3所示的具有更大的厚度就获得更小的孔尺寸的效果。
实施例7：
类型I构造：ePTFE/电纺丝聚氨酯(PU)：
将具有10-30μ模间距(IND)、34μ厚度且起泡点＜3μ的双轴(Biax)延展的大约35cm×40cm的ePTFE片材放置在46cm×36cm的不锈钢片材上并且居中。
将基于在37.5％的丙酮和62.5％的二甲基乙酰胺的混合物中为11％的Chronoflex AR(AdvanSource Biomaterials)(PU)的混合物的大约500cPs的电纺丝溶液放置于配有21号标准针的10ml的塑料注射器中。将注射器放置在KD Scientific Model 780200L注射泵中并且设定0.35ml/小时的泵送速率。将针头定位在距离转鼓组件大约13cm处。转鼓组件的转速为大约30rpm。梁架用于沿着鼓的长度以3.0mm/sec的行进速率移动电纺丝针。梁架的折返点设定在SS片材的末端。使用9.2kV的电压。在这些条件下PTFE在鼓上电纺丝240分钟以获得大约2μ厚的PU纤维的覆盖物。从鼓上取下包含PTFE/PU复合材料膜的片材并且干燥过夜。
实施例8：
类型I构造：ePTFE/电纺丝聚氨酯(PU)：
用表II所示的来自实施例7的改进形式类似地进行实施例8。再一次地，电纺丝PU的较厚的层产生了降低的孔尺寸。
实施例9：
类型II构造：ePTFE/电纺丝PTFE/ePTFE：
将具有30μ模间距(IND)、4mm内径(ID)、0.4mm壁厚(WT)以及80.33％的孔隙度的双轴(Biax)延展的大约10cm的ePTFE管拉伸并且使其居于35cm长的10mm外径(OD)的铝棒中心。将该管组件放置在回转卡盘中以便其定位以允许沿着旋转的管组件的整体长度电纺丝。
将基于4.2％的(PEO/PTFE)、300,000amu的聚氧化乙烯和允许均质化并且之后旋转和过滤以获得平滑一致性的Daikin D210 60％的PTFE分散体的混合物的大约94,000cPs的电纺丝分散体放置于配有16号标准针的10ml的塑料注射器中。将注射器放置在Harvard Model702100注射泵中并且设定0.5ml/小时的泵送速率。将针头定位在距离旋转管组件大约13cm处。旋转管组件的旋转为大约60rpm。梁架用于沿着管的长度以2.5mm/sec的行进速率移动电纺丝针。梁架的折返点设定在Biax管的末端。使用9.3kV的电压。在这些条件下PTFE在管上电纺丝30分钟以获得大约20μ(当烧结后沉积时)厚的PTFE纤维的覆盖物。
在允许管组件干燥过夜后，将基础重量为8.426g/m2且厚度为30μ的ePTFE膜围绕管组件包卷6次。然后管组件在80μ厚的不锈钢箔中包卷，之后进一步用紧密围绕整个装置应用的未烧结的40μ厚ePTFE膜包卷5次。然后将管组件放置在烘箱中预热到385℃4.0分钟。从烘箱中取出后，冷却并且测定卸卷的复合材料管具有0.149mm的厚度。
实施例10-15：
类型II构造：ePTFE/电纺丝PTFE/ePTFE：
用表III所示的每一个实施例的细节特征类似地进行实施例10-15。
实施例16：
类型III构造：电纺丝PTFE/ePTFE/电纺丝PTFE
围绕转鼓包卷46cm×6.2cm的40μ厚的铝箔片。将转鼓组件放置在回转卡盘上以使其定位以允许沿着转鼓组件的整体长度电纺丝。
将基于5.2％的(PEO/PTFE)、300,000amu的聚氧化乙烯和允许均质化并且之后旋转和过滤以获得平滑一致性的Daikin D210 60％的PTFE分散体的混合物的电纺丝分散体放置于配有16号标准针的10ml的塑料注射器中。将注射器放置在KD Scientific Model 780200L注射泵中并且设定0.09ml/小时的泵送速率。将针头定位在距离转鼓组件大约20cm处。转鼓组件的旋转为大约30rpm。梁架用于沿着鼓的长度以3.0mm/sec的行进速率移动电纺丝针。梁架的折返点设定在铝箔的末端。使用18.0kV的电压。在这些条件下PTFE在鼓上电纺丝30分钟以获得大约80μ(当烧结后沉积时)厚的PTFE纤维的覆盖物。从鼓上取下包含PTFE膜的铝箔并且干燥。
干燥后，复合材料的原始强度允许从箔片和放置处取下PTFE膜、居中并且将围绕1.0cm外径(OD)的铝管松开的PTFE膜两次的10cm×6.5cm的部分松卷。然后围绕电纺丝PTFE卷绕膜厚度130μ、IND-12.45μ且孔隙度为51％的ePTFE膜三次以产生管/电纺丝PTFE/ePTFE组件。将该管组件放置在回转卡盘中以使它定位以允许沿着旋转的管组件的整体长度电纺丝。
将基于5.2％的(PEO/PTFE)、300,000amu的聚氧化乙烯和允许均质化并且之后旋转和过滤以获得平滑一致性的Daikin D210 60％的PTFE分散体的混合物的电纺丝分散体放置于配有16号标准针的10ml的塑料注射器中。将注射器放置在KD Scientific Model 780200L注射泵中并且设定0.05ml/小时的泵送速率。将针头定位在距离旋转的管组件大约11.5cm处。管组件的旋转为大约30rpm。梁架用于沿着管的长度以3.0mm/sec的行进速率移动电纺丝针。梁架的折返点设定在电纺丝PTFE/ePTFE组件的末端。使用16.0kV的电压。在这些条件下PTFE在该组件上电纺丝15分钟以获得大约60μ(当烧结后沉积时)厚的PTFE纤维的覆盖物。从鼓上取下该组件、干燥并且将其放置在夹具上。然后将该组件竖直放置在烘箱中预热到385℃4.0分钟。
实施例17：
类型IV构造：基底/电纺丝PTFE/ePTFE
围绕转鼓包卷43cm×38cm的40μ厚的非粘性铝箔片。将约35cm×30cm的基础重量为4.997gsm、厚度为7μ且孔隙度为72％的ePTFE片材放上、居中并且固定在铝箔上。将转鼓组件放置在回转卡盘上以使其定位以允许沿着转鼓组件的整体长度电纺丝。
将基于4.2％的(PEO/PTFE)、300,000amu的聚氧化乙烯和允许均质化并且之后旋转和过滤以获得平滑一致性的Daikin D210 60％的PTFE分散体的混合物的大约163,000cPs的电纺丝分散体放置于配有16号标准针的两个10ml的塑料注射器中。将注射器放置在KDScientific Model 780200L注射泵中并且设定0.75ml/小时的泵送速率。将针头定位在距离转鼓组件大约20.3cm处。转鼓组件的转速为大约30rpm。梁架用于沿着鼓的长度以3.0mm/sec的行进速率移动电纺丝针。梁架的折返点设定在ePTFE膜片材的末端。使用17.5kV的电压。在这些条件下PTFE在鼓上电纺丝30分钟以获得大约50μ(当烧结后沉积时)厚的PTFE纤维的覆盖物。从鼓上取下包含ePTFE/电纺丝PTFE复合材料膜的铝箔片并且干燥过夜。干燥后原始强度足以允许从箔片上取下该ePTFE/电纺丝PTFE复合材料膜。
将5cm宽的复合材料膜的片段围绕5cm长、0.5cm OD的多孔金属管包卷3次，且电纺丝层与管相接触。然后将该整体组件放置在夹具上，在铝箔中包卷并且之后用紧密地围绕整个组件应用的未烧结的40μ厚的ePTFE膜包卷。然后将该组件放置在385℃的烘箱中4分钟。冷却后，复合材料膜具有良好的外观和对金属管粘合性。
表格
表I
类型I：ePTFE/电纺丝PTFE实施例
Figure BDA0000134213490000151
表II
类型I：ePTFE/电纺丝PU实施例
Figure BDA0000134213490000152
表III
类型II：ePTFE/电纺丝PTFE/ePTFE实施例
Figure BDA0000134213490000161
为简洁和明了，说明书中设定的任何值的范围都解释为支持给定任何具有端值的子范围的权利要求的书面的描述，其为讨论的特定范围内的全部数值。通过推定的说明性实例的方法，本说明书中1-5的范围的公开内容应当认为支持了权利要求的任何以下的子范围：1-4；1-3；1-2；2-5；2-4；2-3；3-5；3-4和4-5。
这些和其他对本公开内容的改进和变形可以通过本领域技术人员实践而并不悖离本公开内容的精神和范围，这更特别的列举在后附的权利要求书中。此外，应当理解的是不同实施方案的方面可以全部或部分地互变。而且对本领域技术人员来说显而易见的是前述说明仅通过实例的方式进行，而不意味着限制于本公开内容之内。

Claims (20)

1.一种用于形成多层电纺丝复合结构体的方法，其包括：
形成聚合物纳米纤维、纤维化聚合物和溶剂的分散体，该分散体具有至少大约50,000cPs的粘度；
在第一ePTFE层上由该分散体电纺丝纳米纤维；
在该纳米纤维上施加第二ePTFE层以形成复合结构体；并且
加热该复合结构体。
2.权利要求1的方法，其中该纳米纤维包括PTFE。
3.权利要求2的方法，其中该分散体包括大约50-80重量％的PTFE。
4.权利要求2的方法，其中该分散体包括大约59-61重量％的PTFE。
5.权利要求1的方法，其中所述溶剂包括水。
6.权利要求1的方法，其中所述纤维化聚合物包括聚氧化乙烯。
7.权利要求1的方法，其中所述纤维化聚合物包括聚丙烯酰胺，聚乙烯醇，聚乙烯基吡咯烷酮，葡聚糖，藻酸盐，壳聚糖，瓜耳胶化合物，淀粉，纤维素类化合物，聚丙烯酸酯，聚羧酸酯，聚乳酸，聚甲基丙烯酸或它们的组合。
8.权利要求1的方法，其中所述分散体具有至少大约100,000cPs的粘度。
9.用于形成多层电纺丝复合结构体的方法，其包括：
在ePTFE层的第一侧面上电纺丝具有至少大约50,000cPs的粘度且包括聚合物纳米纤维、纤维化聚合物和溶剂的分散体；
在ePTFE层的第二侧面上电纺丝具有至少大约50,000cPs的粘度且包括聚合物纳米纤维、纤维化聚合物和溶剂的分散体以形成复合结构体；并且
加热该复合结构体。
10.权利要求9的方法，其中至少一部分纳米纤维包括PTFE。
11.权利要求11的方法，其中该分散体包含大约59-61重量％的PTFE。
12.权利要求9的方法，其进一步包括烧结。
13.权利要求9的方法，其中所述溶剂包括水。
14.用于形成多层电纺丝复合结构体的方法，其包括：
形成聚氨酯溶液；
在第一ePTFE层上由该溶液电纺丝纳米纤维；
在该纳米纤维上施加第二ePTFE层以形成复合结构体，并且
加热该复合结构体。
15.用于形成多层电纺丝复合结构体的方法，其包括：
形成聚合物纳米纤维、纤维化聚合物和溶剂的分散体，该分散体具有至少大约50,000cPs的粘度；
在第一ePTFE层上由该分散体电纺丝纳米纤维；
在该纳米纤维上施加基底以形成复合结构体；并且
加热该复合结构体。
16.权利要求15的方法，其中所述纳米纤维包括PTFE。
17.权利要求16的方法，其中该分散体包括大约50-80重量％的PTFE。
18.权利要求15的方法，其中所述基底包括织造织物或无纺织物。
19.权利要求15的方法，其中所述基底包括塑料或陶瓷膜。
20.权利要求15的方法，其中所述基底包括金属、陶瓷或塑料筛网。
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