CN1961030B - 含氟聚合物屏障材料 - Google Patents
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Abstract
描述了一种新型致密化含氟聚合物制品,其水蒸气渗透系数约为0.015g-mm/m2/天或更小,优选在两个正交方向上的矩阵拉伸强度至少为10,000psi。以导致消除孔的压力、温度和时间,通过压缩膨胀型多孔PTFE,然后在晶体熔点以上的温度下进行拉伸,以制备上述制品。
Description
发明领域
本发明涉及含氟聚合物屏障材料,优选包含致密聚四氟乙烯薄板或薄膜,该材料具有非常低的水蒸气渗透性以及在长度和宽度维度(即方向)上改善的拉伸性,并涉及制造所述屏障层的方法,该方法包括聚四氟乙烯的致密化、烧结和拉伸的组合。
发明背景
找出在广泛应用中使用的具有优良屏障性质以及良好机械性质的热稳定聚合物薄膜的挑战将研究导向各个方向。已构建了单片式和多组分、多层薄膜;但是,至今为止,尚未得到具有热稳定性、强度、薄度以及最重要的屏障性质(如表现为耐水蒸气渗透性)的独特组合的合适的材料。
一个解决上述问题的尝试如Tsai等的美国专利6,465,103 B1所述,该专利涉及通过共挤压或层压至少一层PCTFE(聚三氟氯乙烯)含氟聚合物、至少一层聚烯烃均聚物或共聚物,和具有至少一个不饱和羧酸或其羧酐官能部分的中间聚乙烯粘合剂层所形成的高度取向的多层薄膜。聚烯烃层使得含氟聚合物层可被拉伸至其长度的十倍来定向含氟聚合物薄膜并增加薄膜的机械性质和水蒸气性质。这种结构的市售薄膜由Honeywell Corporation以商品名销售。但是,这些材料存在限制,这些限制包括,聚烯烃和粘合剂层的存在不利地增加了最终薄膜的厚度且增加了加工过程中的成本。而且,这些薄膜具有有限的化学和温度耐受性(例如,据报道薄膜的最高热稳定温度约为215℃)以及有限的耐水蒸气渗透性。
还评价了其它材料对高要求屏障应用的适用性。例如,Dow ChemicalCompany(Midland,MI)以商品名SARAN销售的聚偏二氯乙烯(PVDC)共聚物薄膜是普遍知道的用于保护食品免受氧气、水分和化学物质影响以及其它屏障应用的屏障薄膜。但是,这种PVDC薄膜具有有限的化学和温度范围(例如,熔点约为160℃)以及有限的耐水蒸气渗透性。
在恶劣化学环境中以及广泛温度范围内使用聚四氟乙烯(PTFE)的优点是众所周知的。PTFE可用作在其它聚合物会快速降解的恶劣化学环境中使用的材料。PTFE还具有从高达260℃到低至约-273℃的有效温度范围。但是,PTFE具有机械性质差的特征,例如拉伸强度低、耐冷流性差或耐蠕变性差,耐贯穿性差和耐磨损性差,以及通常使其被排除在许多材料工程应用之外的机械完整性差的特征。
过去,通过使用削刮方法制备低孔隙率的PTFE制品,该方法包括从较厚的预成型制品劈出或削出固体PTFE薄膜。这些制品的特征是薄膜长度和宽度方向上的强度低、耐冷流性差和载荷能力差。也可使用包括对PTFE细粉进行糊剂挤压的加工过程来制备低孔隙率PTFE制品,但是它们也表现为机械特征差。还尝试通过在长度方向上拉伸来增强低孔隙率PTFE薄膜。但是,强度增益很小,而且,由于方法本身的限制,只在一个方向上强度增加,因而大大限制了薄膜的应用。
根据美国专利3,953,566所述,可制得PTFE材料,尤其是膨胀型聚四氟乙烯。这种多孔膨胀型聚四氟乙烯(ePTFE)具有由通过纤丝相互连接的结点构成的微观结构。其强度比非膨胀型PTFE高,并且保留非膨胀型PTFE的化学惰性和广泛的有效温度范围。
但是,ePTFE是多孔的,因而不能用作低表面张力流体的屏障层,因为这些表面张力小于50达因-厘米(dyne-cm)的流体可通过膜中的孔。压缩的ePTFE制品如美国专利3,953,566所述,其中,使用加热或不加热的压板使ePTFE薄板致密化。但是,压制中发生冷流,导致不均匀部分,并且不能获得超过2.1g/cc的密度。美国专利3,953,566中使用的ePTFE薄板只在一个方向上拉伸或增强,因而最终制品的应用受到严重限制。
类似地,Cooper等的美国专利4,732,629描述了一种增加PTFE绝缘导体耐贯穿性的方法。膨胀和压缩未烧结的PTFE,然后施涂于导体。但是,不能获得2.1g/cc或更大的密度,也没有报道最终制品在长度或宽度方向上的所得拉伸强度。
Katayama的美国专利5,061,561描述了从ePTFE制备高密度纤维的方法;但是,该方法产生的制品与本发明明显不同,且只可应用于细丝而不是薄板。
在Knox等的美国专利5,374,473中,描述了一种制备致密化ePTFE制品的方法,该方法包括将两层或更多层多孔ePTFE置于热和压力稳定的柔性容器内,排出容器腔室中的气体,将腔室加热加压至压力为1033.5-2411.5KPa、温度为368-400℃,然后冷却容器同时降低压力。当层压至柔性背衬时,所得致密化结构可用于诸如泵膈膜的屏障应用中。虽然Knox等的材料在所述应用中显示改善的屏障性质,所述方法和制品限于制备具有一致的优良屏障性质(例如水蒸气渗透系数为0.10g·mm/m2/天左右)的薄而柔性的PTFE膜。
Fuhr等的美国专利5,792,525描述了从一层或多层致密化的膨胀型聚四氟乙烯原料通过改变尺寸形成耐蠕变制品。致密化膨胀型PTFE材料显示纤丝残迹和结点结构,所得制品在高温和高负荷下耐蠕变。优选以前文所述Knox等的美国专利5,374,473的方法形成原料。然后,通过任何合适的方法如加热成形方法或机械加工成形方法形成具有某种形状的制品。具体描述了压塑和覆以板条作为成形方法。Fuhr等没有公开或提及形成具有优良屏障性质的PTFE薄膜的能力。
WO 02/102572 A1涉及PTFE树脂吹塑制品和树脂吹塑方法。在PTFE开始熔化的温度或高于该温度下(这种温度下PTFE中同时存在结晶和非结晶区域),通过吹塑拉制PTFE起始材料,形成无孔结构。由该篇文献,方法和产品在加工过程和产品性质上发生了显著变化,需要通过反复试验(trial and error)来确定各批材料的拉制温度和拉制率。此外,基于所述加工技术,在材料尺寸和材料强度上存在明显限制。
目前可从W.L.Gore and Associates,Inc.获得的两种产品包括显示屏障性质的致密含氟聚合物薄膜。第一种产品包括粘结在两个多孔PTFE层之间的PTFE屏障层。第二种产品包括粘结在热塑层如FEP(氟化乙丙烯)、PFA(全氟丙烯酸酯)或THV(四氟乙烯、六氟丙烯和偏二氟乙烯的聚合物)一侧上的PTFE屏障层。这些市售产品中的屏障层是在宽度和长度的正交方向上具有优良拉伸性质的高度耐受水蒸气(即低水蒸气渗透性)的PTFE薄膜。本领域技术人员应理解,材料的屏障性能与体积密度正相关。屏障层的体积密度为2.11g/cc或更大,基本上没有孔,在宽度和长度方向上的矩阵拉伸强度为68900KPa或更大,水蒸气渗透系数为0.018g·mm/m2/天。虽然这些材料已成功运用在许多需要具有优良耐化学性和耐水蒸气渗透性的柔性薄层材料的应用中,仍然需要对甚至更高要求的屏障应用具有进一步改进性能的材料。
发明概述
本发明的一个目的是提供具有增强的屏障性能的改进的含氟聚合物屏障材料,增强的屏障性能包括优异的耐水蒸气渗透性(记录为材料的水蒸气渗透系数)和强度,现有技术中尚未实现这些性能。本领域技术人员应理解,给定材料的耐水蒸气渗透性是耐受多种渗透剂透过的有力指标,但本发明绝不限于此。这种改进的屏障性能在许多需要在侵蚀性条件下耐受多种渗透剂的应用中是有价值的。本发明提供改进的含氟聚合物屏障材料,优选包含致密PTFE薄板或薄膜,其水蒸气渗透系数约为0.015g·mm/m2/天或更小,更优选约0.010g·mm/m2/天或更小,甚至更加优选低至约0.003g·mm/m2/天或更小。如上文所述,含PTFE材料的含氟聚合物的重要益处包括对其它聚合物快速降解的恶劣化学环境的耐受性,以及有效温度范围从高达260℃到低至约-273℃。
本发明的另一个目的是通过提供在正交(即长度和宽度等)方向上的改进的拉伸强度,提高这些优选包含致密PTFE薄板或薄膜的含氟聚合物屏障材料的实用性。这种改进在需要改进的挠曲寿命、耐负荷性、耐冲击性和耐破裂性、耐切口延伸性、耐贯穿性和耐磨损性的应用中具有实用性。致密PTFE薄板中可实现长度和宽度方向上改进的拉伸强度而不需要会损害最终制品化学性能的增强材料。本发明不仅给含氟聚合物屏障材料提供较低的水蒸气渗透性,而且在正交方向上提供较大的拉伸强度和较大的韧性,以及常规致密PTFE薄板或薄膜的优异化学和热特征。可将本发明薄板或薄膜制成非常薄的形式。
因此,现在本发明提供具有热稳定性、强度、薄度以及最重要地,优异屏障性质的独特组合的含氟聚合物屏障材料。本发明屏障材料所需的厚度为3毫米左右或更小,更优选0.5毫米或更小,甚至更优选低至18微米以及降低到约2微米或更小。本发明材料优选的拉伸强度是在宽度和长度方向(即两个正交方向)上至少为68900KPa,更优选在至少一个方向上至少为103350KPa,最优选在至少一个方向至少为172250KPa。在整篇申请中,术语宽度和长度分别类同于x和y方向。本发明新型含氟聚合物材料的屏障性质表现为水蒸气渗透系数约为0.015g·mm/m2/天或更小,更优选约0.010g·mm/m2/天或更小,甚至更优选低至约0.003g·mm/m2/天或更小。
本发明涉及产品和方法。方法指按照需要,制备具有低水蒸气渗透性并且在长度和宽度方向上具有高拉伸强度的高密度PTFE、高密度填充的PTFE、高密度PTFE和其它材料的复合体的薄板或薄膜的方法。
这些方法包括在足以基本上消除孔的线速度和压力下,且温度在平常室温(约20℃)以上,通过在合适的间歇压制机如平板压机上,或可选地,以连续方式,在轧棍或其它合适的压制设备间压制多孔ePTFE薄板。随后在PTFE晶体熔点以上的温度下拉伸所得致密材料。
在一个优选的方面,产品是包含具有改进的渗透性质和改进的拉伸性质的高密度PTFE的薄板。具体地说,产品的水蒸气渗透系数约为0.015g·mm/m2/天或更小,更优选约0.010g·mm/m2/天或更小,甚至更优选低至约0.003g·mm/m2/天或更小,至少一个方向上的矩阵拉伸强度至少为103350KPa。
本发明的另一方面,产品可包括含有至少一种填料且具有改进的屏障性质和其它所述性质的高密度PTFE的薄板。
在另一个优选的实施方式中,产品是包含层压至另一种基材的低渗透性PTFE薄膜的薄板。可通过粘合或共连接其它薄膜,例如通过热、化学或机械方式结合材料,以获得层压体。具体地说,这些其它基材包括一种或多种含氟聚合物薄板或薄膜如FEP、PFA、PTFE、THV和其它合适的含氟聚合物。类似地,其它聚合物基底材料包括但不限于:聚氨酯、聚乙烯、聚酰胺、乙烯乙烯醇(EVOH)、聚偏二氯乙烯(PVDC)等。并且,基材可以是金属、玻璃、无机薄板、压敏粘合剂等。可制备各种层叠结构,以进一步促进或提高与附加层(例如,织物等)的结合。该产品屏障组分的水蒸气渗透系数约为0.015g·mm/m2/天或更小,更优选约0.010g·mm/m2/天或更小,甚至更优选低至约0.003g·mm/m2/天或更小。甚至更优选的结构包括具有这些优越的屏障性质且在x和y方向上的拉伸强度都为68900KPa或更大的材料。
所述方法是制备具有改进的水蒸气渗透性且在x和y方向上具有改进的拉伸强度的高密度PTFE、填充的PTFE、或PTFE层压体的薄板的方法。一种这样的方法包括:
(a)根据Knox等在美国专利5,374,473中所述方法,对烧结或未烧结形式的至少一片膨胀型多孔PTFE或一捆层状薄板进行致密化,
(b)将致密的PTFE预先加热至超过PTFE晶体熔点的温度,以及
(c)以任何顺序相继或同时地,在宽度方向、长度方向、或同时在宽度和长度方向上,拉伸经加热的PTFE膜,速率至少为1%/秒,更优选至少3%/秒,更优选5%/秒或更大,拉伸比大于4∶1。应理解,前体的机械性质以及在晶体熔点以上的温度下进行拉伸的拉伸速率和/或拉伸比的相互作用会影响所得材料的屏障性能,如发明详述和实施例中详细所述。
附图简要说明
图1是致密化实施例1的膜的温度和压力条件的图。
图2是实施例1制备的样品的差示扫描量热法(DSC)扫描图谱。
图3是显示本发明材料和多种市售材料的水蒸气渗透系数的图。
发明详述
通过一种方法实现了本发明的目的,该方法包括:第一步,膨胀一片或多片聚四氟乙烯(PTFE)薄板并在与x-y平面垂直(normal)的方向上压缩所述一片或多片薄板,使PTFE体积密度达到2.11g/cc或更大,例如Knox等的美国专利5,374,473(“Knox’473”)所述。压缩后,在下一加工步骤中,将压缩的一片或多片薄板加热至PTFE晶体熔点以上的温度,然后拉伸。所得薄板在拉伸方向上具有比其压缩前体更大的拉伸强度,具有改进的屏障性质,表现为增加的耐水蒸气渗透性,以及起先进行拉伸操作所导致的厚度降低、宽度增加和/或长度增加。本发明的该方面具有新颖性,因为迄今为止没有人制备了具有这种独特性质组合的PTFE材料。
根据美国专利3,953,566所述,制备膨胀型PTFE薄板或薄膜。在本发明的一个实施方式中,得到聚四氟乙烯细粉(PTFE 601A,DuPont,Wilmington,DE)等分试样,然后与润滑剂(Isopar K脂族烃,Exxon,Houston,TX)组合。混合后,将润滑的粉末压制成圆柱形小丸,加热处理18个小时。然后,以压缩比70∶1,将小丸挤压通过矩形模。糊剂挤压的方向称为y,或加工方向(machinedirection)。然后干燥所得条带。然后,在线速度大于10%/秒,鼓温约225℃,拉伸量等于约400%的鼓式干燥机之间,使干燥的PTFE条带在y-方向上膨胀。然后,在线速度大于10%/秒,温度约295℃,拉伸量等于约700%的条件下,在x-方向上膨胀条带。应理解,采用缩放机或连续地在拉伸机或类似机器上,可相继或同时地在任一个方向或同时在两个方向上进行这种膨胀。合适的膨胀比可显著变化,例如从1∶1到100∶1或更高,且在各种膨胀速率下进行。代表性地,但绝不是限制性的,下面的实施例中包括膨胀速率和膨胀比。然后根据Knox’473所述内容压制薄膜。
然后,在超过PTFE晶体熔点的温度下拉伸致密化薄膜。在拉伸速率包括但不限于5%/秒的条件下,拉伸比高达12∶1。应理解,采用缩放机或连续地在拉伸机或类似机器上,可相继或同时地在任一个方向或同时在两个方向上进行这种拉伸。更详细的内容如各个实施例所述。
认为可以在x和y方向上实现高达12∶1或更高的拉伸比,本领域技术人员明白,与拉伸量有关的限制是原始压缩前体的函数。更具体地说,认为拉伸比受压缩前体的原始机械性质和厚度的限制。压缩前体的厚度直接影响获得高拉伸量的能力,因为当在高于ePTFE晶体熔点的温度下拉伸压缩前体时,压缩前体的体积密度增加。拉伸导致单位重量和厚度降低。还观察到所述一片或多片薄板的矩阵拉伸强度显著增加。如下面实施例所示,随着一片或多片PTFE薄板体积密度的增加,矩阵拉伸强度大于551200KPa,表现为水蒸气渗透性的降低。还认为,通过较大量的拉伸可实现较大的矩阵拉伸强度。
本发明具有新颖性,因为首次制备了具有格外低的水蒸气渗透系数且在x和y方向上都具有高拉伸强度的极薄、高PTFE体积密度的薄膜。例如,优选厚度小于250微米,更优选小于150微米,甚至小于50微米,最优选小于10微米。通过拉伸致密PTFE材料从而制备具有较低水蒸气渗透性,强度增加而体积密度不会降低的最终制品并不是显而易见的。
上文详述的新型加工技术使得能够制造新的、独特且新颖的PTFE薄板。如下面实施例进一步所述,新材料是水蒸气渗透系数约为0.015g·mm/m2/天或更小,较优选约0.010g·mm/m2/天或更小,甚至更优选低至约0.003g·mm/m2/天或更小的PTFE。此外,优选这些材料在x和y方向上的矩阵拉伸强度都至少为68900KPa,更优选在至少一个方向上至少为103350KPa,最优选在至少一个方向上至少为172250KPa。制备的这种材料可以具有各种长度和宽度,其厚度低至3.5×10-5英寸(0.9微米)或更低。此外,新型PTFE薄板可填充有一种或多种填料,或包含在一片或多片复合材料薄板中。
从加工的角度来看,该技术是独特的,提供了克服现有局限以制造低渗透性薄膜的方法。总之,加工技术的价值在于能够显著降低一片或多片薄板的水蒸气渗透性,显著增加其矩阵拉伸强度并降低厚度。
下面的实施例不是为了限制本发明方法或由该方法所得材料的范围。
试验方法及过程度量
水蒸气渗透性试验与水蒸气渗透系数测定
根据MOCON,Inc.(Minneapolis,MN)的ASTM F-1249,测定材料的水蒸气渗透性。
具体地说,用于测定材料的水蒸气渗透性的设备是MOCON Permatran W3/31(MOCON/Modern Controls,Inc.,Minneapolis,MN)。所用渗透剂是100%RH水蒸气(49.157mmHg),载气是100%氮气,干燥,环境压力下,并且进行试验的温度为37.8C。
将试验样品切割成约10×10cm,固定在设备扩散池中,根据MOCONPermatran W 3/31的说明书进行老化。设备记录水蒸气传输速率或水蒸气渗透性,表示为g/m2/天。
通过将水蒸气传输速率乘以试验样品的厚度,计算各样品的水蒸气渗透系数。结果记录为g·mm/m2/天。
矩阵拉伸强度试验
根据ASTM D 882-90测定所有样本。20英寸/分钟(508毫米/分钟)十字头速率,2英寸(51毫米)标距长度,并采用长度至少5英寸(127毫米)的矩形样本。
定量矩阵拉伸是表示试验期间形成的最大负荷的一种方式,是样本中材料横截面积的函数。这就提供了通过相对于样品中PTFE的横截面积对最大负荷时的应力进行归一化,在各种密度或孔隙率的PTFE基样品中精确比较拉伸强度的方法。
具体地说:
矩阵拉伸(psi)=最大负荷(磅)x-横截面积PTFE(平方英寸)
其中,最大负荷=试验期间产生的最大负荷样本
x-横截面积PTFE(平方英寸)=gperft/(12×P×2.543)=gperft×2.3×10-3,其中gperft=每一英尺的样本单位克重量
P=PTFE的平均固有密度=2.18g/cc
因此,矩阵拉伸(psi)=最大负荷(磅)/(gperft×2.3×10-3)
类似地,矩阵拉伸(Mpa)=矩阵拉伸(psi)×6.89*10-3
差示扫描量热法(DSC)
采用TA Instruments Q1000 DSC和用于DSC的TA Instruments标准铝托盘和盖子进行试验。使用TA Instruments样品包封压机将盖子包卷在托盘上。在Sartorius MC 210P微量天平上进行重量测定。
在天平上称重一个托盘和盖子,精确至0.01mg。采用6.0mm模冲,将足够的试验样品材料圆片加到托盘上以达到6mg,同样精确至0.01mg。将这些值输入Q1000的Thermal Advantage控制软件。将盖子盖在托盘上,用压机卷边。注意确保盖子与托盘之间的卷边中不卡有样品材料。制备无样品的类似参比托盘,也将其重量输入软件。将含样品的托盘装载在Q1000的样品感应器上,将空托盘装载到参比感应器上。然后,样品经受以下热循环步骤:
1)在-50.00℃下平衡
2)以20.00℃/分钟的速度上升至360.00℃
3)等温5.00分钟
4)标记循环终点
5)以20.00℃/分钟的速度下降至-50.00℃
6)标记循环终点
7)以20.00℃/分钟的速度上升至420.00℃
8)标记循环终点
9)方法结束
使用TA Instruments的Universal Analysis 2000 3.9A版本软件分析没有经过改变的数据。分析步骤7的扫描数据。
实施例
实施例1:
合并240磅的PTFE细粉等分试样(PTFE 601A,DuPont,Wilmington,DE)与44.16磅的润滑剂(Isopar K,Exxon,Houston,TX),然后混合,压制成圆柱形小丸,在温度49℃下热老化18小时。然后,将圆柱体小丸以70∶1的压缩比挤压通过矩形模。然后干燥所得条带以除去润滑剂。
然后,在线速度大于10%/秒,鼓温约225℃,拉伸量等于400%的鼓式干燥机之间,使干燥的PTFE条带在y-方向上膨胀。然后,以线速度大于10%/秒,温度约295℃,拉伸量等于700%的条件,使条带在x-方向上膨胀。所得产品是未烧结的ePTFE膜。
为了确定烧结对膜的水蒸气渗透性的作用,限制一部分这种未烧结的ePTFE膜的尺寸然后烧结,即有两个膜,一个烧结一个未烧结,用于进一步加工。“烧结”指将材料加热至PTFE晶体熔点以上的温度。使膜通过烘箱,暴露于375℃的温度下220秒,完成一个膜的烧结。烧结操作期间不进行附加膨胀。
根据Knox的US 5,374,473,致密化得到的两个膜前体,一个烧结一个未烧结。具体地说,将四层(plies)标示厚度0.013英寸(330微米)的未烧结膜和五层标示厚度0.008英寸(203微米)的烧结膜置于聚酰亚胺薄膜(DuPont的)构成的高压灭菌袋中的两个均衡压力用覆盖板之间。将组件置于高压灭菌器(Vacuum Press International系列24)中,在袋中抽真空,根据图1所示温度和压力条件,逐渐升高高压灭菌器的压力和温度。所得压缩ePTFE薄板(一块烧结一块未烧结)的厚度约为.010英寸。对该中间体PTFE的各烧结和未烧结形式的样品进行水蒸气渗透性测试,发现分别为0.1和0.127g·mm/m2/天。
然后,将所得压缩制品置于缩放机中,通过暴露于约370℃的空气温度持续20分钟,将材料加热至PTFE晶体熔点以上的温度。加热的同时,将样品在x-方向或同时在x和y方向上拉伸,每个方向的拉伸量高达1100%,拉伸速率5%/秒。加工条件总结在表1中。如表1所示,对各个烧结和未烧结膜进行两次熔化拉伸老化。分析烧结条件与熔化拉伸加工各种组合产生的四组试验样本。注意采用两次加工来实现实施方式,其中,第一次熔化拉伸操作的结果用作第二拉伸的前体。
然后采用上文所述方法,对样品进行水蒸气渗透性试验。表2总结了各个样品的水蒸气渗透系数、矩阵拉伸强度、厚度和百分结晶度。
采用差示扫描量热法,对根据表2中的加工条件“D”加工的样品进行热评价,该样品的扫描结果如图2所示。
表1:实施例1的样品的加工条件
样品编号 | 横切方向熔化拉伸(TDMS)比 | 加工方向熔化拉伸(MDMS)比 | PTFE前体 | 第一次TDMS比 | 第一次MDMS比 | 第二次TDMS比 | 第二次MDMS比 |
A-1 | 9 | 3 | 不烧结 | 3 | 3 | 3 | 1 |
样品编号 | 横切方向熔化拉伸(TDMS)比 | 加工方向熔化拉伸(MDMS)比 | PTFE前体 | 第一次TDMS比 | 第一次MDMS比 | 第二次TDMS比 | 第二次MDMS比 |
A-2 | 9 | 3 | 不烧结 | 3 | 3 | 3 | 1 |
A-3 | 9 | 3 | 不烧结 | 3 | 3 | 3 | 1 |
A-4 | 9 | 3 | 不烧结 | 3 | 3 | 3 | 1 |
B-1 | 12 | 3 | 不烧结 | 3 | 3 | 4 | 1 |
B-2 | 12 | 3 | 不烧结 | 3 | 3 | 4 | 1 |
B-3 | 12 | 3 | 不烧结 | 3 | 3 | 4 | 1 |
B-4 | 12 | 3 | 不烧结 | 3 | 3 | 4 | 1 |
C-1 | 9 | 3 | 烧结 | 3 | 3 | 3 | 1 |
C-2 | 9 | 3 | 烧结 | 3 | 3 | 3 | 1 |
C-3 | 9 | 3 | 烧结 | 3 | 3 | 3 | 1 |
C-4 | 9 | 3 | 烧结 | 3 | 3 | 3 | 1 |
D-1 | 12 | 3 | 烧结 | 3 | 3 | 4 | 1 |
D-2 | 12 | 3 | 烧结 | 3 | 3 | 4 | 1 |
D-3 | 12 | 3 | 烧结 | 3 | 3 | 4 | 1 |
D-4 | 12 | 3 | 烧结 | 3 | 3 | 4 | 1 |
表2:实施例1的样品的性质
样品编号 | 水渗透系数(g*mm/m^2/天) | 拉伸强度-长度方向 | 拉伸强度-宽度方向 | 厚度 |
A-1 | .0042 | 30420psi | 71360psi | 9.0微米 |
样品编号 | 水渗透系数(g*mm/m^2/天) | 拉伸强度-长度方向 | 拉伸强度-宽度方向 | 厚度 |
A-2 | .0056 | 32500 | 67600 | 9.0 |
A-3 | .0042 | 31800 | 64920 | 9.0 |
A-4 | .0040 | 30190 | 68940 | 9.0 |
B-1 | .0037 | 26890 | 88880 | 8.5 |
B-2 | .0024 | 24760 | 91910 | 8.5 |
B-3 | .0021 | 24870 | 91660 | 8.5 |
B-4 | .0024 | 28780 | 86910 | 8.5 |
C-1 | .0054 | 29000 | 63670 | 14.0 |
C-2 | .0091 | 30440 | 63800 | 14.0 |
C-3 | .0103 | 29340 | 65340 | 14.0 |
C-4 | .0054 | 28970 | 62540 | 14.0 |
D-1 | .0043 | 24640 | 78060 | 13.0 |
D-2 | .0043 | 25790 | 76910 | 13.0 |
D-3 | .0039 | 23610 | 80460 | 13.0 |
D-4 | .0036 | 26500 | 75310 | 13.0 |
其中,1psi=6.89Kpa
实施例2
以下述方式制备致密PTFE和全氟丙烯酸酯(PFA)层压体。具体地说,使用两次拉伸操作,根据实施例1中描述的“A”样品的加工条件制备PTFE材料。在第二次拉伸之后,从缩放机上除去加热器。拉伸的PTFE屏障薄膜保留在缩放销体上,将PFA薄膜(Part No.100LP,厚度0.001英寸(25微米),得自DuPont,Wilmington,DE)置于PTFE屏障薄膜的一侧上。然后,将两层薄膜加热至370℃持续5分钟,形成PTFE屏障薄膜与PFA的层压体。
实施例3
制备未烧结的膨胀PTFE材料并根据如实施例1所述Knox等的US5,374,473进行致密化,区别是只有一层未烧结材料经历致密化步骤。然后,根据实施例1中描述的加工条件“A”拉伸所得致密材料。所得PTFE屏障薄膜的厚度为0.1密耳(2.5微米),水蒸气渗透系数为0.007g·mm/m2/天。
实施例4
制备未烧结的膨胀PTFE材料并根据如实施例1所述Knox等的US5,374,473进行致密化,区别是只有两层未烧结材料经历致密化步骤。然后,根据实施例1中描述的加工条件“B”拉伸所得致密材料。所得PTFE屏障薄膜的厚度为0.1密耳(2.5微米),水蒸气渗透系数为0.003g·mm/m2/天。
对比例:
为了粗略评估本发明材料与市售含氟聚合物材料的相对水蒸气渗透系数,评价了一系列市售含氟聚合物薄膜。将以下各个薄膜的四个样品送往MOCON,Inc.测定水蒸气渗透系数,结果如图3所示:
材料 来源
2000薄膜 Honeywell Corporation
薄膜(2密耳) DeWAL Industries
FEP(2密耳) DuPont
PFA(2密耳) DuPont
图3对照实施例1的样品D-4进行了比较。
Claims (27)
1.一种包含膨胀型聚四氟乙烯薄膜的制品,其中,所述薄膜的水蒸气渗透系数0.015g·mm/m2/天或更小,在两个正交方向上的矩阵拉伸强度至少为68900KPa。
2.如权利要求1所述的制品,其特征在于,所述薄膜在至少一个方向上的矩阵拉伸强度至少是103350KPa。
3.如权利要求1所述的制品,其特征在于,所述薄膜在至少一个方向上的矩阵拉伸强度至少是172250KPa。
4.如权利要求1所述的制品,其特征在于,所述薄膜的水蒸气渗透系数为0.010g·mm/m2/天或更小。
5.如权利要求1所述的制品,其特征在于,所述薄膜的水蒸气渗透系数为0.003g·mm/m2/天或更小。
6.如权利要求1所述的制品,其特征在于,所述薄膜还包含填料。
7.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为250微米或更小。
8.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为150微米或更小。
9.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为50微米或更小。
10.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为10微米或更小。
11.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为5微米或更小。
12.如权利要求1所述的制品,其特征在于,所述膨胀型聚四氟乙烯薄膜的厚度为1微米或更小。
13.一种层压体,其包括:
(a)膨胀型聚四氟乙烯薄膜,其水蒸气渗透系数为0.015g·mm/m2/天或更小,在两个正交方向上的矩阵拉伸强度至少是68900KPa;和
至少一种基材。
14.如权利要求13所述的制品,其特征在于,所述薄膜的水蒸气渗透系数为0.010g·mm/m2/天或更小。
15.如权利要求13所述的层压体,其特征在于,所述基材包括含氟聚合物。
16.如权利要求13所述的层压体,其特征在于,所述基材包括PFA。
17.如权利要求13所述的层压体,其特征在于,所述基材包括FEP。
18.如权利要求13所述的层压体,其特征在于,所述基材包括四氟乙烯、六氟丙烯和偏二氟乙烯的聚合物。
19.如权利要求13所述的层压体,其特征在于,所述基材包括聚四氟乙烯。
20.如权利要求13所述的层压体,其特征在于,所述层压体包括在两个基材间取向的膨胀型聚四氟乙烯薄膜。
21.如权利要求13所述的层压体,其特征在于,所述基材包括聚三氟氯乙烯。
22.如权利要求13所述的层压体,其特征在于,所述基材包括至少一种选自下组的材料:聚氨酯、聚乙烯、聚酰胺、乙烯乙烯醇共聚物和聚偏二氯乙烯。
23.如权利要求13所述的层压体,其特征在于,所述基材包括至少一种压敏粘合剂。
24.如权利要求13所述的层压体,其特征在于,所述基材包括至少一种织物。
25.如权利要求13所述的层压体,其特征在于,所述基材包括金属。
26.如权利要求13所述的层压体,其特征在于,所述基材包括玻璃。
27.如权利要求13所述的层压体,其特征在于,所述基材包括无机板材。
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- 2005-04-21 CA CA 2563646 patent/CA2563646A1/en not_active Abandoned
- 2005-04-21 EP EP20050736267 patent/EP1737901B1/en active Active
- 2005-04-21 AT AT05736267T patent/ATE548410T1/de active
- 2005-04-21 CN CN2005800177142A patent/CN1961030B/zh active Active
- 2005-04-21 WO PCT/US2005/014114 patent/WO2005105434A2/en active Application Filing
-
2007
- 2007-11-06 US US11/935,769 patent/US7521010B2/en not_active Expired - Lifetime
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2011
- 2011-05-16 JP JP2011109679A patent/JP5204267B2/ja active Active
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Also Published As
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CN1961030A (zh) | 2007-05-09 |
CA2563646A1 (en) | 2005-11-10 |
US20080061472A1 (en) | 2008-03-13 |
JP2007534523A (ja) | 2007-11-29 |
JP2011183814A (ja) | 2011-09-22 |
EP1737901A2 (en) | 2007-01-03 |
US20050238872A1 (en) | 2005-10-27 |
JP4782774B2 (ja) | 2011-09-28 |
WO2005105434A2 (en) | 2005-11-10 |
EP1737901B1 (en) | 2012-03-07 |
US7521010B2 (en) | 2009-04-21 |
WO2005105434A3 (en) | 2006-01-12 |
JP5204267B2 (ja) | 2013-06-05 |
ATE548410T1 (de) | 2012-03-15 |
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