CN106103075A - 具有含颗粒多孔层的双轴取向的薄膜 - Google Patents
具有含颗粒多孔层的双轴取向的薄膜 Download PDFInfo
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- CN106103075A CN106103075A CN201580012406.4A CN201580012406A CN106103075A CN 106103075 A CN106103075 A CN 106103075A CN 201580012406 A CN201580012406 A CN 201580012406A CN 106103075 A CN106103075 A CN 106103075A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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Abstract
本发明涉及双轴取向的单层或多层多孔薄膜,所述多孔薄膜包括至少一个多孔层并且所述层包含至少一种丙烯聚合物、至少一种β‑成核剂和颗粒,其中所述颗粒具有高于200℃的熔点并且在10mm2的薄膜样品的SEM照片上能够检测出粒子尺寸>1μm的至多一个附聚物或至多一个颗粒。
Description
技术领域
本发明涉及具有至少一个含颗粒多孔层的双轴取向的薄膜及其作为隔板的用途,以及所述薄膜的制备方法。
背景技术
现代设备需要能够实现在空间上独立使用的能源,例如电池或蓄电池。电池的缺点在于必须将其处置。因此越来越多地使用蓄电池(二次电池),该蓄电池可以借助于充电设备在供电系统上一再地充电。在合理使用的情况下,常规的镍-镉-蓄电池(NiCd-蓄电池)可以例如达到约1000次充电循环的寿命。在高能系统或高性能系统中,目前越来越多地使用锂电池、锂离子电池、锂-聚合物电池和碱土金属电池作为蓄电池。
电池和蓄电池总是由两个浸入电解质溶液的电极和分离阳极和阴极的隔板组成。不同的蓄电池类型的区别在于所使用的电极材料、电解质和所使用的隔板。电池隔板的目的是在空间上分离电池中的阴极和阳极,或蓄电池中的负极和正极。隔板必须是将两个电极彼此电隔离的屏障,从而避免内部短路。然而同时隔板必须是离子可透过的,从而可以在电池中进行电化学反应。
电池隔板必须薄,从而内部电阻尽可能小并且可以实现电池中的高填充密度和由此实现高能量密度。只有如此才能实现良好的性能数据和高的电容。
此外还需要的是,隔板吸收电解质并且在填充的电池中保证气体交换。虽然之前尤其使用织物,但是目前主要使用细孔材料,例如无纺布和膜。
在锂电池中短路的发生是一个问题。在热负载下,其可能在锂离子电池中造成电池隔板的熔融并且因此造成具有破坏性后果的短路。当锂电池机械损坏或通过充电设备的有缺陷的电子学过度充电时,存在相似的风险。
为了提高锂离子电池的安全性,过去开发了切断隔板(关闭膜)。这种特别的隔板在一定温度下在最短的时间内闭合其孔,所述一定温度明显低于锂的熔点或燃点。因此在锂电池中大大避免了短路的灾难性后果。
然而同时还希望隔板也具有高的机械强度,其通过具有高熔点的材料来保证。例如,聚丙烯膜由于良好的抗刺穿性而是有利的,但是聚丙烯的约164℃的熔点非常接近锂的闪点(170℃)。
基于锂技术的高能电池用于其中重要的是在最小的空间上有尽可能大量的电能可供利用的应用中。这例如在用于电动车辆的牵引电池中以及在小重量下需要最大能量密度的其它移动应用(例如航空飞行和宇宙飞行)中是必要的。目前在高能电池中实现了350至400Wh/L或150至200Wh/kg的能量密度。通过使用特殊的电极材料(例如Li-CoO2)和更节约使用壳体材料实现所述高的能量密度。例如,在袋装电池类型的Li电池中,单个电池单元仍然仅通过薄膜彼此分离。由于这样的事实,在这些电池中对隔板提出甚至更高的要求,因为在内部短路和过热时爆炸性燃烧反应会蔓延至相邻的电池。
用于这些应用的隔板必须尽可能薄,从而保证低的单位空间需求并且保持小的内部电阻以及具有大的孔隙率。在过热或机械损坏的情况下,正极和负极在任何情况下必须保持分离从而防止进一步的化学反应,该反应造成电池燃烧或爆炸。
现有技术中已知使聚丙烯膜与其它层组合,所述其它层由具有较低熔点的材料(例如聚乙烯)构成。在由于短路或其它外部影响造成过热的情况下,聚乙烯层熔融并且闭合多孔聚丙烯层的孔,因此中断了电池中的离子流并且因此中断了电流。然而在进一步升温(>160℃)时聚丙烯层也熔融并且由于阳极和阴极的接触造成内部短路,并且不再可以防止由此造成的问题例如自燃和爆炸。此外,聚乙烯层在聚丙烯层上的粘附是成问题的,使得这些层仅可以通过层压而组合或者只有这两个种类的选定的聚合物可以共挤出。这些隔板在高能应用中仅提供不足的安全性。这种薄膜描述于WO 2010048395。
US 2011171523描述了通过溶剂法获得的耐热性隔板。在此,在第一步骤中将无机颗粒(白垩、硅酸盐或氧化铝)连同油一起配混到原料(UHMW-PE)中。然后通过模头挤出所述混合物形成预制薄膜。然后通过溶剂从预制薄膜中溶解出油,从而产生孔。然后拉伸薄膜形成隔板。在该隔板中,即使在强烈过热时无机颗粒仍然保证电池中阳极和阴极的分离。
所述方法的缺点在于,颗粒造成隔板的机械性能减弱并且由于颗粒的附聚物可能产生缺陷和不一致的孔结构。
US 2007020525描述了陶瓷隔板,所述陶瓷隔板通过用基于聚合物的粘结剂加工无机颗粒而获得。所述隔板也保证了在剧烈过热的情况下使电池中的阳极和阴极保持分离。但是制备方法复杂并且隔板的机械性能不足。
WO 2013083280中描述了双轴取向的单层或多层的多孔薄膜,所述多孔薄膜具有无机(优选陶瓷)涂层。陶瓷涂层仅以低程度降低薄膜的初始孔隙率。经涂布的多孔薄膜具有<1500s的Gurley值。根据所述教导表明,具有一定表面结构的聚丙烯隔板即使不使用底漆也与水基无机(优选陶瓷)涂层具有足够的粘附。
现有技术中还已知其它与热稳定性的层组合的膜,所述层即使在隔板熔融之后仍然保证电极彼此隔离。在此这些层在基材上的粘附经常是有问题的,使得这些层仅可以通过层压或涂布与真正的膜组合。在本发明的范围内发现,陶瓷涂层的效力也取决于涂层的品质。为了有效隔离电极,在膜熔融之后必须保持由耐温材料组成的连续隔离层,所述隔离层本身不可以具有缺陷、空隙或厚度波动。这对待涂布膜的厚度均匀性和表面特性提出了特殊要求。
具有温度稳定的保护层的隔板材料还必须尽可能薄,从而保证低的空间需求,从而保持小的内部电阻并且具有大的孔隙率。这些性能受涂层的不利影响,因为涂层造成膜的厚度增加和降低的孔隙率并且损害薄膜的表面结构。
在制备隔板薄膜时原则上还总是要求较高的工艺速度。由于脆弱的网络结构,在制备多孔薄膜时较高的工艺速度是特别不希望的,因为其伴随着频繁撕裂和品质缺陷,因此所述工艺整体来说不是更经济的。
聚烯烃隔板目前可以根据各种不同的方法制得:填料法、冷拉伸、提取法和β-结晶法。这些方法的不同之处根本上在于产生孔的各种不同的机理。
例如可以通过加入很高量的填料制备多孔薄膜。在拉伸时由于填料与聚合物基体的不相容性产生孔。然而,为了实现高孔隙率所需的至多40重量%的大的填料量显著损害机械强度(尽管高的拉伸),使得所述产物不可以作为隔板用在高能电池中。
在所谓的提取法中原则上通过合适的溶剂从聚合物基体中溶解出一种组分从而产生孔。在此已经开发出各种变体形式,所述变体形式通过添加剂的类型和合适的溶剂进行区分。有机和无机添加剂均可被提取。在薄膜的制备中所述提取可以作为最后的方法步骤进行或者与随后的拉伸组合。在该情况下不利的是在生态学和经济学方面受到质疑的提取步骤。
一种较老的但是成功的方法基于在很低的温度下拉伸聚合物基体(冷拉伸)。为此首先挤出薄膜,然后退火数小时从而升高结晶比例。在下一个方法步骤中在很低的温度下在纵向方向上进行冷拉伸,从而以最小的微裂纹的形式形成大量缺陷。具有缺陷的预拉伸的薄膜然后在升高的温度下以更高的倍数在相同方向上再次拉伸,其中缺陷变大形成孔,所述孔形成网络状结构。这种薄膜集合了高孔隙率和在其拉伸方向(通常为纵向方向)上的良好机械强度。然而在此在横向方向上的机械强度仍不足,因此抗刺穿性差并且在纵向方向上产生高的撕开倾向。整体来说所述方法成本高。
用于制备多孔薄膜的另一种已知方法基于在聚丙烯中混合β-成核剂。由于β-成核剂,聚丙烯在熔体冷却时以高浓度形成所谓的β-微晶。在随后的纵向拉伸中β-相转化成聚丙烯的α-变体。由于不同的晶体形式的密度不同,在此也首先形成很多微观缺陷,所述微观缺陷通过拉伸裂开形成孔。根据所述方法制得的薄膜具有良好的孔隙率和在纵向方向和横向方向上的良好的机械强度和很好的经济性。所述薄膜在下文中也被称为β-多孔薄膜。为了改进孔隙率可以在横向拉伸之前在纵向方向上引入较高的取向。
发明内容
因此,本发明的目的是提供薄膜,所述薄膜作为隔板即使在电池的很高温度或机械损害下仍然保证电极的隔离。当电池内部的温度超过隔板的聚合物的熔点时,也必须仍然保持所述隔离功能。尽管如此,所述薄膜应当可以有效和低成本地制得。
β-多孔薄膜原则上有待改进。希望提供用于制备多孔薄膜的方法,所述方法可以以更快的工艺速度运行。在此应当提供良好的运转安全性。这意味着,在制备薄膜时即使在升高的工艺速度下也应当仅出现少量撕裂或完全不出现撕裂。一个持续不断的关心的方面是改进孔隙率,其中应特别通过薄膜表面上少量的闭合区域实现低的Gurley值。此外,目的是提供具有小厚度的多孔薄膜,其中即使在小的薄膜厚度下应仍然能够以高的工艺速度进行制备,并且应满足薄膜的低Gurley值。
因此,本发明的另一个目的是提供具有改进的Gurley值(即良好的渗透性)的多孔薄膜。
本发明的另一个目的是在制备具有低Gurley值的多孔薄膜时能够实现高的工艺速度。
通过双轴取向的单层或多层多孔薄膜实现了所述和其它目的,所述多孔薄膜包括至少一个多孔层,其中所述层包含至少一种丙烯聚合物、β-成核剂和颗粒,其中颗粒具有高于200℃的熔点并且在10mm2的薄膜样品的SEM照片上能够检测出粒子尺寸>1μm的至多1个附聚物或的颗粒。
出人意料地,基于根据本发明的薄膜的膜通过加入高熔点颗粒而提供在用作高反应性电池和蓄电池中的隔板时相对于内部短路的充分保护。薄膜中的颗粒甚至在高于160℃(丙烯聚合物的熔点)的很高温度下也形成有效隔离,所述有效隔离保持电极彼此分离。
此外出人意料地发现,在多孔层中加入高熔点颗粒降低多孔薄膜的Gurley值。同样出人意料的是,通过加入颗粒能够实现工艺速度的升高。此外出人意料地发现,即使在升高的工艺速度下,加入所述颗粒仍然有效减少撕裂数目。
此外出人意料地发现,即使预制薄膜中较低含量的β-结晶聚丙烯也足以制备具有很低Gurley值的薄膜。本发明因此能够实现减少多孔薄膜中的β-成核剂的含量或者甚至完全免去β-成核剂。
在本发明的意义上,颗粒为具有高于200℃的熔点的粒子。
根据本发明的β-多孔薄膜可以以单层或多层形式构成并且包括至少一个多孔层,所述层由丙烯聚合物(优选丙烯均聚物和/或丙烯嵌段共聚物)构成并且通常包含至少一种β-成核剂,以及根据本发明的高熔点颗粒。任选地还可以包含少量的其它聚烯烃,只要其不会不利地影响孔隙率和其它主要性能。此外多孔层任选还以相应地有效的量包含常见的添加剂,例如稳定剂和/或中和剂。
用于多孔层的合适的丙烯均聚物包含98至100重量%,优选99至100重量%的丙烯单元并且具有150℃或更高,优选155至170℃的熔点(DSC),和通常在230℃和2.16kg的力(DIN 53735)下的0.5至10g/10min,优选2至8g/10min的熔体流动指数。正庚烷可溶性分数低于15重量%,优选1至10重量%的全同立构的丙烯均聚物是用于所述层的优选的丙烯均聚物。有利地也可以使用具有至少96%,优选97-99%(13C-NMR;三单元组方法)的高的链全同立构规整度的全同立构的丙烯均聚物。这些原料在现有技术中已知被称为HIPP-聚合物(高全同立构聚丙烯)或HCPP(高结晶聚丙烯)并且特征在于聚合物链的高的立构规整性、更高的结晶度和更高的熔点(相比于13C-NMR-全同立构规整度为90至<96%的丙烯聚合物,所述丙烯聚合物也可以使用)。
丙烯嵌段共聚物具有高于140至170℃,优选145至165℃,特别是150至160℃的熔点和在高于120℃,优选在125-160℃范围内开始的熔程。共聚单体含量,优选乙烯含量,例如在1和20重量%之间,优选在1和10重量%之间。丙烯嵌段共聚物的熔体流动指数通常在1至20g/10min,优选1至10g/10min的范围内。
任选地,多孔层还可以包含其它聚烯烃,只要其不会不利影响性能,特别是孔隙率和机械强度。其它聚烯烃为例如乙烯含量为20重量%或更低的乙烯和丙烯的无规共聚物,烯烃含量为20重量%或更低的丙烯与C4-C8烯烃的无规共聚物,乙烯含量为10重量%或更低并且丁烯含量为15重量%或更低的丙烯、乙烯和丁烯的三元聚合物。
在一个优选的实施方案中,多孔层仅由丙烯均聚物和/或丙烯嵌段共聚物和β-成核剂和颗粒以及任选的稳定剂和中和剂构成。
在另一个实施方案中,多孔层仅由丙烯均聚物和/或丙烯嵌段共聚物和颗粒以及任选的稳定剂和中和剂构成。所述实施方案不包含β-成核剂。
在冷却聚丙烯熔体时促进聚丙烯的β-晶体的形成的所有已知添加剂原则上都适合作为多孔层的β-成核剂。这种β-成核剂及其在聚丙烯基体中的作用方式自身是现有技术中已知的并且将在下文详细描述。
已知聚丙烯具有各种不同的结晶相。在冷却熔体时通常主要形成α-结晶聚丙烯,所述α-结晶聚丙烯的熔点在155-170℃,优选158-162℃的范围内。通过一定的温度控制,可以在冷却熔体时产生低比例的β-结晶相,其相对于单斜晶α-变体具有明显更低的熔点,为145-152℃,优选148-150℃。在现有技术中已知在冷却聚丙烯时导致升高比例的β-变体的添加剂,例如γ-喹吖啶酮,二氢喹吖啶,或邻苯二甲酸的钙盐。
为了本发明的目的,优选使用在冷却丙烯均聚物熔体时产生40-95%,优选50-85%(DSC)的β-比例的高活性β-成核剂。β-比例由经冷却的丙烯均聚物熔体的DSC确定。优选的是例如描述于DE3610644中的由碳酸钙和有机二羧酸组成的双组分β-成核体系,对所述文献由此明确进行参考。特别有利的是二羧酸的钙盐,例如如DE4420989中描述的庚二酸钙或辛二酸钙,对所述文献也明确进行参考。EP-0557721中描述的二甲酰胺,特别是N,N-二环己基-2,6-萘二甲酰胺,也是合适的β-成核剂。
除了β-成核剂之外,在冷却未拉伸的熔体膜时保持一定的温度范围和在该温度下的停留时间对于获得高比例的β-结晶聚丙烯来说是重要的。熔体膜的冷却优选在60至140℃,特别是80至130℃,例如85至128℃的温度下进行。缓慢的冷却同样促进β-微晶的生长,因此引出速度(即熔体膜经过第一冷却辊的速度)应当缓慢,由此在所选择的温度下的必要停留时间足够长。由于本发明能够实现升高的工艺速度,在根据本发明的方法中原则上还可以在对于多孔薄膜而言相对较宽的范围内改变引出速度。引出速度通常为1至100m/min,优选1.2至60m/min,特别是1.3至40m/min,特别优选1.5至25m/min,或1至20m/min。停留时间可以相应延长或缩短并且例如为10至300s,优选20至200s。
多孔层包含通常40至<98重量%,优选40至90重量%的丙烯均聚物和/或丙烯嵌段共聚物和通常0.001至5重量%,优选50至10000ppm的至少一种β-成核剂和2至<70重量%的颗粒,基于多孔层的重量计。对于多孔层中不具有β-成核剂的实施方案,丙烯均聚物和/或丙烯嵌段共聚物的比例相应提高。对于该层中包含其它聚烯烃的情况,丙烯均聚物或嵌段共聚物的比例相应降低。通常地,当包含额外聚合物时,多孔层中的额外聚合物的量为0至<10重量%,优选0至5重量%,特别是0.5至2重量%。同样适用的是,当使用至多5重量%的较高量的成核剂时,所述丙烯均聚物或丙烯嵌段共聚物的比例降低。所述层还可以以低于2重量%的常见低用量包含常见的稳定剂和中和剂以及任选的其它添加剂。
在一个优选的实施方案中,多孔层包含丙烯均聚物和丙烯嵌段共聚物的混合物作为聚合物。在该实施方案中,多孔层包含通常10至93重量%,优选20至90重量%的丙烯均聚物和5至88重量%,优选10至60重量%的丙烯嵌段共聚物,和0.001至5重量%,优选50至10000ppm的至少一种β-成核剂和2至60重量%的颗粒,基于多孔层的重量计,以及任选的上文已经提及的添加剂例如稳定剂和中和剂。同样地在此合适的是,可以以0至<10重量%,优选0至5重量%,特别是0.5至2重量%的量包含其它聚烯烃,并且丙烯均聚物或嵌段共聚物的比例则相应降低。
根据本发明的多孔薄膜的特别优选的实施方案包含50至10000ppm,优选50至5000ppm,特别是50至2000ppm的庚二酸钙或辛二酸钙作为多孔层中的β-成核剂。
多孔薄膜可以为单层或多层的。薄膜的厚度通常在10至100μm,优选15至60μm,例如15至40μm的范围内。多孔薄膜可以在其表面上进行电晕处理、火焰处理或等离子体处理,例如从而改进用电解质的填充和/或改进粘附性能。通过根据本发明加入颗粒还可以以提高的工艺速度和/或少量撕裂制备厚度小于25μm的多孔薄膜。
在一个简单的实施方案中,薄膜为单层的并且这样仅由上述含颗粒多孔层组成。在该情况下,颗粒比例为优选5至50重量%,特别是10-40重量%,基于薄膜的重量计。
在另一个实施方案中,薄膜为多层的并且包括至少两个上述含颗粒多孔层,其中所述多孔层在颗粒含量和/或聚合物方面不同。
在另一个实施方案中,含颗粒多孔层为在其它多孔层II上的单面外部覆盖层I。在该情况下,覆盖层I中的颗粒比例为优选10至70重量%,特别是15至60重量%,基于覆盖层I的重量计。所述薄膜则至少包括含颗粒多孔覆盖层I和其它多孔层II。
在另一个实施方案中,含颗粒多孔层作为外部覆盖层从两面施加到多孔层II上。在该情况下,两个覆盖层中的颗粒比例各自彼此独立地为优选10至70重量%,特别是15至60重量%,基于各个覆盖层的重量计。
这些实施方案的共同之处在于,薄膜的所有层是多孔的,因此得自这些层构造的薄膜本身也是多孔薄膜。在多层实施方案中,所述一个或多个含颗粒的层I和/或层II各自的组成可以相同或不同。
所述一个或多个其它多孔层II原则上以与上述含颗粒多孔层相同的方式构成,但是其中不包含颗粒。所述多孔层II中的丙烯聚合物的比例相应提高。所述一个或多个其它多孔层因此如下组成。
所述其它多孔层II通常包含45至<100重量%,优选50至95重量%的丙烯均聚物和/或丙烯嵌段共聚物和0.001至5重量%,优选50-10000ppm的至少一种β-成核剂,基于多孔层的重量计。对于层II中包含其它聚烯烃的情况,丙烯均聚物或嵌段共聚物的比例相应降低。通常地,当包含额外聚合物时,层II中的额外聚合物的量为0至<10重量%,优选0至5重量%,特别是0.5至2重量%。同样合适的是,当使用至多5重量%的较高量的成核剂时,所述丙烯均聚物或丙烯嵌段共聚物的比例降低。此外,层II还可以以低于2重量%的常见低用量包含常见的稳定剂和中和剂以及任选的其它添加剂。
在本发明的其它实施方案中,当例如为了其它目的想要利用特殊的孔结构时,多孔层还可以与额外的无孔层组合。所述薄膜则不具有透气性并且包括至少一个含颗粒的多孔层I作为薄膜的多层实施方案的一个或多个覆盖层、一个或多个内部中间层或作为基础层。
多孔薄膜或多孔层的密度通常在0.1至0.6g/cm3,优选0.2至0.5g/cm3的范围内。具有另外的无孔层的实施方案的薄膜的密度可以在很宽范围内变化。
根据本发明的多孔薄膜的特征在于如下其它性能:
根据本发明的多孔薄膜的(通过泡点)测得的最大孔尺寸通常为<350nm,并且优选在20至350nm,特别是40至300nm,特别优选40至200nm的范围内。平均孔直径应当通常在20至150nm的范围内,优选在30至100nm的范围内,特别是在30至80nm的范围内。多孔薄膜的孔隙率通常在30%至80%,优选50%至70%的范围内。根据本发明的薄膜的特征优选在于低于500s/100cm3,特别是低于200s/100cm3,特别是10至150s/100cm3的Gurley值。
在多孔层中加入颗粒导致出人意料的效果,所述效果可以以不同方式有利地利用。已经发现,即使当电池内部的温度超过聚合物的熔点时,颗粒仍然保证电极的分离。所述保护作用不仅对于其孔在温度升高时闭合的隔板起作用,而且对于不具有所谓的切断功能(在高温下多孔薄膜的Gurley值升高)的隔板也起作用。因此由根据本发明的多孔薄膜构成的隔板相对于由于短路、机械损害或过热造成的电池燃烧或甚至爆炸提供更好的保护。
出人意料地,加入颗粒有利地影响薄膜的透气性。相对于具有相似组成但是不具有颗粒的薄膜,通过加入颗粒降低了Gurley值。在颗粒本身通常不发挥β-成核作用的背景下,这是出人意料的。此外,在现有技术中已知的是,粒子尺寸小于1μm的颗粒在聚丙烯基体中也不具有形成空泡或形成孔的作用。因此不能理解所述颗粒如何或为什么有助于较低的Gurley值。
在此另外完全出人意料地发现,颗粒的加入并不像初始预期的那样造成薄膜制备时的更频繁的撕裂。这是出人意料地,因为在现有技术中已知的是,例如成核剂的附聚物造成撕裂频率显著升高。近期的专利申请描述了如何实现粒子尺寸为5至50nm的成核剂在聚丙烯中的均匀分布而无附聚物,从而提高β-多孔薄膜的制备时的方法安全性(WO2011047797A1)。
根据本发明加入的熔点高于200℃的颗粒包括无机和有机颗粒。在本发明的意义上,颗粒不是导致较高比例的β-结晶聚丙烯的物质。其因此不是β-成核剂。在本发明的意义上,颗粒为非引发空泡的颗粒。优选地,根据本发明使用的颗粒为大致球状颗粒或球状颗粒。
引发空泡的颗粒是现有技术中已知的并且在拉伸时在聚丙烯薄膜中产生空泡。空泡为闭合空腔并且同样地相对于起始材料的计算密度降低薄膜的密度。相反,多孔薄膜或层具有由彼此连接的孔构成的网络。孔因此不是闭合空腔。多孔薄膜和含空泡薄膜均具有低于0.9g/cm3的密度。含空泡的双轴拉伸的聚丙烯薄膜的密度通常为0.5至<0.85/cm3。通常地,颗粒需要高于1μm的粒子尺寸,从而充当聚丙烯基体中的引发空泡的粒子。可以借助于由丙烯均聚物构成的对照薄膜检查颗粒是否是引发空泡的粒子还是非引发空泡的粒子。
为此,根据常见的boPP方法制备由丙烯均聚物和8重量%待检查颗粒构成的双轴拉伸的薄膜。在此应用通常的拉伸条件(在110℃的拉伸温度下的纵向拉伸倍数为5,在140℃的横向拉伸温度下的横向拉伸倍数为9)。然后确定薄膜的密度。当薄膜的密度≤0.85g/cm3时,颗粒为引发空泡的颗粒。当薄膜的密度高于0.85g/cm3,优选高于0.88g/cm3,特别是高于≥0.9g/cm3时,颗粒为本发明意义上的非引发空泡的颗粒。
在本发明的意义上,无机颗粒为所有天然或合成矿物,只要其具有高于200℃的上述熔点。在本发明的意义上,无机颗粒包括基于硅酸盐化合物、氧化原料(例如金属氧化物)和非氧化和非金属原料的材料。
无机颗粒为例如氧化铝、硫酸铝、硫酸钡、碳酸钙、碳酸镁、硅酸盐例如硅酸铝(高岭土)和硅酸镁(滑石)和二氧化硅,其中优选使用二氧化钛、碳酸钙和二氧化硅。
合适的硅酸盐包括具有SiO4-四面体的材料,例如层状硅酸盐或架状硅酸盐。合适的氧化原料(特别是金属氧化物)为例如氧化铝、氧化锆、钛酸钡、锆钛酸铅、铁氧体和氧化锌。合适的非氧化和非金属原料为例如碳化硅、氮化硅、氮化铝、氮化硼、硼化钛和硅化钼。
优选的是金属Al、Zr、Si、Sn、Ti和/或Y的氧化物。这种颗粒的制备例如详细描述于DE-A-10208277中。
特别优选的是基于总式为SiO2的硅的氧化物以及总式为AlNaSiO2的混合氧化物和总式为TiO2的钛的氧化物的颗粒,其中所述颗粒可以以结晶、无定形或混合形式存在。
优选的二氧化钛颗粒通常以至少95重量%的比例由金红石组成并且优选带有无机氧化物的覆层使用,如其通常作为纸张或涂布剂中TiO2白色颜料的覆层用于改进耐光牢度那样。具有覆层的TiO2颗粒例如描述于EP-A-0 078 633和EP-A-0 044 515。
覆层任选还包含具有极性和非极性基团的有机化合物。优选的有机化合物为烷基中具有8至30个C原子的烷醇和阴离子和阳离子表面活性剂,特别是具有12至24个C原子的脂肪酸和正伯烷醇,以及聚二有机硅氧烷和/或聚有机氢硅氧烷以及聚二甲基硅氧烷和聚甲基氢硅氧烷。
TiO2粒子上的覆层通常由1至12g,特别是2至6g的无机氧化物组成,任选额外包含0.5至3g,特别是0.7至1.5g的有机化合物,分别基于100g TiO2粒子计。被证明特别有利的是,TiO2粒子用Al2O3或用Al2O3和聚二甲基硅氧烷涂布。
其它合适的无机氧化物为铝、硅、锌或镁的氧化物或两种或更多种所述化合物的混合物。其由水溶性化合物,例如碱金属-,特别是铝酸钠、氢氧化铝、硫酸铝、硝酸铝、硅酸钠或二氧化硅,在水悬浮液中沉淀而得。
有机颗粒基于与含颗粒多孔层的丙烯聚合物不相容的聚合物。有机颗粒优选基于如EP-A-O 623 463中描述的环烯烃(COC)的共聚物,聚酯,聚苯乙烯,聚酰胺,卤化有机聚合物,其中优选聚酯例如聚对苯二甲酸丁二醇酯和环烯烃共聚物。有机颗粒应当与聚丙烯不相容。在本发明的意义上,“不相容”表示材料或聚合物在薄膜中以独立的粒子形式存在。
颗粒具有至少200℃,特别是至少250℃,非常特别优选至少300℃的熔点。此外,所述颗粒应当在所述温度下通常也不经历分解。上述数据可以经由已知方法例如DSC(差式扫描量热法)或TG(热重分析法)确定。
优选的无机颗粒通常具有在500至4000℃,优选700至3000℃,特别是800至2500℃范围内的熔点。TiO2的熔点例如为约1850℃。
使用的有机颗粒也具有高于200℃的熔点并且应当特别在所述温度下不经历分解。
有利的是,颗粒具有最高1μm的平均粒子尺寸,因为更大的颗粒导致薄膜制备时更多的撕裂。优选的是10至800nm,特别是50至500nm的平均粒子尺寸。颗粒应当以尽可能不具有附聚物的细分布的形式存在于多孔层中,因为否则即使少量的自一定临界尺寸(例如>1μm,特别是1至3μm)以上的附聚物也会以低数量升高撕裂频率。平均粒子尺寸因此有助于薄膜不包含或包含少于1个具有的粒子尺寸>1μm的附聚物,在此其对于10mm2的薄膜样品通过SEM照片确认。对于具有低于1μm的尺寸(绝对)的单个非附聚粒子,情况也是如此。相应地,10mm2的所述薄膜样品也显示出少于一个或没有粒子尺寸大于1μm的非附聚粒子。通过选择不太或完全不倾向于附聚并且具有小的平均粒子尺寸并且具有一定粒子尺寸分布(所述粒子尺寸分布使得不存在或仅存在粒子尺寸>1μm的单独粒子)的颗粒,可以制备多孔薄膜并且实现本发明的多种多样的优点。
为了保证少量附聚物,原则上优选的是在薄膜制备时通过批料或预混料掺入颗粒。批料或预混料包含丙烯聚合物和颗粒以及任选额外常见的添加剂。在制备批料时优选使用双螺杆挤出机和/或以高剪切速率混合,从而实现颗粒在聚合物中的更好分散。加入表面活性物质也有助于颗粒在聚合物中的均匀分布。还适宜的是在上游步骤中为颗粒本身设置涂层。特别在使用无机颗粒时,所述手段是值得推荐的。通过现有技术中已知的所述和其它手段可以保证可以使用不含附聚物的批料或预混料。
本发明还涉及制备根据本发明的含颗粒多孔薄膜的方法。根据本发明,工艺速度可以在宽范围内变化。本发明能够实现更高的工艺速度,其不伴随更差的透气性或更多的撕裂数目。根据本发明的方法的速度通常在3至400m/min之间,优选在5至250m/min之间,特别是在6和150m/min之间,或者在6.5和100m/min之间。
根据所述方法,多孔薄膜根据自身已知的平膜-挤出法或共挤出法制得。在所述方法的范围内如下进行,使得混合各个层的聚合物(丙烯均聚物和/或丙烯嵌段共聚物)和通常β-成核剂和颗粒和任选其它聚合物的混合物,在挤出机中熔融,并且共同地和同时地通过扁平模头挤出或共挤出至引出辊上,在所述引出辊上单层或多层熔体膜凝固和冷却而同时形成β-微晶。这样选择冷却温度和冷却时间,使得在预制薄膜的多孔层中产生尽可能高比例的β-结晶聚丙烯。通常地,一个或多个引出辊的温度为60至140℃,优选80至130℃。在该温度下的停留时间可以变化并且应当为至少20至300s,优选30至100s。这样获得的预制薄膜在多孔层中通常包含40-70%,优选50-90%的β-微晶比例(第一次加热)。
多孔层中具有高比例的β-结晶聚丙烯的所述预制薄膜然后这样进行双轴拉伸,使得在拉伸时导致β-微晶向α-结晶聚丙烯的转化并且导致网络状多孔结构的形成。双轴拉伸(取向)通常相继进行,其中优选首先纵向(沿加工方向上)拉伸并然后横向(垂直于加工方向)拉伸。
为了在纵向方向上拉伸,预制薄膜首先导引经过一个或多个加热辊,所述加热辊将薄膜加热至合适的温度。所述温度通常小于140℃,优选70至120℃。然后通常借助于两个根据目标拉伸比例而以不同速度运转的辊进行纵向拉伸。纵向拉伸比例在此在2:1至6:1,优选3:1至5:1的范围内。
在纵向拉伸之后,首先再次通过相应调温的辊冷却薄膜。然后在所谓的加热场中再次加热至横向拉伸的温度,所述温度通常为120-145℃的温度。然后借助于相应的拉幅机(Kluppenrahmen)进行横向拉伸,其中横向拉伸比例在2:1至9:1,优选3:1至8:1的范围内。为了实现根据本发明的高的孔隙率,优选使用>0至40%/s,优选在0.5至30%/s,特别是1至15%/s范围内的适中至缓慢的横向拉伸速度进行横向拉伸。
任选地,可以在最后的拉伸(通常为横向拉伸)之后,根据已知的方法之一电晕处理、等离子体处理或火焰处理薄膜的表面,从而有利于用电解质的填充。
最后任选进行热定型(热处理),其中例如通过辊或空气加热箱,将薄膜保持在110至150℃,优选125至145℃的温度下约5至500s,优选10至300s长的时间。任选地,薄膜紧接着在热定型之前或者在热定型的过程中收拢地行进,其中收拢率为优选5-25%,特别是8至20%。“收拢率”被理解为是指横向拉伸框架略微合拢,使得在横向拉伸过程结束时给出的框架的最大宽度大于在热定型结束时的宽度。相应地,薄膜幅面的宽度当然也是同样情况。横向拉伸框架的合拢程度作为收拢率给出,所述收拢率从横向拉伸框架的最大宽度Bmax和最终薄膜宽度B薄膜根据下式计算:
收拢率[%]=100×(Bmax-B薄膜)/Bmax
最后用卷绕设备以常规方式卷绕薄膜。
在已知的顺序方法中,其中纵向拉伸和横向拉伸在一个工艺中相继进行,不仅仅是横向拉伸速度取决于工艺速度。引出速度和冷却速度也随着工艺速度变化。这些参数因此不能彼此独立地选择。其结果是,在其它方面相同的条件下,较快的工艺速度不仅提高横向拉伸速度而且提高引出速度,但是同时降低预制薄膜的冷却时间。这可能(但是不一定强制地)构成额外的问题。
上述“工艺速度”被理解为是指薄膜在每种情况下最后的卷绕时运行/卷绕所采用的相应的那个速度,例如单位为m/min。
根据本发明的用于制备多孔薄膜的方法中的方法条件与通常在制备双轴取向的薄膜时所遵守的方法条件不同。为了获得高的孔隙率和渗透性,在固化成预制薄膜时的冷却条件和拉伸时的温度和倍数是关键的。首先必须通过相应缓慢和适中的冷却,即在相对高的温度下,实现预制薄膜中的高比例的β-微晶。在随后的纵向拉伸时β-晶体转化成α变体,因此产生微裂纹形式的缺陷。为了产生足够数目和正确形式的所述缺陷,纵向拉伸必须在相对低的温度下进行。在横向拉伸中,该缺陷撕裂开形成孔,因此产生所述多孔薄膜的特征性网络结构。
特别是在纵向拉伸中的相对于常规BOPP方法低的温度决定了需要高的拉伸力,所述高的拉伸力一方面在聚合物基体中引入高的取向,另一方面增加撕裂风险。期望的孔隙率越高,拉伸时必须选择越低的温度并且拉伸倍数必须越高。因此,期望的薄膜的孔隙率和渗透性越高,原则上该过程越关键。因此不可以通过更高的拉伸倍数或降低拉伸温度而随意提高孔隙率。特别地,降低的纵向拉伸温度造成严重受损的薄膜的运行安全性,并且造成不期望的撕裂倾向的升高。因此不再可以通过例如低于70℃的更低的纵向拉伸温度进一步改进孔隙率。
还有可能额外通过横向拉伸时的拉伸速度影响薄膜的孔隙率和渗透性。缓慢的横向拉伸进一步提高孔隙率和渗透性,而不会在生产过程中造成增加的撕裂或其它干扰。然而缓慢的工艺速度显著提高生产成本。
根据本发明加入颗粒特别有利地支持多孔结构的形成,尽管颗粒单独并不导致孔的形成。看起来颗粒结合一定含量的β-结晶聚丙烯以出人意料的方式支持孔结构的形成,因此在预制薄膜中给定的β-微晶比例下,通过加入颗粒实现显著更高的孔隙率,所述孔隙率在给定的β-比例下在不相应加入颗粒的情况下不能实现。颗粒与β-微晶以协同方式共同作用,因此薄膜中β-比例的降低不导致更低的Gurley值。也可以通过提高工艺速度以有利方式利用改进的透气性,因为颗粒有助于改进Gurley值,即根据本发明的具有相同Gurley值的含颗粒薄膜更快速(即成本更低)地制得。
出人意料地发现,当薄膜包含根据本发明的颗粒时,尽管工艺速度升高,但是撕裂数目不显著增加。
或者通过本发明可以提供薄膜,所述薄膜由于特别高的渗透性而适合用于高能电池。
薄膜还可以有利地用在其它应用中,在所述应用中需要很高的渗透性或者很高的渗透性是有利的。例如作为电池(特别是具有高的性能要求的锂电池)中的高孔隙率隔板。
为了表征原料和薄膜,利用如下测量方法:
粒子尺寸/颗粒尺寸:
通过激光散射法根据ISO 13320-1确定平均粒子尺寸。合适的分析用测量设备为例如Microtrac S 3500。
可以通过扫描电子显微镜研究附聚物的尺寸和绝对粒子尺寸。为此,拍摄涂抹在样品支架上的颗粒的SEM照片,或拍摄尺寸为10mm2的铂蒸镀或金蒸镀的薄膜样品的SEM照片,或拍摄母料粒料的SEM照片。光学研究薄膜样品或颗粒或批料的其它相应照片是否存在粒子尺寸大于1μm的颗粒。
熔体流动指数
丙烯聚合物的熔体流动指数根据DIN 53 735在2.16kg载荷和230℃下测得。
熔点
在本发明的意义上,熔点为DSC曲线的最大值。为了确定熔点,以10K/1min的加热和冷却速度在20至200℃的范围内绘制DSC-曲线。为了确定熔点,如通常那样评价在200至20℃范围内以10K/1min冷却之后的第二次加热曲线。
β-含量
β-结晶聚丙烯的比例经由DSC确定。该表征描述于Varga的J.o.Appl.PolymerScience,第74卷,第2357-2368页,1999并且如下进行:添加有β-成核剂的样品在DSC中首先以20℃/min的加热速度加热至220℃并且熔融(第一次加热)。然后以10℃/min的冷却速度将其冷却至100℃,然后将其以10℃/min的加热速度(第二次加热)再次熔融。
由第一次加热的DSC曲线,由β-结晶相的熔融焓(Hβ)与β-结晶相和α-结晶相的熔融焓的总和(Hβ+Hα)的比例确定所测量样品(未拉伸的薄膜,注塑部件)中存在的结晶度Kβ,DSC(β-结晶聚丙烯的比例)。百分比值如下计算:
Kβ,DSC[%]=100×(Hβ)/(Hβ+Hα)
由第二次加热的DSC曲线,由β-结晶相的熔融焓(Hβ)与β-结晶相和α-结晶相的熔融焓的总和(Hβ+Hα)的比例确定提供可以实现的相应聚丙烯样品的最大β-比例的结晶度Kβ,DSC(第二次加热)。
密度
密度根据DIN 53 479的方法A确定。
最大孔尺寸和平均孔尺寸
最大孔尺寸和平均孔尺寸通过泡点法根据ASTM F316测得。
孔隙率
作为孔隙率,如下计算薄膜相对于纯聚丙烯的密度ρpp的密度减小(ρ薄膜-ρpp):
孔隙率[%]=100×(ρpp-ρ薄膜)/ρpp
透过性/渗透性(Gurley值)
薄膜的透过性使用Gurley测试机4110根据ASTM D 726-58测得。在此确定100cm3空气透过1平方英寸(6.452cm2)的薄膜表面积所需的时间(单位为秒)。穿过薄膜的压差在此对应于12.4cm高度水柱的压力。所需的时间则对应于Gurley值,即单位为秒/100cm3。
现在通过如下实施例解释本发明。
具体实施方式
实施例:
实施例A:批料制备
在第一步骤中制备由聚合物和颗粒形成的批料,所述批料用在如下试验中。该批料如下制得:
在双螺杆挤出机中,在230℃的温度和270 1/min的螺杆旋转速度下,将60重量%的TiO2颜料(Huntsmann TR28)连同0.04重量%的作为成核剂的庚二酸钙(庚二酸钙)与39.96重量%的全同立构聚丙烯均聚物的粒料(熔点162℃;MFI 3g/10min)混合、熔融并且造粒。批料的SEM照片显示了粒子尺寸为20至500nm的细分布的TiO2颗粒而无大于1μm的附聚物。在第二次加热时,批料的β-活性显示出91%的值。
实施例B:薄膜制备
薄膜实施例:1
在挤出方法之后从宽缝模头在240至250℃的挤出温度下挤出双层预制薄膜。在此选择挤出机的通过量,使得层的厚度比例A:B为1:2。首先在冷却辊上引出和冷却多层预制薄膜。然后使预制薄膜在纵向方向和横向方向上取向,最后定型。薄膜的层具有如下组成:
层A的组成:
40重量%的根据实施例A的由如下组成的TiO2批料
60重量%的TiO2
约39.96重量%的丙烯均聚物
0.04重量%的成核剂
分别基于批料计
60重量%的由如下组成的聚丙烯混合物:
约60重量%的丙烯均聚物(PP),所述丙烯均聚物具有4.5重量%的正庚烷可溶性比例(基于100%PP计)和165℃的熔点;和在230℃和2.16kg载荷下的3.2g/10min的熔体流动指数(DIN 53 735),和
约39.96重量%的丙烯-乙烯-嵌段共聚物,所述丙烯-乙烯-嵌段共聚物具有基于嵌段共聚物计的约5重量%的乙烯比例和6g/10min的熔体流动指数(230℃和2.16kg)
0.04重量%的纳米级庚二酸钙作为β-成核剂
分别基于混合物计
层B的组成:
约80重量%的丙烯均聚物(PP),所述丙烯均聚物具有4.5重量%的正庚烷可溶性比例(基于100%PP计)和165℃的熔点;和在230℃和2.16kg载荷下的3.2g/10min的熔体流动指数(DIN 53 735),和
约19.96重量%的丙烯-乙烯-嵌段共聚物,所述丙烯-乙烯-嵌段共聚物具有基于嵌段共聚物计的约5重量%的乙烯比例和6g/10min的熔体流动指数(230℃和2.16kg)
0.04重量%的纳米级庚二酸钙作为β-成核剂
薄膜的层还包含常见量的稳定剂和中和剂。纳米级庚二酸钙如WO2011047797的实施例1a或1b所述制得。
聚合物混合物在挤出之后通过第一引出辊和另一个三辊组(Walzentrio)引出、冷却和凝固,然后纵向拉伸、横向拉伸和定型,其中具体地选择如下条件:
挤出:挤出温度245℃
冷却辊:温度125℃,
引出速度:1.5m/min(在引出辊上的停留时间:55秒)
纵向拉伸:预热辊:92
拉伸辊T=90℃
纵向拉伸倍数为3.6
横向拉伸:加热场T=145℃
拉伸场T=145℃
横向拉伸倍数为4.8
收拢率:13%
无撕裂地运行了运行长度为1500m的卷筒。这样所制得的多孔薄膜厚度为约30μm并且具有0.33g/cm3的密度并且显示出均匀的白色不透明外观。孔隙率为66%并且Gurley值为160s。在所研究的10mm2的表面积上A侧表面的SEM照片未显示粒子尺寸>1μm的TiO2附聚物和颗粒。
薄膜实施例2
如薄膜实施例1中所述制备双层薄膜。不同于薄膜实施例1,引出速度升高至2.5m/min。层的组成以及其它方法条件不变。尽管引出速度升高,仍然完成800m的运行长度而无撕裂。在此厚度降低至20μm。尽管在引出辊上的停留时间较短,Gurley值出人意料地降低至约140秒。在该薄膜的情况下,在A侧在10mm2的表面积上通过SEM也不能识别到粒子尺寸>1μm的TiO2附聚物和颗粒。
薄膜实施例3
如薄膜实施例1中所述制备薄膜。不同于薄膜实施例1,此时层B具有与层A相同的组成。层A的组成以及方法条件不变。因此实际上制备的是单层薄膜。薄膜的厚度为31μm并且Gurley值出人意料地降低至低于100秒。所述组成也显示出很好的运行安全性,因此生产了运行长度为2000m的卷筒。薄膜两侧在10mm2的表面积上在SEM中未显示粒子尺寸>1μm的TiO2附聚物和颗粒。
薄膜实施例4
如薄膜实施例3中所述制备具有24重量%TiO2的实际上单层的薄膜。引出速度(如薄膜实施例2中)升高至2.5m/min。层A和B的(相同)组成以及其它方法条件不变。采用2.5m/min的升高的引出速度,制成运行长度为1000m的卷筒而无撕裂。在此厚度降低至20μm并且Gurley值如实施例3那样出人意料地低于100秒。在该薄膜的情况下,在两侧上在10mm2的表面积上通过SEM不能识别到粒子尺寸>1μm的附聚物和颗粒。
薄膜实施例5
如薄膜实施例3中所述制备具有24重量%TiO2的薄膜。不同于薄膜实施例3,聚丙烯混合物此时不包含成核剂,因此具有如下组成:
约60重量%的丙烯均聚物(PP),所述丙烯均聚物具有4.5重量%的正庚烷可溶性比例(基于100%PP计)和165℃的熔点;和在230℃和2.16kg载荷下的3.2g/10min的熔体流动指数(DIN 53 735),和
约40重量%的丙烯-乙烯-嵌段共聚物,所述丙烯-乙烯-嵌段共聚物具有基于嵌段共聚物计的约5重量%的乙烯比例和6g/10min的熔体流动指数(230℃和2.16kg)
此外,层的组成和TiO2批料的组成以及方法条件相对于实施例3不变。
在此也可以制成运行长度为1000m的卷筒而无撕裂。薄膜的厚度为28μm,在此Gurley值仍如薄膜实施例3中那样出人意料地低于100秒。在该薄膜的情况下,在两层中在10mm2的表面积上通过SEM也不能识别到粒子尺寸>1μm的附聚物和颗粒。
薄膜实施例6
如薄膜实施例1中所述制备双层薄膜。不同于薄膜实施例1,层A中ΤiO2批料的浓度升高至60%并且聚丙烯混合物的比例降低至40%,使得层A中存在36重量%的TiO2。层B的组成以及方法条件不变。所述组成也显示出很好的运行安全性,并且生产了运行长度为1000m的卷筒。薄膜的厚度为27μm并且Gurley值出人意料地降低至低于100秒。薄膜A侧在10mm2的表面积上在SEM中未显示>1μm的附聚物。然而识别出粒子尺寸约为1.2μm的颗粒。
薄膜实施例7
在与薄膜实施例2相同的条件下以相同配方制成双层薄膜。然而引出速度升高至5m/min,因此最终薄膜速度升高至19m/min。为了保证在所述条件下制备具有相同厚度的薄膜,额外使挤出通过量加倍。在更高的工艺速度下,所述组成也显示出很好的运行安全性,并且生产了运行长度为1000m的卷筒。薄膜的厚度为27μm,Gurley值相比于实施例2升高至170秒,其中对预制薄膜测得的β-含量略微降低至57%。薄膜A侧在10mm2的表面积上在SEM中未显示粒子尺寸>1μm的附聚物和颗粒。
薄膜实施例8
在与薄膜实施例2相同的条件下以相同配方制成双层薄膜。然而引出速度升高至7.5m/min,因此最终薄膜速度升高至28m/min。为了保证在所述条件下制备具有相同厚度的薄膜,额外使挤出通过量加倍。在更高的工艺速度下,所述组成也显示出很好的运行安全性,并且生产了运行长度为1000m的卷筒。薄膜的厚度为24μm,Gurley值相比于实施例7升高至198秒,其中对预制薄膜测得的β-含量略微降低至54%。薄膜A侧在10mm2的表面积上在SEM中未显示粒子尺寸>1μm的附聚物和颗粒。
薄膜实施例9
在与薄膜实施例2相同的条件下以相同配方制成双层薄膜。然而引出速度升高至10m/min,因此最终薄膜速度升高至37m/min。为了保证在所述条件下制备具有相同厚度的薄膜,额外使挤出通过量加倍。在更高的工艺速度下,所述组成也显示出很好的运行安全性,并且生产了运行长度为1000m的卷筒。薄膜的厚度为24μm,Gurley值相比于实施例8升高至222秒,其中对预制薄膜测得的β-含量略微降低至51%。薄膜A侧在10mm2的表面积上在SEM中未显示粒子尺寸>1μm的附聚物和颗粒。
薄膜实施例10
在与薄膜实施例2相同的条件下制成双层薄膜。然而在层A和层B中通过升高丙烯均聚物(PP)的比例替代丙烯-乙烯-嵌段共聚物。
尽管缺少嵌段共聚物,所述组成也显示出很好的运行安全性,并且生产了运行长度为1000m的卷筒。薄膜的厚度为27μm并且Gurley值为170秒。所述组成也显示出很好的运行安全性,因此生产了运行长度为1000m的卷筒。薄膜A侧在10mm2的表面积上在SEM中未显示粒子尺寸>1μm的附聚物和颗粒。
对比实施例1
在与薄膜实施例1中所述相同的条件下制备薄膜。不同于薄膜实施例1,对于层A,使用与层B相同的混合物,因此免除加入TiO2。层B的组成以及方法条件不变。因此实际上制备的是单层薄膜。薄膜的厚度为29μm并且Gurley值为200秒。
对比实施例2
在与对比实施例1中所述相同的条件下制备薄膜。不同于对比实施例1,引出速度在此升高至2.5m/min。采用升高的引出速度,完成500m的运行长度而无撕裂。在此厚度降低至20μm并且Gurley值升高至280秒。
对比实施例3
在与薄膜实施例1中所述相同的条件下制成双层薄膜。不同于薄膜实施例1,层A的批料的组成变化。通过平均粒子直径为3μm的Al2O3替代TiO2。层A的聚丙烯混合物的组成、层B的组成以及方法条件不变。然而实际上由于大量撕裂而不能制备薄膜。
对比实施例4
在与薄膜实施例1中所述相同的条件下制成双层薄膜。然而通过直接计量加入挤出机而掺混入ΤiO2取代批料。制备时出现频繁撕裂。制备的少量薄膜原则上显示出与实施例1的薄膜相同的性能。薄膜的A侧在10mm2的表面积上在SEM中显示出更多的尺寸为1至3μm的附聚物。
Claims (26)
1.双轴取向的单层或多层多孔薄膜,所述多孔薄膜包括至少一个多孔层并且所述层包含至少一种丙烯聚合物、至少一种β-成核剂和颗粒,其特征在于,所述颗粒具有高于200℃的熔点并且在双轴取向的单层或多层多孔薄膜的10mm2的薄膜样品的SEM照片上能够检测出粒子尺寸>1μm的至多一个附聚物或至多一个颗粒。
2.根据权利要求1所述的薄膜,其特征在于,在拉伸薄膜时通过β-结晶聚丙烯的转化产生孔隙率,其中在薄膜中存在至少一种β-成核剂。
3.根据权利要求1或2所述的薄膜,其特征在于,基于多孔层的重量计,薄膜包含2至60重量%的颗粒。
4.根据权利要求1至3任一项所述的薄膜,其特征在于,β-成核剂为庚二酸的钙盐和/或辛二酸的钙盐和/或氧化铁和/或庚二酸镍。
5.根据权利要求1至4任一项所述的薄膜,其特征在于,在10mm2的薄膜样品的SEM照片上不能检测出粒子尺寸>1μm的附聚物和颗粒。
6.根据权利要求1至5任一项所述的薄膜,其特征在于,所述颗粒具有<1μm的平均粒子尺寸。
7.根据权利要求1至6任一项所述的薄膜,其特征在于,所述颗粒为非引发空泡的颗粒。
8.根据权利要求1至7任一项所述的薄膜,其特征在于,所述薄膜的多孔层包含至少65重量%的丙烯聚合物。
9.根据权利要求1至8任一项所述的薄膜,其特征在于,多孔薄膜包含至少65重量%的丙烯聚合物。
10.根据权利要求1至9任一项所述的薄膜,其特征在于,所述薄膜的多孔层包含50至85重量%的丙烯均聚物,15至50重量%的丙烯嵌段共聚物和50至10000ppm的β-成核剂。
11.根据权利要求1至10任一项所述的薄膜,其特征在于,所述薄膜的密度在0.1至0.5g/cm3的范围内并且具有低于150s的Gurley值。
12.根据权利要求1至11任一项所述的薄膜,其特征在于,所述颗粒为无机球状颗粒。
13.根据权利要求1至12任一项所述的薄膜,其特征在于,所述颗粒不是引发空泡的颗粒,其中引发空泡的颗粒为在双轴拉伸不具有β-成核剂的聚丙烯薄膜时使聚丙烯薄膜的密度降低至<0.85g/cm3的那样的颗粒。
14.根据权利要求1至13任一项所述的薄膜,其特征在于,所述颗粒为无机颗粒,优选金属Al、Zr、Si、Sn、Ti和/或Y的非导电性氧化物。
15.根据权利要求1至14任一项所述的薄膜,其特征在于,所述颗粒为TiO2。
16.根据权利要求1至15所述的薄膜,其特征在于,所述颗粒为有机颗粒。
17.制备多孔薄膜的方法,包括如下措施:
(i)挤出至少单层的聚丙烯薄膜,其中丙烯聚合物和β-成核剂和熔点高于200℃的颗粒在挤出机中熔融并且通过扁平模头挤出至引出辊上,
(ii)然后将经挤出的熔体膜冷却和凝固而同时形成β-微晶,
(iii)然后在纵向方向上并之后在横向方向上拉伸所述薄膜,并且
(iv)工艺速度为5至200m/min。
18.根据权利要求17所述的方法,其特征在于,所述颗粒与至少一种聚丙烯混合形成批料并且在挤出机中使含颗粒批料与聚丙烯混合和熔融。
19.根据权利要求17或18所述的方法,其特征在于,在制备含颗粒批料时加入分散剂。
20.根据权利要求1至16任一项所述的薄膜作为高能系统或高性能系统,特别是锂电池、锂离子电池、锂-聚合物电池和碱土金属电池中的隔板的用途。
21.包括根据权利要求1至16任一项所述的薄膜的高能系统或高性能系统,特别是锂电池、锂离子电池、锂-聚合物电池和碱土金属电池。
22.双轴取向的单层或多层薄膜,所述薄膜包括至少一个多孔层并且所述层包含至少一种丙烯聚合物、β-成核剂和颗粒,其中所述颗粒具有高于200℃的熔点和<1μm的平均粒子尺寸。
23.双轴取向的单层或多层薄膜,所述薄膜包括至少一个多孔层并且所述层包含至少一种丙烯聚合物和颗粒,其中所述颗粒具有高于200℃的熔点和<1μm的粒子尺寸,其特征在于,所述多孔层不包含β-成核剂。
24.双轴取向的单层或多层薄膜,所述薄膜包括至少一个多孔层并且所述层包含至少一种丙烯聚合物和颗粒,其中所述颗粒具有高于200℃的熔点和<1μm的粒子尺寸,其特征在于,所述多孔层不包含β-成核剂和嵌段共聚物并且所述多孔层具有低于500s的Gurley值。
25.根据权利要求22、23或24任一项所述的双轴取向的单层或多层薄膜,其特征在于,在双轴取向的单层或多层多孔薄膜的10mm2的薄膜样品的SEM照片上能够检测出粒子尺寸>1μm的至多一个附聚物或至多一个颗粒。
26.制备多孔薄膜的方法,包括如下措施:
(i)挤出至少单层的聚丙烯薄膜,其中将丙烯聚合物和熔点高于200℃的颗粒在无β-成核剂的情况下在挤出机中熔融并且通过扁平模头挤出至引出辊上,
(ii)然后将经挤出的熔体膜冷却和凝固而同时形成β-微晶,
(iii)然后在纵向方向上并之后在横向方向上拉伸所述薄膜,
其特征在于,所述薄膜以5m/min至200m/min的工艺速度制得并且在双轴取向的单层或多层多孔薄膜的10mm2的薄膜样品的SEM照片上能够检测出粒子尺寸>1μm的至多一个附聚物或至多一个颗粒。
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KR102148075B1 (ko) * | 2018-07-26 | 2020-08-25 | 한화토탈 주식회사 | 고온 셧다운 기능을 가지며 횡 방향 물성이 우수한 미세 다공성 다층 필름의 제조 방법 |
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2015
- 2015-02-03 DE DE102015001215.0A patent/DE102015001215A1/de not_active Withdrawn
- 2015-04-21 US US15/306,615 patent/US20170047567A1/en not_active Abandoned
- 2015-04-21 EP EP15717808.8A patent/EP3134260A1/de not_active Withdrawn
- 2015-04-21 WO PCT/EP2015/000829 patent/WO2015161920A1/de active Application Filing
- 2015-04-21 JP JP2016564172A patent/JP2017513996A/ja active Pending
- 2015-04-21 MX MX2016013967A patent/MX2016013967A/es unknown
- 2015-04-21 CA CA2946783A patent/CA2946783A1/en not_active Abandoned
- 2015-04-21 KR KR1020167027304A patent/KR20160146684A/ko unknown
- 2015-04-21 CN CN201580012406.4A patent/CN106103075A/zh active Pending
- 2015-04-21 BR BR112016018066A patent/BR112016018066A8/pt not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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JP2017513996A (ja) | 2017-06-01 |
KR20160146684A (ko) | 2016-12-21 |
BR112016018066A8 (pt) | 2020-06-23 |
BR112016018066A2 (pt) | 2017-08-08 |
EP3134260A1 (de) | 2017-03-01 |
CA2946783A1 (en) | 2015-10-29 |
MX2016013967A (es) | 2017-01-11 |
US20170047567A1 (en) | 2017-02-16 |
WO2015161920A1 (de) | 2015-10-29 |
DE102015001215A1 (de) | 2016-08-04 |
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