CN1139622C - 多孔特别是高比表面复合产品、制备方法和多孔复合膜电化学组件电极 - Google Patents
多孔特别是高比表面复合产品、制备方法和多孔复合膜电化学组件电极 Download PDFInfo
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- CN1139622C CN1139622C CNB988023555A CN98802355A CN1139622C CN 1139622 C CN1139622 C CN 1139622C CN B988023555 A CNB988023555 A CN B988023555A CN 98802355 A CN98802355 A CN 98802355A CN 1139622 C CN1139622 C CN 1139622C
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Classifications
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Abstract
本发明涉及特别是具有高比表面的多孔复合产品,其特征在于:它由聚合材料和至少20%的一种或几种填料形成,还在于所述产品可以通过挤塑而得到。本发明还涉及一种多孔复合产品的制造方法,其中包括:a)形成含有一种或几种不溶聚合物、一种或几种可溶或可煅烧聚合物、一种或几种填料的混合物;b)挤塑所述混合物,形成挤塑的产品前体;c)从所述挤塑的产品前体中除去一种或几种可溶和可煅烧的聚合物;d)回收多孔复合产品。本发明还涉及由特别是具有高比表面的多孔复合产品组成的各种挤塑制品。本发明最后涉及由多孔复合产品的膜形成的电极。
Description
本发明涉及多孔的,特别是呈膜状的,特别是高比表面的复合产品,以及制备这种产品的方法。
本发明还涉及实施所述方法的复合产品的前体。
本发明还涉及呈膜状多孔复合产品作为电化学装置组件中电极的应用,以及在包装或催化领域选择性膜作为高比表面、多孔复合产品的常见应用。
人们尤其是通过专利申请书EP-A-283 187已经对在第一种热塑性聚合物和第二种热塑性聚合物混合物熔融温度下通过挤塑然后借助于适当的溶剂除去第二种聚合物所得到的低密度多孔膜有所了解。这样的多孔膜可以应用于特别是过滤或分离之类不同应用领域。
专利申请书EP-A-430 439叙述了制备这种膜的改进的方法,其中第一种热塑性聚合物和第二种不相容的热塑性聚合物的混合物通过模具进行挤塑,然后借助于溶剂除去不相容的聚合物,该方法的特征在于,在模具的上游插入一个多孔的挡板,以得到一种多孔结构,它包括一个低孔隙率的纵向区和另一个较高孔隙率的纵向区。
另外我们知道可以在双层类型电容器中使用的可以充上较多电量或者放出该电量的可极化电极。
可以在超电容器中使用的可极化电极是基于轻而且具有大的交换表面的可完满地极化材料如作为高比表面,特别是大于1000m2/g碳质材料的活性炭。
对于具有最大功效的电极,它应该具有最大含量的有效质量,而且这部分质量要最容易到达。后一个性能意味着它具有开孔结构。比如活性织物电极就是这种情况:我们由粘胶基的织物或聚丙烯腈的织物,先碳化然后活化制造出活性炭的织物。
但是,这样的电极价格昂贵,厚度厚而且不均匀(一般超过300μm)。再有,尽管这样实施至少在理论上允许使用缠绕技术,但在实际上被证实这样的使用难以进行。
我们还可以通过烧结得到一种有效质量很高(一般高于98%)的电极。将活性炭和不同的添加剂,特别是黑色导电体与液体机械混合,直至得到一种悬浮液为止。将得到的溶液倒入部分抽真空的过滤壁上。在一定时间以后,各组分均匀地沉积在过滤壁上,这时液体通过此壁。该部分真空在各组分之间建立了内聚力,这相当于被压实。在该壁上回收的干材料就是电极。
但正如在前面所指出的,此技术具有许多缺点。特别是它很难适合于使用缠绕技术,电极的厚度、均匀性和规整性难以控制。再者,该方法在选择聚合物方面受到限制。特别是不能使用聚烯烃。
还可以将含碳的填料与含有少量比如3%聚四氟乙烯的聚合物粘接剂机械混合,直至得到很粘的膏状物为止,然后进行层合使其成片状,将此片用冲压刀切割制成电极。
此方法与上述实施方法具有同样的缺点。
还可以举出通过涂布制造的方法,在该方法中,将活性填料和一种或几种添加剂,比如聚合物粘接剂在溶剂中混合,直至得到粘度被控制的膏状物为止。将该膏状物涂布在支持片上,以后该支持片就是电流的集电极。将此片放入烘箱中蒸发掉溶剂。
该沉积物可以是较薄(直至几微米)且厚度均匀,有效质量含量高。
然而,由于该方法视具体情况而定使用可能有毒的溶剂,因此是一个难于实施的方法。
我们还知道呈薄膜,特别是聚烯烃薄膜状的电极可以使用缠绕技术。
这些可极化的电极基于含碳材料如高比表面,特别是大于1000m2/g的活性炭以及基于如聚烯烃,特别是聚乙烯、聚丙烯或其它聚合物如聚酯、聚碳酸酯、聚酰亚胺的粘接剂。
例如,曾经提出过使用聚乙烯或聚丙烯粘接剂和活性炭粉的可极化电极(见JP-A-22062/92)。
但是,基于如聚乙烯或聚丙烯粘接剂的可极化电极具有很低的孔隙率。
上面所举出的其它的粘接剂也具有这些现象。
文献BE-A-693 135叙述了一种多孔和整体上呈原纤维状,含有直至占其总重量98%导电填料如石墨或金属的聚四氟乙烯片。
这类结构是通过将聚四氟乙烯颗粒的水分散液和可提取的聚合物混合,然后烧结而得到的。此烧结过程包括一个导致聚四氟乙烯颗粒发生剪切变形并且将颗粒转化为伸长纤维网的关键步骤。然后进行挤塑,再以后除去可提取的聚合物。最终的结构具有大于0.1μm的孔隙。此片状物可以在燃料电池中用作电极。
日文文献JP-A-57100142的摘要叙述了多孔膜的制造方法,其中包括将15-60%(体积)的聚烯烃树脂、3-40%(体积)的聚醚、20-80%(体积)的细分散可提取粉末、0.5-10%(体积)的不溶粉末的混合物挤塑,然后提取出聚醚和可提取粉末。申请人证实,不可能使用在此文献中叙述的方法得到在含有高填料含量的同时其机械性能不会受到严重影响的片状物。
因此都希望制造由粘接剂和填料组成的、特别是具有高比表面、能够使用缠绕技术大量制造的多孔电极。
确切地说,本发明的目的是提出一种解决这种技术问题的方法。
本发明的目的之一是提供特别是具有高比表面的新型多孔复合产品。
本发明的另一个目的是提供特别是具有高比表面,高填料含量,能够使用缠绕技术的复合薄膜。
本发明的再一个目的是能够广泛地选择使用聚合物。
本发明的又一个目的是提供制造成本低廉的多孔复合产品或薄膜。
本发明的又一个目的是能够由挤塑技术得到各种形状的可以使用的产品,比如管材、线材、薄膜或其它的挤塑物品。
本发明的又一个目的是提供厚度薄、均匀的呈多孔薄膜状可充分极化而且具有很高有效质量含量的含碳电极。
本发明的又一个目的涉及该多孔复合产品作为选择性隔膜、包装膜、隔离膜的应用。
本发明首先涉及具有特别高比表面的多孔复合产品,其特征在于,它包括聚合材料和至少20%的一种或几种特别是高比表面的填料,所述产品易于通过挤塑的方法得到。
“产品”一词指的是一种组合体,其内聚力足以使其在无载体条件下保持其完整性。
明显地引人注意的是,本发明产品的初始结构表明在聚合材料中尤其是具有高比表面的填料分布非常均匀,其结构是连续的。此外,聚合材料呈非纤维状。
作为本发明产品的根本特征,申请人注意到,对于上述的填料含量,不具有足够均匀性的产品会导致机械性能不足。
“易于通过挤塑的方法得到”表明该复合产品具有挤塑产品的特征。
为了使“易于通过挤塑方法得到”的产品具有所需的均匀度,必须由尽可能均匀的混合物制造。可以由双螺杆挤塑机得到这种均匀的混合物。也可以使用其它适用的混合装置。
因此,涉及到与能够用前面叙述过的涂敷技术得到的产品存在本质区别的产品。
本发明多孔复合产品的根本特征优选是它具有高比表面。
通过在比如Jean Charpin和Bernard Rasneur的工程师技术出版物Pbis 45-1[《结构研究-比表面测量》中叙述的“BET”测量方法评价比表面。
本发明的多孔复合产品的比表面大于大约10m2/g,优选大于20m2/g,最好在20-100m2/g之间。
该产品的体积孔隙率大于5%。一般低于大约80%。
对于超电容器或蓄电池中的应用,孔隙率一般在15-50%之间。
其平均孔径一般小于1μm,按照一个优选方案,平均孔径小于0.5μm,优选小于0.1μm,最好小于0.02μm。
在特定的含氟聚烯烃的情况下,孔径一般小于0.5μm,特别是在聚四氟乙烯的情况下。
除了有比较高的BET比表面和机械性能以外,这些产品的明显特征是其电化学容量大于2F/g,优选大于10F/g。
在超容量电极的情况下,所需的孔隙率是中孔性的,在比利时专利693135中就是如此,该专利涉及用于“燃料电池”的电极,所需的孔隙应该是开孔(大孔)的,使得燃料流量较大。
在膜状多孔复合产品的情况下,注意到这些薄膜具有卓越的机械性能,这使得可以使用缠绕技术。一般说来,在室温下这些薄膜的拉伸断裂强度高于4MPa,优选高于6MPa。
在填料中,可以举出碳,如石墨、低比表面碳黑,金属氧化物、氧化硅、滑石等。
在一般用来制造这样的复合产品的高比表面填料中,可以特别举出高比表面的含碳材料、矿物颗粒和金属颗粒,比如阮内金属、稀土氧化物、多孔陶瓷、珍珠岩、沸石、粘土等。
对于含碳材料所需要的性能是单位重量的高表面积、低电阻、良好的电化学稳定性。
该含碳材料可以呈粉末形状,由比如石油沥青、酚醛树脂、椰子壳和其它的有机化合物得到。
活性炭特别是具有300-3000m2/g,优选大于1000m2/g的比表面积(BET)。
该聚合材料由不溶解于水性溶剂和/或有机溶剂并且保证该化合物(结构的聚合物或弹性体)的内聚力的弹性体或热塑性聚合物以及含有极性基团的存在于实施得到所述多孔产品或薄膜的制造方法以后的产品中的聚合物或热塑性弹性体形成。
在不溶性弹性体或聚合物当中,可以特别举出如聚丙烯、聚乙烯等聚烯烃、乙烯和丙烯的共聚物。这些聚烯烃可以是膜状产品,特别已知可作为包装膜。这涉及比如低密度或高密度聚乙烯,作为共聚物时它们可视具体情况而定含有或多或少的α-烯烃。
还可以涉及如聚醚嵌段聚酰胺的聚酰胺、聚酰亚胺、高乙烯单体含量的乙烯基共聚物如高乙烯单体含量聚乙烯醋酸乙烯共聚物、丙烯酸类共聚物、如聚苯乙烯的芳香族聚合物,比如苯乙烯-丁二烯共聚物、如聚偏氟乙烯的含氟聚合物、由属于上述单体之一形成的共聚物,比如偏氟乙烯和六氟丙烯的共聚物、偏氟乙烯和三氟乙烯的共聚物。
在溶剂中不溶的弹性体或热塑性聚合物优选自聚烯烃。
在可溶的聚合物当中,可以特别举出可以溶解于如下溶剂的聚合物:水、醇、二甲基甲酰胺、二甲基亚砜、四氢呋喃、丙酮。
当然除此以外,聚合度要适合于用溶剂除去,可溶的聚合物优选自如聚氧亚乙基、聚氧亚丙基的聚醚、如聚乙烯醇的多元醇、乙烯-乙烯基醇的共聚物。在这些聚合物中,特别举出其分子量为200,000-1,000,000的化合物,优选聚醚。
还可以举出能够按照通常方法煅烧的聚合物。
可煅烧的聚合物相当于在上述溶剂中可溶的聚合物,也可以选自其分解温度比结构聚合物或弹性体的分解温度低的聚合物,比如纤维素。
这些聚合物的选择可以用简单实验以本领域专业人员已知方式进行。
该复合产品优选含有至少20%(重量)的填料,优选30-90%,更优选50-85%。
该复合产品优选含有10-40%的不溶于含水和/或有机溶剂的聚合物或热塑性弹性体,以及5-40%的可溶于水和/或有机溶剂的聚合物。
该复合产品还优选含有:
-10-40%的聚烯烃,
-5-40%的聚醚,
-填料适量到100%。
本发明多孔复合产品的其他特征在于,它具有均匀和规则的形状,这就是说,填料与聚合材料紧密地混合,这与比如通过涂布含碳填料与少量聚四氟乙烯型聚合物粘接剂的混合物得到的片状物是不同的。
本发明的复合产品可以呈薄膜状,其优点是可以按照缠绕技术来使用。
这些薄膜避免使用载体。
本发明还涉及如上所述的复合产品的制造方法,该方法的特征在于:
a)制成含有一种或几种不溶性聚合物、一种或几种可溶的或可煅烧的聚合物、一种或几种高比表面填料的混合物,
b)将该混合物挤塑,形成挤塑的产品前体,
c)从此挤塑的产品前体中除去一种或几种可溶的或可煅烧的聚合物,
d)回收多孔复合产品。
因此所述的方法是一种能够得到具有高比表面多孔复合产品的挤塑-消除方法。
“消除”指的是除去大部分可溶的或可煅烧的聚合物,以形成孔隙,条件是尤其是因为这些聚合物与活性炭有亲合性,因而不易被完全除去。
在本方法的步骤a)中,均匀地混合,以便使各个组分成为溶液或分散液,这些组分就是对应于形成该复合产品结构的聚合材料的一种或几种在溶剂中不溶的聚合物、另一种或几种在溶剂中可溶的或可煅烧的聚合物,以及一种或几种具有高比表面的填料,条件是能够保证该复合产品具有内聚力的聚合物(不溶的聚合物)和具有高比表面的填料在步骤c)不被除去。也可以借助于可以实施步骤b)的挤塑机来进行此混合。
在将要在步骤c)中除去的可溶性聚合物当中,可以选择能够按照步骤a)被混合的各种可溶性聚合物,可以特别举出在比如水、醇、二甲基甲酰胺、二甲基亚砜、四氢呋喃和丙酮中溶解的聚合物。
当然除此以外,聚合度要适合于用溶剂除去,该可溶性聚合物特别选自如聚氧亚乙基、聚氧亚丙基的聚醚、如聚乙烯醇的多元醇、乙烯-乙烯基醇的共聚物。
作为能够被除去而形成孔隙的聚合物,也可以举出能够按照通常的方法进行煅烧的聚合物。
该可煅烧的聚合物可以选自其分解温度低于结构聚合物或弹性体的分解温度的聚合物,比如纤维素。
这些聚合物的选择可以用简单实验以本领域专业人员已知方式进行。
该产品不同的组分的混合是在适当的温度下,特别借助于挤塑机进行的。在此情况下,同时进行步骤a)和步骤b),给出具有很小BET比表面(低于约1m2/g)的中间产品前体。
该产品前体可以重新挤塑成为膜的形状,特别是其厚度小于大约300μm的薄膜。
因此,按照一个优选的实施方案,步骤b)按两步实施:
-第一步挤塑(i),包括形成颗粒,
-第二步挤塑(ii),包括形成膜。
第一步优选在一个具有比如线材模头的同向转动的双螺杆挤塑机中进行,而第二步优选在一个具有片状模头的单螺杆挤塑机中进行。
然后将呈颗粒状或膜状的挤塑产品前体进行步骤c)以便除去可溶性聚合物。
此消除步骤可以特别通过使可溶聚合物与适当溶剂接触进而将其溶解来实现。
也可以按照已知的方法进行煅烧,这包括慢慢地将温度升至该有待消除的聚合物的分解温度。
然后回收该产品,它具有的BET比表面大于大约10m2/g,优选大于大约20m2/g。
因此,本发明的再一个目的是一种由聚合材料和一种或几种高比表面填料形成的具有高比表面的多孔复合产品,其特征在于,它可以通过如上所述的挤塑-消除方法得到。
本发明的又一个目的是在消除步骤前得到的产品前体,此产品前体特别可用于实施上述的方法,它包括一种或几种在溶剂中不溶的聚合物、一种或几种另外的可溶于溶剂或可煅烧的聚合物和一种或几种具有高比表面的填料。
不溶聚合物/可溶或可煅烧聚合物的重量比优选0.1-5,更优选0.1-2。
在可形成该产品前体的不含溶剂的混合物中,具有高比表面的填料的含量在20-60%(重量)。
本发明还涉及由本发明的高比表面多孔复合产品形成的膜状电极。
一般说来,此多孔膜状电极可用于制造如蓄电池、双层电容或超电容器的电化学装置。
由两个可极化电极和一个浸有电解液的分隔层按照已知的方式形成超电容器。还用双电解层电容器来说明这些装置。
本发明的电极特别是通过能够得到很高的有效质量含量显著地改善了膜的容量。
特别举出了如下的应用领域:
-电化学储能用的多孔电极,被用于例如电化学发电器、氧化还原蓄电池、空气蓄电池、双层电容器或电化学超电容器、燃料电池等。
-电渗析方法使用的多孔电极,被用于例如制造饮用水、由海水制盐、有机化合物(乳清、奶、葡萄酒等)脱除矿物质、饮用水脱盐、锅炉水软化、核反应中心的流出物去污染。
-电容去离子化方法中使用的多孔电极,被用于例如制造饮用水、由海水制盐、有机化合物(乳清、奶、葡萄酒等)脱除矿物质、饮用水脱盐、锅炉水软化、核反应中心的流出物去污染。
-电解方法中使用的多孔电极,被用于例如制造氯气和氢氧化钠、电解水、由盐制造酸和碱。
-渗析和电渗析方法中使用的电透膜,被用于例如制造饮用水、由海水制盐、有机化合物(乳清、奶、葡萄酒等)脱除矿物质、饮用水脱盐、锅炉水软化、核反应中心的流出物去污染。
-过滤方法中使用的电透膜,被用于例如有机化合物选择性电过滤、微量过滤等。
本发明还涉及这些呈颗粒状或膜状复合产品的应用:
-在过滤和吸附的方法中,比如气体或液体环境的脱湿、选择性吸附(物理吸附和/或化学吸附)、分子筛、污染空气过滤等,
-用于催化剂,
-用于能量交换,比如热绝缘或隔音、换热器等,
-包装,特别是需要选择性渗透性的易碎产品的包装。
下面以说明性实施例来说明本发明:
实施例1
各原料化合物(粉末)的质量分数如下:
-活性炭40%(比表面1250m2/g)
-乙烯-丙烯共聚物20%
-聚氧亚乙基40%(POE300,000)
借助长度为40D,具有两个混合区和三个传送区的同转向双螺杆挤塑机将粉末状的各个组分尽可能均匀地混合。使用的机器是直径58mm的双螺杆,温度分布曲线如下:
50/120/120/110/110/100/100/120/120/150/170℃
模头压力:8MPa
转速:85转/min
流量:34kg/hr
将得到的颗粒加入到长度30D的单螺杆中进行第一次挤塑,使用的机器是直径30mm的双螺杆,温度分布曲线如下:
165/170/170/170/185℃
模头压力:8MPa
转速:10转/min
流量:2kg/hr
得到的膜厚度为200μm。
下面的步骤包括将得到的膜浸入环境温度的水中5分钟。随后在40℃下将膜干燥1小时。
处理以后各化合物的平均含量是:
-活性炭52%重量
-乙烯-丙烯共聚物26%重量
-聚氧亚乙基22%重量
可以在金属化机器中,在处理前或处理后在约0.01Pa(10-4mbar)的压力下将得到的薄膜用铝金属化(比如0.5Ω/□)。
得到的金属化或未金属化薄膜的物理特征导致如下的数据:
-断裂伸长率(见下面的表)
-缠绕强度(直径6mm的芯上):0.05g/μm/mm。
-电极的电化学容量26F/g,(通过超电容器放电曲线的斜率测量,用强静电模式)
-由挤塑机中出来的膜的BET比表面小于1m2/g,在按照在大约5分钟的时间内浸渍电极方法通过水以后,膜的BET比表面为28m2/g。
实施例2
各原料化合物(粉末)的质量分数如下:
-活性炭40%(比表面1250m2/g)
-乙烯-丙烯共聚物10%
-聚氧亚乙基50%(POE300,000)
借助于长度为25D,具有两个混合区和三个传送区的同转向双螺杆挤塑机将粉末状的各个组分尽可能均匀地混合。使用的机器是直径19mm的双螺杆,温度分布曲线如下:
160/170/180/190/200℃
模头压力:10.5MPa
转速:400转/min
流量:1.8kg/hr
将得到的颗粒加入到长度30D的单螺杆中进行第一次挤塑,使用的机器是直径30mm的双螺杆,温度分布曲线如下:
160/170/180/190/220℃
模头压力:17.5MPa
转速:15转/min
流量:2.5kg/hr。得到的膜厚度为180μm。
下面的步骤包括将得到的膜浸入环境温度的水中5分钟。随后在40℃下将膜干燥1小时。
处理以后各化合物的平均重量含量是:
-活性炭60%
-乙烯-丙烯共聚物15%
-聚氧亚乙基25%
可以在金属化机器中,在0.01Pa(10-4mbar)的压力下将得到的薄膜用铝金属化(比如0.5Ω/□)。
得到的金属化或未金属化薄膜的物理特征导致如下的数据:
-断裂伸长率(见下面的表)
-缠绕强度(直径6mm的芯上):0.05g/μm/mm。
-按照在实施例1中叙述的方法,电极的电化学容量为26F/g。
-由挤塑机中出来的膜的BET比表面小于1m2/g,在按照在实施例1中叙述的方法通过水以后,膜的BET比表面为60m2/g。
得到的膜的机械特征的测量
实施例3各原料化合物(粉末)的质量分数如下:-活性炭40%(比表面1250m2/g)-乙烯-丙烯共聚物20%-聚氧亚乙基40%(POE300,000)
温度 | 膜 | 断裂伸长率(%) | 弹性模量(Dn/mm2) | 力(MPa) |
20℃ | 实施例1 | 0.97 | 134 | 8.3 |
20℃ | 实施例2 | 0.89 | 170 | 9.3 |
40℃ | 实施例1 | 1.14 | 88 | 6.1 |
40℃ | 实施例2 | 1.20 | 125 | 7.2 |
60℃ | 实施例1 | 5.73 | 22 | 2.0 |
60℃ | 实施例2 | 1.68 | 30 | 2.6 |
借助于长度为40D,具有两个混合区和三个传送区的同转向双螺杆挤塑机将粉末状的各个组分尽可能均匀地混合。使用的机器是直径58mm的双螺杆,温度分布曲线如下:
50/120/120/110/110/100/100/120/120/150/170℃
模头压力:8MPa
转速:85转/min
流量:34kg/hr
下面的步骤包括在环境温度的水中浸渍得到的颗粒(2mm2/mm)5分钟。随后在40℃下将膜干燥1小时。
处理以后各化合物的平均重量含量是:
-活性炭60%
-乙烯-丙烯共聚物15%
-聚氧亚乙基25%
得到的颗粒具有30m2/g的可展曲面。
Claims (19)
1.具备均匀结构的多孔复合产品,其特征在于由聚合材料和至少20%一种或多种填料形成,所述产品可以通过挤塑得到。
2.按照权利要求1的多孔复合产品,其特征在于具有高比表面。
3.按照权利要求1的复合产品,其特征在于孔的平均直径小于0.5μm。
4.按照权利要求1的复合产品,其特征在于该聚合材料包括的弹性体或聚合物选自视具体情况而定被氟取代的聚烯烃、丙烯酸类聚合物、芳族聚合物、聚酰胺、聚酰亚胺、高乙烯基单体含量的乙烯基聚合物以及视具体情况而存在的可溶于在实施该制备方法以后存在的有机极性溶剂或水中的热塑性聚合物或弹性体。
5.按照权利要求4的复合产品,其特征在于该聚合材料包括的弹性体或聚合物选自聚乙烯、聚丙烯、乙烯-α-烯烃共聚物以及视具体情况而存在的可溶于在实施该制备方法以后存在的极性有机溶剂或水中的热塑性聚合物或弹性体。
6.按照权利要求4或5的复合产品,其特征在于可溶于在实施该制备方法以后存在的极性有机溶剂或水中的热塑性弹性体选自聚醚、聚乙烯醇、乙烯-乙烯基醇共聚物。
7.按照权利要求6的复合产品,其特征在于可溶于在实施该制备方法以后存在的极性有机溶剂或水中的热塑性弹性体是分子量为200,000-1,000,000的聚醚。
8.按照权利要求6的复合产品,其特征在于该复合产品包括:
-10-40%聚烯烃
-5-40%聚醚
-填料,适量至100%。
9.按照权利要求1的复合产品,其特征在于该填料选自具有高比表面的填料。
10.按照权利要求9的复合产品,其特征在于所述填料包括活性炭、无机颗粒或金属颗粒。
11.按照权利要求9或10的复合产品,其特征在于该填料具有的比表面为300-3000m2/g。
12.按照权利要求1的复合产品,其特征在于含有30-85%(重量)填料。
13.按照权利要求12的复合产品,其特征在于含有50-85%(重量)填料。
14.按照权利要求1的复合产品,其特征在于它具有的BET比表面大于10m2/g。
15.按照权利要求14的复合产品,其特征在于它具有的BET比表面大于20m2/g。
16.按照权利要求1的复合产品,其特征在于它呈膜状。
17.按照权利要求16的复合产品,其特征在于该膜状产品的断裂拉伸强度大于4MPa。
18.按照权利要求17的复合产品,其特征在于所述产品的断裂拉伸强度大于6MPa。
19.按照权利要求1的复合产品,其特征在于它呈颗粒形状。
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AU6105898A (en) | 1998-08-26 |
EP0960154B1 (fr) | 2003-01-15 |
CA2295841A1 (fr) | 1998-08-13 |
JP5085581B2 (ja) | 2012-11-28 |
JP2001511825A (ja) | 2001-08-14 |
US20030175494A1 (en) | 2003-09-18 |
US6962745B2 (en) | 2005-11-08 |
AU749708B2 (en) | 2002-07-04 |
EP0960154A1 (fr) | 1999-12-01 |
WO1998034977A1 (fr) | 1998-08-13 |
ATE231173T1 (de) | 2003-02-15 |
US6702965B2 (en) | 2004-03-09 |
CA2295841C (fr) | 2007-09-25 |
US20020136887A1 (en) | 2002-09-26 |
FR2759087A1 (fr) | 1998-08-07 |
DE69810752D1 (de) | 2003-02-20 |
CN1341679A (zh) | 2002-03-27 |
ES2192321T3 (es) | 2003-10-01 |
CN1246877A (zh) | 2000-03-08 |
DE69810752T2 (de) | 2003-11-13 |
JP2009197227A (ja) | 2009-09-03 |
US7384686B2 (en) | 2008-06-10 |
FR2759087B1 (fr) | 1999-07-30 |
CN1341679B (zh) | 2010-04-28 |
HK1026443A1 (en) | 2000-12-15 |
JP4884576B2 (ja) | 2012-02-29 |
US20030157314A1 (en) | 2003-08-21 |
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