CN1293692B - 聚烯烃纳米复合材料 - Google Patents

聚烯烃纳米复合材料 Download PDF

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CN1293692B
CN1293692B CN998040371A CN99804037A CN1293692B CN 1293692 B CN1293692 B CN 1293692B CN 998040371 A CN998040371 A CN 998040371A CN 99804037 A CN99804037 A CN 99804037A CN 1293692 B CN1293692 B CN 1293692B
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M·亚历山大
P·G·杜波依斯
R·J·E·G·杰罗姆
M·加西亚-马蒂
孙韬
J·M·加西斯
D·M·米拉
A·库珀曼
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Abstract

本发明公开了一种为衍生自层状金属氧化物或金属氧化物盐的纳米填料粒子的分散体的纳米复合材料。该纳米复合材料优选通过下述方法制备，即首先在水中使未处理的粘土溶胀，然后除去水，形成可在非极性有机溶剂中分散的亲有机物质的粘土。然后用烷基铝氧烷处理该亲有机物质的粘土，随后用催化剂处理，形成可促进烯烃或苯乙烯类聚合以及薄片分散的复合物。该纳米复合材料可在纳米填料粒子不受剪切作用、不用进行离子交换步骤、不需要向聚烯烃或聚苯乙烯中掺入极性取代物的条件下通过烯烃或苯乙烯的原位聚合直接制得。

Description

聚烯烃纳米复合材料
本发明涉及薄片(platelet)粒子在聚烯烃基质中的分散体，特别是通过聚烯烃的原位聚合制备的分散体。
为至少一个方向小于20nm的粒子在连续聚合物基质中的分散体的纳米复合材料(nanocomposite)与通常的玻璃或矿物增强的填充聚合物相比，可以以低得多的粒子含量赋予聚合物物理性能的提高。纳米复合材料公开于U.S.P.4739007；4618528；4528235；4874728；4889885；4810734；5385776和5578672，以及WO 93/11190中。
通常，这些纳米复合材料可以两步法合成。在第一步中，通常通过用有机阳离子如烷基硅酸铵或适当官能化的有机硅烷离子交换碱金属或碱土金属离子(存在于天然形式的云母型硅酸盐中)，对粘土或层状硅酸盐进行改性。这一改性步骤使通常亲水性的云母型硅酸盐能亲有机物质；同时使在邻近硅酸盐层之间的层间距增加，从而提高了改性粒子在聚合物基质中的分散性。在第二步中，可熔融加工的聚合物与亲有机物质的粒子在高剪切作用下相容，形成物理性能提高的聚合物。或者是，原位生成的聚合物可以与亲有机物质的粒子中的官能团反应。
通常，相对非极性的聚合物如聚烯烃需要进行共聚合或接枝上极性取代物如马来酸酐，以促进多层粒子的剥落(参见《大分子》，Vol.30，p.6333(1997))。不进行这样的改性，所得的复合材料将不具有提高的物理性能。
如现有技术所述的改性粘土在极性取代的聚烯烃中的复合材料存在许多缺点。首先，离子交换步骤费用高、耗时，并且可能引入使最终复合材料物理性能降低的化学物质。第二，聚合物的改性增加了不期望的成本，并且可能因氧加入到聚合物中而生成更容易降解的聚烯烃。第三，高剪切的使用可导致不期望的聚合物降解。
基于这些缺点，期望制备不需要粘土的预处理或聚合物的改性或高剪切加工的聚烯烃或聚苯乙烯纳米复合材料。
本发明通过提供含有原位制备的聚烯烃的纳米复合材料而克服了上述缺点，其中聚烯烃中分散有衍生自金属层状氧化物或金属氧化物盐的纳米填料粒子。
本发明的第二方面内容是一种制备纳米复合材料的方法，该方法包括下述步骤：
(a)将亲水性粘土分散在水中，以使粘土溶胀；
(b)从溶胀的粘土中除去水，制得亲有机物质的粘土；
(c)在对亲有机物质的粘土为惰性的溶剂和烷基铝氧烷的存在下，使亲有机物质的粘土与烷基铝氧烷接触，以形成粘土/烷基铝氧烷复合物；
(d)使该复合物与可促进烯烃聚合的催化剂相接触，以形成粘土/甲基铝氧烷/催化剂复合物；和
(e)在聚合条件下使步骤(d)的复合物与烯烃或苯乙烯单体接触，形成纳米复合材料。
上述方法还包括在步骤(e)中加入一种链转移剂，该链转移剂为氢气。
本发明的第三方面内容是一种制备纳米复合材料的方法，该方法包括下述步骤：
(a)将亲水性蒙脱石粘土分散在水中，以使粘土溶胀；
(b)通过冷冻干燥从溶胀的粘土中除去水，制得亲有机物质的粘土；
(c)在对亲有机物质的粘土为惰性的溶剂和甲基铝氧烷的存在下，使冷冻干燥的亲有机物质的粘土与过量的甲基铝氧烷接触，以形成粘土/甲基铝氧烷复合物；
(d)从该复合物中除去溶剂和过量的甲基铝氧烷；
(e)在非极性惰性溶剂的存在下，使步骤(d)的复合物与金属茂或Ziegler-Natta催化剂相接触，以形成粘土/甲基铝氧烷/催化剂复合物；和
(f)在聚合条件下使步骤(e)的复合物与乙烯或丙烯接触，形成纳米复合材料。
上述方法还包括在步骤(f)中加入一种链转移剂，该链转移剂为氢气。
本发明提供一种制备具有改进物理性能的聚烯烃纳米复合材料的方式，它不需要离子交换步骤或极性基团改性的聚合物。而且，该聚烯烃纳米复合材料可在无剪切作用下制备。
有利地，本发明的聚烯烃纳米复合材料是这样制备的，即首先在使粒子溶胀的条件下将多层粒子分散入水中。这些多层粒子优选为蒙脱石粘土，如蒙脱石、钠蒙脱石、锂蒙脱石、皂石、锌蒙脱石和蛭石，或层状硅酸盐如麦羟硅钠石和水羟硅钠石。其它适用的多层粒子包括伊利石矿物和层状磷酸铝或锆，以及上述多层粒子的混合物。
首先通过在水中，优选热的去离子水中使粒子溶胀，形成凝胶状浆料而使亲水性多层粒子具有亲有机物质性。可优选对浆料进行离心或滗析，并除去任何在从浆料中除去水之前形成的沉淀物。
可例如通过冷冻干燥、减压蒸馏或常压蒸馏，或结合使用这些方法除去水。然后优选地，将脱水的多层材料分散在非极性惰性溶剂如戊烷、己烷、庚烷、辛烷和甲苯中，优选其浓度以溶剂和处理的粘土重量计小于10重量％。
然后在非极性惰性溶剂中将烷基铝氧烷，优选甲基铝氧烷(MAO)，与通常为基本上无水溶液形式的脱水粘土的分散体混合，形成MAO/处理的粘土复合物。相对于脱水粘土中的MAO活性点，优选化学计量过量地加入MAO。由于期望尽可能地除去任何未反应的MAO，因此优选汽提溶液以除去溶剂，并优选对所得的固体用MAO的溶剂进行洗涤，溶剂例如为甲苯或二甲苯，以基本上除去所有的未反应MAO。这里所用术语“未反应的MAO”是指可以通过溶剂洗涤而从固体复合物上除去的MAO。
然后优选将基本上无未反应MAO的MAO/脱水粘土复合物连同可促进α-烯烃或苯乙烯聚合的催化剂一起重新分散在溶剂中。这些催化剂包括Ziegler-Natta催化剂、金属茂催化剂和单环戊二烯基配合物、双环戊二烯基配合物、柄型金属茂和茚基-芴基取代的金属茂，如本领域公知的那些(参见USP 3645922；5064802；5374696和5470993)。然后在聚合条件下使MAO/脱水粘土复合物/催化剂分散体与一种α-烯烃、α，ω-二烯烃、非共轭的α-内双键二烯烃或苯乙烯单体接触，以形成聚烯烃或聚
苯乙烯纳米复合材料。适宜的单体和/或共聚单体的实例包括乙烯、丙烯、1-丁烯、4-甲基-1-戊烯、1-己烯、1-辛烯、1-癸烯、苯乙烯、乙烯-丙烯-二烯烃单体、1，4-己二烯、1，5-己二烯、1，7-辛二烯、1，9-癸二烯、二聚环戊二烯、亚乙基降冰片烯，以及其混合物。该复合材料含有分散在聚合物基质内的纳米填料粒子。
优选聚烯烃基本上不含极性取代基，更优选不含极性取代基。这里所用的术语“极性取代基”是指任何可增加聚烯烃或聚苯乙烯极性的取代基。这些取代基的实例包括羧酸基团、酸酐基团、甲硅烷基和羟基。这里所用的术语“基本上无”是指基于聚合物的重量，小于约1％，更优选小于约0.1％，最优选小于约0.01％。
聚合物基质中分散粒子的浓度优选不大于约10体积％，更优选不大于约5体积％，并优选不小于约0.5体积％，更优选不小于约1体积％。
本发明的聚烯烃纳米复合材料与通常的聚烯烃相比具有提高的性能，如屈服应力或断裂应力。这些性能的提高可使复合材料用于制备模塑部件。
下述实施例仅是说明性的，而并不有意要限制本发明的范围。
实施例1
80℃下在烧瓶中将蒙脱石(40g，Crook County，Wyoming，USA)与去离子水(1升)一起搅拌2小时。将所得的凝胶状浆料在2000rpm下进行30分钟离心处理。将离心过程中形成的沉淀物除去，并将滤液分装入两个1升的烧瓶中，并将这两个烧瓶放入Labconco冷冻干燥机8(Labconco Corporation，Kansas City，MO)中，在真空下除去水。从冷冻的滤液中除去水后，得到蓬松的白色固体。
将所得固体的一部分(2.5g)在真空下于105℃进一步脱气过夜。搅拌下并且不暴露于空气，将脱气的固体分散在300ml新蒸馏并干燥的庚烷中。将MAO的甲苯溶液(Witco，Corporation，25ml，1.65M的溶液)放置在烧瓶中并加热至50℃，以蒸发掉甲苯和残余的三甲基铝。将所得的干燥MAO重新溶解在25ml新干燥的甲苯中。搅拌下于50℃，将MAO溶液转移至冷冻干燥的粘土/庚烷浆料中。连续加热1小时，由此在真空下于50℃除去溶剂。将所得的粉末加热至150℃持续2小时，然后冷却至室温。用新干燥的甲苯洗涤该粉末三次(80℃，3×150ml)，以除去过量的MAO，并在搅拌下分散在新干燥的庚烷(250ml)中。
将一部分MAO/脱水粘土/庚烷浆料(100ml)转移至200ml圆底烧瓶中并在搅拌下加热至80℃。然后将催化剂(叔丁基氨基(amido))二甲基(四甲基-η5-环戊二烯基)硅烷二甲基钛(The Dow ChemicalCompany，4.55×10-3M庚烷溶液，1ml)加入到该浆料中，形成黄色的浆料(即认为是活化的粘土催化剂浆料)。将该浆料在80℃下陈化1小时，然后转移至火焰干燥的200ml圆底烧瓶中，以进行乙烯的聚合。
在70℃、172kPa(1.7大气压或25磅/平方英寸表压)的压力下，将乙烯加入到活化的粘土催化剂浆料中。用导热流量计监测乙烯的消耗量。在聚合过程中，聚合物负载的粘土粒子很好地分散在反应溶剂中，未观察到复合物沉淀。反应6小时后除去溶剂，得到35g呈自由流动粉末状的聚乙烯-粘土填料复合材料。将该粉末压制成圆盘状，然后再压制成对可见光透明的膜。该粘土填充的复合材料的扫描透射电子显微镜照片显示，纳米级的粘土粒子均匀地分散在聚乙烯基质内。
实施例2
重复实施例1的步骤，其中多处不同列于下表1中。
表I
  样品   填料   状态   填料质量<sup>a)</sup>(g)   MAO10<sup>-3</sup>摩尔   催化剂10<sup>-6</sup>摩尔   Al/Ti起始比   填料添加量(wt％)
  LD-21   ma   未煅烧   0.5   8.25   2.6   3170   -
  样品   填料   状态   填料质量<sup>a)</sup>(g)   MAO10<sup>-3</sup>摩尔   催化剂10<sup>-6</sup>摩尔   Al/Ti起始比   填料添加量(wt％)
  LD-22   ma   未煅烧   0.5   8.25   5.21   1580   -
  LD-23   mo   煅烧   0.5   8.25   2.6   3170   -
  LD-25   无   -   -   24.75   15.63   1580   0
  LD-26   h   未煅烧   3   33   15.63   2110   4.2
  LD-27   mo   未煅烧   2.44   27.22   12.5   2180   3.3
  LD-29   h   未煅烧   2.55   19.8   13.66   1450   3.8
  LD-31   h   未煅烧   2.55   19.8   13.66   1450   4.0
  LD-32   mo   未煅烧   2.55   19.8   13.66   1450   3.9
  LD-33   mo   未煅烧   2.55   19.8   13.66   1450   4.1
  LD-34   h   未煅烧   2   15.5   10.63   1450   18.2
  LD-35   k   煅烧   3.05   23.76   16.19   1470   2.3
  LD-36   h   未煅烧   3.06   23.76   16.19   1470   3.4
  LD-36A   h   未煅烧   3.06   23.76   16.19   1470   -
  LD-36B   h   未煅烧   3.06   23.76   16.19   1470   -
  LD-36C   h   未煅烧   3.06   23.76   30.75   770   4.5
  LD-36D   h   未煅烧   3.06   23.76   30.75   770   13.0
  LD-36E   h   未煅烧   3.06   23.76   30.75   770   2.8
  LD-36F   h   未煅烧   3.06   33   30.75   1075   11.4
  LD-37   ma1   未煅烧   3.06   23.76   30.75   770   4.6
  LD-38   ma2   未煅烧   3.06   16.5   30.75   535   -
k＝高岭土，h＝锂蒙脱石，mo＝蒙脱石，ma＝麦羟硅钠石(第一批)，ma1＝麦羟硅钠石(Na+H+)，ma2＝麦羟硅钠石(H+)
a)干燥前的起始重量
在样品LD-36至LD-38的聚合过程中，加入0.3巴的H2
应当指出的是，样品LD-35为微米级复合材料”，严格地说不是“纳米复合材料”。还应当指出的是，样品LD-25不是“纳米复合材料”，而是一个对照物，即没有添加填料。在样品LD-36至LD-38的聚合过程中，加入了氢气。氢气的加入通过链转移降低了聚合物的分子量，即氢气为链转移剂，从本发明广泛的意义上来说，可使用任何适宜的链转移剂。表II列出了表I中多数样品聚合中的催化剂活性，活性表示为所用每克催化剂制得的聚合物的千克数。
表II
  纳米复合材料   活性   纳米复合材料   活性
  LD25(HDPE)   50   LD35(高岭土)   89
  LD26(锂蒙脱石)   5.19   LD36(锂蒙脱石)   49.4
  LD27(蒙脱石)   164.7   LD36C(锂蒙脱石)   40.9
  LD29(锂蒙脱石)   129.5   LD36D(锂蒙脱石)   21.6
  LD31(锂蒙脱石)   108.0   LD36E(锂蒙脱石)   56.9
  LD32(蒙脱石)   178.0   LD36F(锂蒙脱石)   ＜7.4
  LD33(蒙脱石)   102.4   LD37(麦羟硅钠石Na<sup>+</sup>/H<sup>+</sup>)   145.3
表III列出了许多表I样品在每分钟1.25的应变速率下的各种拉伸测试。表III中的数据显示，添加氢气聚合所得的样品具有令人惊奇的高模量和高断裂应变组合。
表III
Figure G998040371D00081

Claims (8)

1.一种制备复合材料的方法，该方法包括下述步骤：
(a)将亲水性粘土分散在水中，以使粘土溶胀；
(b)从溶胀的粘土中除去水，制得亲有机物质的粘土；
(c)在对亲有机物质的粘土为惰性的溶剂和烷基铝氧烷的存在下，使亲有机物质的粘土与烷基铝氧烷接触，以形成粘土/烷基铝氧烷复合物；
(d)使该复合物与可促进烯烃聚合的催化剂相接触，以形成粘土/烷基铝氧烷/催化剂复合物；和
(e)在聚合条件下使步骤(d)的复合物与烯烃单体接触，形成复合材料。
2.根据权利要求1所述的方法，其中粘土为钠蒙脱石、皂石或锂蒙脱石。
3.根据权利要求1或2所述的方法，其中通过冷冻干燥除去水。
4.根据权利要求1或2所述的方法，其中催化剂为齐格勒-纳塔催化剂或金属茂催化剂。
5.根据权利要求1所述的方法，其中：
在步骤(a)中，所述亲水性粘土是含有碱金属或碱土金属阳离子的亲水性蒙脱石粘土；
在步骤(b)中，通过冷冻干燥从溶胀的粘土中除去水；
在步骤(c)中，使亲有机物质的粘土与过量的甲基铝氧烷接触；
该方法进一步包括以下步骤：
c1)从复合物中除去溶剂和过量的甲基铝氧烷；
在步骤(d)中，在非极性惰性溶剂存在下，使步骤c1)的复合物与金属茂或齐格勒-纳塔催化剂接触；和
在步骤(e)中，所述烯烃单体是乙烯或丙烯。
6.根据权利要求5所述的方法，其中蒙脱石粘土为钠蒙脱石。
7.根据权利要求1、2、5或6任一项所述的方法，还包括在步骤(e)中加入一种链转移剂。
8.根据权利要求7所述的方法，其中链转移剂为氢气。
CN998040371A 1998-03-16 1999-03-16 聚烯烃纳米复合材料 Expired - Lifetime CN1293692B (zh)

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CA2323667A1 (en) 1999-09-23
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