CN102712714A - 超高分子量聚乙烯 - Google Patents

超高分子量聚乙烯 Download PDF

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CN102712714A
CN102712714A CN2011800067294A CN201180006729A CN102712714A CN 102712714 A CN102712714 A CN 102712714A CN 2011800067294 A CN2011800067294 A CN 2011800067294A CN 201180006729 A CN201180006729 A CN 201180006729A CN 102712714 A CN102712714 A CN 102712714A
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L.卢克索瓦
L.克林
S.米汉
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Basell Polyolefine GmbH
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Abstract

本发明设计一种显示极佳耐磨强度等性质的新的UHMW聚乙烯材料。

Description

超高分子量聚乙烯
本发明涉及一种新的超高分子量聚乙烯。新聚合物由于其高耐磨强度而显示优越性。
超高分子量聚乙烯(UHMW-PE)是一类主要包含乙烯单元的线型聚合物的常用名称，其中聚合物具有约1-1.5·106g/mol或甚至更高的重均分子量。这些聚合物由于它们的高冲击强度和高耐磨强度在本领域熟知，这使它们使用优良，因为较低分子量聚乙烯由于不良的机械性质而不太适用。尤其是，超高分子量聚乙烯可用于制造齿轮、轴承、导轨和输送机中的滑床(slider bed)及其它类似制品。实际上，UHMWPE是所有塑料中最坚韧的。在工业标准磨损试验中，UHMWPE可显示碳钢耐磨强度的大约10倍。那是最坚韧弹性体——聚氨酯的3倍，也是硬氯丁二烯橡胶的大约80倍。当然，UHMWPE是刚性的硬材料。显示最高耐磨强度的那些等级未发现可由标准挤出设备加工，而需要特殊技术(柱塞挤出)。对PE的标准分析也不再适用于那些极刚性、高耐磨UHMWPE等级。例如，用于分析PE质量分布的在三氯苯中的高温GPC分析不再适用于所述UHMWPE等级。
超高分子量聚乙烯描述于US 3,882,096。此现有技术参考文献描述了一种混合铬/钛催化剂，和在它的存在下在常用聚合条件下制备聚合物。该参考文献描述的聚合物具有最多3·106g/mol的分子量。
WO98/20054描述了一种气相流化床聚合方法，和在置于热活化二氧化硅载体材料上的铬茂催化剂存在下制备超高分子量聚乙烯。按那种聚合制备的聚乙烯具有0.929-0.936g/cm3的密度和0.7-1mm的平均粒径。
数种其它公布，如EP-A-0 645 403，描述在齐格勒催化剂存在下制备的超高分子量聚乙烯。由此制备的聚合物具有约0.2mm或更小的平均粒径和350-460g/l的容积密度。
现有技术有将可观的耐磨强度与其它性质组合的问题，所述其它性质如反应器产物的平均粒度、耐冲击强度或可达到的密度范围。
本发明的目的是设计一种大约中密度的新UHMW-PE，其具有优良耐磨强度，优选与优良沙尔皮耐冲击强度组合。另外，由于它的受限制的加工性，在离开反应器时，产物应具有足够的平均粒度，此方面分别紧密联系于所用催化剂的具体生产能力和其中可行的反应器操作的模式。
通过用两种不同的金属茂类型催化剂产生UHMW PE作为反应器掺合物，和产生因此包含适合的双金属催化剂残余物的新PE，解决了这一问题。
根据本发明，本发明设计了一种聚乙烯，所述聚乙烯具有<1g/10min的HLMI(在21.6kg/190℃)，0.925-0.940g/cm3的密度，优选0.928-0.938g/cm3，最优选0.930-0.936g/cm3，并且所述聚乙烯具有根据ISO 11542-2:1998测量>150kJ/m2的沙尔皮耐冲击强度，具有根据ISO 15527:2007用Al2O3作为试验磨料测量<1.1指数单位的耐磨强度，如实验部分进一步描述。耐磨强度的精确试验条件在实验部分给出。所述聚乙烯进一步包含Hf和Cr两者作为催化剂残余物，优选其条件为Cr催化剂不以氧化形式包含在聚乙烯中。由于其它考虑，后者排除菲利普催化剂的催化剂残余物。“作为催化剂残余物”意指它们有效存在，超出这些金属的一般公认的微量杂质水平，尤其是Cr，其已知为微量金属中的主要组分。金属一般作为离子化合物(例如，盐)或作为任何种类的金属络合物存在。通常且优选，在本发明的语境下，优选Hf和Cr源于包含有机多齿配位体的金属茂和/或半夹心金属茂类型的单中心催化剂。还应了解，制备铪茂使用的铪盐通常包含一些量的锆，这是由于最初从中提取它们的混合矿石。因此，与发现同时可检测的Hf为催化剂残余物并非相反，在这些聚乙烯样品中可进一步存在Zr。在UHMW产物中，不可能以完整形式检出原始的催化剂络合物，因此，为了本发明的目的，只为了鉴定和定性或半定量地将原始催化剂络合物的以上所述两种Hf-和Cr-金属中心区别于一般水平的微量杂质而进行分析。在本发明的语境下，这些通过TOF(飞行时间)-质谱法或通过根据L'vov在石墨管炉(例如，适当装配有用于固体材料的样品载体)中的原子吸收光谱法(AAS)合适地进行。进行AAS必须分别对于Hf和Cr的特定吸收波长适当调节阴极灯，并优选在还原条件下，例如，将氧化亚氮加到载气。这种方法学为本领域的技术人员所熟悉。给定了样品的固体性质，TOF质谱法应利用场解吸(FD)或基质辅助激光解吸(MALDI)离子化来进行。分析前，应将UHMW聚乙烯的样品加热到高于其熔点，以允许软化物质的某种均匀化。两种方法通常会使多种分子例如任何种类的有机金属络合物或普通盐离解，并允许均匀分离和检测在聚合物中隐藏的游离金属原子或游离离子的信号。TOF-质谱法是一种优选的方法。应认识到，直接分析固体物质的方法(如SIMS质谱法)不适用于本发明的目的，因为从聚合得到的树脂颗粒可能不包含均匀分布形式的固体负载型催化剂颗粒，特别是不接近所述树脂颗粒的表面。
固体氧化物通常发现对以上方法是难熔的(refractory)，但相信不是使用本发明的以上所述催化剂而随之产生的，因此不认为是优选的。分析方法允许对聚合物中发现的Hf或Cr的相对量定量，尤其在使用质谱法结合Hf和Cr盐或络合物的参比混合物用来校准时。优选本发明的聚乙烯包含为30-80μmol:70-20μmol的摩尔比[Hf]:[Cr]的Hf和Cr，更优选40-55μmol:40-25μmol的摩尔比，最优选45-50μmol:35-30μmol的摩尔比。30-80μmol:70-20μmol的摩尔比[Hf]:[Cr]意指在本文语境下1:2,3直至4:1的[Hf]:[Cr]摩尔比；即，使该比的值归一化到100μmol所用的全部催化剂。
更优选本发明的聚乙烯包含的Hf和/或Cr各自至少1ppm，它们优选以阳离子形式存在，可以为盐或任何有机金属络合物或任选包含无机阴离子的化合物，优选作为阳离子络合物存在，并且阳离子络合物具有的多齿有机配位体包含η-5-环戊二烯基(Cpd)部分。在此语境中的部分涉及构成η-5-环戊二烯基(Cpd)基团的官能等价物的任何芳族或杂芳族基团，例如茚基。
更优选聚乙烯，单独或与前面段落中所述结合，聚乙烯包含的Hf和/或Cr各自最高200ppm，更优选Hf和/或Cr各自为2-150ppm，最优选Hf和/或Cr各自为5-100ppm。
优选催化剂残余物在聚乙烯内共定位到固体耐火载体材料(更优选金属氧化物)的粒状夹杂物，优选其条件为Cr催化剂的所述载体材料不是铝硅酸盐。如对例如分析聚合物掺合物中的白色斑点或凝胶所进行的那样，可从聚乙烯机械剖析粒状夹杂物，通过用最大50um、通常小于30um的切片机切片可识别，并在光学显微镜下目视分析它们。然后，主要由这些粒状夹杂物和一些外围附着的聚合物基质组成的这些样品，可优选用于由质谱法或AAS进一步分析，如以上更详细解释的。更优选产生Cr催化剂残余物的Cr催化剂或所述Cr催化剂的载体未经过氟化处理。
优选本发明的聚乙烯具有<0.01g/10min的HLMI。
优选，单独或与以下或以上所述本发明的聚乙烯的任何其它特征结合，聚乙烯具有>160kJ/m2的沙尔皮耐冲击强度，优选至少170kJ/m2。
进一步优选，在从中得到聚乙烯的聚合期间，没有多不饱和单体或共聚单体作为交联剂加到聚乙烯，并且其中聚乙烯尚未称为用于聚合物链交联的聚合后电子束处理的对象。
本发明的聚乙烯为UHMW聚乙烯，因此，利用用于吹塑或薄膜吹塑所用的标准挤出设备没有实质的可挤出性，如以上引用的极端HLMI所示。由于相同原因，聚乙烯不顺应常规用于质量分布分析和实验测定Mw、Mn的在三氯苯中的标准高温GPC分析。与大多数热塑性塑料不同，UHMW PE在加热到高于其熔点时不液化。由于它的高熔体强度，它可在其结晶熔融温度以上进行处理和成形。概念上，由于作为UHMW PE的不良可挤出性和很小标准熔体指数值的上述性质，可以可靠地推断，作为进一步的优选特征，本发明的聚乙烯具有至少>1,500,000Da的理论平均分子量。可能会提到，UHMWPE当然可以挤出，尽管只通过特殊技术，例如通过柱塞(RAM-)挤出。
实验
密度［g/cm3］根据ISO 1183测定。
根据ISO 1133，在190℃在21.6kg负荷(190℃/21.6kg)下测定熔体流动速率。
沙尔皮耐冲击强度根据ISO 11542-2:1998测定，尤其参照附录B。如正文3-5部分中所述，通过压缩模塑制备样品。
耐磨强度基本上根据ISO 15527:2007测定，将刚玉即Al2O3(为标准中所指出的粒度)用作试验磨料。以下修改的条件(根据一般公认工业标准)：使用60%(w/w)氧化铝和40%(w/w)水(蒸馏水，aqua dest.)的浆料，在1750rpm试验磨损2小时。也如ISO标准中所述地计算结果，基于相对质量损失比较，使用相同的样品用于参照，此样品以相同方式处理，但在试验期间浸入水中时没有氧化铝存在。较低的值指示较佳耐磨强度，因为相对于参照样品磨损性损失了较少的质量。
催化剂1：
二氯化双(正丁基-环戊二烯基)合铪，购自Chemtura Inc.。
催化剂2：
氯化η5-[2-((3-三甲基甲硅烷基-1H-茚-1-基)甲基)吡啶基]合铬(IV)
对于类似化合物，例如，在WO 01/12641中提供了合成方案
Figure 896404DEST_PATH_IMAGE001
。
载体预处理：将XPO-2408，一种购自Grace(Grace & Co. Columbia/Maryland, U.S.A.)的喷雾干燥硅胶，在600℃煅烧6小时，随后将2.5Kg经干燥硅胶放入10L容器，并在10℃冷却。
共负载
将9.9g煅烧的(6h，600℃) 硅胶XPO 2408放入250ml圆底烧瓶，并冷却到0℃。使Cr络合物催化剂2(123mg，305,7μmol)和Hf络合物催化剂1(243mg，494μmol)溶于MAO(16,8ml，79.97mmol，30%在甲苯中，4.75mol/l)，并在环境温度(22℃)搅拌20分钟。
在5分钟内在0℃向冷却的二氧化硅滴加MAO溶液。随后，将粉末搅拌1小时，并令其达到环境温度。分两部分加入60ml正庚烷，同时继续搅拌1分钟。通过连续通过Ar流，使催化剂粉末干燥1小时。得到15.2g浅绿色自由流动的粉末。
聚合(发明)
在氮下，在10L高压釜反应器中装入4L异丁烷。反应器顶部空间用氮清扫，通过用约2反应器体积的乙烯冲洗连续地去除氮。然后，基本在开始反应前，用乙烯将反应器以40巴加压。将如前面部分中制备的155g共负载型催化剂(总共达到50umol 铪茂和30umol Cr-催化剂)通过进料阀进料到反应器。催化剂进料从经过35巴的加压后开始，并在达到40巴最终压力时完成。反应在搅拌下在70℃进行1小时。产率为10Kg聚乙烯聚合物/g负载型催化剂。
聚合(比较实施例A、B)
以类似方式，只用负载于载体上的络合催化剂中的任一种进行聚合，如下表所示。来自本发明和比较例二者的聚合结果显示于以下表I中：
表I
Figure 2011800067294100002DEST_PATH_IMAGE002
可从上表推断，通过使用本发明的双催化剂系统，所设计的混合UHMWPE保持每种单独催化剂的相应最佳性质。它保持铬催化剂的极佳耐磨强度(其优于铪茂催化剂)，然而在较高的密度，这可与铪茂催化剂相比，反之，选择性保持甚至侵占孤立的铪茂产物的非常优良的沙尔皮性质。这明显有协同效应发生，此协同效应尚未由我们完全了解。从两种催化剂，产物保持相应的较佳性质，在组合用于产生单一产物的相应催化剂时甚至改进这些性质。同样，产物具有在技术上合乎需要的至少1mm的优良平均粒度，实际上是在一直相同的反应条件下相应的催化剂一般平均值之间的半途折衷。尽管如此，在机械性质方面，产物仍是极佳耐磨强度和沙尔皮耐冲击强度的选择性并且意外的组合。

Claims (9)

1. 一种聚乙烯，所述聚乙烯具有：<1g/10min的HLMI(在21.6kg/190℃)，0.925-0.940g/cm3的密度，>150kJ/m2的沙尔皮耐冲击强度，<1.1指数单位的耐磨强度，所述沙尔皮耐冲击强度根据ISO 11542-2:1998，所述耐磨强度根据ISO 15527:2007利用Al2O3作为试验磨料、优选在说明书中所给出的其它试验条件下；并且聚乙烯进一步包含Hf和Cr两者作为催化剂残余物，优选其中所述Cr催化剂残余物来自菲利普催化剂以外的催化剂。
2. 权利要求1的聚乙烯，所述聚乙烯包含摩尔比[Hf]:[Cr]为30-80μmol:70-20μmol的Hf和Cr两者作为催化剂残余物。
3. 权利要求1或2的聚乙烯，所述聚乙烯包含的Hf和/或Cr各自为至少1ppm，其以阳离子形式存在，优选作为具有包含η-5-环戊二烯基部分的多齿有机配位体的阳离子络合物存在，更优选其中聚乙烯包含的Hf和/或Cr各自为最高200ppm，更优选Hf和/或Cr各自为2-150ppm，最优选Hf和/或Cr各自为5-100ppm。
4. 权利要求1-3的聚乙烯，其中催化剂残余物在聚乙烯内共定位到固体耐火载体材料更优选金属氧化物的粒状夹杂物，优选其条件为Cr催化剂的所述载体材料不是铝硅酸盐。
5. 前述权利要求中一项的聚乙烯，其条件为产生Cr催化剂残余物的Cr催化剂或所述Cr催化剂的载体未经过氟化处理。
6. 前述权利要求中一项的聚乙烯，所述聚乙烯具有<0.01g/10min的HLMI。
7. 前述权利要求中一项的聚乙烯，所述聚乙烯具有>160kJ/m2的沙尔皮耐冲击强度，优选至少170kJ/m2。
8. 前述权利要求中一项的聚乙烯，其中，在从中得到聚乙烯的聚合期间没有多不饱和单体或共聚单体作为交联剂加入，并且其中聚乙烯没有为用于聚合物链交联的聚合后电子束处理的对象。
9. 前述权利要求中一项的聚乙烯，所述聚乙烯仅通过分子结构为金属茂或半夹心金属茂催化剂的单中心催化剂制备。
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