CN1111550C - 改进的易于加工的线型低密度聚乙烯 - Google Patents

改进的易于加工的线型低密度聚乙烯 Download PDF

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CN1111550C
CN1111550C CN98803686A CN98803686A CN1111550C CN 1111550 C CN1111550 C CN 1111550C CN 98803686 A CN98803686 A CN 98803686A CN 98803686 A CN98803686 A CN 98803686A CN 1111550 C CN1111550 C CN 1111550C
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吕清泰
N·A·麦瑞尔
M·E·穆尔
G·A·沃格翰
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Abstract

乙烯和至少一种具有至少5个碳原子的α-烯烃的聚合物，是通过使用载体催化剂的连续气相聚合制备的，催化剂为活性分子分散的催化剂，如金属茂，大体上不含有烷基铝清除剂，聚合物具有如此处定义的熔体指数(MI)为0.1到15；如此处定义的组成分布宽度指数(CDBI)至少为70％，密度为0.910到0.930克/毫升；如此处定义的雾度值小于20％；如此处定义的熔体指数比(MIR)为35到80；如此处定义的平均模量(M)为20000到60000psi(磅每平方英寸)，M与落镖冲击强度(克/密耳)(DIS)的关系依从式(I)。

Description

改进的易于加工的线型低密度聚乙烯
发明领域
本发明涉及新型聚乙烯组合物，特别是具有改进的剪切稀化性能(以助于熔融状态下这些聚合物的加工)和冲击强度(以助于成品使用性能)的聚乙烯。最优地可在连续气相过程中制备聚合物，其中流化床反应器中加入了载体催化剂。
发明背景
在EP-A-495099、EP-A-452920、EP-A-676421和EP-A-659773中介绍了由气相过程制备的具有支化度以改善熔体流变性的聚乙烯。WO96/08520(Exxon化学专利公司)论述了低清除剂环境中的气相聚合，即在聚合过程中，没有使用或只用了少量的清除剂如三乙基铝。
WO-A-93/08221中介绍了由单环戊二烯化合物制备的具有改善的流变性的聚乙烯。
EP-A-495099用具有多齿配体(即其有两个由桥连接的茂基环体系)的铪金属茂化合物制备了聚乙烯(见第6页)。特别指定的铪化合物是桥联的。介绍的聚合反应在间歇系统中进行。尽管第13页第12行中提到了气相操作，但聚合是在含有无载体催化剂的溶液相中进行。得到的聚乙烯的具有窄分子量分布，熔体流动速率(MFR以克每10分钟表示，是190℃下负荷为2.16千克时的值)为8-50。随来源不同，缩写MFR是指熔体流动速率或熔体流动比。必须参考初始来源，以防止在特定情况下确定MFR的含义时产生疑问。
EP-A-452920例示了制备聚乙烯所用的载体催化剂的使用。在气相中用三异丁基铝作为清除剂进行聚合。过渡金属成分包括二茂锆。实施例9和其它实施例用乙烯桥连的双(茚基)锆作为过渡金属化合物。实施例10使用的Al/Zr比为112。清除剂有助于避免附着在实验设备上的或由各种成分引入的外来毒物的影响。据称熔体张力得到了改善。
WO-A-95/07942论述了在聚乙烯的制备中，在气相中，使用载体上的单环戊二烯基化合物。活化剂不是甲基铝氧烷，而是在EP-A-277003和EP-A-277004中首先介绍的非配位的大阴离子。在间歇反应器中进行聚合。没有提及清除剂。
US-A-5466649在实施例17中介绍了用二甲甲硅基双(四氢茚基)二氯化锆附在一种载体上、TMA(三甲基铝)单独地附在另一种载体上的间歇气相聚合方法制备聚乙烯的方法。这是间歇反应，没有给出聚乙烯的具体的性质。
WO96/08520(Exxon化学专利公司)介绍了连续工业气相操作方法，其中没有清除剂或只有少量的清除剂。一个实施方案(见第12页，第28行)定义了基本上没有清除剂的系统，即含有小于基于进料气总重的10ppm的清除剂，进料气指的是循环气流。此外，低清除剂的条件的定义，与金属茂有关。第14页中，摩尔比的范围为300到10。第15页指出，得到的聚合物中的烯或不饱和低聚物的含量大大降低了。
EP-A-676421(BP)例示了制备聚乙烯的间歇方法和连续方法，其中通过具有亚烷基或甲硅基桥连的载体双环戊二烯基过渡金属化合物与甲基铝氧烷助催化剂一同使用，引入长链支化，可得到改进流变性的产品。这些催化剂是有载体的。间歇反应中有清除剂(见第5页第28行)。此专利出版物的实施例10中介绍了在190℃、负荷为2.16千克时测得的熔体指数(MI)，为0.3克每10分钟；没有给出分子量分布，组成分布也未给出，密度为0.916克/毫升，雾度为11％，没有在不同负荷下测得的MI的比，落镖冲击强度为210克/密耳，没有以模量表示的聚合物的劲度。根据Mark、Bikales、Overberger和Menges的《聚合物科学和工程百科全书》第6卷，第二版，第447页(1986年)中给出的密度与正割模量之间的关系，这种材料的正割模量估计约为30,000到32,000磅/平方英寸(205到220牛顿/毫米2)。
EP-A-659773(Union Carbide)在聚乙烯的聚合中使用桥连催化剂，并给出了连续方式运转的反应器的实施例。说明书讲授了载体的使用(见第6页第30行)，但实施例中没有使用载体，所以铝氧烷是在溶剂中注入的。这会引起污染，而且铝氧烷会含有大量的未反应的三甲基铝(TMA)，三甲基铝会作为清除剂，使乙烯基不饱和度显著增大。由于用多于一种的金属茂成分，生成了多于一种的不同的聚合物成分，分子量分布变宽，熔体加工受到了进一步的影响。依其申述，这样做是为了提供对长链支化(LCB)度的控制，由GPC测定的LCB程度和粘度数据所表示。熔体流动比(MFR)也是用来表征聚合物的。MFR为不同负荷下的熔体指数比和反映了LCB与高的Mw/Mn。通过使用多于一种的金属茂，可得到高Mw/Mn，进而增大MFR值。实施例指出，桥的种类对于提高LCB的程度是最有用的。但是，实施例5表明，单独用桥金属茂制备的聚合物具有很低的分子量，意味着低分子量聚合物种类是得到高MFR值的主要因素。EP-A-659773没有指出如何制备具有改进流变性的低熔体指数的材料，流变性以由LCB得到的MFR表示。EP-A-659773没有公开有助于确定所制备的聚合物的商品品质的CDBI、雾度和DIS值。
EP-A-743327介绍了具有高多分散性指数(等于Mw/Mn)的乙烯聚合物的制备，其中在挤出中需要低压头。改进的流变性以RSI(松弛谱指数)表示，据称RSI对分子量分布、分子量和长链支化敏感。聚合方法的细节的描述并不充分。EP-A-743327包括与EP-A-659773中所列的催化剂相似的金属茂作为催化剂。
EP-A-729978用流动活化能表征乙烯聚合物。聚合物是用一个茂基环系统为芴基多核配体结构的桥连双茂基催化剂成分制备的。高活化能是高度长链支化的结果。
在得到的聚合物的熔体加工中，为达到需要的效果，上述方法中介绍了许多不同的方法或催化剂的选择。但是，由于催化剂会有低生产率，在长期大规模的反应器中使用易于污染和/或生成低分子量的材料，因而这些方法都有缺点，使其工业应用受到限制。此外，现行提议会导致物理性质的过度损失，如透明度的损失，与食物接触的应用中有害的提取性的增大，或薄膜韧性如DIS(落镖冲击强度)的损失。
本发明的目的之一是提供在工业规模的工厂中制备具有优良的熔体流动性质和平衡的强度和劲度的商业所需的聚合物的比较简单的制备方法。
可在不会引起污染的条件下，在长期的生产运转中制备聚合物。
发明概要
本发明提供了乙烯聚合物和至少一种具有至少5个碳原子的α-烯烃的聚合物，它们是通过使用载体催化剂的连续气相聚合制备的，催化剂为活性分子分散的催化剂，如金属茂，大体上不含有烷基铝清除剂(如三乙基铝(TEAL)、三甲基铝(TMAL)、三异丁基铝(TIBAL)、三正己基铝(TNHAL)等等)，聚合物如此处定义的熔体指数(MI)为0.1到15：如此处定义的组成分布宽度指数(CDBI)至少为70％，密度为0.910到0.930克/毫升；如此处定义的雾度值小于20；如此处定义的熔体指数比(MIR)为35到80；如此处定义的平均模量为20000到60000psi(磅每平方英寸)(13790到41369牛顿/厘米2)，M与落镖冲击强度(克/25微米，克/密耳)(DIS)的关系依从下式： DIS ≥ 0.8 × [ 100 + e ( 11.71 - 0.000268 × M + 2.183 × 10 - 9 × M 2 ) ] , 其中“e”代表2.7183，自然对数的底，M为平均模量psi(磅/平方英寸)，DIS为26英寸(66厘米)落镖冲击强度(克/25微米，克/密耳)。
虽然许多当前技术文献都介绍了用相同的单体和类似的方法制备聚合物和方法，没有介绍兼有[A]良好的剪切稀化以及因而具有的比较优良的挤出和其它熔体加工性能和[B]高劲度以及[C]高冲击强度的聚合物。到目前为止，看起来由连续气相方法制备的LLDPE(线型低密度聚乙烯)很难兼有这些性能。本发明提供了令人惊讶的兼有这些性能的聚合物，可以重复地制备聚合物。
与高压方法制备的具有可比密度和MI的LDPE(低密度聚乙烯)相比，本发明的聚乙烯具有良好的DIS-模量平衡，例如落镖冲击强度(DIS)(克/25微米，克/密耳)等于或大于由下式预测的值： DIS × 0.8 × [ 100 + e ( 11.71 - 0.000268 × M + 2.183 × 10 - 9 × M 2 ) ] , 其中“e”。为自然对数的底，M为平均模量(磅/平方英寸)，DIS为落镖冲击强度(克/25微米，克/密耳)。
与用传统齐格勒一纳塔载体催化剂的气相方法制备的LLDPE相比，本发明的聚乙烯具有改善的剪切稀化。这些常规制备的LLDPE具有较低的CDBI和较差的DIS-模量平衡，例如落镖冲击强度(克/密耳)小于由上式预测的值。
与用金属茂载体催化剂的气相方法制备的EXCEEDTM材料(由Exxon化学公司制造)相比，本发明的聚乙烯具有更好的剪切稀化性能以及其它相当的性能。这些EXCEED材料的MIR为16到18。
本发明的优选的形式中，聚乙烯由乙烯和高达15重量％的1-己烯得到。优选地模量和落镖冲击强度的关系依从下式： DIS ≤ 2.0 × [ 100 + e ( 11.71 - 0.000268 × M + 2.183 × 10 - 9 × M 2 ) ] , 其中“e”为自然对数的底，M为平均模量(磅/平方英寸)，DIS为落镖冲击强度(克/25微米，克/密耳)。
有利地，聚合物具有以下特征之一或其组合：密度为0.915到O.927克/毫升，MI为O.3到10，CDBI至少为75％。最优选的DIS为120到1000克/25微米(克/密耳)，特别是小于800且大于150克/25微米(克/密耳)。优选地，由GPC测得的Mw/Mn为2.5到5.5。优选地，可提取性小于2.6重量％。
至于工艺条件，可以采用WO96/08520(Exxon化学专利公司)，中介绍的全部条件。发明者相信特定过程条件的组合有助于制备本发明的聚乙烯。特别地，一般认为需要用催化剂体系，其中金属茂有一对桥连茂基，优选地具有由单个碳、锗或硅原子组成的桥，以在催化活性阳离子上提供表面活性部位。引发剂可为如EP-129368中介绍的甲基铝氧烷或如EP-277004中介绍的非配位的阴离子。通常认为需要大体上没有清除剂，清除剂会妨碍生成的聚合物的乙烯不饱和端与阳离子上的表面活性部位之问的反应。表述“大体上没有清除剂”是指进料气体中应含有小于100ppm重量的这种清除剂，或优选地不加入清除剂，例如除了可能在载体上的清除剂外，烷基铝或路易斯酸清除剂。
生产本发明的聚乙烯的最优的条件也需要不变的聚合条件，间歇生产中催化剂毒的量会变化，共聚单体的浓度也会变化，间歇反应不可能提供不变的聚合条件。
因此，聚乙烯的聚合的整个连续气相方法包括：
连续地循环含有单体和惰性气体的料气物流，以流化并搅拌聚合物颗粒层，把金属茂催化剂加入床层并移出聚合物颗粒，其中：
a)催化剂包含在共同或单独的多孔载体上的至少一种桥连双环戊二烯基过渡金属和铝氧烷引发剂；
b)进料气体中大体上没有路易斯酸清除剂，其中任何路易斯酸清除剂的含量优选地为小于料气重量的100ppm；
c)床层的温度比由DSC测定的聚合物的熔融温度不高于20℃，乙烯的绝对分压超过60磅每平方英寸(414千帕，绝压)；
d)移出的聚合物颗粒的过渡金属的灰分含量小于500重量ppm，MI小于10，MIR至少为35，由HNMR测定，聚合物大体上没有可检测的链端不饱和。
聚合物大体上没有链端不饱和的陈述，是指聚合物的乙烯基不饱和为，聚合物中每1000个碳原子中有少于0.1个乙烯基，如每1000个碳原子中有少于0.05个乙烯基，如每1000个碳原子中有少于0.01个乙烯基或更少。
该方法的目的是通过使用单一催化剂提供本发明的聚乙烯，方法不依赖桥连和非桥连物质的作用。优选地，催化剂大体上没有具有一对π键配体、不是通过共价桥连接的金属茂(如茂基化合物)，换句话说，催化剂中不加入这种金属茂，或优选地，在此催化剂中找不到这种金属茂，方法使用大体上单一的金属茂物质，其中含有一对π键配体，至少其中之一具有至少两个稠环(如茚环)的结构。可通过使用大体上单一的金属茂物质，得到最好的结果，金属茂中含有单原子硅桥连的两个多核配体，配体通过π键与过渡金属原子相连。
优选地，把催化剂附在二氧化硅上，使催化剂均匀地分布在二氧化硅的孔中。优选地，应用相当少量的methyl铝氧烷，使Al与过渡金属的比为400到30，尤其为200到50。
为了得到需要的熔体指数比，可以改变乙烯与共聚单体的摩尔比，也可改变共聚单体的浓度。控制温度有助于控制MI。可根据LLDPE气相聚合的传统实践，决定所用的全部单体的分压。
权利要求和实施例中所用的参数的定义如下：
熔体指数：      ASTM D-1238-条件E
熔体指数比：    由ASTM D-1238测定的I21与I2的比。
Mw、Mn和Mw/Mn： 由使用DRI(示差折光率)检测器的GPC测定。
在带有DRI检测器的Waters 150C的GPC仪器中进行凝胶渗透色谱测定。
通过试验一系列有限的聚苯乙烯标准，校准GPC柱。除了聚苯乙烯的聚合物的分子量照惯例通过所讨论的聚合物的马克-豪温克系数计算。
按照WO9303093中第7和第8栏所述测定CDBI。
SCB(短链支化)：由HNMR(氢核磁共振)测定，在500Mhz处收集数据。通过把聚合物主链信号设在1.347ppm，得到参考谱。乙烯/1-烯烃共聚物中甲基的含量由HNMR光谱，通过下式计算：
甲基/1000个碳原子＝(ICH3*0.33*1000)/(I0.5-2.1ppm*0.5)其中ICH3为0.88到1.05ppm之间的归一化甲基信号面积，I0.5-2.1ppm为0.50到2.10ppm之间的面积。
假定短链支链含有1个甲基(-CH3)，且所有的甲基都是短链支化的结果，甲基的含量会与聚合物中短链支链的数目一致。可用同样的NMR方法测定乙烯端基不饱和。
密度：                        ASTM D-1505
雾度％：                      ASTM D-1003-95
落镖冲击强度，26英寸(66厘米)：ASTM D1709-91
1％正割模量：                      ASTM D-882-91
“平均模量”为纵向与横向上的1％正割模量的和被二除的结果。
埃尔曼多夫抗撕强度ASTM D1922-94
颗粒堆密度：把粒状聚合物颗粒用2.2cm(7/8”)直径的漏斗倒入400毫升的量筒中。堆密度由树脂的重量被400毫升除得到单位为克/毫升的值。
粒度：通过测定在一系列的美国标准筛上收集的材料的重量，并测定所用的筛系列的重均粒度(微米)，得到粒度。
提取性：按照FDA条例21CFR177.1520(d)(3)(ii)测定。
实施例
下面详细说明了两个试验。催化剂的制备试验1载体催化剂的制备：把1300毫升30重量％的铝氧烷(MAO)的甲苯溶液装入2加仑(7.57升)的夹套玻璃壁反应器中，溶液浓度按照Al的总含量决定，溶液中可能含有未水解的TMA，反应器配有螺带式搅拌器和螺旋式的轴。加入2080毫升的甲苯并搅拌。把31.5克二甲甲硅基-双-(四氢茚基)氯化锆(Me2Si(H4Ind)2ZrCl2)在320毫升从Albemarle实验室购买的甲苯中形成的悬浮液，通过套管加入反应器。在氮压下，用另外一瓶干甲苯(250毫升)把金属茂固体结晶通过套管冲入反应器。把金属茂加入MAO溶液后，颜色由无色变为黄色/橙色。在把混合物在氮氛中转移到4升的锥形瓶前，把混合物在69°F(20.6℃)下搅拌1小时。把二氧化硅(1040克，Davison MS948，孔体积1.65毫升/克)装入反应器。然后把一半溶液从4升锥形瓶中转移回2加仑(7.57升)的搅拌玻璃反应器中。经过5分钟的放热，反应温度从70°F(21.1℃)升到100°F(37.8℃)。随后把4升锥形瓶中剩余的溶液加回玻璃反应器中，并搅拌20分钟。然后，加入甲苯(273毫升，238克)以稀释活性催化剂浆液，并再搅拌25分钟。把Antistat AS-990，Witco化学公司销售的由乙氧基硬脂酰胺制备的表面改性剂(73毫升甲苯中有7克)，通过套管加入反应器和搅拌了30分钟的浆液中。通过把压力降到小于18英寸汞柱(457毫米汞柱)，同时把少量的氮气流加入反应器底部并把温度从74°F(23.3℃)升到142°F(61.1℃)，经过1小时，除去溶剂。在5英寸到22英寸汞柱(127到559毫米汞柱)的真空、142°F(61.1℃)到152°F(66.7℃)的温度下，再干燥5小时，使载体干燥，并产生1709.0克自由流动的活性载体催化剂物料。顶空气相色谱(HSGC)测量表明，有百万分之13,000重量(1.3重量％)的残余甲苯。在更强的真空条件下第二次干燥后，HSGC分析的结果是残余甲苯为0.18％。元素分析表明有0.40％的Zr、10.75％的Al、30.89％的Si、0.27％的Cl、9.26％的C、2.05％的H(此处所示的所有的百分比都是重量百分比)。试验2载体催化剂的制备：
把1125毫升30重量％的铝氧烷(MAO)的甲苯溶液装入2加仑(7.57升)的夹套玻璃壁反应器中，溶液浓度按照Al的总含量决定，溶液中可能含有未水解的TMA，反应器配有螺带式搅拌器和螺旋式的轴。加入1800毫升的甲苯并搅拌。把30.8克二甲甲硅基-双-(四氢茚基)氯化锆(Me2Si(H4Ind)2ZrCl2)在320毫升从Albemarle实验室购买的甲苯中形成的悬浮液，通过套管加入反应器。在氮压下，用另外150毫升甲苯把金属茂固体结晶通过套管冲入反应器。把金属茂加入MAO溶液后，颜色由无色变为黄色/橙色。在把混合物在氮氛中转移到4升的锥形瓶前，把混合物在69°F(20.6℃)下搅拌1小时。把二氧化硅(899克，Davison MS 948，孔体积V为1.65毫升/克)装入反应器。然后把一半溶液从4升锥形瓶中转移回2加仑(7.57升)的搅拌玻璃反应器中。经过5分钟的放热，反应温度从70°F(21.1℃)升到100°F(37.8℃)。随后把4升锥形瓶中剩余的溶液加回玻璃反应器中，并搅拌20分钟。然后，加入甲苯(273毫升，238克)以稀释活性催化剂浆液，并再搅拌25分钟。把Antistat AS-990，Witco化学公司销售的表面改性剂(30毫升甲苯中有6克)，通过套管加入反应器和搅拌了30分钟的浆液中。通过把压力降到小于18英寸汞柱(457毫米汞柱)，同时把少量的氮气流加入反应器底部并把温度从74°F(23.3℃)升到142°F(61.1℃)，经过1小时，除去溶剂。在5英寸到22英寸汞柱(127到559毫米汞柱)的真空、142°F(61.1℃)到152°F(66.7℃)的温度下，再干燥9个半小时，使载体干燥，并产生1291.4克自由流动的活性载体催化剂物料。流化床聚合
在直径为16.5英寸(41.9厘米)、床层高度约为12英尺(3.6米)的连续气相流化床反应器中进行聚合。流化床层由聚合物颗粒组成。在T形混合装置中把乙烯和氢气的气体进料流与液体共聚单体混合，并在反应器的床层以下引入循环气体管。控制乙烯、氢气和共聚单体的各自的流量，以保持固定组成的指标。控制乙烯的浓度，以保持乙烯的分压恒定。控制氢气，以保持恒定的氢气/乙烯摩尔比。所有气体的浓度通过在线气相色谱测定，以确保循环气流的组成比较恒定。
用纯氮气作载气，把固体催化剂直接注入流化床中。调节注入的速度，以保持聚合物的生产率恒定。通过使补充进料和循环气连续流经反应区，保持增长的聚合物颗粒的反应床层的流化状态。使用1-3英尺/秒(0.3到0.9米/秒)的空塔气速以达到此目的。反应器在300磅/平方英寸(表压)(2068千帕表压)的总压下操作。为保持恒定的反应器温度，连续地调节循环气的温度，使其升高或降低，以适应由于聚合引起的放热速率的任何变化。
通过以与颗粒产物生成速率相同的速率抽出部分床层，保持流化床的高度不变。通过一系列的阀门把产物半连续地移到固定体积的室中，同时将其排出回到反应器。这样可以高效地移出产物，同时把大部分未反应的气体循环回反应器。把产物净化以除去夹带的碳氢化合物，并用少量的湿氮气流处理，以使任何微量的残余催化剂和助催化剂失活。表1聚合试验条件                          试验1      试验2Zr(重量％)                            0.43       0.50Al(重量％)                            11.6       11.4Al/Zr(摩尔/摩尔)                      91.2       77.1温度(℃)                              79.4       85压力(巴)                              21.7       21.7乙烯(摩尔％)                          25.0       49.9氢气(摩尔ppm)                         275        445己烯(摩尔％)                          0.23       0.32床层重(千克PE)                        113        121生产率(千克PE/小时)                   27.6       35.5催化剂生产能力(千克PE/千克催化剂)     1690       2287堆密度(克/毫升)                       0.448      0.450平均粒度(微米)                        920        803灰分(ppm)                             507        386
如前所述测定参数，通过元素分析测定Zr、Al的重量百分比和灰分含量。
反应器中不加入用作清除剂的烷基铝化合物。连续进行试验约3天。
得到的聚合物经过另外的检验，在聚合物最初形成薄膜后适当进行。聚合物特性表2A
                          试验1            试验2密度                          0.9190           0.9257MI                            1.10             0.62MIR                           46.0             57.6DRI检测器Mw                            92,200           104700Mn                            18,300           7900Mz                            208,400          287500Mw/Mn                         5.04             5.85DSC第二次的熔体-见注1第一次熔融峰(C)               108.6            122.6第二次熔融峰(C)               119.3            117.3CDBI                          86               83.10SCB(/1000C)                   15.4             10.6C6的重量％                    9.3              6.4C6的摩尔％                    3.3              2.2注1：以前已经把试样熔化并冷却过一次表2B薄膜特性
                                     试验1      试验2吹胀比                                    2.5       2.5厚度(密耳，1密耳＝25.4微米)               2.1       2.01％的正割模量，磅/平方英寸(牛顿/厘米2)   29420     45070MD(纵向)                                  (20284)   (31075)TD(横向)，磅/平方英寸                     31230     47420(牛顿/厘米2)                             (21532)   (32695)MD+TD平均，磅/平方英寸(牛顿/厘米2)       30325     46245
                                      (20908)   (31885)埃尔曼多夫抗斯强度(克/25微米，克/密耳)MD                                        207       134TD                                        430       47726英寸(66厘米)落镖冲击强度(DIS)           410       156(克/25微米，克/密耳)按照公式计算的模量的函数DIS               386       154雾度(％)                                  10.2      9.9提取性                                    1.0       未得到
用根据本发明以类似的方法制备的不同试样进行了大量的其它试验，结果示于图1中。权利要求1中的函数以实线表示。
表3列出了一些示范值。表3
测定的平均1％正割模量，M 落镖冲击强度(26英寸)(66厘米)
磅/平方英寸 牛顿/厘米2 由以下公式计算的值克/25微米(克/密耳) 测定值克/25微米(克/密耳)
 25,575  17,633  508  611
 28,580  19,705  353  456
 28,990  19,987  337  553
 29,145  20,094  332  451
 30,325  20,908  294  410
 31,450  21,684  264  284
 31,610  21,794  260  257
 32,000  22,063  251  349
 32,140  22,159  248  223
 33,780  23,290  217  251
 34,160  23,552  211  262
 35,170  24,248  196  223
 35,970  24,800  186  261
 37,870  26,110  167  251
 39,325  27,113  155  197
 39,390  27,158  154  193
 43,675  30,112  131  167
 46,245  31,884  123  156
 47,730  32,908  119  147
 49,460  34,101  115  143
因此，本权利要求包括图1中实线上方区域的DIS和平均模量的组合。
根据说明书中给出的关于催化剂的选择、催化剂载体和气相过程操作的指示，有可能制备出如权利要求所述的乙烯聚合物，此聚合物同时具有光透明性、比较容易制备和加工以及由落镖冲击强度所测定的高强度的特性。
薄膜可用于强力袋子、收缩薄膜、农用薄膜，尤其是低级用品，如厚度为12.7至17.7微米(0.5到7密耳)的垃圾袋和购物袋。可通过吹胀挤出、挤塑、共挤出制备薄膜，也可制成层状结构。

Claims (13)

1.乙烯和至少一种具有至少5个碳原子的(α-烯烃的聚合物，其中聚合物具有的如此处定义的熔体指数为O.1到15，由ASTM D-1238条件E测定；如此处定义的组成分布宽度指数至少为70％，密度为0.910到0.930克/毫升，由ASTM D-1505测定；如此处定义的雾度值小于20％，由ASTM D-1003-95测定：如此处定义的熔体指数比为35到80，由ASTMD-1238测定的I21/I2；如此处定义的平均模量为20,000到60,000磅每平方英寸(13,790到41,369牛顿/厘米2)，由ASTM D-882-91测定，纵向与横向的总和被2除)，以及平均模量与落镖冲击强度(克/25微米，克/密耳)的关系依从下式： DIS ≥ 0.8 × [ 100 + e ( 11.71 - 0.000268 × M + 2.183 × 10 - 9 × M 2 ) ] . 其中“e”代表2.7183，自然对数的底。
2.根据权利要求1的聚合物，其中平均模量与落镖冲击强度的关系依从下式： DIS ≤ 2.0 × [ 100 + e ( 11.71 - 0.000268 × M + 2.183 × 10 - 9 × M 2 ) ] .
3.根据上述权利要求中任何权利要求的聚合物，其中密度为0.915到0.927克/毫升，MI为0.3到10，CDBI至少为75％。
4.根据上述权利要求中任何权利要求的聚合物，其中DIS为120到1000克/25微米(克/密耳)。
5.根据上述权利要求中任何权利要求的聚合物，其中按照FDA条例21CFR 177.1520(d)(3)(ii)测定的可提取性小于2.6重量％。
6.含有至少一层上述权利要求中任何权利要求的聚合物的薄膜。
7.根据权利要求6的薄膜，其中层的厚度为12.7到177.8微米(0.5到7密耳)。
8.根据权利要求7的薄膜，为单层薄膜。
9.根据上述权利要求1到4中任何权利要求的聚合物的聚合的连续气相方法，包括：
连续地循环含有单体和惰性气体的料气物流，以流化并搅拌聚合物颗粒床，把金属茂催化剂加入床层并移出权利要求1到4的聚合物颗粒，其中：
催化剂包含在共同或单独的多孔载体上的至少一种桥连双环戊二烯基过渡金属和铝氧烷引发剂；
进料气体中大体上没有路易斯酸清除剂，其中路易斯酸清除剂的含量优选地为小于料气的100ppm；
床层的温度比由DSC测定的权利要求1到4的聚合物的熔融温度低至多20℃，乙烯的绝对分压超过75磅每平方英寸(517千帕，绝压)；
移出的权利要求1到4的聚合物颗粒的过渡金属的灰分含量小于500重量ppm，聚合物大体上没有由HNMR测定的可检测的链端不饱和。
10.根据权利要求9的方法，其中催化剂大体上没有具有一对π键配体、不是通过共价桥连接的金属茂。
11.根据权利要求9或10的方法，其中使用大体上单一的金属茂，金属茂中含有一对π键配体，至少其中之一具有至少两个稠环的结构。
12.根据权利要求9到11中任何权利要求的方法，其中使用大体上单一的金属茂，金属茂中含有单原子硅桥连接的两个多核配体，配体通过π键连接在过渡金属原子上。
13.根据权利要求9到11中任何权利要求的方法，其中移出的权利要求1到4的聚合物的颗粒的MI小于10，MIR至少为40。
CN98803686A 1997-04-01 1998-03-27 改进的易于加工的线型低密度聚乙烯 Expired - Lifetime CN1111550C (zh)

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DE69819314D1 (de) 2003-12-04
JP2002513437A (ja) 2002-05-08
AU6781798A (en) 1998-10-22
WO1998044011A1 (en) 1998-10-08
CN1272853A (zh) 2000-11-08
EP0973814A1 (en) 2000-01-26
DE69819314T2 (de) 2004-08-26
JP4982003B2 (ja) 2012-07-25
EA002321B1 (ru) 2002-04-25
KR20010005690A (ko) 2001-01-15
CA2283246C (en) 2008-08-05
TW422853B (en) 2001-02-21
US6476171B1 (en) 2002-11-05
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AU733306B2 (en) 2001-05-10
CA2283246A1 (en) 1998-10-08

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