CN1150594A - 具有极高透明度、增强的韧性、低排出性和易于加工的乙烯聚合物 - Google Patents

具有极高透明度、增强的韧性、低排出性和易于加工的乙烯聚合物 Download PDF

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CN1150594A
CN1150594A CN96108932A CN96108932A CN1150594A CN 1150594 A CN1150594 A CN 1150594A CN 96108932 A CN96108932 A CN 96108932A CN 96108932 A CN96108932 A CN 96108932A CN 1150594 A CN1150594 A CN 1150594A
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ethene polymers
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CN1095854C (zh
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G·N·福斯特
T·陈
R·H·福格尔
S·H·瓦泽曼
D·C·李
W·T·莱希勒
F·J·卡罗尔
G·T·韦蒂克
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Ulivisen Technologies Corp.
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Union Carbide Chemicals and Plastics Technology LLC
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Abstract

本发明能提供乙烯聚合物，它具有约2-约4的多分散性指数；熔体指数，MI，和松弛谱指数，RSI，致使(RSI)(MI0.6)约2.5-约6.5；c)结晶链长度分布指数，Lw/Ln，约1.0-约9；和d)密度ρ，和光雾百分率，当制成膜时光雾百分率低于370ρ-330，这些乙烯聚合物把优良的透明度和韧性和低排出性以及增强加工的容易性良好地结合起来。

Description

具有极高透明度、增强的韧性、低 排出性和易于加工的乙烯聚合物
本专利申请是于1995年3月29日提出的美国专利申请号08/412964的继续申请。
本发明涉及具有狭窄分子量分布和狭窄组分分布的乙烯聚合物，该聚合物易于在较窄的松弛时间分布下处理。由这种乙烯聚合物制成的制品具有极好的透明度和韧性以及很低的排出性。
金属茂催化剂，由于其能够在极佳的聚合速度下形成具有较窄分子量和共聚单体分布的乙烯聚合物，已受到广泛地注意。这种窄分子量和共聚单体分布有助于具有密度远低于0.95g/cc的乙烯聚合物在透明度、韧性和提取物水平方面上改进。然而，对于某些需要加工性能如挤出性的用途来说，由于其狭窄的分子量分布而使这些乙烯聚合物存在不足。例如U.S.P5,420,220和5,324,800公开了由金属茂制得的，线型低密度聚乙烯，它具有特殊狭窄的分子量和共聚单体分布，以及加工性能方面的有关限制。
遗憾地是，当为了促进加工性能而使乙烯聚合物的分子量分布变宽时，(乙烯聚合物的透明度和冲击强度会减小。另外，可提取物增加，尤其是对具有密度远低于0.93g/cc的乙烯聚合物。为了在保持狭窄分子量分布的同时改进乙烯聚合物的加工性能，可把长链支化引入聚合物中。例如，U.S.P5,272,236和5,278,272和PCT申请号W094/07930描述了由金属茂制成的，极低密度和低密度长支化结构的聚乙烯，据报道这种结构促进了加工性能。但是，长链支化结构在制造过程中有时会促进定向取向而导致机械性能失去平衡并降低耐冲击性和撕裂性。制品如吹制膜的透明度也低于(优化长链支化乙烯聚合物，甚至具有狭窄的分子量和共聚单体分布的这种聚合物的最佳值。
申请人现已发现一类乙烯聚合物，对比由齐格勒-纳塔型(Ziegler-Natta)催化剂制造的常规线型低密度聚乙烯来说，该聚合物具有狭窄分子量分布和狭窄组成分布。然而，出乎人们意外的是该乙烯聚合物还具有比较狭窄的松弛时间分布(按其松弛谱指数(RS1)确定)，因此，本发明的乙烯聚合物的加工性能在相同熔体指数不可与由Ziegler-Natta型催化剂制成的常规线型低密度聚乙烯(它们具有较宽分子量分布)相比，并且优于许多市售由金属茂制成的聚乙烯。
由本发明乙烯聚合物制成的膜制品特征在于高度透明度、高冲击强度(如突然冲出)、和低的提取物。同样地，由本发明乙烯聚合物制成的注射成型。
制品具有改进的透明度和韧性(如低温性能和ESCR)，其特征在于与已知线型低密度聚乙烯对比具有高冲击强度。与申请人的乙烯聚合物有关的增强韧性，在保留足够强度的同时可以使膜标准降低并且使成型部件“薄壁”。此外，该乙烯聚合物能为大量膜应用如拉伸、高透明度以及其它的包装膜。提供优越的操作功能。而且由于本发明的低排出性，由它们制成的膜和成型制品用于食品包装行业是有吸收力的。
本发明提供一种乙烯聚合物，它具有a)约2-约4的多分散指数；b)熔体指数，MI，和松弛谱指数，RSI，致使(RSI)(MI0.6)约2.5-约6.5；c)结晶链长度分布指数，LW/Ln，约1-约9；和d)密度，ρ，和光雾百分率，当制成膜对光雾百分率低于370ρ-330。
本发明还涉及通过将乙烯和任选地一种高级α-烯烃与无载体的、液体形式催化剂组合物在聚合条件下接触而制得的乙烯聚合物，该催化剂组合物由基本上不产生长链支化的过渡金属催化剂组成。
本发明的乙烯聚合物包括乙烯均聚物和乙烯与含3一约20个碳原子的直链或支链高级α-烯烃的共聚物，其密度范围约0.90-约0.95，熔体指数约0.1-200。合适的高级α-烯烃包括例如丙烯、1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯、1-辛烯、和3，5，5-三甲基1-己烯。环烯如乙烯基环己烷或降冰片烯也可与乙烯聚合。作为共聚用单体的还可包括具有乙烯基不饱和度的芳族化合物，如苯乙烯和取代苯乙烯。最佳乙烯聚合物包括乙烯和约1-约40％(按重量计)的一种或多种上述共聚单体。
本发明乙烯聚合物未对长链支化校准的多分散性指数为约2.0-约4.0，优选约2.5-约3.5。聚合物的多分散性指数(PDI)定义为聚合物的重量平均分子量与聚合物的数学平均分子量的比值(Mw/Mn)。PDI(未对长链支化校准的)可在140℃下采用流速为1ml/分的1，2，4-三氯苯操作WATERS1500 GPC型的筛析色谱仪(SEC)而测定。规定色谱柱的孔径范围能保证MW分离范围在200-10,000,000道尔顿。采用国家标准技术研究所(National Institute of Standards Technology)的聚乙烯标准NBS1475或1496作校准标准以获得未校准(假设线型聚合物)的分子量分布。
本发明乙烯聚合物具有独特的流变性，这使得制品具有不同分子结构并赋予优良的韧性。这种独特的流变性使有助于比较容易地形成制品，尤其是薄膜挤塑。特别是，该乙烯聚合物对于一种给定的乙烯聚合物具有下列熔体指数，MI，和松弛谱指数，RS1；
约2.5＜(RSI)  (MI0.6)＜约6.5。
优选的是
约3.0＜(RSI)  (MI0.6)＜约5.0。
在上述式中，MI是该聚合物以重10分数克数报导的熔体指数，按ASTM D-1238，条件E，於190℃下测定的，而RSI是无量纲单位的聚合物松弛谱指数。
测量乙烯聚合物的RSI最先是使聚合物经剪切形变再用流变仪测量其形变的特性曲线。正如在已知技术中所了解的，基于聚合物的特性曲线和所用流变仪的机理和几何结构，松弛模量G(t)或动态模量G′(ω)和G″(ω)都可以分别做为时间或频率ω的函数进行测量(参见J.M.Dealy和K.F.Wissbrun，Melt Rheology andIts Role in Plastics Processing，Van Nostrand Reinhold，1990，PP.269-297)。动态模量与储能模量间的数学关系是傅里叶转换积分关系，但也可用已知的松弛谱根据另一组数据计算出来一组数据(参见S.H.Wasserman，J.Rhology，vol.39，PP.601-625(1995))。使用经典机械模型，可以确定由一系列松弛或“模式”(mode)组成的离散松弛谱，这些松弛或“模式”各具有特征强度或“重量”和松弛时间。使用这样的谱，可把模量再表示成 G ′ ( ω ) = Σ i = l N g i ( ωλ i ) 2 l + ( ωλ i ) 2 G ′ ′ ( ω ) = Σ i = l N g i ωλ i l + ( ωλ i ) 2 G ( t ) = Σ i = l N g i exp ( - t / λ i ) 其中N是模式数而gi和λi是各种模式的重量和时间(参见J.D.Ferry，Viscoelastic Properties of Polymers，John Wiley&Sons，1980，PP.224-263)。聚合物的松弛谱可用软件如IRIS流变软件确定，该软件可从IRISDevelopmenf处买到。一旦计算出松弛谱的模式分布，第一和第二分布矩数(与Mn和Mw类似)，第一和第二分子量分布矩数，如下所述计算： g l = Σ i = l N g i / Σ i = l N g i / λ i g ll = Σ i = l N g i λ i / Σ i = l N g i RSI定义为gII/gI。
由于RSI对像聚合物的分子量分布、分子量和长链支化那样的参数敏感，所以它是一种聚合物的应力松弛的灵敏和可靠的指示剂。RSI值越高，聚合物的松弛时间分布越宽，因此聚合物的加工性能越好。
另外，本发明乙烯聚合物具有约1-约9的结晶链长度分布指数，Lw/Ln，优选约1-约6，这表明聚合物具有比较窄的共聚单体分布，因此具有相当高的组成均匀性。结晶链长度分布指数可采用如Wild等人，J.Polym-er Sci.，Poly.Phvs.Ed.，Vol20，P.441(1982)所描述的温度升高洗脱分馏(Temperature Rising ElutionFractionation)(TREF)法测量。将乙烯聚合物在溶剂如1，2，4-三氯苯中的稀溶液，以1-4mg/ml在高温下加入到填充柱中。然后使该柱以0.1℃/分的可控制方式缓慢冷却下来直到室温，随着温度的降低而增加支化(或降低或结晶度)结果使乙烯聚合物在填料上结晶，再以0.7℃/分的可控方式把柱加热到140℃以上，同时使溶剂以恒定流速为2ml/分流过填充柱。当将聚合物馏份洗脱时，它们随温度升高支化降低(或提高结晶度)。使用红外浓度检测器检测流出物的浓度。根据TREF温度数据，可获得给定的共聚单体的支化频率。因此，支链间的主链长度，用Lw和Ln表示，可按如下方式计算。Lw是支链间的重量平均链长：
                Lω＝∑iωiLiLn是支链间的数学平均链长：
                Ln＝1/∑i(ωi/Li)其中Wi是两个相邻支链点间具有平均主链间隔为Li的聚合物组分i的重量分数。
本发明的乙烯聚合物制成膜时光雾很低，这表明在指定的聚合物密度上有优良的透明度。尤其是，乙烯聚合物具有下列光雾百分率(当以膜形式时)和密度(对于指定的乙烯聚合物)：
          ％光雾＜(370ρ－330)其中ρ是聚合物密度。优选的是，
          ％光雾＜(370ρ－335)。密度按ASTM检验法D1505(G-101)测量。光雾百分率的测量是按ASTM检验法D1003进行，该法测量由于向前散射而偏离入射光(穿过样品)的透射光。就该检验方法来说，平均偏离2.5°以上的光通量是光雾。
用于制造本发明乙烯聚合物的催化剂组合物是无载体的液体并且包含基本上不产生长链支化的、优选没有长链支化的过渡金属催化剂。该过渡金属催化剂包括由过渡金属、取代的或未取代的π-链配位体，和杂烯丙基部分(如描述於1995年3月29日登记的待批U.S申请号08/412,964中的)的配合物组成的化合物。最好的是，这种化合物具有下列化学式中的一种：
Figure A9610893200111
其中：
M是过渡金属，优选Zr或Hf，
L是与M配位的取代的或未取代的、π键配位体，优选是环烷链二烯基配位体；
各个Q独立地选自由-O-、-NR-、-CR2-和-S-组成的组中，优选氧；
y或是C或是S，优选碳；
Z选自由-OR、-NR2、-CR3、-SR、-SiR3、-PR2和-H组成的组，先决条件是当Q是-NR-时Z选自由-OR、-NR2、-SR、-SR3、-PR2和-H组成的组，优选Z选自由-OR、-CR3和-NR2组成的组；
n是1或2；
当n是2时A是一价阴离子或当n是1时A是二价阴离子，优选地A是氨基甲酸酯、羧酸酯或其它由Q、y和Z组合所述的杂烯丙基部分；和
各R独立地为含碳、硅、氮、氧、和/或磷的基团，此处一个或多个R基因与L取代基连接，优选R是含1-20个碳原子的烃基，最好是烷基、环烷基或芳基和并且其中一个或一个以上的R基团与L取代基连接；
Figure A9610893200121
其中：
M是过渡金属，优选Zr或Hf，
L是与M配位的取代的或未取代的、π链配位体，优选是环烷二链烯基配位体；
各Q独立地选自由-O-、-NR-、-CR2-和-S-组成的组中，优选氧；
y或是C或是S，优选碳；
Z选自由-OR、-NR2、-CR3、-SR、-SiR3、-PR2和-H组成的组，必要条件是当Q是-NR-时，Z选自由-OR、-NR2、-SR、-SiR3、-PR2和-H组成的组，优选Z选自由-OR、-CR3和-NR2组成的组；
n是1或2；
当n是2时A是一价阴离子或当n是1时A是二价阴离子，优选地A是氨基甲酸酯、羧酸酯、或按Q、y和z组合所述的杂烯丙基部分；
各个R独立地为含碳、硅、氮、氧、和/或磷的基团，此处一个或多个R基因与L取代基连接，优选R是含1-20个碳原子的烃基团，最好的是烷基、环烷基或芳基并且一个或多个R基团与L取代基相连；
T是选自由含1-10个碳原子的亚烷基和亚芳基基团组成的组的桥链基团，任选为碳或杂原子、锗、硅和烷基膦取代；和
阴是1-7，优选2-6；最好2或3。
特别优选的由过渡金属、取代或未取代的π一键配位体和杂烯丙基部分的配合物组成的化合物是三(二乙基氨基甲酸)茚基锆和三新戊酸茚基锆。
可用于制备乙烯聚合物的其它过渡金属催化剂是单和非桥键双以及三环戊二烯基与过渡金属配位的配合物衍生物，如U.S.P4,542,199、5,324、800和欧洲专利250601-131所述的，它们在乙烯聚合物中基本上不产生，优选没有长链支化。这种催化剂的实例是二氯化双(环戊二烯基)锆和二苯氧基diphenoxide双(环戊二烯基)锆。
该催化剂与活化的助催化剂如铝噁烷，即甲基铝烷(MAO)或改性甲基铝噁，烷(MMAO)，或烷基硼共轭使用以形成用来生产乙烯聚合物的无载体的液体形式的催化剂组合物。铝噁烷是优选的助催化剂，其制备方法以及用途在本领域内是众所周知的。
用于产生乙烯聚合物的催化剂组合物按U.S.P.5317036所述必须以无载体的、液体形式引入到反应区。在本发明所使用的，“无载体的、液体形式”包括液体催化剂、液体助催化剂、催化剂溶液(多种)和在相同或不同溶剂(多种)中的助催化剂，及其组合物。除了它们具有制备具有良好性能的本发明乙烯聚合物的能力以外，可溶性催化剂组合物还具有许多另外的实际效果。无载体的催化剂组合物可避免与载体材料及其制备有关的费用，并且可保证实现催化剂表面积与体积的很高比值。除此之外，无载体的催化剂组合物可生产出残留灰分含量比用载体的催化剂组合物生产的聚合物低得多的聚合物。
乙烯聚合物可用任何常规的悬浮、溶液、浆料或气相聚合法制造、所用反应条件在技术上是已知的。可使用一个反应器或成系列的多个反应器。使用一个或多个流化床反应器的气相聚合是优选的。
聚合反应最好以气相在搅拌的或流化床反应器中进行，使用的设备和程序为已知技术。优选使用范围在1-1000psi内的超计大气压，优选50-400psi，最好100-300psi，和范围在30-130℃内的温度，优选65-110℃。乙烯和其它共聚用单体(如使用的话)与有效量催化剂组合物在足以引发聚合的一温度和压力下接触。
合适的气相聚合反应体系包括加入单体(多种)和催化剂组合物的反应器，该反应器包括一个形成聚乙烯颗粒的床。本发明不限於任何专用类型的气相反应体系。作为实例，常规流化床法的进行是在反应条件下和催化剂组合物存在下，使含一种或多种单体的气流在足以维持固体颗粒床呈悬浮态条件的速度下连续流过流化床。含未反应的气体单体气流从反应器连续地排出、加压、冷却，任选部分或充分冷凝，再循环到反应器。产品从反应器排出后往循环气流中加入补充的单体。
常规的添加剂也可用于本方法中，但必要条件是使它们不干扰催化剂组合物的功能。
当氧在工艺过程中作链转移剂使用时，其使用量可在每摩尔所加总单体约0.001-约10摩尔氦之间变化。此外，按对体系的温度控制的要求，任何对于催化剂组合物和反应物是不活泼的气体都可在气流中存在。
为了提高催化剂的活性，有机金属化合物可作为毒物的消除剂使用。这些化合物的实例是烷基金属，优选烷基端，最好的是三异丁基铝、三-正-己基铝。使用这种消除剂是现有技术。
乙烯聚合物可与其它聚合物和树脂按要求采用已知技术混合。另外，各种添加剂和试剂可与乙烯聚合物混合。特别是，可添加附加的热和光氧化稳定剂，包括位阻酚和羟基氨基抗氧化剂、位阻胺光稳定剂、硫酯、或二硫化物和亚磷酸芳基酯或膦酸芳基酯(arylPhosphonites)，为满足特殊产品的要求，可与本发明的乙烯聚合物按要求混合的物质包括过氧化二枯基的交联剂、包括炭黑和二氧化钛的着色剂、包括金属硬脂酸盐的润滑剂、包括含氟弹性体的操作助剂、包括油酰胺或芥酰胺(erucamide)的制浆剂、包括硬脂酰胺、亚乙基双硬脂酰胺的防粘剂或脱模剂、可控粒径的沸石、碳酸钙、滑石或二氧化硅、发泡剂、阻燃剂以及其它常规物质。
本发明的乙烯聚合物可以形成多种成品，如包括透明膜和收缩膜在内的膜，挤出涂料，金属丝和电缆的绝缘材料和护套，交联输电绝缘材料，由注塑、吹塑或滚塑制成的模塑制品，管、软管、型材和片材的挤塑品，和绝缘的和半导体护套和/或护罩。制造这些制品的方法是已知方法。
有关上述专利公开的内容作为参考而引入本发明。
下列非限制性实施例用来进一步说明本发明。实施例
测量
测量分子量和分子量分布如下。使用装有测量分子量的混合孔径柱的WATERS150C GPC色谱仪。对于筛析色谱(SEC)，使用来自Polymer Labs的25cm长初级柱，公称孔径50A，随后是3根25cm长的ShodexA-80M/S(Showa)柱，对约200-10,000,000道尔顿的线型乙烯聚合物进行分子量分离。两种均含有多孔聚(苯乙烯-二乙烯基苯)填料，采用1，2，4-三氯苯作溶剂制备聚合物溶液和色谱洗脱液。所有的测量均在140±0.2℃温度下进行。收集由质量和粘度检测器产生的模拟信号送入计算机系统。使用从市场上可以买到的来自若干来源(Waters公司和Viscotek公司)的未对长链支化校准的分子量分布标准软件处理所收集的数据。校准使用宽MWD校准法并把线型聚合物作校准物(见W.W.Yan，J.J.Kirkland和D.D.Bly，ModernSige-Exchusion Liquid Chromatography，Wiley，1979，P.289-313)。对于后者，与两种NW有关的统计量如数学和重量平均分子量值对于聚合物校准物来说必须是已知的。基于MW校准结果，把洗脱液体积换算成假定的线型乙烯聚合物的分子量。
流变测量是借助动态振荡剪切实验采用在从市场上可买到的TA仪器公司新型的Weissenberg流变仪来进行。实验於190℃的氮气氛下以平行板模式操作。样品大小从约1100-1500μm，直径4cm。频率扫描实验复盖范围0.1-100秒-1，应变幅度为2％。转矩特性曲线用TA仪器公司的流变仪控制软件转化成各自频率下的动态模量和动态粘度数据。使用IRIS市售软件使离散松弛谱适於每种样品的动态模量数据。
TREF实验如上描述进行。聚合物的熔体指数定为每10分钟的克数，其测量可按ASTM D1238，条件E。按ASTM检验法D1505(G-101)进行密度测量。按ASTM检验法D1003测量光雾。
           实施例1-19和A-N
将一系列本发明的乙烯聚合物(实施例1-19)就其各种性能与已知的聚乙烯样品进行比较，对比的性能包括多分散性指数(PDI)、结晶链长度分布指数(LW/Ln)、熔体指数(MI)、松弛谱指数(RSI)、光雾百分率、以及密度。结果列于表中。
实施例1-19中的乙烯聚合物用14英寸公称直径的、气相的、流化床反应器制造，该反应器床高10英尺。实施例1-19中的每种催化剂组合物都是无载体的液体。
用于制造实施例1-12的催化剂组合物包括三(二乙基氨基甲酸)茚基锆催化剂和改性甲基铝  烷活化助催化剂。
用于制造各实施例13-17的催化剂组合物包括三(新戊酸)茚基锆催化剂和改性甲基铝烷活化助催化剂。
用于制造实施例18和19的催化剂组合物分别包括二氯化双(环戊二烯基)锆和二苯氧基双(环戊二烯基)锆，和改性甲基铝＿烷活化助催化剂。
实施例9-12是乙烯和1-丁烯的线型共聚物，而实施例1-8和13-19是乙烯和1-己烯的线型共聚物。
对比例A和B是市场上可买得到的Dow化学公司的AFFINITY聚烯烃弹性体，如表中所说明的。
对比例C-H是市场上可买得到的Exxon化学公司的EXCEED和EXACT线型乙烯聚合物，如表中所说明的。
对比例I是市场上可买得到的BASF的线型乙烯共聚物，如表中所说明的。
对比例丁是乙烯和1-己烯的线型共聚物，它也是用14英寸公称直径、气相、流化床反应器制造的，该反应器的床高10英尺。用于制造对比例J的催化剂组合物包括二氯化双(正-丁基环戊二烯基)锆催化剂和改性的负载于二氧化硅上的甲基铝  烷活化助催化剂。
对比例K-N是用气相、流化床反应器通过UNIPOLR方法(Union Carhide公司)制造的市售线型低密度聚乙烯。它们是1-丁烯或1-己烯的乙烯共聚物，可以从市场上买到，产品标志为HS7093、HS7037、HS7028和DFDA9064。
对比例0是按实施例18相同方式制造的乙烯和1-己烯的线型共聚物，除了所用催化剂组合物是二氯化双(环戊二烯基锆和负载于二氧化硅上的改性甲基铝烷活化助催化剂以外。
本发明乙烯聚合物是与约1500ppmIRGANOXB-900(Ciba-Geigy公司)干混并且以40磅/小时(～98rpm)的速度在具有标准LLDPE混合螺杆(30/1长度直径比)的1-1/2英寸Killion挤出机内混合。本发明的球形乙烯聚合物和对比例聚乙烯在表中所例的具模温度和吹胀比的典型操作条件下被挤出或吹制膜。吹胀比定义为最终泡(管)直径与模直径的比位。吹制膜挤出设备由1英寸直径的装有24：1L/D的Sterling挤出机、通用LLDPE螺杆(等距螺纹、收敛式深度，Maddox混合头式螺杆)和螺旋芯棒模头组成的。吹制膜挤出设备以45磅/小时速度(-)98rpm)操作。
                                   表
                                 实施例
     1     2     3     4     5     6
           MI     0.44     0.68     0.68     0.85     1.70     1.83
       密度(g/cc)     0.938     0.937     0.937     0.937     0.929     0.929
          PDI     3.47     2.78     2.78     2.66     2.70     2.52
         Lw/Ln     8.90     5.31     5.31     4.13     7.24     5.88
          RSI     5.7     3.6     3.6     3.1     2.2     2.1
       光雾(％)     7.5     5.2     4.1     5.2     6.0     5.6
      己烷提取物     0.6     0.4     0.3     0.6     0.4     0.4
      突然下落(g)     50     50     50     50     77     73
      模头缝(mils)     100     100     100     100     100     100
     熔化温度(°F)     500     500     455     450     379     380
        吹胀比     2.6     2.6     2.6     2.6     2.6     2.6
      压头(psi)     2550     2200     2650     2350     1975     2200
       安培数     14.1     14.2     14.2     14.2     14.5     14.5
   模头速度(lb/hr/in)     6.5     6.7     6.4     6.7     7.0     7.2
    A＝370ρ-335     14.27    13.94     13.94     13.79     10.78     10.93
    B＝BSI★MI∧0.6     3.47     2.85     2.85     2.81     3.04     3.04
       光雾＜A     是     是     是     是     是     是
      2.5＜B＜6.5     是     是     是     是     是     是
      2＜PDI＜4     是     是     是     是     是     是
      1＜CCLDI＜9     是     是     是     是     是     是
                                      表
                                    实施例
     7     8       9     10     11     12
          MI     1.99     2.29     1.23     1.41     1.66     1.67
     密度(g/cc)     0.926     0.915     0.924     0.923     0.924     0.925
         PDI     3.13     2.66     2.61     2.49     2.51     2.74
        Lw/Ln     6.44     3.48     5.79     5.80     5.78     5.98
         RSI     2.4     1.9     2.7     2.3     2.2     2.2
      光雾(％)     3.6     3.0     7.2     7.4     6.4     8.6
     己烷提取物     2.6     1.2     0.4     0.6     0.5     0.4
     突然下落(g)     131     482     53     62     58     65
    模头缝(mils)     100     100     100     100     100     100
    熔化温度(°F)     388      428     405     402     402     400
       吹胀比     2.6     2.6     2.6     2.6     2.6     2.6
     压头(psi)     1800     900     2550     2200     2225     2400
       安培数     13.8     9.5     15.0     14.8     14.6     13.1
  模头速度(lb/hr/in)     7.1     6.4     6.5     6.7     6.9     6.5
    A＝370ρ-335     9.82     5.84     8.89     8.55     8.89     9.48
    B＝BSI★MI∧0.6     3.65     3.15     3.06     2.84     3.00     3.01
       光雾＜A     是     是     是     是     是     是
     2.5＜B＜6.5     是     是     是     是     是     是
     2＜PDI＜4     是     是     是     是     是     是
     1＜CCLDI＜9     是     是     是     是     是     是
                                                  表
                                                实施例
    13     14      15     16      17     18
          MI     0.50     0.79     0.93     1.05     1.07     0.52
     密度(g/cc)     0.937     0.922     0.920     0.916     0.929     0.920
          PDI     2.70     2.89     3.40     2.93     2.62     2.87
         Lw/Ln     6.57     8.58     8.11     7.61     7.55     1.78
          RSI     4.1     4.6     4.1     4.2     3.3     6.3
       光雾(％)     5.6     5.2     3.0     3.0     4.8     3.7
      己烷提取物     0.5     1.2     1.1     1.7     0.6     0.4
      突然下落(g)     109     200     234     383     71     770
     模头缝(mils)     100     100     100     100     100     100
     熔化温度(°F)     500     470     423     423     429     480
        吹胀比     2.6     2.6     2.3     2.6     2.6     4.4
      压头(psi)     2300     1850     2200     2000     2000     2050
        安培数     14.8     14.0     14.8     14.0     14.5     15.0
 模头速度(1b/hr/in)     6.5     7.2     7.1     6.1     6.9     7.1
    A＝370ρ-335    13.90    8.33     7.59     6.10     10.78     7.59
   B＝BSI★MI∧0.6     2.68    3.97     3.92     4.33     3.44     4.22
        光雾＜A     是     是     是     是     是     是
     2.5＜B＜6.5     是     是     是     是     是     是
      2＜PDI＜4     是     是     是     是     是     是
     1＜CCLDI＜9     是     是     是     是     是     是
                                       表
                                      实施例
    19      AAffinity 1570      BAffinity 1840     CExceed 399L60     DExceed 350B60     EExceed 350D60
          MI     0.82     1.10     0.99     0.70     0.96     0.97
     密度(g/cc)     0.920     0.915     0.910     0.925     0.917     0.917
         PDI     3.35     2.26     2.11     2.47     2.34     2.45
        Lw/Ln     1.95     1.90       -      -     4.78     4.48
         RSI     6.4     7.4     8.2     2.4     2.4     2.2
      光雾(％)     3.6     7.9     5.6     10.6     8.3     9.3
    己烷提取物     1.8     0.5     0.7     0.3     0.3     0.4
    突然下落(g)     275     413     362     157     61     710
    模头缝(mils)     100     100     100     100     100     100
    熔化温度(°F)     460     410     392     435     432     432
       吹胀比     2.6     2.6     2.6     2.6     2.6     2.6
     压头(psi)     1650     1400     2250     2005     2170     2005
       安培数     13.5     11.6     13.9     14.9     14.9     14.9
  模头速度(lb/hr/in)      6.3     6.9     6.7     6.8     6.9     6.8
    A＝370ρ-335     7.40     5.73     3.87     9.44     6.47     6.47
    B＝BS★MI∧0.6     5.66     7.84     8.16     1.93     2.34     2.16
       光雾＜A     是     否     否     否     否     否
     2.5＜B＜6.5     是     否     否     否     否     否
      2＜PDI＜4     是     是     是     是     是     是
     1＜CCLDI＜9     是     是     是     是     是     是
                                          表
                                         实施例
     FExceed 350L65     GExceed 357C80       HAExact 2010       IBASF KR1922     J     KHS7093
         MI     1.08     3.45     1.55     1.10     0.73     1.97
    密度(g/cc)     0.917     0.917     0.925     0.909     0.923     0.927
         PDI     2.50     2.24     2.03     1.98     2.16     4.10
        Lw/Ln     2.80     2.66     1.22     1.89     3.01     13.97
         RSI     2.1     1.5     1.8     2.2     2.8     2.8
     光雾(％)     14.4     20.7     6.5     1.3     6.7     15.6
    己烷提取物     0.6     1.0     0.3     0.9     0.5     2.2
    突然下落(g)     770     368     137     410     158     59
    模头缝(mils)     100     100     100     100     100     100
    熔化温度(°F)     435     388     430     430     490     391
       吹胀比     2.6     2.6     2.6     2.6     2.6     2.6
     压头(psi)     1910     1375     1625     1850     2600     1600
       安培数     15.7     13.2     14.7     11.8     15.5     13.0
 模头速度(lb/hr/in)     6.6     7.4     6.9     6.6     6.6     7.1
    A＝370ρ-335     6.47     6.47     9.44     3.50     8.70     10.04
    B＝BSI★MI∧0.6     2.20     3.20     2.35     2.3     2.31     4.23
       光雾＜A     否     否     是     是     是     否
     2.5＜B＜6.5     否     是     否     否     否     是
      2＜PDI＜4     是     是     是     否     是     否
     1＜CCLDI＜9     是     是     是     是     是     否
                                      表
                                    实施例
      LHS7037      MHS7028       NDFDA9064     O
         MI     0.52     1.00     1.02     0.90
     密度(g/cc)     0.923     0.920     0.911     0.916
        PDI       -      -     3.70     2.83
       Lw/Ln       -      -     11.64     2.49
        RSI       -     4.8     5.6     8.90
      光雾(％)     10.5     13.5     5.7      -
    己烷提取物     1.0     3.5     5.9      -
    突然下落(g)     50     101     112      -
    模头缝(mils)     100     100     100      -
    熔化温度(°F)     484     420     395      -
       吹胀比     2.6     2.6     2.6      -
      压头(psi)     2200     2100     2075      -
       安培数     14.5     1.5     14.4      -
  模头速度(lb/hr/in)     6.9     7.3     7.1      -
    A＝370ρ-335     8.74     7.51     4.39     6.10
   B＝BSI★MI∧0.6     4.79     5.65     8.31
       光雾＜A     否     否     否     -
      2.5＜B＜6.5     否     是     是     否
      2＜PDI＜4     否     是     是     是
      1＜CCLDI＜9     否     是     否     是

Claims (7)

1.一种乙烯聚合物，具有：
a)约2-约4的多分散性指数；
b)熔体指数，MI，和松弛谱指数，RSI，使(RSI)(MI0.6)为约2.5-约6.5；
c)约1-约9的结晶链长分布指数，Lw/Ln；和
d)密度，ρ，和光雾百分率，当制成膜时光雾百分率低于370ρ-330。
2.权利要求1的乙烯聚合物，含有3-约20个碳原子的约1-约40％(按重量计)线型或支链α-烯烃。
3.权利要求1的乙烯聚合物，含有选自丙烯、1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯及其混合物约1-约40％(按重量计)共聚单体。
4.膜、挤出涂料、金属丝和电缆的绝缘材料和/或护套、交联的输电绝缘材料、模塑制品、或绝缘护套和或半导体护套和/或护罩含有权利要求的乙烯聚合物。
5.乙烯聚合物，通过在聚合条件下将乙烯和任选地高级α-烯烃与无载体的、液体形式催化剂组合物接触而制备，所述催化剂组合物包含基本上不产生长链支化的速度金属催化剂。
6.权利要求5的乙烯聚合物，其中过渡金属催化剂是三(二乙基氨基甲酸)茚基锆或三(新戊酸)茚基锆。
7.权利要求5的乙烯聚合物是由气相聚合物制备的。
CN96108932A 1995-03-29 1996-03-29 具有极高透明度、增强的韧性、低排出性和易于加工的乙烯聚合物 Expired - Lifetime CN1095854C (zh)

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BR9601206A (pt) 1998-01-06
US6159617A (en) 2000-12-12
AU720692B2 (en) 2000-06-08
CA2173005A1 (en) 1996-09-30
DE69624398D1 (de) 2002-11-28
EP0735060A2 (en) 1996-10-02
ATE226601T1 (de) 2002-11-15
MXPA96001224A (es) 2005-07-12
PT735060E (pt) 2003-03-31
DE69624398T2 (de) 2003-06-12
PL313556A1 (en) 1996-09-30
EP0735060B1 (en) 2002-10-23
CZ291970B6 (cs) 2003-06-18
HU9600824D0 (en) 1996-05-28
CN1095854C (zh) 2002-12-11
SK42096A3 (en) 1997-03-05
CZ93996A3 (en) 1996-10-16
KR960034236A (ko) 1996-10-22
AU5038096A (en) 1996-10-10
KR100281368B1 (ko) 2001-02-01
HUP9600824A2 (en) 1997-04-28
CA2173005C (en) 2000-02-01
PL188130B1 (pl) 2004-12-31
EP0735060A3 (en) 1998-04-08
HUP9600824A3 (en) 1997-11-28
ES2182946T3 (es) 2003-03-16

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