CN1398272A - 丙烯抗冲共聚物 - Google Patents
丙烯抗冲共聚物 Download PDFInfo
- Publication number
- CN1398272A CN1398272A CN01804671A CN01804671A CN1398272A CN 1398272 A CN1398272 A CN 1398272A CN 01804671 A CN01804671 A CN 01804671A CN 01804671 A CN01804671 A CN 01804671A CN 1398272 A CN1398272 A CN 1398272A
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- indenyl
- dichloro
- rac
- Prior art date
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及丙烯抗冲共聚物组合物。尤其,这些独特和改进的组合物能够用常规工业规模方法来生产。
Description
发明领域
本发明涉及丙烯抗冲共聚物组合物。尤其,这些独特和改进的组合物能够使用金属茂催化剂以工业规模方法来生产。
背景技术
丙烯抗冲共聚物通常用于其中需要强度和抗冲性的各种应用,如模塑和挤出汽车部件、家用电器、行李箱和家具。丙烯均聚物通常不适合于这些应用,因为它们太脆且抗冲性低(尤其在低温下),而丙烯抗冲共聚物特别设计用于诸如此类的应用。
典型的丙烯抗冲共聚物含有两种相或组分,均聚物组分和共聚物组分。这两种组分通常以序列聚合方法来生产,在该方法中,将在第一反应器中生产的均聚物转移到其中共聚物被生产并被引入均聚物组分基质内的第二反应器。共聚物组分具有橡胶状特性和提供了所需的抗冲性,而均聚物组分提供了全部劲度。
许多工艺变量影响所得抗冲共聚物,它们已被广泛研究,并进行控制,以获得各种所希望的效果。例如,U.S.专利No.5,166,268描述了用于生产丙烯抗冲共聚物的“冷成型”方法,其中成品在预成型材料(在这种情况下为丙烯抗冲共聚物)的熔点以下的温度制造。该专利方法使用由均聚物或结晶共聚物基质(第一组分)和至少10wt%的乙烯和少量丙烯的“共聚合物”(第二组分)组成的丙烯抗冲共聚物。将共聚单体加到第一组分中降低了它的劲度。乙烯/丙烯共聚物第二组分能使冷成型成品更好地保持其形状。
U.S.专利No.5,258,464描述了具有改进抗“应力发白”性的丙烯抗冲共聚物。应力发白是指在冲击或其它应力处出现的白点。这些不同的常规丙烯抗冲共聚物具有第一和第二组分,特征在于第二组分特性粘度与第一组分特性粘度的数值比接近于1。
在U.S.专利No.5,362,782中,将成核剂加到具有接近1的共聚物橡胶相(第二组分)的特性粘度与均聚物相(第一组分)的特性粘度的数值比的丙烯抗冲共聚物中,以及共聚物相的乙烯含量在38-60wt%的范围内。这些丙烯抗冲共聚物据说生产出了具有良好透明度以及冲击强度和抗应力发白性的制品。成核剂增加了劲度和抗冲强度。
U.S专利No.5,250,631描述了具有均聚丙烯第一组分和乙烯/丁烯/丙烯三元共聚物第二组分的丙烯抗冲共聚物。再次,目标是获得与抗应力发白性相配的高抗冲强度。
如U.S.专利No.5,948,839中所述丙烯抗冲共聚物还用于生产薄膜。在该专利中所述的抗冲共聚物含有常规第一组分和25-45wt%的乙烯/丙烯第二组分,该第二组分具有55-65wt%的乙烯。该抗冲共聚物组合物具有7-60dg/min的熔体流速。这些薄膜在如尿布之类的制品中使用。
最近,人们致力于使用新开发的金属茂催化剂技术来制备丙烯抗冲共聚物,以便利用这些催化剂提供的固有益处。众所周知的是,用这些“单位点”催化剂制备的均聚物具有分子量分布狭窄,以及可萃取物含量低和与此相关的各种其它有利性能。除了分子量分布窄和可萃取物含量低以外,金属茂催化的共聚物具有窄的组成分布。
遗憾的是,已知金属茂在工业相关工艺条件下不能提供具有足够高分子量的共聚物组分。与常规催化的对应物相比,所得丙烯抗冲共聚物具有低劣的抗冲强度。
U.S.5,990,242通过使用乙烯/丁烯(或高α-烯烃)共聚物第二组分而非丙烯共聚物解决了该问题,该第二组分使用二茂铪(hafnocene)类金属茂制备。这些铪金属茂通常已知用于生产相对高分子量的聚合物;然而,它们的活性比更通常使用的二茂锆低得多。在任何情况下,第二组分分子量和特性粘度都低于良好抗冲强度的要求。
本发明人已经发现除了高抗冲强度所需的性能以外还具有金属茂催化的聚合物的益处的新型丙烯抗冲共聚物组合物。重要的是,这些聚合物能够使用工业规模方法来经济地生产。
本发明的概述
本发明提供了反应器生产的丙烯抗冲共聚物组合物,包括:
(a)大约40wt%到大约95wt%的组分A,以抗冲共聚物的总重量为基准,组分A包括丙烯均聚物或共聚物,其中共聚物包括10wt%或10wt%以下的乙烯、丁烯、己烯或辛烯共聚单体,
(b)大约5wt%到大约60wt%的组分B,以抗冲共聚物的总重量为基准,组分B包括丙烯共聚物,其中共聚物包括大约20wt%到大约70wt%乙烯、丁烯、己烯和/或辛烯共聚单体,以及大约80wt%到大约30wt%丙烯,其中组分B:
(i)具有至少100,000的重均分子量;
(ii)高于60%的组成分布;和
(iii)大于1.00dl/g的特性粘度。
本发明还提供了以多段工艺生产丙烯抗冲共聚物的方法,其中包括丙烯均聚物或共聚物的组分A在初始阶段生产,其中共聚物包括10wt%或10wt%以下的乙烯、丁烯、己烯或辛烯共聚单体,组分B在后续阶段中生产,组分B包括丙烯共聚物,其中共聚物包括大约20wt%到大约70wt%乙烯、丁烯、己烯和/或辛烯共聚单体,和大约80wt%到大约30wt%丙烯,其中组分A和/或B的至少一种使用选自以下的金属茂来聚合:rac-二氯·二甲基硅杂二基(2-iPr,4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[邻甲基苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
附图简述
图1是来自表8的缺口艾佐德强度值与弯曲模量数据的函数关系的曲线图。
本发明的描述
本发明的丙烯抗冲共聚物(“ICP”)包括至少两种主要组分,组分A和组分B。组分A优选是全同立构丙烯均聚物,虽然可以使用少量共聚单体以获得特定性能。一般,组分A的这种共聚物含有10wt%或低于10wt%,优选低于6wt%或更少的共聚单体,如乙烯、丁烯、己烯或辛烯。最优选使用低于4wt%的乙烯。最终结果通常是产物与均聚物组分A相比劲度降低,但抗冲强度有一些增加。
这里使用的组分A通常指ICP组合物的二甲苯不溶性部分,以及组分B通常指二甲苯可溶性部分。在二甲苯可溶性部分明显具有高分子量组分和低分子量组分的场合,我们发现低分子量组分归属于无定形低分子量丙烯均聚物。因此,组分B在这些情况下仅指高分子量部分。
组分A优选具有窄分子量分布Mw/Mn(“MWD”),即低于4.0,优选低于3.5,更优选低于3.0,和最优选2.5或更低。这些分子量分布使用过氧化物或设计用于减小分子量的其它补充反应器处理在没有减粘裂化的情况下获得。组分A优选具有至少100,000,优选至少200,000的重均分子量(Mw,根据GPC测定)和至少145℃,优选至少150℃,更优选至少152℃和最优选至少155℃的熔点(Mp)。
ICP的另一重要特征是它们含有的无定形聚丙烯的量。本发明的ICP以具有低无定形聚丙烯,优选低于3wt%,更优选低于2wt%,甚至更优选低于1wt%和最优选没有可测得的无定形聚丙烯为特征。
组分B最优选是基本由丙烯和乙烯组成的共聚物,尽管其它丙烯共聚物、乙烯共聚物或三元共聚物可以是适合的,取决于所需特定产品的性能。例如,可以使用丙烯/丁烯,己烯或辛烯共聚物和乙烯/丁烯、己烯或辛烯共聚物,以及可以使用丙烯/乙烯/己烯-1三元共聚物。然而在优选的实施方案中,组分B是包括至少30wt%丙烯,更优选大约80wt%到大约30wt%丙烯,甚至更优选大约70wt%到大约35wt%丙烯的共聚物。组分B的共聚单体含量优选是在大约20wt%到大约70wt%共聚单体,更优选大约30wt%到大约65wt%共聚单体,甚至更优选大约35wt%到大约60wt%的共聚单体的范围内。最优选的是,组分B基本由丙烯和大约20%到大约70%乙烯,更优选大约30%到大约65%乙烯,和最优选大约35%到大约60%乙烯组成。
对于其它组分B共聚物,共聚单体含量需要根据所需的特殊性能来进行调节。例如,对于乙烯/己烯共聚物,组分B应该含有至少17wt%己烯和至少83wt%乙烯。
组分B优选具有窄分子量分布Mw/Mn(“MWD”),即低于5.0,优选低于4.0,更优选低于3.5,甚至更优选低于3.0和最优选2.5或2.5以下。这些分子量分布应该在没有减粘裂化或过氧化物或设计用于降低分子量的其它补充反应器处理的情况下获得。组分B优选具有至少100,000,优选至少150,000和最优选至少200,000的重均分子量(Mw,通过GPC测测定)。
组分B优选具有高于1.00dl/g,更优选高于1.50dl/g和最优选高于2.00dl/g的特性粘度。术语“特性粘度”或“IV”这里通常用来指聚合物如组分B在给定溶剂中的溶液在给定温度下的粘度,当聚合物组合物在无限稀释下时。根据ASTM标准试验方法D 1601-78,IV测量涉及使用标准毛细管粘度测量设备,其中在给定温度下测定一系列浓度的聚合物在溶剂中的粘度。对于组分B,十氢萘是适合的溶剂和典型温度是135℃。从不同浓度的溶液的粘度值可以看出,在无限稀释下的“值”能够通过外推法来测定。
组分B优选具有高于60%,更优选高于65%,甚至更优选高于70%,还更优选高于75%,进一步优选高于80%,和最优选高于85%的组成分布(CD)。CD规定了总体上就共聚物的乙烯(或其它共聚单体)含量而论的聚合物链中的组成变化。CD的测定详细描述在U.S.专利No.5,191,042中,该专利在这里全面引用供参考。CD在这里被定义为具有共聚单体含量在50%的中值总摩尔共聚单体含量内的共聚物分子的重量百分数。
如在U.S.专利No.5,191,042中所述,CD通过用适合的试验如ASTM D-3900首先测定共聚物的平均乙烯(或其它共聚单体)含量来测定。接着,将共聚物样品溶解在溶剂如己烷中,许多不同组成的级分通过添加递增量的其中共聚物不溶的液体如异丙醇来沉淀。通常,以这种方式大约4到6个级分被沉淀出来,以及在去除溶剂后测定各级分的重量和乙烯(或其它共聚单体)含量。根据各级分的重量和其乙烯含量,可以定出聚合物的wt%组成对累积wt%的各点位置,再通过各点绘制平滑曲线。
ICP的组分B优选具有低结晶度,优选低于10wt%的结晶部分,更优选低于5wt%的结晶部分。在组分B具有结晶部分的场合,就总共聚单体重量百分数而论,它的组成优选与组分B的剩余物相同或至少类似(在15wt%内)。
本发明的ICP是“反应器生产的”,意思是组分A和B并非以物理或机械方式共混在一起。相反,它们在至少一个反应器中共聚合。然而,从反应器中获得的最终ICP能够与包括其它聚合物的各种其它组分共混。
这些ICP的优选熔体流速(“MFR”)取决于所需的最终用途,但通常是在大约0.2dg/min到大约200dg/min,更优选大约5dg/min到大约100dg/min的范围内。重要地,高MFR,即高于50dg/min是可以获得的。MFR通过常规步骤如ASTM-1238 Cond.L来测定。ICP优选具有至少145℃,优选至少150℃,更优选至少152℃和最优选至少155℃的熔点。
ICP包括大约40wt%到大约95wt%组分A和大约5wt%到大约60wt%组分B,优选大约50wt%到大约95wt%组分A和大约5wt%到大约50wt%组分B,甚至更优选大约60wt%到大约90wt%组分A和大约10wt%到大约40wt%组分B。在最优选的实施方案中,ICP基本由组分A和B组成。总ICP的总共聚单体(优选乙烯)含量优选是在大约2wt%到大约30wt%,优选大约5wt%到大约25wt%,甚至更优选大约5wt%到大约20wt%,还更优选大约5wt%到大约15wt%的共聚单体的范围内。
各种添加剂可以因各种目的而引入到ICP中。这些添加剂包括例如稳定剂,抗氧化剂,填料,着色剂,成核剂和脱模剂。
本发明的ICP组合物可以通过常规聚合方法如二步法来制备。虽然目前无法实施,但可以设想在单一反应器中工业化生产ICP。各步骤可以独立在气相或液体淤浆相中进行。例如,第一步可以在气相中进行和第二步在液体淤浆中进行,反之亦然。另外,各相可以是相同的。优选,本发明的ICP在串联操作的多个反应器,优选两个或三个中生产,组分B优选在第二个气相反应器中进行聚合。组分A优选以液体淤浆或溶液聚合方法最先聚合。
在供选择的实施方案中,组分A在至少两个反应器中制备,以便获得具有不同熔体流速的级分。发现如此可以改进ICP的加工性能。
这里所使用的“阶段”被定义为聚合过程的一部分,在该过程中,ICP的一种组分,即组分A或组分B被生产。在每一阶段中可以使用一个或多个反应器。
氢可以加到一个或两个反应器中,以控制分子量、IV和MFR。氢用于这些目的的用途对本领域中那些技术人员来说是公知的。
优选,使用金属茂催化剂体系来生产本发明的ICP组合物。迄今为止,看起来最适合的金属茂是在桥接、取代的双(环戊二烯基)金属茂,具体说,已知用于生产高分子量、高熔点、高度全同立构丙烯聚合物的桥接、取代的双(茚基)金属茂的类属中的那些。一般而言,在U.S.专利No.5,770,753(这里全面引用供参考)中公开的类属中的那些应该是适合的,然而,已经发现,所获得的确切聚合物高度取决于金属茂的具体取代方式。
我们已经发现,以下外消旋金属茂对于制备本发明的ICP组合物是最适合的:rac-二氯·二甲基硅杂二基(2-iPr,4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr,4-[邻甲基苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。本领域中的那些技术人员将马上会清楚,这些金属茂物质的某些改变不大可能导致明显变化的ICP组合物,虽然活性或合成的容易性可能受影响。虽然不希望受理论的制约,据信这些特殊金属茂的关键特征是它们在碱性茚基上的取代方式。因此,可以认为改变桥基,例如用碳取代硅,或将金属换为铪或钛,或将金属二氯化物改变为一些其它的二卤化物或二甲基,将不会明显改变本发明的ICP组合物。另一方面,用在茚基上的任意位置上的基团取代另一个或增加一个或多个基团或取代基很可能导致明显不同的组合物,它们可以与本发明的ICP相同或不同。
金属茂一般与某些形式的活化剂结合使用以便产生活性催化剂体系。术语“活化剂”这里被定义为任意化合物或组分,或化合物或组分的结合物,能够增强一种或多种金属茂对聚合烯烃的能力。烷基铝氧烷如甲基铝氧烷(MAO)通常用作金属茂活化剂。通常,烷基铝氧烷含有5到40个以下重复单元:
R(AlRO)xAlR2(线性物质)和(AlRO)x(环状物质),
其中R是C1-C8烷基,包括混合烷基。其中R为甲基的化合物是特别优选的。铝氧烷溶液,尤其甲基铝氧烷溶液可以从商家那里以具有各种浓度的溶液获得。这里有制备铝氧烷的各种方法,它们的非限制性实例描述在U.S.专利No.4,665,208,4,952,540,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235,081,5,103,031以及EP-A-0 561 476,EP-B1-0 279 586,EP-A-0 594 218和WO 94/10180中,其分别在这里全面引用供参考。
还可以使用电离活化剂来活化金属茂。这些活化剂是中性或离子型的,或是诸如四(五氟苯基)硼酸三(正丁基)铵之类的化合物,它们可以电离中性金属茂化合物。这些电离化合物可以含有活性质子,或与电离化合物的其余离子相连,但不配位或仅松散地配位于它们的一些其它阳离子。还可以使用活化剂的结合物,例如,铝氧烷和电离活化剂结合物,例如参阅WO 94/07928。
包括由非配位阴离子活化的金属茂阳离子的用于配位聚合的离子催化剂的描述出现在早期的文献如EP-A-0 277 003,EP-A-0 277004和US专利5,198,401和WO-A-92/00333中(这里引用供参考,目的是为了实施U.S.专利)。它们教导了理想的制备方法,其中金属茂(双Cp和单Cp)用阴离子前体质子化,使得烷基/氢化物基团从过渡金属中被夺取,以使其变成两个阳离子和被非配位阴离子平衡电荷。适合的离子盐包括具有氟化芳基组分如苯基、联苯基和萘基的四取代的硼酸盐或铝盐。
术语“非配位阴离子”(NCA)是指不配位于所述阳离子或仅弱配位于所述阳离子,从而保持充分容易被中性路易斯碱置换的阴离子。“相容的”非配位阴离子是当初始形成的配合物分解时不被降解为中性的那些。此外,该阴离子不将阴离子取代基或片段转移到阳离子上,以使它形成中性四配位金属茂化合物和来自于阴离子的中性副产物。尤其有用的非配位阴离子是相容的,在平衡其离子电荷的意义上稳定金属茂阳离子在+1价态,还保持在聚合期间被烯属或炔属不饱和单体置换的足够倾向性的那些。
使用不含活性质子,但能够产生活性金属茂阳离子和非配位阴离子的电离离子化合物也是已知的。例如参阅EP-A-0 426 637和EP-A-0 573 403(在这里引用供参考,以便实施U.S.专利)。制备离子催化剂的其它方法使用电离阴离子前体,它们最初是中性路易斯酸,但在用金属茂化合物进行电离反应,例如使用三(五氟苯基)硼烷时形成了阳离子和阴离子。参阅EP-A-0 520 732(这里引用供参考,以便U.S.专利的实施)。用于加聚的离子催化剂还能够通过过渡金属化合物的金属中心用含有金属氧化基团与阴离子基团的阴离子前体氧化来制备,参阅EP-A-0 495 375(这里引用供参考,以便U.S.专利的实施)。
在金属配体包含在标准条件下不能电离夺取的卤素结构部分(例如二氯·双环戊二烯基合锆)的场合,它们能够通过与有机金属化合物如氢化或烷基锂或铝,烷基铝氧烷,格利雅试剂等的已知烷基化反应来转化。关于就地方法,参阅EP-A-0 500 944和EP-A1-0 570982(这里引入供参考,以便U.S.专利的实施),它们描述了烷基铝化合物与二卤代金属茂化合物在添加活化阴离子化合物之前或同时进行反应。
负载包括金属茂阳离子和NCA的离子催化剂的方法描述在U.S.专利No.5,643,847,1998年11月2日提出的U.S.专利申请No.09184358和1998年11月2日提出的U.S.专利申请No.09184389中(全部在这里全面引用供参考,以便U.S.专利的实施)。
当用于金属茂负载催化剂的活化剂是NCA时,优选首先将NCA加到载体组合物中,随后添加金属茂催化剂。当活化剂是MAO时,优选将MAO和金属茂催化剂一起溶解在溶液中。载体然后与MAO/金属茂催化剂溶液接触。其它方法和添加的次序对本领域中的那些技术人员来说是显而易见的。
用于制备本发明的组合物的催化剂体系优选使用多孔颗粒状材料,例如滑石、无机氧化物、无机氯化物和树脂材料如聚烯烃或聚合化合物来负载。
优选的是,负载材料是多孔无机氧化物材料,包括来自于元素周期表的2、3、4、5、13或14族金属氧化物的那些。二氧化硅、氧化铝、二氧化硅-氧化铝以及它们的混合物是特别优选的。可以单独或与二氧化硅、氧化铝或二氧化硅-氧化铝结合使用的其它无机氧化物是氧化镁、二氧化钛、氧化锆等。
优选,载体材料是表面积在10-700m2/g范围内,总孔体积在0.1-4.0cc/g范围内和平均粒度在10-500μm范围内的多孔二氧化硅。更优选,表面积是在50-500m2/g的范围内,孔体积在0.5-3.5cc/g的范围内和平均粒度在20-200μm的范围内。最理想的是,表面积是在100-400m2/g的范围内,孔体积在0.8-3.0cc/g的范围内和平均粒度在30-100μm的范围内。典型多孔载体材料的平均孔径是在10-1000的范围内。优选,使用平均孔径为50-500,最好75-300的载体材料。特别希望,将二氧化硅在100-800℃的温度下脱水3-24小时,无论是在何处。
金属茂、活化剂和载体材料可以许多方式结合。适合的负载技术描述在U.S.专利Nos.4,808,561和4,701,432(各自全面引用供参考)中。优选,如在U.S.专利No.5,240,894和WO 94/28034,WO96/00243和WO96/00245(各在这里全面引用供参考,以便U.S.专利的实施)中所述,将金属茂和活化剂合并,再将它们的反应产物负载在多孔载体材料上。另外,金属茂可以单独预活化,然后与载体材料单独或一起合并。如果金属茂单独负载,那么优选将它们干燥,然后在聚合中使用前作为粉末合并。
不管金属茂和它们的活化剂是单独预接触,还是金属茂和活化剂立刻合并,施用于多孔载体的反应溶液的总体积理想地低于多孔载体总孔体积的4倍,更希望低于多孔载体总孔体积的3倍,甚至更希望为多孔载体总孔体积的大于1到低于2.5倍。测量多孔载体的总孔体积的步骤在本领域是公知的。一种这样的方法描述在Volume 1,Experimental Methods in Catalyst Research,Academic Press,1968,67-96页中。
负载包括金属茂阳离子和非配位阴离子的离子催化剂的方法描述在WO 91/09882,WO 94/03506,WO 96/04319和在1994年8月3日提出的待审查U.S.Ser.No.08/248,284中(在这里作为参照引用,以便U.S.专利的实施)。这些方法通常包括在传统聚合或无机载体(其已经大量脱水和脱羟基)上的物理吸收,或者使用属于足够强的路易斯酸的中性阴离子前体,以活化在含二氧化硅的无机氧化物载体中的保留羟基,使得路易斯酸变成共价结合和羟基的氢可用于使金属茂化合物质子化。
负载催化剂体系可以在聚合中直接使用,或者催化剂体系可以使用本领域中公知的方法来预聚合。关于预聚合的详细情况,参阅美国专利Nos.4,923,833和4,921,825,EP 0 279 863和EP 0 354 893,各自在这里全面引用供参考。
虽然已经参照特定的实施方案描述和举例说明了本发明,但本领域中的那些普通技术人员将会清楚,本发明本身提供了这里没有说明的许多不同的变化。因为这些原因,应该单独参照所附权利要求书来确定本发明的真正范围。
按照U.S.专利惯例,虽然附属权利要求具有单一附属性,但在任意附属权利要求中的每一个特征可以与其它附属权利要求或主权利要求的每一个特征相结合。
实施例
所有空气敏感实验是在氮气吹扫的干燥箱中进行。所有溶剂从商业来源购买。4-氯-2-异丙基茚从商业来源购买。烷基铝以烃溶液从商业来源购买。工业甲基铝氧烷(“MAO”)以30wt%甲苯溶液从Albemarle购买。
金属茂合成
金属茂A:外消旋二氯·二甲基硅杂二基(2-异丙基-4-苯基茚基)2合锆从商业来源获得,并按来样使用。
金属茂B:外消旋二氯·二甲基硅杂二基(2-异丙基-4-[1-萘基]茚基)2合锆从商业来样获得,并按来样使用。
金属茂C:外消旋二氯·二甲基硅杂二基(2-异丙基-4-[2-甲基-苯基]茚基)2合锆如下制备:
4-(2-甲基苯基)-2-异丙基茚
将4-氯-2-异丙基茚(9.8g,51mmol)和NiCl2(PPh3)2(1.8g,2.8mmol)溶解在150mL的Et2O中。将作为Et2O溶液的溴化2-甲基苯基镁(51mmol)加到溶液中,反应物在室温下搅拌一整夜。在彻夜搅拌后,将反应物用H2O缓慢骤冷,以中和未反应的格利雅试剂。溶液随后用100mL的10% HCl(aq)处理,再用饱和碳酸氢钠水溶液中和。有机层用硫酸镁干燥,再通过旋转蒸发除去溶剂。剩余的残留物装填到硅胶柱中,然后用己烷洗脱。产量是6.6g(52%)。
4-(2-甲基苯基)-2-异丙基茚化锂
将4-(2-甲基苯基)-2-异丙基茚(6.6g,26.5mmol)溶解在80mL戊烷中。向该溶液添加10.6mL的正丁基锂(2.5M,在己烷中),再让反应物在室温下搅拌4小时。从溶液中沉淀出白色固体,通过玻璃滤器过滤来收集,再用另外的戊烷洗涤。产量是5.8g(88%)。
二甲基硅杂二基双[4-(2-甲基苯基)-2-异丙基茚]
将SiMe2Cl2(0.88g,6.8mmol)溶解在60mL的THF中。在搅拌的同时,添加干燥粉末状的4-(2-甲基苯基)-2-异丙基茚化锂(3.5g,13.7mmol),再将内容物在室温下搅拌一整夜。在真空中去除溶剂,将残余物溶解在戊烷中,再过滤,以除去LiCl盐。在真空中去除戊烷,以获得薄片状白色固体(3.0g)。
二甲基硅杂二基双[4-(2-甲基苯基)-2-异丙基茚基]ZrCl2
将二甲基硅杂二基双[4-(2-甲基苯基)-2-异丙基茚](3.0g,5.4mmol)溶解在60mL的Et2O中。在搅拌的同时,添加4.5mL的正丁基锂(2.5M,在己烷中),再在室温下搅拌2小时。在这之后,将溶液冷却到-35℃,添加ZrCl4(1.25g,5.4mmol),再在室温下搅拌3小时。然后在真空中去除溶剂,将残留物溶解在二氯甲烷和戊烷的混合物中,再过滤,以除去LiCl盐。然后浓缩滤液,再冷冻至-35℃,以诱发结晶。获得了0.26g(6.7%)的纯外消旋化合物。
金属茂D:外消旋二氯·二甲基硅杂二基(2-异丙基-4-[3,5-二甲基苯基]茚基)2合锆如下制备:
4-(3,5-二甲基苯基)-2-异丙基茚
将4-氯-2-异丙基茚(10.4g,54mmol)和NiCl2(PPh3)2(1.8g,2.8mmol)溶解在150mL的Et2O中。在强烈搅拌下,添加作为Et2O溶液的3,5-二甲基苯基溴化镁(54mmol),反应物再在室温下搅拌一整夜。在彻夜搅拌后,将反应物用H2O缓慢骤冷,以中和未反应的格利雅试剂。溶液随后用100mL的10% HCl(aq)处理,再用饱和碳酸氢钠水溶液中和。有机层用硫酸镁干燥,再通过旋转蒸发除去溶剂。剩余的残留物装填到硅胶柱中和用己烷洗脱。产量是5.5g(39%)。
4-(3,5-二甲基苯基)-2-异丙基茚化锂
将4-(3,5-二甲基苯基)-2-异丙基茚(5.5g,21mmol)溶解在80mL戊烷中。向该溶液添加8.3mL的正丁基锂(2.5M,在己烷中),再让反应物在室温下搅拌4小时。从溶液中沉淀出白色固体,通过玻璃滤器过滤来收集,再用另外的戊烷洗涤。产量是3.28g(60%)。
二甲基硅杂二基双[4-(3,5-二甲基苯基)-2-异丙基茚]
将SiMe2Cl2(0.69g,5.4mmol)溶解在80mL的THF中。在搅拌的同时,添加作为干燥粉末的4-(3,5-二甲基苯基)-2-异丙基茚化锂(2.9g,10.8mmol),再将内容物在室温下搅拌一整夜。在真空中去除溶剂,将残余物溶解在戊烷中,再过滤,以除去LiCl盐。在真空中去除戊烷,以获得薄片状白色固体(2.1g,67%)。
二甲基硅杂二基双[4-(3,5-二甲基苯基)-2-异丙基茚基]ZrCl2
将二甲基硅杂二基双[4-(3,5-二甲基苯基)-2-异丙基茚](2.1g,3.6mmol)溶解在60mL的Et2O中。在搅拌的同时,添加2.9mL的正丁基锂(2.5M,在己烷中),再在室温下搅拌2小时。在这之后,将溶液冷却到-35℃,添加ZrCl4(0.83g,3.6mmol),再在室温下搅拌3小时。然后在真空中去除溶剂,将残留物溶解在甲苯中,再过滤,以除去LiCl盐。然后浓缩滤液,再冷冻至-35℃,以诱发结晶。获得了0.24g(6.0%)的纯外消旋化合物。
金属茂E:外消旋二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆如下制备:
Ph2Si
(2-甲基-4-[1-萘基]茚) 2
将2-甲基-4-[1-萘基]茚基锂(5.5g,21mmol)加到Ph2Si(OSO2CF3)2(4.8g,10mmol)和二乙醚(50mL)的溶液中。将混合物搅拌一整夜,然后通过过滤分离产物,用二乙醚(4×50mL)洗涤,然后在真空中干燥。产量4.71g,68%。
使Ph2Si(OSO2CF3)2与2-甲基-4-[1-萘基]茚基锂反应以形成具有Ph2Si桥基的配体体系的上述方法是一般性方法。各种环戊二烯基或茚基金属盐能够与Ph2Si(OSO2CF3)2反应,当Ph2Si(Cl)2与环戊二烯基或茚基金属盐试剂不反应或反应慢时。
Ph2Si
(2-甲基-4-[1-萘基]茚基SnMe 3)2
通过将正丁基锂和戊烷(1.5mL,3.0mmol)的2.0M溶液加到Ph2Si(2-甲基,4-萘基茚)2(1.0g,1.44mmol)和二乙醚(20mL)的混合物中来制备Ph2Si(2-甲基-4-[1-萘基]茚基锂)2的淤浆。在搅拌2小时后,添加氯化三甲基锡(0.6g,3.0mmol)。颜色立即从强改变为浅黄色。除去醚和产物用戊烷(3×20mL)萃取。除去溶剂获得了产物。产量是0.88g,60%。
外消旋-Ph 2 Si(2-甲基-4-[1-萘基]茚基) 2ZrCl2
在100mL烧瓶中添加ZrCl4(180mg,0.77mmol),甲苯(20mL),然后加入Ph2Si(2-甲基-4-[1-萘基]茚基SnMe3)2(815mg,0.8mmol)。将混合物搅拌一整夜,然后在真空中在90℃下加热48小时。将橙色粉末溶解在甲苯(5mL)中,然后用0.45μm过滤器过滤。将二乙醚(2-3mL)加到甲苯溶液中,再将溶液冷却到-30℃。在长期的冷却后,分离晶体,然后先后用冷甲苯(3×1mL)和戊烷(3×5mL)洗涤。在进一步用甲苯(3×1mL)和己烷(3×5mL)洗涤后,干燥样品,获得了产物。产量17mg,2.6%。
对比金属茂 1:外消旋二氯·二甲基硅杂二基(2-甲基-4-苯基茚基)2合锆从商业来源获得,并且按来样使用。
对比金属茂 2:外消旋二氯·二甲基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆从商业来源获得,并且按来样使用。
对比金属茂 3:外消旋二氯·二甲基硅杂二基(2-甲基-4-苯基茚基)2合锆从商业来源获得,并且按来样使用。
对比金属茂 4:外消旋二氯·二甲基硅杂二基(2-乙基-4-苯基茚基)2合锆从商业来源获得,并且按来样使用。
负载催化剂体系合成
负载金属茂催化剂体系A
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆(A,0.060g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时20分钟。负载催化剂作为红紫色自由流动的固体回收(5.71g)。
负载金属茂催化剂体系B
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-异丙基-4-[1-萘基]茚基)2合锆(B,0.069g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948Regular,600℃脱水)。将该淤浆搅拌30分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体再干燥总共大约2小时20分钟。负载催化剂作为浅紫色自由流动的固体回收(5.4g)。
负载金属茂催化剂体系C
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-异丙基-4-[2-甲基-苯基]茚基)2合锆(C,0.069g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison948 Regular,600℃脱水)。将该淤浆搅拌30分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时20分钟。负载催化剂作为浅紫色自由流动的固体回收(5.4g)。
负载金属茂催化剂体系D
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-异丙基-4-[3,5-二甲基-苯基]茚基)2合锆(D,0.066g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时20分钟。负载催化剂作为紫色自由流动的固体回收(5.11g)。
负载金属茂催化剂体系E
在100mL圆底烧瓶中,将二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆(E,0.017g)加到MAO-甲苯溶液(1.52g)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(3.2mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时20分钟。负载催化剂作为橙色自由流动的固体回收(1.06g)。
负载金属茂催化剂体系F
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆(F,0.065g)加到MAO-甲苯溶液(5.1g,5.35mL)中,再搅拌15分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(11mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将甲苯(2mL)加到该淤浆中,搅拌20分钟,用旋转蒸发仪在真空和40℃下干燥10分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时23分钟。负载催化剂作为浅紫色自由流动的固体回收(5.58g)。
负载金属茂催化剂体系G
在100mL圆底烧瓶中,将二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆(G,0.065g)加到MAO-甲苯溶液(5.1g,5.4mL)中,再搅拌50分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(13mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,用旋转蒸发仪在真空和40℃下干燥10分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约3小时。负载催化剂作为紫色自由流动的固体回收(5.45g)。
负载对比金属茂催化剂体系1
在100mL圆底烧瓶中,将外消旋二氯·二甲基硅杂二基(2-甲基-4-苯基茚基)2合锆(对比金属茂1,0.055g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时22分钟。负载催化剂作为浅橙色自由流动的固体回收(5.63g)。
负载对比金属茂催化剂体系2
在100mL圆底烧瓶中,将外消旋二氯·二甲基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆(对比金属茂2,0.064g)加到MAO-甲苯溶液(6.74g,7.2mL)中,再搅拌20分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(14mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison 948 Regular,600℃脱水)。将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥2分钟,直到液体蒸发为止,然后将固体进一步干燥总共大约2小时。负载催化剂作为橙色自由流动的固体回收(4.72g)。
负载对比金属茂催化剂体系3
在2加仑混合机中,将外消旋二氯·二甲基硅杂二基(2-甲基-4-苯基茚基)2合锆(对比金属茂3,13.0g)溶解在MAO溶液(300mL)中。将所得物加到MAO溶液(用1600mL甲苯稀释的800mL),再添加另外150mL甲苯。所得物混合1小时。将该溶液的一半加到脱水二氧化硅(802.2g,Davison 948 Regular,600℃脱水)中,再搅拌5分钟。然后添加剩余的溶液,再搅拌20分钟。添加另外的甲苯(450mL)。将该淤浆搅拌20分钟,然后在氮气流下于46℃下干燥11.5小时。负载催化剂作为橙色自由流动的固体回收(1092.2g),该固体通过了25目筛。
负载对比金属茂催化剂体系4
在100mL圆底烧瓶中,将外消旋二氯·二甲基硅杂二基(2-乙基-4-苯基茚基)2合锆(对比金属茂4,0.065g)加到MAO-甲苯溶液(5.1g,5.5mL)中,再搅拌15分钟。所得物用中等玻璃多孔漏斗过滤,再用甲苯(11mL)洗涤。向合并的滤液中添加脱水二氧化硅(4.0g,Davison948 Regular,600℃脱水)。在添加另外1mL甲苯之后,将该淤浆搅拌20分钟,然后用旋转蒸发仪在真空和40℃下干燥,直到液体蒸发为止,然后将固体进一步干燥总共2小时23分钟。负载催化剂作为粉红色自由流动的固体回收(5.56g)。
聚合
全同立构聚丙烯均聚物
用负载催化剂生产均聚物的聚合步骤如下所示。在已用丙烯蒸汽吹洗的清洁干燥的两升高压釜中,添加TEAL清除剂(0.3mL,1.5M)。在此加入氢气。关闭反应器,填充800mL液体丙烯。在加热反应器至70℃之后,通过用丙烯(200mL)洗入添加催化剂。在指示时间(通常1小时)之后,冷却反应器,放出过量丙烯。除去聚合物,再干燥。结果表示在表1A和2A中。
抗冲共聚物(ICP)
用负载催化剂生产ICP的聚合步骤如下所示。在已用丙烯蒸汽吹洗的清洁干燥的两升高压釜中,添加TEAL清除剂(0.3mL,1.5M)。在此加入氢气。关闭反应器,填充800mL液体丙烯。在将反应器加热至70℃之后,通过用丙烯(200mL)洗入添加催化剂。在指示时间(通常1小时)之后,将反应器排空到大约170psig(1172kPa)压力,然后以指定的速率将乙烯/丙烯气体混合物通入反应器,同时保持200psig(1379kPa)。在气相阶段的最后(通常90-150分钟),排空反应器,再在N2下冷却。除去和干燥颗粒状ICP聚合物。结果表示在表1A和2A中。
聚合物分析
结果表示在表1B、2B和3-8。根据以下技术通过凝胶渗透色谱法(GPC)进行分子量测定。使用装有Shodex(Showa Denko)AT-80M/S柱和差示折射指数(DRI)检测器的Waters 150℃凝胶渗透色谱仪,在145℃于1.0mL/min流速下用1,2,4-三氯苯作为流动相操作来测定分子量和分子量分布。样品注射体积是300微升。柱使用窄聚苯乙烯标准校准,以产生通用的校准曲线。聚丙烯校准曲线使用k=8.33×10-5和a=0.800作为Mark-Houwink系数来建立。数值分析使用Waters“Millennium”软件来进行。
DSC熔点用商购DSC仪器测定,并且作为第二熔点来报道。将聚合物样品经10分钟加热至230.0℃,然后以10℃/分钟从230℃冷却至50℃。样品在50℃下保持5分钟。然后当以10℃/分钟的速度将样品从50℃加热到200℃时,记录第二熔点。峰温度记录为第二熔点。
ICP聚合物萃取方法
将ICP聚合物溶解在热二甲苯中,然后冷却一整夜。在过滤后,干燥不溶物质。蒸发二甲苯可溶性部分,再回收可溶性物质。通过使用已知方法和仪器如Schott A VSPro Viscosity AutomaticSampler在135℃下于十氢萘中测定回收的可溶性物质的IV。
在非常高的ICP MFR下,该方法能够萃取一些低分子量全同立构PP,因此降低了所测IV。
ICP聚合物分馏方法
将ICP样品送到Polyhedron Laboratories,Inc.进行分馏,再用GPC分析。步骤的一般描述可以在参考文献J.C.Randall,J.Poly.Sci.:Part A Polymer Chemistry,36卷,1527-1542页(1998)中发现。
物理性能测量
来自反应器的ICP产物与添加剂(1000ppm Irganox 3114;600ppmIrgafos 168;500ppm Kemamide U;2000ppm苯甲酸钠;600ppm DSTDP)干法共混,随后用实验室挤出生产线配混/造粒以制备粒料。在造粒后,使用Butler实验室注塑机(No.10/90V型)生产注塑棒材(127mm×12.7mm×3.2mm)。用注塑样品进行ASTM类试验,以测定1%正割挠曲模量(ASTM D-790A);66psi(455kPa)下的热变形温度(ASTMD-648);艾佐德抗冲强度(缺口:23℃,无缺口:-40℃,ASTM D-256)。
如在类似挠曲模量下的室温缺口艾佐德强度值所测定的那样,本发明的抗冲共聚物显示了改进的抗冲性能。这能够通过检查表8来发现。例如,用发明金属茂F的本发明试验43的ICP具有151.8kpsi(1046.9MPa)的挠曲模量与1.57ft.lb/inch(83.8J/m)值的缺口艾佐德强度,以及用发明金属茂G的本发明试验50的ICP具有158.3kpsi(1091.5MPa)的挠曲模量与1.7ft.lb/inch(90.7J/m)值的缺口艾佐德强度。对比实施例表示在试验46、47和48中,其中各自的第二值为158.6kpsi(1093.7MPa),155.8kpsi(1074.1MPa)和155.7kpsi(1073.5MPa),并且具有1.25(66.7),0.81(43.2)和0.74(39.5)ft.lb/inch(J/m)值的低级缺口艾佐德强度。因此,如在类似的挠曲模量下的缺口艾佐德强度所测定的那样,两个本发明试验43和50比对比试验具有更佳的抗冲强度。
这可以通过用所有数据绘制各对比实施例与发明实施例的缺口艾佐德强度/挠曲模量的曲线来进一步说明。如图1所示,本发明实施例在等同挠曲模量下具有更高的抗冲性能(缺口艾佐德)。
在可比模量下的改进抗冲强度由较高分子量的组分B(如由IV测定的那样)产生。组分B的分子量越高,抗冲试验值越好。
如由组分B的IV所测定的那样,已知对比金属茂1和2受该分子量低值的限制。对比金属茂的最高IV值是试验9的大约1.7dl/g的值(表1B),其中乙烯/丙烯为4.2/0.8比率。在该比率下的本发明金属茂B产生了试验13中1.99dl/g到试验18中2.338dl/g的IV。本发明金属茂D产生了试验40中具有3.508dl/g的IV的ICP。事实上,对于用本发明金属茂D的所有试验,所有ICP产物的IV值均大于2.2dl/g,并且在2.202dl/g(试验39)到3.667dl/g(试验38)的范围内。这些高IV值获得了进一步改进的抗冲性能。
要求了优选权的所有申请和所有指定的试验步骤在这里作为参照全面引用。
表1A
试验号 | 负载金属茂催化剂体系 | 催化剂量(mg) | 产量(g) | 效率(Kg/g cat) | H2(mmol) | 时间分割(min) | C2 =/C3 =流速(l/min) |
1 | E | 31 | 243.9 | 7.87 | 78 | 60/150 | 4.1/0.9 |
2 | E | 30 | 155.1 | 5.17 | 78 | 60 | |
3 | 对比1 | 31 | 198.9 | 6.42 | 78 | 60 | |
4 | 对比1 | 30 | 224.8 | 7.49 | 78 | 60/90 | 4.1/0.9 |
5 | A | 59 | 226.1 | 3.83 | 47 | 60/120 | 4.2/0.8 |
6 | A | 59 | 212.8 | 3.61 | 47 | 60/120 | 4.4/0.6 |
7 | A | 59 | 191.1 | 3.24 | 47 | 60 | |
8 | A | 60 | 215.6 | 3.59 | 47 | 60/120 | 4.7/0.3 |
9 | 对比2 | 60 | 272.6 | 4.54 | 54 | 60/120 | 4.2/0.8 |
10 | 对比2 | 61 | 196.9 | 3.23 | 54 | 60 | |
11 | A | 61 | 141.8 | 2.32 | 47 | 60/120 | 4.4/0.6 |
12 | A | 60 | 192.4 | 3.21 | 47 | 60/120 | 4.7/0.3 |
13 | B | 63 | 80.0 | 1.27 | 23 | 60/120 | 4.2/0.8 |
14 | B | 63 | 97.8 | 1.55 | 23 | 60/120 | 4.4/0.6 |
15 | B | 60 | 72.2 | 1.20 | 23 | 60 | |
16 | B | 61 | 82.2 | 1.35 | 23 | 60/120 | 4.0/1.0 |
17 | B | 60 | 89.0 | 1.48 | 23 | 60/120 | 4.1/0.9 |
18 | B | 150 | 180.2 | 1.20 | 23 | 30/120 | 4.2/0.8 |
19 | B | 152 | 153.8 | 1.01 | 23 | 30/120 | 4.0/1.0 |
20 | B | 151 | 87.4 | 0.58 | 23 | 30 | |
21 | E | 43 | 139.0 | 3.23 | 62 | 60 | |
22 | E | 44 | 154.0 | 3.50 | 62 | 60/150 | 4.1/0.9 |
23 | E | 43 | 102.2 | 2.38 | 62 | 60/150 | 3.6/1.4 |
24 | E | 43 | 81.1 | 1.89 | 78 | 60/150 | 4.0/1.0 |
25 | E | 41 | 53.3 | 1.30 | 78 | 60 |
表1B
试验号 | 总乙烯(wt%) | 组分B中的乙烯(wt%) | 总组分B(wt%) | 最终MFR(dg/min) | 熔点(℃) | MW(×10-3) | MWD | 组分BIV(dl/g) |
1 | 10.24 | 50.80 | 20.16 | 114.0 | 151.1 | 103.5 | 2.88 | 0.9786 |
2 | 459.2 | 150.2 | 75.4 | 3.15 | ||||
3 | 58.95 | 150.9 | 135.7 | 3.15 | ||||
4 | 7.82 | 50.04 | 15.63 | 127.16 | 150.0 | 100.4 | 3.11 | 0.708 |
5 | 3.87 | 47.36 | 8.17 | 490 | 149.6 | 116.5 | 4.18 | 1.637 |
6 | 5.93 | 51.70 | 11.5 | 118 | 149.8 | 148.7 | 4.74 | 2.362.46 |
7 | 123 | 148.6 | 73.5 | 2.78 | ||||
8 | 8.13 | 58.96 | 13.8 | 74.2 | 150.3 | 160.0 | 4.98 | 2.2212.199 |
9 | 9.74 | 51.52 | 18.91 | 4.98 | 151.0 | 210.4 | 2.96 | 1.7127 |
10 | 3.12 | 151.0 | 278.0 | 2.49 | ||||
11 | 5.23 | 55.72 | 9.39 | 129.0 | 150.4 | 147.4 | 4.25 | 2.18 |
12 | 12.08 | 63.62 | 18.99 | 10.02 | 150.3 | 1,139.0 | 456 | 1.55 |
13 | 6.19 | 47.44 | 13.05 | 21.1 | 154.97 | 168.6 | 2.84 | 1.99 |
14 | 8.81 | 54.69 | 16.11 | 19.9 | 155.3 | 169.7 | 3.00 | 2.37 |
15 | 72.84 | 156.57 | 158.2 | 2.77 | ||||
16 | 4.12 | 40.33 | 10.22 | 53.03 | 154.7 | 148.1 | 2.74 | 1.585 |
17 | 3.59 | 45.88 | 7.82 | 51.27 | 154.2 | 145.2 | 2.79 | 1.351 |
18 | 11.10 | 49.56 | 22.40 | 15.47 | 155.5 | 192.8 | 3.09 | 2.338 |
19 | 8.80 | 43.02 | 20.46 | 16.95 | 155.3 | 194.1 | 3.47 | 1.742 |
20 | 30.26 | 154.63 | 106.6 | 2.27 | ||||
21 | 10.3 | 151.83,较小138.33 | 225.6 | 1.93 | ||||
22 | 10.95 | 50.37 | 21.74 | 3.66 | 151.97 | 302.3 | 2.78 | 2.185 |
23 | 6.46 | 36.4 | 17.75 | 7.01 | 152.77 | 240.3 | 2.44 | 2.11 |
24 | 9.37 | 47.34 | 19.79 | 131.01 | 150.83 | 122.6 | 4.26 | 2.063 |
25 | 681.8 | 151.23 | 76.9 | 3.5 |
表2A
试验号 | 负载金属茂催化剂体系 | 催化剂量(g) | 产量(g) | 效率(Kg/g cat) | H2(mmol) | 时间分割(min) | C2 =/C3 =流速(l/min) |
26 | C | 61 | 158.2 | 2.59 | 47 | 60/120 | 4.0/1.0 |
27 | C | 60 | 139.9 | 2.33 | 47 | 60 | |
28 | C | 61 | 168.9 | 2.77 | 47 | 60/120 | 4.4/0.6 |
29 | C | 60 | 42.3 | 0.71 | 16 | 60 | |
30 | C | 61 | 94.7 | 1.55 | 31 | 60 | |
31 | C | 300 | 159.8 | 0.53 | 7.8 | 60 | |
32 | C | 300 | 51.4 | 0.17 | 7.8 | 21 | |
33 | C | 300 | 276.2 | 0.92 | 7.8 | 64/180 | 4.0/1.0 |
34 | D | 121 | 63.0 | 0.52 | 7.8 | 60 | |
35 | D | 120 | 79.4 | 0.66 | 7.8 | 60/90 | 4.0/1.0 |
36 | D | 122 | 99.1 | 0.81 | 7.8 | 60/90 | 4.1/0.9 |
37 | D | 123 | 71.2 | 0.58 | 7.8 | 60/90 | 3.6/1.4 |
38 | D | 120 | 95.2 | 0.79 | 7.8 | 60/120 | 4.0/1.0 |
39 | D | 121 | 143.7 | 1.19 | 16 | 60/90 | 4.0/1.0 |
40 | D | 124 | 167.6 | 1.35 | 16 | 60/90 | 4.2/0.8 |
41 | D | 120 | 101.5 | 0.85 | 16 | 60 | |
42 | D | 121 | 121.2 | 1.00 | 16 | 60/90 | 4.4/0.6 |
表2B
试验号 | 总乙烯(wt%) | 组分B中的乙烯(wt%) | 总组分B(wt%) | 最终MFR(dg/min) | 熔点(℃) | MW(×10-3) | MWD | 组分B的IV(dl/g) |
26 | 3.584 | 43.25 | 8.3 | 971.02 | 152.17 | 75.6 | 2.50 | 1.121 |
27 | 1013.8 | 152.1(157.17较小) | 70.9 | 2.27 | ||||
28 | 4.62 | 57.52 | 8.0 | 954.7 | 151.57 | 69.2 | 2.39 | 2.083 |
29 | 142.5 | 152.91 | 120.1 | 2.38 | ||||
30 | 420.7 | 152.1 | 91.7 | 2.19 | ||||
31 | 129.85 | 153.23 | 127.3 | 3.62 | ||||
32 | 268.69 | 152.97 | 108.1 | 4.41 | ||||
33 | 15.07,14.24 | 48.96,47.85 | 30.8,29.8 | 11.94 | 154.1 | 238.1 | 14.49 | 1.993 |
34 | 76.55 | 151.83 | 138.5 | 2.20 | ||||
35 | 8.199 | 39.92 | 20.5 | 14.16 | 153.43 | 213.6 | 3.05 | 2.833 |
36 | 7.068 | 42.81 | 16.5 | 15.43 | 152.03 | 196.3 | 3.01 | 2.505 |
37 | 8.294 | 26.52 | 31.3 | 4.92 | 152.77 | 248.0 | 3.28 | 2.662 |
38 | 15.85 | 39.17 | 40.5 | 0.479 | 153.23 | 306.7 | 4.14 | 3.667 |
39 | 7.521 | 37.72 | 19.9 | 27.72 | 153.03 | 204.7 | 3.61 | 2.202 |
40 | 10.02 | 44.73 | 22.4 | 5.8 | 152.63 | 235.8 | 3.58 | 3.508 |
41 | 75.86 | 151.03 | 135.8 | 2.30 | ||||
42 | 21.21 | 56.17 | 37.8 | 0.53 | 152.10 | 280.9 | 3.84 |
表3
应用试验号 | 说明 | 负载金属茂催化剂体系 | MFR(dg/min) | 二甲苯可溶性物质%(wt%) | 二甲苯不溶性物质%(wt%) | FTIR数据 | ||
总C2(wt%) | 组分B中的C2(wt%) | 总组分B(wt%) | ||||||
5 | ICP | A | 490 | 6.6 | 93.8 | 3.87 | 47.36 | 8.2 |
6 | ICP | A | 118 | 6.8 | 93.2 | 5.93 | 51.7 | 11.5 |
7 | 均聚PP | A | 123 | 1 | 98.8 | |||
8 | ICP | A | 74.2 | 5.4 | 94.5 | 8.13 | 58.96 | 13.8 |
11 | ICP | A | 129.0 | 6.7 | 93.5 | 5.23 | 55.72 | 9.5 |
12 | ICP | A | 10.02 | 4.3 | 95.9 | 12.08 | 63.62 | 19 |
13 | ICP | B | 21.1 | 13.3 | 86.7 | 6.19 | 47.44 | 13 |
14 | ICP | B | 19.9 | 14.3 | 85.7 | 8.81 | 54.69 | 16.1 |
15 | 均聚PP | B | 72.84 | 1.1 | 99 | |||
16 | ICP | B | 53.03 | 11.7 | 88.5 | 4.12 | 40.33 | 10.2 |
17 | ICP | B | 51.27 | 8.4 | 91.6 | 3.59 | 45.88 | 7.8 |
18 | ICP | B | 15.47 | 19.2 | 80.4 | 11.1 | 49.56 | 22.4 |
19 | ICP | B | 16.95 | 20.9 | 79.2 | 8.8 | 43.02 | 20.5 |
20 | 均聚PP | B | 30.26 | 1.1 | 98.9 |
表4
应用试验号 | 说明 | 负载金属茂催化剂体系 | MFR(dg/min) | 二甲苯可溶性物质%(wt%) | 二甲苯不溶性物质%(wt%) | FTIR数据 | |||
总C2(wt%) | 组分B中的C2(wt%) | 总组分B(wt%) | 组分B的IV(dl/g) | ||||||
1 | ICP | E | 114.0 | 25.6 | 74.5 | 10.24 | 50.8 | 20.2 | 0.979 |
2 | 均聚PP | E | 459.2 | 1.2 | 98.8 | ||||
3 | 均聚PP | 对比1 | 58.95 | 0.6 | 99.4 | ||||
4 | ICP | 对比1 | 127.16 | 20.4 | 79.7 | 7.82 | 50.04 | 15.6 | 0.708 |
9 | ICP | 对比2 | 4.98 | 23.5 | 76.2 | 9.74 | 51.52 | 18.9 | 1.713 |
10 | 均聚PP | 对比2 | 3.12 | 0.9 | 99.1 | ||||
13 | ICP | B | 129.0 | 12.4 | 86.9 | ||||
21 | 均聚PP | E | 10.3 | 0.7 | 99.3 | ||||
22 | ICP | E | 3.66 | 24 | 75.6 | 10.95 | 50.37 | 21.7 | 2.185 |
23 | ICP | E | 7.01 | 20.9 | 79.3 | 6.46 | 36.4 | 17.7 | 2.11 |
24 | ICP | E | 131.01 | 22 | 78.1 | 9.37 | 47.34 | 19.8 | 2.06 |
25 | 均聚PP | E | 681.8 | 2.1 | 98 |
表5
应用试验号 | 说明 | 负载金属茂催化剂体系 | MFR(dg/min) | 二甲苯可溶性物质(低MW峰) | 二甲苯可溶性物质(高MW峰) | 二甲苯不溶物质 | |||||||||
Mn | Mw | Mz | Mw/Mn | Mn | Mw | Mz | Mw/Mn | Mn | Mw | Mz | Mw/Mn | ||||
1 | ICP | E | 114.0 | 1251 | 1554 | 1874 | 1.24 | 38015 | 74567 | 115589 | 1.96 | 12314 | 32426 | 54966 | 2.63 |
2 | 均聚PP | E | 459.2 | 1513 | 2013 | 2599 | 1.33 | 18384 | 30191 | 45639 | 1.64 | 17552 | 41149 | 67038 | 2.34 |
3 | 均聚PP | 对比1 | 58.95 | 1441 | 1952 | 2630 | 1.35 | 14448 | 22536 | 35314 | 1.56 | 30510 | 63658 | 97817 | 2.09 |
4 | ICP | 对比1 | 127.16 | 981 | 1062 | 1140 | 1.08 | 15647 | 33205 | 51601 | 2.12 | 16342 | 42791 | 71409 | 2.62 |
9 | ICP | 对比2 | 4.98 | 987 | 1180 | 1433 | 1.2 | 48475 | 118629 | 214628 | 2.45 | 41276 | 106195 | 179010 | 2.57 |
10 | 均聚PP | 对比2 | 3.12 | 1071 | 1376 | 1834 | 1.29 | 15113 | 30638 | 56220 | 2.03 | 61668 | 142260 | 249807 | 2.31 |
13 | ICP | B | 21.1 | 941 | 1099 | 1308 | 1.17 | 44501 | 187149 | 515199 | 4.21 | 69282 | 167811 | 342963 | 2.42 |
21 | 均聚PP | E | 10.3 | 1114 | 1383 | 1715 | 1.24 | 12228 | 23656 | 42278 | 1.93 | 82347 | 184675 | 309914 | 2.24 |
22 | ICP | E | 3.66 | 929 | 1153 | 1502 | 1.24 | 77378 | 211251 | 413832 | 2.73 | 97431 | 248553 | 471070 | 2.55 |
23 | ICP | E | 7.01 | 982 | 1165 | 1403 | 1.19 | 57316 | 166144 | 312133 | 2.9 | 85158 | 206876 | 354334 | 2.43 |
24 | ICP | E | 131.01 | 1515 | 2556 | 4282 | 1.69 | 74803 | 161031 | 319874 | 2.15 | 27750 | 76477 | 129002 | 2.76 |
25 | 均聚PP | E | 681.8 | 1430 | 1868 | 2472 | 1.31 | 10530 | 13500 | 17834 | 1.28 | 24398 | 76119 | 137103 | 3.12 |
表6
应用试验号 | 说明 | 负载金属茂催化剂体系 | MFR(dg/min) | 二甲苯可溶性物质(低MW峰) | 二甲苯可溶性物质(高MW峰) | 二甲苯不溶物质 | |||||||||
Mn | Mw | Mz | Mw/Mn | Mn | Mw | Mz | Mw/Mn | Mn | Mw | Mz | Mw/Mn | ||||
5 | ICP | A | 490 | 713 | 740 | 772 | 1.04 | 46485 | 196796 | 608279 | 4.23 | 36452 | 117941 | 384107 | 3.24 |
6 | ICP | A | 118 | 721 | 751 | 786 | 1.04 | 32808 | 173994 | 652286 | 5.3 | 38405 | 150533 | 577951 | 3.92 |
7 | 均聚PP | A | 123 | 746 | 775 | 805 | 1.04 | 2224 | 3418 | 6092 | 1.54 | 31525 | 77176 | 139014 | 2.45 |
8 | ICP | A | 74.2 | 714 | 743 | 776 | 1.04 | 36731 | 157042 | 553553 | 4.28 | 37994 | 133529 | 493184 | 3.51 |
11 | ICP | A | 129.0 | 712 | 741 | 774 | 1.04 | 39823 | 188272 | 544445 | 4.73 | 39618 | 147046 | 523576 | 3.71 |
12 | ICP | A | 10.02 | 739 | 774 | 814 | 1.05 | 22407 | 91802 | 367841 | 4.1 | 49352 | 214835 | 834003 | 4.35 |
13 | ICP | B | 21.1 | 741 | 775 | 814 | 1.05 | 32783 | 134448 | 347619 | 4.1 | 73240 | 168231 | 330135 | 2.3 |
14 | ICP | B | 19.9 | 774 | 822 | 884 | 1.06 | 76080 | 247012 | 646524 | 3.25 | 48027 | 140429 | 300877 | 2.92 |
15 | 均聚PP | B | 72.84 | 720 | 756 | 800 | 1.05 | 11124 | 16144 | 23634 | 1.45 | 65242 | 150447 | 276068 | 2.31 |
16 | ICP | B | 53.03 | 735 | 765 | 803 | 1.04 | 26643 | 128696 | 380989 | 4.83 | 67746 | 158765 | 317323 | 2.34 |
17 | ICP | B | 51.27 | 733 | 759 | 790 | 1.04 | 40054 | 99847 | 204429 | 2.49 | 37641 | 130382 | 468779 | 3.46 |
18 | ICP | B | 15.47 | 721 | 741 | 764 | 1.03 | 61128 | 250368 | 694151 | 4.1 | 50670 | 134806 | 284392 | 2.66 |
19 | ICP | B | 16.95 | 710 | 726 | 744 | 1.02 | 71050 | 246743 | 632260 | 3.47 | 53550 | 131611 | 251500 | 2.46 |
20 | 均聚PP | B | 30.26 | 857 | 1043 | 1371 | 1.22 | 9567 | 16302 | 25965 | 1.7 | 75064 | 161464 | 317578 | 2.15 |
表7A
试验号 | 负载金属茂催化剂体系 | TEAL量(ml) | 催化剂量(mg) | 产量(g) | 效率(Kg/g cat) | H2(mmol) | 时间分割(min) | C2 =/C3 =流速(l/min) |
43 | F | 0.3 | 123 | 261.1 | 2.12 | 697.5 | 60/90 | 4.0/1.0 |
44 | F | 0.3 | 120 | 289.8 | 2.42 | 542.5 | 60/90 | 4.0/1.0 |
45 | 对比3 | 0.3 | 60 | 219.6 | 3.66 | 930.0 | 60/75 | 4.8/1.2 |
46 | 对比3 | 0.3 | 64 | 220.0 | 3.44 | 930.0 | 60/75 | 2.0/0.5 |
47 | 对比4 | 0.3 | 61 | 275.9 | 4.52 | 1007.5 | 35/45 | 4.8/1.2 |
48 | 对比4 | 0.3 | 61 | 278.4 | 4.56 | 1007.5 | 35/45 | 2.0/0.5 |
49 | G | 0.3 | 124 | 246.3 | 1.99 | 542.5 | 60/90 | 4.0/1.0 |
50 | G | 0.3 | 122 | 269.5 | 2.21 | 542.5 | 60/90 | 4.0/1.0 |
表7B
试验号 | 总乙烯(wt%) | 橡胶中的乙烯(wt%) | 总橡胶(wt%) | 最终MFR(dg/min) | 熔点(℃) | 共聚物的IV(dl/g) |
43 | 6.34 | 43.23 | 14.7 | 206 | 147.98 | 1.678 |
44 | 2.07 | 40.89 | 5.1 | 671 | 148.05 | |
45 | 12.66 | 50.85 | 24.9 | 27.0 | 149.69 | 0.789 |
46 | 8.60 | 47.40 | 18.1 | 33.2 | 149.04 | 0.651 |
47 | 11.48 | 53.03 | 21.6 | 18.2 | 151.61 | 0.637 |
48 | 7.61 | 49.49 | 15.4 | 44.6 | 151.69 | 0.786 |
49 | 7.09 | 44.46 | 15.9 | 69.2 | 147.55 | 1.618 |
50 | 5.15 | 43.51 | 11.8 | 132 | 147.34 | 1.619 |
表8
应用试验号 | 负载金属茂催化剂体系 | MFR(dg/min) | HDT(℃) | 挠曲模量(psi)[MPa] | 缺口艾佐德强度(23℃)(ft.lb./in.)[J/m] |
43 | F | 206 | 95.8 | 151846[1046.9] | 1.57[83.8] |
44 | F | 671 | 114.9 | 211749[1460.0] | 0.42[22.4] |
46* | 对比3 | 33.2 | 81 | 97490[672.2] | 1.86[99.3] |
98 | 158627[1093.7] | 1.25[66.7] | |||
47* | 对比4 | 18.2 | 87 | 124709[859.9] | 1.4[74.7] |
107 | 155790[1074.1] | 0.81[43.3] | |||
48* | 对比4 | 44.6 | 76 | 91609[631.6] | 1.51[80.60] |
102 | 155702[1073.5] | 0.74[39.5] | |||
49 | G | 69.2 | 95 | 136745[942.8] | 2.37[126.5] |
50 | G | 132 | 97.5 | 158309[1091.5] | 1.7[90.7] |
* 进行两种抗冲/模量试验,因为来自这些试验的样品具有不同的视觉外观。
Claims (34)
1.一种反应器生产的丙烯抗冲共聚物组合物,包括:
(a)基于抗冲共聚物的总重量的大约40wt%到大约95wt%的组分A,组分A包括丙烯均聚物或共聚物,其中共聚物包括10wt%或10wt%以下的乙烯、丁烯、己烯或辛烯共聚单体,
(b)基于抗冲共聚物的总重量的大约5wt%到大约60wt%的组分B,组分B包括丙烯共聚物,其中共聚物包括大约20wt%到大约70wt%乙烯、丁烯、己烯和/或辛烯共聚单体,以及大约80wt%到大约30wt%丙烯,其中组分B:
(i)具有至少100,000的重均分子量;
(ii)高于60%的组成分布;和
(iii)大于1.00dl/g的特性粘度。
2.权利要求1的组合物,其中组分A是丙烯均聚物。
3.权利要求1的组合物,其中组分B基本由丙烯和大约20wt%到大约70wt%乙烯组成。
4.权利要求1的组合物,其中组分B基本由丙烯和大约30wt%到大约65wt%乙烯组成。
5.权利要求1的组合物,其中组分B具有低于3.5的分子量分布。
6.权利要求1的组合物,其中组分B具有至少200,000的重均分子量。
7.权利要求1的组合物,其中组分B具有高于70%的组成分布。
8.权利要求1的组合物,其中组分B具有高于2.00dl/g的特性粘度。
9.权利要求1的组合物,其中组分B具有低于10wt%的结晶部分。
10.权利要求1的组合物,其中组分B具有低于10wt%的结晶部分和该结晶部分,倘若能检测到的话,具有与组分B的剩余物相同的共聚单体含量。
11.权利要求1的组合物,其中组分A基本由聚丙烯均聚物组成和具有低于2wt%的无定形聚丙烯。
12.权利要求1的组合物,其中组分A具有至少155℃的熔点。
13.一种反应器生产的丙烯抗冲共聚物组合物,包括:
(a)基于抗冲共聚物的总重量的大约40wt%到大约95wt%的组分A,组分A包括熔点为至少155℃和无定形聚丙烯少于2wt%的丙烯均聚物;
(b)基于抗冲共聚物的总重量的大约5wt%到大约60wt%的组分B,组分B包括丙烯共聚物,其中该共聚物包括大约30wt%到大约65wt%乙烯以及大约70wt%到大约35wt%丙烯,其中组分B:
(i)具有至少150,000的重均分子量;
(ii)低于3.5的分子量分布;
(iii)高于65%的组成分布;和
(iv)大于2.00dl/g的特性粘度;
(v)低于10wt%的结晶部分。
14.权利要求13的组合物,基本由大约60wt%到大约90wt%的组分A和大约10wt%到大约40wt%组分的B组成。
15.权利要求13的组合物,其中组分B基本由丙烯和大约35%到大约60%乙烯组成。
16.使用包括选自以下的金属茂的金属茂催化剂体系以两段聚合法制备的丙烯抗冲共聚物:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
17.使用包括选自以下的金属茂的金属茂催化剂体系以两段聚合法制备的丙烯抗冲共聚物:rac-氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;和rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆。
18.使用包括选自以下的金属茂的金属茂催化剂体系以两段聚合法制备的丙烯抗冲共聚物:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;和rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆。
19.使用包括选自以下的金属茂的金属茂催化剂体系以两段聚合法制备的丙烯抗冲共聚物:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;和rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆。
20.一种反应器生产的丙烯抗冲共聚物组合物,包括:
(a)基于抗冲共聚物的总重量的大约40wt%到大约95wt%的组分A,组分A包括熔点为至少155℃和无定形聚丙烯少于2wt%的丙烯均聚物;
(b)基于抗冲共聚物的总重量的大约5wt%到大约60wt%的组分B,组分B包括丙烯共聚物,其中该共聚物包括大约30wt%到大约65wt%乙烯以及大约70wt%到大约35wt%丙烯,其中组分B:
(i)具有至少150,000的重均分子量;
(ii)低于3.5的分子量分布;
(iii)高于65%的组成分布;和
(iv)大于2.00dl/g的特性粘度;
(v)低于10wt%的结晶部分,
其中该抗冲共聚物使用包括选自以下的金属茂的金属茂催化剂体系制备:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
21.一种生产丙烯抗冲共聚物的方法,包括以下步骤:
(a)在一个阶段中将组分A聚合;和
(b)在组分A的存在下在另一阶段中将组分B聚合,
其中组分A包括丙烯均聚物或含有10wt%或10wt%以下的乙烯、丁烯、己烯或辛烯共聚单体的共聚物,和组分B包括丙烯共聚物,其中该共聚物含有大约20wt%到大约70wt%乙烯、丁烯、己烯、和/或辛烯共聚单体,和大约80wt%到大约30wt%丙烯,其中组分A和/或B的至少一种由使用选自以下的金属茂聚合:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
22.权利要求20的方法,其中丙烯抗冲共聚物在两个阶段中生产,组分A在第一阶段中生产和组分B在第二阶段中生产。
23.权利要求21的方法,其中第二阶段是气相法。
24.权利要求21的方法,其中第一阶段是液体淤浆法和第二阶段是气相法。
25.权利要求20的方法,其中组分A和B二者使用选自以下的相同金属茂来制备:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
26.权利要求20的方法,其中组分B(i)具有至少150,000的重均分子量;(ii)低于2.5的分子量分布;(iii)高于65%的组成分布;(iv)大于2.00dl/g的特性粘度;和(v)低于10wt%的结晶部分。
27.权利要求20的方法,其中组分A基本由熔点为至少155℃的丙烯均聚物组成。
28.一种生产丙烯抗冲共聚物的方法,包括以下步骤:
(a)在第一阶段中将组分A聚合,其中组分A基本由丙烯均聚物组成;和然后
(b)在组分A的存在下在后续阶段中将组分B聚合,其中组分B包括丙烯共聚物,其中该共聚物包括大约20wt%到大约70wt%乙烯、丁烯、己烯和/或辛烯共聚单体,以及大约80wt%到大约30wt%丙烯;
其中组分A和B均使用选自以下的金属茂聚合:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
29.权利要求28的方法,其中金属茂是被负载的。
30.权利要求28的方法,其中金属茂用甲基铝氧烷活化。
31.权利要求28的方法,其中金属茂用离子活化剂活化。
32.权利要求28的方法,其中组分B(i)具有至少150,000的重均分子量;(ii)低于3.0的分子量分布;(iii)高于65%的组成分布;(iv)大于2.00dl/g的特性粘度;和(v)低于10wt%的结晶部分。
33.权利要求21的方法,其中组分A具有至少155℃的熔点。
34.一种生产丙烯抗冲共聚物的方法,包括以下步骤:
(a)在第一阶段中将组分A聚合,其中组分A基本由熔点为至少155℃的丙烯均聚物组成;和然后
(b)在组分A的存在下在后续阶段中将组分B聚合,其中组分B包括丙烯共聚物,其中该共聚物包括大约20wt%到大约70wt%乙烯,以及大约80wt%到大约30wt%丙烯,和其中组分B(i)具有至少150,000的重均分子量;(ii)低于3.5的分子量分布;(iii)高于65%的组成分布;(iv)大于2.00dl/g的特性粘度;和(v)低于10wt%的结晶部分;
其中组分A和B均使用选自以下的金属茂聚合:rac-二氯·二甲基硅杂二基(2-iPr-4-苯基茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[1-萘基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[3,5-二甲基苯基]茚基)2合锆;rac-二氯·二甲基硅杂二基(2-iPr-4-[2-甲基-苯基]茚基)2合锆;和rac-二氯·二苯基硅杂二基(2-甲基-4-[1-萘基]茚基)2合锆。
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US9670347B2 (en) | 2013-08-14 | 2017-06-06 | Borealis Ag | Propylene composition with improved impact resistance at low temperature |
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CN107922537A (zh) * | 2015-06-05 | 2018-04-17 | 埃克森美孚化学专利公司 | 气相或淤浆相中多相聚合物的制备 |
CN107922537B (zh) * | 2015-06-05 | 2021-07-27 | 埃克森美孚化学专利公司 | 气相或淤浆相中多相聚合物的制备 |
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Publication number | Publication date |
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DE60108075T2 (de) | 2005-12-08 |
EP1254186A1 (en) | 2002-11-06 |
JP2003522259A (ja) | 2003-07-22 |
KR20020073209A (ko) | 2002-09-19 |
ATE286082T1 (de) | 2005-01-15 |
BR0108150A (pt) | 2003-01-21 |
EP1481997B1 (en) | 2006-08-16 |
US6384142B1 (en) | 2002-05-07 |
US6492465B1 (en) | 2002-12-10 |
WO2001058970A1 (en) | 2001-08-16 |
EP1481997A1 (en) | 2004-12-01 |
EP1254186B1 (en) | 2004-12-29 |
KR20020074509A (ko) | 2002-09-30 |
US6342566B2 (en) | 2002-01-29 |
US20020086947A1 (en) | 2002-07-04 |
CA2398509A1 (en) | 2001-08-16 |
US20010034411A1 (en) | 2001-10-25 |
US6472474B2 (en) | 2002-10-29 |
DE60108075D1 (de) | 2005-02-03 |
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