CN100528356C - 烯烃聚合催化剂 - Google Patents
烯烃聚合催化剂 Download PDFInfo
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- CN100528356C CN100528356C CNB038020580A CN03802058A CN100528356C CN 100528356 C CN100528356 C CN 100528356C CN B038020580 A CNB038020580 A CN B038020580A CN 03802058 A CN03802058 A CN 03802058A CN 100528356 C CN100528356 C CN 100528356C
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
一种聚合催化剂体系,含有特定比例的两种铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物,其制备出的聚烯烃具有不同分子量;适用于制备聚烯烃,特别是聚乙烯,该聚烯烃特别适用于吹塑加工。
Description
发明领域
一种聚合催化剂体系,含有两种铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物,制备一种含有不同分子量的聚烯烃的混合物。该聚烯烃混合物特别适用于吹塑加工。
背景技术
聚烯烃,包括聚乙烯,是很重要的商业产品,其被用于各种不同的用途。其中一种应用是吹塑加工,该加工工艺特别适用于制备大的中空产品,如由热塑性塑料制备出的瓶子、桶和管材。吹塑加工典型地分为三种加工类型:挤出吹塑加工、注射吹塑加工和拉伸吹塑加工。在典型的挤出吹塑加工操作中,一个熔融聚合物材料的管材被挤出,然后管材的开口端被密封。将该密封管材,也称为“料泡”,包裹在一个(“对开”)塑模中,然后往管材的内部通入气压(“吹”),这样管材被气压压到冷的塑模表面,因而形成一个密闭的形状。成型制品的管材末端被切割掉,并进行修剪,这样一个中空形状的制品就形成了。由于所需要的压力很低,该方法特别适用于制备大的中空制品。
在料泡的形成和处理过程中,优选熔融的热塑性塑料具备适当的粘弹性能。对于在料泡通过挤出形成的过程中,优选热塑性塑料在相对高的剪切速率下不具备太高的熔融粘度。这就限制了极高分子量聚合物的用量;否则,挤出步骤可能会更困难。在另一个方面,优选聚合物的低剪切粘度(有时也称为熔融强度)足够高以避免“垂挂”。在料泡的形成期间和之后,其通常在从挤出模头出来后被悬挂较短时间,并且人们不希望料泡在实际的模塑步骤之前流动或明显变形(“垂挂”)。高的熔融强度通常来自于较高分子量的聚合物。因此,用作吹塑加工的聚合物通常具有相对少量的高分子量组份,以赋予材料良好的熔融强度,而不使高剪切粘度太高。
美国专利6,214,761和6,297,338描述了含有至少一种铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物,和至少一种其他聚合催化剂的聚合催化体系的应用,另外一种其他聚合催化剂也可以是一种铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物。但是其未提及本申请描述的具体组合物或用于制备特别适用于吹塑加工的聚合物的用途。
国际专利申请01/15899描述了由铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物制备吹塑加工中的聚乙烯的用途。但是其未提及由两种该聚合催化剂的混合物来制备聚乙烯。
发明概述
本发明提供了一种聚合催化剂,包括:
a)主要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第一铁配合物;和
b)次要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第二铁配合物,其中在聚合条件下,由第二铁配合物制备的第二聚烯烃具有高于由第一铁配合物制备的第一聚烯烃的重均分子量。
本发明也提供了一种使用2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的铁配合物作为部分聚合催化剂体系来聚合烯烃的方法,其中改进之处包括使用如下组份作为部分聚合催化剂体系:
a)主要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第一铁配合物;和
b)次要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第二铁配合物,其中在聚合条件下,由第二铁配合物制备的第二聚烯烃具有高于由第一铁配合物制备的第一聚烯烃的重均分子量。
本发明中也公开了一种吹塑加工聚烯烃混合物来成型中空制品的方法,包括:
a)通过在聚合条件下使一种或多种烯烃与一种聚合催化剂体系接触来制备聚烯烃混合物,聚合催化剂体系包括:
i)主要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第一铁配合物;和
ii)次要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第二铁配合物,其中在聚合条件下,由第二铁配合物制备的第二聚烯烃具有高于由第一铁配合物制备的第一聚烯烃的重均分子量;
b)熔融所述的聚烯烃混合物,形成聚烯烃的熔融混合物;和
c)吹塑加工该聚烯烃的熔融混合物。
发明详述
本申请中使用了一定的术语,其中一些术语限定如下:
本申请中“主要部分”的铁配合物表示为,该铁配合物含量占聚合催化剂体系总的所有铁配合物含量的50摩尔%以上。
本申请中“次要部分”的铁配合物表示为,该铁配合物含量占聚合催化剂体系总的所有铁配合物含量的50摩尔%以下。
本申请中“聚合物”表示为平均聚合度至少约为50的聚合材料,优选平均聚合度至少约100,更优选约200。“平均聚合度”表示为在平均聚合物链中,单体(烯烃)的重复单元数目。本申请中的一种聚合催化剂制备一种聚合物。
“烃基基团”为只含有碳和氢的单价基团。如果没有具体说明,本申请中优选的烃基基团(和烷基基团)含有1-约30个碳原子。
本申请中的“取代烃基”表示为含有一个或多个取代基团的烃基基团,该取代基团基本上不影响该聚合催化剂体系的聚合过程或操作。如果没有具体说明,本申请中优选的取代烃基含有1-约30个碳原子。
“取代”的含义包括含有一个或多个杂原子,如氮、氧和/或硫的链或环。取代烃基的自由价可以由杂原子决定。在取代烃基中,所有的氢原子都可以被取代,如四氟甲基。
本申请中的“(惰性)官能团”表示为烃基或取代烃基之外的基团,其在含有该基团的化合物所处的加工条件下是惰性的。这些官能团也基本上不影响本申请中描述的、含有该基团的化合物可能参与的任何加工过程。例如官能团包括卤素(氟、氯、溴和碘)和醚,如-OR30,此处R30为烃基或取代的烃基。在该官能团接近一个过渡金属原子(如铁原子)的情形下,该官能团和过渡金属原子的配位作用应该弱于本申请中描述的和过渡金属原子进行配位的化合物中的基团。也就是说,该官能团不应该替换所期望的配位基团。
“芳基”表示为单价的芳香基团,其自由价由芳环的碳原子决定。一个芳基可以有一个或多个芳环,这些芳环可以是稠合的、或通过单键或其他基团连接。
“取代芳基”表示为单价的芳香基团以如前所述定义的“取代烃基”中的方式被取代。和芳基类似,一个取代的芳基可以有一个或多个芳环,这些芳环可以是稠合的、或通过单键或其他基团连接。但是,当取代芳基含有一个芳杂环时,取代芳基中的自由价可以由芳杂环的杂原子(如氮)而非碳原子决定。
本申请中的聚烯烃通过使用两种或多种铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物作为部分聚合催化剂体系,聚合一种或多种烯烃来制备。这些铁的配合物及其作为聚合催化剂的使用记载在如美国专利5955555和WO99/12981或WO99/50273(相应于美国专利申请序列号09/277910,申请日为1999年3月29日)和WO00/08034中(也在本申请中一并作为参考)。参考文献可能对于这些催化剂配合物及其制备有更详细的描述。使用这些催化剂聚合的优选烯烃为乙烯,单独使用或与其他共聚单体一起使用,尤其是与一种或多种α-烯烃如1-丁烯、1-己烯、1-戊烯、1-辛烯等。优选为乙烯的均聚。
优选的一种聚合催化剂体系形式为,铁的三配位配合物负载在一种固体颗粒载体上。用于含有过渡金属的聚合催化剂的各种通用载体是公知的,这些载体大部分都适合本发明的应用。这些载体包括硅石、硅石和蒙脱土的混合物、氧化铝、MgCl2、各种粘土和其他。优选载体为硅石。负载这些催化剂的方法是本领域公知的,例如参见国际专利申请99/46303、99/46304、00/15646、01/32722、01/32723和美国专利6,214,761和5,955,555。所有这些在此一并作为参考。
用于聚合的方法可以是任何在文献里已经描述的用于这些聚合催化剂类型的方法,如间歇式、半间歇式或连续式。其也可以为气相(流化床)、液体浆料或溶液聚合。其他公知的加工条件,如前述的温度和/或压力,也可以采用。其他试剂,如氢等链转移剂,可以采用和/或存在。
一种形式中,“2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺”表示为式(I)的化合物:
此处,R1、R2、R3、R4和R5分别独立的为氢、烃基、取代烃基、或一个惰性官能团;R6和R7为芳基、取代芳基或一个官能团。
典型地在铁的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺配合物中,在配合物中铁原子周围具有足够的空间位阻,以至于烯烃可以被聚合。在式(I)中空间位阻通常,至少部分,由R6和R7基团提供。例如R6可以为式(II)的苯环
和R7可以为式(III)的苯环
此处,R8、R9、R10、R11、R12、R13、R14、R15、R16和R17分别独立的为氢、烃基、取代烃基、或一个官能团。在苯环邻位的取代,即R8、R12、R13和R17在决定铁原子周围的空间集群效应上特别重要。
由于此空间集群效应的大小是一种控制制备的聚烯烃分子量的方法(在给定的聚合条件下),因此,其在本申请情形中是很重要的。
总的来说,铁原子的空间集群效应越大,制备的聚烯烃分子量,包括重均分子量也越大。例如参看B.L.Small等,J.Am.Chem.Soc.,120,4049-4050(1998)和A.M.A.Bennett,Chemtech,29(7),24-28(1999),两篇文献在此一并作为参考。当存在(II)和(III)时,4个芳基邻位,即R8、R12、R13和R17,在决定配合物中铁原子周围的空间集群效应方面特别重要。特别地,这些基团越大,铁原子的空间集群效应也越大。在乙烯的聚合中,如果R8、R12、R13和R17为氢,通常只能制备出较低分子量的乙烯聚合物(低聚体)。如果R8、R12、R13和R17都为甲基,就可以制备出聚乙烯,而当R8、R12、R13和R17都为异丙基时,就可以制备出更高分子量的聚乙烯。
本申请中由第二聚合催化剂制备的聚烯烃具有高于由第一聚合催化剂制备的聚烯烃的重均分子量。优选使用第二聚合催化剂的聚烯烃重均分子量为使用第一聚合催化剂的聚烯烃重均分子量的1.1倍,更优选为1.2倍,最优选为1.5倍。为了确定由每种聚合催化剂制得的聚烯烃的重均分子量,在和复合(混合)催化剂相同的聚合条件下,制备了由单独的催化剂聚合的聚烯烃。随后测量每种聚烯烃的重均分子量(见下文)并进行比较。例如,如果在使用硅石作为载体的浆料聚合过程中,使用两种催化剂,并使用氢作为一种链转移剂,每种催化剂将分别负载在载体上,在和使用两种催化剂一起负载在载体上相同的聚合条件下,分别进行使用每种催化剂的聚合过程。然后比较由每种单独的催化剂制备的聚合物重均分子量。
在聚合过程中(相应地在获得的聚合产物中)优选烯烃单体为乙烯。也可以优选乙烯和α-烯烃如1-丁烯、1-己烯、1-戊烯、1-辛烯等的共聚,尤其是当聚烯烃产物中乙烯衍生的重复单元至少为重复单元总量的约80摩尔%,更优选至少为约90摩尔%。特别优选为乙烯均聚物。
总的来说,认为在制备的聚合物产品中,应该只有相对少量的聚合物是由第二催化剂制备出的。实际的相对量将取决于使用的第一和第二聚合催化剂的相对量和它们的相对聚合速率。优选第一聚合催化剂为使用的总的铁配合物的至少约75摩尔%,更优选为至少约80摩尔%。优选第一聚合催化剂不超过第一和第二聚合催化剂总量的约95摩尔%,更优选为不超过约90摩尔%。任何最小量可以和任何最大量进行组合。
由该聚合方法制备出的聚合产物通常具有双峰分子量分布,在双峰分子量分布中,较高分子量聚合物具有较小量。由于这些铁配合物之一有时单独制备出聚合产物,其本身具有存在相对小量的低分子量聚合物的双峰分布,因此可能制备出三峰或更多峰分布的聚合物。优选由第二聚合催化剂制备的高分子量聚合物占聚合产物的约2-约25wt%,更优选占约5-约20wt%。
使用两种相似但化学结构不同的铁三配位催化剂的聚合方法,特别适用于制备具有宽分子量分布的聚合物共混物,特别地具有更高分子量组份(有时也称为高分子量“拖尾”)的聚合物共混物。通过使用两种化学相似的聚合催化剂,而非两种不同类型的催化剂(如一种铁三配位催化剂和一种茂金属型或Ziegler-Natta型催化剂),对于存在两种聚合催化剂的聚合条件将更容易配合和控制。例如,如果希望使用氢作为链转移剂来控制聚合物分子量,则铁三配位催化剂通常需要比茂金属型或Ziegler-Natta型催化剂更高的氢浓度,来获得给定的分子量降低。
本发明聚合过程的聚合产物,特别适用于各种类型的吹塑加工,也特别适用于挤出吹塑加工。吹塑加工是公知的熔融成型加工。例如参看,H.Mark等编辑,Encyclopediea of Polymer Science and Engineering,2nd Ed.,Vol.2,John Wiley & Sons,New York,1985,p.447-178和N.C.Lee,Understanding Blow Molding,Hanser Publishers,Munich,2000,两篇文献在此一并作为参考。本发明聚合过程的聚合产物具有宽分子量分布,和相对大量的低分子量聚合物和相对少量的高分子量聚合物。这种组合具有如前所述用于吹塑加工所期望的粘弹性能。
Claims (8)
1.一种聚合催化剂,包括:
a)主要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第一铁配合物;和
b)次要部分的2,6-二酰基吡啶二亚胺或2,6-吡啶二羧酸醛二亚胺的第二铁配合物,其中在聚合条件下,由第二铁配合物制备的第二聚烯烃具有高于由第一铁配合物制备的第一聚烯烃的重均分子量。
2.一种使用权利要求1的聚合催化剂作为部分聚合催化剂体系来聚合烯烃的方法。
3.如权利要求2所述的方法,其中所述的烯烃包括乙烯。
4.如权利要求2所述的方法,其中所述的烯烃为乙烯。
5.一种吹塑加工聚烯烃混合物来成型中空制品的方法,包括:
a)通过在聚合条件下使一种或多种烯烃与一种聚合催化剂体系接触来制备聚烯烃混合物,聚合催化剂体系包括权利要求1的聚合催化剂;
b)熔融所述的聚烯烃混合物,形成聚烯烃的熔融混合物;和
c)吹塑加工该聚烯烃的熔融混合物。
6.如权利要求5所述的方法,其中所述的聚烯烃为聚乙烯。
7.如权利要求5所述的方法,其中所述的聚烯烃为乙烯均聚物。
8.如权利要求5所述的方法,其中所述的加工为挤出吹塑加工。
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US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US20050187098A1 (en) | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
US7384886B2 (en) | 2004-02-20 | 2008-06-10 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
WO2006010065A2 (en) | 2004-07-09 | 2006-01-26 | E.I. Dupont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
US7268096B2 (en) | 2005-07-21 | 2007-09-11 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
US7727926B2 (en) | 2005-07-21 | 2010-06-01 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and method of using in oligomerization and polymerization |
US7271121B2 (en) | 2005-07-21 | 2007-09-18 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
US7723448B2 (en) * | 2005-10-14 | 2010-05-25 | Basell Polyolefine Gmbh | Hybrid catalyst systems supported on magnesium halide |
US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
EP2526130B1 (en) * | 2010-01-21 | 2014-04-30 | Basell Polyolefine GmbH | Process for the preparation of ethylene copolymer compositions in the presence of an oligomerization catalyst |
CN103534279B (zh) | 2011-05-13 | 2016-08-17 | 尤尼威蒂恩技术有限责任公司 | 喷雾干燥的催化剂组合物及使用其的聚合方法 |
US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
EP2743000A1 (en) * | 2012-12-13 | 2014-06-18 | Basell Poliolefine Italia S.r.l. | Catalyst system for the preparation of polyolefins |
US9944661B2 (en) | 2016-08-09 | 2018-04-17 | Chevron Phillips Chemical Company Lp | Olefin hydroboration |
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IL129929A0 (en) * | 1996-12-17 | 2000-02-29 | Du Pont | Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis (imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
US6417305B2 (en) * | 1996-12-17 | 2002-07-09 | E. I. Du Pont De Nemours And Company | Oligomerization of ethylene |
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