2-(3',5'-di-tert-butyl)phenylindene | 218604-62-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: 2-(3',5'-di-tert-butyl)phenylindene
• 英文别名: 2-(3,5-di-t-Butylphenyl)indene；2-(3,5-ditert-butylphenyl)-1H-indene
• CAS: 218604-62-7
• 化学式: C₂₃H₂₈
• 分子量: 304.475
• InChiKey: AWEIZPJLIGMMLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  溴甲苯 、 2-(3',5'-di-tert-butyl)phenylindene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 26.0h， 以62%的产率得到1-benzyl-2-(3',5'-di-tert-butyl)phenylindene
  参考文献：
  名称：

  乙烯共聚物的序列分布控制：共聚单体序列对乙烯共聚物熔融行为的影响

  摘要：

  在乙烯-丙烯（EP）和乙烯-1-己烯（EH）的共聚反应中，合成，表征和研究了新的未桥接混合配体锆茂。MAO活化的茂金属[1-苄基-2-（3'，5'-二叔丁基）苯基茚基] [2-苯基茚基]二氯化锆（8）催化的EP和EH共聚反应活性比大于1 （r e r p = 2.4，r e r h =2.2）产生橡胶状，半结晶，高熔点的聚合物。通过差示扫描量热法（DSC）在仅含50mol％乙烯的EP和EH共聚物中检测结晶度。高乙烯含量的EH共聚物的溶剂分馏表明，这些共聚物由少量醚溶性馏分和庚烷可溶及庚烷不溶性馏分组成，其组成和序列分布与未分级分离的聚合物非常匹配。总的来说，反应率，DSC和分馏结果表明这些共聚物含有长的可结晶的乙烯序列。一系列乙烯-1-己烯共聚物与80摩尔％乙烯的熔点行为的比较表明，熔融转变对共聚单体序列分布的敏感依赖性。

  DOI：

  10.1021/ma021779v
• 作为产物：
  描述：

  1,3,5-三叔丁基苯 在 叔丁基邻苯二酚 、 溴 、 叔丁基锂 、 铁粉 作用下， 以 四氯化碳 、 乙醚 、 正戊烷 为溶剂， 反应 11.0h， 生成 2-(3',5'-di-tert-butyl)phenylindene
  参考文献：
  名称：

  立体受阻的未桥联2-芳基茚金属茂进行丙烯聚合

  摘要：

  衍生自二氯化双（2-苯基茚基）锆的茂金属催化剂体系（1）产生低至中规整度的弹性体聚丙烯。位阻金属茂双（2-（3,5-二叔丁基苯基）茚基）二氯化锆（2）产生的全同立构规整度比1高（[mmmm] = 78％，而液态丙烯中为44％）。用1 / MMAO和2 / MMAO进行的聚合反应的动力学曲线表明，聚合的初始速率随温度的升高而增加；两种催化剂的活性均随时间降低，但对于2 / MMAO而言，降低的幅度不如1。/ MMAO。聚合物的微观结构高度依赖于聚合条件：全同立构规整度随温度升高和单体浓度降低而降低。在低单体浓度下由2 / MMAO生成的较低立构规整度的聚丙烯（[mmmm] = 40％）包含较高百分比的[mmrm]立体误差，这表明立体嵌段微结构由相对构型相反的全同立构立体序列组成。用[Ph 3 C] [B（C 6 F 5）4 ]（4）或B（C 6 F 5）活化双（2-（3,5-二叔丁基苯基）茚

  DOI：

  10.1021/ma012241c

文献信息

• <i>C</i>₁-Symmetric Si-bridged (2-indenyl)(1-indenyl) <i>ansa</i>-metallocenes as efficient ethene/1-hexene copolymerization catalysts
  作者：Dmitry V. Uborsky、Dmitry Y. Mladentsev、Bogdan A. Guzeev、Ilya S. Borisov、Antonio Vittoria、Christian Ehm、Roberta Cipullo、Coen Hendriksen、Nic Friederichs、Vincenzo Busico、Alexander Z. Voskoboynikov

  DOI：10.1039/c9dt04896k

  日期：——

  Synthesis, ethene/1-hexene copolymerization screening, and QSAR study of 28 silicon bridged (2-indenyl)(1-indenyl) zirconocenes: new promising catalysts for LLDPE were identified.

  28个硅桥联的(2-茚基)(1-茚基) 锆茂金属催化剂的合成、乙烯/1-己烯共聚筛选以及QSAR研究：为LLDPE新的有前景的催化剂被鉴定。
• Catalyst systems for high melting thermoplastic elastomeric alpha-olefin polymers and plastomers
  申请人：The Board of Trustees of the Leland Stanford Junior University

  公开号：US20030195308A1

  公开（公告）日：2003-10-16

  This invention relates generally to low ethylene insertions into &agr;-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point &agr;-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of &agr;-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10× or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. The amount of ethylene included in the reaction system can be selected and controlled to be so small as to result in essentially minimal (<2 mole %) incorporation of ethylene units into the resulting elastomeric polymer and the molecular weight may be increased. Amounts of ethylene to generate the PRE effect may be greater than 0.1 wt. % and preferably range up to about 2 wt. %. However, if a polymer with more ethylene is desired, additional ethylene may be incorporated into the polymerization feed, including up to 10 to about 50 mole % based on olefin units. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, &agr;-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. This effect is termed the EPE effect, for Elastomeric Property-Enhancing effect. The EPE amount of ethylene required to produce such elastomers typically overlaps the PRE activity-enhancing amount. Incorporation of up to about 5 mole % or more of ethylene typically will produce an elastomeric polymer using such catalyst systems. Typical useful amounts of incorporated ethylene include about 1 to 3 mole %. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80° C., preferably above 100° C., including in the range of from about 120° C. to about 140° C. and above. Novel flexible &agr;-olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.

  本发明涉及低乙烯插入到α-烯烃聚合物中以及使用未桥联流动金属芳基茚基金属烯催化剂，尤其是取代芳基茚基金属烯催化剂的方法生产这种聚合物的过程，更特别地，使用未桥联、流动的环戊二烯基或茚基金属烯催化剂体系在生产高熔点α-烯烃均聚物和共聚物的方法中，特别是α-烯烃弹性结晶和非晶块状均聚物和共聚物的方法。至少含有一个2-芳基茚烯配体的流动未桥联金属烯聚合催化剂的活性通过向聚合体系中添加少量（通常为0.1-10重量％）乙烯而增加10倍或更多，这种增加被称为聚合速率增强效应（PRE），以无量纲比例的乙烯增强因子（EEF）的形式进行测量，范围为约1.1至约10或以上。可以选择和控制反应系统中包含的乙烯量非常小，以致于在所得到的弹性聚合物中几乎不包含（<2摩尔％）乙烯单元，分子量可以增加。产生PRE效应的乙烯量可能大于0.1重量％，并且最好在约2重量％范围内。但是，如果需要含更多乙烯的聚合物，可以将额外的乙烯并入聚合物化反馈中，包括基于烯烃单位的10至约50摩尔％。本发明的第二个重要方面是，在α-烯烃聚合中使用PRE活性增强量的乙烯而几乎不影响弹性体的物理性质。在本发明的第三个重要方面中，通过使用未桥联流动催化剂体系并将乙烯并入其中，可以生产α-烯烃弹性体，而该催化剂体系可能不会产生可接受的弹性体均聚物。这种效应称为EPE效应，用于弹性物性增强效应。通常需要并入约5摩尔％或更多的乙烯来使用这种催化剂体系生产弹性聚合物。通常有用的并入乙烯量包括约1至3摩尔％。本发明的优选聚合物保持足够的结晶性，以提供高熔点（通过DSC）约80℃，优选高于100℃，包括约120℃至约140℃以上的范围。还公开了具有超过600％的延伸率和基本无保留力的新型柔性α-烯烃均聚物和共聚物。
• Catalyst systems for high melting thermoplastic elastomeric α-olefin polymers and plastomers
  申请人：Waymouth Robert M.

  公开号：US06960550B2

  公开（公告）日：2005-11-01

  A metallocene catalyst system component for polymerization of olefins includes at least one 2-arylindenyl ligand substituted on the 1-position by a substituted or unsubstituted alkyl, alkylsilyl, or aryl substituent of 1 to 30 carbon atoms.

  用于烯烃聚合的茂金属催化剂体系组分包括至少一种2-芳基茚烯基配体，其在1-位置上被1至30个碳原子的取代或未取代烷基，烷基硅基或芳基取代基所取代。
• Fluxional catalysts and related ligands containing bulky substituents
  申请人：BP Corporation North America Inc.

  公开号：US06479424B1

  公开（公告）日：2002-11-12

  A ligand useful to form a metallocene olefin polymerization catalyst comprises: wherein at least R3 and R4 are substituents having at least a bulk of a t-butyl group and, optionally, wherein R1 or R2 may be a bulky substituent group.

  适用于形成金属茂烯烯烃聚合催化剂的配体包括：其中至少R3和R4是具有至少一个叔丁基团体积的取代基，而且可选地，R1或R2可以是一个笨重的取代基团体。
• Ethylene enhancement of processes for synthesis of high melting
  申请人：The Board of Trustees of the Leland Stanford Junior University

  公开号：US06160064A1

  公开（公告）日：2000-12-12

  This invention relates generally to low ethylene insertions into .alpha.-olefin polymers and processes for production of such polymers using unbridged fluxional metallocenes, primarily substituted aryl indenyl metallocenes, and more particularly to use of unbridged, fluxional, cyclopentadienyl or indenyl metallocene catalyst systems in methods of production of high melting point .alpha.-olefin homo- and co-polymers, particularly elastomeric crystalline and amorphous block homo- and co-polymers of .alpha.-olefins. The activity of fluxional unbridged metallocene polymerization catalysts containing at least one 2-arylindene ligand is increased 10.times. or more by the addition of small (typically 0.1-10 wt. %) amounts of ethylene to the polymerization system, which increase is termed the Polymerization Rate-Enhancement effect (PRE), which is measured in terms of an Ethylene Enhancement Factor (EEF) as a dimensionless ratio in the range of from about 1.1 to about 10 or above. A second important aspect of this invention is the ability to use a PRE activity-enhancing amount of ethylene in an olefin polymerization without substantially affecting the physical properties of the elastomer. In a third important aspect of this invention, .alpha.-olefin elastomers are produced through incorporation of ethylene using unbridged fluxional catalyst systems which may not otherwise produce acceptable elastomeric homopolymers. Preferred polymers of this invention retain sufficient crystallinity to provide a high melting point (by DSC) of about 80.degree. C., preferably above 100.degree. C., including in the range of from about 120.degree. C. to about 140.degree. C. and above. Novel flexible .alpha.-olefin homo and copolymers having elongation in excess of 600% and substantially no retained force are disclosed.

  本发明涉及将低乙烯插入到α-烯烃聚合物中，以及使用非桥联流动金属芳基茚基金属卡宾化物，主要是取代芳基茚基金属卡宾化物的生产这种聚合物的工艺。更具体地说，本发明涉及使用非桥联流动环戊二烯基或茚基金属卡宾化物催化剂体系的方法生产高熔点α-烯烃同聚物和共聚物，特别是α-烯烃的弹性结晶和非晶块同聚物和共聚物。含有至少一个2-芳基茚烯配体的流动非桥联金属卡宾化物聚合催化剂的活性通过向聚合体系中添加少量（通常为0.1-10重量％）乙烯而增加10倍或更多，这种增加被称为聚合速率增强效应（PRE），其以无量纲比例的乙烯增强因子（EEF）的形式进行测量，范围为约1.1到约10或以上。本发明的第二个重要方面是在α-烯烃聚合物中使用PRE活性增强量的乙烯，而不会对弹性体的物理性质产生实质影响。在本发明的第三个重要方面中，使用非桥联流动催化剂体系通过乙烯的引入生产α-烯烃弹性体，这种催化剂体系可能不会产生可接受的弹性同聚物。本发明的优选聚合物保持足够的结晶度，以提供约80℃，优选高于100℃，包括从约120℃到约140℃及以上的高熔点（通过DSC）。还揭示了具有超过600％的延展度和基本无保留力的新型柔性α-烯烃同聚物和共聚物。