bis(4-(3,5-di-tert-butylphenyl)-7-methoxy-2-methylindenyl)dimethyl silane | 1379658-33-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚和异茚
• 英文名称: bis(4-(3,5-di-tert-butylphenyl)-7-methoxy-2-methylindenyl)dimethyl silane
• 英文别名: bis[4-(3,5-ditert-butylphenyl)-7-methoxy-2-methyl-1H-inden-1-yl]-dimethylsilane
• CAS: 1379658-33-9
• 化学式: C₅₂H₆₈O₂Si
• 分子量: 753.196
• InChiKey: DWGNDDTYIOUKKB-UHFFFAOYSA-N

物化性质

• 沸点：
  765.8±60.0 °C(predicted)
• 密度：
  1.05±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  14.72
• 重原子数：
  55
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(4-(3,5-di-tert-butylphenyl)-7-methoxy-2-methylindenyl)dimethyl silane 、 氯化铪 在 正丁基锂 作用下， 以 甲苯 、 正戊烷 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  丙烯的高度等选择性聚合的基于超刚性茚基的Ha茂配合物：采用各种立体要求较高的4-芳基取代基的可调聚合性能

  摘要：

  Two novel silyl-bridged C-2-symmetric (2-methyl-4-aryl-7-methoxy) substituted bisindenyl based ansa-hafnocene complexes of varied steric demand (I, 4-phenyl; II, 4-[(3',5'-methyl)-phenyl]) were synthesized and examined in the coordinative polymerization of propene. Both complexes enable a comparative study with the state of the art homogeneous metallocene catalyst (III, 4-[(3',S'-tert-butyl)-phenyl]) for high melting ultrahigh molecular weight isotactic polypropylene. All three activated complexes exhibit extremely concise stereoregularity along with high molecular weights and high melting transitions at low to moderate polymerization temperatures. Increased sterical encumbrance of the 4-aryl substituent prevents the process of chain release reactions more effectively, especially due to enhanced reduction of beta-methyl elimination. Accordingly, end group analysis disclosed the highest selectivity toward allylic chain ends as a result of beta-methyl elimination with the less sterically encumbered complex I. Examination of the catalytic activity of I III disclosed considerable impact of the varied 4-aryl substituents on the maximum productivity with respect to the applied polymerization conditions considering the combined influence of activation, monomer diffusion rate, catalyst deactivation, and rate of chain growth.

  DOI：

  10.1021/acs.organomet.6b00814
• 作为产物：
  描述：

  3,5-二叔丁基溴苯 在 四(三苯基膦)钯 、 正丁基锂 、 sodium carbonate 、 magnesium 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 乙醇 、 正己烷 、 甲苯 为溶剂， 反应 72.0h， 生成 bis(4-(3,5-di-tert-butylphenyl)-7-methoxy-2-methylindenyl)dimethyl silane
  参考文献：
  名称：

  用于丙烯的异丁二烯和区域特异性聚合的超硬金属茂：寻找完美的聚丙烯螺旋

  摘要：

  完美的聚丙烯：提出了一种通用的合成路线，该路线可生成2、4和7个取代的双茚基茂金属（Zr，Hf），即使在高温下也能提供刚性的，因此高度立体和区域选择性的聚合催化剂。尤其是，f茂能够生产具有极高的熔融转变温度的全同立构聚丙烯，所述熔融转变温度超过170℃，且分子量超过5000000g mol -1。

  DOI：

  10.1002/chem.201103547

文献信息

• 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조 방법
  申请人：LG CHEM, LTD. 주식회사 엘지화학(120010134563) Corp. No ▼ 110111-2207995BRN ▼107-81-98139

  公开号：KR20170073465A

  公开（公告）日：2017-06-28

  본 발명에 따르면, 올레핀 중합 반응에서 높은 활성을 나타낼 수 있을 뿐만 아니라, 합성되는 올레핀 중합체의 입체 규칙성 등의 특성을 용이하게 조절할 수 있는 전이 금속 화합물, 이를 포함하는 촉매 조성물 및 상기 촉매 조성물을 이용한 올레핀 중합체의 제조 방법이 제공될 수 있다.

  根据本发明，可以提供一种过渡金属化合物，它不仅可以表现出在α-烯烃聚合反应中的高活性，还可以方便地调节聚合的烯烃聚合物的立体规则性等特性，以及包含该过渡金属化合物的催化剂组合物和使用该催化剂组合物制备α-烯烃聚合物的方法。
• Perfectly Isotactic Polypropylene upon <i>In Situ</i> Activation of Ultrarigid <i>meso</i> Hafnocenes
  作者：Lucas Stieglitz、Tim M. Lenz、Andreas Saurwein、Bernhard Rieger

  DOI：10.1002/anie.202210797

  日期：2022.11.14

  activation, hafnocene meso-I yields isotactic polypropylene instead of atactic polypropylene of meso-I and rac-I. With our easy and convenient isomerization and polymerization protocol, productivities comparable to pure rac-I if applied to pure meso-I or a mixture of both isomers are accessible.

  使用原位活化，hafnocene meso - I产生全同立构聚丙烯，而不是meso - I和rac - I的无规立构聚丙烯。通过我们简单方便的异构化和聚合方案，生产率可与纯外消旋-I 相媲美，如果应用于纯内消旋-I或两种异构体的混合物。
• Titanocenes in Olefin Polymerization: Sustainable Catalyst System or an Extinct Species?
  作者：Martin R. Machat、Christian Jandl、Bernhard Rieger

  DOI：10.1021/acs.organomet.7b00112

  日期：2017.4.10

  Two novel silyl-bridged C-2-symmetric 2-methyl-4-aryl-7-methoxy-substituted bis-indenyl-based titanocene complexes with varied steric demand (a, 4-(3',5'-dimethyl)phenyl; b, 4-(3',5'-di-tert-butyl)phenyl) were synthesized, characterized, and examined in the coordination polymerization of propene. Both adapted ligand structures have proven their capability as precise catalysts in the formation of stereodefect- and regiodefect-free isotactic polypropylene. Several activation pathways to the catalytically active, cationic complexes were analyzed in terms of catalytic activity and stability, taking into account the influence of polymerization temperature, monomer concentration, polymerization time, and type of applied scavenger. The overall lowest activities were observed using the methylaluminoxane (MAO) activated catalyst. The two-step activation mechanism of in situ alkylation with an excess of triisobutylaluminum (TIBA) and subsequent addition of [Ph3C][B(C6F3)(4)] resulted in moderate productivities of the respective catalyst systems. However, the highest catalytic activities were observed when eliminating the in situ alkylation step by application of bis-methylated titanocenes in combination with [Ph3C] [B(C6F5)(4)]. The latter activation mechanism in combination with the sterically more encumbered ligand framework b results in the most productive titanium-based metallocene catalyst for the polymerization of propene to date, at least with respect to reasonable reaction times. The determined molecular weights of the produced polymers were significantly affected by the ligand structures a and b but were only negligibly influenced by the applied activation method. End-group analysis via H-1 NMR spectroscopy disclosed a chain release mechanism dominated by beta-hydride elimination. In accordance with the observed accurate stereo- and regiocontrol mechanism, extraordinarily high melting transitions of up to 170 degrees C (ex reactor) underline the remarkable potential of these titanium-based catalyst systems in the polymerization of propene.
• Ultra-Rigid Metallocenes for Highly Iso- and Regiospecific Polymerization of Propene: The Search for the Perfect Polypropylene Helix
  作者：Alexander Schöbel、Eberhardt Herdtweck、Matthew Parkinson、Bernhard Rieger

  DOI：10.1002/chem.201103547

  日期：2012.4.2

  Perfect polypropylene: A versatile synthesis route leading to 2‐, 4‐, and 7‐ substituted bisindenyl metallocenes (Zr, Hf) affording rigid and thus highly stereo‐ and regioselective polymerization catalysts, even at elevated temperatures, is presented. In particular, the hafnocene is able to produce isotactic polypropylene with extremely high melting transitions, exceeding 170 °C with molecular weights

  完美的聚丙烯：提出了一种通用的合成路线，该路线可生成2、4和7个取代的双茚基茂金属（Zr，Hf），即使在高温下也能提供刚性的，因此高度立体和区域选择性的聚合催化剂。尤其是，f茂能够生产具有极高的熔融转变温度的全同立构聚丙烯，所述熔融转变温度超过170℃，且分子量超过5000000g mol -1。
• Ultrarigid Indenyl-based Hafnocene Complexes for the Highly Isoselective Polymerization of Propene: Tunable Polymerization Performance Adopting Various Sterically Demanding 4-Aryl Substituents
  作者：Martin R. Machat、Dominik Lanzinger、Alexander Pöthig、Bernhard Rieger

  DOI：10.1021/acs.organomet.6b00814

  日期：2017.1.23

  Two novel silyl-bridged C-2-symmetric (2-methyl-4-aryl-7-methoxy) substituted bisindenyl based ansa-hafnocene complexes of varied steric demand (I, 4-phenyl; II, 4-[(3',5'-methyl)-phenyl]) were synthesized and examined in the coordinative polymerization of propene. Both complexes enable a comparative study with the state of the art homogeneous metallocene catalyst (III, 4-[(3',S'-tert-butyl)-phenyl]) for high melting ultrahigh molecular weight isotactic polypropylene. All three activated complexes exhibit extremely concise stereoregularity along with high molecular weights and high melting transitions at low to moderate polymerization temperatures. Increased sterical encumbrance of the 4-aryl substituent prevents the process of chain release reactions more effectively, especially due to enhanced reduction of beta-methyl elimination. Accordingly, end group analysis disclosed the highest selectivity toward allylic chain ends as a result of beta-methyl elimination with the less sterically encumbered complex I. Examination of the catalytic activity of I III disclosed considerable impact of the varied 4-aryl substituents on the maximum productivity with respect to the applied polymerization conditions considering the combined influence of activation, monomer diffusion rate, catalyst deactivation, and rate of chain growth.