Precise synthesis of new polyolefins by post metallocene type transition metal catalysis

后茂金属型过渡金属催化精密合成新型聚烯烃

• 批准号: 13555253
• 负责人: NOMURA Kotohiro
• 金额: $ 5.12万
• 依托单位: NARA INSTITUTE OF SCIENCE AND TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13555253/
• 关键词: Olefin Polymerization; Transition Metal Complex Catalysts; Polyolefins; Precision Polymerization; Titanium Complexes; Vanadium Complexes; Controlled POlymerization; Ethylene

The purpose on this research project is to create new polyolefins that possess unique properties. Olefin polymerization by homogeneous transition metal complex catalysts attracts particular attention in the field of organometallic chemistry, catalysis, and polymer chemistry. This is because the design of an efficient complex catalyst has thus been the key for the precise synthesis by controlled polymerization. We have shown that (cyclopentadienyl)(aryloxy)titanium (IV) complex of the type, Cp'Ti(OAr)X_2 (OAr=aryloxy group), exhibited remarkable catalytic activities for ethylene, α-olefin polymerization in the presence of methylaluminoxane (MAO), and monomer reactivities as well as monomer sequence distributions were directly affected by the substituents in cyclopentadienyl group. We have also shown that the catalyst of this type could be tuned to the efficient catalyst precursor for both styrene polymerization and ethylene/styrene copolymerization by the simple ligand modification. We … More have also shown that efiicient norbornene incorporation in ethylene/norbornene copolymerization can be achieved in this catalyst systems by modifying the substitutent on cyclopentadienyl group like (indenyl)TiCl_2(OAr). Based on these facts, new polyolefins that were difficult/impossible to prepare have been created by using this catalysts. We also explored the effect of ligand in olefin polymerization chemistry by Cp-anilide, Cp-amide and Cp-ketimide titanium complexes. (Anilido)(cyclopentadienyl)titanium(IV)complexes of the type, Cp'TrCl_2[N(R)(XAr)] [Cp'=Cp^*, 1,3 M_2C_5H_3,Cp ; R=SiMe_3 etc.; Ar=2,6-Me_2C_6H_3], and Cp'-amide titanium complexes of the type, Cp'TiCl_2(NMeR) have been prepared, and these complexes exhibited high catalytic activity for ethylene polymerization in the presence of MAO, and the activity increased in the order : Cp'=Cp^*>1,3-Me_2C_5H_3>Cp. The trend observed here was almost the same as that in Cp'-aryloxy titanium complexes. The efficient catalyst for symdiospecific styrene polymerization could be modified only by replacing the substituent on Cp'.We have reported that (arylimido)(aryloxo)vanadium(V) complexes of the type, VCl_2(NAr)(OAr'), exhibited remarkable catalytic activities for ethylene polymerization in the presence of MAO, and that ring-opening metathesis polymerization (ROMP) of norbornene had been initiated by V(CH_2Ph)_2(NAr)(O-2,6Pr_2C_6H_3). Remarkably high catalytic activities for ethylene polymerization were observed if the complex was treated with Et_2AlCl. The low catalytic activity was observed if AlMe_3 was used in place of Et_2AlCl, although the use of AlMe_3 as cocatalyst was effective for the ROMP. We believe that the results observed here would be an interesting contrast among these polymerizations. Less

该研究项目的目的是创建具有独特特性的新聚集蛋白。均质过渡金属复合催化剂通过烯烃聚合的聚合在有机化学，催化和聚合物化学领域引起了特别的关注。这是因为有效的复杂催化剂的设计已成为通过受控聚合的精确合成的关键。我们已经表明，类型的（芳氧基二烯基）（芳氧基）钛（IV）复合物，CP'TI（OAR）X_2（OAR）X_2（OAR = ARYOXY群），暴露于乙烯，α-烯烃，α-烯烃的显着催化活性，α-烯烃，在甲基氨基氨基氧烷（Mohominos and Assodivities）的存在下，α-烯烃的分布良好，甲基氨基氨基氨基化反应率，均为女性反应率。环戊二烯基的亚物质。我们还表明，通过简单的配体修饰，可以将这种类型的催化剂调整为苯乙烯聚合和乙烯/苯乙烯共聚的有效催化剂前体。我们……更多的还表明，在该催化剂系统中可以通过修改（indenenyl）TICL_2（OAR）的环戊二烯基群上的替代品来实现乙烯/诺本烯共聚的层状掺入。基于这些事实，使用该催化剂创建了难以/无法准备的新聚集素。我们还探索了配体通过CP-苯甲酸，CP-酰胺和CP-酮酰亚胺钛络合物中配体在烯烃聚合化学中的影响。 （anilido）（环戊二烯基）类型的钛（IV）复合物，cp'trcl_2 [n（r）（xar）] [cp'= cp^*，1,3 m_2c_5h_3，cp; r = sime_3等。 Ar=2,6-Me_2C_6H_3], and Cp'-amide titanium complexes of the type, Cp'TiCl_2(NMeR) have been prepared, and these complexes exposed high catalytic activity for ethylene polymerization in the presence of MAO, and the activity increased in the order : Cp'=Cp^*>1,3-Me_2C_5H_3>Cp.此处观察到的趋势几乎与CP'-芳基钛合金配合物中的趋势相同。只有通过更换CP'的亚率来修改符号特异性苯乙烯聚合的有效催化剂。我们报告说，（Arylimido）（Arylimido）（Aryloxo）（V）类型的复合物（VCL_2（NAR）（NAR）（NAR）（NAR）（NAR）（oar'），暴露的催化活性供应乙基级别的蛋白质，并在其上进行促催化活性。 Norbornene的聚合（ROMP）由V（CH_2PH）_2（NAR）（O-2,6PR_2C_6H_3）启动。如果用ET_2ALCL处理该复合物，则观察到乙烯聚合的催化活性非常高。如果使用Alme_3用作cocatalyst对ROMP有效，则观察到低催化活性，如果使用ALME_3代替ET_2ALCL。我们认为，这里观察到的结果在这些聚合中会是一个有趣的对比。较少的

项目成果

野村琴広, 他: "A study concerning the effect of organoboron compounds in 1-hexene polymerization catalyzed by Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3)"Inorg.Chim.Acta.. 345. 37-43 (2003)

Kotohiro Nomura 等人：“关于有机硼化合物在 Cp^*TiMe_2(O-2,6-^iPr_2C_6H_3) 催化的 1-己烯聚合中的影响的研究”Inorg.Chim.Acta.. 345. 37-43 (2003)

野村琴広, 他: "Polymerization of 1,5-Hexadiene by Nonbridged Half-Titanocene Complex-MAO Catalyst System : Remarkable Difference in the Selectivity of Repeated 1,2-Insertion"Macromolecules. 37. 1693-1695 (2004)

Kotohiro Nomura 等人：“通过非桥联半二茂钛复合物-MAO 催化剂体系聚合 1,5-己二烯：重复 1,2-插入选择性的显着差异”37. 1693-1695 (2004)。

野村琴広, 他: "Syndiospecific styrene polymerization by (tert-BuC_5H_4)TiCl_2(O-2,6-^iPr_2C_6H_3)-Borate Catalyst System"Catal.Commun.. 4. 269-274 (2003)

Kotohiro Nomura等人：“通过(叔BuC_5H_4)TiCl_2(O-2,6-^iPr_2C_6H_3)-硼酸盐催化剂系统进行同种苯乙烯聚合” Catal.Commun. 4. 269-274 (2003)

野村琴広他: "Effect of aryloxo ligand for ethylene polymerization by (arylimido)(aryloxo)vanadium(V) complexes -MAO catalyst systems. Attempt for polymerization of styrene"Catal. Commun.. (掲載予定).

Kotohiro Nomura 等人：“(芳基酰亚氨基)(芳基氧)钒(V)配合物-MAO催化剂体系对芳基氧配体对乙烯聚合的影响。苯乙烯聚合的尝试”，Commun.（待出版）。

K.Nomura, Y.Hatanaka, H.Okumura, M.Fujiki, K.Hasegawa: "Polymerization of 1,5-hexadiene by nonbridged half-titanocene complex -MAO catalyst system : Remarkable difference in the selectivity of repeated 1,2-insertion"Macromolecules. 37. 1693-1695 (2004)

K.Nomura、Y.Hatanaka、H.Okumura、M.Fujiki、K.Hasekawa：“通过非桥联半二茂钛配合物 -MAO 催化剂体系聚合 1,5-己二烯：重复 1,2- 选择性的显着差异