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造具有独特性能的新型聚烯烃。均相过渡金属配合物催化烯烃聚合是有机金属化学、催化和高分子化学领域的研究热点。这是因为有效的络合催化剂的设计因此成为通过控制聚合进行精确合成的关键。结果表明，在甲基铝氧烷（MAO）存在下，Cp'Ti（OAr）X_2（OAr=芳氧基）型钛（IV）配合物对乙烯、α-烯烃聚合具有显著的催化活性，且Cp' Ti（OAr）X_2上的取代基直接影响单体反应活性和单体序列分布。我们还表明，这种类型的催化剂可以调整为有效的催化剂前体的苯乙烯聚合和乙烯/苯乙烯共聚通过简单的配体改性。我们 ...更多信息 还表明，在该催化剂体系中，通过修饰环戊二烯基（茚基）TiCl_2（OAr）上的取代基，可以实现乙烯/降冰片烯共聚合中降冰片烯的有效掺入。基于这些事实，通过使用这种催化剂已经产生了难以/不可能制备的新聚烯烃。我们还通过偶氮苯胺、偶氮酰胺和偶氮酮酰亚胺钛配合物研究了配体在烯烃聚合反应中的作用。（苯胺基）钛（IV）配合物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]和Cp ′-酰胺钛配合物Cp ′ TiCl_2（NMeR），在MAO存在下，这些配合物对乙烯聚合具有很高的催化活性，其活性顺序为Cp ′ = Cp^*> 1，3-Me_2C_5H_3>Cp。这里观察到的趋势几乎与Cp ′-芳氧基钛络合物中的趋势相同。苯乙烯对称定向聚合的高效催化剂，只需对Cp ′上的取代基进行改性即可。在MAO存在下，VCl_2（NAr）（OAr '）型（芳酰亚胺基）（芳氧基）钒（V）配合物对乙烯聚合表现出显著的催化活性，V（CH_2Ph）_2（NAr）可引发异戊二烯开环易位聚合（ROMP）。（O-2，6Pr_2C_6H_3）。用Et_2AlCl处理配合物后，对乙烯聚合有很高的催化活性。虽然AlMe_3作为助催化剂对ROMP反应是有效的，但如果用AlMe_3代替Et_2AlCl，则催化活性较低。我们相信，这里观察到的结果将是这些聚合反应之间的有趣对比。少

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: "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: "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)。

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

K.Nomura, K.Fujita, M.Fujiki: "Effects of cyclopentadienyl fragment in ethylene, 1-hexene, and styrene polymerizations catalyzed by half-titanocenes containing ketimide ligand of the type, Cp'TiCl_2(N=C^tBu_2)"Catal.Commun.. (accepted.).

K.Nomura、K.Fujita、M.Fujiki：“环戊二烯基片段对含有 CpTiCl_2(N=C^tBu_2) 类型酮酰亚胺配体的半二茂钛催化的乙烯、1-己烯和苯乙烯聚合反应的影响”