DEVELOPMENT OF MIXED-LIGAND-SUPPORTED LANTHANIDE POLYMERIZATION CATALYSTS

混合配体负载的镧系元素聚合催化剂的开发

• 批准号: 11640573
• 负责人: HOU Zhaomin
• 金额: $ 2.18万
• 依托单位: RIKEN (THE INSTITUTE OF PHYSICAL AND CHEMICAL RESEARCH)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11640573/
• 关键词: lanthanide; metallocene catalysis; polymerization; divalent samarium; aryloxide; thiolate; olefin; lactone; エチレンースチレンブロック共重合; 混合配位子型錯体; 配位子効果; lanthanide; metallocene catalysis; polymerization; divalent samarium; aryloxide; thiolate; olefin; lactone; エチレンースチレンブロック共重合; 混合配位子型錯体; 配位子効果

(1) Reactions of (C_5Me_5)_2Sm(THF)_2 with 1 equiv of K(ER) in THF gave in high yields the C_5Me_5/ER-ligated Sm(II) complexes [(C_5Me_5)Sm(THF)_m(ER)(μ-C_5Me_5)K(THF)_n]_∞ (m=0 or 1 ; n=1 or 2 ; ER=OC_6H_2^tBu_2-2,6-Me-4 (1a), OC_6H_3^iPr_2-2,6 (1b), SC_6H_2^iPr_3-2,4,6 (1c), NHC_6H_2^tBu_3-2,4,6 (1d), or N(SiMe_3)_2 (1e)), in which the "(C_5Me_5)K(THF)_n" unit acts as a neutral coordination ligand bonding to the Sm(II) center with the "C_5Me_5" part. These complexes, particularly 1a-c, showed unique reactivity toward styrene and ethylene, which can not only polymerize styrene and ethylene, but also copolymerize them into block styrene-ethylene copolymers under the presence of both monomers. Among the ER ligands, the thiolate ligand SC_6H_2^iPr_3-2,4,6 (1c) showed the highest selectivity for the block copolymerization of styrene and ethylene, while the aryloxide OC_6H_2^tBu_2-2,6-Me-4 (1a) and the silylamide N(SiMe_3)_2 (1e) gave the highest activity for the polymerization of ethylene and that of styrene, respectively.(2) Addition of an appropriate cocatalyst such as MMAO or AlR_3/[Ph_3C][B(C_6F_5)_4] to the samarocene complex (C_5Me_5)_2Sm(THF)_2 or (C_5Me_5)_2Sm(μ-Me)_2AlMe_2 afforded a novel catalytic system for stereospecific 1,4-cis living polymerization of butadiene and copolymerization of butadiene with styrene.(3) The samarium(II) bis (aryloxide) complex Sm(OAr)_2(THF)_3 (Ar=OC_6H_2^tBu_2-2,6-Me-4) showed an extremely high activity for ring-opening polymerization of ε-caprolactone and δ-valerolactone and copolymerization of ε-caprolactone with γ-butyrolactone.

（1）（C_5ME_5）_2SM（THF）_2的反应，1等于K（er）的k（er）的反应高产量为C_5ME_5/ER绑定的SM（II）SM（ii）复合物[（C_5ME_5）SM（c_5me_5）SM（THF）SM（THF）_m（er）_m（er）_-C_5me_5me___________n = 0或1;或2; “（c_5me_5）k（thf）_n”单位充当带有“ C_5ME_5”部分的SM（II）中心的中性配体键合。这些复合物，尤其是1A-C，对苯乙烯和乙烯表现出独特的反应性，不仅可以聚合苯乙烯和乙烯聚合，而且在两个单体存在下都可以将它们共聚在苯乙烯 - 苯乙烯共聚物中。在ER配体中，硫醇酸盐SC_6H_2^IPR_3-2,4,6（1C）表现出对苯乙烯和乙烯共聚的最高选择性，而芳氧化物OC_6H_2^tbu_2^tbu_2-2-2-2,6-me-4（1A）以及SiLylamel lame lame lame lame lame lame lamel lamel lamel lamellam lamellam lamellamel lamel lamel lamel lamel lamellam lamellameliame n（sime_3）的选择性最高（Sime_3） （2）在Samarocene Complex（C_5ME_5）_2SM（THF）_2或（C_5ME_5ME_5ME_5）_5ME_5ME_2SM（c_5me_5）_2sm（c_5me_5）_2或（c_5me_5）_2或2）中，分别分别为乙烯和苯乙烯。丁二烯与丁二烯的丁二烯和共聚的立体特异性1,4-CIS催化系统。 ε-丙酮酸酯和δ-谷酰胺与ε-二苯乙酮与γ-丁二醇的共聚。