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

(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与1当量K（ER）在THF中反应，高产率地合成了C_5Me_5/ER配体Sm（II）配合物[（C_5Me_5）Sm（THF）_m（ER）]。（μ-C_5Me_5）K（THF）_n]_∞（m=0或1 ; n=1或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）），其中“（C_5Me_5）K（THF）_n”单元作为中性配体与Sm（II）中心以“C_5Me_5”部分键合。这些配合物，特别是1a-c，对苯乙烯和乙烯表现出独特的反应活性，不仅能使苯乙烯和乙烯共聚，而且在两种单体存在下还能使它们共聚成苯乙烯-乙烯嵌段共聚物。在ER配体中，硫醇配体SC_6H_2^iPr_3- 2，4，6（1c）对苯乙烯和乙烯的嵌段共聚合具有最高的选择性，芳氧化合物OC_6H_2^tBu_2- 2，6-Me-4（1a）和硅酰胺N（SiMe_3）_2（1 e）分别对乙烯和苯乙烯的嵌段共聚合具有最高的活性。(2)在茂钐配合物（C_5Me_5）_2Sm（THF）_2或（C_5Me_5）_2Sm（μ-Me）_2AlMe_2中加入适当的助催化剂如MMAO或AlR_3/[Ph_3C][B（C_6F_5）_4]，得到了一种新的丁二烯立构定向1，4-顺式活性聚合及丁二烯与苯乙烯共聚合催化体系。(3)Sm（OAr）_2（THF）_3（Ar=OC_6H_2^tBu_2- 2，6-Me-4）配合物对ε-己内酯和δ-戊内酯的开环聚合以及ε-己内酯和γ-丁内酯的共聚反应具有很高的催化活性。

项目成果

Z.Hou, Y.Zhang, H.Tezuka, P.Xie, O.Tardif, T.Koizumi, H.Yamazaki, and Y.Wakatsuki: "C_5Me_5/ER-Ligated Samarium(II) Complexes with the Neutral "C_5Me_5M" Ligand (ER=OAr, SAr, NRR', or PHAr ; M=K or Na) : A Unique Catalytic System for Polymerization and Bl

Z.Hou、Y.Zhang、H.Tezuka、P.Xie、O.Tardif、T.Koizumi、H.Yamazaki 和 Y.Wakatsuki：“C_5Me_5/ER-连接钐(II) 与中性“C_5Me_5M”复合物

Z.Hou: ""Synthesis and Novel Polymerization and Copolymerization Reactions of New Organolanthanide Complexes"."J.Synth.Org.Chem.Jpn. 59. 82-91 (2001)

Z.Hou：“新型有机镧系配合物的合成及新型聚合和共聚反应”。”J.Synth.Org.Chem.Jpn.

Hou,Z. et al.: "C_5Me_5/ER-Ligated Samarium (II) Complexes with the Neutral "C_5Me_5M" Ligand A unique Catalytic System for Polymerization and Block-Copolymerizaton of Styrene and Etylene"J.Am.Chem.Soc.. 122・43. 10533-10543 (2000)

Hou,Z. 等人：“C_5Me_5/ER-连接的钐 (II) 与中性“C_5Me_5M”配体的配合物用于苯乙烯和乙烯的聚合和嵌段共聚的独特催化系统”J.Am.Chem.Soc. 122・43。10533-10543（2000）

Hou,Z.,Zhang,Y.,Tezuka,H.,Xie,P.,Tarolf,O.,Koizumi,T.,Yamazaki,H.,Wakatsuki,Y.: "C_5Me_5/ER-Ligated Samarium(II)Complexes with the Neutral "C_5Me_5M"Ligand : A unique Catalytic System for Polymerization and Block-Copolymerizaton of Styrene and Etylene"J.A

侯Z.、张Y.、手冢H.、谢P.、Tarolf,O.、小泉T.、山崎H.、Wakatsuki,Y.：“C_5Me_5/ER-连接钐(II)

Hou,Z.,Wakatsuki,Y.: "C_5Me_5/ER-Ligated Samarium(II)Complexes(ER=OAr, SAr,NR^1R^2) : a new type of olefin polymerization catalysts"J.Alloy.Compd.. 303-4. 75-82 (2000)

Hou,Z.,Wakatsuki,Y.：“C_5Me_5/ER-连接钐(II)配合物(ER=OAr, SAr,NR^1R^2)：一种新型烯烃聚合催化剂”J.Alloy.Compd..