Development of new rare earth metal polymerization catalysts

新型稀土金属聚合催化剂的研制

基本信息

批准号：
13440203
负责人：
HOU Zhaomin
金额：
$ 3.58万
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 (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2004
项目状态：
已结题

项目摘要

1.1,4-Cis stereospecific polymerization of 1,3-butadiene by samarocene catalystsThe C_5Me_5R-ligated samarocene(II) complexes, (C_5Me_4R)_2Sm(THF)_x(1, R=Me ; 2, R=Et ; 3, R=i-Pr, 4, R=n-Bu, 5 ; R=TMS ; x=1 or 2), in combination with modified methylaluminoxane(MMAO) were examined in cyclohexane with respect to their catalytic performances for the polymerization of butadiene. Complexes 2-5 showed considerable promotion in both catalytic activity and regularity of the resulting polymer as compared to parent 1 : activity,3>>5〜4>2>1 ; 1,4-cis selectivity at 50℃,3〜5>4>2>1.2.1,4-Cis stereospecific polymerization of 1,3-butadiene by cationic rare earth metallocene catalystsCationic metallocene complexes[(C_5Me_5)_2Ln][B(C_6F_5)_4](Ln=Pr, Nd, Gd) in combination with ^iBu_3Al efficiently induce highly 1,4-cis specific polymerization of butadiene. The activity of the Gd complex/^iBu_3Al system is high enough to exhibit good catalytic activity even at low temperature. Polymerization at -78℃ gave … More polybutadiene with nearly perfect 1,4-cis microstructure (>99.9%) with sharp molecular weight distribution (M_w/M_n=1.45) and in reasonable yield.3.Synthesis, Structural Characterization, and Novel Catalysis of Rare Earth Alkyl Complexes Bearing Silylene-Linked Cyclopentadienyl-Phosphido LigandsThe reactions of Ln(CH_2SiMe_3)_3(THF_2)(Ln=Y, Yb, Lu) with 1 equiv of Me_2Si(C_5Me_4H)(PHR)(R=Ph, Cy) afforded the first silylene-linked cyclopentadienylphosphido rare earth alkyl complexes, [Me_2Si(C_5Me_4)(μ-PR)Ln(CH_2SiMe_3)]_2. In contrast with the analogous cyclopentadienyl-amido and metallocene complexes, these complexes adopt a dimeric structure through phosphide bridging, while the alkyl ligand is placed in a terminal position. Owing to their unique steric and electronic ligand environments, most of these complexes showed much higher activity for the polymerization of ethylene and hydrosilylation of olefins than that of the conventional metallocene or amido analogues. Moreover, when treated with [Ph_3C][B(C_6F_5)_4], these complexes showed extremely high regio- and stereoselectivity for the 3,4-polymerization of isoprene, which yielded the isotactic (>99% mmmm) 3,4-poly(isoprene) selectively. This is the first example of stereospecific 3,4-polymerization of isoprene. Less

1.1,4-Cis stereospecific polymerization of 1,3-butadiene by samarocene catalystsThe C_5Me_5R-ligated samarocene(II) complexes, (C_5Me_4R)_2Sm(THF)_x(1, R=Me ; 2, R=Et ; 3, R=i-Pr, 4, R=n-Bu, 5; R=TMS ; x=1 or 2）在环己烷中检查了与丁二烯聚合的催化性能，并在环己烷中检查了经过改性的甲基铝氧烷（MMAO）。与母体1：3 >> 5至4> 2> 1相比，配合物2-5在催化活性和所得聚合物的规律性上都显示出可观的促进。 1,4-CIS的选择性为50℃，3至5> 4> 2> 1.2.1,4-cis立体特异性聚合通过阳离子稀土甲基化甲基化催化属性甲级化甲基酸酯复合物[（C_5ME_5）_2LN] ^ibu_3Al有效地诱导了丁二烯的高度1,4-CIS特异性聚合。 GD复合物/^IBU_3AL系统的活性也足够高，即使在低温下也可以存在良好的催化活性。 Polymerization at -78℃ gave … More polybutadiene with almost perfect 1,4-cis microstructure (>99.9%) with sharp molecular weight distribution (M_w/M_n=1.45) and in reasonable yield.3.Synthesis, Structural Characterization, and Novel Catalysis of Rare Earth Alkyl Complexes Bearing Silylene-Linked Cyclopentadienyl-Phosphido LigandsThe reactions of ln（ch_2sime_3）_3（thf_2）（ln = y，yb，lu），具有1等于ME_2SI（C_5ME_4H）（phr）（r = ph，cy）提供的第一个silylene链硅烷链接环戊二烷基磷酸稀有地球烷基烷基烷基烷基复合物， [me_2si（c_5me_4）（μpr）ln（ch_2sime_3）] _ 2。与类似的环烷基 - 氨基和甲化十足的配合物相反，这些络合物通过磷化物桥梁采用二聚体结构，而烷基配体则将其置于末端位置。由于它们独特的空间和电子配体环境，这些复合物中的大多数在乙烯和氢化的聚合中的活性要高于常规金属钙或amido类似物的活性。此外，当用[ph_3c] [b（c_6f_5）_4]处理这些复合物，这些复合物显示出极高的层次和立体选择性，用于3,4-聚合的异戊二烯化，从而产生了同骨（> 99％MMMM）3,4 poly（iSoperene）。这是异戊二烯立体特异性3,4聚合的第一个例子。较少的