CAJ | 학술논문

合成了一系列吡啶双亚胺酰氯三齿Ni(Ⅱ)配合物(1a~1c,2a~2c),通过傅里叶变换红外光谱和元素分析对配合物进行表征,测定了配合物1a~1c 的晶体结构.3个化合物同属于单斜晶系,且都具有以Ni原子为中心的近似于Cs对称的扭曲三角双锥构型.该系列配合物通过倍半乙基氯化铝(EASC)活化,在20℃下对丁二烯聚合表现出良好的催化活性,得到分子量为4700~5200、cis-1,4含量为74.8%~77.2%(摩尔分数)的液体聚丁二烯.通过改变配体的结构和聚合条件,可在一定范围内调控聚丁二烯的结构和分子量。
합성료일계렬필정쌍아알선록삼치Ni(Ⅱ)배합물(1a~1c,2a~2c),통과부리협변환홍외광보화원소분석대배합물진행표정,측정료배합물1a~1c 적정체결구.3개화합물동속우단사정계,차도구유이Ni원자위중심적근사우Cs대칭적뉴곡삼각쌍추구형.해계렬배합물통과배반을기록화려(EASC)활화,재20℃하대정이희취합표현출량호적최화활성,득도분자량위4700~5200、cis-1,4함량위74.8%~77.2%(마이분수)적액체취정이희.통과개변배체적결구화취합조건,가재일정범위내조공취정이희적결구화분자량。
A series of bis(arylcarboximidoylchloride) pyridine Ni(Ⅱ) complexes with the general formula [2,6-(ArN CCl) 2 C5 H3 N]NiX2 [Ar=2,6-Me2 C6 H3 , X=Br(1a) or Cl(2a); Ar=2,4,6-Me3 C6 H2 , X=Br (1b) or Cl(2b); Ar= 4-Cl-2,6-Me2 C6 H2 , X = Br(1c) or Cl(2c)] were synthesized and characterized by FTIR and elemental analysis. The molecular structures of 1a-1c were further characterized by X-ray single crystal diffraction, and the geometry at the metal centre for all the three complexes can be best described as distorted trigonal bipyramidal. At the presence of ethylaluminum sesquichloride( EASC), all the Ni( Ⅱ)-based complexes performed high activities towards butadiene polymerization at 20 ℃, liquid polybutadienes (PB) with molecular weight of 4700-5200 and medium cis-1,4-PB content (74. 8% -77. 2% ) was ob-tained. Catalytic activities of the catalysts and the microstructures of the resulting polymers were little depen-dent on the ligand environment and highly dependent on polymerization conditions.