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Late transition metal catalysis for olefin polymerization: New monomers and new materials
( Kohtaro Osakada ) 한국공업화학회 2018 한국공업화학회 연구논문 초록집 Vol.2018 No.1
Molecular transition metal catalysis in synthetic organic reactions has long been studied as the media for production of various organic materials. Late transition metal catalysts for productive olefin polymerization were reported much later (1990’s), but they have advantages in smooth copolymerization of hydrocarbon olefins with functionalized vinyl-compounds. Recent studies on the polyolefin materials with new properties, including environmentally favorable ones. We have studied in the polymerization of new monomers, such as dienes, highly functionalized olefins, strained olefins, and sterically bulky olefins, suited for polymerization catalyzed by the Ni, Fe, Co, and Pd complexes. Homo- and co-polymerization of the new monomers provided the polymer materials, such as aliphatic liquid-crystalline polymers, a component of the physical gels that undergo a sol-gel transition at the definite temperature, highly-ordered polymers having small membered ring, etc. Use of double-decker type bimetallic complexes as the catalysts for the olefin polymerization enabled the reaction at higher temperatures than the reaction using mononuclear catalysts. It is caused by cooperative interaction of the two metal centers to the polymer backbone and its end group, which not only stabilize the polymer end group but enhance selective insertion of monomer molecules into the polymer-metal bond. The complexes have the shorter metal-metal bond than most of the recently reported dinuclear transition metal complexes for olefin polymerization, and their structure supported by the rigid macrocyclic ligands influences the polymerization in a positive fashion.
포스핀류가 배위된 팔라듐 착물에 의한 불포화카르복실산의 카르보닐화고리 반응 (제 1 보). 불포화카르복실산이 배위된 팔라듐(0, Ⅱ) 착물의 합성과 구조
Myung-Ki Doh,Maeng-Jun Jung,Dong-Jin Lee,Kohtaro Osakada,Akio Yamamoto 대한화학회 1993 대한화학회지 Vol.37 No.4
$trans-PdEt_2(PMe_3)_2$와 styrene을 반응시켜 얻어진 $Pd(PMe_3)_2$(styrene)에 methacrylic acid와 trans-crotonic acid를 각각 반응시켜 새로운 팔라듐(O)-올레핀착물로서 $(PMe_3)_2Pd{CH_2=C(CH_3)COOH}$와 (PMe_3)_2Pd{(CH_3)CH=CHCOOH}$를 합성하고, 구조와 특성을 원소분석, IR 및 $^1H-,\;^{13}C-,\;^{31}P-NMR$ 등의 분광학적 방법으로 조사하였다. methacrylic acid 와 trans-crotonic acid에 존재하는 올레핀의 이중결합은 팔라듐(O)에 ${\pi}$-결합을 형성하였고, 카르복실산은 팔라듐에 결합되지 않았음을 알게되었다. 그리고 동일한 반응에서 metallacycle을 형성하는 3-butenoic acid와 비교 검토하였다. New Palladium(0)-olefin complexes, $(PMe_3)_2Pd{CH_2=C(CH_3)COOH} \;and\;(PMe_3)_2Pd{(CH_3)CH=CHCOOH}$ have been prepared by treating $Pd(PMe_3)_2$(styrene) with methacrylic acid and trans-crotonic acid, respectively. These complexes were characterized by elemental analysis, IR and $^1H-,\;^{13}C-,\;and\;^{31}P$-NMR spectroscopy. The carboxylic acid entity was found non-bonded with palladium while ${\pi}$-bond is formed between the olefin double bond and Pd(0). The results are compared with the metallacycle formation the reaction of Pd(PMe3)2(styrene) with 3-butenoic acid.