Vinyl Addition Polymerization of Norbornene Derivatives by Palladium(II) complexes in situ : In Situ에서 Palladium(II) 착물에 의한 Norbornene 유도체의 Vinyl 첨가 중합

국문 초록 (Abstract)

Palladium 착물은 norbornene(NB)의 첨가 중합을 위한 활성 전촉매 역활을 한다. 이 실험에서는 norbornene (NB)의 in situ 첨가 중합을 위해 palladium(II) acetate [Pd(OAc)2]와 함께 리간드 2-(piperidin-1-ylmethyl)quinoline (LA)와 1-(naphthalen-2-ylmethyl)piperidine (LB), 그리고 보조 촉매인 N,N-Dimethylanilinium tetrakis(pentafluorophenyl)borate (Borate)를 사용했다. LB 촉매 시스템은 LA 촉매 시스템보다 chlorobenzene(25 oC)에서 각각 99%와 90%로 높은 전환율을 달성했다. In situ 촉매 시스템의 촉매 활성을 확인하기 위해 Pd(II) 착물인 [LAPd(OAc)2]] 와 [LBPd(-OAc)]2를 합성하고 특성을 분석했다. X -선 회절 분석 결과, [LAPd(OAc)2]는 정사각형 평면 형상을 취한 반면, [LBPd(-OAc)]2는 “조개 껍질” 구조를 보였다. 이 복합체는 in situ 촉매 시스템을 사용하여 동일한 조건에서 NB의 vinyl 첨가 중합에 이용되었다. Pd(II) 착물은 각각 76%와 90%로 in situ 촉매에 비해 낮은 전환율을 보였다. 또한 이 두 촉매 시스템은 5-butylbicyclo[2.2.1]hept-2-ene (Bu-NB), methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (Me-NB)와 bicyclo[2.2.1]hept-5-ene-2-methanol (AAc-NB)의 중합에 사용되어 더 낮은 전환율을 보였다.

다국어 초록 (Multilingual Abstract)

Palladium complexes serve as active precatalysts for the addition polymerization of norbornene (NB). In this study, 2-(piperidin-1-ylmethyl)quinoline (LA) and 1-(naphthalen-2-ylmethyl)piperidine (LB) were used as ligands, along with an N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate co-catalyst, and palladium(II) acetate [Pd(OAc)2] for in situ addition polymerization of NB. LB system achieved a higher conversion than the LA system, with 99% and 90%, respectively, at 25 oC in chlorobenzene. To confirm the catalytic activities of these in situ catalytic systems, Pd(II) complexes, [LAPd(OAc)2] and [LBPd(-OAc)]2, were synthesized and characterized. X-ray diffraction revealed square planar geometry for [LAPd(OAc)2], whereas, [LBPd(-OAc)]2 exhibited a “clamshell” structures. These complexes were then utilized for vinyl addition polymerization of NB under the same conditions with in situ catalytic system. The Pd(II) complexes demonstrated lower conversions than the in situ system, with respective values of 76% and 90%. Additionally, both catalytic systems were subsequently used for the polymerization of 5-butylbicyclo[2.2.1]hept-2-ene (Bu-NB), methyl bicyclo[2.2.1]hept-5-ene-2-carboxylate (Me-NB) and bicyclo[2.2.1]hept-5-ene-2-methanol (AAc-NB) which resulted in lower conversions.

목차 (Table of Contents)

• I. Introduction 1
• 1.1. Metal complexes containing piperidine ligand 1
• 1.2. Polymerization of NB and its derivatives 7
• 1.3. Aim of the research 10
• II. Experimental 12
• 2.1. Chemical and physical measurement 12
• 2.2. Preparation of ligands and complexes 13
• 2.3. X-ray crystallographic data collection and refinement 16
• 2.4. General procedure of cyclic olefins polymerization 16
• III. Results and discussion 19
• 3.1. Synthesis of ligands and complexes 19
• 3.2. NMR and FT-IR spectroscopy 19
• 3.3. X-ray crystallography 24
• 3.4. Polymerization of cyclic olefins 30
• IV. Conclusions 36
• V. References 37
• VI. The appendixes 41
• VII. Abstract 97