• Vinyl Addition Copolymerization of Norbornene/5-Vinyl-2-norbornene with Cationic η3-Allyl Palladium Catalyst and Their Post-Reaction
  • Ahn JC, Park SH, Lee KH, Park KH
  • 양이온성 η3-알릴 팔라듐 촉매를 사용한 노보넨/5-비닐-2-노보넨의 비닐 부가 공중합과 이를 이용한 고분자 후반응
  • 안재철, 박수현, 이광희, 박기홍
Abstract
Vinyl addition copolymerizations of norbornene (NB) and 5-vinyl-2-norbomene (VNB) were carried out using a cationic η3-allyl palladium catalyst in the various mole ratio of comonomers. The copolymers could be obtained in good yield (65 ~ 85 %) with high weight-average molecular weights (Mw>760,000). Depending on increasing VNB contents, the molecular weight and yield of the copolymers decreased. FT-IR analysis confirmed that actual contents of VNB in polymer were proportional to the feeding content of VNB. From 1H-NMR spectroscopy, we found that both exo and endo VNB isomer were copolymerized with NB. Thermal stabilities of NB-VNB copolymers were independent on the VNB content and their initial decomposition temperatures were about 300 ℃. The NB-VNB copolymers were followed by epoxidation by using m-CPBA and hydroxylation by 9-BBN, respectively, and these post-polymers were characterized by FT-IR spectroscopy and 1H-NMR analysis.

양이온 η3-알릴 팔라듐 촉매를 사용하여 환상형 올레핀 단량체인 노보넨 (NB)과 5-비닐-2-노보넨(VNB)을 조성별로 비닐 부가 공중합하였다. 공중합체는 고수율과 고분자량 (Mw>760000)으로 얻을 수 있었다. VNB 함량이 많아질수록 공중합체의 분자량과 수득율은 감소하였으며, 첨가한 공단량체의 양과 공중합한 후 함유된 단량체의 양이 비례함을 FT-IR 분광분석으로 확인하였다. 1H-NMR 분석 결과 VNB는 exo, endo 이성체 모두 중합에 참여하는 것을 알 수 있었다. NB-VNB 공중합체의 분해 개시 온도는 약 300 ℃이었고, 열안정성은 VNB 함량과 관계없이 유사한 거동을 나타내었다. 합성된 NB-VNB 공중합체의 곁사슬 비닐기는 m-CPBA를 이용하여 에폭시화 하였고, 또한 9-BBN을 이용하여 수산화기를 도입하였다. 조성별 공중합체에 각각의 치환기가 도입된 것은 FT-IR, 1H-NMR분석으로 확인하였다.

Keywords: allyl palladium; norbornene; 5-vinyl-2-norbornene; vinyl addition polymerization; epoxidation; hydroxylation

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  • Polymer(Korea) 폴리머
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This Article

  • 2003; 27(5): 429-435

    Published online Sep 25, 2003

  • Received on May 22, 2003
  • Accepted on Aug 16, 2003