Elastomers and Composites

The Rubber Society of Korea (한국고무학회)
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Highly active and trans-1,4-specific polymerization of 1,3-butadiene catalyzed by bis(benzimidazolyl)amine chromium complexes activated with methylaluminoxane

메틸알루미녹산으로 활성화시킨 고활성 bis(benzimidazolyl)amine 크롬 착물을 이용한 부타디엔 중합에 의한 트랜스 폴리부타디엔 제조

  • Moon, Byeong Kyu (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University) ;
  • Song, Ga Young (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University) ;
  • Zhang, Lin (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University) ;
  • Shin, Jin Young (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University) ;
  • Chang, Hyuk Chul (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University) ;
  • Shim, Sang Eun (Department of Chemical Engineering, Inha University) ;
  • Yun, Ju Ho (Enviromental Materials & Components R&D Center, Korea Automotive Technology Institute) ;
  • Kim, Il (The WCU Center for Synthetic Polymer Bioconjugate Hybrid Materials, Department of Polymer Science and Engineering, Pusan National University)
  • 문병규 (부산대학교 고분자공학과) ;
  • 송가영 (부산대학교 고분자공학과) ;
  • 장린 (부산대학교 고분자공학과) ;
  • 신진영 (부산대학교 고분자공학과) ;
  • 장혁철 (부산대학교 고분자공학과) ;
  • 심상은 (인하대학교 화학공학과) ;
  • 윤주호 (자동차부품연구원) ;
  • 김일 (부산대학교 고분자공학과)
  • Received : 2012.12.24
  • Accepted : 2013.01.10
  • Published : 2013.03.31
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Abstract

A family of Cr(III) complexes supported on tridentate dibenzimidazolyl ligands having a general formula: $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [where Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn (3c)] have been synthesized and utilized them for the trans-1,4-specific polymerizations of 1,3-butadiene (BD), activated with methylalumoxane (MAO). The activity of BD polymerizations was sensitive to the type of ligand on the Cr metal, so that the activity decreases in the order of 3a > 3c > 3b. All the catalysts combined with MAO yielded polybutadienes with perfect trans-1,4 structure with moderate molecular weight.

일반식을 $[N(CH_3)(CH_2)_2(Bm-R)_2]CrCl_3$ [여기에서 Bm = benzimidazolyl, R = H (3a); -Me(3b); -Bn(3c)]으로 나타낼 수 있는 일련의 세 다리 dibenzimidazolyl 리간드를 갖는 크롬(III) 착물을 합성, 메틸알루미녹산으로 활성화시켜 이를 부타디엔의 입체규칙성 중합을 통해 trans-1,4-polybutadiene을 제조하였다. 크롬 착물의 부타디엔 중합 활성은 리간드의 구조에 따라 달라졌으며, 활성은 3a > 3c > 3b 순으로 낮아졌다. 모든 착물을 이용하여 제조된 폴리부타디엔의 미세구조를 조사한 결과 거의 완벽한 trans-1,4 구조를 보였으며, 분자량도 비교적 높게 나타났다.

Keywords

References

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