Chem. J. Chinese Universities ›› 2012, Vol. 33 ›› Issue (05): 1095.doi: 10.3969/j.issn.0251-0790.2012.05.042

• Polymer Chemistry • Previous Articles     Next Articles

Copolymerization of Norbornene with Isoprene Catalyzed by TiCl4/Al(#em/em#-Bu)3 System

LI Xin, NI Xu-Feng, SHEN Zhi-Quan   

  1. Key Laboratory of Macromolecular Synthesis and Functionalization, Ministry of Education, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2011-08-01 Online:2012-05-10 Published:2012-05-10

Abstract: Copolymerization of norbornene(NBE) with isoprene(IP) catalyzed by traditional Ziegler-Natta system composed of TiCl4 and Al(#em/em#-Bu)3 was studied. The PNBE-co-IP copolymers obtained have number-average molecular weights of 2.0×104-6.5×104 as well as relatively narrow molecular weight distribution from the range of 1.5 to 2.9, and soluble in common organic solvents. The influences of catalyst composition, polymerization conditions, and the monomer feeding ratio on the copolymerization were investigated. The copolymer with 96% yield, 45%(molar fraction) of NBE, and number-average molecular weight of 6.5×104 can be prepared under the following optimum conditions: n(NBE)∶n(IP)=4∶6, n(Al)∶n(Ti)=5∶1, n(Monomer)∶n(Ti)=200∶1, 40 ℃, polymerized in toluene for 6 h. The NBE content in copolymer can be controlled in the range of 26%-60% by varying the feeding ratio of comonomer, and the Tg of the copolymer increased with the increasing of NBE content in copolymer. The microstructures of the obtained copolymers were confirmed by 1H NMR and 13C DEPT135 NMR, and indicate that the NBE monomer undergo an addition-type polymerization during the copolymerization with isoprene. The reactivity ratios of two monomers were determined to be rNBE=0.07 and rIP=0.44 by the Kelen-Tüdös method.

Key words: Ziegler-Natta catalyst, Norbornene, Isoprene, Copolymerization

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