Synthesis of cyclic olefin polymers with high glass transition temperature by ring-opening metathesis copolymerization and subsequent hydrogenation

Abstract

Novel cyclic olefin polymers (COPs) derived from bulky cyclic olefin, exo-1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l, 4-methanoanthracene (HBMN), with high glass transition temperature (T g), excellent thermal stability, high transparency, and improved mechanical performance, have been achieved by ring-opening metathesis polymerization and subsequent hydrogenation. The "first-generation Grubbs" catalyst, RuCl2(PCy3)2(CHPh) (Cy = cyclohexyl) (G1), displays very high activity for homo/copolymerization with complete conversion. Homopolymer of the HBMN after complete hydrogenation showed a highest Tg of 223.6 °C. Copolymerization of HBMN with tricyclo[4.3.0.12,5]deca-3-ene or 5-n-hexylnorbornene was also carried out. These two series of COPs were characterized by gel permeation chromatography, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. The Tg of the resulted COPs linearly increased with HBMN content, which is easily controlled by changing feed ratios. The tensile test indicates that these copolymers have good mechanical performance as all these copolymers show a higher strain at break compared with commercial products (TOPAS®). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2654-2661 A series of high-performance cyclic olefin polymers derived from exo-1,4,4a,9,9a,10- hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene with high glass transition temperature (Tg = up to 220 ° C), excellent transparency (transmittance, >88%), and improved mechanical performance (strain at break, 3-5%) have been synthesized via ring-opening metathesis polymerization and subsequent complete hydrogenation. Copyright © 2014 Wiley Periodicals, Inc.