Synthesis and properties of cyclic olefin polymers by ring-opening metathesis (co)polymerization of α-methyl-substituted norbornene lactones

Abstract

Previously, we prepared new cyclic olefin polymers (COPs) by performing a ring-opening metathesis polymerization (ROMP) of endo- and exo-norbornene lactones (NBLs) and then hydrogenation. In this study, we produced new...

Ring-opening metathesis polymerization of ester-functionalizedendo-tricyclo[4.2.2.02,5]deca-3,9-dienes and thermal properties of the resulting polymers

“…endo -Tricyclo[4.2.2.0 2,5 ]deca-3,9-diene-7,8-dicarboxylic anhydride, 11,12 2 , 10 endo -NBLs, and exo -NBLs 31–33 were synthesized according to previously reported procedures.…”

“…We have previously reported the synthesis and properties of COPs through a ring-opening metathesis (co) polymerization of norbornene lactones (NBLs). 31,32 The resulting COPs show good solubility, high thermal stability, and low birefringence. Given the extensive studies on the ROMP of ester-functionalized NB monomers for versatile applications, we have focused on ester-functionalized TDD monomers, 4-oxa-endo-tetracyclo[5.4.2.0 2,6 .0 8,11 ]trideca-9,12-dien-3-one (1) and endo-endo-tricyclo[4.2.2.0 2,5 ]deca-3,9-diene-7,8-dicarboxylate (2) (Scheme 1).…”

Spiro-Fluorene-Containing Cyclic Olefin Polymers

“…The design of the monomer structure and the copolymer sequence are critical for the resulting COP properties, and polycyclic polymer structures are required to obtain a high glass-transition temperature ( T g ) of around 150 °C. Various COPs have been produced from polycyclic NB derivatives, including conventional hydrocarbons (dicyclopentadienes, − tetracyclododecenes, − and others), ester-, , imide-, epoxy-substituted NBs, anthracene-derived NBs, NB lactones (NBL), , and cyclopropane-containing norbornadiene dimers (NBDDs) …”

“…Endo -/ exo -isomerism practically affects the polymerization rate as well as T g , and thus, this is also an important factor for the precise control of the properties of (co)­polymers. Endo -isomers are polymerized slower than exo -isomers because of the steric hindrance and/or chelation to the metal catalyst at the polymer terminals. − Endo -isomeric polymers show higher T g values than exo -isomers; − ,, however, it is unclear how the structural difference affects their physical properties. In this context, we previously proposed that the higher T g and lower solubility of endo -isomers are due to more regularly arranged structures of endo -isomers, as indicated by sharper X-ray diffraction (XRD) patterns based on the analysis of the polymers derived from the four isomers ( exo - exo -, exo - endo -, endo - exo -, and endo - endo -) of NBDDs …”

Simultaneously improving of thermal resistance and mechanical performances of cyclic olefin copolymers by incorporation of bulky adamantane side group

“…Cyclic olefin copolymers (COCs) always show high transparency, outstanding chemical resistance, and dimensional stability. [1][2][3][4][5][6][7] Furthermore, COCs display lower moisture absorption, better radiation resistance and lower birefringence compared to the common optical plastics as polymethylmethacrylate (PMMA) and polycarbonate (PC). [8][9][10][11][12] Therefore, COCs could be employed as an ideal alternative of PMMA and PC in various fields.…”