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 (Tg), 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

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

“…For COPs, which can be viewed conceptually as an alternating copolymer of ethene and a cyclic monomer, a sterically hindered cycloolefin seems the only way to improve their Tg [4]. Recently, we have obtained a novel COP by ROMP of HBM and subsequent hydrogenation (2 in Scheme 2) with high Tg value of about 220 °C [32,33]. The Tg can be adjusted at an attractive region of 160-220 °C via copolymerization of HBM with less bulky monomer (3 in Scheme 2).…”

“…The obtained white polymer was dried under vacuum at 50 °C for 24 h. The yields of all the saturated polymers were higher than 85%. The 1 H NMR spectra for the homopolymer have been reported [32], and copolymers were provided in Figures 1A and A1 (in Appendix).…”

“…All solvents were purified from MBraun solvent purification system (SPS, MBraun, Munich, Germany). Exo- 1,4,4a,9,9a,10-hexahydro-9,10(1′,2′)-benzeno-l,4-methanoanthracene (HBM) were synthesized according to our previous reports [31,32]. Tetrachloroethane was dried over CaH2 and distilled before use.…”

Synthesis of novel cyclic olefin polymers with excellent transparency and high glass-transition temperature via gradient copolymerization of bulky cyclic olefin andcis-cyclooctene

“…However, the T g was as low as 112 °C, due to the low content of cyclic structure mole fraction of 25 mol %. Very recently, we reported the ROMP of HBMN utilizing G1 catalyst, the T g of this hydrogenised homopolymer was as high as 223.6 °C ( 4 in Scheme ) . To the best of our knowledge, this value is the highest T g reported for COPs prepared by ROMP approach.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…74) [318]; (7) a tris(norbornenecarboxylate) connected to a carbon nanotube [319]; (8) bis(norbornenecarboxylate ester)s (e.g. 73) [320]; (9) 5-ethylidenenorbornene (68) [321], including its use as a part of a self-healing system [322]; (10) vinylnorbornene [323]; (11) tetracyclododecene (69) [324]; (12) norbornadienes connected to various hydrophobic groups, including a steroid system [325]; (13) dicyclopentadiene [326,327,328,329,330,331,332,333,334,335,336], including polymerizations performed in the presence zinc oxide nanoparticles [337], urea formaldehyde microcapsules [338],mildly oxidized graphene oxide [339], barium titanate [340], and high internal phase emulsions [341,342]; (14) the norbornadiene-anthracene Diels-Alder adduct (76) [343,344]; (15) norbornenedicarboxylate esters connected to cyanobiphenyl groups [345], to anthracene groups [346], and to nitroxide groups (e.g. 79) [347]; (16) the three stereoisomeric dimethyl norbornenedicarboxylates (determination of the relative rates of ROMP) [348]; …”