Synthesis of hydrocarbon polymers containing bulky dibenzobicyclic moiety by ROMP and their characteristic optical properties

Abstract

The eight-membered cyclic monomer, prepared by Diels-Alder reaction of 1,5-cyclooctadiene and anthracene, polymerized via Ru-catalyzed ring-opening metathesis to efficiently afford high polymers (M n up to 631,000). Unsaturated moieties in the main chain of the obtained polymer were hydrogenated with a homogeneous ruthenium catalyst in quantitative conversion, confirmed by 1 H-NMR measurement. The self-standing membranes were provided by casting the tetrahydrofuran solutions of both nonhydrogenated and hydrogenated polymers. The obtained membranes showed high transparency in the region of >300 nm with mechanical flexibility. Thermal gravimetric analysis revealed that both nonhydrogenated and hydrogenated polymers decomposed in two stages. The first-stage decomposition starting at around 230 C was caused by retro Diels-Alder reaction forming anthracene, proven by pyrolysis gas chromatography mass spectroscopy (GC-MS) analyses. Mechanical grinding of the polymers induced the formation of anthracene in solid state, which transformed the polymer into blue-luminescent materials under UV irradiation.

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

“…Usually, products prepared by this route are called COPs . A sterically hindered monomer is essential to improve the T g of the COPs prepared by ROMP . For instance, the ROMP product derived from dicyclopentadiene was expected to have a T g of 95 °C, and T g value can reach up to 174 °C if 1,4,5,8‐dimethano‐1,2,3,4,4a,5,8,8a‐octahydronaphtalene was used .…”

“…18 A sterically hindered monomer is essential to improve the T g of the COPs prepared by ROMP. [19][20][21] For instance, the ROMP product derived from dicyclopentadiene was expected to have a T g of 95 C, and T g value can reach up to 174 C if 1,4,5,8dimethano-1,2,3,4,4a,5,8,8a-octahydronaphtalene was used. 22,23 In addition, the cyclic olefin can be fully converted into polymer if the ROMP preparation was used.…”

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

“…As shown in Scheme 1, COCs are obtained through copolymerization of cycloolefin with ethylene or α-olefin [5][6][7][8][9][10][11][12][13][14], and commercialized under the trade names APEL ® by Mitsui and TOPAS ® by TOPAS advanced polymers (TAP: formerly Ticona and Hoechst) [15,16]. COPs are prepared via ring-opening metathesis polymerization (ROMP) of cycloolefin followed by hydrogenation [17][18][19][20][21][22][23][24], and commercialized under the trade names Zeonex ® and Zeonor ® by Zeon [25] and Arton ® by Japan Synthetic Rubber (JSR) [20,21]. Scheme 1.…”

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

“…86) in an equilibrium polymerization process [379]; (4) cyclooctene or substituted cyclooctene derivatives [380,381,382,383]; (5) 1,5-cyclooctadiene [384,385]; (6) the 1,5-cyclooctadiene anthracene Diels-Alder adduct (e.g. 87) [386]; (7) cyclooctene fused to a dichlorocyclopropane ring (e.g. 88) [387]; (8) a dithiacyclooctene derivative (e.g.…”