Thermal isomerization of 1-methylcyclopentadiene

Thermally Crosslinked Functionalized Polydicyclopentadiene with a High Tg and Tunable Surface Energy

“…However, to the best of our knowledge, there are only two publications describing the polymerization of a prefunctionalized DCPD monomer (Scheme 1B). 15,16 Both reports (by Xu in 2015 15 and Lemcoff in 2016 16 ) took advantage of a known SeO 2 -mediated allylic oxidation on DCPD, 17 followed by further esterification or etherification and Ru-catalyzed ROMP to achieve a new family of odorless f PDCPD polymers. These novel f PDCPDs mostly possessed glass-transition temperatures ( T g ) ranging from 80 to 143 °C, 16,18 which is between those of linear PDCPD ( T g ∼ 53 °C) 19 and crosslinked PDCPD ( T g ∼ 155–165 °C).…”

“…Indeed, many groups have developed postpolymerization strategies to functionalize the residual double bonds in PDCPD by bromination, epoxidation, inverse-demand Diels–Alder, radical-initiated thiol–ene addition, etc. However, to the best of our knowledge, there are only two publications describing the polymerization of a prefunctionalized DCPD monomer (Scheme B). , Both reports (by Xu in 2015 and Lemcoff in 2016) took advantage of a known SeO 2 -mediated allylic oxidation on DCPD, followed by further esterification or etherification and Ru-catalyzed ROMP to achieve a new family of odorless f PDCPD polymers. These novel f PDCPDs mostly possessed glass-transition temperatures ( T g ) ranging from 80 to 143 °C, , which is between those of linear PDCPD ( T g ∼ 53 °C) and crosslinked PDCPD ( T g ∼ 155–165 °C). , The glass-transition temperature is closely related to the maximum service temperature for PDCPD .…”

ROMP of acetoxy-substituted dicyclopentadiene to a linear polymer with a high Tg

“…The AcO-DCPD was synthesized referring to the modied Mironov's method. 22 To a solution of 50 g of DCPD in 110 mL of acetic anhydride, 30 mL of acetic acid and 40.2 g of SeO 2 were added. The mixture was stirred at room temperature for 24 h. Aer cooling, the mixture was ltered through a celite pad, diluted with H 2 O and extracted with 100 mL of hexane three times.…”

A Single-Atom Upgrade to Polydicyclopentadiene

“…To date, two general strategies have emerged to permit functionalization of the DCPD monomer, in such a way that polymerization is still maintained and a functionalized polymer product is produced. In the first of these strategies, the Xu and Lemcoff , groups separately reported the allylic oxidation of dicyclopentadiene − using stoichiometric quantities of toxic selenium dioxide. , The resulting allylic alcohol ( 2 m , Figure ) could be further functionalized by esterification or etherification, after which polymerization afforded the desired functionalized material ( 2 p and 2 p,c ). Unfortunately, the presence of allylic alcohol or allylic ester/ether groups within the final product allows for facile heterolytic bond cleavage at elevated temperatures, which leads polymers 2 p,c to exhibit step-function decomposition above ca.…”