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

Abstract

The acetoxy group was introduced to polydicyclopentadiene via ROMP of acetoxy-substituted dicyclopentadiene resulting in a linear polydicyclopentadiene derivative with high Tg.

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).…”

“…22 The relatively low T g values for the f PDCPDs summarized in Scheme 1B (most of which were <100 °C) may suggest a low degree of crosslinking relative to the parent material; indeed, the 1-hydroxydicylopentadiene-derived polymers were originally designed to disfavor crosslinking. 15 In addition, both reports described substantial mass losses occurring at temperatures above ∼220 °C, 15,16 presumably owing to loss of the allylic acetate or ether leaving groups. Thus, while existing f PDCPDs have interesting properties that may be useful in certain applications, the low T g values and poor thermal stability may undercut their industrial utility.…”

Combining a ligand photogenerator and a Ru precatalyst: a photoinduced approach to cross-linked ROMP polymer films

“…This is in contrast with the 1 st generation Grubbs catalysts which are effective only at polymerizing the norbornene ring, thus undermining the production of cross-linked materials. 52,58,59 FTIR spectroscopy. Turning to chemical structure of the polymer network, the same series of ve lms was analyzed by ATR-FTIR spectroscopy.…”

Production and Dynamic Mechanical Analysis of Macro-Scale Functionalized Polydicyclopentadiene Objects Facilitated by Rational Synthesis and Reaction Injection Molding

“…pre-polymerization functionalization). 21,27 We rationally designed a functionalized form of polydicyclopentadiene (fPDCPD, Figure 1), in which an ester group was incorporated at the unstrained olefin within the dicyclopentadiene monomer. 28,29 This material undergoes polymerization and thermal crosslinking similarly to traditional DCPD, with the exception that the two steps can now be done separately.…”