Synthesis and thermal properties of linear polydicyclopentadiene via ring‐opening metathesis polymerization with a third generation grubbs‐type ruthenium‐alkylidene complex

Abstract

Linear polydicyclopentadiene was produced with a third generation Grubbs‐type Ru–alkylidene complex. At high catalyst loadings, the polymer shows a portion of the polymer with a low degree of branching owing to secondary ROCM as seen in the SEC analysis. Distinct signals are observed via low angle scattering analysis for polymers with twice or another multiple of the average molecular weight of the linear polymer hence strongly affecting the controlled‐living nature of the polymerization.

Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

“…Most existing bulk ROMP methods to generate linear telechelics (Table ) rely on dilute conditions with high catalyst loadings and are not scalable. − A notable exception from Goetz and Boydston involved metal-free conditions to generate linear copolymers of DCPD and norbornene. While this impressive method works efficiently for copolymers composed of <30% DCPD content, DCPD homopolymerization in dichloromethane only achieves 14% total conversion.…”

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

“…Although synthesis of linear unfunctionalized PDCPD has been reported by other groups, it is generally more challenging to achieve. 30,31,32,33,34 The incorporation of the ester functional group within our fPDCPD confers several advantages -the surface energy of the final product can now be readily tuned through (fractional) saponification, and the monomer itself has a more pleasant smell owing to the presence of the ester. 28 Moreover, while the exact structure of the chemical crosslinks within traditional PDCPD has been a matter of considerable debate, 35,36 the presence of the ester group reduces the number of reasonable crosslinking reactions.…”

“…If desired, linear f PDCD can easily be isolated and purified prior to the cross-linking event. Although synthesis of linear unfunctionalized PDCPD has been reported by other groups, it is generally more challenging to achieve. − …”

Flow Optimization of Photoredox-Mediated Metal-Free Ring-Opening Metathesis Polymerization

“…During this process, back-electron transfer from the reduced photocatalyst and degenerative electron transfer from neutral enol ethers are each envisioned, offering a photomediated, spatiotemporally controlled polymerization with living characteristics . Also noteworthy, only highly strained alkenes show conversion in MF-ROMP, leaving less-strained alkenes intact, enabling access to valuable ROMP polymers that are typically difficult to produce via metal-mediated pathways, such as linear poly­(dicyclopentadiene) (pDCPD). − MF-ROMP has been demonstrated to produce high-conversion linear pDCPD, with the caveat of requiring low temperatures, which presents an opportunity for improvement with an appropriate flow process.…”