Synthesis and characterization of hydrogenated poly(norbornene endo-dicarboximide)s prepared by ring opening metathesis polymerization

Poly(phenylnorbornene) from Ring‐Opening Metathesis and Its Hydrogenated Derivatives

“…Even though the phenyl substituent comprises nearly half of the repeat unit mass in PhNb, the insensitivity of T g to endo / exo ratio indicates that for PPhNb, the stereochemical configuration of the substituent has a negligible influence on the segmental packing and energetics of the backbone motions, which occur at the glass transition. This result contrasts considerably with the limited prior work on this question,17–20 where the exo, exo form of disubstituted norbornenes yielded a polymer with a T g some ≈30 °C lower than the endo, endo form; this ≈30 °C difference is also observed when the polymer backbones are hydrogenated 18. It may be significant that in those prior reports,17–20 the side groups had a substantial dipole moment, versus the phenyl group in the present work, as strong dipoles can influence segmental packing and backbone motions.…”

“…This result contrasts considerably with the limited prior work on this question,17–20 where the exo, exo form of disubstituted norbornenes yielded a polymer with a T g some ≈30 °C lower than the endo, endo form; this ≈30 °C difference is also observed when the polymer backbones are hydrogenated 18. It may be significant that in those prior reports,17–20 the side groups had a substantial dipole moment, versus the phenyl group in the present work, as strong dipoles can influence segmental packing and backbone motions. In analogy with the effects of tacticity on T g in vinyl polymers, those larger‐dipole ROMP polymers17–20 may be more like PMMA (where a strong effect is observed), while PPhNb is more like PS (where the effect is negligible).…”

“…The limited data for ROMP polymers suggest that endo isomers can produce polymers with a higher T g : a disubstituted norbornene, with cyano and ethyl ester substituents at the 5‐ and 6‐positions, showed a T g higher by 38 °C for polymer from the endo, endo versus exo, exo monomer 17. Similarly, polymers made from the endo form of norbornene dicarboximides consistently showed a higher T g over the exo form, for a variety of substituents: by 42 °C for the n ‐propyl derivative,18 31 °C for n ‐hexyl,19 ≈45 °C for n ‐octyl,20 37 °C for cyclohexyl,18 and 17 °C for phenyl 18…”

The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers

“…3 A small selection of these interesting applications include cell adhesion materials, membranes, insulating materials and various optics applications. [4][5][6][7][8][9] This breadth of applications can be attributed to the fact that, as a polymer class, poly(NDI)s have been demonstrated to exhibit favorable thermal and mechanical properties, which greatly extend their range of practical applications. [10][11][12][13][14] Furthermore, ring-opening metathesis polymerization allows the preparation of well-defined random, block and alternating copolymers that extend the utility of poly(NDI)s as a system to prepare reactive and functional polymers.…”

Unique post-functionalization method for ROMP polymers based on Triazolinedione Alder-ene chemistry

“…5A, The TGA curve (black) of Poly-1 behaved one step of weight loss, in which the decomposition temperature (T d ) at 5% weight loss was 403.7 C and a 10.8% residue left behind at 600 C. For the p-NO 2 -PhTAD modified Poly-1, however, the TGA curve (red) shows two steps of weight loss, where T d at 5% weight loss significantly decreased to 258.3 C and the residue at 600 C increased to 30.4%. According to the literature, the decreased T d after the modification could be mainly caused by the relatively poor thermal stability of urazole group [39,40] and the decomposition of nitro group [41,42]. Fig.…”