Poly(norbornene imide)s: synthesis and simulations

Abstract

SUMMARY: The contribution reports on the vinylic polymerisation of exo N-o/m/p tolyl (Io/Im/Ip)-nadimides using a Pd(II) catalyst, on computer simulations on the chain conformation and dynamics as well as on the structure and glass transition in the condensed state. The poly(norbornene imide)s are densely coiled yet highly rigid chain molecules. The energy barriers are sufficiently high to prevent rotational motions for temperatures up to 380 8C. This rigidity causes the formation of a glassy state and a glass transition temperature of as high as 330 8C.

Palladium(II)-catalyzed addition polymerizations of nadimides with linear alkyl and alicyclic pendant groups

“…Nadimide monomers were prepared according to procedure in the literature [8,14,15] with a slight modification, and the general scheme of monomer and polymer syntheses is shown in Scheme 2. In a typical procedure, exo-NDA was dissolved in glacial actetic acid (20% w/v) in a three-necked flask under a nitrogen atmosphere.…”

“…Dichloroethane (from Aldrich) was dried over CaH 2 and distilled under nitrogen. Exo-norbornene-2,3-dicarboxylic anhydride (exo-NDA) was prepared by thermal isomerization of commercially available endo-NDA (from Aldrich) [8]. Primary amines such as cyclopentylamine, cyclohetylamine, 1-hexylamine, and 1-pentylamine were purchased from Aldrich and used without further purification.…”

“…Other than the aforementioned PNBs, poly(N-o/m/p-tolyl nadimide)s with aromatic imide groups display good solubility [8], and fluorinated polynadimides possess low dielectric constants (2.31) [9] while maintaining good thermal stability. Unfortunately, the NB derivatives with imide groups tend to have a lower rate of addition polymerization, requiring either longer reaction times or higher amounts of catalyst [8,9].…”

“…Unfortunately, the NB derivatives with imide groups tend to have a lower rate of addition polymerization, requiring either longer reaction times or higher amounts of catalyst [8,9]. ROMP of nadimides with linear alkyl and alicyclic substituents has also been performed, and the resulting polymers show good thermal properties and gas separations, as well as low dielectric constants [10].…”

Vinyl‐Type Polymerization of Alkylester‐Substituted Norbornenes Without Endo/Exo Separation

“…To improve these properties, many derivatives have been synthesized and polymerized. [4,11,13,14,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] Tailored monomer synthesis is possible by Diels-Alder reactions (Scheme 2); [36][37][38][39][40] however, endo/ exo isomers are usually obtained with an excess of endo monomers.…”