Versatile Route to Functionalized Vinylic Addition Polynorbornenes

Abstract

Vinylic addition polynorbornenes bearing functional groups can be obtained in a versatile way by nucleophilic substitution of a halogen in new vinylic haloalkyl polynorbornenes. The latter are obtained by vinylic homo and copolymerization of norbornene and haloalkyl norbornenes catalyzed by [Ni(C 6 F 5 ) 2 (SbPh 3 ) 2 ]. This method circumvents the problem of catalyst deactivation encountered in classical copolymerizations with polar monomers. The content of substituted monomer in the copolymers is in the range 26-59%, depending on the monomer ratio in the feed. Nucleophilic substitution reactions afford polymers with ester, cyano, phenylthio, or azido groups in the same wide range of composition. Click chemistry on the azido polynorbornenes give polynorbornenes with pendant triazole groups.

Novel quaternary ammonium functional addition-type norbornene copolymer as hydroxide-conductive and durable anion exchange membrane for direct methanol fuel cells

“…[21][22][23] We have applied PNB to PEMFC in our previous studies. [21][22][23] We have applied PNB to PEMFC in our previous studies.…”

Advances in Organic and Organic-Inorganic Hybrid Polymeric Supports for Catalytic Applications

“…The catalysts 93a-d and 94b were prepared following the synthetic strategy depicted in the Scheme 32. In the first step, the ω-bromoalkyl functionalized polynorbornene (90a-d), having bromoalkyl chains of different length (n = 1 and 4) and two levels of functionalization for each bromoalkyl chain length, were prepared by Ni-catalyzed copolymerization of norbornene and ω-bromoalkylnorbornenes [58]. Then, copolymers 90a-d were treated with sodium azide to afford ω-azidoalkyl functionalized polynorbornene 91a-d. Copolymer 90b (x/y = 1.6; n = 1) was also treated with p-ethynylbenzoic acid to afford the alkynyl functionalized resin 92b.…”

Poly(ω-bromoalkylnorbornenes-co-norbornene) by ROMP-hydrogenation: a robust support amenable to post-polymerization functionalization

“…6 We have previously done some work on the vinylic addition copolymerization of haloalkylsubstituted norbornenes and norbornene (VA-PNB, Figure 1), which gives a saturated polycyclic polymeric material easy to functionalize by nucleophilic substitution of the halogen group. 7 These polymers have been used, for example, as precursors of supported stannyl reagents in the Stille reaction, 8 or of supported oganocatalysts, 9 and they can be recycled. With the aim to develop versatile saturated polymeric scaffolds for a variety of applications, we rationalized that a halo-substituted polymer obtained by ring opening metathesis polymerization of the above-mentioned norbornenyl monomers (ROMP-PNB, Figure 1) could be an excellent precursor to obtain a variety of materials by postpolymerization reactions.…”