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Article Dans Une Revue Macromolecular Chemistry and Physics Année : 1998

New super-hairy semi-rigid polymers

Bruno Grassl
S. Rempp
  • Fonction : Auteur

Résumé

Living monofunctional poly(tetramethylene oxyde) (PTMO) (THF bulk polymerization initiated at 20°C by methyl triflate) was end capped by reaction with 3-(dimethylamino)propyl isocyanide. Selective and quantitative quaternization of the tertiary amine function results in the straightforward synthesis of PTMO macromonomers of the isocyanide type with a fairly good control of molecular weight and polydispersity (M̄n ≈ 1800-4400, M̄w/M̄n ≈ 1.2). Their homopolymerization at 40°C in highly concentrated methanol solution (macromonomer weight fraction ≈0.80) initiated by NiCl2 quantitatively yields the corresponding poly(macromonomers) of high degrees of polymerization (DPw, > 103) and of very unusual and maximum branching density: one graft chain per every backbone carbon atom. According to a semi-quantitative analysis of their radius of gyration, as derived from light scattering measurements (EtOAc-iPrOH 9 : 1 by vol., Et4N+CF3SO-3 0.05 M), an increase of the intrinsic rigidity (persistence length) of the worm-like poly-(isonitrile) backbone induced by the PTMO branches cannot be ruled out. These super-hairy polymers may be considered as exotic comb-shaped cationic poly(amphiphiles) of potential interest as new lyotropic and thermotropic materials.

Domaines

Chimie
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Dates et versions

hal-01598485 , version 1 (29-09-2017)

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  • HAL Id : hal-01598485 , version 1

Citer

Bruno Grassl, S. Rempp, J.C. Galin. New super-hairy semi-rigid polymers. Macromolecular Chemistry and Physics, 1998, 199 (2), pp.239-246. ⟨hal-01598485⟩
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