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New super‐hairy semi‐rigid polymers
Author(s) -
Grassl Bruno,
Rempp Sandra,
Galin Jean Claude
Publication year - 1998
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/(sici)1521-3935(19980201)199:2<239::aid-macp239>3.0.co;2-5
Subject(s) - macromonomer , polymer chemistry , chemistry , radius of gyration , dispersity , cationic polymerization , branching (polymer chemistry) , polymerization , polymer , hydrodynamic radius , isocyanide , copolymer , organic chemistry
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 (M̄ n ≈ 1800–4400, M̄ w /M̄ n ≈ 1.2). Their homopolymerization at 40°C in highly concentrated methanol solution (macromonomer weight fraction ≈0.80) initiated by NiCl 2 quantitatively yields the corresponding poly(macromonomers) of high degrees of polymerization (DP w > 10 3 ) 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., Et 4 N + CF 3 SO 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.