Abstract
Polytriarylamine copolymers can be prepared by
Suzuki-Miyaura cross-coupling reactions of bis N-methyliminodiacetic
acid (MIDA) boronate ester substituted arylamines
with dibromo arenes. The roles of solvent composition, temperature,
reaction time, and co-monomer structure were examined
and (co)polymers prepared containing 9, 9-dioctylfluorene
(F8), 4-sec-butyl or 4-octylphenyl diphenyl amine, and N, N0-
bis(4-octylphenyl)-N, N0-diphenyl phenylenediamine units,
using Pd(OAc)2/2-dicyclohexylphosphino-20,60-dimethoxybiphenyl (SPhos) catalyst system. The performance of a difunctionalized MIDA boronate ester monomer was compared
with that of an equivalent pinacol boronate ester. Higher molar
mass polymers were produced from reactions starting with a
difunctionalized pinacol boronate ester monomer than the
equivalent difunctionalized MIDA boronate ester monomer in
biphase solvent mixtures (toluene/dioxane/water). Matrixassisted
laser desorption/ionization mass spectroscopic analysis
revealed that polymeric structures rich in residues associated
with the starting MIDA monomer were present,
suggesting that homo-coupling of the boronate ester must be
occurring to the detriment of cross-coupling in the step-growth
polymerization. However, when comparable reactions of the
two boronate monomers with a dibromo fluorene monomer
were completed in a single phase solvent mixture (dioxane1
water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction
Suzuki-Miyaura cross-coupling reactions of bis N-methyliminodiacetic
acid (MIDA) boronate ester substituted arylamines
with dibromo arenes. The roles of solvent composition, temperature,
reaction time, and co-monomer structure were examined
and (co)polymers prepared containing 9, 9-dioctylfluorene
(F8), 4-sec-butyl or 4-octylphenyl diphenyl amine, and N, N0-
bis(4-octylphenyl)-N, N0-diphenyl phenylenediamine units,
using Pd(OAc)2/2-dicyclohexylphosphino-20,60-dimethoxybiphenyl (SPhos) catalyst system. The performance of a difunctionalized MIDA boronate ester monomer was compared
with that of an equivalent pinacol boronate ester. Higher molar
mass polymers were produced from reactions starting with a
difunctionalized pinacol boronate ester monomer than the
equivalent difunctionalized MIDA boronate ester monomer in
biphase solvent mixtures (toluene/dioxane/water). Matrixassisted
laser desorption/ionization mass spectroscopic analysis
revealed that polymeric structures rich in residues associated
with the starting MIDA monomer were present,
suggesting that homo-coupling of the boronate ester must be
occurring to the detriment of cross-coupling in the step-growth
polymerization. However, when comparable reactions of the
two boronate monomers with a dibromo fluorene monomer
were completed in a single phase solvent mixture (dioxane1
water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction
Original language | English |
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Journal | Journal of Polymer Science. Part A: Polymer Chemistry |
Early online date | 3 Jul 2017 |
DOIs | |
Publication status | Published - 2017 |
Keywords
- N-methyliminodiacetic acid (MIDA) boronate esters
- polytriarylamines
- Suzuki cross-coupling polymerization