Atom transfer radical copolymerization of N‐phenylmaleimide and styrene initiated with dendritic polyarylether 2‐bromoisobutyrate

Abstract

Dendritic polyarylether 2-bromoisobutyrates with different generations (Gn-Br, n ϭ 1-3) were prepared by reaction of the Fréchet-type hydroxyl-terminated polyarylether with 2-bromoisobutyryl bromide and triethylamine. Gn-Br as a macroinitiator for the controlled free-radical polymerization of N-phenylmaleimide (PhMI, M 1 ) and styrene (St, M 2 ) was investigated. The copolymerization carried out in anisole with CuBr/bpy catalyst afforded polymers with well-defined molecular weights and low polydispersities (1.12 Ͻ M w /M n Ͻ 1.35). When the molar fraction of PhMI was 0.50, the apparent activation enthalpy of copolymerization was 38.2 kJ/mol. The effects of monomer feed on the apparent activation enthalpy and copolymer composition were also studied. The monomer reactivity ratios were determined to be r 1 ϭ 0.0325 and r 2 ϭ 0.0524 according to the Kelen-Tü dős method.

Tailored Polymer Microstructures Prepared by Atom Transfer Radical Copolymerization of Styrene and N‐substituted Maleimides

“…[71,72] It should be noted that ATRP cannot be used for the copolymerization of styrene and MAh since ATRP catalysts interact with the anhydride. [70] On the other hand, several examples of atom transfer radical copolymerization of styrene and MIs (e.g., N-phenyl maleimide, [70,73] N-(2-acetoxyethyl) maleimide, [70] N-cyclohexyl malei- [74] N-hexyl maleimide, [75] or N-butyl maleimide [76] ) have been reported. Yet, in all the aforementioned examples, standard alternating copolymers were targeted (i.e., copolymers containing equimolar amounts of donor and acceptor monomers).…”

“…Moreover, ATRP was selected among other CRP methods, since the ATRP kinetics of styrene homopolymerization and styrene/MIs copolymerizations have been described in details in the literature. [70,73,75,76,[79][80][81] Figure 1 shows the kinetic of copolymerization observed for the atom transfer radical copolymerization of styrene with N-propyl maleimide (PMI), N-benzyl maleimide (BzMI) or N-methyl maleimide (MMI). [24] In all cases, it appears clearly that the acceptor comonomer is consumed much faster than styrene (i.e., in the early stages of copolymerization as described by Hawker and co-workers [71] ).…”

Synthesis of Dendron Functionalized Core Cross-linked Star Polymers

“…A promising strategy is to replace the starting linear polymers with hybrid dendron-block-linear copolymers, which have multiple chain end functionalities per macromolecule and have recently gained significant interest. [14][15][16] A convenient route to prepare such polymers is to synthesize a dendritic macroinitiator with a single functionality at the focal point capable of initiating polymerization. [14][15][16] The resulting hybrid dendritic-linear macromolecule can then be used in the usual manner to form star polymers by the "arm first" approach to give highly functionalized CCS polymers with a core-shell morphology.…”

Spontaneous bulk organization of molecular assemblers based on aliphatic polyether and/or poly(benzyl ether) dendrons

“…28 Instead of the long alkyl chains, a shorter tetradecyl chain was chosen as the peripheral alkyl chain. The triblock block copolymers have two third-generation aliphatic polyether 17 dendrons at both ends and a PEO middle, with different molecular weights ( Figure 7). The triblock copolymers showed interesting thermal properties as a function of the middle PEO coil length.…”

“…In the early stage, the aim was focused on the construction of the dendron-coil molecular architecture by using diverse synthetic strategies [15][16][17] or the study of the self-assemblies in solution. [18][19][20] However, the recent interest has shifted to the bulk assemblies of dendron-coil molecules.…”