Novel polyethylene (PE)-based 3-miktoarm
star copolymers A2B, (AB)2B and terpolymers
(AC)2(BC)
[A: PE; B, C: polystyrene (PS) or poly(methyl methacrylate) (PMMA)]
were synthesized by combining boron chemistry, polyhomologation, and
atom transfer radical polymerization (ATRP). 1,4-Pentadiene-3-yl 2-bromo-2-methylpropanoate
was first synthesized followed by hydroboration with thexylborane
to afford B-thexylboracyclanes, a multi-heterofunctional initiator
with two initiating sites for polyhomologation and one for ATRP. After
polyhomologation of dimethylsulfoxonium methylide the α,ω-dihydroxyl
polyethylene (PE-OH)2-Br produced served as macroinitiator
for the ATRP of styrene to afford (PE-OH)2-(PS-Br). Both
(PE-OH)2-Br and (PE-OH)2-(PS-Br) were transformed
to two new trifunctional macroinitiators (PE-Br)2-Br and
(PE-Br)2-(PS-Br) through esterification reactions and used
for the synthesis of (AB)2B and (AC)2(BC) 3-miktoarm
star co/terpolymers. All intermediates and final products were characterized
by 1H NMR, high temperature gel permeation chromatography
(HT-GPC), and differential scanning calorimetry (DSC). The synthetic
method is a general one and can be used for the synthesis of complex
PE-based architectures by combination with other living/living-controlled
polymerization techniques.
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