Reported is a novel and simple method for the preparation of polymer spheres bearing hemispherical surface bumps where one type of polymer chains concentrates. The method is used to produce spheres with a diameter between approximately 30 and approximately 500 nm. Spheres with chain-segregated bumpy surfaces may find applications in drug delivery and other areas.

Homopolycouplings of aryltriynes Ar(C⋮CH)3 and their copolycouplings with monoyne Ar‘C⋮CH are effected by CuCl in air under Glaser-Hay oxidative coupling conditions, giving soluble hyperbranched polyynes (hb-PYs). Hyperbranched poly[tris(4-ethynylphenyl)amine] emits bright blue light (λ em = 440 nm) and shows high light refractivity (n = 1.770−1.861). Its peripheral terminal triple bonds can be 100% end-capped by aromatic rings via palladium-catalyzed coupling with aryliodides. The carbon-rich polyynes are readily curable (from ∼150 °C), thermally stable (T d up to ∼550 °C), and pyrolytically carbonizable (W r up to ∼80% at 900 °C). Complexations with cobalt carbonyls metallify the hb-PYs, and ceramizations of the cobalt−polyyne complexes afford soft ferromagnetic materials with high magnetizability (M s up to ∼118 emu/g) and low coercivity (H c down to ∼0.045 kOe).

A new synthetic route to hyperbranched polymers is developed. Polycyclotrimerizations of functional diynes 1−3 initiated by a simple base of piperidine lead to the formation of hyperbranched poly(aroylarylene)s P1−P3 with perfect 1,3,5-regioregularity and high degree of branching (up to 100%) in high yields (up to 99%). The polymers show high photosensitivities and can be readily photo-cross-linked to give photoresist patterns with nanometer resolutions.