A process for making
hyperbranched polymers from An-Lz(XY)m type monomers wherein A is a polymerizable group
moiety, XY is a telogen group
moiety in which Y is a transferable atom or group which can participate in a transfer reaction with the formation of reactive X*, L is a linkage between A and XY, z is 0 or 1, and n and m are integers of at least 1, comprising: (a) initiating reaction by forming activated species from reaction between either an A or an XY group of the An-Lz(XY)m type
monomer and an external stimulus to form activated
monomer species with an activated polymerizable group
moiety A* or an activated moiety X* derived from the telogen group moiety XY; and (b)
polymer segment chain growth by (i) propagation reaction between the polymerizable group A moieties of the An-Lz(XY)m type monomers with the activated moieties A* and X* of activated species, and further reaction between the polymerizable group moieties with the activated moieties of the reaction products thereof, and (ii)
chain transfer reaction between the activated A* polymerizable group moieties of activated species or of
polymer segments formed in (b)(i) with XY telogen group moieties of the An-Lz(XY)m type monomers or of
polymer segments formed in (b)(i), whereby activated X* moieties and inactive A-Y moieties are formed by transfer of transferable atom or group Y of the telogen group moiety XY to the activated A* moiety; wherein the reaction rates of the (b)(i) propagation reaction and of the (b)(ii)
chain transfer reaction are within 2 orders of magnitude of each other, more preferably within one
order of magnitude of each other, such that the combination of propagation reaction and
chain transfer reaction results in formation of a highly branched polymer from the An-Lz(XY)m type
monomer.