Cis-trans isomer effect in complex-radical copolymerization of methylallylmaleates (fumarates)

Hyperbranched macromolecules through donor‐acceptor type copolymerization of allyl–vinylene bifunctional monomers

“…Analogous inhibition of degradative chain transfer by CTCs was observed in complex‐radical copolymerization of several bifunctional monomers with an allyl group in such molecules as allyl(metha)acrylates,73 monoallyl maleate,84, 85 methylallyl maleate (fumarate)74 and allyl trans‐cinnamate 75. 76…”

“…Earlier investigations had shown that kinetic regularities of alternating copolymerization of maleic anhydride (acceptor, A) with allyl monomers affording high‐molecular weight products are reasonably intelligible, in terms of the formation of CTCs in the initial monomer mixture leading to inhibition of degradative chain transfer 7. 71–77…”

“…Complex‐radical cyclocopolymerization of selective bifunctional monomers containing two polymerizable double bonds of electron‐donor (allyl or vinyl) and electron‐acceptor (vinylene) type with MA (acceptor) or styrene (or vinyl acetate) as a typical electron‐donor monomer allow to design and synthesize alternating unsaturated cyclocopolymers–‘macromonomers’6, 72–75, 84, 85, 88, 116–118 which easily can be transformed into hyperbranched macromolecular architectures.…”

“…Several studies have been denoted to the synthesis of photocrosslinkable multifunctional macromonomers based on maleate (fumarate),73, 84, 85 maleimide88, 116 cinnamate74, 75 and acrylates72, 127–129 copolymers, the acrylate/polyimide system130 and maleimide modified acrylate 131. These copolymers show a high sensitivity to different kinds of irradiation such as photo‐irradiation, E‐beams and X‐rays and are easily transferred to their insoluble form that allows one to use them as negative resists in nanolithography 74.…”

“…Alternating methylallyl malaeate (fumarate)–MA (or St) cyclocopolymers with controllable content of photochromatic groups in the macromolecule also have high lithographic characteristics (light sensitivity at λ = 405 nm 6.6–21.6 cm 2 J 1 , quantum yield 0.054–0.16 mole Einstein −1 , X‐ray sensitivity 5–10 mJ cm −2 , E‐beam sensitivity 0.2 × 10 −6 –0.8 × 10 −6 C cm −2 and resolving capacity 0.5–0.8 µm), and may be used in the technology of electron (X‐ray) lithography as negative resists 73…”