N-Vinylcarbazole is proposed as an additive
for
epoxy ring-opening polymerization ROP upon visible light exposure.
This compound can convert hardly oxidizable radicals to carbon centered
radicals by an addition process onto the N-vinylcarbazole
double bond. The generated radicals can be further easily oxidized
by an iodonium salt thereby leading to efficient initiating cations
for the ROP of epoxides. Different visible light photoinitiating systems
have been investigated: Type I photoinitiators (derived from phosphine
oxides) and dye/iodonium salt couples. The underlying chemical mechanisms
are investigated by electron spin resonance (ESR) experiments.
International audienceDifferent polyaromatic structures (truxene derivatives and tris(aza)pentacene) are presented as new metal-free organic photocatalysts (OPC) to promote free radical polymerization FRP and ring-opening polymerization (ROP) under halogen lamp, household LED bulb, and laser diode (405 nm). These OPCs exhibit interesting light absorption properties and lead, through an oxidative catalytic cycle, to the formation of radicals and ions that can initiate both free radical polymerization FRP and ring-opening polymerization ROP. Interestingly, excellent polymerization profiles are obtained even upon visible light exposure. Using these very soft irradiation conditions, acrylate/epoxide blends are also easily polymerized under air and lead to the formation of interpenetrated polymer networks IPN exhibiting no phase separation
International audienceThe photoredox catalysis approach is used to initiate the free radical promoted cationic photopolymerization of N-vinylcarbazole (NVK) under very soft irradiation conditions (halogen lamp, blue or green LED bulbs) using visible-light harvesting photocatalysts (mainly Ir(III) complexes) in iodonium salt and silane containing photoinitiating systems. The reactions were shown to proceed via an oxidative catalytic cycle where the generated free radicals are oxidized into cations. The effect of NVK on this catalytic cycle is discussed. Epoxy/NVK matrixes can also be polymerized. The luminescent properties of the synthesized polymers are presented
SummaryIn the present paper, the photoredox catalysis is presented as a unique approach in the field of photoinitiators of polymerization. The principal photocatalysts already reported as well as the typical oxidation and reduction agents used in both reductive or oxidative cycles are gathered. The chemical mechanisms associated with various systems are also given. As compared to classical iridium-based photocatalysts which are mainly active upon blue light irradiation, a new photocatalyst Ir(piq)2(tmd) (also known as bis(1-phenylisoquinolinato-N,C
2’)iridium(2,2,6,6-tetramethyl-3,5-heptanedionate) is also proposed as an example of green light photocatalyst (toward the long wavelength irradiation). The chemical mechanisms associated with Ir(piq)2(tmd) are investigated by ESR spin-trapping, laser flash photolysis, steady state photolysis, cyclic voltammetry and luminescence experiments.
International audienceA new iridium complex (nIr) was designed and investigated as a photoinitiator catalyst for radical and cationic polymerizations upon very soft irradiations (lights ranging from 457 to 532 nm). A ring-opening polymerization (ROP) of an epoxy monomer was easily promoted through the interaction between nIr and an iodonium salt (Iod) upon light. The addition of N-vinylcarbazole (NVK) enhances the performance. In radical polymerization, nIr can be efficient in combination with phenacyl bromide (PBr) and optionally an amine: these photoinitiating systems work according to an original oxidative cycle and a regeneration of nIr is observed. A control of the methyl methacrylate polymerization (conducted under a 462 nm light) with 1.2–1.6 polydispersity indexes was displayed. Surface modifications by direct laser write was also easily carried out for the first time through surface re-initiation experiments, i.e. the dormant species being reactivated by light in the presence of nIr; the polymer surfaces were analyzed by XPS. The chemical mechanisms were examined through laser flash photolysis, NMR, ESR and size exclusion chromatography experiment
New photoinitiating systems based on boron-dipyrromethene
dye (bodipy)/iodonium
salt and optionally tris(trimethylsilyl)silane are proposed for the
polymerization of divinylether and epoxy monomers upon visible-light
exposure. The presence of the silane increases the epoxide rate of
polymerization and conversion. Using acrylate/vinyl ether blends,
the synthesis of cross-linked polymer networks (possessing two T
g values: −11 and 111 °C) is also
successfully achieved through concomitant cationic and radical polymerization
pathways. The chemical mechanisms associated with these initiating
systems are investigated by steady-state photolysis and ESR experiments.
An
innovative model-based design strategy to synthesize well-defined
sequence-controlled polymers is presented, enabling selection of both
the most appropriate mediating agent and reaction conditions. In combination
with experimental analysis, advanced kinetic Monte Carlo simulations
are conducted, allowing a visualization of the connectivity of all
monomer units of ca. 105 individual copolymer chains. The
product quality can therefore be uniquely and unambiguously predicted
for the first time at the molecular level, explicitly accounting for
chain-to-chain deviations. The strategy is illustrated for BlocBuilder
MA-initiated nitroxide-mediated polymerization, with styrene and N-benzylmaleimide as comomomers, and is generally
applicable for all reversible deactivation radical polymerization
(RDRP) techniques. Further design of the nitroxide-mediating capabilities
and the reaction conditions allows the realization of a targeted (multi)functionalization
pattern, including an increase of the contribution of trifunctionalized
chains above 75%. The reported results are interpreted in terms of
the individual activation–growth–deactivation cycles
and provide an unprecedented mechanistic understanding of RDRP in
general.
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