NIR Light‐Induced ATRP for Synthesis of Block Copolymers Comprising UV‐Absorbing Moieties

NIR exposure at 790 nm activated photopolymerization of monomers comprising UV‐absorbing moieties by using [CuII/(TPMA)]Br2 (TPMA=tris(2‐pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton trans...

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Published inChemistry : a European journal Vol. 26; no. 46; pp. 10444 - 10451
Main Authors Kütahya, Ceren, Meckbach, Nicolai, Strehmel, Veronika, Gutmann, Jochen S., Strehmel, Bernd
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 17.08.2020
John Wiley and Sons Inc
Subjects
Block copolymers
Chemical synthesis
Chemistry
Copolymers
copper catalysis
cyanine
Molecular weight
Molecular weight distribution
Monomers
near-infrared radiation
photo-ATRP
Photopolymerization
Polymerization
Polymers
Structural members
cyanine
block copolymers
copper catalysis
photo-ATRP
near-infrared radiation
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Summary:NIR exposure at 790 nm activated photopolymerization of monomers comprising UV‐absorbing moieties by using [CuII/(TPMA)]Br2 (TPMA=tris(2‐pyridylmethyl)amine) in the ppm range and an alkyl bromide as initiator. Some of them comprised structural elements selected either from those showing proton transfer or photocycloaddition upon UV excitation. Polymers obtained comprise living end groups serving as macroinitiator for controlled synthesis of block copolymers with relatively narrow molecular weight distributions. Chromatographic results indicated formation of block copolymers produced by this synthetic approach. Free‐radical polymerization of monomers pursued for comparison exhibited the expected broader dispersity of molecular weight compared to photo‐ATRP. Polymerization of these monomers by UV photo‐ATRP failed on the contrary to NIR photo‐ATRP demonstrating the UV‐filter function of the monomers. This work conclusively provides a new approach for the polymerization of monomers comprising UV‐absorbing moieties through photo‐ATRP in the NIR region. This occurred in a simple and efficient pathway. However, studies also showed that not all monomers chosen successfully proceeded in the NIR photo‐ATRP protocol. Does it work or not? NIR‐sensitized photo‐ATRP facilitates controlled radical polymerization of monomers comprising UV‐absorbing moieties. New block copolymers were synthesized with special functionalities. UV ATRP failed with UV‐absorbing monomers.
Bibliography:ATRP=atom transfer radical polymerization.
These authors contributed equally to this work.
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202001099