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Issue 1, 2019
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Polymer networks based on photo-caged diene dimerization

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A powerful, simple and efficient method for photochemical crosslinking, exploiting the self-dimerization of photo-caged dienes based on o-methylbenzaldehydes (o-MBAs) is introduced. Using a small molecule model system it is possible to identify the intermediate and final products of this light induced dimerization process. The bi-functional photocurable monomers contain o-MBA as well as vinylic units, which enables radical copolymerization with other monomers to tune the mechanical properties of the resulting networks. Crosslinked materials with reduced E-moduli ranging from 0.29 to 5.76 GPa and a hardness between 52 and 329 MPa were obtained, thus spanning a wide regime of different ‘soft’ to ‘hard’ material properties. The functional groups can be addressed through simultaneous reaction or in a λ-orthogonal fashion. This orthogonality can be achieved by inducing the free radical polymerization independently of the dimerization either thermally or via photoinitiation at a wavelength higher than the wavelength used for the non-radical dimerization process (>400 nm). Critically, this allows for a spatially defined adjustment of both the E-modulus and hardness within the respective material by controlling the irradiation parameters, such as wavelength, curing time and intensity. The introduced self-dimerizing resists thus represent a highly controllable combined radical/non-radical and λ-orthogonal curing system.

Graphical abstract: Polymer networks based on photo-caged diene dimerization

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Article information

09 Aug 2018
18 Sep 2018
First published
24 Sep 2018

Mater. Horiz., 2019,6, 81-89
Article type

Polymer networks based on photo-caged diene dimerization

T. Krappitz, F. Feist, I. Lamparth, N. Moszner, H. John, J. P. Blinco, T. R. Dargaville and C. Barner-Kowollik, Mater. Horiz., 2019, 6, 81
DOI: 10.1039/C8MH00951A

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