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Development of radical initiator based on o-imino-isourea capable of photo/thermal polymerization.

ABSTRACT: Using o-imino isourea, three photo- and thermal dual-responsive radical initiators dicyheDCC, CyheDCC, and BnDCC were systematically developed and synthesized. By adding an aromatic ring to the free radical initiators, the ultraviolet-visible absorption was redshifted, and the absorption coefficient was increased. Compared with other initiators, BnphDCC exhibited an exceptional photoinitiation rate under photo-differential scanning calorimetry (DSC) and a high absorption coefficient (ε = 15 420 M^-1 cm^-1). Therefore, it is an appropriate potential photoinitiator. DicyheDCC, which was composed of a cyclic hydrocarbon, exhibited rapid thermal initiation (T_peak = 82 °C) during thermal DSC, making it a valuable thermal radical initiator. Because of the low stiffness of the N-O link in radical initiators, density functional theory predicts that the aliphatic ring has a significantly lower enthalpy than the aromatic ring. Moreover, in this study, CyhephDCC and BnphDCC, as dual-responsive radical initiators, indicated the potential for a photo- and heat dual-curing system through the universal free-radical polymerization of acrylates. These significant discoveries may be useful for developing efficient and diversified polymer network systems that require synergistic photo- and thermal effects.

SUBMITTER: Seo EJ

PROVIDER: S-EPMC10719897 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature

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Development of radical initiator based on o-imino-isourea capable of photo/thermal polymerization.

Seo Eun Jeong EJ Jung Hyocheol H Jeong Ji-Eun JE Lee Sang-Ho SH Kim Jin Chul JC Kim Dong Yeon DY Kim Seungju S Lee Kyu Cheol KC Park Young Il YI

RSC advances 20231214 51

Using o-imino isourea, three photo- and thermal dual-responsive radical initiators dicyheDCC, CyheDCC, and BnDCC were systematically developed and synthesized. By adding an aromatic ring to the free radical initiators, the ultraviolet-visible absorption was redshifted, and the absorption coefficient was increased. Compared with other initiators, BnphDCC exhibited an exceptional photoinitiation rate under photo-differential scanning calorimetry (DSC) and a high absorption coefficient (ε ...[more]

PMID: 38099255

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Project description:Copper-catalyzed atom transfer radical polymerization (Cu-ATRP) is one of the most widely used controlled radical polymerization techniques. Notwithstanding the extensive mechanistic studies in the literature, the transition states of the activation/deactivation of the growing polymer chain, a key equilibrium in Cu-ATRP, have not been investigated computationally. Therefore, the understanding of the origin of ligand and initiator effects on the rates of activation/deactivation is still limited. Here, we present the first computational analysis of Cu-ATRP activation transition states to reveal factors that affect the rates of activation and deactivation. The Br atom transfer between the polymer chain and the Cu catalyst occurs through an unusual bent geometry that involves pronounced interactions between the polymer chain end and the ancillary ligand on the Cu catalyst. Therefore, the rates of activation/deactivation are determined by both the electronic properties of the Cu catalyst and the ligand-initiator steric repulsions. In addition, our calculations revealed the important role of ligand backbone flexibility on the activation. These theoretical analyses led to the identification of three chemically meaningful descriptors, namely HOMO energy of the catalyst ( EHOMO), percent buried volume ( Vbur%), and distortion energy of the catalyst (Δ Edist), to describe the electronic, steric, and flexibility effects on reactivity, respectively. A robust and simple predictive model for ligand effect on reactivity is thereby established by correlating these three descriptors with experimental activation rate constants using multivariate linear regression. Validation using a structurally diverse set of ligands revealed the average error is less than ±2 kcal/mol compared to the experimentally derived activation energies. The same approach was also applied to develop a predictive model for reactivity of different alkyl halide initiators using R-X bond dissociation energy (BDE) and Cu-X halogenophilicity as descriptors.

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Development of radical initiator based on o-imino-isourea capable of photo/thermal polymerization.

Publications

Development of radical initiator based on <i>o</i>-imino-isourea capable of photo/thermal polymerization.

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