Peroxide-containing photoinitiators of radical polymerization

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Шибанов С. В., Shybanov V. V., Slobodianyk V. H. № 2 (57) 26-35 Image Image

The article describes the methods of synthesis of new photoinitiators of radical polymerization of acrylic monomers and photopolymerizable composite materials. The synthesized substances are characterized by the presence of two types of energy-sensitive groups in their composition, namely: thermally stable peroxide-containing fragments which containing -O:O-group and absorbing UV-chromophore group (aromatic ke­to­nes, colorants, azo-, diazocompounds). Such photoinitiators with a wide spectrum of UV radiation can be used for the two-stage initiation of radical polymerization: in the initial stages, as photoinitiators, and then in deep stages for the complete stitching of unsaturated monomers by thermolysis of peroxide groups.

Synthesis of peroxide-containing photoinitiators has been carried out by acylating alcohols or hydroperoxides with chlorohydrides of benzoyl benzoic acid in the presence of organic amines in an inert, light-flowing solvent medium. The completeness of the reaction has been monitored by thin-layer chromatography on the Sulyfol 254 plates. The interaction of the potassium salt of benzoyl benzoic acid and bromo-derivative peroxide has been carried out at a temperature of up to 5°C in a medium of dimethylformamide. Solid products are crystallized in a mixture of diethyl ether-hexane

The kinetics of photoinitized polymerization of monomers has been studied by dilatometric method. It has been shown that the effectiveness of initiation of po­ly­me­ri­za­tion of MMA for the studied photoinitiators in all cases is greater than that of styrene. The stitch rate has been determined by the Charlesby method.

Peroxide compounds containing a thermoplastic peroxide group coupled with a chromo-morphine UV absorbing fragment are effective photoinitiatory radicals of ra­dical polymerization. The comparison of the initiating activity of the synthesized pe­ro­xidines indicates their higher activity in comparison with benzophenone. These com­pounds are also capable of thermolysis at temperatures higher than 90°C, which allows them to be considered as effective thermo-photoinitiators, which are capable of gradually initiation of radical processes.

Keywords: photoinitiators, organic peroxides, photodecay, kinetics of polymerization, light sensitivity, thermometric measurements.

doi: 10.32403/1998-6912-2018-2-57-26-35

  • 1. Antonovskii, V. L. (1972). Organicheskie perekisnye initciatory. Moskva: Khimiia (in Russian).
  • 2. Oster, G., & Yang, N.-L. (1968). Photopolymerization of vinyl monomers: Chem. Rev, 68, 2, 125–151 (in English).
  • 3. Shibanov, V. V., Volkova, G. A., Smirnov, V. A., & Gorbacheva, S. V. (1987). Izv. vuzov SSSR: Khimiia i khimich. tekhnol., 30, 5, 34–37 (in Russian).
  • 4. Karpukhin, O. N., & Slobodetckaia, E. M. (1973). Kinetika fotookisleniia poliolefinov: Us­pe­khi khimii., 42, 3, 391–422 (in Russian).
  • 5. Thjs, L., Gupta, S. N., Neckers, D. C. (1979). Photochtmistry of Perester Iniziators: J. Org. Chem, 44, 23, 4123–4128 (in English).
  • 6. Shibanov, V. V., Miziuk, V. L., & Miliashkevich, P. E. (1982). Aromaticheskie ketoperoksidy – fotoinitciatory radikalnykh reaktcii. Poluchenie benzoil-tret-butilperoksimetanola reaktciei fenilglioksalia s tret-butilgidroksiperoksidom: ZhorKh, 43, 5, 1113–1114 (in Russian).
  • 7. Shibanov, V. V., Miziuk, V. L., & Protciuk, G. V. (1980). Sintez, termo i fotoinitciiruiushchaia aktivnost karbonilsoderzhashchikh peroksidov: tezisi dokl. Vsesoiuznoi konf. po khimii peroksidov. Volgograd (in Russian).
  • 8. Antonovskii, V. L., & Buzlanova, M. M. (1978). Analiticheskaia khimiia organicheskikh pe­roksidnykh soedinenii. Moskva: Khimiia (in Russian).
  • 9. Shliapintokh, V. Ia., Kormukhin, O. N., & Postnikov, L. M. i dr. (1966). Khemiliuminestcentnye metody issledovaniia medlennykh khimicheskikh protcessov. Moskva: Nauka (in Russian).
  • 10. Grishchenko, V. K., Masliuk, A. F., & Gudzera, S. S. (1985). Zhidkie fotopolimerizuiushchiesia kompozitcii. Kiev: Nauk. Dumka (in Russian).
  • 11. Kochetov, D. P., Gritcenko, F. R., & Grishchenko, V. A. (1975). Raschet kineticheskikh parametrov initciirovaniia polimerizatcii.:Vysokomol. soed.,18 A, 2, 467–468 (in Russian).
  • 12. Rot, A. S., Snitcar, A. P., & Kirkach, E. F. i dr. (1988). Fotopolimerizuiushchaiasia rele­fo­obrazuiushchaia kompozitciia dlia opticheskikh diskov: Lakokrasoch. mater., 4, 26–27 (in Russian).
  • 13. Charlzbi, A. (1962). Iadernoe izluchenie i polimery. Moskva (in Russian).