2019 (3) 5

https://doi.org/10.15407/polymerj.41.03.179

Synthesis and properties of silicone oligomeric photoinitiators

N.A. Busko, V.K. Grishchenko, A.V. Barantsova, N.V. Gudzenko, Ya. V. Kochetova

Institute of Macromolecular Chemistry NAS of Ukraine

48, Kharkiv highway, Kyiv, 02160, Ukraine, oligomer8@bigmir.net

Polym. J., 2019, 41, no. 3: 179-189.

Section: Synthesis of polymers.

Language: Ukrainian.

Abstract:

The aim of the work was to develop methods for the synthesis and study of the properties of silicon-containing oligomeric photoinitiators, which will further be used for the synthesis of block copolymers. A method for the synthesis of monomeric photoinitiator with isophoronisocyanate group (DRIF) have been developed and the kinetic laws of its formation have been investigated. It has been shown that the kinetic curve of the formation of the urethane groups of the initiator of the IFDR is complex. First, the reaction rate increases linearly, then slows down due to the increase in viscosity and decrease in the concentration of active NCO groups. At the third stage, a gradual acceleration of the reaction in an S-shaped type is observed. Methods for the synthesis of oligomeric photoinitiators (OFI) based on the DRIF and organosilicons oligomers of dihydroxy(polydimethylsiloxane) (PDMS) and (3-aminopropyl)triethoxysilane (APTES) have been developed. The kinetic laws of synthesis and the structure of the initiators obtained by the method of IR-spectroscopy were investigated. The study of the thermostability of synthesized OFI by the method of thermogravimetric analysis showed that both oligomeric photoinitiators are characterized by three stages of weight loss. The main weight loss starts at temperatures above 230 °C. The study of relaxation transitions in oligomeric organosiliconе initiators by the DSC method showed that during the first heating of the OFI, PDMS-DRIF has two crystalline microphases, PDMS and final DRIF groups. After changing the thermal history, the microphase PDMS remains crystalline with a constant melting point, and the DRIF end groups, as before, are separated into a separate microphase, but lose their orderliness and become amorphous. In the oligomeric photoinitiator APTES-DRIF, during the first heating, there are two transitions in the glass transition of APTES and DRIF microphases. In the second scan, one relaxation transition is observed in the glass transition of an amorphous microphase, which may consist of interpenetrating APTES and DRIF segments. That is, OFI PDMS-DRIF is a two-phase system, and OFI APTES-DRIF is a single-phase system.

Key words: block copolymers, oligomeric photoinitiators, silicon organic oligomers, radical photopolymerization.

References

1. Ueda A., Agari Y., Nagai S., Minamii N. Synthesis of new macro-azo-initiators for block copolymerization. Chem. Express. 1989, 4, no. 3: 193–196.
2. Alli A., Hazer B., Baysal B. M. Determination of solubility parameters of cross-linked macromonomeric initiators based on polypropylene glycol. Eur. Polym. J., 2006, 42, no. 11: 3024–3031. https://doi.org/10.1016/j.eurpolymj.2006.07.012
3. Alli A., Hazer B. Poly(N-isopropylacrylamide) thermoresponsive cross-linked conjugates containing polymeric soybean oil and/or polypropylene glycol. Eur. Polym. J., 2008, 44, no. 6: 1701–1713. https://doi.org/10.1016/j.eurpolymj.2008.04.004
4. Yildiz U., Landfester K. Miniemulsion polymerization of styrene in the presence of macromonomeric initiators. Polymer, 2008, 49: 4930–4934. https://doi.org/10.1016/j.polymer.2008.09.036
5. Maintaining organic compounds in photochemistry. Ed. G.O. Becker – L .: Chemistry (Rus.), 1976: 384.
6. Rutnakornpituk M. Modifcation of epoxy-novolac resins with polysiloxane containing nitrile functional groups: synhesis and characterization. Eur. Polym. J, 2005, 41: 1043–1052. https://doi.org/10.1016/j.eurpolymj.2004.11.013
7. Brachaczek W. Comparative analysis of organosilicon polymers of varied chemical composition in respect of their application in silicone-coating manufacture. Progress in Organic Coatings, 2014, no. 77: 609–615. https://doi.org/10.1016/j.porgcoat.2013.11.026
8. Bes L., Huan K., Khoshdel E., Martin J. L., McConville C.F., Handdleton D.M. Poly(methylmethacrylate-dimethilsiloxane) triblock copolymers synthesized by transition metal mediated living radical polymerization: bulk and sulface characterization. Eur. Polym. J., 2003, 39: 5–13. https://doi.org/10.1016/S0014-3057(02)00177-5
9. Busko N. A., Grishchenko V. K., Kochetov D.P. Photoinitiated radical polymerization of a urethane-containing copolymer. Teoret. and experiment. Chemistry (Rus.), 1993, 29, no. 6: 539–544. https://doi.org/10.1007/BF00530621
10. Busko N. A., Grishchenko V. K., Kochetov D.P. Block copolymers based on reactive oligomers. Ukr. chemical journals (Rus.), 1996, 62, no. 1: 65–69.
11. Busko N. A., Grishchenko V. K., Kochetov D.P., Privalko V.P. Properties of three-block copolymers based on reactive oligomers and styrene. Composite polymeric materials (Rus.), 1996, 57: 150–156.
12. Busko N. A., Grishchenko V. K., Shtompel V. I., Babkina N. V., Rosovitski V. F., Privalko V. P. Phase morphology and dynamic mechanical properties of model polyblock copolymers prepared from reactive oligomers. Polymers & Polymer Composites, 2001, 9, no. 8: 509–513. https://doi.org/10.1177/096739110100900803
13. Busko N., Grishchenko V., Barantsova A., Babkina N., Silchenko Yu. Physico-chemical properties of block copolymers based on polyazoinitiator and butylmethacrylate. Kautshuk Gummi Kunstoffe, 2010, no. 1–2: 36–39.
14. Busko N., Grishchenko V., Barantsova A., Babkina N., Silchenko Yu., Kochetova Ya, Gudzenko N. Synthesis and study of the chemical structure of castor oil block copolymers based on oligomeric azo initiators. Polym. J., 2017, 39, no. 3: 195–201. https://doi.org/10.15407/polymerj.39.03.195
15. Sardon H., Irusta L., Fernandez-Berridi M.J. Synthesis of isophorone diisocyanate (IPDI) based waterborne polyurethanes: Comparison between zirconium and tin catalysts in the polymerization process. Progress in Organic Coatings, 2009, 66: 291–295. https://doi.org/10.1016/j.porgcoat.2009.08.005
16. Prabhakar A., Chattopadhyay D.K.., Jagadeesh B. Structural investigations of polypropylene glycol (PPG) and isophorone diisocyanate (IPDI)-based polyurethane prepolymer by 1D and 2D NMR spectroscopy. J. Polym. Sci., Part B: Polym. Chem., 2005, 43, no. 6: 1196–1209. https://doi.org/10.1002/pola.20583
17. Ono H.K., Jones F.N., Pappas S.P. Relative reactivity of isocyanate groups of isophorone diisocyanate. Unexpected high reactivity of the secondary isocyanate group. J. Polym. Sci. C: Polym. Lett., 1985, 23: 509–515. https://doi.org/10.1002/pol.1985.130231003
18. Silverstein R., Bassler G., Moril T. Spectrometric identification of organic compounds (Rus.). M: Mir, 1977: 590.
19. Semenovich G.M., Khramova T.S. Handbook of the physical chemistry of polymers. Kiev: Sciences. Dumka (Rus.). 1985, 3: 589.
20. Sardon H., Irusta L., Fernandez-Berridi M.J. Synthesis of isophorone diisocyanate (IPDI) based waterborne polyurethanes: Comparison between zirconium and tin catalysts in the polymerization process. Progress in Organic Coatings, 2009, 66: 291–295. https://doi.org/10.1016/j.porgcoat.2009.08.005
21. Prabhakar A., Chattopadhyay D.K., Jagadeesh B. Structural investigations of polypropylene glycol (PPG) and isophorone diisocyanate (IPDI)-based polyurethane prepolymer by 1D and 2D NMR spectroscopy. J. Polym. Sci., Part B: Polym. Chem., 2005, 43, no. 6: 1196–1209. https://doi.org/10.1002/pola.20583
22. Sundararajan P. R., Hamer G. K., and Croucher M. D. Low-Temperature Crystallization of Poly(dimethylsi1oxane) from Solution. Macromolecules, 1980, 13: 973–977. https://doi.org/10.1021/ma60076a040
23. G. David, J.J. Robin , B. Boutevin, S. Andre Synthesis of poly(styrene-b-dimethylsiloxane) multi-block copolymers via polyhydrosilylation reaction. Eur. Polym. J., 2006, 42: 109–118. https://doi.org/10.1016/j.eurpolymj.2005.06.028
24. Feng Daan, Wilkes Garth L., Crivello James V. Structure-property behaviour of free radical synthesized polydimethylsiloxanepolystyrene multiblock polymers: 1. Effect of the siloxane block length. Polymer, 1989, 60: 1800–1813. https://doi.org/10.1016/0032-3861(89)90349-2