Functional polysiloxanes and silicone-based materials

Research Projects #1

Basic silicone rubbers and materials based on them

1. Hydrosilylation of polysiloxanes by new platinum group catalysts

Hydrosilylation of alkenes is the key reaction for obtaining industrially important organosilicon compounds. Catalytic hydrosilylation is especially important for polysiloxanes cross-linking and obtaining rubbers with useful properties, such as high and low temperature resistance, good electrical insulation, radiation resistance, oil- and petrol-resistance at increased temperatures, high chemical and biological inertness, environmental safety, etc.

We search and develop effective hydrosilylation catalysts and we create new polymer compositions with improved characteristics based on them.

At the moment we suggested relatively cheap, accessible, effective and in the same time selective platinum group catalysts as alternative to Karstedt’s catalyst that is used in most part of industrial processes of polysiloxane cross-linking.

Our platinum catalysts allowed to obtain composition “smart plasticine” for modelling, copying, making crafts and cast molds of different objects and surfaces.

• Molecules. 2016. V. 21. P. 311-321. DOI:10.3390/molecules21030311.
• ChemPlusChem. 2015. V. 80, N 11. Р. 1607-1614. DOI: 10.1002/cplu.201500327.

Patent RU No. 2579143 С1 (14.04.2015).

Thermally stable and luminescent silicone rubbers were obtained with new iridium catalysts. It allows creating silicone coatings with controllable thickness and substantially extends potential application of such materials (including special coatings for passive thermal control systems in spacecraft (DOI:10.1007/978-3-319-19309-0_5).

Catalysis Science & Technology. 2017. V. 7. No. 24. P. 5843-5846. DOI: 10.1039/c7cy02013a.

Patent RU No. 2579117 C1 (10.03.2015).

Interview of Regina Islamova for cultural & political magazine “E-vesti”

We proposed rhodium catalysts that allow to obtain high-elasticity silicone rubbers at room temperature without defects (cracks, bubbles).

Journal of Catalysis. 2019. V. 372. P. 193–200. DOI: 10.1016/j.jcat.2019.03.004.

2. Peroxide curing of polysiloxanes

Peroxide curing at elevated temperatures (> 100 °C) is alternative to catalytic hydrosilylation for producing cured silicone rubbers. However, the use of traditional organic peroxides as sources of free radicals leads to the formation of mechanically unstable silicone rubbers (without fillers) with structural defects due to the evolution of gaseous products. An addition of inhibitors into reaction mixture complicates the process and contributes to impurity of the obtained product. The search for new initiators of peroxide curing, which both are structurally similar to silicones and allow solving the above problems, is relevant task. Together with laboratory for studies of homolytic reactions (N.D. Zelinsky Institute of Organic Chemistry, Moscow) we have proposed and studied new vinyl-selective organosilicon peroxides, which were used to obtain antibacterial silicone rubbers with improved mechanical characteristics without using inhibitors at (150–200) °C.

New Journal of Chemistry. 2018. V. 42. No. 18. P. 15006–15013. DOI: 10.1039/C8NJ02499E.

Research Projects #2

Hybrid polysiloxanes and materials based on them

1. Hybrid polysiloxanes and materials based on them

Development of effective methods for synthesis of new smart and “super-smart” polymers and creation of new materials and devices based on them is related to Targeted Programme for Research and Development in Priority Areas of Development of the Russian Scientific and Technological Complex as well as they are relevant tasks of modern chemistry.

We synthesize novel hybrid metal-containing (co)polysiloxanes (remarkable due to electrically conductive fragments in its structure) for creation of flexible electrochemical sensors, biosensors, molecular electronic devices, liquid crystals in non-linear optical systems and others.

At the moment we have obtained unique ferrocene-containing silicones, which found its application as materials for medical neural implants, that help to cure serious neurological diseases and training of damaged functions (motor activity, visceral systems, sight, hear) (together with prof. P.E. Musienko, Institute of Translational Biomedicine SPbU).

Grant RFBR No. 18-33-20062. Project: «Guided synthesis and properties of electrically conductive silicone materials for medical neural implants» (grant owner: Islamova R.M.). 2019-2020.

• Applied Organometallic Chemistry. 2019. DOI: 10.1002/aoc.5300.
• Organic & Biomolecular Chemistry. 2019. V. 17. Р. 5545-5549. DOI: 10.1039/C9OB00791A.

2. Self-healing silicone materials

Self-healing materials are one of the perspective and fast developing fields of material science. Self-healing polymers are necessary for creation of super flexible sensors, actuators and stimuli-sensitive materials (including artificial skin or “second skin”), additive technologies and other flexible devices.

We synthesize complexes of (co)polysiloxanes and metal centers (iron, nickel, cobalt, etc.) and use them to make self-healing elastomers and stimuli-sensitive materials, which can be used for creation of artificial muscles (Nature Chem. 2016. 8, No. 6. >618–624), as well as for flexible sensors (Adv. Sci. 2019. 1900186).

Grant RFBR No. 19-33-90134. Project: «Synthesis and research of complexes of (co)polysiloxanes with electroactive centers as self-healing materials» (Islamova R.M., Deriabin K.V.). 2019–2021.

• Polymer. 2021. V. 212. P. 123119. DOI: 10.1016/j.polymer.2020.123119.
• Organometallics. 2021. V. 40(15). P. 2750–2760. DOI: 10.1021/acs.organomet.1c00392.

3. Glycosilicones

The main goal of this research direction is to develop new methods for synthesis of novel polymers — glycosilicones, which structure combine different fragments: hydrophobic and hydrophilic (polysiloxanes and poly/oligosaccharides), as well as to obtain materials based on them: next generation surfactants, drug dermal penetration enhancers, surface modificators in cosmetology and medicine and others. At the moment we have obtained cellulose-based glycosilicones that can be used to make facepowder.

Grant RFBR No. 19-33-90130. Project: «Directed macromolecular design of graft-copolymer hybrid structures based on polysiloxanes and saccharides» (Islamova R.M., Dobrynin M.V.). 2019–2021.

Carbohydr. Polym. 2020. V. 241. P. 116327. DOI: 10.1016/j.carbpol.2020.116327.

Publications

2021

• Miroshnichenko A.S., Deriabin K.V., Baeva M., Kochetkov F.M., Neplokh V., Fedorov V.V., Mozharov A.M., Koval O.Yu., Krasnikov D.V., Sharov V.A., Filatov N.A., Gets D.S., Nasibulin A.G., Makarov S.V., Mukhin I.S., Kukushkin V.Yu., Islamova R.M. //J. Phys. Chem. Lett. 2021. V. 12, P. 9672–9676. DOI: 10.1021/acs.jpclett.1c02611.
  
• Deriabin K.V., Ignatova N.A., Kirichenko S.O., Novikov A.S., Kryukova M.A., Kukushkin V.Yu., Islamova R.M. // Organometallics. 2021. V. 40 (15). P. 2750–2760. DOI: 10.1021/acs.organomet.1c00392.
  
• Talianvov P.M., Rzhevskii S.S., Pankin D.V., Deriabin K.V., Islamova R.M., Manshina A.A. // J. of Polymer Research. 2021. V. 28 (2). P. 37. DOI: 10.1007/s10965-021-02409-0.
  
• Dobrynin M.V., Sokolova E.V., Kinzhalov M.A., Smirnov A.S., Starova G.L., Kukushkin V.Yu., Islamova R.M. // ACS Applied Polymer Materials. 2021. DOI: 10.1021/acsapm.0c01190.
  

2020

• Deriabin K.V., Ignatova N.A., Kirichenko S.O., Novikov A.S., Islamova R.M. // Polymer. 2020. P. 123119. DOI. 10.1016/j.polymer.2020.123119.
• Deriabin K.V., Dobrynin M.V. and Islamova R.M. // Dalton Transactions. 2020. DOI:10.1039/D0DT01061H.
• Dobrynin M.V., Kukushkin V.Y. and Islamova R.M. // Carbohydrate polymers. 2020. V. 241, P. 116327. DOI: 10.1016/j.carbpol.2020.116327.
• Neplokh V., Kochetkov F.M., Deriabin K.V., Fedorov V.V., Bolshakov A.D., Eliseev I.E., Mikhailovskii V.Y., Ilatovskii D.A., Krasnikov D.V., Tchernycheva M., Cirlin G., Nasibulin A.G., Mukhin I.S., Islamova R.M. // Journal of Materials Chemistry C. 2020. DOI: 10.1039/C9TC06239D.

2019

• Deriabin, K.V., Lobanovskaia, E.K., Kirichenko S.O., Barshutina, M.N., Musienko, P.E., Islamova, R.M. // Applied Organometallic Chemistry. 2019. V. 34. e5300. DOI: 10.1002/aoc.5300.
• Deriabin, K.V., Lobanovskaia, E.K., Novikov, A.S., Islamova, R.M. // Organic & Biomolecular Chemistry. 2019. V. 17. P. 5545–5549. DOI: 10.1039/C9OB00791A.
• Dobrynin, M.V, Pretorius, C., Dumisani V.K., Roodt, A., Boyarskiy, V.P., Islamova, R.M. // Journal of Catalysis. 2019. V. 372. P. 193–200. DOI: 10.1016/j.jcat.2019.03.004.

2018

• Deriabin, K. V., Yaremenko, I. A., Chislov, M. V., Fleury, F., Terent’ev, A. O., & Islamova, R. M. // New Journal of Chemistry. 2018. V. 42. No. 18. P. 15006–15013. DOI: 10.1039/C8NJ02499E.

2017

• Islamova R.M., Dobrynin M.B., Vlasov A.V., Eremina A.A., Kinzhalov M.A., Kolesnikov I.E., Zolotarev A.A., Masloborodova E.A., Luzyanin K.V. // Catalysis Science & Technology. 2017. V. 7. No. 24. P. 5843-5846. DOI: 10.1039/c7cy02013a.
• Masloborodova E.A., Kaganova E.V., Gusakova N.S., Agibalova L.V., Maretina E.Yu., Baranets I.V., Islamova R.M. // Rus. J. Gen. Chem. 2017. V. 87. No. 5. Р. 1038–1046. DOI: 10.1134/S1070363217050243.

2016

• Islamova R.M., Dobrynin M.V., Ivanov D.M., Vlasov A.V., Kaganova E.V., Grigoryan G.V., Kukushkin V.Yu. // Molecules. 2016. V. 21. No. 3. P. 311-321. DOI:10.3390/molecules21030311.
• Islamova R.M. // Rus. J. Gen. Chem. 2016. V. 86, No. 1. P. 125-143. DOI: 10.1134/S1070363216010217.

2015

• Demakova M.Ya., Bolotin D.S., Bokach N.A., Islamova R.M., Starova G.L., Kukushkin V.Yu. // ChemPlusChem. 2015. V. 80, No. 11. Р. 1607-1614. DOI: 10.1002/cplu.201500327.
• Islamova R.M., Vlasov A.V., Dobrynin M.V., Masloborodova E.A., Kaganova E.V. // Rus. J. Gen. Chem. 2015. V. 85, No. 11. Р. 2609–2613. DOI: 10.1134/S1070363215110171.

Grants

• Grant RSF No. 20-19-00256. (grant owner: Islamova R.M.) 2020–2022.
• Grant RFBR No. 19-33-90130. (grant owner: Islamova R.M.) 2019–2021.
• Grant RFBR No. 19-33-90134. (grant owner: Islamova R.M.) 2019–2021.
• Grant RFBR No. 18-33-20062. (grant owner: Islamova R.M.) 2019–2020.
• Grant RFBR No. 18-33-00769 mol_a (grant owner: Dobrynin M.V.) 2018–2019.
• Grant RFBR No. 14-03-00260-а. (grant owner: Islamova R.M.). 2014–2016.