polymers Review From Amorphous Silicones to Si-Containing Highly Ordered Polymers: Some Romanian Contributions in the Field † Maria Cazacu * , Carmen Racles, Mirela-Fernanda Zaltariov, Mihaela Dascalu, Adrian Bele , Codrin Tugui, Alexandra Bargan and George Stiubianu Department of Inorganic Polymers, “Petru Poni” Institute of Macromolecular Chemistry, Aleea Gr. Ghica, Voda 41A, 700487 Iasi, Romania;
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[email protected]; Tel.: +40-232-217-454; Fax: +40-232-211-299 † Dedicated to 100 years from the birth of Professor Cristofor I. Simionescu (1920–2007). Tribute to the Memory of Dr. Mihai Marcu, recently passed away (1933–2020). Abstract: Polydimethylsiloxane (PDMS), in spite of its well-defined helical structure, is an amorphous fluid even at extremely high molecular weights. The cause of this behavior is the high flexibility of the siloxane backbone and the lack of intermolecular interactions attributed to the presence of methyl groups. These make PDMS incompatible with almost any organic or inorganic component leading to phase separation in siloxane-siloxane copolymers containing blocks with polar organic groups and in siloxane-organic copolymers, where dimethylsiloxane segments co-exist with organic ones. Self-assembly at the micro- or nanometric scale is common in certain mixed structures, including micelles, vesicles, et cetera, manifesting reversibly in response to an external stimulus. Polymers Citation: Cazacu, M.; Racles, C.; with a very high degree of ordering in the form of high-quality crystals were obtained when silox- Zaltariov, M.-F.; Dascalu, M.; Bele, A.; ane/silane segments co-exist with coordinated metal blocks in the polymer chain.