Dehydrocoupling Polymerization: Poly(silylether) Synthesis by Using an Iron β-Diketiminate Catalyst.

Area of Science:

• Polymer Chemistry
• Organometallic Catalysis
• Materials Science

Background:

• Poly(silylether)s are versatile polymers with tunable properties.
• Efficient and scalable polymerization methods are crucial for their broader application.

Purpose of the Study:

• To develop an iron-catalyzed polymerization method for synthesizing novel poly(silylether)s.
• To explore the scope of monomers and characterize the resulting polymers.

Main Methods:

• Iron-catalyzed polycondensation of diols and silanes.
• Characterization using IR, DSC, TGA, NMR, GPC, and MALDI-TOF.
• In situ monitoring of polymerization via gas evolution and GPC.

Main Results:

• Synthesis of fourteen poly(silylether)s with molecular weights up to 36.3 kDa.
• Polymers exhibit low glass transition temperatures (-70.6 to 19.1 °C) and high thermal stability (up to 421.6 °C).
• A correlation between silane structure (1° vs. 2°) and thermal stability was observed.

Conclusions:

• Iron catalysis provides a robust and versatile route to poly(silylether)s.
• The synthesized polymers possess desirable thermal properties for various applications.
• The polymerization proceeds via a condensation mechanism, controllable through reaction monitoring.