Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources

Abstract

The design of new materials with tunable properties and intrinsic recyclability, derived from biomass under mild conditions, stands as a gold standard in polymer chemistry. Reported herein are platinum complexes which catalyze the formation of poly(silylether)s (PSEs) at low catalyst loadings. These polymers are directly obtained from dual-functional biobased building blocks such as 5-hydroxymethylfurfural (HMF) or vanillin, coupled with various dihydrosilanes. Access to different types of copolymer architectures (statistical or alternating) is highlighted by several synthetic strategies. The materials obtained were then characterized as low T g materials (ranging from À 60 to 29 °C), stable upon heating (T À 5% up to 301 °C) and resistant towards uncatalyzed methanolysis. Additionally, quantitative chemical recycling of several PSEs could be triggered by acid-catalyzed hydrolysis or methanolysis. These results emphasize the interest of biobased poly(silylether)s as sustainable materials with high recycling potential.

Controllable Degradation of Polyurethane Thermosets with Silaketal Linkages in Response to Weak Acid

“…Following this idea, mild degradability is anticipated if PU networks could be incorporated with hydrolyzable bonds in response to mild conditions. Among cleavable linkages, silaketal, usually applied as the protector for the hydroxyl group, is adequate to achieve controllable bond formation and fragmentation under different acid/base environments. − In general, silaketal is usually prepared from the condensation reaction between chloroalkylsilane and hydroxyl groups in the presence of a Lewis base, and the silaketal linkages can be further hydrolyzed under mild acidic conditions . It is noteworthy that the reaction activity of silaketal hydrolysis varies concomitantly with the change of alkyl substituents on silicon atoms, and the acidity of the environment also dominates the hydrolysis rate. , In that case, introducing silaketal linkages with different alkyl substituents into thermosetting PU materials will be a feasible approach to regulate the degradation rate as well as accomplish moderate recyclization …”

2,5-Furandicarboxylic Acid: An Intriguing Precursor for Monomer and Polymer Synthesis

“…An alternative attractive pathway to BHMF-based polyesters from FDCA was recently introduced by Thomas and Gauvin relying on one-pot catalysis [45,46]. Thus, an esterification-hydrogenation-copolymerization sequence was developed using molecular catalysis, enabling the one-pot transformation of FDCA into the desired polyesters.…”

One-pot catalysis from renewable resources: A direct route to recyclable camphor-based polycarbonates

“…Methanolysis is one of the most commonly used protocols to investigate the degradation behavior of polymers. 64 However, it has been widely reported that polycarbonates are resistant to methanolysis in the absence of catalysts. 65,66 Although large amounts of concentrated acids or bases can act as catalysts, 51 a substantial drawback of this approach is the generation of large quantities of inorganic salts and aqueous wastes.…”