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.

One-step synthesis of amphiphilic copolymers PDMS-b-PEG using tris(pentafluorophenyl)borane and subsequent study of encapsulation and release of curcumin

“…PR11 micelle has a silyl ether linkage (–Si–O–C–), which can be cleavaged under acidic and even upon basic conditions. 91,92 This silyl ether bond was hydrolyzed at pH 1.2 to obtain silanols and alcohols as byproducts, releasing curcumin from the micelle core. The breaking of the –Si–O–C– bond has also been reported under basic conditions, obtaining byproducts similar to those at acidic pH; however, the degradation of the micelle is slower.…”

“…The breaking of the –Si–O–C– bond has also been reported under basic conditions, obtaining byproducts similar to those at acidic pH; however, the degradation of the micelle is slower. 91,92 In addition, these byproducts are not toxic to cells, 93 so PR11 micelles could be an alternative to hydrophobic drug delivery, especially for curcumin.…”

Efficient synthesis of camphor-based polycarbonates: a direct route to recyclable polymers

“…Finally, the degradability and potential chemical recyclability of our polycarbonates were investigated. Methanolysis is one of the most commonly used protocols to study the degradation behavior of polymers, 64,65 although ethanol has already been shown to be more effective than methanol in degrading certain polymers such as PC. 66,67 In addition, it has been widely reported that polycarbonates are resistant to methanolysis in the absence of catalysts.…”

Synthesis of fluorescent poly(silyl indole)s via borane-catalyzed C–H silylation of indoles

“…They are widely used as oils, rubbers, silicone resins, heat-resistant materials and optoelectronic materials, because of their excellent thermal, electronic and optical properties. 23–26 Progress has been made towards the application of organocatalytic step-growth polymerizations in the synthesis of organosilicon polymers, with such reactions including dehydrogenative coupling, 27–32 hydrosilylation of silanes with ketones, alkenes or alkynes, 33–37 the Piers–Rubinsztajn reaction 38,39 and others. 40,41 Using the indole skeleton to construct polymeric materials has also attracted intense attention.…”