Biodegradable polymers based on renewable resources. IX. Synthesis and degradation behavior of polycarbonates based on 1,4:3,6‐dianhydrohexitols and tartaric acid derivatives with pendant functional groups

Abstract

Novel polycarbonates, with pendant functional groups, based on 1,4:3,6‐dianhydrohexitols and L‐tartaric acid derivatives were synthesized. Solution polycondensations of 1,4:3,6‐dianhydro‐bis‐O‐(p‐nitrophenoxycarbonyl)hexitols and 2,3‐di‐O‐methyl‐L‐threitol or 2,3‐O‐isopropylidene‐L‐threitol afforded polycarbonates having pendant methoxy or isopropylidene groups, respectively, with number average molecular weight (Mn) values up to 3.61 × 104. Subsequent acid‐catalyzed deprotection of isopropylidene groups gave well‐defined polycarbonates having pendant hydroxyl groups regularly distributed along the polymer chain. Differential scanning calorimetry (DSC) demonstrated that all the polycarbonates were amorphous with glass transition temperatures ranging from 57 to 98 °C. Degradability of the polycarbonates was assessed by hydrolysis test in phosphate buffer solution at 37 °C and by biochemical oxygen demand (BOD) measurements in an activated sludge at 25 °C. In both tests, the polycarbonates with pendant hydroxyl groups were degraded much faster than the polycarbonates with pendant methoxy and isopropylidene groups. It is noteworthy that degradation of the polycarbonates with pendant hydroxyl groups was remarkably fast. They were completely degraded within only 150 min in a phosphate buffer solution and their BOD‐biodegradability reached nearly 70% in an activated sludge after 28 days. The degradation behavior of the polycarbonates is discussed in terms of their chemical and physical properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3909–3919, 2005

Synthetic Polymers from Sugar-Based Monomers

“…The procedure used to synthesize the reduction-sensitive multiamine copolymers was analogous to the method mentioned above for multiallyl-based copolyurethanes; the chosen sugar-based diol monomer was Ar(NHBoc) 3 , with the amine groups conveniently protected to prevent undesirable side reactions (Scheme 46). Once the polymerization was accomplished, deprotection of the amine groups led to the target materials in high yields.…”

Production and applications of carbohydrate-derived sugar acids as generic biobased chemicals

“…These types of silicone surfactants are used in the textile, fibre, paint and cosmetic industries. There are also examples of sugar acid-based polyanhydrides (Mehtiö et al, 2014) and polycarbonates (Yokoe et al, 2005).…”

Monomers and Macromonomers from Renewable Resources

“…Among the recent studies, the most interesting deal with the synthesis of biodegradable polycarbonates with anhydroalditols [74] , optically active hydrophilic aliphatic polyamides [75] capable of associating themselves to produce supramolecular stereocomplexes [76] , and polyurethanes with different diisocyanates bearing COOH side groups, which displayed a unique proneness to degrade with water upon incubation under physiological conditions [77] . Succinic acid, readily available from the fermentation of glucose, is a very prolifi c molecule that can be usefully exploited in the synthesis of a large spectrum of interesting compounds, including, of course, monomeric structures [78] .…”