Photocatalytic Direct Decarboxylation of Carboxylic Acids to Derivatize or Degrade Polymers

Abstract

Visible light-mediated direct decarboxylation of carboxylic acids with an acridine photocatalyst is a convenient and powerful method to generate carboncentered radicals in polymer chains. Advantageously, this process proceeds under mild conditions, without preactivation of the acid groups. We utilize decarboxylation in the presence of a hydrogen atom donor to form statistical acrylate-ethylene and acrylate-propylene copolymers, which are challenging to obtain by direct polymerization. We additionally show that decarboxylation of methacrylic acid units within polymethacrylates can trigger degradation of the polymer backbones. Moreover, a dual catalytic approach, which combines the function of an acridine photocatalyst with that of a cobaloxime catalyst, is leveraged to furnish unique copolymers with pendent alkenes. Our work indicates that direct decarboxylation is a versatile technique for the synthesis of functional materials with tailored compositions and properties.

Anthranilamide-protected vinylboronic acid: rational monomer design for improved polymerization/transformation ability providing access to conventionally inaccessible copolymers

“…26 Quite recently, Theato and Sumerlin have independently reported radical copolymerizations of N -(acryloyloxy)phthalimide with acrylate, followed by a decarboxylation in the presence of a hydrogen-atom donor to access ethylene–acrylate copolymers that are unusually rich in ethylene units. 27,28 The copolymerization ability of VBaam and its transformation into ethylene via protodeboronation after polymerization could also be expected to improve the restricted range of ethylene units in acrylate–ethylene copolymers. We thus examined the radical copolymerization of VBaam with tert -butyl acrylate (TBA), followed by the transformation of VBaam into ethylene.…”

Solvent-Free Chemical Recycling of Polymers made by ATRP and RAFT polymerization: High-Yielding Depolymerization at Low Temperatures

“…[14][15][16][17][18] Although excellent degradation strategies have been widely developed, these approaches focus on breaking down the polymer into small molecules rather than retrieving the starting monomer. [19][20][21][22][23][24] Instead, chemical recycling is essential if we are going to make polymers more sustainable, reduce waste and prevent their continued accumulation in the environment. [25][26][27][28] Achieving depolymerization of vinyl polymers is particularly challenging, as the carboncarbon bonds that form the polymer backbone have extremely high thermal stability.…”

A Comprehensive Investigation into the Crystallology, Molecule, and Quantum Chemistry Properties of Two New Hydrous Long-Chain Dibasic Ammonium Salts CnH2n+8N2O6 (n = 35 and 37)

“…Long-chain saturated fatty acids play various roles in the new metabolism of animals and plants [ 1 , 2 , 3 , 4 ]. Due to their carboxyl group, long-chain saturated fatty acids can undergo an esterification reaction [ 5 , 6 ], acylation reaction [ 7 , 8 ], salt formation reaction [ 9 ], oxidation-reduction reactions [ 10 ], and decarboxylation reactions [ 11 , 12 , 13 ]. In recent years, in addition to being widely studied in the field of biochemistry, long-chain saturated fatty acids have also drawn much attention in the field of thermodynamics [ 14 , 15 ], especially in the area of phase change energy storage [ 16 , 17 , 18 , 19 , 20 , 21 , 22 ], where they are becoming increasingly popular.…”