Preparation, characterization and application of maleic anhydride-modified polylactic acid macromonomer based on direct melt polymerization

A one-pot two-step method based on direct melt polymerization (DMP) for the synthesis of polylactic acid (PLA) macromonomer and its further functionalized application has been developed. The first stage of the reaction is a copolycondensation of lactic acid (LA) and maleic anhydride (MAH) to obtain the macromolecule poly(lactic acid-co-maleic anhydride) (PLAM) with reactive double bonds, and the second stage is a radical copolymerization of different acrylates with PLAM to afford the modified PLA functional materials. The influences of the acrylates have been investigated. The results show that the species with substituted methyl groups in acrylate can polymerize relatively stable. On the other hand, the more carbon atoms in the ester segment of acrylate, the higher intrinsic viscosity [η] and terminal decomposition temperature for the acrylate-modified PLAMs. Among six kinds of acrylates used as the third monomer, such as acrylic acid (AA), methyl acrylate (MA), butyl acrylate (BA), methacrylic acid (MAA), methyl methacrylate (MMA), and butyl methacrylate (BMA), the BMA-modified PLAM has the biggest [η] (0.7566 dL/g) and the terminal decomposition temperature (418 °C) for there are more carbon atoms in BMA. Due to excellent reactivity of the intermediate PLAM, the final modified product can have the anticipated properties for the PLA material by the controllable regulating as different purposes. Thus, this strategy as a green and simple method provides well application prospect for PLA materials in industrial plastics, biomedicine etc.