Renewable Biobased Polymeric Materials: Facile Synthesis of Itaconic Anhydride-Based Copolymers with Poly(l-lactic acid) Grafts

Abstract

This paper reports a new synthesis of biobased polymers by using itaconic anhydride (IAn) and lactic acid (LA) as renewable starting materials. Poly(lactic acid) (PLA)-graft copolymers were synthesized via two approaches. First, the macromonomer approach utilized IAn for Sn-catalyzed synthesis of PLA-containing macromonomers (IAn-PLA Macro). The macromonomer was radically copolymerized with n-butyl methacrylate (BMA), n-butyl acrylate (BA), methyl methacrylate (MMA), and ethyl methacrylate (EMA) to give efficiently graft copolymers (PLA-Graft copolymer (I)) with molecular weight M n up to 1.61 × 105 having biomass content higher than 34 wt %. Second, the copolymer approach employed first IAn as comonomer for radical copolymerization with BMA, giving rise to IAn-BMA copolymer with M n higher than 5.76 × 104. Then, Sn-catalyzed grafting of PLA onto IAn moiety of the copolymer produced PLA-Graft copolymer (II) with M n higher than 5.88 × 104, showing biomass content ≥29 wt %. In addition, radical homopolymerization of IAn was examined to give polyIAn. By using these two approaches employing IAn as a starting reactive material, PLA-graft copolymers were obtained as “biomass-plastics”. Properties of PLA-Graft copolymers (I) were also examined, which revealed possible applications for coatings and plastics. Furthermore, the IAn-containing graft copolymers will be a convenient starting biomass polymer having reactive IAn moiety in the main chain for further grafting or various functional group-introducing reactions.

Design and synthesis of a new polymer network containing pendant spiroacetal moieties

“…Characteristic signals in agreement with the molecular structure [4] of monomers are shown at around from 3.2 to 3.9 ppm-the protons correlated to H-C-O-ethers group of U and the hydrogen from the methylene group in the anhydride ring; at 4.3, 4.9 ppm (-CH 2 =C-), 5.3, 5.4 ppm (=CH 2 -CH-) -characteristics for U, and at 5.8 ppm (=CH-) -specific for U and ItA. The signals registered in the region between 1 and 2 ppm corresponded to R-CH 2 , R-CH and are attributed to the shift δ at 2.1 ppm which can be assigned to the new-CHbond formed between the comonomers.…”

“…[2] In addition, the use of materials from renewable resources and high degree of recycling or degradation are essential advantages for highly demanding applications. [3,4] In a previous article, our group studied a copolymer based on maleic anhydride (MAh) and 3,9-Divinyl-2,4,8,10-tetraoxaspiro [5.5] undecane (U), used as polymeric matrices for potential bioapplications. [5] Itaconic anhydride (ItA), owing to the functional similarity to MAh, has been mentioned as an alternative in applications comparable to those containing MAh.…”

Stable biocompatible cross-linked fluorescent polymeric nanoparticles based on AIE dye and itaconic anhydride

“…Biobased materials have attracted much attention due to the ever-growing environmental problems, such as, consuming fossil fuel resources increases the net amount of carbon dioxide in the atmosphere and affects the global warming eventually [35]. Thus, it is considered very important to do research on polymer synthesis using renewable resources as starting materials.…”

Biobased UV-curable coatings based on itaconic acid

“…The 1,1-disubstituted unsaturation in IA makes it homopolymerizable to some degree because the unsaturation is more reactive compared to the double bond in malate. 13,14 IA has received significant attention during recent years, most likely due to its interesting dual functionality and the possibility of producing it from renewable resources. There are several recent studies on polymerizing IA with different diols to obtain renewable, unsaturated polyesters for various applications, as recently reviewed by Robert and Friebel.…”