Lipase‐catalyzed synthesis of hyperbranched polyester improved by autocatalytic prepolymerization process

Abstract

This work developed a facile and environmentally friendly route for lipase-catalyzed synthesis of a hyperbranched polyester by introducing an autocatalytic prepolymerization of comonomers. Trimethylolpropane, 1,8-octanediol, and adipic acid as comonomers for synthesizing the hyperbranched polyester were first prepolymerized via the automatic catalytic effect of the reactants themselves to obtain an appropriate reaction substrate for further lipase-catalyzed polymerization, where immobilized lipase Novozym 435 was used as a biocatalyst. The acidity and fluidity of optimized oligomers after the autocatalytic prepolymerization provide a benign reaction substrate for the retention of enzymatic activity in the subsequent lipase-catalyzed esterification, which is crucial for the enzymatic polymerization. The optimum reaction temperature and reaction time for prepolymerization were determined to be 120 C and 150 min. The molecular weight (M w ) of the prepared polyester was approximately 26,300 g/mol. Quantitative analysis of 1 H-NMR and inverse-gated 13 C-NMR spectra confirmed the hyperbranched structure of the resulting polyester with a branching degree of 31.3%.

Novozym 435: the “perfect” lipase immobilized biocatalyst?

“…Trimethylolpropane, 1,8-octanediol, and adipic acid were first pre-polymerized via the automatic catalytic effect of the reactants themselves to obtain an appropriate reaction substrate mixture. 376 Dimer acid cyclocarbonate was produced by the N435 catalyzed esterification of glycerol carbonate and dimer acid from Sapium sebiferum oil. 377 This compound could be used in the synthesis of bio-based non-isocyanate polyurethane ions.…”

Lipase-Catalyzed Synthesis and Characterization of Poly(glycerol sebacate)

“…Another important attribute of the biomaterial design is the ability to functionalize biomaterials with various biological factors to control biological processes such as accelerating wound healing and regulating inflammatory processes. 1−3 Herein, we focus on aliphatic biodegradable polyol polyesters, a family of synthetic biomaterials that generally consist of a polyol and diacids such as glycerol, 4−25 sorbitol, 18,23−27 xylitol, 18,28 mannitol, 18,28 sebacic acid, 4−18 adipic acid, [22][23][24]27,29,30 and suberic acid. 31 They were designed to provide a wide range of therapeutic functions.…”

“…Herein, we focus on aliphatic biodegradable polyol polyesters, a family of synthetic biomaterials that generally consist of a polyol and diacids such as glycerol, − sorbitol, ,− xylitol, , mannitol, , sebacic acid, − adipic acid, − ,,, and suberic acid . They were designed to provide a wide range of therapeutic functions.…”

“…Our group, as well as others, reported N435-catalyzed copolymer syntheses in bulk using aliphatic diols, polyols, and diacids as monomers. ,− ,− Investigations have included variables such as a monomer structure, reaction temperature, medium (solvent vs bulk), and catalyst concentration on the polymerization rate, chain structure, and molecular weight averages. ,− , For example, copolymers of glycerol, 1,8-octanediol, and adipic acid (1:0.8:0.2 equiv) were prepared by N435 catalysis in bulk at 70 °C for 42 h, resulting in hyperbranched copolymers with M w 75 600 g/mol and Đ 2.9 . Another example is the N435-catalyzed synthesis of unsaturated polyesters by copolymerization of 1,18- cis -9-octanedecenedioic acid, glycerol, and linoleic acid.…”

Lipase-Catalyzed Poly(glycerol-1,8-octanediol-sebacate): Biomaterial Engineering by Combining Compositional and Crosslinking Variables

“…Historically, a variety of natural and synthetic polymeric biomaterials and hydrogels have been utilized to create physiologically appropriate scaffolds for cardiac tissue engineering applications . Among these, poly­(glycerol sebacate) (PGS) is a noncytotoxic, biodegradable elastomer, which has been frequently used in a variety of tissue engineering applications, including nerve, cardiac, and vascular systems. − However, there is a need to develop PGS analogues that can precisely control the scaffold’s physical and biological properties as well as their biodegradation rates to meet the wide range of healing times encountered in tissue-regenerative challenges. − Apart from modifying the molecular structure of polyols, diacids, and diols, the use of selective enzymatic catalysts provides new options for microstructure control. − …”