Step-Growth Polyesters with Biobased (R)-1,3-Butanediol

Abstract

We present the synthesis and characterization of polymers containing 1,3-butanediol, also known as butylene glycol. Butylene glycol (BG) can be prepared from petroleum or sugar-based feedstocks. Petrolbased BG (petrol-BG) is isolated as a racemic mixture, whereas the biobased BG from sugar that we utilized (bio-BG) is enantiopure upon purification (>99.7%). In the presence of a titanium catalyst, polyesters were prepared by transesterification polymerization between petrol-or bio-BG and various aliphatic and aromatic diacid derivatives. Polymers were analyzed by size-exclusion chromatography (SEC), 1 H NMR and 13 C NMR spectroscopies, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The synthesized polyesters were statistical in nature, according to 13 C NMR spectroscopy, a result of the asymmetric nature of the BG-starting material. As a result, many of the polyesters were amorphous in nature with low thermal glass transitions (T g ) and no melting points (T m ). In many of the polyester derivatives, the racemic petrol-based and enantiopure biobased BG polymers were nearly identical in thermal performance. Differences arose in semicrystalline polyesters with long, aliphatic backbones (e.g., 1,14-tetradecanediocic acid; C14 diacid) or regioregular 4-hydroxybenzoate polyesters. This suggests the polymer microstructure (statistical versus sequenced) and the optical activity (racemic versus enantiopure) are important determinates in establishing the structure−property relationships in BG-containing polyesters. This work establishes synthetic protocols and the foundation for materials based on BG-containing polymers.

From Lab to Market: Current Strategies for the Production of Biobased Polyols

“…In order to move to biobased polyester polyols, several monomeric diols and diacids from renewable resources have been investigated, both in academia and in industry . Linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3- butanediol, and 1,4-cyclohexanedimethanol have been investigated to increase the biobased content in different polyester polyols. − When these diols are polymerized with diacids from renewable resources such as succinic, adipic, or citric acid, fully biobased polyols can be obtained . To compete with their petrochemical-based analogs, multiple companies have developed industrial processes for the production of biobased diols or diacids, including Genomatica for 1,4-butanediol (BioBDO) and adipic acid, Dupont Tate and Lyle BioProducts or Metex Noovista for 1,3-propanediol (Susterra and TILAMAR TM , respectively), and Roquette for succinic acid derived from starch fermentation (BIOSUCCINIUM) .…”

Polybutylene succinate, a potential bio-degradable polymer: synthesis, copolymerization and bio-degradation

“…59 Additional catalysts, such as triazabicyclodecene and tosic acid, were found to be less effective at producing high molecular weight polyesters. 60 The efficiency of TBT and zinc acetate at synthesizing the aromatic/aliphatic copolyester (HBA/PBS) was further systematically investigated. From the results, TBT was found to be a better catalyst than zinc acetate and hydroxyl benzoic acid would undergo the transesterification reaction with PBS to yield PBS rich segment and HBA ( p-hydroxybenzoic acid) rich segment polyesters.…”

A New Approach Utilizing Aza-Michael Addition for Hydrolysis-Resistance Non-Ionic Waterborne Polyester

“…In previous works, various catalysts have been explored for the preparation of polyesters, including organometallic compounds Ti(OBu) 4 [35,36], DBTDL [37], and acid TsOH [38,39]. In this paper, we investigated the influence of the catalyst type on the isomerization extent and molecular weight of the polyester.…”