The effect of me‐substituents of 1,4‐butanediol analogues on the thermal properties of biobased polyesters

Abstract

Biobased 1,4‐butanediol analogues are used to tune the glass transition temperature and crystallization in a series of polyesters and allow for the formation of stereocomplexes.

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) .…”

Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols

“…T g values of 2,5-PHAF0.5 and 2,7-POAF0.5 are comparable to those reported by Arnaud, despite the polymers synthesized in this study having a higher M w . 2,5-PHA and 1,4-PPA 1,14 Literature data for 1,4-PBAFs and PHF are from higher M w materials than those reported in this study; as a result, they have higher T g s (Table S8). 24,29 The tensile properties of these materials were then assessed at room temperature for polyesters where suitable films could be produced (Table 2).…”

“…Arnaud and Boyd, in separate studies, also observed similar trends in degrees of crystallinity: polyesters of the 1° alcohol diol 1,6-HDO were highly crystalline (∼60%), whereas 2,5-HDO polyesters were entirely amorphous (no melting temperature observed). , In these studies, the 2,5-HDO diol was a mixture of stereoisomers, thus it was assumed that the stereo-irregularity disrupted the crystal packing of the polyesters, contributing to their amorphous behavior. This was later confirmed by van der Klis et al , who found a polyester of optically pure 2,5-HDO, poly­(2 S ,5 S -hexylene succinate) to display a melting point ( T m ) at 200 °C, confirming it to be semicrystalline . The thermal stability of the polyesters in these earlier studies was also promising.…”

“…van der Klis et al have preliminarily examined this relationship in homopolymers of 1,4-BDO, 1,4-pentanediol (1,4-PDO), and 2,5-HDO as diols containing 0, 1, and 2 methyl branches per monomer, respectively, with succinic acid, adipic acid, and 2,5-furandicarboxylic acids. 14 The addition of methyl branches was found to reduce polymer crystallinity, linked as noted above to the use of stereo-irregular diols. Interestingly, the introduction of methyl branching raised the T g of the amorphous regions of these materials, though multiple factors are known to affect T g beyond just sterics.…”

“…This was later confirmed by van der Klis et al , who found a polyester of optically pure 2,5-HDO, poly(2 S ,5 S -hexylene succinate) to display a melting point ( T m ) at 200 °C, confirming it to be semicrystalline. 14 The thermal stability of the polyesters in these earlier studies was also promising. Arnaud and co-workers showed their materials to have temperatures of decomposition with 10% mass loss (TD 10 ) to be >280 °C, while van der Klis found TD 5 to be >250 °C for all 2,5-HDO polyesters they prepared.…”