Aliphatic Polyester Materials from Renewable 2,3-Butanediol

Abstract

2,3-Butanediol has emerged as a promising bio sourced monomer for polyester synthesis. However, it has received limited attention as monomer for semicrystalline polyesters, due to the lower reactivity of secondary alcohols often resulting in low molecular weight polymers. Furthermore, the methyl branches of 2,3-butanediol reduce the crystallinity of resulting polyesters, leading to lowered melting temperatures. We report the synthesis of semicrystalline polyesters from 2,3-butanediol with long-chain aliphatic dicarboxylate monomers ranging in chain length from C10 to C48. With appropriate reaction conditions, high molecular weights up to 59,000 g mol–1 were obtained. Polyester-b4.48 (b4 = 2,3-butanediol-based repeat units) features a high melting point of 103 °C and orthorhombic polyethylene-like crystal structure, while shorter dicarboxylate-based polyesters have different crystal structures and polyester-b4.10 is amorphous. Tensile tests of polyester-b4.18 reveal a modulus of elasticity of 290 MPa and elongation at break of 430%. The combination of b4/C10 noncrystallizing repeat units with the well-crystallizable C48 repeat units provides 2,3-butanediol-based thermoplastic elastomers. Faster enzyme-catalyzed hydrolysis rates were measured for polyester-b4.18 compared to the linear polyester-4.18, indicating an increase in biodegradability with decreasing polymer melting points and crystallinities.

Crystallization of Biobased Long-Chain Aliphatic Polyesters as Sustainable Polymers: Effects of the Diol Structure in the Monomer Unit

“… , , Therefore, these polymers were considered as recyclable polyethylene mimics, whereas their properties are dependent on the chain length of each monomer unit (diacid, diol). − Moreover, some of these polymers possessing 1,18-octadecane dicarboxylic acid or 1,18-octadecene dicarboxylic acid units showed biodegradability , and were also called biodegradable HDPE-like materials. There are some reports on the analysis of mechanical properties in films for the long-chain aliphatic polyesters consisting of carbohydrate derivatives incorporated in the monomer units ( Figure ).…”

Crystallization of Biobased Long-Chain Aliphatic Polyesters as Sustainable Polymers: Effects of the Diol Structure in the Monomer Unit

“… , , Therefore, these polymers were considered as recyclable polyethylene mimics, whereas their properties are dependent on the chain length of each monomer unit (diacid, diol). − Moreover, some of these polymers possessing 1,18-octadecane dicarboxylic acid or 1,18-octadecene dicarboxylic acid units showed biodegradability , and were also called biodegradable HDPE-like materials. There are some reports on the analysis of mechanical properties in films for the long-chain aliphatic polyesters consisting of carbohydrate derivatives incorporated in the monomer units ( Figure ).…”

Tunable organo-catalysed ring-opening polymerization of ω-dodecalactone macrolactone by the cyclic triphosphazene base

“…24 In particular, the Mecking group conducted systematic research on this subject. 25–28 The linear aliphatic polyesters obtained in this way by Mecking et al over the last decades not only have mechanical properties comparable to HDPE and can be injection molded or 3D printed but can also be chemically recovered into a mixture of two nonvolatile long-chain monomers (diesters and diols), with recoveries over 96%. The Li group synthesized ALCPEs from 1,5-pentanediol and long-chain α,ω-diacids whose oxygen and water vapor barrier properties increase with the chain length of the diacid.…”

Engineering Saccharomyces cerevisiae and controlling conditions for 2,3- b utanediol production from glycerol

“…[5][6][7] as well as a growth stimulator and drought resistance enhancer of Arabidopsis thaliana, Nicotiana benthamiana tomatoes, turfgrass, soybeans, and strawberries. [8][9][10][11][12] 2,3-BDO can be also used in preparing biodegradable high-elasticity polyester rubber 13,14 and it has been upgraded to aviation fuel. 15 It has been found to be versatile as a bulk chemical compound with potential applications as a precursor for 1,3-butadiene, which can be converted to polybutylene terephthalate resin and rubber, spandex, and pharmaceuticals such as gamma-butyrolactone.…”

Crystallization of Biobased Long-Chain Aliphatic Polyesters as Sustainable Polymers: Effects of the Diol Structure in the Monomer Unit

“… , , Therefore, these polymers were considered as recyclable polyethylene mimics, whereas their properties are dependent on the chain length of each monomer unit (diacid, diol). − Moreover, some of these polymers possessing 1,18-octadecane dicarboxylic acid or 1,18-octadecene dicarboxylic acid units showed biodegradability , and were also called biodegradable HDPE-like materials. There are some reports on the analysis of mechanical properties in films for the long-chain aliphatic polyesters consisting of carbohydrate derivatives incorporated in the monomer units ( Figure ).…”

Tunable organo-catalysed ring-opening polymerization of ω-dodecalactone macrolactone by the cyclic triphosphazene base

“…24 In particular, the Mecking group conducted systematic research on this subject. 25–28 The linear aliphatic polyesters obtained in this way by Mecking et al over the last decades not only have mechanical properties comparable to HDPE and can be injection molded or 3D printed but can also be chemically recovered into a mixture of two nonvolatile long-chain monomers (diesters and diols), with recoveries over 96%. The Li group synthesized ALCPEs from 1,5-pentanediol and long-chain α,ω-diacids whose oxygen and water vapor barrier properties increase with the chain length of the diacid.…”

Engineering Saccharomyces cerevisiae and controlling conditions for 2,3- b utanediol production from glycerol

“…[5][6][7] as well as a growth stimulator and drought resistance enhancer of Arabidopsis thaliana, Nicotiana benthamiana tomatoes, turfgrass, soybeans, and strawberries. [8][9][10][11][12] 2,3-BDO can be also used in preparing biodegradable high-elasticity polyester rubber 13,14 and it has been upgraded to aviation fuel. 15 It has been found to be versatile as a bulk chemical compound with potential applications as a precursor for 1,3-butadiene, which can be converted to polybutylene terephthalate resin and rubber, spandex, and pharmaceuticals such as gamma-butyrolactone.…”

Crystallization of Biobased Long-Chain Aliphatic Polyesters as Sustainable Polymers: Effects of the Diol Structure in the Monomer Unit

“… , , Therefore, these polymers were considered as recyclable polyethylene mimics, whereas their properties are dependent on the chain length of each monomer unit (diacid, diol). − Moreover, some of these polymers possessing 1,18-octadecane dicarboxylic acid or 1,18-octadecene dicarboxylic acid units showed biodegradability , and were also called biodegradable HDPE-like materials. There are some reports on the analysis of mechanical properties in films for the long-chain aliphatic polyesters consisting of carbohydrate derivatives incorporated in the monomer units ( Figure ).…”

Tunable organo-catalysed ring-opening polymerization of ω-dodecalactone macrolactone by the cyclic triphosphazene base

“…24 In particular, the Mecking group conducted systematic research on this subject. 25–28 The linear aliphatic polyesters obtained in this way by Mecking et al over the last decades not only have mechanical properties comparable to HDPE and can be injection molded or 3D printed but can also be chemically recovered into a mixture of two nonvolatile long-chain monomers (diesters and diols), with recoveries over 96%. The Li group synthesized ALCPEs from 1,5-pentanediol and long-chain α,ω-diacids whose oxygen and water vapor barrier properties increase with the chain length of the diacid.…”

Engineering Saccharomyces cerevisiae and controlling conditions for 2,3- b utanediol production from glycerol

“…[5][6][7] as well as a growth stimulator and drought resistance enhancer of Arabidopsis thaliana, Nicotiana benthamiana tomatoes, turfgrass, soybeans, and strawberries. [8][9][10][11][12] 2,3-BDO can be also used in preparing biodegradable high-elasticity polyester rubber 13,14 and it has been upgraded to aviation fuel. 15 It has been found to be versatile as a bulk chemical compound with potential applications as a precursor for 1,3-butadiene, which can be converted to polybutylene terephthalate resin and rubber, spandex, and pharmaceuticals such as gamma-butyrolactone.…”