PET copolyesters made from ad-mannitol-derived bicyclic diol

Abstract

The carbohydrate-based bicyclic diol 2,4:3,5-di-O-methylene-D-mannitol (Manx) was made to react in the melt with ethylene glycol and dimethyl terephthalate to produce random PE x Manx y T copolyesters covering the whole range of molar compositions. The copolyesters had weight-average molecular weights in the 33 000-41 000 g mol À1 interval and were thermally stable up to nearly 380 C. They displayed T g in the 81 to 137 C range with values largely increasing with the content in Manx units. Copolyesters containing minor amounts of Manx were semicrystalline whereas those with contents equal to or more than 30% of Manx were amorphous. Stress-strain parameters were affected by composition, increasing tensile strength and elastic modulus and reducing elongation at break when introducing Manx units. These bio-based PET copolyesters showed enhanced susceptibility to hydrolysis.

Synthetic Polymers from Sugar-Based Monomers

“…Other chiral isosorbide-derived monomers were prepared (Scheme 26) and polycondensated by the same method. 145 Koning et al 146 described fully biobased homo-and copolyamides from sebacic acid, 2,5-diamino-2,5-dideoxy-1,4;3,6-dianhydroiditol (diaminoisoidide, 84), and 1,4-diaminobutane. Low-molecular-weight polyamides were obtained by melt polycondensation of the salts based on these monomers or by interfacial polycondensation.…”

“…Koning et al described some poly-(urethane urea) dispersions containing renewable building blocks including isosorbide (1) 181 and thermoplastic poly(ester urethane urea)s from biobased monomers, such as L-lysine diisocyanate, isoidide diisocyanate, 1,4-diaminobutane, and diaminoisoidide (84). 219 Thiem et al 194 described the preparation of fully sugar-based polyureas by polyaddition reactions of the 1,6-diamino-1,6-dideoxy-dianhydrohexytols (82−84) to the isoidide diisocyanate.…”

Renewable thermoplastic polyurethanes containing rigid spiroacetal moieties

“…A list of the synthesized polyurethanes is presented in Table 1. The ones prepared in bulk have often lower molecular weights (3)(4)(5)(6)(7)(8)(9)(10)(11), determined by SEC, as mechanical stirring stopped soon in the reaction process, limiting further build-up of the polymer chain. Even using EtOAc as solvent, higher molecular weights (8-45 kDa) could only be obtained by applying a mechanical stirrer.…”

“…polymers with spirocyclic units in the main chain [1][2][3][4][5][6][7]. This cyclic structure restricts conformational flexibility and hence results in an increased thermal stability of the polymers.…”

“…Therefore, an alternative synthesis method was applied to obtain spiro-containing polymers. Instead of forming the spirocyclic units upon polymerization, polymers can be built up via polyaddition or polycondensation [5,6,8,9,11,12,14,15] of monomers that already contain spirocyclic units [16][17][18]. For instance, polyurethanes, which constitute a large family of high-performance materials, show a wide variety of properties that are tuneable by a proper control of the molecular design [19].…”