Synthesis and degradabilities of polyesters from 1,4:3,6‐dianhydrohexitols and aliphatic dicarboxylic acids

Abstract

SYNOPSISSix different polyesters (6a-6c and 7a-7c) were prepared by the bulk polycondensations of the respective combinations of 1,4:3,6-dianhydro-~-glucitol (3) and 1,4:3,6-dianhydro-D-mannitol(4) with succinyl dichloride (5a), glutaryl dichloride (5b), and adipoyl dichloride (5c) a t 140-180°C. Polyesters having number average molecular weights up to 2.6 X lo4 were obtained in high yields. Only polyester 7a based on 4 and 5a was partially crystalline, whereas all the other polyesters were amorphous. Thin films of these polyesters except that of 7a were spontaneously hydrolyzed in a neutral phosphate buffer solution a t 50"C, whereas they were reluctant to be hydrolyzed a t 27°C. The polyesters were more or less degraded at 27°C by treatment with an activated sludge or by prolonged burial in soil. 0 CCC 0887-624X/95/162813-08 as well as spontaneous hydrolytic degradation in a neutral phosphate buffer These polyesters were prepared by cationic ring-opening polymerization of bicyclic lactones, 6,g-dioxabicyclo[3.2.l]octan -7 -one and 2,6 -dioxabicyclo [2.2.2]octan-3-one, respectively.

Synthesis and structural characterization of block and random low molecular weight copolymers composed of L-lactic acid and isosorbide succinate moieties

“…The samples of PIS and I were not annealed. The diffraction pattern obtained for PLLA2 is similar to that reported in literature, 33,34 while the diffraction pattern obtained for PIS showed, as expected, 4 only an amorphous halo, characteristic of non-crystalline samples. The diffraction patterns obtained for II-IV are comparable with that obtained for PLLA2, whilst that obtained for I is comparable with that of PIS (see Supplementary Information).…”

“…4,22 The low average molar masses obtained for PLLA are associated with the relatively low purity of the monomer L-lactide used, which serves to the purpose of this study. Perego et al 21 also obtained PLLA with low average molar masses by using less pure L-lactide.…”

“…The reaction temperature (150 ºC) for the syntheses of I and II was based on literature values for the production of PIS homopolymer in bulk. 4 The same temperature was also used for the synthesis of IV to allow complete melting of the starting materials. Purification PLLA1, PLLA2, PIS, and the products I-IV were purified by dissolving in chloroform (1 volume), precipitating in methanol (10 volumes), and drying the filtrated in a vacuum-oven at 40 ºC for 48 h, except PIS and product I, which were vacuum-dried at RT.…”

“…poly(isosorbide succinate) (PIS). 4 The 1,4:3,6-dianhydrohexitols, such as isosorbide (1,4:3,6-dianhydro-D-sorbitol or -D-glucitol), are important monomers in view of their non-toxicity and renewable origin. 5,6 Likewise, succinic acid is produced from glucose by fermentation 7 and is readily metabolized by the Krebs cycle.…”

Biodegradable polymers based on renewable resources. III. copolyesters composed of 1,4:3,6-dianhydro-D-glucitol, 1,1-bis(5-carboxy-2-furyl)ethane and aliphatic dicarboxylic acid units

“…In the course of a series of investigations on the synthesis of biodegradable polymers based on renewable resources, [13][14][15] we also synthesized 11 different polyesters by bulk polycondensation of various combinations of 1,4:3,6-dianhydro-D-glucitol (1) and 1,4:3,6-dianhydro-D-mannitol (2), four aliphatic diols, and three oligo(ethylene glycol)s with bis[5-(methoxycarbonyl)-2-furyl]methane (3a) and 1,1-bis[5-(methoxycarbonyl)-2-furyl]ethane (3b). 16 These polyesters were amorphous and dissolved in various common organic solvents.…”