Abdelilah Alla

High Tg bio-based aliphatic polyesters from bicyclic D-mannitol

The carbohydrate-based diol 2,4:3,5-di-O-methylene-d-mannitol (Manx) has been used to obtain aliphatic polyesters. Manx is a symmetric bicyclic compound consisting of two fused 1,3-dioxane rings and bearing two primary hydroxyl groups. In terms of stiffness, it is comparable to the widely known isosorbide, but it affords the additional advantages of being much more reactive in polycondensation and capable of producing stereoregular polymers with fairly high molecular weights. A fully bio-based homopolyester (PManxS) has been synthesized by polycondensation in the melt from dimethyl succinate and Manx. The high thermal stability of PManxS, its relatively high glass transition temperature (Tg = 68 °C) and elastic modulus, and its enhanced sensitivity to the action of lipases point to PManxS as a polyester of exceptional interest for those applications where biodegradability and molecular stiffness are priority requirements. In addition, random copolyesters (PBxManxyS) covering a broad range of compositions have been obtained using mixtures of Manx and 1,4-butanediol in the reaction with dimethyl succinate. All PBxManxyS were semicrystalline and displayed Tg values from -29 to +51 °C steadily increasing with the content in Manx units. The stress-strain behavior of these copolyesters largely depended on their content in Manx and they were enzymatically degraded faster than PBS.

Bio-based PBT copolyesters derived from D-glucose: influence of composition on properties

Two series of bio-based PBT copolyesters were obtained by polycondensation in the melt of 2,4:3,5-di-O-methylene-D-glucitol (Glux-diol) or dimethyl 2,4:3,5-di-O-methylene-D-glucarate (Glux-diester) with 1,4-butanediol and dimethyl terephthalate. The glucose-based bicyclic compounds used as comonomers were synthesized from commercially available 1,5-D-gluconolactone. The prepared PBT copolyesters had weight-average molecular weights in the 30000–50000 range; they had a random microstructure, and they were stable above 300 °C. The copolyesters containing less than 30% of sugar-based units were semicrystalline and were found to adopt the triclinic structure of PBT. These copolyesters with low contents in Glux were able to crystallize from the melt but at lower rates than PBT. The Tg value of PBT steadily increased with the incorporation of Glux units in the polyester chain with an increasing ratio of ∼1.7 °C or ∼1 °C per %Glux point, depending on which unit, the diol or the diacid, was replaced. The copolyesters hydrolyzed at higher rates than PBT, and those containing glucarate units displayed an appreciable susceptibility towards biodegradation.

D-Glucose-derived PET copolyesters with enhanced Tg

2,4:3,5-Di-O-methylene-D-glucitol (Glux-diol) and dimethyl 2,4:3,5-di-O-methylene-D-glucarate (Glux-diester) have been copolymerized with ethylene glycol and dimethyl terephthalate by polycondensation in the bulk to produce PET copolyesters as well as their respective homopolyesters. These sugar-based bicyclic monomers were synthesized from 1,5-D-gluconolactone, a commercially accessible compound derived from D-glucose. The PET copolyesters with either the diol or the diacid counterpart partially replaced by Glux had molecular weights in the 20000–40000 range and a random microstructure, and they were stable well above 300 °C. The PET copolyesters containing more than 10–15% of sugar-based units were amorphous while those displaying crystallinity were observed to crystallize from the melt at much lower rates than PET. The glass transition temperature of PET dramatically increased with the incorporation of Glux, whichever unit, diol or diacid, was replaced, but the enhancing effect was stronger in the former case. A preliminary evaluation of the mechanical behaviour of these copolyesters indicated that the genuine properties of PET were not substantially impoverished by the insertion of Glux. Compared to PET, the copolyesters exhibited a higher hydrolysis rate and an appreciable susceptibility towards biodegradation. The homopolyesters made of these sugar-based monomers could not be obtained with high enough molecular weights so as to be comparatively evaluated with copolyesters.

Bio-based aromatic copolyesters made from 1,6-hexanediol and bicyclic diacetalized D-glucitol

The diacetalized diol 2,4:3,5-di-O-methylene-D-glucitol (Glux), a bicyclic compound derived from D-glucose, was used as a comonomer of 1,6-hexanediol in polycondensation in the melt with dimethyl terephthalate to produce a set of aromatic copolyesters (PHxGluxyT) with Glux contents ranging from 5 to 32%-mole. These sustainable copolyesters had molecular weights within the 12,000 to 45,000 g mol−1 range, and polydispersities between 2.0 and 2.5. They all had a random microstructure and displayed slight optical activity. PHxGluxyT showed a good thermal stability and were semicrystalline with both crystallinity degree and crystallization rate decreasing as the content in Glux increased. Conversely, Tg increased with the incorporation of Glux going from 8 °C in PHT to near 60 °C in the copolyester containing 32%-mole Glux. Compared to PHT, PHxGluxyT copolyesters showed not only an enhanced susceptibility to hydrolysis but also an appreciable biodegradability in the presence of lipases.

Copolyesters made from 1,4-butanediol, sebacic acid, and D-glucose by melt and enzymatic polycondensation

Biotechnologically accessible 1,4-butanediol and vegetal oil-based diethyl sebacate were copolymerized with bicyclic acetalized D-glucose derivatives (Glux) by polycondensation both in the melt at high temperature and in solution at mild temperature mediated by polymer-supported Candida antarctica lipase B (CALB). Two series of random copolyesters (PB(x)Glux(y)Seb and PBSeb(x)Glux(y)) were prepared differing in which d-glucose derivative (Glux diol or Glux diester) was used as comonomer. The three parent homopolyesters PBSeb, PBGlux, and PGluxSeb were prepared as well. Both methods were found to be effective for polymerization although significant higher molecular weights were achieved by melt polycondensation. The thermal properties displayed by the copolyesters were largely dependent on composition and also on the functionality of the replacing Glux unit. The thermal stability of PBSeb was retained or even slightly increased after copolymerization with Glux, whereas crystallinity and melting temperature were largely depressed. On the contrary, the glass-transition temperature noticeably increased with the content in Glux units. PGluxSeb distinguished in displaying both T(g) and T(m) higher than PBSeb because a different crystal structure is adopted by this homopolyester. The hydrolytic degradability of PBSeb in water was enhanced by copolymerization, in particular, when biodegradation was assisted by lipases.

Poly(ester amide)s derived from tartaric and succinic acids : Changes in structure and properties upon hydrolytic degradation

The changes in structure and properties taking place in a set of tartaric acid-based polyamides and poly(ester amide)s upon hydrolytic degradation were examined. Poly(hexamethylene 2,3-di-O-methyl-L-tartaramide)s, either pure or containing minor amounts of succinate ester groups (≤10%), were exposed to humidity or incubated in buffered water at pH 7.4 and 37°C, and their thermal and mechanical properties were evaluated as a function of time. Both moisture uptake and hydrolysis induced a noticeable decay in the tensile properties of polymers. These effects were greatly enhanced by the presence of ester groups, whereas no large differences were noticed for changes in the enantiomeric composition. Variations in the glass transition temperatures and melting points appeared to be slight, whereas crystallinity clearly increased with incubation time. The latter effect was most apparent in poly(ester amide)s with a nearly racemic composition, in which a crystal-to-crystal transition was observed to take place upon degradation.

Carbohydrate-based PBT copolyesters from a cyclic diol derived from naturally occurring tartaric acid: a comparative study regarding melt polycondensation and solid-state modification

2,3-O-Methylene-L-threitol (Thx) is a cyclic carbohydrate-based diol prepared by acetalization and subsequent reduction of the naturally occurring tartaric acid. The structure of Thx consists of a 1,3-dioxolane ring with two attached primary hydroxyl groups. Two series of partially bio-based poly(butylene terephthalate) (PBT) copolyesters were prepared using Thx as a comonomer by melt polycondensation (MP) and solid-state modification (SSM). Fully random copolyesters were obtained after MP using mixtures of Thx and 1,4-butanediol in combination with dimethyl terephthalate. Copolyesters with a unique block-like chemical microstructure were prepared by the incorporation of Thx into the amorphous phase of PBT by SSM. The partial replacement of the 1,4-butanediol units by Thx resulted in satisfactory thermal stabilities and gave rise to an increase of the Tg values, this effect was comparable for copolyesters prepared by MP and SSM. The partially bio-based materials prepared by SSM displayed higher melting points and easier crystallization from the melt, due to the presence of long PBT sequences in the backbone of the copolyester. The incorporation of Thx in the copolyester backbone enhanced the hydrolytic degradation of the materials with respect to the degradation of pure PBT.

Poly(ethylene terephthalate) terpolyesters containing 1,4-cyclohexanedimethanol and isosorbide

A series of poly(ethylene terephthalate) terpolyesters containing varying amounts of both 1,4-cyclohexylenedimethylene and isosorbide units were prepared by melt phase polycondensation. These terpolymers were obtained with high molecular weights and polydispersities around 2.0–2.5. The nuclear magnetic resonance data revealed that they were all random terpolymers and that small amounts of isosorbide were lost during the polycondensation reaction. Thermal data showed that terpolymers with 90 mol% of ethylene units were crystalline, whereas the two other series containing 80 and 70 mol% were unable to crystallize from the melt. For the three series studied, it was observed that the glass transition temperature increased steadily with the content of isosorbide units, and that they had similar thermal stability.

Bio-based PBS copolyesters derived from a bicyclic D-glucitol

2,4:3,5-di-O-methylene-D-glucitol (Glux-diol) was used for the synthesis of poly(butylene succinate) (PBS) copolyesters by melt polycondensation. Glux-diol possess a rigid bicyclic asymmetric structure made of two fused 1,3-dioxane rings and two hydroxyl functions at the end positions. Copolyesters were prepared over the whole range of compositions with molecular weights varying from 26 000 to 46 000 g mol−1 and a random microstructure. The thermal stability of PBS did not significantly alter with the presence of Glux units. The glass transition temperatures (Tg) steadily increased from −28 to 80 °C along the whole copolyester series with the insertion of Glux. On the contrary, melting temperature (Tm) and crystallinity decreased because of the lack of regularity of the polymer chain although copolyesters with contents of Glux units up to 30 mole% were semicrystalline. The stress–strain behavior changed according to variations produced in thermal transitions. The replacement of 1,4-butanediol by Glux-diol slightly increased both the hydrolytic degradability and the biodegradability of PBS. Compared to other bicyclic sugar-based diols reported in the literature, Glux-diol appeared to be more efficient in both increasing the Tg and enhancing the susceptibility to hydrolysis of PBS.

Hairy-rod random copoly(β,l-aspartate)s containing alkyl and benzyl side groups

Hairy random copoly(β,l-aspartate)s were prepared by anionic ring opening polymerization of mixtures of (S)-4-octadecoxycarbonyl and (S)-4-benzyloxycarbonyl 2-azetidinones at 3:1, 1:1 and 1:3 molar ratios. The three resulting copolymers had molar ratios of octadecyl to benzyl units of 68:32, 44:56 and 12:88, respectively. They all were found to adopt the rigid α-helix-like conformation characteristic of poly(β,l-aspartate)s, but only the first one displayed crystallization of the alkyl side chains. This copolymer showed thermochromic behavior with color changes taking place when heated above the side chain melting temperature. These results evidenced the ability of the benzyl group to be accommodated within the layered structures of comb-like poly(β,l-aspartate)s and to modify the temperature range in which chromatic changes are observed in these systems.