Sebastián Muñoz-Guerra

A review on the potential biodegradability of poly(ethylene terephthalate)

This paper reviews the state of the art in the field of the hydrolytic degradation of poly(ethylene terephthalate) (PET) under bio-environmental conditions. Most of the papers published so far on this subject have been focused on the hydrolysis of PET at high temperatures. Although some authors claim to enhance the biodegradation properties of this aromatic polyester by copolymerization with readily hydrolysable aliphatic polyesters, no clear and satisfying conclusions can yet be formulated. Poly(ethylene terephthalate-co-lactic acid), poly(ethylene terephthalate-co-ethylene glycol), and poly(ethylene terephthalate-co-e-caprolactone) block and random copolymers are the modifications mainly investigated for biodegradable applications. The hydrodegradability and biodegradability of PET, PET copolymers and PET blends are detailed in this review. A total of 89 references including 16 patents are cited. © 1999 Society of Chemical Industry

Biosynthesis and ultrasonic degradation of bacterial poly(γ-glutamic acid)

A study of the production of poly(γ-glutamic acid) (PGGA) by Bacillus licheniformis NCIMB 11709 grown on medium E in shake flasks at 30°C is reported. The enantiomeric composition of PGGA was found to be highly sensitive to the concentration of Mn++, especially when the ion is present in small amounts (⩽ 20 μM). Polymers with D-unit contents ranging from 10 to 90 % and Mw between 0.4 and 2.0 million g mol−1 were obtained for [Mn++] ranging from 0 to 1230 μM. Ultrasonic degradation was proven to be an effective method to reduce both the molecular weight and the polydispersity of naturally produced PGGA without disturbing the chemical constitution of the polymer.

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.

Renewable terephthalate polyesters from carbohydrate-based bicyclic monomers

Poly(alkylene terephthalate)s, PET and PBT in particular, are materials of great relevance and growing projection in the thermoplastic field but are today almost totally produced from fossil resources. The current huge consumption of these polyesters necessitates urgent actions addressed to make them renewable by using naturally-occurring raw materials. Among the different approaches that are being followed to develop bio-based poly(terephthalate)s, the use of bicyclic carbohydrate-derived difunctional compounds as building-blocks is receiving much attention in the last few years because partially renewable polyesters with high Tg may be thus obtained. This review presents a critical account of the terephthalate homopolymers and copolymers that have been synthesized using the two types of carbohydrate-based bicyclic monomers, isohexides and diacetals, explored to date. The properties displayed by the novel bio-based poly(terephthalate)s in relation to the bicyclic structure of the used monomers are comparatively reviewed and their potential as emergent materials for thermoplastic applications is evaluated.

Degradable poly(ester amide)s based on l-tartaric acid

Abstract A series of poly(ester amide)s with ester/amide group ratios ranging from 1 99 to 1 4 were obtained using 1,6-hexanediamine, 1,6-hexanediol and 2,3-di-O-methoxy- l -tartaric and succinic acids as building blocks. The ester linkages were introduced in pairs using as comonomer the diacid resulting from the esterification of 1,6-hexanediol with 2 mol of succinic anhydride. Polycondensastion reactions were carried out in solution at room temperature with the diamine activated as the N,N′-bis(trimethylsilyl) derivative and the two diacids as bis(pentachlorophenyl) esters. The prepared poly(ester amide)s have number average molecular weights in the range 10 000–40 000, display optical activity and are soluble in chloroform. These copolymers were found to be highly crystalline with melting points above 200°C and mechanical moduli comparable to those reported for the parent polyamide poly(hexamethylene-di-O-methyl- l -tartaramide). They were degraded by aqueous buffer of pH 7.4 at a rate that increased with the content of the copolymer in succinic acid units. 1H n.m.r. evidenced that no reactions other than those entailing the hydrolysis of the main chain ester bonds appear to take place at polymer degradation.

On the helical conformation of un-ionized poly(γ-d-glutamic acid)

Abstract The conformational preferences of the naturally occurring poly(γ- d -glutamic acid) in the un-ionized state were investigated using a combination of molecular dynamics and quantum mechanical calculations. Results indicated that a left-handed helix with 19-membered ring hydrogen bonds set between the CO of the amide group i and the NH of amide group i+3 is the most stable conformation for this poly(γ-amino acid). Weak intramolecular interactions between the oxygens of the carboxyl side groups and the NH of the backbone amide groups were detected. They are assumed to be responsible for the unexpected handedness exhibited by the helix with regards to the stereochemistry of the compound.

PET copolyesters made from a D-mannitol-derived bicyclic diol

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 PExManxyT copolyesters covering the whole range of molar compositions. The copolyesters had weight-average molecular weights in the 33000–41000 g mol−1 interval and were thermally stable up to nearly 380 °C. They displayed Tg 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.

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.

Comparison of lamellar crystal structure and morphology of nylon 46 and nylon 5

A comparative study of the crystal structure of lamellar crystals of the isomeric nylons 46 and 5 was carried out. A lattice made of hydrogen-bonded sheets with chains in fully extended conformation and hydrogen bonds in the normal scheme was proposed for the two nylons according to the great similarities in morphology and diffraction data observed for their solution grown crystals. Energy calculations and modeling simulations showed that a model consisting of a statistical arrangement of progressive and alternating intersheet shearing is the most appropriate and consistent to describe the structure of both nylons. A preliminary investigation on the possibility of cocrystallizing nylon 46 and nylon 5 was undertaken. First experimental results were found to be compatible with the occurrence of cocrystallization. Molecular mechanics calculations indicated that insertion of one nylon in the crystal lattice of the other is energetically disfavored. However, cocrystals would be acceptable if they were made of homogeneous blocks of each nylon comprised of about 10 or more hydrogen-bonded sheets.