Structural Effects on the Biodegradation of Aliphatic Polyesters

In advance of a discussion on structural effects on biodegradation, aliphatic polyesters as biodegradable structural materials were classified into four types regarding chemical structure, that is poly(ω-hydroxy acid), poly(β-hydroxyalkanoate), poly(ω-hydroxyalkanoate) and poly(alkylene dicarboxylate), and reviewed on synthesis route, thermal and physical properties, and biodegradability. The biodegradation mechanism of these aliphatic polyesters were discussed on the major mode of hydrolysis reaction in regard whether it was enzyme-catalyzed or not, and the substrate specificities of enzymes, such as lipases or PHA depolymerases, were discussed on the hydrolysis of the aliphatic polyesters in respect of primary structure. Moreover, the biodegradation behaviors were exceedingly influenced by solid-state morphology in addition to primary structure. The rate of enzymatic degradation of polycaprolactone fibers drawn with various draw ratios was dependent on draw ratios, suggesting that crystallinity and orientation of them affected biodegradability by lipase. In the study of enzymatic degradation of films made from butylene succinate – ethylene succinate copolymer, the dependence of degradation rate on polymeric compositions was ascribed to the degree of crystallinity rather than the primary structure. These studies revealed that the degree of crystallinity was the major rate-determining factor of biodegradation of solid polymers. © 1997 John Wiley & Sons, Ltd.     

Aromatic components in copolyesters: Model structures help to understand biodegradability

Copolyesters build of aliphatic and aromatic components have been shown to be degraded by microorganisms in a certain range of composition. While aliphatic polyesters of diol and dicarbonic acid often are hydrolyzed e.g. by lipases, pure aromatic polyesters like polyethylene terephthalate are not biodegradable. To understand the degradation mechanism of complex aliphatic/aromatic copolymers, we performed degradation experiments with different enzymatic systems and also especially screened highly active microorganisms. Several polymers and monomeric esters representing distinct structure elements within the polymer-chain have been synthesized. These model structures were investigated in terms to understand the correlation of the stereo selectivity of the tested enzymes and the biodegradability of the polymer structure.     

Effect of molecular weight on thermal degradation mechanism of the biodegradable polyester poly(ethylene succinate)

A series of aliphatic polyesters, in particular poly(ethylene succinate), having different molecular weights, were synthesized from succinic acid and ethylene glycol, following the melt polycondensation process. Intrinsic viscosities (IV), GPC, DSC, ¹H NMR and carboxylic end group measurements were used for their characterisation. From thermogravimetric analysis, it was concluded that the molecular weight of polyesters achieved during polycondensation are strongly related to thermal stabilities of initial oligomers. In order to synthesise high molecular weight polyesters, the number average molecular weight of oligomers must not be lower than 2300–3000 g/mol, since thermal decomposition begins at temperatures lower than 200 °C. However, even in that case, polycondensation temperatures must not exceed 230–240 °C. From TGA studies, it was found that sample having different molecular weights could be divided into two groups characterized by different thermal stability. In the first group, belong samples with intrinsic viscosity of IV = 0.08 dL/g and in the second one all the other samples (IV > 15 dL/g). From kinetic analysis of thermal degradation, it was found that degradation of all polyesters takes place in three stages, its one corresponding to a different mechanisms. Degradation of samples with low molecular weight is more complex that that of polyesters having high molecular weights. The values of the activation energy and the exponent n for the two groups of samples—with different molecular weight—are similar, regarding the first two mechanisms, while there is an alteration in the case of the third mechanism.     

Effect of metal compounds on thermal degradation behavior of aliphatic poly(hydroxyalkanoic acid)s

Effect of metal compounds on the thermal degradation behaviors of poly(3-hydroxybutyric acid) (P(3HB)), poly(4-hydroxybutyric acid) (P(4HB)), and poly(?-caprolactone) (PCL) was investigated by means of thermogravimetric and pyrolysis-gas chromatograph mass spectrometric analyses. Na and Ca compounds accelerated a random chain scission of P(3HB) molecules resulting in a decrease of thermal degradation temperature, whereas the contribution of Zn, Sn, Al compounds to the thermal degradation of P(3HB) was very small. In contrast to P(3HB), Zn, Sn and Al compounds induced the thermal degradation of PCL at lower temperature range by catalyzing the selective unzipping depolymerization from ω-hydroxyl chain end. Transesterification reaction of PCL molecules could be facilitated by the presence of Ca compound, while the gravimetric change was detected at almost identical temperature region regardless of the content of Ca compound. According to the lactonizing characteristic of monomer unit, the thermal degradation of P(4HB) progressed by the cyclic rupture via unzipping reaction from the ω-hydroxyl chain end or/and random intramolecular transesterification at the main chain with a release of γ-butyrolactone as volatile product. Each of metal compounds used in this study was effective to catalyze the cyclic rupture of P(4HB) molecules, and the degradation rate was accelerated by the presence of metal compounds.     

Thermal and mechanical behaviour of flexible poly(vinyl chloride) mixed with some saturated polyesters

Four saturated polyesters poly(hexamethylene adipate), poly(ethylene adipate), poly(hexamethylene terephthalate) and poly(ethylene terephthalate) were prepared. The resulting materials were characterized by IR and ¹H NMR, end group analysis and gel permeation chromatography. The effect of blending these polyesters (5 and 10%) with poly(vinyl chloride) (PVC) in the melt was investigated in terms of changes in the thermal behaviour of PVC by studying the weight loss after 50 min at 180 °C, colour changes of the blend before and after aging for one week at 90 °C, the variation in glass transition temperature and the initial decomposition temperature. The results gave proof for the stabilizing role played by the investigated polyesters against the thermal degradation of PVC. The best results are obtained when PVC is mixed with 5% aliphatic polyesters rather than with aromatic ones. This is well illustrated not only from the increase in the initial decomposition temperature (IDT), but also from the decrease of % weight loss and from the lower extent of discolouration of PVC, which is a demand for the application of the polymer. It was also found that blending PVC with 5% of the four investigated polyesters before and after aging for one week at 90 °C gave better mechanical properties even than that of the unaged PVC blank.     

Perspectives for Biotechnological Production and Utilization of Biopolymers: Metabolic Engineering of Polyhydroxyalkanoate Biosynthesis Pathways as a Successful Example

This article provides an overview of biopolymers, classed according to their chemical structures, function and occurrence, the principles of biosynthesis and metabolism in organisms. It will then focus on polyhydroxyalkanoates (PHA) for which technical applications in several areas are currently considered. PHAs represent a complex class of bacterial polyesters consisting of various hydroxyalkanoic acids that are synthesized by bacteria as storage compounds for energy and carbon if a carbon source is present in excess. Poly(3‐hydroxybutyrate), poly(3HB), is just one example. Most other PHAs are only synthesized if pathways exist which mediate between central intermediates of the metabolism or special precursor substrates on one side and coenzyme A thioesters of hydroxyalkanoic acids, which are the substrates of the PHA synthase catalyzing the polymerization, on the other side. During the last decade, basic and applied research have revealed much knowledge about the biochemical and molecular basis of the enzymatic processes for the synthesis of PHAs in microorganisms. The combination of detailed physiological studies, utilization of the overwhelming information provided by the numerous genome sequencing projects, application of recombinant DNA technology, engineering of metabolic pathways or enzymes and molecular breeding techniques applied to plants have provided new perspectives to produce these technically interesting biopolymers by novel or significantly improved biotechnological processes or by agriculture. Some examples for successful in vivo and in vitro engineering of pathways suitable for the synthesis and biotechnological production of PHAs consisting of medium‐chain‐length 3‐hydroxyalkanoic acids and short‐chain‐length hydroxyalkanoic acids will be provided.     

Water absorption and degradation characteristics of chitosan-based polyesters and hydroxyapatite composites

Blends of chitosan and biodegradable synthetic aliphatic polyesters (polycaprolactone, poly(butylene succinate), poly[(butylene succinate)-co-adipate], poly[(butylene terephthalate)-co-adipate], and poly(lactic acid)) were injection-molded. These samples were immersed in isotonic solution at 37 degrees C for a period of 60 d. The water uptake and the degradation properties, as measured by the loss in tensile strength, were evaluated as a function of time. In this study, the rate and the equilibrium water uptake were proportional to the amount of chitosan in the blend. The addition of HA to chitosan and polyester significantly reduced the equilibrium water uptake. The water uptake did not follow the classical Fickian phenomena and could be expressed by a two-stage sorption non-Fickian diffusion model. Contact angle measurement was used to quantify the changes in surface hydrophilicity as a function of chitosan and polyester composition. The glycerol contact angle decreased with increasing synthetic components in the blend. The blends and composites also showed increased degradation, as quantified by a loss in their mechanical properties, with increase in natural content. The degradation of properties was directly related to the water uptake of the blends; the higher the water uptake, the higher the degradation. Pure polyesters, while having low water uptake, nevertheless showed significant degradation by a precipitous drop in the strain at break. Among the polyesters, poly(lactic acid) displayed maximum degradation, while polycaprolactone displayed the least.     

Renewable Polyethers via GaBr3‐Catalyzed Reduction of Polyesters

Herein, a novel approach is reported for the synthesis of medium‐ and long‐chain aliphatic polyethers 2 based on the GaBr₃‐catalysed reduction of polyesters 1 with TMDS as the reducing agent. Thus, various linear and branched aliphatic polyesters 1 were prepared and systematically investigated for this reduction strategy, demonstrating the applicability and versatility of this new polyether synthesis protocol. Medium‐ and long‐chain chain polyethers were obtained from the respective polyesters without or with minor chain degradation, whereas short‐chain polyesters, such as poly‐l ‐lactide 1 i and poly[(R)‐3‐hydroxybutanoate] 1 j , showed major chain degradation. In this way, previously unavailable and uncommon polyethers were obtained and studied.     

Synthesis, characterization and thermal degradation mechanism of three poly(alkylene adipate)s: Comparative study

Three high molecular weight aliphatic polyesters derived from adipic acid and the appropriate diol - poly(ethylene adipate) (PEAd), poly(propylene adipate) (PPAd) and poly(butylene adipate) (PBAd) - were prepared by two-stage melt polycondensation method (esterification and polycondensation) in a glass batch reactor. Intrinsic viscosities, GPC, DSC, NMR and carboxylic end-group measurements were used for their characterization. Mechanical properties of the prepared polyesters showed that PPAd has similar tensile strength to low-density polyethylene while PEAd and PBAd are much higher. From TGA analysis it was found that PEAd and PPAd have lower thermal stability than poly(butylene adipate) (PBAd). The decomposition kinetic parameters of all polyesters were calculated while the activation energies were estimated using the Ozawa, Flynn and Wall (OFW) and Friedman methods. Thermal degradation of PEAd was found to be satisfactorily described by one mechanism, with activation energy 153 kJ/mol, while that of PPAd and PBAd by two mechanisms having different activation energies: the first corresponding to a small mass loss with activation energies 121 and 185 kJ/mol for PPAd and PBAd, respectively, while the second is attributed to the main decomposition mechanism, where substantial mass loss takes place, with activation energies 157 and 217 kJ/mol, respectively.     

The thermal degradation of poly(-(d)-β-hydroxybutyric acid): Part 3—The reaction mechanism

The products and general characteristics of the thermal degradation of poly(-(d)-β-hydroxybutyric acid) have been accounted for in terms of a comprehensive reaction mechanism.     

Biological basis of enzyme-catalyzed polyester degradation: 59 C-terminal amino acids of poly(3-hydroxybutyrate) (PHB) depolymerase a from pseudomonas lemoignei are sufficient for PHB binding

Biodegradable polyesters such as biologically produced poly[(R)-3-hydroxybutyric acid], (PHB) other polyhydroxyalkanoic acids and related chemosynthetic polyesters have attracted industrial interest, and bacterial produced PHB is commercially available since 1990. A large variety of polyester degrading microorganisms have been found to be present in environment. The microorganisms decompose the polymers by secretion of extracellular polyester depolymerases and utilize low molecular weight degradation products for growth. Microbial polyester depolymerases have the unique property to be water soluble and to be able to bind specifically to polyester surfaces. The objective of this contribution is a functional analysis of a bacterial PHB depolymerase polyester binding domain. In addition, a detailed summary of the present knowledge on the biochemistry of enzymatic polyester hydrolysis is provided.     

Macro-azo-initiators composed of various polyesters: Their syntheses,thermal properties,and application to block copolymerization

Various aliphatic polyesters such as poly (ethyleneadipate), poly (tetramethylene adipate), poly (caprolactone), and poly (carbonate) were condensed with 4,4'-azobis-4-cyanopentanoyl chloride to prepare macro-azo-initiators. Their thermal properties, observed by differential scanning calorimetry, showed similar decomposition behavior to each other. Block copolymers containing each of these polyesters as a block segment combined with polystyrene or poly (methylmethacrylate) have been derived by the polymerization of monomers initiated with these macro-azo-initiators. © 1994 John Wiley & Sons, Inc.     

Mechanism of high thermal stability of commercial polyesters and polyethers conjugated with bio‐based caffeic acid

In previous report, we discovered that a novel improvement technique to enhance the thermal properties of poly(L ‐lactide)s (PLLAs) by terminal conjugation with 3,4‐diacetoxycinnamic acid (DACA). In this study, we clarified the mechanism of the enhancement of thermal stability by using commercial polyesters and polyethers. The effect of thermal improvement by the terminal conjugation of DACA on poly(DL ‐lactide), poly(ε‐caprolactone), and poly(ethylene glycol) was almost the same as about 100 °C increase. The amount of residual tin catalyst, which enhances the thermal degradation of polyesters, was reduced at undetected level after the terminal conjugation of DACA probably due to the removal of tin during DACA conjugation process. Furthermore, the π‐π stacking interactions of DACA units and the chemical protection of terminal hydroxyl groups, which enhances intramolecular scission, were also important for the high thermal stability. We clarified that the extreme high thermal stability by DACA conjugation was induced by these above mechanisms. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis and hydrolytic degradation of poly (glycerol succinate) based polyesters

The limited availability of petroleum resources motivates the research towards value-added products production from bio-resources. This study reports the synthesis of glycerol and succinic acid-based polyesters and their detailed characterization. The modification of poly (glycerol succinate) was done by using other diacids like glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid. The sysnthesized polyesters were characterized using various techniques such as thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), Nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). The addition of different dicarboxylic acids to poly (glycerol succinate) based co-polyesters increased the thermal stability of poly (Glycerol succinate). Glass transition temperatures were obtained in the range of ?17.2 to ?22.5 °C and it increased with chain length. The progress of reaction was monitored by determining acid number, ester number, and degree of esterification. The hydrolytic degradation of polyesters was carried out in acidic and basic medium. The polyesters was found to degrade under basic conditions whereas no weight loss of poly (glycerol succinate) was found under acidic conditions. Particularly, about 40% of poly (glycerol succinate) was degraded within 24 h under basic conditions (pH = 12). The analysis of morphology of polyesters during degradation showed that the increase in hydrolysis time increased the heterogeneity in polyester matrix.     

Effects of residual metal compounds and chain-end structure on thermal degradation of poly(3-hydroxybutyric acid)

Thermal degradation behaviours of poly(3-hydroxybutyric acid) (P(3HB); bacterial poly[(R)-3-hydroxybutyric acid] and synthetic poly[(R,S)-3-hydroxybutyric acid] samples, were examined under both isothermal and non-isothermal conditions. The inverse of number-average degree of polymerisation for all P(3HB) samples decreased linearly with degradation time during the initial stage of isothermal degradation at a temperature ranging from 170-190 °C. In addition, crotonyl unit was detected in the residual polymer samples as main ω-chain-end. These results indicate that the dominant thermal degradation reaction for P(3HB) is a random chain scission via cis-elimination reaction of P(3HB) molecules. It was found that the presence of either Ca or Mg ions enhances the depolymerisation of P(3HB) molecules, while that Zn ions hardly catalyse the reaction. As a result, a shift of thermogravimetric curves toward the lower temperature regions was observed for the P(3HB) samples containing high amounts of Ca and Mg compounds.     

A review on thermal decomposition and combustion of thermoplastic polyesters

An overview is presented of the literature on the thermal decomposition and combustion of thermoplastic polyesters, especially commercially important poly(ethylene terephthalate) (PET) and poly(1,4‐butylene terephthalate) (PBT). Although the literature is not clear as to whether heterolytic or homolytic scission of aliphatic fragments is the first step in the thermal decomposition of polyesters, in any case volatilization of light aliphatic fragments make polyesters easily ignitable polymers. Despite the presence of benzene groups in the main polymer chain, thermoplastic polyesters show very limited tendency to char, but instead, aromatic‐containing polymer fragments volatilize and feed the flame. Fire retardant additives, although they usually facilitate decomposition of the polyesters at lower temperature, also usually promote charring and therefore suppress combustion. Copyright © 2004 John Wiley & Sons, Ltd.     

Influence of ozone treatment on structure and thermal properties of bis-2-hydroxyethyl terephthalate-based copolymers

Polyesters are a particularly interesting group of polymers because of their ester bonds in the main chain, which are sensitive to degradation. It has been shown that aromatic polyesters [eg. poly(ethylene terephthalate) (PET)] can be degraded when they are copolymerized with aliphatic polyesters. In this regard, the objective of our previous study was to obtain and investigate new copolymers with some fragments of PET and its hydrolytic degradation. In this work, the impact of ozone degradation on properties of bis-2-hydroxyethyl terephthalate-based copolymers was researched. Apart from the bis-2-hydroxyethyl terephthalate, the copolymers comprised oligomers of lactic acid and glycolic acid in different combination. During ozone degradation, samples were kept for 24 h in atmosphere containing 0.51 vol.% of ozone. Structure changes were determined by means of FTIR spectroscopy. In the IR spectra of ozonised samples, new bonds characteristic for ozonised polymers were observed. Thermal properties of copolymers before and after degradation process were reviewed based on differential scanning calorimetry (DSC) and thermogravimetry. DSC results revealed that melting point increased, especially for copolymers displaying higher quantity of PET units.     

Degradation of aliphatic and aliphatic–aromatic co-polyesters by depolymerases from Roseateles depolymerans strain TB-87 and analysis of degradation products by LC-MS

The degradation activities of bacterium, Roseateles depolymerans TB-87 and its depolymerases Est-H and Est-L against aliphatic as well as aliphatic–aromatic co-polyesters, were investigated. Strain TB-87 and its enzymes exhibited an ability to degrade aliphatic and aliphatic–aromatic co-polyesters. Monomers produced as a result of degradation of aliphatic polyesters [poly(butylene succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA)] as well as aliphatic–aromatic co-polyester [poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL) by depolymerases Est-H and Est-L were investigated by liquid chromatography mass-spectrometry (LC-MS). Some common monomers like succinic acid and 1,4-butanediol were detected besides adipic acid and terephthalic/isophthalic acids as degradation products from PBSA and PBSTIL, respectively, whereas lactic acid was not detected. The succinic acid monomer was detected prior to adipic acid as a result of degradation of PBSA. The enzymes depolymerized PBS also into respective monomers. The analysis of PBSTIL degradation products revealed that enzymes easily degraded aliphatic segments as compared to aromatic segments and resulted in production of succinic acid prior to terephthalic and isophthalic acid. On the basis of these results, we speculate that both the enzymes Est-H and Est-L, attacked succinic acid segments (BS) first instead of adipic acid (BA) and terephthalic/isophthalic acid (BT or BI) segments of PBSA and PBSTIL, respectively. It is concluded from the results that R. depolymerans strain TB-87 can depolymerize aliphatic as well as aliphatic–aromatic co-polyesters; therefore, its enzymes can be applied in the process of biochemical monomer recycling.     

Synthesis,thermal, rheological characteristics,and enzymatic degradation of aliphatic polyesters with lignin‐based aromatic pendant groups

This research aims to produce lignin‐based biodegradable polyesters with improved thermal quality. A series of aliphatic polyesters with lignin‐based aromatic side groups were synthesized by conventional melt‐polycondensation. Decent molecular weight (21–64 kg mol^?1) was achieved for the polymerizations. The molecular structures and thermal and mechanical properties of the obtained polyesters were characterized. As a result, the obtained polyesters are all amorphous, and their glass‐transition temperature (T_g) depends on the size of the pendant aromatic group (31–51 °C). Furthermore, according to the TGA results, the thermal decomposition temperatures of the polyesters are all above 390 °C, which make them superior compared with commercial biodegradable polyesters like polylactic acid or polyhydroxyalkanoates. Finally, rheological characteristics and enzymatic degradation of the obtained polyesters were also measured. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2314–2323     

Preparation and structure/property relationships of polyesters containing conjugated diacetylene groups

A series of novel polyesters containing conjugated diacetylenes (DA‐polyesters) were prepared from various diacetylene diols with/without methyl side groups and isomers of aromatic acid chlorides via an interfacial condensation. A fully aliphatic DA‐polyester was also prepared for comparison. All synthesised DA‐polyesters are soluble in m‐cresol, and the intrinsic viscosities were measured. In addition, compact and coherent films and sheets can be obtained from some of the polymers via solution or melt casting. The structure, morphology, and properties were characterized using spectroscopic methods, including FTIR, Raman, and WAXD and thermal analysis including TGA, DSC techniques. DMA was carried out on the solution‐cast thin films and melt‐processed samples. Close correlation was found between the structure and properties in these DA‐polyesters. In particular, through analysis using isothermal DSC and Raman spectroscopy, the solid‐state reactivity of the diacetylene groups in these polyesters was found related to the interchain spacings, which are, in turn, controlled by the molecular structure of the polymers. Results have shown that the aliphatic DA‐polyester behaves very differently compared to the aromatic ones. Distinct differences were also observed among meta‐ and para‐disubstituted isomers of the DA‐polyesters. Furthermore, the introduction of methyl side groups has dramatically affected the thermal and thermal mechanical behavior by altering the interchain spacing of the polymers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 965–974, 1999