Graphene oxide induced hydrolytic degradation behavior changes of poly(l-lactide) in different mediums

Graphene oxide (GO) has been widely used in polymer-based composites due to their promising properties originated from the two-dimensional platelet-like structure and a large number of oxygen-containing groups, including reinforcement effect, nucleation effect, barrier effect, etc. In this work, GO was introduced into poly(l-lactide) (PLLA) and the main attention was focused on investigating the effect of GO on hydrolytic degradation behavior of PLLA. The hydrolytic degradation measurements were carried out in three different mediums, including alkaline solution with a pH value of 12, acidic solution with the pH value of 2 and deionized water with the pH value of 7. It was demonstrated that in all mediums, the hydrolytic degradation of PLLA was greatly accelerated by adding GO and specifically, the more the GO in the composites, the more apparent the acceleration effect of the hydrolytic degradation was, furthermore, GO didn't change the hydrolytic degradation mechanisms of the PLLA matrix in all mediums. The microstructure evolution of the PLLA matrix during the hydrolytic degradation process was also comparatively investigated. The results demonstrated that crystallization occurred during the hydrolytic degradation process and the crystallization of the composites was also greatly promoted by GO. This work provides valuable information for the application and reclamation of the PLLA/GO composites.     

Greatly enhanced hydrolytic degradation ability of poly(L-lactide) achieved by adding poly(ethylene glycol)

Plasticized poly(L-lactide)(PLLA) materials have been applied in many fields and the microstructure performance of such materials attracts much attention of researchers. However, few reports declared the hydrolytic degradation ability of the plasticized PLLA materials. In this article, a small quantity of poly(ethylene glycol)(PEG) was introduced into PLLA, which aimed to understand the hydrolytic degradation behavior of the plasticized PLLA materials. The microstructures of the plasticized samples were comparatively investigated using scanning electron microscopy(SEM), wide angle X-ray diffraction(WAXD), differential scanning calorimetry(DSC) and Flourier transform infrared spectroscopy(FTIR), etc. The results demonstrated that PEG improved the hydrophilicity of sample surface, and the relatively high content of PEG enhanced the crystallization ability of PLLA matrix. The hydrolytic degradation measurement was carried out at 60 ℃ in an alkaline solution of pH = 12. The results demonstrated that the plasticized PLLA samples exhibited accelerated hydrolytic degradation compared with the pure PLLA sample, and the hydrolytic degradation was also dependent on the PEG content. Further results demonstrated that PEG induced the change of hydrolytic degradation mechanism possibly due to the good dissolution ability of PEG in water, which provided more paths for the penetration of water. Furthermore, the microstructure evolution of the plasticized PLLA during the hydrolytic degradation process was also investigated, and the results demonstrated the occurrence of PLLA crystallization, which was possibly contributed to the decreased hydrolytic degradation rate observed at relatively long hydrolytic degradation time. This work is of great significance and may open a new way for promoting the reclamation of PLLA waste material.     

Synthesis and hydrolytic degradation of poly(ethylene succinate) and poly(ethylene terephthalate) copolymers

The conditions of synthesis of statistical poly(ethylene succinate-co-terephthalate) copolymers (2GTS) and high molecular weight poly(ethylene succinate) (PES) with good hydrolytic and optical parameters, designed for the production of biodegradable products and resins, are presented in this article. Copolymers were prepared by melt polycondensation of bis-(β-hydroxyethylene terephthalate) (BHET) and succinic acid (SA) with excess of ethylene glycol (2G) in the presence of a novel titanium/silicate catalyst (C-94) and catalytic grade of germanium dioxide (GeO₂) as cocatalyst. The chemical structure and physical properties of those materials were characterized by ¹H NMR, FT-IR, dynamical-mechanical thermal analyses (DMTA), differential scanning calorimetry (DSC), solution viscosity and spectroscopic methods. The hydrolytic degradation was performed in a water solution with variable pH, also in garden soil and in compost. The highest hydrolytic degradation rate was observed for pH 4 and for compost. Better hydrolytic degradation values in compost medium were observed for copolyester prepared in the presence of GeO₂ as polycondensation cocatalyst. The copolyester with 40 mol% of aliphatic units was chosen for industrial syntheses which were performed in ELANA and subsequently the processing parameters and compatibility with potato starch of this polyester were checked by BIOP Biopolymer Technologies AG.     

Biodegradable liquid crystalline aromatic/aliphatic copolyesters. Part I: Synthesis, characterization, and hydrolytic degradation of poly(butylene succinate-co-butylene terephthaloyldioxy dibenzoates)

To increase the thermal and mechanical properties of the aliphatic polyester poly(butylene succinate) (PBS), a series of potentially biodegradable liquid crystalline aromatic/aliphatic random copolyesters were prepared by melt polycondensation of new mesogenic monomers dimethyl 4,4′-(terephthaloyldioxy) dibenzoate (MTB), dimethyl succinate, and 1,4-butanediol. The synthesized copolyesters were characterized by means of proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), viscosity measurements, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction (XRD), polarizing light microscopy (PLM) and mechanical property measurements. The MTB content was varied so that the effects of the mesogen content on the thermal and mechanical properties, degradable behaviours and mesophase were examined. It was found that introducing the rigid rod mesogens could increase the thermal stability and the mechanical properties, while it reduced the melting temperature (T_m), the crystallization temperature (T_c), the degree of relative crystallinity (X_c) and the hydrolytic degradation rate. Only the homopolyester poly(butylenes terephthaloyldioxy dibenzoates) was able to show the schlieren texture characteristic of nematics.     

Thermal degradation mechanism of poly(ethylene succinate) and poly(butylene succinate): Comparative study

Two aliphatic polyesters that consisted from succinic acid, ethylene glycol and butylene glycol, —poly(ethylene succinate) (PESu) and poly(butylene succinate) (PBSu)—, were prepared by melt polycondensation process in a glass batch reactor. These polyesters were characterized by DSC, ¹H NMR and molecular weight distribution. Their number average molecular weight is almost identical in both polyesters, close to 7000 g/mol, as well as their carboxyl end groups (80 eq/10⁶ g). From TG and Differential TG (DTG) thermograms it was found that the decomposition step appears at a temperature 399 °C for PBSu and 413 °C for PESu. This is an indication that PESu is more stable than PBSu and that chemical structure plays an important role in the thermal decomposition process. In both polyesters degradation takes place in two stages, the first that corresponds to a very small mass loss, and the second at elevated temperatures being the main degradation stage. The two stages are attributed to different decomposition mechanisms as is verified from the values of activation energy determined with iso-conversional methods of Ozawa, Flyn, Wall and Friedman. The first mechanism that takes place at low temperatures, is auto-catalysis with activation energy E = 128 and E = 182 kJ/mol and reaction order n = 0.75 and 1.84 for PBSu and PESu, respectively. The second mechanism is nth-order reaction with E = 189 and 256 kJ/mol and reaction order n = 0.68 and 0.96 for PBSu and PESu, respectively, as they were calculated from the fitting of experimental results.     

Preparation, characterization and hydrolytic degradation of poly[p-dioxanone-(butylene succinate)] multiblockcopolymer

A series of poly[p-dioxanone-(butylene succinate)] (PPDOBS) copolymers were prepared from p-dioxanone (PDO), 1,4-butanediol and succinate acids through a two-step process including the initial prepolymer preparation of poly(p-dioxanone)diol (PPDO-OH) and poly(butylene succinate)diol (PBS-OH) and the following copolymerization of the two kinds of prepolymers by coupling with hexamethylene diisocyanate (HDI). The molecular structures of the prepared PPDO-OH, PBS-OH and PPDOBS were characterized by hydrogen nuclear magnetic resonance spectroscopy (¹H NMR). The crystallization of the copolymers was investigated by using differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide angle X-ray diffraction (WAXD). It has been shown that the crystallization rate and the degree of crystallization increases with the increase of the weight fraction of poly(butylene succinate) (PBS) blocks in the copolymers. In phosphate buffer solution with pH 7.4 at 37 °C for 18 weeks, the hydrolytic degradation behaviors of the copolymers were studied. The changes of retention weight, water absorption, pH value, and surface morphologies with the degradation time showed that the hydrolytic degradation rate of PPDOBS could be controlled by adjusting the weight fraction of poly(p-dioxanone) (PPDO) and PBS blocks in the copolymers. The changes of the thermal properties of PPDOBS during the degradation were also investigated by DSC.     

Morphological behaviour of poly(lactic acid) during hydrolytic degradation

The hydrolytic degradation and the morphological behaviour of a packaging grade of poly(lactic acid) (PLA) were characterized by a series of techniques. During the initial degradation process (stage 1) at a temperature near the glass transition temperature (T_g), the molecular weight of PLA decreased as degradation time increased following a bulk erosion mechanism while the crystallinity increased simultaneously, but no observable weight loss occurred at stage 1. Mainly α-form PLA crystal structure was formed for the crystalline PLA with a low content of d stereo-isomers, but the material displayed a lower regularity, smaller domain size, lower melting temperatures T_m and different motional dynamics as compared to the original PLA with a similar level of crystallinity achieved by annealing. The amorphous PLA with a higher amount of d stereo-isomers also yielded the α crystalline phase as well as stereo-complex crystals at stage 1. When the molecular weight and the crystallinity reached a stable level, PLA started erosion into the degrading aqueous medium. During this stage of degradation (stage 2), the crystalline structure in PLA residues was further modified and both pH and temperature influenced the modification. The degradation at stage 2 was likely to follow a surface erosion mechanism with lactic acid as the major product of the weight loss. Besides the crystallinity effect on the degradation, temperature also played a key role in determining the rate of PLA degradation in both stages. The process was very slow at temperatures below the T_g of PLA but the rate was greatly enhanced at temperatures above the T_g.     

PMMA对聚氧乙烯β转变的影响

对半结晶聚氧乙烯（PEO)/PMMA共混体系的DSC及动态力学行为研究表明：PEO在和PMMA形成半结晶PEO/PMMA共混体系后，其β转变的峰温没有明显移动；β峰只出现在淬炎的半结晶PEO/PMMA共混体系中，而在完全非晶的相容性共混体系以及退火的半结晶共混体系不出现；在β转变区，对应的模量反常地增大，对应的DSC曲线有明显阶跃。可见，半结晶PEO的β转变并不象通常所认为的源于PEO非晶区的玻璃化转变。在接受半结晶PEO及半结晶PEO/PMMA共混体系的PEO结晶区存在结晶-非晶中间相观点的基础上，认为β转变源于PEO结晶区结晶-非晶中间相的玻璃化转变过程。     

Hydrolytic Degradation and Monomer Recovery of Poly(butylene succinate) and Poly(butylene succinate/adipate) in the Melt

Aliphatic dicarboxylic acid/aliphatic diol‐derived polyesters, poly(butylene succinate) and poly(butylene succinate/adipate), have been hydrolytically degraded in the melt in high‐temperature and high‐pressure water over a wide temperature range of 180–300 °C for periods of up to 30 min. The formation/decomposition of succinic acid (SA), adipic acid (AA), and butane‐1,4‐diol (BD), plus the molecular weight change of PBS and PBSA were then investigated. SA and AA were recovered at maximum yields of 65–80%, whereas BD was recovered at a maximum yield of only 30%, probably because of its decomposition. The obtained results were compared with those reported for aliphatic hydroxycarboxylic acid‐derived polyesters and aromatic dicarboxylic acid/aliphatic diol‐derived polyesters.

     

Effect of microstructure on hydrolytic degradation studies of poly (l-lactic acid) by FTIR spectroscopy and differential scanning calorimetry

Structural changes during thermally induced crystallization and alkaline hydrolysis of Poly(l-lactic acid) (PLLA) films were investigated using differential scanning calorimetry (DSC), FTIR spectroscopy, weight loss, HPLC and optical microscopy. It was shown that crystallinity (χ_c), glass transition temperature (T_g) and melting temperature (T_m) were found to be strongly annealing temperature (T_a) dependent. The FTIR study of PLLA films suggested that the bands at 921 and 956 cm⁻¹ could be used to monitor the structural changes of PLLA. An independent infrared spectroscopic method was developed for the first time to determine crystallinity of PLLA before degradation and it showed good qualitative correlation with DSC crystallinity. The higher crystallinity values determined by FTIR were attributed to the intermediate phase included in the IR crystallinity. Both the weight loss data and the percentage of lactic acid obtained by HPLC showed that the alkaline hydrolysis of PLLA films increased with increasing crystallinity. The DSC observation showed an increase in T_g and no significant change in T_m and heat of fusion, while IR showed an increase in IR crystallinity with increasing hydrolysis time. The increase in IR crystallinity and T_g with hydrolysis time suggested that degradation progressed from the edges of the crystalline lamellas without decreasing lamellar thickness, but increased the intermediate phase and the short-range order.     

Studies on hydrolytic degradation of poly(ester-anhydride)s based on oligosuccinate and aliphatic diacids

This paper describes synthesis, characteristics and hydrolytic degradation of functional poly(ester-anhydride)s based on oligo(3-allyloxy-1,2-propylene succinate) (OSAGE) and aliphatic diacids (DA). The polymers were obtained by polycondensation of OSAGE with adipic (ADP), sebacic (SBA) or dodecanedicarboxylic acid (DDC). The carboxyl groups in OSAGE and in diacids were converted to mixed anhydride groups by acetylation with acetic anhydride. After that, prepolymers thus obtained were condensed in vacuum to yield poly(ester-anhydride)s. The structure of copolymers was confirmed by NMR spectroscopy. Influence of the kind of diacid and the OSAGE to diacid ratio on selected properties of poly(ester-anhydride)s were examined. Poly(ester-anhydride)s were subjected to hydrolytic degradation at 37 °C, in aqueous phosphate buffer solution of pH 7.41 (PBS). The course of degradation was monitored by determination of weight loss of samples, ¹H NMR and DSC. Fracture surfaces of samples during degradation were examined by scanning electron microscopy.     

Non-isothermal depolymerisation kinetics of poly(ethylene oxide)

The depolymerisation of low molecular weight poly(ethylene oxide) (PEO) under mild conditions was studied using a linear temperature ramped non-isothermal technique and the results compared with those obtained from a conventional isothermal technique. The analysis of the non-isothermal kinetic (NIK) data was performed using an original computer program incorporating an algorithm that systematically minimizes the sum of the squares of the residuals between the experimental data and the calculated theoretical kinetic profile in order to extract the kinetic parameters. The results revealed that the depolymerisation of PEO proceeds in accordance with the Ekenstam model and follows the Arrhenius equation over the temperature range of ca. 40-130 °C. The NIK analysis resulted in a two-dimensional convergence to produce a unique solution set for the kinetic parameters of E_a = 89.4 kJ mol⁻¹ and A = 9.6 × 10⁶ h⁻¹. These data are consistent with the results obtained from the isothermal experiments. It is proposed that NIK analysis is a quick and reliable means of obtaining kinetic parameters relevant to lifetime predictions in polymers whose degradation behaviour can be considered to be close to ideal.     

Crystallization,thermal behavior,and compatibility of poly(ethylene oxide)/poly(propylene oxide) blends

Isothermal and nonisothermal crystallization kinetics of different poly(ethylene oxide)/poly(propylene oxide) blends were investigated by means of differential scanning calorimetry (DSC). Glass transition temperature of quenched samples have also been reported. Phase morphologies and poly(ethylene oxide) spherulite growth rates were analyzed by polarizing light transmission microscopy. Results show morphological changes along with regime transitions of poly(ethylene oxide) crystal growth. Kinetic analyses of the data suggest that, although the blend behaves as a noncompatible, phase-separated system, there exists a certain degree of interaction between polymer chains. © 1996 John Wiley & Sons, Inc.     

Effect of temperature and nanoparticle type on hydrolytic degradation of poly(lactic acid) nanocomposites

PLA and its nanocomposite films based on modified montmorillonite (CLO30B) or fluorohectorite (SOM MEE) and unmodified sepiolite (SEPS9) were processed at a clay loading of 5 wt% and hydrolytically degraded at 37 and 58 °C in a pH 7.0 phosphate-buffered solution. An effective hydrolytic degradation for neat PLA and nanocomposites was obtained at both temperatures of degradation, with higher extent at 58 °C due to more extensive micro-structural changes and molecular rearrangements, allowing a higher water absorption into the polymer matrix.The addition of CLO30B and SEPS9 delayed the degradation of PLA at 37 °C due to their inducing PLA crystallization effect and/or to their high water uptake reducing the amount of water available for polymer matrix hydrolysis. The presence of SOM MEE also induced polymer crystallization, but it was also found to catalyze hydrolysis of PLA. Concerning hydrolysis at 58 °C, the presence of any nanoparticle did not significantly affect the degradation trend of PLA, achieving similar molecular weight decreases for all the studied materials. This was related to the easy access of water molecules to the bulk material at this temperature, minimizing the effect of polymer crystallinity clay nature and aspect ratio on the polymer degradation.     

Porous thermosets via hydrolytic degradation of poly(ε-caprolactone) fragments in cyanurate-based hybrid networks

New nanoporous film thermosets were developed from polycyanurates (PCNs) obtained by polycyclotrimerization of dicyanate ester of bisphenol E in the presence of hydrolytically labile poly(ε-caprolactone) (PCL). During the synthesis of PCL-modified PCN networks, it was established that PCL was partially incorporated into the PCN structure. Porous frameworks were then derived from such PCN/PCL-based hybrid networks by selective hydrolysis of a significant part of PCL sub-chains under mild conditions. The structure and properties of the precursory networks as investigated by FTIR, solid-state ¹³C NMR, DSC, TGA, and pycnometry were compared to those of the resulting porous materials. Thermogravimetric analyses showed that the porous hybrid systems were characterized by thermal and thermal oxidative stabilities higher than those of their non-hydrolyzed homologues. The porosity of the resulting hydrolyzed networks was examined by SEM and DSC-thermoporometry: pore sizes ranging from 10 to 150 nm - at most - were thus determined.     

Hydrolytic degradation behavior of poly(l-lactide)/SiO2 composites

In this work, different contents of nano-silica (SiO₂) particles were introduced into poly(l-lactide) (PLLA) to prepare PLLA/SiO₂ composites though a two-step compounding method, i.e. solution compounding (preparing master batch) and subsequent melt compounding (master batch dilution). The dispersion of SiO₂ was characterized using scanning electron microscope (SEM). The hydrophilicity of the material was evaluated by measuring the contact angle of water on the sample surface. The hydrolytic degradation measurements of the nanocomposites were carried out in alkaline solution at two different temperatures, i.e. 37 and 55 °C. Subsequently, microstructure evolution of PLLA matrix during the hydrolytic degradation process was systematically investigated using wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). The results showed that SiO₂ had good dispersion in the PLLA matrix. Largely enhanced hydrolytic degradation ability was achieved for PLLA/SiO₂ composites. Increasing the content of SiO₂ or enhancing the hydrolytic degradation temperature accelerated the hydrolytic degradation of PLLA matrix. Further results showed that SiO₂ promoted the reorganization of microstructure of PLLLA matrix during the hydrolytic degradation process.     

Melting behavior of poly(butylene succinate) during heating scan by DSC

The melting behavior of isothermally crystallized poly(butylene succinate) (PBS) has been investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray analysis. The samples crystallized between 80°C to 100°C show middle endotherm at the position just before the high exotherm, while the others under 80°C show two endotherms (low and high). From the results of the melting peak vs. crystallization temperature plot, it was suggested that the middle endotherm corresponds to the melting process of the original crystallites and the high endotherms to the melting process of the recrystallized ones. As the DSC heating rate was increased, the peak temperature of the low and middle endotherms increased and that of the high endotherm decreased, indicating that the low endotherm was due to the original crystallites as well as the middle endotherm. Consequently, in the heating scan of PBS, the existence of two kinds of morphologically different crystallites as well as the process of melting and recrystallization becomes evident. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1357–1366, 1999     

Poly[(methylene oxide) oligo(ethylene oxide)] vs. poly(ethylene oxide) as hosts for neodymium compounds

In view of the residual crystallinity in PEO found to limit the solubility of some Nd³⁺-compounds, amorphous PEO (aPEO) was synthesized for exploration as an alternative host. Complexation, solubility limit, morphology, and response to moisture absorption in the doped systems were investigated using FTIR, DSC, TGA, and WAXD techniques. Representing a perturbation to the structural regularity present in PEO, aPEO was found to present lower solubilities for dopants (Nd(act)₃ and Nd(acac)₃, both characterized by a weak Nd³⁺–ether oxygen interaction. On the other hand, no difference in solubility was observed for dopant Nd(NO₃)₃, characterized by a strong Nd³⁺–ether oxygen interaction. Laser interferometry was employed to assess film homogeneity of the Nd(NO₃)₃-doped systems across a 20-mm diameter, and the measured peak-to-valley distortion values were observed to be encouraging for practical applications. © 1994 John Wiley & Sons, Inc.     

Multiple melting behavior of poly(butylene succinate)

The multiple melting behavior of poly(butylenes succinate) (PBS) isothermally crystallized from the melt was investigated using differential scanning calorimetry (DSC), temperature modulated DSC (MDSC) and polarized optical microscopy. PBS exhibits at most four melting endotherms (denoted as T_m1, T_m2, T_m3, and T_m4 from high to low temperatures) and a crystallization exotherm (denoted as T_re) in the DSC heating trace. Multiple melting endotherms were observed even at high heating rates. The origins of each endothermal and exothermal peak were discussed in detail. It is suggested that: (i) the crystallization exothermic peak, T_re, relates to the recrystallization of the melt of the crystallites with lower thermal stability; (ii) the T_m1 is ascribed to the melting of crystallites formed through recrystallization; (iii) two crystal populations with different thermal stability are responsible for the T_m2 and T_m3; (iv) the T_m4, which is the annealing peak, represents the transition of the rigid amorphous fraction (RAF) from solid-like RAF into liquid-like amorphous fraction.     

Fungal degradation of poly(ethylene succinate)

Twenty fungi, which all formed a clear zone around the colony on a poly(ethylene succinate) (PESu)-containing medium, were isolated from various environmental samples. Mesophilic strain NKCM1003, with the highest PESu hydrolytic activity among all the isolates, degraded a PESu film at the rate of 21 ± 2 μg/cm²/h when it was aerobically incubated at 30 °C on a medium containing PESu as the sole carbon source. SEM observations showed that the strain gradually degraded the film starting from the amorphous regions of the surface. Phylogenetic analysis revealed that the strain was closely related to the species Aspergillus clavatus. Zymogram analysis suggested that the secreted enzyme with PESu hydrolytic activity is a P(3HB) depolymerase. The strain also utilized the enzymatic products of PESu, permitting it to grow well. These results indicate that the strain NKCM1003 plays an important role in the PESu-degrading process in the field.