Enzymatic Degradation of Poly(l-Lactic Acid): Effects of UV Irradiation

Amorphous and crystallized poly(l-lactic acid) (PLLA-A and PLLA-C, respectively) films were prepared, and the proteinase K-catalyzed enzymatic degradation of UV-irradiated and non-irradiated PLLA-A and PLLA-C films was investigated for periods up to 10 h (PLLA-A) and 60 h (PLLA-C). The molecular weights of both the PLLA-A and PLLA-C films can be manipulated by altering the UV irradiation time. The enzymatic weight loss values of the UV-irradiated PLLA films were higher than or similar to those of the non-irradiated PLLA film, when compared with the specimens of same crystallinities. UV irradiation is expected to cause the PLLA films to undergo chain cleavage (a decrease in molecular weight) and the formation of C=C double bonds. It seems that the acceleration effects from decreased molecular weight on enzymatic degradation were higher than or balanced with the disturbance effects caused by the formation of C=C double bonds. After enzymatic degradation, a fibrous structure appeared on the spherulites of the UV-irradiated PLLA-C film. This structure may have arisen from chains containing or neighboring on the C=C double bonds, which were enzymatically undegraded and assembled on the film surface during enzymatic degradation. The results of this study strongly suggest that UV irradiation will significantly affect the biodegradation behavior of PLLA materials in the environment.     

Photodegradation of Poly(lactic acid) Stereocomplex by UV-Irradiation

Neat poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) films and PLLA/PDLA blend films were prepared by solution casting, and their photodegradation by UV-irradiation was investigated using wide-angle X-ray scattering (WAXS), gel permeation chromatography, differential scanning calorimetry, tensile testing, and polarized optical microscopy. The PLLA/PDLA blend film was more photodegradation-resistant than the neat PLLA and PDLA films when photodegradation was monitored by molecular weight, melting temperature, and WAXS crystalline peak positions. This indicates that the chains in both amorphous and crystalline regions of the PLLA/PDLA blend film were photo-cleavage-resistant compared to those of the neat PLLA and PDLA films. The changes in melting temperature and WAXS crystalline peak positions before and after photodegradation respectively indicated the increased crystalline lattice disorder and the decreased crystalline lattice sizes of the neat PLLA and PDLA films, whereas these changes were insignificant for the blend films. Photodegradation caused no significant change in tensile properties, with the exception of significant decreases in the tensile strength and elongation at break of PLLA/PDLA blend film. However, the tensile strength and elongation at break of the PLLA/PDLA blend film retained higher values compared to those of the neat PLLA and PDLA films during photodegradation. In spite of the slower photodegradation of the PLLA/PDLA blend film traced by M _n, T _m, and WAXS crystalline peak positions than that of neat PLLA and PDLA films, the rapid decrease in tensile strength and elongation at break of the former than that of the latter should be due to the highly-ordered structural difference between them, i.e., the three dimensional dry gel of the former and the spherulites of the latter.     

The Effect of Nanoclays on the Properties of PLLA-modified Polymers Part 1: Mechanical and Thermal Properties

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.     

Preparation and Optimization of Starch/Poly Vinyl Alcohol/ZnO Nanocomposite Films Applicable for Food Packaging

Pollution and destruction of the environment due to the accumulation of non-degradable plastics are some of the most important concerns in the world. A significant amount of this waste is related to the polymers used in food packaging. Therefore, experts in the food industry have been looking for suitable biodegradable alternatives to synthetic polymers. Preparing biocompatible and biodegradable films based on starch is a good choice. In this study, various factors affecting films of starch/polyvinyl alcohol (PVA)/containing ZnO nanoparticles such as the amount of starch, PVA, glycerol, and ZnO were evaluated by response surface methodology (RSM). Film formation by solvent casting method, mechanical properties, swelling, solubility, and water vapor permeability (WVP) were selected as responses of RSM. The results showed that hydrogen bonding interactions between polyvinyl alcohol and starch improved the film formation. The effect of glycerol and PVA content on the mechanical strength was contrary to each other. As the amount of PVA increased, the tensile strength first decreased and then increased. The value of WVP was for all Runs from 0 to 6.77?×?10^??8 g m^??1 s^??1 Pa^??1. Finally, films with high film formation, maximum tensile strength, and high elongation at break, minimum solubility, permeability, and swelling were optimized.

     

Improvement of Physico-Mechanical Properties of Photo-Cured Chitosan Films with Ethylene Glycol Dimethacrylate and (2-Hydroxyethyl) Methacrylate

Chitosan, a natural polymer, was prepared by deacetylation of chitin which was obtained from dried prawn shell and was characterized. Thin chitosan film of chitosan was prepared by casting method from 0.2 % chitosan in 2 % acetic acid solution. Five formulations were developed with ethylene glycol dimethacrylate and (2-hydroxyethyl) methacrylate along with photo-initiator, Darocur-1664 (4 %). The chitosan film was soaked in the formulations at different soaking times and irradiated under UV-radiation at different intensities for the improvement of its physical and mechanical properties. The cured chitosan films were then subjected to various mechano-chemical tests like tensile strength, elongation at break, polymer loading, water absorption and gel content. The formulation containing 30 % ethylene glycol dimethacrylate and 66 % (2-hydroxyethyl) methacrylate showed the best performance at the 30th UV pass of UV-radiation for 3 min soaking time.     

Feasibility study of the separation of chlorinated films from plastic packaging wastes

This study describes the possible separation of chlorinated plastic films (PVC and PVDC) from other heavy plastic packaging waste (PPW) by selective twist formation and gravity separation. Twists formation was mechanically induced in chlorinated plastic films, whereas twist formation did not occur in PS and PET films. After twist formation, all the films had the apparent density of less than 1.0 g/cm³ and floated in water even though the true density was more than 1.0 g/cm³. However, the apparent density of the PS and the PET films increased with agitation to more than 1.0 g/cm³, whereas that of chlorinated plastic films was kept less than 1.0 g/cm³. The main reason would be the air being held inside the chlorinated plastic films which was difficult to be removed by agitation. Simple gravity separation after twist formation was applied for artificial film with 10 wt.% of the chlorinated films and real PPW films with 9 wt.% of the chlorinated films. About 76 wt.% of the artificial PPW films and 75 wt.% of real PPW films after the removal of PP and PE were recovered as settling fraction with 4.7 wt.% and 3.0 wt.% of chlorinated plastic films, respectively. These results indicate that simple gravity separation process after twist formation can be used to reduce the chlorinated plastic concentration from mixed heavy PPW films.     

The Effect of Polymeric Chain Extenders on Physical Properties of Thermoplastic Starch and Polylactic Acid Blends

The effects of a polymeric chain extender on the properties of bioplastic film made from blends of plasticized polylactic acid (p-PLA) and thermoplastic starch (TPS) were studied. Joncryl^? ADR 4370S, a polymeric chain extender, was blended with TPS and p-PLA at a level of 1% (w/w). A co-rotating twin-screw extrusion process was used to prepare films with various ratios of TPS and p-PLA. Mechanical and physical properties of films, including film tensile properties, surface energy, moisture content, hydrophilicity, moisture sorption behaviour and thermal mechanical properties were determined. During extrusion, films enhanced by 1% Joncryl addition demonstrated more desirable and consistent qualities, such as smoother film edge and surface. Addition of Joncryl significantly improved film tensile strength, 0.2% offset yield strength, and elongation, especially evident with the 250% elongation of 70/30 (TPS/p-PLA) film. Total surface energy of films was not significantly influenced by addition of Joncryl. However, the polar contribution to the total surface energy of 70/30 (TPS/p-PLA) film increased after the addition of Joncryl. The study showed that blending TPS with p-PLA transformed TPS film from being highly hydrophilic to highly hydrophobic. On the other hand, addition of Joncryl had limited effects on moisture content, water solubility, glass transition temperature and moisture sorption behaviour of TPS/p-PLA blend films.     

Chitosan/Hydrophilic Plasticizer-Based Films: Preparation,Physicochemical and Antimicrobial Properties

The addition of plasticizers to biopolymer films is a good method for improving their physicochemical properties. The aim of this study was to evaluate the effect of chitosan (CHI) blended with two hydrophilic plasticizers glycerol (GLY) and sorbitol (SOR), at two concentrations (20 and 40 wt%) on their mechanical, thermal, barrier, structural, morphological and antimicrobial properties. The chitosan was prepared through the alkaline deacetylation of chitin obtained from fermented lactic from shrimp heads. The obtained chitosan had a degree of deacetylation (DA) of 84 ± 2.7 and a molecular weight of 136 kDa, which indicated that a good film had formed. The films composed of CHI and GLY (20 wt%) exhibited the best mechanical properties compared to the neat chitosan film. The percentage of elongation at break increase to over 700 % in the films that contained 40 % GLY, and these films also exhibited the highest values for the water vapor transmission rate (WVTR) of 79.6 ± 1.9 g m² h^?1 and a yellow color (b _o  = 17.9 ± 2.0) compared to the neat chitosan films (b _o  = 8.8 ± 0.8). For the structural properties, the Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analyses revealed an interaction in the acetamide group and changes in the crystallinity of plasticized films. The scanning electron micrographs revealed that all formulations of the chitosan films were smooth, and that they did not contain aggregations, pores or microphase separation. The thermal analysis using differential scanning calorimetry (DSC) revealed a glass transition temperature (Tg) of 130 °C for neat chitosan film, but the addition of SOR or GLY elicited a decrease in the temperature of the peak (120 °C). In addition, the antimicrobial activity of the chitosan films was evaluated against Listeria monocytogenes, and reached a reduction of 2 log after 24 h. The plasticizer concentration of 20 % GLY is sufficient for obtaining flexible chitosan films with good mechanical properties, and it could serve as an alternative as a packaging material to reduce environmental problems associated with synthetic packaging films.     

A Processing,Characterization and Marine Biodegradation Study of Melt-Extruded Polyhydroxyalkanoate (PHA) Films

A series of polyhydroxyalkanoates (PHA), all containing 1% nucleating agent but varying in structure, were melt-processed into films through single screw extrusion techniques. This series consisted of three polyhydroxybutyrate (PHB) and three polyhydroxybutyrate-valerate (PHBV) resins with varying valerate content. Processing parameters of temperature in the barrel (165–173 °C) and chill rolls (60 °C) were optimized to obtain cast films. The gel-permeation chromatography (GPC) results showed a loss of 8–19% of the polymer’s initial molecular weight due to extrusion processing. Modulated differential scanning calorimetry (MDSC) displayed glass transition temperatures of the films ranging from −4.6 to 6.7 °C depending on the amount of crystallinity in the film. DSC data were also used to calculate the percent crystallinity of each sample and slightly higher crystallinity was observed in the PHBV series of samples. X-ray diffraction patterns did not vary significantly for any of the samples and crystallinity was confirmed with X-ray data. Dynamic mechanical analysis (DMA) verified the glass transition trends for the films from DSC while loss modulus (E′) reported at 20 °C showed that the PHBV (3,950–3,600 MPa) had the higher E′ values than the PHB (3,500–2,698 MPa) samples. The Young’s modulus values of the PHB and PHBV samples ranged from 700 to 900 MPa and 900 to 1,500 MPa, respectively. Polarized light microscopy images revealed gel particles in the films processed through single-screw extrusion, which may have caused diminished Young’s modulus and tensile strength of these films. The PHBV film samples exhibited the greatest barrier properties to oxygen and water vapor when compared to the PHB film samples. The average oxygen transmission rate (OTR) and water vapor transmission rate (WVTR) for the PHBV samples was 247 (cc-mil/m²-day) and 118 (g-mil/m²-day), respectively; while the average OTR and WVTR for the PHB samples was 350 (cc-mil/m²-day) and 178 (g-mil/m²-day), respectively. Biodegradation data of the films in the marine environment demonstrated that all PHA film samples achieved a minimum of 70% mineralization in 40 days when run in accordance with ASTM 6691. For static and dynamic incubation experiments in seawater, microbial action resulting in weight loss as a function of time showed all samples to be highly biodegradable and correlated with the ASTM 6691 biodegradation data.     

Evaluation of Biodegradable Films Made of Waste Mycelium and Poly (Vinyl Alcohol) on the Yield of Pak-Choi

Novel biodegradable films were prepared via blending of poly (vinyl alcohol) and waste mycelium from sauce residue and citric acid fermentation residue, respectively. The performance of these two types of films when used as alternative covers for pak-choi growth under semi-arid climatic conditions was evaluated via field test towards their abilities for water retention and biodegradation, together with the impact on the yield and nutritional quality of pak-choi. Experimental results showed that the use of these films could result in 50% higher water retention than a blank control film after 96-h treatment at 40?°C. Films were biodegraded within 14?weeks under natural conditions, leading to a significant mineralization, progressively releasing over 56% of K⁺, NO₃ ^?, Mg²⁺ and organics, beneficial for plant growth as fertilizer. The yield of pak-choi was increased by 80% in weight when using these films compared with the unmulched control. Compared to those treated with traditional LDPE mulching film, the average contents of chlorophyll, crude protein and soluble sugar in pak-choi were increased by 52.9, 7.2, 80.7% (blends of sauce residue) and 26.7, 11.4, 10.8% (blends of citric acid fermentation residue), respectively.     

Mechanical Performance and Design Criteria of Biodegradable Low-tunnel Films

The overall mechanical behaviour of a series of experimental Mater-Bi made thin low-tunnel films is analysed with respect to the effect of two major factors: the film processing optimisation during manufacturing and the design of the low-tunnels structural system. The analysis of the mechanical behaviour of the biodegradable low-tunnel films, based on the results of extensive full-scale and small-scale experiments, combined with laboratory testing of the mechanical properties of the film, proves that a rather good mechanical behaviour is possible for these films, comparable to the behaviour of conventional agricultural films in terms of strength, provided that two criteria are met: (a) the low tunnel structural design is based on the initial stress at yield value of the film, which represents the asymptotic value of the tensile strength of the film, following its evolution with the time of exposure to real field conditions; (b) the processing of the film is optimised for the particular biodegradable material and film thickness under consideration. It is also confirmed that the stabilisation schemes used with conventional polyethylene films are not suitable for the biodegradable films.

Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Degradation of a Terephthalate-containing Polyester by Thermophilic Actinomycetes and <Emphasis Type="Italic">Bacillus</Emphasis> Species Derived from Composts

We intended to find thermophilic degraders of terephthalate-containing Biomax^® films. Films in mesh bags were buried in composts (inside temperature: approximately 55–60 °C), resulting in the degradation of them in 2 weeks. Fluorescent microscopy of films recovered from composts showed that microorganisms gradually covered the surface of a film during composting. DGGE analysis of microorganisms on the composted film indicated the presence of Bacillus species as main species (approximately 80% of microbial flora) and actinomycetes (approximately 10–20%) as the second major flora. Isolation of Biomax^®-utilizing bacteria was focused on these two genera: two actinomycetes and one Bacillus species were isolated as pure best degraders from the composted polymer films, which were fragmented into small pieces. All the strains were thermophilic and identified, based on their 16S rDNA analyses. Degradation of polymer films was confirmed by (1) accelerated fragmentation of films in composts, compared with a control (no inoculum) and resultant decrease in molecular weights, (2) growth in a powdered Biomax^® medium, compared with a control without powdered Biomax^®, and (3) production of terephthalate in a powdered Biomax^® medium. In this way, we concluded that these bacteria were useful for degradation of thermostable Biomax^® products.     

Pure-culture and enzymatic assay for starch-polyethylene degradable plastic biodegradation withStreptomyces species

Eleven starch-polyethylene degradable plastic films were prepared from masterbatches from Archer Daniels Midland Inc. (ADM), EcoStar Inc. (SLS), and Fully Compounded Plastic Inc. The biodegradability of initial and 70°C heat-treated materials was determined using a pure-culture assay withStreptomyces badius 252,S. setonii 75Vi2, orS. viridosporus T7A or without bacterial culture (control). Films were treated with 10-foldS. setonii culture concentrates and compared with inactive enzyme controls. Changes in each films mechanical property, molecular weight distribution, and Fourier-transformed infrared spectrum (FT-IR) were determined, and results were evaluated for significant differences by analysis of variance. Cell mass accumulation on each film was quite pronounced. In pure-culture studies, biodegradation was demonstrated for ADM-7 and SLS-2 initial films and for ADM-6 heat-treated films, whereas after 3-week treatment with activeS. setonii culture concentrates (enzyme assay), reductions in mechanical properties and changes in FT-IR spectrum were illustrated by all the films except SLS-2. Thus the absence of biofilm formation on the film surface permitted enzymatic attack of the materials. Furthermore, inhibition of chemical oxidative degradation in the pure-culture assay was demonstrated for ADM-11, SLS-5, and SLS-10 initial materials and for ADM-4, ADM-7, SLS-8, and SLS-10 heat-treated films. These data suggest that biological and chemical degradation were directly affected by the reduction in oxygen tension on the plastic film surface due to cell mass accumulation. This same phenomenon could be the cause for slow degradation rates in nature.Journal Paper No. J-15061 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Project Nos. 0178 and 2889.     

Biodegradability of Chemically Modified Starch (RS4)/PVA Blend Films: Part 2

Biodegradable films were successfully prepared by using cornstarch (CS), chemically modified starch (RS4), polyvinyl alcohol (PVA), glycerol (GL), and citric acid (CA). The physical properties and biodegradability of the films using CS, RS4, and additives were investigated. The results of the investigation revealed that the RS4-added film was better than the CS-added film in tensile strength (TS), elongation at break (%E), swelling behavior (SB) and solubility (S). Especially, the RS4/PVA blend film with CA as an additive showed physical properties superior to other films. Furthermore, when the film was dried at low temperature, the properties of the films clearly improved because the hydrogen bonding was activated at low temperature. The biodegradation of films was carried out using the enzymatic, microbiological and soil burial test. The enzyme used in this study was amyloglucosidase (AMG), α-amylase (α-AM) and β-amylase (β-AM). At the enzymatic degradation test, the GL-added films had an approximately 60% degradation, while the CA-added films were degraded about 25%. The low degradation value on CA-added film is attributed to low pH of film added CA that deactivated the enzymatic reaction. The microbiological degradation teat was performed by using Bacillus subtilis and Aspergillus niger.     

Active Bio-composite Sodium Alginate/Maltodextrin Packaging Films for Food Containing Azolla pinnata Leaves Extract as Natural Antioxidant

The aim of the current work was to produce sodium alginate (SA) maltodextrins (MD) based functional films incorporated with phenolic extract of Azolla pinnata leaves fern (AF) by solution molding technique. AF with different concentrations (0.8, 1.2 and 1.6% w/w) were integrated inside SA.MD films. The resulted films were characterized to investigate the surface structure by scanning electron microscope (SEM), thermal disposal by (DSC), crystallization by X-ray diffraction (XRD), potential interaction by (FT-IR) and some mechanical properties. The SEM micrographs indicated that the higher concentration (1.6%) of AF extract caused development of wrinkles on the surface of films. And as a result, there were a significant decrease of elongation at break (EB) and tensile strength properties of films to 55.01 and 58.42%, respectively. By continues addition of AF extract to SA.MD films, the film thickness increased from 0.124 to 0.181 mm, the scavenging and antimicrobial properties were enhanced by the attendance of ferulic acid, rutin, thiamine, tamarixetin, astragalin, quercetin, chlorogenic acid and epicatechin inside extracts. Furthermore, the films solubility, swelling degree and water vapor permeability were decreased to 13.08%, 26.41% and 1.662?×?10^??10 g H₂O/m s p.a. The resulted films could be utilized as composite packaging material for different food applications.

     

Environmental Degradation of Biodegradable Polyesters: 3. Effects of Alkali Treatment on Biodegradation of Poly(ε-Caprolactone) and Poly[(R)-3-Hydroxybutyrate) Films in Controled Soil

The poly(-caprolactone) (PCL) and poly[(R)-3-hydroxybutyrate] (R-PHB) films with a hydrophilic surface were prepared by the alkali treatment of their as-cast films in NaOH solutions of different concentrations. The alkali-treated PCL and R-PHB films, as well as the as-cast PCL and R-PHB films, were biodegraded in soil controlled at 25°C and the effects of alkali treatment or surface hydrophilicities on their biodegradation were investigated by the use of gravimetry, gel permeation chromatography (GPC), scanning electron microscopy (SEM), and polarization optical microscopy. It became evident that the alkali treatment enhanced the hydrophilicities and biodegradabilities of the PCL and R-PHB films in soil. The biodegradabilities of the as-cast aliphatic polyester films in controlled soil decreased in the following order: PCL > R-PHB > PLLA, in agreement with that in controlled static seawater.     

Fabrication and Characterization of Biodegradable Composite Films Made of Using Poly(caprolactone) Reinforced with Chitosan

Chitosan was dissolved in 2?% aqueous acetic acid solution and the films were prepared by solution casting. Values of tensile strength (TS), tensile modulus (TM), elongation at break (Eb?%) and water vapor permeability (WVP) of the chitosan films were found to be 30?MPa, 450?MPa, 8?% and 4.7?g?mm/m²?day?kPa, respectively. Poly(caprolactone) (PCL) films were prepared from its granules by compression molding and the values of TS, TM, Eb and WVP were 14?MPa, 220?MPa, 70?% and 1.54?g?mm/m²?day?kPa, respectively. PCL was reinforced with chitosan films, and composite films were prepared by compression molding. Amount of chitosan in the composite films varied from 10 to 50?% (w/w). It was found that with the incorporation of chitosan films in PCL, both the values of TS and TM of composite films increased significantly. The highest mechanical properties were found at 50?% (w/w) of chitosan content. The Oxygen transmission rate (OTR) of composite film was found to decrease significantly than PCL films. Thermal properties of the composite were also improved as compared to PCL. The water uptake test of the composite also showed promising results with a good stability of composite films. The interface of the composite was investigated by scanning electron microscopy and showed good interfacial adhesion between PCL and chitosan films.     

Preparation of Chitin/Cellulose Films Compatibilized with Polymeric Ionic Liquids

This paper reports the preparation of chitin/cellulose films compatibilized with polymeric ionic liquids. In-situ (co)polymerization of polymerizable ionic liquids, 1-(3-methacryloyloxypropyl)-3-vinylimidazolium bromide (1) and 1-methyl-3-vinylbenzylimidazolium chloride (3), was carried out in the presence of a radical initiator, AIBN, in the chitin/cellulose solution with ionic liquid solvents (1-butyl-3-methylimidazolium acetate and chloride, BMIMOAc and BMIMCl, respectively), followed by the appropriate procedure to give the desired films. The presence of the polymeric ionic liquid in the film was confirmed by the IR measurement. The powder X-ray diffraction analysis suggested that crystalline structures of the polysaccharides were largely disrupted in the film, as same as that of a chitin/cellulose film prepared by the AMIMOAc/BMIMCl system. These results were different from the XRD result of a chitin/cellulose film prepared by the 1-allyl-3-methylimidazolium bromide/BMIMCl system reported in our previous study, in which some crystalline structures were still remained in the film. Furthermore, the mechanical properties of the present films were evaluated by tensile testing, which were affected by the molar ratios of the polymeric ionic liquids to the polysaccharides and the compositional ratios of the two units 1 and 3.     

Crystallization Behavior and Dynamic Mechanical Properties of Poly(l-Lactic Acid) with Poly(Ethylene Glycol) Terminated by Benzoate

Effect of the addition of poly(ethylene glycol) terminated by benzoate (PEG-BA) on the crystallization behavior and dynamic mechanical properties of poly(l-lactic acid) PLLA is studied as compared with poly(ethylene glycol) (PEG-OH). It is found that PEG-BA is miscible with PLLA and shows good plasticizing effect. Because PEG-OH having the same degree of polymerization is immiscible with PLLA, the end group in PEG-BA, i.e., benzoate, plays an important role in the miscibility. Furthermore, PEG-BA does not induce the PLLA degradation at melt-processing, whereas PEG-OH leads to the hydrolysis degradation. Finally, the addition of PEG-BA pronounces the crystallization rate of PLLA at low crystallization temperatures and thus enhances the degree of crystallinity at conventional processing. Consequently, the temperature dependence of dynamic mechanical properties are similar to that for isotactic polypropylene.