Suspension Polymerization of Poly(l-lactide-co-p-dioxanone) in Supercritical Carbon Dioxide

Biodegradable copolymers of l-lactide(l-LA) and p-dioxanone(PDO) were synthesized in supercritical carbon dioxide (scCO₂) with stannous octoate as the ring-opening catalyst and a fluorocarbon polymer surfactant as an stabilizer. Fine powderous products were achieved when more than 90% (w/w) l-LA was fed. Scanning electron micrographic images and laser diffraction particle size analysis of the products showed the mean diameter of particles greatly increased as the content of PDO increased. The obtained polymers had the number-average molecular weights ranging from 15,000 to 26,000 g mol⁻¹ (polydispersity index ranging from 1.3 to 2.1) according to the gel permeation chromatography measurements. The polymer structure was characterized by NMR spectroscopy, indicating the formation of copolymers. Thermal properties of the obtained polymers investigated using differential scanning calorimetry showed that the morphology of products was directly relevant to the crystallinity of the copolymers. The polymerization of l-LA and PDO copolymers in scCO₂ is also proposed as a novel production technique for high-purity, biodegradable polymers.     

Synthesis of Segmented Polyurethane Based on Polymeric Soybean Oil Polyol and Poly (Ethylene Glycol)

Polyurethane (PUR) plastic sheets were prepared by reacting hydroxylated polymeric soybean oil (PSbOH) synthesized from autoxidized soybean oil with polyethylene glycol (PEG) in the presence of isophorone diisocyanate (IPDI). FTIR technique was used to identify of chemical reactions. These polyurethanes have different valuable properties, determined by their chemical composition. The effect of stoichiometric balance (i.e., PSbOH/PEG-2000/IPDI weight ratio) on the final properties was evaluated. The polyurethane plastic sheets with the PSbOH/PEG-2000/IPDI weight ratio 1.0/1.0/0.67 and 1.0/0.3/0.3 had excellent mechanical properties indicating elongation at break more than 200%. Increase in IPDI and decrease in PEG weight ratio cause the higher stress–strain value. The properties of the materials were measured by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA), stress–strain measurements and FTIR technique.     

Novel Environmentally Friendly Copolymers Carboxymethyl Starch Grafted Poly(Lactic Acid)

Modified natural polymers have been gaining increasing scientific interest for many years. In this study carboxymethyl starch (CMS) was grafted with L(+)-lactic acid (LA) in different molar ratios CMS/LA (1/36, 1/22 and 1/12), resulting carboxymethyl starch-g-poly(lactic acid) (CMS-g-PLA) copolymers. The grafting reaction was carried out by solution polycondensation procedure in toluene and stannous 2-ethyl hexanoate Sn(Oct)₂ as catalyst was utilized. Poly(lactic acid) (PLA) was synthesized in the same conditions with the copolymers for comparative analyses of the physico-chemical and thermal properties. The copolymers and PLA were structurally and morphologically characterized by FT-IR, ¹H-NMR spectroscopy, WAXD and SEM analyses, taking CMS as reference. The molecular weight of the copolymers, CMS and PLA were determined, using a dynamic light scattering technique. The thermal behavior of the products was studied by DSC and TG-DTG analyses. The CMS-g-PLA graft copolymers exhibited lower Tg and thermal stability than pure CMS.     

Poly(aspartic acid): Synthesis, biodegradation, and current applications

Poly(aspartic acid) is a biodegradable, water-soluble polymer that is valuable in numerous industrial applications. A variety of synthetic methods can be utilized to prepare poly(aspartic acid) and related polymeric materials with a range of tailored physical and chemical characteristics. This review of current investigative and patent literature describes methods of synthesis, biodegradative studies, and important current and potential applications of both poly(aspartic acid) homopolymers and copolymers.     

Synthesis and Properties of Biodegradable Poly(vinyl alcohol)/Organo-nanoclay Bionanocomposites

Biodegradable nanocomposites comprising of biodegradable polymers and bioactive organically modified layered silicates commonly reveal extremely enhanced mechanical and various other properties when compared to those of virgin polymers. This work was undertaken with a view to preparation of polymer bionanocomposites consisting of biodegradable poly(vinyl alcohol) (PVA) and organo-nanoclay. Cloisite Na⁺ and ammonium salt of l-isoleucine amino acid was used for the preparation of the novel chiral organo-nanoclay via an intercalation reaction in an aqueous solution. PVA/organo-nanoclay bionanocomposites of various compositions were created through the solution intercalation method by ultrasound-assisted technique. The resulting novel materials were characterized by X-ray diffraction and Fourier transform infrared spectroscopy techniques. Thermogravimetric analysis (TGA) and UV/vis spectroscopy were applied to test the properties of PVA bionanocomposites. TGA indicate that the thermal stability is enhanced distinctly, without a sacrifice in optical clarity. The improvement of thermal properties was attributed to the homogeneous and good dispersion of organo-nanoclay in polymeric matrix and the strong hydrogen bonding between O?CH groups of PVA and the oxygen atoms of silicate layers or carbonyl group as well as OH group of intercalated amino acid. The morphology of the organo-nanoclay and PVA bionanocomposites was examined by scanning electron microscopy and transmission electron microscopy techniques. Uniform distribution of clay due to intimate interaction between clay and polymer appears to be the cause for improved properties.     

Characterization and Release Kinetics of Allylthiosufinate and its Transforments from Poly(d,l-Lactide) Microspheres

In this work was described poly(d,l-lactide) microwave synthesis using tin(II) 2-ethylhexanoate initiated ring-opening polymerization. Polymerization was performed at 100 °C with monomer to initiator molar ratio ([M]/[I]) of 5,000 in 30 min. The achieved number average molar mass of obtained polymers (determined by gel permeation chromatography) was 102,320 g/mol, with the polydispersion index, Q, 2.80. Structural characterization was performed by FT-IR spectroscopy followed characteristic bands. For applicative purposes the obtained polymer was purified during the procedure of microsphere preparation. Biodegradable microspheres prepared from poly(d,l-lactide) have been widely studied in recent years and have become well established controlled drug delivery systems. In this work microspheres were loaded with allyl thiosulfinate (allicin) and its transforments products (ajoene and vinyldithiine), as pharmacological active substances. The morphology of the microspheres was analyzed using a scanning electron microscope. Allicin was synthesized by acid oxidation of allyl disufide and purification of obtained products by liquid–liquid extraction with diethyl ether. Obtained allicin, purity 73%, was transformed using microwave in acetone solution, at solvent boiling temperature, for 5 min. For the quality and quantity analysis of allicin and its transformation process was used LC/MS chromatography. (E)- and (Z)-ajoene were detected at retention time 3.1 and 3.3 min, respectively, whence 3-vynil-4H-1,2-dithiine and 2-vynil-4H-1,3-dithiine were detected at 4.3 and 4.8 min, respectively. Retention time of allicin was 2.93 min, according to liquid chromatography results. HPLC method was used for assessment of pharmaceutical substances (alicine and alicine transforments) releasing from microspheres at room temperature in solutions with different pH (pH = 3 and pH = 8) for 24 h.     

Biodegradation of Poly(Aspartic Acid-Itaconic Acid) Copolymers by Miscellaneous Microbes from Natural Water

Poly(aspartic acid-itaconic acid) copolymers (PAI) is a new scale inhibitor for water treatment. Thus, it is necessary to investigate its biodegradability. The biodegradability of PAI was investigated through CO₂ evolution tests under different conditions based on determination of carbon dioxide production. The investigation results showed that the degradation rate of PAI on day 10 and day 28 were respectively 38.7 and 79.5%, indicating that PAI was one kind of easily biodegradable scale inhibitors. With the increase in the content of itaconic acid in copolymerization process, the biodegradability of PAI was significantly reduced. In addition, the high biodegradability might be attributed to the existence of C–N bone-structure and more –COO–. Finally, Cu²⁺ could decrease the degradation percentage and the enzyme inhibition effect of Cu²⁺ was not the linear effect, but the “low-dosage effect”.     

Poly(Lactic Acid)-co-Aspartic Acid Copolymers: Possible Utilization in Drug Delivery Systems

The synthesis and characterization of poly(lactic acid)-co-aspartic acid copolymers (PLA-co-Asp) were presented. Subsequently, the synthesized PLA-co-Asp copolymers were tested as biodegradable carriers in drug delivery systems. PLA-co-Asp copolymers were synthesized by solution polycondensation procedure, using different molar ratios PLA/l-aspartic acid (2.33/1, 1/1, 1/2.33), manganese acetate and phosphoric acid as catalysts and N,N′-dimethyl formamide (DMF)/toluene as solvent mixture. The copolymers were characterized by FT-IR and ¹H-NMR spectroscopy, gel permeation chromatography (GPC), DSC and TG-DTG analyses. Diclofenac sodium, a non steroidal anti-inflammatory drug was subsequently loaded into PLA-co-Asp copolymers. The in vitro drug release experiments were done by dialysis of the copolymer/drug systems, in phosphate buffer solution (pH = 7.4, at 37 °C) and monitored by UV spectroscopy.     

Effect of Biaxial Stretching on Thermal Properties, Shrinkage and Mechanical Properties of Poly (Lactic Acid) Films

This study produced poly (lactic acid) sheets using a biaxial stretching process, to investigate the effects of biaxial stretching on thermal properties, crystallinity, shrinkage and mechanical properties of PLA films. The results of differential scanning calorimetry show that the glass temperature peak of PLA films, which weakened after stretching. The cold crystallization peak of PLA films nearly disappeared at stretch ratios of 4 × 4 with a stretching rate above 50 %/s. The orientation and strain crystallization of PLA films were suppressed at stretching temperatures of approximately 100–110 °C. The shrinkage of PLA decreased proportionally to the stretch rate and inversely proportional to the stretching temperature, suggesting that the internal stresses frozen in the amorphous phase were an indication of a decrease in the crystallinity of the films, implying that PLA films would be best suited to low-shrinkage applications. The stress–strain of the PLA films increased considerably following the biaxial stretching process. In addition, PLA films exposed to hot water treatment show a slight decrease in stress values, probably attributable to a relaxation of the molecules, which have undergone orientation but failed to crystallize.     

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.     

Synthesis,Characterization and Nanocomposite Formation of Poly(glycerol succinate-co-maleate) with Nanocrystalline Cellulose

A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with nanocrystalline cellulose. This glycerol-based polymer is thermally stable as a consequence of its targeted cross-linked structure. To broaden its range of properties, it was specifically formulated with nanocrystalline cellulose (NCC) at concentrations of 1, 2 and 4 wt%, and showed improved mechanical properties with NCC. Specifically, the effect of reinforcement on mechanical properties, thermal stability, structure, and biodegradability was evaluated, respectively, by tensile tests and thermogravimetric analyses, X-ray diffraction and respirometry. The neat poly(GlySAMA) polymer proved flexible, exhibiting an elongation-to-break of 8.8 % while the addition of nanowhiskers (at 4 wt%) caused tensile strength and Young’s modulus to increase, 20 and 40 %, respectively. Stiffness improved without significantly decreasing thermal stability as measured by thermogravimetric analysis. Biodegradation tests indicated that all samples were degradable but NCC reduced the rate of biodegradation.     

Thermal and Rheological Properties of Commercial-Grade Poly(Lactic Acid)s

Poly(lactic acid) is the subject of considerable commercial development by a variety of organizations around the world. In this work, the thermal and rheological properties of two commercial-grade poly(lactic acid)s (PLAs) are investigated. A comparison of the commercial samples to a series of well-defined linear and star architecture PLAs provides considerable insight into their flow properties. Such insights are valuable in deciding processing strategies for these newly emerging, commercially significant, biodegradable plastics. Both a branched and linear grade of PLA are investigated. The crystallization kinetics of the branched polymer are inferred to be faster than the linear analog. Longer relaxation times in the terminal region for the branched material compared to the linear material manifests itself as a higher zero shear rate viscosity. However, the branched material shear thins more strongly, resulting in a lower value of viscosity at high shear rates. Comparison of the linear viscoelastic spectra of the branched material with the spectra for star PLAs suggests that the branched architecture is characterized by a span molecular weight of approximately 63,000 g/mol. The present study conclusively demonstrates that a wide spectrum of flow properties are available through simple architectural modification of PLA, thus allowing the utilization of this important degradable thermoplastic in a variety of processing operations.     

Mechanical Properties and Morphology of Polypropylene/Poly(ethylene-co-octene) Blends

The polypropylene (PP)/poly(ethylene-co-octene) (POE) blends was prepared by means of a twin screw extruder in a range of temperature from 185 to 195 °C. The mechanical properties including tensile, flexural and impact of the PP/POE blends were measured at room temperature to identify the effect of the POE content on the mechanical properties. It was found that the Young’s modulus, tensile strength and tensile elongation at break decreased nonlinearly with increasing the POE weight fraction. While the V-notched and unnotched impact fracture strength increased nonlinearly with an increase of the POE weight fraction. The flexural modulus and strength decreased roughly linearly with increasing the POE weight fraction. Furthermore, the impact fracture surface of the blends was observed by using a scanning electronic microscope and the toughening mechanisms were discussed.     

Tensile Properties of Polylactide/Poly(ethylene glycol) Blends

The blends of polylactide (PLA) and poly(ethylene glycol) (PEG) with different contents (0, 5, 10, 15, and 20 wt%) and molecular weights (\( \overline{M}_{w} \) 6000, 10,000 and 20,000, called respectively as PEG 6000, PEG 10,000, and PEG 20,000) were prepared by means of melt blending method. The effects of tensile speed, content and molecular weight of the PEG on the tensile properties of the PLA/PEG blends were investigated using a universal testing machine at 24 °C. With increasing tensile speed, the tensile modulus, strength and stress at break of the PLA/PEG blends marginally increased, while the tensile modulus and stress at break declined non-linearly, and the tensile strength dropped nearly linearly with increasing PEG 10,000 content. When the PEG 10,000 content was 5–15 wt%, the tensile strain at break of the PLA/PEG 10,000 blend markedly increased, and then decreased as the PEG 10,000 content exceeded 15 wt%. With increasing the molecular weight of PEG, tensile modulus and strength increased, whereas the tensile strain at break decreased. This showed that the application of right amount of lower molecular weight PEG was more conducive to improving the tensile toughness of the PLA/PEG blends, which was attributed to its better miscibility with PLA and increased mobility of PLA molecular chains.     

Mechanical, Thermal and Water Absorption Properties of Kenaf-Fiber-Based Polypropylene and Poly(Butylene Succinate) Composites

The use of composites made from non-biodegradable conventional plastic materials (e.g., polypropylene, PP) is creating global environmental concern. Biodegradable plastics such as poly(butylene succinate) (PBS) are sought after to reduce plastic waste accumulation. Unfortunately, these types of plastics are very costly; therefore, natural lignocellulosic fibers are incorporated to reduce the cost. Kenaf fibers are also incorporated into PP and PBS for reinforcing purposes and they have low densities, high specific properties and renewable sourcing. However without good compatibilization, the interfacial adhesion between the matrix and the fibers is poor due to differences in polarity between the two materials. Maleic anhydride-grafted compatibilizers may be introduced into the system to improve the matrix-fiber interactions. The overall mechanical, thermal and water absorption properties of PP and PBS composites prepared with 30 vol.% short kenaf fibers (KFs) using a twin-screw extruder were being investigated in this study. The flexural properties for both types of composites were enhanced by the addition of compatibilizer, with improvements of 56 and 16 % in flexural strength for the PP/KF and PBS/KF composites, respectively. Good matrix-fiber adhesion was also observed by scanning electron microscopy. However, the thermal stability of the PBS/KF composites was lower than that of the PP/KF composites. This result was confirmed by both DSC and TGA thermal analysis tests. The water absorption at equilibrium of a PBS composite filled with KFs is inherently lower than of a PP/KF composite because the water molecules more readily penetrate the PP composites through existing voids between the fibers and the matrix. Based on this research, it can be concluded that PBS/KF composites are good candidates for replacing PP/KF composites in applications whereby biodegradability is essential and no extreme thermal and moisture exposures are required.     

Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

Synthesis and Physical Properties of Biodegradable Nanocomposites Fabricated Using Acrylic Acid-Grafted Poly(butylene carbonate-co-terephthalate) and Organically-Modified Layered Zinc Phenylphosphonate

Journal of Polymers and the Environment - A set of novel biocompatible aliphatic–aromatic nanocomposites, including numerous acrylic acid-grafted poly(butylene carbonate-co-terephthalate)...     

Thermal Properties and Biodegradability Studies of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.     

Effect of Poly(Vinyl Acetate) on Mechanical Properties and Characteristics of Poly(Lactic Acid)/Natural Rubber Blends

Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10–20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan δ of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71 °C (pure PLA) to 63 °C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.