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.     

Effect of Tacticity of Poly(Methyl Methacrylate) on Conductivity of Poly(Ethylene Oxide)-Poly(Methyl Methacrylate) Blend-Based Polymeric Electrolytest

Abstract

Polymer electrolytes based on blends of poly(ethylene oxide) (PEO) with various stereoisomers of poly(methyl methacrylate) (PMMA) were studied by means of impedance spectroscopy and DSC. It was found that isotactic poly(methyl methacrylate) (1PMMA)-based electrolytes exhibit ambient temperature conductivities at least one order of magnitude higher than the electrolytes containing other stereoisomers of PMMA. The highest value of room temperature conductivity equal to 9 × 10^?5 S/cm was measured for a sample containing 30 wt% IPMMA. The effect observed results from the presence of a flexible amorphous phase in PEO-IPMMA blends which is favorable for fast ionic transport. A small increase of ionic conductivity with decreasing molecular weight of the added atactic poly(methyl methacrylate) was also observed.     

Poly(Urethane)-Crosslinked Poly(HEMA) Hydrogels

Abstract

Hydrogels have been prepared from 2-hydroxyethyl methacrylate polymerized in the presence of isocyanate-terminated poly(ethylene glycol) (PEG) crosslinking agents. PEGS of molecular weights 200, 400, and 1000 were investigated. The crosslinked nature of the hydrogels was demonstrated by their insolubility in solvents which normally dissolve poly(HEMA). Hexamethylene diisocyanate (HDI) was mainly used as the isocyanate. The molecular weight of the PEG and the crosslinker content significantly influenced the equilibrium water sorption and mechanical properties of the saturated networks. It was observed that as the molecular weight of the PEG increased, the water sorption increased and the nominal modulus decreased. However, for higher levels of cross-linker, water sorption decreased and modulus increased at low molecular weight PEG; for PEG 1000, water absorption increased as crosslinker content increased. These results are explained by the competing effects of flexibility, crosslink density, and hydrophobicity contributed by the various constituents of the hydrogels.     

Poly(lactide) stereocomplexes: formation, structure, properties, degradation, and applications

Poly(lactide)s [i.e. poly(lactic acid) (PLA)] and lactide copolymers are biodegradable, compostable, producible from renewable resources, and nontoxic to the human body and the environment. They have been used as biomedical materials for tissue regeneration, matrices for drug delivery systems, and alternatives for commercial polymeric materials to reduce the impact on the environment. Since stereocomplexation or stereocomplex formation between enantiomeric PLA, poly(L-lactide) [i.e. poly(L-lactic acid) (PLLA)] and poly(D-lactide) [i.e. poly(D-lactic acid) (PDLA)] was reported in 1987, numerous studies have been carried out with respect to the formation, structure, properties, degradation, and applications of the PLA stereocomplexes. Stereocomplexation enhances the mechanical properties, the thermal-resistance, and the hydrolysis-resistance of PLA-based materials. These improvements arise from a peculiarly strong interaction between L-lactyl unit sequences and D-lactyl unit sequences, and stereocomplexation opens a new way for the preparation of biomaterials such as hydrogels and particles for drug delivery systems. It was revealed that the crucial parameters affecting stereocomplexation are the mixing ratio and the molecular weight of L-lactyl and D-lactyl unit sequences. On the other hand, PDLA was found to form a stereocomplex with L-configured polypeptides in 2001. This kind of stereocomplexation is called "hetero-stereocomplexation" and differentiated from "homo-stereocomplexation" between L-lactyl and D-lactyl unit sequences. This paper reviews the methods for tracing PLA stereocomplexation, the methods for inducing PLA stereocompelxation, the parameters affecting PLA stereocomplexation, and the structure, properties, degradation, and applications of a variety of stereocomplexed PLA materials.     

Accelerated Microbial Degradation of Poly(L-lactide)

Acceleration of the biodegradation of poly(L -lactide) (PLA) was studied. We found that the degradation rate of high molecular weight (1.3×10⁵) PLA film was greatly increased by the addition of gelatin into the culture medium of the microorganisms. 100 mg of PLA film was almost completely degraded by the fungus, Tritirachium album (eukaryotic microorganisms), and by an actinomycete, Saccharothrix waywayandensis (prokaryotic microorganisms). In addition to gelatin, various insoluble proteins, peptides and amino acids also accelerate the biodegradation of PLA. Silk fibroin was the best inducer for the production of PLA-degrading enzymes of an actinomycete, Amycolatopsis orientalis.     

高分子量聚对二氧环己酮改进聚DL-乳酸柔韧性的研究

为了提高DL-聚乳酸(PDLLA)的柔韧性,将10～20wt%不同比例的由本课题组自主合成的高分子量聚对二氧环己酮(PPDO)加入到PDLLA基体中,对共混物的微观两相形态、力学性能、热学性能和表面性质、降解性能等物化性质进行了研究.实验结果表明,PPDO加入后,在PDLLA/PPDO共混物的柔韧性得到显著提高的同时,共混物表面亲水性相应提高,降解速率也随之加快.     

Size Exclusion Chromatography of Poly(vinylpyrrolidone)

Abstract

Poly(vinylpyrrolidone) and poly(ethylene oxide) separate by hydrodynamic volume on Toyo Soda TSK-PW columns in a mixed solvent mobile phase of 50:50 (v/v) MeOH/H₂O containing 0.1M LiNO₃. From this separation a single universal calibration curve based on hydrodynamic volume [η]M can be obtained. Accurate weight average molecular weights of PVP were obtained by both SEC/LALLS and universal calibration showing good agreement between the two methods. SEC/LALLS overestimates the number average molecular weight for broad distribution polymers due largely to the lack of sensitivity of the LALLS detector to the low molecular weight portion of the polymers, while the universal calibration method slightly underestimates the number average molecular weight as compared to osmometric values.     

Properties and Polymerization of Biodegradable Thermoplastic Poly(Ester-urethane)

Abstract

Aliphatic polyesters, such as poly(lactic acids), need high molecular weight for acceptable mechanical properties. This can be achieved through ring-opening polymerization of lactides. The lactide route is, however, relatively complicated, and alternative polymerization routes are of interest. In this paper we report the properties of a polymer made by a two-step process: first a condensation polymerization of lactic acid and then an increase of the molecular weight with diisocyanate. The end product is then a thermoplastic poly(ester-urethane). The hydroxylterminated prepolymer was made with condensation polymerization of L–lactic acid and a small amount of 1,4-butanediol. The polymerization was performed in the melt under nitrogen and reduced pressure. The preparation of poly(ester-urethane) was done in the melt using aliphatic diisocyanates as the chain extenders reacting with the end groups of the prepolymer. The polymer samples were carefully characterized, including preliminary degradation studies. The results indicate that this route to convert lactic acid into thermoplastic biodegradable polymer has high potential. Lactic acid is converted into a mechanically attractive polymer with high yield, which could make the polymer suitable for high volume applications. The mechanical properties of the poly(ester-urethane) are comparable with those of poly(lactides). Capillary rheometer measurements indicate that the polymer is processible both by injection molding and extrusion.     

Preparation and characterization of biodegradable poly(lactic acid)‐ block‐poly(ε‐caprolactone) multiblock copolymer

Biodegradable copolymers of poly(lactic acid)‐block‐poly(ε‐caprolactone) (PLA‐b‐PCL) were successfully prepared by two steps. In the first step, lactic acid monomer is oligomerized to low molecular weight prepolymer and copolymerized with the (ε‐caprolactone) diol to prepolymer, and then the molecular weight is raised by joining prepolymer chains together using 1,6‐hexamethylene diisocyanate (HDI) as the chain extender. The polymer was carefully characterized by using ¹H‐NMR analysis, gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FTIR). The results of ¹H‐NMR and TGA indicate PLA‐b‐PCL prepolymer with number average molecular weights (M_n) of 4000–6000 were obtained. When PCL‐diols are 10 wt%, copolymer is better for chain extension reaction to obtain the polymer with high molecular weight. After chain extension, the weight average molecular weight can reach 250,000 g/mol, as determined by GPC, when the molar ratio of –NCO to –OH was 3:1. DSC curve showed that the degree of crystallization of PLA–PCL copolymer was low, even became amorphous after chain extended reaction. The product exhibits superior mechanical properties with elongation at break above 297% that is much higher than that of PLA chain extended products. Copyright © 2009 John Wiley & Sons, Ltd.     

Poly(lactic acid) Synthesis in Solution Polymerization

The step-growth polymerization of L-lactic acid in solution was studied in this work. In order to attain a polymer with high molecular weight, the water formed during the polymerization must be continuously removed. The use of organic solvents with high boiling point, drying agents and reduced pressure led to poly(lactic acid) (PLA) with high molecular weight, directly from the monomer. Tin (II) chloride dihydrate, SnCl₂.2H₂O, was the best of the catalysts tested as it allowed achieving PLA with a molecular weight close to 80 000 g.mol⁻¹. However, the stereoregurarity control is a severe problem in PLA synthesis by step-growth due to transesterification reactions, which lead to an inversion of the conformation and a decrease of the optical purity of the polymer. Specific rotation measurements were used in this work and showed to be a powerful technique to evaluate the racemization extent. The thermal stability of the PLA samples was evaluated by DSC which exhibits a thermal behaviour similar to the commercial Polylactide.     

Degradation of Poly(L‐lactide) by a Fungus

Fungal degradation of poly(L ‐lactide) (PLA) was studied using Tritirachium album ATCC 22563. In liquid culture using basal medium and PLA film, no film degradation was observed. However, by the addition of 0.1% gelatin, about 76% of the PLA film was degraded after 14 days of cultivation at 30°C. Furthermore, the culture filtrate showed degradation activity against PLA, silk fibroin and elastin, but not against poly(β‐hydroxybutyrate), poly(butylene succinate) and poly(ε‐caprolactone). The PLA‐degrading enzyme produced is likely to be protease rather than lipase or poly(β‐hydroxybutyrate)‐depolymerase.     

Toughening Poly(lactic acid) with Imidazolium-based Elastomeric Ionomers

Imidazolium-based elastomeric ionomers (i-BIIR) were facilely synthesized by ionically modified brominated poly(isobutylene-co-isoprene) (BIIR) with different alkyl chain imidazole and thoroughly explored as novel toughening agents for poly(lactic acid) (PLA). The miscibility, thermal behavior, phase morphology and mechanical property of ionomers and blends were investigated through dynamic mechanical analyses (DMA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), tensile and impact testing. DMA and SEM results showed that better compatibility between the PLA and i-BIIR was achieved compared to the PLA/unmodified BIIR elastomer. A remarkable improvement in ductility with an optimum elongation at break up to 235% was achieved for the PLA/i-BIIR blends with 1-dodecylimidazole alkyl chain (i-BIIR-12), more than 10 times higher than that of pure PLA. The impact strengths of PLA were enhanced from 1.9 kJ/m² to 4.1 kJ/m² for the PLA/10 wt% i-BIIR-12 blend. Toughening mechanism had been established by systematical analysis of the compatibility, intermolecular interaction and phase structures of the blends. Interfacial cavitations initiated massive shear yielding of the PLA matrix owing to a suitable interfacial adhesion which played a key role in the enormous toughening effect in these blends. We believed that introducing imidazolium group into the BIIR elastomer was vital for the formation of a suitable interfacial adhesion.     

Thermal degradation of poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) and their blends upon melt processing

Poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable aliphatic polyesters, which being semicrystalline and thermoplastic can be processed by conventional methods. Their blends give interesting materials for industrial packaging applications, due to their increased ductility as PBAT content increases. However, like many aliphatic polyesters, the PLA matrix degrades upon melt processing thus affecting the thermo-mechanical features of the blended material. In this work, we studied the effect of processing at high temperature on the molecular weight distribution, morphology, and thermo-mechanical properties of both homopolymers, as well as the PLA/PBAT 75/25 blend. Notably, different processing conditions were adopted in terms of temperature (range 150-200 °C) and other relevant processing parameters (moisture removal and nitrogen atmosphere). Analysis of PLA/PBAT blends indicated that intermolecular chain reactions took place under strong degradative conditions of PLA, yielding PLA/PBAT mixed chains (copolymers). Increasing amounts of copolymers resulted in improved phase dispersion and increased ductility, as SEM and mechanical tests indicated. Conversely, reduced PLA degradation with less copolymer formation, afforded higher modulus materials, owing to poorer dispersion of the soft phase (PBAT) into the PLA matrix.     

Effect of the Poly(Methyl Methacrylate) Molecular Weight on the Mechanical Properties BisGMA/TEGDMA Semi-interpenetrating Polymer Networks

Abstract

The effect of poly(methyl methacrylate) [PMMA], with different molecular weights on the mechanical properties of a polymerized BisGMA/TEGDMA base monomer resin was investigated. With the aid of acetone solvent, PMMA could be readily dissolved in BisGMA/TEGDMA mixtures. The addition of PMMA can significantly improve the compressive strengths and decrease the Knoop hardness values of the BisGMA/TEGDMA/PMMA semi-IPNs. The thermal expansion coefficients rapidly increased before T_g, and decreased after T _g. The observed properties could be attributed to the effect of the molecular weight of the PMMA on the phase structures of the semi-IPNs.     

Biodegradable Polymers for Orthopedic Applications: Synthesis and Processability of Poly (l-Lactide) and Poly (Lactide-co-€-Caprolactone)

Abstract

The synthesis of poly(l-lactide) (PLLA), poly(l-lactide-co-e-caprolactone), and poly(DL-lactide-co-e-caprolactone) by ring-opening bulk polymerization was investigated. Polymerization temperature had a significant effect on the PLLA molecular weight. At 184°C a polymer with a molecular weight of only 10 × 10⁴ resulted. This was lower by a factor of 2 than that obtained at 103 and 145°C. The stannous octoate (SnOct) concentration, with a monomer/SnOct molar ratio in the range of 1,000 to 10,000, was not found to have a significant effect on the PLLA molecular weight. A heterogeneous structure in polymerized PLLA was observed. The intrinsic viscosity of poly(lactide-co-€-caprolactone), obtained at 130°C, monomer/SnOct molar ratio 5,000, and polymerization time of 30 hours, decreased with increasing €-caprolactone content within the first 9 wt% and then leveled off. Die-drawing of PLLA cylinders, for the purpose of increasing the polymer's mechanical strength, was unsuccessful due to the brittleness of the polymer. The drawability of poly(l-lactide), however, was greatly improved by copolymerization with €-caprolactone. With only 3 wt% of €-caprolactone, for example, the tensile strength of die-drawn poly(l-lactide-co-e-caprolactone) was increased by a factor of more than 3. Polymer processing temperature was also investigated. The requirement for low processing temperatures in melt manufacture of controlled release matrix devices containing thermal sensitive drugs was accomplished by three methods: through the use of low molecular weight poly(DL-lactide), adding (DL-lactic) acid oligomer to high molecular weight PDLLA, and copolymerizing DLLA with €-caprolactone. The glass transition temperatures of the modified high molecular weight PDLLA decreased significantly. Melt extrusion below 100°C could be performed.     

Compatibility of Poly(vinyl chloride) with Polyalkyleneoxides. I. Poly(methylene oxide) and Poly(ethylene oxide)

The compatibility of poly(vinyl chloride) (PVC) with linear polyethers is examined over the entire composition range. This study examines blends with poly(methylene oxide) (PMO) and poly(ethylene oxide) (PEO) of medium (MMW) and high (HMW) molecular weight. The techniques used are dynamic mechanical analysis, DSC, and optical microscopy (phase contrast and polarizing). The results indicate that all polyethers show limited miscibility in the melt at high PVC contents. Proper analysis of the T_m data using the Kwei-Frisch and Hoffman-Weeks procedures allows the determination of the thermodynamic interaction parameter, which is found to be close to zero for all pairs of blends.     

Linear and Hyperbranched Poly(arylene ether)s from a New Semifluorinated AB Monomer

A new trifluoromethyl-activated AB monomer has been successfully synthesized by Pd-initiated coupling of 4-bromo anisole with 4-fluoro-3-trifluoromethylphenylboronic acid followed by demethylation. The monomer leads to a semifluorinated poly(arylene ether) by nucleophilic displacement polymerization reaction. The AB monomer has been further copolymerized with a corresponding AB ₂ monomer to form the corresponding semifluorinated hyperbranched (hb) poly(arylene ether). The resulting linear and hb poly(arylene ether)s exhibited weight average molecular weight of 75700 and 144100 g/mol, respectively. The hb copolymer exhibited better solubility in different organic solvents compared to the linear poly(arylene ether). The polymers showed excellent thermal stability up to 522°C at 10% wt loss in air and glass transition temperatures as high as 187°C. The mechanical properties of the linear poly(arylene ether) film 1a exhibited tensile strength at break of 89 MPa, elongation at break of up to 3% and a Young’s modulus value of 2.66 GPa. The films of the polymers were hydrophobic in nature and showed water contact angle as high as 93.6°.     

不同催化剂作用下聚乳酸/聚碳酸亚丙酯的酯交换反应

选用辛酸亚锡[Sn(Oct)₂]和钛酸四丁酯(TBT)作为聚乳酸(PLA)/聚碳酸亚丙酯(PPC)的酯交换反应催化剂, 研究了溶液条件下单一催化剂及复合催化剂对PLA/PPC酯交换反应的催化作用. 通过对反应产物的分子结构、 热力学及流变学行为进行分析, 结果发现, 无论在单一催化剂还是复合催化剂作用下, PLA与PPC分子间均发生了酯交换反应, 同时伴随着断链反应. 其中, 当Sn(Oct)₂作为单一催化剂或Sn(Oct)₂/TBT作为复合催化剂时, 样品更倾向发生断链反应而非显著的酯交换反应. 进一步分析纯样品在催化剂Sn(Oct)₂或TBT作用下的反应情况, 结果发现, PPC在反应最初阶段以高分子量的分子链断链为主, 且会发生明显的解拉链降解, 从而导致PLA/PPC在等质量比时酯交换反应程度不高, 这为今后更好地研究PLA/PPC酯交换反应提供了思路.     

Poly(lactic acid) Polymerized by Aluminum Triflate

The ring-opening polymerization of L -lactide (LA) has been initiated by aluminum triflate (trifluoromethanesulfonate) in air using a simple glass tube at 100 °C without desiccation steps and stirring. It was found that the molecular weight of poly(lactic acid) (PLA) was increased by the addition of an alcohol as an initiator to the reaction mixture. The highest number averaged molecular weight, molecular weight distribution, and recovery of the obtained PLA at 100 °C for 6 h were 18,200, 1.20, and 73%, respectively. With the addition of a small percentage of alcohol and a long reaction time of the polymerization method with the re-addition of LA, PLA (ca. 80 wt%) with a higher molecular weight (ca. 30,000) initiated by the added alcohol was produced with PLA (ca. 20 wt%) with a lower molecular weight (ca. 2,000) initiated by impurities such as water, which exist in a monomer, initiator, or catalyst.     

Poly(Aryl Ether)s from a Novel Biphenol Monomer Containing a Dicyanoarylene Group

Abstract

The preparation of a novel biphenol, 1,4-bis(4-hydroxyphenyl)-2,3-dicyanonaphthalene, from phenolphthalein is described. This biphenol was prepared in high yield in a four-step reaction sequence. The biphenol can be polymerized with activated dihalides such as 1,2-bis-(4-fluorobenzoyl)-3,4,5,6-tetraphenylbenzene, bis(4-fluorophenyl) sulfone, and 4,4′-dichlorobenzophenone to give high molecular weight amorphous poly(aryl ether)s. The polymers have glass transition temperatures ranging from 284 to 319°C and are easily cast into flexible, colorless, and transparent films. The 5% weight loss temperatures of these polymers, by thermogravimetric analysis in air and nitrogen, are all above 500°C.