Diffusivities of dichloromethane in poly(lactide‐co‐glycolide)

Diffusion of dichloromethane in poly(lactide‐co‐glycolide) (PLGA), the rate‐limiting step in the later stages of drying of microparticles formed in common encapsulation processes, was studied by the step‐change sorption technique in a dynamic vapor sorption apparatus. Methods were developed to create films of polymer with the appropriate thicknesses for accurate diffusion determination over a wide range of solvent composition. Mutual diffusivities were measured at 5, 25, and 35°C from 10 to 70 wt % solvent. Values range from 2 × 10^?10 m²/s at high solvent compositions to as low as 1 × 10^?13 m²/s at solvent compositions just above the glass transition of the mixture. Equilibrium sorption isotherms were measured in the same apparatus and agreed favorably with Flory‐Huggins theory using a value of χ = 0.31. The glass transition temperatures of the system were measured over the range of 0–11 wt % solvent content by modulated differential scanning calorimetry. The composition dependence was fit to the Fox equation, which estimated values of the pure polymer and the solvent T_g to be 39.3 and ?131°C, respectively. These values, along with the diffusivity data, were used to deduce the free‐volume parameters specific to PLGA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Isothermal annealing of poly(lactide‐co‐glycolide) (PLGA) and its effect on radiation degradation

The purpose of this study was to examine how the presence of crystals can retard electron‐beam (e‐beam) radiation degradation, and their effects on the thermal and morphological properties of poly(lactide‐co‐glycolide) (PLGA) upon e‐beam irradiation. Isothermal annealing at 115 °C was carried out on PLGA films and the effect of different annealing times on the degree of crystallinity (DOC) of PLGA was recorded. The DOC increased with annealing time to a maximum value, and remained unchanged with further annealing. The annealed films were then e‐beam irradiated at doses of 5, 10, 20 and 30 Mrad. The degradation of the films was studied by measuring the changes in their molecular weight, DOC, thermal properties and FTIR spectra. It was observed that, regardless of the DOC of the films, the molecular weight of PLGA generally decreased with increasing radiation dose, indicating that chain scission is dominant. However, the extent of degradation is less for the films with a higher DOC. The thermal properties of PLGA also decreased with increasing radiation dose. Radiation increases the DOC for films with initial crystallinity below 5 % but decreases the DOC for films with initial crystallinity above 5 %. Crystals in PLGA films decreased the extent of radiation degradation. Copyright © 2005 Society of Chemical Industry     

Preparation of porous poly(D,L‐lactide) and poly(D,L‐lactide‐co‐glycolide) membranes by a phase inversion process and investigation of their morphological changes as cell culture scaffolds

Porous membranes composed of the biodegradable polyesters poly(D,L ‐lactide) (PLA) and poly(D,L ‐lactide‐co‐glycolide) (PLGA) were prepared by a phase inversion process. The molecular weights of the polymers and the concentrations of the polymer solutions affected the pore size and structure of the PLA and PLGA membranes. The molecular weights and morphological changes of the membranes as a function of time were investigated under incubation at 37°C in a humidified 5% CO₂ atmosphere. The pores that formed in the membranes changed dramatically with increasing time under these conditions. From the thermal characterization of the polymers in their dry and wet states, we found that the glass‐transition temperatures of PLA and PLGA affected morphological structure changes in the porous membranes. We also prepared a collagen‐coated membrane to improve the interaction between the cell and the substrate, and we observed that the collagen coating enhanced the attachment and growth of Chinese hamster ovary cells on the substrate. Finally, we found that only PLA was a suitable material to prepare a porous membrane scaffold with the phase inversion process with PLA, and a collagen coating was necessary for cell culture on the membrane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2082–2092, 2004     

Preparation and release characteristics of dexamethasone acetate loaded organochlorine‐free poly(lactide‐co‐glycolide) nanoparticles

Dexamethasone‐loaded poly(lactide‐co‐glycolide) (PLGA) devices are commonly used as model systems for controlled release. In this study, PLGA nanoparticles containing dexamethasone acetate were prepared by a nanoprecipitation technique in the absence of organochlorine solvents and were characterized by their mean size, ζ potential, scanning electron microscopy, and differential scanning calorimetry to develop a controlled release system. The analytical method for the quantification of dexamethasone acetate by high‐performance liquid chromatography was validated. The results show that it was possible to prepare particles at a nanometric size because the average diameter of the drug‐loaded PLGA particles was 540 ± 4 nm with a polydispersity index of 0.07 ± 0.01 and a ζ potential of ?2.5 ± 0.3 mV. These values remained stable for at least 7 months. The drug encapsulation efficiency was 48%. In vitro tests showed that about 25% of the drug was released in 48 h. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41199.     

The effect of fabrication methods on the mechanical and thermal properties of poly(lactide‐co‐glycolide) scaffolds

The purpose of this research was to evaluate the effects of the fabrication method, poly(ethylene glycol) (PEG) molecular weight, and PEG concentration on the mechanical and thermal properties of blended poly (lactide‐co‐glycolide) (PLGA)/PEG scaffolds. The manufacturing process was the dominant factor. The tested fabrication processes were compression, heat molding, and solvent casting/vacuum drying. The scaffolds produced by compression were strong and brittle with mechanical properties [compressive modulus (E) ～ 400 N/mm²] comparable to those of trabecular bone. The heat‐molded scaffolds were weaker and more ductile (E ～ 45 N/mm²) than the compressed scaffolds, so they were more applicable to non‐load‐bearing applications. The vacuum‐dried scaffolds completely lacked compressive strength (E ～ 5 N/mm²) and were considered unsuitable for scaffolding applications. The miscibilities of the blends were also affected by the processing method and were evaluated on the basis of the melting‐point depression of crystalline PEG. The miscibility of PLGA in PEG was greatest with vacuum drying (6–13%), followed by heat molding (0.4–1.5%) and then compression (0.2–0.8%). The application of heat and solvent to the blend successfully altered the miscibility of the two polymers. Overall, this study demonstrates the ability to fabricate scaffolds with distinct thermal and mechanical characteristics by the manipulation of the fabrication method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 944–949, 2007     

Surfactant‐free nanoparticles of poly(DL‐lactide‐co‐glycolide) prepared with poly(L‐lactide)/ poly(ethylene glycol)

Surfactant‐free nanoparticles of poly(DL ‐lactide‐co‐glycolide) (PLGA) nanoparticles were prepared with or without poly(L ‐lactide)‐poly(ethylene oxide) (LE) diblock copolymer (abbreviated as PLGA/LE and PLGA nanoparticles) by dialysis method. LE diblock copolymer was used to make PLGA nanoparticles to alternate conventional surfactant. The size of PLGA and PLGA/LE nanoparticles was 295.3 ± 171.3 and 307.6 ± 27.2 nm, respectively, suggesting LE diblock copolymer might be coated onto the surface of nanoparticles. Observation of scanning electron microscope (SEM) showed that PLGA/LE nanoparticles have spherical shapes ranging ～ 200–500 nm. In ¹H‐NMR study, characteristic peaks of the methyl protons of PLGA disappeared in D₂O, whereas characteristic peaks of the methyl proton of both PEG and PLGA were shown in both CDCl₃ and D₂O, indicating that LE diblock copolymer coated on the surface of the PLGA nanoparticles. The higher the initial content of drug, the higher the drug contents and the lower the loading efficiency. PLGA/LE nanoparticles at higher drug contents resulted in slower adriamycin·HCl (ADR) release rate than that of lower drug contents. Also, slower release rate of ADR was achieved by entrapped into the PLGA/LE nanoparticles, whereas LE polymeric micelles showed rapid ADR release. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1116–1123, 2003     

Preparation of poly(DL‐lactide‐co‐glycolide) nanoparticles without surfactant

The preparation of poly(DL ‐lactide‐co‐glycolide) (PLGA) nanoparticles was performed by a dialysis method without surfactant or emulsifiers. The size of the PLGA nanoparticles prepared from dimethylacetamide (DMAc) as an initial solvent was smaller than that from acetone. The sizes of the PLGA nanoparticles from DMAc and acetone were 200.4 ± 133.0 and 642.3 ± 131.1 nm, respectively. The effects of the initial solvent selected to dissolve the copolymer and the lactide:glycolide ratio were investigated. The PLGA nanoparticles were spherical as revealed by the results of scanning electron microscopy and transmission electron microscopy observations. From these results it was shown that PLGA nanoparticles could be formed by the dialysis method without surfactant. The drug‐loading contents and efficiency were also dependent on the lactide:glycolide ratio and initial feeding amount of the drug. A higher lactide ratio resulted in higher drug loading and higher loading efficiency. However, a higher initial feeding amount of the drug resulted in higher drug loading and lower loading efficiency. Clonazepam was released for at least 2 days and the release rate was slower with a higher lactide:glycolide ratio and a larger amount of drug‐loading nanoparticles than that with a lower lactide:glycolide ratio and a smaller amount of drug‐loading nanoparticles. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2228–2236, 2001     

Shape‐memory behaviors of biodegradable poly(L‐lactide‐co‐ϵ‐caprolactone) copolymers

A series of biodegradable poly(L ‐lactide‐co‐?‐caprolactone) (PCLA) copolymers with different chemical compositions are synthesized and characterized. The mechanical properties and shape‐memory behaviors of PCLA copolymers are studied. The mechanical properties are significantly affected by the copolymer compositions. With the ?‐caprolactone (?‐CL) content increasing, the tensile strength of copolymers decreases linearly and the elongation at break increases gradually. By means of adjusting the compositions, the copolymers exhibit excellent shape‐memory effects with shape‐recovery and shape‐retention rate exceeding 95%. The effects of composition, deformation strain, and the stretching conditions on the recovery stress are also investigated systematically. A maximum recovery stress around 6.2 MPa can be obtained at stretching at T_g ? 15°C to 200% deformation strain for the PCLA70 copolymer. The degradation results show that the copolymers with higher ?‐CL content have faster degradation rates and shape‐recovery rates, meanwhile, the recovery stress can maintain a relative high value after 30 days in vitro degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical properties of (poly(L‐lactide‐co‐glycolide))‐based fibers coated with hydroxyapatite layer

This article presents the results of the experimental study on manufacturing and mechanical evaluation of poly(L ‐lactide‐co‐glycolide) (PLGA)‐based fibers modified with ceramic nanoparticles. Study was conducted to establish the effect of biomimetic formation of apatite layers on polymeric fibers on their mechanical properties. The tensile tests were performed to determine the influence of polymer crystallinity and the presence of hydroxyapatite nanoparticles (nanoHAp) on mechanical properties of PLGA fibers coated with hydroxyapatite (HAp) layer. HAp deposits on the surfaces of the fibers precipitated from simulated body fluid (SBF). Three types of fibers coated with HAp layers were compared in mechanical tests. The results indicated that by using a biomimetic fiber coating method the mechanical properties of the fibers are affected by their crystallinity. The nanoHAp modified polymer fibers after incubation in SBF were found to have a continuous HAp layer. The layer affected the mechanical behavior (force–strain function) of the fibers from nonlinear to linear, typical of ceramic materials. The tensile modulus of the fibers with a continuous layer was found to increase with the apatite layer thickness, whereas the tensile strength decreases. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of degraded hydrogels based on poly(vinyl alcohol) grafted with poly(lactide‐co‐glycolide)

Poly(vinyl alcohol) (PVA) grafted with poly(lactide‐co‐glycolide) and cross‐linked as a material of increased hydrophobicity relative to PVA was produced. The properties were examined with respect to the mass loss, water uptake, hydrophilicity, and mechanical characteristics upon hydrolytical degradation. The hydrogels investigated display water uptake increasing with degradation time because of increasing hydrophilicity. The mass loss amounts up to 15% after eight weeks of degradation. The mechanical properties of the hydrogels are within the range of those of natural tissue, the E modulus is 18 MPa, or even 100–200 MPa, depending on the structure of material. The mechanical characteristic and their dependence degradation show the most recognizable correlation with the chemical structure. Studies of the topography of degraded samples (scanning electron microscopy) and IR measurements demonstrate the degradation to occur at slow rate due to the high degree of grafting. The mass loss is rather low and a bulk degradation mechanism takes place. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Poly(D,L‐lactide‐co‐glycolide)/poly(ethylenimine) blend matrix system for pH sensitive drug delivery

Poly(D ,L ‐lactide‐co‐glycolide) (PLGA) and poly(ethylenimine) (PEI) were blended and found to form a homogeneous pH sensitive matrix for drug release. Differential scanning calorimetry (DSC) studies of the PLGA/PEI blends showed a single glass transition temperature at all compositions. Fourier transform infrared spectroscopy (FTIR) demonstrated that the PLGA carbonyl peak at 1760 cm^?1 shifted to 1666 cm^?1 as a result of amide bond formation between the two polymers. This was confirmed by ¹³C nuclear magnetic resonance studies. A PLGA/PEI matrix of 90/10 weight ratio was chosen for evaluation for controlled drug release. Both hydrophobic β‐lapachone and hydrophilic rhodamine B showed pH dependent release profiles with faster release kinetics at lower pH values. The observed pH sensitive drug release was mainly attributed to two factors, pH dependent swelling and protonation of the PEI‐PLGA matrix. These results demonstrate utility of a PLGA/PEI matrix and its potential application in pH responsive drug delivery. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 89–96, 2006     

Compatibility of poly(butadiene‐co‐acrylonitrile) with poly(L‐lactide) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)

Poly(L ‐lactide) (PLLA) and poly(3‐hydrobutyrate‐co‐3‐hydroxyvalerate) (PHBV) were blended with poly(butadiene‐co‐acrylonitrile) (NBR). Both PLLA/NBR and PHBV/NBR blends exhibited higher tensile properties as the content of acrylonitrile unit (AN) of NBR increased from 22 to 50 wt %. However, two separate glass transition temperatures (T_g) appeared in PLLA/NBR blends irrespective of the content of NBR, revealing that PLLA was incompatible with NBR. In contrast, a single T_g, which shifted along with the blend composition, was observed for PHBV/NBR50 blends. Moreover NBR50 suppressed the crystallization of PHBV, indicating that PHBV was compatible with NBR50. Decrease of both elongation modulus and stress at maximum load was less significant and increase of elongation at break was more pronounced in PHBV/NBR50 blends than in PLLA/NBR50 blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3508–3513, 2004     

Enhanced crystallization of poly(L‐lactide‐co‐ε‐caprolactone) in the presence of water

Poly(L ‐lactide‐co‐ε‐caprolactone) [P(LLA‐CL)], which is used in biodegradable biomedical materials such as drug‐delivery systems, surgical sutures, orthopedics, and scaffolds for tissue engineering, has been reported to crystallize upon storage in a dry state even at room temperature; this results in rapid changes in the mechanical properties. In biomedical applications, P(LLA‐CL) is used in the presence of water. This study investigated the effects of water on the crystallization of P(LLA‐CL) at 37°C in phosphate buffered solution, which was anticipated to alter its mechanical properties and hydrolytic degradation behavior. Surprisingly, the crystallinity of P(LLA‐CL) in the presence of water rapidly increased in 6–12 h and then slowly increased up to 120 h. The period of time for the initial rapid crystallization increase in the presence of water was much shorter than that in the absence of water. The obtained information would be useful for the selection, preparation, and use of P(LLA‐CL) in various biomedical applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Particle size and distribution of biodegradable poly‐D,L‐lactide‐co‐poly(ethylene glycol) block polymer nanoparticles prepared by nanoprecipitation

A biodegradable block copolymer, poly‐D ,L ‐lactide (PLA)‐co‐poly(ethylene glycol) (PEG), was prepared by the ring‐opening polymerization of lactide with stannous caprylate [Sn(Oct₂)] as a catalyst; then, the PLA–PEG copolymer was made into nanoparticles by nanoprecipitation under different conditions. The average molecular weight and structure of PLA–PEG were detected by ¹H‐NMR and gel permeation chromatography. The sizes and distributions of the nanoparticles were investigated with a laser particle‐size analyzer. The morphologies of the nanoparticles were examined by transmission electron microscopy. The effects of the solvent–nonsolvent system, operation conditions, and dosage of span‐80 on the sizes and distributions of the nanoparticles are discussed. The results show that acetone–water was a suitable solvent–nonsolvent system and the volume ratio of the nonsolvent phase to the solvent phase (O/W) (v/v), the concentration of PLA–PEG in the solvent phase, and the dosage of span‐80 had important effects on the particle sizes and distributions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1884–1890, 2005     

Synthesis and characterization of poly(L‐lactide‐co‐ϵ‐caprolactone)‐b‐poly(L‐lactide) biodegradable diblock copolyesters: Effect of the block lengths on their thermal properties

Poly(L ‐lactide‐co‐ε‐caprolactone)‐b‐poly(L ‐lactide) [P(LL‐co‐CL)‐b‐PLL] diblock copolyesters were synthesized in a two‐step process with 1‐dodecanol (DDC) and stannous octoate as the initiating system. In the first‐step reaction, a 50:50 mol % amorphous poly(L ‐lactide‐co‐ε‐caprolactone) [P(LL‐co‐CL)] copolyester was synthesized via the bulk copolymerization of L ‐lactide and ε‐caprolactone, which was followed by the polymerization of the PLL crystalline block at the end chain in the second‐step reaction. The yielded copolyesters were characterized with dilute‐solution viscometry, gel permeation chromatography, ¹H‐ and ¹³C‐NMR, and differential scanning calorimetry methods. The molecular weights of the P(LL‐co‐CL) copolyesters from the first‐step reaction were controlled by the DDC concentrations, whereas in the second‐step reaction, the molecular weights of the P(LL‐co‐CL)‐b‐PLL diblock copolyesters depended on the starting P(LL‐co‐CL) copolyester molecular weights and L ‐lactide/prepolymer molar ratios. The starting P(LL‐co‐CL) copolyester molecular weights and PLL block lengths seemed to be the main factors affecting specific thermal properties, including the melting temperature (T_m), heat of melting (ΔH_m), crystallizing temperature (T_c), and heat of crystallizing (ΔH_c), of the final P(LL‐co‐CL)‐b‐PLL diblock copolyester products. T_m, ΔH_m, T_c, and ΔH_c increased when the PLL block lengths increased. However, these thermal properties of the diblock copolyesters also decreased when the P(LL‐co‐CL) block lengths increased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Comparison of the degradation and release behaviors of poly(lactide‐co‐glycolide)–methoxypoly(ethylene glycol) microspheres prepared with single‐ and double‐emulsion evaporation methods

The purpose of this study was to compare the degradation and release behaviors of poly(lactide‐co‐glycolide) (PLGA)–methoxypoly(ethylene glycol) microspheres fabricated by the single‐emulsion evaporation method (DEEM) and double‐emulsion evaporation methods (DEEM). Vancomycin and mizolastine were used as the hydrophilic and hydrophobic model drugs, and they were encapsulated into microspheres through DEEM and SEEM, respectively. The two types of microspheres were similar in size distribution, but the mizolastine‐loaded microspheres showed a much higher encapsulation efficiency than those loaded with vancomycin. Scanning electron microscopy, size, and molecular weight (Mw) analyses during the degradation revealed that the microspheres fabricated by DEEM underwent a bulk degradation process and showed a faster MW reduction rate during the early degradation period than the microspheres fabricated by SEEM, which exhibited a surface‐to‐bulk degradation process according to the Mw and morphological changes. The mass loss rates of the two types of microspheres were similar, but the mean size decrease rates showed a little difference. The mizolastine‐loaded microspheres exhibited an approximately linear release profile after the initial burst release, whereas the vancomycin‐loaded microspheres showed a more severe burst release, a faster release rate, and thus, a shorter time to full release. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41943.     

Blends of aliphatic polyesters. VIII. Effects of poly(L‐lactide‐co‐ε‐caprolactone) on enzymatic hydrolysis of poly(L‐lactide), poly(ε‐caprolactone), and their blend films

Poly(L ‐lactide), that is, poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their blend (50/50) films containing different amounts of poly(L ‐lactide‐co‐ε‐caprolactone) (PLLA‐CL), were prepared by solution casting. The effects of added PLLA‐CL on the enzymatic hydrolysis of the films were investigated in the presence of proteinase K and Rhizopus arrhizus lipase by use of gravimetry. The addition of PLLA‐CL decreased the proteinase K–catalyzed hydrolyzabilities of the PLLA and PLLA/PCL (50/50) films as well as the Rhizopus arrhizus lipase‐catalyzed hydrolyzability of the PCL and PLLA/PCL (50/50) films. The decreased enzymatic hydrolyzabilities of the PLLA and PCL films upon addition of PLLA‐CL are attributable to the fact that the PLLA‐CL is miscible with PLLA and PCL and the dissolved PLLA‐CL must disturb the adsorption and/or scission processes of the enzymes. In addition to this effect, the decreased enzymatic hydrolyzabilities of the PLLA/PCL (50/50) films upon addition of PLLA‐CL can be explained by the enhanced compatibility between the PLLA‐rich and PCL‐rich phases arising from the dissolved PLLA‐CL. These effects result in decreased hydrolyzable interfacial area for PLLA/PCL films. The decrement in proteinase K–catalyzed hydrolyzability of the PLLA film upon addition of PLLA‐CL, which is miscible with PLLA, was in marked contrast with the enhanced proteinase K–catalyzed hydrolyzability of the PLLA film upon addition of PCL, which is immiscible with PLLA. This confirms that the miscibility of the second polymer is crucial to determine the proteinase K–catalyzed hydrolyzabilities of the PLLA‐based blend films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 412–419, 2003     

A biodegradable diblcok copolymer poly(ethylene glycol)‐block‐poly(L‐lactide‐co‐2‐methyl‐2‐carboxyl‐propylene carbonate): Docetaxel and RGD conjugation

A diblcok copolymer monomethoxy poly (ethyleneglycol)‐block‐poly(L ‐lactide‐co‐2‐methyl‐2‐carboxyl‐propylene carbonate) (MPEG‐b‐P(LA‐co‐MCC)) was obtained by copolymerization of L ‐lactide (LA) and 2‐methyl‐2‐benzoxycarbonyl‐propylene carbonate (MBC) and subsequent catalytic hydrogenation. The pendant carboxyl groups of the copolymer MPEG‐b‐P(LA‐co‐MCC) were conjugated with antitumor drug docetaxel and tripeptide arginine‐glycine‐aspartic acid (RGD), respectively. ¹H‐NMR spectra confirmed the structure of the copolymer MPEG‐b‐P(LA‐co‐MCC/docetaxel) and MPEG‐b‐P(LA‐co‐MCC/RGD). In vitro antitumor assay indicates that the MPEG‐b‐P(LA‐co‐MCC/docetaxel) conjugate shows high cytotoxic activity against HeLa cancer cells. Cell adhesion and spreading experiment shows that copolymer MPEG‐b‐P(LA‐co‐MCC/RGD) is of benefit to cell adherence and is a promising biodegradable material for cell and tissue engineering. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and chain extension of poly(L‐lactic acid‐co‐succinic acid‐co‐1,4‐butene diol)

L ‐Lactic acid (LA) was copolymerized with succinic acid (SA) and 1,4‐butenediol (1,4‐BED) in bulk state with titanium(IV) butoxide as a catalyst to produce poly(LA‐co‐SA‐co‐1,4‐BED) (PLASBED). Poly(L ‐lactic acid) (PLLA) homopolymer obtained from a direct condensation polymerization of LA had weight average molecular weight (M_w) less than 4.1 × 10⁴ and was too brittle to prepare specimens for the tensile test. Addition of SA and 1,4‐BED to LA produced PLASB with M_w as high as 1.4 × 10⁵ and exhibited tensile properties comparable to a commercially available high‐molecular‐weight PLLA. Chain extension by intermolecular linking reaction through the unsaturated 1,4‐BED units in PLASBED with benzoyl peroxide further increased the molecular weight and made PLASBED more ductile and flexible to show elongation at break as high as 450%. Biodegradability of PLASBED measured by the modified Sturm test was nearly independent of the 1,4‐BED content. Gel formation during the chain extension did not exert any significant influence on the biodegradability either. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1116–1121, 2005