Porous biodegradable polyesters. II. Physical properties,morphology, and enzymatic and alkaline hydrolysis of porous poly(ϵ‐caprolactone) films

Porous poly(?‐caprolactone) (PCL) films were prepared by water extraction of poly(ethylene oxide) (PEO) from their solution‐cast phase‐separated blend films and the dependence of their blend ratio [X_PCL = PCL/(PEO + PCL)] and molecular weight of PEO on the porosity, pore size, crystallinity, crystalline thickness, mechanical properties, morphology, and enzymatic and alkaline hydrolysis of the porous PCL films were investigated. The film porosity or extracted weight ratio was in good agreement with the expected values, irrespective of X_PCL and molecular weight of PEO. The maximum pore size was larger for the porous films prepared using PEO having a lower molecular weight, compared with films prepared using PEO having a higher molecular weight at the same X_PCL. Differential scanning calorimetry of the porous PCL films revealed that their crystallinity and crystalline thickness were almost constant, regardless of X_PCL and molecular weight of PEO. The Young's modulus and tensile strength of the porous films decreased, whereas the elongation‐at‐break increased with decreasing X_PCL. The enzymatic and alkaline hydrolysis rates of the porous films increased with a decrease in X_PCL and an increase in the molecular weight of PEO. The porous PCL films having Young's modulus in the range of 2–24 kg/mm² and enzymatic hydrolysis rate in the range of one‐ to 20‐fold that of the nonporous PCL film could be prepared by altering X_PCL and the molecular weight of PEO. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2281–2291, 2001     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Porous poly(L‐lactic acid)/poly(ethylene glycol) blend films

Poly(L ‐lactic acid) (PLLA: M_w = 19.4 × 10⁴)/poly(ethylene glycol) (PEG: M_w = 400) blend films were formed by use of a solvent‐cast technique. The properties and structures of these blend films were investigated. The Young's modulus of the PLLA decreased from 1220 to 417 MPa with the addition of PEG 5 wt %, but the elongation at break increased from 19 to 126%. The melting point of PLLA linearly decreased with increases in the PEG content (i.e., pure PLLA: 172.5°C, PLLA/PEG = 60/40 wt %: 159.6°C). The PEG 20 wt % blend film had a porous structure. The pore diameter was 3–5 μm. The alkali hydrolysis rate of this blend film was accelerated due to its porous structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 965–970, 2004     

Stereocomplex formation between poly(L‐lactic acid) and poly(D‐lactic acid) with disproportionately low and high molecular weights from the melt

Poly(L ‐lactic acid) (PLLA) and poly(D ‐lactic acid) (PDLA) with very different weight‐average molecular weights (M_w) of 4.0 × 10³ and 7.0 × 10⁵ g mol^?1 (M_w(PDLA)/M_w(PLLA) = 175) were blended at different PDLA weight ratios (X_D = PDLA weight/blend weight) and their crystallization from the melt was investigated. The presence of low molecular weight PLLA facilitated the stereocomplexation and thereby lowered the cold crystallization temperature (T_cc) for non‐isothermal crystallization during heating and elevated the radial growth rate of spherulites (G) for isothermal crystallization, irrespective of X_D. The orientation of lamellae in the spherulites was higher for the neat PLLA, PDLA and an equimolar blend than for the non‐equimolar blends. It was found that the orientation of lamellae in the blends was maintained by the stereocomplex (SC) crystallites. Although the G values are expected to decrease with an increase in X_D or the content of high‐molecular‐weight PDLA with lower chain mobility compared with that of low‐molecular‐weight PLLA, G was highest at X_D = 0.5 where the maximum amount of SC crystallites was formed and the G values were very similar for X_D = 0.4 and X_D = 0.6 with the same enantiomeric excess. This means that the effect of SC crystallites overwhelmed that of chain mobility. The nucleating mechanisms of SC crystallites were identical for X_D = 0.1–0.5 in the T_c range 130–180 °C. Copyright © 2011 Society of Chemical Industry     

Part 7. Effects of poly(L‐lactide‐co‐ϵ‐caprolactone) on morphology,structure, crystallization,and physical properties of blends of poly(L‐lactide) and poly(ϵ‐caprolactone)

Blended films of poly(L ‐lactide) [ie poly(L ‐lactic acid)] (PLLA) and poly(?‐caprolactone) (PCL) without or mixed with 10 wt% poly(L ‐lactide‐co‐?‐caprolactone) (PLLA‐CL) were prepared by solution‐casting. The effects of PLLA‐CL on the morphology, phase structure, crystallization, and mechanical properties of films have been investigated using polarization optical microscopy, scanning electron microscopy, differential scanning calorimetry and tensile testing. Addition of PLLA‐CL decreased number densities of spherulites in PLLA and PCL films, and improved the observability of spherulites and the smoothness of cross‐section of the PLLA/PCL blend film. The melting temperatures (T_m) of PLLA and PCL in the films remained unchanged upon addition of PLLA‐CL, while the crystallinities of PLLA and PCL increased at PLLA contents [X_PLLA = weight of PLLA/(weight of PLLA and PCL)] of 0.4–0.7 and at most of the X_PLLA values, respectively. The addition of PLLA‐CL improved the tensile strength and the Young modulus of the films at X_PLLA of 0.5–0.8 and of 0–0.1 and 0.5–0.8, respectively, and the elongation at break of the films at all the X_PLLA values. These findings strongly suggest that PLLA‐CL was miscible with PLLA and PCL, and that the dissolved PLLA‐CL in PLLA‐rich and PCL‐rich phases increased the compatibility between these two phases. © 2003 Society of Chemical Industry     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Casting solvent effect on crystallization behavior of poly(vinyl acetate)/poly(ethylene oxide) blends: DSC study

Poly(vinyl acetate) (PVAc)/poly(ethylene oxide) (PEO) blends were prepared by casting from either benzene or chloroform. The solvent effects on the crystallization behavior and thermodynamic properties of the blends were studied by the differential scanning calorimeter (DSC). Two grades of PEO with different molecular weights (PEO200 with M_w = 200,000 g/mol and PEO2 with M_n = 2000 g/mol) were used in this work. The thermal analysis revealed that the blends cast from either benzene or chloroform were miscible in the molten state. The crystallization of PEO in the benzene-cast blends was more easily suppressed than it was in the chloroform-cast blends. Furthermore, the benzene-cast blends showed a greater negative value of Flory-Huggins interaction parameter than those cast from chloroform in the PVAc/PEO200 poly-blend system. It was supposed that the benzene-cast blends had more homogeneous morphology. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 411–421, 1997     

Improvement of the mechanical properties of chitosan films by the addition of poly(ethylene oxide)

The mechanical properties of films prepared from mixed acetic acid aqueous solutions of chitosan (M_w = 400,000; M_w/M_n = 3.8) and poly(ethylene oxide) (PEO) (viscosity average molecular weight of 200,000 or 600,000) were determined. A chitosan:PEO weight ratio of 10:2 improved the mechanical properties compared with pure chitosan films. The improvement of the mechanical properties correlated with a small reduction of the correlation length measured by small‐angle neutron scattering (SANS).     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

Thermally induced crystallization and enzymatic degradation studies of poly (L‐lactic acid) films

Poly(L ‐lactic acid) (PLLA) films with different crystallinities were prepared by solvent casting and subsequently annealed at various temperatures (T_a) (80–110°C). The effects of crystallinity on enzymatic degradation of PLLA films were examined in the presence of proteinase K at 37°C by means of weight loss, DSC, FTIR spectroscopy, and optical microscopy. DSC and the absorbance ratio of 921 and 956 cm^?1 (A₉₂₁/A₉₅₆) were used to evaluate crystallinity changes during thermally induced crystallization and enzymatic hydrolysis. The highest percentage of weight loss was observed for the film with the lowest initial crystallinity and the lowest percentage of weight loss was observed for the film with highest crystallinity. FTIR investigation of degraded films showed a band at 922 cm^?1 and no band at 908 cm^?1 suggested that all degraded samples form α crystals. The rate of degradation was found to depend on the initial crystallinity of PLLA film and shown that enzymatic degradation kinetics followed first‐order kinetics for a given enzyme concentration. DSC crystallinity and IR absorbance ratio, A₉₂₁/A₉₅₆ ratio, showed no significant changes with degradation time for annealed PLLA films whereas as‐cast PLLA film showed an increase in crystallinity with degradation; this revealed that degradation takes place predominantly in the free amorphous region of annealed PLLA films without changing long range and short range order © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Highly enhanced accelerating effect of melt‐recrystallized stereocomplex crystallites on poly(L‐lactic acid) crystallization: effects of molecular weight of poly(D‐lactic acid)

The effects of the molecular weight of poly(D ‐lactic acid) (PDLA), which forms stereocomplex (SC) crystallites with poly(L ‐lactic acid) (PLLA), and those of processing temperature T_p on the acceleration (or nucleation) of PLLA homocrystallization were investigated using PLLA films containing 10 wt% PDLA with number‐average molecular weight (M_n) values of 5.47 × 10⁵, 9.67 × 10⁴ and 3.67 × 10⁴ g mol^–1 (PDLA‐H, PDLA‐M and PDLA‐L, respectively). For the PLLA/PDLA‐H and PLLA/PDLA‐M films, the SC crystallites that were ‘non’‐melted and those that were ‘completely’ melted at T_p values just above their endset melting temperature and recrystallized during cooling were found to act as effective accelerating (or nucleation) agents for PLLA homocrystallization. In contrast, SC crystallites formed from PDLA‐L, having the lowest M_n, were effective accelerating agents without any restrictions on T_p. In this case, the accelerating effects can be attributed to the plasticizer effect of PDLA‐L with the lowest M_n. The accelerating effects of SC crystallites in the PLLA/PDLA‐H and PLLA/PDLA‐M films was dependent on crystalline thickness for T_p values below the melting peak temperature of SC crystallites, whereas for T_p values above the melting peak temperature the accelerating effects are suggested to be affected by the interaction between the SC crystalline regions and PLLA amorphous regions.     

Change in the molecular weight distribution of poly(ethylene oxide) caused by the complexation with poly(acrylic acid)

The complexation between poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) was made by using double the molar quantity of either polymer component at pH 2 where the resulting complex completely precipitates. After the removal of the precipitate, PEO or PAA remaining in the supernatant was subjected to gel permeation chromatography to investigate the change in the molecular weight distribution (MWD) caused by the complexation. No remarkable difference is observed in the MWD curves for PEO[1] (M_w=1.37 × 10⁴) before and after the complexation with PAA[1] (M_w=1.10 × 10³) and PAA[2] (M_w=4.16 × 10⁵). However, the MWD curves of PEO[2] (M_w=1.26 × 10⁵) and PAA[2] become shortened and shift to the low molecular weight side after the complexation with PAA[1] or [2] and PEO[2], respectively. This tendency is enhanced by increasing the complexation temperature. From these results, it is indicated that the complexation between PEO and PAA deals with an equilibrium reaction, and the equilibrium constant is dependent on the chain length of both polymer components and also on the complexation temperature.     

Study on the properties of crosslinking of poly(ethylene oxide) and hydroxyapatite–poly(ethylene oxide) composite

This study covers the crosslinking of poly(ethylene oxide) (PEO) and its composite with calcium hydroxyapatite (HA), their mechanical and swelling properties, and morphology. Sheets of the composites of PEO (two different grades with M_v: 5 × 10⁶ and 2 × 10⁵) and HA and neat PEO were prepared by compression molding. The prepared composite and PEO (0.1‐mm‐thick) sheets were crosslinked with exposure of UV‐irradiation in the presence of a photoinitiator, acetophenone (AP). This simple method for crosslinking, induced by UV‐irradiation in the presence of AP, yielded PEO with gel content up to 90%. Gel content, equilibrium swelling ratio, and mechanical and morphological properties of the low molecular weight polyethylene oxide (LMPEO)–HA crosslinked and uncrosslinked composites were evaluated. Although the inclusion of HA into LMPEO inhibits the extent of crosslinking, the LMPEO–HA composite with 20% HA by weight shows the highest gel content, with appreciable equilibrium swelling and mechanical strength. The growth of HA in simulated body fluid solutions on fractured surfaces of LMPEO and also LMPEO–HA was found to be very favorable within short times. The dimensional stability of these samples was found to be satisfactory after swelling and deposition experiments. The good compatibility between the filler hydroxyapatite and poly(ethylene oxide) makes this composite a useful tissue‐adhesive material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 488–496, 2003     

Blends of aliphatic polyesters. IV. Morphology,swelling behavior,and surface and bulk properties of blends from hydrophobic poly(L-lactide) and hydrophilic poly(vinyl alcohol)

Blend films were prepared from hydrophobic poly(L -lactide) (PLLA) and hydrophilic poly(vinyl alcohol) (PVA) with different PLLA contents [X_PLLA (w/w) = PLLA/(PVA + PLLA)] by solution casting and melt quenching. Their morphology, swelling behavior, and surface and bulk properties were investigated. Polarizing optical microscopy, scanning electron microscopy, differential scanning calorimetry, X-ray diffractometry, and tensile testing revealed that PLLA and PVA were phase separated in these blend films and the PLLA-rich and PVA-rich phases both formed a continuous domain in the blend film of X_PLLA = 0.5. The water absorption of the blend films was higher for the blend films of low X_PLLA values when compared at the same immersion time, and it was larger than expected from those of nonblended PLLA and PVA films. The dynamic contact angles of the blend films were linearly increased with an increase in X_PLLA. The tensile strength and Young's modulus of the dry blend films decreased with a rise in X_PLLA, but this dependence was reversed because of the large decreases in tensile strength and Young's modulus for the blend films having high X_PLLA values after immersion in water. The elongation at break was higher for the wet blend film than for the dry blend film when compared at the same X_PLLA and that of the dry and wet blend films decreased with an increase in X_PLLA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2151–2160, 2001     

Water vapor permeability of poly(lactide)s: Effects of molecular characteristics and crystallinity

Amorphous‐made poly(L ‐lactide) [i.e., poly(L ‐lactic acid) (PLLA)], poly(L ‐lactide‐co‐D ‐lactide)[P(LLA‐DLA)](77/23), and P(LLA‐DLA)(50/50) films and PLLA films with different crystallinity (X_c) values were prepared, and the effects of molecular weight, D ‐lactide unit content (tacticity and optical purity), and crystallinity of poly(lactide) [i.e., poly(lactic acid) (PLA)] on the water vapor permeability was investigated. The changes in number‐average molecular weight (M_n) of PLLA films in the range of 9 × 10⁴–5 × 10⁵ g mol^?1 and D ‐lactide unit content of PLA films in the range of 0–50% have insignificant effects on their water vapor transmission rate (WVTR). In contrast, the WVTR of PLLA films decreased monotonically with increasing X_c from 0 to 20%, while leveled off for X_c exceeding 30%. This is probably due to the higher resistance of “restricted” amorphous regions to water vapor permeation compared with that of the “free” amorphous regions. The free and restricted amorphous regions are major amorphous components of PLLA films for X_c ranges of 0–20% and exceeding 30%, respectively, resulting in the aforementioned dependence of WVTR on X_c. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Blends of aliphatic polyesters. III. Biodegradation of solution-cast blends from poly(L-lactide) and poly(ε-caprolactone)

Phase-separated blend films were prepared with the solution casting method from poly(L -lactide) (PLLA) and poly(ε-caprolactone) (PCL) with different PLLA contents [X_PLLA (w/w) = PLLA/(PCL + PLLA)] and their biodegradation was investigated in soil up to 20 months by gravimetry, gel permeation chromatography, tensile testing, differential scanning calorimetry, and scanning electron microscopy. The nonblended PCL film and the blend film with X_PLLA = 0.25 disappeared in 4 and 12 months, respectively, while most of the initial mass remained for the blend film of X_PLLA = 0.75 and the nonblended PLLA film. The decrease in weight remaining, molecular weight, tensile strength, and elongation-at-break was higher for blend films of low X_PLLA. The melting temperature of PLLA in blend films of X_PLLA = 0.5 and 0.75, and of nonblended film, remained around 179°C upon biodegradation in soil for 20 months. The preferred biodegradation of PCL in blend films resulted in formation of microspheres of a PLLA-rich phase at the surface for the blend film of X_PLLA = 0.25 and the porous structure for blend films of X_PLLA = 0.5 and 0.75. Comparison of the weight loss of blend films in biodegradation in soil with that of the nonenzymatic hydrolysis in phosphate-buffered solution revealed preferred enzymatic degradation of PCL and insignificant attack to PLLA in the blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2259–2268, 1998     

Preparation of high‐molecular‐weight poly(L‐lactic acid)‐based polymers through direct condensation polymerization in bulk state

Poly(L ‐lactic acid‐co‐succinic acid‐co‐1,4‐butanediol) (PLASB) was synthesized by a direct condensation copolymerization of L ‐lactic acid, succinic acid (SA), and 1,4‐butanediol (BD) in bulk state using titanium(IV) butoxide (TNBT) as a catalyst. Weight average molecular weight (M_w) of PLASB increased from 3.5 × 10⁴ to 2.1 × 10⁵ as the content of SA and BD went up from 0.01 to 0.5 mol/100 mol of L ‐lactic acid (LA). PLASB having M_w in the range from 1.8 × 10⁵ to 2.1 × 10⁵ showed tensile properties comparable to those of commercially available poly(L ‐lactic acid) (PLLA). In sharp contrast, homopolymerization of LA in bulk state produced PLLA with M_w as low as 4.1 × 10⁴, and it was too brittle to prepare specimens for the tensile tests. M_w of PLASB synthesized by using titanium(IV)‐2‐ethyl(hexoxide), indium acetate, indium hydroxide, antimony acetate, antimony trioxide, dibutyl tin oxide, and stannous‐2‐ethyl 1‐hexanoate was compared with that of PLASB obtained by TNBT. Ethylene glycol oligomers with different chain length were added to LA/SA in place of BD to investigate effect of chain length of ethylene glycol oligomers on the M_w of the resulting copolymers. Biodegradability of PLASB was analyzed by using the modified Sturm test. Toxicity of PLASB was evaluated by counting viable cell number of mouse fibroblast cells that had been in contact with PLASB discs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 466–472, 2006     

High molecular weight poly( -lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties

The miscibility of high molecular weight poly( -lactide) PLLA with high molecular weight poly(ethylene oxide) PEO was studied by differential scanning calorimetry. All blends containing up to 50 weight% PEO showed single glass transition temperatures. The PLLA and PEO melting temperatures were found to decrease on blending, the equilibrium melting points of PLLA in these blends decreased with increasing PEO fractions. These results suggest the miscibility of PLLA and PEO in the amorphous phase. Mechanical properties of blends with up to 20 weight% PEO were also studied. Changes in mechanical properties were small in blends with less than 10 weight% PEO. At higher PEO concentrations the materials became very flexible, an elongation at break of more than 500% was observed for a blend with 20 weight% PEO. Hydrolytic degradation up to 30 days of the blends showed only a small variation in tensile strength at PEO concentrations less than 15 weight%. As a result of the increased hydrophilicity, however, the blends swelled. Mass loss upon degradation was attributed to partial dissolution of the PEO fraction and to an increased rate of degradation of the PLLA fraction. Significant differences in degradation behaviour between PLLA/PEO blends and (PLLA/PEO/PLLA) triblock-copolymers were observed.     

Reactive blending of poly(L‐lactic acid) with poly(ethylene‐co‐vinyl alcohol)

Poly(L ‐lactic acid) (PLLA) was blended with poly(ethylene‐co‐vinyl alcohol) (EVOH) in the presence of an esterification catalyst to induce reaction between the hydroxyl groups of EVOH and the terminal carboxylic group of PLLA. Nascent low‐molecular‐weight PLLA, obtained from a direct condensation polymerization of L ‐lactic acid in bulk state, was used for the blending. Domain size of the PLLA phase in the graft copolymer was much smaller than that corresponding to a PLLA/EVOH simple blend. The mechanical properties of the graft copolymer were far superior to those of the simple blend, and the graft copolymer exhibited excellent mechanical properties even though the biodegradable fraction substantially exceeded the percolation level. The grafted PLLA reduced the crystallization rate of the EVOH moiety. Melting peak temperature (T_m) of the PLLA phase was not observed until the content of PLLA in the graft reaction medium went over 60 wt %. The modified Sturm test results demonstrated that biodegradation of EVOH‐g‐PLLA took place more slowly than that of an EVOH/PLLA simple blend, indicating that the chemically bound PLLA moiety was less susceptible to microbial attack than PLLA in the simple blend. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 886–890, 2005     

Properties and morphology of poly(L‐lactide). III. Effects of initial crystallinity on long‐term in vitro hydrolysis of high molecular weight poly(L‐lactide) film in phosphate‐buffered solution

The effects of crystallinity (x_c) on the hydrolysis of high molecular weight poly(L ‐lactide) (PLLA) films in a phosphate‐buffered solution at 37°C was investigated by gel permeation chromatography, tensile testing, differential scanning calorimetry, scanning electron microscopy, and polarizing optical microscopy. The change in molecular weight distribution and surface morphology of the PLLA films after hydrolysis revealed that the hydrolysis of PLLA film in a phosphate‐buffered solution proceeded homogeneously along the film cross section, mainly via the bulk‐erosion mechanism. The induction period until the start of the decrease in mass remaining and the tensile strength became longer with a decrease in the initial x_c of the PLLA films. The rate of molecular weight reduction was higher as the initial x_c of the PLLA films increased when hydrolysis was carried out up to 24 months. Melting and glass transition temperatures of the PLLA films increased in the first 12 months of hydrolysis, while they decreased in another 24 months, irrespective of the initial x_c. The x_c value of the PLLA films increased monotonously by hydrolysis. The lamella disorientation in PLLA spherulites after hydrolysis implied that the hydrolysis of PLLA chains occurred predominantly in the amorphous region between the crystalline regions in the spherulites. The area of a specific molecular weight in GPC spectra at 36 months increased with increase in the initial x_c of the PLLA film, suggesting that the specific peak should be due to the component of one fold in the crystalline region. The reason for enhanced hydrolysis of PLLA films having higher initial crystallinities was discussed in terms of tie chains and terminal groups of PLLA. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1452–1464, 2000