Surface hydrophilicity and enzymatic hydrolyzability of biodegradable polyesters: 1. effects of alkaline treatment

Surface treatment using alkaline solutions was attempted to enhance the surface hydrophilicity and enzymatic hydrolyzability of hydrophobic poly(L ‐lactide) [ie poly(L ‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL). The alkaline treatment was performed by immersing the PLLA and PCL films in 0.01 and 4 N NaOH solutions, respectively, for various periods of time. The effects of the alkaline treatment on the hydrophilicity of the films were monitored by dynamic contact angle measurements, while the enzymatic hydrolyzability of the PLLA and PCL films after the alkaline treatment were evaluated by weight losses in the presence of proteinase K and Rhizopus arrhizus lipase, respectively. With the alkaline treatment the hydrophilicity of the PLLA and PCL films was controllable in the advancing contact angle (θ_a) ranges of 84–108° and of 69–93°, respectively, by varying the alkaline treatment time. The enzymatic hydrolysis rates of the PLLA films became higher with decrease of the θ_a, irrespective of the crystallinity, strongly suggesting that the surface hydrophilicity or the surface molecular weight is crucial to determine their enzymatic hydrolyzability. In contrast, the enzymatic hydrolyzability of the PCL films remained unchanged even when the θ_a decreased from 93° to 73° by alkaline treatment for 4 h. However, prolonged alkaline treatment for periods of time exceeding 4 h, which insignificantly altered the θ_a but caused the formation of pores and cracks on the PCL film surface, accelerated the enzymatic hydrolysis of the PCL films. This indicates that the enzymatic hydrolyzability of the PCL film depends on the surface area per unit weight rather than the surface hydrophilicity. Copyright © 2003 Society of Chemical Industry     

Poly(L‐Lactide), 8. High‐Temperature Hydrolysis of Poly(L‐Lactide) Films with Different Crystallinities and Crystalline Thicknesses in Phosphate‐Buffered Solution

Poly(L ‐lactide) (PLLA) films having different crystallinities (X_c's) and crystalline thicknesses (L_c's) were prepared by annealing at different temperatures (T_a's) from the melt and their high‐temperature hydrolysis was investigated at 97°C in phosphate‐buffered solution. The changes in remaining weight, molecular weight distribution, and surface morphology of the PLLA films during hydrolysis revealed that their hydrolysis at the high temperature in phosphate‐buffered solution proceeds homogeneously along the film cross‐section mainly via the bulk erosion mechanism and that the hydrolysis takes place predominantly and randomly at the chains in the amorphous region. The remaining weight was higher for the PLLA films having high initial X_c when compared at the same hydrolysis time above 30 h. However, the difference in the hydrolysis rate between the initially amorphous and crystallized PLLA films at 97°C was smaller than that at 37°C, due to rapid crystallization of the initially amorphous PLLA film by exposure to crystallizable high temperature in phosphate‐buffered solution. The hydrolysis constant (k) values of the films at 97°C for the period of 0–8 h, 0.059–0.085 h^–1 (1.4–2.0 d^–1), were three orders of magnitude higher than those at 37°C for the period of 0–12 months, 2.2–3.4×10^–3 d^–1. The melting temperature (T_m) and X_c of the PLLA films decreased and increased, respectively, monotonously with hydrolysis time, excluding the initial increase in T_m for the PLLA films prepared at T_a = 100, 120, and 140°C in the first 8, 16, and 16 h, respectively. A specific peak that appeared at a low molecular weight around 1×10⁴ in the GPC spectra was ascribed to the component of one fold in the crystalline region. The relationship between T_m and L_c was found to be T_m (K) = 467·[1–1.61/L_c (nm)] for the PLLA films hydrolyzed at 97°C for 40 h.     

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     

Plasticization of Poly‐L‐lactide with L‐lactide,D‐lactide,and D,L‐lactide monomers

Poly‐L ‐lactide (PLLA) is being widely considered for repair of damaged tissues, for controlled antibiotic release, and also as scaffolds for cultured cells. PLLA was blended with the lactide monomer in its two enantiomeric forms: D ‐lactide (D ‐la) and L ‐lactide (L ‐la) and with the cyclic dimmer D ,L ‐la, in order to enhance its flexibility and thereby overcome its inherent problem of brittleness. In this work, the crystallization, phase structure, and tensile properties of PLLA and PLLA plasticized with 5, 10, 15, and 20 wt% of D ‐la, L ‐la, and D ,L ‐la are explored. The three plasticizers used were effective in lowering the glass transition temperature (T_g) and the melting temperature (T_m) of PLLA, around 20°C for a plasticizer content of 20 wt%. The tensile strength and modulus of the blends decreased following the increasing content of plasticizers from approximately 58 MPa to values below 20 MPa, and from 1667 to 200 MPa, respectively. Aging the blends at storage ambient temperature revealed that the enhanced flexibility as well as the morphological stability was lost over time due to the migration of the plasticizer to the surface, this being less marked in the case of D ‐la as a result of interactions between the polymer and its enantiomeric monomer of complementary configuration. POLYM. ENG. SCI., 53:2073–2080, 2013. © 2013 Society of Plastics Engineers     

Morphology and melt crystallization of poly(L‐lactide) obtained by ring opening polymerization of L‐lactide with zinc catalyst

The morphology and melt crystallization of zinc catalyzed poly(L ‐lactide) (PLLA) were investigated by using differential scanning calorimetry (DSC), polarized optical microscopy, and scanning electron microscopy. Isothermal melt crystallization performed at 95–135°C showed that the morphology depends on the degree of supercooling, as illustrated by crystallite perfection and lamellar thickening behaviors. Double melting peak was observed on DSC thermograms and attributed to the melt‐recrystallization mechanism, small and imperfect crystals becoming gradually more stable ones. Circumferential and hexagonal cracks were detected in PLLA spherulites, which were formed during melt‐crystallization at 135°C and quenching in liquid nitrogen. Rhythmic growth and thermal shrinkage are suggested to be the two main factors accounting for the formation of periodic cracks. Spherulite growth rates of PLLA were evaluated by using combined isothermal and nonisothermal procedures, and were analyzed by the secondary nucleation theory. The maximum growth rate reached 9.1 μm/min at 130°C. The temperature range investigated (120–155°C) belongs to the Regime II of crystallization. The value of U* was found to be 1890 cal/mol, instead of 1500 cal/mol commonly used in literature, and K_g and σ were estimated to be 3.03 × 10⁵ K² and 1.537 × 10^?4 J/m², respectively. As a result, no distinct difference between PLLA catalyzed by zinc metal and those prepared with stannous octoate catalyst exists in this work. POLYM. ENG. SCI., 46:1583–1589, 2006. © 2006 Society of Plastics Engineers.     

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     

Effect of poly(l‐lactide)/poly(d‐lactide) block length ratio on crystallization behavior of star‐shaped asymmetric poly(l(d)‐lactide) stereoblock copolymers

Effect of Poly(l ‐lactide)/Poly(d ‐lactide) (PLLA/PDLA) block length ratio on the crystallization behavior of star‐shaped poly(propylene oxide) block poly(d ‐lactide) block poly (l ‐lactide) (PPO–PDLA–PLLA) stereoblock copolymers with molecular weights (M_n) ranging from 6.2 × 10⁴ to 1.4 × 10⁵ g mol^?1 was investigated. Crystallization behaviors were studied utilizing differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). Only stereocomplex crystallites formed in isothermal crystallization at 140 to 156°C for all samples. On one hand, the overall crystallization rate decreased as PLLA/PDLA block length ratio increased. As PLLA/PDLA block length ratio increased from 7:7 to 28:7, the value of half time of crystallization (t_1/2) delayed form 2.85 to 5.31 min at 140°C. On the other hand, according to the Lauritzen–Hoffman theory, the fold‐surface energy (σ_e) was calculated. σ_e decreased from 77.7 to 73.3 erg/cm² with an increase in PLLA/PDLA block length ratio. Correspondingly increase in nucleation density was observed by the polarized optical microscope. Results indicated that the PLLA/PDLA block length ratio had a significant impact on the crystallization behavior of PPO–PDLA–PLLA copolymers. POLYM. ENG. SCI., 55:2534–2541, 2015. © 2015 Society of Plastics Engineers     

Investigations on the morphology and melt crystallization of poly(L‐lactide)‐poly(ethylene glycol) diblock copolymers

Ring opening polymerization of L ‐lactide was realized in the presence of monomethoxy poly(ethylene glycol), using zinc lactate as catalyst. The resulting PLLA‐PEG diblock copolymers were characterized by using ¹H‐NMR, SEC, WAXD, and DSC. All the copolymers were semicrystalline, one or two melting peaks being detected depending on the composition. Equilibrium melting temperature (T_m⁰) of PLLA blocks was determined for three copolymers with different EO/LA molar ratios. T_m⁰ decreased with decreasing PLLA block length. A copolymer with equivalent PLLA and PEG block lengths was selected for melt crystallization studies and the resulting data were analyzed with Avrami equation. The obtained Avrami exponent is equal to 2.6 ± 0.2 in the crystallization temperature range from 80 to 100°C. In addition, the spherulite growth rate of PLLA‐PEG was analyzed by using Lauritzen‐Hoffmann theory in comparison with PLLA homopolymers. The nucleation constant was found to be 2.39 × 10⁵ K² and the free energy of folding equal to 53.8 erg/cm² in the range of 70–94°C, both higher than those of PLLA homopolymers, while the spherulite growth rate of the diblock copolymer was lower. POLYM. ENG. SCI., 2008. © 2007 Society of Plastics Engineers     

Characterization of modulus and glass transition phenomena in poly(L‐lactide)/hydroxyapatite composites

In order to study the dynamic‐mechanical properties of Poly(L‐lactide)/Hydroxyapatite (PLLA/HA) composites, two different molecular weight (inherent viscosity (η_inh): 4.0 (dL/g), and 7.8 (dL/g)) poly(L‐lactide) (PLLA) were synthesized by bulk polymerization and filled with 10%, 30%, and 50% (w/w) with medical grade HA (size range: 25–45 μm and Ca/P = 1.69). The plain PLLA polymers and PLLA/HA composites were compression molded and machined to yield 50 × 3 × 2 mm³ specimens. The composites were investigated by dynamic mechanical thermal analyzer (DMTA) of imposed bending load on rectangular specimens over a temperature range from 30 to 120°C using multiple frequencies (0.3–50 Hz). The results showed that the bending storage modulus (E′) of the composites increased linearly with the percentage of the filler, reaching at 37°C and 0.1 Hz about 2.5, 3.7 and 5.0 GPa with 10, 30 and 50% of HA respectively. The glass transition temperature, evaluated at the tan δ peaks, were in the range 70–80°C and 50–70°C for PLLA matrix and PLLA composites respectively. The activation energies at the glass transition temperature were calculated from the Arrhenius plot in the range of 102–111 Kcal/mol for the composites, whereas 132 and 148 Kcal/mol were found for low and high molecular weight of PLLA respectively. The content of amorphous phase was evaluated from the intensity of tan δ peak. Results showed that HA causes an amorphous phase with a greater mobility with respect to the pure PLLA.     

Physical properties and enzymatic hydrolysis of poly(L‐lactide)–TiO2 composites

Amorphous poly(L ‐lactide) (PLLA) composite films with titanium dioxide (TiO₂) particles were prepared by solution‐casting using methylene chloride as a solvent, followed by quenching from the melt. The effects of surface treatment, volume fraction, size, and crystalline type of the TiO₂ particles on the mechanical properties and enzymatic hydrolysis of the composite films were investigated. The tensile strength of the PLLA composite films containing TiO₂ particles except for anatase‐type ones with a mean particle size of 0.3–0.5 μm was lowered and the Young's modulus became higher with increasing the content of TiO₂ particles. The tensile strength of the composite films containing anatase‐type TiO₂ with a mean particle size of 0.3–0.5 μm at contents of 20 wt % or less was almost the same as that of the pure PLLA film. The enzymatic hydrolysis of PLLA matrix was accelerated by the addition of the hydrophilic anatase‐type TiO₂ particles (nontreated or Al₂O₃ treated) with a mean particle size of 0.3–0.5 μm at relatively high contents such as 20 wt %. On the other hand, the enzymatic hydrolysis of PLLA matrix was inhibited by composite formation with the hydrophobic rutile‐type TiO₂ particles (Al₂O₃‐stearic acid treated, or ZrO₂‐Al₂O₃‐stearic acid treated). These results suggest that the mechanical properties and enzymatic hydrolyzability of the PLLA can be controlled by the kind and amount of the added TiO₂ particles. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 190–199, 2005     

Poly(L‐lactide): v. effects of storage in swelling solvents on physical properties and structure of poly(L‐lactide)

The effects of storage at 25°C in swelling solvents having different solubility parameter (δ_s) values of 16.8–26.0 J^0.5 cm^−1.5 on the physical properties and structure of as‐cast poly(L ‐lactide) (PLLA) films was investigated by the degree of swelling (DS), differential scanning calorimetry (DSC), and tensile tests. It was found that PLLA film shows durabity to swelling solvents having δ_s values much lower or higher than the value range of 19–20.5 J^0.5 cm^−1.5 and that the polymer solubility parameter (δ_p) for PLLA is in the value range of 19–20.5 J^0.5 cm^−1.5. The decrease in the glass transition temperature (T_g) and tensile properties and the increase in melting temperature (T_m) and crystallinity (x_c) were larger for PLLA films swollen in solvents having a high DS at 7 days (DS_7days). The slight increase in T_m and x_c for PLLA films after swelling in solvents with high DS_7days values was due to the crystallization of PLLA that occurred during swelling, while the small increase in T_g and elongation at break (ε_B) for PLLA films after immersion in the solvents having low DS_7days values was ascribed to stabilized chain packing in the amorphous region. The T_g, ε_B, and Young's modulus of the PLLA films after swelling in the solvents varied in the ranges of 47–57°C, 4–8%, and 55–77 kg/mm², depending on their DS_7days or δ_s values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1582–1589, 2001     

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     

Plasticization of poly‐L‐lactide for tissue engineering

Plasticization of medical grade poly‐L ‐lactide (PLLA) by addition of polyethylene glycol (PEG) with various molar masses has been evaluated as means of producing low stiffness matrices for bioresorbable scaffolds for soft‐tissue engineering applications. As reported previously, the T_g of injection molded specimens of the PLLA/PEG blends decreased strongly with PEG content, so that at PEG contents of 15 and 25 wt % it became significantly lower than normal human body temperature, implying an essentially rubber‐like mechanical response in vivo. The degree of crystallinity of the moldings also increased strongly with PEG content, reaching a maximum of about 60 wt % at 25 wt % PEG. Moreover, after the immersion in phosphate‐buffered saline for 5 days in 37°C to simulate conditions in vivo, the moldings with the highest PEG contents showed increased water uptake and, for relatively low molar mass PEG, significant mass loss, associated with phase separation and leaching of the PEG. Blends with relatively low PEG contents also showed large increases in their degree of crystallinity. The implications of these changes for the in vivo performance of the blends and their potential for development as matrices for bioresorbable scaffolds are discussed in the light of results from a series of PLLA/PEG copolymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Accelerated crystallization of poly(L‐lactide) by physical aging

The low‐temperature physical aging of amorphous poly(L ‐lactide) (PLLA) at 25–50°C below glass transition temperature (T_g) was carried out for 90 days. The physical aging significantly increased the T_g and glass transition enthalpy, but did not cause crystallization, regardless of aging temperature. The nonisothermal crystallization of PLLA during heating was accelerated only by physical aging at 50°C. These results indicate that the structure formed by physical aging only at 50°C induced the accelerated crystallization of PLLA during heating, whereas the structure formed by physical aging at 25 and 37°C had a negligible effect on the crystallization of PLLA during heating, except when the physical aging at 37°C was continued for the period as long as 90 days. The mechanism for the accelerated crystallization of PLLA by physical aging is discussed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Effect of crystallization temperature on crystal modifications and crystallization kinetics of poly(L‐lactide)

The crystalline structure of poly(L ‐lactide) (PLLA) have been found to quite depend on the crystallization temperatures (T_cs), especially in the range of 100?120°C, which is usually used as the crystallization temperature for the industrial process of PLLA. The analysis of wide‐angle X‐ray diffraction and Fourier transformed infrared spectroscopy revealed that 110°C is a critical temperature for PLLA crystallization. At T_c < 110°C and T_c ≥ 110°C, the α′ and α crystals were mainly produced, respectively. Besides, the structural feature of the α′‐form was illustrated, and it was found that the α′‐form has the larger unit cell dimension than that of the α‐form. Moreover, the crystallization kinetics of the α′ and α crystals are different, resulting in the discontinuousness of the curves of spherulite radius growth rate (G) versus T_c and the half time in the melt‐crystallization (t_1/2) versus T_c investigated by Polarized optical microscope and Differential scanning calorimetry, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ring‐opening graft polymerization of L‐lactide onto starch granules in an ionic liquid

A room temperature ionic liquid 1‐allyl‐3‐methylimidazolium chloride ([AMIM]Cl) was a promising direct solvent for starch and nonderivitizing solvent for starch‐effective dissolution, in which the ring‐opening graft polymerization (ROGP) of L ‐lactide (L ‐LA) onto starch chains was carried out homogeneously. The obtained starch grafted poly(L ‐lactide) (starch‐g‐PLLA) was characterized by FTIR, ¹³C NMR, DSC, and WAXD, and the good adhesion between the two components was evidenced by SEM observations although the chains of grafted PLLA were not long. The grafting efficiency of PLLA reached 30% when the ROGP proceeded at 100°C for 10 h with L ‐LA/starch 0.5 : 1 (wt/wt) and stannous octoate (Sn(Oct)₂) as a catalyst, which was calculated according to a standard curve newly created by FTIR method. The homopolymerization of L ‐LA and the disconnection of grafted PLLA from starch‐g‐PLLA were the main competition reactions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of poly(L‐lactide) membranes prepared by γ‐radiation‐induced grafting of N‐vinyl pyrrolidone

A copolymer, poly(L ‐lactide)‐g‐poly(N‐vinyl pyrrolidone) (PLLA‐g‐PVP) was prepared with poly(L ‐lactide) (PLLA) and N‐vinyl pyrrolidone in the presence of methanol as a solvent by γ‐ray irradiation. The structure of PLLA‐g‐PVP was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. The PLLA‐g‐PVP graft ratio calculated by the percentage increase in weight increased with the increase of absorbed dose, and the percentage crystallinity of PLLA‐g‐PVP decreased with increasing graft ratio. The introduction of the poly(N‐vinyl pyrrolidone) chain into PLLA resulted in a decrease in the contact angle of PLLA‐g‐PVP with increasing graft ratio. In vitro degradation testing showed that PLLA‐g‐PVP had a higher degradation rate both in the weight‐loss test and molecular weight measurement because of a lower crystalline percentage and higher hydrophilicity compared to PLLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Crystalline structure and morphology of poly(L‐lactide) formed under high pressure

The poly(l ‐lactide) (PLLA) samples were prepared by the annealing under 100 MPa at 75–145^°C and 200 MPa at 105–145^°C for 6 h, respectively. The crystalline structures, thermal properties and morphology were investigated using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), and scanning electron microscopy (SEM). On the basis of the DSC and WAXD results, it can be seen that the α′ form was formed by the annealing under 100 MPa at 85–95°C but not found under 200 MPa at 105–145°C. A phase diagram of PLLA crystal form under high pressure was constructed under the given experimental conditions, which displayed the α′ form was formed at limited temperature and pressure range. Besides, SEM suggested that the PLLA samples annealed under 100 MPa crystallize to form lamellar‐like crystals due to the low growth rate and the confined crystallization behavior under high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40637.     

Porous biodegradable polyesters. I. Preparation of porous poly(L‐lactide) films by extraction of poly(ethylene oxide) from their blends

Porous poly(L ‐lactide) (PLLA) films were prepared by water extraction of poly(ethylene oxide) (PEO) from solution‐cast PLLA and PEO blend films. The dependence of blend ratio and molecular weight of PEO on the porosity and pore size of films was investigated by gravimetry and scanning electron microscopy. The film porosity and extracted weight ratio were in good agreement with the expected for porous films prepared using PEO of low molecular weight (M_w = 1 × 10³), but shifted to lower values than expected when high molecular weight PEO (M_w = 1 × 10⁵) was utilized. The maximum pore size was larger for porous films prepared from PEO having higher molecular weight, when compared at the same blending ratio of PLLA and PEO before water extraction. Differential scanning calorimetry of as‐cast PLLA and PEO blend films revealed that PLLA and PEO were phase‐separated at least after solvent evaporation. On the other hand, comparison of blend films before and after extraction suggested that a small amount of PEO was trapped in the amorphous region between PLLA crystallites even after water extraction and hindered PLLA crystallization during solvent evaporation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 629–637, 2000