Unique crystallization behavior of poly(l-lactide)/poly(d-lactide) stereocomplex depending on initial melt states

A unique crystallization behavior of poly(l-lactide) (PLLA)/poly(d-lactide) (PDLA) stereocomplex was observed when a PLLA/PDLA blend (50/50) was subjected to specific melting conditions. PLLA and PDLA were synthesized by ring opening polymerization of l- or d-lactide using zinc lactate as catalyst. PLLA/PDLA blend was prepared through solution mixing followed by vacuum drying. The blend was melted under various melting conditions and subsequent crystallization behaviors were analyzed by using DSC, XRD, NMR and ESEM. Stereocomplex was exclusively formed from the 50/50 blend of PLLA and PDLA with relatively low molecular weights. Surprisingly, stereocomplex crystallization was distinctly depressed when higher melting temperature and longer melting period were applied, in contrast to homopolymer crystallization. Considering predominant interactions between PLLA and PDLA chains, a novel model of melting process is proposed to illustrate this behavior. It is assumed that PLLA and PDLA chain couples would preserve their interactions (melt memory) when the stereocomplex crystal melts smoothly, thus resulting in a heterogeneous melt which can easily crystallize. The melt could gradually become homogeneous at higher temperature or longer melting time. The strong interactions between PLLA and PDLA chain segments are randomly distributed in a homogeneous melt, thus preventing subsequent stereocomplex crystallization. However, the homogeneous melt can recover its ability to crystallize via dissolution in a solvent.     

Controlled crystal nucleation in the melt-crystallization of poly(l-lactide) and poly(l-lactide)/poly(d-lactide) stereocomplex

Among the various inorganic nucleators examined, Talc and an aluminum complex of a phosphoric ester combined with hydrotalcite (NA) were found to be effective for the melt-crystallization of poly(l-lactide) (PLLA) and PLLA/poly(d-lactide) (PDLA) stereo mixture, respectively. NA (1.0 phr (per one hundred resin)) can exclusively nucleate the stereocomplex crystals, while Talc cannot suppress the homo crystallization of PLLA and PDLA in the stereo mixture. Double use of Talc and NA (in 1.0 phr each) is highly effective for enhancing the crystallization temperature of the stereo complex without forming the homo crystals. The stereocomplex crystals nucleated by NA show a significantly lower melting temperature (207 °C) than the single crystal of the stereocomplex (230 °C) in spite of recording a large heat of crystallization ΔH_c (54 J/g). Photomicrographic study suggests that the spherulites with a symmetric morphology are formed in the stereo mixture added with NA while the spherulites do not grow in size in the mixture added with Talc. The exclusive growth of the stereocomplex crystals by the melt-crystallization process will open a processing window for the PLLA/PDLA.     

Stereocomplex crystallization and spherulite growth behavior of poly(l-lactide)-b-poly(d-lactide) stereodiblock copolymers

The non-isothermally and isothermally crystallized stereodiblock copolymers of poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA) with equimolar l-lactyl and d-lactyl units and different number-average molecular weights (M_n) of 3.9 × 10³, 9.3 × 10³, and 1.1 × 10⁴ g mol⁻¹, which are abbreviated as PLLA-b-PDLA copolymers, contained only stereocomplex crystallites as crystalline species, causing higher melting temperatures of the PLLA-b-PDLA copolymers compared to those of PLLA homopolymers. In the case of non-isothermal crystallization, the cold crystallization temperatures of the PLLA-b-PDLA copolymers during heating and cooling were respectively lower and higher than those of PLLA homopolymers, indicating accelerated crystallization of PLLA-b-PDLA copolymers. In the case of isothermal crystallization, in the crystallizable temperature range, the crystallinity (X_c) values of the PLLA-b-PDLA copolymers were lower than those of the PLLA homopolymers, and were susceptible to the effect of crystallization temperature in contrast to that of homopolymers. The radial growth rate of the spherulites (G) of the PLLA-b-PDLA copolymers was the highest at the middle M_n of 9.3 × 10³ g mol⁻¹. This trend is different from that of the PLLA homopolymers where the G values increased monotonically with a decrease in M_n, but seems to be caused by the upper critical M_n values of PLLA and PDLA chains as in the case of PLLA/PDLA blends (in other papers), above which homo-crystallites are formed in addition to stereocomplex crystallites. The disturbed crystallization of PLLA-b-PDLA copolymers compared to that of the PLLA/PDLA blend is attributable to the segmental connection between the PLLA and PDLA chains, which interrupted the free movement of those chains of the PLLA-b-PDLA copolymers during crystallization. The crystallite growth mechanism of the PLLA-b-PDLA copolymers was different from that of the PLLA/PDLA blend.     

Effect of the addition of poly(d-lactic acid) on the thermal property of poly(l-lactic acid)

Thermal property and crystallization behavior of PLLA blended with a small amount of PDLA (1-5 wt%) were studied. PDLA molecules added in PLLA formed stereocomplex crystallites in the PLLA matrix. When the blend was cooled to a temperature below T_m of PLLA, stereocomplex crystallites acted as nucleation sites of PLLA and enhanced the crystallization of PLLA significantly (heterogeneous nucleation). Such crystallization enhancement was not observed when the blend with lower PDLA content was cooled from 240 °C at which both PLLA crystal and the stereocomplex disappeared. Low molecular weight PDLA isolated in the matrix of PLLA did not form a stereocomplex crystallite with a large surface area enough to act as a nucleation site. On the other hand, high molecular weight PDLA chains formed a large stereocomplex crystallite. With increasing PDLA content, stereocomplex crystallites were more easily formed and they acted as nucleation sites. PLLA crystal near the stereocomplex crystallites has an incomplete structure and showed a melting peak at a lower temperature than pure PLLA crystal.     

Hetero-stereocomplex formation between substituted poly(lactic acid)s with linear and branched side chains,poly(l-2-hydroxybutanoic acid) and poly(d-2-hydroxy-3-methylbutanoic acid)

Differential scanning calorimetry and wide-angle X-ray diffractometry first revealed the formation of hetero-stereocomplex (HTSC) between biodegradable, optically active, and isotactic poly(2-hydroxyalkanoic acid)s having different chemical structures and opposite configurations, i.e., l-configured substituted poly(lactic acid) (PLA) [poly(l-2-hydroxybutanoic acid), P(l-2HB)] with linear side chains (ethyl groups) and d-configured substituted PLA [poly(d-2-hydroxy-3-methylbutanoic acid), P(d-2H3MB)] with branched side chains (isopropyl groups) in solution and in bulk from the melt. The melting temperature of P(l-2HB)/P(d-2H3MB) HTSC crystallites was 197–204 °C, which is much higher those of P(l-2HB) and P(d-2H3MB) homo-crystallites (100–101 °C and 158–165 °C, respectively). The interplain distances and crystalline lattice sizes of P(l-2HB)/P(d-2H3MB) HTSC crystallites were respectively larger and smaller than those of P(l-2HB)/P(d-2HB) and P(l-2H3MB)/P(d-2H3MB) homo-stereocomplexes. The HTSC formation of substituted PLA with opposite configurations reported in the present study will provide a versatile way to prepare poly(2-hydroxyalkanoic acid)-based biodegradable materials having a wide variety of physical properties and biodegradability.     

Synthesis, characterization and thermal properties of hexaarmed star-shaped poly(ε-caprolactone)-b-poly(d,l-lactide-co-glycolide) initiated with hydroxyl-terminated cyclotriphosphazene

Hexakis[p-(hydroxymethyl)phenoxy]cyclotriphosphazene was prepared by the reaction of hexachlorocycltriphosphaneze with the sodium salt of 4-hydroxybenzaldehyde and subsequent reduction of aldehyde groups to alcohol groups by using sodium borohydride. Hexaarmed star-shaped hydroxyl-terminated poly(ε-caprolactone) (PCL) were successfully synthesized via ring-opening polymerization of ε-caprolactone (CL) with the above hydroxyl-terminated cyclotriphosphazene initiator and stannous octoate catalyst in bulk. The number-average molecular weight of PCL linearly increased with the molar ratio of monomer to initiator. The star-shaped PCL with hydroxy end groups could be used as a macroinitiator for block copolymerization with d,l-lactide (d,l-LA) and glycolide (GA) using stannous octoate catalyst. IR, ¹H NMR and GPC analysis showed the star-block copolymers were successfully synthesized and the molecular weights and the unit composition of the star-shaped block copolymers were controlled by the molar ratios of d,l-LA and GA monomers to CL. The copolymer presented a two-phase structure, namely, PCL crystalline and d,l-LAGA amorphous domains, which made the copolymer different from linear PCL and star-shaped PCL in crystallinity and thermal behaviors.     

Long terminal linear alkyl group as internal crystallization accelerating moiety of poly(l-lactide)

Poly(l-lactide) (PLLA) polymers having terminal n-alkyl groups with a wide variety of lengths (C₀–C₂₂) were synthesized by ring-opening polymerization of l-lactide in the presence of coinitiators of l-lactic acid (C₀), 1-hexanol (C₆), 1-dodecanol (C₁₂), and 1-docosanol (C₂₂) and their segmental mobility and non-isothermal and isothermal crystallization behavior were investigated by differential scanning calorimetry (DSC) and wide-angle X-ray diffractometry (WAXD). Glass transition and cold crystallization temperatures of melt-quenched samples during heating decreased with an increase in the length of terminal n-alkyl groups. The enhanced PLLA segmental mobility and hydrophobic interaction-based accelerated PLLA nucleation by the presence of terminal long n-alkyl groups should have caused the accelerated non-isothermal and isothermal crystallization of PLLA segments traced by cold crystallization temperature during heating and by radial growth rate of spherulites, respectively. The crystallization accelerating effect became higher with the length of terminal n-alkyl groups. The effects of the length of terminal n-alkyl group on the crystalline growth mechanism of PLLA at the lowest crystallizable temperature was insignificant, whereas the effects of the length of terminal n-alkyl group on the nucleation mechanism of PLLA chains were significant and insignificant for PLLA having M_n of 6–7 × 10³ of 2 × 10⁴ g mol⁻¹, respectively. WAXD measurements revealed that the transition crystallization temperature at which crystalline modification changes from δ-form to α-form was affected by the length of terminal n-alkyl group for PLLA having M_n of 6–7 × 10³ g mol⁻¹, but was not altered by the length of terminal n-alkyl group for PLLA having M_n of 2 × 10⁴ g mol⁻¹.     

Evidence of sequential ordering during cold crystallization of poly (l-lactide)

The structural development during cold crystallization of poly (l-lactide) has been explored by time-dependent Fourier transform infrared spectroscopy and depolarized light scattering, respectively. It is indicated that the conformation-sensitive 956 cm⁻¹ band changes first during induction period, followed by formation of 10₃ helix sequence (921 cm⁻¹ band) in the disordered crystals; after that, the inner structure of new-formed disordered crystals is further perfected, giving rise to frequency shift of 871 cm⁻¹ band to higher wavenumber. Moreover, the formation and subsequent perfection of disordered crystals are also evidenced by the sharp transition of integrated scattering intensity revealed by depolarized light scattering measurements. It is strongly suggested that the cold crystallization of poly (l-lactide) follows a sequential ordering or multi-step process at atomic scale. Furthermore, such a sequential ordering is independent of crystallization temperature and the thermal history (melt cooling rate) of samples prior to cold crystallization. Increasing crystallization temperature or decreasing melt cooling rate just shortens the onset time related to above-referred each step.     

Transcrystalline structures of poly(l-lactide)

Poly(l-lactide) (PLLA) film containing transcrystalline (TC) structures can easily be obtained by placing PLLA films melted between two poly(tetrafluoroethylene) (PTFE) sheets, followed by isothermal crystallization at 122 °C. The fine structures of the PLLA-TC film were studied by various structural techniques such as X-ray diffractometry, optical microscopy and transmission electron microscopy. We also examined the purification effect upon the morphology of PLLA-TC film. The formation of the TC structures revealed that one-dimensional spherulitic growth occurred from the assembling impurities as nucleation agent near the PTFE substrate in the heterogeneous nucleation system. We found that the b-axis of PLLA crystal was parallel to the lamellae growth direction confirmed using X-ray diffraction. The precipitated PLLA film crystallized in a similar process exhibited scanty TC textures, suggesting that the existence of impurity in the PLLA sample was an important factor for the formation of those structures.     

Isothermal and non-isothermal crystallization behavior of poly(l-lactic acid): Effects of stereocomplex as nucleating agent

The effects of incorporated poly(d-lactic acid) (PDLA) as poly(lactic acid) (PLA) stereocomplex crystallites on the isothermal and non-isothermal crystallization behavior of poly(l-lactic acid) (PLLA) from the melt were investigated for a wide PDLA contents from 0.1 to 10 wt%. In isothermal crystallization from the melt, the radius growth rate of PLLA spherulites (crystallization temperature (T_c)≥125 °C), the induction period for PLLA spherulite formation (t_i) (T_c≥125 °C), the growth mechanism of PLLA crystallites (90 °C≤T_c≤150 °C), and the mechanical properties of the PLLA films were not affected by the incorporation of PDLA or the presence of stereocomplex crystallites as a nucleating agent. In contrast, the presence of stereocomplex crystallites significantly increased the number of PLLA spherulites per unit area or volume. In isothermal crystallization from the melt, at PDLA content of 10 wt%, the starting, half, and ending times for overall PLLA crystallization (t_c(S), t_c(1/2), and t_c(E), respectively) were much shorter than those at PDLA content of 0 wt%, due to the increased number of PLLA spherulites. Reversely, at PDLA content of 0.1 wt%, the t_c(S), t_c(1/2), and t_c(E) were longer than or similar to those at PDLA content of 0 wt%, probably due to the long t_i and the decreased number of spherulites. This seems to have been caused by free PDLA chains, which did not form stereocomplex crystallites. On the other hand, at PDLA contents of 0.3-3 wt%, the t_c(S), t_c(1/2), and t_c(E) were shorter than or similar to those at PDLA content of 0 wt% for the T_c range below 95 °C and above 125 °C, whereas this inclination was reversed for the T_c range of 100-120 °C. In the non-isothermal crystallization of as-cast or amorphous-made PLLA films during cooling from the melt, the addition of PDLA above 1 wt% was effective to accelerate overall PLLA crystallization. The X-ray diffractometry could trace the formation of stereocomplex crystallites in the melt-quenched PLLA films at PDLA contents above 1 wt%. This study revealed that the addition of small amounts of PDLA is effective to accelerate overall PLLA crystallization when the PDLA content and crystallization conditions are scrupulously selected.     

Thermal degradation of poly(l-lactide): effect of alkali earth metal oxides for selective l,l-lactide formation

To achieve the feed stock recycling of poly(l-lactide) (PLLA) to l,l-lactide, PLLA composites including alkali earth metal oxides, such as calcium oxide (CaO) and magnesium oxide (MgO), were prepared and the effect of such metal oxides on the thermal degradation was investigated from the viewpoint of selective l,l-lactide formation. Metal oxides both lowered the degradation temperature range of PLLA and completely suppressed the production of oligomers other than lactides. CaO markedly lowered the degradation temperature, but caused some racemization of lactide, especially in a temperature range lower than 250 °C. Interestingly, with MgO racemization was avoided even in the lower temperature range. It is considered that the effect of MgO on the racemization is due to the lower basicity of Mg compared to Ca. At temperatures lower than 270 °C, the pyrolysis of PLLA/MgO (5 wt%) composite occurred smoothly causing unzipping depolymerization, resulting in selective l,l-lactide production. A degradation mechanism was discussed based on the results of kinetic analysis. A practical approach for the selective production of l,l-lactide from PLLA is proposed by using the PLLA/MgO composite.     

Poly(l-lactide)/nano-structured carbon composites: Conductivity, thermal properties, crystallization, and biodegradation

The effects of nano-structured carbon fillers [fullerene C₆₀, single wall carbon nanotube (SWCNT), carbon nanohorn (CNH), carbon nanoballoon (CNB), and ketjenblack (KB)] and conventional carbon fillers [conductive grade and graphitized carbon black (CB)] on conductivity (resistance), thermal properties, crystallization, and proteinase K-catalyzed enzymatic degradation of poly(l-lactide) [i.e., poly(l-lactic acid) (PLLA)] films were investigated. Even at low filler concentrations such as 1 wt%, the addition of SWCNT effectively decreased the resistivity of PLLA film compared with that of conventional CB, and PLLA-SWCNT film with filler concentration of 10 wt% attained the resistivity lower than 100 Ω cm. The crystallization of PLLA further decreased the resistivity of films. The addition of carbon fillers, except for C₆₀ and CNB at 5 wt%, lowered the glass transition temperature, whereas the addition of carbon fillers, excluding C₆₀, elevated softening temperatures, if an appropriate filler concentration was selected. On heating from room temperature, cold crystallization temperature was determined mainly by the molecular weight of PLLA, whereas on cooling from the melt, the carbon fillers, excluding KB, elevated the cold crystallization temperature, reflecting the effectiveness of most of the carbon fillers as nucleating agents. Despite the nucleating effects, the addition of carbon fillers decreased the enthalpy of cold crystallization of PLLA on both heating and cooling. The addition of CNH, CNB, and CB elevated the starting temperature of thermal degradation of PLLA, whereas the addition of SWCNT reduced the thermal stability. Furthermore, the addition of C₆₀ and SWCNT enhanced the enzymatic degradation of PLLA, whereas the addition of KB and CNB disturbed the enzymatic degradation of PLLA. The reasons for the effects of carbon fillers on the physical properties, crystallization, and enzymatic degradation of PLLA films are discussed.     

Crystallization and morphology of stereocomplexes in nonequimolar mixtures of poly(l-lactic acid) with excess poly(d-lactic acid)

Crystallization of nonequimolar compositions of poly(d-lactic acid) with low-molecular-weight poly(l-lactic acid) (PDLA/LM_w-PLLA) blends leads to formation of various fractions of stereocomplexed PLA (sc-crystallites) and homocrystallites (PDLA or PLLA). For the PDLA/LM_w-PLLA blends within the composition window of LM_w-PLLA content between 30 and 50 wt%, only sc-crystal exists and no homocrystal is present. On the other hand, for PDLA/LM_w-PLLA blends with excess PDLA, e.g. PDLA/LM_w-PLLA = 90/10, atomic-force microscopy (AFM) characterization on various stages of crystallization of sc-PLA crystal with PDLA homocrystal shows a repetitive stacking of excess PDLA on pre-formed sc-PLA crystal serving as crystallizing templates. The crystallization initially begins with string-like (fibril-like) PDLA lamellae, followed with PDLA aggregating on sc-PLA crystal into a bead-on-string crystal, then growing to thicker irregularly-shaped dough-like lamellae. Repetitive growth cycle from strings to bead-on-string lamellae continues on top of the dough-like lamellae as new substrates, until ending impingement of the PDLA spherulites.     

Autocatalytic hydrolysis of amorphous-made polylactides: effects of l-lactide content, tacticity, and enantiomeric polymer blending

Poly(dl-lactide), i.e., poly(dl-lactic acid) (PDLLA), poly(l-lactide), i.e. poly(l-lactic acid) (PLLA), and poly(d-lactide), i.e., poly(d-lactic acid) (PDLA) were synthesized to have similar molecular weights. The non-blended PDLLA, PLLA, and PDLA films and PLLA/PDLA(1/1) blend film were prepared to be amorphous state, and the effects of l-lactide unit content, tacticity, and enantiomeric polymer blending on their autocatalytic hydrolysis were investigated in phosphate-buffered solution (pH7.4) at 37 °C for up to 24 months. The results of gravimetry, gel permeation chromatography (GPC), and tensile testing showed that the autocatalytic hydrolyzabilities of polylactides, i.e. poly(lactic acid)s (PLAs) in the amorphous state decreased in the following order: nonblended PDLLA>nonblended PLLA, nonblended PDLA>PLLA/PDLA(1/1) blend. The high hydrolyzability of the nonblended PDLLA film compared with those of the nonblended PLLA and PDLA films was ascribed to the lower tacticity of PDLLA chains, which decreases their intramolecular interaction and therefore the PDLLA chains are susceptible to the attack from water molecules. In contrast, the retarded hydrolysis of PLLA/PDLA(1/1) blend film compared with those of the nonblended PLLA and PDLA films was attributable to the peculiar strong interaction between PLLA and PDLA chains in the blend film, resulting in the disturbed interaction of PLLA or PDLA chains and water molecules. The X-ray diffractometry and differential scanning calorimetry (DSC) elucidated that all the initially amorphous PLA films remained amorphous even after the autocatalytic hydrolysis for 16 (PDLLA film) and 24 [nonblended PLLA and PDLA films, PLLA/PDLA(1/1) blend film] months and that the melting peaks observed at around 170 and 220 °C for the PLLA/PDLA(1/1) blend film after the hydrolysis for 24 months were ascribed to those of homo- and stereocomplex crystallites, respectively, formed during heating at around 100 and 200 °C but not during the autocatalytic hydrolysis.     

Plasticization of semicrystalline poly(l-lactide) with poly(propylene glycol)

Plasticization of semicrystalline poly(l-lactide) (PLA) with a new plasticizer - poly(propylene glycol) (PPG) is described. PLA was plasticized with PPG with nominal M_w of 425 g/mol (PPG4) and 1000 g/mol (PPG1) and crystallized. The plasticization decreased T_g, which was reflected in a lower yield stress and improved elongation at break. The crystallization in the blends was accompanied by a phase separation facilitated by an increase of plasticizer concentration in the amorphous phase and by annealing of blends at crystallization temperature. The ultimate properties of the blends with high plasticizer contents correlated with the acceleration of spherulite growth rate that reflected accumulation of plasticizer in front of growing spherulites causing weakness of interspherulitic boundaries. In PLA/PPG1 blends the phase separation was the most intense leading to the formation of PPG1 droplets, which facilitated plastic deformation of the blends that enabled to achieve the elongation at break of about 90-100% for 10 and 12.5 wt% PPG1 content in spite of relatively high T_g of PLA rich phase of the respective blends, 46.1-47.6 °C. Poly(ethylene glycol) (PEG), long known as a plasticizer for PLA, with nominal M_w of 600 g/mol, was also used to plasticize PLA for comparison.     

Mechanical properties, morphology, and crystallization behavior of blends of poly(l-lactide) with poly(butylene succinate-co-l-lactate) and poly(butylene succinate)

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate) (PBS) and poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% were prepared by melt-mixing and subsequent injection molding, and their mechanical properties, morphology, and crystallization behavior have been compared. Dynamic viscoelasticity and SEM measurements of the blends revealed that the extent of the compatibility of PBSL and PBS with PLLA is almost the same, and that the PBSL and PBS components in the blends with a low content of PBSL or PBS (5-20 wt%) are homogenously dispersed as 0.1−0.4 μm particles. The tensile strength and modulus of the blends approximately followed the rule of mixtures over the whole composition range except that those of PLLA/PBS 99/1 blend were exceptionally higher than those of pure PLLA. All the blends showed considerably higher elongation at break than pure PLLA, PBSL, and PBS. Differential scanning calorimetric analysis of the blends revealed that the isothermal and non-isothermal crystallization of the PLLA component is promoted by the addition of a small amount of PBSL, while the addition of PBS was much less effective.     

Formation of banded and non-banded poly(l-lactic acid) spherulites during crystallization of films of poly(l-lactic acid)/poly(ethylene oxide) blends

In this study, a series of poly(l-lactic acid) (PLLA)/poly(ethylene oxide) (PEO) blends with different PLLA concentrations was prepared. Films of these blends crystallized with and without a coverslip were characterized by the presence and absence of banded structures, respectively. This difference in morphology was observed because the PEO component of the blends was oxidized at a high temperature (125 °C) in air without the protection of a coverslip. X-ray photoelectron spectroscopy (XPS) results showed that the surface of the blends crystallized in nitrogen without a coverslip contained mostly PLLA while the surfaces of the same blends crystallized under a coverslip contained only a moderately higher concentration of PLLA than their bulks. The migration of PLLA to the surface of the blends during crystallization in nitrogen when no coverslip was used was due to its low surface tension. Phase images obtained using atomic force microscopy (AFM) indicated that the banded structures consisted of valleys and ridges, which were in fact flat-on and edge-on lamellae, respectively. A detailed time-of-flight secondary ion mass spectrometry (ToF-SIMS) examination suggested that PLLA and PEO were located mainly on the surfaces of the ridges and valleys, respectively.     

Mechanical properties, morphologies, and crystallization behavior of plasticized poly(l-lactide)/poly(butylene succinate-co-l-lactate) blends

The blends of poly(l-lactide) (PLLA) with poly(butylene succinate-co-l-lactate) (PBSL) containing the lactate unit of ca. 3 mol% and Rikemal PL710 (RKM) which is a plasticizer mainly composed of diglycerine tetraacetate were prepared by melt-mixing and subsequent injection molding. The studied RKM content of the PLLA/PBSL/RKM blends was 0-20 wt%, and the PLLA/PBSL weight ratio was 100/0 to 80/20. Although elongation at break in the tensile test did not increase by the addition of 10 wt% RKM to PLLA, the addition of a small amount of PBSL to the PLLA/RKM blend caused a considerable increase of the elongation. The SEM and DSC analyses revealed that all the PLLA/PBSL/RKM blends are immiscible blends where the PBSL particles are finely dispersed, and that there is some compatibility between PLLA-rich phase and PBSL-rich phase in the amorphous state when the RKM content is 20 wt%. As a result of investigation of the crystallization behavior by DSC and polarized optical microscopic measurements, it was revealed that the addition of RKM causes the acceleration of crystalline growth rate at a lower annealing temperature, and the addition of PBSL mainly enhances the formation of PLLA crystal nucleus.     

Temperature dependent variations in the lamellar structure of poly(l-lactide)

Time- and temperature-dependent SAXS and WAXS experiments on poly(l-lactide) were used (i) to establish the relationships between the crystallization temperature, the crystal thickness and the melting point, (ii) to follow recrystallization processes during heating, and (iii) to detect perturbations of the crystalline order. The studies showed several peculiarities: (i) although no solid state thickening occurs during a crystallization, crystal thicknesses are with values between 11 and 20 nm very large (ii) crystal thicknesses and long spacings have a minimum at 120 °C and increase for both higher and lower crystallization temperatures. The anomalous behavior at low crystallization temperatures is to be related with a disordering of the crystal lattice (iii) there exists an extended temperature range where crystal thicknesses change in controlled manner by recrystallization processes (iv) as it appears, a triple point where the fluid, the crystalline and a mesomorphic phase coexist is located near to normal pressure and a temperature of 190 °C.     

Miscibility and properties of linear poly(l-lactide)/branched poly(l-lactide) copolyester blends

Polymer blends consisting of linear poly(l-lactide) (PLLA) and different proportions of dendritic PLLA-based copolyesters (hb-PLLA) characterized by different degrees of branching (DB) were obtained in melt. The solid-state properties of poly(l-lactide)s and their blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), atomic force microscopy (AFM) and stress-strain measurements. DSC and DMA methods proved miscibility of PLLA/hb-PLLA blends for the studied composition range. AFM indicated that no phase separation occurs in PLLA/hb-PLLA blends and that PLLA and hb-PLLA cocrystallize in one single lamellae type. The mechanical characteristics of PLLA/hb-PLLA blends deteriorated with an increase of the DB and with changing blend composition. Susceptibility of the blends to biodegradation was studied by measuring the weight loss in two different biodegradation media. PLLA/hb-PLLA blends showed more pronounced hydrophilic character and higher susceptibility to biodegradation with an increase in the degree of branching.