Effect of multi‐branched PDLA additives on the mechanical and thermomechanical properties of blends with PLLA

Stereocomplex formation between poly(l ‐lactic acid) (PLLA) and poly(d ‐lactic acid) (PDLA) in the melt state was investigated and altered via the addition of multi‐branched poly(d ‐lactide) (PDLA) additives. Two different multi‐branched PDLA additives, a 3‐arm and 4‐arm star‐shaped polymeric structure, were synthesized as potential heat resistance modifiers and incorporated into PLLA at 5, 10, and 20 (w/w) through melt blending. Mechanical and thermomechanical properties of these blends were compared with linear poly(l ‐lactide) (PLLA) as well as with blends formed by the addition of two linear PDLA analogs that had similar molecular weights to their branched counterparts. Blends with linear PDLA additives exhibited two distinct melting peaks at 170–180°C and 200–250°C which implied that two distinct crystalline domains were present, that of the homopolymer and that of the stereocomplex, the more stable crystalline structure formed by the co‐crystallization of both d ‐ and l ‐lactide enantiomers. In contrast, blends of PLLA with multi‐branched PDLA formed a single broad melting peak indicative of mainly formation of the stereocomplex, behavior which was confirmed by X‐ray diffraction (XRD) analysis. The heat deflection temperature determined by thermal mechanical analysis was improved for all blends compared to neat PLLA, with increases of up to180°C for 20% addition of the 3‐arm PLLA additive. Rheological properties of the blends, as characterized by complex viscosity (η*), remained stable over a wide temperature range. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42858.     

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     

Regulation of the mechanical properties and heat resistance of the poly(l‐lactide‐co‐trimethylene carbonate) copolymer by the incorporation of a stereocomplex crystal and graphene oxide

Stereocomplex crystals of polylactide and graphene oxide (GO) were simultaneously used to regulate the mechanical properties and heat resistance of a poly(l ‐lactide‐co‐trimethylene carbonate) [P(LLA‐co‐TMC)] copolymer. The crystallization behaviors in the nonisothermal cold‐crystallization process of P(LLA‐co‐TMC)–poly(d ‐lactide) (PDLA) blends and P(LLA‐co‐TMC)–PDLA–GO composites were investigated by differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. Data from the crystallization kinetics and the crystallization active energy indicated that GO both promoted nucleation and limited growth during the stereocomplex crystallization process. Three kind of samples (without crystallization, with low crystallinity, and with high crystallinity) were used to investigate the mechanical properties and heat resistance. We found a decrease in the elongation at break when the stereocomplex crystal and GO contents were increased, and this was accompanied by an improvement in the tensile strength. The change in the storage modulus value determined by dynamic mechanical analysis demonstrated that both the stereocomplex crystal and GO effectively improved the heat resistance. These results indicate that this study provided a new strategy for fabricating a P(LLA‐co‐TMC) copolymer with good comprehensive properties at was entirely different from common chemical crosslinking methods. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45248.     

Crystallization behavior and nucleation analysis of poly(l‐lactic acid) with a multiamide nucleating agent

To accelerate the crystallization of poly(L ‐lactic acid) (PLLA) and enhance its crystallization ability, a multiamide nucleator (TMC) was introduced into the PLLA matrix. The thermal characteristics, isothermal and nonisothermal crystallization behavior of pure PLLA and TMC‐nucleated PLLA were investigated by differential scanning calorimetry. The determination of thermal characteristics shows that the addition of TMC can significantly decrease the onset temperature of cold crystallization and meanwhile elevate the total crystallinity of PLLA. For the isothermal crystallization process, it is found that the overall crystallization rate is much faster in TMC‐nucleated PLLA than in pure PLLA and increases as the TMC content is increased, however, the crystal growth form and crystalline structure are not influenced much despite the presence of TMC. In the case of nonisothermal crystallization, the nucleation efficiency and nucleation activity were estimated and the results indicate that excellent nucleation‐promoting effect could be achieved when the weight percentage of TMC is chosen between 0.25% and 0.5%. Polarized optical microscopy observation reveals that the nuclei number of PLLA increases and the spherulite size reduces greatly with the addition of TMC. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synergistic effects of N,N′‐bis (benzoyl) sebacic acid dihydrazide and talc on the physical and mechanical behaviors of poly(l‐latic acid)

The important practical problem of poor heat stability of poly(l ‐lactic acid) (PLLA) is addressed by the addition of N, N′‐bis (benzoyl) sebacic acid dihydrazide (BSAD) and talc as a nucleating agent system. The idea of incorporating talc into the PLLA/BSAD composites is that talc can provide supplementary nucleation effect with very small amount of BSAD (0.2 wt %) and therefore can improve the heat deflection resistance of PLLA materials. Effects of BSAD/talc on morphology, crystallization behavior, heat resistance, and mechanical properties of PLLA/BSAD/talc were investigated after annealing processes. The results indicated that the BSAD/talc system increased the crystallinity from 6.0% of pure PLLA to a maximum 42.9% by the synergistic effects of BSAD and talc increasing the growth of spherulites and nucleation density, respectively. After annealing at different temperatures, the heat deflection temperature (HDT) of PLLA was improved dramatically due to synergistic effects of BSAD/talc between restricted chain movement and acceleration of crystallization. At high temperature (above T_g), the thermo‐mechanical properties of PLLA is mainly determined by the crystallinity and the reinforcement effect of talc acted as a filler. Moreover, effects of BSAD/talc on mechanical properties were discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41454.     

Fully bio‐based poly(ɛ‐capolactone)/poly(lactide) alternating multiblock supramolecular polymers: Synthesis,crystallization behavior,and properties

Supramolecular poly(?‐capolactone)/poly(lactide) alternating multiblock copolymers were prepared by UPy‐functionalized poly(lactide)‐b‐ poly(?‐capolactone)‐b‐ poly(lactide) copolymers. The prepared supramolecular polymers (SMPs) exhibit the characteristic properties of thermoplastic elastomers. The stereo multiblock SMPs (sc‐SMPs) were formed by blending UPy‐functionalized poly(l ‐lactide)‐b‐ PCL‐b‐ poly(l ‐lactide) (l ‐SMPs) and UPy‐functionalized poly(d ‐lactide)‐b‐ PCL‐b‐ poly(d ‐lactide) (d ‐SMPs) due to stereocomplexation of the PLLA and PDLA blocks. Sc‐SMPs with low content of d ‐SMPs (≤20%) are transparent, elastic solids, while those having high d ‐SMPs content are opaque, brittle solids. The effects of l ‐SMPs/d ‐SMPs mixing ratios on thermal, crystallization behaviors, crystal structure, mechanical and hydrophilic properties of sc‐SMPs were deeply investigated. The incorporation of UPy groups depresses the crystallization of polymer, and the stereocomplex formation accelerates the crystallization rate. The used initiator functionalized polyhedral oligomeric silsesquioxanes causes a different effect on the crystallization of PLA and PCL blocks. The tensile strength and elongation at break of l _d /d _d ‐SMPs (d represents the initiator diethylene glycol) are significantly larger than that of l _p /d _p ‐SMPs (p represents the initiator polyhedral oligomeric silsesquioxanes), and their heat resistance and hydrophilicity can be also modulated by the l ‐SMPs/d ‐SMPs mixing ratios and the different initiators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45575.     

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     

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     

Effect of interface and confinement size on the crystallization behavior of PLLA confined in coaxial electrospun fibers

Poly(l ‐lactide)/polyacrylonitrile (PLLA/PAN) core‐sheath composite fibers were fabricated by coaxial electrospinning. The crystallization behavior of PLLA within the coaxial electrospun fibers was studied by differential scanning calorimetry (DSC). The PLLA/PAN coaxial electrospun fiber with a PLLA diameter of ～32 nm (C1) exhibits a crystallization temperature (T_c) of 22.5 °C higher but a cold‐crystallization temperature (T_cc) of 10 °C lower than bulk PLLA. The crystallinity of C1 fiber is also higher than bulk PLLA. In both isothermal melt‐ and cold‐crystallization, PLLA in C1 fiber crystallizes faster than the bulk PLLA, as revealed by the smaller half crystallization times (t_1/2). The enhanced crystallizability of PLLA in the C1 fiber may be attributed to the increased nuclei number and crystal growth rate induced by the PAN surface, i.e., surface‐induction effect. However, PLLA also suffers a nano‐confinement effect exerted by PAN sheath in the coaxial electrospun fiber, which can suppress PLLA crystallization. When the diameter of PLLA is too small (< 32 nm), the nano‐confinement effect may prevail over the surface‐induction effect, leading to a slower crystallization rate and smaller crystallinity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45980.     

Effect of zinc phenylphosphonate on the crystallization behavior of poly(l‐lactide)

The effect of zinc phenylphosphonate (PPZn) on the crystallization behavior of poly(l ‐lactide) (PLLA) was investigated using differential scanning calorimetry (DSC) and Polarized Optical Microscopy (POM) measurements. The non‐isothermal cold crystallization results showed that the addition of PPZn obviously decreased the cold crystallization temperature of PLLA and increased the degree of crystallinity of PLLA. The isothermal crystallization kinetics results showed that the crystallization rate of PLLA with small amount of PPZn was much higher than that of neat PLLA, and the half‐time (t_1/2) of PLLA/PPZn sample is far less than that of neat PLLA. As an effective nucleating agent, PPZn particles had also some influence on nucleation mechanism and crystal growth of PLLA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2744–2752, 2013     

Non‐isothermal crystallization behavior of stereo diblock polylactides with relatively short poly(d‐lactide) segments from the melt

Stereo diblock polylactides (SDB‐PLAs) composed of relatively short poly(d ‐lactide) (PDLA) segments and relatively long poly(l ‐lactide) (PLLA) segments were synthesized to have a wide number‐average molecular weight (M_n) range of 2.5 × 10⁴–2.0 × 10⁵ g mol^?1 and d ‐lactyl unit content of 0.9–38.6%. The effects of incorporated short PDLA segments (M_n = 2.0 × 10³–7.7 × 10³ g mol^?1) on crystallization behavior of the SDB‐PLAs were first investigated during heating after complete melting and quenching or during slow cooling after complete melting. Stereocomplex (SC) crystallites can be formed at d ‐lactyl unit content as low as 4.3 and 5.8% for heating and slow cooling, respectively, and for M_n of PDLA segments as low as 2.0 × 10³ and 3.5 × 10³ g mol^?1, respectively. With decreasing M_n and increasing d ‐lactyl unit content, the cold crystallization temperature during heating decreased and the crystallization temperature during slow cooling increased. With increasing d ‐lactyl unit content, the melting enthalpy (ΔH_m) of SC crystallites during heating and the crystallinity (X_c) of SC crystallites after slow cooling increased, whereas ΔH_m of PLLA homo‐crystallites during heating and X_c of PLLA homo‐crystallites after slow cooling decreased. The total ΔH_m of SC crystallites and PLLA homo‐crystallites during heating and the total X_c after slow cooling became a minimum at d ‐lactyl unit content of 10–15% and gave a maximum at d ‐lactyl unit content of 0%. Despite the accelerated crystallization of some of SDB‐PLAs, the low values of total ΔH_m and X_c at d ‐lactyl unit content of 10–15% are attributable to the formation of two crystalline species of SC crystallites and PLLA homo‐crystallites.     

Stretch‐induced molecular ordering in amorphous/crystalline polylactide blends

The effect of amorphous poly(D ,L ‐lactide) (PDLLA) on the molecular orientation and crystallization of crystalline poly(L ‐lactide) (PLLA) on stretching is reported in this study. It is indicated that the presence of PDLLA in its miscible blends with PLLA is not favorable for either cohesive mesophase formation below T_g or strain‐induced crystallization above T_g at strains beyond the segmental extensibility limit. Because of lack of constraints imposed by cohesive mesophase or crystals, oriented segments are liable to slide each other or recoil, responsible for low‐molecular orientation in the stretched blends. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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     

The role of polycarbonate molecular weight in the poly(L‐lactide) blends compatibilized with poly(butylene succinate‐co‐L‐lactate)

Poly(butylene succinate‐co‐L ‐lactate) (PBSL)–compatibilized poly(L ‐lactide) (PLLA) polymer blends with two commercial grades of polycarbonate (PC) were investigated. The capillary tests showed that the steady shear viscosity of high molecular weight PC (PC‐L) was 10 times higher than that of low molecular weight PC (PC‐AD) throughout the shear rate range under investigation. Morphologic examination revealed that the shape of the dispersed PC‐L phase in the as‐extruded blends was largely spherical, but the PC‐AD phase was more like a rod and elongated further during injection molding. Notched Izod impact strength (IS) of the unmodified PLLA/PC‐L blend was higher than that of PC‐AD blend. The IS of modified ternary blends increased with PBSL content because of enhanced phase interaction indicated from thermal and morphologic analysis. The PBSL modification also enhanced IS more significantly in PLLA/PC‐L than in PLLA/PC‐AD blends. On the contrary, the heat deflection temperature (HDT) of PLLA/PC‐L binary system was much lower than that of PLLA/PC‐AD. HDT of PBSL‐modified PLLA/PC‐AD blends dropped with increasing PBSL content, which is a ductile polymer. Thermal and dynamic mechanical analysis of the ternary blends showed that individual components were immiscible with distinct T_gs for PC and PLLA and distinct T_ms for PBSL and PLLA. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis and characterization of AB‐type copolymers poly(L‐lactide)‐block‐poly(methyl methacrylate) via a convenient route combining ROP and ATRP from a dual initiator

Diblock copolymers of poly(L ‐lactide)‐block‐poly(methyl methacrylate) (PLLA‐b‐PMMA) were synthesized through a sequential two‐step strategy, which combines ring‐opening polymerization (ROP) and atom transfer radical polymerization (ATRP), using a bifunctional initiator, 2,2,2‐trichloroethanol. The trichloro‐terminated poly(L ‐lactide) (PLLA‐Cl) with high molecular weight (M_n,GPC = 1–12 × 10⁴ g/mol) was presynthesized through bulk ROP of L ‐lactide (L ‐LA), initiated by the hydroxyl group of the double‐headed initiator, with tin(II) octoate (Sn(Oct)₂) as catalyst. The second segment of the block copolymer was synthesized by the ATRP of methyl methacrylate (MMA), with PLLA‐Cl as macroinitiator and CuCl/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst, and dimethyl sulfoxide (DMSO) was chosen as reaction medium due to the poor solubility of the macroinitiator in conventional solvents at the reaction temperature. The trichloroethoxyl terminal group of the macroinitiator was confirmed by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR spectroscopy. The comprehensive results from GPC, FTIR, ¹H‐NMR analysis indicate that diblock copolymers PLLA‐b‐PMMA (M_n,GPC = 5–13 × 10⁴ g/mol) with desired molecular composition were obtained by changing the molar ratio of monomer/initiator. DSC, XRD, and TG analyses establish that the crystallization of copolymers is inhibited with the introduction of PMMA segment, which will be beneficial to ameliorating the brittleness, and furthermore, to improving the thermal performance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

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     

Effect of the melting temperature on the crystallization behavior of a poly(l‐lactide)/poly(d‐lactide) equimolar mixture

The effect of the final melting temperature (T_f) on the crystallization of poly(l ‐lactide) (PLLA)/poly(d ‐lactide) (PDLA) was studied via a combination of differential scanning calorimetry, wide‐angle X‐ray scattering, polarized optical microscopy, and Fourier transform infrared (FTIR) spectroscopy. We observed that a residual stereocomplex (SC) crystal induced the formation of SC crystals during cooling from a T_f (230°C) just above the melting peak of the SC crystals. On cooling from a T_f (240°C) just above the endset temperature of SC crystal melting [T_m(S)(E)], the possible order structure and the strong interchain interaction promoted the preferential crystallization of SC crystals; this enhanced the formation of α crystals. During cooling from a T_f (≥250°C) far above T_m(S)(E), the crystallization peaks of α and SC crystals converged. The FTIR results indicated that the residual SC crystals, possible ordered structure, and interchain interactions in the melt might have been the key factors for the different crystallization of PLLA/PDLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43015.     

A bioresorbable cardiovascular stent prepared from L‐lactide,trimethylene carbonate and glycolide terpolymers

High molecular weight terpolymers based on L ‐lactide (LLA), trimethylene carbonate (TMC) and glycolide (GA) are synthesized and characterized with the aim of assessing their potential in the development of bioresorbable cardiovascular stents. The effect of the composition on the thermal and mechanical properties of terpolymers is investigated in comparison with the corresponding PLLA‐TMC copolymers as well as a PLLA homopolymer. Incorporation of GA units strongly decreases the crystallinity of PLLA‐TMC‐GA terpolymers due to its more random microstructure as evidenced by ¹³C NMR. Meanwhile, the toughness is greatly improved, with only a slight loss of tensile strength. Plasma‐treated poly[(L ‐lactide)‐co‐glycolide] (PLGA) fibers are used to reinforce the terpolymer matrix. Composite with 8 wt% fibers exhibits much higher tensile strength and modulus. A minitube is fabricated using a single‐screw extruder, and a stent prototype is successfully manufactured from a terpolymer by a CNC engraving machine, thus showing the feasibility of the terpolymers for the development of bioresorbable cardiovascular stents. POLYM. ENG. SCI., 54:1418–1426, 2014. © 2013 Society of Plastics Engineers