Isothermal crystallization behavior of poly(L‐lactide) in poly(L‐lactide)‐block‐poly(ethylene glycol) diblock copolymers

The crystal unit‐cell structures and the isothermal crystallization kinetics of poly(L ‐lactide) in biodegradable poly(L ‐lactide)‐block‐methoxy poly(ethylene glycol) (PLLA‐b‐MePEG) diblock copolymers have been analyzed by wide‐angle X‐ray diffraction and differential scanning calorimetry. In particular, the effects due to the presence of MePEG that is chemically connected to PLLA as well as the PLLA crystallization temperature T_C are examined. Though we observe no variation of both the PLLA and MePEG crystal unit‐cell structures with the block ratio between PLLA and MePEG and T_C, the isothermal crystallization kinetics of PLLA is greatly influenced by the presence of MePEG that is connected to it. In particular, the equilibrium melting temperature of PLLA, T, significantly decreases in the diblock copolymers. When the T_C is high so that the crystallization is controlled by nucleation, because of the decreasing T and thereafter the nucleation density with decreasing PLLA molecular weight, the crystallinity of PLLA also decreases with a decrease in the PLLA molecular weight. While, for the lower crystallization temperature regime controlled by the growth mechanism, the crystallizability of PLLA in copolymers is greater than that of pure PLLA. This suggests that the activation energy for the PLLA segment diffusing to the crystallization site decreases in the diblocks. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2438–2448, 2006     

Characteristics of the biodegradability and physical properties of stereocomplexes between poly(L‐lactide) and poly(D‐lactide) copolymers

Random and block copolymerizations of L ‐ or D ‐lactide with ε‐caprolactone (CL) were performed with a novel anionic initiator, (C₅Me₅)₂SmMe(THF), and they resulted in partial epimerization, generating D ,L ‐ or meso‐lactide polymers with enhanced biodegradability. A blend of PLLA‐r‐PCL [82/18; PLLA = poly(L ‐LA) and PCL = poly(ε‐caprolactone)] and PDLA‐r‐PCL [79/21; PDLA = poly(D ‐LA)] prepared by the solution‐casting method generated a stereocomplex, the melting temperature of which was about 40 °C higher than that of the nonblended copolymers. A blend of PLLA‐b‐PCL (85/15) and PDLA‐b‐PCL (82/18) showed a lower elongation at break and a remarkably higher tensile modulus than stereocomplexes of PLLA‐r‐PCL/PDLA‐r‐PCL and PLLA/PDLA. The biodegradability of a blend of PLLA‐r‐PCL (65/35) and PDLA‐r‐PCL (66/34) with proteinase K was higher than that of PLLA‐b‐PCL (47/53) and PDLA‐b‐PCL (45/55), the degradability of which was higher than that of a PLLA/PDLA blend. A blend film of PLLA‐r‐PDLLA (69/31)/PDLA‐r‐PDLLA (68/32) exhibited higher degradability than a film of PLLA/PDLLA [PDLLA = poly(D ,L ‐LA)]. A stereocomplex of PLLA‐r‐PCL‐r‐PDMO [80/18/2; PDMO = poly(L ‐3,D ,L ‐6‐dimethyl‐2,5‐morpholinedion)] with PDLA‐r‐PCL‐r‐PDMO (81/17/2) showed higher degradability than PLLA‐r‐PDMO (98/2)/PDLA‐r‐PDMO (98/2) and PLLA‐r‐PCL (82/18)/PDLA‐r‐PCL (79/21) blends. The tensile modulus of a blend of PLLA‐r‐PCL‐r‐PDMO and PDLA‐r‐PCL‐r‐PDMO was much higher than that of a blend of PLLA‐r‐PDMO and PDLA‐r‐PDMO. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 438–454, 2005     

Alkaline and enzymatic degradation of L‐lactide copolymers. II. Crystallized films of poly(L‐lactide‐co‐D‐lactide) and poly(L‐lactide) with similar crystallinities

Films of poly(L ‐lactide‐co‐D ‐lactide) [P(LLA‐DLA); 95/5] and poly(L ‐lactide) [i.e., poly(L ‐lactide acid) (PLLA)] were prepared by crystallization from the melt, and a comparative study of the crystallization effects on the alkaline and proteinase K catalyzed hydrolysis of the films was carried out. The hydrolyzed films were investigated with gravimetry, differential scanning calorimetry, polarimetry, and gel permeation chromatography, and the results were compared with those reported for amorphous‐made specimens. The alkaline hydrolyzability of the P(LLA‐DLA) (95/5) and PLLA films was determined solely by the initial crystallinity (X_c) and was not affected by the content of the incorporated D ‐lactide (DLA) unit in the polymer chain; this was in marked contrast to the fact that the enzymatic hydrolyzability depended on not only the initial X_c value but also the DLA unit content. The alkaline hydrolysis rate of the P(LLA‐DLA) (95/5) and PLLA films and the enzymatic hydrolysis rate (R_EH) of the P(LLA‐DLA) (95/5) films decreased linearly as the initial X_c value increased. This meant that the hydrolyzability of the restricted amorphous regions was very similar to that of the free amorphous regions. In contrast, R_EH of the PLLA films decreased nonlinearly with the initial X_c value, and this nonlinear dependence was caused by the fact that in the PLLA films the restricted amorphous regions were much more hydrolysis‐resistant than the free amorphous regions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1064‐1075, 2005     

Polyethylene‐poly(L‐lactide) diblock copolymers: Synthesis and compatibilization of poly(L‐lactide)/polyethylene blends

A model polyethylene‐poly(L ‐lactide) diblock copolymer (PE‐b‐PLLA) was synthesized using hydroxyl‐terminated PE (PE‐OH) as a macroinitiator for the ring‐opening polymerization of L ‐lactide. Binary blends, which contained poly(L ‐lactide) (PLLA) and very low‐density polyethylene (LDPE), and ternary blends, which contained PLLA, LDPE, and PE‐b‐PLLA, were prepared by solution blending followed by precipitation and compression molding. Particle size analysis and scanning electron microscopy results showed that the particle size and distribution of the LDPE dispersed in the PLLA matrix was sharply decreased upon the addition of PE‐b‐PLLA. The tensile and Izod impact testing results on the ternary blends showed significantly improved toughness as compared to the PLLA homopolymer or the corresponding PLLA/LDPE binary blends. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2755–2766, 2001     

Synthesis and characterization of poly(L‐lactic acid)–poly(ε‐caprolactone) multiblock copolymers by melt polycondensation

An Erratum has been published for this article in J. Polym. Sci. Part A: Polym. Chem. (2004) 42(22) 5845 New multiblock copolymers derived from poly(L‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL) were prepared with the coupling reaction between PLLA and PCL oligomers with ? NCO terminals. Fourier transform infrared (FTIR), ¹³C NMR, and differential scanning calorimetry (DSC) were used to characterize the copolymers and the results showed that PLLA and PCL were coupled by the reaction between ? NCO groups at the end of the PCL and ? OH (or ? COOH) groups at the end of the PLLA. DSC data indicated that the different compositions of PLLA and PCL had an influence on the thermal and crystallization properties including the glass‐transition temperature (T_g), melting temperature (T_M), crystallizing temperature (T_c), melting enthalpy (ΔH_m), crystallizing enthalpy (ΔH_c), and crystallinity. Gel permeation chromatography (GPC) was employed to study the effect of the composition of PLLA and PCL and reaction time on the molecular weight and the molecular weight distribution of the copolymers. The weight‐average molecular weight of PLLA–PCL multiblock copolymers was up to 180,000 at a composition of 60% PLLA and 40% PCL, whereas that of the homopolymer of PLLA was only 14,000. A polarized optical microscope was used to observe the crystalline morphology of copolymers; the results showed that all polymers exhibited a spherulitic morphology. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5045–5053, 2004     

Effects of carbon nanotubes on crystallization and melting behavior of poly(L‐lactide) via DSC and TMDSC studies

In this work, multiwalled carbon nanotubes (MWNTs) were surface‐modified and grafted with poly(L ‐lactide) to obtain poly(L ‐lactide)‐grafted MWNTs (i.e. MWNTs‐g‐PLLA). Films of the PLLA/MWNTs‐g‐PLLA nanocomposites were then prepared by a solution casting method to investigate the effects of the MWNTs‐g‐PLLA on nonisothermal and isothermal melt‐crystallizations of the PLLA matrix using DSC and TMDSC. DSC data found that MWNTs significantly enhanced the nonisothermal melt‐crystallization from the melt and the cold‐crystallization rates of PLLA on the subsequent heating. Temperature‐modulated differential scanning calorimetry (TMDSC) analysis on the quenched PLLA nanocomposites found that, in addition to an exothermic cold‐crystallization peak in the range of 80–120 °C, an exothermic peak in the range of 150–165 °C, attributed to recrystallization, appeared before the main melting peak in the total and nonreversing heat flow curves. The presence of the recrystallization peak signified the ongoing process of crystal perfection and, if any, the formation of secondary crystals during the heating scan. Double melting endotherms appeared for the isothermally melt‐crystallized PLLA samples at 110 °C. TMDSC analysis found that the double lamellar thickness model, other than the melting‐recrystallization model, was responsible for the double melting peaks in PLLA nanocomposites. Polarized optical microscopy images found that the nucleation rate of PLLA was enhanced by MWNTs. TMDSC analysis found that the incorporation of MWNTs caused PLLA to decrease the heat‐capacity increase (namely, ΔC_p) and the C_p at glass transition temperature. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1870–1881, 2007     

Nanoindentation of biodegradable cellulose diacetate‐graft‐poly(L‐lactide) copolymers: Effect of molecular composition and thermal aging on mechanical properties

Nanoindentation of cellulose diacetate‐graft‐poly(lactide)s (CDA‐g‐PLLAs) synthesized by ring opening graft copolymerization of L ‐lactide in bulk onto the residual hydroxyl positions on CDA were conducted to investigate the effect of the molecular composition and thermal aging on mechanical properties and creep behavior. Continuous stiffness measurement (CSM) technique was used to obtained hardness and elastic modulus. These material properties were expressed as a mean value from 100 to 300 nm depths and an unloading value at final indentation depth. The hardness and elastic modulus in all CDA‐g‐PLLAs were higher than those in pure CDA, indicating that the introduction of PLLA increases the hardness and elastic modulus. With an increase of crystallinity by thermal aging, the hardness and elastic modulus were increased in both CDA‐g‐PLLA and PLLA. The creep test performed by CSM showed that the creep strain of CDA was decreased by the grafting of PLLA. Thermal aging decreased the creep strain of CDA‐g‐PLLA and PLLA. With an increase of holding time, hardness was decreased, whereas elastic modulus was kept almost constant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1114–1121, 2007     

Poly(L‐lactide)/C60 nanocomposites: Effects of C60 on crystallization of poly(L‐lactide)

The effects of solvent type and concentration of C₆₀ on the crystallization of poly(L ‐lactide) (PLLA) during solvent evaporation, heating from room temperature, and cooling from the melt were investigated by polarized optical microscopy and differential scanning calorimetry. The addition of C₆₀ enhanced the PLLA crystallization during solvent evaporation, during heating of the melt‐quenched films, and during cooling from the melt of As‐cast films, except for heating and cooling of the PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. In the case of solvent evaporation, the difference in crystallinity between the PLLA films with and without C₆₀ became higher for the solvent with a lower boiling point. In the case of heating of melt‐quenched films, the addition of C₆₀ had a small effect on the crystallinity of PLLA, whereas significantly lowered the peak top and ending temperatures of cold crystallization, except for melt‐quenched PLLA film with 1 wt % of C₆₀ prepared with dichloromethane. The crystallinity of PLLA was determined by the solvent type, rather than by the C₆₀ concentration. In the case of cooling from the melt of As‐cast films, the addition of C₆₀ elevated the crystallinity and cold crystallization temperature values of PLLA films, except for PLLA films prepared with dichloromethane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2167–2176, 2007     

Fabrication and characterization of poly(butylene succinate)‐grafted carbon fiber/poly(L‐lactide) nanocomposites

A new poly(butylene succinate) (PBS)‐grafted vapor grown carbon fiber (VGCF)/poly(L ‐lactide) (PLLA) nanocomposites were successfully prepared by an in situ condensation reaction between PBS (M_w = 6,000) and surface oxidized VGCF, followed by direct melt mixing technique, and their mechanical and thermal properties were evaluated. Fourier transform infrared spectroscopy and scanning electron microscopy studies indicate a chemical interaction between the PBS and the surface of VGCF. It was found that the maximum tensile strength and modulus of PBS‐grafted VGCF/PLLA nanocomposites were 135 MPa (27% increase relative to neat PLLA) and 4,400 MPa (29% increase relative to neat PLLA), respectively. The results indicate that significant improvement in the mechanical properties can be accomplished by optimizing the surface modification conditions for VGCF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4433–4441, 2008     

Linear and four‐armed poly(l‐lactide)‐block‐poly(d‐lactide) copolymers and their stereocomplexation with poly(lactide)s

Linear and four‐armed poly(l ‐lactide)‐block‐poly(d ‐lactide) (PLLA‐b‐PDLA) block copolymers are synthesized by ring‐opening polymerization of d ‐lactide on the end hydroxyl of linear and four‐armed PLLA prepolymers. DSC results indicate that the melting temperature and melting enthalpies of poly (lactide) stereocomplex in the copolymers are obviously lower than corresponding linear and four‐armed PLLA/PDLA blends. Compared with the four‐armed PLLA‐b‐PDLA copolymer, the similar linear PLLA‐b‐PDLA shows higher melting temperature (212.3 °C) and larger melting enthalpy (70.6 J g^?1). After these copolymers blend with additional neat PLAs, DSC, and WAXD results show that the stereocomplex formation between free PLA molecular chain and enantiomeric PLA block is the major stereocomplex formation. In the linear copolymer/linear PLA blends, the stereocomplex crystallites (sc) as well as homochiral crystallites (hc) form in the copolymer/PLA cast films. However, in the four‐armed copolymer/linear PLA blends, both sc and hc develop in the four‐armed PLLA‐b‐PDLA/PDLA specimen, which means that the stereocomplexation mainly forms between free PDLA molecule and the inside PLLA block, and the outside PDLA block could form some microcrystallites. Although the melting enthalpies of stereocomplexes in the blends are smaller than that of neat copolymers, only two‐thirds of the molecular chains participate in the stereocomplex formation, and the crystallization efficiency strengthens. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1560–1567     

Characteristic properties of film prepared from poly(L‐lactide)‐grafted dextran of a relatively high sugar unit content as a degradable biomaterial

To develop novel biomedical soft materials with degradability, amphiphilic poly(L ‐lactide)‐grafted dextrans (Dex‐g‐PLLAs) of relatively high sugar unit contents were synthesized with the trimethylsilyl protection method. The characteristic properties of solution‐cast films prepared from the obtained Dex‐g‐PLLAs were investigated. The water absorption and degradation rate of the Dex‐g‐PLLA films increased with increasing sugar unit content. The morphology of the bulk phase and top surface of the Dex‐g‐PLLA films was evaluated with transmission electron microscopy and atomic force microscopy, respectively. The bulk phase of the Dex‐g‐PLLA films with a sugar unit content of 16–25 wt % was found by transmission electron microscopy to form a lamellar type of phase‐separated structure composed of approximately 80–100‐nm‐wide nanodomains because of their amphiphilic and branched structures. The hydrophobic top surface for a Dex‐g‐PLLA film with a sugar unit content of 25 wt % covered with PLLA segments was confirmed by atomic force microscopy phase images to be easily converted to a wettable top surface covered with hydrophilic dextran aggregates showing an 8–10‐nm‐wide honeycomb pattern by means of annealing in water. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6402–6409, 2006     

Syntheses,characterization, and properties of multiblock copolymers consisting of polyisobutylene and poly(L‐lactide) segments

The syntheses of {‐poly(L ‐lactide) (PLLA)‐b‐polyisobutylene (PIB)‐}_n multiblock copolymers were accomplished for the first time by chain extension of PLLA‐b‐PIB‐b‐PLLA triblock copolymers. Well‐defined PLLA‐b‐PIB‐b‐PLLA triblock copolymers with predictable M_ns, low PDIs (1.10–1.18) and excellent blocking efficiencies were prepared by anionic ring‐opening polymerizations of L ‐lactide initiated with hydroxyallyl telechelic PIB (HO‐Allyl‐PIB‐Allyl‐OH) in toluene at 110 °C. The triblock copolymers were successfully chain extended with 4,4′‐methylenebis(phenylisocyanate) (MDI) to obtain the multiblock copolymers with good gravimetric yields of ～86 to 96%. The chain‐extended polymers were soluble in a range of common organic solvents. The block copolymers showed two glass transition temperatures in differential scanning calorimetric analysis for the PIB and PLLA blocks indicating microphase separation, which was supported by atomic force microscopy images. The as‐synthesized compression molded multiblock copolymers exhibited tensile strengths in the range of 8–24 MPa with elongations at break in the range of 2.5–400%. The static and dynamic mechanical properties showed a strong dependence on the relative PLLA content in the copolymer. The dynamic mechanical analysis also indicated microphase separation at higher PLLA compositions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3490–3505, 2009     

Effects of carbon nanotubes on dynamic mechanical property,thermal property,and crystal structure of poly(L‐lactic acid)

Effects of carbon nanotubes (CNT) on the dynamic mechanical property, thermal property, and crystal structure of poly(L ‐lactic acid) (PLLA) were investigated. Dynamic mechanical analysis (DMA) found that CNT via grafting modification with PLLA (CNT‐g‐PLLA) could result in effective reinforcing effects. Tan δ of DMA found that CNT‐g‐PLLA was compatible with the PLLA matrix, giving a single T_g of the composite with a higher CNT‐g‐PLLA loading giving a higher T_g of the composite. Wide angle X‐ray diffraction (WAXD) data demonstrated that CNT could assist the disorder‐to‐order (α′‐to‐α) transition in PLLA crystals but did not lead to a more compact chain packing of the crystal lattice in PLLA composites than in pure PLLA. The equilibrium melting temperature (T) obtained from Hoffman‐Weeks plots were found to increase with increasing CNT‐g‐PLLA content. Small angle X‐ray scattering data revealed that thicknesses of crystal layer and amorphous layer of PLLA both decreased with increasing CNT contents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 145–152, 2010     

Random multiblock poly(ester amide)s containing poly(L‐lactide) and cycloaliphatic amide segments: Synthesis and biodegradation studies

Novel multiblock poly(ester amide)s containing poly(L ‐lactide) and cycloaliphatic amide segments were synthesized from telechelic oligomer of α,ω‐hydroxyl terminated poly(L ‐lactide), 1,3‐cyclohexylbis(methylamine), and sebacoylchloride by the “two‐step” interfacial polycondensation method. The blocky nature of PEAs was established by FTIR and ¹H NMR spectroscopies. The effect of relative content of ester and amide segments on the crystallization nature of PEAs was investigated by WAXD and DSC analyses. PEAs having lower content of PLLA, PEA 1 and PEA 2, showed a crystallization pattern analogous to polyamides, whereas PEA 3, having higher content of PLLA, showed two crystalline phases characterized by polyester and polyamide segments. Random nature of PEAs was observed from single T_g values. Biodegradation studies using the enzyme lipase from Candida Cylindracea showed higher degradation rate for PEA 3 than that for PEA 1 and PEA 2. FTIR, ¹H NMR, and DSC analyses of the degraded products indicated the involvement of ester linkages in the degradation process. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3250–3260, 2006     

Visualization of spontaneous aggregates by diblock poly(styrene)‐b‐poly(L‐lactide)/poly(D‐lactide) pairs in solution with new fluorescent CdSe quantum dot labels

Spontaneous stereocomplex aggregation of diblock poly(styrene)‐b‐poly(L ‐lactide) PS‐b‐PLLA/poly(D ‐lactide) PDLA pairs has been investigated under ambient temperature in tetrahydrofuran solution. First, diblock PS₂₆₀‐b‐PLLA₁₆₅ and PS₂₆₀‐b‐PDLA₁₆₂ bearing similar lengths of respective PLLA and PDLA blocks were synthesized through controlled atom‐transfer radical polymerization of styrene, and a subsequent living ring‐opening polymerization of optically pure lactides, and their structures were further characterized by nuclear magnetic resonance spectroscopy (NMR) and gel‐permeation chromatography (GPC). Subsequently, new enantiomeric poly(D ‐lactide) stabilized core‐shell fluorescent CdSe quantum dots (CdSe/PDLA QD) were designed and prepared as sensitive fluorescence labels to shed new lights on the spontaneous stereocomplex aggregation in THF, which was mediated by stereocomplexation of the PLLA and PDLA chains. Upon simply mixing two individual THF solution of diblock PS₂₆₀‐b‐PLLA₁₆₅ and HO‐PDLA₃₀‐SH, spontaneous stereocomplex aggregation was studied, and the aggregated uniform spherical particles were observed by scanning electronic microscopy (SEM) to exhibit average particle diameters of 2.0 μm. Finally, utilizing the prepared CdSe/PDLA QDs as new fluorescent labels, morphologies of the spontaneous aggregates by new diblock PS₂₆₀‐b‐PLLA₁₆₅/HO‐PDLA₃₀‐SH pair were for the first time directly visualized by a confocal laser scanning fluorescence microscopy (CLSFM). These results might suggest alternative ways to simply prepare functional fluorescent particles with tunable diameter sizes and would be helpful to understand the mechanism of stereocomplex particle aggregation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1393–1405, 2009     

Synthesis and new application of green and recyclable cyclic poly(L‐lactide)‐clay hybrid

We report on the application of biodegradable cyclic poly(L ‐lactide) (PLLA) as new stabilizer; synthesis and application of a cyclic PLLA‐clay hybrid material as recyclable catalyst support. Cyclic PLLAs were used to stabilize palladium nanoparticles synthesized by a wet chemical method. It was found that the palladium particles were smaller with cyclic PLLA stabilizer (～5–10 nm) than the particles obtained from linear PLLA. The cyclic PLLA‐clay hybrid was prepared by a zwitterionic ring‐opening polymerization catalyzed by in situ‐generated N‐heterocyclic carbene catalyst. Palladium (0) nanoparticles were supported and well dispersed on the cyclic PLLA‐clay hybrid to form a new nanocomposite. The nanocomposite was found to be a highly efficient and recyclable catalyst for the aminocarbonylation reactions of aryl halides with various amines. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4167–4174     

Synthesis and characterization of multiblock copolymers composed of poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one) outer blocks and poly(L‐lactide) inner blocks

Ethylene glycol (EG) initiated, hydroxyl‐telechelic poly(L ‐lactide) (PLLA) was employed as a macroinitiator in the presence of a stannous octoate catalyst in the ring‐opening polymerization of 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) with the goal of creating A–B–A‐type block copolymers having polycarbonate outer blocks and a polyester center block. Because of transesterification reactions involving the PLLA block, multiblock copolymers of the A–(B–A)_n–B–A type were actually obtained, where A is poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one), B is PLLA, and n is greater than 0. ¹H and ¹³C NMR spectroscopy of the product copolymers yielded evidence of the multiblock structure and provided the lactide sequence length. For a PLLA macroinitiator with a number‐average molecular weight of 2500 g/mol, the product block copolymer had an n value of 0.8 and an average lactide sequence length (consecutive C₆H₈O₄ units uninterrupted by either an EG or MBC unit) of 6.1. For a PLLA macroinitiator with a number‐average molecular weight of 14,400 g/mol, n was 18, and the average lactide sequence length was 5.0. Additional evidence of the block copolymer architecture was revealed through the retention of PLLA crystallinity as measured by differential scanning calorimetry and wide‐angle X‐ray diffraction. Multiblock copolymers with PLLA crystallinity could be achieved only with isolated PLLA macroinitiators; sequential addition of MBC to high‐conversion L ‐lactide polymerizations resulted in excessive randomization, presumably because of residual L ‐lactide monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6817–6835, 2006     

Synthesis,characterization, effect of architecture on crystallization,and spherulitic growth of poly(L‐lactide)‐b‐poly(ethylene oxide) copolymers with different branch arms

Well‐defined poly(L ‐lactide)‐b‐poly(ethylene oxide) (PLLA‐b‐PEO) copolymers with different branch arms were synthesized via the controlled ring‐opening polymerization of L ‐lactide followed by a coupling reaction with carboxyl‐terminated poly(ethylene oxide) (PEO); these copolymers included both star‐shaped copolymers having four arms (4sPLLA‐b‐PEO) and six arms (6sPLLA‐b‐PEO) and linear analogues having one arm (LPLLA‐b‐PEO) and two arms (2LPLLA‐b‐PEO). The maximal melting point, cold‐crystallization temperature, and degree of crystallinity (X_c) of the poly(L ‐lactide) (PLLA) block within PLLA‐b‐PEO decreased as the branch arm number increased, whereas X_c of the PEO block within the copolymers inversely increased. This was mainly attributed to the relatively decreasing arm length ratio of PLLA to PEO, which resulted in various PLLA crystallization effects restricting the PEO block. These results indicated that both the PLLA and PEO blocks within the block copolymers mutually influenced each other, and the crystallization of both the PLLA and PEO blocks within the PLLA‐b‐PEO copolymers could be adjusted through both the branch arm number and the arm length of each block. Moreover, the spherulitic growth rate (G) decreased as the branch arm number increased: G_{6sPLLA‐b‐PEO} < G_{4sPLLA‐b‐PEO} < G_{2LPLLA‐b‐PEO} < G_{LPLLA‐b‐PEO}. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2034–2044, 2006     

Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide)

Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to ¹H and ¹³C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226     

Effects of chain configuration on UCST behavior in blends of poly(L‐lactic acid) with tactic poly(methyl methacrylate)s

Chain configuration influences phase behavior of blends of poly(methyl methacrylate) (PMMA) of different tactic configurations (syndiotacticity, isotacticity, or atacticity) with poly(L ‐lactic acid) (PLLA). Blends system of sPMMA/PLLA is immiscible with an asymmetry‐shaped UCST at ～250 °C. The phase behavior of the sPMMA/PLLA blend is similar to the aPMMA/PLLA blend that has been already proven in the previous work to exhibit similar UCST temperatures (230–250 °C) and asymmetry shapes in the UCST diagrams. On the other hand, the iPMMA/PLLA blend remains immiscible up to thermal degradation without showing any transition to UCST upon heating. The blend system with UCST, that is, sPMMA/PLLA, can be frozen in a state of miscibility by quenching to rapidly solidify from the homogeneous liquid at UCST, where the T_g‐composition relationship for the sPMMA/PLLA blend fits well with the Gordon‐Taylor T_g model with k = 0.15 and the blend's T leads to χ₁₂ = ?0.26 for the UCST‐quenched sPMMA/PLLA blend. Both parameters (k and χ) as characterized for the frozen miscible blend suggest a relatively weak interaction between the two constituents (sPMMA and PLLA) in the blends. The interaction strength is likely not strong enough to maintain a thermodynamic miscibility when the blend is at ambient temperature or any lower temperatures below UCST. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2355–2369, 2008