Preferred alkaline reduction-clearing conditions for use with dyed Ingeo poly(lactic acid) fibres

A short study has been conducted to examine the efficiency of different alkaline reduction-clearing conditions on Ingeo [poly(lactic acid)] fibres, dyed with disperse dyes. The results indicate that the preferred conditions are 15 min at 60 °C in the presence of 2 g/l sodium carbonate and 2 g/l 'hydros', conditions which avoid any significant change of shade by colour loss and lead to optimised wash fastness.     

Blends of poly(ε‐caprolactone‐b‐lactic acid) and poly(lactic acid) for hot‐melt applications

The condensation reaction product of poly(lactic acid) (PLA) and a hydroxyl‐terminated four‐armed poly(ε‐caprolactone) (PCL) was studied by size‐exclusion chromatography, DSC, and NMR. The use of both L ‐lactic acid (LLA) and rac‐lactic acid (rac‐LA) was studied and the use of two different catalysts, stannous 2‐ethylhexanoate [Sn(Oct)₂] and ferrous acetate [Fe(OAc)₂], was also investigated. The thermal stability and adhesive properties were also measured for the different formulations. The characterization results suggested the formation of a blend of PLA and a block‐copolyester of PLA and PCL. The results further indicated partial miscibility in the amorphous phase of the blend showing only one glass‐transition temperature in most cases, although no randomized structures could be detected in the block‐copolymers. The polymerization in the Fe(OAc)₂‐catalyzed experiments proceeded slower than in the Sn(Oct)₂‐catalyzed experiments. The discoloring of the polymer was minor when Fe(OAc)₂ was used as catalyst, but significant when Sn(Oct)₂ was used. The ferrous catalyst also caused a slower thermal degradation. Differences in the morphology and in the adhesive properties could be related to the stereochemistry of the poly(lactic acid). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 196–204, 2004     

Telechelic poly(L‐lactic acid) for dilactide production and prepolymer applications

The suitability of different types of telechelic poly(lactic acid) (PLA) copolymers for dilactide production and prepolymer products was evaluated. L ‐lactic acid (L ‐LA) was copolymerized with 1,4‐butanediol, pentaerythritol, adipic acid, or 1,2,3,4‐butanetetracarboxylic acid (1,2,3,4‐BTCA). The influence of branching, the choice of catalyst, and the type of terminal groups on the properties and the thermal stability of the end product was determined. Carboxyl‐termination of PLA was shown to lead to higher molar masses than hydroxyl‐termination. The observed differences in the molar masses were explained by the lower thermal stability of the hydroxyl‐terminated PLA, as evidenced by the faster depolymerization rate of the hydroxyl‐terminated polymers and their higher tendency to undergo racemization. Sn(Oct)₂ was found to be a more effective copolymerization catalyst than Fe(OAc)₂ in terms of the final molar masses obtained. It was additionally found that the amount of chains not attached to the comonomers decreased toward longer polymerization times and was typically higher for the hydroxyl‐terminated copolymers. The results suggest that predominant carboxyl‐termination would increase the thermal stability of PLA polymers, whereas hydroxyl‐termination could be utilized to increase the production speed and efficiency of dilactide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Dyeing poly(lactic acid) fibres in supercritical carbon dioxide

A study has been conducted into the dyeing of poly(lactic acid) fibres in supercritical carbon dioxide. The fibres were completely dyed using disperse dyes at 50 °C as shown by fibre cross-sections, although high colour depths in dark shades still prove challenging. Dye uptake increased significantly at temperatures ≥80 °C. At 95 °C in supercritical carbon dioxide, shrinkage and hardening of raw poly(lactic acid) were observed which could partly be overcome by the supercritical carbon dioxide extraction step. Afterclearing with cold supercritical carbon dioxide (to remove unfixed dye after dyeing) decreased the colour depth and led to non-uniform dyeing results on poly(lactic acid). Wash and rub fastness was good to very good also when poly(lactic acid) was not aftercleared in supercritical carbon dioxide. Fibre damage and elongation at break in supercritical carbon dioxide were similar to water.     

The difference of equilibrium melting point between poly(l‐lactic acid) and poly(l‐lactic acid)/poly(d‐lactic acid) blends: cases with three molecular weights

In order to explore the origin of the higher melting point of poly(lactic acid) (PLA) stereocomplex crystal (SC) than that of homo‐crystal (HC), the equilibrium melting point () differential between SC and HC was determined using the Hoffman–Weeks method. The results showed that, for PLA samples with M_n around 16, 20 and 65 kg mol^?1, the differential between SC and HC is around 36, 42 and 55 °C, respectively. Thus, the higher melting point of SC compared to HC does not stem from differential only. For PLA samples with lower M_n, the supercooling differential between poly(l ‐lactic acid) (PLLA)/poly(d ‐lactic acid) (PDLA) blends and PLLA is smaller than that with higher M_n, which means chain diffusion behavior is crucial for SC formation in PLLA/PDLA blends. The fact that the SC adopts the intermolecular parallel arrangement rather than the adjacent chain folding is verified by the greater slope of the melting point of SC versus crystallization temperature fitting curve when M_n is relative higher. © 2018 Society of Chemical Industry     

Poly(lactic acid)/poly(3‐hexylthiophene) composite nanofiber fabrication for electronic applications

Fibers of the biopolymer poly(lactic acid) (PLA) and the p‐type semiconducting polymer poly(3‐hexylthiophene) (P3HT) were fabricated using the electrospinning technique at low PLA concentration (5 wt%) in CHCl₃. The fibers were several millimeters long and had diameters in the range 100 nm–4 µm. Nanofibers containing 63%/37% of PLA/P3HT were electroactive, and therefore were used to construct p–n diodes whose ideality parameter was 2.4 and rectification (on/off) ratio was 400 at ±1 V. These diodes were also able to sense UV radiation and remain operable with an increase in the on/off ratio and a lowering of the turn‐on voltage. By fabricating reusable and low‐cost multifunctional diodes from PLA/P3HT, the applications of PLA as a biocompatible and biodegradable polyester are expanded to include electronic device fabrication with low environmental impact. © 2016 Society of Chemical Industry     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

UV‐excitable fluorescent poly(lactic acid) fibers

The UV‐excitable fluorescent poly(lactic acid) (PLA) fibers were spun by the traditional melt spinning process, and the effects of the fluorescent powder content (w(FP)) and draw ratio (DR) on the structure and properties of the fluorescent PLA fibers were investigated, respectively. The results showed that the emission spectra of fluorescent PLA fibers were peaked at 530 nm after UV excitation, indicating the PLA fibers would emit green light under UV light. With the increasing of w(FP), the relative fluorescence intensity of PLA fibers increased gradually, whereas more and larger protrusions were formed on the fiber surface due to the agglomeration of fluorescent powder, both the crystallinity and mechanical properties of fluorescent PLA fiber showed the decreasing trend with the increase of w(FP). With the increase of DR, the tensile strength of fluorescent PLA fibers increased gradually, whereas the relative fluorescence intensity of PLA fibers increased firstly and then decreased, and the highest fluorescence intensity was obtained when the DR was 3.6. In addition, the confocal laser scanning microscope can be used well to simulate the 3D distribution of fluorescent powder among the PLA fibers. POLYM. ENG. SCI., 56:373–379, 2016. © 2016 Society of Plastics Engineers     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Factors affecting the degradation and drug‐release mechanism of poly(lactic acid) and poly[(lactic acid)‐co‐(glycolic acid)]

This paper reviews the most important factors affecting the degradation and drug‐release rate of bio‐erodible polymers for better control in biomedical applications. There are several factors that influence the overall rate of degradation, in addition to pH and copolymer composition. In general, polymer degradation is accelerated by greater hydrophilicity in the backbone or end groups, lesser crystallinity, lower average molecular weight, and smaller size of the finished device. At the moment, literature reflects contradictions about the role played by chemically reactive additives, crystallinity and degradation path. Factors affecting degradation and drug‐release rate are discussed in their decreasing order of importance, including intrinsic properties of polymers and processing parameters. Copyright © 2004 Society of Chemical Industry     

Compatibilization of the poly(lactic acid)/poly(propylene carbonate) blends through in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) copolymer

The in situ formation of poly(lactic acid)‐b‐poly(propylene carbonate) (PLA‐b‐PPC) block copolymers were carried out by the reaction between PLA and PPC in the presence of tetrabutyl titanate via transesterification. Molecular weight measurements and ¹³C nuclear magnetic resonance spectroscopy revealed that PLA‐b‐PPC block copolymers with higher molecular weight were obtained by controlling the reactivity point ratio between PLA chains and PPC chains in PLA/PPC reaction system. The sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % had a more proportionable reactivity point ratio between PLA chains and PPC chains compared with other samples, resulting in a most conspicuous transesterification and inconspicuous chain scission reaction. Therefore, its high molecular weight fraction (M_w > 40.0 × 10⁴) increased 80%. The formation of macromolecular PLA‐b‐PPC copolymer could strengthen the entanglement between PLA and PPC molecular chains, which resulted in an increased viscosity of blends at low shear rate. In addition, the elongation at break of sample with a composition of PLA:PPC = 40:60 (wt %) and a catalyst amount of 0.5 wt % was nearly as twice as which without catalyst because of the improving miscibility of PLA domains and PPC matrix by the compatibilization of PLA‐b‐PPC copolymer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46009.     

Synthesis of poly(lactic acid)‐based polyurethanes

Poly(lactic acid) (PLA) is a biodegradable aliphatic polyester, but its brittleness makes it unsuitable for many packaging and appliance applications. The goal of the work reported was to create novel poly(ester urethane)s that incorporate biodegradable poly(lactic acid) diols (PLA‐OHs) and good mechanical properties of increased molecular weight via crosslinked network formation for engineering plastics applications. Three kinds of polyols (PLA‐OHs, PLA‐OHs/poly(tetramethylene ether) glycol or PLA‐OHs/poly(butylene adipate) glycol (PBA)) and two kinds of diisocyanates (4,4‐diphenylmethane diisocyanate (MDI) or toluene 2,4‐diisocyanate (TDI)) were chosen for the soft and hard segments to compare their mechanical properties. In addition, 1,4‐butanediol and trimethylolpropane were each used as chain extender agents. Results showed the PLA/PBA‐polyurethanes (PLA/PBA‐PUs) of the MDI series and the PLA/PBA‐PUs of the TDI series had improved thermal stability and enhanced mechanical properties. Degradation behavior showed the PLA‐based polyurethanes could be degraded in phosphate‐buffered saline solution and enzyme solution. © 2012 Society of Chemical Industry     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid) copolymer by electron beam radiation

This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission G_s and crosslinking G_x of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (T_g) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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

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

Effect of the melt‐mixing condition on the physical property of poly(l‐lactic acid)/poly(d‐lactic acid) blends

The effect of the mixing condition in a mill‐type mixer on the thermal property and the crystal formation of the poly(l ‐lactide)/poly(d ‐lactide) blends is investigated. The blends melt‐mixed at 200 and 210 °C under application of a high shear flow tend to show a single melting peak of the stereocomplex crystal (SC) in the differential scanning calorimetry first and second heating processes without indicating the trace of the melting of homo‐chiral crystal. The mixing at an elevated temperature causes a serious thermal degradation. Further kneading of the blends at an elevated temperature higher than T_m of SC causes the transesterification between the same enatiomeric chains forming block copolymers of l ‐ and d ‐chains. This block copolymer acts as a nucleating agent of SC and the compatibilizing agent between poly(l ‐lactide) and poly(d ‐lactide) and promotes the formation of SC. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45489.     

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     

Thermal migration of selected disperse dyes on poly(ethylene terephthalate) and poly(lactic acid) (Ingeo†) fibres

A study has been carried out to correlate the wet fastness properties of dyed knitted fabrics, derived from both poly(ethylene terephthalate) and poly(lactic acid) (Ingeo) fibres, with the thermal migration properties of the disperse dyes during heat treatment. The results indicate a greater amount of disperse dye at the surface of the Ingeo fibre fabric than the poly(ethylene terephthalate) fabric, after post heat‐setting using the conditions needed for fabric stabilisation, correlating well with its slightly lower wash fastness properties.     

Mesomorphic phase formation of plasticized poly(l‐lactic acid)

The effects of the crystallization temperature, T_c, on the crystal structure as well as its thermal behavior of plasticized poly(l ‐lactic acid) were investigated by means of wide‐angle X‐ray diffraction (WAXD), Fourier‐transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC). PLLA blended with succinic acid‐bis[2‐[2‐(2‐methoxyethoxy)ethoxy]ethyl] ester (SAE) showed clear difference in T_c dependence of crystalline form compared to PLLA homopolymer. PLLA with 26 wt % SAE crystallized into orthorhombic α form for T_c above 80°C, while a peculiar disordered structure (mesophase) was obtained for T_c at 40°C. A detailed FTIR analysis of the mesophase of PLLA, focusing on the intra‐ and inter‐chain interaction in the structure, indicated that mesophase had a large degree of disorder in 10/3 helical conformation as well as its packing manner of disordered 10/3 helical chain. Upon heating, mesophase showed a steep exothermic peak at 80°C in DSC thermogram, indicating the phase transformation from mesophase to a form crystal. FTIR results showed that the degree of interchain interaction of C=O in PLLA started to decrease above 60°C, followed by steep increase at 80°C due to the recrystallization into a form. Melt‐recrystallization process in mesophase‐α transformation was clarified. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39762.     

Properties of aligned poly(L‐lactic acid) electrospun fibers

Poly(L‐lactic acid) (PLLA)‐aligned fibers with diameters in the nano‐ to micrometer size scale are successfully prepared using the electrospinning technique from two types of solutions, different material parameters and working conditions. The fiber quality is evaluated using scanning electron microscopy (SEM) to judge fiber diameter, diameter uniformity, orientation, and appearance of defects or beads. The smoothest fibers, most uniform in diameter and defect free, were found to be produced from 10% w/v chloroform/dimethylformamide solution using an accelerating voltage from 10–20 kV. Addition of 1.0% multiwalled carbon nanotubes (MWCNT) into the electrospinning solution decreases fiber diameter, improves diameter uniformity, and slightly increases molecular chain alignment. The fibers were cold crystallized at 120°C and compared with their as‐spun counterparts. The influences of the crystalline phase and/or MWCNT addition were examined using fiber shrinkage, temperature‐modulated calorimetry, X‐ray diffraction, and dynamic mechanical analysis. Crystallization increases the glass transition temperature, T_g, slightly, but decreases the overall fiber alignment through shrinkage‐induced buckling of the fibers when heated above T_g. MWCNT addition has little impact on T_g, but significantly increases the orientation of crystallites. MWCNT addition slightly reduces the dynamic modulus, whereas crystallization increases the modulus in both neat‐ and MWCNT‐containing fibers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41779.