Preparation of poly(lactic acid) fiber by dry–jet–wet spinning. II. Effect of process parameters on fiber properties

The dry–jet–wet spinning process was employed to spin poly(lactic acid)(PLA) fiber by the phase inversion technique using chloroform and methanol as solvent and nonsolvent, respectively, for PLA. The as spun fiber was subjected to two‐stage hot drawing to study the effect of various process parameters, such as take‐up speed, drawing temperature, and heat‐setting temperature on the fiber structural properties. The take‐up speed had a pronounced influence on the maximum draw ratio of the fiber. The optimum drawing temperature was observed to be 90°C to get a fiber with the tenacity of 0.6 GPa for the draw ratio of 8. The heat‐setting temperature had a pronounced effect on fiber properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3774–3780, 2006     

Characterization of poly(L‐lactic acid) fibers produced by melt spinning

Biodegradable poly(L ‐lactic acid) (PLLA) fibers were processed by a two‐step melt‐spinning method (melt extrusion and hot draw) from PLLA with three different viscosity‐average molecular weights (494,600, 304,700, and 262,800). Before spinning, the polymer flakes were first milled into powders and dried under vacuum. Viscosity‐average molecular weight of PLLA following the fabrication process was monitored. Tensile properties of as‐spun and hot‐drawn fibers were investigated. Morphology of the PLLA fibers was viewed under a scanning electron microscope. Crystallinity of these fibers was assessed by thermogram analysis of differential scanning calorimetry. Results showed that the extent of decrease in the viscosity‐average molecular weight of PLLA dropped sharply by 13.1–19.5% during pulverization and by 39.0–69.0% during melt‐extrusion. The hot‐draw process in this study had a little effect on the viscosity‐average molecular weight of PLLA. Smoother fibers could be obtained for the die temperature at least 230°C for raw materials with higher crystallinity (more than 75%) and at least 220°C for raw materials with lower crystallinity (about 60%). The as‐spun fibers showed crystallinity of 16.5–22.8% and the value increased to 50.3–63.7% after hot draw. Tensile moduli of the as‐spun fibers were in the range of 1.2–2.4 GPa, which were raised to 3.6–5.4 GPa after hot draw. The final PLLA fibers with 110–160 μm diameters showed tensile strengths of 300–600 MPa. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 251–260, 2001     

In vitro degradation of dry‐jet‐wet spun poly(lactic acid) monofilament and knitted scaffold

In vitro degradation behavior of dry‐jet‐wet spun poly(lactic acid) (PLA) monofilament and knitted scaffold were studied at three different pH i.e., at 4.6, 7.4, and 8.0 at 37°C for 20 weeks. Characterization of PLA by intrinsic viscosity, thermal properties, and scanning electron microscopy (SEM) was carried out. It is observed that the pH of the medium has significant role on degradation behavior of PLA. The degradation at pH 4.6 is observed to be maximum, which is confirmed by the drop of 52% in intrinsic viscosity. The degradation process has effect on the hydrophobicity of the PLA. The decrease in contact angle from 73° to 48° indicates that the PLA surface tends to become more hydrophilic as the degradation proceeds. The SEM analysis showed that with the degradation, surface deterioration takes place. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2006–2012, 2007     

Investigating the spinnability in the dry‐jet wet spinning of PAN precursor fiber

The spinnability of a spinning solution using DMSO as the solvent was investigated for dry‐jet wet spinning of PAN precursor fiber. Among many variables responsible for spinnability, the coagulating conditions, the air gap length, the nonsolvent content in spinning solution, and the spinning temperature have been viewed as the key factors, and they were investigated in this study. It was found however, unlike in the wet spinning, the spinnability in dry‐jet wet spinning process was barely influenced by the coagulating conditions, likely attributable to the existence of the air gap. However, the spinnability worsened when the air gap was longer than 30 mm. The quality of the spinning solution deteriorated with the increasing water content in it. The spinnability improved when the spinning temperature was maintained between 60 and 72°C and turned down once the temperature was over 72°C. The experimental results indicated that all the factors should be comprehensively considered to ensure good spinnability in dry‐jet wet spinning process. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of high‐molecular‐weight poly(L‐lactic acid)‐based polymers through direct condensation polymerization in bulk state

Poly(L ‐lactic acid‐co‐succinic acid‐co‐1,4‐butanediol) (PLASB) was synthesized by a direct condensation copolymerization of L ‐lactic acid, succinic acid (SA), and 1,4‐butanediol (BD) in bulk state using titanium(IV) butoxide (TNBT) as a catalyst. Weight average molecular weight (M_w) of PLASB increased from 3.5 × 10⁴ to 2.1 × 10⁵ as the content of SA and BD went up from 0.01 to 0.5 mol/100 mol of L ‐lactic acid (LA). PLASB having M_w in the range from 1.8 × 10⁵ to 2.1 × 10⁵ showed tensile properties comparable to those of commercially available poly(L ‐lactic acid) (PLLA). In sharp contrast, homopolymerization of LA in bulk state produced PLLA with M_w as low as 4.1 × 10⁴, and it was too brittle to prepare specimens for the tensile tests. M_w of PLASB synthesized by using titanium(IV)‐2‐ethyl(hexoxide), indium acetate, indium hydroxide, antimony acetate, antimony trioxide, dibutyl tin oxide, and stannous‐2‐ethyl 1‐hexanoate was compared with that of PLASB obtained by TNBT. Ethylene glycol oligomers with different chain length were added to LA/SA in place of BD to investigate effect of chain length of ethylene glycol oligomers on the M_w of the resulting copolymers. Biodegradability of PLASB was analyzed by using the modified Sturm test. Toxicity of PLASB was evaluated by counting viable cell number of mouse fibroblast cells that had been in contact with PLASB discs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 466–472, 2006     

聚（乳酸⁃乙醇酸）薄膜制备及其性能研究

以左旋乳酸（L?LA）和乙醇酸（GA）为原料,利用一步法熔融共聚合成聚（乳酸?乙醇酸）（PLLGA）共聚物,通过差示扫描量热仪（DSC）对共聚物薄膜的结晶性能进行了表征,并利用Avrami方程对其进行了等温结晶动力学研究,通过万能拉伸试验机和压差法气体透过仪对共聚物薄膜的力学性能和气体阻隔性能进行测试。结果表明,PLLGA共聚物薄膜中GA的引入对材料结晶性能有较大影响,在GA含量为4 %（摩尔分数,下同）的PLLGA中,GA表现为成核剂作用,共聚物结晶比纯聚左旋乳酸（PLLA）薄膜快,半结晶时间减少;而在GA含量为8 %的PLLGA中,GA则表现出限制分子链运动的作用,破坏共聚物分子间的规整度,导致材料结晶性能大幅度降低,处于非晶态;随着GA含量的增加,PLLGA薄膜的拉伸强度和弹性模量逐步下降,而断裂伸长率大幅度增加,GA含量为8 %的PLLGA的断裂伸长率达到了130.1 %,是纯PLLA薄膜的21.3倍;同时,PLLGA薄膜的气体阻隔性显著增加,5 ℃时,相比于纯PLLA薄膜,GA含量为8 %的PLLGA薄膜的O₂、CO₂、N₂透过量分别降低了47 %、41 %和39 %。     

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     

可生物降解聚乳酸类胶粘剂的研究进展

对可生物降解的聚乳酸类胶粘剂的种类、应用及最新的研究进展等几个方面进行了综述。特别介 绍了工业用聚乳酸类胶粘剂和医学用聚乳酸类胶粘剂的研究进展。     

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     

Investigation the jet stretch in PAN fiber dry‐jet wet spinning for PAN‐DMSO‐H2O system

The jet stretch of dry‐jet wet spun PAN fiber and its effects on the cross‐section shape of fibers were investigated for a PAN‐DMSO‐H₂O system. Clearly, the spinning parameters, such as dope temperature, bath concentration, bath temperature, and air gap, all influenced the jet stretch. Also, under uniform conditions, the postdrawing ratio as well as that of jet stretch changed. Under given conditions, as the bath temperature was below 30°C or above 45°C, jet stretch had little effect on the cross‐sectional shapes of PAN fiber. Within the temperature of 30–45°C, fiber's cross‐section shapes change obviously from round over an approximate circular shape into to an elliptical or a flat shape. The scope of jet stretch produced PAN fiber with circular cross‐section was bigger than that in wet spinning. These results indicated that appropriate air gap height, under milder formation conditions in dry‐jet wet spinning, could result in higher jet stretch and higher postdrawing ratio. The appropriate jet stretch and postdrawing ratio could result in circular profile of PAN fiber, which were helpful to produce round PAN precursor with finer size and better properties for carbon fiber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Compatible and crystallization properties of poly(lactic acid)/poly(butylene adipate‐co‐terephthalate) blends

Differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and dynamic mechanical analysis (DMA) properties of poly(lactic acid)/ poly(butylene adipate‐co‐terephthalate) (PLA/PBAT) specimens suggest that only small amounts of poor PLA and/or PBAT crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature and onset re‐crystallization temperature values of PLA/PBAT specimens reduce gradually as their PBAT contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA analysis reduce to the minimum value as the PBAT contents of PLA_xPBAT_y specimens reach 2.5 wt %. Further morphological and DMA analysis of PLA/PBAT specimens reveal that PBAT molecules are miscible with PLA molecules at PBAT contents equal to or less than 2.5 wt %, since no distinguished phase‐separated PBAT droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/PBAT specimens, respectively. In contrast to PLA, the PBAT specimen exhibits highly deformable properties. After blending proper amounts of PBAT in PLA, the inherent brittle deformation behavior of PLA was successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tensile properties of PLA/PBAT specimens are proposed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal and mechanical properties of biodegradable blends of poly(L‐lactic acid) and lignin

The thermal and mechanical properties of the biodegradable blends of poly(L ‐lactic acid) (PLLA) and lignin prepared by manual mixing have been investigated. Both the results of DSC and FTIR spectral analyses indicated the existence of intermolecular interaction between PLLA and lignin. Furthermore, FTIR elucidated the existence of an intermolecular hydrogen‐bonding interaction. Study of the mechanical properties of the blends indicated that the maximum strength and the elongation of the material decreased and the Young's modulus remained almost constant when the lignin content reached 20%. Thermogravimetry indicated that lignin would accelerate the thermal degradation of PLLA when the content of lignin was more than 20%. Compared with some other biodegradable polymers, the blend of PLLA and lignin is thought to be a promising material, because the material properties, as well as the price, are at an acceptable level when the content of lignin is less than about 20%. Copyright © 2003 Society of Chemical Industry     

The skin‐core structure of poly(acrylonitrile‐itaconic acid) precursor fibers in wet‐spinning

The skin‐core structure of poly(acrylonitrile‐itaconic acid) [P(AN‐IA)] precursor fibers in wet‐spinning has been analyzed by the means of electron probe microanalyser (EPMA), scanning electron microscope (SEM), and transmission electron microscope. The numerical solution of Fick's second law equations for diffusion in the nascent fiber was obtained by using the Method of Lines. It has been found that [P(AN‐IA)] precursor fiber composed of four parts had remarkable skin‐core structure. The sheet‐like skin, which was compact and homogeneous, had high crystallization and highly oriented structure. However, the core with low crystallization and some voids was loose, somewhat disorderly and unsystematic. Moreover, the precursor fiber had a pillar‐like layered structure along the fiber axis. The average thickness of each layer increased gradually from the skin to the endothecium. Meanwhile, a structural model of PAN precursor fiber has been built. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of polyacrylonitrile and cellulose acetate blend fibers through wet‐spinning

Fibers containing both polyacrylonitrile (PAN) and cellulose acetate (CA) were prepared through wet‐spinning by using N,N‐dimethylformamide (DMF) as a solvent. Compatibility of PAN and cellulose acetate blend (PCB) fibers was investigated by means of scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and infrared (IR) spectrophotometry. The absorptive capacity and mechanical properties of the fibers were measured. It was observed that the surface and the cross section of PAN fibers were quite smooth and free from voids and microcracks, whereas cracks and voids were present on the surface and cross section of blend fibers, which increased with the incorporation of CA in the blend. Moisture regains of blend fibers were quite high while their tensile properties showed a partial decrease. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2000–2005, 2007     

Synthesis and physical properties of poly(l‐lactic acid)‐poly(dimethyl siloxane) multiblock copolymers prepared by direct polycondensation

Multiblock copolymers consisting of poly(l ‐lactic acid) and poly(dimethyl siloxane) were prepared by the polycondensation of oligo(l ‐lactic acid) (OLLA) with dihydroxyl‐terminated oligo(dimethyl siloxane) and dicarboxyl‐terminated oligo(dimethyl siloxane). Copolymers with number‐average molecular weights of 18,000?33,000 Da and various content ratios of oligo(dimethyl siloxane) (ODMS) unit were obtained by changing the feed ratio of these oligomers. A film prepared from the copolymer with an ODMS content ratio of 0.37 exhibited two independent peaks at ?107°C and 37°C in the mechanical loss tangent for temperature dependence, suggesting the formation of microphase separation between the OLLA and ODMS segments. The film had a tensile strength of 3.2 MPa and a high elongation of 132%. The film also exhibited a high strain recovery even after repeated straining. The incorporation of dimethyl siloxane units as multiblock segments was confirmed to improve the flexibility of poly(l ‐lactic acid). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40211.     

聚乳酸及其纤维的发展概况和应用前景

介绍了聚乳酸及其纤维的发展现状,纺丝成型及纤维的性能和主要应用领域。由于聚乳酸纤维采用了天然可再生的植物资源,使用后可自然降解,所以在纺织、医学、农业等领域都有广阔的发展前景。     

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

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

Compatibility,crystallinity and mechanical properties of poly(lactic acid)‐poly(ether‐block‐amide) based copper nanocomposites

Binary and ternary composites of poly(lactic acid) (PLA), poly(ether‐block‐amide) (PEBAX) and copper nanoparticles were prepared by melt blending in an internal mixer. Compatibility and molecular interactions between the three components of the nanocomposites were evaluated using scanning electron microscopy and Fourier transform infrared spectroscopy. It was found that the carbonyl groups of the PLA and copper nanoparticles interact. Also, PLA and PEBAX are compatible and develop molecular interactions between the C=O of PLA and the C=O and NH of PEBAX, forming dipole–dipole bonds and hydrogen bonds. The compatibility and molecular interaction between PLA and PEBAX are reduced by copper nanoparticles. The reduction of compatibility between PLA and PEBAX produced a lower storage modulus and lower strain at break in the ternary systems than in the blend PLA‐PEBAX. Copper nanoparticles enhanced the crystallinity of PLA. PLA responded more strongly to the nucleating effect of copper when PEBAX was added indicating a synergistic effect. The strain at break of PLA was enhanced by the addition of PEBAX but was severely reduced by the presence of nanoparticles. © 2020 Society of Chemical Industry     

Synthesis and characterization of star‐shaped poly(ethylene glycol)‐block‐poly(L‐lactic acid) copolymers by melt polycondensation

Compared with linear diblock or triblock poly(ethylene glycol)‐block‐poly(L ‐lactic acid) copolymer (PEG‐b‐PLLA), star‐shaped PEG‐b‐PLLA (sPEG‐b‐PLLA) copolymers exhibit smaller hydrodynamic radius and lower viscosity and are expected to display peculiar morphologies, thermal properties, and degradation profiles. Compared with the synthesis routine of PEG‐b‐PLLA form lactide and PEG, the traditional synthesis routine from LA and PEG were suffered by the low reaction efficiency, low purity, lower molecular weight, and wide molecular weight distribution. In this article, multiarm sPEG‐b‐PLLA copolymer was prepared from multiarm sPEG and L ‐lactic acid (LLA using an improved method of melt polycondensation, in which two types of sPEG, that is, sPEG₁ (four arm, Mn = 4300) and sPEG₂ (three arm, Mn = 3200) were chosen as the core. It was found the molecular weight of sPEG‐b‐PLLA could be strongly affected by the purity of LLA and sPEGs, and the purification technology of vacuum dewater and vacuum distillation could help to remove most of the impurities in commercial available LLA. The polymers, including sPEG and sPEG‐b‐PLLA with varied core (sPEG₁ and sPEG₂) and LLA/sPEG feeding ratios, were characterized and confirmed by ¹H‐NMR and ¹³C‐NMR spectroscopy, Fourier transform infrared spectroscopy (FT‐IR) and gel permeation chromatography, which showed that the terminal hydroxyl group in each arm of sPEGs had reacted with LLA to form sPEG‐b‐PLLA copolymers with fairly narrow molecular weight distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and adsorption properties of poly(N‐vinylformamide/acrylonitrile) chelating fiber for heavy metal ions

In this article we report a new chelating fiber that was prepared from a hydrolyzate of poly(N‐vinylformamide/acrylonitrile) by a wet‐spinning method. This fiber contains chelating groups, such as amidine groups, amino groups, cyano groups, and amide groups, with high densities. We examined the chelating abilities for several metal ions with this fiber, and present the morphological merit of the fibrous product compared with the globular resin. Based on the research results, it is shown that the fiber has higher binding capacities and better adsorption properties for heavy metal ions than the resin. The pH value of the metal ion solution shows strong influences on the adsorption of the metal ions. The maximum adsorption capacities of the fiber for Cu²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Mn²⁺ are 112.23, 88.11, 141.04, 108.06, and 73.51 mg/g, respectively. In mixed metal ions solution, the fiber adsorbs Cr³⁺, Cu²⁺ and Co²⁺ efficiently. The adsorbed metal ions can be quantitatively eluted by hydrochloric acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1378–1386, 2002