Adherability and weldability of poly(lactic acid) and basalt fibre-reinforced poly(lactic acid)

The adherability and weldability of pure poly(lactic acid) (PLA) and basalt fibre-reinforced PLA were investigated in this research. The joining efficiency rate is introduced as a comparative parameter among different joining processes. In the case of adhesive bonding, 16 different adhesives were used to join specimens together. The highest bond strength and joining efficiency rate for both the pure (16 MPa, 78%) and basalt fiber-reinforced (18 MPa, 44%) adhesive-bonded specimens was achieved with acrylate-based two-component adhesives. The bond strength and joining efficiency rates of bonded specimens manufactured with four welding technologies (hot gas welding, friction stir welding, ultrasonic welding, laser welding) were also investigated. The highest bond strength for both pure PLA and basalt fibre-reinforced PLA specimens (51 and 125 MPa, respectively) was attained by laser welding. The highest joining efficiency rate for pure PLA specimens (85%) was attained by ultrasonic welding, while it was achieved by laser welding for basalt-fibre reinforced PLA specimens (70%).     

Production of optically pure poly(lactic acid) from lactic acid

Optically pure poly(lactic acid) (PLA) was obtained from lactic acid via purification of the corresponding lactide. The optical purity of PLA was determined using polarimetry and NMR. In the depolymerization process, the effect of the reaction conditions and catalysts on optical purity of the lactide was examined with temperature having a significant effect. In addition, the degree of racemization increased with increasing molecular weight of the oligomeric PLA. The effects of temperature, time, solvent, and stirring speed (RPM) on the lactide purification process were examined in order to improve optical purity. Optical purity was maximized when separation was carried out at 25 °C. The optical purity of PLA was significantly affected by that of lactide used.     

Hollow porous poly(lactic acid) microspheres

On the basis of the water solubility of poly(N‐vinyl‐2‐pyrrolidinone), hollow porous poly(lactic acid) microspheres (HPPLAs) were prepared by a water‐in‐oil‐in‐water multiple‐emulsion solvent evaporation method. The influence of the concentration of the stabilizer Span80 in the oil phase on the morphology was investigated. It was found that when the content of Span80 solutions was 3.5 wt %, most HPPLAs were about 2 μm in diameter. Field scanning electron microscopy results show that the HPPLAs were porous and hollow. The structure and crystal form of the HPPLAs were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction analysis. Using these HPPLAs as degradable templates, we successfully synthesized Litchi‐like polystyrene (PS) microspheres about 2 μm in diameter by the emulsion method. When used as drug carriers, these HPPLAs would be convenient in which to embed drugs, whereas the Litchi‐like PS microspheres may have potential as new materials for polymer modification. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Radiation effects on poly(lactic acid)

The effect of γ-irradiation on poly(lactic acid), PLA, synthesized by the solution polymerization of lactic acid in air and N₂ atmosphere, is studied. From the intrinsic viscosity and average molecular weight data of γ-irradiated samples, radiation chemical yields G(s) and G(x) for chain scission and crosslinking respectively were determined. Results indicate that the presence of air causes a decrease in both chain scission and crosslinking. Furthermore, the melting temperature decreased with dose and by using the Flory equation, the value of G (crystalline units) was estimated in air and N₂ atmosphere as 19 and 14 respectively.     

生物降解材料聚乳酸的改性

为降低聚乳酸(PLA)的成本、改善其亲水性、提高其力学性能和加工性能以及利用PLA改性其他高分子,可使用基体扩链、表面改性、接枝、增塑、共混、复合等技术对PLA类生物降解材料进行改性。乳酸直接共聚合改性、合成PLA类材料以及从廉价天然资源出发追求PLA改性的工业化是未来主要发展方向。     

Halochromic poly (lactic acid) film for acid base sensor

A novel strategy to engineer biodegradable halochromic film based on poly (lactic acid) (PLA) for pH sensorial substances was presented. The effect of polyethylene glycol (PEG) compositions and dye amount on the efficiency of halochromic pH film was observed. The interactions between PLA, PEG, and dye was evidence by Fourier transform infrared. UV–VIS results indicated the sensitivity of the halochromic film through color changes. Mechanical performance was investigated by tensile testing to assess the potential of the halochromic film. It was found that the halochromic pH film has a clear color response from yellow to purple at pH 3–11 with a rapid response time within a minute. The results also revealed that varying content of PEG showed a significant effect on response time compared with varying dye compositions. PLA/PEG film and dye formed new interactions where PEG increased the free volume of PLA and made it possible for the PEG and the dye to diffuse and entrap between PLA chain. In term of the film strength, the addition of PEG and dye improved the flexibility of PLA film, which enables great potential in many applications such as medical, textile, and packaging.     

Preparation of single poly(lactic acid) composites

An approach for making poly(lactic acid) (PLA) single‐polymer composites (SPCs) on the basis of PLA's slowly crystallizing characteristics was investigated. As a slowly crystallizing polymer, PLA can be processed with standard polymer processing techniques into end‐use products with varied crystallinities, from amorphous films to highly crystalline fibers. In this study, amorphous PLA sheets and crystalline PLA fibers/fabrics were laminated and compression‐molded to form an SPC at a processing temperature substantially lower than PLA's melting temperature. The effects of the major process conditions on the performance of the SPC were studied. The processing temperature played a profound role in affecting the fiber–matrix bonding properties. As the processing temperature increased, a drastic improvement in the interfacial bonding occurred at a temperature of around 135°C, which indicated the lower boundary of the process window. The compression‐molded SPC exhibited enhanced mechanical properties; particularly, the tearing strength of the fabric‐reinforced SPC was almost an order higher than that of the nonreinforced PLA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Using maleic anhydride grafted poly(lactic acid) as a compatibilizer in poly(lactic acid)/layered‐silicate nanocomposites

The goal of this work was to prepare exfoliated poly(lactic acid) (PLA)/layered‐silicate nanocomposites with maleic anhydride grafted poly(lactic acid) (PLA–MA) as a compatibilizer. Two different layered silicates were used in the study: bentonite and hectorite. The nanocomposites were prepared by the incorporation of each layered silicate (5 wt %) into PLA via solution casting. X‐ray diffraction of the prepared nanocomposites indicated exfoliation of the silicates. However, micrographs from transmission electron microscopy showed the presence of intercalated and partially exfoliated areas. Tensile testing showed improvements in both the tensile modulus and yield strength for all the prepared nanocomposites. The results from the dynamic mechanical thermal analysis showed an improvement in the storage modulus over the entire temperature range for both layered silicates together with a shift in the tan δ peak to higher temperatures. The effect of using PLA–MA differed between the two layered silicates because of a difference in the organic treatment. The bentonite layered silicate showed a more distinct improvement in exfoliation and an increase in the mechanical properties because of the addition of PLA–MA in comparison with the hectorite layered silicate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1852–1862, 2006     

马来酸酐/二乙烯基苯接枝聚乳酸对微晶纤维素/聚乳酸复合材料性能的影响

研究了马来酸酐(MAH)/二乙烯基苯(DVB)接枝聚乳酸(PLA-g-DVB/MAH)对微晶纤维素(MCC)/聚乳酸(PLA)复合材料性能的影响。首先采用熔融接枝法,将DVB作为MAH的共聚单体接枝到PLA分子链上制备PLA-g-DVB/MAH接枝聚合物,然后以PLA-g-DVB/MAH为相容剂,采用注射成型法制备MCC/PLA复合材料。利用FTIR对PLA-g-DVB/MAH进行表征,探究了PLA-g-DVB/MAH对MCC/PLA复合材料流变及力学性能的影响。结果表明,MAH成功接枝到PLA上,并得到接枝聚合物PLA-g-DVB/MAH;添加PLA-g-DVB/MAH后,MCC/PLA复合材料的储能模量、复数黏度、平衡扭矩以及剪切热都有明显升高;PLA-g-DVB/MAH的添加有利于改善MCC和PLA的界面相容性,进而提高了MCC/PLA复合材料的力学性能。     

The synthesis of poly (lactic acid)-fulvic acid graft polymer and its effect on the crystallization and performance of poly (lactic acid)

ABSTRACT

The poly (lactic acid)-fulvic acid graft polymer (PLA-FA) was synthesized with lactic acid and fulvic acid (FA). The optimum parameters were determined by orthogonal experiment. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy exhibited that FA was successfully grafted onto PLA. Then, PLA/PLA-FA composites were prepared with PLA-FA as fillers by melt blending. The structure characterization and performance tests demonstrated that PLA-FA effectively enhanced the comprehensive performance of PLA composites. The rheological analysis demonstrated that PLA-FA had plasticization effect. The non-isothermal crystallization kinetics demonstrated that PLA-FA promoted the crystallization rate of PLA composites, improving toughness of PLA composites.     

Preparation and degradability of poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid)/SiO2 hybrid material

Poly(lactic acid)–poly(ethylene glycol)–poly(lactic acid) (PLA‐PEG‐PLA)/SiO₂ hybrid material is prepared by sol–gel method using tetraethoxysilane (TEOS) and PLA‐PEG‐PLA as raw material. From Fourier transform infrared spectroscopy (FTIR) and X‐ray photoelectron spectroscopy (XPS) spectra, the hydroxyl groups of the silica sol derived from partially hydrolysis of TEOS and the unhydrolyzed ethoxy groups of TEOS can react with PLA‐PEG‐PLA. Differential scanning calorimetry (DSC) curves imply that the glass transition temperature (T_g) of PLA‐PEG‐PLA/SiO₂ hybrid material is higher than that of PLA‐PEG‐PLA and increases with the increase of silica content. X‐ray diffraction (XRD) analysis results show that PLA‐PEG‐PLA and PLA‐PEG‐PLA/SiO₂ hybrid material are both amorphous. Field scanning electron microscope (FSEM) photographs show that when PLA‐PEG‐PLA/SiO₂ hybrid material has been degraded for 12 weeks in normal saline at 37°C, a three‐dimensional porous scaffold is obtained, which is available for cell growth and metabolism. Moreover, the hydroxyl (? OH) groups on SiO₂ of PLA‐PEG‐PLA/SiO₂ hybrid material could buffer the acidity resulted from the degradation of PLA, which is beneficial to proliferation of cell in tissue repairing. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization behavior of poly(lactic acid)/elastomer blends

Differential Scanning Calorimetry (DSC) was used to evaluate the crystallization behavior of poly(lactic acid) and its blends with elastomer. It has been observed that the cold crystallization temperature of the blends decreased as the weight fraction of elastomer increased as well as the onset temperature of cold crystallization also shifted to lower temperature. In non-isothermal crystallization experiments, the crystallinity of poly(lactic acid) increased with a decrease in the heating and cooling rate. The melt crystallization of poly(lactic acid) appeared in the low cooling rate (1, 5 and 7.5 °C/min). The presence of low elastomer tends also to increase the crystallinity of poly (lactic acid). The DSC thermogram at ramp of 10 °C/min showed the maximum crystallinity of poly(lactic acid) is 36.95% with 20 wt% elastomer contents in blends. In isothermal crystallization, the cold crystallization rate increased with increasing crystallization temperature in the blends. The Avrami analysis showed that the cold crystallization was in two stages process and it was clearly seen at low temperature. The Avrami exponent (n) at first stage was varying from 1.59 to 2 which described a one-dimensional crystallization growth with homogeneous nucleation, whereas at second stage was varying from 2.09 to 2.71 which described the transitional mechanism to three dimensional crystallization growth with heterogeneous nucleation mechanism. The equilibrium melting point of poly(lactic acid) was also evaluated at 176 °C.     

A DFT study on poly(lactic acid) polymorphs

Poly(lactic acid) (PLA) can crystallize in α-, β-, γ- and stereocomplex (sc)- forms. It has been shown that the formation of stereocomplex between poly(l-lactic acid) and poly(d-lactic acid) significantly improve thermal stability and mechanical properties. However the mechanisms of enhancements are still unclear. In this study, we investigate the PLA polymorphs from the first-principles theoretical perspective in order to understand the intermolecular interaction in the crystals. Density functional theory at the level of Perdew-Wang generalized-gradient approximation was applied to optimize PLA crystal unit cells. A comparison of energies in the various unit cells reveals that sc-form is the most energetically favorable form among the four PLA polymorphs. The order of thermodynamically relative stability is that sc-form is 0.3, 1.1, and 1.3 kcal/mol more stable than α-form, β-form, and γ-form, respectively (when using the ultrasoft pseudopotential and a plane-wave basis set with an energy cutoff of 380 eV) or 0.4, 1.1, and 1.3 kcal/mol more stable than α-form, β-form, and γ-form, respectively (when employing the density functional semi-core pseudopotentials and the double numerical plus polarization orbital basis set with a global orbital cutoff of 3.7 Å). In addition to the energetic properties, structural and electronic properties were calculated as well. The theoretical predicted stability rank is in agreement with some reported observations. Such as, sc-form has higher melting point and larger heat of fusion than those of α-form. The enhanced thermal stability of the sc-form compared to the other three homopolymer forms may be attributed to the unique intermolecular non-conventional hydrogen bonding C-H?O(C) network in the stereocomplex.     

Citrate esters as plasticizers for poly(lactic acid)

Citrate esters were used as plasticizers with poly(lactic acid) (PLA). Films were extruded using a single-screw extruder with plasticizer contents of 10, 20, and 30% by weight. All of the citrate esters investigated were found to be effective in reducing the glass transition temperature and improving the elongation at break. It was observed that the plasticizing efficiency was higher for the intermediate-molecular-weight plasticizers. Hydrolytic and enzymatic degradation tests were conducted on these films. It was found that the lower-molecular-weight citrates increased the enzymatic degradation rate of PLA and the higher-molecular-weight citrates decreased the degradation rate as compared with that of unplasticized PLA. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1507–1513, 1997     

Toughening semicrystalline poly(lactic acid) by morphology alteration

The incorporation of the triblock copolymer (PDLA-PEG-PDLA) into Poly(l-Lactic Acid) (PLLA) has produced a semicrystalline polymer of substantial modulus and strength. These improvements in mechanical properties could potentially increase the utility of this biomass-based polymer. The blended samples have a continuous amorphous phase with crystalline regions being the discontinuous portion. Micro-Raman spectroscopy revealed that a stereocomplex involving PDLA and PLLA chains exists in the crystalline region. It can be concluded that the poly(ethylene glycol), the flexible midblock component, is necessarily dispersed in these crystalline regions. Both morphological features can contribute to the improvement in mechanical properties. Therefore, the successful toughening of PLA may be achieved due to several mechanisms working synergistically.     

Thoughening of poly(lactic acid) with silicone rubber

In this study, poly(lactic acid) (PLA) was blended with silicone rubber (SR) to improve its impact strength and toughness by using dynamic crosslinking in the presence of peroxide during melt compounding. The SR to PLA ratio, peroxide and coagent concentrations were taken as experimental parameters. Blends were evaluated in terms of their thermal properties, tensile and impact strengths, dynamic mechanical properties, and micro‐structure. Results showed that PLA was successfully toughened with SR using dynamic crosslinking. Impact strength and energy of fracture in tensile test improved up to 4 and 10 times, respectively. On the other hand, yield strength and stiffness of blends deteriorated by the incorporation of SR. Thermal analysis pointed out that presence of SR decreased the cold crystallization temperature. It was observed from scanning electron microscopy (SEM) that the energy absorbing mechanism under impact loads in PLA/SR blends is tortuosity in the crack patterns. POLYM. ENG. SCI., 54:2029–2036, 2014. © 2013 Society of Plastics Engineers     

Filling of poly(lactic acid) with native starch

Poly(lactic-acid) (PLA), a biodegradable polyester with excellent properties for different polymer applications, will play a major role in future markets for biodegradable polymers. But only if the currently very high price level can be reduced significantly to at least 4 $US/kg. Therefore, studies to fill poly(lactic acid) (PLA) with relative inexpensive native corn starch were conducted. Because PLA is a very brittle material with a glass transition point at 54°C, filling of PLA with native starch might seem unrealistic, as the brittleness is increased by the dispersed starch granules. To avoid this, low molecular weight poly(ethylene glycol) (PEG) is introduced into the PLA to enhance crystallization and to lower the glass transition temperature significantly under possible usage temperatures. The polymer that is modified in this way is then filled with native starch. The thermal behavior of the achieved di- or triblends is determined by means of differential scanning calorimetry (DSC) and the degradation behavior at high temperature has been looked at with the help of thermogravimetric analysis (TGA).     

Degradation kinetics of photopolymerizable poly(lactic acid) films

A series of acrylic poly(lactic acid) (PLA) films were produced via photopolymerization. Enzymatic degradation of the films was investigated by submerging or spraying the films with a solution of proteinase K, Chromobacterium viscosum (CvL), Rhizomucor miehei (RmL), or Candida cylindracea (CcL). Degradation was monitored by titration of the carboxylic acid groups, MS, and MS/MS. It was found that the degradation rate of the films was dependent on the water uptake of the film and enzyme solution used. The highest degradation rates, for both systems, were obtained by use of a proteinase K solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40475.     

聚乳酸熔融缩聚的研究

综述了近年来国内外聚乳酸熔融聚合的研究情况,概述了直接熔融缩聚、熔融-固相和熔融-扩链合成聚乳酸的研究,并研究探讨了熔融聚合中影响聚乳酸相对分子质量的因素。     

Hydrolysis of lactic acid based poly(ester-urethane)s

The hydrolysis behaviour of lactic acid based poly(ester-urethane)s has been studied in a buffer solution of pH 7·00 at 37 and 55°C. Samples were prepared using a straight two step lactic acid polymerization process. The lactic acid was first polymerized by condensation with a low molecular weight by hydroxyl terminated telechelic prepolymer and the molecular weight then was increased with a chain extender such as a diisocyanate. In the hydrolysis study, the effect on the hydrolysis rate of different stereostructures (different amount of D -units in the polymer chain) and the length of the ester units were studied. The rate of hydrolysis was examined by various techniques including weighing (water absorption and weight loss), GPC (molecular weight and polydispersity), and DSC (thermal properties). GPC measurements showed that at 37°C the weight average molecular weight of the poly(ester-urethane)s started to decrease slowly during the first week of hydrolysis, but that at 55°C the weight average molecular weight decreased dramatically during the first week of hydrolysis. Significant mass loss occurred later at both temperatures. © 1998 Society of Chemical Industry