Facile Preparation of Linear Polyurethane from UPy‐Capped Poly(dl‐Lactic Acid) Macrodiol

Linear polyurethanes based on poly(dl ‐lactic acid) (PDLLA) macrodiol are promising materials in tissue engineering, yet their synthesis requires rigorous control on various parameters. A facile way to prepare linear polyurethanes by capping the PDLLA macrodiol (M _n = 4536) with 2‐ureido‐4[1H]‐pyrimidone (UPy) is reported. The obtained low‐molecular‐weight UPy‐capped polyurethane can form flexible, stretchable, and hydrophobic supramolecular films due to the strong and unidirectional quadruple hydrogen bonding of UPy dimers. Tensile tests, shape recovery, and self‐healing observations indicate that, compared with conventional PDLLA macrodiol‐based linear polyurethane (M _n = 48840 and PDI = 1.8), the UPy‐capped polyurethane films have comparable mechanical properties (tensile modulus: 900 ± 38 MPa; ultimate strength: 9.6 ± 0.8 MPa) yet significantly better shape memory and self‐healing properties. These results suggest that the UPy‐capped polyurethane might become an alternative for conventional linear polyurethane as a new biomedical material.     

Structure and Mechanical Properties of Poly(lactic acid) Filled with (Starch nanocrystal)‐graft‐poly(ε‐caprolactone)

Poly(ε‐caprolactone) (PCL) was grafted to the surface of starch nanocrystals (StN) via microwave‐assisted ROP. The resultant nanoparticles were then incorporated into a poly(lactic acid) matrix to produce fully‐biodegradable nanocomposites with good mechanical properties. A loading level of 5 wt.‐% StN‐g‐PCL resulted in simultaneous enhancements of strength and elongation. The StN‐g‐PCL self‐aggregated as rubbery microparticles to enhance the elongation by ca. 10‐fold over that of neat PLA. Meanwhile, the grafted PCL chains were miscible with PLA and formed a stress‐transferring interface to the StN, providing a reinforcing function.

     

橡实淀粉/聚乳酸复合材料的制备与结构性能研究

采用熔融挤出法制备了橡实淀粉 (AS)/聚乳酸 (PLA)二元复合材料。通过对复合材料力学性能、吸水性、熔融指数 (MIR)、扫描电镜 (SEM)、动态机械热分析 (DMA)和热稳定性 (TG)的测试,研究了橡实淀粉含量对复合材料的力学性能、疏水性能和热性能的影响。研究表明,随着AS加入量的增加,复合材料的刚性逐渐增强,在AS质量分散50%的情况下,拉伸强度仍达47.19 MPa。熔融流动性能、拉伸和弯曲强度则略微有所下降,其玻璃化转变温度略向高温偏移,保持在57 ℃。制备的复合材料具有优异的疏水性能,即使在AS加入量高达50%的情况下,接触角可达63.26°,吸水率仅为2.68%。     

聚乳酸的化学合成与应用

简述了近年来聚乳酸(PLA)尤其是聚左旋乳酸(PLLA)的化学合成方法(缩合聚合和开环聚合)及其结构与性能,并对这类材料的应用和发展作了展望。     

Dramatic Improvements in Mechanical Properties of Poly(L‐lactide)/Silica Nanocomposites by Addition of Hyperbranched Poly(ester amide)

Biodegradable hyperbranched poly(ester amide) (HBP) was used as a compatibilizer to modify PLA/SiO₂ nanocomposites for the first time. The ternary composites displayed dramatically improved mechanical properties including excellent toughness and fairly high stiffness. TEM images revealed that an encapsulation structure was formed by HBP surrounding SiO₂ nanoparticles, and their surfaces became flocculent due to the migration process of silica. The linear viscoelastic behavior of the nanocomposites measured by parallel plate rheometer indicated that strong interface adhesion existed between PLA matrix and silica nanofiller after incorporating of HBP. The compatibilization effect of HBP and the enhanced mobility of nanoparticles contributed to the improved mechanical properties.

     

凹凸棒石/聚乳酸纳米复合材料的力学性能和流变性能

采用熔融共混法制备凹凸棒石(ATT)质量分数分别为1%、3%和5%的ATT/聚乳酸(PLA)纳米复合材料,研究了ATT/PLA纳米复合材料的力学性能和流变性能。红外光谱分析结果表明:ATT与PLA基体之间存在较强的相互作用,使得二者之间具有较好的相容性。当ATT含量低于5%时,其可均匀分散在PLA基体中,而达到5%时,则会发生部分团聚。添加ATT后,PLA基体从脆性材料变为韧性材料,ATT起到增韧作用,并显著提高了复合材料的力学性能。当ATT含量为3%时,断裂伸长率达到26.36%,比纯PLA增加了297.6%,并且复合材料的冲击强度也比纯PLA增加了19.7%。ATT/PLA纳米复合材料的复数黏度、储能模量和损耗模量随ATT含量的增加呈先增大后减小趋势。由于ATT与PLA之间有良好的结合力,ATT的加入增大了复合材料的弹性和黏性,且低频区的变化明显高于高频区的变化。     

Photodegradation of Poly(L‐lactic acid): Effects of Photosensitizer

Summary: Amorphous and crystallized poly(L ‐lactic acid) (PLLA‐A and PLLA‐C, respectively) films with different contents of N,N,N′,N′‐tetramethyl‐1,4‐phenylenediamine (TMPD) as a photosensitizer were prepared, and the effects of the addition of TMPD on the photodegradation of PLLA films were investigated. It was found that the addition of TMPD effectively enhanced the photodegradation of PLLA films and thereby decreased their molecular weight of PLLA films regardless of their crystallinity, and that PLLA films with different molecular weights can be prepared by the addition of different amounts of TMPD and subsequent UV irradiation. Too high contents of TMPD however caused the brittleness of PLLA films due to a large decrease in molecular weight. The PLLA chains in crystalline regions as well as those in amorphous regions are photodegradable even at an early stage, in marked contrast to their hydrolytic degradation, where the chains in the amorphous regions are selectively degraded. The basic changes in glass transition, cold crystallization, and melting temperatures (T_g, T_cc, and T_m, respectively) of PLLA films during UV irradiation can be ascribed to low‐temperature annealing effects; i.e., annealing‐induced stabilization in chain packing should have elevated T_g, and annealing‐induced formation of crystallite nuclei should have lowered T_cc and increased T_m. The exceptional large decreases in T_cc and T_m of UV‐irradiated PLLA‐A films and in T_g of UV‐irradiated PLLA‐C films at high TMPD contents are attributable to the large decrease in molecular weight, whereas the exceptional decrease in T_m of PLLA‐C films at high TMPD contents can be due to the folding surface structural change of crystalline regions or to the lattice disorder caused by molecular structural changes.

of PLLA‐A films before UV irradiation and after UV irradiation for 60 h as a function of TMPD content.     

聚乳酸的合成技术及应用进展

较全面地介绍了聚乳酸的合成方法和应用现状,重点阐述了聚乳酸的合成技术和应用的最新进展。分析了聚乳酸的发展前景和制约因素,提出了我国发展聚乳酸的思路和建议。     

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     

Electrospun Poly(l‐Lactic Acid) Nanofibers for Nanogenerator and Diagnostic Sensor Applications

This paper presents for the first time that poly(l ‐lactic acid) (PLLA) nanofibers can show the piezoelectricity along the fiber direction (d₃₃) by using an electrospinning method. First, the electrospun fiber bundles are characterized by scanning electron microscope, X‐ray, and piezoelectric coefficient measurements. The data show that the supercritical CO₂ treatment can greatly enhance the piezoelectricity of electrospun PLLA fibers, which can be resulting from the increased crystallinity of the fibers. Later, it is found that the electrospun PLLA fiber can generate a current of 8 pA and a voltage of 20 mV by a simple push–release process. Further, a single PLLA fiber‐based blood pulse sensor is also fabricated and tested and shows around a 2 pA output for blood pulse. Due to easy fabrication and relatively simple structure, this device enables a broad range of promising future applications in the medical sensor area.

     

聚乳酸阻燃改性研究进展

综述了近年来国内外聚乳酸( PLA)阻燃改性的研究进展,对磷系、氮系、硅系、膨胀型阻燃体系,无机及纳米粉体等各种环保型阻燃体系在PLA中的应用情况进行探讨,并对未来的发展趋势进行了展望.     

Poly(dimethylsiloxane)‐toughened syntactic foams

The potential of preformed elastomers as a toughening agent for epoxy–glass syntactic foam has been explored. Poly(dimethylsiloxane) microspheres were prepared by suspension polymerization. The microsphere dimensions could be varied from 58 to 255 µm by tuning the reaction parameters, particularly the stirring speed and feed concentration. Rheological studies indicated that the introduction of microballoons led to an increase in the viscosity of the resin, with the extent being proportional to the microballoon content. The zero shear viscosity increased from ～10³ mPa s at 30 °C to 10⁵ mPa s as the microballoon loading was increased to 40%. Syntactic foams containing varying amounts of microballoons (40–60% v/v) were prepared, and an analogous set of toughened foams were also prepared, where a fraction of the microballoons was replaced with poly(dimethylsiloxane) microspheres (3–7%). The effect of increasing dimensions of the elastomeric microspheres on the mechanical properties was also studied. The improvement in properties was more pronounced when the microsphere size was equivalent to that of the constituent microballoons. An improvement of 40% and 185% in flexural strength and flexural toughness was observed upon the introduction of poly(dimethylsiloxane) microspheres of optimal dimensions (diameter ～63 µm, 5% loading), without any undesirable increase in foam density. However, the compressive properties remained practically unaltered. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45882.     

Poly(L‐lactide): v. effects of storage in swelling solvents on physical properties and structure of poly(L‐lactide)

The effects of storage at 25°C in swelling solvents having different solubility parameter (δ_s) values of 16.8–26.0 J^0.5 cm^−1.5 on the physical properties and structure of as‐cast poly(L ‐lactide) (PLLA) films was investigated by the degree of swelling (DS), differential scanning calorimetry (DSC), and tensile tests. It was found that PLLA film shows durabity to swelling solvents having δ_s values much lower or higher than the value range of 19–20.5 J^0.5 cm^−1.5 and that the polymer solubility parameter (δ_p) for PLLA is in the value range of 19–20.5 J^0.5 cm^−1.5. The decrease in the glass transition temperature (T_g) and tensile properties and the increase in melting temperature (T_m) and crystallinity (x_c) were larger for PLLA films swollen in solvents having a high DS at 7 days (DS_7days). The slight increase in T_m and x_c for PLLA films after swelling in solvents with high DS_7days values was due to the crystallization of PLLA that occurred during swelling, while the small increase in T_g and elongation at break (ε_B) for PLLA films after immersion in the solvents having low DS_7days values was ascribed to stabilized chain packing in the amorphous region. The T_g, ε_B, and Young's modulus of the PLLA films after swelling in the solvents varied in the ranges of 47–57°C, 4–8%, and 55–77 kg/mm², depending on their DS_7days or δ_s values. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1582–1589, 2001     

Porous biodegradable polyester blends of poly(L‐lactic acid) and poly(ε‐caprolactone): physical properties,morphology, and biodegradation

Poly(L ‐lactic acid) (PLLA), poly(ε‐caprolactone) (PCL), and their films without or blended with 50 wt% poly(ethylene glycol) (PEG) were prepared by solution casting. Porous films were obtained by water‐extraction of PEG from solution‐cast phase‐separated PLLA‐blend‐PCL‐blend‐PEG films. The effects of PLLA/PCL ratio on the morphology of the porous films and the effects of PLLA/PCL ratio and pores on the physical properties and biodegradability of the films were investigated. The pore size of the blend films decreased with increasing PLLA/PCL ratio. Polymer blending and pore formation gave biodegradable PLLA‐blend‐PCL materials with a wide variety of tensile properties with Young's modulus in the range of 0.07–1.4 GPa and elongation at break in the range 3–380%. Pore formation markedly increased the PLLA crystallinity of porous films, except for low PLLA/PCL ratio. Polymer blending as well as pore formation enhanced the enzymatic degradation of biodegradable polyester blends. Copyright © 2006 Society of Chemical Industry     

Crosslinking of poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] using dicumyl peroxide as initiator

In order to modify poly [(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (PHBV), the crosslinking of this copolymer was carried out at 160 °C using dicumyl peroxide (DCP) as the initiator. The torque of the PHBV melt showed an abrupt upturn when DCP was added. Appropriate values for the gel fraction and crosslink density were obtained when the DCP content was up to 1 wt% of the PHBV. According to the NMR spectroscopic data, the location of the free radical reaction was determined to be at the tertiary carbons in the PHBV chains. The melting point, crystallization temperature and crystallinity of PHBV decreased significantly with increasing DCP content. The effect of crosslinking on the melt viscosity of PHBV was confirmed as being positive. Moreover, the mechanical properties of PHBV were improved by curing with DCP. When 1 wt% DCP was used, the ultimate elongation of PHBV increased from 4 to 11 %. A preliminary biodegradation study confirmed the total biodegradability of crosslinked PHBV. Copyright © 2004 Society of Chemical Industry     

Crystallization,Morphological, and Mechanical Response of Poly(Lactic Acid)/Lignin-Based Biodegradable Composites

Green/bio-based composites of poly(lactic acid) and lignin were prepared by melt blending in a twin-screw extruder. Thermal and mechanical properties, phase interaction, and morphology of the composites have been investigated. Fourier transform infrared studies elucidated the existence of intermolecular hydrogen bonding between poly(lactic acid) and lignin. Scanning electron microscopy studies revealed an extent of diffused phase boundaries between poly(lactic acid) and lignin which also indicated significant interaction between them. Tensile properties showed significant increase over neat poly(lactic acid) with lignin loading (0–0.28 volume fraction) which further justified using theoretical models. Izod impact strength decreased with lignin content.     

Effect of γ‐radiation on the thermal and mechanical properties of a commercial poly(butylene adipate‐co‐terephthalate)

BACKGROUND: Poly(butylene adipate‐co‐terephthalate) (PBAT) has attracted wide interest as a biodegradable polymer. However, its use is restricted in certain applications due to its low melting point. RESULTS: PBAT was treated using γ‐radiation. The radiation features were analyzed using Soxhlet extraction, and the ratio of chain scission and crosslinking and gelation dose were determined using the classical Charlesby–Pinner equation. The results showed that PBAT is a radiation‐crosslinkable polymer. The degree of crosslinking increased with increasing radiation dose; the relation between sol fraction and dose followed the Charlesby–Pinner equation. Differential scanning calorimetry analyses showed that the melting temperature (T_m) and the heat of fusion (ΔH_m) of PBAT exhibited almost no change in the first scan. The second scan, however, showed a decrease in T_m and ΔH_m. The glass transition temperature of irradiated PBAT increased with increasing radiation dose. The weight loss of control and irradiated PBAT resulting from thermal degradation was a one‐step process. Moreover, the tensile strength and elongation at break decreased with an increase in radiation dose. However, the Young's modulus and stress at yield were not greatly affected by γ‐radiation. CONCLUSION: PBAT can be crosslinked using γ‐radiation. The crosslinking efficiency is relatively low. The thermal and mechanical properties of PBAT are affected by γ‐radiation. Copyright © 2009 Society of Chemical Industry     

Blends of poly(L‐lactic acid) with poly(ω‐pentadecalactone) synthesized by enzyme‐catalyzed polymerization

Poly(ω‐pentadecalactone) (PPDL) was synthesized by enzyme‐catalyzed polymerization. The molecular weight of the PPDL was about 35,000. Opaque poly(L ‐lactic acid) (PLLA)/PPDL blend films were created by the solvent casting technique. The addition of PPDL led to PLLA crystallization. Furthermore, the addition of PPDL with PLLA increased both the Young's modulus [pure PLLA : 0.67 GPa, PLLA/PPDL (70/30 wt %) : 1.01 GPa] and the PLLA glass transition temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semiquantitative FTIR Analysis of the Crosslinking Density of Poly(ester amide)‐Based Thermoset Elastomers

Thermoset elastomers represent a class of polymers for a wide range of biomedical applications. Crosslinking density of thermoset elastomers is considered as an important parameter. In this study, semiquantitative Fourier transform infrared (FTIR) analysis is developed as a novel method to determine crosslinking density of poly (ester amide) thermoset elastomers. Poly(1,3‐diamino‐2‐hydroxypropane‐co‐polyol sebacate) (APS) is an example of poly(ester amide) thermoset elastomer. Polyethylene glycol (PEG) has been recently incorporated into APS polymer structure to obtain novel PEGylated APS‐based elastomers with tunable properties. The crosslinking densities of different APS and APS‐co‐PEG films are determined by the theory of rubber elasticity and FTIR. These results show that the intensity ratios between amide and carbonyl peak correlate well with the calculated crosslinking density from the elastic modulus. Thus, semiquantitative FTIR analysis offers a direct, facile, and less variable method to determine the crosslinking density and guide the consistent synthesis of poly(ester amide) thermoset elastomers.

     

Mechanical Properties and Degrading Behaviors of Aluminum Hypophosphite-Poly(Lactic Acid) (PLA) Nanocomposites

The flame retardancy of poly(lactic acid) (PLA)/aluminum hypophosphite (AHP, phosphorous content = 41.87 wt.%) nanocomposites (PLA/(AHP-x), x = 15%, 20%, 25%; and x denotes the weight percentage content of AHP) was greatly enhanced by melt blending of AHP into PLA through twin-screw extruder and injection-molding process. The UL 94 V-0 flammability rating can be reached for PLA/(AHP-20%) with the LOI value over 28.8. The well dispersion of the AHP in PLA/(AHP-x) was investigated by FT-IR spectra under the line mapping model. Based on TGA results under a non-isothermal condition, the thermal degradation kinetics of PLA/(AHP-x) composites were studied by Kissinger’s, Ozawa’s and Flynn-Wall-Ozawa’s (FWO’s) methods. And those thermal degradation dynamic analyses showed lower activation energy (E_K or E_O) (from 155 to 122 kJ·mol^–1) corresponded to higher content of AHP (from 15 to 25 wt.%) for PLA/(AHP-x) nanocomposites. Kissinger’s, FWO’s and Coast-Redfern’s methods were used to discriminate the kinetic models and kinetic parameters for the thermal degradation of PLA/(AHP-x), which suggested conversion function G (α) = [-ln(1-α)]^2/3 or G (α) = α for the investigated process. The flame retardant PLA nanocomposites obtained in this study will become safety environment-friendly potential candidates in household and automobile engineering with high performance.