聚碳酸亚丙酯-聚乳酸共混熔纺纤维的制备与性能

以乙烯-马来酸酐共聚物(ZeMac)作为反应性相容剂,利用熔融纺丝法制备了聚碳酸亚丙酯(PPC)-聚乳酸(PLA)共混纤维。通过傅里叶变换红外光谱仪、热重分析仪、差示扫描量热分析仪、纤维强伸度仪等分别研究了共混纤维的分子结构、热稳定性、相容性及力学性能。结果表明:PLA的引入较大地提高了PPC的力学性能,加入少量的ZeMac可以有效地改善PPC的热稳定性,同时也能够提高共混体系的相容性。当PPC-PLA与PPC-PLA-ZeMac体系组分质量比分别为70/30和70/30/0.7时,其抗拉强度分别为11.23 MPa和20.83 MPa,较未改性的PPC分别提高了6.5倍和12.1倍,同时还能保持较高的断裂伸长率。该项研究为完全可生物降解PPC熔融共混纤维的工业化提供了可能性。     

Review of Multifarious Applications of Poly (Lactic Acid)

Poly (lactic acid) is considered to be a promising alternative to petroleum-based polymers due to its renewability, biodegradability, biocompatibility, and good mechanical properties. Because of the high cost, the applications of poly (lactic acid) were limited to the medical field. Over the past decade, improvements in polymerization allow the economical mass production of high molecular weight poly (lactic acid). Therefore, the applications of poly (lactic acid) have recently spread to domestic, commercial packaging, and textile applications. This review outlines the chemical, thermal characteristics of poly (lactic acid) and discusses the use of poly (lactic acid) in medical applications such as sutures, stents, drug carrier, orthopaedic devices, scaffolds, as well as commercial applications in textile and packaging fields with superior properties such as high wicking performance, good dyeability, antibacterial feature, good ultraviolet resistance, high water vapor transmission rates, shrink wrapping, and dead fold property. While the drawbacks of poly (lactic acid) utilized in these fields are also discussed. It is clear that the advantages of using poly (lactic acid) outlined in this review will ensure that the market for poly (lactic acid) products will continue to expand.     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.     

Morphological and Mechanical Properties of Poly (Vinyl Alcohol) Doped with Inorganic Fillers

A number of polymer composite films using polyvinyl alcohol (PVA) as the preorganized polymer matrix were synthesized embedding different metal salts of transition elements like copper, cobalt, nickel, iron, cadmium, and zinc by a biomimetic route. The metal salts present in composites were reduced in situ to metallic form. The composites were characterized by FTIR, SEM, and EDAX. The SEM analysis confirmed the presence of nano-sized metal particles uniformly distributed in the polymer matrix. Mechanical properties were measured for various composite and PVA films. Significant improvement in some of the mechanical properties of polymer composites was realized in comparison with PVA.     

Synthesis and Characterization of Hydroxyapatite/Poly(Vinyl Alcohol Phosphate) Nanocomposite Biomaterials

A hydroxyapatite (HAp)/poly(vinyl alcohol phosphate) (PVAP) nanocomposite has been prepared by a chemical method by varying the HAp content by 10–60% (w/w). The bonding between HAp and PVAP has been investigated through Fourier transform infrared absorption spectra, X-ray diffraction, and thermogravimetric analyses. Transmission electron microscopy study shows a homogeneous dispersion of nanoparticles in the polymer matrix. Scanning electron microscopy study shows enhancement of the surface roughness of the composite with an increase in the nanoparticle content. The mechanical properties of the composites improve significantly with an increase in the HAp content. The HAp/PVAP nanocomposite prepared may have bone–implant applications.     

Influence of the Polymer Architecture and Functionalization with Carboxylate Groups over the Release of Octenidine Hydrochloride from Poly(lactic acid)-Based Nanoparticles

Healthcare-associated infections affect every year more than four million people due to the increasing resistance of bacteria to traditional antibiotics. In turn, the systematic use of quaternary ammonium salts as antiseptics is hampered by their inherent toxicity and high hydrophilicity that leads to their rapid elimination from the body. Therefore, a carefully controlled release of these antiseptics is pivotal to achieve prolonged therapeutic efficacy reducing the side effects. In this work, high encapsulation efficiencies and good control over the release of octenidine hydrochloride from poly(lactic acid) (PLA)-based nanoparticles (NPs) is achieved by introducing functional carboxylate groups in the polymer. The influence of the polymer structure and functionalization over the drug release is systematically investigated. Star-like and brush-like polymers with tunable number of ionizable chain end-groups are synthesized via combination of ring-opening polymerization and reversible addition−fragmentation chain transfer polymerization. These polymers are formulated in NPs and loaded with octenidine through emulsion/solvent evaporation. Brush-like polymers demonstrate to be a versatile tool for the modulation of the initial burst and long term release of the antiseptic through the tuning of the electrostatic interactions between the negative groups on the polymer, whose number can be precisely controlled, and the positively charged drug.     

聚乙二醇对聚乳酸纤维性能的改善

采用在双螺杆中熔融共混,以不同相对分子质量聚乙二醇(PEG)作为增塑剂,对聚乳酸(PLA)进行增塑改性,并把改性后的PLA进行熔融纺丝。用扫描电子显微镜(SEM)、熔体流动速率仪(MFR)、单纤维电子强力仪(EYST)和差示扫描量热仪(DSC)对改性PLA纤维进行表征。讨论了不同相对分子质量的PEG对PLA纤维性能的影响,发现随着PEG含量的增加,改性PLA的流动性增加。当PEG质量分数≤8%时,随着PEG含量的增加,改性PLA纤维强度增加,断裂伸长率增加,玻璃化转变温度(Tg)和熔点(Tm)下降。PLA与PEG组分间表现出较好的相容性。PEG200改性的PLA纤维综合效果最好。     

A Comparative Study on the Mechanical, Thermal and Morphological Characterization of Poly(lactic acid)/Epoxidized Palm Oil Blend

In this work, poly(lactic acid) (PLA) a fully biodegradable thermoplastic polymer matrix was melt blended with three different epoxidized palm oil (EPO). The aim of this research was to enhance the flexibility, mechanical and thermal properties of PLA. The blends were prepared at various EPO contents of 1, 2, 3, 4 and 5 wt% and characterized. The SEM analysis evidenced successful modification on the neat PLA brittle morphology. Tensile tests indicate that the addition of 1 wt% EPO is sufficient to improve the strength and flexibility compared to neat PLA. Additionally, the flexural and impact properties were also enhanced. Further, DSC analysis showed that the addition of EPO results in a decrease in T(g), which implies an increase in the PLA chain mobility. In the presence of 1 wt% EPO, TGA results revealed significant increase in the thermal stability by 27%. Among the three EPOs used, EPO(3) showed the best mechanical and thermal properties compared to the other EPO's, with an optimum loading of 1 wt%. Conclusively, EPO showed a promising outcome to overcome the brittleness and improve the overall properties of neat PLA, thus can be considered as a potential plasticizer.     

An Efficient Preparation and Characterization of Nanocomposite Films Based on Poly(vinyl chloride) and Modified ZnO Quantum Dot with an Optically Active Diacid Containing Amino Acid as Coupling Agent

The nanocomposites were manufactured by the incorporation of modified ZnO into the poly(vinyl chloride). ZnO nanoparticles were modified with diacid containing alanine amino acid. Ultrasonic irradiation was used for all process. The PVC/ZnO@DA nanocomposites were investigated by field emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, thermogravimetric, and mechanical analysis. Results showed the uniform dispersion of particles in the polymer matrix and ZnO@DA nanoparticles in quantum dot size. The optical properties of PVC were affected by the incorporation of modified quantum dot ZnO; also mechanical properties of PVC/ZnO@DA nanocomposites were improved.     

Preparation and Characterization of Poly L-Lactide/Triclosan Nanoparticles for Specific Antibacterial and Medical Applications

This work aims at preparation of poly-L-lactide (PLLA)/triclosan nanoparticles as antibacterial products used in some specific medical applications. PLLA was synthesized by the reaction extrusion via the ring opening polymerization of L-lactide using a continuous single-stage process, which is a fast and easy method. The PLLA triclosan nanoparticles were prepared by the emulsification–diffusion process with few modifications. Chloroform was used for the surface reaction of triclosan without any chemical shifts. The resulting nanoparticles with various triclosan quantities were fully characterized. The release as well as its kinetics was studied using the UV-visible spectroscopy. All the results confirmed the high stability and process efficiency of molecular dispersion and attachment of triclosan to PLLA. The sample containing 30% triclosan showed the best form among the others with the highest encapsulation efficiency. The synthesized nanoparticles with the controlled antibacterial activity could be considered as an appropriate alternative for application as antibacterial agent in the implantable surgical products as well as the drug delivery and wound-dressing applications.     

Degradation of Polymer-Drug Conjugate Nanoparticles Based on Lactic and Itaconic Acid

Tuberculosis (TB) is still a significant threat to human health. A promising solution is engineering nanoparticulate drug carriers to deliver anti-TB molecules. Itaconic acid (ITA) potentially has anti-TB activity; however, its incorporation in nanoparticles (NP) is challenging. Here we show an approach for preparing polymer-ITA conjugate NPs and a methodology for investigating the NP degradation and ITA release mechanism. The conjugate was synthesized by the two-directional growing of polylactic acid (PLA) chains, followed by capping their extremities with ITA. The poly(lactate)-itaconate PLA-ITA was then used to formulate NPs. The degradation and drug release processes of the polymer conjugate NPs were studied qualitatively and quantitatively. The molecular structures of released species were characterized by using liquid NMR spectroscopy and mass spectrometry. We discovered a complex NP hydrolysis process forming diverse oligomers, as well as monomeric lactic acid (LA) and drug ITA. The slow degradation process led to a low release of free drugs, although raising the pH from 5.3 to 7.4 induced a slight increase in the amounts of released products. TEM images showed that bulk erosion is likely to play the primary role in the degradation of PLA-ITA NPs. The overall results and methodology can be of interest for understanding the mechanisms of NP degradation and drug release of this new polymer-drug conjugate system.     

Poly(3-hydroxybutyrate)/ZnO Bionanocomposites with Improved Mechanical,Barrier and Antibacterial Properties

Poly(3-hydroxybutyrate) (PHB)-based bionanocomposites incorporating different contents of ZnO nanoparticles were prepared via solution casting technique. The nanoparticles were dispersed within the biopolymer without the need for surfactants or coupling agents. The morphology, thermal, mechanical, barrier, migration and antibacterial properties of the nanocomposites were investigated. The nanoparticles acted as nucleating agents, increasing the crystallization temperature and the degree of crystallinity of the matrix, and as mass transport barriers, hindering the diffusion of volatiles generated during the decomposition process, leading to higher thermal stability. The Young’s modulus, tensile and impact strength of the biopolymer were enhanced by up to 43%, 32% and 26%, respectively, due to the strong matrix-nanofiller interfacial adhesion attained via hydrogen bonding interactions, as revealed by the FT-IR spectra. Moreover, the nanocomposites exhibited reduced water uptake and superior gas and vapour barrier properties compared to neat PHB. They also showed antibacterial activity against both Gram-positive and Gram-negative bacteria, which was progressively improved upon increasing ZnO concentration. The migration levels of PHB/ZnO composites in both non-polar and polar simulants decreased with increasing nanoparticle content, and were well below the current legislative limits for food packaging materials. These biodegradable nanocomposites show great potential as an alternative to synthetic plastic packaging materials especially for use in food and beverage containers and disposable applications.     

Polymer-Biologically Active Principle Conjugates Obtained by Esterification of Poly(Vinyl Alcohol)

The paper deals with the study of some polymer-biologically active principle systems characterized by the controlled release of the bioactive component by hydrolyze followed by diffusion. The systems were obtained by coupling the 2-mercapto-benzotiazolyl-acetic acid and N-(m-nitrobenzoyl)-L-methionine on poly(vinyl alcohol) by means of esteric bonds in the presence of diciclohexylcarbodiimide as an activator. The influence of some coupling process parameters on the reaction efficiency was studied, such as the drug/support and activator/support ratios. The coupling products with a maximum content of biologically active compound were characterized by spectral measurements, also as regards the capacity of bioactive compound release under the conditions simulating those within the gastro-intestinal tract. The antibacterial activity of the conjugates against Staphylococcus aureus, Eschrichia coli, Sarcina lutea, and Bacillus subtilis was determined.     

聚乳酸立构复合物的合成与表征

采用直接熔融缩聚法制备不同分子量特征的聚乳酸预聚物,将分子量相近的PLLA和PDLA预聚物等量混合,经过熔融共混后再进行固相聚合,制备得到聚乳酸立构复合物.结果表明:sc-PLA与两种PLA预聚物相比,熔点提高50℃左右,通过固相聚合PLA的分子量也得到显著提高.该方法工艺简单,产物纯净,是改善聚乳酸耐热性的一种有效途径.     

硼酸改性聚乙烯醇薄膜的制备及性能研究

将溶液浇铸法制得的聚乙烯醇(PVA)薄膜用不同温度的硼酸饱和溶液进行不同时间的改性处理,对改性后薄膜的耐热性和耐水性进行了研究。结果表明:经过硼酸溶液改性处理后,PVA薄膜的热变形温度Tg小幅度上升,Tm呈下降趋势;从吸湿率的变化来看,改性处理后,薄膜的耐水性得到明显提高。     

Dispersion of Surface Modified Nanostructure Zinc Oxide in Optically Active Poly(Amide-Imide) Containing Pyromellitoyl-bis-L-isoleucine Segments: Nanocomposite Preparation and Morphological Investigation

Optically active zinc oxide/poly(amide-imide) (PAI) nanocomposites (NC)s were synthesized by using ultrasonic assisted technique. The polymers and zinc oxide (ZnO) nanoparticles were physically and/or chemically connected with each other through different kinds of interactions such as physical van der Waals forces, hydrogen bonding and/or covalent interactions. ZnO/PAI NCs were characterized by Fourier transform infrared spectra, X-ray diffraction patterns, and field emission scanning electron microscopy. The thermal stability studies indicated an enhancement of thermal stability of new NC materials compared with the pure polymer.     

Hot Melt Reactive Extrusion of Chitosan with Poly(acrylic acid)

The hot melt reactive extrusion of blends of chitosan and poly(acrylic acid) (PAA) was carried out without any process additives such as organic solvent or plasticizer. The maximum amount of chitosan in the blend during the extrusion process was kept at 40 wt%, since the melt viscosity of a system containing 50 wt% of chitosan exceeded the torque limitation of the equipment. The carboxylic groups of PAA interacted with the amine groups of chitosan during the melt process, and the system exhibited good melt flow. The interactions between these two polymers were explained by investigating the results obtained by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal transition behavior of PAA was altered with a decrease of more than 10°C in the peak melting point after extrusion. The infrared (IR) spectroscopic data confirmed the existence of a complex formation and possible hydrogen bonding between chitosan and PAA during the melt process. Scanning electron microscopy (SEM) micrographs indicated that chitosan was well-dispersed in the PAA blends up to 30 wt% chitosan, with no indication of loose particles or other disruptions on the upper and lower fractured faces. This smooth interface might have been caused by the interaction between amide bonds of chitosan and carboxylic groups of PAA.     

Degradability Enhancement of Poly(Lactic Acid) by Stearate-Zn(3)Al LDH Nanolayers

Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn₃Al LDH. A solution casting method was used to prepare PLA/stearate-Zn₃Al LDH nanocomposites. The anionic clay Zn₃Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn₃Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn₃Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn₃Al LDH nanocomposites showed that the presence of around 1.0–3.0 wt % of the stearate-Zn₃Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn₃Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.     

Mechanical and Dynamic Analysis of Poly (Vinyl Alcohol)-Modified Wood Dust Nanocomposite

Wood dust was modified by maleic anhydride and to know the effect of various filler loading on the properties of PVA-modified wood dust composite prepared by a conventional solvent casting technique. The as-synthesized composite films were typically characterized by FTIR spectroscopy and X-ray diffraction. To study the temperature dependencies of the dynamic modulii, stress relaxation, mechanical loss, and damping phenomena of the composite material, dynamic mechanical analysis (DMA) was done. The tensile behavior of the composite films was analyzed. The biodegradability study of the composite materials was done by soil burial test and their morphological modification study was done using SEM.     

超支化聚酰胺酯对聚乳酸增韧改性的研究

采用熔融共混的方法,用生物可降解的超支化聚酰胺酯(HBP)对聚乳酸(PLA)进行增韧改性,制备出具有良好韧性的PLA复合材料。对不同HBP含量的共混物的红外光谱、热性能和力学性能进行了测试和分析。红外光谱显示PLA和HBP间存在氢键作用。HBP的加入使PLA的结晶度从30.99%降低到18.58%。当HBP含量增加到10%时,PLA共混物的拉伸强度略有提高,且断裂伸长达到43.06%。结果表明:HBP的加入对PLA起到了很好的增韧作用。