聚乳酸/蒙脱土纳米复合材料研究进展

分析了聚乳酸(PLA)/蒙脱土(MMT)纳米复合材料的结构,介绍了溶液插层复合法、原位插层复合法、熔融插层复合法等PLA/MMT纳米复合材料的制备方法,从力学性能、热稳定性能、降解性能、气体阻隔性能等方面阐述了PLA/MMT纳米复合材料的性能,并对PLA/MMT纳米复合材料的发展前景进行了展望。     

PLA/OMMT纳米插层复合材料的合成、表征及降解性研究

以乳酸单体和有机蒙脱土(OMMT)为原料,通过原位插层聚合法合成了聚乳酸(PLA)/OMMT纳米插层复合材料, 分别采用傅立叶变换红外光谱( FT-IR)、X 射线衍射（XRD）、透射电子显微镜（TEM）等对PLA/OMMT复合材料的结构、形貌进行了表征和分析,同时研究了材料的降解性能。FT-IR表明,OMMT在聚合过程中被剥离成很小的粒子并分散在PLA基体中形成PLA/OMMT复合材料。由XRD分析可知MMT的层间距为1.260 nm,OMMT层间距为1.993 nm,PLA/OMMT复合材料中OMMT层间距为2.287 nm,层间距明显增大,表明PLA分子链插入到OMMT片层间,实现了原位插层聚合。透射电镜（TEM）分析表明,制备的PLA/OMMT复合材料形成了插层型结构,与红外光谱与XRD表征结果吻合。降解试验表明,介质对材料降解作用的次序为：NaOH＞HCl＞去离子水。在磷酸盐缓冲溶液中,随着降解时间的延长,材料的特性黏度在降解过程中不断下降。PLA/OMMT复合材料的降解速度要快于PLA,表明由于OMMT纳米粒子的存在,会加速材料的降解。     

丁苯橡胶/纳米硅铝管复合材料的制备工艺与性能

分别采用直接共混法、填料预处理法、原位改性分散法、乳液法制备了丁苯橡胶/纳米硅铝管（SBR/SANT）复合材料,并对其结构和性能进行了表征。结果表明：采用原位改性分散的方法能够有效改善填料与橡胶间的界面强度,制备得到力学性能优异的SBR/SANT复合材料。采用乳液法制得复合材料的填料分散较好,扫描电子显微镜观察到SANT基本以单管分散,其导热性能明显优于干法混合。随着纳米硅铝管用量增大,SBR/SANT复合材料的硬度、定伸应力、拉伸强度、撕裂强度和导热系数提高,拉断伸长率下降。     

功能纳米填料在橡胶中的作用及橡胶纳米复合材料的制备

综述了功能纳米填料在橡胶中的作用,如可提高橡胶力学性能,改善橡胶硫化性能、抗老化性能、阻隔及隐身等性能;介绍了橡胶纳米复合材料的制备方法,主要有共混法、原位聚合法、溶胶-凝胶法及层间插入法;展望了功能纳米填料在橡胶中的作用及橡胶纳米复合材料制备的发展前景。     

原位聚合法制备聚乳酸/滑石粉复合材料

用硅烷偶联剂对超细滑石粉（Talc）改性后,采用原位聚合法制备出不同质量分数的聚乳酸/滑石粉（PLA/Talc）复合材料,并采用傅里叶变换红外光谱仪（FTIR）、扫描电子显微镜（SEM）、核磁共振波谱仪（NMR）、热失重分析仪（TG）、偏光显微镜（POM）等方法对复合材料进行表征。结果表明,Talc粒子在复合材料中均匀分散;PLA/含量3 %Talc的复合材料的拉伸强度、冲击强度分别比纯PLA增加了102.56 %和47.83 %,复合材料的热稳定性也明显提高;Talc促进了PLA结晶性能,在一定程度上提高其力学性能,复合材料降解速率比于纯PLA明显加快。     

纳米硅补强氟橡胶的研究

以热弧等离子体法制备高纯度纳米硅，通过机械共混法制备炭黑/氟橡胶（FKM-C）和纳米硅/氟橡胶（FKM-Si）复合材料，与不加填料的纯氟橡胶（P-FKM）复合材料相比，研究填料对氟橡胶性能的影响。结果表明：FKM-Si复合材料的脆性温度低于P-FKM复合材料；FKM-Si复合材料的硬度、拉伸强度和拉断伸长率均高于FKM-C复合材料，分别达到70度、12.16 MPa和289%；FKM-Si复合材料的截面无缺陷，说明纳米硅与氟橡胶的相容性好；FKM-Si复合材料的热稳定性比FKM-C复合材料好。     

原位聚合抗磨损PA6/纳米SiO2复合材料制备及其性能研究

为提高聚酰胺6（PA6）的抗磨损性能,采用原位聚合法合成并制备了PA6/纳米SiO2复合材料,研究了该材料的抗磨损性能、耐热性能、力学性能和结晶性能。结果表明,原位聚合PA6/纳米SiO2复合材料具有良好的抗磨损特性,当纳米SiO2含量为1 %(质量分数,下同)时,复合材料抗磨损性能最佳,该材料的热变形温度、拉伸强度、弹性模量和断裂伸长率均明显高于原料PA6;当纳米SiO2含量为3 %时,复合材料热变形温度由原料PA6的64.6 ℃提高到130 ℃。采用原位聚合母料法制备的PA6/纳米SiO2复合材料同样具有理想的抗磨损性能,并可获得更好的力学性能,且可大幅降低材料制备成本。     

海藻酸盐协效碳酸钙对聚乳酸热性能及断面形貌的影响

聚乳酸(PLA)是一种典型的脂肪族聚酯,因其优异的性能逐渐成为一种有前途的石油基聚合物替代物。对PLA的改性研究受到越来越多的关注。以PLA为基体,以纳米无机材料纳米碳酸钙(nano-CaCO_3)、海藻酸以及海藻酸盐为填料,通过熔融共混制备了填充型PLA复合材料。并通过场发射扫描电子显微镜(SEM)、动态力学分析(DMA)、差示扫描量热分析(DSC)等表征手段对复合材料的热力学性能、结晶性能及形貌等进行了分析评价。结果表明:海藻酸及其盐类的添加可适当改善复合材料的相容性,随着填料添加量的增加,PLA复合材料的结晶度均有所增加,同时各组分的加入充当了成核剂的作用,缩短了结晶诱导时间,但冷结晶过程的结晶速度相对纯PLA均有所下降;各体系PLA复合材料均表现出脆性断裂面形貌,单纯的加入nanoCaCO_3断口表面较粗糙,局部产生凹坑;而复配组分的加入,则使得凹坑减少,界面更平整。     

纳米羟基磷灰石／聚氨酯复合材料的制备与表征

以模拟体液（SBF）为介质,采用仿生法制备了纳米羟基磷灰石（n-HA）,通过原位聚合法制备了纳米羟基磷灰石／聚氨酯（n-HA／PU）复合材料。利用x射线衍射（XRD）、红外光谱（FT-IR）、热重分析（TGA）、扫描电镜（SEM）研究了n—HA和复合材料的结构和热稳定性、表面形貌特征。结果表明,在SBF中用浓度为0．200mol／L硝酸钙溶液制备出具有良好结晶度的n-HA,由此制备的n—HA／PU复合材料开孔率良好,有望成为一种性能良好的医用组织支架材料。     

聚氯乙烯纳米复合材料研究进展

阐述了共混法、原位聚合法和插层聚合法等聚氯乙烯(PVC)纳米复合材料的制备方法,介绍了PVC/无机粒子、PVC/黏土等几种纳米复合材料的性能,指出了PVC纳米复合材料的发展方向。     

可降解聚乳酸复合材料研究进展

对聚乳酸（PLA）复合材料的生物降解性能进行综述,总结PLA与有机物（如木质素、纤维素等）、无机物（如碳酸钙、纳米银颗粒等）复合后力学性能、热性能、生物相容性、抗菌性的变化及在不同环境条件下生物降解速率的变化,梳理了PLA复合材料结构、组成与降解性能的相互关系,对降解性能可控的PLA复合材料应用前景进行了展望。     

聚乳酸与常用纳米材料复合工艺的研究进展

根据近几年国内外的研究文献,综述了聚乳酸与几种常用纳米材料(如纳米纤维素、纳米二氧化硅、羟基磷灰石、蒙脱土、石墨烯、碳纳米管等)复合的制备工艺,并对复合材料的性能进行了简要阐述,最后对聚乳酸与纳米粒子复合工艺的发展作出了展望。     

Synthesis,Characterization of Fulvic Acid–Poly(Methylmethacrylate) Graft Copolymers Based on Surface-Initiated Atom Transfer Radical Polymerization and its Effect on Performance of Poly(Lactic Acid)

Fulvic acid–poly(methylmethacrylate) graft copolymers were synthesized by surface-initiated atom transfer radical polymerization with fulvic acid. The result demonstrated that the hydrophobicity of fulvic acid–poly(methylmethacrylate) was improved after modification by surface-initiated atom transfer radical polymerization. Furthermore, poly(lactic acid)/fulvic acid–poly(methylmethacrylate) composites were prepared to improve the performances of poly(lactic acid) by blend melting. Compared to poly(lactic acid) with X_c of 5.38%, the X_c of poly(lactic acid)/fulvic acid–poly(methylmethacrylate) composites was 19.94%. Moreover, the impact strength of poly(lactic acid)/fulvic acid–poly(methylmethacrylate) composites was increased by 5.19% compared to poly(lactic acid). In all, this study provided an effective and feasible method for optimizing interface performance and enhancing the thermal stability of poly(lactic acid).     

Fabrication of poly(lactic acid)/graphene oxide/stearic acid composites with improved tensile strength

For the purpose of the development of poly(lactic acid)/graphene oxide composites with improved tensile properties, a stearic acid compatibilizer was used to enhance the compatibility of the graphene oxide sheets with the poly(lactic acid) polymer matrix. Graphene oxide was modified with stearic acid at different mass ratios of 1:1, 1:3, and 1:5 prior to forming the composites with poly(lactic acid). Characterization showed positive effects of stearic acid attached to GO in every mass ratio and also enhanced compatibility with the poly(lactic acid) matrix. Stearic acid could strengthen the interfacial interactions between the flat graphene oxide sheets and the poly(lactic acid) matrix resulting in improved tensile strength. The tensile strength of the poly(lactic acid)/graphene oxide/stearic acid composite with a mass ratio of graphene oxide and stearic acid 1:1 increased by 32% compared to poly(lactic acid) alone. Based on these results, the graphene oxide/stearic acid composites show potential for use as nanosheet fillers for tensile strength enhancement in poly(lactic acid). POLYM. COMPOS., 38:2272–2282, 2017. © 2015 Society of Plastics Engineers     

Wood‐fiber‐reinforced poly(lactic acid) composites: Evaluation of the physicomechanical and morphological properties

This article presents the results of a study of the processing and physicomechanical properties of environmentally friendly wood‐fiber‐reinforced poly(lactic acid) composites that were produced with a microcompounding molding system. Wood‐fiber‐reinforced polypropylene composites were also processed under similar conditions and were compared to wood‐fiber‐reinforced poly(lactic acid) composites. The mechanical, thermomechanical, and morphological properties of these composites were studied. In terms of the mechanical properties, the wood‐fiber‐reinforced poly(lactic acid) composites were comparable to conventional polypropylene‐based thermoplastic composites. The mechanical properties of the wood‐fiber‐reinforced poly(lactic acid) composites were significantly higher than those of the virgin resin. The flexural modulus (8.9 GPa) of the wood‐fiber‐reinforced poly(lactic acid) composite (30 wt % fiber) was comparable to that of traditional (i.e., wood‐fiber‐reinforced polypropylene) composites (3.4 GPa). The incorporation of the wood fibers into poly(lactic acid) resulted in a considerable increase in the storage modulus (stiffness) of the resin. The addition of the maleated polypropylene coupling agent improved the mechanical properties of the composites. Microstructure studies using scanning electron microscopy indicated significant interfacial bonding between the matrix and the wood fibers. The specific performance evidenced by the wood‐fiber‐reinforced poly(lactic acid) composites may hint at potential applications in, for example, the automotive and packaging industries. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4856–4869, 2006     

聚乳酸纳米复合材料流变性能研究进展

综述了各种纳米粒子,包括生物质基纳米粒子、碳基纳米粒子、纳米黏土等对聚乳酸(PLA)在剪切力场作用下的流变性能影响及其各自含量、表面处理和与PLA基体之间相互作用等对其流变性能的影响,并总结了纳米粒子对PLA流变性能的作用机理。     

Thermal properties of extruded/injection‐molded poly(lactic acid) and biobased composites

To determine the degree of compatibility between poly(lactic acid) and different biomaterials (fibers), poly(lactic acid) was compounded with sugar beet pulp and apple fibers. The fibers were added in 85 : 15 and 70 : 30 poly(lactic acid)/fiber ratios. The composites were blended by extrusion followed by injection molding. Differential scanning calorimetry and thermogravimetric analysis were used to analyze the extruded and extruded/injection‐molded composites. After melting in sealed differential scanning calorimetry pans, the composites were cooled through immersion in liquid nitrogen and aged (stored) at room temperature for 0, 7, 15, and 30 days. After storage, the samples were heated from 25 to 180°C at 10°C/min. The neat poly(lactic acid) showed a glass‐transition transition at 59°C with a change in heat capacity (ΔC_p) value of 0.464. The glass transition was followed by crystallization and melting transitions. The enthalpic relaxation of the poly(lactic acid) and composites steadily increased as a function of the storage time. Although the presence of fibers had little effect on the enthalpic relaxation, injection molding reduced the enthalpic relaxation. The crystallinity percentage of the unprocessed neat poly(lactic acid) dropped by 95% after extrusion and by 80% for the extruded/injection‐molded composites. The degradation was performed in air and nitrogen environments. The degradation activation energy of neat poly(lactic acid) exhibited a significant drop in the nitrogen environment, although it increased in air. This meant that the poly(lactic acid) was more resistant to degradation in the presence of oxygen. Overall, injection molding appeared to reduce the activation energy for all the composites. Sugar beet pulp significantly reduced the activation energy in a nitrogen environment. In an air environment, both sugar beet pulp and apple fibers increased the activation energy. The enzymatic degradation of the composites showed a higher degradation rate for the extruded samples versus the extruded/injection‐molded composites, whereas the apple composites exhibited higher weight loss. The thermogravimetric analysis data showed that the degradation of unprocessed and extruded neat poly(lactic acid) followed a one‐step mechanism, whereas extruded/injection‐molded composites showed two‐step degradation. A higher fiber content resulted in up to three‐step degradation mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effects of Poly(ϵ-caprolactone) on Structure and Properties of Poly(lactic acid)/Poly(ϵ-caprolactone) Meltblown Nonwoven

To obtain flexile poly(lactic acid)-based melt-blown nonwoven filtration material, poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven with various components were melt-spun by melt-blown processing in the Melt-blown Experiment Line. The 3 wt.% tributyl citrate to poly(?-caprolactone) was added in the composites as compatibilizer. The effect of poly(?-caprolactone) on the structure, morphology, mechanical and filtration properties of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven was reported. Scanning electron microscopy micrographs revealed good dispersion of the additive in the fiber webs. The crystallinity of melt-blown webs with poly(?-caprolactone) was more than that of poly(lactic acid) alone. The tensile strength, ductility and air permeability of poly(lactic acid) melt-blown nonwovens were enhanced significantly. The input of poly(?-caprolactone) increased the diameter of fibers and decreased the filtration efficiency of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven.     

不同粒径氧化锌以及改性纳米氧化锌对多功能PBAT复合膜的影响

采用溶剂铸膜法制备了聚己二酸/对苯二甲酸丁二酯（PBAT）/聚乳酸（PLA）/对苯二甲酸二辛酯（DOTP）/氧化锌（ZnO）复合膜材料,并通过硬脂酸改性纳米ZnO,探讨了不同粒径ZnO以及改性纳米ZnO对复合薄膜力学性能、热性能、疏水性能、耐抽出性能以及抗菌性能的影响。结果表明,通过硬脂酸代替纳米ZnO表面的羟基极性基团,复合膜的耐抽出性能提高。硬脂酸的长链烷基与高分子链的链纠缠改善了改性纳米ZnO与PBAT的相容性。随着ZnO粒径的减小以及改性纳米ZnO含量的增大,复合薄膜的热性能有所下降,但耐抽出性能提高。拉伸强度提高,最高达到13.8 MPa。复合膜的疏水性能得到改善,接触角最高达到110°,复合膜材料的抑菌区域增大,抗菌性能有所增强。     

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.