生物降解PHBV/天然植物纤维复合材料的界面改性研究进展

总结了近年来国内外关于聚羟基丁酸酯-co-羟基戊酸酯共聚物（PHBV）/天然植物纤维复合材料界面改性的研究进展。从天然植物纤维表面改性、在PHBV和天然植物纤维体系中添加界面改性剂以及对PHBV树脂基体进行改性等方面,来增强天然植物纤维与PHBV界面结合力,并使纤维在PHBV基体中分散更好。同时比较了这些改性方法的优劣,展望了此类材料的发展前景。     

PHB和PHBV注塑和挤出成型工艺研究

对聚3-羟基丁酸酯(PHB)和聚3-羟基丁酸3-羟基戊酸酯(PHBV)的热性能和流变性能进行了测试和比较。结果表明:两者的加工温度范围均较窄,剪切变稀严重;PHBV比PHB的熔融温度和分解温度稍低。以此为依据,通过注塑和挤出成型实验,分析了PHB和PHBV的加工特点,确定了其注塑和挤出成型工艺条件。     

聚羟基丁酸酯在生物医用材料中的应用

聚羟基丁酸酯(PHB)是原核微生物在碳、氮营养失衡的情况下,作为碳源和能源贮存在生物体内的一类热塑性聚醋。简要介绍了生物可降解聚合物聚羟基丁酸酯(PHB)的合成,重点评述了PHB在生物医学材料中的研究进展。     

聚乳酸/聚羟基烷酸酯全生物降解共混物研究进展

介绍了聚乳酸(PLA)/聚羟基烷酸酯(PHA)全生物降解共混物研究进展,包括PLA/聚羟基丁酸酯(PHB)共混物、PLA/β-羟基丁酸酯与β-羟基戊酸酯共聚物(PHBV)共混物等,其中重点介绍了其相容性与相态结构、结晶性能、热性能、力学性能、降解性能等方面的研究成果。     

活性污泥合成PHAs单体组分的调控方法

聚羟基烷酸酯（PHAs）是一类生物合成的环境友好高分子塑料，具有广泛应用前景。活性污泥合成PHAs可降低PHAs生产成本，实现废物资源化。PHAs的物化性质取决于其单体组分的结构和含量。基于优化PHAs产量的工艺研究，总结了调控活性污泥合成的聚羟基丁酸 羟基戊酸（PHBV）中羟基戊酰含量的工艺措施和生化原理。已有研究表明，好氧时，碳源类型决定PHBV中的单体组分;一般地，溶解氧浓度（DO）降低，PHBV中HV含量会增加;污泥来源、pH值以及碳源与氮磷浓度比的变化都会影响HV含量;各参数对PHAs组分的影响存在关联性。展望了调控活性污泥合成PHAs中单体组分的进一步研究方向。     

聚(3-羟基丁酸酯-co-3-羟基戊酸酯)的改性研究

细菌合成的聚（3－羟基丁酸酯－co-3-羟基戊酸酯）（PHBV）具有优良的生物降解和生物相容性。本文从热性能、机械性能和降解性等方面综述了PHBV近年来在物理改性和化学改性方面的进展。     

PHB和PHBV增韧、增塑改性研究进展

总结了近年来国内外关于聚羟基丁酸酯(PHB)和聚羟基丁酸酯-co-羟基戊酸酯共聚物(PHBV)在增韧和增塑改性方面的研究进展。通过应力-应变行为和冲击强度等性能指标,对弹性体、酚类化合物、反应性增韧、超高相对分子质量聚乙二醇、淀粉、羟基烷酸酯、热处理等增韧改性方法和效果、改性产物进行了评述；通过熔点、玻璃化转变温度、冷结晶温度等性能指标,对共聚改性、中小相对分子质量聚乙二醇、环氧大豆油等增塑剂增塑改性方法、效果以及改性产物进行了详细介绍。最后对PHB和PHBV生物降解材料的发展前景进行了展望。     

生物可降解塑料——聚羟基脂肪酸酯（PHA）的生产技术研究

清华大学和中国科学院微生物研究所合作超额完成了可生物降解塑料专题的攻关任务,该专题包括用废糖蜜为原料生产可生物降解塑料聚羟基丁酸酯(PHB)、基因工程菌生产可生物降解塑料PHB、用水解淀粉为原料生产可生物降解塑料PHB及其共聚物PH-BV、可生物降解塑料PHB的改性和应用研究等4个子专题。并在此基础上实现了世界上首次规模化生产第三代PHA——羟基丁酸共聚羟基己酸酯(PHBHHx),为我国的生物可降解塑料工业化研究开辟了广阔的前景。     

材料生物降解能力评价方法的研究

采用纤维素、淀粉、聚羟基丁酸酯（Polyhydroxybutyrate．PHB）、聚羟基丁酸／戊酸酯[polyhydroxybutyrateco—hydroxyvalerate），PHBV]、聚乙烯／淀粉共混物和聚乙烯等6种试验材料，在可控堆肥条件下通过测定释放的二氧化碳的方法，以及在水性培养液中需氧条件下分别通过测定氧气消耗量和释放的二氧化碳的方法，测定材料的生物分解能力。结果表明3种方法测得的材料生物降解百分率（%）分别依次为：纤维素（76．9）〉淀粉（74．3）〉PHB（73．3）〉PHBV（7 0．5）〉〉聚乙烯／淀粉共混物（20．3）〉〉聚乙烯（0．3）：PHB（78．7）〉PHBV（71．2）〉纤维素（70．7）〉〉聚乙烯／淀粉共混物（24．4）〉〉聚乙烯（0．3）：PHB（73．6）〉PHBV（72．4）〉纤维素（71．9）〉〉聚乙烯／淀粉共混物（26．2）〉〉聚乙烯（0．2），在评价聚合物生物降解能力上基本具有等效性。     

活性污泥合成聚羟基烷酸酯中单体组分的调控

聚羟基烷酸酯(PHAs)是一类生物合成的环境友好高分子塑料,具有广泛应用前景.活性污泥合成PHAs可降低PHAs生产成本,实现废物资源化.PHAs的物化性质取决于其单体组分的结构和含量.基于优化PHAs产量的工艺研究,总结了调控活性污泥合成的聚羟基丁酸-羟基戊酸(PHBV)中羟基戊酰含量的工艺措施和生化原理.已有研究表明,好氧时,碳源类型决定PHBV中的单体组分;一般地,溶解氧浓度(DO)降低,PHBV中HV含量会增加;污泥来源、pH值以及碳源与氮磷浓度比的变化都会影响HV含量;各参数对PHAs组分的影响存在关联性.展望了调控活性污泥合成PHAs中单体组分的进一步研究方向.     

Mechanical characterization and modeling of poly (β‐hydroxybutyrate)‐co‐poly(β‐hydroxyvalerate)–Alfa fiber‐reinforced composites

The mechanical properties of biobased composites of poly(β‐hydroxybutyrate)‐co‐poly(β‐hydroxyvalerate) biopolymer continuously reinforced with unidirectional Alfa fibers are investigated via tensile testing of oriented composite laminates. Simple mechanical models for the elastic stiffness, strength, and nonlinear hardening of the biobased composites are proposed with an emphasis on techniques that only require the independent properties of the fiber and matrix to facilitate composite design. Rule of mixtures (ROM) approaches are found to effectively predict the elastic properties of the composites but generally overestimate strength. Modified ROM approaches that discount the contribution of the matrix in the fiber loading direction and the contribution of the fiber in the transverse loading direction provide the most accurate strength predictions. Apparent elastic properties for composites with varying fiber orientations are predicted using a modified orthotropic laminate plate method which was found to overestimate composite stiffness in off‐axis loading directions. Postyield nonlinear hardening is modeled using a calibrated continuum yield and plasticity model and demonstrated to provide a close match of the experimental results. POLYM. COMPOS., 35:1758–1766, 2014. © 2014 Society of Plastics Engineers     

Study on short glass fiber‐reinforced poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) composites

Biobased non‐fossil polyester poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P3/4HB) containing 4.0 mol % 4‐hydroxybutyrate (4HB) was melt‐mixed with short glass fibers (SGF) via a co‐rotating twin‐screw extruder. The compositing conditions, average glass fiber length and distribution, thermal, crystallization, and mechanical properties of the P3/4HB/SGF composites were investigated. Calcium stearate, two kinds of paraffin wax and modified ethylene bis‐stearamide (TAF) were investigated as lubricants for the P3/4HB/SGF composites. It revealed that TAF is the most efficient lubricant of the P3/4HB/SGF composites. Coupling agents 2,2′‐(1,3‐phenylene)bis‐2‐oxazoline (1,3‐PBO) and pyromellitic dianhydride (PMDA) were used as end‐group crosslinkers to reduce the degradation of P3/4HB and increase the mechanical properties of the P3/4HB/SGF composites. It showed that 1,3‐PBO is the efficient coupling agent. The optimum condition of the P3/4HB/SGF composites is 1.5 phr TAF, 1.0 phr 1,3‐PBO, and 30 wt % glass fiber content. And the maximum of tensile strength, tensile modulus, and impact strength of the composites is 3.7, 6.6, 1.8 times of the neat P3/4HB polymer, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Morphology,mechanical property,and modeling evaluation of P(3HB‐co‐4HB)/nano‐ZnO composites

Poly(3‐hydroxybutyrate‐co‐4‐hydroxybutyrate) (P(3HB‐co‐4HB)) and nanometer zinc oxide (nano‐ZnO) modified by solid titanate coupling agent (TMC980) were selected to prepare P(3HB‐co‐4HB)/nano‐ZnO composites via melt blending. Scanning electron microscope (SEM), capillary rheometer, polarized optical microscopy (POM), and universal testing machine were used to characterize the fracture morphology, rheological property, spherulitic morphology, and mechanical properties of P(3HB‐co‐4HB)/nano‐ZnO composites. Halpin‐Tsai equation was used to quantitatively evaluate the dispersion and enhancement effects of modified nano‐ZnO on P(3HB‐co‐4HB). The results demonstrated that modified nano‐ZnO at 0.2%∼0.3% of volume fraction could significantly improve the tensile strength, elastic modulus and toughness, increase the melt viscosity, refine the spherulitic size, and rough the fracture morphology of P(3HB‐co‐4HB)/nano‐ZnO composites. Based on the effective aspect ratio (ξ) from Halpin‐Tsai model evaluation, the optimal dosage of nano‐ZnO for P(3HB‐co‐4HB)/nano‐ZnO composites was also at 0.2%∼0.3% of volume fraction. The Halpin‐Tsai equation was found to predict the experimental data most accurately for the P(3HB‐co‐4HB)/nano‐ZnO composites. POLYM. COMPOS., 37:3113–3121, 2016. © 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     

Incorporation of epoxidized soybean oil as co‐matrix in epoxy resin toward developing plastisol/particulate toughened glass fiber composites

Epoxidized soybean oil was incorporated as a co‐matrix into an epoxy resin, and the hybrid resin system was used for preparing glass fiber‐reinforced composites. Effect of addition of poly(vinyl chloride) plastisol and selected particulate fillers (fly ash and wood flour) to epoxy/epoxidized soybean oil matrix on mechanical and water uptake properties of glass fiber‐reinforced composites were studied. Fourier transform infrared spectroscopy was used to reveal the curing state of these composites. It was observed that tensile strengths and moduli decreased with the inclusion of all additives. However, addition of poly(vinyl chloride) plastisol, fly ash, and wood flour particulate fillers showed significant increase in impact strengths compared with neat epoxy composite in a synergistic manner. Water uptake results of the composites were found to be in good agreement with ? OH peak intensities obtained from Fourier transform infrared spectroscopy. Finally, acousto‐ultrasonic nondestructive technique was successfully used to assess damage states and to relate stress wave factors with tensile strength properties of modified epoxy‐based glass fiber composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40586.     

Water bamboo husk‐reinforced poly(butylene succinate) biodegradable composites

The water bamboo husk is one of major agricultural wastes in Taiwan. In this study, the fiber and powder obtained from the water bamboo husk were chemically modified by coupling agents. Furthermore, the modified fiber and powder were added to the biodegradable polymer poly(butylene succinate) (PBS) separately, to form novel fiber‐reinforced composites. Morphologies, mechanical properties, and heat resistance of these water bamboo husk‐reinforced composites were investigated. The results indicate that the fibers modified by coupling agents exhibited better compatibility with the polymer matrixes than did the untreated fibers. Moreover, it is found that the thermal properties were improved as plant fiber was incorporated to those polymers. Furthermore, the mechanical properties were also increased with the addition of coupling agent‐treated fiber. On the other hand, it is found that the homogeneity of untreated powder‐containing samples is better than that of untreated fiber‐containing samples. Moreover, the results reveal that the powders modified with coupling agents were not effective in improving the mechanical properties of the reinforced PBS. This is due to the bulky structure of lignin leading to a smaller reaction ratio with the coupling agents. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 188–199, 2006     

连续纤维增强聚环状对苯二甲酸丁二醇酯复合材料的研究进展

介绍了环状对苯二甲酸丁二醇酯(CBT)树脂的合成机理及其开环聚合机理,对比了聚环状对苯二甲酸丁二醇酯(PCBT)与聚对苯二甲酸丁二醇酯(PBT)的性能并介绍了纤维增强聚环状对苯二甲酸丁二醇酯复合材料的力学性能,综述了聚环状对苯二甲酸丁二醇酯(PCBT)基复合材料制备工艺的研究进展。     

Dynamic mechanical thermal analysis of biocomposites based on PLA and PHBV—A comparative study to PP counterparts

The primary objective of this study was the investigation of thermo‐mechanical behavior of cellulosic fiber reinforced polylactid (PLA) and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV) biopolymers. Both PLA and PHBV were processed with 30 wt % of cellulosic fibers; moreover, to improve the processability and mechanical performance, PHBV was previously blended with 30% by weight poly(butylene adipate‐co‐butylene terephthalate) (PBAT). Secondary target was the comparison of the obtained results to natural fiber reinforced polypropylene (PP) composites reinforced with exact the same fibers and processed by using identical techniques. For validation the thermo‐mechanical properties, a dynamic mechanical thermal analysis (DMTA) was applied. Storage modulus (E′), loss modulus (E″), and loss factor (tan δ) were determined. The DMTA results indicate decreased polymer chain motion with resulting improvement of stiffness expressed by the storage modulus. Finally, the effectiveness of fiber on the moduli was investigated. The C coefficient differs in dependence on fiber type, use of coupling agent, and the reference temperature in glassy state. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3175–3183, 2013     

The morphology and degradation behavior of electrospun poly(3‐hydroxybutyrate)/Magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/Magnetite composites

Electrospinning of biodegradable poly(3‐hydroxybutyrate) (PHB)/magnetite and poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV)/magnetite composites in 2,2,2‐trifluoroethanol (TFE) and chloroform are investigated to develop nonwoven nanofibrous structure. Ultrafine PHB/magnetite fibers are obtained and the resulting fiber diameters are in the range of 690–710 nm and 8.0–8.4 µm for the polymer dissolved in TFE and chloroform. The surface of PHB composites fiber fabricated in chloroform contains porous structures, which are not observed for the sample of PHB composites fiber dissolved in TFE. The fiber diameters for PHBV5/magnetite composites are in the range of 500–540 nm and 2.3–2.5 µm, depending on the use of TFE and chloroform. The average diameters of PHBV5/magnetite composite fibers are smaller than those of PHB/magnetite composites fiber. All electrospun PHB/magnetite and composite fibers are superparamagnetic. The degradation behaviors of PHB/magnetite and PHBV5/magnetite composite fibers were investigated using Caldimonas manganoxidans. For the fabricated composite fibers, it is found that the degradation rate increased with the increasing loading of magnetite nanoparticles. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41070.     

Mechanical properties and biodegradability of green composites based on biodegradable polyesters and lyocell fabric

Green composites composed of regenerated cellulose (lyocell) fabric and biodegradable polyesters [poly(3‐hydroxybutyrate‐co‐3‐hydroxyvarelate) (PHBV), poly(butylene succinate) (PBS), and poly(lactic acid) (PLA)] were prepared by compression‐molding method. The tensile moduli and strength of all the biodegradable polyester/lyocell composites increased with increasing fiber content. When the obtained PLA/lyocell composites were annealed at 100°C for 3 h, the tensile strength and moduli were lowered despite the increase of degree of crystallization of the PLA component. The SEM observation of the composites revealed that the surface of the annealed composite has many cracks caused by the shrinkage of the PLA adhered to lyocell fabric. Multilayered PLA/lyocell laminate composites showed considerably higher Izod impact strength than PLA. As a result of the soil viral test, although the order of higher weight loss for the single substance was lyocell > PHBV > PBS > PLA, the biodegradability of the green composites did not reflect the order of a single substance because of the structural defect of the composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3857–3863, 2004