淀粉/聚乙烯醇活性包装薄膜及其在食品包装应用中的研究进展

综述了淀粉/聚乙烯醇（PVA）活性包装薄膜及其在食品包装中的研究进展，主要对从不同比例共混、疏水改性、增强改性等方面对淀粉/PVA薄膜的改性研究，从功能特性和活性物质对薄膜性能的影响2个方面对淀粉/PVA活性薄膜研究和薄膜在食品包装中的应用3个方面进行了归纳总结，旨在为以淀粉/PVA为基材的活性包装薄膜研究提供参考。     

水溶性PVA薄膜的制备及其改性研究进展

综述了近年来水溶性聚乙烯醇(PVA)薄膜的制备工艺进展,介绍了其在共聚改性、共混改性、复合改性方面的研究进展,以及在制备工艺、改性方法上的优缺点。共混改性可简单通过材料混合显著提高性能;与共混改性相比,共聚改性的组分混合较为均匀,但是条件较难控制;复合改性可以综合共聚改性和共混改性的优点。     

聚乙烯醇共混薄膜研究进展

从近年来聚乙烯醇（PVA）与天然高分子［淀粉、壳聚糖（CS）及蛋白质］、合成型生物降解高分子［聚乳酸（PLA）、聚己内酯（PCL）及聚乙二醇（PEG）］以及合成型不可生物降解高分子［聚苯胺（PANI）、低密度聚乙烯（PE⁃LD）及聚氨酯（PU）］进行共混研究角度进行分析,总结了共混薄膜的制备方法及结构性能,并介绍了PVA共混膜材料在医疗、分离、食品包装及农业领域的应用情况,最后对PVA共混薄膜未来的研究方向进行了展望。     

异丁基乙烯基醚/马来酸酐共聚物改性聚乙烯醇的研究

采用异丁基乙烯基醚/马来酸酐共聚物对聚乙烯醇(PVA)进行共混改性,研究了改性 PVA 的耐水性及力学性能,发现改性后的 PVA 的耐水性及力学性能有明显提高,其中当异丁基乙烯基醚/马来酸酐共聚物的含量为2%时,共混薄膜的断裂伸长率达到300%。同时从增塑性及结晶性等多方面对共混体系的改性机理进行了分析。     

魔芋全降解塑料薄膜的制备和性能研究

魔芋精粉（KF）糊化后与聚乙烯醇（PVA）共混，同时加入增塑剂甘油、交联剂甲醛。共混结束后将共混物流延成膜。考察了共混体系中魔芋精粉与聚乙烯醇质量比、甘油用量、甲醛用量、共混温度、共混时间对薄膜性能的影响，并表征了薄膜的结构。结果表明：当m（KF）：m（PVA）=3：2、甘油用量0．4mL、甲醛用量2mL、共混温度80℃、共混时间1-1.5h时，制得的塑料薄膜断裂伸长率、拉伸强度和透光率较高，具有较好的相容性、热稳定性；魔芋葡甘聚糖（KGM）与PVA分子间发生了多种交联作用。     

PVA／PS共混改性及对拉伸性能的影响

对不同配比的聚乙烯醇／聚苯乙烯（PVA／PS）共混物进行共混改性研究。使用拉力试验机测试了PVA／PS共混物的拉伸强度,使用扫描电镜（SEM）分析试样的断口,并分析共混物的分散性及相容性。实验结果表明：PVA含量在10％以内对共混物的拉伸强度影响不大,主要表现为PS的拉伸强度;而PVA含量在10％～50％的范围内,扛伸强度明显下降,在50％时达到最小值。     

水溶性沙林树脂对低温型PVA水溶速度的影响

为了实现调控低温型PVA薄膜的水溶解速率,利用水溶性沙林树脂(Surlyn)作改性剂,将水溶性沙林树脂与PVA共混流延制备水溶性沙林树脂改性PVA薄膜,通过控制水溶性沙林树脂的含量来调控PVA薄膜的溶解速率。结果表明:在室温下,当水溶性沙林树脂的含量小于40%时,PVA薄膜可完全溶解于25℃的冷水中,且随着水溶性沙林树脂含量的增加,PVA薄膜的水溶解速率逐渐降低;当水溶性沙林树脂的含量大于等于40%时,PVA薄膜不溶于冷水但适当加热可完全溶解。     

PVA与丁二酸酯化淀粉共混膜的力学性能

制备了不同改性程度的丁二酸酯化淀粉,并与聚乙烯醇（PVA）以溶液共混法制备了丁二酸酯淀粉/PVA共混膜,通过X射线衍射仪表征共混膜与酯化膜的结构,通过扫描电子显微镜观测其表面结构,并测试了共混膜的力学性能。结果表明,丁二酸酯化改性程度、PVA分子结构以及酯化淀粉/PVA的共混比对共混膜的力学性能有影响;随着改性程度的增加,共混膜的断裂强度及断裂伸长率均增大;随着PVA聚合度与醇解度的增大,共混膜的断裂强度及断裂伸长率均增大;随着淀粉含量的增加,共混膜的断裂强度先减小后增大,断裂伸长率逐渐减小;当共混比为50:50时,断裂强度最小。     

基于a-PVA／s-PVA／NaCl共混体系的薄膜制备和表征

以两种等规度不同的聚乙烯醇（PVA）为原料，水作溶剂，加入不同含量的氯化钠（NaCl），在室温干燥、水洗、再干燥后制成无规聚乙烯醇（a-PVA）／间规聚乙烯醇（s-PvA）共混薄膜。采用差示扫描量热仪（DSC）、傅立叶红外光谱仪（FT-IR）、力学性能测试以及热失重分析（TG）等方法对薄膜进行表征。结果显示，随NaG和s-PVA的含量变化，共混膜的吸收峰和熔点规律变化，并在3％（w）NaC1时获得最佳拉伸强度和弹性模量，分别为47．54MPa与1．95GPa。共混膜的热性能随着s-PVA含量增加而提高，s-PVA所占比例从0提高到40％时，相应地薄膜的熔点从231.4℃增至239.8℃。     

改性聚乙烯醇膜的研究进展

聚乙烯醇（PVA）因其良好的化学稳定性、耐酸碱、耐有机溶剂性以及优异的成膜性和生物安全性,成为应用最广泛的亲水性膜材料之一。但亲水性PVA膜力学性能弱和耐水性能差等缺点严重限制其实际应用。近些年,人们通过共混、纳米复合、热处理、化学交联以及协同改性等方法对PVA膜进行了大量的改性研究工作并取得了众多成果。本文总结了不同PVA膜改性方法的特点及存在的问题,重点阐述了性能优异的填料在纳米复合改进PVA膜力学性能上的研究现状,简述了共混、热处理、化学交联对改性PVA膜的作用,强调了协同改性对提高PVA膜综合性能的重要意义,为设计和制备高性能的PVA膜提供一定的参考。指出改性后的PVA膜在水处理和食品包装领域具有良好的应用前景。     

Studies of chitosan. I. Preparation and characterization of chitosan/poly(vinyl alcohol) blend films

Various blending ratios of chitosan/poly (vinyl alcohol) (CS/PVA) blend films were prepared by solution blend method in this study. The thermal properties and chemical structure characterization of the CS/PVA blend films were examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR). Based upon the observation on the DSC thermal analysis, the melting point of PVA is decreased when the amount of CS in the blend film is increased. The FTIR absorption characteristic is changed when the amount of CS in the blend film is varied. Results of X‐ray diffraction (XRD) analysis indicate that the intensity of diffraction peak at 19° of PVA becomes lower and broader with increasing the amount of CS in the CS/PVA blend film. This trend illustrates that the existence of CS decreases the crystallinity of PVA. Although both PVA and CS are hydrophilic biodegradable polymers, the results of water contact angle measurement are still shown as high as 68° and 83° for PVA and for CS films, respectively. A minimum water contact angle (56°) was observed when the blend film contains 50 wt % CS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Enhanced oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) blended with poly(acrylic acid) for packaging applications

To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m^?1 day^?1 with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry     

Properties of soy protein isolate/poly(vinyl alcohol) blend “green” films: Compatibility,mechanical properties,and thermal stability

Blend films from nature soy protein isolates (SPI) and synthetical poly(vinyl alcohol) (PVA) compatibilized by glycerol were successfully fabricated by a solution‐casting method in this study. Properties of compatibility, mechanical properties, and thermal stability of SPI/PVA films were investigated based on the effect of the PVA concentration. XRD tests confirm that the SPI/PVA films were partially crystalline materials with peaks of 2θ = 20°. And, the addition of glycerol will insert the crystalline structure and destroy the blend microstructure of SPI/PVA. Differential scanning calorimetry (DSC) tests show that SPI/PVA blend polymers have a single glass transition temperature (T_g) between 80 and 115.0°C, which indicate that SPI and PVA have good compatibility. The tension tests show that SPI/PVA films exhibit both higher tensile strength (σ_b) and percentage elongation at break point (P.E.B.). Thermogravimetric analysis (TGA) and water solubility tests show that SPI/PVA blend polymer has more stable stability than pure SPI. All the results reflect that SPI/PVA/glycerol blend film provides a convenient and promising way to prepare soy protein plastics for practical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development and characterization of poly(vinyl alcohol) and casein blend films

Blends of plasticized casein (CA) and poly(vinyl alcohol) (PVA) at various ratios were prepared using the solution‐casting method. The prepared blend solutions were cast onto polystyrene petri plates and bend films were obtained. The characterization of films was performed using Fourier transform infrared spectroscopy, tensile testing, thermogravimetric analysis, contact angle measurements and water vapour permeability. According to spectroscopic analysis, there were interactions between the CA and PVA molecules. The tensile test results showed that the tensile strength of CA increased with increasing PVA content. The flexibility of plasticized CA film increased with the incorporation of PVA. The thermal stability and water vapour barrier properties of plasticized CA improved on blending with PVA. As a result, it was seen that blend films were successfully produced using plasticized CA and PVA with potential for use in biodegradable packaging applications. © 2019 Society of Chemical Industry     

聚乳酸/聚乙烯醇纳米纤维的制备及结构

以二甲基亚砜为溶剂,制备不同配比的聚乳酸(PLLA)和聚乙烯醇(PVA)的混合溶液,静电纺丝制得PLLA/PVA纳米纤维。采用红外光谱仪、原子力显微镜等对PLLA/PVA纳米纤维结构与性能进行了表征。结果表明:PLLA/PVA纳米纤维中PVA上的羟基与PLLA上的羰基形成了氢键,PLLA与PVA之间存在一定的相互作用,但PLLA/PVA纳米纤维存在相分离现象;混合溶液的PLLA质量分数为11%,PVA质量分数为8%时可以得到较好的PLLA/PVA纳米纤维,但PVA质量分数为6%时出现液滴及珠丝,PVA质量分数为4%时,不能制得纳米纤维。     

Blends of aliphatic polyesters. IV. Morphology,swelling behavior,and surface and bulk properties of blends from hydrophobic poly(L-lactide) and hydrophilic poly(vinyl alcohol)

Blend films were prepared from hydrophobic poly(L -lactide) (PLLA) and hydrophilic poly(vinyl alcohol) (PVA) with different PLLA contents [X_PLLA (w/w) = PLLA/(PVA + PLLA)] by solution casting and melt quenching. Their morphology, swelling behavior, and surface and bulk properties were investigated. Polarizing optical microscopy, scanning electron microscopy, differential scanning calorimetry, X-ray diffractometry, and tensile testing revealed that PLLA and PVA were phase separated in these blend films and the PLLA-rich and PVA-rich phases both formed a continuous domain in the blend film of X_PLLA = 0.5. The water absorption of the blend films was higher for the blend films of low X_PLLA values when compared at the same immersion time, and it was larger than expected from those of nonblended PLLA and PVA films. The dynamic contact angles of the blend films were linearly increased with an increase in X_PLLA. The tensile strength and Young's modulus of the dry blend films decreased with a rise in X_PLLA, but this dependence was reversed because of the large decreases in tensile strength and Young's modulus for the blend films having high X_PLLA values after immersion in water. The elongation at break was higher for the wet blend film than for the dry blend film when compared at the same X_PLLA and that of the dry and wet blend films decreased with an increase in X_PLLA. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2151–2160, 2001     

New chitin-based polymer hybrids, 4: soil burial degradation behavior of poly(vinyl alcohol)/chitin derivative miscible blends

Soil burial degradation behavior of miscible blend systems of poly(vinyl alcohol) (PVA)/partially deacetylated chitin (1), PVA/chitin-graft-poly(2-methyl-2-oxazoline) (2), and PVA/chitin-graft-poly(2-ethyl-2-oxazoline) (3) was investigated in comparison with the case of a pure PVA film. The degradation of the blend films was followed by the weight changes, scanning electron microscopic observation, Fourier transform infrared spectroscopy, ¹H-NMR, and size exclusion chromatography analyses. The rate of weight decrease in these PVA/chitin derivative hybrids was higher than that of control PVA in the soil burial test. Fourier transform infrared spectra of the recovered samples of the blends showed an apparent increase of the absorption intensity due to β-diketone structure in PVA, which reflects the progress of biodegradation of PVA by PVA-oxidizing enzymes. Scanning electron microscopic observation revealed that these blend films were degraded by bacteria and actinomycetes. The triad tacticity and number-average molecular weight of PVA in the hybrids after soil burial determined by ¹H-NMR and size exclusion chromatography, respectively, were almost the same as those before soil burial. These results suggested that enzymatic degradation of the hybrid films occurred mainly on the surface and that degradation of the PVA-based samples in the soil was accelerated by blending the chitin derivatives. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1171–1179, 1999     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001     

PPC/PDAP共混膜的制备和性能

将过氧化二异丙苯(DCP)置于特定温度下,引发邻苯二甲酸二烯丙酯(DAP)在聚碳酸亚丙酯(PPC)溶液中聚合,制备得到聚碳酸亚丙酯/聚邻苯二甲酸二烯丙酯(PPC/PDAP)共混膜。采用红外光谱仪(FTIR)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)、热重分析仪(TGA)、万能试验机和水蒸气透过率测试仪对共混膜的红外吸收、结晶性、热、力学和阻隔性能进行了表征。结果表明,通过DAP的聚合,提高了PPC的结晶性,使PDAP在PPC基体中形成交联网络,提高了共混膜的热、力学和阻隔性能。相比纯PPC,当DAP含量为20%时,共混膜的玻璃化转变温度和拉伸强度分别提高了5.3℃和266%;当DAP含量为40%时,共混膜的失重5%热分解温度提高了50.9℃,透湿系数下降了25%,因此,阻隔性能得到了提升。