混合多元醇水性聚氨酯的合成与性能

采用六亚甲基二异氰酸酯（HDI）,聚酯多元醇（PBA）,聚醚多元醇（PPG）,二羟甲基丙酸（DMPA）为主要原料,制得各种聚酯聚醚混合型水性聚氨酯乳液。讨论了PBA/PPG配比、相对分子质量对水性聚氨酯乳液性能和力学性能的影响。结果表明：随着软段中聚酯组分含量的增加,涂膜的拉伸强度有增加的趋势,软段为纯聚醚和纯聚酯的聚氨酯膜表现出较好的伸长率;随着软段相对分子质量的增加,聚醚型聚氨酯膜的拉伸强度减小,聚酯型聚氨酯膜的拉伸强度增加。     

Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay bio-nanocomposite film

Multilayer films composed of PLA and agar/κ-carrageenan/clay (Cloisite® Na⁺) nanocomposite films were prepared, and the effect of lamination of PLA layers on the performance properties such as optical, mechanical, gas barrier, water resistance, and thermal stability properties was determined. The tensile strength (TS) of the agar/κ-carrageenan/clay nanocomposite films (67.8 ± 2.1 MPa) was greater than that of PLA films (43.3 ± 3.6 MPa), and the water vapor permeability (WVP), water uptake ratio (WUR), and water solubility (WS) of the nanocomposite films were higher than those of PLA films. The film properties of the multilayer films exhibited better properties of the component film layers. Especially, the WVP and water resistance of the bionanocomposite film were improved significantly, while the OTR of the PLA film decreased profoundly after lamination with PLA layers. Thermal stability of the bionanocomposite also increased after lamination with PLA layers.     

Effect of Plasticizers on Mechanical and Barrier Properties of Rice Starch Film

The effect of plasticizers, glycerol, sorbitol and poly(ethylene glycol) 400 (PEG 400), on mechanical and barrier properties of rice starch film has been investigated. Sorbitol‐ and glycerol‐plasticized starch films appeared homogeneous, clear, smooth, and contained less insoluble particles compared to unplasticized rice starch films. PEG 400 did not form plasticized films of suitable characteristics. The softness and stickiness of films improved with increasing concentrations of glycerol and sorbitol. In general, films plasticized with glycerol and sorbitol displayed a better solubility in water than unplasticized films, i.e. 35% (w/w) glycerol and 45% w/w (sorbitol) (optimum solubility). The tensile strength of films decreased especially in the high concentration regime of plasticizers, between 20–45% (w/w) of plasticizer/rice starch film. Through the entire concentration regime, the tensile strength of glycerol‐plasticized films was significantly lower than that of sorbitol‐plasticized films, but their elongation was larger. The water vapor transmission rate (WVTR) through plasticized films and the oxygen transmission rate (OTR) increased with glycerol and sorbitol concentrations, however, glycerol was revealed to be significantly more effective in reducing the tensile strength as well as increasing the WVTR and the OTR compared to sorbitol. With the higher tensile strength and the smaller OTR and WVTR, the 30% sorbitol‐plasticized film reveals an improved coating performance in terms of a reduction of coating failures.     

Developing Biodegradable Mulch Films from Starch‐Based Polymers

This paper examines the development of starch‐based plastics for use as biodegradable mulch film. A variety of starch‐based polymers are blended with high performance biodegradable polyester polymers in order to determine the applicability of films to be processed on a film blowing line and to perform well in mulch film field trials. The process of material formulation, film blowing processing and scale‐up and performance properties are highlighted for a successful material. Insights into future developments of starch‐derived biodegradable polymers are given.     

Development and characterisation of polylactic acid–gliadin bilayer/trilayer films as carriers of thymol

Biodegradable food packaging promises a more sustainable future. Poly(lactic acid) (PLA) is a promising alternative for petroleum‐derived polymers. However, PLA films suffer from poor barrier properties compared with petroleum‐derived ones. To address this issue, we designed bilayer and sandwich‐architectured trilayer films based on PLA and gliadin. We reported firstly the direct formation of PLA–gliadin bilayer/trilayer films without surface modification on PLA film. The films were compact and uniform, and double/triple layers were combined firmly, preventing delamination. This strategy enhanced mechanical resistance, ductility and moisture barrier of gliadin films and concomitantly enhanced the oxygen barrier for PLA films. Thymol loadings endowed bilayer/trilayer films with antimicrobial activity and antioxidant activity. The antimicrobial activity of the films depended on film types, and gliadin layer presented larger inhibition zone than PLA layer, hinting that the films possessed directional releasing role. This study opens a promising route to fabricate bilayer/trilayer architecture helping to create synergism of the biopolymers.     

Soy protein – Poly (lactic acid) bilayer films as biodegradable material for active food packaging

The preparation and characterization of biodegradable bilayer films from isolated soy protein (SPI) and poly (lactic acid) (PLA) were carried out in this work. The films showed high transparency and strong adhesion between layers without adding an extra component, or without chemically modifying the film surfaces. The application of the PLA layer largely increased the mechanical properties of the films with respect to those of pure SPI films. Furthermore, the hydrophobic characteristics of the PLA layer improved film performance under conditions in which water was involved, markedly decreasing the amount of total soluble matter, the swelling index and the water vapor permeability. The biodegradation under soil burial conditions was evaluated measuring weight loss as a function of time, showing a two-step degradation and a faster degradation rate for the protein component compared to those of PLA layer. The films prepared were evaluated as active packaging by incorporation of an antifungal and an antibacterial agent (natamycin and thymol, respectively) to the SPI layer, showing a marked growth inhibition of mold, yeast and two strains of bacteria by in-vitro microbiological assays.     

Effect of Molecular Weight,Acid, and Plasticizer on the Physicochemical and Antibacterial Properties of β‐Chitosan Based Films

Abstract: Effects of chitosan molecular weight (1815 and 366 kDa), type of acid (1% acetic, formic, and propionic acid, or 0.5% lactic acid) and plasticizer (0, 25% glycerol or sorbital w/w chitosan) on the mechanical, water barrier, and antibacterial properties of β‐chitosan films were investigated. Tensile strength (TS) of high molecular weight (Hw) films was 53% higher than that of low molecular weight (Lw) ones, acetate, and propionate films had the highest TS (43 and 40 MPa) among tested acids, and plasticizer‐reduced film TS 34%. Film elongation at break (EL) was higher in Hw films than in Lw ones, in which formate and acetate films were the highest (9% and 8%, respectively), and plasticizer increased the film EL 128%. Molecular weight of chitosan did not influence water vapor permeability (WVP) of the films. Acetate and propionate films had lower WVP than other acid types of films, and plasticizer increased film WVP about 35%. No difference was found between glycerol and sorbitol films in terms of film mechanical and water barrier properties. Lw β‐chitosan films showed significant antibacterial activity against E. coli and L. innocua. This study demonstrated that β‐chitosan films are compatible to α‐chitosan films in physicochemical properties and antibacterial activity, yet with simple sample preparation. Practical Application: β‐chitosan based edible films at molecular weight of about 300 kDa showed great antibacterial activity against Gram‐positive and Gram‐negative bacteria. The films have similar mechanical and water barrier properties to α‐chitosan based films at the similar molecular weight, but simple sample preparation procedures and more attractive color. The release of active chitosan fragment from the film matrix acts as an antibacterial agent, making β‐chitosan films suitable as intelligent food wraps or coatings for a wide range of food products to control moisture loss and prevent surface bacterial growth.     

Emulsifier Composition of Solid Lipid Nanoparticles (SLN) Affects Mechanical and Barrier Properties of SLN‐Protein Composite Films

Protein films can be applied to improve food quality and to reduce packaging waste. To overcome their poor water barrier properties, lipids are often incorporated. The function of incorporated lipid depends on the interface between filler and matrix. This study aimed to tailor the properties of a protein–lipid film by designing the oil/water interface to see if the concept of inactive/active filler is valid. Therefore, we varied the emulsifier stabilizing solid lipid nanoparticles (SLN) to promote (via β‐lactoglobulin) or to minimize (via Tween 20) interactions between particle surface and protein. SLN were incorporated into protein films and film properties were determined. Addition of SLN led to significantly decreased water vapor permeability (WVP) of protein films. However, WVP was mainly affected by the emulsifiers and not by the lipid. Protein‐stabilized SLN (BS) replaced a lacking protein in the protein network and therefore did not influence the mechanical properties of the films at ambient temperature. BS‐composite films were temperature sensitive, as lipid and sucrose palmitate melted at temperatures above 40 °C. Tween 20‐stabilized SLN (TS) led to reduced tensile strengths, probably due to perturbative effects of TS and plasticizing effects of Tween 20. Dynamic mechanical analysis showed that TS and Tween 20 increased film mobility. Melting of lipid and emulsifiers, and temperature‐dependent behavior of Tween 20 led to a strong temperature dependence of the film stiffness. By designing the interface, particles can be used to tailor mechanical properties of protein films. Tuned edible films could be used to control mass transfers between foods.     

紫外照射下聚己二酸/对苯二甲酸丁二醇酯/纳米复合膜的性能和纳米成分的迁移

为探究紫外光（ultraviolet,UV）照射对聚己二酸/对苯二甲酸丁二酯（poly (butyleneadipate-co-terephthalate),PBAT）的影响,本实验研究了PBAT/纳米ZnO和PBAT/纳米TiO2复合膜的性能及纳米成分在UV照射前后向3 g/100 mL乙酸溶液迁移的情况,并通过衰减全反射傅里叶变换红外光谱、场发射扫描电子显微镜、X射线衍射表征并分析变化原因。结果表明,未经UV照射时,两种纳米颗粒的加入对复合膜阻隔性的影响较小,纳米ZnO使复合膜的拉伸强度下降22.88%～40.99%,断裂伸长率下降至纯PBAT的86.07%～90.98%,最大迁移量为11.82 mg/kg。纳米TiO2的加入对复合膜的拉伸强度影响较小,断裂伸长率下降至纯PBAT的73.48%～87.18%,未检测到其迁出（方法检出限为0.009 mg/kg）。随UV照射时间延长,复合膜的断裂伸长率和拉伸强度均逐渐降低,但相同照射时间下,PBAT/纳米ZnO力学性能的下降程度低于纯PBAT和PBAT/纳米TiO2。在UV照射2 d后,复合膜的透氧系数显著增大（P＜0.05）,透湿系数变化较小;纳米ZnO的最大迁移量为16.66 mg/kg,而仍未检测到纳米TiO2迁出;且复合膜酯键断裂,结晶度降低,表面变得粗糙,产生破裂的孔洞。综上,UV照射破坏了PBAT纳米复合膜的结构,使其性能降低,纳米ZnO可在一定程度上抑制复合膜力学性能的下降,但其迁移量会逐渐增加。     

转谷氨酰胺酶改性明胶高强度薄膜的制备

在研究制备转谷氨酰胺酶（mTG）改性明胶可食性薄膜工作的基础上，通过在成型工艺中进一步采用室温干燥和湿态二次定向处理的方法，获得了抗张强度达18．3MPa，韧度达8．4J／cm^2的可食性明胶薄膜。在配料中添加质量分数2％的聚乙烯醇（PVA）并采用相同的成型工艺，所制备明胶薄膜的机械性能得到进一步提高。生物降解性实验表明，在被质量分数0．5％的Alcalase碱性蛋白酶作用4h后，不含PVA的可食性明胶薄膜的降解率可达99．2％，含PVA明胶薄膜的降解率也达到了97．5％。     

金属或金属氧化物对聚乳酸薄膜性能影响的研究进展

聚乳酸（polylactic acid, PLA）是一种以植物资源为原料合成的聚酯,可用于包装材料,对环境不产生任何污染。但聚乳酸耐热性差、脆性大限制了在行业中的实际应用,将PLA膜同金属及金属氧化物纳米粒子复合是一种可以有效改善聚乳酸膜性能的方式,本文概括了聚乳酸薄膜制备方法及特点,介绍了Ag、TiO₂、ZnO、SiO₂纳米粒子和聚乳酸复合膜,主要综述了这些纳米粒子对聚乳酸膜性能的影响及机制,最后对此类复合膜存在问题和未来发展进行展望。     

辣根过氧化物酶催化淀粉接枝丙烯酸甲酯浆料制备及其上浆性能

为改善淀粉浆液对涤棉混纺纱的黏附性和浆膜的力学性能,采用辣根过氧化物酶(HRP)/乙酰丙酮(ACAC)/过氧化氢(H2O2)引发体系,催化酸解淀粉接枝丙烯酸甲酯。通过傅里叶红外光谱、扫描电子显微镜和X射线衍射对接枝淀粉进行表征,并分析其流变特性。结果表明,在HRP酶催化作用下丙烯酸甲酯与未糊化酸解淀粉发生接枝共聚反应,且对酸解淀粉结晶度影响不大;淀粉接枝改性后浆液黏度增大,黏弹性增加,呈现更具弹性的流体特征;相比于酸解淀粉,含有柔性接枝支链的淀粉浆液对涤/棉黏附性有明显提高,浆膜断裂伸长率和断裂强度均有增加,力学性能得到改善。     

Development of moisture‐absorbing and antioxidant active packaging film based on poly(vinyl alcohol) incorporated with green tea extract and its effect on the quality of dried eel

Active packaging film with functions of moisture‐absorbing and antioxidant activity was developed based on poly(vinyl alcohol) (PVA) incorporated with green tea extract (GTE). The effects of GTE concentrations of 0, 0.5, 1, 1.5, and 2% on the physical, structural, and antioxidant properties of PVA films were investigated. The PVA film containing 2% GTE had lower moisture absorbing efficiency relatively and better antioxidant activity through DPPH radical‐scavenging ability experiment. A packaging system of GTE‐incorporated PVA films was applied to package dried eel and quality of dried eel was evaluated during storage. The result showed that dried eel packed with GTE‐incorporated PVA films showed lower weight change, peroxide value and TBARS value during storage than that packed without PVA films or with PVA films but no GTE. The PVA film containing 2% GTE showed the best quality protective effectiveness to prevent the dried eel from absorbing moisture and oxidizing of lipid.

Practical applications

Poly(vinyl alcohol) (PVA) is a synthetic polymer that is widely used in packaging applications because of its excellent film forming, biodegradability, good mechanical, and gas barrier properties. The present study evidenced that the PVA films incorporated with GTE showed good quality protective effectiveness to prevent the dried eel packed with these films from absorbing moisture and oxidizing of lipid. This active packaging film could be used as inner layer or intermediate layer in the composite packaging film system to improve the storage quality of moisture‐sensitive and high‐fat food. Based on this concept, the moisture‐absorbing agents and antioxidant can be incorporated into the packaging structures to develop an active multifunctional food packaging material potentially to remove or reduce moisture inside the food packaging system instead of desiccants and preservative added in the food.     

Physicochemical, nutritional, and antimicrobial properties of wine grape (cv. Merlot) pomace extract-based films

Abstract: Wine grape pomace (WGP) (cv. Merlot) extract‐based films were studied in terms of their physicochemical, mechanical, water barrier, nutritional, and antibacterial properties. Pomace extract (PE) was obtained by hot water extraction and had a total soluble solid of 3.6% and pH 3.65. Plant‐based polysaccharides, low methoxyl pectin (LMP, 0.75% w/w), sodium alginate (SA, 0.3% w/w), or Ticafilm^® (TF, 2% w/w), was added into PE for film formation, respectively. Elongation at break and tensile strength were 23% and 4.04 MPa for TF‐PE film, 25% and 1.12 MPa for SA‐PE film, and 9.89% and 1.56 MPa for LMP‐PE film. Water vapor permeability of LMP‐PE and SA‐PE films was 63 and 60 g mm m^?2 d^?1 kPa, respectively, lower than that of TF‐PE film (70 g mm m^?2 d^?1 kPa) (P < 0.05). LMP‐PE film had higher water solubility, indicated by the haze percentage of water after 24 h of film immersion (52.8%) than that of TF‐PE (25.7%) and SA‐PE (15.9%) films, and also had higher amount of released phenolics (96.6%) than that of TF‐PE (93.8%) and SA‐PE (80.5%) films. PE films showed antibacterial activity against both Escherichia coli and Listeria innocua, in which approximate 5‐log reductions in E. coli and 1.7‐ to 3.0‐log reductions in L. innocua were observed at the end of 24 h incubation test compared with control. This study demonstrated the possibility of utilizing WGP extracts as natural, antimicrobial, and antioxidant promoting film‐forming material for various food applications. Practical Application: WGP extract‐based edible films with the addition of a small amount of commercial polysaccharides showed attractive color and comparable mechanical and water barrier properties to other edible films. The films also demonstrated their potential antioxidant and antimicrobial functions. Hence, they may be used as colorful wraps or coatings for food, pharmaceutical, or other similar applications.     

Physical Properties of Whey Protein–Hydroxypropylmethylcellulose Blend Edible Films

ABSTRACT: The formations of glycerol (Gly)‐plasticized whey protein isolate (WPI)–hydroxypropylmethylcellulose (HPMC) films, blended using different combinations and at different conditions, were investigated. The resulting WPI: Gly‐HPMC films were analyzed for mechanical properties, oxygen permeability (OP), and water solubility. Differences due to HPMC quantity and blend method were determined via SAS software. While WPI: Gly and HPMC films were transparent, blend films were translucent, indicating some degree of immiscibility and/or WPI–HPMC aggregated domains in the blend films. WPI: Gly‐HPMC films were stronger than WPI: Gly films and more flexible and stretchable than HPMC films, with films becoming stiffer, stronger, and less stretchable as the concentration of HPMC increased. However, WPI: Gly‐HPMC blended films maintained the same low OP of WPI: Gly films, significantly lower than the OP of HPMC films. Comparison of mechanical properties and OP of films made by heat‐denaturing WPI before and after blending with HPMC did not indicate any difference in degree of cross‐linking between the methods, while solubility data indicated otherwise. Overall, while adding HPMC to WPI: Gly films had a large effect on the flexibility, strength, stretchability, and water solubility of the film polymeric network, results indicated that HPMC had no effect on OP through the polymer network. WPI–HPMC blend films had a desirable combination of mechanical and oxygen barrier properties, reflecting the combination of hydrogen‐bonding, hydrophobic interactions, and disulfide bond cross‐linking in the blended polymer network.     

Combined effects of lemon essential oil and surfactants on physical and structural properties of chitosan films

The aim of this research was to evaluate the effects of lemon essential oil (LO, at 0.5%, 1%, 2% v/v film‐forming solutions) and surfactants (Tween 80 and Span 80 at 0.1% v/v film‐forming solutions) on physical, optical and structural properties of chitosan (CH) films. The films were formed by casting method. Results showed that the incorporation of LO provoked a decrease in water content, water vapour permeability (WVP) and mechanical properties. Less transparency and higher total colour difference were observed in CH–LO composite films. The addition of surfactants significantly increased WVP and solubility in water of CH–LO films. The film containing Tween 80 showed lower mechanical strength and higher transparency. The morphology was different depending on the LO contents and surfactant types used. Tween 80 improved the stability of LO in the film, whereas Span 80 promoted the movement of oil droplets to the film surface.     

Effects of monomer compatibility on sizing properties of feather keratin-g-P(AA-co-MA)

In order to endow feather keratin with good sizing properties for all-polyester or high-polyester yarns, methyl acrylate (MA) and acrylic acid (AA) monomers with a variation in feed molar ratio from 10/90 to 30/70 were grafted onto the molecular chains of native feather keratin under equal monomer concentration. Effects of monomer compatibility of MA/AA on sizing properties of the feather keratin-g-P(AA-co-MA) were studied in terms of apparent viscosity, contact angle of sizing paste on polyester fibers, mechanical properties of sizing film, and adhesion to polyester fibers. It was found that grafting MA & AA monomers with rational compatibility onto the molecular chains of feather keratin was an effective method to improve sizing properties of grafted feather keratin, such as adhesion to polyester fibers and toughness of sizing film. In view of overall performance of the grafted feather keratin sizes, the appropriate feed molar ratio of MA/AA should be 20/80.     

玉米-小麦淀粉/玉米醇溶蛋白双层膜热学及微观特性

研究了玉米-小麦淀粉成膜液与玉米醇溶蛋白成膜液不同配比制作的5 种可食用复合膜理化特性的差异, 并分别通过扫描电子显微镜观察、热重分析、差示扫描量热分析、X射线衍射分析、傅里叶变换红外光谱分析对其 热学特性和微观结构进行研究。结果表明：添加一层玉米醇溶蛋白后,双层膜阻水性提高,机械性能得到改善,由 扫描电子显微镜观察结果可知双层膜间结合紧密,热重分析和差示扫描量热分析结果显示双层膜热稳定性得到提 高,X射线衍射结果表明生物大分子之间相容性较好,傅里叶变换红外光谱分析结果发现双层膜间产生了新的氢键 等作用力,为玉米-小麦淀粉/玉米醇溶蛋白双层膜在食品包装中的应用提供了重要的参考依据。     

Influences of degree of hydrolysis and molecular weight of poly(vinyl alcohol) (PVA) on properties of fish myofibrillar protein/PVA blend films

Biodegradable blend films based on fish myofibrillar protein (FMP) and poly(vinyl alcohol) (PVA) were prepared and characterized. PVA with different degrees of hydrolysis (DH) and molecular weights (MW) had the impact on properties of FMP/PVA (1:1, w/w) blend film. The blend films with higher MW of PVA were more tensile resistant, as indicated by the greater tensile strength (TS) and elongation at break (EAB), while the films with PVA of lower DH were more flexible. The blend film with PVA-BP26 (DH: 86–98% mol; MW: 124,000–130,000 g/mol) exhibited the greatest tensile performance and the lowest water vapor permeability (p < 0.05), compared with other films. SEM and FTIR results revealed that FMP and PVA were compatible and their intermolecular interaction was enhanced, providing the blend film with desirable properties. Therefore, incorporation of PVA with appropriated DH and MW could improve the properties of the FMP-based film.     

Moisture Loss and Lipid Oxidation for Precooked Ground-Beef Patties Packaged in Edible Starch-Alginate-Based Composite Films

Edible films of starch‐alginate (SA), starch‐alginate‐stearic acid (SAS), SA‐tocopherol, SAS‐tocopherol, tocopherol‐coated SA film, and tocopherol‐coated SAS film were evaluated for their effectiveness in maintaining quality of precooked beef patties stored at 4 °C. Patty weight loss, moisture loss, 2‐thiobarbituric acid‐reactive substances value, the formation of hexanal, pentane, and total volatiles of samples differed with film composition. SAS‐based films were more effective (P < 0.05) in controlling moisture loss than lipid oxidation. Tocopherol‐treated films were more effective (P < 0.05) in inhibiting lipid oxidation than were nontocopherol films. Most of the tested edible films were not as effective as polyester vacuum bags in retarding moisture loss and lipid oxidation.