PE-HD／PA6／EVOH阻透容器成型工艺与性能研究

将高密度聚乙烯（阻HD）、聚酰胺6（PA6）与乙烯-乙烯醇共聚物（EVOH）的复配体和相容剂初混合后，通过挤出机熔融共混、中空吹塑制得阻透容器。考察了树脂及共混物的流变性能，研究了相容剂用量、阻透树脂用量和成型工艺条件对容器阻透性能的影响。利用扫描电镜（SEM）观察了瓶壁的层状结构。实验结果表明，PA6／EVOH复配体增加了阻透树脂的熔体黏度，提高了层状共混工艺的稳定性。与PE-HD／PA6二元共混容器相比。PE-HD／PA6／EVOH三元共混容器所需相容剂更少。当阻透树脂用量为15～18份、相容剂用量为2～3份、加工温度在225～230℃之间、螺杆转速控制在30r／min左右、停留时间在3min时，PE-HD／PA6／EVOH共混容器的阻透性能得到明显提高。     

PE-HD/EVOH共混阻透管材的研制

将高密度聚乙烯(PE-HD)、乙烯一乙烯醇共聚物(EVOH)和相容剂混合后,加人塑料管材挤出成型机中,经熔融共混、冷却定型、辅机牵引制得层状共混阻透管材。研究了相容剂用量、阻透树脂用量和成型工艺参数对管材阻透性能的影响,考察了树脂的流变性能及共混阻透管材的力学性能,并与PE-HD)/聚酞胺6(PA-6)共混管材性能进行比较。利用扫描电镜观察阻透管材壁面的层状结构。实验结果表明,与PE-HD/PA6共混管材相比,PE-HD/EVOH共混管材所需相容剂少,成型工艺参数易于控制,其阻透性能及力学性能更好。当阻透树脂用量为16~18份,相容剂用量为1-3份,加工温度在225℃左右,螺杆转速控制在20 r/min左右,牵伸速度为1. 5一1. 6 m/min时,PE-HD/EVOH共混管材的阻透性能得到明显提高     

阻透性材料——聚酰胺MXD6

聚酰胺MXD6是由间苯二甲胺(MXDA)为原料的聚酰胺的统称。三菱瓦斯化学是以MXDA和己二酸作为原料商业生产聚酰胺的厂家。聚酰胺MXD6对于氧气、二氧化碳具有优良的阻透性能,所以被广泛用于食品包装材料和工业。聚酰胺MXD6在世界上被用作软饮料、茶饮料、碳酸饮料的PET瓶的阻透材料。中国饮料的市场多样     

交联型聚酰胺11／乙烯-乙烯醇共聚物高阻透材料的研究

采用原位交联技术制备聚酰胺11(PA11)/乙烯-乙烯醇共聚物(EVOH)高阻透材料,以过氧化二异丙苯(DCP)为交联剂,研究其用量对体系凝胶含量、力学性能、阻透性能及形态结构的影响。结果表明:随着 DCP 含量的增加,体系的冲击强度、拉伸强度、凝胶含量、阻透性能均呈现先升高后降低的趋势;红外光谱(FT-IR)表明,PA11末端羧基和 EVOH 的侧羟基反应生成了酯基;差示扫描(DSC)分析表明,体系的玻璃化转变温度随着 DCP 含量的增加先升高后降低;扫描电子显微镜(SEM)分析显示,DCP 含量对 EVOH 在 PA11中分散形态有很大的影响,DCP 的质量分数为1.5%时,EVOH 以相互交叠的不连续的片层状结构分散于 PA11树脂中,其力学性能和阻透性能得到大幅度的提高。     

阻透性包装技术进展

综述了国内外阻怀包装市场、阻透性树脂性能、阻生新材料开发、阻透性薄膜和容器所用树脂加工技术和发展动向,重点介绍了多层复合膜和ＰＥＴ瓶技术的最新进展。     

聚酰胺6／乙烯-乙烯醇无规共聚物共混体系的相容性及性能研究

研究了不同比例乙烯-乙烯醇无规共聚物(EVOH)和聚酰胺6(PA6)共混物的相容性及性能。扫描电子显微镜下观察结果表明二者具有较好的相容性;红外光谱分析和流变实验证实了EVOH与PA6分子间氢键的存在,氢键的作用会随着EVOH含量的增加而增强;阻透性能的测试表明在PA基体中加入EVOH会极大提高基体的阻透性,在EVOH基体中加入少量的PA6对EVOH的阻透性影响很小。     

PBS/EVOH共混材料的阻透性能研究

通过对聚丁二酸丁二醇酯/乙烯-乙烯醇共聚物(PBS/EVOH)共混物的阻透性和力学性能测试,确定PBS/EVOH的最佳配比为90/10。研究了PBS接枝马来酸酐(PBS-g-MAH)用量对材料阻透性和相容性的影响;并通过DMA、SEM和IR对材料的相容性进行了分析。结果表明:PBS-g-MAH的加入,使材料的阻透性和相容性得到改善,力学性能有所提高;与未加相容剂相比,加入7 phr PBS-g-MAH后,阻透性提高了74%,缺口冲击强度提高了68%;SEM分析结果表明,相结构由两相海岛结构变为类层状结构。     

挤出机螺杆转速对HDPE／MPA共沸物结构和阻透性能的影响

从理论上分析了挤出机螺杆转速与聚合物中分散相颗粒数的关系以及螺杆转速对共混物阻透性能的影响,实验测定了在不同转速下制得的共混物的阻透性能。并根据阻透性能与结构参数之间的对应关系,从渗透实验数据推算出不同转速下共混物内不可透薄片的形状参数。实验表明,一般情况下溶剂透过共混物的渗稼率随着转速的增加,有一个先锋后升的变化过程。渗透率最低点对应的转速为最佳转速。分散相体积分数不同,其最佳共混转速不同。当共混转速超过临界转速后,溶剂渗透率的对数值随转速线性增加。     

HDPE／EVOH共混阻透容器的研制

将HDPE、EVOH和PE－g-MAH等混合后，吹瓶制成共混阻透容器，考察了EVOH和PE－g-MAH的用量及成型工艺对容器阻透性能的影响。结果表明，较低的增容剂用量和剪切速率及在适当的温度下制备的容器，其阻透性能得到大幅度提高。     

LDPE／PA6共混阻透薄膜的研制

将LDPE、PA6和PE-g-MAH等混合后加入单螺杆挤出机内,经熔融挤出吹塑制成LDPE/PA6共混阻透薄膜。通过考察成型工艺条件及PA6和PE-g-MAH的用量对薄膜阻透性能和力学性能的影响,确定了共混配方和薄膜制备工艺,阻透薄膜的阻透性能与纯LDPE薄膜相比提高了10倍以上。     

Paint Solvent Permeation Resistance of Polyethylene,Polyethylene/Polyamide and Polyethylene/Modified Polyamide Bottles

The main objective of this study is to investigate the barrier mechanisms and properties of polyethylene, polyethylene (PE)/polyamide (PA) and polyethylene/modified polyamide (MPA) bottles against paint solvent permeation. In addition to the paint mixed solvent, the barrier properties of these bottles against the permeation of pure main solvents contained in the paint mixed solvent were investigated to understand the permeation mechanisms of the paint solvents. The paint solvent permeation resistance improves dramatically after blending PA and MPA barrier resins in PE matrices during blow‐molding. In fact, by using proper compositions, the white spirit permeation rates of PE/MPA and PE/PA bottles at 40°C are about 360 and 50 times slower than that of the PE bottle, respectively. Further investigations showed that, after blending the MPA and PA barrier resins in PE matrices, the hydrocarbon solvents present in the white spirit were nearly blocked without permeation during the permeation tests, i. e., PE/MPA bottles inhibited the permeation of hydrocarbon solvents more successfully than PE/PA bottles. In contrast, the rates of polar solvents with ketone, ether and alcohol functional groups permeating through the PE bottles are much slower than that of the white spirit and only slightly faster than those through the PE/PA and PE/MPA bottles. On the other hand, the paint mixed solvent permeation rates of PE bottles are approximately equal to the summation of permeation rates of the solvents present in mixed solvents calculated using a simple mixing rule. Somewhat surprising, the permeation rates of mixed solvents of PE/MPA bottles are dramatically faster than those calculated using a simple mixing rule, when the polar solvent contents are in a certain range.     

Oxygen permeation resistance of polyethylene,polyethylene/ethylene vinyl alcohol copolymer,polyethylene/modified ethylene vinyl alcohol copolymer,and polyethylene/modified polyamide–ethylene vinyl alcohol copolymer bottles

The oxygen permeation resistance of polyethylene (PE), polyethylene/ethylene vinyl alcohol copolymer (PE/EVOH), polyethylene/modified ethylene vinyl alcohol copolymer (PE/MEVOH), and polyethylene/modified polyamide–ethylene vinyl alcohol copolymer (PE/MPAEVOH) bottles was investigated. The oxygen permeation resistance improved significantly after the blending of ethylene vinyl alcohol copolymer (EVOH) barrier resins in PE matrices during blow molding; less demarcated EVOH laminas were found on the fracture surfaces of the PE/EVOH bottles. Surprisingly, the oxygen permeation resistance of the PE/MEVOH bottles decreased significantly, although more clearly defined modified ethylene vinyl alcohol copolymer (MEVOH) laminas were found for the PE/MEVOH bottles as the compatibilizer precursor contents present in the MEVOH resins increased. In contrast, after the blending of modified polyamide (MPA) in EVOH resins, more demarcated modified polyamide–ethylene vinyl alcohol copolymer (MPAEVOH) laminar structures were observed in the PE/MPAEVOH bottles as the MPA contents present in the MPAEVOH resins increased. In fact, with proper MPAEVOH compositions, the oxygen permeation resistance of the PE/MPAEVOH bottles was even better than that of the PE/EVOH bottles. These interesting oxygen barrier and morphological properties of the PE, PE/EVOH, PE/MEVOH, and PE/MPAEVOH bottles were investigated in terms of the free volumes, barrier properties, and molecular interactions in the amorphous‐phase structures of the barrier resins present in their corresponding bottles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2528–2537, 2004     

Effects of composition of modified polyamide on barrier properties of polyethylene/modified polyamide blends

A systematic study on the effects of types and contents of compatibilizer precursors (CPs) on degrees of crystallinity (W_c), melt shear viscosities (η_s), and permeation barrier properties of modified polyamides (MPAs) and on their corresponding morphology and barrier properties of bottles blow-molded from polyethylene (PE)/MPA blends is reported. Two alkylcarboxyl-substituted polyolefins were selected as CPs to modify PA and to improve its permeation resistance to xylene by the “reactive extrusion” process. The barrier improvements of MPAs prepared in this study depend significantly on the type and content of CP present in the MPA. A maximum improvement in barrier properties of each MPA series samples were found as the contents of CP reached an “optimum” value. On the other hand, it is interesting to note that bottles blow-molded from PE/MPA series samples exhibited better barrier properties because the MPAs used were associated with better permeation resistance to xylene. The melt shear viscosities of MPAs were found to depend on the type of CP used and increase with increasing CP contents. In contrast, the W_c of MPAs decreased with increasing CP contents. Further analysis of the fracture surfaces of bottles blow-molded from PE/MPA blends also indicated that the morphology of MPA laminas depended on the type of CP present in the MPA, and these MPA laminar structures became clearer as the contents of CPs increased. Possible mechanisms accounting for the interesting behaviors described above are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1531–1540, 1997     

Effects of compatibilizer precursors on the barrier properties and morphology of polyethylene/polyamide blends

Summary A systematic investigation on the effects of type of compatibilizer precursors (CP) upon the barrier properties and morphology of PE/PA blends was reported. Three alkyl carboxyl-substituted polyolefins were selected to modify PA in a twin screw extruder by reactive extrusion process. The barrier property of the modified PA (MPA) was better than pure PA, and the amount of barrier improvement of the blend of PE and MPA dependended significantly on the barrier property of the MPA prepared. The extent of mixing PE and MPA before blow-molding has a significant effect on its corresponding barrier properties. Further analysis of the fracture surfaces indicated that a more demarcated laminar structure of MPA dispersed in PE matrix is essential for better barrier properties of PE/MPA blends. It is not completely clear how the type of CP added affects the barrier properties of MPAs. However, it is suggested that long PA sequence with shorter grafted CP chain and high normalized grafting efficiency of MPA are essential for preparing a clear laminar structure of MPA, and a good barrier properties of PE/MPA blends.     

阻隔改性组分PA6对HDPE/PA6合金性能的影响

研究了ＨＤＰＥ／ＰＡ６合金阻隔改性组分ＰＡ６的筛选及其含量对该合金阻隔性能和力学性能的影响。结果表明，在增容剂的条件下，具有适当粘度的ＰＡ６能与ＨＤＰＥ共混制得宏观均匀的合金材料；ＰＡ６含量对共混体系的阻隔性能影响显著；当ＰＡ６占３０份以上时，ＨＤＰＥ／ＰＡ６合金阻隔非极性溶剂的性能大幅度提高，同时，ＰＡ６的加入对合金有一定的增强作用。     

Gasoline Permeation Resistance of Containers of Polyethylene,Polyethylene/Modified Polyamide and Polyethylene/Blends of Modified Polyamide and Ethylene Vinyl Alcohol

An investigation of the gasoline permeation resistance of polyethylene (PE), polyethylene/modified polyamide (MPA), and polyethylene/blends of modified polyamide and ethylene vinyl alcohol (MPAEVOH) bottles is reported. The gasoline permeation resistance improves slightly after blending EVOH barrier resins in PE matrices during blow‐molding, wherein only broken and less demarcated EVOH laminas were found on the fracture surfaces of the PE/EVOH bottle. In contrast, much better permeation resistance and more clearly defined MPA and MPAEVOH laminas were found for PE/MPA and PE/MPAEVOH bottles, respectively. The gasoline barrier properties and MPAEVOH laminar structures of PE/MPAEVOH bottles improve and become more demarcated, respectively, as the MPA contents present in MPAEVOH resins increase. In fact, by using the proper composition, the gasoline permeation rate of PE/MPAEVOH bottles is about 450 and 3 times slower than that of the PE and PE/MPA bottles, respectively. These interesting gasoline barrier and morphological properties of PE, PE/MPA and PE/MPAEVOH were investigated in terms of melt shear viscosities and thermal properties of the base resins, and the chemical and physical amorphous phase structure present in their corresponding bottles.     

新型EVOH/PE⁃RT合金包覆PE⁃RT双层阻氧管的制备及性能研究

针对市场上常见的阻氧管存在难以热熔回收再用的问题,制备了新型乙烯?乙烯醇共聚物（EVOH）/耐热聚乙烯（PE?RT）合金包覆PE?RT双层阻氧管,其内层工作管为PE?RT材质,外层为EVOH/PE?RT合金阻隔材料;研究了EVOH和相容剂含量对EVOH/PE?RT合金阻隔膜阻氧性能的影响,并对新型双层阻氧管的氧气透过量和热熔回收情况以及新型双层阻氧管回收料的力学性能进行了测试。结果表明,EVOH/PE?RT合金阻隔膜的氧气透过量随EVOH含量的增加而降低,随相容剂含量的增加而上升;含30 %（质量分数,下同）EVOH、64 % PE?RT和6 %相容剂的新型双层阻氧管的氧气透过量接近市售3层、5层阻氧管,并且能够实现热熔回收,回收料具有较好的力学性能。     

吹塑工艺对改性共聚尼龙/高密度聚乙烯中空吹塑瓶阻隔性能的影响

将由乙烯-丙烯酸酯-马来酸酐共聚物(CP)与共聚尼龙(PA-54)在双螺杆挤出机中反应共混制得的改性共聚尼龙(MCOPA)与高密度聚乙烯(HDPE)通过层状共混工艺制备高阻隔性中空吹塑瓶。研究表明,吹塑工艺对阻隔瓶的阻隔性能具有很大的影响。     

Effects of processing conditions on the barrier properties of polyethylene (PE)/modified polyamide (MPA) and modified polyethylene (MPE)/polyamide (PA) blends

Different modified polyamide (MPA) and modified polyethylene (MPE) resins were prepared by reactive extrusion of different contents of a compatibilizer precursor (CP) with either polyamide (PA) or polyethylene (PE). The MPE and MPA resins were then blow‐molded with designed amounts of PA or PE resins to prepare four different sets of MPE/PA and PE/MPA bottles with the same CP, PA, and PE compositions. Somewhat surprisingly, the xylene permeation resistance of the MPE bottles is worse than that of the base PE bottle and decreases consistently as MPE contains more CP. In contrast, the MPE/PA and PE/MPA bottles exhibit much better xylene permeation resistance than that of the base PE bottle, wherein the PE/MPA bottles show significantly better permeation resistance than that of the corresponding MPE/PA bottles prepared at the same blow‐molding conditions. On the other hand, it is worth noting that the xylene permeation rate of each of the MPE/PA and PE/MPA bottles prepared at a fixed extrusion temperature reaches a minimum when prepared with an optimum screw speed near 400 rpm. Similarly, at a fixed screw speed, the highest permeation resistance of each PE/MPA bottle is always obtained when prepared at an optimum extrusion temperature of about 230^oC. However, the xylene permeation resistance of each MPE/PA bottle improves consistently when prepared at the higher extrusion temperatures used in this study. These interesting phenomena were investigated in terms of the morphology, thermal analysis of the PE/MPA and MPE/PA blends, the compatibility between PE (or MPE) and MPA (or PA), and the viscosity ratios of MPA (or PA) to PE (or MPE) during the blow‐molding process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1997–2008, 2000     

Polar and Non-Polar Solvent Permeation Resistance of Blow-Molded Bottles of Polyethylene/Blends of Modified Polyamide and Polyamide 6 Clay Nanocomposite

Investigations on white spirit and acetone permeation resistance of modified polyamide and nylon 6 clay (MPANYC) blends and their corresponding polyethylene/MPANYC bottles were reported in this study. The white spirit and acetone permeation resistance of MPANYC sheets improve consistently with increasing NYC contents present in MPANYC resins after blending nylon 6 clay (NYC) in modified polyamide (MPA) resins. However, the order of barrier improvement of the PE/MPANYC and PE/NYC bottle specimens is not corresponding to the order of barrier improvement of the MPANYC and/or NYC barrier resins added in PE. The blow-molded PE/NYC bottle specimen exhibits similarly worse white spirit and acetone solvent permeation resistance as the PE bottle specimen, wherein no clearly formed NYC laminas but only dispersed NYC droplets or agglomerates were found on the fracture surfaces of the PE/NYC bottles. However, after blending optimum compositions of MPANYC in PE, the PE/MPANYC bottles with demarcated MPANYC laminas exhibit significantly better white spirit and acetone permeation resistance than the PE/MPA bottle, wherein the white spirit and acetone permeation rates of the PE/MPA₈NYC₁ bottle are about 1.3 and 1.4 times slower than those of the PE/MPA bottle, respectively. In order to understand these interesting barrier properties of PE/MPANYC and PE/NYC bottles, rheological, thermal, wide angle X-ray diffraction and morphological properties of the base MPANYC and NYC resins and their corresponding morphology present in the blow-molded bottles were investigated.