Effect of temperature and type of food simulant on antioxidant stability

Additive migration levels in food simulants from polimeric materials that are intended to be into contact with food can be affected by additive stability under the migration test conditions. In this work, the stability of some phenolic antioxidants and one oxidized phosphite antioxidant was studied in four food simulants: distilled water, 3% (w/v) acetic acid, 10% (v/v) ethanol, and the fatty food simulant olive oil, under different temperatures 5, 40, and 70°C, during ～20 days. Samples were analyzed by reversed‐phase high performance liquid chromatography (HPLC) with UV diode‐array detector. In general, antioxidants appeared to be more stable in olive oil than in the aqueous simulants. Among aqueous simulants, water and 10% ethanol allowed the highest stability of antioxidants at low temperatures. The 3% acetic acid allowed good stability for the lowest phenolic compounds even at high temperatures, but the highest molecular weight compounds decomposed very fast even at low temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 656–663, 2006     

超高效液相色谱法测定食品包装材料中五种抗氧化剂迁移量

采用水基模拟物(蒸馏水、3%乙酸水溶液、10%乙醇水溶液)和油脂模拟物(异辛烷),建立了超高效液相色谱法测定食品包装材料中BHA、BHT、DLTP、DMTP、抗氧化剂CA等5种抗氧化剂迁移量的检测方法。结果表明:在2.00~100.00 mg/kg浓度范围内,具有良好的线性关系,相关系数≥0.999 5;检出限0.50~1.00 mg/kg、定量限范围1.50~3.00 mg/kg;加标回收率在80.7%~115.7%之间,相对标准偏差(RSD)在0.5%~2.8%之间,表明该方法简便、准确,可用于食品包装材料中5种抗氧化剂迁移量的同时检测。     

Effect of the structure on the morphology and spherulitic growth kinetics of polyolefin in‐reactor alloys

Four polyolefin in‐reactor alloys with different compositions and structures were prepared by sequential polymerization. All the alloys were fractionated into five fractions: a random copolymer of ethylene and propylene (25°C fraction), an ethylene–propylene segmented copolymer (90°C fraction), an ethylene homopolymer (110°C fraction), an ethylene–propylene block copolymer (120°C fraction), and a propylene homopolymer plus a minor ethylene homopolymer of high molecular weight (>120°C fraction). The effect of the structure on the morphology and spherulitic growth kinetics of the polypropylene (PP) component in the alloys was investigated. The polyolefin alloys containing a suitable block copolymer fraction and a larger amount of PP had a more homogeneous morphology, and the crystalline particles were smaller. Quenching the polyolefin alloys led to smaller crystallites and a more homogeneous morphology as well. Isothermal crystallization was carried out above the melting temperature of polyethylene, and the growth of PP spherulites was monitored with polarized optical microscopy with a hot stage. The alloys with higher propylene contents exhibited a faster spherulitic growth rate. The fold surface free energy was derived, and it was found that a large amount of block copolymer fractions and random copolymer fractions could reduce the fold surface free energy. The structure of the alloys also affected the crystallization regime of PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 632–638, 2005     

Influence of polymer swelling and dissolution into food simulants on the release of graphene nanoplates and carbon nanotubes from poly(lactic) acid and polypropylene composite films

The study compared the effects of swelling and dissolution of a matrix polymer by food simulants on the release of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) from poly(lactic) acid (PLA) and polypropylene (PP) composite films. The total migration was determined gravimetrically in the ethanol and acetic acid food simulants at different time and temperature conditions, while migrants were detected by laser diffraction analysis and transmission electron microscopy. Swelling, thermal analysis, and scanning electron microscopy were applied to characterize the degradation of polymer films at the migration conditions. The release of nanoparticles was found in a high‐temperature migration test of 4 h at 90 °C. The hydrolytic dissolution of the PLA polymer in the food simulants caused a migration of GNPs (>100 nm) from the PLA/GNP/MWCNT films into the simulant solvents, while the entangled MWCNTs formed a network on the film surface, preventing their migration from the PLA composite films. In contrast, the PP polymer slightly swells in ethanol solvents, allowing some short carbon nanotubes to be released from the surface and cut edges of the PP/MWCNT film into food simulants. Mathematical modeling of diffusion was applied that accounts for type of polymer, time–temperature conditions, and solvent concentration; model parameters were validated with experimental results. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45469.     

抗冲聚丙烯结构与性能研究

对部分国内外抗冲聚丙烯(PP)产品进行了微观形态和结构分析，研究其对材料宏观力学性能的影响。实验结果表明：抗冲PP是一个含有PP均聚物、丙烯与乙烯-丙烯两嵌段共聚物、乙丙橡胶(EPR)、聚乙烯均聚物等的多相体系。EPR的分子序列结构对聚合物抗冲击性能起主要作用。在序列结构中，丙烯、乙烯单体在分子链上的位置交换越频繁，抗冲击性能越得到提高。丙烯序列平均长度的增大对抗冲击性能有一定的削弱作用。     

聚烯烃弹性体改性聚丙烯的研究进展

介绍了新型聚烯烃弹性体(POE)的优异特性,综述了POE与通用塑料聚丙烯共混改性的研究进展。POE既有高弹性、高强度、高伸长率和良好的低温性能,又有优异的耐热老化和抗紫外性能。无论是均聚、共聚还是高流动性聚丙烯,POE的增韧效果都优于三元乙丙橡胶(EPDM)或乙丙橡胶(EPM)。与EPDM等改性剂相比,POE能在较低含量下实现材料的脆-韧转变,减少因加入弹性体造成的材料强度和模量的损失。作为聚丙烯改性剂可在改善聚丙烯冲击强度的同时适当保持其刚性和光学透明性。     

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene

The functions of crystallizable ethylene‐propylene copolymers in the formation of multiple phase morphology of high impact polypropylene (hiPP) were studied by solvent extraction fractionation, transmission electron microscopy (TEM), selected area electron diffraction (SAED), nuclear magnetic resonance (¹³C‐NMR), and selected reblending of different fractions of hiPP. The results indicate that hiPP contains, in addition to polypropylene (PP) and amorphous ethylene‐propylene random copolymer (EPR) as well as a small amount of polyethylene (PE), a series of crystallizable ethylene‐propylene copolymers. The crystallizable ethylene‐propylene copolymers can be further divided into ethylene‐propylene segmented copolymer (PE‐s‐PP) with a short sequence length of PE and PP segments, and ethylene‐propylene block copolymer (PE‐b‐PP) with a long sequence length of PE and PP blocks. PE‐s‐PP and PE‐b‐PP participate differently in the formation of multilayered core‐shell structure of the dispersed phase in hiPP. PE‐s‐PP (like PE) constructs inner core, PE‐b‐PP forms outer shell, while intermediate layer is resulted from EPR. The main reason of the different functions of the crystallizable ethylene‐propylene copolymers is due to their different compatibility with the PP matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

密胺塑料中三聚氰胺在食品模拟物中的迁移规律研究

采用超高效液相色谱串联质谱(UPLC-MS/MS)法,研究食品模拟物种类、接触时间、接触温度、乙酸浓度、乙醇浓度、重复使用和微波加热等迁移条件下,密胺塑料中三聚氰胺在水、4%乙酸(w/v)、10%乙醇(v/v)、95%乙醇(V/V)和异辛烷等5种食品模拟物和牛奶样品中的迁移规律。结果表明:模拟物的属性对迁移行为有显著影响,迁移量随温度的升高和时间的增加而变大。酸性食品和牛奶中的三聚氰胺迁移风险较高,且需控制密胺塑料的使用温度、盛放时间、重复使用次数及微波加热功率和时间以降低密胺塑料中三聚氰胺迁移风险。     

Migration of styrene from plastic packaging based on polystyrene into food simulants

Migration of potentially toxic substances from plastic packaging materials is very important in the food industry since it determines the suitability of polymers when used in food packaging. In this work, results are presented on the migration of styrene monomer from plastic packaging based on either rigid or foamed polystyrene. Water, ethanol/water solution and isooctane (resembling oil) were considered as food simulants. Experiments were carried out at various temperatures and migration was tested from 30 min to 30 days. Measurements were carried out using gas chromatography with external calibration and styrene standard solutions. No styrene was measured in water, except at high temperatures and long time periods, while the amount in ethanol/water was always grater than that in isooctane. Finally, the styrene diffusion coefficients for all the various experimental conditions were estimated using a rigorous model based on the Fick diffusion equation and the partitioning of the monomer between the two phases and consequently the activation energy of the migration process was evaluated. Copyright © 2011 Society of Chemical Industry     

Characterization of microstructure of polypropylene alloys

Two polypropylene (PP) alloys, which have similar composition, molecular weight and molecular weight distribution, but different processing and application properties, were fractionated using a preparative temperature rising elution fractionation (TREF) technique. It was found that PP alloys are mainly composed of four components: ethylene–propylene random copolymer, block-type copolymer, transition copolymer and propylene homopolymer. However, the fractionation data show that the distribution and the composition are different for these two samples. A possible mechanism is proposed for the formation of PP alloys of different compositions. Based on this mechanism, some possible adjustment of the polymerization parameters is suggested to control the microstructure. © 1998 Society of Chemical Industry     

Influence of copolymerization conditions on the structure and properties of polyethylene/polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys synthesized in gas‐phase with spherical ziegler‐natta catalyst

A spherical TiCl₄/MgCl₂‐based catalyst was used in the synthesis of polyethylene/polypropylene/poly (ethylene‐co‐propylene) in‐reactor alloys by sequential homopolymerization of ethylene, homopolymerization of propylene, and copolymerization of ethylene and propylene in gas‐phase. Different conditions in the third stage, such as the pressure of ethylene–propylene mixture and the feed ratio of ethylene, were investigated, and their influences on the compositions, structural distribution and properties of the in‐reactor alloys were studied. Increasing the feed ratio of ethylene is favorable for forming random ethylene–propylene copolymer and segmented ethylene–propylene copolymer, however, slightly influences the formation of ethylene‐b‐propylene block copolymer and homopolyethylene. Raising the pressure of ethylene–propylene mixture results in the increment of segmented ethylene–propylene copolymer, ethylene‐b‐propylene block copolymer, and PE fractions, but exerts a slight influence on both the random copolymer and PP fractions. The impact strength of PE/PP/EPR in‐reactor alloys can be markedly improved by increasing the feed ratio of ethylene in the ethylene–propylene mixture or increasing the pressure of ethylene–propylene mixture. However, the flexural modulus decreases as the feed ratio of ethylene in the ethylene–propylene mixture or the pressure of ethylene–propylene mixture increases. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2481–2487, 2006     

超高效液相色谱⁃四极杆⁃飞行时间质谱对含PET食品接触材料中可迁移非挥发性物质的筛查研究

采用超高效液相色谱⁃四极杆⁃飞行时间高分辨质谱（UPLC⁃Q⁃TOF）对4类不同类型的含聚对苯二甲酸乙二醇酯（PET）材质的食品接触材料在4 %乙酸和50 %乙醇模拟物中的迁移出的非挥发性未知物进行筛查解析。结果表明,产品在4 %乙酸模拟物的迁移风险远小于50 %乙醇模拟物,主要迁移物质为聚合单体形成的寡聚物,抗氧剂、润滑剂、胶黏剂等加工助剂以及生产加工、迁移过程中形成的非有意添加物（NIAS）物质;纯PET材质的产品迁移物质较少,多层复合材料迁移物质较多。复合材质的产品中,PET材质可能在生产时添加了己二酸、癸二酸、新戊二醇等物质,进行了改性处理;此外,部分迁移物质会与模拟物中的乙醇发生反应,生成新的NIAS物质。     

新型聚烯烃弹性体的性能及其应用进展

介绍了使用茂金属催化剂合成的聚烯烃弹性体的优异特性,综述了聚烯烃弹性体与通用塑料(如聚丙烯)、工程塑料共混改性的进展。聚烯烃弹性体既有高弹性、高强度、高伸长率和良好的低温性能,又有优异的耐热老化和抗紫外性能。无论是均聚、共聚还是高流动性聚丙烯,POE的增韧效果都优于三元乙丙橡胶(EPDM)或乙丙橡胶(EPM)。与EPDM等改性剂相比,聚烯烃弹性体能在较低含量下实现材料的脆-韧转变,减少因加入弹性体造成的材料强度和模量的损失。作为聚丙烯改性剂可在改善聚丙烯冲击强度的同时适当保持其刚性和光学透明性。     

Partial replacement of EPR by GTR in highly flowable PP/EPR blends: Effects on morphology and mechanical properties

This research analyzes the effect of ground tire rubber (GTR) and a novel metallocene‐based ethylene–propylene copolymer (EPR), with high propylene content, on the morphology and mechanical behavior of ternary polymer blends based on a highly flowable polypropylene homopolymer (PP). The PP/EPR blends morphology, with very small domains of EPR dispersed in the PP matrix, indicates a good compatibility among these materials, which leads to a significant improvement on elongation at break and impact strength. The incorporation of EPR on the rubber phase of thermoplastic elastomeric blends (TPE) based on GTR and PP (TPE^GTR) has a positive effect on their mechanical performance, attributed to the toughness enhancement of the PP matrix and to the establishment of shell‐core morphology between the rubber phases. The mechanical properties of the ternary blends reveal that TPE^GTR blends allow the upcycling of this GTR material by injection molding technologies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42011.     

Effect of composition and component structure on thermal behavior and miscibility of polypropylene catalloys

The thermal behavior and the miscibility of an in‐situ polypropylene blend named polypropylene catalloys (PP‐cats) were investigated by using modulated differential scanning calorimeter (MDSC). It is found that all PP‐cats samples present two glass transitions, one of which is ascribed to the ethylene‐propylene random copolymer (EPR), and the other, to isotactic polypropylene (PP). However, no glass transition of ethylene‐propylene block copolymer (E‐b‐P) responsible for a third component in PP‐cats could be found. With the increase of EPR, the glass transition temperatures responding to PP and EPR components, T_g, _PP and T_g, _EPR, shift to low temperature, because of the enhancement of the interaction between PP and EPR component and the increase of ethylene content in EPR, respectively. Furthermore, the difference between T_g, _PP and T_g, _EPR remarkably decreases with the increase of the total ethylene content in PP‐cats, which indicates that the miscibility of PP‐cats is strongly dependent on the composition. Comparing the T_g, _PP and T_g, _EPR with T_g of fractionated PP and EPR, we ascribe the T_g change of PP fraction to the increase of EPR content; while that of EPR, to the increase of ethylene content in EPR. These experimental results suggest that the existence of E‐b‐P plays an important role in improving the miscibility between propylene homopolymer and EPR in PP‐cats. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Fat-simulating and accelerating solvents for polyolefins and MWD of solvent extracts of polyethylenes

Migration kinetics of straight-chain oligomers and antioxidants from several polyolefins at different temperatures into various solvents have been studied by radioactive tracer techniques. Anhydrous ethanol appears to be a well suited food-oil or liquid-fat simulant for extracting different types of migrants from polyolefins. Pure and mixed triglycerides are also good oil or fat simulants, but the triglycerides offer no simpler analytical procedures than the use of oil or fat themselves. n-Octanol may also be considered as a reasonable oil or fat simulant; however, its action depends somewhat on the choice of migrants. The accelerating action of n-heptane over that of oil or simulants is quantitatively demonstrated. The accelerating effects are greater for migration systems with lower diffusion coefficients. The diffusion coefficients for migration into n-heptane are about 20 times greater than the diffusion coefficients into ethanol or oil for otherwise identical migration systems yielding diffusion coefficients of about 10^?7 cm²s^?1 into oil or ethanol. For systems yielding diffusion coefficients into oil or ethanol of about 10^?12 cm²s^?1, the corresponding diffusion coefficients into n-heptane are about 1000 times greater. The molecular weight distributions (MWDs) of the n-heptane and ethanol extracts of polyolefins have been analysed. n-Heptane can not only accelerate the migration of the individual migrant but also remove oligomer species that are slightly soluble or present at low levels in the oil or simulant extracts.     

抗冲聚丙烯管材专用树脂的结构与性能

研究了乙丙嵌段共聚聚丙烯(PP-B)管材专用树脂的结构与性能。PP-B具有典型的乙丙嵌段共聚物序列结构,是含有丙烯均聚物(PP-H)、乙丙橡胶(EPR)及可结晶乙丙共聚物的抗冲聚丙烯(PP);其中,均聚物与共聚物比例合理,形成的EPR多、粒径小,对提高冲击强度有利。提高PP-H的质量分数和等规指数,可有效提高PP- B的刚性。PP-B的熔点与PP-H近似;相对分子质量分布较宽,流变性能好;微观与亚微观结构合理,宏观性能优良。     

Structural characterization of reactor blends of polypropylene and ethylene‐propylene rubber

Blends of isotactic polypropylene (PP), ethylene‐propylene rubber copolymer (EPR), and ethylene‐propylene crystalline copolymer (EPC) can be produced through in situ polymerization processes directly in the reactor and blends with different structure and composition can be obtained. In this work we studied the structure of five reactor‐made blends of PP, EPR, and EPC produced by a Ziegler‐Natta catalyst system. The composition of EPR was related to the ratio between ethylene and propylene used in the copolymerization step. The ethylene content in the EPR was in the range of 50–70 mol %. The crystallization behavior of PP and EPC in the blends was influenced by the presence of the rubber, and some specific interactions between the components could be established. By preparative temperature rising elution fractionation (P‐TREF) analysis, the isolation and characterization of crystalline EPC fractions were made. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2155–2162, 2004     

Morphology and mechanical properties of biaxially oriented films of polypropylene and HDPE blends

Biaxially oriented films of blends of high-density polyethylene (HDPE) with polypropylene (PP) homopolymer and PP copolymers prepared by twin-screw extrusion and lab-stretcher have been investigated by scanning electron microscopy (SEM), polarized microscopy, differential-scanning calorimeter, and universal testing machine. Three different kinds of PP copolymers were used: (i) ethylene–propylene (EP) random copolymer; (ii) ethylene–propylene (EP) block copolymer; (iii) ethylene–propylene–buttylene (EPB) terpolymer. In the SEM study of the morphology of films of HDPE with various PP blends, phase separation is observed between the PP phase and the HDPE phase for all blends and compositions. In all blends, HDPE serves to reduce the average spherulites size, probably acting as a nucleating agent for PP. The reduction of spherulite size appeared most significantly in the blend of EPB terpolymer and HDPE. A large increase of crystallization temperature was found in the blend of EPB terpolymer and HDPE compared with the unblended EPB terpolymer. For the blend of EPB terpolymer and HDPE, the improvement of tensile strength and modulus is observed with an increase of HDPE content, and this can be considered as a result of the role of HDPE in reducing average spherulite size. © 1994 John Wiley & Sons, Inc.     

Preparation and characterization of high MFR polypropylene and polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys

In this work, high melt flow rate (MFR) polypropylene (HF‐PP) and polypropylene/poly(ethylene‐co‐propylene) in‐reactor alloys (HF‐PP/EPR) with MFR ≈ 30 g/10 min were synthesized by spherical MgCl₂‐supported Ziegler–Natta catalyst with cyclohexylmethyldimethoxysilane (CHMDMS) or dicyclopentyldimethoxysilane (DCPDMS) as external donor (De). The effects of De on polymerization activity, chain structure, mechanical properties, and phase morphology of HF‐PP and HF‐PP/EPR were studied. Adding CHMDMS caused more sensitive change of the polymers MFR with H₂ than DCPDMS, and produced PP/EPR alloys containing more random ethylene‐propylene copolymer (r‐EP) and segmented ethylene‐propylene copolymer (s‐EP). CHMDMS also caused formation of s‐EP with higher level of blockiness than DCPDMS. HF‐PP/EPR alloy prepared in the presence of DCPDMS exhibited higher flexural properties but lower impact strength than that prepared with CHMDMS. Toughening efficiency of the rubber phase was nearly the same in the alloys prepared using CHMDMS or DCPDMS as De, but stiffness of the alloy can be improved by using DCPDMS. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42984.