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1.
Blends of linear polyethylene (LPE) and branched polyethylene (BPE) display very good mechanic properties that can be beneficial for various applications such as shear thinning and melt elasticity. LPE, BPE and amorphous polyethylene can be produced using nickel diimine (DMN) catalyst under various polymerization conditions, while LPE can be obtained using metallocene catalyst. Thus, LPE/BPE blends can be achieved by in situ polymerization using a hybrid DMN/metallocene catalyst. A novel hybrid catalyst made of DMN and Cp2TiCl2 was designed and used for ethylene polymerization. A synergistic effect of the two active sites in the hybrid DMN/metallocene catalyst was observed. Blends of linear and low branched polyethylene were synthesized when polymerization was conducted at low temperature (0 °C), while blends of linear and highly branched polyethylene were obtained at high temperature (50 °C). However, the miscibility of the polymers obtained at 50 °C was dramatically reduced as compared to those obtained at 0 °C. Mesoporous particles (MCM‐41) consisting of aluminosilicate with cylindrical pores were used to support the hybrid catalyst, in which MCM‐41 provides sufficient nanoscale pores to facilitate the polymerization in well‐controlled confined spaces. Blends of LPE and BPE were synthesized by in situ polymerization without adding comonomer and characterized. The miscibility of the polymer blends can be improved by supporting the hybrid catalyst on MCM‐41. Copyright © 2009 Society of Chemical Industry 相似文献
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基于相转化法制备了复合微球载体负载的(n-BuCp)2ZrCl2/PSA/TiCl3复合催化剂。利用聚合物膜将两个传统的催化剂（茂金属和Ziegler-Natta催化剂）隔开,即先将Ziegler-Natta催化剂负载于无机载体上作为内核,随后将聚合物膜均匀沉积在无机载体催化剂表面,最后将茂金属催化剂溶液迅速负载于聚合物膜上,得到“内钛外茂”型(n-BuCp)2ZrCl2/PSA/TiCl3复合催化剂。在实验室条件下,模拟工业淤浆双釜串联反应工艺,在第一段反应中制备超高分子量(1.4×106 g/mol)高支化度的乙烯/1-己烯共聚物,在第二段反应中,制备低分子量低支化度的聚合物。调节两段反应的聚合时间,制备了不同组成的聚乙烯共混物。通过DSC和流变学的方法研究了聚乙烯共混物的共混性能,并与机械共混法得到的聚乙烯共混物的共混性质进行比较。 相似文献
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V. H. Antolín‐Cerón S. Gómez‐Salazar V. Soto M. Ávalos‐Borja S. M. Nuño‐Donlucas 《应用聚合物科学杂志》2008,108(3):1462-1472
Four binary polymer blends containing poly [ethylene‐co‐(acrylic acid)] (PEAA) as one component, and poly(4‐vinyl phenol‐co‐2‐hydroxy ethyl methacrylate) (P4VPh‐co‐2HEMA) or poly(2‐ethyl‐2‐oxazoline) (PEOx) or poly(vinyl acetate‐co‐vinyl alcohol) (PVAc‐co‐VA) or poly (vinylpyrrolidone‐co‐vinyl acetate) (PVP‐co‐VAc) as the other component were prepared and used as a matrix of a series of composite materials. These binary mixtures were either partially or completely miscible within the composition range studied and were characterized by differential scanning calorimetry (DSC) and Fourier transformed infrared spectroscopy (FTIR). Carbon nanotubes (CNTs) were prepared by a thermal treatment of polyester synthesized through the chemical reaction between ethylene glycol and citric acid over an alumina boat. High resolution transmission electron microscopy (HRTEM) was used to characterize the synthesized CNTs. Films of composite materials containing CNTs were obtained after evaporation of the solvent used to prepare solutions of the four types of binary polymer blends. Young's moduli of the composites were obtained by thermomechanical analysis at room temperature. Only one glass transition temperature was detected for several compositions on both binary blends and the composite material matrices. Evidence of hydrogen bond formation was recorded for both miscible blends and composite materials. The degree of crystallinity and Young's moduli of the CNT‐polymer composites increased compared to the single polymer blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008 相似文献
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Branched polyethylenes, low‐density polyethylenes (LDPE1 and LDPE2) or long‐chain‐branched very low density polyethylenes (VLDPE2), were blended with very low density polyethylenes containing short branches (VLDPE1 and VLDPE3). The rheological and thermal measurements of the pure copolymers and their blends (VLDPE1–LDPE1, VLDPE1–LDPE2, VLDPE1–VLDPE2, and VLDPE2–VLDPE3) were taken by controlled stress rheometry and differential scanning calorimetry, respectively. The shear‐thinning effect became stronger with increasing long‐chain‐branched polymer compositions when it was correlated with the flow behavior index, and the extent of shear thinning was different for each blend set. Stronger shear thinning and a linear composition dependence of the zero‐shear viscosity were observed for the VLDPE1–LDPE1 and VLDPE1–LDPE2 blends. These blends followed the log additivity rule, and this indicated that they were miscible in the melt at all compositions. In contrast, a deviation from the log additivity rule was observed for the VLDPE1–VLDPE2 blend compositions with 50% or less VLDPE2 and for the VLDPE3–VLDPE2 blends with 50% or more VLDPE2. The thermal properties of the blends were consistent with the rheological properties. VLDPE1–LDPE1 and VLDPE1–LDPE2 showed that these blends were characteristic of a single‐component system at all compositions, whereas the phase separation (immiscibility) was detected only for VLDPE1–VLDPE2 blends with 50% or less VLDPE2 and for VLDPE3–VLDPE2 blends with 50% or more VLDPE2. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1549–1557, 2005 相似文献
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Polypropylene (PP) was blended with a linear low-density polyethylene (LLDPE, containing 5% hexene comonomer) over a composition range of 10–90% of PP. The crystallization and morphology of the PP–LLDPE blends were studied by differential scanning calorimetry (DSC), polarized optical microscopy with a hot stage (HSOM), and scanning electron microscopy (SEM). In particular, the isothermal crystallization of PP in molten LLDPE was investigated. It was observed that the crystallization and melting behavior of PP and LLDPE changed in the blends, indicating that there was some degree of miscibility between the PP and the LLDPE. A depression of the equilibrium melting temperature (T) of PP in the blends with no more than 15% of PP confirmed that PP was miscible with LLDPE at and below 15% of PP. In addition, a drastic decrease in T from the 25% PP blend to the 20% blend led us to conclude that the miscible behavior between PP and LLDPE became favorable at a PP concentration of 20%. The optical microscopic images showed that, in the blends with 10 and 15% of PP, the PP crystallized as open-armed diffuse spherulites, similar to those in the miscible blends. In contrast, the PP crystallized in a phase-separated matrix or droplets with more than 25% of PP, when obvious phase separation occurred. The SEM image revealed that the PP lamella was able to penetrate the PP and LLDPE phase boundary and grow in the LLDPE phase. The above results displayed that the PP dissolved in the LLDPE, and, particularly, when the PP concentration was below 20%, the dissolution was substantial. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 628–639, 2001 相似文献
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A commonly used nylon 6 two‐step VK tubular reactor is simulated in this work. To verify the reliability of the model, careful comparison with results obtained on different continuous plants is made. The effect of various conditions and parameters, e.g. feed composition, temperature, pressure, etc. on the product properties such as caprolactam conversion, degree of polymerization (DP), dimer, integral heat and their distribution index is studied. It is observed that the caprolactam conversion and DP of the product may be affected by various conditions in the first stage and the temperature profile at the top of the second stage, but they finally reach the equilibrium values if the residence time is long enough. The most effective way to increase DP of the product is to increase the vacuum at the top of the second stage.
CPL conversion and DP profile for pressure of tube 2: 0.032, 0.037, 0.042 mPa; other parameters as given for example A of Table 5 . 相似文献
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Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002 相似文献
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采用溶胶-凝胶法,将苯乙烯-丙烯酸(PSA)共聚物包覆在以硅胶/MgCl2为载体的TiCl3催化剂上,负载(n-BuCp)2ZrCl2后制得Ziegler-Natta/茂金属复合催化剂。实验在同一反应釜中进行两段反应模拟双釜串联聚合工艺。在第一段反应中制备高分子量高支化度的乙烯/1-己烯共聚物,在第二段反应中,制备低分子量低支化度的聚合物。淤浆聚合结果表明,所得聚乙烯的熔融流动比(MI21.6/MI2.16)较宽,达到79,分子量分布达到18.6。两段反应得到的聚乙烯共混物的结晶度和熔融温度介于第一段、第二段单独反应时所得产物的结晶度和熔融温度之间,且DSC曲线具有单一的熔融峰,说明该两段反应法制备的聚乙烯共混物具有良好的共结晶行为。动力学研究同时表明,苯乙烯-丙烯酸共聚物的引入,使得催化剂的活性缓慢释放,活性持续时间明显长于负载于无机载体的催化剂,有利于灵活地调节各段反应的停留时间。 相似文献
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Matthias Schnell Julio Borrajo Roberto J. J. Williams Bernhard A. Wolf 《大分子材料与工程》2004,289(7):642-647
Summary: Solutions containing 15 wt.‐% of a low‐molar‐mass polyethylene (PE) in isobornyl methacrylate (IBoMA), containing 0, 5 or 10 wt.‐% of 1,4 butanediol dimethacrylate (BDDMA) as crosslinker, were polymerized using either benzoyl peroxide (BPO), at 80 °C, or dicumyl peroxide (DCPO), with a thermal cycle attaining 150 °C, as initiators. Phase separation of an amorphous PE‐rich phase took place when carrying out the reaction at temperatures higher than the PE melting temperature. Partial crystallization of PE was observed when cooling to room temperature. Depending on the initial amount of BDDMA, the fraction of PE that was phase separated varied between 57 and 66% of the initial amount, with crystalline fractions in the range of 15 to 42%. The use of IBoMA as a reactive solvent of PE has two main advantages over other reactive solvents reported in the literature: a) it has a very low vapor pressure, and b) its free‐radical polymerization gives a polymer with a relatively high glass transition temperature.
Part of the cloud‐point curve for IBoMa, PIBoMA and PE solutions at 80 °C. 相似文献
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Solution miscibility of chitosan/polyethylene glycol fumarate blends dissolved in acetate buffer solution was investigated in different blend compositions by viscosity, density, and refractive index measurement techniques at 30, 40, and 50°C. In order to quantify the miscibility of the polymer pair, degree of miscibility was studied by means of two criteria known as interaction parameters i.e., μ and α. On the basis of the sign convention involved in these criteria, these values revealed that the blend solution was miscible when the chitosan content was more than 80% (w/w) of the composition. The results were confirmed by density, and refractive index measurements. Furthermore, the results showed that the miscibility window of chitosan/polyethylene glycol fumarate blends was independent with respect to the changes in solution temperature. Therefore, these results suggested due to intermolecular hydrogen‐bonding interaction between amino and hydroxy groups of chitosan and hydroxy groups of polyethylene glycol fumarate which play an important role in the formation of miscible phase. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013 相似文献
12.
The miscibility behavior of dextran (Dx) with synthesized functional binary poly(citraconic anhydride‐acrylamide) (poly(CA‐alt‐AAm) and ternary poly(citraconic anhydride‐acrylamide‐vinyl acetate) (poly(CA‐co‐AAm‐co‐VA) copolymers was investigated in dilute aqueous solutions by viscometry and in a solid state by Fourier transform infrared (FTIR) spectroscopy. The relative viscosities of each polymer and their blends with Dx/related copolymer ratios of 20 : 80, 50 : 50, and 80 : 20 were measured at body temperature, 37°C, in bidistilled and deionized water. Starting with the classical Huggins equation, results of the viscosity measurements of each parent polymer and their blends were interpreted in terms of miscibility parameters: Δk, Δb, α, β, ΔB, and μ. Based on the sign convention used with these criteria, the miscibility between Dx and related copolymers was found to increase with the weight fraction of Dx in the blends and with the number of AAm units in the copolymer composition. From FTIR spectral analysis, supporting results were achieved that explained the interactions between Dx and the copolymers. Miscibility behavior was also investigated theoretically with Askadskii's miscibility criterion, and the theoretical calculations provided strong evidence supporting the experimental results. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2132–2141, 2006 相似文献
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采用胺基取代单茂钛{Cp*TiCl2N[Si(CH3)3]2}与甲基铝氧烷组成的催化体系进行乙烯聚合,得到聚乙烯 (PE)。该体系催化活性在40℃下最高,达78．5 kg,(mol·h)。PE的相对分子质量随聚合温度的下降有明显增大,在 0-60℃时重均分子量为(16-60)×104。对PE的差示扫描量热法及核磁共振碳谱表征结果表明,通过控制不同的聚合条件,PE的熔融温度可以在118-130℃变化。聚合温度和n(Al)/n(Ti)对PE的支化度都有显著影响,PE的支化类型主要为丁基支链。 相似文献
14.
气相聚乙烯BCG催化剂的工业应用 总被引：3，自引：0，他引：3
介绍了BCG催化剂在Unipol气相法聚乙烯装置上的工业应用。工业试用表明,BCG催化剂的流动性能、氢调和共聚合性能良好,活性较高,综合性能优良;树脂性能测试表明,用BCG催化剂生产的薄膜级线型低密度聚乙烯树脂的加工性能良好,产品物理、机械性能达到优级品标准。 相似文献
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N. R. Manoj P. Sivaraman S. Praveen R. D. Raut L. Chandrasekhar B. C. Chakraborty 《应用聚合物科学杂志》2005,97(5):1763-1770
Ternary blends of thermoplastic polyurethane and a poly(vinyl chloride)/nitrile rubber blend were investigated in this work. The blends, with weight ratios of 100/0, 80/20, 40/60, 60/40, 80/20, and 0/100, were prepared via melt blending. Dynamic mechanical analysis showed that the blends with ratios of 20/80 and 80/20 were miscible, whereas the 40/60 and 60/40 blends were partially miscible. IR spectroscopy studies showed shifts in the peaks due to specific interactions in the blends. The blends showed degradation behavior between the blend components. The fracture toughness was investigated with the J‐integral by the locus method; the components and the miscible blends had good fracture toughness, whereas the other blends had lower toughness. Similar behavior was observed for the tensile properties. Scanning electron microscopy studies showed the morphological variations in the blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1763–1770, 2005 相似文献
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S. G. Adoor L. S. Manjeshwar K. S. V. Krishna Rao B. V. K. Naidu T. M. Aminabhavi 《应用聚合物科学杂志》2006,100(3):2415-2421
The blend miscibility of poly(vinyl alcohol) and poly(methyl methacrylate) in N,N′‐dimethylformamide solution was investigated by viscosity, density, ultrasonic velocity, refractive index, and UV and fluorescence spectra studies. Differential scanning calorimetry and scanning electron microscopy were used to confirm the blend miscibility in the solid state. Blends were compatible when the concentration of poly(vinyl alcohol) was greater than 60 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2415–2421, 2006 相似文献
18.
The miscibility, crystallization behavior, and component interactions of two binary blends, poly(L ‐lactide) (L ‐PLA)/poly(vinylpyrrolidone) (PVP) and poly(D ,L ‐lactide) (DL ‐PLA)/PVP, were studied with differential scanning calorimetry and Fourier transform infrared (FTIR) spectroscopy. The composition‐dependent changes of the glass‐transition temperature (Tg) and degree of crystallinity (Xc) of the L ‐PLA phase indicated that L ‐PLA and PVP were immiscible over the composition range investigated. However, the sharp decrease of Xc with increasing PVP content in the second heating run demonstrated that the cold crystallization process of L ‐PLA was remarkably restricted by PVP. In DL ‐PLA/PVP blends, the existence of two series of isolated Tg's indicated that DL ‐PLA and PVP were phase‐separated, but evidence showed that there was some degree of interaction at the interface of the two phase, especially for the blends with low DL ‐PLA contents. FTIR measurements showed that there was no appreciable change in the spectra of L ‐PLA/PVP with respect to the coaddition of each component spectrum, implying the immiscibility of the two polymers. In contrast to L ‐PLA, the intermolecular interaction between DL ‐PLA and PVP was detected by FTIR; this was evidenced by the observation of a high‐frequency shift of the C?O stretching vibration band of PVP with increasing DL ‐PLA content, which suggested some degree of miscibility. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 973–979, 2003 相似文献
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On purpose to examine the effect of branch length on the miscibility of polyolefin blends, miscibility behavior of linear polyethylene/poly(ethylene‐co‐1‐octene) blend was studied and compared to that of linear polyethylene/poly(ethylene‐co‐1‐butene) blend. Miscibility of the blend was determined by observing the morphology quenched from the melt, and by using the relation between interaction parameter and copolymer composition. When the weight composition and molecular weight was the same, poly(ethylene‐co‐1‐octene) was slightly more miscible with linear polyethylene than poly(ethylene‐co‐1‐butene) was. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
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The miscibility of blends of a polyarylate (PAr) with poly(trimethylene terephthalate) (PTT) was investigated in the whole composition range by DSC measurements. With the exception of the 90/10 composition, which was fully miscible, the blends showed partial miscibility, and contained a nearly pure PTT phase and a PAr‐rich phase with 18% PTT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1559–1561, 2004 相似文献