Blends of thermoplastic polyurethane and polypropylene. I. Mechanical and phase behavior

Pure thermoplastic polyurethane (TPU), polypropylene (PP), and TPU/PP blends with different weight ratios prepared in a twin‐screw extruder were investigated by dynamic mechanical analysis (DMA), the universal tester for mechanical investigation, and by wide‐angle X‐ray diffraction (WAXD). The addition of PP above 20 wt % to the TPU stepwise changed the ductility and Young's modulus, i.e., apparently a kind of ductile → brittle transition occurred between TPU/PP 80/20 and TPU/PP 60/40 blends. This fact and the result of analysis of WAXD curves indicated matrix → dispersed phase inversion in this concentration region. TPU melt enabled easier migration of the PP chains and prolonged crystallization of PP matrix during solidification process affecting thus crystallite size, orientation, and crystallinity. In accordance to this fact, DMA results indicated partial miscibility of PP with polyurethane in the TPU/PP blends due to the lack of interfacial interaction and adhesion between the nonpolar crystalline PP and polar TPU phases. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3980–3985, 2007     

The influence of filler treatment on the properties of TPU/PP blends: I. Thermal properties and stability

Commercially available organosilane (3‐glycidoxypropyltrimethoxysilane (GPTMS)) coupling agent was used to treat talc in order to improve the affinity relative between the filler and the polymer in composites as well as filler and polymer in the thermoplastic polyurethane/polypropylene (TPU/PP) blends (talc content was 5 wt%). The talc particles were first modified with GPTMS and then introduced into TPU, PP as well as TPU/PP blends with different weight ratios of polymers using blending method and subsequently injection molded in a hydraulic press. The aim was to report the effect of silane coupling agent on the thermal and morphological properties of talc filled composites and blends. The results showed that the thermal properties of the TPU, PP composites and TPU/PP blends were improved with the addition of silane treated talc (higher melting (T_m), crystallization (T_c) temperatures and degree of crystallinity (χ_c)). The glass transition temperature (T_g) obtained by dynamic mechanical analysis (DMA) of the TPU soft segments in TPU/PP blends increased with the addition of untreated and silane treated talc due to lower mobility of the soft segments in TPU and better miscibility of TPU and PP. TPU/PP blends with the silane treated talc show better thermal stability than the TPU/PP blends with untreated talc. POLYM. ENG. SCI., 55:1920–1930, 2015. © 2014 Society of Plastics Engineers     

Preparation and characterization of nanoclay‐filled polyurethane/polypropylene blends

Ester‐based thermoplastic polyurethane (TPU) nanocomposites were prepared by melt blending at 190°C, using 3 wt% Cloisite 10A (organically modified montmorillonite clay) as the nanoscale reinforcement [TPU(C10A)]. The nanocomposites were subsequently melt‐blended with polypropylene (PP) using maleic anhydride–grafted polypropylene (MA‐g‐PP) as a compatibilizer [in the ratio of 70/30‐TPU/PP, 70/25/5‐TPU/PP/MA‐g‐PP, 70/25/5‐TPU (C10A)/PP/MA‐g‐PP]. Besides giving substantial increase in modulus, tensile strength, and other properties, organoclay reinforcement functions as a surface modifier for TPU hard segment resulting in improved dispersion. The morphology and other characteristics of the nanocomposite blends were investigated in terms of X‐ray diffraction, fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, tensile properties, scanning electron microscopy, and atomic force microscopy. The results indicate that the ester‐TPU(C10A)/PP/MA‐g‐PP exhibited better dispersion than other blend systems; abrasion resistance and water absorption resistance were also better for this system. POLYM. ENG. SCI., 50:1878–1886, 2010. © 2010 Society of Plastics Engineers     

Nonisothermal crystallization kinetics of polypropylene/polypropylene‐g‐polystyrene/polystyrene blends

The nonisothermal crystallization kinetics of polypropylene (PP), PP/polystyrene (PS), and PP/PP‐g‐PS/PS blends were investigated with differential scanning calorimetry at different cooling rates. The Jeziorny modified Avrami equation, Ozawa method, and Mo method were used to describe the crystallization kinetics for all of the samples. The kinetics parameters, including the half‐time of crystallization, the peak crystallization temperature, the Avrami exponent, the kinetic crystallization rate constant, the crystallization activation energy, and the F(T) and a parameters were determined. All of the results clearly indicate that the PP‐g‐PS copolymer accelerated the crystallization rate of the PP component in the PP/PP‐g‐PS/PS blends. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

含异氰酸酯基的低聚物和聚醚增容改性POM/TPU共混物

利用双螺杆挤出机制备了聚甲醛(POM)/热塑性聚氨酯弹性体(TPU)、POM/TPU/含异氰酸酯基的低聚物(Z)以及POM/TPU/Z/聚醚3种共混物。采用力学性能测试、差示扫描量热分析(DSC)、偏光显微镜(PLM)、傅里叶转换红外线光谱 (FTIR)、扫描电子显微镜(SEM)、动态力学性能分析(DMA)等,研究了3种共混物的力学性能、结晶行为及形态结构。结果表明：共混物的缺口冲击强度和断裂伸长率随TPU含量的增加而提高;异氰酸酯基低聚物（Z）和聚醚在促进分散相分散、增强两相间的相容性方面发挥重要作用,降低了聚甲醛的结晶度,能够有效地提高共混物的缺口冲击强度和断裂伸长率。     

Thermoplastic polyurethane/polypropylene blends based on novel vane extruder: A study of morphology and mechanical properties

Thermoplastic polyurethane (TPU) polypropylene (PP) blends of different weight ratios were prepared with a self‐made vane extruder (VE), which generates global dynamic elongational flow, and a traditional twin‐screw extruder (TSE), which generates shear flow. The mechanical properties, phase morphology, thermal behavior, and spherulite size of the blends were investigated to compare the different processing techniques. Samples prepared with a VE had superior mechanical properties than the samples prepared with a TSE. Scanning emission micrographs show that the fiber morphology of the TPU/PP blends (<60 wt% TPU) was improved by elongational flow in VE. Differential scanning calorimetry curves indicate that a dynamical elongational flow could improve the miscibility of the TPU/PP blends. The U‐shaped spherulite size curve indicates the changes in the spherulite size, as observed from a polarization microscope. Interlocked spherulites also reveal the apparent partial miscibility of the TPU/PP blends under elongational flow. POLYM. ENG. SCI., 54:716–724, 2014. © 2013 Society of Plastics Engineers     

Nonisothermal crystallization,melting behavior,and morphology of PP/EPPE blends

Nonisothermal crystallization, melting behavior, and morphology of polypropylene (PP)/Easy processing polyethylene (EPPE) blends were studied by differential scanning alorimetry (DSC) and scanning electron microscope (SEM). The results showed that PP and EPPE are miscible, and there is no obvious phase separation in microphotographs of the blends. The modified Avrami analysis, Ozawa equation, and also Mo Z.S. method were used to analyze the nonisothermal crystallization kinetics of the blends. Values of Avrami exponent indicated the crystallization nucleation of the blends is homogeneous, the growth of spherulites is tridimensional, and crystallization mechanism of PP is not affected much by EPPE. The crystallization activation energy was estimated by Kissinger method. The result obtained from modified Avrami analysis, Mo Z.S. method, and Kissinger methods were well agreed. The addition of minor EPPE phase favored to decrease the overall crystallization rate of PP, showing some dilution effect of EPPE on PP. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crystallization behaviors of polypropylene and functional polypropylene

The crystallization behaviors of polypropylene (PP) homopolymer and its blends with 0–15% functional polypropylene (FPP), the backbones of which were grafted with guanidine and diamide polymer chains, were investigated with differential scanning calorimetry and wide‐angle X‐ray scattering. The crystallization kinetics were studied with spectral depolarization. The results revealed that the presence of FPP reduced the crystallinity and crystallite size of PP. Meanwhile, FPP increased the crystallization rate. Compared with that of the PP homopolymer, the crystallization temperature of PP/FPP blends was increased by more than 10°C. During isothermal crystallization, the relative crystallinity, developed as a function of time, was described by the Avrami equation. The half‐time of crystallization for PP/FPP blends was much shorter than that for the PP homopolymer. The half‐time of crystallization of PP/FPP blends depended much less on the crystallization temperature than that of the PP homopolymer. Therefore, FPP accelerated the crystallization rate of PP in a manner similar to that of a nucleator. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 872–877, 2003     

Crystallization and dynamic mechanical properties of polypropylene/polystyrene blends modified with maleic anhydride and styrene

Polypropylene (PP)/polystyrene (PS) blends modified with reactive monomers, such as maleic anhydride (MAH) and styrene (St), and in situ formed PP/PS blends were prepared by melting extrusion. The crystallization and melting behavior and the dynamic mechanical properties of the PP/PS blends, including the structure of the grafted copolymer, were investigated with differential scanning calorimetry, dynamic mechanical analysis, and Fourier transform infrared. The results indicated that the addition of MAH hardly influenced the crystallization temperature of PP in the blends, but the addition of MAH and St increased the crystallization temperature of PP in its blends. The blends showed no remarkable variety for the melting temperature, but the shapes of the melting peaks were influenced by the addition of the reactive monomers. In addition, a significant increase in the storage and loss moduli of all the modified PP/PS blends was observed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2038–2045, 2005     

POM与POM/TPU共混物非等温结晶动力学的研究

利用差示扫描量热仪对聚甲醛（POM）非等温结晶动力学进行了研究,并考察了热塑性聚氨酯弹性体(TPU)的加入对POM结晶动力学的影响。通过几种理论模型分析了非等温结晶数据。结果表明, Jeziorny法、莫志深法能够成功描述POM及POM/TPU共混体系的非等温结晶过程。POM的Avrami指数n稍大于POM/TPU共混物的。半结晶时间t1/2与动力学速率参数Zc的值表明POM与POM/TPU共混物的结晶速率随冷却速率的增加而增大,但相同冷却速率下POM的结晶速率要快于POM/TPU共混物。由Kissinger法估算的POM与POM/TPU共混物的活化能分别为513.5、390.5 kJ/mol。     

Preparation and structure of rare earth/thermoplastic polyurethane fiber for X-ray shielding

Rare earth/polypropylene (PP)/thermoplastic polyurethane (TPU) fibers were prepared by melting spinning with different mass ratios of PP to TPU. Then the rare earth/TPU shielding fiber was obtained by removing the PP matrix phase from the blend fiber using xylene. The fibers were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), thermogravimetric analyzer (TG), and scanning electron microscopy (SEM). Short fibers were compression-molded for the test of lead equivalent. The results showed that the lead equivalent of the rare earth/TPU composite fibers was 0.19 mmPb when the mass ratio of PP/TPU increased to 60/40. At this mass ratio, the X-ray shielding performance of the fiber was the best. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47435.     

Comparing the compatibility of various functionalized polypropylenes with thermoplastic polyurethane (TPU)

Three functionalized polypropylenes (PP), a maleated PP (PP-g-MA), primary amine functionalized PP (PP-g-NH₂), and secondary amine functionalized PP (PP-g-NHR), were melt blended with a thermoplastic polyurethane (TPU) at different compositions. Compatibility of each functionalized PP with TPU was compared by investigating the binary blends using rheological (mixer torques, dynamic shear rheometry), thermal (dynamic mechanical analysis), mechanical (tensile test), and morphological (scanning electron microscopy with image analysis, particle size analysis) measurements. Compatibility of the three functionalized PP's with TPU is ranked in a decreasing order as follows: PP-g-NHR≥PP-g-NH₂?PP-g-MA, which is attributed to higher reactivity of amine (primary and secondary) with urethane linkages. Accordingly, the TPU blends with the two types of amine functionalized PP's exhibited much better synergy, as reflected by much improved mechanical properties including higher tensile strength and ultimate elongation, and finer and more stable morphologies.     

Nonisothermal crystallization behavior of glass‐bead‐filled polypropylene

The effects of the glass‐bead content and size on the nonisothermal crystallization behavior of polypropylene (PP)/glass‐bead blends were studied with differential scanning calorimetry. The degree of crystallinity decreased with the addition of glass bead, and the crystallization temperature of the blends was marginally higher than that of pure PP at various cooling rates. Furthermore, the half‐time for crystallization decreased with an increase in the glass‐bead content or particle size, implying the nucleating role of the glass beads. The nonisothermal crystallization data were analyzed with the methods of Avrami, Ozawa, and Mo. The validity of various kinetic models for the nonisothermal crystallization process of PP/glass‐bead blends was examined. The approach developed by Mo successfully described the nonisothermal crystallization behavior of PP and PP/glass‐bead blends. Finally, the activation energy for the nonisothermal crystallization of pure PP and PP/glass‐bead blends based on the Kissinger method was evaluated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2026–2033, 2006     

Morphology and nonisothermal crystallization behavior of PP/Novolac blends

The morphology and nonisothermal crystallization behavior of PP/Novolac blends were studied with scanning electron microscopy, differential scanning calorimeter, polarized optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). The results showed that the crystallization of PP in PP/Novolac blends was strongly influenced by cooling rate, size of Novolac particles, crosslinking, and compatibilizer maleic anhydride‐grafted PP (MPP). In dynamically cured PP/MPP/Novolac blends, the MPP grafted on the surface of cured Novolac particles and formed a chemical linkage through the reaction of anhydride groups with the hexamethylenetetramine. The graft copolymer not only improved interfacial compatibility but also acted as an effective heterogeneous nucleating agent, which accelerates the crystallization of PP. The combination of Avrami and Ozawa equations exhibited great advantages in treating the nonisothermal crystallization kinetics in dynamically cured PP/MPP/Novolac blends. The POM results showed that the spherulite morphology and the size of PP in PP/MPP/Novolac blends were greatly affected by Novolac. WAXD experiment demonstrates that the PP and dynamically cured PP/MPP/Novolac blends showed only the α crystal form. At the same time, the addition of Novolac resin also affects the crystal size of PP. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

聚丙烯/超高相对分子质量聚乙烯共混物的结晶动力学及发泡性能研究

采用差示扫描量热仪（DSC）对含有不同含量超高分子量聚乙烯（UHMWPE）的聚丙烯进行测试和表征,采用Ozawa方法、莫志深方法和Kissinger方法分析了该体系的非等温结晶动力学。利用自行研制的超临界流体挤出发泡实验装置,对含有UHMWPE的PP进行了超临界二氧化碳挤出发泡实验研究。结果表明：超高分子量聚乙烯的加入降低了PP的结晶活化能,含有UHMWPE的PP在较高的温度下开始结晶,且由于超高分子量聚乙烯大分子链的存在,与聚丙烯分子链发生缠结,阻碍聚丙烯分子链排入晶格,降低了结晶速率,结晶温区拓宽,有利于聚丙烯挤出发泡成型;加入UHMWPE后,PP的发泡效果明显改善,泡孔平均直径减小,泡孔尺寸分布更加均匀,PE-UHMW的含量为5份时,表观密度达到0.038g/cm-3。     

Melting,nonisothermal crystallization behavior and morphology of polypropylene/random ethylene—propylene copolymer blends

The melting, nonisothermal crystallization behavior and morphology of blends of polypropylene (PP) with random ethylene–propylene copolymer (PP‐R) were studied by differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy, and X‐ray diffraction. The results showed that PP and PP‐R were very miscible and cocrystallizable. Modified Avrami analysis was used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was heterogeneous, the growth of the spherulites was tridimensional, and the crystallization mechanism of PP was not affected by PP‐R. The crystallization activation energy was estimated using the Kissinger method. An interesting result was obtained with the modified Avrami analysis and the Kissinger method, whose conclusions were in good agreement. The addition of a minor PP‐R phase favored an increase in the overall crystallization rate of PP. Maximum enhancing effect wass found to occur with a PP‐R content of 20 wt %. The relationship between the composition and the morphology of the blends is discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 670–678, 2006     

高温熔融对PP/EPR/PE-UHMW分子链扩散作用以及流变和结晶性能的影响

采用一种简便易行的方法使高度缠结的超高相对分子质量聚乙烯（PE-UHMW）与乙丙橡胶（EPR）的分子链得到有效的扩散,并最终将EPR/PE-UHMW预混物与聚丙烯（PP）共混形成PP/EPR/PE-UHMW三元共混物。并研究了该三元共混物的流变性能和结晶性能。结果表明,在预混物体系中,经历高温熔融处理后,流变曲线出现不同于一般EPR材料的难松弛结构的低频平台区,说明PE-UHMW与EPR分子链相互扩散形成长分子链缠结结构;其缠结结构在PP/EPR/PE-UHMW共混物中减慢了PP基体流变曲线低频平台区出现的趋势,限制了EPR向PP基体的扩散; EPR与PE-UHMW分子链之间的相互扩散,对高度缠结的PE-UHMW具有增塑作用,导致PE-UHMW结晶温度下降和结晶度上升;二元预混物添加进入PP基体中,促使PP多重熔融现象的发生。     

Mechanical properties and morphology of polyethylene–polypropylene blends with controlled thermal history

The effect of time–temperature treatment on the mechanical properties and morphology of polyethylene–polypropylene (PE–PP) blends was studied to establish a relationship among the thermal treatment, morphology, and mechanical properties. The experimental techniques used were polarized optical microscopy with hot‐stage, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and tensile testing. A PP homopolymer was used to blend with various PEs, including high‐density polyethylene (HDPE), low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and very low density polyethylene (VLDPE). All the blends were made at a ratio of PE:PP = 80:20. Thermal treatment was carried out at temperatures between the crystallization temperatures of PP and PEs to allow PP to crystallize first from the blends. A very diffuse PP spherulite morphology in the PE matrix was formed in partially miscible blends of LLDPE–PP even though PP was present at only 20% by mass. Droplet‐matrix structures were developed in other blends with PP as dispersed domains in a continuous PE matrix. The SEM images displayed a fibrillar structure of PP spherulite in the LLDPE–PP blends and large droplets of PP in the HDPE–PP blend. The DSC results showed that the crystallinity of PP was increased in thermally treated samples. This special time–temperature treatment improved tensile properties for all PE–PP blends by improving the adhesion between PP and PE and increasing the overall crystallinity. In particular, in the LLDPE–PP blends, tensile properties were improved enormously because of a greater increase in the interfacial adhesion induced by the diffuse spherulite and fibrillar structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1151–1164, 2000     

Melting behavior and isothermal crystallization kinetics of PP/mLLDPE blends

The melting/crystallization behavior and isothermal crystallization kinetics of polypropylene (PP)/metallocene-catalyzed linear low density polyethylene (mLLDPE) blends were studied with differential scanning calorimetry (DSC). The results showed that PP and mLLDPE are partially miscible and interactions mainly exist between the mLLDPE chains and the PE segments in PP molecules. The isothermal crystallization kinetics of the blends was described with the Avrami equation. Values of the Avrami exponent indicated that crystallization nucleation of the blends is heterogeneous, the growth of spherulites is almost three-dimensional, and the crystallization mechanism of PP is not affected much by mLLDPE. The Avrami exponents of the blends are higher than that of pure PP, showing that the mLLDPE helps PP to form perfect spherulites. The crystallization rates of PP are decreased by mLLDPE because the crystallization temperature of PP was decreased by addition of mLLDPE and consequently the supercooling of the PP was correspondingly lower. The crystallization activation energy was estimated by the Friedman equation, and the result showed that the activation energy increased by a small degree by addition of mLLDPE, but changed little with increasing content of mLLDPE in the blends. The nucleation constant (K _g) was determined by the Hoffman–Lauritzen theory. Supported by the Science Foundation of Hebei University (2006Q13).     

Nonisothermal crystallization,melting behavior,and morphology of polypropylene/metallocene‐catalyzed polyethylene blends

The nonisothermal crystallization, melting behavior, and morphology of blends of polypropylene (PP) and a metallocene‐catalyzed polyethylene (mPE) elastomer were studied with differential scanning calorimetry, scanning electron microscopy, polarized optical microscopy, and X‐ray diffraction. The results showed that PP and mPE were partially miscible and could form some cocrystallization, although the extent was very small. A modified Avrami analysis and the Mo method were used to analyze the nonisothermal crystallization kinetics of the blends. The values of the Avrami exponent indicated that the crystallization nucleation of the blends was homogeneous, the growth of the spherulites was three‐dimensional, and the crystallization mechanism of PP was not affected by mPE. The crystallization activation energy was estimated with the Kissinger method. Interesting results were obtained with the modified Avrami analysis and Mo and Kissinger methods, and the conclusions were in good agreement. The addition of less mPE increased the overall crystallization rate of PP. The relationship between the composition and morphology of the blends was examined. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1203–1210, 2004