PVA/TPU共混材料热塑加工性能及相容性的研究

采用热塑加工方法制备了聚乙烯醇/热塑性聚氨酯(PVA/TPU)共混材料,系统研究了共混材料的热塑加工性能、相容性及力学性能。结果表明:TPU的引入对共混材料的熔点影响不大,但其与PVA间的氢键作用可屏蔽PVA的羟基,较大幅度地提高了PVA初始热分解温度,获得更宽的热塑加工窗口;引入适量的TPU还可降低共混材料的熔体黏度,改善材料的热塑加工性能,另外,还可获得良好的材料相容性;随着TPU用量的增加,共混材料的拉伸强度先增后降,并在TPU用量为50 phr时达到最大值。     

Reactive blending of thermoplastic polyurethane in situ with poly(vinyl chloride)

In this study, a novel reactive blending process was developed for producing poly(vinyl chloride)/thermoplastic polyurethane (PVC/TPU) blends. An alternative to melt or solution blending, the advantages to such a blending technique are fewer processing steps and less cost, no solvent removal, reduced PVC degradation, and the potential for producing otherwise unobtainable blend morphologies and properties. Using an internal mixer, PVC was compounded and plasticized with the polyol and chain extender of a polyester‐based TPU. Then, upon addition of the stoichiometric amount of TPU diisocyanate, a high molecular weight TPU was polymerized in situ with PVC. Because of reaction‐induced phase separation, the resulting partially miscible PVC/TPU blends were characterized by heterogeneous, multiphase morphologies. In addition, they exhibited excellent tensile properties intermediate between that of neat PVC and TPU. POLYM. ENG. SCI., 45:876–887, 2005. © 2005 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     

聚氨酯增韧聚甲醛的研究

采用机械共混的方法，制备了聚甲醛(POM)／热塑性聚氨酯弹性体(TPU)复合材料；研究了缺口曲率半径对纯POM以及TPU增韧体系冲击韧性的影响；并对其形态结构进行了测试分析。结果表明，纯POM的冲击韧性受缺口尖锐程度影响大，TPU能减小POM结晶度，缩小球晶尺寸，显著降低POM的缺口敏感性；POM／TPU形成双连续结构时成为超韧体系。     

Polyoxymethylene/thermoplastic polyurethane blends compatibilized with multifunctional chain extender

Novel compatibilized polyoxymethylene/thermoplastic polyurethane (POM/TPU) blends are successfully developed using multifunctional chain extender, Joncryl ADR‐4368, as the compatibilizer. The outstanding compatibilization efficiency of Joncryl on POM/TPU blend was demonstrated by its even higher mechanical properties with only 0.5 wt % of Joncryl than those with 5 wt % of three commonly used compatibilizers. Addition of only 0.5 wt % Joncryl can double the impact strength and significantly improve its tensile strength and flexural strength for POM/TPU (75/25) blend. SEM images show that Joncryl can reduce TPU particle size and enhance the interfacial interactions between POM and TPU. The interparticle distance of TPU in POM/TPU/Joncryl blends was calculated as 0.2 μm, quite close to the critical matrix ligament thickness of POM/TPU blends (0.18 μm). The impact force profile vividly shows that the addition of Joncyl in POM/TPU blends can dramatically increase the total impact energy absorbed by this blend system and enhance the interfacial interactions between POM and TPU. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The mechanical and rheological behavior of the PA/TPU blend with POE‐g‐MA modifier

In this research, we attempt to improve the impact strength and the viscosity of PA (polyamide) by blending two elastomers, TPU (thermoplastic polyurethane) and POE‐g‐MA (maleic anhydride‐grafted polyethylene‐octene elastomer), in PA matrix with twin screw extruder. The ratio of blending is 80PA/20TPU and 80PA/20TPU/20POE‐g‐MA (66.66PA/16.67TPU/16.67POE‐g‐MA). Results indicate that POE‐g‐MA improves the low viscosity of PA and TPU during the blending process, and also their compatibility. Thus, the 80PA/20TPU/20POE‐g‐MA blend has better tensile stress and elongation than 80PA/20TPU blend, and furthermore POE‐g‐MA significantly improves the impact strength of PA, even to super‐toughness grade. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Studies on thermal stability and behaviour of polyacetal and thermoplastic polyurethane elastomer blends

The influence of thermoplastic polyurethane (TPU) elastomer on the rigidity of polyacetal (polyoxymethylene, POM) was studied by determining heat deflection temperature (HDT). The higher the content of TPU in the POM/TPU blend, the lower the HDT of the blend, as would be expected. A comparative study of the recycle capability of POM and the blends was carried out by measuring melt flow index (MFI) on each successive extrusion. Stress-strain behaviour of the virgin material and that obtained after fourth-time extrusion was analysed for POM and the blends. The effect of γ-radiation on the mechanical behaviour of the blends was investigated. The kinetics of thermal degradation of POM, TPU and their blends was studied. The kinetic parameters, viz. activation energy and the order of reaction, were established. The values of the activation energy of the blends were found to be higher than those of the POM and TPU, indicating improved stability of the resultant blends.     

Super‐Tough and Highly‐Ductile Poly(l‐lactic acid)/Thermoplastic Polyurethane/Epoxide‐Containing Ethylene Copolymer Blends Prepared by Reactive Blending

Ethylene‐methyl acrylate‐glycidyl methacrylate copolymer (E‐MA‐GMA) is employed to improve the impact toughness of poly(l ‐lactic acid) (PLLA)/thermoplastic polyurethane (TPU) blends by reactive melt‐blending. The reaction and miscibility between the components are confirmed by Fourier transform infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. A super‐tough PLLA/TPU/E‐MA‐GMA multiphase blend (75/10/15) exhibits a significantly improved impact strength of 77.77 kJ m^?2, which is more than 17 times higher than that of PLLA/TPU (90/10) blend. A co‐continuous‐like TPU phase structure involving E‐MA‐GMA phase at the etched cryo‐fractured surface and the high‐orientated matrix deformation at the impact‐fractured surface are observed by scanning electron microscopy. The high‐orientated matrix deformation induced by the co‐continuous TPU phase structure is responsible for the super toughness of PLLA/TPU/E‐MA‐GMA blends.     

聚甲醛/聚氨酯高韧合金的研究

通过机械共混法制备了ＰＯＭ／ＴＰＵ合金,考查了ＴＰＵ含量、增容剂以及开矿结构对共混物韧性的影响。结果表明,共混方法以及形态结构对共混物的性能有较大影响,增窝剂Ｇ是促进ＴＰＵ分散、使共混物实现高韧化的关键组分。     

Enhanced properties of polyvinyl chloride modified by graphene reinforced thermoplastic polyurethane

Graphene sheets with a range of unusual properties and thermoplastic polyurethane (TPU ) were combined to modify polyvinyl chloride (PVC ), and the enhanced properties such as flexibility, thermal stability and mechanical properties of the PVC were investigated. In order to avoid the C ? Cl bonds in PVC being weakened, graphene was incorporated into TPU in the melting state first and then this TPU was employed as a modifier to enhance and plasticize PVC in another melt blending step. In comparison with the ternary blending method, this step‐by‐step melt blending method was more efficient and convenient. The distribution of graphene sheets in the polymer matrix is uniform and no C ? Cl bond weakened effect can be observed. Due to the similar polarity, TPU showed good compatibility with PVC and its plasticizing effect allowed a broader range of low temperature flexibility of the modified PVC matrix. Moreover, other properties of the resultant PVC matrix (PTG ‐x ) including mechanical properties, thermal stability and plasticizer migration resistance were all found to be improved. With innovative applications in mind, the development of new graphene‐based materials will certainly lead to many future advances in science and technology. © 2017 Society of Chemical Industry     

Properties and preparation of olefin block copolymer/thermoplastic polyurethane blends

The properties of olefin block copolymer (OBC)/thermoplastic polyurethane (TPU) blends with or without maleic anhydride (MA) modification were characterized and compared. Compared with the OBC/TPU blends, OBC‐g‐MA/TPU blends displayed finer morphology and reduced domain size in the dispersed phase. The crystallization temperatures of TPU decreased significantly from 155.9 °C (OBC/TPU) to 117.5 °C (OBC‐g‐MA/TPU) at low TPU composition in the blends, indicating the inhibition of crystallization through the sufficient interaction of modified OBC with TPU composition. The modified systems showed higher thermal stability than the unmodified systems over the investigated temperature range due to the enhanced interaction through inter‐bonding. The highest improvement in tensile strength was more than fivefold for OBC‐g‐MA/TPU (50/50) in comparison with its unmodified blend via the enhanced interfacial interaction between OBC‐g‐MA and TPU. This also led to the highest Young's modulus of 77.8 ± 3.9 MPa, about twofold increase, among the investigated blend systems. A corresponding improvement on the ductility was also observed for modified blends. The modification did not vary the glass transition temperature and crystalline structure much, thus the improvement in the mechanical properties was mainly attributed to the improved compatibility and interaction from the compatibilization effect as well as increased viscosity from the crosslinking effect for modified blends. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43703.     

Dynamic mechanical and morphological studies on the compatibility of plasticized PVC/thermoplastic polyurethane blends

In this work, the compatibility of blends of plasticized poly(vinyl chloride) (p‐PVC) and thermoplastic polyurethane (TPU) was investigated using a dynamic mechanical analyzer and scanning electron microscopy. Two kinds of TPU with different ratios of hard to soft segments, i.e., TPU90 and TPU70 were compared. p‐PVC/TPU90 and p‐PVC/TPU70 blends with variable weight ratios (100/0, 90/10, 80/20, 70/30, 60/40, 50/50, 0/100) were prepared by melt blending. PVC was plasticized with 40 phr of dioctyl phthalate. It was found that TPU with a lower hard segment (i.e., TPU70) is more compatible with plasticized PVC than TPU with a higher hard segment (i.e., TPU90) in over the composition ranges examined. It was concluded that the compatibility of plasticized PVC and TPU are dependent on the ratio of hard to soft segments in TPU. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 415–422, 1999     

Synergetic effect of polyamide 1212 and diisocyanate on performance improving of thermoplastic polyurethane via melt compounding

To improve the heat resistance of thermoplastic polyurethane (TPU), in the melt blending process polyamide 1212 (PA1212) and trace amount of 4, 4′-diphenylmethane diisocyanate (MDI) were used as modifier and reactive solubilizer, respectively. Compared with pure TPU, the combinatorial addition of PA1212 and MDI resulted in remarkable improvement of mechanical, thermal, environmental, and aging properties of the TPU matrix. The reactive MDI contributes to the better interfacial adhesion between TPU and PA1212, and the dispersed PA1212 particles act as fillers as well as crosslinking points in the TPU/PA1212/MDI ternary blend. It was revealed that the synergetic effect of PA1212 and MDI is responsible for the enhanced performance of modified TPU. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Tensile behavior of glass‐fiber‐filled polyacetal: Influence of the functional groups of polymer matrices

We investigated the tensile behavior of glass‐fiber‐filled polyacetal [i.e., polyoxymethylene (POM)], focusing on the mutual influence of the functional groups in the POM matrices and the glass binder system. The different POM matrices were compounded with three kinds of glass fibers (20 wt %) treated with different glass binders, namely, epoxy resin, thermoplastic polyurethane (TPU), and a mixture of TPU and epoxy resin. A good correlation between the tensile strength and elongation at break was observed, regardless of the difference in the glass binders. The composites based on the modified POM matrix, which had both a carboxyl end group and a hydroxyl end group, improved the tensile properties noticeably in comparison with those based on the normal POM matrix. The composites were strengthened with an increase in the concentration of the functional groups. The results of scanning electron microscopy observations indicated that the fractured surfaces of a specimen having maximum tensile strength and elongation exhibited cohesion of the modified POM on the surfaces of the glass fibers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

改性碳纳米管增强热塑性聚氨酯复合材料的性能研究

以碳纳米管（CNTs）和热塑性聚氨酯（TPU）为原料,通过硫酸（H₂SO₄）/硝酸（HNO₃）混合溶液处理碳纳米管颗粒表面以达到改性的效果,使用改性过后的碳纳米管熔融共混制备出TPU/CNTs复合材料。研究了不同含量的CNTs对TPU基体的流变、力学、耐磨性以及热性能的影响。结果表明, 改性过后的CNTs在TPU基体中形成了良好的分散性和相容性;TPU/CNTs复合材料在高频剪切下保留了复合材料的加工流动性,并且复合材料的拉伸强度以及耐磨性相较于TPU有明显的增强,其中在改性碳纳米管含量较低时,复合材料的力学性能改善较为明显;改性CNTs的加入提高了TPU基体的熔融温度和结晶度;改性CNTs的加入提高了复合材料的热降解温度,提高了TPU基体的热稳定性。     

环氧聚合型扩链剂对POM/TPU共混体系的相容作用

使用环氧聚合型扩链剂作为POM/TPU共混物的相容剂,研究其对POM/TPU共混物的流变性能、力学性能、结晶性能和耐热性的影响。结果表明,添加环氧聚合型扩链剂后,POM/TPU共混物的熔体流动速率先升高然后降低;冲击强度提高,断裂伸长率大幅提高;结晶度先升高后降低;热变形温度提高。     

Morphology and properties of renewable poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) blends with thermoplastic polyurethane

Poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate)/thermoplastic polyurethane (PHBV/TPU) composites were prepared by solution blending combined with melt processing in an effort to improve the toughness of PHBV and overcome the coalescence phenomena of TPU at the same time. The compatibility, cross‐section morphology, crystal structure, thermal behaviour, and mechanical properties of composites were investigated. Field emission scanning electron microscopy results showed that no distinct interface was found in composites, uniformly dispersed PHBV/TPU composites were obtained. The incorporation of TPU did not change the basic crystalline structure of PHBV, but decreased its crystallinity. What's more, the integrity of PHBV spherulites structure was destroyed and the radial growth rate of spherulites was inhibited. Differential scanning calorimetry results analyzed by Jeziorny method indicated that the nucleation mode of composites did not change. Besides, when TPU content was up to 40 wt%, the initial degradation temperature of PHBV/TPU composite was increased by 5°C, and the elongation‐at‐break was increased by 225% compared with those of PHBV. POLYM. ENG. SCI., 54:1113–1119, 2014. © 2013 Society of Plastics Engineers     

热塑性聚氨酯与聚氯乙烯共混改性研究

采用机械共混法制备了热塑性聚氨酯(TPU)与聚氯乙烯(PVC)共混物。探讨了共混比对TPU／PVC共混物性能的影响，优化出TPU／PVC共混比30／70(质量比)，在此基础上研究了增塑剂、热稳定剂、填料对TPU／PVC共混物力学性能、流变性能和耐油、耐溶剂性能的影响。研究结果表明，TPU／PVC共混物的力学性能在共混时有协同作用，耐油、耐溶剂性均较好，从成本和实用两方面出发，选择TPU／PVC=30／70共混比更有实用性。随增塑剂DOP的增加，共混物的力学性能呈下降趋势。在所选热稳定剂中，以硬脂酸钙制得共混物的力学性能最好；在所选填料中，白炭黑的补强效果最好。扫描电镜观察共混物的微观结构显示，TPU／PVC共混比为30／70有较好的相容性，这与力学性能结果相一致。TGA分析显示，TPU的加入提高了共混物的热稳定性。红外光谱分析表明，TPU和PVC共混只是一个简单的物理共混过程。     

Novel thermoplastic natural rubber based on thermoplastic polyurethane blends: influence of modified natural rubbers on properties of the blends

Three different forms of natural rubber: maleated natural rubber (MNR), epoxidized natural rubber (ENR) and natural rubber-graft-poly(methyl methacrylate) (NR-g-PMMA) were prepared. Degree of functional groups in rubber molecules was quantified using the integrated peak areas of ¹H NMR. It was found that the modified rubbers with similar level of functionality had been successfully prepared. Thermoplastic natural rubber (TPNR) based on blending of thermoplastic polyurethane (TPU) and various forms of rubber were then prepared using melt blending method. The properties of the blends were studied and compared together in relation to different types of natural rubbers prepared (i.e., unmodified NR, MNR, ENR and NR-g-PMMA). It was found that the blends with modified NR exhibited superior stiffness, entropy effect and damping factor compared to other blends with unmodified NR. This is attributed to the chemical interaction between the functional groups of modified NR molecules and polar functional groups in TPU molecules which facilitated higher interfacial adhesion between both phases. The chemical interaction was verified by ATR-FTIR and TSSR techniques. It was also found that the MNR/TPU blend showed the highest tensile modulus, mechanical and elastic properties with smallest and finer grain dispersion of co-continuous phase compared to ENR/TPU, NR-g-PMMA/TPU and unmodified NR/TPU blends, respectively. This might be due to higher chemical interactions between MNR and TPU phases. Furthermore, the incorporation of rubber did reduce hardness (i.e., <60 Shore A) with improvement of elasticity of the blends compared with the original TPU (i.e., ~85 Shore A).     

Investigation of structure and mechanical properties of toughened poly(l‐lactide)/thermoplastic poly(ester urethane) blends

In this study, poly(l ‐lactide) (PLA) is melt‐blended with thermoplastic polyurethane (TPU) to modify the brittleness of PLA. An aliphatic ester‐based TPU was selected in order to have an ester sensitivity for degradation and an inherent biocompatibility. Using this compatible TPU, there was no need to apply problematic compatibilizers, so the main positive properties of PLA such as biocompatibility and degradability were not challenged. The detected microstructure of PLA/TPU blends showed that when the TPU content was lower than 25 wt %, the structure appeared as sea‐islands, but when the TPU content was increased, the morphology was converted to a cocontinuous microstructure. A higher interfacial surface area in the blend with 25 wt % TPU (PLA25) resulted in a higher toughness and abrasion resistance. The various analyses confirmed interactions and successful coupling of two phases and confirmed that melt‐blending of PLA with the aliphatic ester‐based TPU is a convenient, cost‐effective, and efficient method to conquer the brittleness of PLA. The prepared blends are general‐purpose plastics, but PLA25 showed an optimum mechanical strength, toughness, and biocompatibility suitable for a wide range of applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43104.