热塑性聚氨酯弹性体合金研究进展

热塑性聚氯酯是一类具有良好耐低温、高弹性和耐磨性能的新型弹性体。笔者综述了热塑性聚氯酯弹性体合金的研究进展，分析了国内热塑弹性体生产现状及未来的发展趋势。     

PVC/NBR热塑性弹性体加工流变性能研究

采用反应挤出动态硫化法制备了聚氯乙烯／丁腈橡胶(PVC／NBR)热塑性弹性体，用锥板流变仪、毛细管流变仪和转矩流变仪研究了动态硫化的PVC／NBR热塑性弹性体的流交性能和塑化性能。实验结果表明，动态硫化的PVC／NBR热塑性弹性体的熔体属于剪切稀化的假塑性流体，具有良好的返炼性能，综合性能超过国外同类产品。     

聚烯烃弹性体/聚丙烯热塑性弹性体的制备及力学性能

以过氧化物为硫化剂,用动态硫化法制备了聚烯烃弹性体(POE)/聚丙烯(PP)热塑性弹性体,研究了硫化剂用量、填料种类和加工次数对体系力学性能的影响。结果表明,增加硫化剂用量可以提高体系的拉伸强度,降低拉伸永久变形和压缩永久变形。碳酸钙和滑石粉对POE/PP体系无明显增强作用,炭黑的增强作用较此二者明显一些,这三种填料加入后都会使体系的扯断伸长率降低而硬度增大。加入石蜡油会使体系的扯断伸长率和压缩永久变形增大、硬度和拉伸强度降低。加工次数对POE/PP体系的力学性能无明显影响,说明体系具有较好的重复加工性能。     

Phase transitions and mechanical properties of nitrocellulose plasticized by glycidyl azide polymer and nitroglycerine

Films of nitrocellulose (NC), glycidyl azide polymer (GAP), and nitroglycerine (NG) have been evaluated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), and tensile testing. The SEM micrographs demonstrate that, even at low GAP concentration, a portion of GAP will coalesce into spherical domains due to a saturation effect. This is related to the inability of higher molecular weight GAP to effectively situate itself between NC polymer chains. The addition of a small fraction of lower molecular weight NG completely changes this behavior. DMA confirms that two transitions are present and can be attributed to a plasticizer rich phase (β), a polymer rich phase (α) and that NC plasticized with GAP is in accordance with the Gordon-Taylor equation. Tensile results show that the addition of a small fraction of NG to a NC/GAP based-formulation increases elongation at break to values similar to that of the NC/NG base formulation. The combination of these two plasticizers, GAP and NG, allows for the plasticization of NC at significantly lower environmental and human toxicity levels.     

Phase behavior, morphology and interfacial structure in thermoset/thermoplastic elastomer blends of poly(propylene glycol)-type epoxy resin and polystyrene–b-polybutadiene

Thermoset/thermoplastic elastomer (TPE) blends of poly(propylene glycol) (PPG)-type epoxy resin (ER) and a diblock copolymer, polystyrene–b-polybutadiene (SB, with 30% styrene content), were prepared using 4,4′-diaminodiphenylmethane (DDM) as curing agent. The miscibility and thermal transition behavior of DDM-cured ER/SB blends were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The existence of three separate glass transitions, which are independent of the blend composition, indicates that SB is immiscible with DDM-cured ER. Neither the PS block nor the PB block exhibits miscibility with the cured ER. There exist three phases in the blends: a PS microphase, an ER-rich phase and a PB microphase. The phase structure and morphology of the ER/SB blends were studied using both scanning and transmission electron microscopy (SEM and TEM); a variety of morphologies were observed, depending on the blend composition. For the blends with 5 and 10 wt% SB, SB domains with irregular shapes and broadly distributed sizes are dispersed in a continuous cured ER matrix. For the blends with 20–60 wt% SB, interpenetrating bicontinuous phase structures are observed. For the blends with 70 wt% and more SB, a dispersion of cured ER particles in the SB matrix is obtained. The TEM observation showed that the two phases in the blends exhibit a good interfacial adhesion. The interfacial layer between the ER and SB phases varies from 100 to 300 nm for the blend with 20 wt% SB content, SB micelles are formed surrounding the SB domains in the ER matrix. Small-angle X-ray scattering (SAXS) experiments reveal that the SB diblock polymer still exhibits a lamellar microphase structure within the SB phase and the long spacing of lamellae nearly does not change in the blends. The SB diblock copolymer is microphase separated in the macroscopically phase separated ER/SB blends.     

Preparation,morphology, and mechanical properties of elastomers based on polydimethylsiloxane/ polystyrene blends

Polydimethylsiloxane/polystyrene (PDMS/PS) blends were prepared by radical copolymerization of styrene (St) and divinylbenzene (DVB) in the presence of α,ω‐dihydroxy‐polydimethylsiloxane (PDMS), using benzoyl peroxide as initiator. The PDMS/PS blends obtained by this method are a series of stable, white gums, when the feed ratio of PDMS to St is 60/40 and DVB to St is not more than 2.0 wt %. Elastomers based on PDMS/PS blends were formed by crosslinking PDMS with methyl‐triethoxysilicane (MTES). The MTES dosage was much larger than the amount necessary for end‐linking hydroxy‐terminated chains of PDMS, with the excess being hydrolyzed to crosslinked networks, which were similar to SiO₂ and acted as filler. Mechanical property measurements show that the elastomers thus formed exhibit superior mechanical properties with respect to pure PDMS elastomer and the elastomers based on PDMS/PS system we prepared before. Moreover, investigations were carried out on the elastomers by extraction measurement and scanning electron microscopy (SEM). The extraction data show that the sol‐fraction decreases with increasing the feed ratio of DVB to St. SEM observation demonstrates that the elastomer has a microphase‐separated structure consisting of dispersed PS domains within a continuous PDMS matrix, and the extracted material exhibits a porous structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adhesion between individual components and mechanical properties of natural rubber-polypropylene thermoplastic elastomeric blends

Adhesion between individual components and the mechanical properties of natural rubber (NR)-polypropylene (PP) thermoplastic elastomeric blends with reference to adhesion have been studied. The adhesion strength between the component phases was varied by incorporating a third component, namely ethylene propylene diene rubber (EPDM) or chlorinated polyethylene (CPE), and their effects on the mechanical properties were also studied. It was observed that the level of adhesion between NR and PP is improved by incorporating 20 parts of EPDM or CPE in NR. The mechanical properties of the blends are also improved for a particular composition. The enhancement in the strength properties and modulus of an NR:X:PP (where X is the third component) (70:10:30 or 70:20:30) blend is apparent when a correction due to the hard-phase contribution of the blend is made by taking the ratio of the strength of the composite to the strength of the hard phase or modulus of the blends. When the three-component blends were compared with a 90:30 blend of NR-PP, the role of adhesion played by EPDM or CPE in improving the strength and modulus could be demonstrated. In fact, there is a direct qualitative relationship between the adhesion and the mechanical properties in such composites. The stronger the adhesion, the greater the tensile strength and modulus. The higher adhesion strength is further reflected from the morphology of various blends. Separation of the phases during swelling and subsequent drying is restricted in the systems exhibiting higher adhesion strength between the components.     

共混热塑性弹性体热熔压敏胶的制备及性能研究

以苯乙烯热塑性弹性体(HYBRAR7311)和丙烯酸酯热塑性弹性体(LA2250)为主体树脂,2种材料优势互补,制备的热熔压敏胶(HMPSA)性能优良,且工艺设备简单。采用正交实验较优热熔压敏胶配比,在此基础上探讨了填料硅微粉对热熔压敏胶性能的影响,并比较了较优配方热熔压敏胶与自制SIS热熔压敏胶和乳液压敏胶的力学性能。针对3种压敏胶力学性能上的差异,对3种压敏胶的粘弹性能进行了对比研究,结果表明,压敏胶在低频区(0.01~0.1 Hz)贮能模量越小,初粘性越大,E’’(f 1)/E’(f 2)越大(f 1=32.03 Hz,f 2=0.07 Hz),剥离强度越大。     

PA1010/TPU共混物流变性能的研究

以尼龙1010(PA1010)为基体，以聚酯型热塑性聚氨酯弹性体(TPU)为增韧剂，采用Haake PTW16／25p型双螺杆挤出机制备了PA1010／TPU共混增韧尼龙材料。测试了PA1010／TPU共混物的表观粘度、非牛顿指数等流变参数，并重点讨论了其流变性能。实验结果表明：共混物熔体的表现粘度随剪切速率的增大而降低，非牛顿指数小于1，符合假塑性流体流动规律。此外共混物的表观粘度随着组成和温度的变化呈现了一种极为特殊的变化行为。即在相同温度下，共混物的表观粘度随着TPU含量增加而增加；在相同组成下，共混物的表观粘度随着温度升高而升高。     

低硬度EPDM/PP热塑性弹性体力学性能的研究

就不同参数的三元乙丙橡胶(EPDM)、酚醛树脂硫化剂用量和催化剂与活化剂质量比对三元乙丙橡胶／聚丙烯(EPDM／PP)热塑性弹性体的力学性能和交联密度的影响进行了研究，结果表明：选择END型高不饱和度、适中乙烯含量、高充油型EPDM是制备低硬度热塑性弹性体的较佳选择；当酚醛树脂用量5-7份，催化剂／活化剂质量比为0．12—0．2时，获得的弹性体综合力学性能最好；比较发现，自制的低硬度热塑性弹性体力学性能已接近或达到国外同类产品水平。     

SBR/PP动态硫化热塑性弹性体的制备及其力学性能的研究

研究了聚丙烯（PP）牌号、橡塑比、硫化体系和不同填料对丁苯橡胶／聚丙烯（SBR／PP）动态硫化热塑性弹性体力学性能的影响。研究结果表明：选用牌号为EPC-30R—H的PP与SBR共混，橡塑比为70／30（质量比），硫磺的用量为1．25份左右（或DCP的用量为1．5份左右），沉淀白炭黑用量为30份，而滑石粉用量为30份时，共混物的综合力学性能较好。     

Polyethylene-octene elastomer/starch blends: miscibility,morphology and mechanical properties

In this paper, polyethylene-octene elastomer (POE) and starch blends were studied. The compatibility beyween POE and starch was improved by adding polyethylene-octene/maleic anhydride graft copolymer (POE-MA) as compatibilizer. The compatibilization reaction was followed by FTIR spectra. The morphology of the blends was investigated using scanning electron microscopy (SEM). It was found that the size of the starch phase increased with an increasing content of starch for the blends. The addition of POE-MA can lower the size of the starch phase in the POE matrix, and this was due to the formation of an ester carbonyl function group by the chemical reaction between the anhydride groups and hydroxyl groups on starch. This was reflected in the mechanical properties of the blends, the addition of POE-MA compatibilizer can improve the mechanical properties of POE/starch blends. The thermogravimetric analysis of POE/starch blends was also conducted.     

Rheological and mechanical properties of thermoplastic polyurethane elastomer derived from CO2 copolymer diol

CO₂ copolymer diol‐based thermal polyurethane elastomers (PPC‐TPU) were prepared by the reaction of CO₂ copolymer diol and methylene diphenyl diisocyanate and chain extender (ethylene glycol/1,4‐butanediol/1,6‐hexanediol) (EG/BDO/HG). The rheological and mechanical properties of PPC‐TPU were analyzed. The effects of shear rate, shear temperature, hard segment content, and variety of chain extender on the properties of PPC‐TPU were studied. The results showed that the apparent viscosity (η) of PPC‐TPU decreased with the increasing shear rate (τ), and the non‐Newtonian index (n) was less than 1. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. The degradation during the processing was obviously inhibited by adding plasticizer and antioxidant. It was also discovered that the apparent viscosity varied with the content of hard segment and chain extender. Under the same temperature (185 °C) and shear rate (50 s^?1), the apparent viscosity increased considerably with the raise of hard segment content, and the apparent viscosity and tensile strength of PPC‐TPU with EG as chain extender was the maximum. It can be seen that with the apparent shear rate increasing, the variation tendency of apparent shear stress levels off, and the nonlinear relationship of τ–γ curve tended to be obvious. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45974.     

Compatibilisation of various PLA/thermoplastic elastomer blends with diisocyanate coupling agent

Poly(lactic acid) (PLA) is characterised by its inherent brittleness, a detrimental feature for the production of durable bioplastics. PLA has been toughened by a low amount (12?wt-%) of various thermoplastic elastomers (TPE) including poly(ether-b-ester) (PEEs), poly(ether-b-amide) (PEBA) and poly(ether-b-urethane) (PEU). PLA–TPE blends were prepared by using a twin screw extruder. Ductility and impact resistance can be slightly improved with the incorporation of TPEs but but PEBA appears the most efficient. Reactive compatibilisation has been performed with the addition in the melt of a low amount (2?wt-%) of 4,4-methylene diphenyl diisocyanate. All compatibilised blends exhibit high toughness with similar ductility. These blends preserve good stiffness and high tensile strength. Compatibilised PEBA blends can be considered as super tough poly(lactic acid) materials. This work confirms that the flexibility of the elastomer together with the quality of the interfacial adhesion between the rigid (PLA) and the soft (TPE) phases are the primary factors influencing the toughness.     

Rheological,mechanical, thermal,and morphological properties of blends poly(butylene adipate-co-terephthalate), thermoplastic starch,and cellulose nanoparticles

The objective of the present study was the preparation and characterization of poly(butylene adipate-co-terephthalate) (PBAT) and thermoplastic starch (TPS) blends reinforced with cellulose nanoparticles (CNCs) by extrusion. The work was conducted in four steps. Initially, the CNCs were prepared from eucalyptus cellulose pulp by acid hydrolysis. The second step was the preparation of the nanocomposite (TPS-CNC), composed of cassava starch, CNC, glycerol, and citric and stearic acids, by double screw extrusion. The third step was the preparation of PBAT/TPS-CNC blends in twin-screw extruders. In the fourth step, the films were produced by flat extrusion. Blends exhibited similar rheological behavior, increasing the CNC concentration in blends increased the viscosity as a function of the shear rate, and altered the behavior of the shear storage (G′) and shear loss (G″) curves as a function of the oscillation frequency (ω). The presence of CNC in blend provided improvements significant in mechanical properties, with 120% increase in Young's modulus, and 46% increase in maximum tensile. Thermal behavior (thermogravimetric analysis and differential scanning calorimetry) was altered with the incorporation of the CNC, showing a single melt peak (T_m) and a slight increase in T_g, indicating good dispersion between the phases of the blends, corroborating with the fracture surface microscopy of films.     

Mechanical and thermal properties of polyolefin thermoplastic elastomer blends

ABSTRACT

Polyolefin thermoplastic elastomers (POEs) are a class of thermoplastic elastomer (TPE) that can be easily processed. POEs have broad applications from automobiles to footwear and it is desirable to be able to alter the microstructure and properties. In this work, a systematic study of how blending and thermal processing of POEs affects mechanical and thermal properties is undertaken. Ethylene-octene copolymer POEs with different degrees of crystallinity are blended, compounded, and moulded and then slow cooled, quenched, or annealed. Differential scanning calorimetry (DSC) results show that the blends are immiscible and that quenching suppresses crystallinity while annealing thickens crystals. More crystals of the same thickness or thicker crystals of the same amount in the blends result in a higher modulus, lower elastic recovery, and more residual strain or permanent deformation after tensile testing. Microstructural control will allow for the optimal design of elastomeric materials with anticipated properties.     

Morphologies and mechanical properties of polylactide/thermoplastic polyurethane elastomer blends

To explore a potential method for improving the toughness of a polylactide (PLA), we used a thermoplastic polyurethane (TPU) elastomer with a high strength and toughness and biocompatibility to prepare PLA/TPU blends suitable for a wide range of applications of PLA as general‐purpose plastics. The structure and properties of the PLA/TPU blends were studied in terms of the mechanical and morphological properties. The results indicate that an obvious yield and neck formation was observed for the PLA/TPU blends; this indicated the transition of PLA from brittle fracture to ductile fracture. The elongation at break and notched impact strength for the PLA/20 wt %TPU blend reached 350% and 25 KJ/m², respectively, without an obvious drop in the tensile strength. The blends were partially miscible systems because of the hydrogen bonding between the molecules of PLA and TPU. Spherical particles of TPU dispersed homogeneously in the PLA matrix, and the fracture surface presented much roughness. With increasing TPU content, the blends exhibited increasing tough failure. The J‐integral value of the PLA/TPU blend was much higher than that of the neat PLA; this indicated that the toughened blends had increasing crack initiation resistance and crack propagation resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

动态硫化对聚烯烃热塑性弹性体力学性能的影响

通过分析动态化过程中橡胶相硫化和相反转之间的关系,从粘弹性角度出发,提出用压敏模型来描述橡胶弹性对橡塑间界面结构全的影响,此模型讨论了硫化速度和剪切速度对界面和力学性能的影响。采用分步动态硫化法使弹性体的力学性能得到明显提高。     

Morphology and mechanical properties of polyolefinic thermoplastic elastomer I. Characterization of deformation process

The structural origin of rubber elasticity in the polyolefinic thermoplastic elastomers composed of isotactic polypropylene (iPP) matrix and ethylene-propylene-diene rubber (EPDM) domains was investigated using scanning and transmission electron microscopes under uniaxial deformation and the computational analysis by a three dimensional finite element method. The rubber domains were dominantly deformed and elongated by accompanying localized yielding in iPP region between neighboring EPDM domains perpendicular to the stretching direction. The iPP region between adjacent EPDM domains in the stretching direction remained undeformed, suggesting that the undeformed iPP region plays the role in connecting rubber domains.