EPDM熔融接枝甲基丙烯酸缩水甘油酯及其与NR动态硫化共混物的性能

研究了三元乙丙橡胶熔融接枝甲基丙烯酸缩水甘油酯（ＧＭＡ）的接枝反应温度、过氧化二异丙苯（ＤＣＰ）及ＧＩＭ用量对ＥＰＤＭ－ｇ－ＧＭＡ／ＮＲ动态硫化共混物力学性能的影响。结果表明：与直接静硫化胶相比,动态硫化胶的拉伸强度提高了４８．２％;接枝反应温度８为１６０℃、ＤＣＰ用量为０．３份、ＧＭＡ用量为３￣５份时,动态硫化共混物的力学性能较好。另外红外光谱测试结果表明,在ＥＰＤＭ上已成功接枝了ＧＭＡ。     

On the compatibilization and dynamic vulcanization of polyacetal/ethylene propylene diene terpolymer blends

This study describes an attempt to improve the impact resistance of polyacetal (POM)/ethylene propylene diene terpolymer (EPDM) blends by means of compatibilization and dynamic vulcanization. A commerical copolymer, poly(acrylic acid)-grafted polypropylene (PGP), has been used as a compatibilizer to control the phase morphology of the blend system. Dicumyl peroxide is used to dynamically vulcanize the EPDM elastomer in the blend. At temperatures higher than 185°C, the compatibilizer decreases the viscosity of compatibilized and dynamically vulcanized (cdv) POM/EPDM blends. Impact strength of the cdv blend system increases considerably with a marginal decrease in tensile yield stress and heat deflection temperature as the PGP content increases. The significant increase in impact strength seems to be due to the role of PGP as a linking agent for the binary blends rather than as a third component. Though dynamic mechanical studies do not indicate any compatibility in cdv-POM/EPDM blends, scanning electron microscopy reveals the strong interpenetrating interphase in the compatibilized blend system. Dynamic vulcanization raises elastic recovery and tensile modulus of the blends. Hysteresis energies of the blends increase consistently with the addition of PGP. The crystalline structure of POM is not affected by compatibilization and vulcanization. © 1994 John Wiley & Sons, Inc.     

氟橡胶/EPDM动态硫化共混物的研究

研究了动态硫化工艺条件和共混比对氟橡胶（ＦＫＭ）／ＥＰＤＭ共混物拉伸性能拉、热油老化性能和应力松弛性能的影响。结果表明：与直接静态硫化相比,动态硫化可避免两种硫化体系的相互影响;静态硫化共混物拉伸强度只有２ＭＰａ,而动态硫化共混物可达１０ＭＰａ以上;工艺条件对动态硫化共混物性能的影响不大;随共混物中ＥＰＤＭ用量的增大,共混物的热空气老化和热油老化性能均有所下降     

The control of miscibility of PP/EPDM blends by adding lonomers and applying dynamic vulcanization

The control of miscibility for isotactic polypropylene (PP) and ethylene-propylene-diene terpolymer (EPDM) has been attempted by adding poly(ethylene-comethacrylic acid) (EMA) ionomers and by applying dynamic vulcanization. The rheological properties, crystallization behavior, and morphology of the dynamically vulcanized EPDM/PP/ionomer ternary blends were investigated with a Rheometrics dynamic spectrometer (RDS), a differential scanning calorimeter (DSC), and a scanning electron microscope (SEM). Two kinds of EMA ionomers neutralized with different metal ions (Na⁺ and ZN⁺⁺) were investigated. Blends were prepared on a laboratory internal mixer at 190°C. Blending and curing were performed simultaneously, i.e., EPDM was vulcanized with dicumyl peroxide (DCP) in the presence of PP/ionomer. The composition of PP and EPDM was fixed at 50/50 by wt% and the contents of EMA ionomer were vaired from 5 to 20 parts based on the total amount of PP and EPDM. It was found that the addition of ionomers and the application of the dynamic vulcanization were effective in enhancing the miscibility of PP and EPDM. The structure of the blends was controlled by the following three component phases, i.e., the phase of the dynamially valcanized EPDM, PP, and Zn-neutralized ionomer. The ternary blends showed more miscibility than the PP/EPDM binary blend. This is due to the thermoplastic interpenetrating polymer network (IPN) of the ternary blends. The structure and properties of the ternary blends differed, depending on the types and contents of ionomer, i.e., the ternary blend containing Na-neutralized ionomer did not show a thermoplastic IPN structure clearly, even though the blend was prepared by dynamic vulcanization. The ternary blend containing Zn-neutralized ionomer clearly showed the behavior of a thermoplastic IPN when the contents of ionomer and DCP were 15 parts and 1.0 part, respectively.     

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) and ethylene propylene diene rubber

Compatibilized and dynamically vulcanized thermoplastic elastomer blends of poly(butylene terephthalate) (PBT) and ethylene propylene diene terpolymer (EPDM) can be prepared by using an EPDM rubber that contains reactive epoxy groups. During melt mixing the epoxy groups react with PBT endgroups to form graft copolymer. The compatibilized blends can be dynamically vulcanized by conventional vulcanization agents for EPDM such as peroxides or by vulcanization agents that react with residual epoxy groups on the EPDM such as diamines. This paper describes the effects of compatibilization and dynamic vulcanization on microstructure and mechanical properties.     

Mechanical properties,morphological structure,and thermal behavior of dynamically photocrosslinked PP/EPDM blends

A dynamically photocrosslinked polypropylene (PP)/ethylene–propylene–diene (EPDM) rubber thermoplastic elastomer was prepared by simultaneously exposing the elastomer to UV light while melt‐mixing in the presence of a photoinitiator as well as a crosslinking agent. The effects of dynamic photocrosslinking and blend composition on the mechanical properties, morphological structure, and thermal behavior of PP/EPDM blends were investigated. The results showed that after photocrosslinking, tensile strength, modulus of elasticity, and elongation at break were improved greatly. Moreover, the notched Izod impact strength was obviously enhanced compared with corresponding uncrosslinked blend. Scanning electron microscopy (SEM) morphological analysis showed that for uncrosslinked PP/EPDM blends, the cavitation of EPDM particles was the main toughening mechanism; whereas for dynamically photocrosslinked blends, shear yielding of matrix became the main energy absorption mechanism. The DSC curves showed that for each dynamically photocrosslinked PP/EPDM blend, there was a new smaller melting peak at about 152°C together with a main melting peak at about 166°C. Dynamic mechanical thermal analysis (DMTA) indicated that the compatibility between EPDM and PP was improved by dynamic photocrosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3371–3380, 2004     

Tensile properties and morphology of the dynamically cured EPDM and PP/HDPE ternary blends

The tensile properties and morphology of the polyolefin ternary blends of ethylenepropylene–diene terpolymer (EPDM), polypropylene and high density polyethylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured in the presence of PP and HDPE under shear with dicumyl peroxide (DCP). For comparison, blends were also prepared from EPDM which was dynamically cured alone and blended with PP and HDPE later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastics composition was studied. The tensile strength and modulus increased with increasing DCP concentration in the blends of EPDM-rich compositions but decreased with increasing DCP concentration in blends of PP-rich compositions. In the morphological analysis by scanning electron microscopy (SEM), the small amount of EPDM acted as a compatibilizer to HDPE and PP. It was also revealed that the dynamic curing process could reduce the domain size of the crosslinked EPDM phase. When the EPDM forms the matrix, the phase separation effect becomes dominant between the EPDM matrix and PP or HDPE domain due to the crosslinking in the matrix.     

Effect of dynamic crosslinking on tensile yield behavior of polypropylene/ethylene‐propylene‐diene rubber blends

Tensile yield behavior of the blends of polypropylene (PP) with ethylene‐propylene‐diene rubber (EPDM) is studied in blend composition range 0–40 wt % EPDM rubber. These blends were prepared in a laboratory internal mixer by simultaneous blending and dynamic vulcanization. Vulcanization was performed with dimethylol phenolic resin. For comparison, unvulcanized PP/EPDM blends were also prepared. In comparison to the unvulcanized blends, dynamically vulcanized blends showed higher yield stress and modulus. The increase of interfacial adhesion caused by production of three‐dimensional network is considered to be the most important factor in the improvement. It permits the interaction of the stress concentrate zone developed at the rubber particles and causes shear yielding of the PP matrix. Systematic changes with varying blend composition were found in stress‐strain behavior in the yield region, viz., in yield stress, yield strain, width of yield peak, and work of yield. Analysis of yield stress data on the basis of the various expressions of first power and two‐thirds power laws of blend compositions dependence and the porosity model led to consistent results from all expression about the variation of stress concentration effect in both unvulcanized and vulcanized blend systems. Shapes and sizes of dispersed rubber phase (EPDM) domains at various blend compositions were studied by scanning electron microscopy. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2104–2121, 2000     

VMQ/LLDPE动态硫化热塑性弹性体的制备与性能

采用动态硫化法制备了甲基乙烯基硅橡胶(VMQ)/线形低密度聚乙烯(LLDPE)热塑性弹性体。考察了共混比、硫化剂种类、动态硫化时间对VMQ/LLDPE热塑性弹性体力学性能的影响,并研究了VMQ/LLDPE热塑性弹性体的热失重情况。结果表明:共混比为60/40、选用DBPH为硫化剂、动态硫化时间为5 min时,VMQ/LLDPE热塑性弹性体具有较好的力学性能。     

Studies on mechanical and morphological behavior of hybrid nanoclay‐reinforced EPDM‐g‐TMEVS/PS blends

A new copolymer of tris(2‐methoxyethoxy) vinylsilane (TMEVS)‐grafted ethylene–propylene–diene elastomer (EPDM‐g‐TMEVS) has been developed by grafting of TMEVS onto EPDM by using dicumylperoxide (DCP) initiator. The linear polystyrene blends (EPDM‐g‐TMEVS/PS) based on EPDM‐g‐TMEVS have been synthesized with varying weight percentages of polystyrene in a twin‐screw extruder. In a similar manner, the dynamically vulcanized and nanoclay‐reinforced polystyrene blends have also been developed using DCP and organically modified montmorillonite clay separately by means of a twin‐screw extruder. The grafting of TMEVS onto EPDM at allylic position present in the third monomer of EPDM has been confirmed by Fourier Transform infrared spectroscopy. The effect of silane‐grafted EPDM and concentration of nanoclay on mechanical properties of polystyrene blends has been studied as per ASTM standards. The morphological behavior of these blends has been investigated using scanning electron microscope. It was observed that the incorporation of silane‐grafted EPDM enhanced the impact strength and the percentage elongation of linear‐ and dynamically vulcanized blends. However, the values of tensile strength, flexural strength, flexural modulus, and hardness of the blends were found to be decreasing with the increase of silane‐grafted EPDM. In the case of nanoclay‐reinforced polystyrene blends, the values of impact strength, tensile strength, flexural strength, flexural modulus, and hardness were increased with an increase in the concentration of nanoclay. XRD studies have been carried out to confirm the formation of nanoclay‐reinforced EPDM‐g‐TMEVS/PS blends. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and properties of dynamically cured EPDM/PP blends

The structure and properties of polyolefin blends of ethylene–propylene–diene terpolymer (EPDM) and polypropylene were studied. Blends were prepared in a laboratory internal mixer where EPDM was cured with PP under shear with dicumyl peroxide (DCP) at different shear conditions (blend–cure). Blends were also prepared for comparison from EPDM which were dynamically cured in the absence of PP and blended later (cure–blend). The effect of DCP concentration, intensity of the shear mixing, and rubber/plastic composition were studied. In blend–cure, the melt viscosity increased with increasing DCP concentration in blends of 75% EPDM and 25% PP, but it decreased with increasing DCP concentration in blends of 75% PP and 25% EPDM. In cure–blend, however, the melt viscosity increased with increasing DCP concentration for all compositions. The melt viscosity decreased with increasing intensity of the shear mixing presumably due to the formation of the smaller segregated microdomain of the crosslinked EPDM gels in both blend–cure and cure–blend materials. The crystallization rate was higher in EPDM/PP blends than in PP homopolymer. The crystallization rates for various blending conditions were also compared.     

Dynamic properties of rubber vibration isolators and antivibration performance of ethylene–propylene–diene monomer/nylon 6 blend systems

This article examines thermoplastic elastomers (TPEs) and thermoplastic vulcanizates (TPVs) as two types of elastomers from melt-blended and dynamically vulcanized ethylene–propylene–diene monomer (EPDM) rubber materials and nylon 6 plastic materials. A series of investigations were conducted on the mechanical properties, morphology, dynamic mechanical properties, hysteresis behavior, and dynamic antivibration properties with different nylon 6 contents. The experimental results showed that the incompatibility between EPDM and nylon 6 led to the easy destruction of the TPV materials in two interfacial polymers upon the application of an external force. Thus, after a dynamic vulcanization process, the mechanical properties of the EPDM/nylon 6 blends were not as good as those of the TPE materials. In terms of morphology, nylon 6 plastics were uniformly distributed in the EPDM/nylon 6 blends during the EPDM rubber phase before vulcanization was performed. After the dynamic vulcanization, phase inversion was produced in which rubber microparticles were formed and dispersed in the nylon 6 plastic phase. The results of dynamic mechanical analysis, compression vibration hysteresis behavior, and dynamic property antivibration experiments showed that the blends provided better vibration isolation and antivibration performance after the amount of nylon 6 was increased and EPDM and nylon 6 were blended through dynamic vulcanization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effect of the compatibilization of linear low‐density polyethylene‐g‐acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low‐density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low‐density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method. For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE‐g‐AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE‐g‐AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE‐g‐AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/LLDPE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE‐g‐AA decreased. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1059–1066, 2002; DOI 10.1002/app.10399     

氟橡胶/三元乙丙橡胶并用胶的性能

研究了不同并用比(质量比)时氟橡胶(FKM)/三元乙丙橡胶(EPDM)并用胶动态硫化和静态硫化后的低温性能、物理机械性能、耐老化性能和热稳定性,并用扫描电子显微镜表征了并用胶.结果表明,当并用比为30/70时,并用胶有较好的相容性;EPDM可以改善FKM的低温性能;随着EPDM用量的增加,并用胶的拉伸强度及邵尔A硬度降低;动态硫化FKM/EPDM并用胶比静态硫化FKM/EPDM并用胶具有更好的耐老化性能,但老化前前者的拉伸强度稍低于后者;FKM/EPDM并用胶的热稳定性优于纯EPDM;静态硫化FKM/EPDM并用胶中片层现象严重,动态硫化FKM/EPDM并用胶的EPDM包覆在FKM中,但相畴偏大.     

EPDM/ENR共混胶力学性能的研究

探讨了三元乙丙橡胶(EPDM)和环氧化天然橡胶(ENR)的共混比、加料顺序、硫化体系对EPDM/ENR共混物的硫化特性、力学性能和耐热空气老化性能的影响。结果表明,共混比不同,共混胶的性能均有差异,且共混物的力学性能低于单组分的线性加和值,但综合比较而言,当EPDM/ENR=40/60时共混胶的力学性能较好;在所研究的四种加料顺序中,以配合剂先与EPDM制成母炼胶后再与ENR共混的这一种加料顺序下所得的共混物硫化胶的力学性能最好;采用半有效硫化体系所制得的共混物硫化胶的力学性能较好。     

Influence of premade and in situ compatibilizers in polypropylene/ethylene–propylene–diene terpolymer thermoplastic elastomeric olefins and thermoplastic vulcanizates

During dynamic vulcanization of polypropylene (PP)/ethylene–propylene–diene terpolymer (EPDM) blends with dicumyl peroxide/triallyl cyanurate, there is a possibility of the generation of in situ graft links at the interface. Three potential compatibilizers (PP‐grafted EPDM, styrene–ethylenebutylene–styrene, and trans‐polyoctenamer) for PP/EPDM blends were first investigated as references to obtain a quantified insight into the effects to be expected from in situ graft links. Only the first compatibilizer showed some compatibilizing action in straight, unvulcanized blends, as evidenced by a slight increase in the tensile strength of the blend and a somewhat smaller EPDM particle size within the PP matrix. Also, dynamic mechanical testing, in particular, the glass‐transition temperatures of the PP and EPDM components, showed some signs of compatibilization. The PP‐grafted EPDM resembled most closely the structures of PP and EPDM. In the spectra obtained with high temperature, solid‐state NMR, there was an indication that PP–EPDM graft links were generated during the dynamic vulcanization process that still remained after the extraction of the free PP phase from the thermoplastic vulcanizate film. NMR relaxation experiments gave further evidence for the graft links formed in situ. In all cases, only qualitative indications could be achieved because of the extremely low number of graft links formed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3877–3888, 2006     

Dynamic mechanical properties of polypropylene‐g‐maleic anhydride and ethylene–propylene–diene terpolymer blends: Effect of blend preparation methods

In this work, we attempted two different ways of processing to improve interfacial adhesion of polypropylene (PP) and ethylene–propylene–diene terpolymer (EPDM) by introducing maleic anhydride (MAH); In one way, the in situ grafting and dynamic vulcanization (ISGV) were performed simultaneously from PP and EPDM with MAH in the presence of dicumyl peroxide (DCP) in an intensive mixer. In another way, PP was first grafted with MAH and then the PP‐g‐MAH was blended with EPDM in the intensive mixer in the presence of DCP by the dynamic vulcanization (DV). It was found that the glass transition temperatures (T_gs) of both PP and EPDM phases were shifted to higher temperature as the EPDM content increased for the blends prepared by both IGSV and DV methods, mainly due to the crosslinking of EPDM. The higher T_gs and larger storage moduli were observed for the blends prepared by the ISGV method than those prepared by the DV method, while the morphology showed that the size reduction of dispersed particles in latter blends was larger than that of the former blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2777–2784, 2000     

Effect of EPDM on LDPE/LLDPE blends: mechanical properties

Blends of two polyethylenes and an elastomer were prepared to investigate the effect of the latter polymer. The blends contain equal parts of low density (LDPE) and linear low density polyethylene (LLDPE), and ethylene–propylene–diene rubber (EPDM) with variable content ranging from 0 to 17.5%. Melt-mixed blends were prepared using a single-screw extruder. The influence on the mechanical properties of the following factors were analyzed: EPDM content, stretching rate in the range from 10 to 750 mm/min, and two cooling conditions. From the equilibrium torque the miscibility was analyzed. The structure exhibited by the stress–strain (–) curve of the polyethylenes blend is reduced with the addition of the elastomeric phase, and the ultimate properties increase because the amorphous phase becomes softer and reduces its capability to transmit the applied stress to the crystalline particles. The slope of the – curve in the strain hardening region shows a maximum value at the stretching rate ∼ 50–80 mm/min, which is explained partially in terms of the strain-induced crystallization of the polyethylene components. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 677-683, 1997     

The Effect of Dynamic Vulcanization on the Properties of Polypropylene/Ethylene-Propylene Diene Terpolymer/Natural Rubber (PP/EPDM/NR) Ternary Blend

The effects of dynamic vulcanization on the process development and some properties, such as tensile properties, swelling index, gel content, crystallinity, and morphology, of the polypropylene (PP)/ethylene-propylene diene terpolymer (EPDM)/natural rubber (NR) blends were investigated. Dynamically vulcanized blends show higher stabilization torque than unvulcanized blends. In terms of tensile properties, the tensile strength and tensile modulus (stress at 100% elongation, M₁₀₀) of the vulcanized blends have been found to increase as compared with the unvulcanized blends, whereas the elongation at break is higher in the blend with richer EPDM content. These results can be attributed to the formation of cross-linking in the rubber phase. The formation of cross-links in the rubber phase has also been proved by swelling index and gel content. The percentage of crystallinity of the blends is decreased by dynamic vulcanization. Scanning electron microscopy (SEM) micrographs from the surface extraction of the blends support that the cross-links occurred during dynamic vulcanization.     

EPDM/POE动态硫化热塑性硫化胶的性能与结构

采用动态硫化法制备EPDM/聚烯烃弹性体(POE)热塑性硫化胶(TPV),研究共混温度和硫化体系配比对其性能的影响,并对其形态结构进行表征.结果表明:随着共混温度的升高和硫化体系用量的增大,共混体系的硫化速率逐渐加快;TPV的拉伸强度和拉断伸长率在共混温度为150℃左右时达到最大,拉断伸长率随着硫化体系用量的增大而减小,而拉伸强度则先减小后略有增大;随着共混温度的升高和硫化体系用量的增大,TPV撕裂强度呈现先增大后减小趋势;当硫黄用量为0.2份时,体系出现了明显的Payne效应,EPDM交联相以平均粒径为1μm左右的颗粒状态分散于POE连续相中.