动态硫化溴化丁基橡胶/聚丙烯热塑性弹性体制备及性能的影响因素

采用密炼工艺制备了动态硫化溴化丁基橡胶(BIIR)/聚丙烯(PP)热塑性弹性体(TPV),考察了加工温度、硫化时间对TPV力学性能、微观相态结构、交联密度和流动性的影响。结果表明,当加工温度为180℃时,TPV的力学性能较好,且橡胶相粒子均匀分散于树脂相中。在TPV制备过程中,当硫化时间为10～12min时,胶料的交联密度趋于稳定,胶料达到完全硫化;在硫化3min时,共混物完成了以BIIR和PP为双连续相到以BIIR为分散相、PP为连续相的转变;随着硫化时间的延长,TPV的流动性逐渐增加。     

CIIR/PA12 TPV的制备与性能研究

采用动态硫化方法制备CIIR/聚十二内酰胺(PA12)热塑性硫化胶(TPV),研究CIIR/PA12共混比、硫化剂用量、相容剂品种和动态硫化加工工艺对CIIR/PA12 TPV物理性能、流变性能和气密性的影响.结果表明,采用双螺杆挤出机进行动态硫化,当CIIR/PA12共混比为65/35～60/40、N,N'-间亚苯基双马来酰胺亚胺用量为2份、添加5份相容剂马来酸酐接枝聚丙烯时,CIIR/PA12 TPV的物理性能、流变性能和气密性较好.     

EPDM／HDPE热塑性硫化胶的结构与性能研究

采用动态硫化法制备了三元乙丙橡胶（EPDM）／高密度聚乙烯（HDPE）热塑性硫化胶（TPV）,并对其力学性能和微观相结构进行了研究。结果表明。EPDM/HDPE TPV的力学性能随HDPE含量的增加而提高,其应力-应变曲线呈现出典型的弹性体特征;当EPDM／HDPE共混比为60／40时,所制备的TPV表现出了良好的综合性能;EPDM分散相的粒径在1～20μm之间且较均匀地分散于基体中;HDPE连续相在拉伸断裂过程中于断面处形成了成簇的纳米级微纤维;TPV两相结合良好。     

硫化体系对动态硫化NBR/PA6热塑性硫化胶性能的影响

采用动态硫化法制备NBR/聚己内酰胺(PA6)热塑性硫化胶(TPV),研究硫化体系对其性能的影响.结果表明:与硫化剂HVA-2/促进剂DM硫化体系相比,采用硫化剂SP-1045/促进剂氯化亚锡硫化体系制备NBR/PA6TPV的加工性能和物理性能较好,且体系中PA6结晶度较小;当硫化剂HVA-2/促进剂DM并用比为1.95/0.49或硫化剂SP-1045/促进剂氯化亚锡并用比为2.6/0.32时,制备NBR/PA6 TPV的NBR分散相粒径较小、分散较均匀和综合物理性能较好.     

高密度聚乙烯/硅橡胶热塑性硫化胶的制备与性能

采用动态硫化法制备了高密度聚乙烯（HDPE）/硅橡胶（MVQ）热塑性硫化胶（TPV）,考察了HDPE与MVQ的质量比及压片工艺对TPV的硫化特性、力学性能及表面亲疏水性能的影响。结果表明,随着MVQ用量的增加,TPV的动态硫化程度逐渐升高。随着压片时间的延长,TPV的拉伸强度、撕裂强度和扯断伸长率均大幅提高。随着MVQ用量的增加,TPV与水的接触角逐渐增加,相应的表面张力逐渐减小。     

Pt催化剂对动态硫化SR/TPU热塑性弹性体力学性能及相态结构的影响

采用动态硫化法制备了加成型有机硅橡胶(SR)/聚氨酯(TPU)热塑性弹性体(TPV),系统研究了Pt催化剂含量对共混扭矩、SR相交联度、SR/TPU热塑性弹性体相形态以及力学性能的影响。结果表明:随着Pt催化剂含量的增加,橡胶相交联度以及试样力学性能逐渐提高;当Pt催化剂含量高于0.16 phr,交联度基本保持不变,TPV的力学性能稳定。相态结构研究表明:随着动态硫化的进行,体系发生由双连续相向"海-岛"结构的相反转,且随着Pt催化剂含量的提高和硫化时间的延长,橡胶相尺寸减小。此外,还研究了SR/TPU配比对其TPV力学性能的影响,发现当SR/TPU配比为60/40时,热塑性弹性体的综合力学性能最佳。     

三元乙丙橡胶/聚丙烯动态硫化热塑性弹性体的相态结构

用扫描电镜研究了三元乙丙橡胶(EPDM)聚/丙烯(PP)动态硫化热塑性弹性体(TPV)相态结构的形成过程,探讨了交联密度、制备工艺、螺杆转速对EPDM/PP TPV相态结构的影响。结果表明,采用以酚醛树脂为硫化剂的动态硫化工艺制备的EPDM/PP TPV,其相态结构实现了由EPDM和PP组成的双连续相到以EPDM为分散相、PP为连续相的转变;当硫化剂用量为7份时,橡胶相硫化速率和交联密度最大;当螺杆转速为180 r/m in时,反应性挤出工艺较之密炼机工艺制备的EPDM/PP TPV的橡胶粒子更细小、分散更均匀。     

硫化体系对氯化丁基橡胶/尼龙12动态硫化胶性能的影响

研究了氧化锌、N,N’-间苯撑双马来酰亚胺(HVA-2)/氧化锌和1,3-双柠糠酰亚胺甲基苯(PK 900)/氧化锌3种硫化体系下氯化丁基橡胶(CIIR)/尼龙(PA)12混炼胶的硫化特性及CIIR/PA 12动态硫化胶(TPV)的物理机械性能和微观相结构,并考察了PK 900与氧化锌不同配比对CIIR/PA 12TPV物理机械性能、流变性能及微观相结构的影响。结果表明,PK 900/氧化锌的硫化速率介于氧化锌和HVA-2/氧化锌两者之间,由其制备的TPV橡胶相粒径为1～2μm,均匀分布在树脂相中,物理机械性能最优;固定PK 900用量为3份时,随着氧化锌用量的减少,CIIR/PA 12 TPV的拉伸强度、扯断伸长率和100%定伸应力均呈现先增大后减小的趋势;当PK 900/氧化锌(质量比)为3/5时,CIIR/PA 12TPV的物理机械性能最佳,且呈现低剪切速率高黏度、高剪切速率低黏度的特性。     

聚乳酸/邻苯二甲酸二辛脂/丁腈橡胶热塑性硫化胶的形态演变

采用动态硫化法制备了聚乳酸(PLA)/邻苯二甲酸二辛脂(DOP)/丁腈橡胶(NBR)共混型热塑性硫化胶(TPV),通过场发射扫描电子显微镜研究了动态硫化过程中橡胶相的形态演变,采用能量分散X射线谱研究了动态硫化产物微观相态的结构,并考察了动态硫化时间对TPV力学性能的影响。结果表明,随着动态硫化反应的进行,NBR相在交联的同时增大了与树脂相之间的黏度差,并形成独特的双连续相结构。在动态硫化过程中,两相的尺寸均随动态硫化时间的延长而明显减小,并由此带来了TPV力学性能的改善。     

动态硫化工艺对丁基橡胶/聚丙烯热塑性硫化胶性能的影响

考察了3种不同动态硫化工艺(M 1、M 2和M 3)对丁基橡胶(IIR)/聚丙烯(PP)热塑性硫化胶(TPV)结构与性能的影响,并考察了转子转速和动态硫化时间对IIR/PP TPV物理机械性能的影响。结果表明,不同动态硫化工艺制备的TPV的Payne效应均随着应变的增大而减小,采用M 3工艺制备的TPV的网络结构最强。采用3种工艺制备的TPV的拉伸强度由大到小依次为:M 3、M 2、M 1。采用M 2和M 3工艺制备的TPV中IIR与PP相容性较好。不同动态硫化工艺制备的TPV中IIR均呈不规则长条状分散在PP中,采用M 1工艺制备的TPV中交联IIR颗粒的尺寸最大,采用M 3工艺制备的TPV中交联IIR相颗粒和滑石粉填料分散较均匀。随着动态硫化过程中转子转速的提高及动态硫化时间的延长,采用M 3工艺制备的TPV的拉伸强度和扯断伸长率均先增加后减小。当转子转速为80 r/min、动态硫化时间为5 min时,IIR/PP TPV的物理机械性能较好。     

剪切速率对乙烯-丙烯酸酯橡胶/聚偏氟乙烯热塑性硫化胶性能的影响

采用动态硫化法制备了乙烯-丙烯酸酯橡胶（AEM）/聚偏氟乙烯（PVDF）热塑性硫化胶（TPV）,考察了动态硫化过程中转子剪切速率对TPV微观相态结构及性能的影响。结果表明,动态硫化过程中转子的剪切速率越快,AEM和PVDF更易发生相转变,微观相态结构更加精细,形成具有“海-岛”结构的TPV。随转子的剪切速率加快,TPV的拉伸强度和扯断伸长率均先增大后减少。当剪切速率为75 r/min时,AEM/PVDF TPV具有较好的力学性能,拉伸强度达到14.84 MPa,扯断伸长率为246%,TPV具有更加优异的耐热油和热空气老化性能。     

Study on the microstructure and properties of bromobutyl rubber (BIIR)/polyamide‐12 (PA12) thermoplastic vulcanizates (TPVs)

In this study, polyamide‐12 (PA12)/brominated isobutylene‐isoprene (BIIR) TPVs with good mechanical properties and low gas permeability were prepared by dynamic vulcanization in a twin‐screw extruder. The effects of three kinds of compatibilizers on the microstructure and properties of BIIR/PA12 TPV were studied. The compatibility between BIIR and PA12 was improved when maleated hydrocarbon polymeric compatibilizer is added. The reaction between maleic anhydride and amine in polyamide leads to the in situ formation of hydrocarbon polymer grafted polyamide which subsequently can be used to lower the interfacial tension between BIIR and polyamide. The compatibilizing effect of maleic anhydride modified polypropylene (PP‐g‐MAH) on BIIR/PA12 blends is the best among these compatibilizers because the surface energy of PP‐g‐MAH is very close to that of BIIR. The dispersed rubber phase of the blend compatibilized by PP‐g‐MAH shows the smallest size and more uniform size distribution, and the resulting TPVs show the best mechanical properties. The effects of fillers on the properties of BIIR/PA12 TPV were also investigated. The size of the BIIR phase increases with the increase in the content of CaCO₃. The modulus and tensile strength of TPVs increased with the increase in the content of CaCO₃ because of the reinforcing effect of CaCO₃ on TPVs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43043.     

动态硫化丁腈橡胶/尼龙6热塑性弹性体的制备及性能

采用动态硫化法制备了丁腈橡胶/尼龙6热塑性弹性体(NBR/PA 6 TPV),考察了硫化体系、羧基丁腈橡胶(XNBR)以及增塑剂高密度氧化聚乙烯蜡(AC-316 A)和正丁基苯磺酰胺(BBSA)对TPV硫化特性、力学性能和微观形貌的影响。结果表明,以促进剂HVA-2/促进剂DM为硫化体系,动态硫化过程体系黏度的变化比以酚醛树脂/SnCl2为硫化体系时更平稳;但用后者制备TPV,其撕裂强度和扯断伸长率等力学性能更优,PA 6的结晶度更低。XNBR能对NBR和PA 6起到增容作用,当XNBR与NBR的质量比为10/90时,TPV的力学性能最好,NBR在PA 6中分散得最均匀。AC-316 A和BBSA都能对TPV起到增塑作用,随其用量的增加,体系黏度降低。     

Thermoplastic natural rubber based on polyamide‐12: Influence of blending technique and type of rubber on temperature scanning stress relaxation and other related properties

Thermoplastic natural rubber based on polyamide‐12 (PA‐12) blend was prepared by melt blending technique. Influence of blending techniques (i.e., simple blend and dynamic vulcanization) and types of natural rubber (i.e., unmodified natural rubber (NR) and epoxidized natural rubber (ENR)) on properties of the blends were investigated. It was found that the simple blends with the proportion of rubber ～ 60 wt % exhibited cocontinuous phase structure while the dynamically cured blends showed dispersed morphology. Furthermore, the blend of ENR exhibited superior mechanical properties, stress relaxation behavior, and fine grain morphology than those of the blend of the unmodified NR. This is attributed to chemical interaction between oxirane groups in ENR molecules and polar functional groups in PA‐12 molecules which caused higher interfacial adhesion. It was also found that the dynamic vulcanization caused enhancement of strength and hardness properties. Temperature scanning stress relaxation measurement revealed improvement of stress relaxation properties and thermal resistance of the dynamically cured ENR/PA‐12 blend. This is attributed to synergistic effects of dynamic vulcanization of ENR and chemical reaction of the ENR and PA‐12 molecules. Furthermore, the dynamically cured ENR/PA‐12 blend exhibited smaller rubber particles dispersed in the PA‐12 matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

增塑体系对CIIR/PA12 TPV性能的影响

采用动态硫化方法制备CIIR/聚十二内酰胺(PA12)热塑性硫化胶(TPV),研究增塑剂环烷油、聚异丁烯和N-丁基苯磺酰胺对CIIR/PA12 TPV物理性能、流变性能、结晶性能、动态力学性能和气密性的影响.结果表明:N-丁基苯磺酰胺对CIIR/PA12 TPV有一定的增塑效果;与环烷油和聚异丁烯相比,N-丁基苯磺酰胺...     

Scrutinizing the influence of peroxide crosslinking of dynamically vulcanized EVA/TPU blends with special reference to cable sheathing applications

A novel thermoplastic vulcanizate (TPV) based on the blends of ethylene vinyl acetate/thermoplastic polyurethane (EVA/TPU) at various blend ratios has been developed via dynamic vulcanization at 180 °C using di‐(2‐tert‐butyl peroxy isopropyl) benzene (DTBPIB) peroxide as the cross‐linking agent. Modification of the EVA/TPU blends via dynamic crosslinking significantly improves the tensile strength and modulus of the system and the improvement is more significant for EVA/TPU 50/50 and 60/40 blends. AFM study shows that crosslinked EVA particles are dispersed in the continuous TPU matrix and the dispersed EVA domain sizes are relatively smaller in EVA/TPU 50/50 and 60/40 blends leading to good mechanical properties. FTIR spectroscopy has been used to characterize the specific chemical changes occurring due to dynamic vulcanization. This TPV has excellent retention of physico‐mechanical properties even after reprocessing twice and the blends also have very good thermal resistance as indicated by aging study. The samples were found to exhibit remarkable improvement in oil resistance property as compared to their uncrosslinked counterpart. The creep behavior of the blends significantly improves after dynamic crosslinking and blends with higher TPU content show better creep resistance. Volume resistivity of all the peroxide vulcanized blends is in the range of 10¹³ ohm cm, which is suitable for cable sheathing application. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43706.     

动态三螺杆挤出机制备热塑性硫化胶的研究

对比分析了动态热塑性硫化胶(TPV)的加工设备,着重介绍了附加振动力场的三螺杆反应挤出机的结构特点以及利用该机进行三元乙丙橡胶/聚丙烯(EPDM/PP)的动态全硫化,对制品的物理力学性能和微观结构分别进行了测试分析和电镜扫描。结果表明,振动力场作用下EPDM/PP共混体系反应挤出动态硫化加工可有效地实现动态硫化反应、硫化橡胶的粉碎和分散以及相态反转,振动力场的作用明显提高了TPV性能。     

Morphological evolution and property changes of acrylate rubber/polyacetal thermoplastic vulcanizates during dynamic vulcanization process

A new type of thermoplastic vulcanizates (TPV) that is resistant to hot oil, high temperature, and aging was prepared using acrylate elastomer (ACM) and polyoxymethylene (POM) as raw materials. The phase transition process and micromorphology development of the blends with the change of dynamic vulcanization (DV) time, and to illustrate the effects of the phase transition and the degree of elastomer phase crosslinking on the macroscopic properties of TPV were investigated. It was shown that ACM crosslinking occurs continuously during 0–8 min of DV, whereas the phase inversion process occurs predominantly during 0–3 min. In contrast, the cross-section of the blends after phase inversion is flat, The constant elongation stress under small deformation, hardness, and permanent deformation after break are reduced, and the elongation at break, nonrelaxable modulus, and aging resistance are improved. The increase in the degree of vulcanization of the ACM phase resulted in a significant increase in the modulus of the blends under large deformation, an increase in the nonrelaxable modulus and relaxable modulus, an increase in the aging resistance, and a decrease in the elongation at tear were observed.