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。     

动态硫化对三元乙丙橡胶/聚丙烯共混体系等温结晶行为和形态结构的影响

研究了三元乙丙橡胶/聚丙烯(EPDM/PP)共混物和动态硫化EPDM/PP热塑性弹性体(TPV)的等温结晶行为及形态结构,并用Avrami方程对其进行等温结晶动力学分析。结果表明,EPDM/PP共混物和EPDM/PP TPV的等温结晶行为符合Avrami方程,在相同的结晶温度下,TPV比共混物的Avrami指数小,半结晶时间短,结晶速率常数大;EPDM/PP共混物为双连续相结构,而EPDM/PP TPV是以硫化的细小橡胶颗粒为分散相、PP为连续相的"海-岛"结构,橡胶颗粒尺寸约为0.5μm。     

丁基橡胶/聚丙烯动态硫化热塑性弹性体的制备和性能研究

以丁基橡胶(IIR)和聚丙烯(PP)为基体材料,利用动态硫化的方法制备了丁基橡胶/聚丙烯热塑性弹性体(IIR/PP TPV),主要研究了硫化剂用量和制备工艺参数对IIR/PP TPV力学性能和动态力学性能的影响。结果表明,随着硫化剂用量的增加,IIR/PP TPV的力学性能得到提高,硫化剂用量为9 phr时,IIR/PP TPV的综合性能优异;动态硫化温度为180℃时,IIR/PP TPV有优异的力学性能和阻尼性能;随着动态硫化时间的增加,拉伸强度呈现先增加后减小而断裂伸长率呈现逐渐增大的趋势,硫化时间超过10 min之后,IIR/PP TPV的阻尼性能开始下降,当硫化时间为10 min时,IIR/PP TPV的力学性能和动态力学性能优异。     

挤出工艺对POE/PP热塑性硫化胶性能的影响

采用双螺杆挤出机制备茂金属聚烯烃弹性体(POE)/聚丙烯(PP)热塑性硫化胶(TPV),研究螺杆转速和硫化温度对TPV微观结构和物理性能的影响。结果表明,POE/PPTPV中POE为分散相,PP为连续相;当挤出机螺杆转速为400r.min-1、硫化温度为190～200℃时,TPV的综合物理性能良好。     

硫化体系对动态硫化EPDM/POE热塑性弹性体性能的影响

采用动态硫化的方法在Haake转矩流变仪上制备了三元乙丙橡胶/聚烯烃(EPDM/POE)热塑性弹性体(TPV),并分别对不同硫化体系和硫化剂用量对TPV交联密度和性能的影响进行了研究。结果表明,随硫化剂用量的增加,TPV的交联密度增大,其中硫黄硫化体系的TPV变化最明显;采用硫黄硫化体系和酚醛树脂硫化体系制备的TPV性能优于过氧化物硫化体系,并且DCP和硫黄分别在用量为0.5份,酚醛树脂在1.0份时性能较佳。     

剪切速率对动态硫化PP/EPDM热塑性弹性体相态结构及性能的影响

采用动态硫化法,在双螺杆挤出机中制备以聚丙烯(PP)/三元乙丙橡胶(EPDM)为基体材料的热塑性弹性体,研究螺杆转速对PP/EPDM热塑性弹性体相态结构及性能的影响;采用差示扫描量热(DSC)仪分析了PP/EPDM热塑性弹性体的结晶性能,通过扫描电子显微镜(SEM)分析PP/EPDM热塑性弹性体的微观相态结构,并用万能试验机等对其力学性能进行测试。结果表明,随着螺杆转速的增加,PP/EPDM热塑性弹性体的结晶温度降低,凝胶含量、拉伸强度和断裂伸长率先增大后减小,压缩永久变形先减小后增大,而螺杆转速对硬度的影响不明显。当螺杆转速为180 r/min时,PP/EPDM热塑性弹性体的凝胶含量、拉伸强度和断裂伸长率均达到最大值,分别为56.8%,15.9 MPa和634%,压缩永久变形和硬度(邵A)均达到最小值,分别为68.8%,88。     

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。     

硫化体系对EPDM/PP TPV性能的影响

采用动态硫化的方法用双螺杆挤出机制备三元乙丙橡胶/聚丙烯(EPDM/PP)热塑性弹性体(TPV),研究了硫化体系的变化对TPV熔体流动性、邵尔硬度、拉伸强度、断裂伸长率、100%定伸应力等性能的影响,表征了其微观结构。结果表明,EPDM均匀地分散在PP连续相中,粒经约为0.5μm;随着酚醛树脂硫化体系含量的增加,EPDM大分子链之间相互交联密度增大,使TPV的熔体流动速率减小,体系的硬度增大,但当硫化剂含量过大时,体系的硬度降低;增加酚醛树脂/促进剂的含量,体系的拉伸强度、断裂伸长率和100%定伸应力均增加,但是当硫化剂用量超过一定值时,体系的拉伸强度和断裂伸长率下降,而100%定伸应力变化不大,在生产中需要根据产品最终用途来确定硫化剂使用的最佳量。     

低硬度EPDM/PP热塑性动态硫化胶Ⅱ.制备工艺条件对微观相态结构的影响

通过正交试验设计,研究了低硬度EPDM/PP共混型热塑性动态硫化胶的反应挤出动态硫化制备工艺,初步探讨了机筒温度、喂料螺杆驱动电压及主机螺杆转速等主要工艺因素对挤出物徽观相态结构的影响。     

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。     

The effects of nanoclay dispersion levels and processing parameters on the dynamic vulcanization of TPV nanocomposites based on PP/EPDM prepared by reactive extrusion

The study considers the effects of different dispersion levels of nanoclay on the crosslinking reaction of thermoplastic vulcanizate (TPV) nanocomposites based on polypropylene/ethylene propylene diene M‐class rubber (PP/EPDM). PP nanocomposites with dispersion level ranging from intercalated structures to a mixture of intercalated tactoids and exfoliated layers were used as the thermoplastic phase. Dimethylol phenolic resin or octylphenol‐formaldehyde resin was used as curing agents, along with stannous chloride dihydrate as the catalyst, to vulcanize the rubber phase during the reactive extrusion process. Initially, temperature effects were investigated in internal batch mixer. Subsequently, the effects of screw speed (i.e., shear rate and residence time) were evaluated along the screw length. Different criteria such as nuclear magnetic resonance (NMR) signal line width, bound curative content, and residual diene concentration were used to evaluate the extent of crosslinking, along with normalized storage modulus and gel content. X‐ray diffraction (XRD) analysis and transmission electron microscopy (TEM) micrographs showed that the dynamic vulcanization process improves the dispersion level of nanoclay in the final TPVs. It was found that the presence of nanoclay influences the crosslinking reaction, mainly through its effect on the continuity index of the EPDM phase. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

动态硫化EPDM／PP热塑性弹性体的流变性能

研究了共混工艺条件，橡塑比，橡胶相交联速率及交联密度，ＰＰ的熔体流动指数对ＥＰＤＭ／ＰＰ共混物流变性能的影响。结果表明，当降低ＥＰＤＭ含量，减小ＥＰＤＭ相粒径时，共混物的流动性增强。共混物发生熔体破裂是由于ＥＰＤＭ和ＰＰ相在挤出后两相大分子的弛豫行为不同所致。提高ＰＰ含量，降低了ＥＰＤＭ相粒径，同时ＥＰＤＭ分散相具有适宜的交联密度时，可以得到挤出表面光滑的共混物。     

Phase morphology and melt rheological behavior of uncrosslinked and dynamically crosslinked polyolefin blends: role of macromolecular structure

Thermoplastic vulcanizates (TPVs) based on polypropylene (PP) with ethylene–octene copolymer (EOC) and ethylene propylene diene rubber (EPDM) have been prepared by co-agent-assisted peroxide crosslinking system. The study was pursued to explore the influence of two dissimilar polyolefin polymers having different molecular architecture on the state and mode of dispersion of the blend components and their influence on melt rheological properties. The effects of dynamic crosslinking of the PP/EOC and PP/EPDM have been compared with special reference to the concentration of crosslinking agent and ratio of blend components. Morphological analyses show that, irrespective of blend ratio, dynamic vulcanization exhibits a dispersed phase morphology with crosslinked EOC or EPDM particles in the continuous PP matrix. It was found that viscosity ratio plays a crucial role in determining the state and mode of dispersion of blend components in the uncrosslinked system. The lower viscosity and torque values of uncrosslinked and dynamically crosslinked blends of PP/EOC in the melt state indicates that they exhibit better processing characteristics when compared to corresponding PP/EPDM blends.     

Effects of compounding procedure on morphology development,melt rheology,and mechanical properties of nanoclay reinforced dynamically vulcanized EPDM/polypropylene thermoplastic vulcanizates

New nanocomposite thermoplastic vulcanizates (TPVs) comprising dynamically cross‐linked nanoscale EPDM rubber particles dispersed throughout the polypropylene (PP) matrix have been prepared by both batch and continuous melt blending of PP with EPDM in the presence of vulcanizing ingredients, nanoclay and maleated EPDM (EPDM‐g‐MA) as compatibilizer. X‐ray diffraction, linear melt viscoelastic measurement, and tensile mechanical behavior results revealed that the developed microstructure is strongly affected by the type of the melt compounding process as well as the route of material feeding. When EPDM phase was precompounded with a vulcanizing agent, nanoclay, and EPDM‐g‐MA prior to the melt blending with PP, not only nanosize cross‐linked rubber particles appeared uniformly throughout the PP continuous phase, but also the melt blending leads to the significant enhancement of the mechanical properties compared with counterpart samples prepared by one‐step melt mixing process. Also better dispersion of nano layers in the rubber compound before melt blending with PP results in higher mechanical properties of the resulted TPV. POLYM. ENG. SCI., 56:914–921, 2016. © 2016 Society of Plastics Engineers     

动态硫化EPDM／PP热塑性弹性体的结构与性能

研究了用密炼机制备的ＥＰＤＭ／ＰＰ共混型动态全硫化热塑性橡胶（ＴＰＶ）的拉伸性、耐溶胀性、耐压缩性在各种影响因素下的变化规律。结果表明：在橡塑表面能相近的条件下，选择分子量大且结晶度高的ＰＰ作为基体组分，同时选择具有适宜交联速率的硫化体系作为橡胶相的交联组分制备的ＴＰＶ性能最佳。     

一维多壁碳纳米管增强丁基橡胶/聚丙烯热塑性弹性体复合材料的相态结构及热电性能研究

制备一维多壁碳纳米管(MWCNTs)增强丁基橡胶(IIR)/聚丙烯(PP)动态硫化热塑性弹性体(TPV)复合材料,研究IIR/PP用量比(简称橡塑比)对复合材料相态结构、介电性能、导热性能和物理性能的影响。结果表明:复合材料呈现“海-岛”相结构,IIR相以微米级交联颗粒分散在PP相中;MWCNTs主要分散在PP中,随着橡塑比的增大,MWCNTs有少量团聚现象;随着橡塑比的增大,复合材料的交流电导率、介电常数和热导率增大,且橡塑比大于6/4时增速减小;随着橡塑比的减小,复合材料的拉伸强度先增大后减小;当橡塑比为5.5/4.5时,复合材料的物理性能较好。     

Relationship between the rheology and morphology of dynamically vulcanized thermoplastic elastomers based on EPDM/PP

Relationship between the rheological properties and morphology of dynamically vulcanized thermoplastic elastomers (TPVs) based on Ethylene Propylene Diene Monomer (EPDM) and Polypropylene (PP) blends containing 20, 40 and 60% of EPDM were studied. The samples were prepared in a laboratory internal mixer at a rotor speed of 60 rpm. We performed morphological studies on the cryogenically fractured samples using scanning electron microscopy (SEM). The rheological behavior and melt viscoelastic properties of the samples were studied by rheometric mechanical spectrometry (RMS) at a temperature of 220°C. The TPV samples showed a significant viscosity upturn and a strong storage modulus that tended to plateau at low shear rates, with the highest extent for the sample containing 60% of EPDM. These results were attributed to a network structure resulting from agglomerates formed between the cured rubber particles, as evidenced by the morphological features of the samples. The multiple elastic response, expressed in terms of relaxation time distribution, H(λ), exhibited by the molten TPV sample containing 60% of EPDM suggests that apart from the contribution of flow‐induced molecular orientation of the PP matrix, there may also exist some elastic response induced by agglomerates formed between the cured rubber particles. The results predicted from the linear viscoelastic model proposed in the present work were found to be in good agreement with the experimental results. POLYM. ENG. SCI. 45:84–94, 2005. © 2004 Society of Plastics Engineers.     

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.     

Crosslink densities and phase morphologies in thermoplastic vulcanizates

The degree of EPDM crosslinking during dynamic vulcanization of a PP/ EPDM thermoplastic vulcanizate (TPV) was modified by varying its phenolic curative content. The rise in TPV viscosity, the drop in its swelling, the change in its NMR MAS lineshape, and the increase in its EPDM domain AFM force modulation hardness verified the increase in EPDM crosslink density with increasing curative content. Further, the EPDM crosslink extent in TPV was measured by either the bound phenolic or the residual diene content both determined by solid state NMR. SEM morphologies of cryo-faced and ruthenium-stained TPVs with varying curative contents were analyzed to determine the effects of cure on EPDM domain sizes and PP ligament thickness. A narrowing of the EPDM domain size distribution, with a decrease in the third moment of the distribution, was observed with increasing EPDM crosslink density. Correspondingly, the PP ligament number-average thickness was raised slightly.