动态硫化EPDM/PP热塑性弹性体的制备与研究
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摘要
EPDM/ PP热塑性弹性体具有优异的耐候性、良好的高温性能、电性能、耐油和溶剂性能。随着汽车产业和电线电缆等行业的发展,对EPDM/ PP热塑性弹性体的需求急剧增加。但国内对EPDM/ PP热塑性弹性体的研究才起步,与国外还有一定的距离。因此,采用动态硫化法制备高性能EPDM/ PP热塑性弹性体具有重要的研究意义和应用前景。
本文首先采用不同过氧化二异丙苯(DCP)含量的硫化体系对EPDM/PP共混物进行动态硫化。通过交联密度、熔融指数、拉伸性能、磨耗性能、SEM、DSC、TG等测试与表征,研究了DCP用量对动态硫化EPDM/PP体系中EPDM的形态结构特征和性能的影响,SEM结果显示EPDM/PP熔融共混物经动态硫化后,交联EPDM粒子以微米级均匀分布在PP连续相中,呈典型的“海-岛”两相结构。随着DCP用量的增加,体系的交联密度和热稳定性增加,熔融指数和磨耗呈先降低后增加,而硬度和拉伸强度呈先增加后降低的趋势。当DCP用量为2份的时候,此时综合性能最佳。
为了进一步改善EPDM/ PP热塑性弹性体的力学性能,固定DCP用量为2份,选用硫(S)来替代TAIC作为体系的交联助剂,并研究了S用量对动态硫化EPDM/PP体系形态结构和性能的影响,结果表明S是EPDM/PP/DCP体系高效的交联助剂,不仅加入0.1份的S(0.1份)可取代1份TAIC而且S的加入还可明显提高体系的拉伸强度。随着S的含量增加,其体系的交联密度、熔融指数和硬度变化不大,但其拉伸强度呈先增加后降低的趋势,当S用量为0.3份,拉伸强度提高到13.97Mpa。
在确定了体系最佳的硫化体系之后,通过改变橡塑比,研究了橡塑比对对动态硫化EPDM/PP体系中EPDM的形态结构和性能的影响,结果表明,随着橡塑比例的减小,体系的弹性和断裂伸长率降低,交联密度、硬度和强度随之增加,且加工流动性能也有所提高。
本文还研究了碳纳米管(CNTs)用量对动态硫化EPDM/PP体系形态结构和性能的影响。通过SEM和力学性能测试可知,当CNTs为1份的时候, CNTs在基体的均匀分散,且与基体有较强的相互作用,从而提高了材料的加工流动性和力学性能。
EPDM / PP thermoplastic elastomer which is prepared by dynamic vulcanization has excellent weather resistance, good high temperature properties, electrical properties, oil-resistant and solvent-resistant properties.As the development of auto and cable industry, the application of EPDM/ PP thermal plastic elastomer becomes wider. However the research of EPDM/ PP thermal plastic elastomer in Domestic is slower than in developed countries. So the research of dynamic vulcanization in producing high performance EPDM/ PP thermal plastic elastomer is significant and promising.
First, the dynamic vulcanizate EPDM/ PP blends with different content of DCP have been studied. The effects of the content of DCP on the structure and properties of the dynamic vulcanizate EPDM/ PP blends have been researched by the test of cross linking density, melt index, tensile, abradability, SEM, DSC, and TG. It has been showned by SEM that in the dynamic vulcanization of EPDM/ PP melt blend, cross-linked EPDM particles are adequate distribution in PP, known as the typical two phase structure. When the dosage of DCP is two, its combination property is best.
In order to promote the mechanical property of EPDM/ PP thermal plastic elastomer, the influence of moderate sulfur(S), as a substitute for TAIC which acted on a crosslinking coagent, on property was investigated, when the DCP dosage was fixed. And the effect of S content on morphological structure and property of EPDM is also studied and the result shows that S is effective coagent. 0.1 dosage of S has the function of one dosage of TAIC. When S dosage is 0.3, the mechanical property and system intensity is not obviously changed. But tensile-strength increases, then decreases. And the system tensile-strength is promoted to 13.97Mpa compared to those without S.
After the determination of best sulfurizing system, the paper focuses on the impact of rubber ratio on the morphological characteristics and property of EPDM through change the rubber ratio. And the result shows that the cross-linking density, hardness, intensity and processing liquid of composite are improved as the rubber ratio decreases, and its resiliency and elongation rate decrease.
Finally, the influence of the quantity of CNTs on the morphological characteristic and property of EPDM/ PP (TPV) is also been tested. Through the test of SEM and mechanical property, the result indicates that when one dosage of CNTs is added, the mechanical working property and mechanical property of composite have been improved.
本文首先采用不同过氧化二异丙苯(DCP)含量的硫化体系对EPDM/PP共混物进行动态硫化。通过交联密度、熔融指数、拉伸性能、磨耗性能、SEM、DSC、TG等测试与表征,研究了DCP用量对动态硫化EPDM/PP体系中EPDM的形态结构特征和性能的影响,SEM结果显示EPDM/PP熔融共混物经动态硫化后,交联EPDM粒子以微米级均匀分布在PP连续相中,呈典型的“海-岛”两相结构。随着DCP用量的增加,体系的交联密度和热稳定性增加,熔融指数和磨耗呈先降低后增加,而硬度和拉伸强度呈先增加后降低的趋势。当DCP用量为2份的时候,此时综合性能最佳。
为了进一步改善EPDM/ PP热塑性弹性体的力学性能,固定DCP用量为2份,选用硫(S)来替代TAIC作为体系的交联助剂,并研究了S用量对动态硫化EPDM/PP体系形态结构和性能的影响,结果表明S是EPDM/PP/DCP体系高效的交联助剂,不仅加入0.1份的S(0.1份)可取代1份TAIC而且S的加入还可明显提高体系的拉伸强度。随着S的含量增加,其体系的交联密度、熔融指数和硬度变化不大,但其拉伸强度呈先增加后降低的趋势,当S用量为0.3份,拉伸强度提高到13.97Mpa。
在确定了体系最佳的硫化体系之后,通过改变橡塑比,研究了橡塑比对对动态硫化EPDM/PP体系中EPDM的形态结构和性能的影响,结果表明,随着橡塑比例的减小,体系的弹性和断裂伸长率降低,交联密度、硬度和强度随之增加,且加工流动性能也有所提高。
本文还研究了碳纳米管(CNTs)用量对动态硫化EPDM/PP体系形态结构和性能的影响。通过SEM和力学性能测试可知,当CNTs为1份的时候, CNTs在基体的均匀分散,且与基体有较强的相互作用,从而提高了材料的加工流动性和力学性能。
EPDM / PP thermoplastic elastomer which is prepared by dynamic vulcanization has excellent weather resistance, good high temperature properties, electrical properties, oil-resistant and solvent-resistant properties.As the development of auto and cable industry, the application of EPDM/ PP thermal plastic elastomer becomes wider. However the research of EPDM/ PP thermal plastic elastomer in Domestic is slower than in developed countries. So the research of dynamic vulcanization in producing high performance EPDM/ PP thermal plastic elastomer is significant and promising.
First, the dynamic vulcanizate EPDM/ PP blends with different content of DCP have been studied. The effects of the content of DCP on the structure and properties of the dynamic vulcanizate EPDM/ PP blends have been researched by the test of cross linking density, melt index, tensile, abradability, SEM, DSC, and TG. It has been showned by SEM that in the dynamic vulcanization of EPDM/ PP melt blend, cross-linked EPDM particles are adequate distribution in PP, known as the typical two phase structure. When the dosage of DCP is two, its combination property is best.
In order to promote the mechanical property of EPDM/ PP thermal plastic elastomer, the influence of moderate sulfur(S), as a substitute for TAIC which acted on a crosslinking coagent, on property was investigated, when the DCP dosage was fixed. And the effect of S content on morphological structure and property of EPDM is also studied and the result shows that S is effective coagent. 0.1 dosage of S has the function of one dosage of TAIC. When S dosage is 0.3, the mechanical property and system intensity is not obviously changed. But tensile-strength increases, then decreases. And the system tensile-strength is promoted to 13.97Mpa compared to those without S.
After the determination of best sulfurizing system, the paper focuses on the impact of rubber ratio on the morphological characteristics and property of EPDM through change the rubber ratio. And the result shows that the cross-linking density, hardness, intensity and processing liquid of composite are improved as the rubber ratio decreases, and its resiliency and elongation rate decrease.
Finally, the influence of the quantity of CNTs on the morphological characteristic and property of EPDM/ PP (TPV) is also been tested. Through the test of SEM and mechanical property, the result indicates that when one dosage of CNTs is added, the mechanical working property and mechanical property of composite have been improved.
引文
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