废旧环氧树脂资源化利用技术研究
摘要
电子废弃物是指在消费过程中产生的各种废旧电子电气产品。层出不穷的信息技术创新与持续膨胀的市场需求加速了电子产品的更新换代,产生大量电子废弃物。由于其内含的热固性塑料,具有不熔不溶的特性,国内外目前尚缺乏经济有效的手段对其进行回收利用,大部分只能填埋或焚烧处理,不仅占用大量的土地资源,还会因其含有多种有害物质造成二次污染。
课题采用红外光谱和扫描电子显微镜等手段对废旧电子元件粉末进行成份分析,结果表明,废旧电子元件粉末的主要成份为固化环氧树脂和二氧化硅填料。在高温和磨擦等作用下,来自固化环氧树脂和二氧化硅填料中的羟基、环氧基、羰基、醇氧基等极性基团,会与极性树脂聚氯乙烯反应,改善其与废旧环氧树脂的相容性。因此,本课题提出采用共混的方法,开展对废旧电子元件资源化利用的研究。以在市场上占有份额较多的环氧树脂电子废弃物为例,将其与聚氯乙烯(PVC)共混,制备复合材料。选用扫描电子显微镜观察、红外光谱分析、热重分析、示差量热扫描分析、气相色谱-质谱分析等方法观察原料及复合材料的微观形态,为废旧环氧树脂与聚氯乙烯共混制备复合材料找到了理论依据。
在上述研究的基础上,课题还对废旧环氧树脂与聚氯乙烯共混的配方、加工条件进行了摸索,并对制成复合材料的力学性能和可能应用的范围进行了分析研究。将废旧环氧树脂经干燥后,与聚氯乙烯和相关助剂在高速混合机内混合均匀,置于转矩流变仪中塑化充分,后经液压机模压成型制备复合材料。考察复合材料的拉伸性能和冲击性能,研究了废旧环氧树脂粉末的目数,流变仪温度、转速,液压机温度、压力,稳定剂的种类和添加量、润滑剂的种类和添加量,其它助剂的种类和添加量等因素对复合材料加工成型的影响,优化共混配方和工艺参数。为提高废旧环氧树脂的利用率,主要考虑了废旧环氧树脂粉末与聚氯乙烯以7:3的比例混合时,最佳配方和工艺参数:废旧环氧树脂目数为80目;流变仪温度为205℃,转数为45rpm;液压机温度为185℃,液压压力为15MPa;选择钙锌稳定剂作为稳定剂,添加量为3份;选择硬脂酸作为润滑剂,添加量为1份;丙烯酸酯添加量为2份,氯化聚乙烯添加量为2份,该条件下复合材料拉伸强度为77.73kJ/m~2,冲击强度为4.8MPa,力学性能满足类似产品的行业标准《挤压木塑复合板材》(中华人民共和国林业行业标准LY/T1613-2004)的相关要求。
本课题的研究成果不仅大大提高了废旧环氧树脂的利用率,对废旧环氧树脂的资源化具有很高的实用价值,而且也为其他热固性废弃物的回收提供重要的参考价值。
E-waste is generated in the process of consumption of various waste electrical and electronic products.The continuous information technology innovation and market demand expansion will accelerate the replacement of electronic products,and they also bring a large amount of E-waste. Because of embedded thermosetting plastic with non-melting and insoluble characteristics,there is still no economic and effective way to recycle them at home and abroad currently.And most of them have to be buried in landfills or incinerated,which will not only take up a lot of land resources,but also cause secondary pollution because of a variety of harmful substances.
By the component analysis results of IR spectroscopy and scanning electron microscopy,the E-waste powder used in this item is mainly composed of thermosetting epoxy resin and silica filler. In the blending process,due to the role of temperature and friction and so on,the hydroxyl,epoxy, carbonyl,alcohol and other polar oxy group from curing epoxy resin and silica filler will reaction with resin polarity PVC,and furthermore it will improve the compatibility between the PVC and the waste epoxy.So it is feasible that waste epoxy resin and PVC can be blended to prepare composite material.Therefore,this item has proposed a method of blending to carry out the study on the recycling of E-waste.Take the epoxy E-waste which has the main market share as an example,it will be blended with polyvinyl chloride(PVC) to prepare the composite materials. Such tools as scanning electron microscopy,infrared spectroscopy,thermal gravimetric analysis, and differential scanning calorimetry(DSC),gas chromatography mass spectrometry(GC-MS) analysis will be adopted to observe the micro-morphology of raw materials and composite materials which will help to conduct the study the feasibility study of blend.
On the basis of the feasibility study,the waste epoxy resin will be dried,and it will be mixed with polyvinyl chloride and related additives in a high-speed mixer,then it will be plasticized by the torque rheometer,at last it will be molded by the hydraulic press to produce composite sample. We not only study the tensile properties and impact properties by analyzing the effects of waste epoxy resin powder mesh,temperature and speed of rheometer,temperature and pressure of hydraulic press,type and addition amount of stabilizer type and addition amount of lubricant,type and addition amount of other auxiliary to the composite materials processing,but also optimize blend formulation and processing parameters.To improve the utilization of waste epoxy resin, mainly considering the waste epoxy resin powder mixed with PVC as 7:3,the best formula and process parameters is:when waste epoxy is added with 80 mesh;205℃of torque rheometer processing temperature,45rpm rotation,15MPa hydraulic pressure,temperature of 185℃,added with Ca-Zn stabilizer 3 portion;added with stearic acid 1 portion;added with acrylic ester 2 portion,added with chlorinated polyethylene 2 portion,77.73kJ/m~2 the tensile strength,4.8MPa impact strength,the needs of related products standard "wood-plastic composite sheet extrusion "(The People's Republic of China Forestry Industry Standard LY/T1613-2004) can be met. Furthermore,it greatly improved the utilization of obsolete electronic components.The topics of research results not only greatly improved the utilization of waste epoxy resin with a high practical value,but also provide an important reference value for the recycling of other thermoset waste.
课题采用红外光谱和扫描电子显微镜等手段对废旧电子元件粉末进行成份分析,结果表明,废旧电子元件粉末的主要成份为固化环氧树脂和二氧化硅填料。在高温和磨擦等作用下,来自固化环氧树脂和二氧化硅填料中的羟基、环氧基、羰基、醇氧基等极性基团,会与极性树脂聚氯乙烯反应,改善其与废旧环氧树脂的相容性。因此,本课题提出采用共混的方法,开展对废旧电子元件资源化利用的研究。以在市场上占有份额较多的环氧树脂电子废弃物为例,将其与聚氯乙烯(PVC)共混,制备复合材料。选用扫描电子显微镜观察、红外光谱分析、热重分析、示差量热扫描分析、气相色谱-质谱分析等方法观察原料及复合材料的微观形态,为废旧环氧树脂与聚氯乙烯共混制备复合材料找到了理论依据。
在上述研究的基础上,课题还对废旧环氧树脂与聚氯乙烯共混的配方、加工条件进行了摸索,并对制成复合材料的力学性能和可能应用的范围进行了分析研究。将废旧环氧树脂经干燥后,与聚氯乙烯和相关助剂在高速混合机内混合均匀,置于转矩流变仪中塑化充分,后经液压机模压成型制备复合材料。考察复合材料的拉伸性能和冲击性能,研究了废旧环氧树脂粉末的目数,流变仪温度、转速,液压机温度、压力,稳定剂的种类和添加量、润滑剂的种类和添加量,其它助剂的种类和添加量等因素对复合材料加工成型的影响,优化共混配方和工艺参数。为提高废旧环氧树脂的利用率,主要考虑了废旧环氧树脂粉末与聚氯乙烯以7:3的比例混合时,最佳配方和工艺参数:废旧环氧树脂目数为80目;流变仪温度为205℃,转数为45rpm;液压机温度为185℃,液压压力为15MPa;选择钙锌稳定剂作为稳定剂,添加量为3份;选择硬脂酸作为润滑剂,添加量为1份;丙烯酸酯添加量为2份,氯化聚乙烯添加量为2份,该条件下复合材料拉伸强度为77.73kJ/m~2,冲击强度为4.8MPa,力学性能满足类似产品的行业标准《挤压木塑复合板材》(中华人民共和国林业行业标准LY/T1613-2004)的相关要求。
本课题的研究成果不仅大大提高了废旧环氧树脂的利用率,对废旧环氧树脂的资源化具有很高的实用价值,而且也为其他热固性废弃物的回收提供重要的参考价值。
E-waste is generated in the process of consumption of various waste electrical and electronic products.The continuous information technology innovation and market demand expansion will accelerate the replacement of electronic products,and they also bring a large amount of E-waste. Because of embedded thermosetting plastic with non-melting and insoluble characteristics,there is still no economic and effective way to recycle them at home and abroad currently.And most of them have to be buried in landfills or incinerated,which will not only take up a lot of land resources,but also cause secondary pollution because of a variety of harmful substances.
By the component analysis results of IR spectroscopy and scanning electron microscopy,the E-waste powder used in this item is mainly composed of thermosetting epoxy resin and silica filler. In the blending process,due to the role of temperature and friction and so on,the hydroxyl,epoxy, carbonyl,alcohol and other polar oxy group from curing epoxy resin and silica filler will reaction with resin polarity PVC,and furthermore it will improve the compatibility between the PVC and the waste epoxy.So it is feasible that waste epoxy resin and PVC can be blended to prepare composite material.Therefore,this item has proposed a method of blending to carry out the study on the recycling of E-waste.Take the epoxy E-waste which has the main market share as an example,it will be blended with polyvinyl chloride(PVC) to prepare the composite materials. Such tools as scanning electron microscopy,infrared spectroscopy,thermal gravimetric analysis, and differential scanning calorimetry(DSC),gas chromatography mass spectrometry(GC-MS) analysis will be adopted to observe the micro-morphology of raw materials and composite materials which will help to conduct the study the feasibility study of blend.
On the basis of the feasibility study,the waste epoxy resin will be dried,and it will be mixed with polyvinyl chloride and related additives in a high-speed mixer,then it will be plasticized by the torque rheometer,at last it will be molded by the hydraulic press to produce composite sample. We not only study the tensile properties and impact properties by analyzing the effects of waste epoxy resin powder mesh,temperature and speed of rheometer,temperature and pressure of hydraulic press,type and addition amount of stabilizer type and addition amount of lubricant,type and addition amount of other auxiliary to the composite materials processing,but also optimize blend formulation and processing parameters.To improve the utilization of waste epoxy resin, mainly considering the waste epoxy resin powder mixed with PVC as 7:3,the best formula and process parameters is:when waste epoxy is added with 80 mesh;205℃of torque rheometer processing temperature,45rpm rotation,15MPa hydraulic pressure,temperature of 185℃,added with Ca-Zn stabilizer 3 portion;added with stearic acid 1 portion;added with acrylic ester 2 portion,added with chlorinated polyethylene 2 portion,77.73kJ/m~2 the tensile strength,4.8MPa impact strength,the needs of related products standard "wood-plastic composite sheet extrusion "(The People's Republic of China Forestry Industry Standard LY/T1613-2004) can be met. Furthermore,it greatly improved the utilization of obsolete electronic components.The topics of research results not only greatly improved the utilization of waste epoxy resin with a high practical value,but also provide an important reference value for the recycling of other thermoset waste.
引文
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