CN108017820A - 一种纤维增强高密度聚乙烯/石墨烯复合材料及其制备方法 - Google Patents
一种纤维增强高密度聚乙烯/石墨烯复合材料及其制备方法 Download PDFInfo
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Abstract
本发明公开一种纤维增强高密度聚乙烯/石墨烯复合材料及其制备方法。由以下重量份配比制得:天然植物纤维15~60份、石墨烯0.5~2份、聚烯烃40~60份、发泡剂1~10份、交联剂0.5~1份、增塑剂5~8份、润滑剂1~10份、活化剂1~10份。将天然植物纤维进行处理,辅配其他加工助剂制成的纤维增强高密度聚乙烯/石墨烯材料具有优良的加工性能和物理机械性能。解决天然植物与聚烯烃相容性的问题,从而得到一种强度高,韧性好的复合材料,添加石墨烯有效增加本发明复合材料的导热性能,增加使纤维增强高密度聚乙烯/石墨烯复合材料具有广阔的应用前景。
Description
技术领域
本发明涉及一种聚乙烯材料,更具体地,涉及一种纤维增强高密度聚乙烯/ 石墨烯复合材料及其制备方法。
背景技术
高密度聚乙烯(HDPE)为白色粉末或颗粒状产品.无毒,无味,结晶度为 80%~90%,软化点为125~l35℃,使用温度可达100℃;硬度、拉伸强度和蠕变性优于低密度聚乙烯;耐磨性、电绝缘性、韧性及耐寒性较好;化学稳定性好,在室温条件下,不溶于任何有机溶剂,耐酸、碱和各种盐类的腐蚀;薄膜对水蒸气和空气的渗透性小,吸水性低;耐老化性能差,耐环境应力开裂性不如低密度聚乙烯,高密度聚乙烯薄膜在受力情况下热变形温度较低,应用时多有不便。
氧化石墨烯薄片是石墨粉末经化学氧化及剥离后的产物,氧化石墨烯是单一的原子层,可以随时在横向尺寸上扩展到数十微米。因此,其结构跨越了一般化学和材料科学的典型尺度。氧化石墨烯可视为一种非传统型态的软性材料,具有聚合物、胶体、薄膜,以及两性分子的特性。氧化石墨烯可如同界面活性剂一般存在界面,并降低界面间的能量。
经检索,暂未发现现有的石墨烯用于纤维增强高密度聚乙烯材料中。
发明内容
本发明提供一种纤维增强高密度聚乙烯/石墨烯复合材料,将天然植物纤维进行处理,辅配其他加工助剂制成的纤维增强高密度聚乙烯/石墨烯材料具有优良的加工性能和物理机械性能。主要的技术关键是解决天然植物与聚烯烃相容性的问题,从而得到一种强度高,韧性好的复合材料,石墨烯作为润滑剂,可减小橡胶材料的摩擦因数,提高橡胶材料的耐磨性能,有效延长橡胶制品的使用寿命。
本发明的另一目的在于提供一种纤维增强高密度聚乙烯/石墨烯复合材料的制备方法。
本发明通过以下技术方案予以实现:
公开一种纤维增强高密度聚乙烯/石墨烯复合材料,由以下重量份配比制得:天然植物纤维15~60份、石墨烯0.5~2份、聚烯烃40~60份、发泡剂1~10份、交联剂0.5~1份、增塑剂5~8份、润滑剂1~10份、活化剂1~10份。
进一步地,所述石墨烯为氧化石墨烯,所述氧化石墨烯的比表面在500~ 1000m2/g,层数为1~5层。
进一步地,所述天然植物纤维为黄麻纤维或剑麻纤维。
进一步地,所述聚烯烃为高密度聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯中的一种或几种。
进一步地,所述发泡剂为偶氮二甲酰胺、碳酸氢钠中的至少一种。
进一步地,所述交联剂为过氧化二异丙苯、聚乙二醇的至少一种。
进一步地,所述增塑剂为邻苯二甲酸二乙酯、乙酰柠檬酸三丁酯的至少一种。
进一步地,所述润滑剂为聚乙烯蜡、羟基硬脂酸、硬脂酸正丁酯、硬脂酸单甘油酯的至少一种。
进一步地,所述活化剂为氧化锌、氧化镁、氧化铝中的至少一种。
本发明的另一目的在于,公开上述纤维增强高密度聚乙烯/石墨烯复合材料的制备方法,由以下步骤制备:
S1.处理天然植物纤维:
S11.将天然植物纤维洗去表面的杂质,再用去离子水反复洗涤,放入恒温烘箱,在85~90℃恒温条件下烘3~6h进行干燥;
S12.将步骤S11所得的天然植物纤维称取3~5g放入100mL水热反应釜的聚四氟乙烯内胆中,加入70mL浓度为1.5~2.5mol/L的强碱溶液,放入恒温烘箱,在170~190℃下恒温加热10~12h自然冷却后拿出,用去离子水将固体物质洗至中性后,放入恒温鼓风烘箱中在70~80℃恒温条件下进行烘干处理10~12h,获得干燥的白色絮状前驱体;备用;
S2.制备天然植物纤维处理溶液:称取一定量的低密度聚乙烯粉料,加入对二甲苯溶剂中,用水浴锅加热到80~100℃并不断搅拌致粉料完全溶解,配制成低密度聚乙烯浓度为2~5wt%的溶液冷却,待用;
S3.将温度降至60~80℃,加入天然植物纤维和石墨烯,浸入上述低密度聚乙烯溶液中30~50min,取出放入110~120℃的烘箱中,烘干处理7~9h;
S4.将聚烯烃、发泡剂、活化剂、交联剂、增塑剂和润滑剂加入混合机中搅拌,搅拌速度为800~1000r/min,混合15~25min;
S5.将步骤S4所得混合物放入平板硫化机上模压成型,制成聚烯烃薄板,模压温度为150~180℃,压力为5~15MPa,时间为10~15min;
S6.将步骤S3处理的天然植物纤维织物,与步骤S5制得的聚烯烃薄板放入模具中在平板硫化机上模压成型,制得天然植物纤维聚烯烃复合材料,模压温度为150~180℃,压力为5~15MPa,时间为10~15min。
与现有技术相比,本发明具有如下有益效果:
本发明创造性的利用高韧性、耐腐蚀、环保的天然植物纤维,石墨烯和聚烯烃作为原料,制备出拉伸强度高、抗冲击性强的纤维增强高密度聚乙烯/石墨烯复合材料。
本发明使用剑麻纤维处理溶液对天然植物维纤进行处理,不仅解决了天然植物维纤与聚烯烃的相容性,还增强了天然植物纤维与聚烯烃的结合力。同时,本发明使用能产生均匀泡孔的复合发泡剂,使复合材料轻量化,交联剂使聚合物单体发生交联,提高了复合材料的力学性能,硬脂酸和PE蜡作为润滑剂有效改善了熔体的流动性和复合材料的表面光滑度。
石墨烯能有效增加本发明复合材料的导热性能,增加使纤维增强高密度聚乙烯/石墨烯复合材料具有广阔的应用前景。
通过利用模压成型工艺成功的将天然植物维纤与聚烯烃复合,制备得到具有高强度、导热性能好、耐磨性、耐冲击性好,并且加工简单、环保的纤维增强高密度聚乙烯/石墨烯复合材料。
具体实施方式
下面结合具体实施例进一步详细说明本发明。除非特别说明,本发明实施例使用的各种原料均可以通过常规市购得到,或根据本领域的常规方法制备得到,所用设备为实验常用设备。除非另有定义或说明,本文中所使用的所有专业与科学用语与本领域技术熟练人员所熟悉的意义相同。
本发明公开了公开一种纤维增强高密度聚乙烯/石墨烯复合材料,由以下重量份配比制得:天然植物纤维15~60份、石墨烯0.5~2份、聚烯烃40~60份、发泡剂1~10份、交联剂0.5~1份、增塑剂5~8份、润滑剂1~10份、活化剂1~10份。
其中,石墨烯为氧化石墨烯,所述氧化石墨烯的比表面在500~1000m2/g, 层数为1~5层;天然植物纤维为黄麻纤维或剑麻纤维;聚烯烃为高密度聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯中的一种或几种;发泡剂为偶氮二甲酰胺、碳酸氢钠中的至少一种;交联剂为过氧化二异丙苯、聚乙二醇的至少一种;增塑剂为邻苯二甲酸二乙酯、乙酰柠檬酸三丁酯的至少一种;润滑剂为聚乙烯蜡、羟基硬脂酸、硬脂酸正丁酯、硬脂酸单甘油酯的至少一种;活化剂为氧化锌、氧化镁、氧化铝中的至少一种。
具体实施如下。
实施例1
(1)纤维增强高密度聚乙烯/石墨烯复合材料
由以下重量份配比制得:天然植物纤维60份、石墨烯0.5份、聚烯烃50 份、发泡剂10份、交联剂1份、增塑剂8份、润滑剂10份、活化剂10份。本实施例中,天然植物纤维为黄麻纤维;聚烯烃为高密度聚乙烯、聚丙烯按1:1质量比混合;发泡剂为偶氮二甲酰胺;交联剂为过氧化二异丙苯;增塑剂为邻苯二甲酸二乙酯;润滑剂为聚乙烯蜡;活化剂为氧化锌。
(2)纤维增强高密度聚乙烯/石墨烯复合材料的制备方法
本实施例的纤维增强高密度聚乙烯/石墨烯复合材料的制备方法,包括以下步骤:
S1.处理天然植物纤维:
S11.将天然植物纤维洗去表面的杂质,再用去离子水反复洗涤,放入恒温烘箱,在90℃恒温条件下烘3h进行干燥;
S12.将步骤S11所得的天然植物纤维称取3~5g放入100mL水热反应釜的聚四氟乙烯内胆中,加入70mL浓度为1.5~2.5mol/L的强碱溶液,放入恒温烘箱,在170~190℃下恒温加热10~12h自然冷却后拿出,用去离子水将固体物质洗至中性后,放入恒温鼓风烘箱中在70~80℃恒温条件下进行烘干处理10h,获得干燥的白色絮状前驱体;备用;
S2.制备天然植物纤维处理溶液:称取一定量的低密度聚乙烯粉料,加入对二甲苯溶剂中,用水浴锅加热到100℃并不断搅拌致粉料完全溶解,配制成低密度聚乙烯的浓度为5wt%的溶液冷却,待用;
S3.将温度降至80℃,加入天然植物纤维和石墨烯,浸入上述低密度聚乙烯溶液中50min,取出放入120℃的烘箱中,烘干处理7h;
S4.将聚烯烃、发泡剂、活化剂、交联剂、增塑剂和润滑剂加入混合机中搅拌,搅拌速度为800r/min,混合15min;
S5.将步骤S4所得混合物放入平板硫化机上模压成型,制成聚烯烃薄板,模压温度为150℃,压力为15MPa,时间为15min;
S6.将步骤S3的处理的天然植物纤维织物,与步骤S5制得的聚烯烃薄板放入模具中在平板硫化机上模压成型,制得天然植物纤维聚烯烃复合材料,模压温度为150℃,压力为15MPa,时间为15min。
实施例2
(1)纤维增强高密度聚乙烯/石墨烯复合材料
由以下重量份配比制得:天然植物纤维30份、石墨烯2份、聚烯烃40 份、发泡剂1份、交联剂0.5份、增塑剂5份、润滑剂1份、活化剂1份。本实施例中的天然植物纤维为剑麻纤维;聚烯烃为聚氯乙烯;发泡剂为碳酸氢钠;交联剂为聚乙二醇;增塑剂为邻乙酰柠檬酸三丁酯;润滑剂为硬脂酸正丁酯种;活化剂为氧化铝。
(2)纤维增强高密度聚乙烯/石墨烯复合材料的制备方法
本实施例的纤维增强高密度聚乙烯/石墨烯复合材料的制备方法,包括以下步骤:
S1.处理天然植物纤维:
S11.将天然植物纤维洗去表面的杂质,再用去离子水反复洗涤,放入恒温烘箱,在85℃恒温条件下烘6h进行干燥;
S12.将步骤S11所得的天然植物纤维称取3~5g放入100mL水热反应釜的聚四氟乙烯内胆中,加入70mL浓度为1.5~2.5mol/L的强碱溶液,放入恒温烘箱,在170~190℃下恒温加热10~12h自然冷却后拿出,用去离子水将固体物质洗至中性后,放入恒温鼓风烘箱中在70~80℃恒温条件下进行烘干处理12h,获得干燥的白色絮状前驱体;备用;
S2.制备天然植物纤维处理溶液:称取一定量的低密度聚乙烯粉料,加入对二甲苯溶剂中,用水浴锅加热到80℃并不断搅拌致粉料完全溶解,配制成低密度聚乙烯的浓度为2wt%的溶液冷却,待用;
S3.将温度降至60℃,加入天然植物纤维和石墨烯,浸入上述低密度聚乙烯溶液中30min,取出放入110℃的烘箱中,烘干处理9h;
S4.将聚烯烃、发泡剂、活化剂、交联剂、增塑剂和润滑剂加入混合机中搅拌,搅拌速度为1000r/min,混合25min;
S5.将步骤S4所得混合物放入平板硫化机上模压成型,制成聚烯烃薄板,模压温度为180℃,压力为25MPa,时间为10min;
S6.将步骤S3的处理的天然植物纤维织物,与步骤S5制得的聚烯烃薄板放入模具中在平板硫化机上模压成型,制得天然植物纤维聚烯烃复合材料,模压温度为180℃,压力为25MPa,时间为10min。
实施例3
(1)纤维增强高密度聚乙烯/石墨烯复合材料
由以下重量份配比制得:天然植物纤维40份、石墨烯1份、聚烯烃60 份、发泡剂5份、交联剂0.5份、增塑剂5份、润滑剂6份、活化剂8份。本实施例中,天然植物纤维为剑麻纤维;聚烯烃为高密度聚乙烯;发泡剂为偶氮二甲酰胺;交联剂为过氧化二异丙苯、聚乙二醇按1:1质量比混合;增塑剂为邻苯二甲酸二乙酯、乙酰柠檬酸三丁酯按1:1质量比混合;润滑剂为硬脂酸正丁酯;活化剂为氧化镁。
(2)纤维增强高密度聚乙烯/石墨烯复合材料的制备方法
本实施例的制备方法与实施例1基本相同,其不同之处在于,步骤S3.将温度降至80℃,加入天然植物纤维和石墨烯,浸入上述低密度聚乙烯溶液中40min,取出放入110℃的烘箱中,烘干处理8h。
实施例4
(1)纤维增强高密度聚乙烯/石墨烯复合材料
由以下重量份配比制得:天然植物纤维15份、石墨烯1.5份、聚烯烃50 份、发泡剂5份、交联剂0.5份、增塑剂5份、润滑剂6份、活化剂8份。本实施例中,天然植物纤维为剑麻纤维;聚烯烃为聚氯乙烯;发泡剂为偶氮二甲酰胺;交联剂为过氧化二异丙苯、聚乙二醇按2:1质量比混合;增塑剂为邻苯二甲酸二乙酯、乙酰柠檬酸三丁酯按1:1质量比混合;润滑剂为硬脂酸正丁酯;活化剂为氧化铝。
(2)纤维增强高密度聚乙烯/石墨烯复合材料的制备方法
本实施例的制备方法与实施例1基本相同,其不同之处在于,步骤S3.将温度降至80℃,加入天然植物纤维和石墨烯,浸入上述低密度聚乙烯溶液中40min,取出放入110℃的烘箱中,烘干处理8h。
对比例1
由以下重量份配比制得:天然植物纤维60份、聚烯烃50份、发泡剂10份、交联剂1份、增塑剂8份、润滑剂10份、活化剂10份。本对比例中,天然植物纤维为黄麻纤维;聚烯烃为高密度聚乙烯、聚丙烯按1:1质量比混合;发泡剂为偶氮二甲酰胺;交联剂为过氧化二异丙苯;增塑剂为邻苯二甲酸二乙酯;润滑剂为聚乙烯蜡;活化剂为氧化锌。
本对比例的纤维增强高密度聚乙烯材料的制备方法,包括以下步骤:
S1.处理天然植物纤维:
S11.将天然植物纤维洗去表面的杂质,再用去离子水反复洗涤,放入恒温烘箱,在90℃恒温条件下烘3h进行干燥;
S12.将步骤S11所得的天然植物纤维称取3~5g放入100mL水热反应釜的聚四氟乙烯内胆中,加入70mL浓度为1.5~2.5mol/L的强碱溶液,放入恒温烘箱,在170~190℃下恒温加热10~12h自然冷却后拿出,用去离子水将固体物质洗至中性后,放入恒温鼓风烘箱中在70~80℃恒温条件下进行烘干处理10h,获得干燥的白色絮状前驱体;备用;
S2.制备天然植物纤维处理溶液:称取一定量的低密度聚乙烯粉料,加入对二甲苯溶剂中,用水浴锅加热到100℃并不断搅拌致粉料完全溶解,配制成低密度聚乙烯的浓度为5wt%的溶液冷却,待用;
S3.将温度降至80℃,加入天然植物纤维浸入上述低密度聚乙烯溶液中 50min,取出放入120℃的烘箱中,烘干处理7h;
S4.将聚烯烃、发泡剂、活化剂、交联剂、增塑剂和润滑剂加入混合机中搅拌,搅拌速度为800r/min,混合15min;
S5.将步骤S4所得混合物放入平板硫化机上模压成型,制成聚烯烃薄板,模压温度为150℃,压力为15MPa,时间为15min;
S6.将步骤S3的处理的天然植物纤维织物,与步骤S5制得的聚烯烃薄板放入模具中在平板硫化机上模压成型,制得天然植物纤维聚烯烃复合材料,模压温度为150℃,压力为15MPa,时间为15min。
将实施例1~实施例4和对比例1进行性能测试,其结果见下表:
表1
Claims (10)
1.一种纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,由以下重量份配比制得:天然植物纤维15~60份、石墨烯0.5~2份、聚烯烃40~60份、发泡剂1~10 份、交联剂0.5~1份、增塑剂5~8份、润滑剂1~10份、活化剂1~10 份。
2.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述石墨烯为氧化石墨烯,所述氧化石墨烯的比表面在500~1000m2/g,层数为1~5层。
3.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述天然植物纤维为黄麻纤维或剑麻纤维。
4.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述聚烯烃为高密度聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯中的一种或几种。
5.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述发泡剂为偶氮二甲酰胺、碳酸氢钠中的至少一种。
6.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述交联剂为过氧化二异丙苯、聚乙二醇的至少一种。
7.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述增塑剂为邻苯二甲酸二乙酯、乙酰柠檬酸三丁酯的至少一种。
8.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述润滑剂为聚乙烯蜡、羟基硬脂酸、硬脂酸正丁酯、硬脂酸单甘油酯的至少一种。
9.根据权利要求1所述纤维增强高密度聚乙烯/石墨烯复合材料,其特征在于,所述活化剂为氧化锌、氧化镁、氧化铝中的至少一种。
10.根据权利要求1~9任意一项所述纤维增强高密度聚乙烯/石墨烯复合材料的制备方法,其特征在于,由以下步骤制备:
S1. 处理天然植物纤维:
S11. 将天然植物纤维洗去表面的杂质,再用去离子水反复洗涤,放入恒温烘箱,在85~90℃恒温条件下烘3~6h进行干燥;
S12. 将步骤S11所得的天然植物纤维称取3~5g放入100mL水热反应釜的聚四氟乙烯内胆中,加入70mL浓度为1.5~2.5mol/L的强碱溶液,放入恒温烘箱,在170~190℃下恒温加热10~12h自然冷却后拿出,用去离子水将固体物质洗至中性后,放入恒温鼓风烘箱中在70~80℃ 恒温条件下进行烘干处理10~12h,获得干燥的白色絮状前驱体;备用;
S2. 制备天然植物纤维处理溶液: 称取一定量的低密度聚乙烯粉料,加入对二甲苯溶剂中,用水浴锅加热到80~100℃并不断搅拌致粉料完全溶解,配制成低密度聚乙烯浓度为2~5wt%的溶液冷却,待用;
S3. 将温度降至60~80℃,加入天然植物纤维和氧化石墨烯,浸入上述低密度聚乙烯溶液中30~50min,取出放入110~120℃的烘箱中,烘干处理7~9h;
S4. 将聚烯烃、发泡剂、活化剂、交联剂、增塑剂和润滑剂加入混合机中搅拌,搅拌速度为800~1000r/min,混合15~25min;
S5. 将步骤S4所得混合物放入平板硫化机上模压成型,制成聚烯烃薄板,模压温度为150~180℃,压力为5~15MPa,时间为10~15min;
S6. 将步骤S3处理的天然植物纤维织物,与步骤S5制得的聚烯烃薄板放入模具中在平板硫化机上模压成型,制得天然植物纤维聚烯烃复合材料,模压温度为150~180℃,压力为5~15MPa,时间为10~15min。
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