CN104072852A - 一种纳米碳酸钙填充hdpe材料及其制备方法 - Google Patents

一种纳米碳酸钙填充hdpe材料及其制备方法 Download PDF

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CN104072852A
CN104072852A CN201410340570.5A CN201410340570A CN104072852A CN 104072852 A CN104072852 A CN 104072852A CN 201410340570 A CN201410340570 A CN 201410340570A CN 104072852 A CN104072852 A CN 104072852A
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王森贤
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Abstract

本发明公开了一种纳米碳酸钙填充HDPE材料及其制备方法,称取HDPE、抗氧剂DSTP、纳米碳酸钙、UV-327、ACR、亚磷酸酯、CPE、二硫化四乙基秋兰姆、钛酸酯、硬脂酸铅、抗冲击改性剂、氧化铝、石油醚和增塑剂,将原料经过处理、混合后造粒;产品冲击强度24-36kJ/m2,是纯HDPE的1.7倍;摩擦系数0.116,表面洛氏硬度为81.5;拉伸强度70-80MPa,断裂伸长率660%-700%;紫外光照射2500h后伸长率保持率99%-100%,可以广泛生产并不断代替现有材料。

Description

一种纳米碳酸钙填充HDPE材料及其制备方法
技术领域
本发明涉及一种HDPE材料,尤其涉及一种纳米碳酸钙填充HDPE材料及其制备方法,属于塑料材料技术领域。 
背景技术
高密度聚乙烯是一种结晶度高、非极性的热塑性树脂。原态HDPE的外表呈乳白色,在微薄截面呈一定程度的半透明状。PE具有优良的耐大多数生活和工业用化学品的特性。某些种类的化学品会产生化学腐蚀,例如腐蚀性氧化剂,芳香烃和卤化烃。该聚合物不吸湿并具有好的防水蒸汽性,可用于包装用途。HDPE具有很好的电性能,特别是绝缘介电强度高,使其很适用于电线电缆。中到高分子量等级具有极好的抗冲击性,在常温甚至在-40摄氏度低温度下均如此。高密度聚乙烯为无毒,无味,无臭的白色颗粒,熔点为130℃,相对密度为0.946~0.976g/cm3,它具有良好的耐热性和耐寒性,化学稳定性好,还具有较高的刚性和韧性,机械强度好,介电性能,耐环境应力开裂性亦较好。
高密度聚乙烯是种白色粉末颗粒状产品,无毒、无味,密度在0.940~0.976 g/cm3范围内;结晶度为80%~90%,软化点为125~135℃,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、韧性及耐寒性均较好,但与低密度绝缘性比较略差些;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,耐环境开裂性不如低密度聚乙烯,特别是热氧化作用会使其性能下降。
纳米碳酸钙又称超微细碳酸钙。标准的名称即超细碳酸钙。纳米碳酸钙应用最成熟的行业是塑料工业主要应用于高档塑料制品。可改善塑料母料的流变性,提高其成型性。用作塑料填料具有增韧补强的作用,提高塑料的弯曲强度和弯曲弹性模量,热变形温度和尺寸稳定性,同时还赋予塑料滞热性。纳米碳酸钙用于油墨产品中体现出了优异的分散性和透明性和极好的光泽、及优异的油墨吸收性和高干燥性。纳米碳酸钙在树脂型油墨中作油墨填料,具有稳定性好,光泽度高,不影响印刷油墨的干燥性能.适应性强等优点。
纳米碳酸钙是20世纪80年代发展起来的一种新型超细固体粉末材料,其粒度介于0.01~0.1μm之间。由于纳米碳酸钙粒子的超细化,其晶体结构和表面电子结构发生变化,产生了普通碳酸钙所不具有的量子尺寸效应。由于活性纳米碳酸钙表面亲油疏水,与树脂相容性好,能有效提高或调节制品的刚、韧性、光洁度以及弯曲强度;改善加工性能,改善制品的流变性能、尺寸稳定性能、耐热稳定性具有填充及增强、增韧的作用,能取代部分价格昂贵的填充料及助济,减少树脂的用量,从而降低产品生产成本,提高市场竞争力。
中国专利CN103497395A,公开日为2014年1月8日,公开了一种增强型HDPE管,主要采用HDPE100-120份、纳米碳酸钙20-30份、短切玻璃纤维20-30份、润滑剂2-3份制成,解决了拉伸强度、弯曲强度、冲击强度存在的缺陷,但是断裂伸长率、摩擦系数、表面洛氏硬度和耐光老化性等没有改进,随着社会城市化、科技化、人性化的发展,设计一种断裂伸长率、摩擦系数、表面洛氏硬度高和耐光老化性好的纳米碳酸钙填充HDPE材料及其制备方法,以满足市场需求,是非常必要的。 
发明内容
解决的技术问题:
本申请针对现有HDPE材料断裂伸长率、摩擦系数、表面洛氏硬度和耐光老化性没有很大改进的技术问题,提供一种利用纳米碳酸钙填充HDPE材料及其制备方法。
技术方案:
一种纳米碳酸钙填充HDPE材料,原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.3-0.7份,纳米碳酸钙10-30份,UV-327为0.5-2.5份,ACR10-20份,亚磷酸酯0.2-0.8份,CPE15-25份,二硫化四乙基秋兰姆0.15-0.35份,钛酸酯10-20份,硬脂酸铅1.5-2.5份,抗冲击改性剂5-15份,氧化铝1-5份,石油醚20-30份,增塑剂60-90份。
作为本发明的一种优选技术方案:所述纳米碳酸钙填充HDPE材料的原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.4-0.6份,纳米碳酸钙15-25份,UV-327为1-2份,ACR13-17份,亚磷酸酯0.3-0.7份,CPE18-22份,二硫化四乙基秋兰姆0.2-0.3份,钛酸酯12-18份,硬脂酸铅1.8-2.2份,抗冲击改性剂7-13份,氧化铝2-4份,石油醚22-17份,增塑剂70-80份。
作为本发明的一种优选技术方案:所述纳米碳酸钙填充HDPE材料的原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.5份,纳米碳酸钙20份,UV-327为1.5份,ACR15份,亚磷酸酯0.5份,CPE20份,二硫化四乙基秋兰姆0.25份,钛酸酯15份,硬脂酸铅2份,抗冲击改性剂10份,氧化铝3份,石油醚25份,增塑剂75份。
作为本发明的一种优选技术方案:所述抗冲击改性剂采用MBS。
作为本发明的一种优选技术方案:所述增塑剂采用DOP或DBP。
所述纳米碳酸钙填充HDPE材料的制备方法步骤为:
第一步:按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在100-120℃烘40-60min除去溶剂;
第二步:利用振动研磨机分散1-2h后加入剩余原料,在110-130℃下搅拌20-40min;
第三步:将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
有益效果:
本发明所述一种纳米碳酸钙填充HDPE材料及其制备方法采用以上技术方案和现有技术相比,具有以下技术效果:1、产品冲击强度24-36kJ/m2,是纯HDPE的1.7倍;2、摩擦系数0.116,表面洛氏硬度为81.5;3、拉伸强度70-80MPa,断裂伸长率660%-700%;4、紫外光照射2500h后伸长率保持率99%-100%,可以广泛生产并不断代替现有材料。 
具体实施方式
实施例1:
按重量份数配比称取HDPE100份,抗氧剂DSTP0.3份,纳米碳酸钙10份,UV-327为0.5份,ACR10份,亚磷酸酯0.2份,CPE15份,二硫化四乙基秋兰姆0.15份,钛酸酯10份,硬脂酸铅1.5份,MBS5份,氧化铝1份,石油醚20份,DBP60份,按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在100℃烘40min除去溶剂,利用振动研磨机分散1h后加入剩余原料,在110℃下搅拌20min,将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
产品冲击强度24kJ/m2,摩擦系数0.116,表面洛氏硬度为81.5,拉伸强度70MPa,断裂伸长率660%;紫外光照射2500h后伸长率保持率99%。 
实施例2:
按重量份数配比称取HDPE100份,抗氧剂DSTP0.7份,纳米碳酸钙30份,UV-327为2.5份,ACR20份,亚磷酸酯0.8份,CPE25份,二硫化四乙基秋兰姆0.35份,钛酸酯20份,硬脂酸铅2.5份,MBS15份,氧化铝5份,石油醚30份,DBP90份,按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在120℃烘60min除去溶剂,利用振动研磨机分散2h后加入剩余原料,在130℃下搅拌40min,将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
产品冲击强度28kJ/m2,摩擦系数0.116,表面洛氏硬度为81.5,拉伸强度72MPa,断裂伸长率670%;紫外光照射2500h后伸长率保持率99%。 
实施例3:
按重量份数配比称取HDPE100份,抗氧剂DSTP0.4份,纳米碳酸钙15份,UV-327为1份,ACR13份,亚磷酸酯0.3份,CPE18份,二硫化四乙基秋兰姆0.2份,钛酸酯12份,硬脂酸铅1.8份,MBS7份,氧化铝2份,石油醚22份,DBP70份,按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在105℃烘45min除去溶剂,利用振动研磨机分散1h后加入剩余原料,在115℃下搅拌25min,将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
产品冲击强度30kJ/m2,摩擦系数0.116,表面洛氏硬度为81.5,拉伸强度75MPa,断裂伸长率680%;紫外光照射2500h后伸长率保持率99%。 
实施例4:
按重量份数配比称取HDPE100份,抗氧剂DSTP0.6份,纳米碳酸钙25份,UV-327为2份,ACR17份,亚磷酸酯0.7份,CPE22份,二硫化四乙基秋兰姆0.3份,钛酸酯18份,硬脂酸铅2.2份,MBS13份,氧化铝4份,石油醚17份,DOP80份,按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在115℃烘55min除去溶剂,利用振动研磨机分散2h后加入剩余原料,在125℃下搅拌35min,将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
产品冲击强度32kJ/m2,摩擦系数0.116,表面洛氏硬度为81.5,拉伸强度78MPa,断裂伸长率690%;紫外光照射2500h后伸长率保持率99%。 
实施例5:
按重量份数配比称取HDPE100份,抗氧剂DSTP0.5份,纳米碳酸钙20份,UV-327为1.5份,ACR15份,亚磷酸酯0.5份,CPE20份,二硫化四乙基秋兰姆0.25份,钛酸酯15份,硬脂酸铅2份,MBS10份,氧化铝3份,石油醚25份,DOP75份,按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在110℃烘50min除去溶剂,利用振动研磨机分散1.5h后加入剩余原料,在120℃下搅拌30min,将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
产品冲击强度36kJ/m2,摩擦系数0.116,表面洛氏硬度为81.5,拉伸强度80MPa,断裂伸长率700%;紫外光照射2500h后伸长率保持率100%。
以上实施例中的所有组分均可以商业购买。
上述实施例只是用于对本发明的内容进行阐述,而不是限制,因此在和本发明的权利要求书相当的含义和范围内的任何改变,都应该认为是包括在权利要求书的范围内。

Claims (6)

1.一种纳米碳酸钙填充HDPE材料,其特征在于,所述纳米碳酸钙填充HDPE材料的原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.3-0.7份,纳米碳酸钙10-30份,UV-327为0.5-2.5份,ACR10-20份,亚磷酸酯0.2-0.8份,CPE15-25份,二硫化四乙基秋兰姆0.15-0.35份,钛酸酯10-20份,硬脂酸铅1.5-2.5份,抗冲击改性剂5-15份,氧化铝1-5份,石油醚20-30份,增塑剂60-90份。
2.根据权利要求1所述的一种纳米碳酸钙填充HDPE材料,其特征在于,所述纳米碳酸钙填充HDPE材料的原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.4-0.6份,纳米碳酸钙15-25份,UV-327为1-2份,ACR13-17份,亚磷酸酯0.3-0.7份,CPE18-22份,二硫化四乙基秋兰姆0.2-0.3份,钛酸酯12-18份,硬脂酸铅1.8-2.2份,抗冲击改性剂7-13份,氧化铝2-4份,石油醚22-17份,增塑剂70-80份。
3.根据权利要求1所述的一种纳米碳酸钙填充HDPE材料,其特征在于,所述纳米碳酸钙填充HDPE材料的原料按重量份数配比如下:HDPE100份,抗氧剂DSTP0.5份,纳米碳酸钙20份,UV-327为1.5份,ACR15份,亚磷酸酯0.5份,CPE20份,二硫化四乙基秋兰姆0.25份,钛酸酯15份,硬脂酸铅2份,抗冲击改性剂10份,氧化铝3份,石油醚25份,增塑剂75份。
4.根据权利要求1所述的一种纳米碳酸钙填充HDPE材料,其特征在于,所述抗冲击改性剂采用MBS。
5.根据权利要求1所述的一种纳米碳酸钙填充HDPE材料,其特征在于:所述增塑剂采用DOP或DBP。
6.一种权利要求1所述纳米碳酸钙填充HDPE材料的制备方法,其特征在于,包括如下步骤:
第一步:按重量份数配比称取原料,将钛酸酯在石油醚中溶解后处理纳米碳酸钙,混合均匀后让如烘箱中在100-120℃烘40-60min除去溶剂;
第二步:利用振动研磨机分散1-2h后加入剩余原料,在110-130℃下搅拌20-40min;
第三步:将第二步搅拌后的物料投放到长径比为30:1的双螺杆挤出机中熔融造粒,挤出机温度设置为:150℃、170℃、190℃、190℃、190℃、190℃和180℃。
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