CN106279750B - 环保废旧pe料及制备方法和用其制得的改性环保废旧pe料及制备方法 - Google Patents
环保废旧pe料及制备方法和用其制得的改性环保废旧pe料及制备方法 Download PDFInfo
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Abstract
本发明涉及一种环保废旧PE料及制备方法和用其制得的改性环保废旧PE料及制备方法,属于PE材料技术领域。该环保废旧PE料的制备方法,包括如下步骤:一次水洗、二次水洗、干燥、处理液Ⅰ清洗、处理液Ⅱ清洗、水洗干燥。按照本发明方法处理后的废旧PE料,因较彻底地清除了PE料上的污染物,其物理性能与全新料相差不大,甚至可以替代全新料使用,同时经过本发明改性后得到的改性环保废旧PE料其性能与全新料相当,甚至优于全新料的性能,同时还具有优异的抗菌性。
Description
技术领域
本发明属于PE材料技术领域,具体涉及一种环保废旧PE料及制备方法和用其制得的改性环保废旧PE料及制备方法。
背景技术
PE塑料即聚乙烯塑料,是最重要的通用塑料之一,具有优异的物理性能,起其产量也一直稳居各塑料之首。聚乙烯是由乙烯聚合而得的高分子化合物,是非极性聚合物,故其具有优良的耐酸碱及耐化学物质腐蚀的特性,此外还具有良好的电气性和可加工性,因此被广泛应用在家电、汽车、包装材料及日用品领域,而且在工业领域如保温材料等领域也有较广泛的应用。
但是PE塑料存在难降解的问题,加之现在多数由PE塑料加工而成的产品在一次使用后即会被废弃,大量的废弃PE塑料随意堆放,对日益严峻的环境来讲可谓是雪上加霜。而目前国内外仍缺少一种有效的可降解PE料,因此对废旧PE料的回收再利用,就显得尤为重要。以PE管材为例,目前二次回收利用的废旧PE料,其在之前的使用过程中受到的不同程度的污染,而这些污染物正是导致二次回收的PE料性能减弱的主要原因,若对污染物处理不彻底,直接后果就是限制二次回收PE料的使用范围。近年来,国内有诸多企业在尝试将废旧PE料变废为宝,但是其无法寻找到一种合适的可以有效彻底清洗废旧PE料表面的污染物的处理方法。
发明内容
本发明的目的是为了解决现有技术的不足,而提供一种环保废旧PE料及制备方法和用其制得的改性环保废旧PE料及制备方法,该方法可以较彻底清除废旧PE料表面的污染物,得到一种环保废旧PE料,而改性后的环保废旧PE料具有优异的物理性能和抗菌阻燃性能。
本发明采用如下技术方案:
环保废旧PE料的制备方法,包括如下步骤:
步骤一,一次水洗:将回收的PE废料置于水中浸泡,水温40-50℃,浸泡时间2-4h,滤掉水,得一次水洗PE废料;
步骤二,二次水洗:将步骤一所得一次水洗PE废料粉碎至颗粒状,用高压水冲洗5-10min,得二次水洗PE废料;
步骤三,干燥:将步骤二所得二次水洗PE废料真空干燥,得干燥PE废料;
步骤四,处理液Ⅰ清洗:将步骤三所得干燥PE废料浸入处理液Ⅰ中,升温至40-45℃,恒温匀速搅拌30-50min,过滤取PE废料,得一次处理PE废料,其中所述处理液Ⅰ包括按照质量份数计的如下组分:10-15份月桂酸、1-2份荷荷巴油、20-30份乙醇、100-110份水、0.1-0.5份磷酸、5-10份单硬脂酸甘油酯、2-6份氯化钠;
步骤五,处理液Ⅱ清洗:将步骤四所得一次处理PE废料浸入处理液Ⅱ中,20-40min内搅拌升温至50-55℃,后静置至室温,过滤取PE废料,得二次处理PE废料,其中所述处理液Ⅱ包括按照质量份数计的如下组分:10-15份壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、8-14份油酸聚乙二醇单酯、1-2份月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠,10-20份硅藻土微粉,20-30份乙醇、5-10份乙二醇、150-160份水;
步骤六,水洗干燥:将步骤五所得二次处理PE废料用清水冲洗,再真空干燥,即得环保废旧PE料。
更进一步的,所述的环保废旧PE料的制备方法,其中步骤三中所述真空干燥的真空度为0.7-0.8MPa,温度为40-45℃。
更进一步的,所述的环保废旧PE料的制备方法,其中步骤四中匀速搅拌的搅拌速度为100-150r/min。
更进一步的,所述的环保废旧PE料的制备方法,其中步骤五中所述搅拌的速度为200-250r/min,所述硅藻土微粉的粒径为100-200μm。
本发明还提供一种由所述的环保废旧PE料的制备方法制得的环保废旧PE料。
用上述的环保废旧PE料制备改性环保废旧PE料的方法,步骤如下:按照质量份数计,将70-80份环保废旧PE料、0.5-1.2份双(3,5-二叔丁基-4-羟基苄基)硫醚、2-6份硬脂酸钡、2-5份壳聚糖接枝苯乙烯依次加入高速混合机中混合均匀,后经双螺杆挤出机挤出造粒,即得所述改性环保废旧PE料。
更进一步的,所述的用环保废旧PE料制备改性环保废旧PE料的方法,其中所述高速混合机进行混合时的温度为50-60℃,双螺杆挤出机各段温度为260-270℃。
本发明与现有技术相比,其有益效果为:
一般废旧PE回收料表面的污染物主要分为两类,一类是用清水可以去除的灰尘杂质及一些溶于水的物质如各种盐类,第二类是不溶于水的有机物,PE废料在之前的使用过程中会接触多种成分复杂的有机物如油脂、各类难溶或不溶于水的有机物质,而这些有机物正是影响PE废料性能的主要因素。本发明通过一次水洗、二次水洗、干燥、处理液Ⅰ清洗、处理液Ⅱ清洗及水洗干燥等步骤较彻底地清除了废旧PE回收料表面的污染物,使废旧PE回收料的性能得到大幅改善,其中,一次水洗步骤采用恒温浸泡,有效去除了废旧PE回收料表面的灰尘杂质;二次水洗步骤采用高压水清洗,更进一步清除了废旧PE回收料表面剩余的灰尘杂质及溶于水的物质;处理液Ⅰ清洗步骤首先清除废旧PE回收料表面的粗油脂,处理液Ⅱ清洗步骤较彻底地清除了废旧PE回收料表面的难溶有机物和油脂。
在处理废旧PE料的过程中,为了达到较好的清洗效果,申请人自行配制了处理液Ⅰ和处理液Ⅱ,其中处理液Ⅰ由月桂酸、荷荷巴油、乙醇、水、磷酸、单硬脂酸甘油酯和氯化钠组成,在试验中申请人发现,将月桂酸、单硬脂酸甘油酯、荷荷巴油加入乙醇中,再配合水,其清洗效果会比单纯的月桂酸强很多,而且在清洗过程中泡沫也较少,但是荷荷巴油在温度较低时容易在PE废料表面结晶,而在水中加入极少量磷酸和适量氯化钠后,则可有效抑制荷荷巴油低温下在PE废料表面结晶;处理液Ⅱ的配制,申请人发现将阴离子表面活性剂壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐溶于水、将非离子表面活性剂油酸聚乙二醇单酯溶于乙醇及将阴离子表面活性剂月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠溶于水复配后,可以有效增强润湿性和去污性,且在清洗过程中泡沫很少无须再添加消泡剂进行消泡,但是将上述各组分混合后处理液会有少量沉淀出现,但是加入乙二醇后可以起到增溶的作用,沉淀会消失,硅藻土微粉的加入可以缩短处理液的清洗时间,提高清洗效率。
此外,本发明还对清洗处理后的废旧PE料进行了共混改性,在制得的环保废旧PE料的基础上添加抗氧剂双(3,5-二叔丁基-4-羟基苄基)硫醚、润滑剂硬脂酸钡、抗菌剂壳聚糖接枝苯乙烯,进一步改善了环保废旧PE料的性能,拓宽了其应用范围。因此,本发明真正做到环保节能,变废为宝,制得的废旧PE料性能堪比全新料。
具体实施方式
下面结合实施例对本发明作进一步的详细描述。
本领域技术人员将会理解,下列实施例仅用于说明本发明,而不应视为限定本发明的范围。
实施例1
环保废旧PE料的制备方法,包括如下步骤:
步骤一,一次水洗:将回收的PE废料置于水中浸泡,水温45℃,浸泡时间3h,滤掉水,得一次水洗PE废料;
步骤二,二次水洗:将步骤一所得一次水洗PE废料粉碎至颗粒状,用高压水冲洗8min,得二次水洗PE废料;
步骤三,干燥:将步骤二所得二次水洗PE废料真空干燥,得干燥PE废料,所述真空干燥的真空度为0.7 5MPa,温度为43℃;
步骤四,处理液Ⅰ清洗:将步骤三所得干燥PE废料浸入处理液Ⅰ中,升温至42℃,恒温匀速搅拌40min,搅拌速度为100r/min,过滤取PE废料,得一次处理PE废料,其中所述处理液Ⅰ包括按照质量份数计的如下组分:12份月桂酸、1.5份荷荷巴油、25份乙醇、105份水、0.3份磷酸、8份单硬脂酸甘油酯、4份氯化钠,处理液Ⅰ的制备方法如下:将月桂酸、荷荷巴油、单硬脂酸甘油酯依次加入乙醇中搅拌均匀,将磷酸、氯化钠加入水中搅拌均匀后加入上述混合液中,继续搅拌均匀即可;
步骤五,处理液Ⅱ清洗:将步骤四所得一次处理PE废料浸入处理液Ⅱ中,30min内搅拌升温至53℃,搅拌的速度为200r/min,后静置至室温,过滤取PE废料,得二次处理PE废料,其中所述处理液Ⅱ包括按照质量份数计的如下组分:14份壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、11份油酸聚乙二醇单酯、1.5份月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠,15份硅藻土微粉,25份乙醇、8份乙二醇、155份水,其中硅藻土微粉的粒径为100μm,处理液Ⅱ的制备方法如下:将壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠依次加入水中搅拌均匀,将油酸聚乙二醇单酯加入水中搅拌均匀后加入上述水溶液中搅拌均匀,再加入乙二醇搅拌均匀,最后加入硅藻土微粉即可。
步骤六,水洗干燥:将步骤五所得二次处理PE废料用清水冲洗,再真空干燥,即得环保废旧PE料。
用环保废旧PE料制备改性环保废旧PE料的方法,步骤如下:按照质量份数计,将75份环保废旧PE料、0.8份双(3,5-二叔丁基-4-羟基苄基)硫醚、4份硬脂酸钡、3份壳聚糖接枝苯乙烯依次加入高速混合机中混合均匀,高速混合机进行混合时的温度为55℃,后经双螺杆挤出机挤出造粒,双螺杆挤出机各段温度为265℃,即得所述改性环保废旧PE料。
实施例2
环保废旧PE料的制备方法,包括如下步骤:
步骤一,一次水洗:将回收的PE废料置于水中浸泡,水温40℃,浸泡时间4h,滤掉水,得一次水洗PE废料;
步骤二,二次水洗:将步骤一所得一次水洗PE废料粉碎至颗粒状,用高压水冲洗5min,得二次水洗PE废料;
步骤三,干燥:将步骤二所得二次水洗PE废料真空干燥,得干燥PE废料,所述真空干燥的真空度为0.7MPa,温度为45℃;
步骤四,处理液Ⅰ清洗:将步骤三所得干燥PE废料浸入处理液Ⅰ中,升温至40℃,恒温匀速搅拌50min,搅拌速度为100r/min,过滤取PE废料,得一次处理PE废料,其中所述处理液Ⅰ包括按照质量份数计的如下组分:10份月桂酸、1份荷荷巴油、20份乙醇、100份水、0.1份磷酸、5份单硬脂酸甘油酯、2份氯化钠,处理液Ⅰ的制备方法如下:将月桂酸、荷荷巴油、单硬脂酸甘油酯依次加入乙醇中搅拌均匀,将磷酸、氯化钠加入水中搅拌均匀后加入上述混合液中,继续搅拌均匀即可;
步骤五,处理液Ⅱ清洗:将步骤四所得一次处理PE废料浸入处理液Ⅱ中,20min内搅拌升温至55℃,搅拌的速度为200r/min,后静置至室温,过滤取PE废料,得二次处理PE废料,其中所述处理液Ⅱ包括按照质量份数计的如下组分:10份壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、8份油酸聚乙二醇单酯、1份月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠,10份硅藻土微粉,20份乙醇、5份乙二醇、150份水,其中硅藻土微粉的粒径为200μm,处理液Ⅱ的制备方法如下:将壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠依次加入水中搅拌均匀,将油酸聚乙二醇单酯加入水中搅拌均匀后加入上述水溶液中搅拌均匀,再加入乙二醇搅拌均匀,最后加入硅藻土微粉即可。
步骤六,水洗干燥:将步骤五所得二次处理PE废料用清水冲洗,再真空干燥,即得环保废旧PE料。
用环保废旧PE料制备改性环保废旧PE料的方法,步骤如下:按照质量份数计,将70份环保废旧PE料、0.5份双(3,5-二叔丁基-4-羟基苄基)硫醚、2份硬脂酸钡、2份壳聚糖接枝苯乙烯依次加入高速混合机中混合均匀,高速混合机进行混合时的温度为50℃,后经双螺杆挤出机挤出造粒,双螺杆挤出机各段温度为260℃,即得所述改性环保废旧PE料。
实施例3
环保废旧PE料的制备方法,包括如下步骤:
步骤一,一次水洗:将回收的PE废料置于水中浸泡,水温50℃,浸泡时间4h,滤掉水,得一次水洗PE废料;
步骤二,二次水洗:将步骤一所得一次水洗PE废料粉碎至颗粒状,用高压水冲洗10min,得二次水洗PE废料;
步骤三,干燥:将步骤二所得二次水洗PE废料真空干燥,得干燥PE废料,所述真空干燥的真空度为0.8MPa,温度为40℃;
步骤四,处理液Ⅰ清洗:将步骤三所得干燥PE废料浸入处理液Ⅰ中,升温至45℃,恒温匀速搅拌30min,搅拌速度为150r/min,过滤取PE废料,得一次处理PE废料,其中所述处理液Ⅰ包括按照质量份数计的如下组分: 15份月桂酸、2份荷荷巴油、30份乙醇、110份水、0.5份磷酸、10份单硬脂酸甘油酯、6份氯化钠,处理液Ⅰ的制备方法如下:将月桂酸、荷荷巴油、单硬脂酸甘油酯依次加入乙醇中搅拌均匀,将磷酸、氯化钠加入水中搅拌均匀后加入上述混合液中,继续搅拌均匀即可;
步骤五,处理液Ⅱ清洗:将步骤四所得一次处理PE废料浸入处理液Ⅱ中, 40min内搅拌升温至50℃,搅拌的速度为250r/min,后静置至室温,过滤取PE废料,得二次处理PE废料,其中所述处理液Ⅱ包括按照质量份数计的如下组分:15份壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、14份油酸聚乙二醇单酯、2份月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠,20份硅藻土微粉,30份乙醇、10份乙二醇、160份水,其中硅藻土微粉的粒径为100μm,处理液Ⅱ的制备方法如下:将壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠依次加入水中搅拌均匀,将油酸聚乙二醇单酯加入水中搅拌均匀后加入上述水溶液中搅拌均匀,再加入乙二醇搅拌均匀,最后加入硅藻土微粉即可。
步骤六,水洗干燥:将步骤五所得二次处理PE废料用清水冲洗,再真空干燥,即得环保废旧PE料。
用环保废旧PE料制备改性环保废旧PE料的方法,步骤如下:按照质量份数计,将80份环保废旧PE料、1.2份双(3,5-二叔丁基-4-羟基苄基)硫醚、6份硬脂酸钡、5份壳聚糖接枝苯乙烯依次加入高速混合机中混合均匀,高速混合机进行混合时的温度为60℃,后经双螺杆挤出机挤出造粒,双螺杆挤出机各段温度为270℃,即得所述改性环保废旧PE料。
以未经过本发明清洗处理的废旧PE料为对照例,测试本发明实施例1至3制得的废旧PE塑料及改性废旧PE塑料的拉伸强度(MPa)、断裂伸长率(%)、冲击强度(MPa)及弯曲强度(MPa),并与全新PE塑料的性能数据为基础,计算出废旧PE塑料性能数据所能达到的百分比(%),结果如下表所示。同时还测试了本发明改性废旧PE塑料的杀菌性,其抗菌性满足QB/T-2519-2003 抗菌塑料-抗菌性能实验方法和抗菌效果标准的要求,其对金黄色葡萄球菌、大肠杆菌的杀菌率达到98%以上。
表1 性能测试数据
由上表可见,按照本发明方法处理后的废旧PE料,因较彻底地清除了PE料上的污染物,其物理性能与全新料相差不大,甚至可以替代全新料使用,同时经过本发明改性后得到的改性环保废旧PE料其性能与全新料相当,甚至优于全新料的性能,同时还具有优异的抗菌性。
本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (7)
1.环保废旧PE料的制备方法,其特征在于,包括如下步骤:
步骤一,一次水洗:将回收的PE废料置于水中浸泡,水温40-50℃,浸泡时间2-4h,滤掉水,得一次水洗PE废料;
步骤二,二次水洗:将步骤一所得一次水洗PE废料粉碎至颗粒状,用高压水冲洗5-10min,得二次水洗PE废料;
步骤三,干燥:将步骤二所得二次水洗PE废料真空干燥,得干燥PE废料;
步骤四,处理液Ⅰ清洗:将步骤三所得干燥PE废料浸入处理液Ⅰ中,升温至40-45℃,恒温匀速搅拌30-50min,过滤取PE废料,得一次处理PE废料,其中所述处理液Ⅰ包括按照质量份数计的如下组分:10-15份月桂酸、1-2份荷荷巴油、20-30份乙醇、100-110份水、0.1-0.5份磷酸、5-10份单硬脂酸甘油酯、2-6份氯化钠;
步骤五,处理液Ⅱ清洗:将步骤四所得一次处理PE废料浸入处理液Ⅱ中,20-40min内搅拌升温至50-55℃,后静置至室温,过滤取PE废料,得二次处理PE废料,其中所述处理液Ⅱ包括按照质量份数计的如下组分:10-15份壬基酚聚氧乙烯醚磺基琥珀酸单酯二钠盐、8-14份油酸聚乙二醇单酯、1-2份月桂醇聚氧化烯烃醚琥珀酸单酯磺酸钠,10-20份硅藻土微粉,20-30份乙醇、5-10份乙二醇、150-160份水;
步骤六,水洗干燥:将步骤五所得二次处理PE废料用清水冲洗,再真空干燥,即得环保废旧PE料。
2.根据权利要求1所述的环保废旧PE料的制备方法,其特征在于,步骤三中所述真空干燥的真空度为0.7-0.8MPa,温度为40-45℃。
3.根据权利要求1所述的环保废旧PE料的制备方法,其特征在于,步骤四中匀速搅拌的搅拌速度为100-150r/min。
4.根据权利要求1所述的环保废旧PE料的制备方法,其特征在于,步骤五中所述搅拌的速度为200-250r/min,所述硅藻土微粉的粒径为100-200μm。
5.由权利要求1所述的环保废旧PE料的制备方法制得的环保废旧PE料。
6.用权利要求5所述的环保废旧PE料制备改性环保废旧PE料的方法,其特征在于,步骤如下:按照质量份数计,将70-80份环保废旧PE料、0.5-1.2份双(3,5-二叔丁基-4-羟基苄基)硫醚、2-6份硬脂酸钡、2-5份壳聚糖接枝苯乙烯依次加入高速混合机中混合均匀,后经双螺杆挤出机挤出造粒,即得所述改性环保废旧PE料。
7.根据权利要求6所述的用环保废旧PE料制备改性环保废旧PE料的方法,其特征在于,所述高速混合机进行混合时的温度为50-60℃,双螺杆挤出机各段温度为260-270℃。
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