CN110684258A - 一种聚乙烯改性材料及其制备方法 - Google Patents
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Abstract
本发明属于新材料技术领域,具体涉及一种聚乙烯改性材料及其制备方法;本发明包括聚乙烯树脂、聚乙烯废塑料、固态烷烃的混合物、硬脂酸锌、硬脂酸钙、乙烯基双硬脂酰胺和抗氧剂;本发明以聚乙烯树脂和聚乙烯废塑料为基材,通过添加各种助剂并在本发明研究的制备工艺下,制得聚乙烯改性材料。该改性材料具有优异耐寒性、耐热性、耐化学性、耐磨性和润滑性等优点,从而使其在塑料或者色母料加工成型中起到很好的润滑和相容作用。在塑料或者色母料加工成型时使用聚乙烯改性材料,可以改善物料的流动性,增加产品的光泽、润滑性和加工性能,提高产量,并能够允许更高的填料浓度。
Description
技术领域
本发明属于新材料技术领域,具体涉及一种聚乙烯改性材料及其制备方法。
背景技术
随着工业发展,聚乙烯因为具有优良的耐低温性能(最低使用温度可达-100-70℃),化学稳定性好,能耐大多数酸碱的侵蚀(不耐具有氧化性质的酸),常温下不溶于一般溶剂,吸水性小,电绝缘性优良等而广泛使用。但是随着使用量的增大,其废旧的聚乙烯量也随之增大,给人们生存的环境带来污染。废塑料制品不仅对市容、景观的破坏,而且这些废塑料散落在地面上,或随风挂在树枝上飘扬、或漂浮在水面,污染环境、传播疾病、人民群众对此反映强烈。尤其是废塑料制品进入自然环境后难以降解而带来的长期的深层次环境问题。塑料结构稳定,不易被天然微生物破坏,在自然环境中长期不分离。这就意味着废塑料垃圾如不加以回收,将在环境中变成污染物永久存在并不段累积。在环境中的危害有以下几个方面:
(1)影响工农业生产的发展。废塑料制品混在土壤中不断累积,会影响农作物吸收养分和水分,导致农作物减产;漂浮在长江中的塑料制品给水源取用带来很大困难,造成泵抽空和堵塞,给工业生产和水电站造成巨大损失。
(2)抛弃在陆地上或水体中的废塑料制品,被动物当作食物吞入,导致动物死亡。在动物园、牧区、农村、海洋中,此类情况已屡见不鲜;
(3)废塑料随垃圾填埋不仅会占用大量土地,而且被占用的土地长期得不到恢复,影响土地的可持续利用。进入生活垃圾中的废塑料制品很难回收利用,如果将其填埋,200年的时间不降解,会导致大片土地被长期占用,加剧了土地资源的压力。不仅我们这代要被垃圾包围、也会使子孙后代失去生存的空间。
(4)混有塑料的生活垃圾不适用于堆肥,要从垃圾中分拣出来废塑料,这样又增加了堆肥成本。污染了的废塑料因无法保证质量,其利用价值也很低。
因此,对其进行回收处理成为人们研究的热点。目前,出现了一些方法,例如将废弃聚乙烯塑料为原料制备憎水沙,或者将其用于制备聚乙烯填充料扁丝专用增韧功能调节剂,或者将其改性成的土工网专用料等等。但是现在的方法一方面生产工艺比较复杂,另外一方面对于高密度聚乙烯、低密度聚乙烯及线性低密度聚乙烯需要不同的设备进行分类处理。
发明内容
为了解决上述问题,本发明的目的在于提供一种聚乙烯改性材料,该材料不但具有优异耐寒性、耐热性、耐化学性、耐磨性和润滑性,而且制备成本低廉的同时,尤其是解决废弃聚乙烯的一个好方法。
本发明的目的之二是提供了所述聚乙烯改性材料的制备方法。
本发明是通过以下技术方案来实现的:
一种聚乙烯改性材料,包含了按照重量份比计算的如下原料:
所述固态烷烃的混合物为的分子式为CnH2n+2,其中n=17~35,主要组分为直链烷烃,还有少量带个别支链的烷烃和带长侧链的单环环烷烃;所述聚乙烯废塑料为高密度聚乙烯、低密度聚乙烯、中密度聚乙烯、超高分子量聚乙烯、线性低密度聚乙烯中的一种或几种混合物。
较佳地,包含了按照重量份比计算的如下原料:
较佳地,聚乙烯树脂为氯化聚乙烯、交联聚乙烯、乙烯-丙烯共聚物、EVA、乙烯-丁烯共聚物、乙烯-其它烯烃共聚物、EAA、EMAA、EEA、EMA、EMMA、EMAH中的一种或几种组合物。
较佳地,所述抗氧剂由主抗氧剂和次抗氧剂组成的混合抗氧剂;其中,所述主抗氧剂与次抗氧剂添加量的质量比为1-2:1。
较佳地,所述次抗氧剂为三[2.4-二叔丁基苯基]亚磷酸酯,所述主抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯;更优选二者1:1的混合物。
较佳地,所述聚乙烯树脂的热变形温度为30-60℃,熔点为110-125℃,熔指为1.5-2.2g/10mi n。
较佳地,所述硬脂酸锌的熔点为115-125℃,自燃点为900℃;所述硬脂酸钙的熔点为150-155℃;所述乙烯基双硬脂酰胺的初熔点为:140-146℃。
较佳地,固态烷烃的混合物优选石蜡,
聚乙烯改性材料的制备方法,制备步骤具体如下:
(1)首先将聚乙烯树脂、聚乙烯废塑料加入可加热的密闭反应釜中,反应釜中装备有搅拌装置,通过搅拌和加热使聚乙烯树脂和聚乙烯废塑料在反应釜中进行充分裂解,裂解时的温度为500-600℃,时间为0.3-4小时;
(2)待步骤(1)中裂解产物冷却到100℃时,依次向反应釜中添加固态烷烃的混合物、硬脂酸锌、硬脂酸钙、乙烯基双硬脂酰胺和抗氧剂,在100-150℃下,搅拌0.5-2小时,然后出料;
(3)将步骤(2)中所得到的块状料进行破碎和精制,从而得到所需要的化工材料聚乙烯改性材料。
较佳地,所述步骤(1)中裂解时的搅拌速度为80-100转/分钟,步骤(2)中混合时的搅拌速度为85-110转/分钟。
较佳地,所述精制具体为将破碎后的物料进行喷雾,然后待固化后进行过筛40目-200目,得到所述聚乙烯改性材料。通过检测,聚乙烯改性材料为蜡状低分子聚乙烯。
本发明以聚乙烯树脂和聚乙烯废塑料为基材,通过添加各种助剂并在本发明研究的制备工艺下,制得聚乙烯改性材料。其中,废弃聚乙烯为高密度聚乙烯、低密度聚乙烯、线性低密度聚乙烯中的一种或几种混合物。这些基材,在反应釜中通过较高的温度直接裂解,然后添加其它助剂。对于不同种类的废弃聚乙烯,不需要分类处理,大大节约了制备工序。为保证材料的品质需求,反应釜的加热温度、助剂的投入顺序、时间控制等条件均须优化并严格合理管理。材料配方中原材料的规格型号、比例以及材料加工过程中的加工条件参数,对产品的性能及外观效果有重要影响,在实施中需要合理匹配、严格管理。最终制得的聚乙烯改性材料分子量<10000,具有优异耐寒性、耐热性、耐化学性、耐磨性和润滑性等优点,从而使其在塑料或者色母料加工成型中起到很好的润滑和相容作用。在塑料或者色母料加工成型时使用聚乙烯改性材料,可以改善物料的流动性,增加产品的光泽、润滑性和加工性能,提高产量,并能够允许更高的填料浓度。
具体的实施方式
下面结合具体实施方式对本发明作进一步的详细说明,以助于本领域技术人员理解本发明。
实施例1
一种聚乙烯改性材料,包含了按照重量份比计算的如下原料:
交联聚乙烯25份、低密度聚乙烯35份、固态烷烃的混合物39份、硬脂酸锌0.份、硬脂酸钙0.1份、乙烯基双硬脂酰胺0.7份、三[2.4-二叔丁基苯基]亚磷酸酯0.05份,四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.05份;
制备方法:
(1)首先将聚乙烯树脂、聚乙烯废塑料加入可加热的密闭反应釜中,反应釜中装备有搅拌装置,通过搅拌和加热使聚乙烯树脂和聚乙烯废塑料在反应釜中进行充分裂解,裂解时的温度为600℃,时间为0.3小时;裂解时的搅拌速度为100转/分钟。
(2)待步骤(1)中裂解产物冷却到100℃时,依次向反应釜中添加固态烷烃的混合物、硬脂酸锌、硬脂酸钙、乙烯基双硬脂酰胺和抗氧剂,在150℃下,搅拌0.5小时,然后出料;混合时的搅拌速度为110转/分钟。
(3)将步骤(2)中所得到的块状料进行破碎后的物料进行水喷雾,然后待固化后进行过筛200目,得到所述聚乙烯改性材料。
实施例2
一种聚乙烯改性材料,包含了按照重量份比计算的如下原料:
聚乙烯树脂(氯化聚乙烯、交联聚乙烯、乙烯-丙烯共聚物、EVA、乙烯-丁烯共聚物、乙烯-其它烯烃共聚物、EAA、EMAA、EEA、EMA、EMMA、EMAH中的一种或几种组合物)59份、聚乙烯废塑料(其中,高密度聚乙烯10份、低密度聚乙烯10份、中密度聚乙烯10份)、固态烷烃的混合物20份、硬脂酸锌0.1份、硬脂酸钙0.1份、乙烯基双硬脂酰胺0.3份、三[2.4-二叔丁基苯基]亚磷酸酯0.25份和四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.25份;
制备方法同实施例1,区别具体如下:
(1)裂解时的温度为500℃,时间为4小时;裂解时的搅拌速度为80转/分钟。
(2)在100℃下,搅拌2小时,然后出料;混合时的搅拌速度为85转/分钟。
(3)待固化后进行过筛40目,得到所述聚乙烯改性材料。
实施例3
一种聚乙烯改性材料,包含了按照重量份比计算的如下原料:
EAA 2份、EMAA 15份、EEA 15份、超高分子量聚乙烯30份、固态烷烃的混合物35.6份、硬脂酸锌0.4份、硬脂酸钙0.5份、乙烯基双硬脂酰胺0.5份、三[2.4-二叔丁基苯基]亚磷酸酯0.5份、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.5份;
制备方法同实施例1,区别具体如下:
(1)裂解时的温度为500-600℃,时间为0.3-4小时;裂解时的搅拌速度为80-100转/分钟。
(2)在100-150℃下,搅拌0.5-2小时,然后出料;混合时的搅拌速度为85-110转/分钟。
(3)待固化后进行过筛40目-200目,得到所述聚乙烯改性材料。
实施例4
一种聚乙烯改性材料,包含了按照重量份比计算的如下原料:
氯化聚乙烯48.8份、高密度聚乙烯20份、低密度聚乙烯5份、固态烷烃的混合物25份、硬脂酸锌0.3份、硬脂酸钙0.2份、乙烯基双硬脂酰胺0.5份、抗氧剂(三[2.4-二叔丁基苯基]亚磷酸酯0.1份、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯0.1份;
制备方法同实施例1,区别具体如下:
(1)裂解时的温度为550℃,时间为1小时;裂解时的搅拌速度为85转/分钟。
(2)在120℃下,搅1小时,然后出料;混合时的搅拌速度为100转/分钟。
(3)待固化后进行过筛100目,得到所述聚乙烯改性材料。
上述实施例,只是本发明的较佳实施例,并非用来限制本发明实施范围,故凡以本发明权利要求所述的特征及原理所做的等效变化或修饰,均应包括在本发明权利要求范围之内。
在塑料或者色母料加工成型时使用本发明制得的聚乙烯改性材料,可以改善物料的流动性,增加产品的光泽、润滑性和加工性能,提高产量,并能够允许更高的填料浓度。聚乙烯改性材料由于其优异的性能,其主要用途还可体现在以下几个方面:
(1)在色母料(浓色母和填充母粒)加工中做分散剂,广泛用于聚烯烃色母粒。与聚乙烯、聚氯乙烯、聚丙烯等树脂有很好的相溶性,并具有十分优异的外部润滑和内部润滑作用。
(2)在PVC型材、管材、PVC异型材、管件、PE/PP成型加工过程中做分散剂,润滑剂和光亮剂,增强塑化程度,提高塑料制品的韧性和表面光滑度,同时可在PVC复合稳定剂的生产中广泛应用。
(3)用作颜料的载体,可改进油漆、油墨的耐磨性,改善颜料和填料的分散性,有良好的防沉降作用,可作油漆、油墨的平光剂,使制品有好的光泽和立体感。
(4)用作地板蜡、汽车蜡、蜡烛,蜡笔等各种蜡制品的生产中,提高蜡制品的软化点,增加其强度及表面光泽度。
(5)用作电缆绝缘材料的润滑剂,可增强填充剂的扩散,提高挤压成型速率,增大模具流量,使脱模便利。
(6)用作各种热熔胶,热固性粉末涂料,马路标志漆,划线漆的,做分散剂,有良好的防沉降作用,并使制品有好的光泽和立体感。
(7)用作橡胶加工助剂,可增强填充剂的扩散,提高挤压成型速率,增大模具流量,脱模便利,提高产品脱膜后的表面光亮度及光滑度。
(8)用作化妆品的添加剂,使制品有好的光泽和立体感。
(9)用作注塑领域,可节省机器动力润滑作用,增强制品表面光泽度。
将原料中废旧聚乙烯的量全部改为聚乙烯树脂进行对比实验,其中对比例1、2、3,配方与实施例2、3、4相同,区别在于将废旧聚乙烯的量全部改为聚乙烯树脂。限于篇幅,此处只举几个例子作为代表。
表1
指标 | 实施例1 | 实施例2 | 实施例3 | 实施例4 | 对比例1 | 对比例2 | 对比例3 |
分子量 | 3500 | 4000 | 5500 | 4100 | 6000 | 7200 | 8000 |
熔点 | 100 | 110 | 115 | 102 | 116 | 118 | 120 |
粘度 | 60 | 60 | 65 | 63 | 70 | 75 | 80 |
本发明中,分子量按照国标GB/T 21864-2008进行测试;熔点按照国标GB/T617-2006进行测试;粘度按照国标GB/T22235-2008进行测试。
从表1中可以看出,通过合理控制配方中各组分的比例和成分,加入废旧聚乙烯通过裂解混合等方法可以得到的改性物质,分子量、熔点和粘度更低。其具有更为优异耐寒性、耐热性、耐化学性、耐磨性和润滑性。本发明的制备方法操作简单,所需原材料易得。
Claims (10)
3.如权利要求1或2所述聚乙烯改性材料,其特征在于,所述抗氧剂由主抗氧剂和次抗氧剂组成;其中,所述主抗氧剂与次抗氧剂添加量的质量比为1-2:1。
4.如权利要求3所述聚乙烯改性材料,其特征在于,所述次抗氧剂为三[2.4-二叔丁基苯基]亚磷酸酯,所述主抗氧剂为四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯。
5.如权利要求4所述聚乙烯改性材料,其特征在于,所述四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯与三[2.4-二叔丁基苯基]亚磷酸酯添加量的质量比为1:1。
6.如权利要求1或2所述聚乙烯改性材料,其特征在于,所述聚乙烯树脂的热变形温度为30-60℃,熔点为110-125℃,熔指为1.5-2.2g/10min。
7.如权利要求1所述聚乙烯改性材料,其特征在于,所述硬脂酸锌的熔点为115-125℃,自燃点为900℃;所述硬脂酸钙的熔点为150-155℃;所述乙烯基双硬脂酰胺的初熔点为:140-146℃。
8.如权利要求1-7中任意一项所述聚乙烯改性材料的制备方法,其特征在于,制备步骤具体如下:
(1)首先将聚乙烯树脂、聚乙烯废塑料加入可加热的密闭反应釜中,反应釜中装备有搅拌装置,通过搅拌和加热使聚乙烯树脂和聚乙烯废塑料在反应釜中进行充分裂解,裂解时的温度为500-600℃,时间为0.3-4小时;
(2)待步骤(1)中裂解产物冷却到100℃时,依次向反应釜中添加固态烷烃的混合物、硬脂酸锌、硬脂酸钙、乙烯基双硬脂酰胺和抗氧剂,在100-150℃下,搅拌0.5-2小时,然后出料;
(3)将步骤(2)中所得到的块状料进行破碎和精制,从而得到所需要的化工材料聚乙烯改性材料。
9.如权利要求8所述聚乙烯改性材料的制备方法,其特征在于,所述步骤(1)中裂解时的搅拌速度为80-100转/分钟,步骤(2)中混合时的搅拌速度为85-110转/分钟。
10.如权利要求8所述聚乙烯改性材料的制备方法,其特征在于,所述精制具体为将破碎后的物料进行喷雾,然后待固化后进行过筛40目—200目,得到所述聚乙烯改性材料。
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