CN105602070B - 一种增强聚乙烯膜及其制备方法 - Google Patents
一种增强聚乙烯膜及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种增强聚乙烯膜及其制备方法,属于功能包装材料技术领域。其以改性纳米高岭土为增韧剂、改性有机蒙脱土为增强剂、有机蒙脱土和马来酸酐接枝聚乙烯为增容剂,加一定润滑剂,以PE为基材,经吹塑成膜制得。可获得一种稳定性好、高阻隔性能、具有一定阻燃性能、高拉伸性能和断裂伸长率、耐老化性能好的增强聚乙烯复合薄膜,可广泛应用于日常用品、家用电器等领域,拓宽PE材料的使用范围。
Description
技术领域
本发明涉及一种增强聚乙烯膜及其制备方法,属于功能包装材料技术领域。
背景技术
聚乙烯(PE)是一种应用较广、价格低廉、化学性质较稳定,性能优良的塑料,但聚乙烯存在着强度较低、容易变形、不耐热、易燃等缺点,这些缺点大大限制了聚乙烯的应用范围。为了扩展聚乙烯在日常生活中的应用范围,提高聚乙烯的综合性能,需对聚乙烯进行一定的改性或者是添加功能填料。根据改性方法和添加填料的不同,可以改变聚乙烯的性能。聚乙烯和纳米复合材料复合之后的性能提高,例如力学性能、阻隔性能等的提高是传统聚乙烯和无机填料复合所不能比拟的,由于聚乙烯和纳米复合材料复合具有优良的性能以及较高的可加工性,所以目前纳米材料和聚乙烯复合制备新型功能材料具有很好的应用前景。
纳米高岭土作为一种纳米材料,比表面积大,加入树脂中能够提升树脂的综合性能,但是未经改性处理的纳米材料容易发生团聚,造成成品不均匀,所以要找到一种合适的改性剂对其进行表面改性,从而达到很好的效果。
一定量的改性有机蒙脱土能够有效提高材料的拉伸强度、阻隔性能、结晶温度,并且降低剪切粘度,大大提高材料的加工性能。
马来酸酐接枝聚乙烯或聚丙烯作为一种增容剂,能够增加无机填料在有机树脂中的相容性,并且实验表明,一定量的有机蒙脱土能够和马来酸酐接枝聚乙烯起到协同增容作用,能够提高复合膜的性能,所以本发明最终选择加入这几种成分进行复合薄膜的制作,并且实验证明对聚乙烯膜具有很好的增强效果,综合性能得到很大提升。
发明内容
本发明的目的在于克服上述不足之处,提供一种增强聚乙烯膜及其制备方法。
按照本发明提供的技术方案,一种增强聚乙烯膜,其组分按重量百分比计如下:
纳米高岭土5-15份,有机蒙脱土5-10份,增容剂3-10份,纳米高岭土改性剂2-5份,有机蒙脱土改性剂2-5份,滑石粉2-5份,聚乙烯树脂60-80份;
首先使用纳米高岭土改性剂和有机蒙脱土改性剂分别对纳米高岭土和有机蒙脱土进行改性,然后以改性纳米高岭土为增韧剂、改性有机蒙脱土为增强剂、再加入有机蒙脱土、增容剂和滑石粉,以聚乙烯树脂为基材,经吹塑成膜制得增强聚乙烯膜。
所述增韧剂为改性纳米高岭土,维度尺寸为1-100nm。
所述增容剂为马来酸酐接枝聚乙烯或马来酸酐接枝聚丙烯。增容剂的加入增加了无机填料在复合材料体系中的相容性,使得薄膜易于加工,且成品均匀,表面美观,提高体系的综合性能。
所述纳米高岭土改性剂为丙烯酸丁酯、甲基丙烯酸甲酯、硅烷偶联剂中的一种或几种的混合物。纳米高岭土的加入可以提升聚乙烯复合膜的拉伸性能、断裂伸长率、冲击性能、耐老化性能等。
所述有机蒙脱土改性剂为十二烷基三甲基氯化铵、十六烷基三甲基氯化铵、十六烷基三甲基溴化铵、双十八烷基二甲基氯化铵中的一种或几种的混合物。
所述增强聚乙烯膜的制备方法,按重量份计步骤如下:
(1)改性纳米高岭土制取:
a、取纳米高岭土改性剂2-5份,加入无水乙醇50-60份,水解至澄清,制得改性剂水解液;
b、取纳米高岭土5-15份,悬浮于100-120份蒸馏水中,搅拌均匀,得到纳米高岭土悬浮液;
c、取步骤b制备的纳米高岭土悬浮液加入烧杯中,恒温水浴锅加热至70-90℃,然后加入步骤a制备的改性剂水解液,采用高剪切混合乳化机调节控制对纳米高岭土进行改性;转速为5500-6000r/min,控制改性时间为40-60min,;
d、对所得改性后的纳米高岭土悬浮液用真空泵抽滤,真空度0.05-0.09MPa,将抽滤所得的滤饼放入100-130℃烘箱中干燥1-2h,得到粉末状的改性纳米高岭土;
(2)改性有机蒙脱土制取:
e、将有机蒙脱土3-8份分散于70-90份去离子水中,搅拌均匀得到悬浊液;
f、取有机蒙脱土改性剂2-5份溶于40-50份无水乙醇中,水解至澄清,配置成改性剂溶液;
g、将步骤e所得悬浊液置于60-80℃恒温水浴中,滴加步骤f制备的改性剂溶液,采用高剪切混合乳化机调节改性的转速为5500-6000r/min,改性时间为1-2h,最终得到白色沉淀;
h、用去离子水洗涤步骤g所得白色沉淀,在50-60℃烘箱中烘干1-2h,得到粉末状改性有机蒙脱土;
(3)混料:将步骤(1)、(2)处理过的增韧剂改性纳米高岭土和增强剂改性有机蒙脱土、聚乙烯树脂60-80份、有机蒙脱土2份、增容剂3-10份和滑石粉2-5份置于高速混合机中,在65-80℃下混合10-15min;
(4)成型:将步骤(3)所得混合料送入双螺杆挤出机中,挤出机温度设定为150-160℃,通过口模和切粒机进行挤出造粒,形成粒料;将粒料通过吹塑机进行吹膜,吹塑温度为160-180℃,制得增强聚乙烯膜。
步骤(4)所述吹塑机吹塑时,通过控制吹胀比控制膜厚度,吹胀比为1.9-2.1。
本发明制备的聚乙烯膜外观为无色的透明薄膜,透光率为70.24%-76.31%;拉伸强度为36.32MPa-40.71MPa,相对纯PE(26.43MPa)提高了52.94%-54.01%;断裂伸长率为1300%-1400%,相对于纯PE(850%)提高了60.13%-64.70%;氧气透过率为630cm3/m2·24h·0.1Mpa~754cm3/m2·24h·0.1Mpa,相对于纯PE(1200cm3/m2·24h·0.1Mpa)下降了37.16%-47.50%;水蒸气透过量为1.3g/m2·24h-1.5g/m2·24h,相对于纯PE(2.6g/m2·24h)下降了42.30%-50.00%。所以,材料的强度提升,阻隔性能提升。
本发明的有益效果:
1、制备的增强聚乙烯膜的主要原料及辅料均为成本较低的材料,辅料等无机填料自然界来源广泛,所以比较经济实用。
2、制备的增强聚乙烯膜具有较强的拉伸性能和冲击强度,能够扩展聚乙烯膜的应用领域。
3、制备的增强聚乙烯膜透明度高,外形美观,机械性能和阻隔性能良好,可根据需要制成不同厚度和机械性能的薄膜。
4、制备的增强聚乙烯膜的生产方法安全,生产成本低,操作简单,所以具有很好的市场应用前景。
具体实施方式
下面结合具体实施例对本发明做进一步说明。本发明中,搅拌操作采用上海标本模型厂制造的JB-200-S数字显示转速电动搅拌机;反应温度通过江苏省金坛市荣华仪器制造有限公司制造的YJ501超级恒温水浴锅控制;机械性能测定采用英国LLOYD公司制造的LRX Plus型万能电子材料试验机;透光率测定采用尤尼柯(上海)仪器有限公司制造的UV-2802型紫外可见光分光光度计;混合造粒用科信隆科亚机械有限公司的CTE-35双螺杆挤出机。
实施例1
按重量份计,增强聚乙烯膜:纳米高岭土10份、增容剂马来酸酐接枝聚乙烯4份、聚乙烯树脂75份、有机蒙脱土5份、纳米高岭土改性剂丙烯酸丁酯2份、有机蒙脱土改性剂十六烷基三甲基氯化铵3份、滑石粉3份。
所述增韧剂为改性纳米高岭土,维度尺寸为1-100nm。
所述增强聚乙烯膜的制备方法,按重量份计步骤如下:
(1)改性纳米高岭土制取:
a、取纳米高岭土改性剂,加入无水乙醇50份,水解至澄清,制得改性剂水解液;
b、取纳米高岭土,悬浮于100份蒸馏水中,搅拌均匀,得到纳米高岭土悬浮液;
c、取步骤b制备的纳米高岭土悬浮液加入烧杯中,恒温水浴锅加热至70℃,然后加入步骤a制备的改性剂水解液,采用高剪切混合乳化机调节控制对纳米高岭土进行改性;转速为5500r/min,控制改性时间为60min,;
d、对所得改性后的纳米高岭土悬浮液用真空泵抽滤,真空度0.05MPa,将抽滤所得的滤饼放入100℃烘箱中干燥2h,得到粉末状的改性纳米高岭土;
(2)改性有机蒙脱土制取:
e、将有机蒙脱土3-8份分散于70-90份去离子水中,搅拌均匀得到悬浊液;
f、取有机蒙脱土改性剂3份溶于40份无水乙醇中,水解至澄清,配置成改性剂溶液;
g、将步骤e所得悬浊液置于60℃恒温水浴中,滴加步骤f制备的改性剂溶液,采用高剪切混合乳化机调节改性的转速为5500r/min,改性时间为2h,最终得到白色沉淀;
h、用去离子水洗涤步骤g所得白色沉淀,在50℃烘箱中烘干2h,得到粉末状改性有机蒙脱土;
(3)混料:将步骤(1)、(2)处理过的增韧剂改性纳米高岭土和增强剂改性有机蒙脱土、聚乙烯树脂、有机蒙脱土2份、增容剂和滑石粉置于高速混合机中,在65℃下混合15min;
(4)成型:将步骤(3)所得混合料送入双螺杆挤出机中,挤出机温度设定为150℃,通过口模和切粒机进行挤出造粒,形成粒料;将粒料通过吹塑机进行吹膜,吹塑温度为160℃,制得增强聚乙烯膜。
步骤(4)所述吹塑机吹塑时,通过控制吹胀比控制膜厚度,吹胀比为1.9。
以此组分制备的增强聚乙烯膜的性能为:拉伸强度为36.13MPa;断裂伸长率为1324%;水蒸气透过率为1.3g/m2·24h;氧气透过率为691cm3/m2·24h·0.1MPa。
实施例2
按重量份计,增强聚乙烯膜:纳米高岭土12份、增容剂马来酸酐接枝聚乙烯5份、聚乙烯树脂70份、有机蒙脱土6份、纳米高岭土改性剂硅烷偶联剂2份、有机蒙脱土改性剂十六烷基三甲基溴化铵1份、滑石粉4份。
所述增韧剂为改性纳米高岭土,维度尺寸为1-100nm。
所述增强聚乙烯膜的制备方法,按重量份计步骤如下:
(1)改性纳米高岭土制取:
a、取纳米高岭土改性剂,加入无水乙醇60份,水解至澄清,制得改性剂水解液;
b、取纳米高岭土10份,悬浮于120份蒸馏水中,搅拌均匀,得到纳米高岭土悬浮液;
c、取步骤b制备的纳米高岭土悬浮液加入烧杯中,恒温水浴锅加热至90℃,然后加入步骤a制备的改性剂水解液,采用高剪切混合乳化机调节控制对纳米高岭土进行改性;转速为6000r/min,控制改性时间为40min,;
d、对所得改性后的纳米高岭土悬浮液用真空泵抽滤,真空度0.09MPa,将抽滤所得的滤饼放入130℃烘箱中干燥1h,得到粉末状的改性纳米高岭土;
(2)改性有机蒙脱土制取:
e、将有机蒙脱土4份分散于90份去离子水中,搅拌均匀得到悬浊液;
f、取有机蒙脱土改性剂溶于50份无水乙醇中,水解至澄清,配置成改性剂溶液;
g、将步骤e所得悬浊液置于80℃恒温水浴中,滴加步骤f制备的改性剂溶液,采用高剪切混合乳化机调节改性的转速为6000r/min,改性时间为1h,最终得到白色沉淀;
h、用去离子水洗涤步骤g所得白色沉淀,在60℃烘箱中烘干1h,得到粉末状改性有机蒙脱土;
(3)混料:将步骤(1)、(2)处理过的增韧剂改性纳米高岭土和增强剂改性有机蒙脱土、聚乙烯树脂、有机蒙脱土2份、增容剂和滑石粉置于高速混合机中,在80℃下混合10min;
(4)成型:将步骤(3)所得混合料送入双螺杆挤出机中,挤出机温度设定为160℃,通过口模和切粒机进行挤出造粒,形成粒料;将粒料通过吹塑机进行吹膜,吹塑温度为180℃,制得增强聚乙烯膜。
步骤(4)所述吹塑机吹塑时,通过控制吹胀比控制膜厚度,吹胀比为2.1。
以此组分制备的增强聚乙烯膜的性能为:拉伸强度为37.52MPa;断裂伸长率为1331%;水蒸气透过率为1.4g/m2·24h;氧气透过率为678cm3/m2·24h·0.1MPa。
实施例3
按重量份计,增强聚乙烯膜:纳米高岭土15份、增容剂马来酸酐接枝聚丙烯5份、聚乙烯树脂68份、有机蒙脱土5份、纳米高岭土改性剂硅烷偶联剂2份、纳米高岭土改性剂十六烷基三甲基溴化铵2份、滑石粉5份。
所述增韧剂为改性纳米高岭土,维度尺寸为1-100nm。
所述增强聚乙烯膜的制备方法,按重量份计步骤如下:
(1)改性纳米高岭土制取:
a、取纳米高岭土改性剂,加入无水乙醇55份,水解至澄清,制得改性剂水解液;
b、取纳米高岭土,悬浮于110份蒸馏水中,搅拌均匀,得到纳米高岭土悬浮液;
c、取步骤b制备的纳米高岭土悬浮液加入烧杯中,恒温水浴锅加热至80℃,然后加入步骤a制备的改性剂水解液,采用高剪切混合乳化机调节控制对纳米高岭土进行改性;转速为5800r/min,控制改性时间为50min,;
d、对所得改性后的纳米高岭土悬浮液用真空泵抽滤,真空度0.07MPa,将抽滤所得的滤饼放入115℃烘箱中干燥1h,得到粉末状的改性纳米高岭土;
(2)改性有机蒙脱土制取:
e、将有机蒙脱土3份分散于80份去离子水中,搅拌均匀得到悬浊液;
f、取有机蒙脱土改性剂溶于45份无水乙醇中,水解至澄清,配置成改性剂溶液;
g、将步骤e所得悬浊液置于70℃恒温水浴中,滴加步骤f制备的改性剂溶液,采用高剪切混合乳化机调节改性的转速为5800r/min,改性时间为1.5h,最终得到白色沉淀;
h、用去离子水洗涤步骤g所得白色沉淀,在55℃烘箱中烘干1.5h,得到粉末状改性有机蒙脱土;
(3)混料:将步骤(1)、(2)处理过的增韧剂改性纳米高岭土和增强剂改性有机蒙脱土、聚乙烯树脂、有机蒙脱土、增容剂和滑石粉置于高速混合机中,在72℃下混合13min;
(4)成型:将步骤(3)所得混合料送入双螺杆挤出机中,挤出机温度设定为155℃,通过口模和切粒机进行挤出造粒,形成粒料;将粒料通过吹塑机进行吹膜,吹塑温度为170℃,制得增强聚乙烯膜。
步骤(4)所述吹塑机吹塑时,通过控制吹胀比控制膜厚度,吹胀比为2.0。
以此组分制备的增强聚乙烯膜的性能为:拉伸强度为39.16MPa;断裂伸长率为1358%;水蒸气透过率为1.3g/m2·24h;氧气透过率为678cm3/m2·24h·0.1MPa。
Claims (1)
1.一种增强聚乙烯膜的制备方法,其特征是,制备步骤如下:
(1)改性纳米高岭土制取:
a、取纳米高岭土改性剂2-5份,加入无水乙醇50-60份,溶解至澄清,制得改性剂溶液;
b、取纳米高岭土5-15份,悬浮于100-120份蒸馏水中,搅拌均匀,得到纳米高岭土悬浮液;
c、取步骤b制备的纳米高岭土悬浮液加入烧杯中,恒温水浴锅加热至70-90℃,然后加入步骤a制备的改性剂溶液,采用高剪切混合乳化机调节控制对纳米高岭土进行改性;转速为5500-6000r/min,控制改性时间为40-60min;
d、对所得改性后的纳米高岭土悬浮液用真空泵抽滤,真空度0.05-0.09MPa,将抽滤所得的滤饼放入100-130℃烘箱中干燥1-2h,得到粉末状的改性纳米高岭土;
(2)改性有机蒙脱土制取:
e、将有机蒙脱土3-8份分散于70-90份去离子水中,搅拌均匀得到悬浊液;
f、取有机蒙脱土改性剂2-5份溶于40-50份无水乙醇中,溶解至澄清,配置成改性剂溶液;
g、将步骤e所得悬浊液置于60-80℃恒温水浴中,滴加步骤f制备的改性剂溶液,采用高剪切混合乳化机调节改性的转速为5500-6000r/min,改性时间为1-2h,最终得到白色沉淀;
h、用去离子水洗涤步骤g所得白色沉淀,在50-60℃烘箱中烘干1-2h,得到粉末状改性有机蒙脱土;
(3)混料:将步骤(1)、(2)处理过的增韧剂改性纳米高岭土和增强剂改性有机蒙脱土、聚乙烯树脂60-80份、有机蒙脱土2份、增容剂3-10份和滑石粉2-5份置于高速混合机中,在65-80℃下混合10-15min;
(4)成型:将步骤(3)所得混合料送入双螺杆挤出机中,挤出机温度设定为150-160℃,通过口模和切粒机进行挤出造粒,形成粒料;将粒料通过吹塑机进行吹膜,吹塑温度为160-180℃,制得增强聚乙烯膜;
步骤(4)所述吹塑机吹塑时,通过控制吹胀比控制膜厚度,吹胀比为1.9-2.1;
所述增韧剂为改性纳米高岭土,维度尺寸为1-100nm;
所述增容剂为马来酸酐接枝聚乙烯或马来酸酐接枝聚丙烯;
所述纳米高岭土改性剂为丙烯酸丁酯或甲基丙烯酸甲酯中的一种或几种的混合物;
所述有机蒙脱土改性剂为十二烷基三甲基氯化铵或双十八烷基二甲基氯化铵中的一种或几种的混合物。
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