CN105646984B - 一种抗菌聚乙烯泡沬及其制备方法 - Google Patents
一种抗菌聚乙烯泡沬及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种抗菌聚乙烯泡沫，还涉及其制备方法。该抗菌聚乙烯泡沫由聚乙烯树脂65～80%、无机纳米抗菌剂0.5～4%、发泡剂7～20%、助发泡抗收缩剂3～9%、含有微孔的无机材料成核剂0.5～2%组成。该抗菌聚乙烯泡沫选用纳米氧化锌或纳米氧化铜为抗菌剂，并通过含有微孔无机材料的缓释作用达到长效抑菌的目的，其制备方法使用助发泡抗收缩剂作为无机纳米抗菌剂的分散剂，在恒温研磨机上研磨为纳米材料并分散均匀，然后在热熔状态下再用定量泵在加工设备上注入，很好地解决了纳米材料分散难、颗粒团聚的问题，得到的是一种抗菌性能优异、断裂拉伸强度及断裂伸长率性能明显提高、泡孔细密均匀的聚乙烯泡沬。
Description
技术领域
本发明涉及一种抗菌聚乙烯泡沫，还涉及其制备方法。
背景技术
聚乙烯（PE）作为石油化工领域的大宗产品，具有来源广泛，成本低廉，应用广泛的特点。使用聚乙烯（PE）和发泡剂生产的聚乙烯泡沬是闭孔结构产品，又称 EPE 珍珠棉 ,是一种新型环保的包装材料。产品具有隔水防潮、防震、隔音、保温、可塑性能佳、韧性强、循环再造、环保、抗撞力强等诸多优点。是传统防震包装材料的理想代替品。特别符合塑料产品减量化的国家产业政策。广泛应用于汽车坐垫、抱枕、电子电器、仪器仪表、电脑、音响、医疗器械、工控机箱、五金灯饰、工艺品、玻璃、陶瓷、家电、喷涂、家俱家私、酒类及树脂等高档易碎礼品包装、五金制品、玩具、瓜果、皮鞋的内包装、日用品等多种产品的包装，以及快递包装。
传统的聚乙烯泡沬不具有抗菌防霉的功能。为此，近年来本领域研发人员研发了各种具有抗菌功能的聚乙烯泡沬，如中国专利公开号CN1401695A抗菌防霉聚乙烯泡沬塑料，是在聚乙烯树脂、丁烷、单甘脂、滑石粉中添加抗菌防霉母料，利用挤出机将原料直接挤出发泡定型而制备。中国专利公开号CN102286176A一种抗菌聚丙烯泡沫塑料及其制备方法，由基体树脂、复合抗菌剂、和化学发泡剂、成核剂、抗氧剂、分散剂在内的各组份按所述含量混合均匀，熔融共混造粒后，在模压机内发泡制得，其中的复合抗菌剂为水溶性硅酸盐。中国专利公开号101967244A一种抗菌聚乙烯泡沫塑料及其制备方法，由基体材料、镀银纤维、交联剂、发泡剂和助发泡剂经熔融共混和模压发泡制备而成，所述的基体材料为聚乙烯和乙烯- 醋酸乙烯酯共聚物两种聚合物。
上述抗菌聚丙烯泡沫塑料抗菌效果存在抗菌效果不佳、抗菌有效期短等问题。
发明内容
本发明所要解决的技术问题是提供一种抗菌聚乙烯泡沬，所得聚乙烯泡沬具极强的抗菌防霉功能。该聚乙烯泡沫含有无机纳米抗菌剂，并通过含有微孔的无机材料的缓释作用达到长效抑菌的目的，可被广泛用于抗菌塑料产品、食品保鲜包装产品等抗菌防霉产品领域。
本发明所要解决的另一个技术问题是提供该抗菌聚乙烯泡沫的制备方法，该方法使用助发泡抗收缩剂作为无机纳米抗菌剂的分散剂，在恒温研磨机上研磨为纳米材料并分散均匀，然后在热熔状态下再用定量泵在加工设备上注入，很好地解决了纳米材料分散难、颗粒团聚的问题，得到的是一种抗菌性能优异、断裂拉伸强度及断裂伸长率性能明显提高、泡孔细密均匀的聚乙烯泡沬。
本发明所要解决的技术问题通过以下技术方案予以实现：
一种抗菌聚乙烯泡沬，由如下质量百分比的组分组成：聚乙烯树脂 65～80%、无机纳米抗菌剂0.5～4%、发泡剂 7～20%、助发泡抗收缩剂 3～9%、含有微孔的无机材料成核剂0.5～2%。
优选的，所述聚乙烯的熔融指数为每10分钟1～3克，熔融指数检测标准为ASTM D1238。
优选的，所述无机纳米抗菌剂为纳米氧化锌、纳米氧化铜的至少一种。
优选的，所述发泡剂为丁烷、二甲醚的至少一种。
优选的，所述助发泡抗收缩剂为单硬脂酸甘油脂、聚乙烯蜡、氧化聚乙烯蜡、EVA蜡的至少一种。
优选的，所述含有微孔的无机材料成核剂为滑石粉、碳酸钙晶须、硫酸钙晶须和碳化硅晶须的至少一种。
优选的，上述抗菌聚乙烯泡沬由以下重量百分比的成分组成：聚乙烯树脂 68～78%、无机纳米抗菌剂1～3%、发泡剂 12～18%、助发泡抗收缩剂 4～8%、含有微孔的无机材料成核剂0.8～1.5%。
优选的，上述抗菌聚乙烯泡沬由以下重量百分比的成分组成：聚乙烯树脂 75%、无机纳米抗菌剂2%、发泡剂 15%、助发泡抗收缩剂7%、含有微孔的无机材料成核剂1%。
上述的抗菌聚乙烯泡沬的制备方法按步骤为：
（1）将助发泡抗收缩剂加热到70～100℃作为无机纳米抗菌剂的研磨分散剂，按比例与无机纳米抗菌剂在恒温型研磨机上把无机纳米抗菌剂研磨1～3小时而成粒径为20～100nm的纳米材料，得到含有助发泡抗收缩剂的抗菌母料；
（2）将一部分的聚乙烯树脂、含有微孔的无机材料成核剂在混合器中常温下共混15～30分钟；
（3）将步骤（2）得到的共混物用双螺杆挤出机在140～160℃下挤出、切粒得到功能母料；
（4）将步骤（3）得到的功能母料按一定比例与步骤（2）剩下的聚乙烯树脂在混合器中共混15～30分钟；
（5）将步骤（1）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵的储缸中加热到70～100℃以备按一定比例注入到下一步骤的挤出机中；
（6）将步骤（4）得到的共混物用附有发泡剂注入泵并附有含有助发泡抗收缩剂的抗菌母料注入定量泵及注入口的单台螺杆挤出机中加热至140～160℃进行挤出操作，另将发泡剂用注入泵从挤出机发泡剂注入口注入，同时将步骤（5）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵中定量注入，挤出得到聚乙烯泡沬片材。
优选的，步骤（1）和（5）加热温度为80℃，研磨时间为2小时，所得纳米材料的粒径为53nm；步骤（2）和（4）共混时间为20min；步骤（6）加热温度为150℃。
本发明具有如下有益效果：
本发明使用无机纳米抗菌剂（纳米氧化锌、纳米氧化铜）作为抗菌成分，纳米氧化锌、氧化铜是粒径在1～100 nm之间的颗粒，具有颗粒小、比表面积大等特质，这些特质使其呈现出不同于普通微米氧化锌、微米氧化铜的优良性能，它们更容易释放出金属离子，利用金属离子的抗菌能力，并通过含有微孔无机材料的缓释作用达到长效抑菌的目的，可被广泛用于橡胶产品、塑料产品、食品包装产品、化妆品及医药等领域。
本发明抗菌聚乙烯泡沫的制备方法中，采用组分中的助发泡抗收缩剂作为无机纳米抗菌剂的研磨分散剂，先将无机纳米抗菌剂进行分散再和其它组分熔融挤出成型，克服了纳米材料分散难、颗粒团聚的问题，得到的是一种抗菌性能优异、断裂拉伸强度及断裂伸长率性能明显提高、泡孔细密均匀的聚乙烯泡沬。
附图说明
图1为实施例1抗菌聚乙烯泡沫的德国ZEISS EVO18型扫描电镜的纳米氧化锌50000倍图片。
图2为实施例1抗菌聚乙烯泡沫的 LA960WET粒度仪测得纳米氧化锌均径53.2nm及分布图。
具体实施方式
下面结合附图和实施例对本发明进行详细的说明。
实施例1
一种抗菌聚乙烯泡沬，由以下重量百分比的成分组成：聚乙烯树脂 75%、无机纳米抗菌剂1%、发泡剂 16%、助发泡抗收缩剂7%、含有微孔的无机材料成核剂1%。
其中，聚乙烯树脂的熔融指数为每10分钟1～3克。熔融指数检测标准为ASTM D1238。无机纳米抗菌剂为纳米氧化锌。发泡剂为丁烷、二甲醚两种协同选用。助发泡抗收缩剂为单硬脂酸甘油脂、聚乙烯蜡、氧化聚乙烯蜡、EVA蜡的其中一种；含有微孔的无机材料成核剂为滑石粉、碳酸钙晶须、硫酸钙晶须和碳化硅晶须的其中一种。
实施例2
一种抗菌聚乙烯泡沬，由以下重量百分比的成分组成：聚乙烯树脂 74%、无机纳米抗菌剂2%、发泡剂 16%、助发泡抗收缩剂7%、含有微孔的无机材料成核剂1%。
其中，聚乙烯树脂的熔融指数为每10分钟1～3克。熔融指数检测标准为ASTM D1238。无机纳米抗菌剂为纳米氧化铜。发泡剂为丁烷。助发泡抗收缩剂为单硬脂酸甘油脂和聚乙烯蜡；含有微孔的无机材料成核剂为碳酸钙晶须。
实施例3
一种抗菌聚乙烯泡沬，由以下重量百分比的成分组成：聚乙烯树脂 73%、无机纳米抗菌剂3%、发泡剂 16%、助发泡抗收缩剂7%、含有微孔的无机材料成核剂1%。
其中，聚乙烯树脂的熔融指数为每10分钟1～3克。熔融指数检测标准为ASTM D1238。无机纳米抗菌剂为纳米氧化锌和纳米氧化铜的混合物。发泡剂为二甲醚。助发泡抗收缩剂为氧化聚乙烯蜡和EVA蜡的混合物；含有微孔的无机材料成核剂为滑石粉。
上述实施例的制备步骤为：
（1）将助发泡抗收缩剂加热到80℃作为纳米氧化锌的研磨分散剂按比例与纳米氧化锌在恒温型研磨机上把纳米氧化锌研磨2小时而成平均粒径为53nm的纳米材料而成为含有助发泡抗收缩剂的抗菌母料；
（2）、将一部分的聚乙烯树脂、含有微孔的无机材料成核剂在混合器中常温下共混20分钟；
（3）、将步骤（2）得到的共混物用双螺杆挤出机在140～160℃下挤出、切粒得到粒料为功能母料；
（4）、将步骤（3）得到的功能母料、按一定比例与聚乙烯原料在混合器中共混20分钟；
（5）、将步骤（1）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵的储缸中加热到80℃以备按一定比例注入到下一步骤的挤出机中；
（6）、将步骤（4）得到的共混物用附有发泡剂注入泵和助发泡抗收缩剂的抗菌母料注入定量泵及注入口的单台螺杆挤出机中加热至150℃进行挤出操作，另将发泡剂用注入泵从挤出机发泡剂注入口注入，同时将步骤（5）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵中定量注入，挤出得到聚乙烯泡沬片材。
实施例1~3聚乙烯发泡片性能如下表所示：
| 聚乙烯泡沬性能 | 实施例1 | 实施例2 | 实施例3 | 选用标准或仪器 |
| 无机纳米抗菌剂用量（％） | 1 | 2 | 3 | —— |
| 电镜测平均粒径（nm） | 53 | 53 | 53 | LA960WET粒度仪 |
| 大肠杆菌抗菌率（％） | 94 | 99.5 | 99.9 | ISO22196-2011标准 |
| 断裂拉伸强度（MPa） | 8.12 | 8.56 | 8.82 | CPQ-WD-10试验机 |
| 断裂伸长率（％） | 175 | 186 | 192 | CPQ-WD-10试验机 |
LA960WET粒度仪测得实施例1的纳米氧化锌粒径数据表如下表所示：
通过实施例1至3的检测结果，以及实施例1图1的德国ZEISS EVO18型扫描电镜的纳米氧化锌50000倍图片、图2的LA960WET粒度仪测得纳米氧化锌均径53.2nm及分布图可以看出，所得抗菌聚乙烯泡沬的大肠杆菌抗菌率随纳米氧化锌用量（％）增加而增加，其断裂拉伸强度（MPa）与断裂伸长率（％）也随纳米氧化锌用量（％）增加而增加。
以上所述实施例仅表达了本发明的实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制，但凡采用等同替换或等效变换的形式所获得的技术方案，均应落在本发明的保护范围之内。
Claims (9)
1.一种抗菌聚乙烯泡沬，其特征在于，由如下质量百分比的组分组成：聚乙烯树脂 65～80%、无机纳米抗菌剂0.5～4%、发泡剂 7～20%、助发泡抗收缩剂 3～9%、含有微孔的无机材料成核剂0.5～2%；
所述的抗菌聚乙烯泡沬的制备方法为：
（1）将助发泡抗收缩剂加热到70～100℃作为无机纳米抗菌剂的研磨分散剂，按比例与无机纳米抗菌剂在恒温型研磨机上把无机纳米抗菌剂研磨1～3小时而成粒径为20～100nm的纳米材料，得到含有助发泡抗收缩剂的抗菌母料；
（2）将一部分聚乙烯树脂、含有微孔的无机材料成核剂在混合器中常温下共混15～30分钟；
（3）将步骤（2）得到的共混物用双螺杆挤出机在140～160℃下挤出、切粒得到功能母料；
（4）将步骤（3）得到的功能母料按一定比例与步骤（2）剩下的聚乙烯树脂在混合器中共混15～30分钟；
（5）将步骤（1）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵的储缸中加热到70～100℃以备按一定比例注入到下一步骤的挤出机中；
（6）将步骤（4）得到的共混物用附有发泡剂注入泵并附有含有助发泡抗收缩剂的抗菌母料注入定量泵及注入口的单台螺杆挤出机中加热至140～160℃进行挤出操作，另将发泡剂用注入泵从挤出机发泡剂注入口注入，同时将步骤（5）得到的含有助发泡抗收缩剂的抗菌母料在助发泡抗收缩剂定量泵中定量注入，挤出得到聚乙烯泡沬片材；
在上述制备过程中，助发泡抗收缩机在恒温研磨机上研磨为纳米材料并分散均匀，然后在热熔状态下再用定量泵在加工设备上注入。
2.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于，所述聚乙烯的熔融指数为每10分钟1～3克。
3.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于：所述无机纳米抗菌剂为纳米氧化锌、纳米氧化铜的至少一种。
4.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于：所述发泡剂为丁烷、二甲醚的至少一种。
5.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于：所述助发泡抗收缩剂为单硬脂酸甘油脂、聚乙烯蜡、EVA蜡的至少一种。
6.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于：所述含有微孔的无机材料成核剂为滑石粉、碳酸钙晶须、硫酸钙晶须和碳化硅晶须的至少一种。
7.根据权利要求1~6任一项所述的抗菌聚乙烯泡沬，其特征在于：聚乙烯树脂 68～78%、无机纳米抗菌剂1～3%、发泡剂 12～18%、助发泡抗收缩剂 4～8%、含有微孔的无机材料成核剂0.8～1.5%。
8.根据权利要求1~6任一项所述的抗菌聚乙烯泡沬，其特征在于：由以下重量百分比的成分组成：聚乙烯树脂 75%、无机纳米抗菌剂2%、发泡剂 15%、助发泡抗收缩剂7%、含有微孔的无机材料成核剂1%。
9.根据权利要求1所述的抗菌聚乙烯泡沬，其特征在于：步骤（1）和（5）加热温度为80℃，研磨时间为2小时，所得纳米材料的粒径为53nm；步骤（2）和（4）共混时间为20min；步骤（6）加热温度为150℃。
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