CN103739913B - 一种聚乙烯薄膜材料及其制备方法 - Google Patents

一种聚乙烯薄膜材料及其制备方法 Download PDF

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CN103739913B
CN103739913B CN201310697395.0A CN201310697395A CN103739913B CN 103739913 B CN103739913 B CN 103739913B CN 201310697395 A CN201310697395 A CN 201310697395A CN 103739913 B CN103739913 B CN 103739913B
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polyethylene film
polyethylene
film material
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raw material
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CN103739913A (zh
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柒祥芝
张鹰
张祥福
周文
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Shanghai Pret Composites Co Ltd
Zhejiang Pret New Materials Co Ltd
Chongqing Pret New Materials Co Ltd
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Zhejiang Pret New Materials Co Ltd
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Abstract

本发明公开了一种聚乙烯薄膜材料及其制备方法，由下列重量百分比的原料组成：聚乙烯86～96.5%，改性层状纳米硅酸盐2～8%，LDPE‑g‑MAH1～5%，超细二氧化钛0.5～1.0%。本发明的优点是：1、本发明制备的聚乙烯薄膜维持了聚乙烯材料原有力学性能，同时具有良好的阻隔性，将抗氧剂固定于层状纳米硅酸盐表面可以降低抗氧剂的迁移性，降低了对食品的污染可能性。2、本发明使用超细二氧化钛代替传统的有机紫外光稳定剂，能够有效的降低紫外光稳定剂迁移析出造成的外观问题；同时二氧化钛还具有一定的抗菌效果，可以部分或完全替代传统的抗菌剂。3、本发明提出的制备聚乙烯薄膜的生产工艺简单，成本低，容易工业化。

Description

一种聚乙烯薄膜材料及其制备方法
技术领域
本发明涉及一种新型聚乙烯薄膜材料及其制备方法，属于聚合物改性和加工领域。
背景技术
目前聚合物阻隔材料主要有烯烃类塑料、聚酯类、聚酰胺类、聚氯乙烯类、聚乙烯醇类、含氟类塑料、液晶类聚合物等，其中聚乙烯，尤其是低密度聚乙烯(LDPE)由于其密度小，无毒，柔韧性良好，优越的化学稳定性和成型加工性能，在食品、药品及农产品包装领域有着广泛的应用。对于高阻隔包装材料，LDPE本身并不能达不到使用要求，因此有必要对LDPE材料进行处理，以降低气体、液体、溶剂的溶解度以及扩散性能，提高材料的阻隔性能。目前适用于聚乙烯改性的方法主要有共混改性技术、多层复合技术、氟化处理技术、等离子处理技术等。纳米层状纳米硅酸盐因具有粒径小、比表面积大等特性，如能将其良好分散在聚烯烃材料中，将形成很强的相互作用界面，显著提高聚合物的力学性能、热性能和阻隔性能等。一般通过熔融共混法制备的复合材料需添加相容剂或者进行有机化改性处理提高其在材料中的分散能力。
由于PE薄膜在保存食品药品的特定温度、湿度条件下，其表面容易滋生对人体健康有害的细菌等微生物，会污染食品或药品，使其变质、发霉甚至腐烂，一般需加入一定量的抗菌剂。同时由于PE树脂因分子链中存在双键，在有热或者各种辐射条件下，尤其紫外线，容易使得PE材料老化降解而变色。传统的方法是加入一定量的抗氧剂和光稳定剂来改善。绝大多数光稳定剂，如各种光屏蔽剂、紫外光吸收剂、自由基捕获剂等都是分子量较低的有机化合物或低聚物。当这些光稳定剂在高温或者紫外光照射下，都有逐渐向产品表面析出的趋势。同时传统的抗氧剂1010、168等加入到PE体系中，有可能在PE薄膜的使用过程中迁移发生迁移现象。关于这方面的报道也很多，如：LWT,2007(40),151～156研究发现γ-辐射的剂量越大，LLDPE薄膜中的抗氧剂越容易降解，向食品模拟物发生迁移的可能性增加。食品工业科技,2009,30(2),244～246研究发现含有抗氧剂1076的HDPE薄膜在使用过程中，应当避免包裹高脂肪类食品，以免引起抗氧剂高迁移。因此有必要考虑PE薄膜材料中各种助剂的迁移析出问题。
发明内容
本发明的目的在于提供一种新型聚乙烯薄膜材料及其制备方法，制得的聚乙烯薄膜维持了聚乙烯材料原有的力学性能，同时具有良好的阻隔性和低抗氧剂的迁移性，能更好的满足食品、药品等对包装材料的要求。
为了实现上述目的，本发明的技术方案如下：
一种新型聚乙烯薄膜材料，由下列重量百分比的原料组成：
更进一步地，一种新型聚乙烯薄膜材料，由下列重量百分比的原料组成：
其中，所述的聚乙烯为低密度聚乙烯和线性低密度聚乙烯中的一种或它们的组合物，其熔体流动速率（190℃×2.16kg）为3～40g/10min。
所述的改性层状纳米硅酸盐为未经有机化改性的蒙脱土、高岭土、膨润土、皂石、埃洛石、陶土和粘土中的一种或几种混合物，在催化剂CH3ONa的作用下，将抗氧剂3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯(AO)接枝到纳米硅酸盐表面，其接枝率为5～12%。
所述的LDPE-g-MAH的接枝率为0.8～1%,其熔体流动速率(190℃×2.16kg)为5～30g/10min。
所述的超细二氧化钛粉末，其80%的粒径分布在150-240nm。
上述新型聚乙烯薄膜材料的制备方法，具体步骤如下：
(1)按重量配比称取原料；
(2)将各种原料在高速混合器中混合5～15分钟；
(3)将混合后的原料加入双螺杆挤出机中，经熔融挤出后冷却造粒，制得聚乙烯复合材料，其工艺为：一区160～170℃，二区170～180℃，三区180～190℃，四区175～185℃；整个挤出过程的停留时间为1～2分钟，压力为12～18MPa。
(4)将制备的聚乙烯复合材料置于吹塑成型机中吹制得到聚乙烯薄膜，其中料筒温度为 165～175℃。
本发明的优点是：
1、本发明制备的聚乙烯薄膜维持了聚乙烯材料原有力学性能，同时具有良好的阻隔性，将抗氧剂固定于层状纳米硅酸盐表面可以降低抗氧剂的迁移性，降低了对食品的污染可能性。
2、本发明使用超细二氧化钛代替传统的有机紫外光稳定剂，能够有效的降低紫外光稳定剂迁移析出造成的外观问题；同时二氧化钛还具有一定的抗菌效果，可以部分或完全替代传统的抗菌剂。
3、本发明提出的制备聚乙烯薄膜的生产工艺简单，成本低，容易工业化。
具体实施方式
下面结合实施例，对本发明作进一步详细说明：在实施例及对比例复合材料配方中，聚乙烯选用燕山石化公司生产的LDPE，商品牌号为IF7B。所用的抗氧剂(AO)为3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯，其为市售。改性层状纳米硅酸盐选用经抗氧剂改性的纳米粘土，其接枝率为5～12%，其为试验自制。所用的LDPE-g-MAH的接枝率为0.8～1%，其为试验自制。所用的超细二氧化钛为杜邦公司生产的80%的粒径分布在150-240nm的DLS-210。
将各种原料和添加剂在高速混合器中干混5～15分钟；将混合均匀的原料加入双螺杆挤出机中，经熔融挤出，冷却造粒得到聚乙烯复合材料，其工艺为：一区160～170℃，二区170～180℃，三区180～190℃，四区175～185℃；整个挤出过程的停留时间为1～2分钟，压力为12～18MPa。最后将制备的聚乙烯复合材料置于吹塑成型机中吹制得到聚乙烯薄膜，其中料筒温度为165～175℃。
性能评价方式及实行标准 :
聚乙烯薄膜的综合力学性能通过测试拉伸强度及直角撕裂强度进行评判。拉伸强度按GB/T1040-2006方法测试；直角撕裂强度按QB/T1130-1991方法测试。
气体阻隔性测试：按照GB/T1038-2000方法测试；水蒸汽渗透性测试：按照GB/T1037-1988方法测试；
薄膜的透光率按GB/T2410-2008方法测试。
迁移性测试：按照欧盟82/711/EEC和2002/72/EEC指令，采用95%乙醇作为脂肪模拟物，采用外标法分析LDPE薄膜在测试温度60℃，测试时间为2.5h条件下抗氧剂迁 移到模拟物中的浓度。
实施例及对比例的配方及各项性能测试结果见下各表：
表1实施例1～4和对比例1～5材料配方表（重量%）
表2实施例1～4和对比例1～5测试结果
从实施例1～4和对比例5可以看出，改性纳米粘土加入使得聚乙烯材料原有力学性能和透光性，同时具有良好的阻隔性；虽然随着纳米粘土的增加，抗氧剂迁移量有所增加，但仍然保持很低的迁移量。实施例2～3和对比例1～2可以看出，做为相容剂的LDPE-g-MAH不但可以提高材料的力学性能而且可以改善力学性能，而且可以提高材料的阻隔性能。实施例2～3和对比例3～5可以看出，将抗氧剂固定于纳米粘土的表面可以降低抗氧剂的迁移量。

Claims (6)

1.一种聚乙烯薄膜材料，其特征在于：由下列重量百分比的原料组成：
所述的改性层状纳米硅酸盐为未经有机化改性的蒙脱土、高岭土、膨润土、皂石、埃洛石、陶土和粘土中的一种或几种混合物，在催化剂CH3ONa的作用下，将抗氧剂3-(3,5-二叔丁基-4-羟基苯基)丙酸甲酯接枝到纳米硅酸盐表面，其接枝率为5～12％。
2.根据权利要求1所述的聚乙烯薄膜材料，其特征在于：由下列重量百分比的原料组成：
3.根据权利要求1或2所述的聚乙烯薄膜材料，其特征在于：所述的聚乙烯为低密度聚乙烯和线性低密度聚乙烯中的一种或它们的组合物，其熔体流动速率在190℃×2.16kg的测试条件下为3～40g/10min。
4.根据权利要求1或2所述的聚乙烯薄膜材料，其特征在于：所述的LDPE-g-MAH的接枝率为0.8～1％,其熔体流动速率在190℃×2.16kg的测试条件下为5～30g/10min。
5.根据权利要求1或2所述的聚乙烯薄膜材料，其特征在于：所述的超细二氧化钛，其80％的粒径分布在150-240nm。
6.一种制备权利要求1或2所述聚乙烯薄膜材料的方法，其特征在于：具体步骤如下：
(1)按重量配比称取原料；
(2)将各种原料在高速混合器中混合5～15分钟；
(3)将混合后的原料加入双螺杆挤出机中，经熔融挤出后冷却造粒，制得聚乙烯复合材料，其工艺为：一区160～170℃，二区170～180℃，三区180～190℃，四区175～185℃；整个挤出过程的停留时间为1～2分钟，压力为12～18MPa；
(4)将制备的聚乙烯复合材料置于吹塑成型机中吹制得到聚乙烯薄膜，其中料筒温度为165～175℃。
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