CN105482383B - 一种多层复合高聚物包装材料的制备方法 - Google Patents
一种多层复合高聚物包装材料的制备方法 Download PDFInfo
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Abstract
本发明公开一种多层复合高聚物包装材料的制备方法，属于食品包装材料技术领域，包括如下步骤：第1步、改性PET的制备；第2步、改性PP的制备；第3步、改性EVOH的制备；第4步、将改性PET、改性PP和改性EVOH放入挤出机中，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。本发明提供的多层复合高聚物包装材料的制备方法，进一步加强了多层复合高聚物材料的阻断性能，具有极为优良的气体、气味阻断性能和机械性能、耐撕裂性能。
Description
技术领域
本发明公开了一种多层复合高聚物包装材料的制备方法，属于食品包装材料技术领域。
背景技术
食品包装材料是指包装、盛放食品或者食品添加剂用的纸、竹、木、金属、搪瓷、陶瓷、塑料、橡胶、天然纤维、化学纤维、玻璃等制品和直接接触食品或者食品添加剂的涂料。
对于食品的包装材料，无毒性是最基本要求，由于和食材直接接触，具有毒性的材料会危害人体健康。阻断性能，也是食品包装材料的主要性能，防止外界环境对食材造成影响，阻断性从性能上包括阻氧性、阻湿性、阻光性、阻气味性等。耐高温性能、耐低温性能也是食品包装材料的理想性能。
塑料包装是近现代出现的食品包装材料，当今使用极为广泛，塑料包装材质不仅性能良好，而且便于加工生产运输和携带。我国现在用于食品包装的塑料多达16种，例如PE、PP、PS 、PET、PA、PVDC、EVA、PVA、EVOH、PVC、离子键树脂等。其中具有高阻氧的材料由有PVA、EVOH、PVDC、PET和PA等，高阻湿的材料有PVDC、PP、PE等。各种塑料的单体分子结构不同，聚合度不同，添加剂的种类和数量不同，性能也不同。
其中，EVOH，即乙烯-乙烯醇共聚物，是将乙烯聚合物的加工性和乙烯醇聚合物的阻隔作用相结合，不仅表现出极好的加工性能，而且也对气体、气味、香料、溶剂等呈现出优异的阻断作用。更为重要的是由于同乙烯结合而具有热稳定性，含有EVOH阻隔层的多层容器是完全可以重复利用的，这就增加了EVOH的重复利用率，进一步降低了对环境的影响。
但是虽然EVOH具有极为理想的对气体的阻隔作用，EVOH才是具有两方面缺陷。
第一，由于在EVOH树脂的分子结构中存在着羟基，EVOH树脂具有亲水性和吸湿性。当吸附湿气后，气体的阻隔性能会受到影响。因此，EVOH常作为多层材料的中间层材料。
第二，EVOH加工性能较不理想，一般需要通过改性或者在EVOH薄膜表面涂覆粘结剂，才能与其他高分子材料复合，这是极为需要改进的问题。
CN 104369508A公开了“可降解PP-EVOH高阻隔复合薄膜”的专利文献，所述复合薄膜中的各层材料均通过引入生物基获得趋于一致的生物降解性能，所述添加型母料在各层材料中的添加量控制在该层材料总质量的0.3-15%范围；所述添加型母料中亲水基团的亲水活性应大于或等于各层材料中亲水基团的亲水活性；通过加入添加型母料，使各层材料的亲水基团与碳原子的摩尔比趋于一致，即生物活性趋于一致，从而使复合薄膜的各层材料降解速率趋于一致。
该技术方案是以可降解为技术突破点，PP/EVOH复合多层薄膜，也可作为食品包装材料使用，其中生物活性亲水基团的加入，无疑会对EVOH的阻隔性能产生影响，而这个性能是EVOH的最显著的性能，该技术方案不仅没有进一步巩固该性能，反而降低了该性能，因此，该方案虽然具有一定的生物降解性能，但是本身的性能受到影响。
发明内容
本发明的目的是解决EVOH与其他材料复合性能的不足和缺陷，主要是通过对EVOH、PET和PP进行改性制备得到多层复合高聚物包装材料。
技术方案：
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：按重量计，取聚对苯二甲酸乙二醇酯12～17份、聚对苯二甲酸丁二醇酯5～10份、聚丙烯8～15份、甲基丙烯酸异丁酯0.2～0.8份、聚碳酸酯0.5～1.5份和乙烯-醋酸乙烯共聚物1～3份放入流变仪中，熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：按重量计，取聚丙烯15～25份、纳米氧化钛1～2份、玻璃纤维1～2份、聚烯烃弹性体 3～6份、PP-g-MAH 3～8份、聚丙烯酸酯1～2份、乙烯-醋酸乙烯共聚物2～5份和聚酰胺1～2份，放入密炼机混炼，得到改性PP；
第3步、改性EVOH的制备：按重量份计，取EVOH 20～40份、PP-g-MAH 15～25份和聚丙烯酸2～5份，放入密炼机中密炼，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
所述第1步中，流变仪熔融共混的温度为260～270℃。
所述第2步中，密炼机混炼温度145℃～155℃，混炼时间3min10s。
所述第3步中，密炼机温度210℃，密炼时间3min50s。
所述第4步中，挤出机机头加热温度为260～285℃。
有益效果
本发明提供的多层复合高聚物包装材料的制备方法，是以EVOH材料为核心，为中间阻隔层，在阻隔层外围各设置一层改性PP层，改性PP层中加入PP-g-MAH，在薄膜共挤出时增加与EVOH层的交联，而且，改性PP层对水特别稳定，可减少水对EVOH阻断性能的影响，在其中一层PP层外层设改性PET层，利用改性PET层的耐油、耐腐和阻断性能，进一步加强多层复合高聚物材料的阻断性能，因此，本发明提供的多层复合高聚物包装材料具有极为优良的气体、气味阻断性能和机械性能、耐撕裂性能。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明采用的聚对苯二甲酸乙二醇酯（PET）型号为RE5264 PET，美国杜邦生产。
本发明采用的聚对苯二甲酸丁二醇酯（PBT）型号为EC44G-30 ，日本东丽公司生产。
本发明采用的乙烯-醋酸乙烯共聚物规格为A007027，江莱生物生产。
本发明采用的马来酸酐接枝聚丙烯规格为SWJ-1B2，由沙特基础工业公司（Sabic）生产，接枝率0.6～0.8 MA% 。
本发明采用的聚碳酸酯规格为2605，德国拜耳公司生产。
本发明采用的聚烯烃弹性体规格为8150，美国陶氏生产。
本发明采用的EVOH规格为F171，日本可乐丽生产。
本发明采用的流变仪型号为RM-200C混炼式转矩流变仪，哈尔滨哈普电气技术有限公司生产。
本发明采用的密炼机为青岛光越橡胶机械制造有限公司的陶瓷密炼机。
本发明采用的双螺杆挤出机型号为SAT-95，南京越升挤出设备有限公司生产。
实施例1
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯120g、聚对苯二甲酸丁二醇酯50g、聚丙烯80g、甲基丙烯酸异丁酯2g、聚碳酸酯5g和乙烯-醋酸乙烯共聚物10g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、PP-g-MAH 60g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 200g、PP-g-MAH 150g和聚丙烯酸20g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，控制挤出机机头加热温度为275℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
实施例2
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯170g、聚对苯二甲酸丁二醇酯100g、聚丙烯150g、甲基丙烯酸异丁酯8g、聚碳酸酯15g和乙烯-醋酸乙烯共聚物30g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、PP-g-MAH 60g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 400g、PP-g-MAH 250g和聚丙烯酸50g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，控制挤出机机头加热温度为275℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
实施例3
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯150g、纳米氧化钛10g、玻璃纤维10g、聚烯烃弹性体 30g、PP-g-MAH 30g、聚丙烯酸酯10g、乙烯-醋酸乙烯共聚物20g和聚酰胺10g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 320g、PP-g-MAH 240g和聚丙烯酸30g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，控制挤出机机头加热温度为280℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
实施例4
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯250g、纳米氧化钛20g、玻璃纤维20g、聚烯烃弹性体 60g、PP-g-MAH 80g、聚丙烯酸酯20g、乙烯-醋酸乙烯共聚物50g和聚酰胺20g，放入密炼机152℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 320g、PP-g-MAH 240g和聚丙烯酸30g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，挤出机机头加热温度为277℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
实施例5
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、PP-g-MAH 60g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 320g、PP-g-MAH 240g和聚丙烯酸30g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，挤出机机头加热温度为277℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
对照例1
与实施例5的区别在于：EVOH未改性，直接层叠挤出成型。
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、PP-g-MAH 60g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、将改性PET、改性PP和EVOH放入挤出机中，挤出机机头加热温度为277℃，按照改性PET、改性PP、EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
对照例2
与实施例5的区别在于：改性PP和改性EVOH中未加入PP-g-MAH。
一种多层复合高聚物包装材料的制备方法，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 320g和聚丙烯酸30g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，挤出机机头加热温度为277℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
将上述实施例和对照例制备得到的薄膜材料，厚度为1mm，根据《塑料薄膜和薄片气体透过性试验方法压差法》GB/T1038-2000测试薄膜对气体的阻隔系数，单位ml（cm3，g)•mm/m2•d•MPa，结果如表1所示：
表1 实施例1～5和对照例1～2 薄膜阻隔性能
由上表可知，EVOH未添加PP-g-MAH，在复合薄膜中，其对氧气的阻隔作用有所下降，但仍然具有较为优异的阻隔效果，对二氧化碳的阻隔效果与实施例差距明显，对水蒸气的阻隔效果差距十分明显，只能属于中等偏上阻隔水平；EVOH和改性PP均未添加PP-g-MAH，EVOH和改性PP之间只通过层叠挤出贴合，其对氧气和二氧化碳的阻隔与实施例差距较大，其对水蒸气的阻隔差距十分明显。
测定实施例和对照例薄膜的力学性能，并根据《塑料薄膜和薄片耐撕裂性能的测定第2部分：埃莱门多夫(Elmendor) 法》GB/T16578.2-2009，测试薄膜耐撕裂性能，结果如表2所示：
表2实施例1～5和对照例1～2 薄膜力学性能及耐撕裂性能
由上表可知，实施例1～5在力学性能和耐撕裂性能上均优于对照组对照例1～2，说明EVOH未加入PP-g-MAH对整体性能有一定消极影响，在改性PP也未添加PP-g-MAH时，性能下降十分明显。
Claims (1)
1.一种多层复合高聚物包装材料的制备方法，其特征在于，包括如下步骤：
第1步、改性PET的制备：取聚对苯二甲酸乙二醇酯140g、聚对苯二甲酸丁二醇酯70g、聚丙烯120g、甲基丙烯酸异丁酯5g、聚碳酸酯11g和乙烯-醋酸乙烯共聚物21g放入流变仪中，265℃熔融共混后，冷却，得到改性PET；
第2步、改性PP的制备：取聚丙烯200g、纳米氧化钛15g、玻璃纤维13份、聚烯烃弹性体40g、PP-g-MAH 60g、聚丙烯酸酯15g、乙烯-醋酸乙烯共聚物4g和聚酰胺15g，放入密炼机148℃混炼，混炼时间3min10s，得到改性PP；
第3步、改性EVOH的制备：取EVOH 320g、PP-g-MAH 240g和聚丙烯酸30g，放入密炼机中密炼，密炼机温度210℃，密炼时间3min50s，得到改性EVOH；
第4步、将改性PET、改性PP和改性EVOH放入挤出机中，挤出机机头加热温度为277℃，按照改性PET、改性PP、改性EVOH和改性PP的层叠顺序，四层薄膜共挤成型，即可。
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| CN102001486B (zh) * | 2009-08-28 | 2014-01-15 | 翁文桂 | 一种阻隔性叠层聚合物薄膜包装材料 |
| CN102785809A (zh) * | 2012-07-20 | 2012-11-21 | 武汉华丽生物材料有限公司 | 多层共挤瓶及其制备方法 |
| CN104249525A (zh) * | 2014-09-18 | 2014-12-31 | 希悦尔（中国）有限公司 | Pet复合包装材料及其制备方法 |
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