CN112694670B - 一种玻纤增强废旧pp/pet膜复合材料及其制备方法 - Google Patents

一种玻纤增强废旧pp/pet膜复合材料及其制备方法 Download PDF

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CN112694670B
CN112694670B CN202011574388.8A CN202011574388A CN112694670B CN 112694670 B CN112694670 B CN 112694670B CN 202011574388 A CN202011574388 A CN 202011574388A CN 112694670 B CN112694670 B CN 112694670B
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李�诚
胡志华
汪海
徐冲
罗鹏
杨霄云
程杰
刘思杨
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Abstract

本发明公开了一种玻纤增强废旧PP/PET膜复合材料及其制备方法，涉及高分子材料技术领域。本发明所述玻纤增强废旧PP/PET膜复合材料包含如下重量份的成分：PP/PET膜50～90份、短玻璃纤维10～30份、相容剂2～10份和抗氧剂0.2～0.7份。由本发明所述配方制备的玻纤增强废旧PP/PET膜复合材料具有良好的力学性能和耐热性。

Description

一种玻纤增强废旧PP/PET膜复合材料及其制备方法
技术领域
本发明涉及高分子材料技术领域，尤其涉及一种玻纤增强废旧PP/PET膜复合材料及其制备方法。
背景技术
由于PP与PET相容性不好，大量的PP/PET复合膜材料无法高质化回收，即使熔融造粒后，由于两种树脂相容性差，导致性能极差，无法使用。
专利CN 101580612A公开了一种PP/PET合金材料及其制备工艺，通过加入相容剂、增强剂、偶联剂、抗氧剂等制备了玻纤增强废旧PP/PET合金材料，但是该专利中加入了SEBS-g-MAH，EPDM-g-MAH，PP-g-AA三种相容剂和硅烷偶联剂，所用相容剂种类繁多复杂，且马来酸酐类相容剂在熔融挤出过程中会导致PET降解，因此制备的复合材料性能较差。
发明内容
本发明的目的在于克服上述现有技术的不足之处而提供一种玻纤增强废旧PP/PET膜复合材料，该材料具有良好的力学性能和耐热性，可使废旧的PP/PET膜得到再利用。
为实现上述目的，本发明所采取的技术方案为：一种玻纤增强废旧PP/PET膜复合材料，包含如下重量份的成分：PP/PET膜50～90份、短玻璃纤维10～30份、相容剂2～10份和抗氧剂0.2～0.7份。
通过控制PP/PET膜、短玻璃纤维、相容剂和抗氧剂的含量在上述范围内，可以使PP、PET的相容性更好，另外，PP/PET膜中的PET和短玻璃纤维可共同增强PP/PET膜复合材料的力学性能，并保证制备出的复合材料具有良好的耐热性。
优选地，所述PP/PET膜中PET的质量百分数为1～65％。
优选地，所述PP/PET膜中PET的质量百分数为20～50％。
优选地，所述PP/PET膜在230℃、2.16kg条件下的熔体流动速率为1～100g/10min。
优选地，所述短玻璃纤维为无碱短玻璃纤维。
优选地，所述相容剂为极性单体与聚丙烯的接枝聚合物；所述极性单体包含酯类单体。所述酯类单体包含丙烯酸丁酯、马来酸二丁酯、甲基丙烯酸甘油酯中的至少一种。
优选地，所述抗氧剂包含受阻酚类抗氧剂、磷酸酯类抗氧剂、硫代酯类抗氧剂中的至少一种。
优选地，所述抗氧剂中，受阻酚类抗氧剂、磷酸酯类抗氧剂、硫代酯类抗氧剂的质量比为：受阻酚类抗氧剂：磷酸酯类抗氧剂：硫代酯类抗氧剂＝1:1:2～1:2:2。
同时，本发明还公开了一种所述玻纤增强废旧PP/PET膜复合材料的制备方法，包括如下步骤：
(1)将废旧PP/PET膜进行破碎、清洗、脱水处理后，以单螺杆挤出机熔融、挤出造粒，得到粒子；
(2)将步骤(1)得到的粒子与相容剂、抗氧剂混合均匀，得到混合料；
(3)将混合料投入一阶双螺杆挤出机，将短玻璃纤维从一阶双螺杆挤出机的侧喂口加入，熔融挤出后流入二阶单螺杆挤出机，熔融挤出，再经水冷、风干、切粒，得到所述玻纤增强废旧PP/PET膜复合材料。
优选地，所述二阶单螺杆挤出机的转速高于一阶双螺杆挤出机。通过提高转速可使熔融反应后的复合材料被高速拉伸，PET在高速拉伸过程中经水槽冷却纤维化，与玻璃纤维一起起到复合增强的作用，提高材料的强度，再经切粒机切割成塑料粒子，即可得到具有良好的机械性能和耐热性的玻纤增强废旧PP/PET膜复合材料。
相比于现有技术，本发明的有益效果为：
本发明通过合理选择各成分的含量，对相容剂、PP/PET膜中PET的含量进行选择，改善了PP、PET、短玻璃纤维界面的相容性。此外，本发明选用的PP-g-GMA相容剂是缩水甘油酯类相容剂，避免了酸酐类相容剂在熔融挤出过程中与PET反应，导致PET降解的现象发生。
另外，本发明通过使用“双螺杆+单螺杆”双阶挤出机增加物料在螺杆中的反应时间，从而使相容剂与PP、PET、玻璃纤维等组分充分反应，使相容剂的增容效率提升；挤出过程中通过调整主机和子机的转速，使熔融物料从主机口进入子机过程中形成拉伸，使PET在复合材料中初步纤维化，再通过调整切粒机转速，使经过子机熔融反应后的复合材料能够被高速拉伸，PET在高速拉伸过程中纤维化，与玻璃纤维一起起到复合增强的作用，提高材料的强度。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。
实施例和对比例所用材料如下：
PP/PET膜1，PET的质量分数为1％，熔体流动速率MFR在230℃，载荷2.16kg条件下为15g/10min；
PP/PET膜2，PET的质量分数为20％，熔体流动速率MFR在230℃，载荷2.16kg条件下为14g/10min；
PP/PET膜3，PET的质量分数为30％，熔体流动速率MFR在230℃，载荷2.16kg条件下为12g/10min；
PP/PET膜4，PET的质量分数为50％，熔体流动速率MFR在230℃，载荷2.16kg条件下为11g/10min；
PP/PET膜5，PET的质量分数为65％，熔体流动速率MFR在230℃，载荷2.16kg条件下为10g/10min；
PP/PET膜均采购自惠州丽盈塑料制品有限公司；
相容剂1，PP-g-GMA，购自佛山南海柏晨高分子新材料有限公司，牌号PC-1-G；
相容剂2，PP-g-MAH，购自佛山南海柏晨高分子新材料有限公司，牌号PC-1；
短玻璃纤维，购自巨石集团，牌号：玻纤ECS13-04-508A；
抗氧剂1010，抗氧剂168，购自德国巴斯夫生产的抗氧剂1010和168；
抗氧剂DSTDP为硫代二丙酸二(十八酯)，山东省临沂市三丰化工有限公司生产，其分子量为683.2，熔点67℃。
实施例1
本发明所述玻纤增强废旧PP/PET膜复合材料的一种实施例，本实施例所述玻纤增强废旧PP/PET膜复合材料的配方如表1所示，其制备方法为：将PP/PET膜、相容剂、抗氧剂在高速混合机中混合均匀后投入一阶双螺杆挤出机，将短玻璃纤维从一阶双螺杆挤出机的侧喂口加入，熔融挤出后流入二阶单螺杆挤出机；其中，一阶双螺杆挤出机的转速为350r/min，二阶单螺杆挤出机的转速为550r/min，高速切粒机拉伸速度为50m/min。经过水槽冷却、风干后切粒，得到所述玻纤增强废旧PP/PET膜复合材料。
实施例2～7
本发明所述玻纤增强废旧PP/PET膜复合材料的实施例，实施例2～7的配方如表1所示，制备方法与实施例1相同。
对比例1～2
一种玻纤增强废旧PP/PET膜复合材料，对比例1～2的配方如表1所示，制备方法与实施例1相同。
对比例3
一种玻纤增强废旧PP/PET膜复合材料，其配方与实施例3相同，区别仅在与，制备过程中，全程使用双螺杆挤出机挤出造粒，未使用单螺杆挤出机，双螺杆挤出机的转速为550r/min。
表1配方表(重量份)
Figure BDA0002860623980000051
性能测试
参照表2所述标准对实施例1～7和对比例1～3进行性能测试，测试结果如表3所示。
表2
Figure BDA0002860623980000052
Figure BDA0002860623980000061
表3
Figure BDA0002860623980000062
从表3中可知，实施例1～7的综合性能明显优于对比例1～3，表明相容剂的选择、各成分的配比以及PP/PET膜复合材料的制备方法对性能的影响较大。此外，通过实施例1～5的对比可知，实施例2～4的性能优于实施例1和实施例5，结果表明，PP/PET膜中PET的含量对性能的影响较大，当PET的含量为20～50时，性能最优，主要是PET在材料中纤维化，与玻璃纤维共同起到复合增强效果。实施例3与对比例3对比可知，加工工艺非常关键，双阶机能够使PP/PET膜中的PET纤维化，达到复合增强的效果。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，但并不脱离本发明技术方案的实质和范围。

Claims (7)

1.一种玻纤增强废旧PP/PET膜复合材料，其特征在于，包含如下重量份的成分：PP/PET膜50～90份、短玻璃纤维10～30份、相容剂2～10份和抗氧剂0.2～0.7份；所述PP/PET膜中PET的质量百分数为20～50％；
所述玻纤增强废旧PP/PET膜复合材料的制备方法包括如下步骤：
(1)将废旧PP/PET膜进行破碎、清洗、脱水处理后，以单螺杆挤出机熔融、挤出造粒，得到粒子；
(2)将步骤(1)得到的粒子与相容剂、抗氧剂混合均匀，得到混合料；
(3)将混合料投入一阶双螺杆挤出机，将短玻璃纤维从一阶双螺杆挤出机的侧喂口加入，熔融挤出后流入二阶单螺杆挤出机，熔融挤出，再经水冷、风干、切粒，得到所述玻纤增强废旧PP/PET膜复合材料。
2.如权利要求1所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述PP/PET膜在230℃、2.16kg条件下的熔体流动速率为1～100g/10min。
3.如权利要求1所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述短玻璃纤维为无碱短玻璃纤维。
4.如权利要求1所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述相容剂为极性单体与聚丙烯的接枝聚合物；所述极性单体包含酯类单体。
5.如权利要求1所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述抗氧剂包含受阻酚类抗氧剂、磷酸酯类抗氧剂、硫代酯类抗氧剂中的至少一种。
6.如权利要求5所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述抗氧剂中，受阻酚类抗氧剂、磷酸酯类抗氧剂、硫代酯类抗氧剂的质量比为：受阻酚类抗氧剂：磷酸酯类抗氧剂：硫代酯类抗氧剂＝1:1:2～1:2:2。
7.如权利要求1所述的玻纤增强废旧PP/PET膜复合材料，其特征在于，所述二阶单螺杆挤出机的转速高于一阶双螺杆挤出机。
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