CN112759906A - 一种用于海洋的全生物降解聚乳酸吸油发泡材料 - Google Patents
一种用于海洋的全生物降解聚乳酸吸油发泡材料 Download PDFInfo
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Abstract
一种用于海洋的全生物降解聚乳酸吸油发泡材料，包括如下重量份数的物质：聚乳酸树脂66‑93.2份；增韧剂5‑20份；成核剂0.5‑5份；交联剂0.1‑3份；抗氧剂0.2‑1份；发泡剂1‑5份。本发明制备的聚乳酸吸油发泡材料较现有技术相比具有较高吸油率，且吸水率明显低于现有产品，能做到基本不吸收水的特质，从而解决了现有技术中即吸收油又吸收水的问题，从而解决其在使用过程中存在的浮力差的问题，同时本发明制备的聚乳酸吸油发泡材料使用完成后捞起能够完全降解，避免还需要二次回收处理，有效的节约了资源，保护了环境。
Description
技术领域
本发明属于高分子材料领域，具体地说是一种用于海洋的全生物降解聚乳酸吸油发泡材料。
背景技术
随着世界工业的不断发展，原油和各种油类产品的使用和运输已成为现代生活不可分割的一部分。油污排放日益增加，油品泄漏的途径和机会也越来越多，近年公海上的油船油罐泄漏已引起公众极大的重视。目前，海洋油污染已经严重威胁到近海的生态环境，治理近海水环境的油污染已是刻不容缓，这就迫使人类亟需开发大量优良的吸油材料。
目前主要的吸油材料可以分为三大类，即无机吸油材料、有机合成吸油材料和有机天然吸油材料。无机矿物包括沸石、硅藻土、珍珠岩、石墨、蛭石、粘土和二氧化硅，它们对非极性有机物的吸附量较小。有机合成材料包括聚合材料聚丙烯发泡及纤维无纺布，由于它们具有亲油性和疏水性，与其他类型的材料相比，它具有更好的吸附性能，易制备和重复使用，所以是处理油污染的常用材料，但其存在消耗石化资源而且难降解的问题。有机天然吸附剂包括麦杆、玉米棒、泥炭沼、木质纤维、树皮、洋麻等，其具有较高吸油率，但存在浮力性质差，吸油的同时也吸水的问题，尽管可以通过改性来提高疏水性，但成本较高。
发明内容
本发明提供一种用于海洋的全生物降解聚乳酸吸油发泡材料，用以解决现有技术中的缺陷。
本发明通过以下技术方案予以实现：
一种用于海洋的全生物降解聚乳酸吸油发泡材料，包括如下重量份数的物质：
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的聚乳酸为聚左旋乳酸(PLLA)或聚右旋乳酸(PDLA)其中的任意一种或两种以任意比例混合的混合物。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的聚左旋乳酸的熔点为165-175℃。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的增韧剂为具有生物降解性的二元酸二元醇系列聚酯。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的增韧剂为聚丁二酸丁二醇酯(PBS)、聚对苯二甲酸-己二酸-丁二醇酯(PBAT)、聚丁二酸-己二酸-丁二醇酯(PBSA)或聚对苯二甲酸-丁二酸-丁二醇酯(PBST)其中的任意一种。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的成核剂为的滑石粉(滑石粉(Talc)、二氧化硅(SiO2)、芳族磺酸酯衍生物(Lak-301)其中的任意一种。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的滑石粉的目数为5000-9000。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的二氧化硅为纳米级。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的交联剂为二-(叔丁基过氧异丙基)苯(BIBP)、多苯基多甲基多异氰酸酯(PAPI)、二苯基甲烷二异氰酸酯(MDI)或三烯丙基三聚氰酸酯(TAIC)其中的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的抗氧剂为胺类抗氧剂、酚类抗氧剂、亚磷酸酯类抗氧剂、硫代酯类抗氧剂中其中的任意一种或任意两种以上以任意比例混合的混合物。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，所述的发泡剂为二氧化碳发泡剂。
如上所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其制备方法包括如下步骤：
步骤一：将聚乳酸、增韧剂、成核剂、交联剂、抗氧剂按重量配比称取，并在高速混合机中混合均匀,得到原料混合物；
步骤二：将步骤一中混合好的物料一次加入到双螺杆挤出机的料斗中，物料经过经挤出造粒，制备得到发泡专用树脂；
步骤二中所述挤出机螺杆长径比为44-56，转速100-300转/分钟，喂料速度10-50Kg/h，挤出温度设置如下：
步骤三：将步骤二中制备的发泡专用树脂置于80℃烘箱中4个小时后取出，然后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入二氧化碳发泡剂，经发泡挤出设备进行发泡，得到聚乳酸发泡材料；
步骤三中所述挤出机螺杆长径比为33-48，转速100-200转/分钟，喂料速度10-35Kg/h，发泡剂的注入压力为15-22MPa，挤出温度设置如下：
本发明的优点是：本发明制备的聚乳酸吸油发泡材料较现有技术相比具有较高吸油率，且吸水率明显低于现有产品，能做到基本不吸收水的特质，从而解决了现有技术中即吸收油又吸收水的问题，从而解决其在使用过程中存在的浮力差的问题，同时本发明制备的聚乳酸吸油发泡材料使用完成后捞起能够完全降解，避免还需要二次回收处理，有效的节约了资源，保护了环境。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1是本发明实施例与对照例在多种介质中吸附率的对比图；
图2是本发明实施例1测试过程的操作示意图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
(1)称取76.5份PLLA、20份PBAT,1份成核剂纳米SiO2、2份交联剂BIBP、0.5份抗氧剂，在高搅机中预混合均匀后加入双螺杆挤出机中，物料经过熔融挤出、冷却造粒，得到发泡专用树脂。
(2)将步骤(1)中制备的发泡专用树脂置于80℃烘箱中4个小时后取出，然后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入3份的二氧化碳发泡剂，经发泡挤出设备进行发泡，得到发泡材料。
实施例2
(1)称取84.8份PLLA、5份PDLA、5份PBSA、3份成核剂滑石粉、1份交联剂BIBP、1份交联剂TAIC、0.2份抗氧剂，在高搅机中预混合均匀后加入双螺杆挤出机中，物料经过熔融挤出、冷却造粒，得到发泡专用树脂。
(2)将步骤(1)中制备的发泡专用树脂置于80℃烘箱中4个小时后取出，然后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入5份的二氧化碳发泡剂，经发泡挤出设备进行发泡，得到发泡材料。
实施例3
(1)称取80.7份PLLA、15份PBS、2份成核剂Lak-301、2份交联剂PAPI、1.0份抗氧剂，在高搅机中预混合均匀后加入双螺杆挤出机中，物料经过熔融挤出、冷却造粒，得到发泡专用树脂。
(2)将步骤(1)中制备的发泡专用树脂置于80℃烘箱中4个小时后取出，然后后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入5份的二氧化碳发泡剂，经发泡挤出设备进行发泡，得到发泡材料。
实施例4
(1)称取75.5份PLLA、10份PDLA、10份PBST、2份成核剂Talc、2份交联剂PAPI、0.5份抗氧剂，在高搅机中预混合均匀后加入双螺杆挤出机中，物料经过熔融挤出、冷却造粒，得到发泡专用树脂。
(2)将步骤(1)中制备的发泡专用树脂置于80℃烘箱中4个小时后取出，然后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入2份的二氧化碳发泡剂，经发泡挤出设备进行发泡，得到发泡材料。
对比例1
(1)称取95.9份PLLA、2份成核剂Talc、2份交联剂PAPI、0.1份抗氧剂，在高搅机中预混合均匀后加入双螺杆挤出机中，物料经过熔融挤出、冷却造粒，得到发泡专用树脂。
(2)将步骤(1)中制备的发泡专用树脂置于80℃烘箱中4个小时后后取出，然后加入挤出发泡设备的料斗中，同时在挤出发泡设备的第二段注入5份的二氧化碳发泡剂，经发泡挤出设备进行发泡，得到发泡材料。
将上述各实施例和对比例得到的发泡材料进行吸油(水)倍率测试，具体测试方法如下：
将一定量的发泡材料放入油(水)中，1min后取出，静止30s，分别称取吸油(水)前后材料的质量，最终结果取5次实验的平均值，吸油(水)倍率(Q)计算公式如下所示：
式中m0和m1分别是吸油(水)前发泡材料的质量。
本发明制备的发泡材料的吸油(水)倍率如图1所示，所有柱状图从左至右依次为实施例1、实施例2、实施例3、实施例4以及对照例，本发明进行了柴油、豆油以及水的三种介质的吸附率测试，从图1的柱状图中可以看出，看到，与对比例相比，本发明实施例1-4所制备的发泡材料无论是对柴油还是豆油都具备较高的吸油率，且吸水率明显低于对比例。因此本发明提供的聚乳酸发泡材料不仅有利于水体净化与油水分离中，而且使用后能够完全生物降解，在海洋石油泄漏应用中有很大的价值。
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
Claims (10)
1.一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：包括如下重量份数的物质：
2.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的聚乳酸为聚左旋乳酸(PLLA)或聚右旋乳酸(PDLA)其中的任意一种或两种以任意比例混合的混合物。
3.根据权利要求2所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的聚左旋乳酸的熔点为165-175℃。
4.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的增韧剂为具有生物降解性的二元酸二元醇系列聚酯。
5.根据权利要求4所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的增韧剂为聚丁二酸丁二醇酯(PBS)、聚对苯二甲酸-己二酸-丁二醇酯(PBAT)、聚丁二酸-己二酸-丁二醇酯(PBSA)或聚对苯二甲酸-丁二酸-丁二醇酯(PBST)其中的任意一种。
6.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的成核剂为的滑石粉(Talc)、二氧化硅(SiO2)、芳族磺酸酯衍生物(Lak-301)其中的任意一种。
7.根据权利要求6所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：
所述的滑石粉的目数为5000-9000；
所述的二氧化硅为纳米级。
8.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的交联剂为二-(叔丁基过氧异丙基)苯(BIBP)、多苯基多甲基多异氰酸酯(PAPI)、二苯基甲烷二异氰酸酯(MDI)或三烯丙基三聚氰酸酯(TAIC)其中的任意一种或任意两种以上以任意比例混合的混合物。
9.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的抗氧剂为胺类抗氧剂、酚类抗氧剂、亚磷酸酯类抗氧剂、硫代酯类抗氧剂中其中的任意一种或任意两种以上以任意比例混合的混合物。
10.根据权利要求1所述的一种用于海洋的全生物降解聚乳酸吸油发泡材料，其特征在于：所述的发泡剂为二氧化碳发泡剂。
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