CN114561125A - 一种可生物降解淀粉基薄膜材料的制备方法 - Google Patents
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Abstract
本发明公开了一种可生物降解淀粉基薄膜材料的制备方法，将马铃薯淀粉和水搅拌分散，静置后烘干并磨成粉末得到物料A；将蒙脱土K‑10分散在水中得到物料B；将柠檬酸溶解在水中得到物料C；将D‑山梨醇溶解在水中得到物料D；在95℃油浴条件下，将聚乙烯醇溶解在水中得到物料E；将物料A、物料B、物料C、物料D和物料E混合，于80~120℃搅拌混合均匀得到物料F；将物料F涂覆在聚四氟乙烯板上并干燥得到目标产物可生物降解淀粉基薄膜。本发明制备的可生物降解淀粉基薄膜材料抗拉强度可达15‑40MPa，接触角高达83.71°，疏水性能优良，因此该薄膜材料在可降解塑料领域具有潜在应用前景。
Description
技术领域
本发明属于可生物降解薄膜材料的制备技术领域，具体涉及一种可生物降解淀粉基薄膜材料的制备方法。
背景技术
环境污染和化石能源枯竭日趋严重，引起了人们对利用多糖和蛋白质等可再生聚合物生产可生物降解材料的兴趣。其中，淀粉是地球上最丰富的可再生生物材料之一，由于其低成本、易于裁剪、生物相容性高、来源广泛、可再生等独特优势，被认为是最有前途代替石油基材料的可生物降解天然聚合物。近年来，淀粉基材料的应用倍受关注，但是天然淀粉存在大量的亲水羟基，使得淀粉很容易被水分子侵蚀，而淀粉的高亲水性通常会降低其力学性能和尺寸稳定性。同时，由于淀粉分子内氢键的相互作用，淀粉基材料的机械性能较差。因此，淀粉基材料的进一步加工与应用变得相对困难。为了加快淀粉基材料的应用，急需开发力学性能优良且疏水性能较好的可生物降解淀粉基材料。
淀粉与其它可降解生物材料共混是提高淀粉基材料性能的有效方法，在可与淀粉产生协同效果的材料中，聚乙烯醇（PVA）是一种成本相对较低、生物相容性较好、无毒、加工方便和水渗透性高的可生物降解材料，是改善淀粉材料性质的优良选择。PVA与淀粉进行共混，能极大程度改善热塑性淀粉的机械性能，且不改变淀粉材料的可生物降解性能。天然矿物材料因其能提升淀粉基材料的力学性能受到研究者的青睐，其中蒙脱土因其较高的粘性模量而得到广泛研究。本发明将蒙脱土作为填料加入到淀粉/PVA共混物中，借助蒙脱土的独特层状结构，在淀粉/PVA共混物中作为插层，有效提升淀粉/PVA共混物的机械性能，在可降解塑料领域具有潜在的应用前景，然而目前尚没有该方面的相关文献记载。
发明内容
本发明解决的技术问题是提供了一种工艺简单且成本相对低廉的可生物降解淀粉基薄膜材料的制备方法，该方法利用淀粉和PVA作为淀粉薄膜的主要材料，利用蒙脱土作为薄膜的增强材料，将D-山梨醇作为淀粉的塑化剂，于80~120℃对混合物料进行加热并机械搅拌促进物料混合均匀，再涂覆在聚四氟乙烯板上制得可生物降解淀粉基薄膜材料。本发明制备的可生物降解淀粉基薄膜材料拉伸性能良好且疏水性显著提高。
本发明为解决上述技术问题采用如下技术方案，一种可生物降解淀粉基薄膜材料的制备方法，其特征在于具体过程为：
步骤S1：将马铃薯淀粉和水于10~90℃搅拌分散，静置1h，然后于50~90℃烘干并磨成粉末得到物料A；
步骤S2：将蒙脱土K-10在水中超声均匀分散1.5h得到物料B，将柠檬酸以10%~15%的质量分数溶解在水中得到物料C，将D-山梨醇以5%~10%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将聚乙烯醇以10%~20%的质量分数溶解在水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于80~120℃下以600~1200r/min搅拌速率混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，再于20~40℃干燥得到目标产物可生物降解淀粉基薄膜。
进一步限定，步骤S1中所述的马铃薯淀粉和水的质量比为1:2。
进一步限定，步骤S2中所述蒙脱土K-10分散在水中的质量分数为10%~15%。
进一步优选，步骤S3中所述聚乙烯醇的平均分子量为105000。
本发明所述的可生物降解淀粉基薄膜材料的制备方法，其特征在于具体步骤为：
步骤S1：将10g马铃薯淀粉和20mL水于室温搅拌分散，静置1h，然后于40℃烘干并磨成粉末得到物料A；
步骤S2：将1~4g蒙脱土K-10以15%的质量分数在水中超声均匀分散1.5h得到物料B，将3g柠檬酸以10%~15%的质量分数溶解在水中得到物料C，将1g D-山梨醇以5%~10%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将10g聚乙烯醇以10%~20%的质量分数溶解在水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于95℃搅拌混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，于25℃干燥得到目标产物可生物降解淀粉基薄膜，该薄膜表现出优异的抗拉强度、疏水性能以及塑性性能。
本发明与现有技术相比具有以下优点和有益效果：
1、本发明选用无毒无害、来源广泛的原材料，能够降低可生物降解材料的制备成本；
2、本发明以淀粉和PVA为基底，添加蒙脱土作为增强剂，可以显著提高样品的拉伸性能；
3、本发明制得的可生物降解淀粉基薄膜材料具有优良的抗拉强度和疏水特性。
附图说明
图1为实施例1制备的目标产物G1的扫描电镜图；
图2为实施例1-3制备的目标产物G1-G3的X射线衍射图；
图3为实施例1-3制备的目标产物G1-G3的红外光谱图；
图4为实施例1-3制备的目标产物G1-G3的热重分析图；
图5为实施例1-3制备的目标产物G3的接触角测试图；
图6为实施例1-3制备的目标产物G1-G3的抗拉强度图。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明，但不应该将此理解为本发明上述主题的范围仅限于以下的实施例，凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
步骤S1：将10g马铃薯淀粉和20mL水于室温条件搅拌分散，静置1h，然后于40℃烘干并磨成粉末得到物料A；
步骤S2：将3.88g蒙脱土K-10以15%的质量分数在水中以40KHz超声均匀分散1.5h得到物料B，将3g柠檬酸以15%的质量分数溶解在水中得到物料C，将1g D-山梨醇以5%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将10g聚乙烯醇（平均分子量105000）以600r/min搅拌速率溶解在90mL水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于95℃以1000r/min搅拌速率混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，于25℃干燥得到目标产物G1。
实施例2
步骤S1：将10g马铃薯淀粉和20mL水于60℃搅拌分散，静置1h，然后于60℃烘干并磨成粉末得到物料A；
步骤S2：将1.158g蒙脱土K-10以10%的质量分数在水中以40KHz超声均匀分散1.5h得到物料B，将3g柠檬酸以15%的质量分数溶解在水中得到物料C，将1g D-山梨醇以5%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将10g聚乙烯醇（（平均分子量105000）以600r/min搅拌速率溶解在90mL水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于95℃以1000r/min搅拌速率混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，于25℃干燥得到目标产物G2。
实施例3
步骤S1：将10g马铃薯淀粉和20mL水于80℃搅拌分散，静置1h，然后于80℃烘干并磨成粉末得到物料A；
步骤S2：将2.444g蒙脱土K-10以12%的质量分数在水中以40KHz超声均匀分散1.5h得到物料B，将3g柠檬酸以15%的质量分数溶解在水中得到物料C，将1g D-山梨醇以5%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将10g聚乙烯醇（（平均分子量105000）以600r/min搅拌速率溶解在90mL水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于95℃以1000r/min搅拌速率混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，于25℃干燥得到目标产物G3。
实施例4
将目标产物G1裁剪为10mm×10mm大小，保证样品干燥，对目标产物进行接触角测试。将目标产物G1裁剪为10mm×40mm大小。使用万能材料实验机对目标产物进行拉伸测试，样品在夹具的有效长度为25mm，夹具夹持部分对样品进行保护，防止样品出现损伤造成数据不准确。用同样的方法测试目标产物G2、G3的拉伸性能。
所有实施例中样品的性能如下：如图5所示，为实施例1所得目标产物G1的接触角为83.71°，测试结果表明目标产物的疏水性能大幅提升。如图6所示，为实施例1-3所得目标产物G1、G2和G3的拉伸曲线，抗拉强度分别为15.87MPa、20.08MPa和38.93MPa。以上结果表明，目标产物G1具有优异的抗拉强度，在可降解塑料领域具有潜在应用前景。
以上实施例描述了本发明的基本原理、主要特征及优点，本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明原理的范围下，本发明还会有各种变化和改进，这些变化和改进均落入本发明保护的范围内。
Claims (5)
1.一种可生物降解淀粉基薄膜材料的制备方法，其特征在于具体过程为：
步骤S1：将马铃薯淀粉和水于10~90℃搅拌分散，静置1h，然后于50~90℃烘干并磨成粉末得到物料A；
步骤S2：将蒙脱土K-10在水中超声均匀分散1.5h得到物料B，将柠檬酸以10%~15%的质量分数溶解在水中得到物料C，将D-山梨醇以5%~10%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将聚乙烯醇以10%~20%的质量分数溶解在水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于80~120℃下以600~1200r/min搅拌速率混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，再于20~40℃干燥得到目标产物可生物降解淀粉基薄膜。
2.根据权利要求1所述的可生物降解淀粉基薄膜材料的制备方法，其特征在于：步骤S1中所述的马铃薯淀粉和水的质量比为1:2。
3.根据权利要求1所述的可生物降解淀粉基薄膜材料的制备方法，其特征在于：步骤S2中所述蒙脱土K-10分散在水中的质量分数为10%~15%。
4.根据权利要求1所述的可生物降解淀粉基薄膜材料的制备方法，其特征在于：步骤S3中所述聚乙烯醇的平均分子量为105000。
5.根据权利要求1所述的可生物降解淀粉基薄膜材料的制备方法，其特征在于具体步骤为：
步骤S1：将10g马铃薯淀粉和20mL水于室温搅拌分散，静置1h，然后于40℃烘干并磨成粉末得到物料A；
步骤S2：将3.88g蒙脱土K-10以15%的质量分数在水中超声均匀分散1.5h得到物料B，将3g柠檬酸以10%~15%的质量分数溶解在水中得到物料C，将1g D-山梨醇以5%~10%的质量分数溶解在水中得到物料D；
步骤S3：在95℃油浴条件下，将10g聚乙烯醇以10%~20%的质量分数溶解在水中得到物料E；
步骤S4：将物料A、物料C、物料D、物料B依次加入到物料E中，于95℃搅拌混合3h得到物料F；
步骤S5：将物料F涂覆在聚四氟乙烯板上，于25℃干燥得到目标产物可生物降解淀粉基薄膜，该薄膜表现出优异的抗拉强度、疏水性能以及塑性性能。
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