CN106009571B - 一种聚己内酯/纤维素纳米晶体复合材料的制备方法 - Google Patents
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Abstract
一种聚己内酯/纤维素纳米晶体复合材料的制备方法，涉及生物可降解复合材料的制备方法，本发明将微晶纤维素经酸解形成纤维素纳米晶体，再将纤维素纳米晶体经过乙酰化改性得到乙酰化纤维素纳米晶体，然后再将乙酰化纤维素纳米晶体与聚己内酯溶解于有机溶剂中，取得混合溶液，再将混合溶液流涎成膜，经干燥，取得聚己内酯/纤维素纳米晶体复合材料。本发明可避免纤维素纳米晶体的不可逆团聚，最终得到的乙酰化纤维素纳米晶体在基体分散性更好。
Description
技术领域
本发明涉及生物可降解复合材料的制备方法，特别涉及纤维素改性聚己内酯生产技术领域。
背景技术
随着社会的发展，大量不可降解塑料的使用导致了严重的环境污染，因此生物可降解材料得到了广泛的重视。聚己内酯（PCL）是一种完全可生物降解的高分子材料，目前被运用于手术缝合线、包装材料、低温阻尼材料、工程塑料等。但是未经改性的聚己内酯材料的力学性能有明显的不足：聚己内酯的断裂强度偏低，制约了其作为工程塑料的使用范围；玻璃化转变温度过低；动态热机械性能较差，作为低温采用使用时，强度明显偏低。因此大量研究者采用填充、共混、接枝等手段制备聚己内酯复合材料以改善其性能。
聚己内酯的常规改性方法为填充刚性填料，如碳纳米管、氧化石墨烯、玻璃纤维等，但是这些制备复合材料的方法成本过高、填料与基体的相容性较差、填料不能降解等，很难得到经济成本低、性能好的材料。
发明内容
针对现有技术中存在的不足，本发明提出一种易于降解、强度高、经济的聚己内酯复合材料的制备方法。
本发明将微晶纤维素经酸解形成纤维素纳米晶体，再将纤维素纳米晶体经过乙酰化改性得到乙酰化纤维素纳米晶体，然后再将乙酰化纤维素纳米晶体与聚己内酯溶解于有机溶剂中，取得混合溶液，再将混合溶液流涎成膜，经干燥，取得聚己内酯/纤维素纳米晶体复合材料。
本发明以微晶纤维素为原料酸解制备纤维素纳米晶体，连续的进行乙酰化改性，可以避免纤维素纳米晶体的不可逆团聚，最终得到的乙酰化纤维素纳米晶体在基体分散性更好。
本发明将乙酰化纤维素纳米晶体作为填料形成改性的聚己内酯，从材料性能设计的方面出发，具有乙酰基的纤维素纳米晶体既有亲油性的基团，同时又具备纳米材料特有的纳米效应，聚己内酯和乙酰化纤维素纳米晶体形成强烈的界面相互作用。
复合材料的制备方法一般包括：熔融共混、溶液共混等，本发明选择溶液共混的方法，制备得到的复合材料均一性好。
本发明复合材料中聚己内酯和乙酰化纤维素纳米晶体形成强烈的界面相互作用，因此本发明所述乙酰化纤维素纳米晶体与聚己内酯的混合质量比为1～20∶80～99。乙酰化纤维素纳米晶体用量最高设定为20%。
复合材料的性能提升主要取决于两个因素：填料在基体中的分散、填料和基体的相互作用。因此本发明所述乙酰化纤维素纳米晶体与聚己内酯的质量与有机溶剂体积的混合比为1g∶5mL～6mL。溶剂在此范围内能够确保聚己内酯完全溶解；溶液的黏度只有在合适的范围内，才能流涎成表面平整的薄膜材料，直接用以测定其性能。
优选的有机溶剂为二氯甲烷、三氯甲烷中的任意一种。二氯甲烷、三氯甲烷是聚己内酯的良溶剂，聚己内酯在较短的时间内可以溶解，便于实现工业化生产。
附图说明
图1 为实施例1的拉伸断面扫描电子显微镜照片。
图2 为对比例2的拉伸断面扫描电子显微镜照片。
图3 为对比例1、实施例1～3的拉伸性能测试结果图。
图4 为对比例1、实施例1～3模量与温度关系图。
图5 为对比例1、实施例1～3玻璃化转变曲线图。
图6 为对比例1、实施例1～5的流变性能测试结果图。
具体实施方式
本发明的其它优点和效果将在下面的具体实施方式中继续描述。
以下各例中，聚己内酯牌号为PCL6500，数均分子量约50000 g/mol，熔融温度55～60℃的生物可降解高分子聚酯。
采用现有公知技术，将微晶纤维素经酸解形成纤维素纳米晶体，再将纤维素纳米晶体经过乙酰化改性取代度为2.36的乙酰化纤维素纳米晶体。
一、实施例1：
1、将干燥后的聚己内酯与乙酰化纤维素纳米晶体以99∶1的质量比混合，使用三氯甲烷溶解，三氯甲烷的体积（ml）与复合材料的质量（g）之比为5∶1。混合均匀后流涎成膜，置于室温下干燥成型。
2、使用微型注塑机将出料注射成标准哑铃型样条用于拉伸性能测试；另外80℃热压成型为1 mm的片材，用于动态热机械性能测试及流变性能测试。
二、实施例2至7：
将实施例1的组分比例进行调整，换用不同的有机溶剂，改变有机溶剂的体积（ml）与复合材料的质量（g）的比值，具体表1：
表1
三、对比例1：
1、将干燥后的聚己内酯直接使用三氯甲烷溶解，三氯甲烷的体积（ml）与复合材料的质量（g）之比为5:1。混合均匀后流涎成膜，置于室温下干燥成型，得到纯聚己内酯材料。
2、使用微型注塑机将出料注射成标准哑铃型样条用于拉伸性能测试；另外80℃热压成型为1 mm的片材，用于动态热机械性能测试及流变性能测试。
四、对比例2
1、将干燥后的聚己内酯与微晶纤维素以99:1的质量比混合，使用三氯甲烷溶解，三氯甲烷的体积（ml）与复合材料的质量（g）之比为5:1。混合均匀后流涎成膜，置于室温下干燥成型。
2、使用微型注塑机将出料注射成标准哑铃型样条用于拉伸性能测试；另外80℃热压成型为1 mm的片材，用于动态热机械性能测试及流变性能测试。
五、分析：
表2是实施例1、2、3、6、7，对比例1、2的拉伸性能测试结果，从表中可以看出，添加了乙酰化纤维素纳米晶体的复合材料断裂强度明显高于对比例1（纯聚乳酸）；除了在断裂强度方面的提升，复合材料的断裂伸长率也得到了显著的增大。
表2
实施例1和对比例2，填料的质量分数均为1%，但是在力学性能上却存在着明显的差异。图1和图2分别是两者的拉伸断面扫描电子显微镜照片，通过两者的对比可以发现：本发明中使用的乙酰化纤维素纳米晶体与聚己内酯基体之间的界面粘结作用更强；对比例2的拉伸断面可以明显看到填料和基体之间的结构缺陷。结合图3进一步分析，添加乙酰化纤维素纳米晶体的复合材料在较大伸长率时，呈现了应变硬化的现象。
图4和图5动态热机械性能分析得到的两组结果。图4是材料的模量与温度关系，在低温区域，实施例1～3的模量得到大幅提高，这就弥补了聚己内酯作为低温材料使用时强度不足的缺点。图5曲线的峰值对应的温度是材料的玻璃化转变温度，乙酰化纤维素纳米晶体的加入使复合材料的玻璃化转变温度升高了10℃以上，这就表明填料和基体之间存在着明显的相互作用，填料能够阻碍聚己内酯大分子链的运动。
图6 为对比例1、实施例1～5的流变性能测试结果图，随着乙酰化纤维素纳米晶体质量百分数的增加，复合材料在熔融状态下模量呈数量级增长，表明填料在基体中均匀分散，有较强的界面作用。
以上各例中将有机溶剂改用二氯甲烷，同样也能取得相同的效果。
Claims (2)
1.一种聚己内酯/纤维素纳米晶体复合材料的制备方法，其特征在于将微晶纤维素经酸解形成纤维素纳米晶体，再将纤维素纳米晶体经过乙酰化改性得到取代度为2.36的乙酰化纤维素纳米晶体，然后再将乙酰化纤维素纳米晶体与聚己内酯溶解于有机溶剂中，取得混合溶液，再将混合溶液流涎成膜，经干燥，取得聚己内酯/纤维素纳米晶体复合材料；
所述乙酰化纤维素纳米晶体与聚己内酯的混合质量比为1～20∶80～99；
所述乙酰化纤维素纳米晶体与聚己内酯的总质量与有机溶剂体积的混合比为1g∶5mL。
2.根据权利要求1所述制备方法，其特征在于，所述有机溶剂为二氯甲烷、三氯甲烷中的任意一种。
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| RU2708396C1 (ru) * | 2018-12-19 | 2019-12-06 | Федеральное государственное бюджетное учреждение науки Институт высокомолекулярных соединений Российской академии наук | Биосовместимый биоразлагаемый остеокондуктивный полимерный композиционный материал для регенерации костной ткани |
| CN110670408B (zh) * | 2019-10-17 | 2022-04-22 | 中国科学院理化技术研究所 | 一种疏水浆料及其制备方法与应用 |
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| CN111748183A (zh) * | 2020-06-23 | 2020-10-09 | 南宁学院 | 一种偶联改性cnf/pcl复合材料及其应用 |
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