CN110483747B - 一种聚乳酸接枝壳聚糖纳米晶须的制备方法 - Google Patents

一种聚乳酸接枝壳聚糖纳米晶须的制备方法 Download PDF

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CN110483747B
CN110483747B CN201910942172.3A CN201910942172A CN110483747B CN 110483747 B CN110483747 B CN 110483747B CN 201910942172 A CN201910942172 A CN 201910942172A CN 110483747 B CN110483747 B CN 110483747B
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徐荷澜
罗贵清
马博谋
侯秀良
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WUXI JINTONG HIGH FIBER Co.,Ltd.
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Abstract

本发明公开了一种聚乳酸接枝壳聚糖纳米晶须的制备方法，属于材料技术领域。本发明是将丙交酯、催化剂和壳聚糖混合均匀后进行聚合接枝制备PLA‑g‑CS，再将PLA‑g‑CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须，聚合接枝过程中无溶剂。该方法使得没有良好溶剂的PLA‑g‑CS可以制备得到纳米晶须，整个反应高效清洁，绿色环保。

Description

一种聚乳酸接枝壳聚糖纳米晶须的制备方法
技术领域
本发明涉及一种聚乳酸接枝壳聚糖纳米晶须的制备方法，属于材料领域。
背景技术
有机纳米材料是指基于脂质、蛋白、多糖及有机高分子聚合物的新型纳米材料。随着纳米技术的不断发展和应用，纳米材料已被广泛地应用于食品、生物医药、农业以及环境等领域。纳米材料由于其纳米级别的尺寸效应而具有的独特物理和化学性质，为食品、农业、工业等领域带来了新的创新发展机遇。多糖纳米晶须生物相容性好、生物降解性好、无毒性、易修饰性和纳米尺寸的功能性等优异的生化性能已引起广泛的研究，在不同的领域已有相应的应用，且在复合材料中的应用十分广泛，以天然高分子和聚合物为基质的纳米复合材料的研究日益深入。
近年来，壳聚糖/聚乳酸复合材料因其良好的抗菌性、生物相容性和可降解性得到了人们的广泛关注。目前已有较多将壳聚糖与聚合接枝的文献(壳聚糖-聚乳酸接枝共聚物的制备与表征,化工新型材料,2012,5,4005)和(壳聚糖与丙交酯接枝共聚物的制备与表征,材料科学与工程学报,2008,1,2601)，对于PLA-g-CS颗粒度的研究有通过物理球磨的方法达到15μm的(Poly(l-lactic acid)bio-composites reinforced by oligo(d-lacticacid)grafted chitosan for simultaneously improved ductility,strength andmodulus.International Journal of Biological Macromolecules,2019.131:p.495-504.)，也有以渗滤法和超声波法制得PLA-g-CS纳米颗粒的报道(Preparation ofbiocompatible chitosan grafted poly(lactic acid)nanoparticles.InternationalJournal of Biological Macromolecules,2012.51(3):p.221-227.)。
壳聚糖接上聚乳酸后，本身的氨基与聚乳酸的羧基反应生成酰胺，连接端基为羟基的聚乳酸链段，侧链的整体亲水性下降。由于PLA-g-CS既不溶于醋酸又不溶于氯仿，这使得将PLA-g-CS做到纳米尺寸的颗粒较为困难，因此还未有学者研究过PLA-g-CS的纳米晶须的制备。另外，而上述文献制备得到的是纳米颗粒，纳米颗粒多为球形，而纳米晶须一般是有一定长径比的直径在纳米尺度的小棍，上述文献制备得到的并非纳米晶须，且上述制备纳米颗粒过程中又需使用大量的有机溶剂，对环境造成污染，不够环保。
发明内容
为了解决上述问题，本发明采用干态接枝方法，制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须。该方法使得没有良好溶剂的PLA-g-CS可以制备得到纳米晶须，整个反应高效清洁，绿色环保，具有一定的可推广性。
本发明的第一个目的是提供一种聚乳酸接枝壳聚糖(PLA-g-CS)的纳米晶须制备方法，所述方法包括以下步骤：
(1)制备PLA-g-CS：将丙交酯、催化剂和壳聚糖混合均匀后，进行聚合接枝，制备得到PLA-g-CS，聚合接枝过程中无溶剂；
(2)制备PLA-g-CS纳米晶须：将步骤(1)制备得到的PLA-g-CS分散在NaOH:尿素:H2O或LiOH:KOH:尿素:H2O的混合溶液中，冷冻/解冻、超声、离心、透析后得到PLA-g-CS纳米晶须。
在本发明一种实施方式中，步骤(1)中丙交酯和壳聚糖的质量比为(2～10):1，催化剂为辛酸亚锡，加入量为丙交酯质量百分数的0.1～1‰。
在本发明一种实施方式中，步骤(1)中聚合接枝条件为：氮气气氛；接枝温度：120-180℃；接枝时间：3-5h。
在本发明一种实施方式中，PLA-g-CS添加量为0.25％～1％。
在本发明一种实施方式中，所述步骤(2)中的NaOH:尿素:H2O＝(8-15):(4-8):(80-85)。
在本发明一种实施方式中，所述步骤(2)中的LiOH:KOH:尿素:H2O＝(8-15):7(5-9):8:
(80-85)。
在本发明一种实施方式中，所述步骤(2)中冷冻条件为温度为-80～-20℃，时间为0.5-3h；解冻条件为5-10℃，时间0.1-0.5h，冷冻/解冻循环2-5次。
在本发明一种实施方式中，所述步骤(2)中超声频率为30-60Hz，时间为10-30min。
在本发明一种实施方式中，所述步骤(2)中离心转速为5000-10000r/min，时间为15-30min。
本发明的第二个目的是提供一种上述方法制备得到的PLA-g-CS纳米晶须。
本发明的第三个目的是提供一种上述PLA-g-CS纳米晶须在食品包装、医药和复合材料方面的应用。
本发明的有益效果：
(1)本发明用聚乳酸接枝壳聚糖，可增强壳聚糖的疏水性和机械性能，同时又环保可降解。目前已知的壳聚糖与聚乳酸的接枝方法均是以溶剂作为反应介质，甚至还需要使用大量溶剂将接枝物析出，而本发明所使用的接枝方法，为干态接枝，在120～150℃下丙交酯处于熔融状态，无需使用溶剂作为反应介质，即可使丙交酯发生开环聚合，以及丙交酯与壳聚糖发生聚合反应，反应过程环保且简单高效，接枝率能高达97％，做到了绿色环保，顺应了时代的发展；同时接枝产物在食品包装、医药或作为增强体用于复合材料等方面具有潜在应用。
(2)本发明将几乎无法溶解的PLA-g-CS通过在碱液中反复冷冻解冻得的方法制备得到了纳米晶须。由于壳聚糖具有良好的生物降解性、生物相容性、抗菌性及多功能化学和物理性质，聚乳酸是由乳酸为原料聚合得到的，属于可再生资源，原料来源充足且具有良好的生物降解性，可完全降解成水和二氧化碳，不会对环境造成污染，接枝产物做成纳米晶须后在食品包装、医药或作为增强体用于复合材料等方面具有广阔的应用前景，尤其在生物医疗和增强复合材料方面的应用具有极大的潜力。
附图说明
图1为聚乳酸(PDLA)、壳聚糖(CS)和聚乳酸接枝壳聚糖(Oligo(D-LA)-g-CS)的红外光谱图。
图2是按本发明实施例1所制备的聚乳酸与壳聚糖接枝物的纳米晶须SEM照片。
具体实施方式
以下对本发明的优选实施例进行说明，应当理解实施例是为了更好地解释本发明，不用于限制本发明。
实施例1
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS(见图1)，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须(见图2)，平均直径为281.1nm。
实施例2
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.05g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为502.7nm。
实施例3
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.1g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为893.6nm。
实施例4
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻2h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为699.5nm。
实施例5
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-30℃下冷冻1h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为996.2nm。
实施例6
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:4:85的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为332.0nm。
实施例7
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的NaOH:尿素:H2O＝11:8:81的混合溶液中,然后将悬浮液在-80℃下冷冻0.5h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为725.7nm。
实施例8
将10g的丙交酯、5g壳聚糖和5μL的辛酸亚锡分别快速放入三口烧瓶中进行接枝反应，同时加入磁子进行搅拌。接枝温度：150℃；接枝时间：4h；接枝气氛：氮气气氛；搅拌器旋转速度：150r/min；得到聚乳酸与壳聚糖的接枝物PLA-g-CS，接枝率为95％。将0.025g的将PLA-g-CS分散在9.975g的LiOH:KOH:尿素:H2O＝4.5:7:8:80.5的混合溶液中,然后将悬浮液在-30℃下冷冻3h，再于5℃下搅拌解冻，冷冻/解冻循环3次。使用超声波细胞粉碎机在60Hz下将溶液超声30min，超声后以10000r/min的转速离心15min得到上清液，将上清液装入透析袋透析48h，经冷冻干燥得到长度连续的PLA-g-CS纳米晶须，平均直径为361.9nm。
表1 PLA-g-CS纳米晶须的性能
Figure BDA0002223227140000051
由表1可知，实施例1所得的PLA-g-CS纳米晶须的平均直径最小，达到281.1nm。根据单因素变量原则，在其他条件不变的情况下，随着PLA-g-CS所占溶液的比例的增加，所得纳米晶须的平均直径也不断增大，这是因为PLA-g-CS的比例增加，一定的溶液对其晶区的破坏能力下降，所以得到的纳米晶须的平均直径便越大。在其他条件不变只改变冷冻时间的情况下，由上表可知，冷冻时间越长所得纳米晶须的粒度越小，这说明，溶液对PLA-g-CS晶区的破坏是一个缓慢的过程，因此需要足够的时间来完成这一过程。而在-80℃下所得纳米晶须的平均直径与-20℃所得基本一致，但冷冻时间较短，这是因为-80℃条件对PLA-g-CS晶区的破坏较为剧烈，因此所需的时间较短。NaOH:尿素:H2O＝11:8:81的溶液体系所得的晶须平均直径较大，这是因为该体系不适合用于溶解PLA-g-CS，对PLA-g-CS的晶区破坏能力较弱。以LiOH:KOH:尿素:H2O＝4.5:7:8:80.5的溶液体系所制得的PLA-g-CS纳米晶须的平均直径略小于NaOH:尿素:H2O＝11:4:81的溶液体系，二者基本相当。在同样条件下，未改性的CS和接枝率小于50％的PLA-g-CS无法在相同条件下溶解，因此无法在此条件下制备纳米颗粒或纳米晶须。
虽然本发明已以较佳实施例公开如上，但其并非用以限定本发明，任何熟悉此技术的人，在不脱离本发明的精神和范围内，都可做各种的改动与修饰，因此本发明的保护范围应该以权利要求书所界定的为准。

Claims (5)

1.一种聚乳酸接枝壳聚糖纳米晶须的制备方法，其特征在于，所述方法是将丙交酯、催化剂和壳聚糖混合均匀后进行聚合接枝制备PLA-g-CS，再将PLA-g-CS分散于碱液中，通过反复冷冻/解冻的方法得到纳米晶须，聚合接枝过程中无溶剂；所述方法包括以下步骤：
(1)制备PLA-g-CS：将丙交酯、催化剂和壳聚糖混合均匀后，进行聚合接枝，制备得到PLA-g-CS；丙交酯和壳聚糖的质量比为(2～10):1；聚合接枝条件为：氮气气氛；接枝温度：120-180℃；接枝时间：3-5h；
(2)制备PLA-g-CS纳米晶须：将步骤(1)制备得到的PLA-g-CS分散在NaOH:尿素:H2O或LiOH:KOH:尿素:H2O的混合溶液中，冷冻/解冻、超声、离心、透析后得到PLA-g-CS纳米晶须；NaOH：尿素：H2O＝11:4:81；LiOH：KOH：尿素：H2O＝(8-15)：(5-9)：8：(80-85)；
PLA-g-CS添加量为0.25％～0.5％。
2.根据权利要求1所述的方法，其特征在于，催化剂为辛酸亚锡，加入量为丙交酯的0.1～1‰。
3.根据权利要求1所述的方法，其特征在于，所述步骤(2)中冷冻条件为温度为-80～-20℃，时间为0.5-3h；解冻条件为5-10℃，时间0.1-0.5h，冷冻/解冻循环2-5次。
4.权利要求1～3任一所述的方法制备得到的PLA-g-CS纳米晶须。
5.一种权利要求4所述的PLA-g-CS纳米晶须在食品包装、医药和复合材料方面的应用。
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