CN104130423B - 一种疏水性甲壳素纳米膜的制备方法 - Google Patents
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Abstract
本发明公布一种疏水性甲壳素纳米膜的制备方法。将甲壳素原料由硫酸溶液水解制备出甲壳素纳米晶须，将该晶须分散于二甲亚砜中与3-12倍于甲壳素糖单元的溴代十六烷混合，再在60oC下反应4小时，所得产物取代度为0.52-1.37之间。该晶须产物显示疏水性能。将粉末状试样在60oC，0.01Mpa下热压得到高疏水性甲壳素纳米膜。该纳米膜具有优异的疏水性，同时具有优良的生物相容性和生物可降解性，在化妆品、食品领域具有广阔应用前景。
Description
技术领域
本发明涉及一种疏水性甲壳素纳米膜的制备方法，属于纳米材料和天然高分子材料领域。
背景技术
甲壳素是自然界中含量仅次于纤维素的高分子材料，由于良好的生物相容性和生物可降解性以及特有的抗菌止血，促进伤口愈合等优点，在生物医用、水处理、营养学等领域具有广泛应用前景[J.Mater.Chem.,2011,21,3865]。20世纪90年代以来，高分子纳米材料引起了广泛关注。自然状态下，甲壳素在蛋白质中以纳米级微纤维排列，发明人课题组之前利用酸水解法将无定型甲壳素部分去除，从而制备均一尺寸，高结晶度的甲壳纳米晶须，并得到增强的复合材料[Biomacromolecules.2004,5,1046]。然而由于甲壳素素上大量亲水性羟基使晶须在有机溶剂中难以分散，影响其进一步开发和利用。因此在晶须表面进行疏水性修饰，不仅可以改善甲壳素晶须与不同基底材料的相容性，同时也可开发其在化妆品、营养品、食品增稠、医用敷料、防水胶带等方面的应用。
发明内容
本发明所要解决技术问题是提供一种简单方法对甲壳素晶须进行表面疏水修饰，进而制备出疏水性甲壳素纳米膜的方法。
本发明解决技术问题所采用技术方案为：
一种疏水性甲壳素晶须的制备方法，将甲壳素晶须分散于二甲基亚砜（DMSO）中，以氢氧化钠为催化剂，加入摩尔数3-12倍于甲壳素糖单元的溴代十六烷，于60oC下反应4-6小时，分别用乙醇和蒸馏水洗去杂质，室温下自然风干，得到疏水的甲壳素晶须，取代度在0.52-1.37间。
将上述制备的疏水性甲克素晶须进一步制备疏水性甲克素纳米膜的方法：
将疏水的甲壳素晶须（取代度0.52-1.37）固体粉末在60oC，0.01Mpa下热压15分钟得到疏水性甲壳素纳米膜。
上述甲壳素晶须的制备方法：甲壳素原料与3mol/L硫酸溶液在90oC下反应6-12小时，经离心，透析，超声处理得到稳定悬浮液，冻干即得甲壳素晶须。根据相关文献，也可采用盐酸溶液进行水解制备甲壳素晶须，或者将甲壳素晶须换作甲壳素纳米纤维也可进行相同反应，没有特别限制。
作为一种优选，本发明中反应溶剂为DMSO，若置换为水或异丙醇等文献报道的溶剂也可进行反应，但所得产物取代度较低，原因是反应类型为卤代烃的SN2亲核取代，选用极性非质子溶剂（如DMSO,DMF,乙腈等）可有效避免溶剂解等竞争反应，从而提高反应速率。且甲壳素晶须仅可在极性溶剂如水和DMSO中稳定分散形成胶体，在DMSO中相当于均相反应体系，故可达较高取代度。
本发明所用到的烷基化试剂为溴代十六烷，因其含长链烷基，毒性较小且反应活性较高，操作简单，反应结束后可由醚或醇类洗去，作为一种优选，本实验中多余的溴代十六烷用乙醇反复多次洗去。
本发明所制得的疏水性甲壳素晶须既保持了纳米晶须的形貌（长约300nm，直径20nm的针状晶体），同时具备了优良的防水性，是一种生物相容且可生物降解的环保材料。该方法通过亲核取代反应将甲壳素晶须表面用长链烷基进行修饰，获得最高取代度达1.37的修饰产物。因表面被低表面能的长链烷基所覆盖，经修饰的甲壳素晶须表现出明显的疏水性。由于长链烷烃趋向于有序排列，修饰后的甲壳素晶须在48-53oC（取代度越大转变温度越高）间出现各向异性-各向同性转变，高于此温度粉末样变软变透明。因此选择在60oC进行热压取向，可直接制备出疏水性膜材料。然而甲壳素原料及晶须因无此转变，故先将悬浮液抽滤成片状后后再加以热压以作对比。热压过程中，晶须及其外层长链烷烃形成规整排列的微纳米结构，兼之较低的表面能，从而具备了高疏水材料的特性。修饰后的甲壳素纳米膜接触角均在130°以上，最高者达158°，防水性和耐水性优良，可用于防水涂层，包装材料。制备过程简单，不需要进一步修饰改性，属于可持续发展的范畴。
附图说明
图1，实施例3制备的疏水晶须热压所得薄膜的接触角照片。
具体实施方式
疏水性甲壳素晶须的制备方法：将甲壳素晶须分散于DMSO中，加入一定量氢氧化钠作催化剂后，加入3-12倍于甲壳素糖单元的溴代十六烷，于60oC下反应4小时，分别用乙醇和蒸馏水各洗5次，再用乙醇洗3次后，室温下自然风干，得到疏水的甲壳素晶须，取代度在0.52-1.37之间。
本发明中所用到甲壳素晶须是由甲壳素原料与3mol/L硫酸溶液（30ml/g甲壳素）在90oC下反应6-12小时，经离心，透析，超声处理得到稳定悬浮液，冻干即得甲壳素晶须。
上述疏水性甲壳素晶须制备性甲壳素纳米膜的方法：将修饰得到的疏水性甲壳素晶须固体粉末在60oC，0.01MPa下热压15分钟得到。
以下将通过具体实施例具体说明本发明，但这些具体实施方案不以任何方式限制本发明保护范围。本实施方案所用到原料为已知化合物，可在市场购得。油凝胶的流变行为由ARES-RFSIII流变仪（TAInstruments,USA）测定，超疏水膜接触角由接触角测试仪(OCA20,Germany)测得。
实施例1
将未经修饰的甲壳素晶须悬浮液（3.3wt%）用直径为0.2μm的水相滤膜进行抽滤，所得片状物在相同条件下热压得半透明薄膜，接触角为95.4°。
将2g甲壳素晶须分散于80mlDMSO中（8g氢氧化钠作催化剂）后，加入3倍于甲壳素糖单元的溴代十六烷，在60oC下磁力搅拌4小时，分别用蒸馏水和乙醇洗净残留杂质，风干后所得产物取代度为0.52。将该粉末在60oC，0.01MPa下热压15min，得半透明薄膜，温度下降后变为不透明。经测试，该膜接触角为134.0°，具有高度疏水性。
实施例2
将2g甲壳素晶须分散于80mlDMSO中（8g氢氧化钠作催化剂）后，加入6倍于甲壳素糖单元的溴代十六烷，在60oC下磁力搅拌4小时，分别用蒸馏水和乙醇洗净残留杂质，风干后所得产物取代度为1.17。将该粉末在60oC，0.01MPa下热压15min，得半透明薄膜，温度下降后变为不透明。经测试，该膜接触角为155.7°，膜具有高度疏水性。
实施例3
将2g甲壳素晶须分散于80mlDMSO中（8g氢氧化钠作催化剂）后，加入12倍于甲壳素糖单元的溴代十六烷，在60oC下磁力搅拌4小时，分别用蒸馏水和乙醇洗净残留杂质，风干后所得产物取代度为1.37。将该粉末在60oC，0.01MPa下热压15min，得半透明薄膜，温度下降后变为不透明。经测试，该膜接触角为158.2°具有高度疏水性。
实施例4
将2g甲壳素纳米纤维（高压均质所得）分散于80mlDMSO中（8g氢氧化钠作催化剂）后，加入6倍于甲壳素糖单元的溴代十六烷，在60oC下磁力搅拌4小时，分别用蒸馏水和乙醇洗净残留杂质，风干后所得粉末在60oC，0.01MPa下热压15min，得半透明薄膜，温度下降至室温后变为不透明。经测试，该膜接触角为147.8°，具有高度疏水性。
Claims (3)
1.一种疏水性甲壳素晶须的制备方法，其特征在于：将甲壳素晶须分散于二甲基亚砜中，以氢氧化钠为催化剂，加入摩尔数3-12倍于甲壳素糖单元的溴代十六烷，于60oC下反应4-6小时，分别用乙醇和蒸馏水洗去杂质，室温下自然风干，得到疏水的甲壳素晶须，取代度在0.52-1.37间；
所述甲壳素晶须的制备方法为：甲壳素原料与3mol/L硫酸溶液在90℃下反应6-12小时，经离心，透析，超声处理得到稳定悬浮液，冻干即得甲壳素晶须。
2.一种疏水性甲壳素纳米膜的制备方法，其特征在于：
将甲壳素晶须分散于二甲基亚砜中，以氢氧化钠为催化剂，加入摩尔数3-12倍于甲壳素糖单元的溴代十六烷，于60℃下反应4-6小时，分别用乙醇和蒸馏水洗去杂质，室温下自然风干，得到疏水的甲壳素晶须，取代度在0.52-1.37间；
将疏水的甲壳素晶须固体粉末在60℃，0.01Mpa下热压15分钟得到疏水性甲壳素纳米膜。
3.根据权利要求2所述的制备方法，其特征在于：所述甲壳素晶须的制备方法为：甲壳素原料与3mol/L硫酸溶液在90℃下反应6-12小时，经离心，透析，超声处理得到稳定悬浮液，冻干即得甲壳素晶须。
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| CN101891841A (zh) * | 2010-08-06 | 2010-11-24 | 青岛科技大学 | 微波促进高分子量壳聚糖烷基化新方法 |
| CN102050887A (zh) * | 2010-12-10 | 2011-05-11 | 北京联合大学生物化学工程学院 | O-羟丙基-n-烷基化壳聚糖表面活性剂的制备方法 |
| CN102174184A (zh) * | 2011-01-14 | 2011-09-07 | 中国科学院广州生物医药与健康研究院 | 一种生物可降解的聚合物及其制备方法以及核酸药物运输载体 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891841A (zh) * | 2010-08-06 | 2010-11-24 | 青岛科技大学 | 微波促进高分子量壳聚糖烷基化新方法 |
| CN102050887A (zh) * | 2010-12-10 | 2011-05-11 | 北京联合大学生物化学工程学院 | O-羟丙基-n-烷基化壳聚糖表面活性剂的制备方法 |
| CN102174184A (zh) * | 2011-01-14 | 2011-09-07 | 中国科学院广州生物医药与健康研究院 | 一种生物可降解的聚合物及其制备方法以及核酸药物运输载体 |
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