CN112575574B - 一种官能化纳米片改性胶原纤维及其制备方法 - Google Patents

一种官能化纳米片改性胶原纤维及其制备方法 Download PDF

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CN112575574B
CN112575574B CN202011611867.2A CN202011611867A CN112575574B CN 112575574 B CN112575574 B CN 112575574B CN 202011611867 A CN202011611867 A CN 202011611867A CN 112575574 B CN112575574 B CN 112575574B
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石佳博
张睿祯
杨继凯
朱琳涛
邓博
陈妍羽
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Shaanxi University of Science and Technology
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Abstract

本发明针对现有胶原纤维基材料功能单一、应用领域受限和产品附加值低等问题，公开了一种官能化纳米片改性胶原纤维及其制备方法，其制备过程是首先利用盐酸多巴胺包覆合成纳米片以赋予其表面反应性，之后采用含多官能团的有机分子表面修饰纳米片；通过调节体系pH值等条件可以促进官能化纳米片在胶原纤维中的均匀分散和稳定结合，提高其热稳定性，降低其吸水膨胀性，并赋予其显著的抗氧化性和抗菌性能。本发明制备方法简单，易于操作，所得胶原纤维功能材料有望用于高性能吸附材料、多功能皮革和可降解膜材料等领域，实现其多功能化和高附加值。

Description

一种官能化纳米片改性胶原纤维及其制备方法
技术领域
本发明属于天然高分子材料改性技术领域，涉及一种官能化纳米片改性胶原纤维及其制备方法。
背景技术
胶原是一种广泛存在于自然界中的重要而丰富的可再生生物质资源，并作为间质结缔组织的主要结构蛋白，广泛分布于哺乳动物的结缔组织、骨骼、内脏细胞间质、肌腔、韧带和巩膜等部位。胶原不仅是哺乳动物体中含量最丰富的蛋白质，约占动物体蛋白质总量的25%~30%，而且作为细胞外基质的最主要物质，其重要性主要体现在活体动物中的生理功能。值得注意的是，胶原因其独特的生物学与材料学性质，在制革、医药、食品和化妆品等行业具有广泛的工业应用。
近年来，随着科技和产业的迅猛发展以及消费市场多元化、个性化需求不断涌现，特别是具有阻气隔热、抗静电、导电、电磁屏蔽/吸收、红外隐身、自清洁、防紫外、抗菌和阻燃等多功能胶原纤维材料制品的市场需求逐年增加，传统胶原纤维材料只是具备基本的使用功能，存在功能单一、应用领域受限和产品附加值低等瓶颈问题，已经无法同时满足当前消费者对胶原纤维材料物理性能和多功能的要求。因此，针对目前传统胶原纤维材料存在的不足以及消费市场的新需求和新趋势，有必要寻找新型胶原纤维改性材料用于功能胶原纤维材料制造以拓展其功能和用途，实现其高附加值和功能化。
发明内容
本发明的目的在于针对目前胶原纤维基材料制备中存在的不足，提供一种官能化纳米片改性胶原纤维及其制备方法，促进官能化纳米片在胶原纤维基体中的均匀分散和稳定结合，提高胶原纤维的热稳定性，降低其吸水膨胀性，并赋予其显著的抗氧化性和抗菌性能，实现其多功能化和高附加值。
为达到上述目的，本发明采用的技术方案如下：
一种官能化纳米片改性胶原纤维的制备方法，具体包括以下步骤：
步骤一：称取盐酸多巴胺加入至Na2CO3-NaHCO3缓冲液中，得到盐酸多巴胺溶液；
步骤二：称取纳米片分散至上述盐酸多巴胺溶液中，随后加入乙二胺溶液，保持盐酸多巴胺、乙二胺与纳米片的质量比为0.01～0.05：0.01：1，在室温下反应2 h后向上述反应液中加入改性剂，继续反应2 h后，将所得反应液离心，取上清液，得到官能化纳米片分散液；
步骤三：称取胶原纤维加入至浓度为0.5%～5%的上述官能化纳米片分散液中，在室温下反应4 h后，逐滴加入质量比为1:20的碳酸氢钠溶液将pH值调至4.0～6.0，静置12h，抽滤，水洗，冷冻干燥，即得官能化纳米片改性胶原纤维。
所述纳米片是锂藻土纳米片、磷酸锆纳米片或水滑石纳米片中的任意一种。
所述改性剂为没食子酸、四羟甲基硫酸磷或聚乙二醇中的任意一种，改性剂与纳米片的摩尔比为0.01～0.03：1。
上述制备方法制得的一种官能化纳米片改性胶原纤维。
所述官能化纳米片改性胶原纤维的pH值为4.0～6.0。
与现有技术相比，本发明的有益效果如下：
（1）本发明制备方法简单、易于操作，且原材料来源广泛；
（2）本发明所得官能化纳米片尺寸可控且可与胶原分子中的侧链活性基团结合，提升胶原基纤维材料的热稳定性，降低其吸水膨胀性，并赋予其显著的抗氧化性和抗菌性能。
附图说明
图1为不同方式改性胶原纤维的DSC结果图；
图2为实施例1制得的四羟甲基硫酸磷官能化锂藻土纳米片改性胶原纤维的抗氧化性能结果；
图3为实施例3制得的没食子酸官能化锂藻土纳米片改性胶原纤维的抗氧化性能结果；
图4为不同方式改性胶原纤维的抗菌图。
具体实施方式
下面通过具体实施例，以具体说明本发明所述的一种官能化纳米片改性胶原纤维及其制备方法。有必要在此指出的是，本实施例只用于对本发明进行进一步的说明，不能理解为对本发明保护范围的限制，该领域的技术熟练人员可以根据上述本发明的内容做出一些非本质的改进和调整。
实施例1
称取盐酸多巴胺加入至Na2CO3-NaHCO3缓冲液中，得到盐酸多巴胺溶液；称取锂藻土纳米片分散至上述盐酸多巴胺溶液中，随后加入乙二胺溶液，其中盐酸多巴胺、乙二胺与纳米片的质量比为0.01：0.01：1，在室温下反应2 h后向上述反应液中加入四羟甲基硫酸磷，所用四羟甲基硫酸磷与纳米片的摩尔比为0.01：1，继续反应2 h后，将所得反应液离心，取上清液，得到官能化纳米片分散液；称取胶原纤维加入至浓度为3%的上述官能化纳米片分散液中，在室温下反应4 h后，逐滴加入质量比为1:20的碳酸氢钠溶液将pH值调至5.0，静置12 h，抽滤，水洗，冷冻干燥，即得纳米片改性胶原纤维。
参见图2，图2为实施例1制得的四羟甲基硫酸磷官能化锂藻土纳米片改性胶原纤维的抗氧化性能测试结果，其中a为不同时间下纳米片改性胶原纤维在DPPH溶液中的照片，b为上述溶液对应的UV图谱。
实施例2
称取盐酸多巴胺加入至Na2CO3-NaHCO3缓冲液中，得到盐酸多巴胺溶液；称取锂藻土纳米片分散至上述盐酸多巴胺溶液中，随后加入乙二胺溶液，其中盐酸多巴胺、乙二胺与纳米片的质量比为0.01：0.01：1，在室温下反应2 h后向上述反应液中加入四羟甲基硫酸磷，所用四羟甲基硫酸磷与纳米片的摩尔比为0.02：1，继续反应2 h后，将所得反应液离心，取上清液，得到官能化纳米片分散液；称取胶原纤维加入至浓度为3%的上述官能化纳米片分散液中，在室温下反应4 h后，逐滴加入质量比为1:20的碳酸氢钠溶液将pH值调至5.0，静置12 h，抽滤，水洗，冷冻干燥，即得纳米片改性胶原纤维。
实施例3
称取盐酸多巴胺加入至Na2CO3-NaHCO3缓冲液中，得到盐酸多巴胺溶液；称取水滑石纳米片分散至上述盐酸多巴胺溶液中，随后加入乙二胺溶液，其中盐酸多巴胺、乙二胺与纳米片的质量比为0.01：0.01：1，在室温下反应2 h后向上述反应液中加入没食子酸，所用没食子酸与纳米片的摩尔比为0.01：1，继续反应2 h后，将所得反应液离心，取上清液，得到官能化纳米片分散液；称取胶原纤维加入至浓度为3%的上述官能化纳米片分散液中，在室温下反应4 h后，逐滴加入质量比为1:20的碳酸氢钠溶液将pH值调至5.0，静置12 h，抽滤，水洗，冷冻干燥，即得纳米片改性胶原纤维。
参见图3，图3为实施例3制得的没食子酸官能化锂藻土纳米片改性胶原纤维的抗氧化性能测试结果，其中a为不同时间下纳米片改性胶原纤维在DPPH溶液中的照片，b为为上述溶液对应的UV图谱。
对上述实施例制备得到的纳米片改性胶原纤维及未改性的胶原纤维进行差示扫描量热法DSC测试及大肠杆菌的抑菌圈测试，结果如图1及图4所示。
参见图1，图1为不同方式改性胶原纤维的DSC结果图，图中（A）为未改性胶原纤维，（B）为实施例3制得的没食子酸官能化锂藻土纳米片改性胶原纤维，（C）为实施例1制得的四羟甲基硫酸磷官能化锂藻土纳米片改性胶原纤维，从图中可以看出官能化锂藻土纳米片改性可提升胶原纤维热稳定性。
参见图4，图4为不同方式改性胶原纤维对大肠杆菌的抑菌圈测试结果图，图中（a）为空白样，（b）为未改性胶原纤维，（c）为实施例3制得的四羟甲基硫酸磷官能化锂藻土纳米片改性胶原纤维，（d）为实施例1制得的没食子酸官能化锂藻土纳米片改性胶原纤维。结果表明，官能化锂藻土纳米片改性可赋予胶原纤维抗菌性。
从以上结果表示，实施例3是最佳实施例。

Claims (3)

1.一种官能化纳米片改性胶原纤维的制备方法，其特征在于，具体包括以下步骤：
步骤一：称取盐酸多巴胺加入至Na2CO3-NaHCO3缓冲液中，得到盐酸多巴胺溶液；
步骤二：称取纳米片分散至上述盐酸多巴胺溶液中，随后加入乙二胺溶液，保持盐酸多巴胺、乙二胺与纳米片的质量比为0.01～0.05：0.01：1，在室温下反应2 h后向上述反应液中加入改性剂，继续反应2 h后，将所得反应液离心，取上清液，得到官能化纳米片分散液；
步骤三：称取胶原纤维加入至浓度为0.5%～5%的上述官能化纳米片分散液中，在室温下反应4 h后，逐滴加入质量比为1:20的碳酸氢钠溶液将pH值调至4.0～6.0，静置12 h，抽滤，水洗，冷冻干燥，即得官能化纳米片改性胶原纤维；
所述纳米片是锂藻土纳米片、磷酸锆纳米片或水滑石纳米片中的任意一种；
所述改性剂为没食子酸、四羟甲基硫酸磷或聚乙二醇中的任意一种，改性剂与纳米片的摩尔比为0.01～0.03：1。
2.如权利要求1所述制备方法制得的一种官能化纳米片改性胶原纤维。
3.根据权利要求2所述的一种官能化纳米片改性胶原纤维，其特征在于：所述官能化纳米片改性胶原纤维的pH值为4.0～6.0。
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