CN113527627A - 一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯及其制备方法、用途 - Google Patents
一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯及其制备方法、用途 Download PDFInfo
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Abstract
本发明属于海洋防污技术领域，涉及一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯基底材料及其制备方法、用途。一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，其软段组分为双羟基封端的聚乳酸聚碳酸酯聚合物大分子二元醇；其硬段组分为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6‑己基二异氰酸酯中的任一种。采用本发明提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯材料可以制备出自修复仿生超滑涂层和具有防污剂温敏控释功能的自修复海洋防污涂层，自修复功能和防污剂温敏控释功能赋予涂层更长久的防治生物污损的性能。同时该聚乳酸聚碳酸酯基聚氨酯材料及涂层的制备方法简单，反应条件温和高效。
Description
技术领域
本发明属于海洋防污技术领域，涉及一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯基底材料及其制备方法、用途。
背景技术
近年来，伴随着海洋产业的快速发展，生物污损问题受到了越来越多的关注。海洋生物污损产生的主要原因是海水中的海洋生物在船舶和水下结构物的表面上产生附着，从而造成船体和结构物表面的腐蚀破损，严重影响其安全性。抑制生物的附着成为防止海洋生物腐蚀及污损的关键，而防止生物附着最简便最直接的办法就是使用防污涂层。
随着研究的不断进步，各种类别的防污涂层材料不断的出现，各种新型高效环保型防污涂层相继被研发出来，但是随着人们对于防污涂层设计越来越高的使用需求，现有防污涂层的不足之处也逐渐显现出来，比如涂层受损后维护施工操作困难、防污服役周期短等。仿生（猪笼草）超滑表面因具有良好的防污性能而受到了广泛的关注，大量研究表明了该类涂层不含毒性物质且能够有效预防海洋微生物的附着，但该仿生表面的润滑油膜或者固体基底材料遭到破坏时，表面的防污能力也会受到很大的影响，如何确保防污能力的长效性是仿生超滑涂层在实用当中亟待解决的技术问题。
在实际的海洋生态环境中，在低温状态下微生物通常不具备能够附着到船体表面的活性，防污涂层持续的释放杀菌剂会造成一定的浪费，降低涂层的服役时间。而在温度较高的水域中，则需要释放足够的杀菌剂量以提供良好的防污能力。而当防污涂层收到外界破坏时，表面的防污能力也会受到很大的影响。因此，制备具有杀菌剂温敏控释功能的自修复海洋防污涂层对提高涂层防污性能及丰富防污涂层种类都具有一定的现实意义。
发明内容
针对现有的海洋防污涂层存在的缺陷，本发明提供一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯及其制备方法，利用该聚乳酸聚碳酸酯基聚氨酯为基底材料，可以制备自修复仿生超滑涂层和具有防污剂温敏控释功能的自修复海洋防污涂层。
本发明解决其技术问题采用的技术方案是提供一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，其软段组分为双羟基封端的聚乳酸聚碳酸酯聚合物大分子二元醇；硬段组分为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯中的任一种。
进一步优选地，所述大分子二元醇的引发剂为乙二醇、1,3丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇和二乙二醇中的任一种。
本发明还进一步提供了所述具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法，包括：
在惰性气体保护下，向圆底烧瓶中加入搅拌子和引发剂，并同时加入丙交酯和三亚甲基碳酸酯，丙交酯和三亚甲基碳酸酯分别与引发剂中的羟基的摩尔比为10-200；室温下搅拌，直至两组分固态单体呈共熔状态；
迅速加入有机碱催化剂，有机碱催化剂与引发剂中的羟基的摩尔比为0.1-5，在室温下持续搅拌1 min后，迅速升高反应升温，并继续反应20小时；
待反应结束后加入氯仿溶剂溶解，所得产物除去催化剂和未反应的单体，烘干至恒重，得聚乳酸聚碳酸酯共聚物；
在惰性气体保护下，向干燥的反应器中加入聚乳酸聚碳酸酯共聚物、二异氰酸酯和有机溶剂，90℃反应4小时；缓慢滴加扩链剂和有机锡催化剂，扩链剂氨基与有机锡催化剂的摩尔比为0.1-10；
在110℃下反应2小时后降至室温继续反应一段时间；反应结束后得到具有自修复功能的聚乳酸聚碳酸酯基聚氨酯。
进一步优选地，所述的丙交酯单体为左旋丙交酯、右旋丙交酯、外消旋丙交酯、内消旋丙交酯的一种或两种以上任意比例的混合。
进一步优选地，所述的二异氰酸酯为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯中的任一种。
进一步优选地，所述的有机碱催化剂为1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)、氮甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯(MTBD)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)的一种或两种以上任一比例的混合。
进一步优选地，所述的有机锡催化剂为为辛酸亚锡、二月桂酸二丁基锡的一种或两种以上任意比例的混合。
进一步优选地，所述的有机溶剂为二氯甲烷、三氯甲烷、戊烷、己烷、庚烷、环己烷、苯、甲苯、二甲苯、氯苯、二氯苯、N,N-二甲基甲酰胺、N,N-二甲基亚砜的一种或两种以上任意比例的混合。
本发明还进一步提供所述具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的用途，其作为基底材料，用于制备自修复仿生超滑涂层或者具有防污剂温敏控释功能的自修复海洋防污涂层。
本发明还进一步提供一种自修复仿生超滑涂层，该涂层采用具有自修复功能的聚乳酸聚碳酸酯基聚氨酯作为基底材料，在所述基底材料中添加有润滑油。
本发明还提供一种具有防污剂温敏控释功能的自修复海洋防污涂层，该涂层采用具有自修复功能的聚乳酸聚碳酸酯基聚氨酯作为基底材料，在所述基底材料中添加有防污剂。
本发明具有如下有益效果：
（1）采用本发明提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，制备的仿生超滑涂层，具有通过聚氨酯分子内部氢键作用实现基底材料自修复的功能，使该涂层具有更长久的防治生物污损的性能；
（2）采用本发明提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，制备的自修复海洋防污涂层具有杀菌剂温敏控释功能，在水温升高或降低的同时杀菌剂释放速率随之升高或降低，从而达到杀菌剂缓释的技术效果，解决了传统防污涂层在低温条件下持续释放杀菌剂造成的过度损耗问题；
（3）本发明提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法简单，反应条件温和高效，以该材料制备的防污涂层具备长效性的海洋生物污损防护能力。
附图说明
图1为本发明实施例1制备的具有自修复功能的聚乳酸聚碳酸酯聚合物基聚氨酯的核磁谱图；
图2为液滴(10μl)在本发明实施例3提供的自修复仿生超滑涂层表面的动态润湿性图，该仿生超滑涂层表面的倾斜角为10°；
图3为本发明实施例3提供的自修复仿生超滑涂层自修复过程的图像对比：(a)聚乳酸聚碳酸酯基聚氨酯自修复过程的照片；(b)以该聚氨酯为基体材料制备的仿生超滑涂层自修复过程的激光共聚焦图像；(c)以该聚氨酯为基体材料制备的仿生超滑涂层自修复过程的激光共聚焦3D图像(比例尺＝500μm)；
图4为本发明实施例3提供的自修复仿生超滑涂层自修复前后超滑性能对照；
图5为本发明实施例4提供的具有防污剂温敏控释功能的自修复海洋防污涂层在不同温度条件下的药物累积释放率对照。
具体实施方式
为了便于理解本发明，下面结合附图和具体实施例，对本发明进行更详细的说明。附图中给出了本发明的较佳的实施例。但是，本发明可以以许多不同的形式来实现，并不限于本说明书所描述的实施例。相反地，提供这些实施例的目的是使对本发明公开内容的理解更加透彻全面。
本发明通过聚氨酯分子内的氢键以及分子间渗透压的作用实现基底和润滑油膜的自修复，为涂层在海洋生物污损防护中的长效性问题提供了一种解决方法。
实施例1 本实施例提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，通过以下步骤制备得到：
（1）聚乳酸聚碳酸酯共聚物的制备：首先，向事先经过三次反复抽真空-烘烤-充氮气的圆底烧瓶中加入搅拌子和1,4-丁二醇引发剂（0.0375 g，0.6 mmol），同时加入左旋丙交酯（L-LA，2.88 g，0.02mol.）和三亚甲基碳酸酯（TMC，2.04 g，0.02mol.）。然后，在25 ℃下搅拌30 min直至两组分固态单体呈共熔状态。之后，迅速加入催化剂DBU（0.023 g，0.21mmol）。室温下搅拌20 s开始反应，约40 s后（一共1 min），最先生成的聚乳酸组分开始结晶析出。在这时迅速将反应升温至61 ℃（高于聚乳酸的玻璃化转变温度），并继续反应20小时。待反应结束后需加入氯仿溶剂溶解，打入计量的苯甲酸溶液（聚合反应终止剂），所得产物用过量无水甲醇沉胶除去催化剂和未反应的单体，真空40 ℃烘干至恒重。经有机凝胶色谱（GPC）测试，产物M n为9200，PDI为1.07。
（2）聚乳酸聚碳酸酯基聚氨酯的制备：常温常压，惰性气体氩气保护下，将实施例1中合成的聚乳酸聚碳酸酯共聚物4.5g，异佛尔酮二异氰酸酯0.222g加入到20 mL N,N-二甲基甲酰胺中，在90 ℃下反应4 小时后得到NCO封端的聚氨酯预聚物，然后加热至110℃，在烧瓶中加入0.037g扩链剂 1,3-丙二胺与少量辛酸亚锡催化剂，继续反应2小时后降至室温并继续反应10小时。最终产物在经去离子水沉降后在真空烘箱中80℃干燥12小时。经有机凝胶色谱（GPC）测试，产物M n为3.55×104，PDI为1.21。
对实施例1制备的聚氨酯进行分子结构表征，如图1所示，其中δe=2.89 ppm和δh=1.05 ppm对应于IPDI环上的亚甲基和甲基的特征峰。δf =3.66 ppm和δg=3.70ppm对应于与氨酯键相连接的甲基和亚甲基。扩链剂中的亚甲基则分别归属为δi=1.88 ppm和δj=2.77ppm。综上，聚氨酯的1H-NMR谱的测试结果进一步证实了聚乳酸聚碳酸酯基聚氨酯的成功制备。
实施例2本实施例提供的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，通过以下步骤制备得到：（1）聚乳酸聚碳酸酯共聚物的制备：首先，向事先经过三次反复抽真空-烘烤-充氮气的圆底烧瓶中加入搅拌子和二乙二醇引发剂（0.0368 g，0.5 mmol），同时加入左旋丙交酯（L-LA，7.20 g，0.05mol.）和三亚甲基碳酸酯（TMC，5.10 g，0.05mol.）。然后，在25℃下搅拌30 min直至两组分固态单体呈共熔状态。之后，迅速加入催化剂DBU（0.0575 g，0.525 mmol）。室温下搅拌20 s开始反应，约40 s后（一共1 min），最先生成的聚乳酸组分开始结晶析出。在这时迅速将反应升温至61 ℃（高于聚乳酸的玻璃化转变温度），并继续反应20小时。待反应结束后需加入氯仿溶剂溶解，打入计量的苯甲酸溶液（聚合反应终止剂），所得产物用过量无水甲醇沉胶除去催化剂和未反应的单体，真空40 ℃烘干至恒重。经有机凝胶色谱（GPC）测试，产物Mn为26200，PDI为1.12。
（2）聚乳酸聚碳酸酯聚合物基聚氨酯的制备：常温常压，惰性气体氩气保护下，将合成的聚乳酸聚碳酸酯共聚物5.24g，异佛尔酮二异氰酸酯0.0888g加入到20 mL N,N-二甲基甲酰胺中，在90 ℃下反应4 小时后得到NCO封端的聚氨酯预聚物，然后加热至110℃，在烧瓶中加入0.015g扩链剂 1,3-丙二胺与少量二月桂酸二丁基锡催化剂，继续反应2小时后降至室温并继续反应12小时。最终产物在经去离子水沉降后在真空烘箱中80℃干燥12小时。经有机凝胶色谱（GPC）测试，产物Mn为7.55×104，PDI为1.31。
实施例3 本实施例提供的基于具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的自修复仿生超滑涂层，其基底材料的分子结构为聚乳酸聚碳酸酯基聚氨酯，基底材料中混合有硅油。
本实施例的基于具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的自修复仿生超滑涂层，通过以下方法制备：
（1）采用实施例1的方法制备具有自修复功能的聚乳酸聚碳酸酯基聚氨酯；
（2）将干燥后的聚乳酸聚碳酸酯基聚氨酯和运动粘度为200cst的硅油按合适比例溶解在四氢呋喃中，搅拌加热挥发部分溶剂，然后涂覆在Q235钢表面，然后在室温下完全干燥，得到具有自修复功能的仿生超滑涂层。
通过接触角测量仪测定水滴在倾斜的超滑涂层表面的滑动性，具体为：将水滴(10μl)滴在倾斜度小于10°的实施例3中制备的超滑涂层表面上，然后用接触角测量仪记录液滴在表面滑动一段时间后的距离。
由图2可以看出液滴在实施例3中制备的超滑涂层表面上可以自行滑落，液滴能够稳定较快地滑动，表明该仿生超滑涂层表面具有优异的超滑性能。
通过激光共聚焦显微镜观测划伤的超滑表面划痕的修复情况，具体为：用手术刀垂直于表面将制备好的样品表面划伤，用激光共聚焦显微镜拍摄照片记录。然后将划伤的样品放置在40℃环境中静置修复20分钟，用激光共聚焦显微镜拍摄图片图及3D图像记录。
由图3中（a）、（b）、（c）可知，该具有自修复功能的仿生超滑涂层在接近室温条件下具有可靠的自修复性能。基于其分子链的良好柔韧性和分子间氢键的共同作用，在40℃时，样品可在20分钟内完全修复直至痕迹消失。
由图4可以看出实施例3中制备的具有自修复功能的仿生超滑涂层，在自修复之后重新获得了良好的超滑性能，表明该仿生超滑涂层具有可靠自修复的性能。
实施例4本实施例提供的具有防污剂温敏控释功能的自修复海洋防污涂层，其基底材料的分子结构为具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，基底材料中混合有杀菌剂。
本实施例的具有防污剂温敏控释功能的自修复海洋防污涂层，通过以下步骤制备得到：
（1）采用实施例2的方法制备具有自修复功能的聚乳酸聚碳酸酯基聚氨酯；
（3）将干燥后的聚乳酸聚碳酸酯基聚氨酯和杀菌剂辣椒素按合适比例溶解在二氯甲烷中，搅拌加热挥发部分溶剂，然后涂覆在Q235钢表面，然后在室温下完全干燥，得到具有杀菌剂温敏控释功能的自修复海洋防污涂层。
对实施例4制备的涂层中杀菌剂在不同温度下的累积释放率进行测定，结果如图5所示，随温度的升高，涂层中杀菌剂的累积释放率呈上升趋势。利用该特性，可以达到低温环境中控制涂层中药物缓释的效果，避免在低温条件下持续释放杀菌剂造成的过度损耗问题。同时，当涂层材料受到破坏时可以通过分子内部作用力实现自修复。
Claims (10)
1.一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，其特征在于：所述聚乳酸聚碳酸酯基聚氨酯的软段组分为双羟基封端的聚乳酸聚碳酸酯聚合物大分子二元醇；其硬段组分为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯中的任一种。
2.根据权利要求1所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯，其特征在于：所述大分子二元醇的引发剂为乙二醇、1,3丙二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇和二乙二醇中的任一种。
3.一种具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法，其特征在于，包括：
在惰性气体保护下，向圆底烧瓶中加入搅拌子和引发剂，并同时加入丙交酯和三亚甲基碳酸酯，丙交酯和三亚甲基碳酸酯分别与引发剂中的羟基的摩尔比为10-200；室温下搅拌，直至两组分固态单体呈共熔状态；
迅速加入有机碱催化剂，有机碱催化剂与引发剂中的羟基的摩尔比为0.1-5，在室温下持续搅拌1 min后，迅速升高反应升温，并继续反应20小时；
待反应结束后加入氯仿溶剂溶解，所得产物除去催化剂和未反应的单体，烘干至恒重，得聚乳酸聚碳酸酯共聚物；
在惰性气体保护下，向干燥的反应器中加入聚乳酸聚碳酸酯共聚物、二异氰酸酯和有机溶剂，90℃反应4小时；缓慢滴加扩链剂和有机锡催化剂，扩链剂氨基与有机锡催化剂的摩尔比为0.1-10；
在110℃下反应2小时后降至室温继续反应一段时间；反应结束后得到具有自修复功能的聚乳酸聚碳酸酯基聚氨酯。
4.根据权利要求3所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法，其特征在于：所述的二异氰酸酯为二苯甲基二异氰酸酯、异佛尔酮二异氰酸酯、1,6-己基二异氰酸酯中的任一种。
5.根据权利要求3所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法，其特征在于：所述的有机碱催化剂为1,5,7-三氮杂二环[4.4.0]癸-5-烯(TBD)、氮甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯(MTBD)、1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)的一种或两种以上任一比例的混合。
6.根据权利要求3所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的制备方法，其特征在于：所述的有机锡催化剂为为辛酸亚锡、二月桂酸二丁基锡的一种或两种以上任意比例的混合。
7.一种如权利要求1或2所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的用途，其特征在于：聚乳酸聚碳酸酯基聚氨酯作为基底材料，用于制备自修复仿生超滑涂层。
8.一种如权利要求1或2所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯的用途，其特征在于：聚乳酸聚碳酸酯基聚氨酯作为基底材料，用于制备具有防污剂温敏控释功能的自修复海洋防污涂层。
9.一种自修复仿生超滑涂层，其特征在于：以权利要求1或2所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯作为基底材料，在所述基底材料中添加有润滑油。
10.一种具有防污剂温敏控释功能的自修复海洋防污涂层，其特征在于：以权利要求1或2所述的具有自修复功能的聚乳酸聚碳酸酯基聚氨酯作为基底材料，在所述基底材料中添加有防污剂。
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