CN115141353B - 一种自修复聚氨酯复合材料及其制备方法和应用 - Google Patents

一种自修复聚氨酯复合材料及其制备方法和应用 Download PDF

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CN115141353B
CN115141353B CN202210583963.3A CN202210583963A CN115141353B CN 115141353 B CN115141353 B CN 115141353B CN 202210583963 A CN202210583963 A CN 202210583963A CN 115141353 B CN115141353 B CN 115141353B
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陈守刚
冯荟蒙
王巍
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Ocean University of China
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Abstract

本发明提出了一种自修复聚氨酯复合材料的制备方法，具体方案为：以聚四氢呋喃(PTMEG)为软链段，以异佛尔酮二异氰酸酯(IPDI)和甲苯二异氰酸酯(TDI)为硬链段，以甘油和二甲基乙二肟(DMG)为扩链剂，二月桂酸二丁基锡作为催化剂，采用一锅法缩聚合成聚氨酯材料。通过改变硬链段的材料和比例来调节聚氨酯微相结构，增强聚氨酯材料抗细菌粘附能力，并使聚氨酯材料具有防污性能；进一步引入ZnO形成配位键，改善光热性能，提高复合材料自修复和防污能力。

Description

一种自修复聚氨酯复合材料及其制备方法和应用
技术领域
本发明属于自修复防污复合材料技术领域，具体涉及一种自修复的聚氨酯复合材料及其制备方法和应用。
背景技术
海洋生物污损一直是一个世界性的难题，每年全世界航运业都会因为海洋生物污损消耗数千亿美元，迄今为止，防止海洋生物污损最简便最直接的办法就是使用 防污涂层。聚氨酯涂层因为软硬段之间的热力学不相容性而具有微相分离结构，这 种结构能够抑制蛋白质的吸附而具有防污性能。但现有的聚氨酯防污涂层服役在复杂的海洋环境中，海浪、砂石冲刷作用下易出现涂层破损情况，进一步限制了涂层 的使用寿命，开发具有更长使用寿命和能防止破损的聚氨酯防污涂层是在实际应用 过程重亟待解决的技术问题。
目前聚氨酯防污涂层的设计开发仍然存在很多问题，比如中国专利申请CN113789114A，使用氨基硅油与聚酯多元醇、异氰酸酯共同制备聚氨酯涂层材料, 再加入改性石墨烯，进行自修复抗菌聚氨酯涂层材料的制备，最后进行涂覆。但该 发明方法制备工艺复杂，成本较高，条件苛刻，在涂层方面的应用有较大的局限性。 中国专利申请CN112646110A公开了一种具有抗菌性能的双子季铵盐聚氨酯涂层材料的制备方法，但是其合成过程繁琐，其防污抑菌效果未验证，限制了其应用性。
发明内容
为了克服现有聚氨酯涂层杀菌效果差、自修复时间长的不足，本发明提出了一 锅法制备聚氨酯复合材料，通过改变硬链段的材料和比例来调节聚氨酯微相结构， 增强聚氨酯复合材料抗细菌粘附能力，并使聚氨酯复合材料具有防污性能；进一步 引入ZnO形成配位键，改善光热性能，提高复合材料自修复和防污能力。
为了实现上述目的，本发明采用以下技术方案：
一种自修复聚氨酯复合材料的制备方法，以聚四氢呋喃(PTMEG)为软链段，以 异佛尔酮二异氰酸酯(IPDI)和甲苯二异氰酸酯(TDI)为硬链段，以甘油和二甲基乙二 肟(DMG)为扩链剂，二月桂酸二丁基锡作为催化剂，采用一锅法缩聚合成聚氨酯复 合材料。
具体的，所述制备方法包括如下步骤：
(1)将聚四氢呋喃、二甲基乙二肟和甘油溶解于丙酮，得到溶液A；
(2)将异佛尔酮二异氰酸酯和甲苯二异氰酸酯混溶得到溶液B；将二月桂酸二 丁基锡加入到溶液B，溶解得到溶液C；
(3)将溶液C倒入溶液A，水浴中持续反应至溶液呈现粘稠状为反应结束，得 到溶液D；通常反应时间为1.5-2h；
(4)将溶液D固化得到聚氨酯复合材料。
所述步骤(1)中，为了使聚四氢呋喃、二甲基乙二肟和甘油快速并完全溶解于 丙酮，可以将溶液A在50℃水浴中搅拌，待溶液A中的成分完全溶解，搅拌充分 即可；
所述步骤(3)中，水浴温度为45-65℃。
所述步骤(4)中，将溶液D倒入模板中，在烘箱中固化得到聚氨酯复合材料； 优选在60℃烘箱中固化24h。
所述聚四氢呋喃：二甲基乙二肟：甘油的质量比为2：0.2：0.05；所述异佛尔 酮二异氰酸酯：甲苯二异氰酸酯：二月桂酸二丁基锡的质量比为2～7:8～2:0.2；所述 聚四氢呋喃：二异氰酸酯的质量比为2：1，所述二异氰酸酯是指异佛尔酮二异氰酸 酯与甲苯二异氰酸酯。
为了增强聚氨酯复合材料的光热自修复性能和抗菌性能，在所述步骤(2)中， 向溶液B中加入氧化锌作为填料，所述氧化锌与二月桂酸二丁基锡的质量比为1～3:2。
本发明还保护采用上述方法制备得到的聚氨酯复合材料。
本发明还保护所述聚氨酯复合材料在防污中的应用，使用紫外光照射使用过的聚氨酯复合材料，实现聚氨酯的自修复。
在制备方法上，本发明通过特殊的原料组分、用量和反应条件，实现了一锅法 缩聚制备自修复聚氨酯复合材料，合成方法简单，合成条件易于实现；且本反应没 有副反应产生，一锅法的合成方法没有中间产物的浪费，所以产率高。
本发明选择PTMEG作为软链段，软链段具有柔韧性，促进链运动以实现更好 的自修复；硬段选择IPDI和TDI，将“硬”结晶区嵌入“软”基体中的微相分离体系提高了聚氨酯的力学性能；此外，DMG中的甲基可抑制硬链段的结晶并促进链运 动，这对于聚氨酯的动态网络至关重要。聚氨酯中的异佛尔酮二异氰酸酯/甲苯二异 氰酸酯硬链段在适当的配比时，影响了聚氨酯的微相分离结构，进而影响微生物的表面附着。
进一步地，本发明加入氧化锌作为填料，二甲基乙二肟中相邻的肟基团与ZnO 的锌离子络合形成金属配位键，一方面，锌离子的配位促进了基团的交换反应导致 有效的自我修复，从而加速了聚氨酯复合材料的自修复过程，提高了聚氨酯复合材 料的防污性能；另一方面，ZnO作为光热剂改善光热性能，提高复合材料自修复性 能，作为杀菌剂提高杀菌效果；此外，相邻两个肟基团与ZnO形成的配位键的解离 可在机械变形过程中显著耗散能量，从而导致聚氨酯复合材料具有更高韧性。因此， 聚氨酯包含可逆金属配位键和氢键，它们的重新结合导致有效的自修复，相对较强的共价键可确保机械性能。
附图说明
图1是实施例3和5中制备的修复聚氨酯复合材料的红外光谱(a)和X射线 光电子能谱图(b)。
图2是空白组、实施例1-4和对比例9中制备的聚氨酯复合材料上金黄色葡萄 球菌的黏附效果图。
图3是实施例1-4中制备的聚氨酯复合材料0.01Hz的∣Z∣图。
图4(a)是实施例5中制备的聚氨酯复合材料的热红外成像图，图4(b)是实 施例3中制备的聚氨酯复合材料的热红外成像图。
图5是实施例5中制备的聚氨酯复合材料的电化学阻抗图。
图6是实施例3和5中制备的聚氨酯复合材料的抑菌效果图。
图7是实施例5-7中制备的聚氨酯复合材料的抑菌效果图。
图8是实施例5和对比例1、4-8中制备的聚氨酯复合材料。
图9是对比例3中制备的聚氨酯复合材料上金黄色葡萄球菌的黏附效果图。
图10是实施例5和对比例7-8中制备的聚氨酯复合材料0.01Hz的∣Z∣图。
图11是对比例8中制备的聚氨酯复合材料的X射线光电子能谱图。
具体实施方式
下面结合附图和实施例，对本发明的具体实施方式作进一步详细描述。以下实 施例用于说明本发明，但不用来限制本发明的范围。
实施例1
(1)将2g聚四氢呋喃、0.2g扩链剂二甲基乙二肟和0.05g甘油在50℃水浴中完全溶于5mL丙酮，得到溶液A；
(2)将0.2g异佛尔酮二异氰酸酯和0.8g甲苯二异氰酸酯混溶得到溶液B，将0.02g二月桂酸二丁基锡加入到溶液B，完全溶解得到溶液C；
(3)将溶液A在50℃水浴中磁力搅拌30min，然后将溶液C倒入溶液A，在50℃ 的水浴中持续反应2h，溶液呈现粘稠状，得到溶液D；
(4)将溶液D倒入模板中，在60℃烘箱中固化24h，经过处理最终得到聚氨酯复 合材料PU1。
实施例2-4
实施例2-4的方法步骤与实施例1相同，不同之处在于改变了异佛尔酮二异氰 酸酯和甲苯二异氰酸酯的配比，组分及用量见表1。
实施例5-7
实施例5-7的步骤与实施例1相同，不同之处在于在步骤(2)中将氧化锌连同 二月桂酸二丁基锡加入到溶液B，完全溶解得到溶液C。组分及用量见表1。
表1实施例1-7组分及用量
对比例1-9
对比例1-9的方法步骤参考实施例1-7，组分和用量详见表2。
表2对比例1-9的组分和用量
表2对比例1-9的组分和用量(续)
实施例9(效果实施例)
聚氨酯复合材料的结构表征与性能测试：
(1)复合材料结构表征：
利用傅里叶变换红外光谱(ATR-FTIR)对实施例1-7所获得的聚氨酯组分的官能团进行了表征。在3318和1713cm-1处的峰分别为N-H和C＝O的伸缩振动，表明 聚氨酯的成功合成。从图1a可以看出，在2264cm-1和1202cm-1处分别有可以忽略 的峰，分别对应于N＝C＝O和丙酮分子骨架拉伸振动。结果表明，单体IPDI/TDI和 溶剂丙酮被完全脱除。因此，聚氨酯的自修复性能是由合成的聚合物段引起的而不 是单体的作用。为了进一步揭示ZnO对聚氨酯交联结构的影响。对ZnO-PU样品的 拉曼光谱和XPS光谱结果证实，配位过程中不仅有咪唑基团，还有酰胺键基团。如 图1b所示，在399.2eV处的峰值可以归因于ZnO-PU1的高分辨率N1s光谱中Zn2+-N。 N-H、C-N和C＝N的峰值分别为400.1eV、399.7eV和398.6eV。这些结果为锌离 子的配位键提供了有力的证据。
(2)性能表征：
正是由于聚氨酯软硬段的热不兼容性，才产生了微相分离结构，在应用于海洋 领域时防止了污垢生物的附着。重要的是，通过改变异氰酸酯的种类和配比，探讨 了不同硬段的化学结构对聚氨酯防污性能的影响。
图2为不同硬段配比的聚氨酯材料的防污效果。可以看出，与不含硬链段的空 白组(图2a)和对比例9(图2f)、对比例3(图8)相比，实施例1-4(图2b-e)中 不同硬段比例的聚氨酯涂料表面的金黄色葡萄球菌的生物附着力均明显降低，说明制备的聚氨酯涂料具有良好的防污效果。当TDI与IPDI的比例为1:1时(即PU3)， 生物附着最少，防污性能最好(如图2d所示)。
图3为不同硬段配比的聚氨酯材料在0.01Hz的∣Z∣图，通过∣Z∣图评价聚氨 酯材料的自修复效果。可以看出，实施例1-4(图3)中不同硬段比例的聚氨酯材料均能修复，三小时阻抗值增加，聚氨酯开始修复。
图4研究了在405nm紫外光照射下聚氨酯的光热转换能力。通过热像仪监测 PU3/ZnO-PU1在405nm激光照射下的温度变化。405nm辐照仅60s即可使ZnO-PU1 的温度升高到46.5℃(图4a)，与PU3(32.5℃)相比，ZnO-PU1表现出更高效的光热能 力。
为了评价ZnO-PU1的自修复性能，研究了样品的电化学阻抗谱(EIS)，如图5 所示，图5a为拟合电路图。在图5b的Nyquist图中，掺杂ZnO聚氨酯被划伤后3h 内，圆弧半径有增加的趋势，意味着聚氨酯达到自修复性能。低频阻抗是评价系统 抗腐蚀性能的重要参数，从图5c的Bode图和图5d的相位角图中可以看出，聚氨酯 刮伤1h后，|Z|0.01Hz增加说明复合材料的保护性能在修复后得到了提高。PU3和 ZnO-PU1在划伤/未划伤条件下的抑菌效果如图6所示。
图6a和6b显示ZnO-PU1在划伤和未划伤条件下对金黄色葡萄球菌和铜绿假单 胞菌的菌落数，由此得到图6c和图6d中ZnO-PU1在划伤和未划伤条件下对金黄色 葡萄球菌和铜绿假单胞菌的抑菌率分别为99.2％和98.5％。PU3对金黄色葡萄球菌 的抑菌率仅为50.1％，对铜绿假单胞菌的抑菌率为40.3％，表明复合ZnO具有较好 的抑菌性能。聚氨酯复合材料通过释放锌离子来防污和杀菌。
图7结果表明氧化锌的添加量影响聚氨酯复合材料的抑菌效率，添加量为0.01g时抑菌率低，当添加量达到0.02和0.03g时抑菌率上升，且0.03g时比0.02g的提升 幅度不大。
图8a为实施例5制备的聚氨酯复合材料，其粘度合适，成膜性能良好；对比例 1中无甲苯二异氰酸酯存在时复合材料粘度大，难于应用，如图8b所示。对比例2 仅添加甲苯二异氰酸酯作为硬链段时，复合材料易产生气泡，复合材料韧性差，多 孔隙成型不好，如图8c所示。对比例3中，当异佛尔酮二异氰酸酯与甲苯二异氰酸酯的质量比为1：5时，复合材料抗细菌粘附性效果较差，如图9所示。对比例4中， 水浴温度为40度时，反应制得的聚合物难以成膜，复合材料性能差，如图8d所示； 对比例5中，当水浴温度为70度时，反应速率过快，导致聚氨酯复合材料气泡多， 如图8e所示；对比例6-8合成复合材料粘度大，延展性差，如图8f所示为对比例6 的结果，对比例7为图8g1，对比例8为图8g2。
图10显示了对比例7、对比例8和实施例5制备的聚氨酯复合材料在0.01Hz 的∣Z∣图，实施例5的复合材料在0.5小时即可修复，而对比例7、8需要1小时 修复，显示对比例7、8修复时间延长了，尽管扩链剂替换后仍能合成复合材料，但 是由于反应物中缺乏二甲基乙二肟与ZnO形成配位键，复合材料修复效率低，图11显示的对比例8制备的聚氨酯复合材料的X射线电子能谱图验证这一观点。
以上是通过简单的一锅法制备本征型光热响应自修复聚氨酯复合材料的详细阐述。
应当指出，本发明不限于上述实施例；对于本领域的普通技术人员来说，依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同 替换；而这些修改或替换，并不使相应技术方案的本质脱离本发明所要求保护的技 术方案的精神和范围。

Claims (6)

1.一种自修复聚氨酯复合材料的制备方法，其特征在于，以聚四氢呋喃作为软链段，异佛尔酮二异氰酸酯和甲苯二异氰酸酯作为硬链段，甘油和二甲基乙二肟作为扩链剂，二月桂酸二丁基锡作为催化剂，采用一锅法合成；所述聚四氢呋喃：二异氰酸酯的质量比为2：1；所述聚四氢呋喃：二甲基乙二肟：甘油的质量比为2：0.2：0.05；所述异佛尔酮二异氰酸酯：甲苯二异氰酸酯：二月桂酸二丁基锡的质量比为（2~7）：（8~2）：0.2；所述方法包括如下步骤：
将聚四氢呋喃、二甲基乙二肟和甘油溶于丙酮，得到溶液A；
将异佛尔酮二异氰酸酯和甲苯二异氰酸酯混溶得到溶液B；将二月桂酸二丁基锡加入到溶液B，溶解得到溶液C；
将溶液C倒入溶液A，水浴反应至溶液呈现粘稠状为反应结束，得到溶液D；所述水浴反应的温度为45-65℃；
将溶液D固化得到聚氨酯复合材料。
2.根据权利要求1所述的制备方法，其特征在于，还加入氧化锌作为填料。
3.根据权利要求1所述的制备方法，其特征在于，还加入氧化锌在溶液B中。
4.根据权利要求2或3所述的制备方法，其特征在于，所述氧化锌与二月桂酸二丁基锡的质量比为1~3:2。
5.一种自修复聚氨酯复合材料，其特征在于，采用权利要求1-4任一项所述的方法制备得到。
6.根据权利要求5所述的自修复聚氨酯复合材料在防污中的应用。
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