CN115521700A - 一种基于plga的可控降解聚氨酯防污涂层及其制备方法 - Google Patents
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Abstract
本发明公开了一种基于PLGA的可控降解聚氨酯防污涂层及其制备方法，所述涂层按质量百分比由以下原料组成：可降解聚氨酯PLGA‑PU 70~90%，防污剂10~30%。本发明通过分子结构的设计改进，以生物基高分子材料PLGA为基体设计合成聚氨酯，以调控PLGA作为聚氨酯软段组织的含量，使聚氨酯达到可控降解的目的，之后进一步与防污剂（DCOIT）复合，得到PLGA基可降解聚氨酯防污涂层。该涂层前期可通过其表面亲水形成的水合层来抑制生物膜的生长，中期可通过防污剂的释放来抑制细菌的粘附生长，后期可通过聚氨酯涂层的降解消除生物污垢在材料表面的积累，在海洋、医用材料防污等领域有巨大前景。
Description
技术领域
本发明涉及一种涂层及其制备方法，尤其涉及一种基于PLGA的可控降解聚氨酯防污涂层及其制备方法。
背景技术
微生物在材料表面的定植会对生物医学，水净化学，生物传感器和海洋工业领域造成严重损害，为解决这类有害问题，赋予材料表面抗菌性已被认为是防止细菌粘附和生物污垢积累的有效方法，因此非常需要多功能和生物相容性好的抗生物污损涂层。聚氨酯是一类具有氨基甲酸酯(-NH-COO-)重复结构单元的聚合物，具有硬段和软段两种微相组织，这种结构使聚氨酯材料具有优良的物理机械性能和分子结构设计自由度大，广泛的用于各个领域。传统的石油基聚氨酯涂层因无法降解，溶剂残留严重污染环境等缺点无法用于海洋防污等方面；而以生物基高分子为原料合成的聚氨酯因来源广泛，性能优异，无毒无害以及环境友好等特点已成为生物医用及海洋防污涂料的研究领域的核心方向之一。
聚氨酯涂料的应用十分广泛，由于其优异的性能，一直是研究的热点。“CN107418441A”公开了一种聚氨酯防水涂料，其特征是将氢化焦油作为扩链剂制备防水涂料，煤焦油和氢化焦油的加入虽会提高聚氨酯涂料的防水效果，但同时会环境造成严重危害。为此，研究人员将目标转移到环保型可降解聚氨酯涂料上，“CN106634523A”发明了“一种环境友好聚氨酯阻燃涂料及其制备方法”，该发明通过将二异氰酸酯，多元醇等，在溶剂和催化剂的作用下反应，得到了具有绿色环保可降解和阻燃效果的涂料。“CN111499862A”公开了“一种可降解聚氨酯及其制备方法”，其使用甘油环碳酸酯(A)、11-巯基十一烷酸(B)、植物油等作为原料，经多步反应制备新型植物油基光固化聚氨酯，在具有高效反应活性的同时，具有优异的物理性能兼具高效抗菌性能。
聚乳酸-羟基乙酸共聚物(PLGA)是由乳酸和羟基乙酸无归开环共聚合成的，是一种可降解的功能高分子有机化合物，具有良好的生物相容性、无毒、良好的成囊和成膜的性能，被广泛应用于制药、医用工程材料和现代化工业领域。目前，关于PLGA的研究主要侧重于药物载体，将其作为主要成膜物的研究甚少。“CN114588115A”公开了“一种PLGA药物缓释微球的制备方法”，该发明采用传统的乳化溶剂挥发-沉淀法，利用纳米纤维素自身带有的zeta电位，将其作为稳定剂吸附在PLGA微球表面，通过水相中离子强度的调节，从而调控微球表面带电层的厚度，最后获得粒径分布窄、载药量高，包封率高的药物缓释微球。“CN114569539A”公开了“一种新型抗菌素释缓系统、制备方法及其应用”，其利用PLGA作为微球负载万古霉素，混合得到的万古霉素纳米微球PLGA-PTMC缓释系统和BMSCs-PLGA-PTMAC支架在治疗感染性骨缺损具有良好的应用前景。
上述材料依赖于聚氨酯、PLGA的可降解性来达到功能分子释放的目的，但都存在一定缺陷，比如生物降解材料PLGA无法作为主要原料，只能以载体形式出现；复合材料中功能分子无法控释，以及材料的降解速率无法控制，不能起到长期使用的效果等。
发明内容
发明目的：本发明旨在提供一种能有效稳定释放防污剂的基于PLGA的可控降解聚氨酯防污涂层；本发明的另一目的在于提供一种所述可控降解聚氨酯防污涂层的制备方法。
技术方案：本发明所述的基于PLGA的可控降解聚氨酯防污涂层，按质量百分比由以下原料组成：可降解聚氨酯PLGA-PU 70～90％，防污剂10～30％；所述可降解聚氨酯PLGA-PU按质量百分比由以下原料组成：PLGA 17％～24％，二异氰酸酯5％～14％，1,4-丁二醇2％～5％，N,N-二甲基甲酰胺64％～71％，催化剂1％。
优选地，所述PLGA中的乳酸和羟基乙酸摩尔比为75：25，PLGA的数均分子量为2000～20000。
优选地，所述二异氰酸酯为4,4'-二苯甲烷二异氰酸酯、2,4'-二苯甲烷二异氰酸酯或2,2'-二苯甲烷二异氰酸酯中的一种。
优选地，所述防污剂为4,5-二氯-N-辛基-3-异噻唑啉酮。
所述可降解聚氨酯涂层的制备方法包括如下步骤：
(1)称取PLGA加入到通有氮气并且带有冷凝管的烧瓶中，加入DMF，搅拌直至固体完全溶解；
(2)称取MDI加入至上述烧瓶中，加热反应后冷却至室温；
(3)称取BDO和DBTDL，加入上述烧瓶中，加热反应后冷却至室温；
(4)称取DCOIT加入到步骤(3)的合成产物中，磁力搅拌，然后将其涂敷在基材上。
优选地，步骤(2)中所述加热反应的温度为75～85℃，反应时间为1～3小时。
优选地，步骤(3)中所述加热反应的温度为75～85℃，反应时间为1～3小时。
优选地，步骤(4)中所述磁力搅拌的时间为10～30min，转速为500～1000r/min。。
本发明旨在通过分子结构的设计控制基于PLGA聚氨酯中软硬段比值来解决当前可降解聚氨酯防污涂层的问题：有效控制聚氨酯涂层的降解速率，同时通过涂层的降解释放防污剂，使基材外表面处于一个少菌或无菌的环境中。该涂层具有良好的附着力等力学性能，在使用过程中，前期涂层的亲水性会在材料表面形成水合层，从而防止蛋白质的粘附；随着时间增长，蛋白质粘附后，防污剂释放，抑制细菌的生长；伴随材料涂层表面生物污垢积累，维持材料表面自更新的同时保留材料的各个性能。
有益效果：与现有技术相比，本发明具有如下显著优点：(1)本发明中PLGA不再作为药物载体或修饰部分，而是作为成膜物原料，提高生物基高分子材料在涂层中的应用；(2)本发明中的涂层可在某些生物酶的作用下降解，涂层被降解后的小分子无毒无害；(3)本发明在合成中控制聚氨酯软硬段比例，进而调控可降解聚氨酯涂层的亲水性，提高对涂层降解速率的控制；(4)能有效稳定释放防污剂，本发明在涂层中添加环保型广谱杀菌剂DCOIT，，释放后针对性强，并且不会产生危害环境的有毒物质；(5)本发明作为可降解聚氨酯涂层，合成工艺简单，保留其综合性能的同时，赋予涂层可控的降解，从而达到涂层表面的自更新效果与防污剂控释的目的；(6)所述涂层前期可通过其表面亲水形成的水合层来抑制生物膜的生长，中期可通过防污剂的释放来抑制细菌的粘附生长，后期可通过聚氨酯涂层的降解消除生物污垢在材料表面的积累，在海洋、医用材料防污等领域有巨大前景。
附图说明
图1为(a)PLGA基聚氨酯的红外光谱图；(b)含有10％防污剂的PLGA-PU在人工海水中浸泡时DCOIT的释放速率变化。
具体实施方式
下面结合附图对本发明的技术方案作进一步说明。
实施例1
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取17％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入64％DMF，搅拌直至固体完全溶解；称取14％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取4％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为50％的PLGA基聚氨酯(记为：PLGA-PU-1)；从图1(a)可以看出，本发明成功制备了一种基于PLGA的可控降解聚氨酯。
取上述合成的PLGA-PU-1 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-1涂层的累积降解量为0.0122g，防污剂DCOIT的释放量约为0.0689μg/cm-2，如图1(b)所示。
实施例2
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取18％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入69％DMF，搅拌直至固体完全溶解；称取10％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取2％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为60％的PLGA基聚氨酯(记为：PLGA-PU-2)；
取上述合成的PLGA-PU-2 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-2涂层的累积降解量为0.0308g，防污剂DCOIT的释放量约为0.0659μg/cm-2，如图1(b)所示。
实施例3
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取20％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入71％DMF，搅拌直至固体完全溶解；称取5％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取3％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为70％的PLGA基聚氨酯(记为：PLGA-PU-3)；
取上述合成的PLGA-PU-3 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-2累积降解量为0.024g，防污剂DCOIT的释放量约为0.0662μg/cm-2，如图1(b)所示。
实施例4
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取22％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入65％DMF，搅拌直至固体完全溶解；称取8％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取4％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为50％的PLGA基聚氨酯(记为：PLGA-PU-4)；
取上述合成的PLGA-PU-4 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-2累积降解量为0.028g，防污剂DCOIT的释放量约为0.0632μg/cm-2。
实施例5
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取23％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入68％DMF，搅拌直至固体完全溶解；称取10％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取2％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为60％的PLGA基聚氨酯(记为：PLGA-PU-5)；
取上述合成的PLGA-PU-5 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-2累积降解量为0.037g，防污剂DCOIT的释放量约为0.0745μg/cm-2。
实施例6
一种基于PLGA的可控降解聚氨酯防污涂层的制备方法，涂料合成质量配比为：称取24％PLGA(乳酸：羟基乙酸＝75：25)加入到通有氮气并且带有冷凝管的三口烧瓶中，加入67％DMF，搅拌直至固体完全溶解；称取5％MDI加入三口烧瓶中，在80℃下反应1小时，然后冷却至室温；称取3％BDO和1％DBTDL，加入上述烧瓶中，将反应体系升高至85℃，反应3小时，然后冷却至室温，得到软段含量为70％的PLGA基聚氨酯(记为：PLGA-PU-6)；
取上述合成的PLGA-PU-6 90％，DCOIT 10％，共混涂敷。在人工海水中浸泡15天时，PLGA-PU-2累积降解量为0.048g，防污剂DCOIT的释放量约为0.0762μg/cm-2。
Claims (8)
1.一种基于PLGA的可控降解聚氨酯防污涂层，其特征在于，按质量百分比由以下原料组成：可降解聚氨酯PLGA-PU 70~90%，防污剂10~30%；所述可降解聚氨酯PLGA-PU按质量百分比由以下原料组成：PLGA 17%～24%，二异氰酸酯5%～14%，1,4-丁二醇2%～5%，N,N-二甲基甲酰胺64%～71%，催化剂1%。
2.根据权利要求1所述的可降解聚氨酯涂层，其特征在于，所述PLGA中的乳酸和羟基乙酸摩尔比为75：25，PLGA的数均分子量为2000~20000。
3.根据权利要求1所述的可降解聚氨酯涂层，其特征在于：所述二异氰酸酯为4,4'-二苯甲烷二异氰酸酯、2,4'-二苯甲烷二异氰酸酯或2,2'-二苯甲烷二异氰酸酯中的一种。
4.根据权利要求1所述的可降解聚氨酯涂层，其特征在于，所述防污剂为4,5-二氯-N-辛基-3-异噻唑啉酮。
5.一种权利要求1所述的可降解聚氨酯涂层的制备方法，其特征在于，包括如下步骤：
（1）称取PLGA加入到通有氮气的烧瓶中，加入DMF，搅拌直至固体完全溶解；
（2）称取MDI加入至上述烧瓶中，加热反应后冷却至室温；
（3）称取BDO和DBTDL，加入上述烧瓶中，加热反应后冷却至室温；
（4）称取DCOIT加入到步骤（3）的合成产物中，磁力搅拌，然后将其涂敷在基材上。
6. 根据权利要求5所述的可降解聚氨酯涂层的制备方法，其特征在于，步骤（2）中所述加热反应的温度为75～85 ℃，反应时间为1～3小时。
7. 根据权利要求5所述的可降解聚氨酯涂层的制备方法，其特征在于，步骤（3）中所述加热反应的温度为75～85 ℃，反应时间为1～3小时。
8. 根据权利要求5所述的可降解聚氨酯涂层的制备方法，其特征在于，步骤（4）中所述磁力搅拌的时间为10~30 min，转速为500~1000 r/min。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432802A (zh) * | 2011-09-16 | 2012-05-02 | 海洋化工研究院 | 生物降解型防污涂料用树脂、合成方法，含该树脂的防污涂料组合物 |
| CN102731745A (zh) * | 2012-06-29 | 2012-10-17 | 华南理工大学 | 一种降解型海洋防污材料及其制备方法与应用 |
| CN106317346A (zh) * | 2016-08-17 | 2017-01-11 | 厦门双瑞船舶涂料有限公司 | 一种可降解防污树脂的制备方法及其用途 |
| CN107286313A (zh) * | 2017-07-10 | 2017-10-24 | 陕西瑞盛生物科技有限公司 | 一种可降解的聚氨酯泡沫及其应用 |
| CN110832000A (zh) * | 2018-03-22 | 2020-02-21 | 南京邦鼎生物科技有限公司 | 制备薄膜的组合物和方法及其应用 |
-
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- 2022-09-19 CN CN202211135040.8A patent/CN115521700A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432802A (zh) * | 2011-09-16 | 2012-05-02 | 海洋化工研究院 | 生物降解型防污涂料用树脂、合成方法，含该树脂的防污涂料组合物 |
| CN102731745A (zh) * | 2012-06-29 | 2012-10-17 | 华南理工大学 | 一种降解型海洋防污材料及其制备方法与应用 |
| CN106317346A (zh) * | 2016-08-17 | 2017-01-11 | 厦门双瑞船舶涂料有限公司 | 一种可降解防污树脂的制备方法及其用途 |
| CN107286313A (zh) * | 2017-07-10 | 2017-10-24 | 陕西瑞盛生物科技有限公司 | 一种可降解的聚氨酯泡沫及其应用 |
| CN110832000A (zh) * | 2018-03-22 | 2020-02-21 | 南京邦鼎生物科技有限公司 | 制备薄膜的组合物和方法及其应用 |
Non-Patent Citations (1)
| Title |
|---|
| 马春风: "海洋防污高分子材料的进展" * |
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