环境友好抗吸附自更新防污涂层制备及其协同防污机制的研究

In view of the application of toxic copper(I) antifoulants on ship hulls has resulted in serious environmental pollution, we have designed an enviromental friendly dual-functional marine antifouling coating with interface self-freshed and anti-adsorption, in which non-toxic betaine materials with antifouling property was used to replace the and toxic components; one of motifs of this subjuect will be focused on the preparation of the nanoparticle with hydrophilic polybetaine core and hydrophobic polymer shell via atomic transfer radical polymerization, so that resulting nanoparticle have high compatibility with hydrophobic organosilicon base, instead of the phase separation which leads to short durability of marine coatings; Furhtermore, the key factors, the critical molecular weight and molar ratio of diblock copolymer for nanoparticle, will be detemined to make nanoparticle switch from hydrophobicity to hydrophilicity in water phase. The above results will helpfully disclose the principle of controllable release and switch of the nanoparticle in the marine coating surface under the water, which can illustrate the formation of stable antifouing layer from nanoparticle on the surface of marine coating. Therefore, the dual-functional antifouling mechanism based on the anti-adsorption &self-rerefeshed marine coating will be illustrated along with the sea field test results. . The final motif of this subject is to explore a new synergistic antifouling mechanism by establishing biofouling formation and the fouling-release regularity for this marine coating. On the basis of the obtained results, we will futher develop envirmental friendly & long-term antifouling marine coatings in future.

针对重金属铜等有毒防污涂料造成海洋环境污染的问题，设计了一种以抗吸附甜菜碱材料替代有毒防污组份的环境友好防污涂层，通过其界面不断自更新并在界面形成甜菜碱抗吸附层得双重作用实现防污的目的。重点研究原子转移自由基可控聚合制备内层为甜菜碱结构，外层含疏水结构的纳米粒子方法，从而解决甜菜碱离子化合物与疏水有机硅树脂易发生相分离而影响涂层寿命的难题；通过研究纳米粒子两嵌段共聚物的临界分子量、嵌段比，解决影响纳米粒子在水相中发生疏水亲水结构转换的关键技术问题；揭示自更新防污涂层界面的纳米粒子在水相中发生疏亲转换及可控释放的原理，进而阐明纳米粒子在防污涂层界面形成稳定抗吸附层的规律性。通过海洋场地防污测试等方法，阐述抗吸附自更新防污涂层双重防污机制有效性。本申请的目的是探索一种新型的协同防污的工作机制，并掌握该涂层表面污损生物形成与脱落规律，为研制环保长效的防污涂料提供理论依据。

针对设计的以抗吸附甜菜碱材料环境友好防污涂层，重点研究原子转移自由基可控聚合制备内层为甜菜碱结构，外层含疏水结构的纳米粒子方法，解决甜菜碱离子化合物与疏水有机硅树脂易发生相分离而影响涂层寿命的难题；通过研究纳米粒子两嵌段共聚物的临界分子量、嵌段比，确立了对于PLMAm-b-PSBMAn纳米粒子的关键摩尔比为1:0.6.当n/m大于0.6时，其内层亲水的SBMA在水相中可以发生壳核翻转，而且对于相同的比值，当m值减小时时，其翻转难度降低，防污性能变好，而纳米粒子的稳定性变差；对于PHMAm-b-PSBMAn纳米粒子关键摩尔比为1:0.8，当n/m大于0.8时，其内层亲水的SBMA在水相中可以发生壳核翻转，而且对于相同的比值，当m值增加时，其翻转难度增加，防污性能变差，而纳米粒子的稳定性可提高；上述规律解决纳米粒子在水相中发生疏水亲水结构转换的关键技术问题；从而进一步揭示自更新防污涂层界面的纳米粒子在水相中发生疏亲转换及可控释放的原理，进而阐明纳米粒子在防污涂层界面形成稳定抗吸附层的结构及防污性能的影响规律性。通过海洋场地防污测试对比试验，掺入本项目研制的纳米粒子，验证了抗吸附自更新防污涂层双重防污机制有效性。