【作者】 潘珊珊；

【导师】 高昌录；

【作者基本信息】 哈尔滨工业大学 ， 海洋科学， 2017， 硕士

【摘要】 近年来由于海洋生物污损在船体表面的附着导致船舶航行速度减慢,燃油费逐年增加,对海洋经济造成严重的损失。可水解的阳离子聚电解质作为一种阳离子杀菌剂,水解生成具有抗吸附作用的两性离子聚电解质,已被广泛应用。但由于其有机内盐的结构使其不能与疏水性基料混合。本文制备了两亲性嵌段共聚物,使其在有机溶剂中自组装形成以阳离子聚电解质为核,以疏水段为壳的纳米粒子,解决了阳离子聚电解质在基料中相分离的问题。并考察了纳米粒子翻转的临界条件及涂层的防污性能。首先,采用原子转移自由基聚合(ATRP)的方法,通过连续加料的方式分别以甲基丙烯酸异辛酯(EHMA)、甲基丙烯酸十二酯(LMA)和甲基丙烯酸十六酯(HMA)为疏水性单体,甲基丙烯酸二甲氨基乙酯(DMAEMA)为亲水性单体制备两亲性嵌段聚合物。并且通过核磁共振氢谱(1H NMR)和凝胶渗透色谱(GPC)对结构和分子量进行了表征。然后在氯仿溶液中,两亲性嵌段共聚物与氯乙酸甲酯或氯乙酸乙酯,制备一系列以疏水段为壳,分别以P(DMAEMA-CH2COOCH3)(PCBMAM)或P(DMAEMA-CH2COOCH2CH3)(PCBMAE)为核的纳米粒子。并通过动态光散射(DLS)和扫描电镜(SEM)对其粒度大小和微观形貌进行了表征。水接触角和核磁测试表明,纳米粒子PEHMAx-b-PCBMAMy、PLMAx-b-PCBMAMy、PHMAx-b-PCBMAMy翻转时亲水段与疏水段临界摩尔比均为y/x≥0.75。纳米粒子PEHMAx-b-PCBMAEy、PLMAx-b-PCBMAEy、PHMAx-b-PCBMAEy翻转时亲水段与疏水段临界摩尔比分别为y/x≥0.75、y/x≥0.5、y/x≥0.75。纳米粒子翻转受到疏水段链长及玻璃化温度的影响,疏水段越短,纳米粒子翻转越容易。疏水段玻璃化温度越低,纳米粒子越容易翻转。将纳米粒子掺入到基料中制备防污涂层。防污测试表明纳米粒子具有杀菌性能,涂层的抗牛血清蛋白(BSA)和金黄色葡萄球菌吸附的能力随着纳米粒子掺入量的增加而逐渐增强。综上所述,本研究实现了制备阳离子杀菌和抗菌功能转换纳米粒子的目标。同时,本文采用ATRP本体聚合的方式,实现了定量制备两嵌段共聚物的目标,提高了原子经济效率,因此本研究成果非常实用于工业化生产。更多还原

【Abstract】 In recent years,due to the fouling of biofouling on the surface of the hull,the navigation speed of ships slows down and fuel costs increase year by year,causing serious losses to marine economy.Hydrolyzable cationic polyelectrolytes have been widely used as a cationic bactericide which can be hydrolyzed to zwitterionic polyelectrolytes with anti-adsorption ability.However,due to the structure of its organic internal salt,it can’t be mixed with the hydrophobic base.In this paper,amphiphilic block copolymers were prepared,which were self-assembled in organic solvent to form nanoparticles with cationic polyelectrolyte as core and hydrophobic segment as shell solving the problem of phase separation of cationic polyelectrolyte in the matrix.The critical conditions for nanoparticle reversion and the antifouling properties of the coatings were also investigated.Firstly,by the method of atom transfer radical polymerization(ATRP),amphiphilic block copolymer was prepared by continuous feeding with DMAEMA as a hydrophilic monomer and isooctyl methacrylate(EHMA),lauryl methacrylate(LMA)and hexadecyl methacrylate(HMA)as hydrophobic monomers,respectively.The structure and molecular weight were characterized by NMR(1H NMR)and gel permeation chromatography(GPC).In a chloroform solution,amphiphilic block copolymers were reacted with methyl chloroacetate or ethyl chloroacetate to prepare a series of nanoparticles with hydrophobic segments as the shell and P(DMAEMA-CH2COOCH3)(PCBMAM)or P(DMAEMA-CH2COOCH2CH3)(PCBMAE)as the core.Water contact angle and 1H NMR tests showed that the critical mole ratio of hydrophilic segment and hydrophobic segment of PEHMAx-b-PCBMAMy,PLMAx-b-PCBMAMy and PHMAx-b-PCBMAMy were both y/x≥0.75.The critical mole ratio of hydrophilic segment and hydrophobic segment PEHMAx-b-PCBMAEy,PLMAx-b-PCBMAEy and PHMAx-b-PCBMAEy were respectively y/x≥0.75,y/x≥0.5 and y/x≥0.75.Nanoparticle reversion is affected by the length and the glass transition temperature of the hydrophobic segments.The shorter the hydrophobic segments and the lower the glass transition temperature of the hydrophobic segments,the easier the nanoparticles reversion.The nanoparticles are blended into the substrate to prepare antifouling coatings.The antifouling test indicates that the nanoparticles have the sterilization performance,and the ability of the coated anti-bovine serum protein(BSA)and staphylococcus aureus is gradually enhanced with the increase of the incorporation of nanoparticles.In summary,this paper achieved the goal of preparing cationic bactericidal and antibacterial functional conversion nanoparticles.At the same time,this paper adopts ATRP bulk polymerization method to achieve the goal of quantitative preparation of diblock copolymers and improve the atomic economic efficiency,so the results of this study are very practical for industrial production.更多还原