PMMA/纳米TiO_2复合粒子的制备及其在CNR涂料中的应用
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摘要
纳米二氧化钛具有优异的光催化、紫外光屏蔽等性能,将其添加到高分子材料中可以制备具有无机纳米粒子和有机高分子双重特性的功能性高分子材料。制备过程中,如何提高纳米TiO2与高分子基体材料之间的相容性成为首要解决的问题。表面聚合物接枝通过使高分子链与无机粒子之间产生强的化学键结合,能有效地解决这一问题,同时接枝上的适当厚度的高分子链还能够充当界面缓冲层的作用。本文首先通过硅烷偶联剂KH-570对纳米TiO2进行预处理,在纳米粒子表面引入不饱和双键作为表面聚合接枝活性点,再利用环境友好的乳液聚合法,通过优化聚合体系的工艺条件,在纳米TiO2表面接枝PMMA制备了高接枝率的PMMA/纳米TiO2复合粒子,最后将复合粒子应用到CNR涂料中,并考察了纳米TiO2对复合涂层性能的影响。
首先,硅烷偶联剂KH570在水乳化体系中进行水解后对纳米TiO2进行表面处理。研究了硅烷偶联剂水解时间、pH值和乳化剂SDS浓度对偶联剂水解速度和水解液稳定性的影响,从而初步确定了水解条件。用煅烧法测定了粉体表面偶联包覆率,研究了硅烷偶联剂的水解条件和偶联条件对偶联效果的影响。结果表明,适宜的KH-570水解偶联条件为：乳化剂SDS浓度0.1%,调pH值为3.5,偶联剂浓度2.0%,室温下水解lh,80℃偶联2h。FTIR分析表明硅烷偶联剂与纳米二氧化钛表面的羟基发生了化学键合,TEM表明表面处理后的纳米粒子能在有机溶剂中均匀分散。
其次,通过乳液聚合制备了化学接枝的PMMA/纳米TiO2复合粒子。通过FTIR和TGA分析了聚合物与纳米粒子间的相互作用。结果表明,在丙酮抽提前复合粒子中PMMA以化学接枝和物理包覆两种形式与纳米TiO2粒子发生作用。经丙酮72h抽提后,复合粒子表面物理吸附的PMMA被全部除去,此时对比PMMA/M-TiO2和PMMA/TiO2的FTIR谱图可以发现,PMMA与纳米TiO2之间是通过偶联剂分子的“桥梁”作用相连接的。研究了聚合条件对复合粒子的接枝率和聚合体系的稳定性的影响。在KH-570浓度为2%,SLS浓度为0.1%,APS浓度为0.05%,MMA/纳米TiO2用量为10g/5g时,乳液体系产生的凝胶含量较低,且制得的复合粒子的接枝率可达62.7%。TEM观察表明,聚合物接枝后的复合粒子分散性提高,仍保持在纳米级。
最后,将PMMA/:纳米TiO2复合粒子添加到CNR涂料中制备了纳米TiO2/CNR复合涂料,通过复合涂层的常规性能测试、耐热海水实验和抗菌性实验,发现适当地添加纳米TiO2粒子能够提高涂层的硬度和附着力、耐海水腐蚀性能和抗菌性能。纳米TiO2用量为3.0%时,涂层对大肠杆菌和金黄色葡萄球菌的抗菌率分别达到89%和90%。综合考虑各项性能,纳米TiO2用量为3.0%时复合涂层的综合性能最好。
本文的研究在聚合接枝改性纳米TiO2的基础上,将制得的PMMA/纳米TiO2复合粒子应用于CNR涂料,为纳米粒子在海洋防腐涂料中的应用提供了新思路。
Nano-titanium dioxide has excellent photocatalystic and UV-shielding properties. Functional polymer materials with the characteristics of both inorganic nanoparticles and organic polymer can be prepared by adding nano-TiO2 in polymer materials. However, the principal problem coming up in the preparing process is how to improve the compatibility between nano-TiO2 and polymer matrix materials. Surface grafting with strong chemical bond between polymer chains and inorganic particles can effectively solve this problem; in addition, the polymer chains with appropriate thickness grafted in the nano-particles can serve as interfacial buffer layer. In this paper, we started with the pretreatment of nano-TiO2 by silane coupling agent KH-570, to introduce unsaturated double bonds as active sites for surface grafting. And then environmentally friendly emulsion polymerization was carried out and PMMA/nano-TiO2 composite particles with high grafting rate were prepared through optimizing the conditions of polymerization system. Finally, the composite particles were used in CNR coating, and the influence of nano-TiO2 on composite coating was investigated.
First of all, surface treatment of nano-TiO2 was dealt with silane coupling agent KH-570 after hydrolysis in water emulsion system. The influence of different pH value and emulsifier (SDS) concentration on hydrolysis rate and hydrolytic stability was investigated to set the conditions for hydrolysis. The coupling coating rate of nanoparticles was determined by calcinations, and the affect of hydrolysis and coupling conditions on coupling effect was studied. Results show that the appropriate conditions of hydrolysis and coupling were SDS concentration 0.1%, pH value 3.5, KH-570 concentration 2.0%, hydrolysis in ambient temperature, and coupling for 2 hours under 80℃.FTIR analysis indicates that chemical bonding was generated between the coupling agent and hydroxyl group around the nano-TiO2 surface, TEM shows that the nano-TiO2 after surface treatment can be uniformly dispersed in organic solvent.
Secondly, PMMA/nano-TiO2 composite particles based on chemical grafting were obtained by emulsion polymerization. The interaction between polymer and nano-particles was analyzed with FTIR and TGA. The results show that two kinds of interaction forms, chemical grafting and physical coating, occurred between PMMA and nano-TiO2 before composite particles being extracted by acetone. After 72 hours of acetone extraction, when PMMA that physically adhered on the surface of composite particles was all removed, it can be seen through comparing the FTIR spectrum of PMMA/M-TiO2 with that of PMMA/TiO2 tKD It'V tKH "EUGgH' HIHFt SURvLGHJ Ey Foupling molecules that connected PMMA and nano-TiO2 together. The influence of polymerization conditions on polymer grafting rate and polymerizing stability was also investigated. Comparatively low gel content and grafting rate of 62.7%can be achieved under conditions of KH-570 concentration 2%,SLS concentration 0.1%,APS concentration 0.05%,and MMA/nano-TiO2 content ratio 10:5.TEM shows that dispersity of composite particles was improved after polymer grafting, and the particles stay at nano-level.
Finally, PMMA/nano-TiO2 composite particles were added in CNR coating as to prepare nano-TiO2/CNR composite coating. Through general performance testing, heat sea-water resistance and antibacterial experiment of composite coating, we can found that the properties of coating, hardness and adhesion, corrosion resistance and antibacterial ability, were improved by filling nano-TiO2 with appropriate content. Antibacterial rates of composite coating against E.coli and staphylococcus aurous were 89% and 90%,respectively,as nano-TiO2 content is 3.0%. Considering all the properties, we can get a conclusion that composite coating with 3.0% nano-TiO2 shows the best overall performance.
This paper studied the application of PMMA/nano-TiO2 composite particles in CNR coating, basing on the research of polymer grafting modification of nano-TiO2.lt revealed a new idea for nano-particles using in anticorrosion coating.
首先,硅烷偶联剂KH570在水乳化体系中进行水解后对纳米TiO2进行表面处理。研究了硅烷偶联剂水解时间、pH值和乳化剂SDS浓度对偶联剂水解速度和水解液稳定性的影响,从而初步确定了水解条件。用煅烧法测定了粉体表面偶联包覆率,研究了硅烷偶联剂的水解条件和偶联条件对偶联效果的影响。结果表明,适宜的KH-570水解偶联条件为：乳化剂SDS浓度0.1%,调pH值为3.5,偶联剂浓度2.0%,室温下水解lh,80℃偶联2h。FTIR分析表明硅烷偶联剂与纳米二氧化钛表面的羟基发生了化学键合,TEM表明表面处理后的纳米粒子能在有机溶剂中均匀分散。
其次,通过乳液聚合制备了化学接枝的PMMA/纳米TiO2复合粒子。通过FTIR和TGA分析了聚合物与纳米粒子间的相互作用。结果表明,在丙酮抽提前复合粒子中PMMA以化学接枝和物理包覆两种形式与纳米TiO2粒子发生作用。经丙酮72h抽提后,复合粒子表面物理吸附的PMMA被全部除去,此时对比PMMA/M-TiO2和PMMA/TiO2的FTIR谱图可以发现,PMMA与纳米TiO2之间是通过偶联剂分子的“桥梁”作用相连接的。研究了聚合条件对复合粒子的接枝率和聚合体系的稳定性的影响。在KH-570浓度为2%,SLS浓度为0.1%,APS浓度为0.05%,MMA/纳米TiO2用量为10g/5g时,乳液体系产生的凝胶含量较低,且制得的复合粒子的接枝率可达62.7%。TEM观察表明,聚合物接枝后的复合粒子分散性提高,仍保持在纳米级。
最后,将PMMA/:纳米TiO2复合粒子添加到CNR涂料中制备了纳米TiO2/CNR复合涂料,通过复合涂层的常规性能测试、耐热海水实验和抗菌性实验,发现适当地添加纳米TiO2粒子能够提高涂层的硬度和附着力、耐海水腐蚀性能和抗菌性能。纳米TiO2用量为3.0%时,涂层对大肠杆菌和金黄色葡萄球菌的抗菌率分别达到89%和90%。综合考虑各项性能,纳米TiO2用量为3.0%时复合涂层的综合性能最好。
本文的研究在聚合接枝改性纳米TiO2的基础上,将制得的PMMA/纳米TiO2复合粒子应用于CNR涂料,为纳米粒子在海洋防腐涂料中的应用提供了新思路。
Nano-titanium dioxide has excellent photocatalystic and UV-shielding properties. Functional polymer materials with the characteristics of both inorganic nanoparticles and organic polymer can be prepared by adding nano-TiO2 in polymer materials. However, the principal problem coming up in the preparing process is how to improve the compatibility between nano-TiO2 and polymer matrix materials. Surface grafting with strong chemical bond between polymer chains and inorganic particles can effectively solve this problem; in addition, the polymer chains with appropriate thickness grafted in the nano-particles can serve as interfacial buffer layer. In this paper, we started with the pretreatment of nano-TiO2 by silane coupling agent KH-570, to introduce unsaturated double bonds as active sites for surface grafting. And then environmentally friendly emulsion polymerization was carried out and PMMA/nano-TiO2 composite particles with high grafting rate were prepared through optimizing the conditions of polymerization system. Finally, the composite particles were used in CNR coating, and the influence of nano-TiO2 on composite coating was investigated.
First of all, surface treatment of nano-TiO2 was dealt with silane coupling agent KH-570 after hydrolysis in water emulsion system. The influence of different pH value and emulsifier (SDS) concentration on hydrolysis rate and hydrolytic stability was investigated to set the conditions for hydrolysis. The coupling coating rate of nanoparticles was determined by calcinations, and the affect of hydrolysis and coupling conditions on coupling effect was studied. Results show that the appropriate conditions of hydrolysis and coupling were SDS concentration 0.1%, pH value 3.5, KH-570 concentration 2.0%, hydrolysis in ambient temperature, and coupling for 2 hours under 80℃.FTIR analysis indicates that chemical bonding was generated between the coupling agent and hydroxyl group around the nano-TiO2 surface, TEM shows that the nano-TiO2 after surface treatment can be uniformly dispersed in organic solvent.
Secondly, PMMA/nano-TiO2 composite particles based on chemical grafting were obtained by emulsion polymerization. The interaction between polymer and nano-particles was analyzed with FTIR and TGA. The results show that two kinds of interaction forms, chemical grafting and physical coating, occurred between PMMA and nano-TiO2 before composite particles being extracted by acetone. After 72 hours of acetone extraction, when PMMA that physically adhered on the surface of composite particles was all removed, it can be seen through comparing the FTIR spectrum of PMMA/M-TiO2 with that of PMMA/TiO2 tKD It'V tKH "EUGgH' HIHFt SURvLGHJ Ey Foupling molecules that connected PMMA and nano-TiO2 together. The influence of polymerization conditions on polymer grafting rate and polymerizing stability was also investigated. Comparatively low gel content and grafting rate of 62.7%can be achieved under conditions of KH-570 concentration 2%,SLS concentration 0.1%,APS concentration 0.05%,and MMA/nano-TiO2 content ratio 10:5.TEM shows that dispersity of composite particles was improved after polymer grafting, and the particles stay at nano-level.
Finally, PMMA/nano-TiO2 composite particles were added in CNR coating as to prepare nano-TiO2/CNR composite coating. Through general performance testing, heat sea-water resistance and antibacterial experiment of composite coating, we can found that the properties of coating, hardness and adhesion, corrosion resistance and antibacterial ability, were improved by filling nano-TiO2 with appropriate content. Antibacterial rates of composite coating against E.coli and staphylococcus aurous were 89% and 90%,respectively,as nano-TiO2 content is 3.0%. Considering all the properties, we can get a conclusion that composite coating with 3.0% nano-TiO2 shows the best overall performance.
This paper studied the application of PMMA/nano-TiO2 composite particles in CNR coating, basing on the research of polymer grafting modification of nano-TiO2.lt revealed a new idea for nano-particles using in anticorrosion coating.
引文
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