目的:提高纳米SiO2在有机溶剂及树脂基体中的分散性。方法首先利用普通自由基聚合的方式制备苯乙烯及马来酸酐共聚物( PSMA),再与丙炔醇反应,在分子链上引入多个炔基,然后利用硅烷偶联剂KH560改性纳米SiO2,之后与叠氮化钠反应,在纳米SiO2粒子表面引入多个叠氮基团,最后将带有多个炔基的分子链通过“点击”化学接枝到纳米SiO2表面。结果酸碱反滴定法测得聚合物中马来酸酐的质量分数为26.5%。凝胶渗透色谱测得聚合物数均相对分子质量为36200,相对分子质量分布为1.39。红外表征显示,聚合物上带有多个炔基,纳米SiO2粒子表面带有多个叠氮基,经过24 h“点击”化学反应,聚合物成功接枝到粒子表面,同时叠氮基吸收峰消失。热重( TG)结果表明,接枝率为32.83%。扫描电镜分析表明,接枝聚合物后,粒子的分散性增强。结论分子链上含有多个炔基的共聚物( PSMA)通过“点击”化学反应成功接枝到了纳米SiO2粒子表面,不会引起粒子间的交联,可以明显提高纳米SiO2粒子在有机溶剂中的分散性。
ABSTRACT:Objective To improve the dispersion of nano-silica in organic solvents and resin matrix. Methods Firstly, styrene-maleic anhydride copolymer ( PSMA) was synthesized by common free radical polymerization. Then, the copolymer was reacted with propargyl alcohol to introduce multiple alkynyl groups. Nano-silica was firstly modified by silane coupling agent ( KH560 ) , then reacted with sodium azide to introduce azide groups. Finally, the copolymer ( PSMA) with multiple alkynyl was grafted onto the surface of nano-silica via ‘click’ chemistry. Results The mass fraction of maleic anhydride in polymer was 26. 5% measured by neutralization titration. The number average molecular weight of the polymer was 36200 and the molecular weight distribution was 1. 39 analyzed by gel permeation chromatography. Analysis by IR ( FT-IR) indicated that there were multiple alkynyl on the copolymer, and multiple azide on the surface of nano-silica. After‘click’ chemical reaction for 24 hours, the copolymer was graf-ted onto nano-silica with disappearance of characteristic absorption peaks of azide groups. Analysis of SEM and TG conformed that 32. 83% copolymer (PSMA) was grafted onto nano-silica, and scanning electron microscopy showed the dispersion was improved after the graft. Conclusion Copolymer ( PSMA) with multiple active alkynyl groups can be grafted onto nano-silica via‘click’ chemistry successfully with no occurrence of particle cross-linking, and the dispersion of nano-silica in organic solvents was improved obviously.
参考文献
[1] | 白红英,贾梦秋,毋伟,王金玲.纳米SiO2的原位改性及在耐热涂料中的应用[J].表面技术,2003(06):59-62. |
[2] | GHANBARI A;ATTAR M M .A Study on the Anticorrosion Performance of Epoxy Nanocomposite Coatings Containing Epoxy-silane Treated Nano-silica on Mild Steel Substrate[J].Journal of Industrial and Engineering Chemistry,2014,23:145-153. |
[3] | 毋伟,陈建峰,屈一新.硅烷偶联剂的种类与结构对二氧化硅表面聚合物接枝改性的影响[J].硅酸盐学报,2004(05):570-575. |
[4] | Pramoch Rangsunvigit;Prapon Imsawatgul;Nuchanart Na-ranong .Mixed surfactants for silica surface modification by admicellar polymerization using a continuous stirred tank reactor[J].Chemical engineering journal,2008(2/3):288-294. |
[5] | Xue, LJ;Li, J;Fu, J;Han, YC .Super-hydrophobicity of silica nanoparticles modified with vinyl groups[J].Colloids and Surfaces. A, Physicochemical and Engineering Aspects,2009(1/3):15-19. |
[6] | 张剑 .聚合物分子刷纳米杂化材料[D].南开大学,2010. |
[7] | 张欣萌 .纳米二氧化硅表面改性[D].沈阳工业大学,2006. |
[8] | 王鹏程,柳松,刘梦溪.单分散纳米二氧化硅的制备与分散性研究[J].无机盐工业,2011(02):40-43. |
[9] | Rajesh Ranjan;William J.Brittain .Combination of Living Radical Polymerization and Click Chemistry for Surface Modification[J].Macromolecules,2007(17):6217-6223. |
[10] | Thomas Lummerstorfer;Helmuth Hoffmann .Click Chemistry on Surfaces: 1,3-Dipolar Cycloaddition Reactions of Azide-Terminated Monolayers on Silica[J].The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical,2004(13):3963-3966. |
[11] | 唐炳涛,赵杰,张淑芬,王晓敏.苯乙烯-马来酸酐交替共聚物合成及表征[J].大连理工大学学报,2011(03):326-330. |
[12] | Lin, J.;Chen, H.;Ji, Y.;Zhang, Y..Functionally modified monodisperse core-shell silica nanoparticles: Silane coupling agent as capping and size tuning agent[J].Colloids and Surfaces, A. Physicochemical and Engineering Aspects,2012:111-121. |
[13] | Li, G.L.;Wan, D.;Neoh, K.G.;Kang, E.T. .Binary polymer brushes on silica@polymer hybrid nanospheres and hollow polymer nanospheres by combined alkyne-azide and thiol-ene surface click reactions[J].Macromolecules,2010(24):10275-10282. |
[14] | Xiao-kun Ma;Nam-Hee Lee;Hyo-Jin Oh;Jae-Woo Kim;Chang-Kyu Rhee;Kyoung-Soon Park;Sun-Jae Kim .Surface modification and characterization of highly dispersed silica nanoparticles by a cationic surfactant[J].Colloids and Surfaces, A. Physicochemical and Engineering Aspects,2010(1/3):172-176. |
[15] | Jian-Shu Kang .Effect of Silane Modified SiO_2 Particles on Poly(M MA-HEMA) Soap-free Emulsion Polymerization[J].Iranian polymer journal,2009(12):927-935. |
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