Ingénierie des Matériaux Polymères (UMR CNRS 5223), Université Claude Bernard Lyon 1, 15 Boulevard Latarjet, 69622 Villeurbanne Cedex, France.
Langmuir. 2010 Jan 19;26(2):1304-10. doi: 10.1021/la902482q.
A versatile method for the grafting of azide-terminated polymer chains to alkyne-functionalized pseudobrushes by the Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition has been developed. First, poly[(propargyl methacrylate)-r-(glycidyl methacrylate)-r-(methyl methacrylate)] random copolymers with monomer ratios of respectively 27/27/46, 41/31/28, and 45/55/0 were synthesized by RAFT polymerization. Then, dense alkyne-functionalized pseudobrushes were grafted in melt by thermal ring-opening of the glycidyl groups by the silanols from the silicon substrate. Finally, the grafting of tailor-made alpha-methoxy-omega-azido-poly(ethylene glycol)s (M(w) approximately 5000, 20,000, and 50,000 g/mol) by Cu(I)-catalyzed Huisgen 1,3-dipolar cycloaddition was performed in sealed reactors at 60 degrees C for 72 h using a polymer weight fraction of 10% in tetrahydrofuran and Cu(PPh(3))(3)Br/DIPEA as the catalytic system. Alkyne-functionalized pseudobrushes and poly(ethylene glycol) brushes were characterized by ellipsometry, scanning probe microscopy, and water contact angle measurements. This "grafting-to" approach represents a fast and versatile method to provide thick and homogeneous polymer brushes with a high surface coverage. A major benefit of this strategy is the tunable and versatile tethering of alkyne functionalities to silicon substrates using a straightforward spin-coating procedure.
一种通用的方法，用于通过 Cu(I)催化的 Huisgen 1,3-偶极环加成将叠氮端聚合物链接枝到炔基功能化的假刷上，已经被开发出来。首先，通过 RAFT 聚合合成了单体比分别为 27/27/46、41/31/28 和 45/55/0 的聚[(丙烯酰基甲基丙烯酸酯)-r-(甲基丙烯酸缩水甘油酯)-r-(甲基丙烯酸甲酯)]无规共聚物。然后，通过硅烷醇将环氧基团在热熔融中开环，接枝致密的炔基功能化假刷。最后，在密封反应器中，通过 Cu(I)催化的 Huisgen 1,3-偶极环加成，在 60°C 下进行 72 小时，使用四氢呋喃中 10%的聚合物重量分数和 Cu(PPh(3))(3)Br/DIPEA 作为催化体系，接枝定制的α-甲氧基-ω-叠氮聚（乙二醇）（Mw 约为 5000、20000 和 50000 g/mol）。炔基功能化假刷和聚乙二醇刷通过椭圆测量法、扫描探针显微镜和水接触角测量进行了表征。这种“接枝到”方法代表了一种快速而通用的方法，可以提供具有高表面覆盖率的厚而均匀的聚合物刷。该策略的一个主要优点是可以使用简单的旋涂工艺，灵活地将炔基功能团键合到硅基底上。
