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Comparative Aminolysis Kinetics of Different Active Ester Polymer Brush Platforms in Postpolymerization Modification with Primary and Aromatic Amines
- Arnold, Rachelle
M., Sheppard, Gareth R., Locklin, Jason
- Macromolecules 2012 v.45 no.13 pp. 5444-5450
- adenosine monophosphate, aminolysis, aromatic amines, models, polymers
- The kinetics of aminolysis between two different active ester polymer brush platforms, poly(4-pentafluorophenyl acrylate) (poly(PFPA)) and poly(N-hydroxysuccinimide-4-vinyl benzoate) (poly(NHS4VB)), are compared using primary and aromatic amines with varying reactivity toward postpolymerization modification. UV–vis was used to monitor the aminolysis of both brush platforms with 1-aminomethylpyrene (AMP), 1-aminopyrene (AP), and Ru(bpy)₂(phen-5-NH₂)(PF₆) (Ru²⁺A). Using a pseudo-first-order kinetics model, the pseudo-first-order rate constant (k′) was calculated for each system. The k′ of poly(PFPA) modified with AMP, AP, and Ru²⁺A were 2.46 × 10–¹, 5.11 × 10–³, and 2.59 × 10–³ s–¹, respectively, while poly(NHS4VB) can only be functionalized with the alkyl amine, albeit at a slower rate constant, k′ of 3.49 × 10–³ s–¹, compared to that of poly(PFPA) with AMP. The kinetics of surface-initiated photopolymerization of PFPA from oxide surfaces was also investigated as an effective method to control grafting density and film thickness.