Comparative Aminolysis Kinetics of Different Active Ester Polymer Brush Platforms in Postpolymerization Modification with Primary and Aromatic Amines

Abstract

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-NH 2 )(PF 6 ) (Ru 2+ A). Using a pseudo-firstorder kinetics model, the pseudo-first-order rate constant (k′) was calculated for each system. The k′ of poly(PFPA) modified with AMP, AP, and Ru 2+ 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.

Buckling Instabilities in Polymer Brush Surfaces via Postpolymerization Modification

“…Similar kinetic trends have been well described by others for PPM of polymer brushes under good solvent conditions. 44, 45 …”

Multifunctional Surface Manipulation Using Orthogonal Click Chemistry

“…30 Each postpolymerization modification reaction was first carried out on individual substrates to both ensure full functionalization and characterize the rate and extent of each reaction individually. The poly(PFPA) brushes were reacted with a solution containing 40 mM 4-(2-aminoethyl)benzenesulfonyl fluoride hydrochlor- Langmuir XXXX, XXX, XXX−XXX ide (PEFABLOC) in DMF with 80 mM TEA and 40 mM ODIBO-amine in DMF with 80 mM TEA.…”

Facile method towards functionalization of partially fluorinated polyarylethers via sequential post-polymerization modification

“…To ensure a successful PPM, the polymer backbone should tolerate the post-polymerization modification reaction conditions and modification reactions between reactive units in the side chains of polymer precursor and functional molecules should be very efficient and specific [18]. A number of recent and different chemistries have been employed for PPM, such as thiol-ene coupling reaction [19,20], Diels-Alder cycloaddition reaction [21,22], Michael addition reaction [23], active ester chemistry [24][25][26], and azide-alkyne click reaction [27]. Up to now, various kinds of functional polymers were prepared by PPM [28].…”