A di‐tert‐butyl acrylate monomer for controlled radical photopolymerization

Abstract

A new di‐tert‐butyl acrylate (diTBA) monomer for controlled radical polymerization is reported. This monomer complements the classical use of tert‐butyl acrylate (TBA) for synthesis of poly(acrylic acid) by increasing the density of carboxylic acids per repeat unit, while also increasing the flexibility of the carboxylic acid side‐chains. The monomer is well behaved under Cu(II)‐mediated photoinduced controlled radical polymerization and delivers polymers with excellent chain‐end fidelity at high monomer conversions. Importantly, this new diTBA monomer readily copolymerizes with TBA to further the potential for applications in areas such as dispersing agents and adsorbents. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 801–807

Scalable synthesis of an architectural library of well‐defined poly(acrylic acid) derivatives: Role of structure on dispersant performance

“…The short‐armed comb architectures (SC series) identified by the DoE model contain branches of DP n = 2 with varying backbone lengths. These short chain lengths necessitated the development of a novel di‐ tert ‐butyl acrylate monomer 2 (di‐ t ‐BA, Scheme ), which was prepared from inexpensive, commercially available ketoglutaric acid . Comparable reactivity ratios with t ‐BA and negligible differences between the observed incorporation and initial feed ratio of the two monomers allows well‐defined copolymers to be prepared by ATRP .…”

“…These short chain lengths necessitated the development of a novel di‐ tert ‐butyl acrylate monomer 2 (di‐ t ‐BA, Scheme ), which was prepared from inexpensive, commercially available ketoglutaric acid . Comparable reactivity ratios with t ‐BA and negligible differences between the observed incorporation and initial feed ratio of the two monomers allows well‐defined copolymers to be prepared by ATRP . When deprotected, the incorporated di‐ t ‐BA monomer resembles a precise DP 2 branch of PAA, resulting in a series of short‐chain copolymers with varying di‐ t ‐BA incorporation and accurate control of the overall DP n (polymers with backbone DP n of 15, 39, 61, and 100, containing 6, 10, 13, and 31 branches, respectively) (Table , entries SC1, SC2, SC3, SC4, Supporting Information Figs.…”

Low‐Temperature, Rapid Copolymerization of Acrylic Acid and Sodium Acrylate in Water

“…An alternative strategy for the synthesis of well‐defined PAA is to polymerize tert ‐butyl acrylate via ATRP followed by acidic deprotection of the tert ‐butyl esters. However, additional purification steps and the use of organic solvents/reagents render this strategy burdensome . Although NMP and RAFT can directly polymerize AA, these techniques are characterized by long reaction times, lower conversions, and costly reagents, all of which are undesirable from a commercial standpoint.…”

Aqueous reverse iodine transfer polymerization of acrylic acid

“…Controlled radical polymerization (CRP) techniques, such as nitroxide‐mediated polymerization, atom‐transfer radical polymerization (ATRP), and reversible addition‐fragmentation chain transfer (RAFT), developed to mitigate the deleterious side reactions of conventional FRP, can enable the preparation of well‐defined polymeric materials with predefined molar mass, dispersity ( Ð ), and chain‐end functionality . However, few studies have examined the direct CRP of AA under aqueous conditions . Instead, the conventional synthetic route for PAA using CRP typically involves a two‐step process that begins with the polymerization of a protected AA monomer, most commonly tert ‐butyl acrylate, followed by an acid‐mediated (i.e., TFA) deprotection of the tert ‐butyl group to furnish the desired PAA [Fig.…”