Facile synthesis of controlled‐structure primary amine‐based methacrylamide polymers via the reversible addition‐fragmentation chain transfer process

Abstract

We report here a novel direct method for the syntheses of primary aminoalkyl methacrylamides that requires mild reagents and no protecting group chemistry. The reversible addition‐fragmentation chain transfer polymerization (RAFT) of the aminoalkyl methacrylamide revealed to be highly efficient with 4‐cyanopentanoic acid dithiobenzoate (CTP) as chain transfer agent and 4,4′‐azobis(4‐cyanovaleric acid) (ACVA) as initiator. Cationic amino‐based homopolymers of reasonably narrow polydispersities (Mw/Mn < 1.30) and predetermined molecular weights were obtained without recourse to any protecting group chemistry. A range of block and random copolymers were also synthesized via the RAFT process. The homopolymers and copolymers were characterized by aqueous conventional and triple detection gel permeation chromatography systems. Furthermore, the primary amine‐based methacrylamide monomers and polymers revealed to be highly stable both with the primary amino group in the protonated and deprotonated form. We have also demonstrated that stabilized gold nanoparticles can be generated with the RAFT‐synthesized amine‐based polymers via a photochemical process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4984–4996, 2008

Living Radical Polymerization by the RAFT Process - A Second Update

“…Recently, several groups have reported that the polymerization of monomers with primary amine functionality (273)(274)(275)(276) (Table 16) can be effectively controlled with the monomer as the ammonium salt and with no or minimal loss of the RAFT end-group. [90,152,153,166] Some of the more exotic monomer subjected to RAFT polymerization are included in the tables that follow. They include methacrylates (Table 17), acrylates (Table 18), methacrylamides (Table 19), acrylamides derived from amino acids (Table 20), other acrylamides (Table 21), St derivatives (Table 22), and vinyl monomers (Table 23) Table 20).…”

“…In the case of bis-RAFT agents sequential polymerization of two monomers will yield a triblock. [269] BA [270] MA [270] NIPAM [269,[271][272][273] 420 [274] BA [281] DA [281] St [71,275] 2VP [276] NVP [103] NIPAM/274 [153] DEHEA [280] MA [281] TMAPMA/PEGMA/NIPAM [277] (PEGMA/320) [165] tBA [280] BA/AA [279] (PEGMA/344) [165] 331 [159] AEMA/325/328 [278] DEHEA-b-ODA [280] DMAM-b-331 [159] DMAM-b-331-b-NIPAM [159] DEHEA-b-tBA [280] NIPAM-b-DMAM [272] 2VP-b-EA [276] tBA-b-DEHEA [280] AEME/328/342 [278] 105 [282] [282] PEGA-b-St [282] 106 [188] [188] EHA-b-MA [188] S S S…”

“…The use of macro-RAFT agents as stabilizers in 'surfactantless' emulsion polymerization, [145,181,225,287,300,310,341,393,[443][444][445][446] miniemulsion polymerization, [124,181] suspension polymerization [381] and non-aqueous dispersion polymerization in both organic media, [188] and in supercritical CO 2 [353,389,447,448] [90,451] O O ϩ NH 3 Cl Ϫ APMAM 274 [152,153,168] Cl Ϫ O HN H 3 N ϩ AEMAM 275 [153] ϩ NH 3 Cl Ϫ O HN 276 [166] NH 3 Cl Ϫ O HN N N N ϩ has gained popularity. Particle nucleation and growth during RAFT emulsion polymerization of St and BA mediated by macro-RAFT agents of various compositions has been studied by calorimetry.…”

“…BMA [139] MAA [140] MMA [64,141] AEMA [90,142] DEGMA [141] DMAEMA [143] DPAEMA [144] MAA [145] PEGMA [144,[146][147][148] 383 [149] DMAM [150] NIPAM [151] 274 [152,153] 325 [154] 326 [154] APMAM-b-NIPAM [89,152] AEMAM [153] St [155] 274 [153] 275 [153] 285 [156] 286 [156] 289 [157] 292 [158] 304 [140] 305 [140] 331 [159] 329 [140] 327 [157] 380 [160] 391 [161,162] 389 [104] (390) [104] 416 [163,164] MAA-b-280 [145] BMA-b-MPC [139] PEGMA/ 320 [165] PEGMA/344 [165] DEGMA-b-384 [141] MMA-b-384 …”

Cationic Poly(2-aminoethylmethacrylate) and Poly(N-(2-aminoethylmethacrylamide) Modified Cellulose Nanocrystals: Synthesis, Characterization, and Cytotoxicity

“…AEMA hydrochloride was synthesized according to a reported mild and protecting-group-free method with slight modifications. 38 Ethylenediamine (16 mL, 239 mmol) in MeOH (100 mL) was added to a stirred solution of ethylenediamine hydrochloride (30 g, 226 mmol) in distilled water (100 mL) at 0°C. The resulting mixture was stirred for 1 h. Methacrylic anhydride (68 mL, 459 mmol) and a few crystals of hydroquinone in MeOH (50 mL) were subsequently added dropwise to the reaction mixture.…”