High density cationic polymer brushes from combined “click chemistry” and RAFT‐mediated polymerization

A simple method for preparing cationic poly[(ar‐vinylbenzyl)trimethylammonium chloride)] [poly(VBTAC)] brushes was used by combined technology of “click chemistry” and reversible addition‐fragmentation chain transfer (RAFT) polymerization. Initially, silicon surfaces were modified with RAFT chain transfer agent by using a click reaction involving an azide‐modified silicon wafer and alkyne‐terminated 4‐cyanopentanoic acid dithiobenzoate (CPAD). A series of poly(VBTAC) brushes on silicon surface with different molecular weights, thicknesses, and grafting densities were then synthesized by RAFT‐mediated polymerization from the surface immobilized CPAD. The immobilization of CPAD on the silicon wafer and the subsequent polymer formation were characterized by X‐ray photoelectron spectroscopy, water contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, atomic force microscopy, and ellipsometry analysis. The addition of free CPAD was required for the formation of well‐defined polymer brushes, which subsequently resulted in the presence of free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. In addition, by varying the polymerization time, we were able to obtain poly(VBTAC) brushes with grafting density up to 0.78 chains/nm² with homogeneous distributions of apparent needle‐like structures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of surface‐initiated polymer brushes on silicon substrates by reversible addition fragmentation chain transfer polymerization

Polymer brushes were prepared by using the reversible addition fragmentation chain transfer (RAFT) technique. The silicon substrates (Si (111) surface) were modified with ethyl xanthate groups which were introduced by the treatment of Si (111) surface with sodium ethyl xanthate. The polymer brushes were then prepared under RAFT conditions from the Si (111) wafer. Its “living” characteristics were determined by a series of characterizations including gel permeation chromatography (GPC), ellipsometry, and contact angle measurements. The results showed a well‐defined graft layer consisting of polymer brushes with low‐polydispersity could be prepared directly on Si (111)‐X surface (where X represents an ethyl xanthate groups). The structure of the polymer brushes was characterized and confirmed with the surface sensitive techniques such as X‐ray photoelectron spectroscopy (XPS) and scanning probe microscopy (SPM). Copyright © 2007 John Wiley & Sons, Ltd.     

Stimuli‐responsive diblock copolymer brushes via combination of “click chemistry” and living radical polymerization

pH‐ and temperature‐responsive poly(N‐isopropylacrylamide‐block?4‐vinylbenzoic acid) (poly(NIPAAm‐b‐VBA)) diblock copolymer brushes on silicon wafers have been successfully prepared by combining click reaction, single‐electron transfer‐living radical polymerization (SET‐LRP), and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. Azide‐terminated poly(NIPAAm) brushes were obtained by SET‐LRP followed by reaction with sodium azide. A click reaction was utilized to exchange the azide end group of a poly(NIPAAm) brushes to form a surface‐immobilized macro‐RAFT agent, which was successfully chain extended via RAFT polymerization to produce poly(NIPAAm‐b‐VBA) brushes. The addition of sacrificial initiator and/or chain‐transfer agent permitted the formation of well‐defined diblock copolymer brushes and free polymer chains in solution. The free polymer chains were isolated and used to estimate the molecular weights and polydispersity index of chains attached to the surface. Ellipsometry, contact angle measurements, grazing angle‐Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy were used to characterize the immobilization of initiator on the silicon wafer, poly(NIPAAm) brush formation via SET‐LRP, click reaction, and poly(NIPAAm‐b‐VBA) brush formation via RAFT polymerization. The poly(NIPAAm‐b‐VBA) brushes demonstrate stimuli‐responsive behavior with respect to pH and temperature. The swollen brush thickness of poly(NIPAAm‐b‐VBA) brush increases with increasing pH, and decreases with increasing temperature. These results can provide guidance for the design of smart materials based on copolymer brushes. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2677–2685     

Temperature‐Responsive Glycopolymer Brushes Synthesized via RAFT Polymerization Using the Z‐group Approach

Summary: Stimuli‐responsive glycopolymer brushes composed of N‐acryloyl glucosamine (AGA) and N‐isopropylacrylamide (NIPAAm) were prepared using RAFT polymerization. The RAFT agent was immobilized on the surface of a treated silicon waver via covalent attachment using the Z‐group. PAGA and PNIPAAm brushes showed a linear increase in brush thickness with the consumption of monomer in solution. The polymers generated in solution confirm the living behavior with the molecular weight increasing linearly with monomer conversion while the molecular weight distribution remains narrow. Additionally, the ability of PAGA brushes to grow further in the presence of NIPAAm reveals the presence of an active RAFT end group indicative of a living system. PAGA and PNIPAAm homopolymer brushes up to 30 nm were grown using this technique. PAGA brushes were utilized for further chain extension to generate stimuli‐responsive brushes with block structures of PAGA and PNIPAAm. The PAGA‐block‐PNIPAAm brushes were found to grow in size with the consumption of NIPAAm. Contact angle measurements confirm the suggested mechanism showing that the second monomer is incorporated between the first layer and the silicon surface as expected using the Z‐group approach.

Structure of the stimuli‐responsive glycopolymer brushes.     

Effect of rate retardation in RAFT grafting polymerization from silicon wafer surface

Polystyrene and poly(butyl acrylate) were grafted from silicon wafer surface by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Three RAFT agents were immobilized onto silicon wafer through their leaving/initiating groups (R group). Grafting polymerization of butyl acrylate (BA) and styrene (St) was then carried out from the immobilized RAFT agents. The immobilization of the RAFT agents and the subsequent grafting polymerization of St and BA were evaluated by ellipsometry and X‐ray photoelectron spectroscopy. It was found that type of monomer, structure of RAFT agent, and local RAFT concentration on the surface have dramatic influences on the thickness of grafted polymer layer. The grafting polymerization with more severe rate retardation effect yielded thinner polymer films on the silicon wafer. Selection of a RAFT agent with little rate retardation was critical in the grafting polymerization to achieve thick films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 970–978, 2008     

Synthesis of cationic N‐[3‐(dimethylamino)propyl]methacrylamide brushes on silicon wafer via surface‐initiated RAFT polymerization

Surface‐initiated reversible addition‐fragmentation chain transfer (SI‐RAFT) polymerization of N‐[3‐(dimethylamino)propyl]methacrylamide (DMAPMA) on the silicon wafer was conducted in attempt to create controllable cationic polymer films. The RAFT agent‐immobilized substrate was prepared by the silanization of hydroxyl groups on silicon wafer with 3‐aminopropylthriethoxysilane (APTS) and by the amide reaction of amine groups of APTS with ester groups of 4‐cyano‐4‐((thiobenzoyl) sulfanyl) pentanoic succinimide ester (CPSE); followed by the RAFT polymerization of DMAPMA using a “free” RAFT agent, that is, 4‐cyanopentanoic acid dithiobenzoate (CPAD) and an initiator, that is, 4,4′‐azobis‐4‐cyanopentanoic acid (CPA). The formation of homogeneous tethered poly(N‐[3‐(dimethylamino)propyl]methacrylamide) [poly(DMAPMA)] brushes, whose thickness can be tuned by reaction time varying, is evidenced by using the combination of grazing angle attenuated total reflectance‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, and water contact‐angle measurements. The calculation of grafting parameters from the number‐average molecular weight, M _n (g/mol) and ellipsometric thickness, h (nm) values indicated the synthesis of densely grafted poly(DMAPMA) films and allowed us to predict a polymerization time for forming a “brush‐like” conformation for the chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of dual‐functional poly(6‐azidohexylmethacrylate) brushes by a RAFT agent carrying carboxylic acid end groups

Novel types of dual‐functional surface‐attached polymer brushes were developed by interface‐mediated reversible addition‐fragmentation chain transfer (RAFT) polymerization of 6‐azidohexylmethacrylate using the surface‐immobilized RAFT agent and the free initiator. The interface‐mediated RAFT polymerization produced silicon substrate coated with dual‐functional (azido groups from monomer and carboxylic acid groups from RAFT agent) poly(6‐azidohexylmethacrylate) [poly (AHMA)] with a grafting density as high as 0.59 chains/nm². Dual‐functional polymer brushes can represent an attractive chemical platform to deliberately introduce other molecular units at specific sites. The azido groups of the poly(AHMA) brushes can be modified with alkyl groups via click reaction, known for their DNA hybridization, while the carboxylic acid end groups can be reacted with amine groups via amide reaction, known for their antifouling properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1696–1706     

Controlled grafting from poly(vinylidene fluoride) films by surface‐initiated reversible addition–fragmentation chain transfer polymerization

A reversible addition–fragmentation chain transfer (RAFT) polymerization technique was applied to graft polymerize brushes of poly(methyl methacrylate) (PMMA) and poly(poly(ethylene glycol) monomethacrylate) (PPEGMA) from poly(vinylidene fluoride) (PVDF) surfaces. PVDF surfaces were exposed to aqueous LiOH, followed by successive reductions with NaBH₄ and DIBAL‐H to obtain hydroxyl functionality. Azo‐functionalities, as surface initiators for grafting, were immobilized on the PVDF surfaces by esterification of 4,4′‐azobis(4‐cyanopentanoic acid) and the surface hydroxyl groups. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance‐FTIR spectroscopy, and atomic force microscopy. Kinetics studies revealed a linear increase in the graft concentration of PMMA and PPEGMA with the reaction time, indicating that the chain growth from the surface was consistent with a “controlled” or “living” process. The living chain ends were used as the macroinitiator for the synthesis of diblock copolymer brushes. Water contact angles on PVDF films were reduced by surface grafting of PEGMA and MMA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3071–3082, 2006     

Photoiniferter surface grafting of poly(methyl acrylate) using xanthates

The UV‐induced and catalyst‐free photoiniferter surface grafting using xanthate RAFT agents is studied. First, a novel silane containing a xanthate RAFT agent moiety is synthesized and successfully grafted onto a silicon wafer as confirmed by secondary ion mass spectrometry (SIMS). Next, using only methyl acrylate, solvent and UV light (365 nm) polymer brushes are grafted rapidly from the surface with film thicknesses up to 25 nm reached within half an hour. The obtained polymer films are thoroughly analyzed by X‐ray photoelectron spectroscopy (XPS), ToF‐SIMS, and AFM. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2002–2007     

Functionalization and patterning of reactive polymer brushes based on surface reversible addition and fragmentation chain transfer polymerization

We present the synthesis of reactive polymer brushes prepared by surface reversible addition–fragmentation chain transfer polymerization of pentafluorophenyl acrylate. The reactive ester moieties can be used to functionalize the polymer brush film with virtually any functionality by simple post‐polymerization modification with amines. Dithiobenzoic acid benzyl‐(4‐ethyltrimethoxylsilyl) ester was used as the surface chain transfer agent (S‐CTA) and the anchoring group onto the silicon substrates. Reactive polymer brushes with adjustable molecular weight, high grafting density, and conformal coverage through the grafting‐from approach were obtained. Subsequently, the reactive polymer brushes were converted with amino‐spiropyrans resulting in reversible light‐responsive polymer brush films. The wetting behavior could be altered by irradiation with ultraviolet (UV) or visible light. Furthermore, a patterned surface of polymer brushes was obtained using a lithography technique. UV irradiation of the S‐CTA‐modified substrates leads to a selective degradation of S‐CTA in the exposed areas and gives patterned activated polymer brushes after a subsequent RAFT polymerization step. Conversion of the patterned polymer brushes with 5‐((2‐aminoethyl)amino)naphthalene‐1‐sulfonic acid resulted in patterned fluorescent polymer brush films. The utilization of reactive polymer brushes offers an easy approach in the fabrication of highly functional brushes, even for functionalities whose introduction is limited by other strategies. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Surface‐initiated single‐electron transfer reversible addition–fragmentation chain transfer polymerization of 2‐hydroxyethyl acrylamide on silicon substrate at ambient temperature

2‐Hydroxyethyl acrylamide was successfully polymerized via single‐electron transfer initiation on the silicon surface and propagation through the reversible addition–fragmentation chain transfer (SET‐RAFT) polymerization at ambient temperature for different polymerization times. This work is the first time application of the surface‐initiated SET‐RAFT mechanism to afford the preparation of well‐defined poly(2‐hydroxyethyl acrylamide) [poly(HEAAm)] brushes at ambient temperature. The polymerization was well controlled and produced poly(HEAAm) brushes on the silicon surface with a well‐defined target molecular weight. The controlled nature of the polymerization was further demonstrated in the presence of sulfur atoms at the chain ends in X‐ray photoelectron spectroscopy experiments. The grafting density (σ, chains nm^?2) and the average distance between grafting points (D, nm) were found to be 0.42 chains nm^?2 and 1.74 nm, respectively, indicating moderate grafting density. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1140–1146     

Synthesis and stability of BODIPY‐based fluorescent polymer brushes at different pHs

We report a simple strategy for the grafting of poly(methacrylic acid) [poly(MAA)] brushes from silicon substrate by surface‐initiated RAFT polymerization and the subsequent coupling of BODIPY to these brushes to render them fluorescent. The poly(MAA) brushes were first generated by functionalization of hydrogen‐terminated silicon substrate with methyl‐10‐undecenoate which both leads to the formation of an organic layer covalently linked to the surface via Si? C bonds without detectable reaction of the carboxylate groups and couples to the polymerization initiator, followed by surface‐initiated RAFT polymerization of tert‐butyl methacrylate from these substrate‐bound initiator centers, and finally conversion of tert‐butyl groups to carboxylic acid groups. The poly(MAA) brushes were then made fluorescent by grafting a BODIPY derivative via an ester linkage. The stability of the BODIPY‐based fluorescent polymer brushes in buffer solutions at pH 6.0 to 12.0 with added salt was investigated by ellipsometry, fluorescence microscopy, grazing angle‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy. The results of these measurements indicated that the organic molecule‐initiator bond (ester linkage) is unstable and can be hydrolyzed resulting in detaching of the immobilized polymer from the silicon substrate. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3586–3596     

RAFT‐mediated synthesis of poly[(oligoethylene glycol) methyl ether acrylate] brushes for biological functions

The synthesis of poly[(oligoethylene glycol) methyl ether acrylate] [poly(OEGA)] brushes was achieved via reversible addition‐fragmentation chain transfer (RAFT) polymerization and used to selectively immobilize streptavidin proteins. Initially, gold surfaces were modified with a trithiocarbonate‐based RAFT chain transfer agent (CTA) by using an ester reaction involving a gold substrate modified with 11‐mercapto‐1‐undecanol and bis(2‐butyric acid)trithiocarbonate. poly(OEGA) brushes were then prepared via RAFT‐mediated polymerization from the surface‐immobilized CTA. The immobilization of CTA on the gold surface and the subsequent polymer formation were followed by ellipsometry, X‐ray photoelectron spectroscopy, grazing angle‐Fourier transform infrared spectroscopy, atomic force microscopy, and water contact‐angle measurements. RAFT‐mediated polymerization method gave CTA groups to grafted poly(OEGA) termini, which can be converted to various biofunctional groups. The terminal carboxylic acid groups of poly(OEGA) chains were functionalized with amine‐functionalized biotin units to provide selective attachment points for streptavidin proteins. Fluorescence microscopy measurements confirmed the successful immobilization of streptavidin molecules on the polymer brushes. It is demonstrated that this fabrication method may be successfully applied for specific protein recognition and immobilization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Construction of hydroxyl‐terminated poly(N‐isopropylacrylamide) brushes on silicon wafer via surface‐initiated atom transfer radical polymerization

Surface‐initiated atom transfer radical polymerization (SI‐ATRP) of N‐isopropylacrylamide (NIPAM) on silicon wafer in the presence of 2‐mercaptoethanol (ME) chain transfer agent was conducted in attempt to create controllable hydroxyl‐terminated brushes. The initiator‐immobilized substrate, was prepared by the esterification of hydroxyl groups on silicon wafer with 2‐bromopropionyl bromide (2‐BPB); followed by the ATRP of NIPAM using a catalyst system, that is, Cu(I)Br/2,2′‐bipyridine (2,2′‐bpy) and a chain transfer agent, that is, ME. The formation of homogeneous tethered poly(N‐isopropylacrylamide) (poly(NIPAM) brushes with hydroxyl end‐group, whose thickness can be tuned by chancing ME concentration, is evidenced by using the combination of grazing angle attenuated total reflectance‐Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, ellipsometry, atomic force microscopy, gel permeation chromatography, and water contact‐angle measurements. The calculation of grafting parameters from experimental measurements indicated the synthesis of densely grafted poly(NIPAM) films with hydroxyl end‐group on silicon wafer and allowed us to predict a ME concentration for forming a “brush” conformation for the chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3880–3887, 2010     

甲基丙烯酸甲酯/苯乙烯在硅片表面的RAFT接枝聚合

将3-(2-二硫代苯甲酸基丙酰氧基)丙基二甲基甲氧基硅烷化学键合于硅片表面.以甲基丙烯酸甲酯和苯乙烯为单体,在硅片表面进行可逆加成-断裂链转移(RAFT)接枝聚合.X-射线光电子能谱仪证实聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(PS)、苯乙烯/甲基丙烯酸甲酯的共聚物(poly(MMA-co-St))都接枝到硅片表面.但3个体系表现出不同的性质,甲基丙烯酸甲酯的RAFT聚合可控性差,分子量比设计分子量大得多,分子量分布指数宽,接枝密度仅为0·03chains/nm2;苯乙烯均聚合的活性/可控性好、分子量分布窄,接枝密度提高到0·21chains/nm2;共聚合体系综合了两个均聚体系的优点,分子量分布较窄,接枝密度最高为0·31chains/nm2,聚合物膜厚随转化率、数均分子量基本呈线性增长.     

Synthesis and characterization of surface-initiated polymer brush prepared by reverse atom transfer radical polymerization

Surface-initiated reverse atom transfer radical polymerization (reverse ATRP) technique was used to synthesize well-controlled nanostructure of polymer brushes from silicon wafer. Kinetic studies revealed a linear increase in polymer film thickness with reaction time, indicating that chain growth from surface was a controlled process with a “living” characteristic. This technique provides a simple and efficient approach to create various nanostructures of polymer brushes potentially used for designing nanodevices. Analysis of the polymer brush layers was conducted using ellipsometry, XPS, AFM and contact angle measurements, respectively.     

Electropatterning of Binary Polymer Brushes by Surface‐initiated RAFT and ATRP

A new, simple, and effective method for preparing binary patterned brushes by electrodeposition and self‐assembly is presented. The technique involves the use of electrochemistry to immobilize a chain transfer agent (CTA) on a patterned conducting substrate that mediate surface‐initiated polymerization (SIP) through a reversible addition–fragmentation chain transfer (RAFT) process. The non‐electropatterned surfaces were then backfilled with self‐assembly of an atom transfer radical polymerization (ATRP) silane initiator where the polymerization of the next brush was initiated. The use of techniques such as RAFT and ATRP is well known to give a controlled polymerization mechanism, which would be of great advantage in generating binary patterned brushes. FT‐IR imaging was used to analyze these films.

     

Ion‐exchanger synthesis using reversible addition‐fragmentation chain transfer polymerization

An ion‐exchanger with polyanionic molecular brushes was synthesized by a “grafting from” route based on “surface‐controlled reversible addition‐fragmentation chain transfer polymerization” (RAFT). The RAFT agent, PhC(S)SMgBr was covalently attached to monodisperse‐porous poly(dihydroxypropyl methacrylate‐co‐ethylene dimethacrylate), poly(DHPM‐co‐EDM) particles 5.8 μm in size. The monomer, 3‐sulfopropyl methacrylate (SPM), was grafted from the surface of poly(DHPM‐co‐EDM) particles with an immobilized chain transfer agent by the proposed RAFT protocol. The degree of polymerization of SPM (i. e. the molecular length of the polyanionic ligand) on the particles was controlled by varying the molar ratio of monomer/RAFT agent. The particles carrying polyanionic molecular brushes with different lengths were tested as packing material in the separation of proteins by ion exchange chromatography. The columns packed with the particles carrying relatively longer polyanionic ligands exhibited higher separation efficiency in the separation of four proteins. Plate heights between 130–200 μm were obtained. The ion‐exchanger having poly‐(SPM) ligand with lower degree of polymerization provided better peak‐resolutions on applying a salt gradient with higher slope. The molecular length and the ion‐exchanger group content of polyionic ligand were adjusted by controlling the degree of polymerization and the grafting density, respectively. This property allowed control of the separation performance of the ion‐exchanger packing.     

Branched fluoropolymer-Si hybrids via surface-initiated ATRP of pentafluorostyrene on hydrogen-terminated Si(100) surfaces

Linear, branched, and arborescent fluoropolymer-Si hybrids were prepared via surface-initiated atom transfer radical polymerization (ATRP) from the 4-vinylbenzyl chloride (VBC) inimer and ClSO(3)H-modified VBC that were immobilized on hydrogen-terminated Si(100), or Si-H, surfaces. The simple approach of UV-induced coupling of VBC with the Si-H surface provided a stable, Si-C bonded monolayer of "monofunctional" ATRP initiators (the Si-VBC surface). The aromatic rings of the Si-VBC surface were then sulfonated by ClSO(3)H to introduce sulfonyl chloride (-SO(2)Cl) groups and to give rise to a monolayer of "bifunctional" ATRP initiators. Kinetics study indicated that the chain growth of poly(pentafluorostyrene) from the functionalized silicon surfaces was consistent with a "controlled" or "living" process. The chemical composition and functionality of the silicon surface were tailored by the well-defined linear and branched fluoropolymer brushes. Atomic force microscopy images revealed that the surface-initiated ATRP of pentafluorostyrene (PFS) had proceeded uniformly on the Si-VBC surface to give rise to a dense and molecularly flat surface coverage of the linear brushes. The uniformity of surfaces with branched brushes was controlled by varying the feed ratio of the monomer and inimer (VBC in the present case). The living chain ends on the functionalized silicon surfaces were used as the macroinitiators for the synthesis of diblock copolymer brushes, consisting of the PFS and methyl methacrylate polymer blocks.     

Macromolecular brushes synthesized by “grafting from” approach based on “click chemistry” and RAFT polymerization

Well‐defined macromolecular brushes with poly(N‐isopropyl acrylamide) (PNIPAM) side chains on random copolymer backbones were synthesized by “grafting from” approach based on click chemistry and reversible addition‐fragmentation chain transfer (RAFT) polymerization. To prepare macromolecular brushes, two linear random copolymers of 2‐(trimethylsilyloxy)ethyl methacrylate (HEMA‐TMS) and methyl methacrylate (MMA) (poly(MMA‐co‐HEMA‐TMS)) were synthesized by atom transfer radical polymerization and were subsequently derivated to azide‐containing polymers. Novel alkyne‐terminated RAFT chain transfer agent (CTA) was grafted to polymer backbones by copper‐catalyzed 1,3‐dipolar cycloaddition (azide‐alkyne click chemistry), and macro‐RAFT CTAs were obtained. PNIPAM side chains were prepared by RAFT polymerization. The macromolecular brushes have well‐defined structures, controlled molecular weights, and molecular weight distributions (M_w/M_n ≦ 1.23). The RAFT polymerization of NIPAM exhibited pseudo‐first‐order kinetics and a linear molecular weight dependence on monomer conversion, and no detectable termination was observed in the polymerization. The macromolecular brushes can self‐assemble into micelles in aqueous solution. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 443–453, 2010