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     

Dibenzyl trithiocarbonate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile

Reversible addition–fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain‐transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain‐transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain‐transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry and ¹H NMR analyses have confirmed the chain‐end functionality of the resultant polymer. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 490–498, 2006     

Controlled radical polymerization of N‐acryloylglycinamide and UCST‐type phase transition of the polymers

N‐Acryloylglycinamide was polymerized via the reversible addition fragmentation transfer process without sacrificing its key property, the upper critical solution temperature in water. This could be achieved by choosing an appropriate nonionic initiator [2,2′‐azobis(4‐methoxy‐2.4‐dimethyl valeronitrile) (V‐70)] and nonionic chain‐transfer agent (cyanomethyl dodecyl trithiocarbonate). A good molar mass control was accomplished as proved by the linear increase of molar mass with conversion, a chain extension experiment, and low dispersity. The influence of molar mass, polymer end groups, or salt concentration on the cloud point was analyzed by turbidimetry. Polymer end groups exerted a distinct effect on the cloud points, whereas the influence increased with decreasing molar masses. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Polymer having a trithiocarbonate moiety in the main chain: Application to reversible addition–fragmentation chain transfer controlled thermal and photoinduced monomer insertion polymerizations

A polymer having a trithiocarbonate moiety in its main chain was synthesized with a cyclic, five‐membered dithiocarbonate as a building block. The trithiocarbonate in the polymer acted as a reversible addition–fragmentation chain transfer reagent to mediate a controlled insertion polymerization of styrene into the polymer main chain, giving the corresponding sequence‐ordered polymer having a well‐defined polystyrene segment in the main chain. During the polymerization, the polystyrene segment in the main chain gained its molecular weight, which maintained a linear relationship with the conversion of styrene. The insertion polymerization of styrene was induced not only thermally but also by ultraviolet irradiation. This photoinduced polymerization was well controlled by the trithiocarbonate moiety to give the corresponding polymer, whose structure was virtually the same as that obtained by the thermal polymerization. © 2006 Wiley Periodicals, Inc. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6324–6331, 2006     

Surface‐initiated nitroxide‐mediated polymerization of sodium 4‐styrene sulfonate from latex particles

In this study, we report the use of a double‐headed dialkoxyamine trithiocarbonate ( I ) capable of acting as chain transfer agent via reversible addition‐fragmentation chain transfer polymerization or as initiator via nitroxide‐mediated polymerization. It is worth mentioning that I was revealed as an effective dual chain transfer agent in the synthesis of multiblock copolymers via bulk and emulsion processes. In this article, we report the employing of I in dispersed systems to obtain amphiphilic multiblock copolymers and latexes. In this case, a water soluble macroagent of PAA previously synthetized was used in disperse media using a mixture of methanol/water (70:30, w/w). Stable latexes were obtained via polymerization‐induced self‐assembly and surface‐initiated polymerization of SSNa from alkoxyamine‐functionalized latex PAA‐b‐PS‐b‐PAA was also obtained © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 437–444     

Synthesis and characterization of fluorescence end‐labeled polystyrene via reversible addition‐fragmentation chain transfer (RAFT) polymerization

Fluorescence end‐labeled polystyrene (PS) with heteroaromatic carbazole or indole group were prepared conveniently via reversible addition‐fragmentation chain transfer (RAFT) polymerization using dithiocarbamates, ethyl 2‐(9H‐carbazole‐9‐carbonothioylthio)propanoate (ECCP) and benzyl 2‐phenyl‐1H‐indole‐1‐carbodithioate (BPIC) as RAFT agents. The end functionality of obtained PS with different molecular weights was high. The steady‐state and the time‐resolved fluorescence techniques had been used to study the fluorescence behaviors of obtained end‐labeled PS. The fluorescence of dithiocarbamates resulting PS in solid powder cannot be monitored; however, they exhibited structured absorptions and emissions in solvent DMF and the fluorescence lifetimes of PS had no obvious change with molecular weights increasing. These observations suggested that the polymer chains were possibly stretched adequately in DMF, that is, the fluorescence end group was exposed into solvent molecules and little quenching of excited state occurred upon incorporation into polymer chain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6198–6205, 2008     

Copolymerization of allyl butyl ether with acrylates via controlled radical polymerization

The atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer (RAFT) of acrylates (methyl acrylate and butyl acrylate) with allyl butyl ether (ABE) were investigated. Well‐defined copolymers containing almost 20 mol % ABE were obtained with ethyl‐2‐bromoisobutyrate as an initiator. Narrow molar mass distributions (MMDs; polydispersity index ≤ 1.3) were obtained from the ATRP experiments, and they suggested conventional ATRP behavior, with no peculiarities caused by the incorporation of ABE. The comparable free‐radical (co)polymerizations resulted in broad MMDs. Increasing the fraction of ABE in the monomer feed led to an increase in the level of incorporation of ABE in the copolymer, at the expense of the overall conversion. Similarly, RAFT copolymerizations with S,S′‐bis(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate also resulted in excellent control of the polymerization with a significant incorporation of ABE within the copolymer chains. The formation of the copolymer was confirmed with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF MS). From the obtained MALDI‐TOF MS spectra for the ATRP and RAFT systems, it was evident that several units of ABE were incorporated into the polymer chain. This was attributed to the rapidity of the cross‐propagation of ABE‐terminated polymeric radicals with acrylates. This further indicated that ABE was behaving as a comonomer and not simply as a chain‐transfer agent under the employed experimental conditions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3271–3284, 2004     

Synthesis of thermo‐responsive 4‐arm star‐shaped porphyrin‐centered poly(N,N‐diethylacrylamide) via reversible addition‐fragmentation chain transfer radical polymerization

Tetrafunctional porphyrins‐containing trithiocarbonate groups were synthesized by an ordinary esterification method. This tetrafunctional porphyrin (TPP‐CTA) could be used as a chain transfer agent in a controlled reversible addition‐fragmentation chain transfer (RAFT) radical polymerization to prepare well‐defined 4‐arm star‐shaped polymers. N,N‐Diethylacrylamide was polymerized using TPP‐CTA in 1,4‐dioxane. Poly(N,N‐diethylacrylamide) (PDEA) is known to be a thermo‐responsive polymer, and exhibits a lower critical solution temperature (LCST) in water. The star‐shaped PDEA polymer (TPP‐PDEA) was therefore also thermo‐responsive, as expected. The LCST of this polymer depended on its concentration in water, as confirmed by turbidity, dynamic light scattering (DLS), static light scattering (SLS), and ¹H NMR measurements. The porphyrin cores were compartmentalized in PDEA shells in aqueous media. Below the LCST, the fluorescence intensity of TPP‐PDEA was about six times larger than that of a water‐soluble low molecular weight porphyrin compound (TSPP), whose fluorescence intensity was independent of temperature. Above the LCST, the fluorescence intensity of TPP‐PDEA decreased, while the intensity was about three times higher than that of TSPP. These observations suggested that interpolymer aggregation occurred due to the hydrophobic interactions of the dehydrated PDEA arm chains above the LCST, with self‐quenching of the porphyrin moieties arising from these interactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Synthesis of hydrophilic/CO2‐philic poly(ethylene oxide)‐b‐poly(1,1,2,2‐tetrahydroperfluorodecyl acrylate) block copolymers via controlled/living radical polymerizations and their properties in liquid and supercritical CO2

Hydrophilic/CO₂‐philic poly(ethylene oxide)‐b‐poly(1,1,2,2‐tetrahydroperfluorodecyl acrylate) block copolymers were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization, iodine transfer polymerization (ITP), and atom transfer radical polymerization (ATRP) in the presence of either degenerative transfer agents or a macroinitiator based on poly(ethylene oxide). In this work, both RAFT and ATRP showed higher efficiency than ITP for the preparation of the expected copolymers. More detailed research was carried out on RAFT, and the living character of the polymerization was confirmed by an ultraviolet (UV) analysis of the ? SC(S)Ph or ? SC(S)S? C₁₂H₂₅ end groups in the polymer chains. The quantitative UV analysis of the copolymers indicated a number‐average molecular weight in good agreement with the value determined by ¹H NMR analysis. The properties of the macromolecular surfactants were investigated through the determination of the cloud points in neat liquid and supercritical CO₂ and through the formation of water‐in‐CO₂ emulsions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2405–2415, 2004     

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     

Automated parallel investigations/optimizations of the reversible addition‐fragmentation chain transfer polymerization of methyl methacrylate

Poly(methyl methacrylate)s were successfully synthesized in a controlled fashion via reversible addition‐fragmentation chain transfer polymerizations utilizing an automated synthesizer. Sixteen polymers were synthesized in a parallel way utilizing the Chemspeed Accelerator? SLT100 to investigate the reproducibility and the control over the polymerizations. The obtained polymers were characterized by gel permeation chromatography (GPC) and automated MALDI TOFMS measurements, thereby proving the reproducibility and controllability of the investigated automated setup. Furthermore, temperature optimization reactions were performed utilizing an individually heatable reactor block. Moreover, to demonstrate the presence of active polymer chains in the reaction mixture, chain extension polymerizations were performed on the automated synthesizer. The results obtained from these chain extension experiments demonstrate the possibility to design well‐defined A‐b‐B block copolymers with different monomers as building units. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5775–5783, 2004     

Controlled radical polymerization of fluorinated methacrylates in supercritical CO2: Synthesis and application of a novel RAFT agent

A novel fluorinated reversible addition‐fragmentation chain transfer agent, S,S‐di‐pentaflourobenzyl trithiocarbonate (DPFBTTC), was designed and synthesized. DPFBTTC and dibenzyl trithiocarbonate (DBTTC) were applied in the polymerization of dodecafluoroheptyl methacrylate (DFHMA), hexafluorobutyl methacrylate (HFBMA), and trifluoroethyl methacrylate (TFEMA) in scCO₂. The polymerization processes were monitored using a high‐pressure in‐situ NIR, through which the polymerization kinetics was investigated and the controllability of DPFBTTC was evaluated. It is found that the controllability of DPFBTTC presented in the order of DFHMA > HFBMA > TFEMA, indicating that DPFBTTC may fit for the controlled polymerization of the highly fluorinated methacrylates. Moreover, the controllability of DPFBTTC is verified to be better than that of DBTTC, possibly resulting from the enhanced accessibility/miscibility of DPFBTTC to the fluorinated monomer used. We believe that the employment of DPFBTTC and the resulted introduction of stable pentafluorobenzyl end groups to the polymer are expected to distinctly improve performances of the polymer, and thus will meet the special application requirements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 825–834     

Photo‐initiated thiol–ene “click” hydrogels from RAFT‐synthesized poly(N‐isopropylacrylamide)

Despite the efficiency and robustness of the widely used copper‐catalyzed 1,3‐dipolar cycloaddition reaction, the use of copper as a catalyst is often not attractive, particularly for materials intended for biological systems. The use of photo‐initiated thiol‐ene as an alternative “click” reaction to synthesize “model networks” is investigated here. Poly(N‐isopropylacrylamide) precursors were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization and were designed to have trithiocarbonate moieties as end groups. This structure design provides opportunity for subsequent end‐group modifications in preparation for thiol‐ene “click.” Two reaction routes have been proposed and studied to yield thiol and ene moieties. The advantages and disadvantages of each reaction path were investigated to propose a simple but efficient route to prepare copper‐free “click” hydrogels. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4626–4636     

Synthesis and characterization of telechelic polymethacrylates via RAFT polymerization

The reversible addition–fragmentation chain transfer (RAFT) polymerization technique has been employed to synthesize linear α,ω ‐telechelic polymers with either hydroxyl or carboxyl end groups. Methyl methacrylate, butyl methacrylate, and butyl acrylate were polymerized with RAFT polymerization. The polymerizations exhibited the usual characteristics of living processes. Telechelic polymethacrylates were obtained from a hydroxyl monofunctional RAFT polymer with a two‐step chain‐end modification procedure of the dithioester end group. The procedure consisted of an aminolysis followed by a Michael addition on the resulting thiol. The different steps of the procedure were followed by detailed analysis. It was found that this route was always accompanied by side reactions, resulting in disulfides and hydrogen‐terminated polymer chains as side products next to the hydroxyl‐terminated telechelic polymers. Telechelic poly(butyl acrylates) with carboxyl end groups were produced in a single step procedure with difunctional trithiocarbonates as RAFT agents. The high yield in terms of end group functionality was confirmed by a new critical‐liquid‐chromatography method, in which the polymers were separated based on acid‐functionality and by mass spectrometry analysis. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 959–973, 2005     

Synthesis of high‐molecular‐weight linear methacrylate copolymers with spiropyran side groups: Conformational changes of single molecules in solution and on surfaces

P(BMA‐co‐HEMA‐spiropyran) was synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization of butyl methacrylate (BMA) and 2‐(trimethylsilyloxy)‐ethyl methacrylate (HEMA‐TMS), removal of the TMS‐protective groups, and the polymer analogous esterification of the hydroxyethyl side chains with a spiropyran containing a carboxylic acid group. UV‐induced conformational changes of the synthesized macromolecules and low‐molecular‐weight spiropyran molecules were studied. Rate constants and half‐life times of the ring closure reaction from zwitterionic merocyanine to the spiropyran species were determined in the presence and absence of mica‐dispersed particles in toluene both with the free spiropyran and the polymer‐bound spiropyran. Scanning force microscopy was used to visualize the conformation of spiropyran‐decorated single macromolecular chains and agglomerated polymer‐bound merocyanine adsorbed on mica. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1274–1283, 2009     

Controlled polymerization of methacrylates at ambient temperature using trithiocarbonate chain transfer agents via SET‐RAFT–cyclohexyl methacrylate: A model study

Controlled radical polymerization of cyclohexyl methacrylate (CHMA), at ambient temperature, using various chain transfer agents (CTAs) is successfully demonstrated via single electron transfer‐radical addition fragmentation chain transfer (SET‐RAFT). Well‐controlled polymerization with narrow molecular weight distribution (M_w/M_n) < 1.25 was achieved. The polymerization rate followed first‐order kinetics with respect to monomer conversion, and the molecular weight of the polymer increased linearly up to high conversion. A novel, fluorescein‐based initiator, a novel fluorescent CTA and two other CTAs comprising of butane thiol trithiocarbonate with cyano (CTA 1) and carboxylic acid (CTA 3) as the end group were synthesized and characterized. The polymerization is observed to be uncontrolled under SET and less controlled under atom transfer radical polymerization (ATRP) condition. CTA 2 and 3 produces better control in propagation compared with CTA 1, which may be attributed to the presence of R group that undergoes ready fragmentation to radicals, at ambient temperature. The poly(cyclohexyl methacrylate) [P(CHMA)] prepared through ATRP have higher fluorescence intensity compared with those from SET‐RAFT, which may be attributed to the quenching of fluorescence by the trithiocarbonate and the long hydrocarbon chain. It is observed that block copolymers P(CHMA‐b‐t‐BMA) produced from P(CHMA) macroinitiators synthesized via SET‐RAFT result in lower polydispersity index in comparison with those synthesized via ATRP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

R‐RAFT approach for the polymerization of N‐isopropylacrylamide with a star poly(ε‐caprolactone) core

Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a more robust and versatile approach than other living free radical polymerization methods, providing a reactive thiocarbonylthio end group. A series of well‐defined star diblock [poly(ε‐caprolactone)‐b‐poly(N‐isopropylacrylamide)]₄ (SPCLNIP) copolymers were synthesized by R‐RAFT polymerization of N‐isopropylacrylamide (NIPAAm) using [PCL‐DDAT]₄ (SPCL‐DDAT) as a star macro‐RAFT agent (DDAT: S‐1‐dodecyl‐S′‐(α, α′‐dimethyl‐α″‐acetic acid) trithiocarbonate). The R‐RAFT polymerization showed a controlled/“living” character, proceeding with pseudo‐first‐order kinetics. All these star polymers with different molecular weights exhibited narrow molecular weight distributions of less than 1.2. The effect of polymerization temperature and molecular weight of the star macro‐RAFT agent on the polymerization kinetics of NIPAAm monomers was also addressed. Hardly any radical–radical coupling by‐products were detected, while linear side products were kept to a minimum by careful control over polymerization conditions. The trithiocarbonate groups were transferred to polymer chain ends by R‐RAFT polymerization, providing potential possibility of further modification by thiocarbonylthio chemistry. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Physically cross‐linked networks of POSS‐capped poly(acrylate amide)s: Synthesis,morphologies, and shape memory behavior

In this work, we synthesized a novel organic–inorganic semitelechelic polymer from polyhedral oligomeric silsesquioxane (POSS) and poly(acrylate amide) (PAA) via reversible addition‐fragmentation chain transfer (RAFT) polymerization. The organic–inorganic semitelechelic polymers have been characterized by means of nuclear magnetic resonance spectroscopy, thermal gravimetric analysis, and dynamic mechanical thermal analysis. It was found that capping POSS groups to the single ends of PAA chains caused a series of significant changes in the morphologies and thermomechanical properties of the polymer. The organic–inorganic semitelechelics were microphase‐separated; the POSS microdomains were formed via the POSS–POSS interactions. In a selective solvent (e.g., methanol), the organic–inorganic semitelechelics can be self‐assembled into the micelle‐like nanoobjects. Compared to plain PAA, the POSS‐capped PAAs significantly displayed improved surface hydrophobicity as evidenced by the measurements of static contact angles and surface atomic force microscopy. More importantly, the organic–inorganic semitelechelics displayed typical shape memory properties, which was in marked contrast to plain PAA. The shape memory behavior is attributable to the formation of the physically cross‐linked networks from the combination of the POSS–POSS interactions with the intermolecular hydrogen‐bonding interactions in the organic–inorganic semitelechelics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 587–600     

A simple methodology for the synthesis of heterotelechelic protein–polymer–biomolecule conjugates

A synthetic protocol for the preparation of hetero‐biofunctional protein–polymer conjugates is described. A chain transfer agent, S,S‐bis (α,α′‐dimethyl‐α″‐acetic acid) trithiocarbonate was functionalized with α,ω‐pyridyl disulfide (PDS) groups, Subsequently, one of the PDS groups was covalently attached to bovine serum albumin (BSA) at the specific free thiol group on the cysteine residue through a disulfide linkage. The second PDS group remained intact, as it was found to be inaccessible to further BSA functionalization. The BSA‐macro‐reversible addition‐fragmentation chain transfer (RAFT) agent was then used to prepare BSA‐polymer conjugates via in situ polymerization of oligo (ethyleneglycol) acrylate and N‐(2‐hydroxypropyl) methacrylamide using an ambient temperature initiator, 4,4′‐azobis [2,9‐imidazolin‐2‐ethyl)propane] dihydrochloride in an aqueous medium. Sodium dodecyl sulphate polyacrylamide gel electrophoresis (SDS‐PAGE) confirmed that the in situ polymerization occurred at the protein surface where the RAFT agent was attached and the molecular weights of the BSA–polymer conjugates were found to increase concomitantly with monomer conversion and polymerization time. After polymerization the remaining terminal PDS groups were then utilized to attach thiocholesterol and a flurophore, rhodamine B to the protein–polymer conjugates via disulfide coupling. UV–Vis and fluorescence analyses revealed that ～80% of the protein conjugates were found to retain integral PDS end groups for further attachment to free thiol‐tethered precursors. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1399–1405, 2010     

Controlled synthesis of carboxylic acid end‐capped poly(heptadecafluorodecyl acrylate) and copolymers with 2‐hydroxyethyl acrylate

1H,1H,2H,2H‐Heptadecafluorodecyl acrylate (AC8) was polymerized by reversible addition–fragmentation chain transfer and copolymerized with 2‐hydroxyethyl acrylate with the formation of random and block copolymers, respectively. The kinetics of the (co)polymerization was monitored with ¹H NMR spectroscopy and showed that the homopolymerization and random copolymerization of AC8 were under control. As a result of this control and the use of S‐1‐dodecyl‐S‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate as a chain‐transfer agent, the copolymer chains were end‐capped by an α‐carboxylic acid group. Moreover, the controlled polymerization of AC8 was confirmed by the successful synthesis of poly(1H,1H,2H,2H‐heptadecafluorodecyl acrylate)‐b‐poly(2‐hydroxyethyl acrylate) diblock copolymers, which were typically amphiphilic compounds. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1499–1506, 2007