One‐step synthesis of block‐graft copolymers via simultaneous reversible‐addition fragmentation chain transfer and ring‐opening polymerization using a novel macroinitiator

One‐step synthesis of block‐graft copolymers by reversible addition‐fragmentation chain transfer (RAFT) and ring‐opening polymerization (ROP) by using a novel initiator was reported. Block‐graft copolymers were synthesized in one‐step by simultaneous RAFT polymerization of n‐butylmethacrylate (nBMA) and ROP of ε‐caprolacton (CL) in the presence of a novel macroinitiator (RAFT‐ROP agent). For this purpose, first epichlorohydrin (EPCH) was polymerized by using H₂SO₄ via cationic ring‐opening mechanism. And then a novel RAFT‐ROP agent was synthesized by the reaction of potassium ethyl xanthogenate and polyepichlorohydrin (poly‐EPCH). By using the RAFT‐ROP agent, poly[CL‐b‐EPCH‐b‐CL‐(g‐nBMA)] block‐graft copolymers were synthesized. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the one‐step polymerization reaction were evaluated. The block lengths of the block‐graft copolymers were calculated by using ¹H‐nuclear magnetic resonance (¹H NMR) spectrum. The block length could be adjusted by varying the monomer and initiator concentrations. The characterization of the products was achieved using ¹H NMR, Fourier‐transform infrared spectroscopy, gel‐permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and fractional precipitation (γ) techniques. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2651–2659     

One‐step synthesis of poly(N‐vinylpyrrolidone)‐b‐poly(l‐lactide) block copolymers using a dual initiator for RAFT polymerization and ROP

Amphiphilic, biocompatible poly(N‐vinylpyrrolidone)‐b‐poly(l ‐lactide) (PVP‐b‐PLLA) block polymers were synthesized at 60 °C using a hydroxyl‐functionalized N,N‐diphenyldithiocarbamate reversible addition–fragmentation chain transfer (RAFT) agent, 2‐hydroxyethyl 2‐(N,N‐diphenylcarbamothioylthio)propanoate (HDPCP), as a dual initiator for RAFT polymerization and ring‐opening polymerization (ROP) in a one‐step procedure. 4‐Dimethylamino pyridine was used as the ROP catalyst for l ‐lactide. The two polymerization reactions proceeded in a controlled manner, but their polymerization rates were affected by the other polymerization process. This one‐step procedure is believed to be the most convenient method for synthesizing PVP‐b‐PLLA block copolymers. HDPCP can also be used for the one‐step synthesis of poly(N‐vinylcarbazole)‐b‐PLLA block copolymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1607–1613     

One-step synthesis of poly(alkyl methacrylate)-b-polyester block copolymers via a dual initiator route combining RAFT polymerization and ROP

One-step synthesis of well-defined poly(alkyl methacrylate)-b-polyester block copolymers was successfully performed at 30?°C using a dual initiator for reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening polymerization (ROP). 4-Cyano-1-hydroxypent-4-yl dithiobenzoate, a hydroxyl-functionalized RAFT agent, was used as a dual initiator for the RAFT polymerization of methacrylic monomers and the ROP of lactones. Diphenyl phosphate (DPP) was used as a catalyst for ROP. The two polymerization reactions proceeded in a controlled manner without mutual interference. DPP was found to be a suitable catalyst for a dual initiator route combining RAFT polymerization and the ROP of lactones.     

Ring opening polymerization and copolymerization of L‐lactide and ɛ‐caprolactone by bis‐ligated magnesium complexes

Seven magnesium complexes ( 1–7 ) were synthesized by reaction of new ( L ³ ‐H – L ⁵ ‐H ) and previously reported ketoimine pro‐ligands with dibutyl magnesium and were isolated in 59–70% yields. Complexes 1–7 were characterized fully and consisted of bis‐ligated homoleptic ketoiminates coordinated in distorted octahedral geometry around the magnesium centers. The complexes were investigated for their ability to initiate the ring opening polymerization (ROP) of l ‐lactide (L‐LA) to poly‐lactic acid (PLA) and ?‐caprolactone (?CL) to poly‐caprolactone in the presence of 4‐fluorophenol co‐catalyst. For L‐LA polymerization, complexes containing ligand electron‐donating groups ( 1–5 ) achieved >90% conversion in 2 h at 100 °C, while the presence of CF₃ groups in 6 and 7 slowed or resulted in no PLA detected. With ?CL, ROP initiated with 1–7 resulted in lower percentage conversion with similar electronic effects. Moderate molecular weight PLA polymeric material (14.3–21.3 kDa) with low polydispersity index values (1.23–1.56) was obtained, and ROP appeared to be living in nature. Copolymerization of L‐LA and ?CL yielded block copolymers only from the sequential polymerization of ?CL followed by L‐LA and not the reverse sequence of monomers or the simultaneous presence of both monomers. Polymers and copolymers were characterized with NMR, gel permeation chromatography, and differential scanning calorimetry. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 48–59     

Facile synthesis of star‐shaped copolymers via combination of RAFT and ring opening polymerization

Reversible addition fragmentation chain transfer (RAFT) polymerization and bifunctional sparteine/thiourea organocatalyst‐mediated ring opening polymerization (ROP) were combined to produce poly(L ‐lactide) star polymers and poly(L ‐lactide‐co‐styrene) miktoarm star copolymers architecture following a facile experimental procedure, and without the need for specialist equipment. RAFT was used to copolymerize ethyl acrylate (EA) and hydroxyethyl acrylate (HEA) into poly(EA‐co‐HEA) co‐oligomers of degree of polymerization 10 with 2, 3, and 4 units of HEA, which were in turn used as multifunctional initiators for the ROP of L ‐lactide, using a bifunctional thiourea organocatalytic system. Furthermore, taking advantage of the living nature of RAFT polymerization, the multifunctional initiators were chain extended with styrene (poly((EA‐co‐HEA)‐b‐styrene) copolymers), and used as initiators for the ROP of L ‐lactide, to yield miktoarm star copolymers. The ROP reactions were allowed to proceed to high conversions (>95%) with good control over molecular weights (ca. 28,000‐230,000 g/mol) and polymer structures being observed, although the molecular weight distributions are generally broader (1.3–1.9) than those normally observed for ROP reactions. The orthogonality of both polymerization techniques, coupled with the ubiquity of HEA, which is used as a monomer for RAFT polymerization and as an initiator for ROP, offer a versatile approach to star‐shaped copolymers. Furthermore, this approach offers a practical approach to the synthesis of polylactide star polymers without a glove box or stringent reaction conditions. The phase separation properties of the miktoarm star copolymers were demonstrated via thermal analyses. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6396–6408, 2009     

Miktoarm star copolymers of poly(ϵ‐caprolactone) from a novel heterofunctional initiator

A novel heterofunctional initiator, synthesized from pentaerythritol in a three step reaction sequence with two ring opening polymerization (ROP) and two atom transfer radical polymerization (ATRP) initiating sites, was used to prepare A₂B₂ miktoarm star copolymers of poly(ε‐caprolactone), PεCL, with polystyrene, PS, poly(methyl methacrylate), PMMA, poly(dimethylaminoethyl methacrylate), PDMAEMA, and poly(2‐hydroxyethyl methacrylate), PHEMA. A₂B miktoarm stars, A being PεCL or poly(δ‐valerolactone), PδVL and B PS were also prepared from ω,ω‐dihydroxy‐PS, synthesized from ω‐Br‐PS and serinol, by ROP of εCL or δVL. All polymers were characterized by size exclusion chromatography, ¹H NMR spectroscopy, and membrane osmometry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5164–5181, 2007     

Kinetic investigation of the RAFT polymerization of p‐acetoxystyrene

The kinetics of the RAFT polymerization of p‐acetoxystyrene using a trithiocarbonate chain transfer agent, S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate, DDMAT, was investigated. Parameters including temperature, percentage initiator, concentration, monomer‐to‐chain transfer agent ratio, and solvent were varied and their impact on the rate of polymerization and quality of the final polymer examined. Linear kinetic plots, linear increase of M_n with monomer conversion, and low final molecular weight dispersities were used as criteria for the selection of optimized polymerization conditions, which included a temperature of 70 or 80 °C with 10 mol % AIBN initiator in bulk for low conversions or in 1,4‐dioxane at a monomer‐to‐solvent volume ratio of 1:1 for higher conversions This study opens the way for the use of DDMAT as a chain transfer agent for RAFT polymerization to incorporate p‐acetoxystyrene together with other functional monomers into well‐defined copolymers, block copolymers, and nanostructures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2517–2524, 2010     

An efficient avenue to poly(styrene)‐block‐poly(ε‐caprolactone) polymers via switching from RAFT to hydroxyl functionality: Synthesis and characterization

The recently introduced procedure of quantitatively switching thiocarbonyl thio capped (RAFT) polymers into hydroxyl terminated species was employed to generate narrow polydispersity (PDI ≈ 1.2) sulfur‐free poly(styrene)‐block‐poly(ε‐caprolactone) polymers (26,000 ≤ M_n/g·mol^?1 < 45,000). The ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) was conducted under organocatalysis employing 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). The obtained block copolymers were thoroughly analyzed via size exclusion chromatography (SEC), NMR, as well as liquid adsorption chromatography under critical conditions coupled to SEC (LACCC‐SEC) to evidence the block copolymer structure and the efficiency of the synthetic process. The current contribution demonstrates that the RAFT process can serve as a methodology for the generation of sulfur‐free block copolymers via an efficient end group switch. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Amino‐Acid‐Based Block Copolymers by RAFT Polymerization

This review summarizes recent advances in the design and synthesis of amino‐acid‐based block copolymers by reversible addition–fragmentation chain transfer (RAFT) polymerization of amino‐acid‐bearing monomers. We will mainly focus on stimuli‐responsive block copolymers, such as pH‐, thermo‐, and dual‐stimuli‐responsive block copolymers, and self‐assembled block copolymers, including amphiphilic and double‐hydrophilic block copolymers having tunable chiroptical properties. We will also highlight recent results in RAFT synthesis of amino‐acid‐based copolymers having various properties, such as catalytic and optoelectronic properties, cross‐linked block copolymer micelles, unimolecular micelles, and organic–inorganic hybrids.     

Polymerization of (L,L)‐lactide and copolymerization with ϵ‐caprolactone initiated by dibutyltin dimethoxide in supercritical carbon dioxide

Ring‐opening polymerization (ROP) of (L,L)‐lactide (LA) has been initiated by dibutyltin dimethoxide in supercritical carbon dioxide (sc CO₂). Polymerization is controlled and proceeds at quasi the same rate as in toluene, which indicates that the reactivity of the propagating species is not impaired by parasitic carbonation reaction. Random copolymerization of LA with ?‐caprolactone (CL) has also been studied in sc CO₂, and the reactivity ratios have been determined as 5.8 ± 0.5 for LA and 0.7 ± 0.25 for CL. These values have to be compared to 0.7 ± 0.25 for LA and 0.15 ± 0.05 for CL in toluene. Good control on ROP of CL and LA in sc CO₂ has been confirmed by the successful synthesis of diblock copolymers by sequential polymerization of CL and LA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2777‐2789, 2005     

Synthesis of poly(ω‐pentadecalactone)‐b‐poly(acrylate) diblock copolymers via a combination of enzymatic ring‐opening and RAFT polymerization techniques

Herein the first reported preparation of diblock copolymers of the polyethylene‐like polyester poly(ω‐pentadecalactone) (PPDL) via a combination of enzymatic ring‐opening polymerization (eROP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization techniques is described. PPDL was synthesized via eROP using Novozyme 435 as a catalyst and a bifunctional initiator/chain transfer agent (CTA) appropriate for the eROP of ω‐pentadecalactone (PDL) and RAFT polymerization of acrylic and styrenic monomers. Chain growth of the PPDL macro‐CTA was performed to prepare acrylic and styrenic diblock copolymers of PPDL, and demonstrates a facile, metal‐free, and “greener” alternative to preparing acrylic diblock copolymers of polyethylene (PE). Diblock copolymer architecture was substantiated via analysis of ¹H NMR spectroscopic, UV‐GPC chromatographic, DSC onset crystallization (T_c), and MALDI‐ToF mass spectrometric data. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3326–3335     

Solvent‐free ring‐opening polymerization of lactones with hydrogen‐bonding bisurea catalyst

Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100     

Synthesis of NMP/RAFT inifers and preparation of block copolymers

Two different initiator/transfer agents (inifers) containing an alkoxyamine and a dithiobenzoate were synthetized and used to trigger out either reversible addition‐fragmentation chain transfer (RAFT) polymerization or nitroxide‐mediated polymerization (NMP). α‐Dithiobenzoate‐ω‐alkoxyamine‐difunctional polymers were produced in both cases which were subsequently used as precursors in the formation of block copolymers. This synthetic approach was applied to N‐isopropylacrylamide (NIPAM) or polyethylene oxide methacrylate (EOMA) to form α,ω‐heterodifunctional homopolymers via RAFT at 60°C which were chain extended with styrene by activating the alkoxyamine moiety at 120°C. Under such temperature conditions, it is proposed that a tandem NMP/RAFT polymerization is initiated producing a simultaneous growth of polystyrene blocks at both chain‐ends. Self‐assembled nanostructures of these amphiphilic block copolymers were evidenced by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of photocleavable poly(methyl methacrylate‐block‐d‐lactide) via atom‐transfer radical polymerization and ring‐opening polymerization

The synthesis and characterization of a photocleavable block copolymer containing an ortho‐nitrobenzyl (ONB) linker between poly(methyl methacrylate) and poly(d ‐lactide) blocks is presented here. The block copolymers were synthesized via atom transfer radical polymerization (ATRP) of MMA followed by ring‐opening polymerization (ROP) of d ‐Lactide and ROP of d ‐lactide followed by ATRP of MMA from a difunctional photoresponsive ONB initiator, respectively. The challenges and limitations during synthesis of the photocleavable block copolymers using the difunctional photoresponsive ONB initiator are discussed. The photocleavage of the copolymers occurs under mild conditions by simple irradiation with 302 nm wavelength UV light (Relative intensity at 7.6 cm: 1500 μW/cm²) for several hours. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4309–4316     

Block and random copolymers as surfactants for dispersion polymerization. I. Synthesis via atom transfer radical polymerization and ring‐opening polymerization

Atom transfer radical polymerization (ATRP) and ring‐opening polymerization (ROP) were combined to synthesize poly(?‐caprolactone‐co‐octadecyl methacrylate‐co‐dimethylaminoethyl methacrylate) copolymers possessing a triblock or random block structure. Various synthetic pathways (sequential or simultaneous approaches) were investigated for the synthesis of both copolymers. For the preparation of these copolymers, an initiator with dual functionality for ATRP/anionic ring‐opening polymerization, 2‐hydroxyethyl 2‐bromoisobutyrate, was used. Copolymers were prepared with good structural control and low polydispersities (weight‐average molecular weight/number‐average molecular weight < 1.2), but one limitation was identified: the dimethylaminoethyl methacrylate (DMAEMA) block had to be synthesized after the ?‐caprolactone block. ROP could not proceed in the presence of DMAEMA because the complexation of the amine groups in poly(dimethylaminoethyl methacrylate) deactivated tin(II) hexanoate, which was used as a catalyst for ROP. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1498–1510, 2005     

Y‐shaped poly(ethylene glycol) and poly(trimethylene carbonate) amphiphilic copolymer: Synthesis and for drug delivery

New Y‐shaped (AB₂‐type) amphiphilic copolymers of poly(ethylene glycol) (PEG) with poly(trimethylene carbonate) (PTMC), PEG‐b‐(PTMC)₂, were successfully synthesized by the ring‐opening polymerization (ROP) of TMC with bishydroxy‐modified monomethoxy‐PEG (mPEG). First, a bishydroxy functional ROP initiator was synthesized by esterification of acryloyl bromide with mPEG, followed by Michael addition using excess diethanolamine. A series of Y‐shaped amphiphilic PEG‐(PTMC)₂ block copolymers were obtained via ROP of TMC using this PEG with bishydroxyl end groups as macroinitiator and ZnEt₂ as catalyst. The amphiphilic block copolymers with different compositions were characterized by gel permeation chromatography (GPC) and ¹H NMR, and their molecular weight was measured by GPC. The results showed that the molecular weight of Y‐shaped copolymers increased with the increase of the molar ratio of TMC to mPEG‐(OH)₂ initiator in feed while the PEG chain length was kept constant. The Y‐shaped copolymer mPEG‐(PTMC)₂ could self‐assemble into micelles in aqueous medium and the critical micelle concentration values of the micelles decrease with increase in hydrophobic PTMC block length of mPEG‐(PTMC)₂. The in vitro cytotoxicity and controlled drug release properties of the Y‐shaped amphiphilic block copolymers were also investigated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8131–8140, 2008     

Simultaneous reversible addition fragmentation chain transfer and ring‐opening polymerization

The simultaneous ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) and 2‐hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ε‐CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) under typical ROP conditions (T > 100 °C) using toluene as the solvent in order to lead to the graft copolymer PHEMA‐g‐PCL. Graft copolymer formation is evidenced by a combination of size‐exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000–10,000 g mol^?1) the copolymer grafting density is higher than 90%. The ratio of free HEMA‐PCL homopolymer produced during the “one‐step” process was found to depend on the HEMA concentration, as well as the half‐life time of the radical initiator used. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058–3067, 2008     

Homo‐ and random copolymerizations of ω‐pentadecalactone with ε‐caprolactone using isothiourea‐based dual catalysis

In this study, the catalytic behavior of dual catalysis based on isothioureas (ITUs) for ring‐opening polymerization (ROP) of macrolactone ω‐pentadecalactone (PDL) and its copolymerization with ε‐caprolactone (CL) has been investigated in detail. In the presence of benzyl alcohol (BnOH) initiator, 2,3,6,7‐tetrahydro‐5H‐thiazolo[3,2‐a]pyrimidine (THTP) acted as a representative organic compound, which coupled with magnesium halides (MgX₂) as cocatalysts and catalyzed the polymerization in toluene at 70 °C. Under suitable conditions, an array of polymers with controlled molecular weights and relatively narrow molecular weight distributions were synthesized. The formation of homopolymers and copolymers with different architectures was verified using GPC, DSC, NMR, and matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐ToF) mass. The MALDI‐ToF mass spectrometry (MS) analysis of poly(ω‐pentade‐calactone) (PPDL) provided direct evidence for the successful initiation of ROP of PDL using BnOH to obtain linear PPDL with a very small amount of oligomer. The NMR analysis indicated that the arrangements of PDL and CL units in the copolymer chains were completely random. The thermal stability of copolymers was composition dependent and increased with the increase in the content of PDL unit. Furthermore, the proposed polymerization mechanism is a dual catalytic mechanism. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019     

Aqueous RAFT polymerization of N‐isopropylacrylamide‐mediated with hydrophilic macro‐RAFT agent: Homogeneous or heterogeneous polymerization?

Aqueous RAFT polymerization of N‐isopropylacrylamide (NIPAM) mediated with hydrophilic macro‐RAFT agent is generally used to prepare poly(N‐isopropylacrylamide) (PNIPAM)‐based block copolymer. Because of the phase transition temperature of the block copolymer in water being dependent on the chain length of the PNIPAM block, the aqueous RAFT polymerization is much more complex than expected. Herein, the aqueous RAFT polymerization of NIPAM in the presence of the hydrophilic macro‐RAFT agent of poly(dimethylacrylamide) trithiocarbonate is studied and compared with the homogeneous solution RAFT polymerization. This aqueous RAFT polymerization leads to the well‐defined poly(dimethylacrylamide)‐b‐poly(N‐isopropylacrylamide)‐b‐poly(dimethylacrylamide) (PDMA‐b‐PNIPAM‐b‐PDMA) triblock copolymer. It is found, when the triblock copolymer contains a short PNIPAM block, the aqueous RAFT polymerization undergoes just like the homogeneous one; whereas when the triblock copolymer contains a long PNIPAM block, both the initial homogeneous polymerization and the subsequent dispersion polymerization are involved and the two‐stage ln([M]_o/[M])‐time plots are indicated. The reason that the PNIPAM chain length greatly affects the aqueous RAFT polymerization is discussed. The present study is anticipated to be helpful to understand the chain extension of thermoresponsive block copolymer during aqueous RAFT polymerization. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of statistical and block copolymers containing adamantyl and norbornyl moieties by reversible addition‐fragmentation chain transfer polymerization

The synthesis of statistical and block copolymers, consisting of monomers often used as resist materials in photolithography, using reversible addition‐fragmentation chain transfer (RAFT) polymerization is reported. Methacrylate and acrylate monomers with norbornyl and adamantyl moieties were polymerized using both dithioester and trithiocarbonate RAFT agents. Block copolymers containing such monomers were made with poly(methyl acrylate) and polystyrene macro‐RAFT agents. In addition to have the ability to control molecular weight, polydispersity, and allow block copolymer formation, the polymers made via RAFT polymerization required end‐group removal to avoid complications during the photolithography. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 943–951, 2010