Efficient route to well‐characterized homo,block, and statistical polymers containing terpyridine in the side chain

The incorporation of metal–ligand interactions into macromolecules imparts to them unique and potentially useful properties. We report the synthesis of homo, block, and statistical copolymers with controlled molecular weights, compositions, and relatively narrow polydispersities via atom transfer radical polymerization that contain activated esters for the subsequent incorporation of terpyridine. This approach is universal and allows facile access to macromolecules with rich chemical functions, illustrated here with metal ligands. Comonomers include methyl, n‐butyl, and poly(ethylene glycol) methyl ether methacrylate as well as styrene. The addition of lanthanide ions to the final copolymers generates emissive materials with blue, green, red, or purple light, depending on the metal used. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5831–5843, 2005     

Synthesis and optical properties of green‐light‐emitting copolymers containing side‐chain oxadiazole units

Atom transfer radical polymerization was used to prepare well‐defined vinyl polyoxadiazole homomacromonomers with a properly modified α‐dicarboxylic acid methyl ester as the initiator. Macromonomers of various molecular weights with narrow polydispersities in some cases were obtained, as proved by gel permeation chromatography (GPC). The structures of the obtained macromonomers were then identified with ¹H NMR spectroscopy. These macromonomers were subsequently copolymerized with a dihydroxy anthracene based monomer by a polycondensation technique, and this resulted in polymacromonomers. Coil–rod–coil copolymers containing side‐chain anthracene and oxadiazole units were also synthesized by atom transfer radical polymerization. The resulting copolymers combined an anthracene derivative as the rigid block with a random copolymer of the desired anthracene‐ and/or oxadiazole‐based monomers as the flexible block. These copolymers were primarily characterized with GPC and ¹H NMR techniques. Additionally, the optical properties of all these copolymers were investigated in detail, and they suggested energy transfer from the oxadiazole to the anthracene chromophores, which became much more efficient in the solid state. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1049–1061, 2005     

Synthesis of AB diblock copolymers by atom-transfer radical polymerization (ATRP) and living polymerization of alpha-amino acid-N-carboxyanhydrides

The synthesis of poly(methyl acrylate)-block-poly(gamma-benzyl-L-glutamate) (PMA-b-PBLG) diblock copolymers, using atom-transfer radical polymerization (ATRP) of methyl acrylate and living polymerization of gamma-benzyl-L-glutamate-N-carboxyanhydride (Glu-NCA) is described. Amido-amidate nickelacycle end groups were incorporated onto amino-terminated poly(methyl acrylates), and the resulting complexes were successfully used as macroinitiators for the growth of polypeptide segments. This method allows the controlled preparation of polypeptide-block-poly(methyl acrylate) diblock architectures with control over polypeptide chain length and without the formation of homopolypeptide contaminants.     

Synthesis,characterization, and bulk properties of amphiphilic copolymers containing fluorinated methacrylates from sequential copper‐mediated radical polymerization

The partly fluorinated monomers, 2,2,2‐trifluoroethyl methacrylate (3FM), 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (8FM), and 1,1,2,2‐tetrahydroperfluorodecyl methacrylate (17FM) have been used in the preparation of block copolymers with methyl methacrylate (MMA), 2‐methoxyethyl acrylate (MEA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl bromoisobutyrate and Cu(I)Br/N‐(n‐propyl)‐2‐pyridylmethanimine reveals a living/controlled polymerization in the range 80–110 °C, with apparent rate constants of 1.6 · 10⁻⁴ s⁻¹ to 2.9 · 10⁻⁴ s⁻¹. Various 3FM containing block copolymers with MMA are prepared by sequential monomer addition or from a PMMA macroinitiator in all cases with controlled characteristics. Block copolymers of 3FM and PEGMA resulted in block copolymers with PDI < 1.22, whereas block copolymers from 3FM and MEA have less controlled characteristics. The block copolymers based on MMA with 8FM and 17 FM have PDI's < 1.30. The glass transition temperatures of the block copolymers are dominated by the majority monomer, as the sequential monomer addition results in too short pure blocks to induce observable microphase separation. The thermal stability of the fluorinated poly((meth)acrylate)s in inert atmosphere is less than that of corresponding nonfluorinated poly((meth)acrylate)s. The presence of fluorinated blocks significantly increases the advancing water contact angle of thin films compared to films of the nonfluorinated poly((meth)acrylate)s. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8097–8111, 2008     

Synthesis of coil‐comb block copolymers containing polystyrene coil and poly(methyl methacrylate) side chains via atom transfer radical polymerization

A series of polystyrene‐b‐(poly(2‐(2‐bromopropionyloxy) styrene)‐g‐poly(methyl methacrylate)) (PS‐b‐(PBPS‐g‐PMMA)) and polystyrene‐b‐(poly(2‐(2‐bromopropionyloxy)ethyl acrylate)‐g‐poly(methyl methacrylate)) (PS‐b‐(PBPEA‐g‐PMMA)) as new coil‐comb block copolymers (CCBCPs) were synthesized by atom transfer radical polymerization (ATRP). The linear diblock copolymer polystyrene‐b‐poly(4‐acetoxystyrene) and polystyrene‐b‐poly(2‐(trimethylsilyloxy)ethyl acrylate) PS‐b‐P(HEA‐TMS) were obtained by combining ATRP and activators regenerated by electron transfer (ARGET) ATRP. Secondary bromide‐initiating sites for ATRP were introduced by liberation of hydroxyl groups via deprotection and subsequent esterification reaction with 2‐bromopropionyl bromide. Grafting of PMMA onto either the PBPS block or the PBPEA block via ATRP yielded the desired PS‐b‐(PBPS‐g‐PMMA) or PS‐b‐(PBPEA‐g‐PMMA). ¹H nuclear magnetic resonance spectroscopy and gel permeation chromatography data indicated the target CCBCPs were successfully synthesized. Preliminary investigation on selected CCBCPs suggests that they can form ordered nanostructures via microphase separation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2971–2983     

Synthesis and characterization of sulfonated block copolymers by atom transfer radical polymerization

Well‐defined sulfonated polystyrene and block copolymers with n‐butyl acrylate (nBA) were synthesized by CuBr catalyzed living radical polymerization. Neopentyl p‐styrene sulfonate (NSS) was polymerized with ethyl‐2‐bromopropionate initiator and CuBr catalyst with N,N,N′,N′‐pentamethylethyleneamine to give poly(NSS) (PNSS) with a narrow molecular weight distribution (MWD < 1.12). PNSS was then acidified by thermolysis resulting in a polystyrene backbone with 100% sulfonic acid groups. Random copolymers of NSS and styrene with various composition ratios were also synthesized by copolymerization of NSS and styrene with different feed ratios (MWD < 1.11). Well defined block copolymers with nBA were synthesized by sequential polymerization of NSS from a poly(n‐butyl acrylate) (PnBA) precursor using CuBr catalyzed living radical polymerization (MWD < 1.29). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5991–5998, 2008     

Synthesis of methyl methacrylate,styrene, and isobutylene multiblock copolymers using atom transfer and cationic polymerization

ABCBA‐type pentablock copolymers of methyl methacrylate, styrene, and isobutylene (IB) were prepared by the cationic polymerization of IB in the presence of the α,ω‐dichloro‐PS‐b‐PMMA‐b‐PS triblock copolymer [where PS is polystyrene and PMMA is poly(methyl methacrylate)] as a macroinitiator in conjunction with diethylaluminum chloride (Et₂AlCl) as a coinitiator. The macroinitiator was prepared by a two‐step copper‐based atom transfer radical polymerization (ATRP). The reaction temperature, ?78 or ?25 °C, significantly affected the IB content in the resulting copolymers; a higher content was obtained at ?78 °C. The formation of the PIB‐b‐PS‐b‐PMMA‐b‐PS‐b‐PIB copolymers (where PIB is polyisobutylene), prepared at ?25 (20.3 mol % IB) or ?78 °C (61.3 mol % IB; rubbery material), with relatively narrow molecular weight distributions provided direct evidence of the presence of labile chlorine atoms at both ends of the macroinitiator capable of initiation of cationic polymerization of IB. One glass‐transition temperature (T_g), 104.5 °C, was observed for the aforementioned triblock copolymer, and the pentablock copolymer containing 61.3 mol % IB showed two well‐defined T_g's: ?73.0 °C for PIB and 95.6 °C for the PS–PMMA blocks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3823–3830, 2005     

Synthesis and characterization of graft copolymers containing poly(p-phenylene) main chains and mesogen-jacketed liquid-crystalline polystyrene side chains

A series of novel comblike mesogen-jacketed liquid-crystalline graft copolymers, poly(p-phenylene)-g-poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PPP-g-PMPCS) copolymers, have been designed and successfully synthesized by a Yamamoto coupling reaction and subsequent atom transfer radical polymerization (ATRP). ¹H NMR spectroscopy, ultraviolet–visible spectra, and gel permeation chromatography (GPC) have been used to confirm the molecular structure of the macroinitiator and the copolymers. A study of the polymerization kinetics of ATRP has shown that the molecular weight of the copolymer increases linearly with the conversion of the monomer, whereas the polydispersity remains narrow (≤1.28), indicating that the ATRP of 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene is well controlled. Thermogravimetric analysis and differential scanning calorimetry (DSC) measurements have indicated that the PPP-g-PMPCS copolymers have better thermal stabilities than the macroinitiator, and their thermal stabilities increase with increasing molecular weight. The liquid-crystalline behavior has been examined with polarized optical microscopy, DSC, one-dimensional wide-angle X-ray diffraction (1D WAXD), and two-dimensional wide-angle X-ray diffraction (2D WAXD). The results show that all the comblike copolymers exhibit obvious liquid-crystalline behaviors, even though the GPC molecular weight of the segments of poly{2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene} (PMPCS) have been determined to be far less than the critical value of linear PMPCS. Moreover, 1D WAXD measurements show that the temperature at which the comblike mesogen-jacketed liquid-crystalline copolymers can transform into a liquid-crystalline phase is low; about 20 °C in comparison with the linear ones. 2D WAXD analysis has revealed that these comblike copolymers should be assigned to a hexatic columnar nematic (Φ_HN) phase. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2543–2555, 2007     

Synthesis of double hydrophilic graft copolymer containing poly(ethylene glycol) and poly(methacrylic acid) side chains via successive ATRP

A well‐defined double hydrophilic graft copolymer, with polyacrylate as backbone, hydrophilic poly(ethylene glycol) and poly(methacrylic acid) as side chains, was synthesized via successive atom transfer radical polymerization followed by the selective hydrolysis of poly(methoxymethyl methacrylate) side chains. The grafting‐through strategy was first used to prepare poly[poly(ethylene glycol) methyl ether acrylate] comb copolymer. The obtained comb copolymer was transformed into macroinitiator by reacting with lithium diisopropylamine and 2‐bromopropionyl chloride. Afterwards, grafting‐from route was employed for the synthesis of poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methoxymethyl methacrylate) amphiphilic graft copolymer. The molecular weight distribution of this amphiphilic graft copolymer was narrow. Poly(methoxymethyl methacrylate) side chains were connected to polyacrylate backbone through stable C? C bonds instead of ester connections. The final product, poly[poly(ethylene glycol) methyl ether acrylate]‐g‐poly(methacrylate acid), was obtained by selective hydrolysis of poly(methoxymethyl methacrylate) side chains under mild conditions without affecting the polyacrylate backbone. This double hydrophilic graft copolymer was found be stimuli‐responsive to pH and ionic strength. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4056–4069, 2008     

Synthesis of poly(isobornyl acrylate) containing copolymers by atom transfer radical polymerization

For the first time, a detailed study of the atom transfer radical polymerization of isobornyl acrylate (iBA) is reported. On the basis of these results, well‐defined PiBA‐containing block copolymers were synthesized, focussing on the preparation of amphiphilic poly(acrylic acid) (PAA) containing block copolymers. The precursor monomers 1‐ethoxyethyl acrylate (EEA) as well as tert‐butyl acrylate have been used to synthesize the PAA‐segments of the PiBA‐b‐PAA block copolymers. Finally, the synthesis of “block‐like” copolymers of PiBA and PEEA via a one‐pot procedure was investigated. By optimizing the copper and ligand concentration, and choosing the appropriate solvent, a controlled polymerization behaviour was obtained in all cases, as evidenced by a detailed kinetic analysis, GPC, NMR, and MALDI‐TOF data. Thermogravimetric analysis confirmed the quantitative transformation of the precursor polymer PEEA to the corresponding PAA‐containing copolymers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1649–1661, 2008     

Synthesis of functional block copolymers and terpolymers containing polyglycidyl methacrylate blocks

Here, the synthesis of triblock terpolymers using tert‐butyl acrylate, glycidyl methacrylate, and methyl methacrylate was studied in detail using atom transfer radical polymerization. Those polymers are promising candidates for irreversible linked microstructured layers on surfaces. The experiments showed that the polymerization has to be started with the acrylate and can be extended with the methacrylates. The first two steps can be done in a one pot procedure employing the method of halogen exchange. With optimized reaction conditions in the last step, the obtained terpolymers show narrow molecular weight distributions and the polymerization process is well controlled. Conducting the synthesis in the opposite direction mostly a nonuniform product was obtained as the GPC analysis showed. Further characterization was done with ¹H NMR spectroscopy, thermogravimetric analysis, and differential scanning calorimetry, the latter showing different glass points for the single blocks in the terpolymers if they are not too short. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 675–684     

Synthesis of diblock copolymers by combining stable free radical polymerization and atom transfer radical polymerization

A stable nitroxyl radical functionalized with an initiating group for atom transfer radical polymerization (ATRP), 4‐(2‐bromo‐2‐methylpropionyloxy)‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy (Br‐TEMPO), was synthesized by the reaction of 4‐hydroxyl‐2,2,6,6‐tetramethyl‐1‐piperidinyloxy with 2‐bromo‐2‐methylpropionyl bromide. Stable free radical polymerization of styrene was then carried out using a conventional thermal initiator, dibenzoyl peroxide, along with Br‐TEMPO. The obtained polystyrene had an active bromine atom for ATRP at the ω‐end of the chain and was used as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate to prepare block copolymers. The molecular weights of the resulting block copolymers at different monomer conversions shifted to higher molecular weights and increased with monomer conversion. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2468–2475, 2006     

Block copolymers by chemoenzymatic cascade polymerization: A comparison of consecutive and simultaneous reactions

The synthetic parameters for the chemoenzymatic cascade synthesis of block copolymers combining enzymatic ring‐opening polymerization (EROP) and atom transfer radical polymerization (ATRP) in one pot were investigated. A detailed analysis of the mutual interactions between the single reaction components revealed that the ATRP catalyst system could have a significant inhibiting effect on the enzyme activity. The inhibition of the enzyme was less pronounced in the presence of multivalent ligands such as dinonyl bipyridine, which thus could be used in this reaction as an ATRP catalyst. Moreover, the choice of the ATRP monomer was investigated. Methyl methacrylate interfered with EROP by transesterification, whereas t‐butyl methacrylate was inert. Block copolymers were successfully synthesized with this cascade approach by the activation of ATRP after EROP by the addition of the ATRP catalyst and, with lower block copolymer yields, by the mixing of all the components before the copolymerization. Adetailed kinetic analysis of the reactions and the structure of the block copolymers showed that the first procedure proceeded smoothly to high block copolymer yields, whereas in the latter a noteworthy amount of the poly(t‐butyl methacrylate) homopolymer was detected. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4290–4297, 2006     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Synthesis and properties of comb polymers with semirigid mesogen‐jacketed polymers as side chains

A series of novel comb polymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐g‐polystyrene (PMPCS‐g‐PS), with mesogen‐jacketed rigid side chains were synthesized by the “grafting onto” method from α‐yne‐terminated PMPCS (side chain) and poly(vinylbenzyl azide) (backbone) by Cu(I)‐catalyzed 1,3‐dipolar cycloaddition click reaction. The α‐yne‐terminated PMPCS was synthesized by Cu(I)‐catalyzed atom transfer radical polymerization initiated by a yne‐functional initiator. Poly(vinylbenzyl azide) was prepared by polymerizing vinylbenzyl chloride using nitroxide mediated radical polymerization to obtain poly(vinylbenzyl chloride) as the precursor which was then converted to the azide derivative. The chemical structure and architectures of PMPCS comb polymers were confirmed by ¹H NMR, gel permeation chromatography, and multiangle laser light scattering. Both surface morphologies and solution behaviors were investigated. Surface morphologies of PMPCS combs on different surfaces were investigated by scanning probe microscopy. PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. The PMPCS comb polymers transferred to polymer‐modified silicon wafers using the Langmuir‐Blodgett technique showed a worm‐like chain conformation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and characterization of random and block copolymers with pendant rhenium diimine complexes by controlled radical polymerization

We report the polymerization of rhenium‐containing methacrylates by atom transfer radical polymerization. The structure of the monomer was confirmed by X‐ray crystallography, which showed the bulkiness of the metal‐complex moiety. The rhenium complexes were polymerized in the presence of copper(I) bromide, 1,1,4,7,7‐pentamethyldiethylenetriamine, and methyl 2‐bromopropionate. They were copolymerized with methyl methacrylate in different monomer ratios. An ABA triblock copolymer was also synthesized with poly(methyl methacrylate) as the macroinitiator. When 2,2′‐bipyridine was used as the ligand for the copper catalyst in the polymerizations, it underwent a ligand exchange process with the iminopyridine ligand in the monomer. The neutral rhenium complex in the homopolymers and copolymers could be converted into ionic forms by the replacement of the chloride with an imidazole ligand, and the solubility of the resulting ionic polymers was greatly enhanced. The photosensitizing properties of the doped and undoped polymer films were investigated by the measurement of the photocurrent response under an externally applied electric field. The photoconductivities of the polymers were approximately 10^?12–10^?13 Ω^?1 cm^?1. The experimental quantum efficiencies were simulated with Onsager's theory, and they showed that the initial quantum yield and thermalization distance were 10^?3 and 1.7 nm, respectively. Transmission electron microscopy showed that the rhenium complexes aggregated to form domains with dimensions of approximately 20–30 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1292–1308, 2005     

Novel amphiphilic graft copolymers bearing hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains

A novel amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbones and hydrophobic poly(butyl methacrylate) side chains was synthesized by successive atom transfer radical polymerization followed by hydrolysis of poly‐(methoxymethyl acrylate) backbone. A grafting‐from strategy was employed for the synthesis of graft copolymers with narrow molecular weight distributions (polydispersity index < 1.40). Hydrophobic side chains were connected to the backbone through stable C? C bonds instead of ester connections. Poly(methoxymethyl acrylate) backbone was easily hydrolyzed to poly(acrylic acid) backbone with HCl without affecting the hydrophobic side chains. The amphiphilic graft copolymer could form stable micelles in water. The critical micelle concentration in water was determined by a fluorescence probe technique. The morphology of the micelles was preliminarily explored with transmission electron microscopy and was found to be spheres. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6857–6868, 2006     

ATRP of methyl methacrylate initiated with a bifunctional initiator bearing bromomethyl functional groups: Synthesis of the block and graft copolymers

This article reports the synthesis of the block and graft copolymers using peroxygen‐containing poly(methyl methacrylate) (poly‐MMA) as a macroinitiator that was prepared from the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in the presence of bis(4,4′‐bromomethyl benzoyl peroxide) (BBP). The effects of reaction temperatures on the ATRP system were studied in detail. Kinetic studies were carried out to investigate controlled ATRP for BBP/CuBr/bpy initiating system with MMA at 40 °C and free radical polymerization of styrene (S) at 80 °C. The plots of ln ([M_o]/[M_t]) versus reaction time are linear, corresponding to first‐order kinetics. Poly‐MMA initiators were used in the bulk polymerization of S to obtain poly (MMA‐b‐S) block copolymers. Poly‐MMA initiators containing undecomposed peroygen groups were used for the graft copolymerization of polybutadiene (PBd) and natural rubber (RSS‐3) to obtain crosslinked poly (MMA‐g‐PBd) and poly(MMA‐g‐RSS‐3) graft copolymers. Swelling ratio values (q_v) of the graft copolymers in CHCl₃ were calculated. The characterizations of the polymers were achieved by Fourier‐transform infrared spectroscopy (FTIR), ¹H‐nuclear magnetic resonance (¹H NMR), gel‐permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and the fractional precipitation (γ) techniques. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1364–1373, 2010     

Synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers by combining ATRP and RAFT polymerizations

The synthesis of poly(tert‐butyl acrylate‐block‐vinyl acetate) copolymers using a combination of two living radical polymerization techniques, atom transfer radical polymerization (ATRP) and reversible addition‐fragmentation chain transfer (RAFT) polymerization, is reported. The use of two methods is due to the disparity in reactivity of the two monomers, viz. vinyl acetate is difficult to polymerize via ATRP, and a suitable RAFT agent that can control the polymerization of vinyl acetate is typically unable to control the polymerization of tert‐butyl acrylate. Thus, ATRP was performed to make poly(tert‐butyl acrylate) containing a bromine end group. This end group was subsequently substituted with a xanthate moiety. Various spectroscopic methods were used to confirm the substitution. The poly(tert‐butyl acrylate) macro‐RAFT agent was then used to produce (tert‐butyl acrylate‐block‐vinyl acetate). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7200–7206, 2008