Polyisobutylene‐b‐Poly(N,N‐diethylacrylamide) well‐defined amphiphilic diblock copolymer: Synthesis and thermo‐responsive phase behavior

Polyisobutylene‐b‐poly(N,N‐diethylacrylamide) (PIB‐b‐PDEAAm) well‐defined amphiphilic diblock copolymers were synthesized by sequential living carbocationic polymerization and reversible addition‐fragmentation chain transfer (RAFT) polymerization. The hydrophobic polyisobutylene segment was first built by living carbocationic polymerization of isobutylene at ?70 ° C followed by multistep transformations to give a well‐defined (M_w/M_n = 1.22) macromolecular chain transfer agent, PIB‐CTA. The hydrophilic poly(N,N‐diethylacrylamide) block was constructed by PIB‐CTA mediated RAFT polymerization of N,N‐diethylacrylamide at 60 ° C to afford the desired well‐defined PIB‐b‐PDEAAm diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.26). Fluorescence spectroscopy, transmission electron microscope, and dynamic light scattering (DLS) were employed to investigate the self‐assembly behavior of PIB‐b‐PDEAAm amphiphilic diblock copolymers in aqueous media. These diblock copolymers also exhibited thermo‐responsive phase behavior, which was confirmed by UV‐Vis and DLS measurements. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1143–1150     

Controlled synthesis of amphiphilic block copolymers based on poly(isobutylene) macromonomers

The synthesis of a monoacrylate functionalized poly(isobutylene) (PIB) macromonomer (PIBA) has been achieved by a two‐step reaction starting from a commercially available PIB. Firstly, terminal olefins (vinylidene and trisubstituted olefin) of PIB were transformed to a phenolic residue by Friedel‐Crafts alkylation followed by subsequent esterification of the phenol with acryloyl chloride, catalyzed by triethylamine. PIBA structure was confirmed by ¹H‐NMR, ¹³C‐NMR and GPC before utilizing in the RAFT copolymerization with N,N‐dimethylacrylamide (DMA) to obtain statistical copolymers (P[(DMA‐co‐(PIBA)]). Monomer conversions were consistently higher than 85% for both DMA and PIBA as monomer feed composition was varied. Chain extension of poly(N,N‐dimethylacrylamide) with PIBA to synthesize block copolymers (P[(DMA‐b‐(PIBA)]) was also achieved with near quantitative monomer conversions (>97%). Block formation efficiency was not quantitative but purification of block copolymers was possible by selective precipitation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 634–643     

Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization

Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003     

Synthesis of poly(β‐pinene)‐g‐poly(meth)acrylate by the combination of living cationic polymerization and atom transfer radical polymerization

New graft copolymers of β‐pinene with methyl methacrylate (MMA) or butyl acrylate (BA) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). β‐Pinene polymers with predetermined molecular weights and narrow molecular weight distributions (MWDs) were prepared by living cationic polymerization with the 1‐phenylethyl chloride/TiCl₄/Ti(OiPr)₄/nBu₄NCl initiating system, and the resultant polymers were brominated quantitatively by N‐bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(β‐pinene) macroinitiators with different bromine contents (Br/β‐pinene unit molar ratio = 1.0 and 0.5 for macroinitiators a and b , respectively). The macroinitiators, in conjunction with CuBr and 2,2′‐bipyridine, were used to initiate ATRP of BA or MMA. With macroinitiator a or b , the bulk polymerization of BA induced a linear first‐order kinetic plot and gave graft copolymers with controlled molecular weights and MWDs; this indicated the living nature of these polymerizations. The bulk polymerization of MMA initiated with macroinitiator a was completed instantaneously and induced insoluble gel products. However, the controlled polymerization of MMA was achieved with macroinitiator b in toluene and resulted in the desired graft copolymers with controlled molecular weights and MWDs. The structures of the obtained graft copolymers of β‐pinene with (methyl)methacrylate were confirmed by ¹H NMR spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1237–1242, 2003     

Synthesis of triblock copolymers based on two isomer acrylate monomers by atom transfer radical polymerization

The syntheses of triblock copolymers by the atom transfer radical polymerization of tert‐butyl and iso‐butyl acrylates as inner blocks with cyclohexyl methacrylate as outer blocks are reported. The living behavior and blocking efficiency of these polymerizations were investigated in each case. The use of difunctional macroinitiators led to ABA triblock copolymers with narrow polydispersities and controlled number‐average molecular weights. These copolymers were prepared from bromo‐terminated macroinitiators of poly(tert‐butyl acrylate) and poly(iso‐butyl acrylate), with copper chloride/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalytic system, at 40 °C in 50% (v/v) toluene solutions. The block copolymers were characterized with size exclusion chromatography and ¹H NMR spectroscopy. Differential scanning calorimetry measurements were performed to reveal the phase segregation. The glass transition of the inner block was not clearly detected, with the exception of the copolymer synthesized with the longest poly(iso‐butyl acrylate) macroinitiator length. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4828–4837, 2005     

Peptide block copolymers by N‐carboxyanhydride ring‐opening polymerization and atom transfer radical polymerization: The effect of amide macroinitiators

The synthesis of polypeptide‐containing block copolymers combining N‐carboxyanhydride (NCA) ring‐opening polymerization and atom transfer radical polymerization (ATRP) was investigated. An amide initiator comprising an amine function for the NCA polymerization and an activated bromide for ATRP was used. Well‐defined polypeptide macroinitiators were obtained from γ‐benzyl‐L ‐glutamate NCA, O‐benzyl‐serine NCA, and N‐benzyloxy‐L ‐lysine. Subsequent ATRP macroinitiation from the polypeptides resulted in higher than expected molecular weights. Analysis of the reaction products and model reactions confirmed that this is due to the high frequency of termination reactions by disproportionation in the initial phase of the ATRP, which is inherent in the amide initiator structure. In some cases selective precipitation could be applied to remove unreacted macroinitiator to yield well‐defined block copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Thermosensitive behavior of poly(ethylene glycol)/poly(2‐(N,N‐dimethylamino)ethyl methacrylate) double hydrophilic block copolymers

The poly(ethylene glycol)/poly(2‐(N,N‐dimethylamino)ethyl methacrylate) (PEG/PDMAEMA) double hydrophilic block copolymers were synthesized by atom transfer radical polymerization using mPEG‐Br or Br‐PEG‐Br as macroinitiators. The narrow molecular weight distribution of PEG/PDMAEMA block copolymers was identified by gel permeation chromatography results. The thermosensitivity of PEG/PDMAEMA block copolymers in aqueous solution was revealed to depend significantly on pH, ionic strength, chain structure, and concentration of the block copolymers. By optimizing these factors, the cloud point temperature of PEG/PDMAEMA block copolymers can be limited within body temperature range (30–37 °C), which suggests that PEG/PDMAEMA block copolymers could be a good candidate for drug delivery systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 503–508, 2010     

Synthesis of phosphorescent iridium-containing acrylic monomers and their room-temperature polymerization by Cu(0)-RDRP

A series of acrylic monomers based on cyclometalated iridium(III) complexes have been synthesized based on common phosphorescent emitters for organic light-emitting diodes. A simple room-temperature polymerization procedure for these materials was developed using Cu(0) reversible deactivation radical polymerization, providing polymers with low dispersities of 1.08–1.14 at conversions from 81 to 93% when the Ir complexes are copolymerized with a carbazole-based acrylic host. These methods were also found to be suitable for the preparation of high-molecular-weight polymers with M _n approaching 40,000 Da, as well as block copolymers formed in one pot from the chain extension of methyl acrylate. This scalable room-temperature synthesis of iridium-containing copolymers and block copolymers provides a useful route to optoelectronic materials, which we anticipate can be readily adapted to a broad range of acrylic metallopolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2539–2546     

Styrene polymerization with some new macro or macromonomeric azoinitiators having peg units

Several new macroinitiators and macromerinitiators (macroinimers) were synthesized and evaluated for the bulk polymerization of sytrene at 60°C. Macroinitiators were prepared from the reaction of 4,4′-dicyano-4,4′ azovaleryl chloride ( 1 ) with poly(ethylene glycol) (PEG) with a M_ω of 400 and with either benzoyl chloride, acetyl chloride, phenyl isocyanate, or poly(ethylene glycol) oleyl ether. Macromer initiators were also prepared from the reaction of 1 with PEG having M_ω values of 200, 400, 600, 1000, or 1500 and with 4-vinylbenzyl chloride. The bulk polymerization of styrene by macroinimers gave crosslinked styrene-PEG block copolymers, while the polymerization by macroinitiators gave soluble copolymers. The molecular weights of the styrene-PEG block copolymers obtained with macroinitiators having either oleyl, benzoyl, or phenyl urethane end groups were 22000–29000 g/mol. DSC measurements showed that the crosslinked block copolymers had crystalline PEG units with melting transitions ranging from 11–37°C. © 1994 John Wiley & Sons, Inc.     

Optimization of the nitroxide‐mediated radical polymerization conditions for styrene and tert‐butyl acrylate in an automated parallel synthesizer

Automated parallel synthesizers provide fast and comparable screening of different polymerization parameters under similar conditions. In addition, these robotic systems eliminate handling errors, which may affect the results of a kinetic experiment more than the effect of an important parameter. The polymerization temperature and N,N‐tert‐butyl‐N‐[1′‐diethylphosphono‐2,2′‐dimethylpropyl]nitroxide concentration were optimized for the homopolymerization of both styrene and tert‐butyl acrylate to improve the control over the polymerization while reasonable polymerization rates were retained. Subsequently, polystyrene and poly(tert‐butyl acrylate) macro initiators were synthesized according to the knowledge obtained from the screening results. These macroinitiators were used for the preparation of block copolymers consisting of styrene and tert‐butyl acrylate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6202–6213, 2006     

Effects of stereocomplexation on the physicochemical behavior of PLA/PEG block copolymers in aqueous solution

A series of polylactide/poly(ethylene glycol) (PLA/PEG) block copolymers were synthesized by ring‐opening polymerization of L ‐ or D ‐lactide in the presence of mono‐ or di‐hydroxyl PEG. The effects of stereocomplexation on the physicochemical behavior of PLA/PEG copolymers in aqueous solution were investigated by varying the degree of stereocomplexation or PLLA/PEG to PDLA/PEG ratio. In mixture solutions of insoluble and soluble copolymers, stereocomplexation strongly affects the solubility of the copolymers. In mixture solutions of soluble copolymers, both the size and aggregation number (N_agg) of the aggregates vary as a function of the degree of stereocomplexation. It is suggested that the size variation of the aggregates with increasing the degree of stereocomplexation is dependent on N_agg changes which are determined by two effects: the self‐adjusting of the aggregates so as to minimize the free energy and thus to increase the N_agg, and the kinetics of aggregation which tend to form more aggregates and thus to decrease the N_agg. Combination of the two opposite effects well explains the diverse variations of N_agg and size of the aggregates as a function of the degree of stereocomplexation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis of poly(vinyl acetate)‐b‐polystyrene and poly(vinyl alcohol)‐b‐polystyrene copolymers by cobalt‐mediated radical polymerization

Well‐defined poly(vinyl acetate) macroinitiators, with the chains thus end‐capped by a cobalt complex, were synthesized by cobalt‐mediated radical polymerization and used to initiate styrene polymerization at 30 °C. Although the polymerization of the second block was not controlled, poly(vinyl acetate)‐b‐polystyrene copolymers were successfully prepared and converted into amphiphilic poly(vinyl alcohol)‐b‐polystyrene copolymers by the methanolysis of the ester functions of the poly(vinyl acetate) block. These poly(vinyl alcohol)‐b‐polystyrene copolymers self‐associated in water with the formation of nanocups, at least when the poly(vinyl alcohol) content was low enough. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 81–89, 2007     

ABA-type amphiphilic triblock copolymers containing p-ethoxy azobenzene via atom transfer radical polymerization: Synthesis,characterization, and properties

ABA-type amphiphilic triblock copolymers composed of poly(ethylene glycol)s (PEGs) with different number-average molecular weights as the hydrophilic blocks (B) and poly{6-[4-(4-ethoxyphenylazo)phenoxy]hexyl methacrylate} (PA6C) as the hydrophobic blocks (A) were prepared via atom transfer radical polymerization. These copolymers were prepared from bromo-terminated macroinitiators based on PEG6000, PEG2000, and PEG600, with CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine as the catalytic system, at 85 °C in anisole. The block copolymers were characterized with ¹H NMR spectroscopy and gel permeation chromatography. Differential scanning calorimetry measurements were performed to reveal the phase segregation. In contrast to those polymers with similar compositions and structures in previous reports, these amphiphilic copolymers exhibited unusual liquid-crystalline properties over a wide temperature range, being stable even at room temperature. These copolymers showed photoresponsive isomerization under the irradiation of UV–vis light both in THF solutions and in solid films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2225–2234, 2007     

Construction of PIB‐b‐PDEAEMA well‐defined amphiphilic diblock copolymers via sequential living carbocationic and RAFT polymerization

A series of well‐defined amphiphilic diblock copolymers consisting of hydrophobic polyisobutylene (PIB) and hydrophilic poly(2‐(diethylamino)ethyl methacrylate) (PDEAEMA) segments was synthesized via the combination of living carbocationic polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization. Living carbocationic polymerization of isobutylene followed by end‐capping with 1,3‐butadiene was first performed at ?70 °C to give a well‐defined allyl‐Cl‐terminated PIB with a low polydispersity (M_w/M_n =1.29). This end‐functionalized PIB was further converted to a macromolecular chain transfer agent for mediating RAFT block copolymerization of 2‐(diethylamino)ethyl methacrylate at 60 °C in tetrahydrofuran to afford the target well‐defined PIB‐b‐PDEAEMA diblock copolymers with narrow molecular weight distributions (M_w/M_n ≤1.22). The self‐assembly behavior of these amphiphilic diblock copolymers in aqueous media was investigated by fluorescence spectroscopy and transmission electron microscope, and furthermore, their pH‐responsive behavior was studied by UV‐vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1478–1486     

Poly(dimethylaminoethyl methacrylate)‐b‐poly(hydroxypropyl methacrylate) copolymers: Synthesis and pH/thermo‐responsive behavior in aqueous solutions

The synthesis and self‐assembly properties in aqueous solutions of novel amphiphilic block copolymers composed of one hydrophilic, pH and temperature responsive poly(dimethyl amino ethyl methacrylate) (PDMAEMA) block and one weakly hydrophobic, water insoluble, potentially thermoresponsive poly(hydroxy propyl methacrylate) (PHPMA) block, are reported. The block copolymers were prepared by RAFT polymerization and were molecularly characterized by size exclusion chromatography, NMR, and FTIR spectroscopies. The PDMAEMA‐b‐PHPMA amphiphilic block copolymers self‐assemble in different nanostructured aggregates when inserted in aqueous media. The effects of different solubilization protocols, as well as the effects of solution temperature and pH on the structure of the aggregates, are studied by light scattering and fluorescence spectroscopy measurements. Experimental results indicate that there is a number of solution preparation and physicochemical parameters that allow the control and manipulation of the structure and thermoresponsive properties of PDMAEMA‐b‐PHPMA aggregates in aqueous media. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1962–1977     

Synthesis and characterization of novel dendritic (arborescent,hyperbranched) polyisobutylene–polystyrene block copolymers

The synthesis of novel arborescent (arb; randomly branched, “tree‐like,” and often called “hyperbranched”) block copolymers comprised of rubbery polyisobutylene (PIB) and glassy polystyrene (PSt) blocks (arb‐PIB‐b‐PSt) is described. The syntheses were accomplished by the use of arb‐PIB macroinitiators (prepared by the use of 4‐(2‐methoxyisopropyl) styrene inimer) in conjunction with titanium tetrachloride (TiCl₄). The effect of reaction conditions on blocking of St from arb‐PIB was investigated. Purified block copolymers were characterized by ¹H NMR spectroscopy and Size Exclusion Chromatography (SEC). arb‐PIB‐b‐PSt with 11.7–33.8 wt % PSt and M_n = 468,800–652,900 g/mol displayed thermoplastic elastomeric properties with 3.6–8.7 MPa tensile strength and 950–1830% elongation. Samples with 26.8–33.8 wt % PSt were further characterized by Atomic Force Microscopy (AFM), which showed phase‐separated mixed spherical/cylindrical/lamellar PSt phases irregularly distributed within the continuous PIB phase. Dynamic Mechanical Thermal Analysis (DMTA) and solvent swelling of arb‐PIB‐b‐PSt revealed unique characteristics, in comparison with a semicommercial PSt‐b‐PIB‐b‐PSt block copolymer. The number of aromatic branching points of the arb‐PIB macroinitiator, determined by selective destruction of the linking sites, agreed well with that calculated from equilibrium swelling data of arb‐PIB‐b‐PSt. This method for the quantitative determination of branching sites might be generally applicable for arborescent polymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1811–1826, 2005     

Poly(acrylate‐b‐styrene‐b‐isobutylene‐b‐styrene‐b‐acrylate) Block Copolymers via Carbocationic and Atom Transfer Radical Polymerizations

A series of polyacrylate‐polystyrene‐polyisobutylene‐polystyrene‐polyacrylate (X‐PS‐PIB‐PS‐X) pentablock terpolymers (X=poly(methyl acrylate) (PMA), poly(butyl acrylate) (PBA), or poly(methyl methacrylate) (PMMA)) was prepared from poly (styrene‐b‐isobutylene‐b‐styrene) (PS‐PIB‐PS) block copolymers (BCPs) using either a Cu(I)Cl/1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) or Cu(I)Cl/tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) catalyst system. The PS‐PIB‐PS BCPs were prepared by quasiliving carbocationic polymerization of isobutylene using a difunctional initiator, followed by the sequential addition of styrene, and were used as macroinitiators for the atom transfer radical polymerization (ATRP) of methyl acrylate (MA), n‐butyl acrylate (BA), or methyl methacrylate (MMA). The ATRP of MA and BA proceeded in a controlled fashion using either a Cu(I)Cl/PMDETA or Cu(I)Cl/Me₆TREN catalyst system, as evidenced by a linear increase in molecular weight with conversion and low PDIs. The polymerization of MMA was less controlled. ¹H‐NMR spectroscopy was used to elucidate pentablock copolymer structure and composition. The thermal stabilities of the pentablock copolymers were slightly less than the PS‐PIB‐PS macroinitiators due to the presence of polyacrylate or polymethacrylate outer block segments. DSC analysis of the pentablock copolymers showed a plurality of glass transition temperatures, indicating a phase separated material.     

Poly(p‐phenylene methylene)‐based block copolymers by mechanistic transformation

The synthesis of poly(p‐phenylene methylene) (PPM)‐based block copolymers such as poly(p‐phenylene methylene)‐b‐poly(ε‐caprolactone) and poly(p‐phenylene methylene)‐b‐polytetrahydrofuran by mechanistic transformation was described. First, precursor PPM was synthesized by acid‐catalyzed polymerization of tribenzylborate at 16 °C. Then, this polymer was used as macroinitiators in either ring‐opening polymerization of ε‐caprolactone or cationic ring‐opening polymerization of tetrahydrofuran to yield respective block copolymers. The structures of the prepolymer and block copolymers were characterized by GPC and ¹H NMR investigations. The composition of block copolymers as determined by ¹H NMR and TGA analysis was found to be in very good agreement. The thermal behavior and surface morphology of the copolymers were also investigated, respectively, by differential scanning calorimetry and atomic force microscopy measurements, and the contribution of the major soft segment has been observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of nitroxide‐containing block copolymers for the formation of organic cathodes

This contribution describes the polymerization of 2,2,6,6‐tetramethylpiperidin‐4‐yl methacrylate by atom transfer radical polymerization (ATRP). Different catalytic systems are compared. The CuCl/4,4′‐dinonyl‐2,2′‐dipyridyl catalytic system allows a good control over the polymerization and provides polymers with a polydispersity index below 1.2. The successful polymerization of styrene from PTMPM‐Cl macroinitiators by ATRP is then demonstrated. Successful quantitative oxidation of PTMPM‐b‐PS block copolymers leads to poly(2,2,6,6‐tetramethylpiperidinyloxy‐4‐yl‐methacrylate)‐b‐poly(styrene) (PTMA‐b‐PS). The cyclic voltammogram of PTMA‐b‐PS indicates a reversible redox reaction at 3.6 V (vs. Li⁺/Li). Such block copolymers open new opportunities for the formation of functional organic cathode materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Novel block ionomers. I. Synthesis and characterization of polyisobutylene‐based block anionomers

A series of novel block anionomers consisting of polyisobutylene (PIB) and poly(methacrylic acid) (PMAA) segments were prepared and characterized. The specific targets were various molecular weight diblocks (PIB‐b‐PMAA^?), triblocks (PMAA^?‐b‐PIB‐b‐PMAA^?), and three‐arm star blocks [Φ(PIB‐b‐PMAA^?)₃] consisting of rubbery PIB blocks with a number‐average degree of polymerization of 50–1000 (number‐average molecular weight = 3000–54,000 g/mol) connected to blocks of PMAA^? anions with a number‐average degree of polymerization of 5–20. The overall strategy for the synthesis of these constructs consisted of four steps: (1) synthesis by living cationic polymerization of t‐chloro‐monotelechelic, t‐chloro‐ditelechelic, and t‐chloro‐tritelechelic PIBs; (2) site transformation to obtain PIBs fitted with termini capable of mediating the atom transfer radical polymerization (ATRP) of tert‐butyl methacrylate (tBMA); (3) ATRP of tBMA, and (4) hydrolysis of poly(tert‐butyl methacrylate) to PMAA^?. The architectures created and the synthesis steps employed are summarized. Kinetic and model experiments greatly assisted in the development of convenient synthesis methods. The microarchitectures of the various block anionomers were confirmed by spectroscopy and other techniques. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3662–3678, 2002