Synthesis of hybrid dendritic‐linear block copolymers with dendritic initiators prepared by convergent living anionic polymerization

Hybrid dendritic‐linear block copolymers were made in one‐pot by convergent living anionic polymerization. Dendritic polystyrene macroinitiators were synthesized by slowly adding a mixture of either vinylbenzyl chloride (VBC) or 4‐(chlorodimethylsilyl)styrene (CDMSS) and styrene (1 : 10 molar ratio of coupling agent to styrene) to a solution of living polystyryllithium. The addition was ceased prior to the addition of a stoichiometric amount of coupling agent to retain a living chain end. To the living dendritically branched polystyrene was then added either styrene or isoprene to polymerize a linear block from the dendritic polystyrene. The resulting copolymers were characterized by gel permeation chromatography coupled with multiangle laser light scattering (GPC‐MALLS), which clearly demonstrated the formation of diblock copolymers. The diblock copolymers were further characterized by ¹H NMR, which showed the presence of the two blocks in the case of dendritic polystyrene‐block‐linear polyisoprene. The measurement of intrinsic viscosity showed that the dilute solution properties of the block copolymers are greatly influenced by the dendritic portion. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 152–161, 2001     

Polystyrene with dendritic branching by convergent living anionic polymerization. II. Approach using vinylbenzyl chloride

Vinylbenzyl chloride (VBC) has been used as a coupling agent in Convergent Living Anionic Polymerization to produce polymers with dendritic branching. The slow addition of a stoichiometric amount of VBC to living polystyrene chains allows the coupling to proceed through macromonomer formation followed by vinyl addition. Changing the reaction conditions produced two types of structures. Star‐shaped polymers with a hyperbranched core were made by the continuous slow addition of VBC alone, and chain‐extended hyperbranched structures with varied molecular weight between branch points were produced by the slow addition of VBC mixed with different amounts of styrene monomer. The extent of growth of the two different types of structures ranged from 2.4 to 2.6 generations for the case of VBC added alone, corresponding to an average of 5.3 to 6.1 arms attached to the hyperbranched core, and from 3.2 to 4.2 generations for polymers produced from the addition of VBC mixed with styrene. Relatively low polydispersities were obtained for all samples. The highly branched nature of the polymers was reflected in the low intrinsic viscosity relative to linear polystyrene and in the dependence of glass‐transition temperature on the molecular weight relative to the number of end groups. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4289–4298, 2000     

One‐step synthesis of hyperbranched polyethylene macroinitiator and its block copolymers with methyl methacrylate or styrene via ATRP

Block copolymers of hyperbranched polyethylene (PE) and linear polystyrene (PS) or poly(methyl methacrylate) (PMMA) were synthesized via atom transfer radical polymerization (ATRP) with hyperbranched PE macroinitiators. The PE macroinitiators were synthesized through a “living” polymerization of ethylene catalyzed with a Pd‐diimine catalyst and end‐capped with 4‐chloromethyl styrene as a chain quenching agent in one step. The macroinitiator and block copolymer samples were characterized by gel permeation chromatography, ¹H and ¹³C NMR, and differential scanning calorimetry. The hyperbranched PE chains had narrow molecular weight distribution and contained a single terminal benzyl chloride per chain. Both hyperbranched PE and linear PS or PMMA blocks had well‐controlled molecular weights. Slow initiation was observed in ATRP because of steric effect of hyperbranched structures, resulting in slightly broad polydispersity index in the block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3024–3032, 2010     

Synthesis of macromonomers of acrylic acid by telomerization: Application to the synthesis of polystyrene‐g‐poly(acrylic acid) copolymers

The synthesis of macromonomers of acrylic acid was performed by telomerization in a three‐step process. The first step was the telomerization of tert‐butyl acrylate in the presence of thioglycolic acid. Different molecular weights were obtained with different ratios of the monomer to the transfer agent. Good control of the molecular weights and architectures of the oligomers (e.g., the presence of an acid function on the chain end) was observed. The transfer constant of tert‐butyl acrylate with thioglycolic acid was assessed (chain‐transfer constant = 0.6). In the second step, the terminal unsaturation of the oligomers was obtained by the reaction of the terminal acid groups with 2‐isocyanatoethyl methacrylate to yield the macromonomers of tert‐butyl acrylate. In the last step, the tert‐butyl acrylate groups were hydrolyzed in the presence of trifluoroacetic acid at room temperature. The macromonomers were copolymerized with styrene to obtain graft copolymers, and the reactivity ratios were evaluated. Finally, the copolymers were characterized with surface electron microscopy and atom force microscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 395–415, 2007     

Synthesis of a novel one‐pot approach of hyperbranched polyurethanes and their properties

A new method for the synthesis of hyperbranched polymers involving the use of AB_x macromonomers containing linear units have been investigated. Two types of novel hyperbranched polyurethanes have been synthesized by a one‐pot approach. The structures of monomers and polymers were characterized by elemental analysis, ¹H NMR, ¹³C NMR, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis. The hyperbranched polymers have been proven to be extremely soluble in a wide range of solvents. Polymer electrolytes were prepared with hyperbranched polymer, linear polymer as the host, and lithium perchlorate (LiClO₄) as the ion source. Analysis of the isotherm conductivity dependence of the ion concentration indicated that these hyperbranched polymers could function as a “solvent” for the lithium salt. The conductivity increased with the increasing concentration of hyperbranched polymers in the host polymer. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 344–350, 2002     

Preparation of novel macromonomers and study of their polymerization

Novel macromonomers of polystyrene and poly(tert‐butyl acrylate) containing a methacryloyl group as a polymerizable unit and two chains of the same length were prepared in two steps: the synthesis of the precursors through the atom transfer radical polymerization of styrene and tert‐butyl acrylate initiated by 1‐hydroxymethyl‐1,1‐di[(2‐bromoisobutyryloxy)methyl] ethane and the esterification of the hydroxyl group in the precursors with methacryloyl chloride. The molecular weight and polydispersity of the macromonomers were controllable because of the living nature of the atom transfer radical polymerization. Gel permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, and hydrolysis confirmed the structure of the novel macromonomers. The homopolymerization and copolymerization of the macromonomers were investigated to prepare branched copolymers in which two chains were grafted from every repeating unit. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3887–3896, 2004     

Synthesis of poly(p‐phenylene) macromonomers and multiblock copolymers

Rigid‐rod poly(4′‐methyl‐2,5‐benzophenone) macromonomers were synthesized by Ni(0) catalytic coupling of 2,5‐dichloro‐4′‐methylbenzophenone and end‐capping agent 4‐chloro‐4′‐fluorobenzophenone. The macromonomers produced were labile to nucleophilic aromatic substitution. The molecular weight of poly(4′‐methyl‐2,5‐benzophenone) was controlled by varying the amount of the end‐capping agent in the reaction mixture. Glass‐transition temperatures of the macromonomers increased with increasing molecular weight and ranged from 117 to 213 °C. Substitution of the macromonomer end groups was determined to be nearly quantitative by ¹H NMR and gel permeation chromatography. The polymerization of a poly(4′‐methyl‐2,5‐benzophenone) macromonomer [number‐average molecular weight (M_n) = 1.90 × 10³ g/mol; polydispersity (M_w)/M_n = 2.04] with hydroxy end‐capped bisphenol A polyaryletherketone (M_n = 4.50 × 10³ g/mol; M_w/M_n = 1.92) afforded an alternating multiblock copolymer (M_n = 1.95 × 10⁴ g/mol; M_w/M_n = 6.02) that formed flexible, transparent films that could be creased without cracking. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3505–3512, 2001     

A macromonomer approach to the synthesis of poly(1,1‐bis(ethoxycarbonyl)‐2‐vinyl cyclopropane‐graft‐dimethyl siloxane)

Poly(1,1‐bis(ethoxycarbonyl)‐2‐vinyl cyclopropane (ECVP)‐graft‐dimethyl siloxane) copolymers were prepared using a macromonomer approach. Poly(dimethyl siloxane) (PDMS) macromonomers were prepared by living anionic polymerization of cyclosiloxanes followed by sequential chain‐end capping with allyl chloroformate. These macromonomers were then copolymerized with ECVP. MALDI‐ToF mass spectrometry and ¹H NMR spectroscopy were used to show that the macromonomers had approximately 80% of the end groups functionalized with allyl carbonate groups. Gradient polymer elution chromatography showed that high yields of the graft copolymers were obtained, along with only small fractions of the PECVP and PDMS homopolymers. Differential scanning calorimetry showed that the low glass transition temperature (T_g) of the PDMS component could be maintained in the graft copolymers. However, the T_g was a function of polymer composition and the polymers produced had T_gs that ranged from ?50 to ?120 °C. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Hyperbranched polymers as scaffolds for multifunctional reversible addition–fragmentation chain‐transfer agents: A route to polystyrene‐core‐polyesters and polystyrene‐block‐poly(butyl acrylate)‐core‐polyesters

Polydisperse hyperbranched polyesters were modified for use as novel multifunctional reversible addition–fragmentation chain‐transfer (RAFT) agents. The polyester‐core‐based RAFT agents were subsequently employed to synthesize star polymers of n‐butyl acrylate and styrene with low polydispersity (polydispersity index < 1.3) in a living free‐radical process. Although the polyester‐core‐based RAFT agent mediated polymerization of n‐butyl acrylate displayed a linear evolution of the number‐average molecular weight (M_n) up to high monomer conversions (>70%) and molecular weights [M_n > 140,000 g mol^?1, linear poly(methyl methacrylate) equivalents)], the corresponding styrene‐based system reached a maximum molecular weight at low conversions (≈30%, M_n = 45,500 g mol^?1, linear polystyrene equivalents). The resulting star polymers were subsequently used as platforms for the preparation of star block copolymers of styrene and n‐butyl acrylate with a polyester core with low polydispersities (polydispersity index < 1.25). The generated polystyrene‐based star polymers were successfully cast into highly regular honeycomb‐structured microarrays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3847–3861, 2003     

Multiblock poly(4‐vinylpyridine) and its copolymer prepared with cyclic trithiocarbonate as a reversible addition–fragmentation transfer agent

The polymerization of 4‐vinylpyridine was conducted in the presence of a cyclic trithiocarbonate (4,7‐diphenyl‐[1,3]dithiepane‐2‐thione) as a reversible addition–fragmentation transfer (RAFT) polymerization agent, and a multiblock polymer with narrow‐polydispersity blocks was prepared. Two kinds of multiblock copolymers of styrene and 4‐vinylpyridine, that is, (ABA)_n multi‐triblock copolymers with polystyrene or poly(4‐vinylpyridine) as the outer blocks, were prepared with multiblock polystyrene or poly(4‐vinylpyridine) as a macro‐RAFT agent, respectively. GPC data for the original polymers and polymers cleaved by amine demonstrated the successful synthesis of amphiphilic multiblock copolymers of styrene and 4‐vinylpyridine via two‐step polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2617–2623, 2007     

Synthesis and characterization of hyperbranched amphiphilic block copolymers prepared via self‐condensing RAFT polymerization

Four families of hyperbranched amphiphilic block copolymers of styrene (Sty, less polar monomer) and 2‐vinylpyridine (2VPy, one of the two more polar monomers) or 4‐vinylpyridine (4VPy, the other polar monomer) were prepared via self‐condensing vinyl reversible addition‐fragmentation chain transfer polymerization (SCVP‐RAFT). Two families contained 4VPy as the more polar monomer, one of which possessing a Sty‐b‐4VPy architecture, and the other possessing the reverse block architecture. The other two families bore 2VPy as the more polar monomer and had either a 2VPy‐b‐Sty or a Sty‐b‐2VPy architecture. Characterization of the hyperbranched block copolymers in terms of their molecular weights and compositions indicated better control when the VPy monomers were polymerized first. Control over the molecular weights of the hyperbranched copolymers was also confirmed with the aminolysis of the dithioester moiety at the branching points to produce linear polymers with number‐average molecular weights slightly greater than the theoretically expected ones, due to recombination of the resulting thiol‐terminated linear polymers. The amphiphilicity of the hyperbranched copolymers led to their self‐assembly in selective solvents, which was probed using atomic force microscopy and dynamic light scattering, which indicated the formation of large spherical micelles of uniform diameter. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1310–1319     

Synthesis,characterization, and self‐assembly of comb‐dendronized amphiphilic block copolymers

Novel amphiphilic comb‐dendronized diblock copolymers composed of hydrophobic Percec‐type dendronized polystyrene block and hydrophilic comb‐like poly(ethylene oxide) grafted polymethacrylate P(PEOMA) block were designed and synthesized via two steps of atom transfer radical polymerization (ATRP). The comb‐like P(PEOMA) prepared by ATRP of macromonomers (PEOMA) with two different molecular weights (M_n = 300 and 475) were used to initiate the sequent ATRP of dendritic styrene macromonomer (DS). The molecular weights and compositions of the obtained block copolymers were determined by ¹H NMR analysis. The copolymers with relatively narrow polydispersities (1.27–1.38) were thus obtained. The bulk properties of comb‐dendronized block copolymers were studied by using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction (WAXD). Similar to dendronized homopolymers, the block copolymers exhibited hexagonal columnar liquid‐crystalline phase structure. By using such amphiphilic comb‐dendronized block copolymers as building blocks, the rich self‐assembly morphologies, such as twisted string, vesicle, and large compound micelle (LCM), were obtained in a mixture of CH₃OH and THF. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4205–4217, 2008     

Thermoresponsive hyperbranched polymers via In Situ RAFT copolymerization of peg‐based monomethacrylate and dimethacrylate monomers

Here we report the preparation of PEG‐based thermoresponsive hyperbranched polymers via a facile in situ reversible addition‐fragmentation chain transfer (RAFT) copolymerization using bis(thiobenzoyl) disulphide to form 2‐cyanoprop‐2‐yl dithiobenzoate in situ. This novel one‐pot in situ RAFT approach was studied firstly using methyl methacrylate (MMA) monomer, then was used to prepare thermoresponsive hyperbranched polymers by copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMEMA, M_n = 475), poly(propylene glycol) methacrylate (PPGMA, M_n = 375) and up to 30 % of ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resultant PEGMEMA‐PPGMA‐EGDMA copolymers from in situ RAFT were characterized by Gel Permeation Chromatography (GPC) and ¹H‐NMR analysis. The results confirmed the copolymers with multiple methacrylate groups and hyperbranched structure as well as RAFT functional residues. These water‐soluble copolymers with tailored compositions demonstrated tuneable lower critical solution temperature (LCST) from 22 °C to 32 °C. The phase transition temperature can be further altered by post functionalization via aminolysis of RAFT agent residues in polymer chains. Moreover, it was demonstrated by rheological studies and particle size measurements that these copolymers can form either micro‐ or macro photocrosslinked gels at suitable concentrations due to the presence of multiple methacrylate groups. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3751–3761     

Synthesis of comb‐like polystyrene with poly(N‐phenyl maleimide‐alt‐p‐chloromethyl styrene) as macroinitiator

The copolymerization of N‐phenyl maleimide and p‐chloromethyl styrene via reversible addition–fragmentation chain transfer (RAFT) process with AIBN as initiator and 2‐(ethoxycarbonyl)prop‐2‐yl dithiobenzoate as RAFT agent produced copolymers with alternating structure, controlled molecular weights, and narrow molecular weight distributions. Using poly(N‐phenyl maleimide‐alt‐p‐chloromethyl styrene) as the macroinitiator for atom transfer radical polymerization of styrene in the presence of CuCl/2,2′‐bipyridine, well‐defined comb‐like polymers with one graft chain for every two monomer units of backbone polymer were obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2069–2075, 2006     

Synthesis and characterization of brush diblock and triblock copolymers bearing polynorbornene backbone and poly(l‐lactide) and/or poly(hexyl isocyanate) side chains by a combination of coordination and ring opening metathesis polymerization

We report the synthesis of poly(l ‐lactide) and poly(hexyl isocyanate) macromonomers using bischloro‐η⁵‐cyclopentadienyl(bicyclo[2.2.1]‐hept‐5‐en‐2‐oxy) Titanium (IV), [CpTiCl₂(O‐NBE)]. These macromonomers bearing a norbornene end group were polymerized towards brush copolymers employing Grubbs' first generation catalyst. Brush copolymers consisting of blocks with different side chains were synthesized. The polymers were characterized by Size Exclusion Chromatography, Nuclear Magnetic Resonance, and their thermal properties were investigated by Thermogravimetric Analysis, and Differential Scanning Calorimetry analysis. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3455–3465     

Star polystyrene‐b‐hyperbranched polyglycidol: Synthesis and ionic conductivity

In this work, novel star‐hyperbranched block copolymers containing four polystyrene arms and hyperbranched polyglycidol at the end of each arm (sPS‐b‐HPG) have been synthesized. The polystyrene arms were prepared through atom transfer radical polymerization of styrene starting from a four‐arm initiator. The hydroxyl‐terminated PS star polymers served as precursors for the cationic ring‐opening polymerization of glycidol using BF₃·OEt₂ as the catalyst. The chemical structures of these block copolymers were characterized by using ¹H and ¹³C NMR. DSC analysis indicated that the star‐hyperbranched block copolymers exhibited two distinct glass transition temperatures corresponding to the linear PS and the HPG segments, respectively. The addition of LiClO₄ increased the T_g of HPG segments at low concentrations, however, decreased the T_g at high concentrations. The T_g of PS segments was not affected by the addition of salts at all. Furthermore, the interaction of sPS‐b‐HPG with LiBr was studied by using viscosity analysis based on the Jones–Dole equation. The star‐like PS core strengthened the interaction of sPS‐b‐HPG with Li ions that could facile the inhomogeneous distribution of Li cations and anions in different phases, which is important in polymeric electrolytes for lithium chemical power sources. The ionic conductivity of one sPS‐b‐HPG/LiClO₄ electrolyte was measured to be higher than that of HPG/LiClO₄ electrolyte. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 949–958, 2009     

Controlling the formation of long‐subchain hyperbranched polystyrene from seesaw‐type AB2 macromonomers: Solvent polarity and solubility

Through atom transfer radical polymerization of styrene with 1,3‐dibromomethyl‐5‐propargyloxy‐benzene as initiator followed by the conversion of bromine end‐groups into azide end‐groups, well‐defined seesaw‐type polystyrene (PSt) macromonomers with two molecular weights (M_n = 8.0 and 28.0 k) were obtained. Thus, a series of long‐subchain hyperbranched (lsc‐hp) PSt with high overall molar masses and regular subchain lengths were obtained via copper‐catalyzed azide–alkyne cycloaddition click chemistry performed in THF and DMF, respectively. The polycondensation of seesaw‐type macromonomers was monitored by gel permeation chromatography. Because DMF is the reaction medium with higher polarity, click reaction proceeds more easily in DMF. Therefore, the growth of lsc‐hp PSt in DMF has faster rate than that in THF for the shorter seesaw‐type macromonomer (Seesaw‐8k). However, THF is the solvent with better solubility to PSt and leads to looser conformation of PSt chains. Thus, for the longer seesaw macromonomer (Seesaw‐28k), lsc‐hp PSt in THF has higher overall molar mass. As well, the self‐cyclization of seesaw‐type macromonomers also depends on both solvent and molar mass of macromonomer. The self‐cyclization degrees of Seesaw‐8k in DMF and THF are almost the same while that of Seesaw‐28k macromonomer is obviously lower in THF. The experimental results suggest a physical consideration to control the growth of hyperbranched polymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

New polyphenylene‐g‐polystyrene and polyphenylene‐g‐polystyrene/poly(ε‐caprolactone) copolymers by combined controlled polymerization and cross‐coupling processes

1,4‐Dibromo‐2‐(bromomethyl)benzene and 1,3‐dibromo‐5‐(bromomethyl)benzene were used as initiators in the atom transfer radical polymerization of styrene in conjunction with CuBr/2,2′‐bipyridine as a catalyst. The resulting polystyrene (PSt)‐based macromonomers, possessing at one end a 2,5‐dibromophenylene or 3,5‐dibromophenylene moiety, were used in combination with 2,5‐dihexylbenzene‐1,4‐diboronic acid for Suzuki coupling in the presence of Pd(PPh₃)₄ as a catalyst or with the system NiCl₂/2,2′‐bipyridine/triphenylphosphine/Zn for Yamamoto polymerization. Polyphenylenes (PPs) with PSt chains as substitution groups were obtained. The same macromonomers were used in Yamamoto copolycondensation reactions, in combination with a poly(ε‐caprolactone) (PCL) macromonomer, and this resulted in PPs with PSt/PCL side chains. The obtained PPs had good solubility properties in common organic solvents at room temperature similar to those of the starting macromonomers. The new polymers were characterized with ¹H (¹³C) NMR, IR, and gel permeation chromatography. The optical properties of the polymers were monitored with UV and fluorescence spectroscopy. The thermal behaviors of the macromonomers and final PPs were investigated with differential scanning calorimetry and compared. The morphology of PPs containing PSt and PCL blocks was characterized with atomic force microscopy, and a microphase‐separated layered morphology was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 879–896, 2005     

Facile one‐pot synthesis of linear and radial block copolymers of styrene and isoprene through a novel coupling agent by living anionic polymerization

A new methodology is successfully used for the concurrent synthesis of three different copolymers; diblock, triblock, and three‐armed star‐block copolymers of styrene and isoprene via the living anionic polymerization with control over the molecular weight and weight fractions of each block. The room temperature polymerization process has resulted in the well defined linear and radial block copolymers, when the living di‐block of poly(styrene‐b‐isoprene) was coupled using cheap and readily available malonyl chloride as a novel coupling agent giving nearly 100% yield. The resulting block copolymers have narrow polydispersity index (PDI = 1.01–1.09) with a good agreement between the calculated and the observed molecular weights. The results are further supported by fractionation of the block copolymers by reversed‐phase temperature gradient interaction chromatography (RP‐TGIC) technique followed by size exclusion chromatography (SEC). © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2636–2641, 2010     

Hyperbranched polymers with maleic functional groups as radical crosslinkers

The crosslinking performance of the unsaturated hyperbranched polyester poly(allyloxy maleic acid‐co‐maleic anhydride) (MAHP) was investigated with copolymerizations of three different monomers: styrene, vinyl acetate, and methyl methacrylate. Both styrene and vinyl acetate afforded interpenetrating‐polymer‐network copolymer gels. The gels exhibited crosslink density gradients through the polymer matrices on a macroscopic level, and density maximums were concentrated around the MAHP moieties. The heterogeneity of the gels is briefly discussed in terms of a modified two‐phase model, where one phase consists of an elastic part of low crosslinking density and the other phase consists of an inelastic dendritic part with a highly condensed bond density. Unlike the two‐phase model developed by Choquet and Rietsch, the modified two‐phase model takes into account that both phases swell in good solvents. Unlike copolymerizations employing styrene or vinyl acetate, the copolymerization of MAHP with methyl methacrylate afforded noncrosslinked starbranched copolymers that consisted of a MAHP core from which long poly(methyl methacrylate) branches were protruding. The different behaviors of the copolymerizations of the three monomers used in this study can rationally be explained by their different reactivity ratios with maleic end groups of MAHP. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 964–972, 2001