Synthesis and characterization of the novel block copolymer poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine) by the combination of coordination and controlled free‐radical polymerizations

A novel block copolymer, poly(ε‐caprolactone)‐b‐poly(4‐vinyl pyridine), was synthesized with a bifunctional initiator strategy. Poly(ε‐caprolactone) prepolymer with a 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) end group (PCL_T) was first obtained by coordination polymerization, which showed a controlled mechanism in the process. By means of ultraviolet spectroscopy and electron spin resonance spectroscopy, the TEMPO moiety was determined to be intact in the polymerization. The copolymers were then obtained by the controlled radical polymerization of 4‐vinyl pyridine in the presence of PCL_T. The desired block copolymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, and NMR spectroscopy in detail. Also, the effects of the molecular weight and concentration of PCL_T on the copolymerization were investigated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2280–2285, 2004     

Development and characterization of homopolymers and copolymers from the family of polyphenylene oxides

Poly(2,6‐dimethyl‐1,4‐phenylene oxide), PDMPO, poly(2,6‐diphenyl‐1,4‐phenylene oxide), PDPPO, as well as their copolymers of different compositions, having both random and block structures, have been synthesized and characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, and gel permeation chromatography. Solution‐cast films were prepared from all synthesized polymers using chloroform as a solvent. The thermal properties of the resulting films were characterized by differential thermal analysis and differential scanning calorimetry, whereas their morphology was investigated using X‐ray diffraction. Ultimately, the potential of the synthesized polymers for gas separation was studied by examining gas permeation properties of the respective thin films in single gas permeation tests involving N₂, O₂, CH₄, and CO₂. In general, the O₂ and CO₂ permeability coefficients decrease with the PDPPO content. However, the largest drop in the permeability coefficients occurs between PDMPO and a copolymer having the lowest PDPPO content, and the permeability coefficients PDPPO are comparable or even lower than the permeability coefficients of the copolymers having the largest PDDPO content. On the basis of combination of the permeability coefficients and their ratios for CO₂/CH₄ and O₂/N₂, random copolymers appear to be a better candidate for gas separation membranes than their block counterparts. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of a poly(ether–ester) copolymer from poly(2,6 dimethyl‐1,4‐phenylene oxide) and poly(ethylene terephthalate)

A series of poly(ether–ester) copolymers were synthesized from poly(2,6 dimethyl‐1,4‐phenylene oxide) (PPO) and poly(ethylene terephthalate) (PET). The synthesis was carried out by two‐step solution polymerization process. PET oligomers were synthesized via glycolysis and subsequently used in the copolymerization reaction. FTIR spectroscopy analysis shows the coexistence of spectral contributions of PPO and PET on the spectra of their ether–ester copolymers. The composition of the poly(ether–ester)s was calculated via ¹H NMR spectroscopy. A single glass transition temperature was detected for all synthesized poly(ether–ester)s. T_g behavior as a function of poly(ether–ester) composition is well represented by the Gordon‐Taylor equation. The molar masses of the copolymers synthesized were calculated by viscosimetry. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of poly(methylphenylsiloxane) rich in syndiotacticity by Rh‐catalysed stereoselective cross‐dehydrocoupling polymerization of optically active 1,3‐dimethyl‐1,3‐diphenyldisiloxane derivatives

Cross‐dehydrocoupling reactions of (R)‐methyl(1‐naphthyl)phenylsilane (>99%ee) with (S)‐methyl(1‐naphthyl)phenylsilanol (>99% ee) proceeded with 82–99% retention of configuration of chiral silicon centres in the presence of various Rh‐catalysts. Cross‐dehydrocoupling polymerization of 1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediol with 1,3‐dihydro‐1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxane gave poly(methylphenylsiloxane) of moderate molecular weight in toluene at 60 °C in the presence of [RhCl(cod)]₂ (5.0 mol%) and triethylamine (1.0 equivalent). Assignment of the triad signals of the resulting polymer was made by ¹H NMR spectroscopy of the methyl proton (I = 0.04, H = 0.09 and S = 0.14 ppm) and ¹³C NMR spectroscopy of the ipso carbon of the phenyl group (S = 136.7, H = 136.9, and I = 137.1 ppm). Although the reaction of optically pure (S,S)‐1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediol with 1,3‐dihydro‐1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxane [(S,S):(S,R):(R,R)] = 84:16:0] gave a poly(methylphenylsiloxane) of rather low molecular weight, its triad tacticity was found to be rich in syndiotacticity (S:H:I = 60:32:8) by ¹³C NMR spectroscopy. © 2001 Society of Chemical Industry     

Copolymerization of carbon monoxide with exo‐methylenecycloalkane and dienes: synthesis of functionalized aliphatic polyketones

Synthesis of functional aliphatic polyketones was achieved by co‐ and terpolymerization of the strained exo‐methylenecycloalkane, methylenecyclopropane (MCP), and also the dienes 1,5‐hexadiene, 1,7‐octadiene and 1,6‐heptadien‐4‐ol, with carbon monoxide and propene, using the dicationic palladium(II) phosphine complex [Pd(dppp) (NCCH₃)₂](BF₄)₂ (I) (dppp is 1,3‐bis(diphenyl‐phosphino)propane) as the catalyst precursor. The resulting MCP/CO copolymer contains both ring‐opened and cyclic microstructures. Ring‐opening copolymerization yields exo‐methylene functionalized polyketone. In contrast to hexadiene/carbon monoxide copolymer (Hx/CO), no ring structures were observed in the alternating octadiene/carbon monoxide (Oc/CO) and heptadien‐4‐ol/carbon monoxide (Hp‐ol/CO) copolymers. The remaining double bonds were left intact to yield polymers with olefinic functionalities in the side chains. © 2001 Society of Chemical Industry     

Polymerization of Substituted Acetylenes Using Well‐Defined Rhodium Complex Catalyst. Chirality Transfer and Amplification in Chiral‐Chiral Block and Random Copolymers

Block and random copolymers are synthesized by the copolymerization of N‐tert‐butoxycarbonyl‐?‐valine 4‐ethynylanilide ( 1L ) and N‐tert‐butoxycarbonyl‐d‐valine 4‐ethynylanilide ( 1D ) using [(nbd)Rh{C(Ph) = CPh₂}(PPh₃)]/PPh₃ as a catalyst. The size exclusion chromatography (SEC) peaks show narrow polydispersities from the first stage polymerization to the second one in the block copolymerization. Poly( 1L ₂₅‐ran‐ 1D ₂₅) exhibits no circular dichroism (CD) signal, while poly( 1L ₂₅)‐block‐poly( 1D ₂₅) exhibits weak CD signals with the same sign as those of poly( 1L ₅₀), suggesting the occurrence of chirality transfer from the poly( 1L ) block to poly( 1D) block. The relationship between the |g| values and 1L / 1D contents of the block copolymers becomes almost linear at the region of each unit larger than 60%. On the other hand, the relationship between these two factors of the random copolymers is convex upward.     

Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Novel copolyesters containing naphthalene structure III. Copolyesters prepared from 2,6‐dimethyl naphthalate,ethylene glycol,and 2,2‐dialkyl‐1,3‐propanediols

Poly(ethylene naphthalate) (PEN) copolymers were prepared by melt polycondensation of dimethyl naphthalate and excess ethylene glycol with 5–40 mol % (in feed) of 1,3‐propanediol or 2,2‐dialkyl‐1,3‐propanediols, where the dialkyl groups are dimethyl, diethyl, and butyl‐ethyl. No significant depression of reduced specific viscosity was observed. The comonomer contents in the copolymers are considerably higher than those in the feed. The effects of the copolymer composition on the structures of the films were investigated using thermal analyses, density measurements, X‐ray diffraction methods, and other physical tests. The crystallinities and densities of heat‐treated films decreased with increasing content of comonomer and length of alkyl side chain in the comonomer. The glass transition temperature (T_g) and melting temperature (T_m) were decreased by the copolymerization, while an increase in the length of the alkyl side chain hardly affected T_ms of the heat‐treated films. Alkali resistance, moisture resistance, dye ability, and thermal shrinkage were increased by the incorporation of comonomer having an alkyl side chain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2754–2763, 2001     

Synthesis and surface properties of polydimethylsiloxane‐based block copolymers: poly[dimethylsiloxane‐block‐ (ethyl methacrylate)] and poly[dimethylsiloxane‐block‐(hydroxyethyl methacrylate)]

A polydimethylsiloxane (PDMS) macroazoinitiator was synthesized from bis(hydroxyalkyl)‐terminated PDMS and 4,4′‐azobis‐4‐cyanopentanoic acid by a condensation reaction. The bifunctional macroinitiator was used for the block copolymerization of ethyl methacrylate (EMA) and 2‐(trimethylsilyloxy)ethyl methacrylate (TMSHEMA) monomers. The poly(DMS‐block‐EMA) and poly(DMS‐block‐TMSHEMA) copolymers thus obtained were characterized using Fourier transform infrared and ¹H NMR spectroscopy and differential scanning calorimetry. After the deprotection of trimethylsilyl groups, poly(DMS‐block‐HEMA) and poly(DMS‐block‐EMA) copolymer film surfaces were analysed using scanning electron microscopy and X‐ray photoelectron spectroscopy. The effects of the PDMS concentration in the copolymers on both air and glass sides of films were examined. The PDMS segments oriented and moved to the glass side in poly(DMS‐block‐EMA) copolymer film while orientation to the air side became evident with increasing DMS content in poly(DMS‐block‐HEMA) copolymer film. The block copolymerization technique described here is a versatile and economic method and is also applicable to a wide range of monomers. The copolymers obtained have phase‐separated morphologies and the effects of DMS segments on copolymer film surfaces are different at the glass and air sides. Copyright © 2010 Society of Chemical Industry     

Microwave radiation copolymerization of dibutyltin maleate and allyl thiourea

This article reports on an investigation of microwave radiation copolymerization of dibutyltin maleate (DBTM) with allyl thiourea (AT) and the copolymers it produced. The effect of radiation energy, composition of monomer, amount of initiator, and amount and kind of inorganic oxide (Al₂O₃ or SiO₂) as reaction sensitizers on the copolymerization conversion and polymer‐inherent viscosity were systematically studied, and simultaneously compared with the relevant conventional thermopolymerization. The reactivity ratios for DBTM and AT were determined using liquid chromatography. The copolymerization mechanism of microwave radiation was probed using a free‐radical capturing agent (DPPH). The copolymers obtained were used as heat‐stabilization agent of PVC resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 312–318, 2001     

Synthesis and characterization of thermoplastic poly(ester–siloxane)s

Two series of thermoplastic poly(ester–siloxane)s, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) as the hard segment, were synthesized by two‐step catalyzed transesterification reactions in the melt. Incorporation of soft poly(dimethylsiloxane) segments into the copolyester backbone was accomplished in two different ways. The first series was prepared based on dimethyl terephthalate, 1,4‐butanediol and silanol‐terminated poly(dimethylsiloxane) (PDMS‐OH). For the second series, the PDMS‐OH was replaced by methyl diesters of carboxypropyl‐terminated poly(dimethylsiloxane)s. The syntheses were optimized in terms of both the concentration of catalyst, tetra‐n‐butyl‐titanate (Ti(OBu)₄), and stabilizer, N,N′‐diphenyl‐p‐phenylene‐diamine, as well as the reaction time. The reactions were followed by measuring the inherent viscosities of the reaction mixture. The molecular structures of the synthesized poly(ester–siloxane)s were verified by ¹H NMR spectroscopy, while their thermal properties were investigated using differential scanning calorimetry. © 2001 Society of Chemical Industry     

Synthesis,characterization, and gamma radiation effects over well‐defined poly(vinylsiloxanes) copolymers

Anionic ring‐opening polymerization (AROP) was employed for the controlled synthesis of linear model block copolymers of 1,3,5,7‐tetrametil‐1,3,5,7‐tetravinyl(cyclotetrasiloxane) (V₄) and 1,3,5‐dimethyl(cyclotrisiloxane) (D₃) monomers by using sec‐butyl lithium (sec‐Bu^?Li⁺) as initiator, and high‐vacuum anionic polymerization techniques. V₄ copolymerization was promoted by employing D₃ and sec‐Bu^?Li⁺ producing living silanolates that open the stable V₄ ring. For this purpose, two strategies were applied: (a) sequential addition of monomers, and (b) one‐step copolymerization at different reaction temperatures. According to the experimental results, higher levels of V₄ incorporation (～ 18.14 mol %) were obtained by mixing both co‐monomers and performing the reaction at high temperature (80°C). This strategy allowed the control of the V₄ incorporation into the copolymer structure, giving the opportunity of synthesizing model vinyl‐siloxane polymers. The gamma radiation of these materials showed that lower doses are needed to achieve the same gel content as in a model poly(dimethylsiloxane) (PDMS). In such a sense, these results constitute one of the first reports regarding the effect of gamma radiation on vinyl‐containing silicon polymers, and may be of fundamental importance if a biomedical cross‐linked rubber‐type PDMS is needed at earlier doses of sterilization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study of a new titanium dual initiator for the synthesis of poly(ε‐caprolactone)‐b‐polystyrene block copolymers by the combination of coordination and nitroxide mediated polymerizations

Poly ε‐caprolactone‐polystyrene block‐copolymers (PCL‐b‐PSt) were synthesized using a modified titanium catalyst as the dual initiator. Alcoholysis of Ti(OPr)₄ by 4‐hydroxy 2,2,6,6 tetramethyl piperidinyl‐1‐oxyl (HO‐TEMPO) gave a bifunctional initiator Ti(OTEMPO)₄. Poly ε‐caprolactone prepolymer end‐capped with the nitroxide group was first prepared by ring opening polymerization of ε‐caprolactone with this initiator at high conversion. The nitroxide‐end‐capped structure and molar mass (M_n) of the polymers were demonstrated by typical UV absorption band. This analytical technique indicates a near‐quantitative nitroxide functionality and a M_n in good agreement with size exclusion chromatography (SEC) ones. This polyester prepolymer was used to further initiate the radical polymerization with styrene and reach the block copolymers (PCL‐b‐PSt). All the prepolymers and block copolymers were characterized by SEC and NMR spectroscopy. Additionally, the preparation of star polymers bearing two kinds of arms (PCL and PSt) was envisaged and a preliminary result was given. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of styrene–acrylic ester copolymers

Homopolymers and copolymers of styrene and different acrylic esters (i.e., acrylates) were synthesized by the free‐radical solution polymerization technique. Feed ratios of the monomers styrene and cyclohexyl acrylate/benzyl acrylate were 90 : 10, 75 : 25, 60 : 40, 50 : 50, 40 : 60 and 20 : 80 (v/v) in the synthesis of copolymers. All 6 homopolymerizations of acrylic ester synthesis were carried out in N,N(dimethyl formamide) except for the synthesis of poly(cyclohexyl acrylate) (PCA), where the medium was 1,4‐dioxane. Benzoyl peroxide (BPO) and azobisisobutyronitrile (AIBN) were used as initiators. The polymers synthesized were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and viscosity measurements. The reactivity ratios were determined by the Fineman–Ross method using ¹H‐NMR spectroscopic data. The reactivity ratios (r) for the copolymerization of styrene (r_S) with cyclohexyl acrylate (r_CA) were found to be r_S = 0.930 and r_CA = 0.771, while for the copolymerization of styrene with benzyl acrylate, the ratios were found to be r_S = 0.755 and r_BA = 0.104, respectively. The activation energies of decomposition (E_a) and glass‐transition temperature (T_g) for various homo‐ and copolymers were evaluated using TGA and DSC analysis. The activation parameters of the viscous flow, voluminosity (V_E) and shape factor (ν) were also computed for all systems using viscosity data. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1513–1524, 2001     

Well-defined poly(2-hydroxyethyl methacrylate) and its amphiphilic block copolymers via acidolysis of anionically synthesized poly(2-vinyloxyethyl methacrylate)

Summary A novel approach to a well-defined poly(2-hydroxyethyl methacrylate) [poly(HEMA)] and to its amphiphilic block copolymers was developed. The selective living anionic polymerization of the methacryloyl group of the bifunctional monomer 2-vinyloxyethyl methacrylate (VEMA) generated a functional polymer with a controlled molecular weight and a narrow molecular weight distribution (M_w/M_n= 1.05–1.09). This polymer is very stable under normal conditions. Being soluble in the common organic solvents, its characterization could be carried out easily. The unreacted vinyl groups in the side chains of the resulting polymer were further reacted with hydrochloric acid. This acidolysis changed poly(VEMA) to a well-defined poly(HEMA). In addition, the anionic block copolymerization of VEMA with styrene or methyl methacrylate also proceeded smoothly, generating the corresponding block copolymers. After acidolysis, these copolymers were turned into amphiphilic block copolymers containing a hydrophilic poly(HEMA) block. Received: 22 June 2001/Revised version: 15 August 2001/Accepted: 15 August 2001     

Block copolymerization of poly(ethylene glycol) with methyl methacrylate using redox macroinitiators

A series of block copolymers of poly(ethylene glycol) (PEG) with methyl methacrylate (MMA) were prepared using a redox system consisting of ceric ion and PEG of various molecular weights in aqueous medium. The block copolymerization experiments were carried out under such conditions in which there was no homopolymerization of MMA by Ce⁴⁺ alone. The intermediacy of the PEG macroradical in the redox process was substantiated by ESR spectroscopy and a polymerization proceeding through ‘blocking from’ mechanism was postulated. The formation of the block copolymers was confirmed by chemical test and fractional precipitation as well as by FT-IR and FT-NMR (¹H and ¹³C-(¹H)) spectroscopy. The triblock nature of the block copolymers was ascertained through the cleavage of the ether linkage of the PEG segment. Simultaneous TG/DTA studies of the block copolymers revealed multiple stage decomposition patterns and their DSC curves exhibited two glass transition temperatures. GPC investigation of the block copolymers revealed unimodal molecular weight distribution with M_n values showing a smooth increase with ascending molecular weights of PEG. SEM studies indicated a fine dispersion of PEG in the continuous PMMA matrix.     

Nitroxide‐mediated homopolymerization and copolymerization of 2‐vinylpyridine with styrene

Homopolymerization and copolymerization of 2‐vinylpyridine (2VP) with styrene (S) at 125°C in the presence of 2,2,6,6‐tetramethyl piperidin‐1‐yloxyl (TEMPO) radicals have been studied. The homopolymerization was carried out with 2,2′‐azobis(isobutyronitrile) (AIBN) as a thermal initiator or without AIBN in the initial reaction mixture. In the copolymerization initiated with AIBN, the molar fraction of 2VP in the feed, F_2VP, varied in the range of 0.1–0.9; F_2VP = 0.65 was found to be the azeotropic composition. The linear semilogarithmic time–conversion plots demonstrated a pseudoliving nature of the polymerizations under study. The molecular weight–conversion dependences indicated the participation of side reactions, diminishing the number of TEMPO‐terminated polymer chains. The synthesized homopolymers and copolymers were characterized using size‐exclusion chromatography (SEC), nitrogen analysis, and NMR spectroscopy. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2024–2030, 2001     

Novel amphiphilic polymer gel electrolytes based on (PEG‐b‐GMA)‐co‐MMA

Amphiphilic conetwork–structured copolymers containing different lengths of ethylene oxide (EO) chains as ionophilic units and methyl methacrylate (MMA) chains as ionophobic units were prepared by free radical copolymerization and characterized by FTIR and thermal analysis. Polymer gel electrolytes based on the copolymers complexed with liquid lithium electrolytes (dimethyl carbonate (DMC) : diethyl carbonate (DEC) : ethylene carbonate (EC) = 1 : 1 : 1 (W/W/W), LiPF₆ 1.0M) were characterized by differential scanning calorimetry and impedance spectroscopy. A maximum ion conductivity of 4.27 × 10^?4 S/cm at 25^oC was found for the polymer electrolyte based on (PEG2000‐b‐GMA)‐co‐MMA with long EO groups. Moreover, the effect of temperature on conductivity of the amphiphilic polymer electrolytes obeys the Arrhenius equation. The good room temperature conductivity of the polymer electrolytes is proposed to relate to the enhancement in the amorphous domain of the copolymers due to their amphiphilic conetwork structure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Styrene/phosphonic acid copolymers: Synthesis and thermal,mechanical, and electrochemical characterization

In this study, a series of poly(styrene‐co‐vinyl phosphonic acid) [P(S‐co‐VPA)] copolymers were synthesized by the free‐radical copolymerization of styrene and vinyl dimethyl phosphonate followed by alkaline hydrolysis. The P(S‐co‐VPA) copolymers were characterized by size exclusion chromatography (gel permeation chromatography), Fourier transform infrared vibrational spectroscopy, proton nuclear magnetic resonance, thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and electrochemical impedance spectroscopy. Despite the difference between the copolymerization ratios of styrene and vinyl dimethyl phosphonate, the resulting copolymers presented single glass transitions at temperatures that depended on the acidic group amount. The glass transition shifted to a higher temperature and became broader as the amount of phosphonic acid increased. The storage modulus at temperatures higher than the glass transition also increased with increasing acidic groups because of intramolecular and intermolecular interactions. All of the acid copolymers were thermally stable to at least 300°C. A high oxidative stability was found for 3 : 1 P(S‐co‐VPA), which also presented conductivity values on the order of 10⁻⁶ Ω⁻¹ cm⁻¹ at room temperature. The 1 : 1 P(S‐co‐VPA) membrane presented Arrhenius‐type behavior at temperatures from 30 to 80°C and conductivity on the order of 10⁻⁵ Ω⁻¹ cm⁻¹. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and aggregation behavior of four types of different shaped PCL‐PEG block copolymers

Biodegradable, amphiphilic, linear (diblock and triblock) and star‐shaped (three‐armed and four‐armed) poly[(ethylene glycol)‐block‐(ε‐caprolactone)] copolymers (PEG–PCL copolymers) were synthesized by ring‐opening polymerization of ε‐caprolactone (CL) with stannous octoate as a catalyst, in the presence of monomethoxypoly(ethylene glycol) (MPEG), poly(ethylene glycol) (PEG), three‐armed poly(ethylene glycol) (3‐arm PEG) or four‐armed poly(ethylene glycol) (4‐arm PEG) as an initiator, respectively. The monomer‐to‐initiator ratio was varied to obtain copolymers with various PEG weight fractions in a range 66–86%. The molecular structure and crystallinity of the copolymers, and their aggregation behavior in the aqueous phase, were investigated by employing ¹H‐NMR spectroscopy, gel permeation chromatography and differential scanning calorimetry, as well as utilizing the observational data of gel–sol transitions and aggregates in aqueous solutions. The aggregates of the PEG–PCL block copolymers were prepared by directly dissolving them in water or by employing precipitation/solvent evaporation technique. The enthalpy of fusion (ΔH_m), enthalpy of crystallization (ΔH_crys) and degrees of crystallinity (χ_c) of PEG blocks in copolymers and the copolymer aggregates in aqueous solutions were influenced by their PEG weight fractions and molecular architecture. The gel–sol transition properties of the PEG–PCL block copolymers were related to their concentrations, composition and molecular architecture. Copyright © 2006 Society of Chemical Industry