Biodegradable/biocompatible ABC triblock copolymer bearing hydroxyl groups in the middle block

New biodegradable/biocompatible ABC block copolymers, poly(ethylene oxide)‐b‐poly(glycidol)‐b‐poly(L ,L ‐lactide) (PEO‐PGly‐PLLA), were synthesized. First, PEO‐b‐poly(1‐ethoxyethylglycidol)‐b‐PLLA was synthesized by a successive anionic ring‐opening copolymerization of ethylene oxide, 1‐ethoxyethylglycidyl ether, and L ,L ‐lactide initiated with potassium 2‐methoxyethanolate. In the second step, the 1‐ethoxyethyl blocking groups of 1‐ethoxyethylglycidyl ether were removed at weakly acidic conditions leaving other blocks intact. The resulting copolymers were composed of hydrophilic and hydrophobic segments joined by short polyglycidol blocks with one hydroxyl group in each monomeric unit. These hydroxyl groups may be used for further copolymer transformations. The PEO‐PGly‐PLLA copolymers with a molecular weight of PLLA blocks below 5000 were water‐soluble. Above the critical micellar concentration (ranging from 0.05 to1.0 g/L, depending on the composition of copolymer), copolymers formed macromolecular micelles with a hydrophobic PLLA core and hydrophilic PEO shell. The diameters of the micelles were about 25 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3750–3760, 2003     

阴离子聚合制备聚乙烯-g-聚氧化乙烯接枝共聚物

聚烯烃 (聚乙烯 ,聚丙烯等 )的化学改性一直是科学研究和实际生产的一个热点 ,改性过的聚烯烃可以广泛应用到高分子共混物和复合材料中 .在众多聚烯烃中 ,聚乙烯产量最大 ,但因其惰性也最难于化学改性 .我们采取的改性方法是在聚合物中引入反应性基团 ,可以在温和条件下进行有选择的而且高效的化学改性 .由于两亲性共聚物可用作乳液聚合和悬浮聚合中的表面活性剂及稳定剂 ,塑料的表面改良剂和聚合物的共混相容剂等[1,2 ] ,因此人们对该共聚物的研究越来越多 .过去 ,多数两亲性共聚物的研究局限于聚苯乙烯 (ＰＳ)和聚氧化乙烯 (ＰＥＯ)接枝共…     

Synthesis of amphiphilic copolymer brushes: Poly(ethylene oxide)‐graft‐polystyrene

A well‐defined amphiphilic copolymer brush with poly(ethylene oxide) as the main chain and polystyrene as the side chain was successfully prepared by a combination of anionic polymerization and atom transfer radical polymerization (ATRP). The glycidol was first protected by ethyl vinyl ether to form 2,3‐epoxypropyl‐1‐ethoxyethyl ether and then copolymerized with ethylene oxide by the initiation of a mixture of diphenylmethylpotassium and triethylene glycol to give the well‐defined polymer poly(ethylene oxide‐co‐2,3‐epoxypropyl‐1‐ethoxyethyl ether); the latter was hydrolyzed under acidic conditions, and then the recovered copolymer of ethylene oxide and glycidol {poly(ethylene oxide‐co‐glycidol) [poly(EO‐co‐Gly)]} with multiple pending hydroxymethyl groups was esterified with 2‐bromoisobutyryl bromide to produce the macro‐ATRP initiator [poly(EO‐co‐Gly)_(ATRP). The latter was used to initiate the polymerization of styrene to form the amphiphilic copolymer brushes. The object products and intermediates were characterized with ¹H NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, Fourier transform infrared, and size exclusion chromatography in detail. In all cases, the molecular weight distribution of the copolymer brushes was rather narrow (weight‐average molecular weight/number‐average molecular weight < 1.2), and the linear dependence of ln[M₀]/[M] (where [M₀] is the initial monomer concentration and [M] is the monomer concentration at a certain time) on time demonstrated that the styrene polymerization was well controlled. This method has universal significance for the preparation of copolymer brushes with hydrophilic poly(ethylene oxide) as the main chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4361–4371, 2006     

Synthesis of poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyl groups and its further initiation of the grafting polymerization of styrene

A new stratagem for the synthesis of amphiphilic graft copolymers of hydrophilic poly(ethylene oxide) as the main chain and hydrophobic polystyrene as the side chains is suggested. A poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyls [poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide)] was first prepared by the anionic ring‐opening copolymerization of ethylene oxide and 4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl, and then the graft copolymerization of styrene was completed with benzoyl peroxide as the initiator in the presence of poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide). The polymerization of styrene was under control, and comblike, amphiphilic poly(ethylene oxide)‐g‐polystyrene was obtained. The copolymer and its intermediates were characterized with size exclusion chromatography, ¹H NMR, and electron spin resonance in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3836–3842, 2006     

Rapid metal‐free macromolecular coupling via In Situ nitrile oxide‐activated alkene cycloaddition

Nitrile oxide 1,3 dipolar cycloaddition is a simple and powerful coupling methodology. However, the self‐dimerization of nitrile oxides has prevented the widespread use of this strategy for macromolecular coupling. By combining an in situ nitrile oxide generation with a highly reactive activated dipolarophile, we have overcome these obstacles and present a metal‐free macromolecular coupling strategy for the modular synthesis of several ABA triblock copolymers. Nitrile oxides were generated in situ from chloroxime terminated poly(dimethylsiloxane) B‐blocks and coupled with several distinct hydrophilic (poly(2‐methyloxazoline) and poly(ethylene glycol)), and poly(N‐isopropylacrylamide) or hydrophobic (poly(l ‐lactide) A‐blocks terminated in activated dipolarophiles in a rapid fashion with high yield. This methodology overcomes many drawbacks of previously reported metal‐free methods due to its rapid kinetics, versatility, scalability, and ease of introduction of necessary functionality. Nitrile oxide cycloaddition should find use as an attractive macromolecular coupling strategy for the synthesis of biocompatible polymeric nanostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3134–3141     

Synthesis and characterization of new alternating,amphiphilic, comblike copolymers of poly(ethylene oxide) macromonomer and N‐phenylmaleimide

A surface‐active p‐vinyl benzyloxy‐ω‐hydroxy‐poly(ethylene oxide) macromonomer containing 22 pendant structural units of ethylene oxide (St–PEO₂₂) was synthesized with an initiation method. Because of its solubility in a large variety of solvents, the free‐radical copolymerization with electron‐acceptor N‐phenylmaleimide (NPMI) was performed at 60 °C in benzene and tetrahydrofuran (THF) as isotropic media and in a water–THF mixture or water as a heterogeneous medium. Oil‐soluble 2,2′‐azobisisobutyronitrile and water‐soluble 4,4′‐azobis(4‐cyanovaleric acid) were used as the initiators at fixed concentrations. Two different St–PEO₂₂/NPMI comonomer ratios (1/1 and 3/7) at a fixed total comonomer concentration in the polymerization system were used. The structures, compositions, and microstructure peculiarities of the obtained alternating, amphiphilic, comblike copolymers were determined by NMR analysis. For the copolymers synthesized in hydrophilic media, differential scanning calorimetry showed, near the endothermic peak attributed to the melting of the poly(ethylene oxide) side chains, the presence of a second peak due to the partially ordered phase that could exist between the crystalline state and the isotropic melt. Also, the thermal stability of the obtained copolymers was studied with thermogravimetric analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 479–492, 2005     

Synthesis of well‐defined star‐shaped poly(ε‐caprolactone)/poly(ethylbene glycol) amphiphilic conetworks by combination of ring opening polymerization and “click” chemistry

Well‐defined star‐shaped hydrophobic poly(ε‐caprolactone) (PCL) and hydrophilic poly(ethylene glycol) (PEG) amphiphilic conetworks (APCNs) have been synthesized via the combination of ring opening polymerization (ROP) and click chemistry. Alkyne‐terminated six arm star‐shaped PCL (6‐s‐PCLx‐C?CH) and azido‐terminated PEG (N₃‐PEG‐N₃) are characterized by ¹H NMR and FT‐IR. The swelling degree of the APCNs is determined both in water and organic solvent. This unique property of the conetworks is dependent on the nanophase separation of hydrophilic and hydrophobic phases. The morphology and thermal behaviors of the APCNs are investigated by SEM and DSC respectively. The biocompatibility is determined by water soluble tetrazolium salt reagents (WST‐1) assay, which shows the new polymer networks had good biocompatibility. Through in vitro release of paclitaxel (PTX) and doxorubicin (DOX), the APCNs is confirmed to be promising drug depot materials for sustained hydrophobic and hydrophilic drugs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 407–417     

Poly(ethylene imine)‐graft‐poly(ethylene oxide) brush‐like copolymers: Preparation,thermal properties,and selective supramolecular inclusion complexation with α‐cyclodextrin

Poly(ethylene imine)‐graft‐poly(ethylene oxide) (PEI‐g‐PEO) copolymers were synthesized via Michael addition reaction between acryl‐terminated poly(ethylene oxide) methyl ether (PEO) and poly(ethylene imine) (PEI). The brush‐like copolymers were characterized by means of Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopy. It is found that the crystallinity of the PEO side chains in the copolymers remained unaffected by the PEI backbone whereas the crystal structure of PEO side chains was altered to some extent by the PEI backbone. The crystallization behavior of PEO blocks in the copolymers suggests that the bush‐shaped copolymers are microphase‐separated in the molten state. The PEO side chains of the copolymers were selectively complexed with α‐cyclodextrin (α‐CD) to afford hydrophobic side chains (i.e., PEO/α‐CD inclusion complexes). The X‐ray diffraction (XRD) shows that the inclusion complexes (ICs) of the PEO side chains displayed a channel‐type crystalline structure. It is identified that the stoichiometry of the inclusion complexation of the PEI‐g‐PEO with α‐CD is close to that of the control PEO with α‐CD. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2296–2306, 2008     

Characterization of amphiphilic hydrocarbon modified Poly(ethylene glycol) synthesized through ring-opening reaction of 2-(1-octadecenyl)succinic anhydride

Poly(ethylene glycol) (PEG) triblock and diblock amphiphilic block copolymers were synthesized from poly(ethylene glycol) and poly(ethylene glycol) monomethyl ether, respectively. The hydroxyl groups of PEG readily react with 2-(1-octadecenyl) succinic anhydride (OSA) at 140 °C through ring-opening reaction of the succinic anhydride. Both the PEG-OSA diblock and triblock copolymers are produced without use of any solvent or catalyst. The molecular structure of the copolymers was characterized by ¹H NMR and FTIR spectroscopy, and the thermal properties by DSC. The behavior of the copolymers in selective and nonselective solvents was studied by ¹H NMR spectroscopy in deuterium oxide and d-chloroform. The aggregation of the polymers in water was studied with a particle size analyzer and a transmission electron microscope (TEM) in bright field mode. The results show that the hydrophobic C₁₈ chain with intramolecular succinic anhydride linker can be attached to the hydrophilic PEG chain, an ester bond forming between the blocks. The copolymers exhibit flexible, liquid-like hydrophobic blocks even in water, which is a nonsolvent for OSA. PEG-OSA block copolymers self-organize in water, forming micellar polymer aggregates in nanoscale.     

Preparation of the amphiphilic macro‐rings of poly(ethylene oxide) with multi‐polystyrene lateral chains and their extraction for dyes

A novel method for synthesis of amphiphilic macrocyclic graft copolymers with multi‐polystyrene lateral chains is suggested, by combination of anionic ring‐open polymerization (AROP) with atom transfer radical polymerization (ATRP). The anionic ring‐opening copolymerization of ethylene oxide (EO) and ethoxyethyl glycidyl ether (EEGE) was carried out first using triethylene glycol and diphenylmethylpotassium (DPMK) as coinitiators; the monomer reactivity ratio of them are r_1(EO) = 1.20 ± 0.01 and r_2(EEGE) = 0.76 ± 0.02 respectively. The obtained linear well‐defined α,ω‐dihydroxyl poly(ethylene oxide) with pendant protected hydroxylmethyls (l‐poly(EO‐co‐EEGE)) was cyclized by reaction with tosyl chloride (TsCl) in the presence of solid KOH. The crude cyclized product containing the extended linear chain polymer was hydrolyzed and then purified by treat with α‐CD. The pure cyclic copolymer with multipendant hydroxymethyls [c‐poly(EO‐co‐Gly)] was esterified by reaction with 2‐bromoisobutyryl bromide, and then used as macroinitiators to initiate polymerization of styrene (St), and a series of amphiphilic macrocyclic grafted copolymers composed of a hydrophilic PEO as ring and hydrophobic polystyrene as side chains (c‐PEO‐g‐PS) were obtained. The intermediates and final products were characterized by GPC, NMR and MALDI‐TOF in detail. The experimental results confirmed that c‐PEO‐g‐PS shows stronger conjugation ability with the dyes than the corresponding comb‐PEO‐g‐PS. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5824–5837, 2007     

Synthesis and characterization of hydrophilic polyester‐PEO networks with shape‐memory properties

Shape‐memory polyester‐polyethylene oxide networks are synthesized through photopolymerization of hydrophobic poly[(D,L‐lactide)‐co‐glycolide]tetraacrylate (PLGATA) and hydrophilic poly(ethylene glycol) dimethacrylate (PEGDMA). The materials can recover their original shape either quickly by heating stimulus or slowly upon immersion in water. The wettability, mechanical properties, and transition temperature of the polymer networks could be conveniently adjusted by variation of the compositions of PLGATA and PEGDMA. The hydrophilicity of PEGDMA could prospectively improve blood compatibility of polymer networks. They offer a high potential for biomedical applications such as smart implants, drug delivery systems, or medical devices. Copyright © 2010 John Wiley & Sons, Ltd.     

Controlled synthesis of AB2 amphiphilic triarm star-shaped block copolymers by ring-opening polymerization

This paper describes the synthesis of a novel amphiphilic AB₂ triarm star-shaped copolymer with A = non-toxic and biocompatible hydrophilic poly(ethylene oxide) (PEO) and B = biodegradable and hydrophobic poly(ε-caprolactone) (PCL). A series of AB₂ triarm star-shaped copolymers with different molecular-weights for the PCL block were successfully synthesized by a three-step procedure. α-Methoxy-ω-epoxy-poly(ethylene oxide) (PEO-epoxide) was first synthesized by the nucleophilic substitution of α-methoxy-ω-hydroxy-poly(ethylene oxide) (MPEO) on epichlorohydrin. In a second step, the α-methoxy-ω,ω′-dihydroxy-poly(ethylene oxide) (PEO(OH)₂) macroinitiator was prepared by the selective hydrolysis of the ω-epoxy end-group of the PEO-epoxide chain. Finally, PEO(OH)₂ was used as a macroinitiator for the ring-opening polymerization (ROP) of ε-caprolactone (εCL) catalyzed by tin octoaote (Sn(Oct)₂). PEO-epoxide, PEO(OH)₂ and the AB₂ triarm star-shaped copolymers were assessed by ¹H NMR spectroscopy, size exclusion chromatography (SEC) and MALDI-TOF. The behavior of the AB₂ triarm star-shaped copolymer in aqueous solution was studied by dynamic light scattering (DLS) and transmission electron microscopy (TEM).     

Poly(N-phenyl-2-hydroxytrimethylene amine): Its blends with poly(ϵ-caprolactone) and water-soluble polyethers

A new polymer with pendant hydroxyl groups, namely, poly(N-phenyl-2-hydroxytrime-thylene amine) (PHA), was synthesized by a direct condensation polymerization of aniline and epichlorohydrin in an alkaline medium. The new polymer is amorphous with a glass transition temperature (T_g) of 70°C. Blends of PHA with poly(ϵ-caprolactone) (PCL), as well as with two water-soluble polyethers, poly(ethylene oxide) (PEO) and poly(vinyl methyl ether) (PVME), were prepared by casting from a common solvent. It was found that all the three blends were miscible and showed a single, composition dependent glass transition temperature (T_g). FTIR studies revealed that PHA can form hydrogen bonds with PCL, PEO, and PVME, which are driving forces for the miscibility of the blends. © 1997 John Wiley & Sons, Inc.     

Preparation and properties of alkylated poly(styrene-graft-ethylene oxide)

Poly(styrene-graft-ethylene oxide), having alkyl chains (C₁₂ or C₁₈) on the polystyrene main chain or on the poly(ethylene oxide) (PEO) side chains, were synthesized. The main chain was alkylated by first ionizing amide groups in a styrene/acrylamide copolymer with tert-butoxide, and then using the amide anions as sites for reactions with 1-bromoalkanes. An excess of amide anions was used in the reaction, and the remaining anions were subsequently utilized as initiator sites for the anionic polymerization of ethylene oxide (EO). Synthesis of poly(styrene-graft-ethylene oxide) with alkylated side chains was accomplished by polymerization of EO onto the ionized styrene/acrylamide copolymer, followed by an alkylation of the terminal alkoxide anions with 1-bromoalkanes. The alkylated graft copolymers were structurally characterized by using elemental analysis, ¹H NMR, GPC, and IR spectroscopy. DSC analysis showed that only graft copolymers with PEO contents exceeding about 50 wt % and side chain crystallinities comparable to those of homo-PEO. Main chain alkylated graft copolymers generally had higher crystalinities, as compared to nonalkylated and side chain alkylated samples. The graft copolymers absorbed water corresponding to one water molecule per EO unit at low PEO contents. The water absorption increased progressively at PEO contents above 30 wt % for main chain alkylated samples and above 50 wt % for non-alkylated samples. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Laponite clay in homopolymer and tri-block copolymer matrices

Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH _m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments of the adsorbed macromolecule are anchored to the laponite (RD) particles and the remaining segments are radiating away from the surface. The portion of the macromolecule in contact with RD does not contribute to ΔH _m whereas that radiating away from the clay does. Once that the RD surface is saturated, the excess of the macromolecule behaves like the pure one. The proposed model allowed to compute successfully the ΔH _m values. The X-ray diffraction experiments ruled out the polymer intercalation between the silicate sheets.     

Comblike poly(ethylene oxide)/hydrophobic C6 branched chitosan surfactant polymers as anti-infection surface modifying agents

A series of structurally well-defined poly(ethylene oxide)/hydrophobic C₆ branched chitosan surfactant polymers that undergo surface induced self assembly on hydrophobic biomaterial surfaces were synthesized and characterized. The surfactant polymers consist of low molecular weight (M_w) chitosan backbone with hydrophilic poly(ethylene oxide) (PEO) and hydrophobic hexyl pendant groups. Chitosan was depolymerized by nitrous acid deaminative cleavage. Hexanal and aldehyde-terminated PEO chains were simultaneously attached to low M_w chitosan hydrochloride via reductive amination. The surfactant polymers were prepared with various ratios of the two side chains. The molecular composition of the surfactant polymers was determined by FT-IR and ¹H NMR. Surface active properties at the air–water interface were determined by Langmuir film balance measurements. The surfactant polymers with PEO/hexyl ratios of 1:3.0 and 1:14.4 were used as surface modifying agents to investigate their anti-infection properties. E. coli adhesion on Silastic^® surface was decreased significantly by the surfactant polymer with PEO/hexyl 1:3.0. Surface growth of adherent E. coli was effectively suppressed by both tested surfactant polymers.     

Synthesis and characterization of nanoporous polycaprolactone membranes via thermally- and nonsolvent-induced phase separations for biomedical device application

A family of crosslinked poly(ethylene glycol) diacrylate (XLPEGDA) materials was synthesized via free-radical photopolymerization of poly(ethylene glycol) diacrylate (PEGDA) solutions in water. These materials are potential fouling-resistant coatings for ultrafiltration (UF) membranes. PEGDA chain length (n = 10–45, where n is the average number of ethylene oxide units in the PEGDA molecule) and water content in the prepolymerization mixture (0–80 wt.%) were varied, resulting in XLPEGDA materials with water permeability values ranging from 0.5 to 150 L μm/(m² h bar). Generally, water permeability increased with increasing prepolymerization water content and with increasing PEGDA chain length. Moreover, water permeability exhibits a strong correlation with equilibrium water uptake. However, solute rejection, probed using poly(ethylene glycol)s of well defined molar mass, decreased with increasing prepolymerization water content and increasing PEGDA chain length. That is, there is a tradeoff between water permeability and separation properties. Finally, the fouling resistance of XLPEGDA materials was characterized via contact angle measurements and static protein adhesion experiments. From these results, XLPEGDA surfaces are more hydrophilic in samples prepared at higher prepolymerization water content or with longer PEGDA chains, and the more hydrophilic surfaces generally exhibit less BSA accumulation.     

Effects of temperature on neutron scattering from aqueous solutions of hydrophobically modified poly(ethylene oxide)

The effect of temperature on the structure of aqueous dispersions of hydrophobically end-capped poly(ethylene oxide) (PEOM) was investigated by small angle neutron scattering (SANS). Polymers with hydrogenated or deuterated n-octadecyl end-groups were studied in heavy water or in a mixture heavy water / water, respectively. In the latter case the PEO chains were selectively matched. In all the cases, the scattering curves were characterised by a main peak which revealed organisation of polymers into micelles consisting of hydrophobic cores surrounded by repulsive PEO coronae. Measurements were performed in the semi-dilute regime where micelles coronae overlap. At constant polymer concentration, an increase in temperature leads to decreasing solvent strength of water for the PEO chains and decreasing repulsion between the PEO coronae. As a result, the intensity of the peak in a mixture of water /heavy water decreases with temperature On the contrary, in heavy water, the peak of the scattered intensity increases with increasing temperature. This scattering behaviour is interpreted on the basis of a scaling theory of the semi-dilute solutions of star-like polymer micelles.     

Synthesis of starlike PtBA‐g‐PEO amphiphilic graft copolymer via highly efficient Cu‐catalyzed SET‐NRC reaction at ambient temperature

Two new amphiphilic star graft copolymers bearing hydrophobic poly(tert‐butyl acrylate) backbone and hydrophilic poly(ethylene oxide) (PEO) side chains with different molecular weights were synthesized by sequential reversible addition fragmentation chain transfer (RAFT) polymerization and single electron transfer‐nitroxide radical coupling (SET‐NRC) reaction under mild conditions. RAFT homopolymerization of tert‐butyl 2‐((2‐bromopropanoyloxy)methyl)acrylate was mediated by a four‐armed chain transfer agent in a controlled way to afford a well‐defined starlike backbone with a narrow molecular weight distribution (M_w/M_n = 1.26). The target poly(tert‐butyl acrylate)‐g‐PEO (PtBA‐g‐PEO) star graft copolymers were synthesized by SET‐NRC reaction between Br‐containing PtBA‐based starlike backbone and PEO end functionalized with 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) group using copper/N,N,N′,N′,N″‐pentamethyldiethylenetriamine as catalytic system at ambient temperature via grafting‐onto strategy. The critical micelle concentration values of the obtained amphiphilic star graft copolymers in aqueous media and brine were determined by fluorescence probe technique using pyrene as probe. Diverse micellar morphologies were formed by varying the content of hydrophilic PEO segment as well as the initial concentration of stock solution. In addition, poly(acrylic acid)‐g‐PEO double hydrophilic star graft copolymers were obtained by selective acidic hydrolysis of hydrophobic PtBA starlike backbone without affecting PEO side chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010