Heterograft copolymers of poly(ε‐caprolactone) prepared by combination of ATRA “grafting onto” and ATRP “grafting from” processes

This paper aims at reporting on the synthesis of a heterograft copolymer by combining the “grafting onto” process based on atom transfer radical addition (ATRA) and the “grafting from” process by atom transfer radical polymerization (ATRP). The statistical copolymerization of ε‐caprolactone (εCL) and α‐chloro‐ε‐caprolactone (αClεCL) was initiated by 2,2‐dibutyl‐2‐stanna‐1,3‐dioxepane (DSDOP), followed by ATRA of parts of the chlorinated units of poly(αClεCL‐co‐εCL) on the terminal double bond of α‐MeO,ω‐CH₂?CH? CH₂? CO₂‐poly(ethylene oxide) (PEO). The amphiphilic poly(εCL‐g‐EO) graft copolymer collected at this stage forms micelles as supported by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The unreacted pendant chloro groups of poly(εCL‐g‐EO) were used to initiate the ATRP of styrene with formation of copolymer with two populations of randomly distributed grafts, that is PEO and polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6015–6024, 2006     

Synthesis and antibacterial activities of water‐soluble methacrylate polymers containing quaternary ammonium compounds

New water‐soluble methacrylate polymers with pendant quaternary ammonium (QA) groups were synthesized and used as antibacterial materials. The polymers with pendant QA groups were obtained by the reaction of the alkyl halide groups of a previously synthesized functional methacrylate homopolymer with various tertiary alkyl amines containing 12‐, 14‐, or 16‐carbon alkyl chains. The structures of the functional polymer and the polymers with QA groups were confirmed with Fourier transform infrared and ¹H and ¹³C NMR. The degree of conversion of alkyl halides to QA sites in each polymer was determined by ¹H NMR to be over 90% in all cases. The number‐average molecular weight and polydispersity of the functional polymer were determined by size exclusion chromatography to be 32,500 g/mol and 2.25, respectively. All polymers were thermally stable up to 180 °C according to thermogravimetric analysis. The antibacterial activities of the polymers with pendant QA groups against Staphylococcus aureus and Escherichia coli were determined with broth‐dilution and spread‐plate methods. All the polymers showed excellent antibacterial activities in the range of 32–256 μg/mL. The antibacterial activity against S. aureus increased with an increase in the alkyl chain length for the ammonium groups, whereas the antibacterial activity against E. coli decreased with increasing alkyl chain length. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5965–5973, 2006     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006     

Copolymerization of N‐vinylcaprolactam and glycidyl methacrylate: Reactivity ratio and composition control

Free‐radical copolymerizations of N‐vinylcaprolactam (VCL) and glycidyl methacrylate (GMA) were investigated to synthesize temperature‐responsive reactive copolymers with minimized compositional heterogeneity. The average copolymer composition was determined by Fourier transform infrared and nuclear magnetic resonance techniques. The reactivity ratios for VCL and GMA were found to be 0.0365 ± 0.0009 and 6.44 ± 0.36 by the Fineman–Ross method and 0.039 ± 0.006 and 6.75 ± 0.29 by the Kelen–Tudos method, respectively. When prepared by batch polymerization, VCL–GMA copolymers had a highly heterogeneous composition and fractions of different solubilities in water. The use of a gradual feeding technique, which included the sequential addition of more reactive GMA monomer into the reaction, yielded copolymers with much more homogeneous composition. The produced copolymers with 0.9 and 0.11 fractional GMA contents preserved their temperature‐responsive properties and precipitated from aqueous solutions when the temperature exceeded 31 °C. The GMA units in the VCL–GMA copolymers were capable of reacting with amino end‐functionalized poly(ethylene oxide) at room temperature to produce poly(N‐vinylcaprolactam)–poly(ethylene oxide) graft copolymers. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 183–191, 2006     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Template atom transfer radical polymerization of a diaminopyrimidine‐derivatized monomer in the presence of a uracil‐containing polymer

Uracil‐derivatized monomer 6‐undecyl‐1‐(4‐vinylbenzyl)uracil and diaminopyrimidine‐derivatized monomer 2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine (DMP) were synthesized and polymerized by atom transfer radical polymerization (ATRP). A well‐defined, highly soluble, uracil‐containing polymer, poly[6‐undecyl‐1‐(4‐vinylbenzyl)uracil] (PUVU), was prepared in dioxane at 90 °C with CuBr/1,1,4,7,10,10‐hexamethyltriethylenetetramine as the catalyst and methyl α‐bromophenylacetate as the initiator. PUVU was further used as a template for the ATRP of DMP. The enhanced apparent rate constant of the DMP polymerization in the presence of PUVU indicated that the ATRP of DMP occurred along the PUVU template. The template polymerization produced a stable and insoluble macromolecular complex, PUVU/poly(2,6‐dioctanoylamido‐4‐methacryloyloxypyrimidine). An X‐ray diffraction study confirmed that the complex had strandlike domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6607–6615, 2006     

Synthesis and characterization of mid‐ and end‐chain functional telechelics by controlled polymerization methods and coupling processes

Well‐defined polystyrene‐ (PSt) or poly(ε‐caprolactone) (PCL)‐based polymers containing mid‐ or end‐chain 2,5 or 3,5‐ dibromobenzene moieties were prepared by controlled polymerization methods, such as atom transfer radical polymerization (ATRP) or ring opening polymerization (ROP). 1,4‐Dibromo‐2‐(bromomethyl)benzene, 1,3‐dibromo‐5‐(bromomethyl)benzene, and 1,4‐dibromo‐2,5‐di(bromomethyl)benzene were used as initiators in ATRP of styrene (St) in conjunction with CuBr/2,2′‐bipyridine as catalyst. 2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene initiated the ROP of ε‐caprolactone (CL) in the presence of stannous octoate (Sn(Oct)₂) catalyst. The reaction of these polymers with amino‐ or aldehyde‐functionalized monoboronic acids, in Suzuki‐type couplings, afforded the corresponding telechelics. Further functionalization with oxidable groups such as 2‐pyrrolyl or 1‐naphthyl was attained by condensation reactions of the amino or aldehyde groups with low molecular weight aldehydes or amines, respectively, with the formation of azomethine linkages. Preliminary attempts for the synthesis of fully conjugated poly(Schiff base) with polymeric segments as substituents, by oxidative polymerization of the macromonomers, are presented. All the starting, intermediate, or final polymers were structurally analyzed by spectral methods (¹H NMR, ¹³C NMR, and IR). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 727–743, 2006