Self‐assembly of amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers

Amphiphilic tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers consisting of one polystyrene block and two poly(N‐isopropylacrylamide) blocks were prepared by the “arm‐first” method in which RAFT polymerization and nonconvalent ligand–metal complexation were employed. The prepared amphiphilic star‐shaped metallopolymers are able to form micelles in water. The size and distribution of the micelles were studied by dynamic light scattering and transmission electron microscopy techniques. Preliminary studies indicate that the polymer concentration and the hydrophilic poly(N‐isopropylacrylamide) block length can affect the morphologies of the formed metal‐interfaced core–shell micelles in water. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4204–4210, 2007     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

Yellow‐light‐emitting cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative: Its synthesis and optical properties

A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λ_max ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003     

Sulfonated poly(aryl ether ketone)s containing naphthalene moieties obtained by direct copolymerization as novel polymers for proton exchange membranes

A series of sulfonated poly(aryl ether ketone)s (SPAEKs) were prepared by aromatic nucleophilic polycondensation of 2,6‐dihydroxynaphthalene with 5,5′‐carbonyl‐bis(2‐fluorobenzenesulfonate) and 4,4′‐difluorobenzophenone. The structure and degree of sulfonation (DS) of the SPAEKs were characterized using ¹H NMR spectroscopy. The experimentally observed DS values were close to the expected values derived from the starting material ratios. The thermal stabilities of the SPAEKs were characterized by thermogravimetric analysis, which showed that in acid and sodium salt forms they were thermally stable in air up to about 240 and 380 °C, respectively. Transparent membranes cast from the directly polymerized SPAEKs exhibited good mechanical properties in both dry and hydrated states. The dependence of water uptake and of membrane swelling on the DS at different temperatures was studied. SPAEK membranes with a DS from 0.72 to 1.60 maintained adequate mechanical properties after immersion in water at 80 °C for 24 h. The proton conductivity of SPAEK membranes with different degrees of sulfonation was measured as a function of temperature. The proton conductivity of the SPAEK films increased with increased DS, and the highest room temperature conductivity (4.2 × 10^?2 S/cm) was recorded for a SPAEK membrane with a DS of 1.60, which further increased to 1.1 × 10^?1 S/cm at 80 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2866–2876, 2004     

UV‐ignited frontal polymerization of an epoxy resin

By combining frontal polymerization and radical‐induced cationic polymerization, it was possible to cure thick samples of an epoxy monomer bleached by UV light. The effect of the relative amounts of cationic photoinitiator and radical initiator was thoroughly investigated and was related to the front's velocity and its maximum temperature. The materials obtained were characterized by quantitative conversion also in the deeper layers, not reached by UV light. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2066–2072, 2004     

Synthesis and structural characterization of novel,fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (S_NAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl₃, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 10³ to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004     

Synthesis and characterization of alt‐bipyridinylene‐phenylene copolymers containing ruthenium(II) complexes

Poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3a ), poly{bis(4,4′‐tert‐butyl‐2,2′‐bipyridine)–(2,2′‐bipyridine‐4,4′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3b ), and poly{bis(2,2′‐bipyridine)–(2,2′‐bipyridine‐5,5′‐diyl‐[1,4‐phenylene])–ruthenium(II)bishexafluorophosphate} ( 3c ) were synthesized by the Suzuki coupling reaction. The alternating structure of the copolymers was confirmed by ¹H and ¹³C NMR and elemental analysis. The polymers showed, by ultraviolet–visible, the π–π* absorption of the polymer backbone (320–380 nm) and at a lower energy attributed to the d–π* metal‐to‐ligand charge‐transfer absorption (450 nm for linear 3a and 480 nm for angular 3b ). The polymers were characterized by a monomodal molecular weight distribution. The degree of polymerization was approximately 8 for polymer 3b and 28 for polymer 3d . © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2911–2919, 2004     

New functionalized polyesters to achieve controlled architectures

Following our continued interest in the production of bioerodible and biodegradable functional polymers for biomedical applications, we synthesized and characterized new unsaturated polyesters. The presence of functional groups in the polymer backbone provided sites for chemical modification, and through a variation in the structure, the physical properties, such as the hydrophilicity and solubility, could be affected. With 1,1-di-n-butyl-stanna-2,7-dioxacyclo-4-heptene as the initiator in the ring-opening polymerization of polyesters, a new set of functionalized polyesters was created. The polymerization of ϵ-caprolactone resulted in poly(ϵ-caprolactone) with a double bond incorporated into the structure. The polymers were obtained in a controlled manner with low molecular dispersities. The double bond was previously incorporated into L -lactide polymers, and the two reactions were compared in this study. The conversion of ϵ-caprolactone, with a degree of polymerization of 50, was completed within 140 min, whereas for L -lactide, only a 45% conversion took place in the same period of time. The dispersities were somewhat higher with ϵ-caprolactone because of the higher reaction rate and, therefore, lower selectivity. The incorporated CC double bond in the polyesters provided a variety of opportunities for further modifications. In this case, the double bond of the L -lactide macromonomers was oxidized into epoxides. Epoxidation was carried out with m-chloroperoxybenzoic acid as a chemical reagent. The conversion of the double bonds into epoxides was completed, and the obtained yields were good (>95%). As a result of the mild reaction conditions, the epoxidation of the double bond was carried out quantitatively without any side reactions. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 444–452, 2004     

Functionalization of polyethylene/silane copolymers in posttreatment reactions

7‐Octenyldimethylphenylsilane was copolymerized with ethylene via Et(Ind)₂ZrCl₂ methylaluminoxane catalyst system without loss of catalyst activity or decrease in molar mass. The comonomer contents in the polymer samples were at a level of 0.15–1.0 mol % and the reactive phenylsilane groups were posttreated to different alcoxy‐ and halosilane groups, for example, Si? F, Si? Cl, Si? OCH₃, and Si? OCH₂CH₃. The posttreatment reactions had no major effect on the molar masses or on the thermal properties (measured with differential scanning calorimetry) of the copolymers. The reaction pathways were nearly independent of the comonomer contents and the reactions reached 70–100% conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1461–1467, 2004     

Synthesis and characterization of linear tetrablock quarterpolymers of styrene,isoprene, dimethylsiloxane,and 2-vinylpyridine

A series of five tetrablock quarterpolymers of styrene, isoprene, dimethylsiloxane, and 2-vinylpyridine with molecular weights varying from 117 × 10³ to 177 × 10³ and having different compositions were synthesized. The synthesis was based on recent advances in the controlled high-vacuum anionic polymerization of hexamethylcyclotrisiloxane and on the selective linking of poly(dimethylsiloxane)lithium with the chlorosilane group of the heterofunctional linking agent chloromethylphenylethylene dimethylchlorosilane. Combined characterization results by size exclusion chromatography, membrane osmometry, and NMR spectroscopy suggested that the synthesized multiblock multicomponent polymers had a high degree of structural and compositional homogeneity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 514–519, 2004