Synthesis and characterization of 6‐ and 12‐arm star polymers by nitroxide‐mediated radical polymerization of St and MA from dendritic TIPNO‐based hexafunctional and dodecafunctional macroinitiators

Dendritic multifunctional macroinitiators having six and 12 TIPNO‐based alkoxyamines, TIPNO‐6 and TIPNO‐12 , were synthesized and used in the living radical polymerization of styrene (St), methyl acrylate (MA), N,N‐dimethylacrylamide (DMAAm), and isoprene (IP). The polymerizations of St initiated with TIPNO‐6 gave 6‐arm star polymers with narrow polydispersities of 1.14–1.18. In the polymerizations of MA initiated with TIPNO‐6 and TIPNO‐12 , the influences of added TIPNO on the polydispersity indexes (PDIs) of the resulting star polymers were first investigated, and this led to the successful formation of poly(MA) star polymers with narrow polydispersities (1.10–1.18). Moreover, the polymerizations of DMAAm and IP from TIPNO‐6 in the presence or absence of TIPNO were briefly investigated. The benzyl ether bonds of the poly(St) and poly(MA) star polymers were cleaved by treating with Me₃SiI or Pd/C, and the resulting arm's parts were analyzed with SEC. The PDIs of the resulting arm parts were low (1.19–1.23), and the M_ns agreed with the M_n,theor, indicating that the poly(St) and poly(MA) star polymers had well‐controlled arms. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4364–4376, 2007     

Synthesis and characterization of poly(methyl methacrylate)‐block‐poly(methylphenylsilane)‐ block‐poly(methyl methacrylate) by atom transfer radical polymerization

ABA block copolymers of methyl methacrylate and methylphenylsilane were synthesized with a methodology based on atom transfer radical polymerization (ATRP). The reaction of samples of α,ω‐dihalopoly(methylphenylsilane) with 2‐hydroxyethyl‐2‐methyl‐2‐bromoproprionate gave suitable macroinitiators for the ATRP of methyl methacrylate. The latter procedure was carried out at 95 °C in a xylene solution with CuBr and 2,2‐bipyridine as the initiating system. The rate of the polymerization was first‐order with respect to monomer conversion. The block copolymers were characterized with ¹H NMR and ¹³C NMR spectroscopy and size exclusion chromatography, and differential scanning calorimetry was used to obtain preliminary evidence of phase separation in the copolymer products. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 30–40, 2003     

Cellulose-based fibers from liquid–crystalline solutions. II. Processing and morphology of acetate/butyrate esters

Fibers were spun from isotropic and anisotropic dimethylacetamide solutions of cellulose esters. Take-up speeds of the dry jet/wet spinning process varied. Water served as the coagulant. The mechanical properties of the fibers increased as spinning progressed from the isotropic to the anisotropic state of the solution. A trade-off in solubility and fiber properties was noted as the butyryl acetyl ratio decreased. Whereas high butyryl content enhances both overall solubility and the formation of liquid–crystalline solutions at lower concentration, it results in lower fiber modulus and strength. Morphology of the fibers depended on the coagulation rate which was influenced by the concentration of the sppinning solution. The level of orientation and crystallinity of the fibers increased somewhat when they were spun from liquid-crystalline solutions. © 1993 John Wiley & Sons, Inc.     

Synthesis of the ethyl ester of the mononitrile of malonic acid by the catalytic carbonylation of benzenesulfonyloxyacetonitrile

A new method has been developed for the synthesis of the ethyl ester of the mononitrile of malonic acid by the carbonylation of benzenesulfonyloxyacetonitrile in absolute ethanol in the presence of cobalt carbonyl. The yield of the desired product was 30% with 60–90% conversion of the starting compound. The effects of temperature, pressure, and reaction time were studied.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. S. M. Kirov Urals Polytechnical Institute, Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 215–216, January, 1992.     

Immiscibility,upper critical solution temperature,and miscibility in blends of poly(vinyl ether)s with polyacrylics: Effects of pendant groups

Various phase behavior of blends of poly(vinyl ether)s with homologous acrylic polymers (polymethacrylates or polyacrylates) were examined using differential scanning calorimetry, optical microscopy (OM), and Fourier‐transformed infrared spectroscopy. Effects of varying the pendant groups of either of constituent polymers on the phase behavior of the blends were analyzed. A series of interestingly different phase behavior in the blends has been revealed in that as the pendant group in the acrylic polymer series gets longer, polymethacrylate/poly(vinyl methyl ether) (PVME) blends exhibit immiscibility, upper critical solution temperature (UCST), and miscibility, respectively. This study found that the true phase behavior of poly(propyl methacrylate)/PVME [and poly(isopropyl methacrylate)/PVME)] blend systems, though immiscible at ambient, actually displayed a rare UCST upon heating to higher temperatures. Similarly, as the methyl pendant group in PVE is lengthened to ethyl (i.e., PVME replaced by PVEE), phase behavior of its blends with series of polymethacrylates or polyacrylates changes correspondingly. Analyses and quantitative comparisons on four series of blends of PVE/acrylic polymer were performed to thoroughly understand the effects of pendant groups in either polyethers (PVE's) or acrylic polymers on the phase behavior of the blends of these two constituents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1521–1534, 2007     

Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006     

Thermochemically induced binding of methyl orange to polycations containing primary amine groups

The thermochemical transformation of electrostatically formed complexes of methyl orange (MO) with polycations containing primary amine groups such as ammonium salts afforded new polymers with a high concentration of covalently bound 4‐N,N‐dimethylaminoazobenzene groups in the side chain. Poly(allylamine hydrochloride) and poly(β‐aminoethylene acrylamide hydrochloride) were employed as support polycations for MO. The transformation of sulfonate–ammonium ion pairs into sulfonamide bonds, via heating at an elevated temperature, was supported by the polymer properties before and after the thermal treatment. The polymer structure changes were monitored with elemental analysis, Fourier transform infrared, ¹H NMR, and ultraviolet–visible absorption spectroscopy, and thermogravimetric analysis. The spacer length between the backbone and azobenzene structures used as side chains strongly influenced the polymer properties before and after the heat‐induced reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5898–5908, 2006     

Synthesis of well‐defined syndiotactic poly(methyl methacrylate) with low‐temperature atom transfer radical polymerization in fluoroalcohol

The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (M_n) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured M_n's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr₂) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]₀/[methyl α‐bromoisobutyrate]₀/[CuBr]₀/[CuBr₂]₀/[Me₆TREN]₀ = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of Cu^IBr/Me₆TREN in HFIP, there were [Cu(Me₆TREN)Br]⁺ and [Cu(Me₆TREN)OCH(CF₃)₂]⁺, indicating that HFIP should coordinate to the Cu^I/Me₆TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006     

Further study of the viscoelastic phase separation of cyanate ester modified with poly(ether imide)

In this study, the viscoelastic phase separation process was studied further by time‐resolved light scattering, differential scanning calorimetry, and scanning electron microscopy in the system of poly(ether imide)‐modified bisphenol‐A dicyanate. It was observed that the evolution time of phase structure and relaxation time of diffusion flow of the bisphenol‐A dicyanate were similar with the phase diagram of curing conversion versus content of PEI. The results suggested that the viscoelastic phase separation was affected by the curing conversion of the system at the onset point of phase separation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 517–523, 2006