Radiation grafting of α,β,β-trifluorostyrene onto poly(ethylene-tetrafluoroethylene) film by preirradiation method. II. Properties of cation-exchange membrane obtained by sulfonation and hydrolysis of the grafted film

A Study was made on certain properties of the cation-exchange membranes obtained by the preirradiation grafting of α,β,β-trifluorostyrene (TFS) noto poly(ethylene-tetrafluoroethylene) (ETFE), followed by sulfonation and hydrolysis of the grafted film. Swelling, water uptake, electric conductivity, and transport number of the membranes were measured as a function of ino-exchange capacity. Thermal and chemical stability were also investigated. These properties were found to be mainly dependent on ion-exchange capacity. The stable membrane properties were established due to a homogeneous ion-exchange group distribution in the membrane, as confirmed by x-ray imcroscopy analysis of the membrane cross sections. In addition, the membranes showed good electrochemical, thermal, and chemical properties, and were found to be scceptable for practical use as cation-exchange membranes.     

Radiation grafting of α,β,β-trifluorostyrene onto poly(ethylene–tetrafluoroethylene) film by preirradiation method. I. Effects of preirradiation dose,monomer concentration,reaction temperature,and film thickness

Preirradiation grafting of α,β,β-trifluorostyrene onto poly(ethylene–tetrafluoroethylene) film was studied. The trapped radicals formed upon irradiation were able to induce graft polymerization under appropriate conditions. The influences of the grafting conditions were analyzed kinetically. The grafting rate dependency on the preirradiation dose was found to be of order 0.3, and the monomer concentrations, 1.0. The overall activation energies for this grafting were calculated to be 6.2 × 10⁴ and 9.3 × 10³ J/mol below and above 50°C. The grafting rate was found to be independent of the film thickness, which ranged from 25 to 100 μm.     

Radiation grafting of α,β,β-trifluorostyrene onto poly(ethylene–tetrafluoroethylene) film by preirradiation method. III. Properties of anion-exchange membrane obtained by chloromethylation and quaternization of the grafted film

A study was made of certain properties of the anion-exchange membranes obtained by the preirradiation grafting of α,β,β-trifluorostyrene (TFS) onto poly(ethylene–tetrafluoroethylene) (ETFE), followed by chloromethylation and quaternization of the grafted film. Swelling, water uptake, electric conductivity, and transport number of the membranes were measured as a function of ion-exchange capacity. Thermal and chemical stability were also investigated. These properties were found to be mainly dependent on ion-exchange capacity. The stable membrane properties were established due to a homogeneous ion-exchange group distribution in the membrane, as confirmed by X-ray microscopy analysis of the membrane cross sections. In addition, the membranes showed good electrochemical, thermal, and chemical properties, and were found to be acceptable for practical use as anion-exchange membranes.     

Photochemistry of α,α′-Disubstituted Azoalkanes. I. Photosolvolytic Inversion and Substitution of α,α′-Dichloro- and α,α′-Dialkoyloxyazoalkanes

A series of α,α′-dichloro (α DClA), α,α′-dialkoyloxy- (αDAlA) and α,α′-dibenzoxy-azoalkanes (αDBeA) without α-aryl substituents was found to undergo meso ? dl photointerconversion upon direct irradiation through Pyrex in the presence of oxygen in a number of solvents. Furthermore, irradiation of α,α′-dipropionoxy-azoalkanes in benzene in the presence of excess acetic acid leads to substitution of the propionoxy groups by acetoxy groups in addition to meso ? dl photointerconversion. Similar irradiation in the presence of CH₃CO₂D does not lead to deuterium substitution of the β-hydrogens. The presence of benzenethiol radical scavenger does not affect the course of these photoreactions. Photosolvolysis schemes involving heterolysis (in the case of αDAlA and αDBeA) or an unstable intermediate (in the case of αDClA) are proposed.     

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with γ-olefins were carried out in bulk by γ-ray irradiation at 25°C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r₁ (FAN) and r₂ (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system.     

Partialsynthesen von Cardenoliden und Cardenolid-Analogen. I. α,β- und β,γ-ungesättigte Lactonring-methylierte Cardenolide

Partial Syntheses of Cardenolides and Cardenolide Analogues. I. α,β- and β,γ-Unsaturated Lactone Ring-Methylated Cardenolides Base-catalyzed methylation of digitoxigenin 1a with methyl iodide and sodium hydride in DMF leads to the α,β-unsaturated cardenolides 2–5 and, after rearrangement of the CC-double bond, to the β,γ-unsaturated cardenolides 6 and 7 . Opening of the lactone ring results in the formation of 8 . Allylic oxidation of 4b affords the 14,21-epoxide 10 . Only the 22-methyl derivative 4a and its 3-O-tridigitoxoside 4d show strong biological effectivity, whereas methylation at 21R- or 21S-position results in considerable loss in activity.     

Synthesis of α, α′, β-trideuterovinyl acetate

Reaction conditions for the synthesis of α, α′, β-trideuterovinyl acetate by the continuous vapour phase catalytic reaction of deuteroacetylene and acetic acid-d (CH₃COOD) are described.     

Radiation grafting of acrylic acid onto fluorine-containing polymers. I. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene)

Preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene) film was studied. The trapped radicals formed upon irradiation are able to induce graft polymerization under appropriate conditions. The influence of the grafting conditions were analyzed kinetically. The grafting reaction begins close to the film surface and proceeds into the center with progressive monomer diffusion through the grafted layer. The dependences of the grafting rate on preirradiation dose and monomer concentration were found to be 0.2 and 1.1 order, respectively. The overall activation energies for this grafting were calculated to be 15.2 and 4.8 kcal/mol below and above 35°C, respectively. The relationship between the grafting rate and film thickness gave a negative first-order dependence.     

Poly(α,α,α′,α′-tetrafluoro-p-xylylene)

Poly(α,α,α′,α′-tetrafluoro-p-xylylene) was prepared by the pyrolysis of cyclo-di-(α,α,α′,α′-tetrafluoro-p-xylylene) and by the pyrolysis of α,α′-bis(alkylsulfonyl)-α,α,α′,α′-tetrafluoro-p-xylene. The pyrolysis of α,α′-dibromo-α,α,α′,α′-tetrafluoro-p-xylylene also gave the polymer, but the method is less satisfactory. Poly(α,α,α′,α′-tetrafluoro-p-xylylene) shows remarkable thermal and oxidative stability at elevated temperatures. Useful mechanical and electrical properties are retained after aging for 3000 hr at 250° in air. After initial change due to crystallization, tensile strength remains near 10,000 psi, elongation above 5%, and dielectric constants and dissipation factors at approximately 2.4 and .001, respectively.     

Photoinduced grafting of acrylamide onto polyethylene film by means of two-step method

Benzophenone-coated low-density polyethylene (LDPE) was grafted with acrylic acid (AA), methacrylic acid (MA), acrylonitrile (AN), and methyl methacrylate (MMA) in an aqueous medium by photoirradiation. The first-step graft samples thus prepared with a grafting of about 50% were subjected to second-step photografting with acrylamide (AAm). On AA- and MA-grafted LDPE samples, the second-step grafting of AAm was very smooth, and a high level of grafting up to 800% was attained with ease. On the other hand, grafted LDPE samples employing hydrophobic monomers, AN and MMA, had a lower percent of grafting than those with hydrophilic monomers, AA and MA. By ESR study, a thermally stable radical was found in the first-step graft sample irradiated with light of λ > 330 nm. Mechanisms for the formation of such a radical in the first-step graft sample are proposed, and the contribution of the radical to the second-step grafting is discussed.     

Radiation grafting of vinyl monomers onto poly(tetrafluoroethylene) powder produced by γ irradiation and properties of grafted poly(tetrafluoroethylene) filled low density polyethylene

Scrap poly(tetrafluoroethylene) (PTFE) was γ irradiated under an ambient atmosphere in order to produce extensive chain scission and oxidative degradation. After irradiation the PTFE was ground into a fine powder (2°‐PTFE) and grafted with styrene (St), vinyl acetate (VAc), and 4‐vinylpyridine (4‐VP) by using the direct irradiation technique. The grafted PTFE were then blended with low density polyethylene (LDPE). The study covered the characterization of irradiated PTFE and grafted 2°‐PTFE powder with various methods. Mechanical grinding was found to reduce trapped radicals formed during the irradiation process faster than the annealing process. Grafting on 2°‐PTFE was followed by gravimetric analysis, TGA, and the change in the particle size of the samples. Although we reached almost 20% grafting by weight in the St and 4‐VP monomers, VAc grafting was found to be maximum at around 8% by weight at the maximum absorbed dose. The addition of VAc grafted 2°‐PTFE into LDPE produced better final mechanical properties with a fine dispersion. However, as may be expected, the incorporation of the other two 2°‐PTFEs into LDPE showed low film quality and poor mechanical properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 816–826, 2001     

Mechanism and kinetics of polyethylene crosslinking by α,α′-bis(tert-butylperoxy)-p-diisopropylbenzene

The study of the mechanism of polyethylene crosslinking is realized by a kinetic analysis of the α,α-bis(tert-butylperoxy)-p-diisopropylbenzene decomposition, as well as by the determination of its decomposition products and crosslink formation in the polymer. The experiments were carried out in a temperature range of 118°–148°C in both polyethylene and its low-molecular model, n-octane. From the results obtained it follows that the peroxide decomposition in both hydrocarbon media is kinetically a unimolecular reaction with an activation energy of 36 ± 2 kcal/mole and with an equivalent participation of both peroxidic groups, whereby a biradical formation is improbable. Macroradicals arise by a dehydrogenization reaction in which mainly primary oxyradicals of various types take part and methyl radicals are also formed by a transformation process of the former. Both types of radicals decay exclusively in a substitution reaction with polymer chains. The whole process is terminated by macroradical recombination so leading to crosslink formation in polyethylene.     

Prostaglandins and prostaglandin intermediates. XIV. Synthesis of rac-9α, 11α, 13α-trihydroxy- and rac-9α, 11α, 13β-Trihydroxy-5(Z)-prosten-15-ynoic Acid

Attempts to rearrange a β-hydroxy-alkyne with a secondary hydroxy group into an α,β-unsaturated ketone failed in the case of a potential prostaglandin intermediate. However, it was possible to convert this intermediate into 13-hydroxy-5(Z)-prosten-15-ynoic acids, which are interesting prostaglandin analogues with a modified alkyl side chain.     

Determination of the α, β, and γ crystalline phases of poly(vinylidene fluoride) films prepared at different conditions

Samples containing the three crystalline phases of poly(vinylidene fluoride), α, β, and γ, have been obtained under distinct crystallization conditions. Samples containing exclusively unoriented β phase have been obtained by crystallization from dimethylformamide (DMF) solution at 60°C. Oriented β phase has been obtained by uniaxial drawing, at 80°C, of an originally α phase sample. Samples containing exclusively α phase have been obtained by melting and posterior cooling at room temperature. Samples containing both α and γ phases have been obtained by melt crystallization at 164 °C for 16 and 36 h. Presence of the crystalline phases in each sample were confirmed by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXD), polarized light optical microscopy (PLOM), and scanning electron microscopy (SEM). Infrared absorption bands identifying unequivocally the presence of β and γ phases in a sample are presented. It is shown that solution crystallization at T < 70°C always results in the β phase, regardless of the solvent used. Melt temperatures of the respective phases have also been determined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3272–3279, 2006     

Polymerization of α, α-disubstituted-β-propiolactones and lactams. 9. ABA block copolymers of α-methyl-α-butyl-β-propiolactone and pivalolactone

ABA block copolymers were prepared by the anionic polymerization of α-methyl-α-butyl-β-propiolactone, MBPL (B block), and pivalolactone, PL (A blocks). The MBPL block had a very low decree of crystallinity and a glass temperature of ? 13°C, so phase separation with extensive crystallization of the PL blocks gave thermoplastic elastomers when the MBPL block constituted the principal and continuous phase. The observed crystallinity and melting point of 40–45°C in the MBPL homopolymer have not been previously reported. Measurements were obtained by electron microscopy of the initial size distribution of the PL domains as a function of copolymer composition and degree of polymerization, and on the effect of annealing on this parameter. Tensile strengths and elongations at break were both less than those previously observed for equivalent ABA block copolymers of PL and α-methyl-α-propyl-β-propiolactone.     

Influence of isomer ratio and ring substituents in decomposition activation energies of α,α,α′,α′‐tetrasubstituted dibenzyls

Diethyl‐2,3‐dicyano‐2,3‐di‐(X‐substituted phenyl) succinates (X = p‐OCH₃, p‐CH₃, p‐Cl, H, p‐NO₂) can initiate the free‐radical polymerization of styrene. The decomposition rate constant and activation energy were measured by means of a dilatometer, and the results showed that they were strongly dependent on the ratio of meso‐ and dl‐isomers in the polysubstituted dibenzyl compounds and the properties of the ring substituents. On the other hand, it was found that the polystyrenes, which were obtained by initiation with hydrogen, had a much larger average molecular weight than that with p‐OCH₃ and p‐CH₃. The experimental phenomena were correlated with the structure of the radical resulting from hydrogen. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2964–2971, 2001     

Chemoselective Hydrogenation of α,β‐Unsaturated Nitriles

The chemoselective hydrogenation of cinnamonitrile to 3‐phenylallylamine proceeds with up to 80% selectivity at conversions of >90% with Raney cobalt and up to 60% selectivity with Raney nickel catalysts. Best results were obtained with a doped Raney cobalt catalyst (RaCo/Cr/Ni/Fe 2724) in ammonia saturated methanol at 100 °C and 80 bar. Major problems are the formation of hydrocinnamonitrile and of secondary amines, and overreduction to 3‐phenylpropylamine. Important parameters are the catalyst type and composition, the solvent type and the presence and concentration of ammonia. The catalytic system tolerates functional groups like OH, OMe, Cl, CO, but not aromatic nitro groups. Preliminary experiments indicate that other unsaturated nitriles with di‐ or trisubstituted CC bonds are also suitable substrates.