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. 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. 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.     

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.     

Polymerization of α,β-unsaturated carbonyl monomers initiated by 9-borabicyclo [3.3.1] nonane

9-Borabicyclo[3.3.1]nonane (9-BBN) initiated the polymerization of α,β-unsaturated carbonyl monomers such as ethyl acrylate (EA) without an oxidant at low temperatures (to −90°C) under argon. Hydroquinone and 2,6-di-tert-butyl-p-cresol had little effect on the polymerization, indicating that the propagating chain end is not a free radical. The rate of polymerization was found to be proportional to [9-BBN]^1.0 and [EA]^1.5. Electron spin resonance measurements using 5,5-dimethyl-1-pyrroline-N-oxide as a spin trap showed the absence of any radical species under polymerization conditions. No copolymerization of EA with styrene occurred. On the basis of the results obtained, this polymerization was assumed to proceed via a non-radical mechanism.     

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films. I. Effect of grafting conditions and properties of the grafted films

Radiation‐induced grafting of styrene onto poly(tetrafluoroethylene) (PTFE) films was studied by a simultaneous irradiation technique. Grafting was carried out using γ‐radiation from a ⁶⁰Co source at dose rates of 1.32–15.0 kGy h⁻¹ at room temperature. The effects of type of diluent, dose rate, irradiation dose, and the initial monomer concentration in the grafting solution on the degree of grafting were investigated. The degree of grafting was found to be strongly dependent upon the grafting conditions. The dependence of the initial rate of grafting on the dose rate and the initial monomer concentration in the grafting solution was found to be in the order of 0.6 and 1.7, respectively. The chemical structure and the crystallinity of the grafted PTFE films were studied by means of Fourier‐transform infrared, (FTIR), electron spectroscopy for chemical analysis (ESCA) and X‐ray diffractometry (XRD). © 2000 Society of Chemical Industry     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. I. Effect of grafting conditions

The simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied at room temperature. The effects of grafting conditions (type of solvent, irradiation dose, dose rate, and monomer concentration) were investigated. The degree of grafting was found to be dependent on the investigated grafting conditions. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be of 0.5 and 1.3 orders, respectively. The results suggest that grafting proceeds by the so‐called front mechanism in which the grafting front starts at the surface of the film and moves internally toward the middle of the film by successive diffusion of styrene through the grafted layers. Some selected properties of the grafted films were evaluated in correlation with the degree of grafting. We found that the grafted FEP films possess good mechanical stability, which encourages their use for the preparation of proton exchange membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 220–227, 2000     

Synthesis and characterization of phenolic and amino resins based on α, β-unsaturated aldehydes

Phenolic and amino resins on the basis of α,β-unsaturated aldehydes were synthesized in bulk or solution. Catalysts were HCl, H₃PO₄, or formic acid, and in some cases NaOH. The course of the reactions was followed by GPC and NMR while the structure of the reaction products was determined by one- and two-dimensional NMR. The course of the reactions is influenced by experimental conditions: the type of monomers, their molar ratio, the type and quantity of the catalyst, the reaction time and temperature, and the reaction medium. At the beginning of the reaction the addition of a nucleophile to an aldehyde takes place through parallel 1,2-addition to and 1,4-addition to group. Oligomers with ? OH, , and ? CHO functional groups are able to add new monomer units or to react mutually to form higher molecular weight addition and condensation products. The overall rate constants for the beginning of the reactions were between 10^?3 L/mol s for the high reactive mixtures and 10^?7 L/mol s for the less reactive mixtures. The resins were cured by heating at temperatures above 135°C with the addition of hexamethylenetetramine.     

Kinetics of vinyl polymerization initiated by potassium permanganate/β-hydroxybutyric acid redox system

The aqueous polymerization of acrylamide initiated by potassium permanganate/β-hydroxybutyric acid has been studied volumetrically at 35 ± 0.01°C in an inert medium. The rate of polymerization shows nearly square root dependence on β-hydroxybutyric acid at low concentration (3.12 – 12.5 · 10^?3 mol dm^?3). The order with respect to potassium permanganate has been found to be 0.6 indicating thereby a bimolecular mode of termination. The polymerization rate has been varied linearly at low monomer concentrations i.e. from 2.5 –7.0 · 10^?2 mol dm^?3. The dependence of number average degree of polymerization on the initial rate of polymerization and temperature has been determined. The over-all activation energy has been found to be 51.66 kJ mol^?1. A kinetic reaction scheme is proposed on the basis of experimental results.     

Herstellung und Charakterisierung der Sulfamate von Estra-3,17ξ-diolen. Schnelle Umsetzung von 16α-Fluorestradiol zum 16α-Fluorestradiol-3,17β-disulfamat

Estradiols are able to form two monosulphamates and one disulphamate. In the present work all the sulphamates of 17α-estradiol, 17β-estradiol and 16α-fluoroestradiol were synthesized and characterized. For characterization NMR spectroscopy was used first of all. Because of its high sulphatase inhibitory efficiency 16α-fluoroestradiol-3,17β-disulphamate found a special interest among the new sulphamates. Just the binding between sulphamate and sulphatase favoured 16α-[^18F]fluorestradiol-3,17β-disulphamate to a new radio-pharmaceutical which should be appropriate to image the active sites of sulphatase by positron emission tomography. The preparation of 16α-[¹⁸F]fluoro-estradiol-3,17β-disulphamate requires a simple and rapid procedure. The conditions for such a procedure were also elaborated using non-radioactive substances.     

Highly diastereoselective synthesis of 11β,17β-diaryl-18a-homo-19-nor steroids

In a highly diastereoselective fashion novel 11β, 17β-diaryl steroids 17 and 18 were synthesized via Birch-type reduction [1] of styrylic precursors 11 and 15 . Both precursors were readily available by Suzuki-type coupling reactions [2] of aromatic boronic acids [3] and the corresoponding enol triflates 6, 10 , and 14 . Regioselective 17-enol triflate formation in presence of a 11-keto function could be demonstrated in case of steroid 5 . The remarkably high degree of stereo-selectivity observed parallels results from the natural series [4] and demonstrated a broader applicability of such single electron transfer reductions in stereoselective transformations on the steroid skeleton.     

Mass Transfer Reaction Kinetics of β‐Isophorone Oxidation by Air in an Agitator Bubbling Reactor

The mass transfer reaction kinetics of β‐isophorone (β‐IP) oxidation reaction by air was investigated in a lab‐scale agitator bubbling reactor. This reaction can be regarded as instantaneous and there exists a critical concentration of β‐IP. When the catalyst concentration is kept unchanged, the reaction rate is only controlled by the gas film and the reaction kinetics is of zero order with respect to β‐IP when the β‐IP concentration lies over the critical concentration. The reaction rate is controlled by the dual film and the kinetics is of first order with respect to β‐IP when its concentration is below the critical concentration. Under the gas film‐controlling condition, the effect of temperature, agitator speed, and aeration on the reaction rate is evaluated. A correlation equation of gas phase volumetric mass transfer coefficients combining superficial gas velocity and agitator speed is defined.     

Immobilized metal ions cellophane–PGMA‐grafted membranes for affinity separation of β‐galactosidase enzyme. I. Preparation and characterization

Immobilized Cu²⁺ ions affinity cellophane–poly(glycidyl methacrylate) (PGMA)‐grafted membranes have been prepared through three steps. The first step was introducing of epoxy groups to its chemical structure through grafting process with PGMA. Factors affecting the grafting process have been studied and grafting percentage (GP) up to 233% has been obtained. The second step was converting the introduced epoxy groups to sulfonic ones. It was found that maximum amount of sulfonic groups (2.7 mmol/g) was obtained with minimum GP (46.08%). The third and last step was the immobilization of Cu²⁺ ions into sulfonated grafted membranes obtained from the previous step. Maximum amount of immobilized Cu²⁺ ions was found to be 60.9 ppm per gram of polymer. The verification of the grafting and sulfonation steps has been performed through characterization of the obtained membranes using FTIR, TGA, and EDAX analysis. Finally, Cu²⁺‐immobilized membranes have been evaluated in separation of β‐galactosidase (β‐Gal) enzyme from its mixture with bovine serum albumin (BSA) in different pH medium. Maximum protein adsorption, for both proteins, has been obtained at pH range 4–4.5; as 90 and 45% for β‐Gal and BSA, respectively. The results showed high affinity toward β‐Gal separation although BSA concentration (0.5%) is 20‐folds of β‐Gal (0.025%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The study on radiation grafting of acrylic acid onto fluorine-containing polymers. III. Kinetic study of preirradiation grafting onto poly(tetrafluoroethylene–hexafluoropropylene)

A kinetic study has been made on the preirradiation grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene–hexafluoropropylene) (FEP) film. The effect of grafting conditions was investigated. The dependencies of the grafting rate on preirradiation dose and monomer concentration were found to be 0.58 and 1.25 order, respectively. The overall activation energy for the graft polymerization was 7.4 kcal/mol. The final degree of grafting increased with preirradiation dose and monomer concentration and slightly decreased as the grafting temperature was elevated. The relationship between the grafting rate and film thickness gave a negative first-order dependency, which is in agreement with that obtained for polytetrafluoroethylene—AAc grafting system. It was reasonably concluded that this grafting proceeds from the surface to the center of film with progressive monomer diffusion through the grafted layer which swells in the monomer solution.     

Gold‐Catalyzed Efficient Formation of α,β‐Unsaturated Ketones from Propargylic Acetates

An efficient gold‐catalyzed method for the preparation of α,β‐unsaturated ketones from propargylic acetates has been developed. Under mild reaction conditions, β‐monosubstituted enones were formed mostly with excellent E‐selectivity. β,β‐Disubstituted enones can be prepared from propargylic acetates derived from ketones. The high efficiency and mild nature of this reaction render it a viable alternative for the synthesis of α,β‐unsaturated ketones.     

Ring-opening homopolymerization and copolymerization of lactones. Part 2. enzymatic degradability of poly(β-hydroxybutyrate) stereoisomers and copolymers of β-butyrolactone with ε-caprolactone and δ-valerolactone

In this study, we have prepared poly([R,S ]-β-hydroxybutyrate) (P([R,S ]-β-HB) or PHB) from [R ,S]-β-butyrolactone ([ R,S]-β-BL), using different aluminoxane catalyst systems (triethylaluminium/water, triisobutylaluminium/water, trioctylaluminium/water and tetraisobutyldialuminoxane/water). By varying the ratio of catalyst to water and using a method of fractionation of polymers, PHB with different isotactic diad fractions (i) (from 0.41 to 0.72) and crystallinities were obtained. Copolymers poly(butyrolactone-co-caprolactone) (P(BL-co-CL)) and poly(butyrolactone-co-valerolactone) (P(BL-co-VL)) have also been synthesized from the ring-opening copolymerization of [ R,S]-β-BL with either ε-caprolactone (CL) or δ-valerolactone (VL) using tetraisobutyldialuminoxane (TIBAO) catalyst. The enzymatic degradability of these polymers was studied in aerobic and anaerobic media. The objective of this work was to determine the influence of the tacticity and crystallinity of the polymers on their degree of biodegradation and on their initial degradation rate. It was shown that the degradation rate measured for bacterial PHB 100% [R] was the highest and the degree of aerobic biodegradation reached after 36 days was around 94%. A 40–50% biodegradation was obtained for synthetic PHB, highly isotactic and predominantly syndiotactic. The non-crystalline and atactic PHB synthesized from TIBAO catalyst had a very high degree of biodegradation of around 88%. This result may suggest that not only are the [R ]-BL units hydrolysed but also the [S ]-BL units. The influence of the crystallinity on the initial degradation rate was observed for the copolymers P(BL-co-CL) and P(BL-co -VL) of various feed ratios. All these copolymers synthesized from TIBAO catalyst, exhibit a high degree of biodegradation of around 85% except for copolymers containing a very high portion of unsubstituted units, CL or VL. The anaerobic biodegradation of PHB and copolymers P(BL-co -CL) is much lower than the aerobic biodegradation, as are the initial rates, even for bacterial P([R ]-HB). © 1999 Society of Chemical Industry     

Graft polymerization of some vinyl monomers onto acrylic rubber. I. Chain transfer and grafting reaction

The grafting reactions of styrene (St), methyl methacrylate (MMA), and vinyl acetate (VAc) were investigated in the presence of n-butyl acrylate–acrylonitrile copolymer. Results showed that the nature of monomer and initiator were the major factors influencing the grafting activity. The grafting efficiency was 0.87 for St, 0.26 for MMA, and 0.18 for VAc under the most favorable conditions. Acrylic rubber reduced the rate of polymerization, and the retarding effect increased in the order St, MMA, VAc. The chain transfer constants for acrylic rubber were evaluated to be 4.8 × 10^?4 for St, 1.27 × 10^?3 for MMA, and 1.45 × 10^?3 for VAc. The rate of polymerization and the grafting efficiency decreased with increasing acrylonitrile content in acrylic rubber, while the chain transfer constant of St for acrylic rubber remained practically unchanged.     

Studies on β-picolinium-p-chlorophenacylide initiated copolymerization of methyl methacrylate with styrene

The alternating copolymerization of methyl methacrylate (MMA) with styrene (S) using β-picolinium-p-chlorophenacylide (β-PCPY) as radical initiator at 55, 60, and 65°C for 3 h has been kinetically investigated. The copolymerization rate (R_p) is proportional to the square root of [β-PCPY] and indicates bimolecular termination. The average degree of polymerization decreases as [β-PCPY] increases. The values of k_p²/k_t and energy of activation have been evaluated as 1.43 · 10^-3 l mol^-1 s^-1 and 87 kJ mol^-1, respectively. The NMR spectroscopy has been used to determine the structure, composition, and stereochemistry of copolymers.     

Chemoselective Reduction of α,β‐Unsaturated Carbonyls over Novel Mesoporous CoHMA Molecular Sieves under Hydrogen Transfer Conditions

Chemoselective reduction of α,β‐unsaturated carbonyls to the corresponding alcohols was achieved by a catalytic transfer hydrogenation (CTH) method using cobalt(II)‐substituted hexagonal mesoporous aluminophosphate (CoHMA) molecular sieve catalyst. Further, the catalyst was found to be promising as a heterogeneous catalyst as the yield was practically unchanged after up to six cycles.     

HPLC and 13C-NMR study of carboxymethyl-β-(1 → 6)-D-gluco-β-(1 → 3)-D-glucan derived from saccharomyces cerevisiae

Sodium salt of carboxymethyl-β-(1 → 6)-D-gluco-β-(1 → 3)-D-glucan (CMG-Na) was prepared from β-D-glucan isolated from baker's yeast (Saccharomyces cerevisiae). Three samples, Fractions I, II, and III, were further separated from the crude CMG-Na derivative. For the physicochemical characterization of the separated fractions, the methods of high-performance liquid chromatography (HPLC) in the size-exclusion mode and carbon?13 nuclear magnetic resonance (¹³C-NMR) spectroscopy were applied. The HPLC method revealed that the molecular weights, M_n, M_w, and M_z averages, of Fraction II were 9.71 × 10⁴, 2.27 × 10⁵, and 3.59 × 10⁵ Da, respectively, whereas those of Fraction III were 1.52 × 10⁴, 2.13 × 10⁴, and 3.57 × 10⁴ Da, respectively. The ¹³C-NMR spectra of Fraction II showed a ratio of 3 : 1 for β?(1 → 3) / β?(1 → 6), whereas for Fraction III, the content of β-(1 → 3) units was smaller. © 1993 John Wiley & Sons, Inc.