Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Ultrahigh‐molecular‐weight‐polyethylene‐fiber surface treatment by electron‐beam‐irradiation‐induced graft polymerization and its effect on adhesion in a styrene–butadiene rubber matrix

Aiming to develop a high‐performance fiber‐reinforced rubber from styrene–butadiene rubber (SBR), we applied a special technique using electron‐beam (EB)‐irradiation‐induced graft polymerization to ultrahigh‐molecular‐weight‐polyethylene (UHMWPE) fibers. The molecular interaction between the grafted UHMWPE fibers and an SBR matrix was studied through the evaluation of the adhesive behavior of the fibers in the SBR matrix. Although UHMWPE was chemically inert, two monomers, styrene and N‐vinyl formamide (NVF), were examined for graft polymerization onto the UHMWPE fiber surface. Styrene was not effective, but NVF was graft‐polymerized onto the UHMWPE fibers with this special method. A methanol/water mixture and dioxane were used as solvents for NVF, and the effects of the solvents on the grafting percentage of NVF were also examined. The methanol/water mixture was more effective. A grafting percentage of 16.4% was the highest obtained. This improved the adhesive force threefold with respect to that of untreated UHMWPE fibers. These results demonstrated that EB irradiation enabled graft polymerization to occur even on the inert surface of UHMWPE fibers. However, the mechanical properties of the fibers could be compromised according to the dose of EB irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2595–2603, 2004     

Addition–fragmentation chain transfer: Molecular weight distributions and retardation in the system methyl methacrylate/methyl α‐(bromomethyl)acrylate

A detailed investigation of addition–fragmentation chain transfer (AFCT) in the free‐radical polymerization of methyl methacrylate (MMA) in the presence of methyl α‐(bromomethyl)acrylate (MBMA) was carried out to elucidate mechanistic details with efficient macromonomer synthesis as an underlying goal. Advanced modeling techniques were used in connection with the experimental work. Curve fitting of simulated and experimental molecular weight distributions with respect to the rate coefficient for addition of propagating radicals to MBMA (k_add) over 60–120 °C resulted in E_add = 21.7 kJ mol^?1 and A_add = 2.18 × 10⁶ M^?1 s^?1 and a very weak temperature dependence of the chain‐transfer constant (E_add ≈ E_p). The rate coefficient for fragmentation of adduct radicals at 60 °C was estimated as k_f ≈ 39 s^?1 on the basis of experimental data of the MMA conversion and the concentration of 2‐carbomethoxy‐2‐propenyl end groups. The approach developed is generic and can be applied to any AFCT system in which copolymerization does not occur and in which the resulting unsaturated end groups do not undergo further reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2640–2650, 2004     

Synthesis And Properties Of Functional Ultra-High Molecular Weight Transparent Styrene-Butadiene Block Copolymer

Functional ultra-high molecular weight transparent styrene-butadiene block copolymer possesses both high transparency and impact resistance and has excellent comprehensive properties prior to other transparent resins. In this paper we not only use anionic polymerization process which includes 1 time addition of initiator and 3 time addition of monomers, but also introduce functional coupling agent for the fist time to prepare mentioned functional block copolymer. The typical preparation proces…     

Determination of residual monomers in acrylate dispersions by gas chromatography

The content of residual monomers is one of the most important characteristics of polymer dispersions. As a result of the similar physicochemical parameters of ethyl acrylate and methyl methacrylate, it is very difficult to determine the residual monomers in acrylate dispersions obtained by emulsion polymerization of both monomers. Gas chromatography with capillary columns, however, permits separation of these monomers and their quantitative determination in acrylate dispersions.     

New fluorescence probes for monitoring the kinetics of laser-initiated polymerization

Several new fluorescence probes useful for following photopolymerization have been characterized. Among these are probes which can be used in rapidly gelling monomer mixtures and for photochemical polymerization initiated by very high laser powers. Systems which can be used with polyolacrylates and either with visible initiators or with UV initiators are reported. © 1993 John Wiley & Sons, Inc.     

Hybrid free radical/cationic frontal photopolymerizations

The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007     

Curcumin: A naturally occurring long‐wavelength photosensitizer for diaryliodonium salts

Curcumin, a naturally occurring, intensely yellow dye extracted from the spice turmeric, is an efficient photosensitizer for diaryliodonium salt photoinitiators at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is possible to carry out the cationic photopolymerization of a wide variety of epoxide, oxetane, and vinyl monomers with long‐wavelength UV and visible light. An example of the photopolymerization of an epoxide monomer with ambient solar irradiation is provided. Several other curcumin analogues were synthesized, and their use as photosensitizers is examined. With such photosensitizers, the range of spectral sensitivity can be extended well into the visible region of the electromagnetic spectrum. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5217–5231, 2005     

Developing a hybrid emulsion polymerization system to synthesize Fe3O4/polystyrene latexes with narrow size distribution and high magnetite content

A hybrid emulsion polymerization was formulated for synthesizing Fe₃O₄/polystyrene composite latex. This system, containing binary droplets that are magnetic (Mag)‐droplets with a diameter of 100–200 nm and styrene (St)‐droplets with a diameter of 3–4 μm, was obtained by mixing Mag‐miniemulsion and St‐macroemulsion. With extremely low surfactants concentration (?critical micelle concentration, CMC), the nucleated loci are selectively controlled in the Mag‐droplets, as the result of smaller droplet size and larger surface ratio. Both water‐soluble potassium persulfate (KPS) and oil‐soluble 2,2′‐azobis(2‐isobutyronitrile) was adopted to initiate the polymerization. In the presence of KPS, magnetic polystyrene latices with particles size of 60–200 nm, narrow size distribution, and high magnetite content (86 wt % measured by TGA) were attained successfully. The synthesized magnetic Fe₃O_4/polystyrene latices assembled into well‐ordered hexagonal structure in the surface of a carbon supported copper grid. The influence of various parameters on various aspects of the as‐synthesized Fe₃O₄/polystyrene was investigated in detail: type of initiator on composite morphology, feed ratio of Mag‐miniemulsion and St‐macroemulsion on magnetite content, and hydrophobic agent or amount of surfactant on size and size distribution. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5285–5295, 2007     

Synthesis,dynamic light scattering,and luminescence properties of copolymers containing iridium(III) bisterpyridine in the side chain

Supramolecular block‐random copolymers containing [Ir(terpy)₂]³⁺ in the side chain were synthesized via postfunctionalization of a P(S‐b‐AC_terpy) block copolymer. Absorbance and emission spectra compared to a model compound show that the polymer backbone has a minor effect on the polymer absorbance but produces a larger shift for the phosphorescence signals to higher wavelength. Dynamic light scattering of the metal complex containing copolymer studied in various solvents showed monomodal aggregation with decreasing aggregate size as the solvent dielectric constant increased. The copolymer precursor P(S‐b‐AC_terpy) shows multimodal aggregation in different solvents with the major population consisting of single chains. This difference in behavior between the two polymers is attributed to the electrolytic nature of the complex and the amphiphilicity induced by the charged metal complex. Supramolecular copolymers like these will continue to have interesting self‐organizational properties and may find applications in multicomponent systems for photoinduced charge separation processes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1109–1121, 2007