A comparative study of the effects of UV- and gamma-radiation on copolymers of acrylonitrile/butadiene

The radiolysis of nitrile rubbers with different acrylonitrile/butadiene composition and the homopolymers, poly(butadiene) (PBD) and poly(acrylonitrile) (PAN) has been investigated and compared with the photolysis of the same polymers. A significantly different mechanism of degradation was found for the two types of radiation. The results obtained by ESR, FTIR and measurements of soluble fractions of irradiated samples, indicated that the acrylonitrile units of the nitrile rubbers are more sensitive units to gamma-radiation, with the effects of irradiation increasing with the acrylonitrile content. The reactions observed were consumption of double bonds, crosslinking, and cyclization with the formation of conjugated double bonds. No chain-scission reactions were detected. In contrast to gamma-irradiation, the effects of photolysis were centred at the butadiene units, and increases in the acrylonitrile content resulted in a proportional decrease in the sensitivity of the copolymers. Crosslinking and chain scission were identified as the main effects of photolysis of NBR rubbers. (C) 1999 Society of Chemical Industry.

Improved high-performance liquid chromatography determination of methotrexate and its major metabolite in plasma using a poly(styrene-divinylbenzene) column

A sensitive high-performance liquid chromatographic assay has been developed for measuring plasma concentrations of methotrexate and its major metabolite, 7-hydroxymethotrexate. Methotrexate and metabolite were extracted from plasma using solid-phase extraction. An internal standard, aminopterin was used. Chromatographic separation was achieved using a 15-cm poly(styrene-divinylbenzene) (PRP-1(R)) column. This column is more robust than a silica-based stationary phase. Post column, the eluent was irradiated with UV light, producing fluorescent photolytic degradation products of methotrexate and the metabolite. The excitation and emission wavelengths of fluorescence detection were at 350 and 435 nm, respectively. The mobile phase consisted of 0.1 M phosphate buffer (pH 6.5), with 6% N,N-dimethylformamide and 0.2% of 30% hydrogen peroxide. The absolute recoveries for methotrexate and 7-hydroxymethotrexate were greater than 86%. Precision, expressed as a coefficient of variation (n=6), was

Thermal characterization of copolymers obtained by radiation grafting of styrene onto poly(tetrafluoroethyleneperfluoropropylvinylether) substrates: thermal decomposition, melting behavior and low-temperature transitions

Differential scanning calorimetric (DSC) and thermogravimetric analysis (TGA) have been used to study the thermal decomposition, the melting behavior and low-temperature transitions of copolymers obtained by radiation-induced grafting of styrene onto poly (tetrafluoroethylene- perfluoropropylvinylether) (PFA) substrates. PFA with different contents of perfluoropropylvinylether (PPVE) as a comonomer have been investigated. A two step degradation pattern was observed from TGA thermograms of all the grafted copolymers, which was attributed to degradation of PSTY followed by the degradation of the PFA backbone at higher temperature. One broad melting peak can be identified for all copolymers, which has two components in the samples with higher PPVE content. The melting peak, crystal-crystal transition and the degree of crystallinity of the grafted copolymers increases with radiation grafting up to 50 kGy, followed by a decrease at higher doses. No such decrease was observed in the ungrafted PFA samples after irradiation. This indicated that the changes in the heats of transitions and crystallinity at low doses are due to the radiation effects on the microstructure of PFA (chain scission), whereas at higher doses the grafted PSTY is the driving force behind these changes. (C) 2001 Elsevier Science Ltd. All rights reserved.

Free-radical bulk polymerization of styrene: ESR and near-infrared spectroscopic study of the entire conversion range

The free radical polymerization of styrene in bulk was monitored by ESR and FT near-infrared spectroscopy at 70°C for a series of concentrations of the initiator, dimethyl 2,2′-azobis(isobutyrate). In order to obtain detailed kinetic information over the intire conversion range, and the gel effect range in particular, conversion and free radical concentration data points were accumulated with exceptionally short time intervals. The polystyrene radical concentration ([St•]) went through a sharp maximum at the gel effect, a feature that has hitherto escaped observation due to the rapid concentration changes in the gel effect range relative to the data point time intervals of previous studies. Temperature measurements throughout the polymerization were employed to calculate that a temperature increase was not the cause of the [St•] maximum, which thus appeares to be a genuine feature of the gel effect of this system under isothermal conditions. The propagation rate constant (kp) as a function of monomer conversion exhibited a marked dependence on initiator concentration at high monomer conversion; the sharp decrease in kp with increasing conversion was shifted to higher conversions with increasing initiator concentration.

Copolymers obtained by the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) substrates. 1. Preparation and structural investigation

A study has been made to investigate the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) (PFA) substrates, using the simultaneous irradiation method. Two PFA polymers of different comonomer perfluoropropyl vinyl ether (PPVE) content and degree of crystallinity were used. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate, and irradiation dose on the grafting yield were investigated. Of the six different solvents used, the most efficient in terms of increasing grafting yield were dichloromethane, benzene, and methanol. The degree of grafting increased with increasing radiation dose up to 500 kGy, stabilizing above this dose. However, the grafting yield decreased with an increase in the dose rate. The grafting of styrene onto the PFA substrates was confirmed by FTIR-ATR and micro-Raman spectroscopy, The increase in the overall grafting yield was accompanied by a proportional increase in the penetration depth of the grafts into the substrate.

Comparative study of the radiation-induced grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinyl ether) and polypropylene substrates. I: Kinetics and structural investigation

A comparative study has been made of the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) and polypropylene (PP) substrates, using the simultaneous irradiation method. Effects of grafting conditions such as monomer concentrations, type of solvent, dose rate and irradiation dose on the grafting yield were investigated. Under the same grafting conditions it was found that a higher degree of grafting of styrene was obtained using a mixture of dichloromethane/methanol solvents for PFA and methanol for PP and the degree of grafting was higher in PP than in PFA at all doses. However, the micro-Raman spectroscopy analysis of the graft revealed that, for the same degree of grafting, the penetration depth of the grafted polystyrene into the substrate was higher in PFA than in PP substrates. In both polymers the crystallinity was hardly affected by the grafting process and the degree of crystallinity decreased slightly with grafting dose. The dependence of the initial rate of grafting on the dose rate and the monomer concentration was found to be 0.6 and 1.4 order for PFA and 0.15 and 2.2 for PP, respectively. The degree of grafting increased with increasing radiation dose in both polymers. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield for PFA and PP was accompanied by a proportional increase in the penetration depth of the graft into the substrates. (C) 2003 Society of Chemical Industry.

A kinetic study of the thermally initiated free radical reactions of styrene with octanedithiol as a model for the reactions of multifunctional thiols with divinylbenzene

The kinetics of chain reactions of octanedithiol with styrene, thermally initiated with TX29B50 (a 50:50 wt% solution of TX29 diperoxy initiator in a phthalate plasticizer), have been studied over a range of initiator concentrations, a range of mixture formulations and a range of temperatures. This system has been investigated as a model system for the reactions of polyfunctional thiols with divinyl benzene. The reactions have been shown to follow first-order kinetics for both the thiol and the ene species and to be characterized by a dependence on the initiator concentration to the power of one half. The kinetic rate parameters have been shown to adhere to Arrhenius behaviour. A kinetic model for the chain reactions for this system has been proposed. (C) 2003 Society of Chemical Industry.

A study of the radiation degradation of styrene/alkane and α-methylstyrene/alkane copolymers

The effects of copolymer composition and microstructure on the radiation chemistry of styrene/alkane and alpha-methylstyrene/alkane copolymers have been studied. The primary radical species formed on radiolysis of the copolymers at 77 K, and identified by ESR spectroscopy, are the same as those formed during radiolysis of the homopolymers. The yields of radicals for the copolymer are as predicted assuming that the cross-section is proportional to the electron density of each component; however, there is some evidence of radical migration to aromatic groups at 77 K. Changes in molecular structure on irradiation were detected by using C-13 NMR spectroscopy. Evidence of the consumption of terminal double bonds, and chain scission in alpha-methylstyrene/alkane copolymers was found. Measurements of viscosity supported the mechanism of cross-linking predominating in styrene/alkane copolymers, while in alpha-methylstyrene/alkane copolymers chain scission was the major result of irradiation. (C) 2003 Society of Chemical Industry.

Investigation of the vapor-phase grafting of styrene onto PFA

Poly(tetrafluoroethylene-co-perfluoropropyI vinyl ether), PFA, was grafted with styrene from the vapor phase using a simultaneous radiation grafting method. The graft yields were measured as a function of the dose and dose rate and were found to be initially linearly dependent on the dose and independent of the dose rate up to dose rates of similar to3 kGy/h. However, at a dose rate of 6.2 kGy/h, the slope of the yield-grafting time plot decreased. Raman depth profiles of the grafts showed that the polystyrene concentrations were greatest near the surface of the grafted samples and decreased with depth. The maximum penetration depth of the graft depended on the radiation dose for a fixed dose rate. Fmoc-Rink loading tests showed that the grafts displayed superior loading compared to grafts prepared from bulk styrene or from styrene solutions other than methanol.

An investigation of the nitroxide-mediated preirradiation grafting of styrene onto PFA

Simultaneous and preirradiation grafting of styrene onto fluorinated polyolefins does not enable control of the molecular weights or polydispersities of the styrene grafts. The nitroxide-mediated grafting of styrene onto PFA with TEMPO and TEISO using a preirradiation method has been investigated as a means of controlling the graft properties and especially to produce grafts with improved suitability for SPOC. The yields of graft were found to be in the range 15-20% for nitroxide concentrations between 5 x 10(-3) and 2 x 10(-2) M and were similar for the two nitroxides studied. Raman mapping was used to obtain the depth profile for the styrene grafts. The grafts were found to be principally located within the PFA substrate, and little graft was formed at the PFA surface. Fmoc loading tests were performed to assess the suitability of the grafted PFA as a support for SPOC, but these showed no significant loading was achieved, thus indicating that the graft properties are not suitable for SPOC. However, the study has important implications for the applications of PFA-grafted polymers in other areas, such as chemically resistant ion-exchange and separation membranes.

Determination of domain sizes in blends of poly(ethylene) and poly(styrene) formed in the presence of supercritical carbon dioxide

Well-mixed blends of poly(ethylene) and poly(styrene) have been synthesized using supercritical carbon dioxide as a solvent. The morphology of the blends has been conclusively characterized using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), Raman microprobe microscopy, and C-13 solid-state cross-polarization magic angle spinning NMR (C-13 CPMAS NMR). DSC measurements demonstrate that poly(styrene) in the blends resides solely in the amorphous regions of the poly(ethylene) matrix; however, corroborative evidence from the SAXS experiments shows that poly(styrene) resides within the interlamellar spaces. The existence of nanometer-sized domains of poly(styrene) was shown within a blend of poly(styrene) and poly(ethylene) when formed in supercritical carbon dioxide using Raman microprobe microscopy and C-13 CPMAS NMR spectroscopy coupled with a spin diffusion model. This contrasts with blends formed at ambient pressure in the absence of solvent, in which domains of poly(styrene) in the micrometer size range are formed. This apparent improved miscibility of the two components was attributed to better penetration of the monomer prior to polymerization and increased swelling of the polymer substrate by the supercritical carbon dioxide solvent.

Controlled Radical Polymerization of Styrene and Methyl Acrylate in the Presence of Reversible Addition-Fragmentation Chain Transfer Agents, Phenylethyl Phenyl Dithioacetate and Phenyldithioacetic Acid

The use of phenyldithioacetic acid (PDA) in homopolymerizations of styrene or methyl acrylate produced only a small fraction of chains with dithioester end groups. The polymerizations using 1-phenylentyl phenyldithioacetate (PEPDTA) and PDA in the same reaction showed that PDA had little or no influence on the rate or molecular weight distribution even when a 1:1 ratio is used. The mechanistic pathway for the polymerizations in the presence of PDA seemed to be different for each monomer. Styrene favors addition of styrene to PDA via a Markovnikov type addition to form a reactive RAFT agent. The polymer was shown by double detection SEC to contain dithioester end groups over the whole distribution. This polymer was then used in a chain extension experiment and the M-n was close to theory. A unique feature of this work was that PDA could be used to form a RAFT agent in situ by heating a mixture of styrene and PDA for 24 h at 70 degrees C and then polymerizing in the presence of AIBN to give a linear increase in Mn and low values of PDI (< 1.14). In the case of the polymerization of MA with PDA, the mechanism was proposed to be via degradative chain transfer. (c) 2005 Wiley Periodicals, Inc.

Measurement of glass-rubber transition temperature of skim milk powder by static mechanical test

Stickiness behavior of skim milk powder was investigated based on the mechanical property of the material during the glass-rubber transition. A thermally controlled device was developed for the static mechanical test. This device was attached to a texture analyzer, and skim milk powder, which was used as a model sample, was tested for its glass-rubber transition temperature (Tg-r) using static compression technique (creep test). Changes in compression probe distance as a function of temperature were recorded. Tg-r was determined, in the region where changes in the probe distance were observed, by using linear regression technique. The effect of sample quantity, compression force, and heating rate on the determination of Tg-r was investigated. All these parameters significantly influenced the Tg-r determination (p < 0.05). The Tg-r of skim milk powder measured by this novel technique was found closely correlated to its glass transition temperature (T-g) measured by DSC.