THE EFFECT OF MOBILITY OF MOLECULES ON RADIATION-INDUCED CHAIN SCISSION AND RACEMIZATION OF ISO-POLY(METHYL METHACRYLATE)

The radiation-induced chain-scission and racemization of isotactic poly(methylmethacrylate)(iso-PMMA) in amorphous and semi-crystalline state as well as in solution have been studied with nuclear magnetic resonance and molar mass deter-mination. It is shown that the chain-scission is dominant for iso-PMMA in dilute solution while the racemization reaction is not favorable in this case. On the contrary, the racemization is favorable when iso-PMMA was irradiated in its crystalline state while chain-scission is not. Such experimental results could be well explained by the mobility of molecules and "cage effect". The hypothesis, we proposed previously that the chain-scission, racemization and recombination are in competition and the final result depends on the state of molecular motion at which iso-PMMA was irradiated, has been verified verified once again.

THE EFFECT OF RADIATION-INDUCED CROSS-LINKING ON THE RELAXATION OF TAUT TIE MOLECULES DURING ANNEALING OF DRAWN LDPE

Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by Co-60-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and the degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the a transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2016 cm-1 on that of the band at 1894 cm-1 is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.

XPS STUDIES ON RADIATION-INDUCED STRUCTURAL-CHANGES IN THE COPOLYMER OF TETRAFLUOROETHYLENE AND ETHYLENE

In this work, the radiation-induced structural changes in the copolymer of tetrafluoroethylene and ethylene (F-40) were studied by X-ray photoelectron spectroscopy (XPS). During irradiation, some CF2 groups in the polymer were found to have been converted into carbon structures that bonded indirectly with fluorine atoms.

RADIATION STABILITY OF PERFLUOROETHYLENE PROPYLENE COPOLYMER

The gel content of crosslinked perfluoroethylene-propylene copolymer was obtained by extraction with fluoro-chloro oil. It was then treated by the Charlesby-Pinner equation. The results obtained revealed that both the gelation dose and the ratio of fracture to crosslinking density decreased with increasing irradiation temperature.

RADIATION EFFECTS ON CRYSTALLINE POLYMERS .1. GAMMA-RADIATION-INDUCED CROSS-LINKING AND STRUCTURAL CHARACTERIZATION OF POLYETHYLENE OXIDE

By using WAXD, DSC and gel fraction determination techniques, the mechanism of radiation crosslinking of polyethylene oxide (PEO) was explored, and the dependence of aggregated state on the chemical reaction and physical structure was also discussed. It was found that just like other semi-crystalline polymers, the state of aggregation of the specimen has a profound influence on the radiation effects on PEO. On the contrary, the crystalline structure of the specimen is severely affected with the increase in radiation dose and eventually amorphortized when subjected to an extremely high radiation dose.

STUDIES ON RADIATION-INDUCED LOSS OF WEIGHT OF A COPOLYMER OF TETRAFLUOROETHYLENE AND HEXAFLUOROPROPYLENE

The radiation-induced loss of weight of F-46 was found to be proportional to irradiation dose and affected markedly by irradiation temperature.

XPS STUDY OF RADIATION CROSS-LINKED COPOLYMER OF TETRAFLUOROETHYLENE WITH HEXAFLUOROPROPYLENE

In this work the radiation-induced structural changes in F-46 were studied by XPS. In carbon-1s spectra of a highly crosslinked F-46 sheet, the slight increase observed in relative area under the peak due to CF3 was explained by the radiation-induced scission of polymer chains. The peak at 287.6 eV appearing in the spectra caused by ionizing radiation was attributed to carbon structures without primary fluorine substituents, in both branching and unsaturated structures, while that at 289.3 eV was assigned to = CF groups in mid-chain double bonds.

STUDIES ON RADIATION EFFECTS OF PTFE .2. RADIATION-INDUCED STRUCTURAL-CHANGES AND THE TEMPERATURE EFFECT

In this work PTFE sheets irradiated with gamma-rays at 150-degrees-C and 200-degrees-C were studied using x-ray photoelectron spectroscopy (XPS). The main structural changes in PTFE due to radiation are the formation of CF3 and CF groups. An irradiation temperature dependence of the relative content of the three kinds of groups in irradiated PTFE was observed. The CF3 groups, especially when irradiation is carried out a lower temperatures, can defluorinate in the same manner as previosly reported for CF2 groups. The CF groups, on the other hand, are observed to increase with increasing irradiation dose and irradiation temperature; the latter was explained as due to an increase in branching structures.

CHARACTERIZATION OF GAMMA-RADIATION CROSS-LINKED CRYSTALLINE POLYMERS BY CRYSTALLIZATION TEMPERATURE

The effect of gamma-radlatlon on plain crystalline polymers and crystalline polymers containing different amounts of difunctional monomer both in vacuum and in air at room temperature has been investigated with DSC. It was found that the crystallization temperature T_c of crosslinked sample measured on DSC at a constant cooling rate decreases with increasing radiation dose. The difference between T_c before and after crosslinking (T_(c_0)-T_(c_R)) is linearly related to the radiation dose for plain polymer....

Preparation of low-molecular-weight and high-sulfate-content chitosans under microwave radiation and their potential antioxidant activity in vitro

In the present paper microwave radiation has been used to introduce N-sulfo and O-sulfo groups into chitosan with a thigh degree of substitution and low-molecular weight. The sulfation of chitosan was performed in microwave ovens. It was found that microwave heating is a convenient way to obtain a wide range of products of different degrees of substitution and molecular weight only by changing reaction time or/and radiation power. Moreover, microwave radiation accelerated the degradation of sulfated chitosan, and the molecular weight of sulfated chitosan was considerably lower than that obtained by traditional heating. There are no differences in the chemical structure of sulfated chitosan obtained by microwave and by conventional technology. FTIR and C-13 NMR spectral analyses demonstrated that a significantly shorter time is required to obtain a satisfactory degree of substitution and molecular weight by microwave radiation than by conventional technology. In this present paper, we also determined antioxidant activity of low-molecular-weight and high-sulfate-content chitosans (LCTS). The results showed LCTS could scavenge superoxide and hydroxyl radical. Its IC50 is 0.025 and 1.32mg/mL, respectively. It is a potential antioxidant in vitro. (C) 2004 Published by Elsevier Ltd.