Chemical modification of Hyflon® AD copolymer end groups by means of physical and chemical treatments. A joint spectroscopic and quantum chemical investigation

In this paper is presented a study on the effects of physical treatments, namely electron beam irradiation or fluorination, on a perfluoropolymer copolymer of tetrafluoroethylene with 2,2,4-trifluoro-5-trifluoro- methoxy-1,3-dioxole (Hyflon AD copolymer). The analysis has been carried out by means of IR spectroscopy and quantum chemical modeling based on density functional theory; this combined experimental/theoretical approach has proven effective for the interpretation of previously unassigned IR bands, which are associated to functional groups generated by polymer degradation and chain scission. We performed a systematic screening of chemical groups and structures compatible with degradation pathways that are possible from the chemical point of view: the chemical mechanisms and the correlation with the spectroscopic experimental data (both frequency and intensity) provide guidelines in understanding the phenomena. Moreover, the spectroscopic experimental/theoretical and chemical approaches allowed us to identify some chemical structures responsible for the unassigned IR bands in the C@O stretching frequency region above 1800 cmÀ1, which is typical for carbonyl groups in fluorinated systems

Method for the manufacture of perfluorovinylethers

The invention pertains to a method for the manufacture of a perfluorovinylether by hydrodehalogenation of a halofluoroether (HaloFE) having general formula (I-A) or RtO-CRt-'X-CRt-"Rt-"'X' (I-A. Said method comprising contacting said halofluoroether (HaloFE) with hydrogen in the presence of a catalyst comprising at least one transition metal (M) of group VI 11 B and tin

Pd-Cu interaction in Pd/Cu-MCM-41 catalysts: effect of silica source and metal content

Pd/Cu-MCM-41 catalysts for the hydrodechlorination of CF(3)OCFC1CF(2)C1 to CF3COCF=CF2 were prepared. Palladium- and copper-containing samples (Pd/Cu= 1 molar ratio) were synthesized by adding Pd2+ and Cu2+ during the formation of MCM-41, and then the slurries were aged by microwave-hydrothermal treatment. The effect of the silica source (silicates or TEOS) and total metal loading (2.4 and 4.0 wt.%) on the chemical-physical properties and catalytic performances was studied. Bimetallic silicate-derived samples show features similar to those of the pristine MCM-41, regardless of the total metal content. Conversely, the long-range order of the mesoporous structure decreases for TEOS-derived catalysts, and large metal contents seem to alter the structure for these materials. During template removal by thermal treatment, palladium and copper are on the surface of MCM-41 particles, forming Pd1-xCuxO solid solutions whose composition is silica source-dependent. The amount of copper in Pd1-xCuO is greater for TEOS-derived samples. After reduction, both Pd- and Cu-enriched alloys were found by XRD in silicate-derived samples, while XPS measurements indicated that the surface of the catalyst is enriched with copper. XRD and XPS analyses on TEOS samples indicated that the surface Cu/Pd ratio is closer to 1, and fcc PdCu alloys with a high copper content were identified. The composition of metallic particles modifies the selectivity, TEOS-derived catalysts being more selective to the target CF3'OCF=CF2

Polymorphisms of Metabolizing Enzymes and Susceptibility to Ethmoid Intestinal-type Adenocarcinoma in Professionally Exposed Patients1

Intestinal-type adenocarcinoma (ITAC) of ethmoid is a rare tumor associated with occupational exposure to wood and leather dusts. Polymorphisms in xenobiotic metabolizing enzymes play an important role in gene-environment interactions and may contribute to a high degree of variance in individual susceptibility to cancer risk. The aim of this study was to investigate by polymerase chain reaction the role of polymorphisms at CYP1A1 and GSTM1 genes in 30 ethmoid ITAC patients and 79 healthy donors. The distribution of Thr/Asn genotype at CYP1A1 codon 461 was significantly overrepresented among the patients (23.3%; P = .0422), whereas the Ile/Val genotype at CYP1A1 codon 462 was not significantly different between cases and controls (P = .76). The GSTM1 null genotype was not significantly different between cases and control (P = 1), but we observed that the combined codon 461 Thr/Asn and GSTM1 null genotype was overrepresented in the patient group (P = .0019). The results reveal that patients with CYP1A1 codon 461 polymorphism may be at high genetic risk of ITAC and that the risk increases in the presence of combined polymorphism of CYP1A1 and GSTM1 null genotype. This strongly suggests that CYP1A1 codon 461 and GSTM1 null genotype may be useful in selecting exposed individuals at risk for ethmoid ITAC