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  • Author or Editor: B Howell x
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Abstract  

Vinylidene chloride polymers containing comonomer units capable of consuming evolved hydrogen chloride to expose good radical-scavenging sites might be expected to display greater thermal stability than similar polymers containing simple alkyl acrylates as comonomer. Incorporation of a comonomer containing the phenyl t-butyl carbonate moiety into a vinylidene chloride polymer has the potential to afford a polymer with pendant groups which might interact with hydrogen chloride to expose phenolic groups. Copolymers of vinylidene chloride with [4-(t-butoxycarbonyloxy)phenyl]methyl acrylate have been prepared, characterized, and subjected to thermal degradation. The degradation has been characterized by thermal and spectroscopic techniques. The degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl acrylate copolymers is much more facile than the same process for similar copolymers containing either [4-(isobutoxycarbonyloxy)phenyl]methyl acrylate or methyl acrylate, a simple alkyl acrylate, as comonomer. During copolymer degradation, [4-(t-butoxycarbonyloxy) phenylmethyl acrylate units are apparently converted to acrylic acid units by extensive fragmentation of the sidechain. Thus, the phenyl t-butyl carbonate moiety does function as a labile acid-sensitive pendant group but its decomposition in this instance leads to the generation of a phenoxybenzyl carboxylate capable of further fragmentation.

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Abstract

Fully substituted 1,3-dioxa-2-siloles contain a strained carbon–carbon bond that will undergo thermolysis at modest temperatures to generate a diradical capable of initiating vinyl polymerization. If the substituents contain flame-retarding moieties, e.g., halogen or phophorus-containing groups, the use of such compounds as initiators serves to incorporate a flame-retarding unit into the polymer mainchain. Both 2,2-dialkyl- and 2,2-diaryl-4,4,5,5-tetra(3,5-dibromophenyl)-1,3-dioxa-2-siloles may be prepared from the appropriate tetra(bromoaryl)-1,2-ethanediol and are obtained as white solids. Thermal decomosition (thermogravimetry) of these materials occurs in two stages. Initial decomposition is observed at about 250 °C and corresponds to the loss of nearly half of the initial sample mass.

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Abstract

The thermal degradation of a series of 1,1,2,2-tetraaryl-1,2-ethanediols has been examined using thermogravimetry (TG) and gas chromatography/mass spectrometry (GC/MS). These compounds are smoothly converted to the corresponding diaryl ketone and diaryl carbinol, i.e., the compounds undergo disproportionation arising from homolytic cleavage of the central carbon–carbon bond. Presumably, cleavage of the carbon–carbon bond generates a radical pair which disproportionates to provide the observed products.

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Abstract  

Organoplatinum antitumor agents are very effective, broad-spectrum drugs used for the treatment of a variety of cancerous conditions. The two most prominent of these, Cisplatin [cis-diamminodichloroplatinum(II)] and Carboplatin [diammino(1,1-cyclobutanedicarboxylato)platinum(II)], are large scale commercial successes. The third, Oxaliplatin [((trans-1,2-diamminocyclohexane)oxalato)platinum(II)], is now commercially available. The administration of all these drugs is accompanied by severe side effects. For Cisplatin, the most debilitating of these is kidney damage and extreme nausea. Several approaches to generate drug-release formulations that might mitigate toxic side effects have been explored. Now, platinum(IV) compounds which are more inert than platinum(II) compounds, and consequently less toxic, but which may be reduced to platinum(II) species within the cell are being evaluated for effectiveness in the treatment of cancer. The thermal stability of several precursors to compounds of this kind has been examined by thermogravimetry. In general, these materials lose ligands sequentially to generate a residue of platinum. This behavior may be generally useful for the characterization of such materials.

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Abstract

A difunctional imide monomer may be produced from 4-nitrophthalic anhydride and m-phenylenediamine. The requisite anhydride may be generated by nitration of phthalimide followed by hydrolysis to the corresponding acid and dehydration. All intermediate compounds have been fully characterized using spectroscopic and thermal methods.

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Abstract  

Two standard vinylidene chloride copolymers, the first containing approximately 9 mass% methyl acrylate and the second containing vinyl chloride at a nominal 15 mass% were prepared by radical suspension techniques using a series of peroxide and azo initiators (all of approximately the same half-life temperature for decomposition). The nature of the initiator could impact the stability of the resulting polymer in two ways. Instability could be introduced either via end-group effects or by attack of residual initiator fragments on the finished polymer during isolation and residual monomer stripping. In this case, the relative thermal stability of the resins produced was assessed by exposing samples to heat and shear in an air environment in a two-roll mill (Brabender Prep-Mill). The rate and extent of degradation was most readily apparent from color development during this treatment. The more thermally stable polymers were produced using initiator radicals that did not attack the polymer during isolation/stripping processes.

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