Chlorinated poly mechanism

Polyimides, chlorinated poly(methylstyrene) and novolac resins are all crosslinking polymers under ordinary UV light irradiation, whereas PMMA and PMGI are main-chain scission-type polymers under deep UV irradiation (23). Even for such scission-type polymers, photo-thermal effects cannot be neglected. For crosslinking-type polymers, photo-thermal effects become more important and are the predominant mechanism for photo-ablation. 

Pyrotechnic mixtures may also contain additional components that are added to modify the bum rate, enhance the pyrotechnic effect, or serve as a binder to maintain the homogeneity of the blended mixture and provide mechanical strength when the composition is pressed or consoHdated into a tube or other container. These additional components may also function as oxidizers or fuels in the composition, and it can be anticipated that the heat output, bum rate, and ignition sensitivity may all be affected by the addition of another component to a pyrotechnic composition. An example of an additional component is the use of a catalyst, such as iron oxide, to enhance the decomposition rate of ammonium perchlorate. Diatomaceous earth or coarse sawdust may be used to slow up the bum rate of a composition, or magnesium carbonate (an acid neutralizer) may be added to help stabilize mixtures that contain an acid-sensitive component such as potassium chlorate. Binders include such materials as dextrin (partially hydrolyzed starch), various gums, and assorted polymers such as poly(vinyl alcohol), epoxies, and polyesters. Polybutadiene mbber binders are widely used as fuels and binders in the soHd propellant industry. The production of colored flames is enhanced by the presence of chlorine atoms in the pyrotechnic flame, so chlorine donors such as poly(vinyl chloride) or chlorinated mbber are often added to color-producing compositions, where they also serve as fuels. 

There are numerous misconceptions about the sources of various chemical elements in waste, particularly those that are potential acid formers when the waste is incinerated or mechanically converted and used as a refuse-derived fuel. For example, it is often mistakenly stated that the source of chlorine in waste, hence a potential source of HCl emissions, is poly(vinyl chloride). The relative contents of selected, potentially acid-forming elements in the organic portion of a sample of waste collected from various households in one U.S. East Coast city is given in Table 2 (17). In this city, a chief source of chlorine in the waste is NaCl, probably from food waste. 

Liquid chlorinated paraffins are the main halogen-containing fire-retardant additives used for poly(vinyl chloride) often in combination with a phosphate ester. In this case, the chlorinated paraffins have the secondary function of plasticizers. The thermal degradation mechanism of chlorinated paraffins is similar to that of poly(vinyl chloride), so in this case poly(vinyl chloride) stabilizers have also the secondary function to stabilize chlorinated paraffins. 

Investigation of the kinetics of the reaction of 4-chloro-2-pentene, an allylic chloride model for the unstable moiety of polyfvinyl chloride), with several thermal stabilizers for the polymer has led to a better understanding of the stabilization mechanism. One general feature of the mechanism is complexing of the labile chlorine atom by the metal atom of the stabilizer. A second general feature is substitution of the complexed chlorine atom by a ligand (either carboxylate or mercaptide) bound to the metal. Stabilization requires that the new allylic substituent (ester or sulfide) be more thermally stable than the allylic chlorine. The isolation of products from stabilizer-model compound reactions supports the substitution hypothesis of poly(vinyl chloride) stabilization. 

The reductive photodehalogenation of aryl halides has been actively investigated in recent years. Special attention has been given to (poly)halobenzenes and (poly)halo-biphenyls. The reactions are of interest in view of their mechanisms, and because of the importance of chlorinated aromatic hydrocarbons as environmental pollutants and the possibility of their photoinduced degradation. The photochemistry of aryl halides and related compounds in general14 and the photochemistry of polyhaloarenes in particular18 have been reviewed. 

Internal plasticizers are synthesized by copolymerization of suitable monomers. Polymeric non-extractable plasticizers, mostly copolymers having substantially lower glass transition temperatures due to the presence of plasticizing ( soft ) segments such as poly(ethylene-co-vinyl acetate) with approximately 45 % vinylacetate content, ethylene-vinyl acetate-carbon monooxide terpolymer, or chlorinated PE, are available for rather special applications in medicinal articles (Meier, 1990). In this case, the performance of the internally plasticized polymers is the principal advantage. However, copolymerization may account for worse mechanical properties. A combination with external plasticizers may provide an optimal balance of properties. For example, food contact products made from poly(vinylidene chloride) should have at most a citrate or sebacate ester based plasticizers content of 5 % and at most 10 % polymeric plasticizers. 

On the other hand, some mechanically compatible blends as well as some dispersed two-phase systems have made respectable inroads into the commercial scene. Many of these are blends of low-impact resins with high-impact elastomeric polymers examples are polystyrene/rubber, poly (styrene-co-acrylonitrile) /rubber, poly (methyl methacrylate) /rubber, poly (ethylene propylene)/propylene rubber, and bis-A polycarbonate/ ABS as well as blends of polyvinyl chloride with ABS or PMMA or chlorinated polyethylene. 

Fig. 9. Dynamic mechanical analysis plots of tan 5 against temperature for chlorinated polyethylene (52 % Cl) (4) and blends with poly(butyl acrylate) containing (3) 84.7% PBA, (2) 64.1 % PBA, and (1) 46.1 % PBA. The inset shows a plot of T, against weight percent chlorinated polyethylene where there is a marked deviation from linearity indicative of a specific interaction...

Several papers have appeared in the literature in recent years showing that certain metal acetylacetonates can function as initiators for the polymerisation of vinyl and diene monomers in bulk and solution (1 - 12). Results for the kinetics of bulk and solution polymerisation are consistent with the view that the reaction occurs by a free-radical mechanism. The usual free-radical kinetics are operative, but an unusual feature is that, in some cases, certain additives such as chlorinated hydrocarbons have an activating effect upon the reaction by inducing more rapid decomposition of the initiator (2,11,12,13). Other additives which have been reported as promotors for the polymerisation include pyridlne(14) and aldehydes and ketones(15). The complexity of the reaction in the presence of such additives is evident from the fact that chloroform has been reported to be an inhibitor for the poly-merlsatlon(3). 

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