Polyvinyl chloride structure

This material does not absorb u.v. radiation at all and so is not degraded by sunlight. The structure of polyvinyl chloride is quite similar ... 

Amorphous thermoplastics These are made from polymers which have a sufficiently irregular molecular structure to prevent them from crystallising in any way. Examples of such materials are polystyrene, poly methyl methacrylate and polyvinyl chloride. 

The most common backbone structure found in commercial polymers is the saturated carbon-carbon structure. Polymers with saturated carbon-carbon backbones, such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and polyacrylates, are produced using chain-growth polymerizations. The saturated carbon-carbon backbone of polyethylene with no side groups is a relatively flexible polymer chain. The glass transition temperature is low at -20°C for high-density polyethylene. Side groups on the carbon-carbon backbone influence thermal transitions, solubility, and other polymer properties. 

Figure 22.2 Chemical structure of monomer soluble initiators for polyvinyl chloride a) dilauryl peroxide, b) benzoyl peroxide and c) azobisisobutyronitrile...

Before the mechanism of vinyl polymerization was understood, the question of the structure of vinyl polymers was of considerable interest. Staudinger had written these polymers as having a head-to-tail arrangement of recurring units, but he had not really furnished evidence of the structure. As Carothers once said, Staudinger had assigned the structure by pronouncement. He was as usual correct, and chemical evidence was developed to establish such structures. For example, when monovinyl methyl ketone polymerized, it could produce by head-to-head, tail-to-tail reaction a 1,4-diketone. By head-to-tail polymerization it would give a 1,5-diketone. These two types have different reactions. The study of the polymer proper showed that the polymer was a 1,5-diketone. In the case of polyvinyl chloride, a head-to-head, tail-to-tail polymerization would lead to a 1,2-dihalide compound, and a head-to-tail polymerization would lead to a 1,3-dihalide. 

Stable aggregates have been shown to present a problem in the characterization of polyvinyl chloride (1,2) and it has been suggested that residues of crystalline structures may persist in polyethylene solutions at temperatures below the polymer s crystalline melting point (3-5). 

Olefins or alkenes are defined as unsaturated aliphatic hydrocarbons. Ethylene and propylene are the main monomers for polyolefin foams, but dienes such as polyisoprene should also be included. The copolymers of ethylene and propylene (PP) will be included, but not polyvinyl chloride (PVC), which is usually treated as a separate polymer class. The majority of these foams have densities <100 kg m, and their microstructure consists of closed, polygonal cells with thin faces (Figure la). The review will not consider structural foam injection mouldings of PP, which have solid skins and cores of density in the range 400 to 700 kg m, and have distinct production methods and properties (456). The microstructure of these foams consists of isolated gas bubbles, often elongated by the flow of thermoplastic. However, elastomeric and microcellular foams of relative density in the range 0.3 to 0.5, which also have isolated spherical bubbles (Figure lb), will be included. The relative density of a foam is defined as the foam density divided by the polymer density. It is the inverse of the expansion ratio . 

Other examples of addition polymerization of alkenes are the production of polypropylene from propylene, polyvinyl chloride (PVC) from vinyl chloride, and Teflon from tetrafluoroethylene. The structure of the three monomers is depicted in Figure 15.2. 

Because of its irregular structure, ar-PP is an amorphous polymer with a softening point lower than that of it-PP. In contrast, because of its regular structure, commercial it-PP is a higher-melting crystalline solid. It is important to note that similar stereochemical concepts apply to other vinyl polymers with pendant groups, such as polyvinyl chloride (PVC) and polystyrene (PS). 

The Tg increases as the intermolecular forces in the polymer and the regularity or crystallinity of the polymer chain structure increase. Thus polyvinyl chloride (PVC) has a higher Tg than linear polyethylene (hdpe) because of the presence of dipole-dipole interactions between the chains in PVC. 

Among the naturally occurring filler materials are cellulosics, such as wood flour, alpha cellulose, shell flour, and starch, and proteinaceous fillers, such as soybean residues. Approximately 40,000 tons of cellulosic fillers are used annually by the U.S. polymer industry. Wood flour, which is produced by the attrition grinding of wood wastes, is used as a filler for phenolic resins, dark-colored urea resins, polyolefins, and polyvinyl chloride (PVC). Shell flour, which lacks the fibrous structure of wood flour, is made by grinding walnut and peanut shells. It is used as a replacement for wood flour. 

Polyvinyl Halides. Chlorinated Polyvinyl Chloride It was produced in Germany up to three decades ago, but this was primarily a 1,1-disubstituted product of increased solubility for dry-spinning of fibers. Goodrich has developed a light-activated suspension chlorination process which produces 1,2-dichlorinated structures of increased hot strength, thermal stability, and flame resistance. 

There are a number of examples of systems in which species firmly attached to sites can react with one another. The reaction is usually confined to groups that occupy adjacent sites. A classic example of such a system is the polymer, polyvinyl chloride, whose structure is... 

Now the lone chlorine atom has found itself isolated since the zinc only extracts two adjacent chlorines. Such a result is called reactant isolation, and one wishes to predict the chlorine concentration left in the polymer as a function of time. It was shown by Flory76 that the fraction of chlorines unreacted should approach e 2, and this was used in fact by Marvel77 to determine the structure of polyvinyl chloride. Other examples are the condensation of the polymer of methyl vinyl ketone76 and the vulcanization of natural rubber.78 The vulcanization studies supply another example where a molecular structure was determined by a kinetic scheme. The complete time dependence of the process was recently derived by Cohen and Reiss24 using a novel method of multiplets, which will now be outlined. 

An important conclusion emerging from these studies is that polyvinyl chloride has a three-dimensional network structure where microcrystallites are believed to... 

In conclusion, we may state that viscoelastic data presented in this paper further reaffirm the contention that polyvinyl chloride has a network structure with microcrystallites acting as cross-links. Incorporation of plasticizer affected PVC in a way similar to amorphous polymers mainly by lowering Tg of the amo-rophous regions. Microcrystallites appear to be stable even in the presence of... 

While initial aging did cause some loss in volume resistivity, it was no more severe in unstabilized than in stabilized compositions. The most startling effect was the marked increase in volume resistivity under severe aging conditions. This may be due to volatilization loss of DOP or cross-linking of polyvinyl chloride, both of which could reduce migration of ionic impurities, or it may involve adsorption of ionic impurities by the dark-colored, conjugated, polyene structure which forms by loss of hydrogen chloride. In any case it deserves further study. 

Previous work hod shown that low temperature coke is formed from cools hooted to between 450° and 500° C. by a process of nudeation and growth of spherical bodies in the plastic vitrinite. An essentially similar process has now been found to occur with coke-oven and petroleum pitches, with polyvinyl chloride, and with some polynuclear hydrocarbons, all of which yield carbons which grophitize readily at high temperatures. The process is probably general for the initial stages of formation of such carbons from the liquid phase. Some control of the solidification process has been achieved on the laboratory scale, and the physical and chemical structure of the spherulites has been investigated. 

Recent work in this Division has shown that various substances other than vitrinites, such as pitches from coal tars and petroleum tars, polyvinyl chloride, and polynuclear hydrocarbons, develop similar mosaic structures on heating. In fact this effect occurs with most high carbon materials which pass through a plastic stage during carbonization. 

After the demonstrations of preparation of stereoregular polymers having novel properties by means of special ionic methods, die possibilities of free radical methods were examined extensively. It must be concluded that in free radical systems the structures of homopolymers and copolymers can be little influenced by specific catalysts and other reaction conditions, but are determined largely by monomer structure. This is consistent with the relative uniformity of comonomer reactivity ratios in radical copolymerizations. However, it has been found possible to obtain somewhat more syndiotactic structure, dldl. than normally obtained by radical reactions, at low temperatures and by selecting solvents. Examples are polyvinyl chlorides of higher than usual crystallinity from polymerizations at low temperature e.g.. —50°C under ultraviolet light... 

Polychloroethene (polyvinyl chloride), as usually prepared, is atactic and not very crystalline. It is relatively brittle and glassy. The properties of polyvinyl chloride can be improved by copolymerization, as with ethenyl ethanoate (vinyl acetate), which produces a softer polymer ( Vinylite ) with better molding properties. Polyvinyl chloride also can be plasticized by blending it with substances of low volatility such as tris-(2-methylphenyl) phosphate (tricresyl phosphate) and dibutyl benzene-1,2-dicarboxylate (dibutyl phthalate) which, when dissolved in the polymer, tend to break down its glasslike structure. Plasticized polyvinyl chloride is reasonably flexible and is widely used as electrical insulation, plastic sheeting, and so on. 

To get a better insight into the chlorination reaction, we wanted to avoid a heterogeneous process. Instead of polyethylene or polypropylene, we used polyisobutene, which is soluble in carbon tetrachloride, as are its chlorination products. In addition, we were interested in the structure and properties of the chlorinated products, especially in comparison with polyvinyl chloride (PVC) and vinyl chloride/isobutene (VC/IB) copolymers. 

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