Vinyl chloride 2 molecules

In addition polymerisation a simple, low molecular weight molecule, referred to in this context as a monomer, which possesses a double bond, is induced to break the double bond and the resulting free valences are able to join up to other similar molecules. For example poly(vinyl chloride) is produced by the double bonds of vinyl chloride molecules opening up and linking together (Figure 2.1). 

In principle at least, vinyl chloride molecules can add to one another in any of three ways to form ... 

When the vinyl chloride molecule polymerizes, polyvinylchloride (PVC) is the result. 

Vinyl chloride is the least-oxidized chlorinated aliphatic hydrocarbon, and may serve as an electron donor. A vinyl chloride molecule consists of more hydrogen atoms relative to chloride atoms (3 to 1) thus, reductive dechlorination is not favorable to biodegradation. However, under aerobic conditions, vinyl chloride can serve as an electron donor with oxygen as an electron acceptor. 

This idea becomes even more pointed when we look at polymerization. Polyvinyl chloride is the familiar plastic PVC and is made by reaction of large numbers of monomeric vinyl chloride molecules. There is, of course, an enormous decrease in entropy in this reaction and any polymerization will not occur above a certain temperature. Some polymers can be depolymerized at high temperatures and this can be the basis for recycling, low... 

Contribution from III, IV, and V, and from VII stabilizes the chlorobenzene and vinyl chloride molecules, and gives double-bond character to the carbon-... 

One of the two 77 electrons in the vinyl chloride double bond has been used to form a single bond with the R—O radical. The other remains on the second carbon atom, leaving it as a seven-valence-electron atom that will react with another vinyl chloride molecule ... 

Thus, cement-containing systems provide the conversion of dichloroethane to be increased to more than 70% even at 673K. An important positive factor is that vinyl chloride molecule is stable at this temperature. At 673K, the side reaction of vinyl chloride dehydrochlorination with forming acetylene proceeds slowly, acetylene does not form, and the reaction is not complicated by the formation of a number of by-products, for example, of perchloroethylene. Thus, the above-made supposition about bifunctional character of copper—cement catalytic systems was confirmed in the investigations of their activity in the above-mentioned reactions. 

During a normal chemical reaction to create a particular polymer from a monomer, a catalyst is used to control the reaction. A catalyst is any substance that in a small amount noticeably affects the rate of a chemical reaction, without itself being consumed or undergoing a chemical change. For example, phosphoric acid is used as a catalyst in some polymerization reactions. Once an uncontrolled polymerization starts at an incident scene, it will not be stopped until it has completed its reaction, no matter what responders may try to do. If the polymerization occurs inside a tank, the tank may rupture violently. If a container of a monomer is exposed to fire, it is important to keep the container cool. Heat from an exposure fire may start the polymerization reaction. In Figure 5.18, the monomer vinyl chloride is shown along with the process of polymerization of the vinyl chloride molecules. 

The first step is formation of a dihydropyran ring. This is followed by a retro-Diels-Alder splitting and leads to regeneration of the a,p-unsaturated ketone and to formation of a double bond in the poly (vinyl chloride) molecule. The double bond initiates a subsequent elimination of hydrogen chloride from that molecule [495]. 

Explain how carbanionic centers can be formed on the backbones of poly(vinyl chloride) molecules. Show what subsequent reactions can take place. 

Draw a row of vinyl chloride molecules. Then show how they join up to make polyvinyl chloride. (The drawing for polythene on page 193 might help you.)... 

Olefinic unsaturation, carbonyl and hydroperoxide groups are also incorporated into the poly(vinyl chloride) molecule during the mechanodegra-dation process. 

The above is a double bond polymerization process. One vinyl chloride molecule is made to react with another molecule to form the PVC polymers. 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

Membrane Sep r tion. The separation of components ofhquid milk products can be accompHshed with semipermeable membranes by either ultrafiltration (qv) or hyperfiltration, also called reverse osmosis (qv) (30). With ultrafiltration (UF) the membrane selectively prevents the passage of large molecules such as protein. In reverse osmosis (RO) different small, low molecular weight molecules are separated. Both procedures require that pressure be maintained and that the energy needed is a cost item. The materials from which the membranes are made are similar for both processes and include cellulose acetate, poly(vinyl chloride), poly(vinyHdene diduoride), nylon, and polyamide (see AFembrane technology). Membranes are commonly used for the concentration of whey and milk for cheesemaking (31). For example, membranes with 100 and 200 p.m are used to obtain a 4 1 reduction of skimmed milk. 

The nomenclature of macromolecules can be compHcated when there is Httle or no regularity in the molecules for such molecules, the stmctural details may also be uncertain. In cases where the macromolecule is a polymeric chain with some uncertainties about regularity in its stmcture, a simple expedient is to name the polymer after the monomer that gave rise to it. Thus there are source-based names such as poly(vinyl chloride). 

Photochemistry. Vinyl chloride is subject to photodissociation. Photexcitation at 193 nm results in the elimination of HCl molecules and Cl atoms in an approximately 1.1 1 ratio (69). Both vinyUdene ( B2) [2143-69-3] and acetylene have been observed as photolysis products (70), as have H2 molecules (71) and H atoms [12385-13-6] (72). HCl and vinyUdene appear to be formed via a concerted 1,1 elimination from excited vinyl chloride (70). An adiabatic recoil mechanism seems likely for Cl atom elimination (73). As expected from the relative stabiUties of the 1- and 2-chlorovinyl radicals [50663-45-1 and 57095-76-8], H atoms are preferentially produced by detachment from the P carbon (72). Finally, a migration mechanism appears to play a significant role in H2 elimination (71). 

Of interest is the manner in which cavities of the appropriate size are introduced into ion-selective membranes. These membranes typically consist of highly plasticized poly(vinyl chloride) (see Membrane technology). Plasticizers (qv) are organic solvents such as phthalates, sebacates, trimelLitates, and organic phosphates of various kinds, and cavities may simply be the excluded volumes maintained by these solvent molecules themselves. More often, however, neutral carrier molecules (20) are added to the membrane. These molecules are shaped like donuts and have holes that have the same sizes as the ions of interest, eg, valinomycin [2001-95-8] C H QN O g, and nonactin [6833-84-7] have wrap around stmctures like methyl monensin... 

Fig. 24.1. (a) A copolymer of vinyl chloride and vinyl acetate the "alloy" pocks less regularly, has a lower Tg, and is less brittle than simple polyvinylchloride (PVC). (b) A block copolymer the two different molecules in the alloy ore clustered into blocks along the chain. 

Liquid organic rubbers with reactive functionality can be prepared by several methods. End-functional oligomers are preferred. Chains attached to the network at only one end do not contribute as much strength to the network as those attached at both ends [34], Urethane chemistry is a handy route to such molecules. A hydroxy-terminated oligomer (commonly a polyester or a polyether) can be reacted with excess diisocyanate, and then with a hydroxy methacrylate to form a reactive toughener [35]. The methacrylate ends undergo copolymerization with the rest of the acrylic monomers. The resulting adhesive is especially effective on poIy(vinyl chloride) shown in Scheme 2. 

The molecules join together to form a long chain-like molecule which may contain many thousands of ethylene units. Such a molecule is referred to as a polymer, in this case polyethylene, whilst in this context ethylene is referred to as a monomer. Styrene, propylene, vinyl chloride, vinyl acetate and methyl methacrylate are other examples of monomers which can polymerise in this way. Sometimes two monomers may be reacted together so that residues of both are to be found in the same chain. Such materials are known as copolymers and are exemplified by ethylene-vinyl acetate copolymers and styrene-acrylonitrile copolymers. 

Vinyl chloride, in contrast to ethylene, is an unsymmetrical molecule. We might refer to the CH2 group in vinyl chloride as the head of the molecule and the CHC1 group as the tail ... 

The small molecules used as the basic building blocks for these large molecules are known as monomers. For example the commercially important material poly(vinyl chloride) is made from the monomer vinyl chloride. The repeat unit in the polymer usually corresponds to the monomer from which the polymer was made. There are exceptions to this, though. Poly(vinyl alcohol) is formally considered to be made up of vinyl alcohol (CH2CHOH) repeat units but there is, in fact, no such monomer as vinyl alcohol. The appropriate molecular unit exists in the alternative tautomeric form, ethanal CH3CHO. To make this polymer, it is necessary first to prepare poly(vinyl ethanoate) from the monomer vinyl ethanoate, and then to hydrolyse the product to yield the polymeric alcohol. 

Chain reactions carried out on one type of monomer give rise to homopolymers when using two types of monomer the situation is more complicated. For example, polymerising mixtures of vinyl chloride with acrylate esters gives rise to a range of molecules, the first of which are relatively rich in acrylate molecules formed later, when the amount of acrylate monomer is relatively depleted, are richer in vinyl chloride. In a number of instances, reactions of this kind can be used to prepare polymers containing monomers which will not homopolymerise, e.g. maleic anhydride and stil-bene (vinylbenzene). 

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