480 © RADICAL REACTIONS. FIGURE 10.5 Autoxidation Chain Initiation of a linoleic acid ester. In step Step 1 1 the reaction is initiated by the attack of a radical on one elaie hoebociatcnetst a ae an ail Nye the —CH,— group between ral 7 * 7 the two double bonds; this at ] hydrogen abstraction produces Ln a radical that is a resonance hybrid. In stop 2 this radical Sy or reacts with oxygen in the frst of two chain-propagating steps to Chain Propagation Un produce an oxygen-containing Step 2 radical, which in step 3.can abstract a hydrogen from another molecule of the linoleic ester (Lin—H). The result of this second chain-propagating step is the formation of a hydroperoxide and a radical (Lin) that can bring about a repetition of step 2. Hydrogen abstraction from Anydroperoxide ‘another molecule of the linoleic ester @@ THE CHEMISTRY OF... antioxdants It you want to stop the abilly of radicals to generate more of themselves, especially in scenarios where they could be damaging like autoxidation, you need to find a suitable ‘rapping reagent. Such materials, known as antioxidants, succeed when they can lead to anew, and more stable, radical species that terminates the chain by no longer react- ing, or by further consuming reactive radicals to generate additional nonradical species. ‘Two such compounds are vitamin E (also known as a-tocopherol) and BHT (butylated Spoioapcha our tater CH, i HO. i oy ‘ he wee i GH. 7 i by, oH, ! amin € j (wtocophersh ‘arin sound wget In both cases, reaction with a radical species intially leads to a phenoxy radical, shown below with BHT in its reaction with a peroxy radical (ROO:). This event is the key for antioxidant behavior, in that it turns a highly reactive radical species into a fully covalent molecule that is less reactive (here a hydroperoxide, ROOH), with the newly formed phenoxy radical stabilized by the neighboring aromatic ring and attendant steric bulk ofthe tert-buly! groups. IH oO FOO, “ + ROOH our BHT radical Worth noting is that vitamin E could be considered a natural antioxidant, since its found in many foods and may work in our bodies to scavenge potentially damaging radical species, while BHT is a synthetic material that is added to many foods as a preservative. LnChain-Growth Polymers Polypropylene (syndiotactc) ‘The names Orlon, Plexiglas, Lucite, polyethylene, and Teflon are now familiar to most of us. ‘These “plastics” or polymers are used in the construction of many objects around us—feom the clothing we wear to portions of the houses we live in. Yet all ofthese compounds were tunknown 100 years ago. The development of the processes by which synthetic polymers are made, more than any other single factor, was responsible for the remarkable growth of the chemical industry in the twentieth century Some scientists are now expressing concern about the reliance we have placed on these synthetic materials. Because they are the products of laboratory and industrial processes rather than processes that occur in nature, nature often has no way of disposing of many of them. Although progress has been made in che development of “biodegradable plastics” in recent years, many materials are still used that are not biodegradable. Although most of these objects are combustible, incineration is not always a feasible method of disposal because of attendant air pollution. Nor all polymers are synthetic. Many naturally occurring compounds are polymers as wel. Silk and wool are polymers that we call proteins. The starches of our diet are polymers and so is the celhulose of cotton and wood. Polymers are compounds that consist of very large molecules made up of many repeating subunits. The molecular subunits that are used to synthesize polymers are called monomers and the reactions by which monomers are joined cogether are called polymerization reactions. We studied a radical mechanism for polymerization in Section 10.11. We shall study other mechanisms in Section 17.11, Special Topic D, and Section 21.7. SPECIAL TOPIC GCc2 SPECIAI © CHAN-GROWTH POLYMERS. Propylene (propenc), for example, can be polymerized to form polypropylene, This polymerization occurs by a chain reaction, and, as a consequence, polymers such as polypropylene are called chain-growth or addition polymers: Propylene Polypropylene (PP) Aswe saw in Scetion 10.11, alkenes are convenient starting materials forthe prepara- tion of chain-growth polymers. The addition reactions occur through radical, cationic, or anionic mechanisms depending on how they are initiated. The following examples illustrate these mechanisms. All of these reactions are chain reactions; Radical Polymerization | ang rid ‘ome! ae + Sood — ag-d/ AS, wd-td-d SA. ete UN LIN tN TT TN Cationic Polymerization + Yenc’ — Ns RO Anionic Polymerization Lick ris gf ee A ae \one/ 204 Nox STAN Radical polymerization of chloroethene (vinyl chloride) produces a polymer called poly(vinyl chloride), also known as PVC: oi a a a Vinyl chloride _Poly(viny! chloride) (eve) ‘This reaction produces a polymer that has a molecular weight of about 1,500,000 and thac isa hard, brite, and rigid material. In this form icis often used to make pipes, ods, and compact discs. Poly(vinyl chloride) can be softened by mixing it with esters (called plasticizers). The softer material is used for making “vinyl leather,” plastic raincoats, shower curtains, and garden hoses. Exposure to vinyl chloride has been linked to the development ofa rare cancer of the liver called angiocarcinoma. This link was first noted in 1974 and 1975 among work- «ers in vinyl chloride factories. Since that time, standards have been set to limit workers exposure to less than one part per million average over an 8-hour day. The U.S. Food and Drug Administration (FDA) has banned the use of PVC in packaging materials for food, [there is evidence that poly(vinyl chloride) contains traces of vinyl chloride.] ‘Acrylonitrile (CHz=CHCN) polymerizes to form polyacrylonitrile or Orlon. The F for the polymerization is a mixture of ferrous sulfate and hydrogen peroxide. These two compounds react to produce hydroxyl radicals (OH), which act as chainCHAIN-GROWTH POLYMERS. os ra. éy 0-0 /, cN ‘Acrylonitrile Polyacrylonitile (Orton) Polyacrylonitrile decomposes before it melts, so melt spinning cannot be used for the production of fibers. Polyacrylonitrle, however, is soluble in V,N-dimethylformamide, and these solutions can be used to spin fibers. Fibers produced in this way are used in ‘making carpets and clothing. ‘Teflon is made by polymerizing tetrafluorocthene in aqueous suspension: Polytetrafluoroethylene eflon) ‘The reaction is highly exothermic, and water helps dissipate the heat that is produced ‘Teflon has a melting point (327 °C) chat is unusually high for an addition polymer. Icis also highly resistant to chemical atack (due to the strength of the C—F bonds) and has a low coefficient of friction. Because of these propertics, Teflon is used in greascless bear- ings, in liners for pots and pans, and in many special situations that require a substance that is highly resistant to corrosive chemicals. ‘Vinyl alcohol is an unstable compound that rearranges spontaneously to acetaldehyde = } OH Vinyl alcohol Acetaldehyde Consequently, che water-soluble polymer, poly(vinyl alcohol), cannot be made directly. Ie can be made, however, by an indirect method that begins with the polymerization of vinyl acetate to poly(vinyl acetate). This is chen hydrolyzed co poly(vinyl alcohol). Hydrolysis is rarely carried to completion, however, because the presence ofa few ester groups helps confer water solubility on the product. The ester groups apparently help keep the polymer chains apart, and this permits hydration of the hydroxyl groups. Poly(vinyl alcohol) in which 10% of the ester groups remain dissolves readily in water. Poly(vinyl alcohol) is used to manufacture water-soluble films and adhesives. Poly(vinyl acetate) is used as an emulsion in water-base paints. Ys ‘\=0 a am Vinyl acetate Poly(vinyl Poly(vinyl acetate) ‘alcohol) A polymer with excellent optical properties can be made by the radical polymerization of methyl methacrylate. Poly(methyl methacrylate) is marketed under the names Lucite, Plexiglas, and Perspex: nt — o ComMe ‘COpMe Mothyt Poly(methy!+4 SPECIAL TOPIC C CHAN-GROWTH POLYMERS ‘A mixture of vinyl chloride and vinylidene chloride (1,1-dichlorocthene) polymerizes to form what is known as a copolymer. ne av Scr gy Vinylidene Vinyl Copolymer chloride chloride (excess) The subunits do not necessarily alternate regularly along the polymer chain, .1 STEREOCHEMISTRY OF CHAIN-GROWTH POLYMERIZATION Head-to-tail polymerization of propylene produces a polymer in which every other carbon atom is a chirality center. Many of the physical properties of the polypropylene produced in this way depend on the stereochemistry of these chirality centers: Sy __pobymarzation “ead total)” ‘There are three general arrangements of the methyl groups and hydrogen atoms along the chain, These arrangements are described as being atactic, symdiotactc, and iotactc. the stereochemistry at the chiality centers is random (Fig. C.1), the polymer is said to be atactic (a, without + Greek: taktibos, order). FIGURE 6 Nace prope TITTY In atactic polypropylene the methyl groups arc randomly disposed on cither side of the stretched carbon chain. If we were to arbitrarily designate one end of the chain as having higher preference than the other, we could give (R, 5) designations (Section 5.7) to the chirality centers. In atactic polypropylene the sequence of (R, S) designations along the chain is random, Polypropylene produced by radical polymerization at high pressures is atactic. Because the polymer is atactic, it is noncrystalline, has a low softening point, and has poor mechanical properties ‘A second possible arrangement of the groups along the carbon chain is that of syndiotactie polypropylene. In syndiotactic polypropylene the methyl groups alternate regularly from one side of the stetched chain to the other (Fig. C.2). If we were to anbitearily designate one end of the chain of syndiotaetic polypropylene as having higher preference, the configuration of the chirality centers would alternate, (A), (S), (R), (S$). (8), (S), ), (S), and s0 on.C.1 STEREOCHEMISTRY OF CHAIN-GROWTH POLYMERIZATION cs FIGURE €.2 Syndiotactic polypropylene. id possible arrangement of chirality centers is the isotactie arrangement shown in Fig. C.3. In the isotactic arrangement all of the methyl groups are on the same side of the stretched chain. The configurations of the chirality centers are either all (R) oral (S) depending on which end of the chain is assigned higher preference. “The names isotactic and syndiotactic come from the Greek teem zaktios (order) plus dso (same) and say (evo together) Before 1953 isotactic and syndiotactic addition polymers were unknown. In that qu sano Narra were year, however, a German chemist, Karl Ziegler, and an Ikalian chemist, Giulio Natta, I awarded the Nobel Prize in announced independently the discovery of catalysts that permit stereochemical control of Chemistry for their discoveries polymerization reactions. The Ziegler-Natta catalysts, as they are now called, are prepared jn 4969, from transition metal halides and a reducing agent. The catalysts most commonly used are prepared from titanium tetrachloride (TiCly) and a wrialkylaluminum (AIR). Ziegler—Nacta catalysts are gencrally employed as suspended solids, and polymeriza- tion probably occurs at metal atoms on the surfaces of the particles. The mechanism for the polymerization is an ionic mechanism, but its details are not fully understood. There is evidence that polymerization occurs through an inscrtion of the alkene monomer between the metal and the growing polymer chain. Both syndiotactic and isotactic polypropylene have been made using Ziegler-Narta catalysts. The polymerizations occur at much lower pressures, and the polymers that are produced are much higher melting than atactic polypropylene. Isoractic polypropylene, for example, melts at 175 °C. Isotactic and syndiotactic polymers are also much more cxystalline than atactic polymers. The regular arrangement of groups along the chains allows them co fic cogether becter in a crystal structure. tactic, syndiotactic, and isotactic forms of poly(methy! methacrylate) are known. The atactic form is a noncrystlline glass. The crystalline syndioractic and isotactic forms melt at 160 and 200 °C, respectively. {@) Write structural formulas for portions ofthe chain of the atactic, syndiotactic, and iso- tactic forms of polystyrene (see Practice Problem 10.15). (b) If solutions were made of each of these forms of polystyrene, which solutions would you expect to show optical activity?