1.

4 POLYMER SYNTHESIS AND STRUCTURE

Free-radical Poly eri!a"io# Chain polymerization Addition Polymerization Three distinct stages: initiation, propagation, and termination 1.4.1 C$ai# Poly eri!a"io# Polymers may be synthesized by two major kinetic schemes, chain and stepwise polymerization.The most important of the chain polymerization methods is called free radical polymerization. n a c$ai#-%ro&"$ process monomers add one!by!one to the same end of a growing chain "ach chain has only one growth point. The concentration of monomer decreases grad#ally #ntil it is depleted.

n a '"e(-%ro&"$ process chains ha$e at least two growth points. %ost of the monomer molec#les are cons#med early in the process to gi$e a mi&t#re of compo#nds of intermediate molec#lar weight called oli%o er'.

These oligomers react with one another to form the polymer. The molec#lar weight contin#es to increase e$en after all the monomer molec#les ha$e reacted. n general, chain growth is associated with addition polymerization and step growth with condensation polymerization. t is not always so, howe$er. 'e(ll see an e&ample later in this chapter of an addition polymer in which step growth, not chain growth, characterizes macromolec#le formation. 1.4.1.1 Free Radical Polymerization The synthesis of poly)ethyl acrylate* will be #sed as an e&ample of free radical polymerization. +enzoyl pero&ide is a common initiator. ,ree radical polymerization has three major kinetic stepsinitiation, propagation, and termination. 1.4.1.2 Initiation .n heating, benzoyl pero&ide decomposes to gi$e twofree radicals:

n this reaction the electrons in the o&ygen/o&ygen bond are #npaired and become the acti$e site. 'ith 0 representing a generalized organic chemical gro#p, the free radical can be written 01. ) t sho#ld be pointed o#t that hydrogen pero&ide #ndergoes the same reaction on a wo#nd, gi$ing a b#rning sensation as the free radicals 2kill the germs.3* The initiation step #s#ally incl#des the addition of the first monomer molec#le:

n this reaction the free radical attacks the monomer and adds to it. The do#ble bond is broken open, and the free radical reappears at the far end. 1.4.1.3 Propagation After initiation reactions )4.5* and )4.6*, many monomer molec#les are added rapidly, perhaps in a fraction of a second:

.n the addition of each monomer, the free radical mo$es to the end of the chain. 1.4.1.4 Termination n the termination reaction, two free radicals react with each other. Termination is either by combination where 0 now represents a long!chain portion, or by disproportionation, where a hydrogen is transferred from one chain to the other. This latter res#lt

where 0 now represents a long!chain portion, or by disproportionation, where a hydrogen is transferred from one chain to the other. This latter res#lt
1.4 POLYMER SYNTHESIS AND STRUCTURE 11

prod#ces in two final chains.'hile the normal mode of addition is a head!totail reaction )4.47*, this termination step is normally head!to!head. As a homopolymer, poly)ethyl acrylate* is widely #sed as an elastomer or adhesi$e, being a polymer with a low Tg, !889C. As a copolymer with other acrylics it is #sed as a late& paint.
1.4.1.5 Structure and Nomenclature

Altho#gh the :PAC has set forth r#les for naming polymers according to str#ct#re, an alternati$e :PAC source-based system that names polymers according to the o#o er' from which they are prepared is more widely #sed. ;o#rce!based names are, for e&ample, the ones we are acc#stomed to seeing for polymers s#ch as polyethylene and polystyrene .'hen the name of the monomer is a single word, the polymer deri$ed from it is generated by simply adding the prefi& poly-. 'hen the name of the monomer consists of two words, both words are enclosed in parentheses immediately following poly. Th#s, polyacrylonitrile and poly)$inyl chloride* are the polymers of acrylonitrile and $inyl chloride,respecti$ely.

The con$ention for writing polymer form#las is to enclose the re(ea"i#% )#i" within brackets, followed by the letter n to indicate that the n#mber of repeating #nits is not specified. t is, howe$er, ass#med to be large. ;o#rce!based nomenclat#re does not re<#ire that a partic#lar polymer act#ally be made from the 2so#rce3 monomer. +oth poly)ethylene glycol* and poly)ethylene o&ide*, for e&ample, are made from ethylene o&ide and ha$e the same repeating #nit.

The str#ct#ral difference between the two is that the $al#e of n is larger for poly)ethylene o&ide* than for poly)ethylene glycol*. Therefore, their physical properties are different and they are known by different so#rce!based names. %any polymers are ro#tinely referred to by their common names or trade names. The polymer is almost always called Teflon rather than polytetrafl#oroethylene

STEP POLYMERI*ATION
A Polyester Condensation Reaction Polymeric materials are synthesized from small molec#les called monomer with more than two reacti$e sites on the monomer. There are essentially two types of polymerization reactions. n condensation reaction )or step!growth polymerization*, two reactants with degree of polymerization, m and n, combine to form their respecti$e polymer. Polymers s#ch as polyamides and polyesters can be prepared by condensation polymerization where small molec#les are eliminated as polymer chains are formed. Condensation polymerization of this type is called polycondensation polymerization.

Functionality: a. 8 = >inear molec#le: thermoplastics b. ?8 = Crosslinkable: gel, thermosets Characteristics: a. 0epeat #nit often not same as monomer str#ct#re b. 0elease of small molec#les )@8., @Cl, etc* c. Arad#al growth of molec#lar weight d. ;#ccessi$e condensation reactions,3co#pling3 e. 0elati$ely slow reactions f. ;toichiometric concerns The general reaction to form esters starts with an acid and an alcohol:

The chemicals abo$e cannot form a polyester beca#se they ha$e only one f#nctional gro#p each. 'hen the two reactants each ha$e bif#nctionality, a linear polymer is formed:

n the stepwise reaction scheme, monomers, dimers, trimers, and so on, may all react together. All that is re<#ired is that the appropriate f#nctional gro#ps meet in space. Th#s the molec#lar weight slowly climbs as the small molec#le water is eliminated. Then, the reaction is an ester interchange, releasing methanol. Poly)ethylene terephthalate* is widely known as the fiber BacronC. t is highly crystalline, with a melting temperat#re of abo#t D8EF9C. Another well!known series of polymers made by step polymerization reactions is the polyamides, known widely as the nylons. n fact there are two series of nylons. n the first series, the monomer has an amine at one end of the molec#le and a carbo&yl at the other. ,or e&ample,

which is known as nylon G. The n#mber G indicates the n#mber of carbon atoms in the mer. n the second series, a dicarbo&ylic acid is reacted with a diamine:

which is named nylon G5. Hote that the amine carbon n#mber is written first, and the acid carbon n#mber second. ,or reaction p#rposes, acyl chlorides are fre<#ently s#bstit#ted for the carbo&yl gro#ps. An e&cellent demonstration e&periment is described by %organ and Iwolek )47*, called the nylon rope trick. +elow are the others e&amples for polymerization by condensation: a. Polyesters = carbo&ylic acid D alcohol b. Polyamides = carbo&ylic acid D amine c. Polyethers = dehydration of diols d. Polysilo&anes = condensation of silanols );i.@*

Stepwise omenclat!re and Str!ct!res Table 4.E names some of the more important stepwise polymers.

The polyesters ha$e already been mentioned. The nylons are known technically as polyamides. There are two important s#bseries of nylons, where amine and the carbo&ylic acid are on different monomer molec#les )th#s re<#iring both monomers to make the polymer* or one each on the ends of the same monomer molec#le. These are n#mbered by the n#mber of carbons present in the monomer species. t m#st be mentioned that the proteins are also polyamides.

.ther classes of polymers mentioned in Table 4.E incl#de the poly#rethanes, widely #sed as elastomersJ the silicones, also elastomericJ and the cell#losics, #sed in fibers and plastics. Cell#lose is a nat#ral prod#ct. Another class of polymers are the polyethers, prepared by ring! opening reactions. The most important member of this series is poly)ethylene!o&ide*,

+eca#se of the o&ygen atom, poly)ethylene o&ide* is water sol#ble. To s#mmarize the material in Table 4.E, the major stepwise polymer classes contain the following identifying gro#ps:

at!ral Prod!ct Polymers As yo# take a look more closely at each member of these families of nat#ral polymers, remember this: nat#re was there first, by a long shotK .ne of o#r jobs as scientists is to fig#re o#t how nat#re does s#ch a good job so that we can imitate it. ,or e&ample, once we fig#red why silk had s#ch neat properties we were able to make synthetic silk in the form of nylons. 'e still ha$e a long way to go, tho#gh, before we can make synthetic 0HA and BHA that will lead to synthetic life. 'hile we may ne$er get there, trying to fig#re o#t how is f#n and leads to lots of important de$elopments in synthetic polymers and other areas incl#ding medicine and biochemistry. This raises the important point that science is like life. t doesnLt deal with j#st one thing, b#t e$erything mi&ed together. Polymer science isnLt the only science, and it may not e$en be the most important science )altho#gh we in the b#siness like to think it isK*. t is one of the areas that can help #s #nderstand and #se the knowledge we get from st#dying nat#re. n this way, we de$elop technology. >i$ing organisms make many polymers, nat#re(s best. %ost s#ch nat#ral polymers strongly resemble steppolymerized materials. @owe$er, li$ing organisms make their polymers enzymatically, the str#ct#re #ltimately being controlled by BHA, itself a polymer.

;ome of the more important commercial nat#ral polymers are shown in Table 4.M. People sometimes refer to these polymers as nat#ral prod#cts or renewable reso#rces. 'ool and silk are both proteins. All proteins are act#ally copolymers of polyamide!8 )or nylon!8, old terminology*. As made by plants and animals, howe$er, the copolymers are highly ordered, and they ha$e monodisperse molec#lar weights, meaning that all the chains ha$e the same molec#lar weights. Proteins were the first e&amples of polyamides )a fancy word for nylon*. +oth share many common traits b#t they are $ery different in how they are made and in their physical properties. They are alike in that the both contain amide linkages in the backbone. Amides are made from carbo&ylic acid gro#ps and amine gro#ps thro#gh the loss of water. The amide molec#lar segment is #ni<#e in its str#ct#re and intermolec#lar interactions. +eca#se of the hybridization of the nitrogen, carbon, and o&ygen of the amide gro#p, the segment is basically flat. %ore importantly, the hydrogen on the nitrogen and the carbonyl

o&ygen are capable of a strong interaction called a hydrogen bond. +eca#se of this, the amide gro#ps like each other some m#ch that they for strong associations that gi$e amide! containing polymers #n#s#al properties. This type of interaction is also disc#ssed in the section on nylons, and is the key similarity between nat#ral and synthetic polyamides. The differences between how nat#re does nylons and how we do it is striking. 'e mostly make nylons from molec#les that ha$e lots of C@8 gro#ps in them. The section on nylons shows str#ct#res for nylon E and nylon E,E, two of the most common synthetic polyamides. They possess fo#r, fi$e, or si& C@8 gro#ps between amide #nits. Hat#re, howe$er, is m#ch more economical, choosing to #se only a single carbon between amide gro#ps. 'hat nat#re does differently is to s#bstit#te this carbon with lots of different f#nctional segments and gro#ps.

Cell#lose and starch are both polysaccharides, being composed of chains of gl#cose! based rings b#t bonded differently. Hat#ral r#bber, the hydrocarbon polyisoprene, more closely resembles chain polymerized materials. n fact synthetic polyisoprene can be made either by free radical polymerization or anionic polymerization.The nat#ral and synthetic prod#cts compete commercially with each other. Pitch, a decomposition prod#ct, #s#ally contains a $ariety of aliphatic and aromatic hydrocarbons, some of $ery high molec#lar weight.

CROSS-LINKING, PLASTICIZERS, AND FILLERS All plastic materials consist of complex, very large molecules. In the case of those compounds used as insulation and jacketing materials, they are called polymers. A polymer is a large molecule built up by repetition of many, smaller chemical units. Polyethylene consists of a long chain of units, each made of one carbon atom with two associated hydrogen atoms.

Polyethylene consists of many random molecular chains, with no particu-lar orientation, and no chemical bonds existing between chains. hen heat is applied to such a material, the chains are free to slip and flow under relatively small outside force. !uch a material is called a thermoplastic. If we are able to introduce cross-linking bonds between adjacent molecular chains, this adds form stability at higher temperatures. "here will still be some loss of strength at elevated temperatures, but the crosslinked molec-ular chains are much more resistant to flow when stress is applied. #rosslinking can be accomplished chemically or by irradiation. #hemical crosslinking with rubber material is called $ulcani%ation. It is accom-plished by a heat induced reaction between the polymers and a crosslinking agent. &or wire and cable insulations, chemical crosslinking is performed by passing the wire through a long pressuri%ed steam tube, called a con-tinuous vulcani%ing '#.$.( machine. )ot all materials can be crosslinked, but for those that are able, the results are important. In general, mechanical characteristics are improved, especially at higher temperatures

Plasticizers are small molecules added to soften a polymer by lowering its glass transition temperature or reducing its crystallinity or melting tem-perature. "he most widely plastici%ed polymer is poly'vinyl chloride(. "he distinctive odor of new *vinyl+ shower curtains is caused by the plastici%er, for example. Fillers may be of two types, reinforcing and nonreinforcing. #ommon rein-forcing fillers are the silicas and carbon blacks. "he latter are most widely used in automotive tires to improve wear characteristics such as abrasion resistance. )onreinforcing fillers, such as calcium carbonate, may provide color or opacity or may merely lower the price of the final product.

THE MACROMOLECULAR H POTHESIS

In the nineteenth century, the structure of polymers was almost entirely unknown. "he ,ermans called it Schmierenchemie, meaning grease chemistry, but a better translation might be *the gunk at the bottom of the flask,+ that portion of an organic reaction that did not result in characteri%able prod-ucts. In the nineteenth century and early twentieth century the field of poly-mers and the field of colloids were considered integral parts of the same field. olfgang -stwald declared in ./.01 All those sticky, mucilaginous, resinous, tarry masses which refuse to crystalli%e, and which are the abomination of the normal organic chemist2 those substances which he carefully sets toward the back of his cupboard . . . , just these are the substances which are the delight of the colloid chemist. Indeed, those old organic colloids 'now polymers( and inorganic colloids such as soap micelles and silver or sulfur sols have much in common 1 .. 3oth types of particles are relatively small, .4 -5 to .4-6 mm, and visible via ultramicroscopy7 as dancing light flashes, that is, 3rownian motion. 8. "he elemental composition does not change with the si%e of the particle.

"hus, soap micelles 'true aggregates( and polymer chains 'which repeat the same structure but are covalently bonded( appeared the same in those days. Partial valences seemed to explain the bonding in both types. In ./84 9erman !taudinger enunciated the Macromolecular Hypothesis. It states that certain kinds of these colloids actually consist of very long-chained molecules. "hese came to be called polymers because many 'but not all( were composed of the same repeating unit, or mer. In ./:; !taudinger won the )obel pri%e in chemistry for his discoveries in the chemistry of macro-molecular substance. "he <acromolecular 9ypothesis is the origin of modern polymer science, leading to our current understanding of how and why such materials as plastics and rubber have the properties they do.