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Polyaddition—the same as step-reaction polymerization without formation of byprod ets (@g4 LI oF 1.13), Chain polymerization—the same as chain-eacton polymerization without formation of byproducts (€, 113). Condensative chain polymerization—thes formation of low-molar- mass byproducts (ex as chain-eaction polymerization with the 16) Because the IUPAC classifications have yet to be widely accepted, we shall continue to use the more familie step-reation (or stp-growth) and chain-reation (or chain-growth) termi~ nology. LT Nomenclature Polymer nomenclature is complicated for variety of reasons. Fist, most polymer ames are based on rumes ofthe corresponding monomers, and although this source-based system is widely gocepted, one frequently encounters variations in forma. Second, although the Macromolecular Nomenclaee Commission of the TUPAC has grappled valiantly with the ‘complesities of polymer structure and has proposed perfectly logical ules” the IUPAC sys- tem isnot widely used except in reference works. Third, some polymer siactres are 80 complex, particularly where beanching or roslinkng is involved, that naming them defies all but the most persistent of nomenclature purists, And finally, polymer science has some fairly sharply defined boundaries; rubber chemists, for example, employ terminology that, right be unineligible to a plastics or textiles chemist. All his takes on added significance in this age of computer-based information storage and reieval, where a standardized set of abbreviations isa necessity 232° Given the magnitude ofthe problem, therefore, we will t= tempt in this section to clarify the most generally accepted terminology. "As shouldbe apparent fom the previous sections, polymer types, or failies, are named according tothe fnetional group present inthe repeating unit, with the prefix poly: ply texters, polyamides, polyethers, and so on. Polyamide are unusual in that they ae also called Ilona, a term that originated ae a trade name but then evolved over the years inn general tse If more than one functional group is presen, the polymer is named aceordingl, for ex ample, polyetherimise. ‘Where polymer siricture is complex and not easly definable, the family is usally named for the monomers employed, as with phenol-formaldehyde polymers. Part IT of this book discusses a variety of polymers according to the faily clasification. Polymers derived from ‘monomers containing eazbon-carbon double bonds are often refered 10 as vinyl polymers, although it would be more correct reserve that term for monomers containing the vinyl s10up, CH:=CH-, such as vinyl chloride, CHy=CHCT, or acrylonitile, CHs—=CHCN, ‘The term vinylidene is used with Is|-isubstiuted ethylene, for example, vinylidene chlo- Fide, CHy=CCh. Polymers derived from simple alkenes suchas ethylene or propylene are ‘often elle polyolefins. For the sake of convenience, we shall refer to all polymers prepared by chain-reaction polymerization ofalkeny! monomers as vinyl polymers. LTA. Vinyl Polymers “The most widely accepted method of naming vinyl polymers isto place the prefix poly be fore the name of the corresponding monomer; for example {CHCH:}- Polythene AECR,CE.}- —Payteteafunenetyene ‘Note that common names of the monomers are used. not eene or phenylethene) By this ‘system, the polymer f-CHz-}- prepared according 1 reaction (116i called polymethylene to disingush ic fom the commercial polymer prepared fom ethylene. (In the British lier- ture, polyethylene is frequently called polythene.) Occasionally a trade name may be em ployed in casual usage, for example, Teflon (du Pont) for polyttrafiuoroethylen, but this ‘ecurs only where such names are widely recognized ‘the monomer nanie consists of more than one word, or ifthe name is preceded by a teuer or number, the muna nae is enclosed in parentheses and prefixed with poly HH Poty(acyie ac) com] cH, i cH Poly(aemethysttene) Oo og Poiy(tspentene) CHCH.CH, Unfomunately, one sil sees parentheses omitted —polyzcrylic acd, for example—especially in trade literature. This nomenclature is no longer considered acceptable and should be a8oided “The IUPAC recommends that names be derived from the structure of the base unit or ‘constitutional repeating unit (CRU) a8 the TUPAC prefers to alli, according to the fol lowing steps: 1, The smallest structurl unit (CRU) is identified 2. Substituent groups on the backbone are asigned the lowest possible numbers. 13. The name fs placed in parentheses (or brackets and parentheses, where necessary), and prefied with poly ‘The preceding polymers would ths be named as follows: Source name TUPAC name Polyethylene Poly(ethylene) Polyttrafluoroethylene Poly(dflvoromethylene) Polystyrene Ply(-phenylethylene) Poly(acrylic acid) Poly(1-carboxylatcethylene) oly(a-methystyrene) Poly(J-methyi-I-phenylethylene) Poly(t-peatene) Poly(1-(1-propyethyene] Inthe ILIPAC cystem, parentheses aze ofa used following the profs also ethylene (rather than ethene) isthe acceptable structural name, Furthermore, the IUPAC system makes no Aistinsion between polyethylene and polymethylene. Diene monomers such as 1,3-butaiene (CH;=CH—CH—CHs) create special dif cules because they can undergo both 1,2~ and I -additon. Thus poly(I butadiene) may have two possible repeating unis: cnet -for.ci=crier cu=cH, 124k 1, $-ition withthe Inter capable of exhibiting cis-rans isomerism. To name the polymer by TUPAC rules, the CRU of the 14-addtion product is best welt in the es familia format #CH=CHCH.CH,}- Assuming cach butadiene polymer were to consist ofa single repeating unit the names would be a flows: Source name TUPAC name 1.2.akiton P-Poly(! A-botadiene) —__Ply(I-vinylathylon) 1 4-additon L-Poly(1.3-butaiens) __Ply(I-butene-1,4-