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<ref name='Gold Book "anionic polymerization"'>{{cite web |title=anionic polymerization |url=https://goldbook.iupac.org/terms/view/A00361 |website=Gold Book |publisher=IUPAC |access-date=1 April 2024 |ref=Gold Book A00361 |doi=10.1351/goldbook.A00361}}</ref>
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In [[polymer chemistry]], '''anionic addition polymerization''' is a form of [[chain-growth polymerization]] or addition polymerization that involves the [[polymerization]] of [[monomer]]s initiated with [[anion]]s. The type of reaction has many manifestations, but traditionally [[Vinyl group|vinyl]] monomers are used.<ref name=Hsieh>Hsieh, H.;Quirk, R. ''Anionic Polymerization: Principles and practical applications''; Marcel Dekker, Inc.: New York, 1996.</ref><ref name=Quirk>Quirk, R. Anionic Polymerization. In ''Encyclopedia of Polymer Science and Technology''; John Wiley and Sons: New York, 2003.</ref> Often anionic polymerization involves [[living polymerization]]s, which allows control of structure and composition.<ref name="Hsieh"/><ref name="Quirk"/>
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[[File:ET-coupledStyrene.png|thumb|Product of the reductive coupling of styrene with lithium, 1,4-dilithio-1,4-diphenylbutane. In the original work, Szwarc studied the analogous disodium compound.<ref>{{cite book|chapter=Ionic Polymerization|author=Sebastian Koltzenburg|author2=Michael Maskos|author3=Oskar Nuyken|title=Polymer Chemistry|isbn=978-3-662-49279-6|publisher=Springer|date=2017-12-11}}</ref>]]
As early as 1936, [[Karl Ziegler]] proposed that anionic polymerization of styrene and butadiene by consecutive addition of monomer to an alkyl lithium initiator occurred without chain transfer or termination. Twenty years later, living polymerization was demonstrated by [[Michael Szwarc]] and coworkers.<ref>{{cite journal|title=Polymerization Initiated by Electron Transfer to Monomer. A New Method of Formation of Block Polymers|first1=M.|last1=Szwarc|first2=M.|last2= Levy|first3=R.|last3=Milkovich|journal=J. Am. Chem. Soc.|year=1956|volume=78|issue=11|pages=2656–2657
|doi=10.1021/ja01592a101}}</ref><ref>{{cite journal|author=M. Szwarc |year=1956|title="Living" polymers|journal=Nature|volume=178|issue=4543|page=1168|doi=10.1038/1781168a0|bibcode=1956Natur.178.1168S}}</ref> In one of the breakthrough events in the field of [[polymer science]], Szwarc elucidated that [[electron transfer]] occurred from [[radical anion]] [[sodium naphthalene]] to [[styrene]]. The results in the formation of an organosodium species, which rapidly added styrene to form a "two – ended living polymer." An important aspect of his work, Szwarc employed the [[aprotic solvent]] [[tetrahydrofuran]]. Being a [[physical chemist]], Szwarc elucidated the [[chemical kinetics|kinetics]] and the [[thermodynamics]] of the process in considerable detail. At the same time, he explored the structure property relationship of the various [[ion pair]]s and radical ions involved. This work provided the foundations for the synthesis of polymers with improved control over [[molecular weight]], molecular weight distribution, and the architecture.<ref>Smid, J. Historical Perspectives on Living Anionic Polymerization. ''J. Polym. Sci. Part A.''; '''2002''', ''40'', pp. 2101-2107. [https://archive.today/20121012113202/http://www3.interscience.wiley.com/journal/94515609/abstract DOI=10.1002/pola.10286]</ref>
The use of [[alkali metals]] to initiate polymerization of 1,3-[[diene]]s led to the discovery by [[Frederick W. Stavely|Stavely]] and co-workers at Firestone Tire and Rubber company of cis-1,4-[[polyisoprene]].<ref name=Odian>Odian, G. Ionic Chain Polymerization; In '' Principles of Polymerization''; Wiley-Interscience: Staten Island, New York, 2004, pp. 372-463.</ref> This sparked the development of commercial anionic polymerization processes that utilize alkyllithium initiators.<ref name="Quirk"/>
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The most commercially useful of these initiators has been the [[alkyllithium]] initiators. They are primarily used for the polymerization of styrenes and dienes.<ref name="Quirk"/>
Monomers activated by strong electronegative groups may be initiated even by weak anionic or neutral nucleophiles (i.e. amines, phosphines). Most prominent example is the curing of cyanoacrylate, which constitutes the basis for [[superglue]]. Here, only traces of basic impurities are sufficient to induce an anionic addition polymerization or [[zwitterionic addition polymerization]], respectively.<ref>Pepper, D.C. Zwitterionic Chain Polymerizations of Cyanoacrylates. ''Macromolecular Symposia''; '''1992''',''60'', pp. 267-277. {{doi|10.1002/masy.19920600124}}</ref>
== Propagation ==
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==Additional reading==
*Cowie, J.; Arrighi, V. ''Polymers: Chemistry and Physics of Modern Materials''; CRC Press: Boca Raton, FL, 2008.
*{{cite journal|author=Hadjichristidis, N.|author2=Iatrou, H.|author3=Pitsikalis, P.|author4=Mays, J.|title=Macromolecular architectures by living and controlled/living polymerizations|journal=Prog. Polym. Sci.|year=2006|volume=31|issue=12|pages=1068–1132|doi=10.1016/j.progpolymsci.2006.07.002}}
*{{cite journal|author=Efstratiadis, V.|author2=Tselikas, Y.|author3=Hadjichristidis, N.|author4=Li, J.|author5=Yunan, W.|author6=Mays, J.|title=Synthesis and characterization of poly(methyl methacrylate) star polymers|journal=Polym Int.|year=1994|volume=4|issue=2|pages=171–179|doi=10.1002/pi.1994.210330208}}
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