Ring-opening polymerization: Difference between revisions

In [[polymer chemistry]], '''ring-opening polymerization''' ('''ROP''') is a form of [[chain-growth polymerization]] in which the [[End group|terminus]] of a [[polymer]] chain attacks [[cyclic compound|cyclic monomers]] to form a longer polymer (see figure). The reactive center can be [[Radical (chemistry)|radical]], [[anion]]ic or [[cation]]ic. Some cyclic monomers such as [[norbornene]] or [[cyclooctadiene]] can be polymerized to high [[molecular mass|molecular weight]] polymers by using metal [[Catalysis|catalysts]]. ROP is a versatile method for the synthesis of [[biopolymer]]s.

Ring-opening of cyclic monomers is often driven by the relief of [[ring strain|bond-angle strain]]. Thus, as is the case for other types of polymerization, the [[enthalpy]] change in ring-opening is negative.<ref name=Young>{{cite book|last=Young|first=Robert J.|title=Introduction to Polymers|year=2011|publisher=CRC Press|location=Boca Raton|isbn=978-0-8493-3929-5}}</ref> Many rings undergo ROP.<ref>{{cite journal |doi=10.1007/s00726-006-0432-9}}</ref>

Many [[cyclic compound|Cycliccyclic monomers]] that are amenable to ROP.<ref>{{cite journal |doi=10.3390/polym5020361|doi-access=free |title=Ring-Opening Polymerization—An Introductory Review |date=2013 |last1=Nuyken |first1=Oskar |last2=Pask |first2=Stephen |journal=Polymers |volume=5 |issue=2 |pages=361–403 }}</ref> These include [[epoxide]]s,<ref name=Sarazin>{{cite journal|title=Discrete Cationic Complexes for Ring-Opening Polymerization Catalysis of Cyclic Esters and Epoxides|author=Yann Sarazin |author2=Jean-François Carpentier |journal=Chemical Reviews|year=2015|volume=115|issue=9|pages=3564–3614|doi=10.1021/acs.chemrev.5b00033|pmid=25897976}}</ref><ref name=Longo>{{cite journal|title=Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides with Discrete Metal Complexes: Structure–Property Relationships|first1=Julie M.|last1=Longo|first2=Maria J.|last2= Sanford|first3=Geoffrey W.|last3=Coates|journal=Chemical Reviews|year=2016|volume=116|issue=24|pages=15167–15197|doi=10.1021/acs.chemrev.6b00553|pmid=27936619}}</ref> cyclic trisiloxanes,{{cn|date=December 2023}} some lactones<ref name=Sarazin/><ref name=Jerome>{{Cite journal|last1=JEROME|first1=C|last2=LECOMTE|first2=P|date=2008-06-10|title=Recent advances in the synthesis of aliphatic polyesters by ring-opening polymerization☆|journal=Advanced Drug Delivery Reviews|volume=60|issue=9|pages=1056–1076|doi=10.1016/j.addr.2008.02.008|pmid=18403043|hdl=2268/3723|issn=0169-409X|url=http://orbi.ulg.ac.be/handle/2268/3723|hdl-access=free}}</ref> and [[lactide]]s,<ref name=Jerome/> cyclic [[anhydride]]s,<ref name=Longo/> [[cyclic carbonate]]s,<ref>{{cite journal|last=Matsumura|first=Shuichi|author2=Tsukada, Keisuke |author3=Toshima, Kazunobu |title=Enzyme-Catalyzed Ring-Opening Polymerization of 1,3-Dioxan-2-one to Poly(trimethylene carbonate)|journal=Macromolecules|date=May 1997|volume=30|issue=10|pages=3122–3124|doi=10.1021/ma961862g|bibcode=1997MaMol..30.3122M}}

[[File:Wiki566665.tif|thumb|400px|center|The general mechanism for anionic ring-opening polymerization. Polarized functional group is represented by X-Y, where the atom X (usually a carbon atom) becomes electron deficient due to the highly electron-withdrawing nature of Y (usually an oxygen, nitrogen, sulfur, etc.). The nucleophile will attack atom X, thus releasing Y-⁻. The newly formed nucleophile will then attack the atom X in another monomer molecule, and the sequence would repeat until the polymer is formed.<ref name=dubois />]]

*{{cite journal|lasttitle=SugiyamaOrganocatalytic Ring-Opening Polymerization|firstauthor=JNahrain E. Kamber |author2=R.Wonhee NagahataJeong |author3=Robert M. GoyalWaymouth |author4=MRussell C. AsaiPratt |author5=MBas G. G. UedaLohmeijer |author6=KJames L. TakeuchiHedrick |journal=ACSChemical Polymer PreprintsReviews|year=19982007|volume=40107|seriesissue=112|pages=5813–5840|doi=10.1021/cr068415b|pagepmid=9017988157}}