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Epoxy Vitrimers: the Effect of Transesterification Reactions on The polymers Article Article EpoxyEpoxy Vitrimers:Vitrimers: TheThe EffectEffect ofof TransesterificationTransesterification ReactionsReactions onon thethe NetworkNetwork StructureStructure FacundoFacundo IgnacioIgnacio AltunaAltuna, IDCristina, Cristina Elena Elena Hoppe Hoppe and and Roberto Roberto Juan Juan José Jos Williamsé Williams * * InstituteInstitute ofof MaterialsMaterials ScienceScience andand TechnologyTechnology (INTEMA),(INTEMA), UniversityUniversity of of Mar Mar del del Plata Plata and and National National Research Research CouncilCouncil (CONICET),(CONICET), Av.Av. J.J. B.B. JustoJusto4302, 4302,7600 7600Mar Mardel delPlata, Plata, Argentina; Argentina; faltuna@fi.mdp.edu.ar [email protected] (F.I.A.); (F.I.A.); hoppe@fi[email protected] (C.E.H.)(C.E.H.) ** Correspondence:Correspondence: williams@fi.mdp.edu.ar;[email protected]; Tel.:Tel.: +54-223-481-6600+54-223-481-6600 Received:Received: 29 November 2017; Accepted: 2929 December 2017; Published: 3 January 2018 Abstract:Abstract: Vitrimers areare covalentlycovalently crosslinkedcrosslinked polymerspolymers thatthat behavebehave asas conventionalconventional thermosetsthermosets belowbelow the glass transition temperature temperature (T (Tgg) )but but can can flow flow above above a aparticular particular temperature, temperature, TvT >v T>g, Tbyg, bybond bond exchange exchange reactions. reactions. In Inepoxy epoxy vitrimers, vitrimers, transesterification transesterification reactions reactions are are responsible responsible for theirtheir behaviorbehavior at T > T Tvv thatthat enables enables flow, flow, thermoforming, thermoforming, recycling, recycling, self self-healing-healing and and stress stress relaxation. relaxation. A Astatistical statistical analysis analysis based based on on the the fragment fragment approach approach was was performed performed to to analyze analyze the evolution of the networknetwork structurestructure ofof epoxyepoxy vitrimers during transesterificationtransesterification reactions.reactions. AnAn analytical solution was obtainedobtained forfor aa formulationformulation basedbased onon aa diepoxidediepoxide andand aa dicarboxylicdicarboxylic acid.acid. A numerical solution waswas derivedderived forfor thethe reactionreaction ofof aa diepoxidediepoxide with a tricarboxylictricarboxylic acid, as an example of the way to apply thethe modelmodel toto polyfunctionalpolyfunctional monomers.monomers. As transesterificationtransesterification actsacts asas aa disproportionationdisproportionation reactionreaction thatthat convertsconverts twotwo linearlinear fragmentsfragments (monoesters)(monoesters) intointo aa terminalterminal fragmentfragment (glycol)(glycol) andand aa branchingbranching fragmentfragment (diester),(diester), itsits effecteffect onon networknetwork structurestructure isis toto increaseincrease thethe concentrationconcentration ofof crosslinkscrosslinks andand pendantpendant chainschains whilewhile leavingleaving aa solsol fraction.fraction. Changes in the network structure of the epoxy vitrimer cancan taketake placeplace afterafter theirtheir synthesis,synthesis, during their use at highhigh temperatures,temperatures, a fact that has to bebe consideredconsidered inin theirtheir technologicaltechnological applications.applications. Keywords:Keywords: epoxy-acidepoxy-acid reactions; epoxy vitrimers; fragment approach; network structure; statisticalstatistical analysis;analysis; transesterificationtransesterification reactionsreactions 1.1. Introduction FattyFatty acidsacids havehave beenbeen employedemployed inin epoxyepoxy formulationsformulations forfor varnishesvarnishes andand coatingscoatings sincesince thethe middlemiddle ofof the the last last century. century. The The esters esters generated generated provide provide excellent excellent properties properties to the resulting to the materials,resulting includingmaterials, adhesion,including flexibility, adhesion, water-resistance flexibility, water and-resistance brushing andand grinding brushing ease. and Unsaturated grinding fattyease. acidsUnsaturated are used fatty for air-driedacids are coatingsused for while air-dried saturated coatings fatty while acids saturated are used infatty sub-stoichiometric acids are used in ratios sub- andstoichiometric reaction of ratios the epoxy and reaction excess is of performed the epoxy addingexcess is conventional performed adding hardeners conventional such as polyamines. hardeners Modernsuch as polyamines. high performance-coatings Modern high performance are based- oncoatings the use are of based polycarboxylic on the use of acids polycarboxylic as hardeners acids of acrylate-epoxyas hardeners of monomers acrylate-epoxy [1]. monomers [1]. TheThe additionaddition reactionreaction ofof anan epoxyepoxy group group with with a a carboxylic carboxylic acid acid either either uncatalyzed uncatalyzed or or employing employing a varietya variety of differentof different catalysts, catalysts such, assuch tertiary as tertiary amines oramines triphenyl or phosphine,triphenyl phosphine, generates a βgenerates-hydroxyester a β- ashydroxyester shown in Scheme as shown1. in Scheme 1. Scheme 1. Addition reactionreaction of a carboxylic acidacid toto anan epoxyepoxy group.group. Polymers2018, 10, 43; doi:10.3390/polym10010043 www.mdpi.com/journal/polymers Polymers 2018, 10, 43; doi:10.3390/polym10010043 www.mdpi.com/journal/polymers Polymers 2018, 10, 43 2 of 16 Polymers 2018, 10, 43 2 of 15 Secondary reactions reactions can can take take place place such such as the as theepoxy epoxy homopolymerization homopolymerization initiated initiated by the by same the samecatalysts catalysts or the oresterification the esterification of the ofOH the groups OH groups with the with carboxylic the carboxylic acid leading acid leading to a new to aester new group ester groupand water and as water a reac astion a reaction product. product. In turn, epoxy In turn, groups epoxy can groups be hydrolyzed can be hydrolyzed with the water with generated. the water generated.The sequence The of sequencethese reactions of these was reactions clearly established was clearly by established Dušek and by co Dušek-workers and [2] co-workers. They studied [2]. Theythe reaction studied of the a monoepoxide reaction of a (phenyl monoepoxide glycidyl (phenyl ether) glycidylwith a monocarboxylic ether) with a monocarboxylicacid (hexanoic acid), acid (hexanoiccatalyzed acid),by triethylamine. catalyzed by For triethylamine. every stoichiometric For every ratio stoichiometric investigated, ratio they investigated, found that theythe epoxy found- thatcarboxylic the epoxy-carboxylic acid reaction took acid place reaction first up took to an place almost first complete up to an conversion. almost complete After conversion.completion of After this completionreaction, homopolymerization of this reaction, homopolymerization was observed in wasformulations observed inwith formulations epoxy excess with and epoxy conden excesssation and condensationesterification esterificationin the presence in the of presence a carboxylic of a carboxylic acid excess. acid excess. However, However, they they observed observed that that the concentration ofof thethe monoestermonoester (ME) (ME) produced produced by by the the epoxy-acid epoxy-acid reaction reaction did did not not remain remain constant constant but decreasedbut decrease tod a finalto a constantfinal constant value value after keepingafter keeping the system the sys fortem several for several hours at hours the selected at the reactionselected temperature.reaction temperature. The reason The was reason the partialwas the conversion partial conversion of the monoester of the monoester into a glycol into a (G) glycol and (G) a diester and a (DE)diester by (DE) a transesterification by a transesterification reaction reaction until equilibrium until equilibrium was attained was attained (Scheme (Scheme2). 2). Scheme 2. Convertion of m monoestersonoesters (ME) into a glycol (G) and a diester (DE).(DE). TransesterificationTransesterification reactions were well known in organic chemistry but their presence in the epoxy-acidepoxy-acid chemistry had had not not been been previously previously emphasized. emphasized. A A conclusion conclusion of of this this study study was was that that in in a apolyfunction polyfunctionalal system system this this reaction reaction may may significantly significantly affect affect the the network network structure structure by by breaking the chains and giving place to new crosslinks. The significancesignificance of the experimental findingsfindings of Dušek and co-workersco-workers remained dormant for almost three decades until the group of Leibler in Paris discovered that transesterification reactions almost three decades until the group of Leibler in Paris discovered that transesterification reactions gave unusual properties to the epoxy-carboxylic acid networks giving rise to a new class of materials gave unusual properties to the epoxy-carboxylic acid networks giving rise to a new class of materials called epoxy vitrimers [3–5]. They realized that, in the temperature range where transesterification called epoxy vitrimers [3–5]. They realized that, in the temperature range where transesterification reactions take place, the crosslinked epoxy is able to interchange fragments of the network structure. reactions take place, the crosslinked epoxy is able to interchange fragments of the network structure. This takes place by production and recombination of glycol and diester fragments
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