Unraveling the Heterogeneity of Epoxy-amine Networks by Introducing Dynamic Covalent Bonds

Hu Xu; Yao Zhang; Hao Wang; Jin-Rong Wu

doi:10.1007/s10118-022-2881-3

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Unraveling the Heterogeneity of Epoxy-amine Networks by Introducing Dynamic Covalent Bonds

RESEARCH ARTICLE | Updated：2023-05-26

- Unraveling the Heterogeneity of Epoxy-amine Networks by Introducing Dynamic Covalent Bonds
- Chinese Journal of Polymer Science Vol. 41, Issue 6, Pages: 926-932(2023)
- Affiliations：
  
  State Key Laboratory of Polymer Materials Engineering, College of Polymer Science and Engineering, Sichuan University, Chengdu 610065, China
- Author bio：
  
  wh0507422@gmail.com (H.W.)
  wujinrong@scu.edu.cn (J.R.W.)
- Funds：
- DOI：10.1007/s10118-022-2881-3
  CLC：
- Received：10 July 2022，
  
  Revised：2022-9-15，
  
  Accepted：26 September 2022，
  
  Online First：31 October 2022，
  
  Published：01 June 2023
- Accepted：
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Xu, H.; Zhang, Y.; Wang, H.; Wu, J. R. Unraveling the heterogeneity of epoxy-amine networks by introducing dynamic covalent bonds. Chinese J. Polym. Sci. 2023, 41, 926–932

Hu Xu, Yao Zhang, Hao Wang, et al. Unraveling the Heterogeneity of Epoxy-amine Networks by Introducing Dynamic Covalent Bonds[J]. Chinese Journal of Polymer Science, 2023, 41(6): 926-932.
Xu, H.; Zhang, Y.; Wang, H.; Wu, J. R. Unraveling the heterogeneity of epoxy-amine networks by introducing dynamic covalent bonds. Chinese J. Polym. Sci. 2023, 41, 926–932 DOI： 10.1007/s10118-022-2881-3.

Hu Xu, Yao Zhang, Hao Wang, et al. Unraveling the Heterogeneity of Epoxy-amine Networks by Introducing Dynamic Covalent Bonds[J]. Chinese Journal of Polymer Science, 2023, 41(6): 926-932. DOI： 10.1007/s10118-022-2881-3.

摘要

An indirect strategy to characterize the heterogeneity of non-destructive epoxy resins by replacing the conventional covalent bonds with dynamic covalent bonds. Kohlrausch-Williams-Watts (KWW) stretched exponential function is used to reveal the influence of stoichiometric ratio on heterogeneity.

Abstract

Epoxy resins are a kind of universal thermosetting plastics

which are widely used as structural materials in various applications. Thus

it is necessary to understand the network structure of epoxy resins. However

it is challenging to reveal the network heterogeneity of epoxy resins due to the permanent covalent crosslinking. Here

we provide a novel strategy to characterize the network heterogeneity of epoxy resins by using the dynamic covalent bonds to replace the conventional covalent bonds. The dynamic covalent bonds can reorganize under heat stimulus and the network keeps a constant crosslinking density during topological rearrangement

making it convenience to study the heterogeneity of epoxy resins. Kohlrausch-Williams-Watts (KWW) stretched exponential function is used to fit the stress relaxation data

and the parameters

and

perm

extracted from KWW equation indicate the network becomes more homogenous with the stoichiometric ratio of epoxy groups and amines decreases from 1/1 to 1/1.5. This method proves that the side reaction between epoxy and hydroxyl is the main origin of the structural heterogeneity in epoxy resins compared to the secondary amines network.

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references

Liu,Y.Trendsofpowersemiconductorwaferlevelpackaging. Microelectron. Reliab. 2010 , 50 ,514−521..

Jiang,B.;Huang,Y.D.Qualityinspectionoflaidfabricepoxyresinsprepregbynearinfraredspectroscopy. Compos. Part A Appl. Sci. Manuf. 2008 , 39 ,712−717..

Jin,H.;Mangun,C.L.;Griffin,A.S.;Moore,J.S.;Sottos,N.R.;White,S.R.Thermallystableautonomichealinginepoxyusingadual-microcapsulesystem. Adv. Mater. 2014 , 26 ,282−287..

Liu,H.;Zhang,H.;Wang,H.;Huang,X.;Huang,G.;Wu,J.Weldable,malleableandprogrammableepoxyvitrimerswithhighmechanicalpropertiesandwaterinsensitivity. Chem. Eng. J. 2019 , 368 ,61−70..

He,C.;Shi,S.;Wu,X.;Russell,T.P.;Wang,D.Atomicforcemicroscopynanomechanicalmappingvisualizesinterfacialbroadeningbetweennetworksduetochemicalexchangereactions. J. Am. Chem. Soc. 2018 , 140 ,6793−6796..

Ma,C.;Liu,H.-Y.;Du,X.;Mach,L.;Xu,F.;Mai,Y.W.Fractureresistance,thermalandelectricalpropertiesofepoxycompositescontainingalignedcarbonnanotubesbylowmagneticfield. Compos. Sci. Technol. 2015 , 114 ,126−135..

Bai,N.;Saito,K.;Simon,G.P.Synthesisofadiaminecross-linkercontainingDiels-Alderadductstoproduceself-healingthermosettingepoxypolymerfromawidelyusedepoxymonomer. Polym. Chem. 2013 , 4 ,724−730..

Auvergne,R.;Caillol,S.;David,G.;Boutevin,B.;Pascault,J.P.Biobasedthermosettingepoxy:presentandfuture. Chem. Rev. 2014 , 114 ,1082−1115..

Wang,H.;Liu,H.C.;Zhang,Y.;Xu,H.;Jin,B.Q.;Cao,Z.X.;Wu,H.T.;Huang,G.S.;Wu,J.R.Atriplecrosslinkingdesigntowardepoxyvitrimersandcarbonfibercompositesofhighperformanceandmulti-shapememory. Chinese J. Polym. Sci. 2021 , 39 ,736−744..

Hernandez,E.D.;Bassett,A.W.;Sadler,J.M.;LaScala,J.J.;Stanzione,J.F.Synthesisandcharacterizationofbio-basedepoxyresinsderivedfromvanillylalcohol. ACS Sustain. Chem. Eng. 2016 , 4 ,4328−4339..

Harada,M.;Sumitomo,K.;Nishimoto,Y.;Ochi,M.Relationshipbetweenfracturetoughnessanddomainsizeofliquid-crystallineepoxyresinshavingpolydomainstructure. J. Polym. Sci., Part B: Polym. Phys. 2009 , 47 ,156−165..

Hoshino,T.;Okamoto,Y.;Yamamoto,A.;Masunaga,H.Heterogeneousdynamicsinthecuringprocessofepoxyresins. Sci. Rep. 2021 , 11 ,1−12..

Long,R.;Qi,H.J.;Dunn,M.L.Modelingthemechanicsofcovalentlyadaptablepolymernetworkswithtemperature-dependentbondexchangereactions. Soft Matter 2013 , 9 ,4083−4096..

Izumi,A.;Nakao,T.;Iwase,H.;Shibayama,M.Structuralanalysisofcuredphenolicresinsusingcomplementarysmall-angleneutronandX-rayscatteringandscanningelectronmicroscopy. Soft Matter 2012 , 8 ,8438−8445..

Izumi,A.;Nakao,T.;Shibayama,M.Gelationandcross-linkinhomogeneityofphenolicresinsstudiedby 13 C-NMRspectroscopyandsmall-angleX-rayscattering. Soft Matter 2013 , 9 ,4188−4197..

Izumi,A.;Nakao,T.;Shibayama,M.Gelationandcross-linkinhomogeneityofphenolicresinsstudiedbysmall-andwide-angleX-rayscatteringand 1 H-pulseNMRspectroscopy. Polymer 2015 , 59 ,226−233..

Izumi,A.;Shudo,Y.;Nakao,T.;Shibayama,M.Cross-linkinhomogeneityinphenolicresinsattheinitialstageofcuringstudiedby1H-pulseNMRspectroscopyandcomplementarySAXS/WAXSandSANS/WANSwithasolvent-swellingtechnique. Polymer 2016 , 103 ,152−162..

D.Montarnal;M.Capelot;F.Tournilhac;Leibler,L.Silica-likemalleablematerialsfrompermanentorganicnetworks. Science 2011 , 334 ,965−968..

Hu,W.;Ren,Z.;Li,J.;Askounis,E.;Xie,Z.;Pei,Q.Newdielectricelastomerswithvariablemoduli. Adv. Funct. Mater. 2015 , 25 ,4827−4836..

Peterson,G.I.;Schwartz,J.J.;Zhang,D.;Weiss,B.M.;Ganter,M.A.;Storti,D.W.;Boydston,A.J.Productionofmaterialswithspatially-controlledcross-linkdensity via vatphotopolymerization. ACS Appl. Mater. Interfaces 2016 , 8 ,29037−29043..

Bao,C.;Guo,Z.;Sun,H.;Sun,J.Nitrogen-coordinatedboroxinesenablethefabricationofmechanicallyrobustsupramolecularthermosetscapableofhealingandrecyclingundermildconditions. ACS Appl. Mater. Interfaces 2019 , 11 ,9478−9486..

Hubbard,A.M.;Ren,Y.;Konkolewicz,D.;Sarvestani,A.;Picu,C.R.;Kedziora,G.S.;Roy,A.;Varshney,V.;Nepal,D.Vitrimertransitiontemperatureidentification:couplingvariousthermomechanicalmethodologies. ACS Appl. Polym. Mater. 2021 , 3 ,1756−1766..

Yang,Y.;Terentjev,E.M.;Wei,Y.;Ji,Y.Solvent-assistedprogrammingofflatpolymersheetsintoreconfigurableandself-healing3Dstructures. Nat. Commun. 2018 , 9 ,1−7..

Capelot,M.;Unterlass,M.M.;Tournilhac,F.;Leibler,L.Catalyticcontrolofthevitrimerglasstransition. ACS Macro Lett. 2012 , 1 ,789−792..

Dyre,J.C.Colloquium:theglasstransitionandelasticmodelsofglass-formingliquids. Rev. Mod. Phys. 2006 , 78 ,953−972..

Angell,C.A.Formationofglassesfromliquidsandbiopolymers. Science 1996 , 267 ,1924−1935..

M.D.Ediger;C.A.Angell;Nagel,S.R.Supercooledliquidsandglasses. J. Phys. Chem. 1996 , 100 ,13200−13212..

Chao,A.;Negulescu,I.;Zhang,D.Dynamiccovalentpolymernetworksbasedondegenerativeiminebondexchange:tuningthemalleabilityandself-healingpropertiesbysolvent. Macromolecules 2016 , 49 ,6277−6284..

Fancey,K.S.Amechanicalmodelforcreep,recoveryandstressrelaxationinpolymericmaterials. J. Mater. Sci. 2005 , 40 ,4827−4831..

Li,L.;Chen,X.;Jin,K.;Torkelson,J.M.Vitrimersdesignedbothtostronglysuppresscreepandtorecoveroriginalcross-linkdensityafterreprocessing:quantitativetheoryandexperiments. Macromolecules 2018 , 51 ,5537−5546..

Hayashi,M.;Yano,R.Fairinvestigationofcross-linkdensityeffectsonthebond-exchangepropertiesfortrans-esterification-basedvitrimerswithidenticalconcentrationsofreactivegroups. Macromolecules 2020 , 53 ,182−189..

Porath,L.E.;Evans,C.M.Importanceofbroadtemperaturewindowsandmultiplerheologicalapproachesforprobingviscoelasticityandentropicelasticityinvitrimers. Macromolecules 2021 , 54 ,4782−4791..

Dhinojwala,A.;Hooker,J.C.;Torkelson,J.M.Retardationofrotationalreorientationdynamicsinpolymersneartheglasstransition:anovelstudyoverelevendecadesintimeusingsecond-ordernon-linearoptics. J. Non. Cryst. Solids 1994 , 172 ,286−296..

Rozenberg,B.A.Kinetics,thermodynamicsandmechanismofreactionsofepoxyoligomerswithamines. Epoxy Resins and Composites II 1986 ,113−165..

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