Electronic Supplementary Material (ESI) for RSC Advances.
This journal is © The Royal Society of Chemistry 2016
Suppor&ngInforma&on
Spherical,par&culatepoly(etherketoneketone)
byaFriedelCra=sdispersionpolymerisa&on
KaylieJ.Smith,IanD.H.TowleandMarkG.Moloney
DepartmentofChemistry,ChemistryResearchLaboratory,TheUniversityofOxford,12Mansfield
Road,Oxford.OX13TA.
KetonexLtd,LeafieldTechnicalCentre,Langley,Witney,Oxfordshire,OX299EF.
*Correspondenceto:[email protected]
Materials
Experimental
Instrumenta&on
Inherentviscosity(IV)measurementswerecarriedoutusingPoultenSelfe&LeeglassOstwaldviscometers,sizeD,inaTownsonandMercerE270
viscometerbath.Measurementswerecarriedoutinasolventofconcentratedsulfuricacidat25°C.Meltviscosi`eswererecordedonaMalvern
InstrumentsRosandRH7capillaryrheometerat400°Candatashearrateof30s-1,unlessotherwisestated.Abarrelwithlength290mmandbore
diameter15mmwasused.Atungstencarbidediewithlength16mmandaborediameterof1mmwasused,witha90°dieentrance.Differen`alscanning
calorimetry(DSC)datawererecordedonaNetzschDSC200F3Maia®instrument.Datawasrecordedusingpiercedlidaluminiumcruciblesinanitrogen
atmosphere.Coolingwasachievedviaaforcedairsystemabove20°C,orbyliquidnitrogencoolingforlowertemperaturesandfastcoolingrates.Datawas
analysedusingProteus®sogware.Mel`ngpointandmol%puritywerecalculatedusingthestandardprotocolinProteus®sogware.Par`clesizeanalysiswas
recordedonaMalvernInstrumentsMastersizer2000instrument,coupledwithaHydro2000MUlargevolumemanualwetdispersionaccessory.Analysis
wascarriedoutinadispersantof50:50vol%IPA:water,unlessotherwisestated.Theparametersusedwerepar`clerefrac`veindex1.5,par`cleabsorp`on
index0.1anddispersantrefrac`veindex1.33.Lowresolu`onmassspectrawererecordedonaFisonsPlaiormspectrometerusingelectrosprayionisa`on
(ESI)oraFisonsAutoSpec-oaTofspectrometerusingelectronimpactionisa`on(EI)orfieldionisa`on(FI).Them/zvaluesofmajorpeaksarereportedin
Daltons.Highresolu`onmassspectra(HRMS)wererecordedonaBrukermicroTofspectrometer(ESI).1HNMRspectrawererecordedonBrukerAVN400
(400MHz),andDRX500(500MHz)spectrometers.Chemicalshigs(δH)arereportedinpartspermillion(ppm)andarereferencedtotheresidual
protonatedsolventpeak.Theabbrevia`onsusedtodescribemul`plici`esareasfollows:s(singlet),d(doublet),dd(doubledoublet),t(triplet),q(quartet),
m(mul`plet)andbr(broad).Inmostcases,firstordermul`plici`esarereportedonly.Couplingconstants(J)aregiveninHertz(Hz).TwodimensionalCOSY
(correla`onspectroscopy)wereobtainedonaBrukerAVN400orDRX500spectrometer.13CNMRspectrawererecordedonaBrukerAVN400spectrometer
at100.6MHzoraBrukerDRX500spectrometerat125.8MHzwithprotondecoupling.Chemicalshigs(δC)arereportedinpartspermillion(ppm)andare
referencedtotheresidualprotonatedsolventpeak.AssignmentwasaidedbytheuseofDEPTedi`ngandeditedHSQC,performedoneitherAVN400or
DRX500spectrometers.27AlNMRspectrawererecordedonaBrukerAVN400spectrometerat15kHz.Chemicalshigs(δAl)arereportedinpartspermillion
(ppm).27AlDPMASand13CCPMASsolidstateNMRspectrawereobtainedat104.2and100.5MHzrespec`vely(9.4T)onaBrukerAvanceIIIHD
spectrometer,using4mmO.D.zirconiarotorsandMASrateof15and10kHz.For27Alinordertoobtainquan`ta`veMASspectra,asinglepulseexcita`on
wasappliedusingashortpulselength(0.23μs).2400scanswereacquiredwitha0.1sdelayandaMASrateof15kHz.The27Alchemicalshigwas
referencedtoanaqueoussolu`onofAl(NO3)3(0ppm).13CCPMASNMRspectrawereacquiredusingcross-polariza`onsequencewithavariableXamplitudespin-lockpulseandspinal64protondecouplingatMASratesof8and10kHz.1500transientswereacquiredusingacontact`meof2.5ms,an
acquisi`on`meof25ms(2048datapointszerofilledto16K)andarecycledelayof120s.All13Cspectrawerereferencedtoadamantane(theupfield
methineresonancewastakentobeatδ=29.5ppmonascalewhereδ(TMS)=0)asasecondaryreference.Scanningelectronmicroscopy(SEM)was
carriedoutusingaHitachiHT3000TabletopSEM.Sampleswerespurercoatedwithpla`numpriortoanalysis.Elementalanalysiswasachievedusingbuiltinenergydispersivex-rayspectroscopy(EDS).X-rayphotoelectronspectroscopy(XPS)wascarriedoutusingaVG–EscalabX-RayPhotoelectron
SpectrometerVGX900usingAluminiumKαradia`onwithanenergyof1486eV.Theopera`ngpressurewas<1×10−8mbar.Sampleswerearachedtothe
samplestubusingdoublesidedtape.ThePassEnergywassetat50eVforthewidescanofthesample,and20eVforthemoreintensescansofspecific
areas.Theresul`ngspectrawerethenanalysedusingCasaXPSpeakfixngsogware,andsamplechargingcorrectedusingC1sasareferencesexngat
285.0eV.Op`calmicroscopywascarriedoutusingaReichertPolyvarMetMicroscopewhichoperateswithbrightfield,darkfieldandpolarisa`on
modules.Imageswereanalysedwithdigitalintegra`on.
Materials
Reagentsandsolvents
1,4-Bis(4-phenoxybenzoyl)benzene)(polymerisa`ongrade)(EKKE)maybeobtainedbytheliteratureprocedure.1,2Terephthaloylchloride(99+%)(TPC),
isophthaloylchloride(98%)(IPC),benzoicacid(99%,extrapure),aluminiumchloride(99%,extrapure,anhydrous)andbenzoylchloride(98+%)were
obtainedfromAcrosOrganics.Dichloromethane(DCM)(99.5%)wasobtainedfromAPCPure.Allreagentsandsolventswereusedasreceived.
1.  D.R.Corbin,E.Kumpinsky,US49182371990
2.T.M.Ford,E.Greenville,E.Kumpinsky;A.Vidal,USPat.,US49182371990.
Structuresof100:0PEKKandthe90:10,80:20,70:30and60:40PEKKs,annotatedforNMRassignment
b.
Figure1.Stackeda.1Handb.13CNMRspectraforthe100:0,90:10,80:20,70:30and60:40PEKKstructures,demonstra`ngthe
growinginofthepeaksassociatedwiththeIPConincreasingthequan`tyofIPCinthemonomerfeedandpolymer.Expansionofδ
198-199.5ppm,demonstra`ngthegrowinginoftheisophthaloylcarbonylpeakonincreasingtheisophthaloylcontentofthePEKK
Atom
δH
δC
100:0
60:40
100:0
60:40
1
-
-
161.26**
161.01
2
-
-
119.22
119.21
3
7.98(m)
7.98(m)
133.77
133.65
4
-
-
131.48
131.65
5
7.98(m)
-
199.02
198.33
6
7.27(d)
7.27(m)
140.54
140.56
7
-
-
130.19
130.14*
8
-
-
-
164.04
9
-
7.27(m)
-
119.17
10
-
7.98(m)
-
133.58
11
-
-
-
130.14*
12
-
-
-
198.16
13
-
-
-
137.30
14
-
8.12(d)
-
131.42
15
-
8.23(s)
-
134.56
16
-
7.77(t)
-
129.16
*Peaksareoverlaid
**PeakisoverlaidwithTFA
1
13
Table1. Hand CNMRchemicalshigdataforthe100:0and60:40PEKKstructures,withatomsassignedasdetailedin
Figure1,andsplixngparernsfor1HNMRspectra
0.2
0.2
DSC/mW.mg-1
b. 0.6
DSC/mW.mg-1
a. 0.6
-0.2
-0.6
-0.2
-0.6
100:0PEKK
90:10PEKK
80:20PEKK
-1
-1
70:30PEKK
60:40PEKK
-1.4
-1.4
90
c.
140
190
240
Temperature/°C
290
340
390
d.
0.6
140
190
240
Temperature/°C
290
340
390
90
140
190
240
Temperature/°C
290
340
390
0.6
0.2
DSC/mW.mg-1
DSC/mW.mg-1
0.2
90
-0.2
-0.2
-0.6
-0.6
-1
-1
-1.4
-1.4
90
140
190
240
Temperature/°C
290
340
390
Figure2.DSCtracesfortwocon`nuoushea`ng(20°C.min-1)andcoolingcycles(10°C.min-1)of100:0,90:10,
80:20,70:30and60:40PEKKs,a.Thefirsthea`ngcycleofthepar`culatepolymerfrom90°Cto400°C,b.
Thefirstcoolingcycleofthesamplefrom400°Cto90°C,c.Thesecondhea`ngcycleofthenow
consolidatedsamplefrom90°Cto400°C,d.Thesecondcoolingcycleofthesamplefrom400°Cto90°C
14
100:0PEKK
90:10PEKK
80:20PEKK
70:30PEKK
60:40PEKK
12
Volume/%
10
8
6
4
2
0
0.01
0.1
1
10
Particlediameter/µm
100
1000
10000
Figure3.Par`clesizingdistribu`onsfor100:0,90:10,80:20,70:30and60:40PEKKs,asrecordedbyMastersizer
lightscareringin50:50IPA:watersolvent.
a
c
b
d
Figure4.Spectrafortheisolateddispersant(a)solidstate27AlNMR;(b)solu`on27AlNMR;(c)solidstate13CNMR;(d)solu`on13CNMR.