ARGETATRPASATOOLFOR

CELLULOSEMODIFICATION

SusanneHansson
DoctoralThesis

KungligaTekniskahgskolan,Stockholm2012

AKADEMISKAVHANDLING

som med tillstnd av Kungliga Tekniska hgskolan i Stockholm framlgges till

offentlig granskning fr avlggande av teknologie doktorsexamen fredagen den
14 december 2012, kl. 10.00 i sal K2, Teknikringen 28, KTH, Stockholm.
Avhandlingen frsvaras p engelska. Fakultetsopponent: Dr. Steve Edmondson,
LoughboroughUniversity,UK.

Copyright2012SusanneHansson
Allrightsreserved

PaperI2009TheAmericanChemicalSociety
PaperII2011TheRoyalSocietyofChemistry
PaperIII2012TheRoyalSocietyofChemistry
PaperIV2012TheAmericanChemicalSociety

TRITACHEReport2012:60
ISSN16541081
ISBN9789175015446

Tomyfamily

ABSTRACT

The importance of finding new applications for cellulosebased products has

increased, especially to meet the demand for new environmentally friendly
materials,butalsosincethedigitalizationofoursocietywilleventuallydecrease
the need for paper. To expand the application area of cellulose, modification to
improve and/or introduce new properties can be a requisite. Thus, the focus of
thisstudyhasbeentoachievefundamentalknowledgeaboutpolymergraftingof
celluloseviawellcontrolledradicalpolymerization.
Cellulose, in the form of filter paper, has successfully been grafted via
activators regenerated by electron transfer atom transfer radical polymerization
(ARGET ATRP) of the monomers: methyl methacrylate, styrene, and glycidyl
methacrylate.TheadvantagesofARGETATRParethatonlyasmallamountofa
coppercatalystisrequiredandthereactioncanbeperformedinlimitedamount
of air; yet, providing for relatively wellcontrolled reactions. These benefits can
renderARGETATRPanattractivemethodforindustrialutilization.
Thecontactanglemeasurementsofthegraftedfilterpapersconfirmedthatthe
hydrophobicity of cellulose was significantly increased, even for shorter graft
lengths.FTIRspectroscopyestablishedthattheamountofpolymersuccessively
increasedwithmonomerconversion.HighresolutionFTIRmicroscopy(FTIRM)
wasproventobeaveryusefultechniquefortheanalysisofcellulosesubstrates,
displaying the spatial distribution of polymer content on cellulose fibers. The
polymerwasshowntobefairlyhomogenouslydistributedonthefiber.
Aninitiatorwithareducibledisulfidebondrenderedcleavageofthepolymer
grafts possible, employing mild reaction conditions. The cleaved grafts and the
freepolymersformedfromasacrificialinitiatorinparalleltothegraftingwere
shown to have similar molar masses and dispersities, confirming that the grafts
canbetailoredbyutilizingasacrificialinitiator.Moreover,theinitiatorcontenton
filterpaperandmicrocrystallinecellulosewasassessed.
Acomparisonbetweenthetwograftingtechniques,graftingfromcellulosevia
ARGET ATRP and graftingto cellulose via copper(I)catalyzed alkyneazide
cycloaddition, was performed. To achieve a trustworthy comparison, the free
polymerformedinparalleltothegraftingfromreactionwasemployedasthepre
polymerinthegraftingtoapproach,resultinginnearlyidenticalgraftlengthon
thesubstratesforthetwograftingmethods.FTIRManalysesverifiedthatunder
the selected conditions, the graftingfrom technique is superior to the graftingto
approach with respect to controlling the distribution of the polymer content on
thesurface.TheresultswerecorroboratedwithXrayphotoelectronspectroscopy.

SAMMANFATTNING

Behovetavatthittanyatillmpningarfrcellulosabaseradeprodukterharkat,
framfrallt fr att mta efterfrgan p nya miljvnliga material, men ven d
digitaliseringenavvrtsamhllepsiktkommerattminskapappersbehovet.Fr
att ka cellulosans anvndningsomrde kan modifiering, fr att frbttra
och/eller introducera nya egenskaper, vara en nyckelfrga. Denna studie har
sledes fokuserat p att erhlla grundlggande kunskaper om polymera
ympningsprocesseravcellulosagenomvlkontrolleradradikalpolymerisation.
Cellulosa, i form av filterpapper, ympades framgngsrikt med monomeren
metylmetakrylat, styren samt glycidylmetakrylat via ARGET ATRP (activators
regenerated by electron transfer atom transfer radical polymerization).
Frdelarna med ARGET ATRP r att endast sm mngder kopparkatalysator
krvssamtattreaktionenkanutfrasinrvaroavbegrnsademngderluft,och
trotsdettauppnsrelativtvlkontrolleradereaktioner.DessafrdelargrARGET
ATRPtillenattraktivmetodattanvndaindustriellt.
Kontaktvinkelmtningarna av de ympade filterpapperna bekrftade att
cellulosanshydrofobicitetkadekraftigt,venfrdekortarekedjelngderna.FT
IR spektroskopi bekrftade att polymermngden successivt kade med
monomeromsttningen.HgupplsandeFTIRmikroskop(FTIRM)visadesigatt
varaenmycketanvndbarteknikfranalysavcellulosasubstrat,ddenspatiala
frdelningenavpolymermngdenpcellulosafibrerkundeuppvisas.Polymeren
visadesigvaraganskahomogentfrdeladpfibern.
En initiator med en reducerbar disulfidbindning mjliggjorde klyvningen av
deympadepolymerkedjornaundermildabetingelser.Deklyvdakedjornaochde
friapolymerernapolymeriseradefrnenfriinitiatorparallelltmedympningen
hade liknande molmassor och dispersiteter, vilket visar att de ympade kedjor
kanskrddarsysgenomanvndandetavdenfriainitiatorn.Vidareuppskattades
veninitiatormngdenpfilterpappersamtpmikrokristallincellulosa.
En jmfrelse mellan de tv ympningsteknikerna, ympning frn cellulosa via
ARGET ATRP samt ympning till cellulosa via koppar(I)katalyserad alkynazid
cykloaddition utfrdes. Fr att erhlla en relevant jmfrelse anvndes den fria
polymeren, bildad parallellt med ympningfrnreaktion, som prepolymer i
ympningtillmetoden, vilket resulterade i nst intill identiska kedjelngder p
substraten fr de tv ympningsmetoderna. FTIRM verifierade att under de
gllande reaktionsbetingelserna s r ympningfrntekniken verlgsen
ympningtilltekniken med avseende p kontroll ver polymerfrdelningen p
ytan.DessaresultatbekrftadesmedXPS.

LISTOFPAPERS
Thisthesisisasummaryofthefollowingpapers:

I.

ARGET ATRP for versatile grafting of cellulose using various

monomers Susanne Hansson, Emma stmark, Anna Carlmark, and
EvaMalmstrm,ACSAppliedMaterials&Interfaces2009,1,26512659.

II.

Selectivecleavageofpolymergraftsfromsolidsurfaces:Assessmentof
initiator content and polymer characteristics Susanne Hansson, Per
Antoni, Helena Bergenudd, and Eva Malmstrm, Polymer Chemistry
2011,2,556558.

III.

Visualization of poly(methyl methacrylate) (PMMA) grafts on

cellulose via highresolution FTIR microscopy imaging Susanne
Hansson, Thomas Tischer, Anja S. Goldmann, Anna Carlmark,
Christopher BarnerKowollik, and Eva Malmstrm, Polymer Chemistry
2012,3,307309

IV.

Grafting efficiency of synthetic polymers onto biomaterials: A

comparative study of grafting from versus grafting to Susanne
Hansson,VanessaTrouillet,ThomasTischer,AnjaS.Goldmann,Anna
Carlmark, Christopher BarnerKowollik, and Eva Malmstrm,
Biomacromolecules2012,DOI:10.1021/bm3013132

Mycontributiontotheappendedpapers:

I.
Alloftheexperimentalwork,alloftheanalyses,andmostofthe
preparationofthemanuscript.
II.
Mostoftheexperimentalwork,alloftheanalyses,andmostofthe
preparationofthemanuscript.
III.
Alloftheexperimentalwork,mostoftheanalyses,andmostofthe
preparationofthemanuscript.
IV.
Alloftheexperimentalwork,mostoftheanalyses,andmostofthe
preparationofthemanuscript.

Thisthesisalsocontainsunpublishedresults.

Scientificcontributionsnotincludedinthisthesis:

V.

Thermoresponsivecellulosebasedarchitectures:tailoringLCSTusing
poly(ethylene glycol) methacrylates Christian Porsch, Susanne
Hansson, Niklas Nordgren, and Eva Malmstrm, Polymer Chemistry
2011,2,11141123.

VI.

Surfacegrafted conjugated polymers for hybrid cellulose materials

Joseph Peterson, Markus Willgert, Susanne Hansson, Eva Malmstrm,
andKennethCarter,JournalofPolymerScience,PartA:PolymerChemistry
2011,49,30043013.

VII. Linearvs.hyperbranchedpolymersinthepreparationofpolymer/clay
nanocompositesLindaFogelstrm,SusanneHansson,AnnaCarlmark,
AndersHult,andEvaMalmstrm,manuscript

ABBREVIATIONS

AGU

AFM

Al2O3

ARGET

AsAc

ATR

ATRA

ATRP

BiB

CA

CRP

CuAAC

Cu(II)Br2

CuSO45H2O
DCM

DMAP

DMF

DP

DS

DTT

EBiB

FESEM

FTIR

FTIRM

GMA

HDA

IE

kact

kdeact

Keq

app

kp
kp

kt

MMA

MCC

anhydroglucose
atomicforcemicroscopy
aluminumoxide
activatorsregeneratedbyelectrontransfer
ascorbicacid
attenuatedtotalreflectance
atomtransferradicaladdition
atomtransferradicalpolymerization
bromoisobutyrylbromide
contactangle
controlledradicalpolymerization
copper(I)catalyzedazidealkynecycloaddition
copper(II)bromide
coppersulfatepentahydrate
dichloromethane
4dimethylaminopyridine
N,Ndimethylformamide
degreeofpolymerization
degreeofsubstitution
1,4dithiothreitol
molarmassdispersity
ethyl2bromoisobutyrate
fieldemissionscanningelectronmicroscopy
Fouriertransformationinfrared
FTIRmicroscopy
glycidylmethacrylate
heteroDielsAlder
initiatorefficiency
rateconstantofactivation
rateconstantofdeactivation
equilibriumrateconstant
apparentrateconstantofpropagation
rateconstantofpropagation
rateconstantoftermination
methylmethacrylate
microcrystallinecellulose

NaAsc
NaN3
NCC
NFC
NMP
NMR
PMDETA
RAFT
RDRP
Rp
SETLRP

SI

Sn(EH)2

St

TBAF3H2O
TEA

THF

IUPAC

XPS

sodiumascorbate
sodiumazide
nanocrystallinecellulose
nanofibrillatedcellulose
nitroxidemediatedpolymerization
nuclearmagneticresonance
N,N,N,N,Npentamethyldiethylenetriamine
reversibleadditionfragmentationchaintransfer
reversibledeactivationradicalpolymerization
rateofpolymerization
singleelectrontransfermediatedlivingradical
polymerization
surfaceinitiated
tin(II)2ethylhexanoate
styrene
tetrabutylammoniumfluoridetrihydrate
triethylamine
tetrahydrofuran
internationalunionofpureandappliedchemistry
Xrayphotoelectronspectroscopy

TABLEOFCONTENTS

1. PURPOSE OF THE STUDY .................................................................................... 1
2. INTRODUCTION ..................................................................................................... 2
2.1
CELLULOSE .......................................................................................................... 2
2.1.1
Structure of cellulose ................................................................................... 3
2.1.2
Cellulose types ............................................................................................. 4
2.1.3
Modification of cellulose.............................................................................. 4
2.2
REVERSIBLE-DEACTIVATION RADICAL POLYMERIZATION (RDRP) .. 6
2.2.1
Atom transfer radical polymerization (ATRP) ............................................. 7
2.2.2
Activators regenerated by electron transfer (ARGET) ATRP .................... 12
2.3
CLICK CHEMISTRY POLYMER CONJUGATION REACTIONS........... 13
2.3.1
Copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) ........................ 13
2.4
GRAFTING OF CELLULOSE VIA WELL-CONTROLLED
POLYMERIZATION REACTIONS ................................................................. 14
2.5
CHARACTERIZATION OF MODIFIED CELLULOSE SUBSTRATES ........ 15
2.5.1
High-resolution FT-IR microscopy (FT-IRM) ........................................... 16
3. EXPERIMENTAL ................................................................................................... 18
3.1
MATERIALS .................................................................................................... 18
3.2
INSTRUMENTATION ..................................................................................... 18
3.3
INITIATOR SYNTHESES ................................................................................ 21
3.3.1
Synthesis of disulfide-containing sacrificial initiator ................................ 21
3.3.2
Synthesis of disulfide-containing initiator for immobilization onto cellulose
substrates ................................................................................................................... 22
3.3.3
Synthesis of silane-protected alkyne-functional sacrificial initiator .......... 22
3.3.4
Synthesis of bromine-functional initiator for immobilization onto cellulose
substrates ................................................................................................................... 23
3.4
IMMOBILIZATION OF INITIATORS ONTO CELLULOSE ......................... 23
3.5
GRAFTING OF VARIOUS MONOMERS FROM CELLULOSE VIA ARGET
ATRP ................................................................................................................. 24
3.6
CLEAVAGE OF PMMA GRAFTS FROM MODIFIED CELLULOSE ........... 25
3.7
GRAFTING OF ALKYNE-FUNCTIONAL PMMA TO CELLULOSE VIA
CUAAC ............................................................................................................. 26
3.7.1
Activation of alkyne-functional PMMA...................................................... 26
3.7.2
Grafting to cellulose .................................................................................. 27

4. RESULTS AND DISCUSSION .............................................................................. 28

4.1

GRAFTING OF VARIOUS MONOMERS FROM CELLULOSE VIA ARGET

ATRP ................................................................................................................. 28
4.2
SELECTIVE CLEAVAGE OF POLYMER GRAFTS ...................................... 34
4.3
ASSESSING INITIATOR CONTENT .............................................................. 35
4.4
COMPARISON BETWEEN GRAFTING-FROM AND GRAFTING-TO
CELLULOSE .................................................................................................... 37
4.4.1
Grafting from and grafting to cellulose ..................................................... 38
4.4.2
XPS analysis of modified cellulose substrates ........................................... 40
4.4.3
FT-IRM of modified cellulose substrates ................................................... 44
4.5
TOWARDS INDUSTRIAL GRAFTING OF CELLULOSE ............................. 47
5. CONCLUSIONS ...................................................................................................... 50
6. FUTURE WORK ..................................................................................................... 52
7. ACKNOWLEDGEMENTS .................................................................................... 53
8. REFERENCES ........................................................................................................ 56

PurposeoftheStudy

1.PURPOSEOFTHESTUDY
Theinterestincellulosearenewableandinexpensiveresourcewithastiffness
almost comparable to steel has increased significantly the last decades. Some
requests are to achieving more environmentally friendly materials, as well as to
increase the utilization of cellulose in more advanced applications, compared
withmoretraditionallycommoditiessuchaspaper.However,toexploitthefull
potentialofcellulose,modificationofthenativeresourceisoftenaprerequisite,in
order to improve the properties of cellulose and/or to introduce new
functionalities. The modification in this study was performed by grafting
polymers from and to cellulose; moreover, to have the possibility to tailor the
surface properties, the polymerization should be performed in a wellcontrolled
manner.

Thepurposeofthisstudywastoinvestigatethegraftingprocessbyapplyingthe
method activators regenerated by electron transfer atom transfer radical
polymerization(ARGETATRP)whengraftingfromcellulosesubstrates.Another
importantaimwastodevelopanapproachtodetachthegraftedpolymerchains
under mild reaction conditions; thereby, rendering their postcharacterization
possiblewhilekeepingthesubstrateintact.Theamountofavailablereactivesites
presentonthecellulosesubstratewasalsotheobjectofinvestigation,aswellas
thepolymerdistributiononthesubstratesurface,withthepurposeofobtaining
valuableknowledgeaboutthegraftingprocess.

Anotherobjectivewastosystematicallystudyandcomparethegraftingefficiency
ofthetwograftingapproachesgraftingfromandgraftingtobyinvestigatingthe
polymericamountonthesurface,employingdifferentgraftlengths.

TheARGETATRPprocesswasalsoinvestigatedwiththepurposeofmakingthe
graftingreactionmoreapplicableinanindustrialcontext.

Introduction

2.INTRODUCTION
2.1 CELLULOSE
Cellulosethemaincomponentinplantstogetherwithligninandhemicelluloses
is the most abundant natural resource in the world. It is an attractive and
inexpensive polymeric raw material that is renewable, biocompatible, and has
excellent mechanical properties. The modulus of native cellulose is 138 GPa,
which can be compared to the modulus of steel: 200 GPa.1 Thus, the interest of
utilizingcellulosehasincreasedsignificantlytherecentdecades,especiallydueto
environmental concerns. The focus has lately been to replace petroleumbased
materials with renewable resources like cellulose, employing cellulose in a
broader range of products than only in commodities such as papers and card
boards. Nevertheless, the digitalization of our society will in the long term
decrease the utilization of paper, increasing the importance of finding new
applicationsforcellulosebasedproducts.Asanexample,cellulosefiberscanbe
employedasafillerorreinforcementinapolymericmatrix,formingacomposite,
e.g. sawdust in polypropylene2. The large advantages of cellulose fibers
comparedtotraditionalfillers,suchascarbonfibersorglassfibers,arelowercost
anddensity,highspecificstrength,renewability,degradability,andnontoxicity.3
5However,commondrawbacksaresensitivitytomoisture,bacteria,androt,but
it is especially the poor interfacial adhesion between the hydrophilic cellulose
fibers and the hydrophobic polymer matrix that results in weakened material
performance of the composite.5, 6 Poor compatibility between filler and matrix
rendersthecompositeinhomogeneous,causinglossofmechanicalstrengthsince
it is more difficult to transfer the applied load throughout the material.3
Therefore,surfacemodificationofcelluloseisarequisite.

Introduction

2.1.1 Structureofcellulose
Cellulose is composed of Dglucose units that are linked together with 14
glycosidic bonds, forming a linear polysaccharide with one primary and two
secondary hydroxyl groups on each anhydroglucose unit (AGU), see Figure 1.
The degree of polymerization (DP), i.e., the number of constituent AGUs, of
nativecelluloseisdependentonitsorigin.Themostcommonsourcesarewoodor
cotton, and the DP can then range from 300 to 10,000.7 Cellulose exhibits a
fascinating hierarchical structure from a molecular to macroscopic scale, which
providesfortheoutstandingpropertiesofcellulosefibers,seeFigure1.Inplants,
theextendedcellulosechainsarealignedinsheetsthatarestabilizedbyintraand
intermolecularhydrogenbonds.Thesecrystallinesheetsarecloselypacked,with
secondary forces that are holding them together, forming threedimensional
microfibrils that have both ordered and less ordered regions of cellulose. The
microfibrils are arranged in bundles of microfibrils that together with the
hemicellulosesandligninbuildupthecellwall.Thewoodcellconsistsofseveral
cellwall layers with various cellulosic compositions and with the cellulose
microfibrilsarrangedindifferentorientation,whichisvitalforthehighstrength
of the cellulose fiber. The microfibrils and the microfibril bundles have a lateral
dimensionof1.53.5nmand1030nm,respectively,andthelengthcanbeupto
afewmicrometers.7Thecellulosefiberhasgenerallythewidthofsometensofa
micrometer,andlengthsofafewmillimeters.8

Figure1.Theidealizedschematicpictureofthehierarchicalstructureofcellulose,adopted
fromIsogaietal.8

2.1.2

Introduction

Cellulosetypes

Cellulosecanbeextractedformwoodbyremovingtheligninandhemicelluloses,
resulting in cellulose pulp. By producing cellulose from different cellulose
sources,e.g.flax,hemp,andjute,andnotonlywood,andbyemployingchemical
and/or mechanical methods, it is possible to obtain many different types of
products.7, 9 Cellulose can also be obtained from aerobic bacteria.9 Recently, the
focus has been to achieve nanosized cellulose components, e.g., nanofibrillated
cellulose (NFC) and nanocrystalline cellulose (NCC).9 NFC and NCC can have
rathersimilarwidthsof570nm,butthelengthofNFCisgenerallymuchlonger,
up to several micrometers, compared to the length of NCC that originates from
plant celluloses:100 to250 nm. Furthermore,NCC consists of elongatedrodlike
crystalsandhasnoamorphousregionslikeNFC,limitingtheflexibilityofNCC.
Apartfromnanocellulose,microcrystallinecellulose(MCC)isanotherinteresting
and commercially available substrate. It is derived from cellulose pulp by
hydrolysiswithmineralacids,resultinginparticlesintherangeof10100m.10
Another common cellulose substrate is Whatman filter paper that is produced
from highquality cotton linters, resulting in a very pure product with high
cellulosecontent(>98%)andwithacrystallinityof68%.11

2.1.3

Modificationofcellulose

Themanyhydroxylgroupsalongthebackboneofcellulosearesuitablesitesfor
chemical modification. However, the number of available hydroxyl groups is
dependentonhowthecellulosesubstrateispretreated.Treatmentwithastrong
base such as NaOH (mercerization) breaks the hydrogen bonds, swelling and
increasing the activity of cellulose. Nevertheless, cellulose exists in different
crystallineformsanduponmercerizationthecrystalstructurecelluloseI,whichis
the native form, is converted to cellulose II. Cellulose II has antiparallel chains
andismorethermodynamicallystablethancelluloseI.7Thefunctionalizationof
the available hydroxyl group may have a slight impact on the mechanical
properties, especially if the strong hydrogen bonds that build up the cellulose
structure are affected. The challenge when modifying cellulose fibers can
thereforebetopreservetheinternalstructureofthefiber.

Cellulose can be modified by grafting synthetic polymers onto its surface, an

approachthathasgainedincreasinginterestforthepastyears.1215Thetwomost
commongraftingapproachesarethegraftingfromandgraftingtotechniques,see

Introduction

Figure 2. In the graftingfrom method, i.e., the surfaceinitiated (SI)

polymerization, the polymer chains are built up through successive monomer
additionfrominitiatingsitesonthesurface.Comparatively,whengraftingtothe
surface, a preformed polymer with suitable functionality is covalently or
physically attached to reactive sites on the surface. The graftingfrom method is
assumed to result in a higher grafting efficiency due to less steric hindrance of
diffusing small monomers, compared to the graftingto approach where larger
polymerchainshavetodiffusetothereactivesites,whichmaybeshieldedbythe
already grafted polymer chains.12, 13, 16 In the majority of all grafting studies,
grafting from is reported to yield higher grafting densities,12, 14, 1722 although
examples have been reported where graftingto approaches have provided
graftingdensitiesinthesamerange.2325

Figure2.Theschematicpictureofthegraftingfromandthegraftingtomethod.

The advantage with the graftingto method is that the employed preformed
polymercanbeeasilycharacterized,andtherebythemolarmassandmolarmass
dispersity (M) can be determined prior to the grafting reaction; therefore, the
graftingtomethodispreferredfromanindustrialpointofview.

Thechallengewiththegraftingfromapproachistoknowthecharacteristicsofthe
polymergraftsonthesurface.However,thiscanbecircumventedbyutilizinga
sacrificialinitiatorthatformsanunbound,freepolymerinthereactionmediain
parallel to the grafting process. The freely formed polymer, which easily can be
characterized, has shown to have comparable characteristics to the polymer
grafts,18, 2628 also rendering this an applicable approach to control the polymer
graftsonthesurface,byemployingdifferentratiosbetweenthemonomerandthe

Introduction

initiator (targeted degree of polymerization (DPtarget) = [M]0/[I]). However, to

evaluatethegraftproperties,detachmentofthecovalentlylinkedpolymerchains
and their subsequent analysis is vital. Acidic hydrolysis of cellulose has been
employedasamethodtoisolatethegraftsforsubsequentcharacterization,17,21,29,
30resultinginacompletedegradationofthesubstrate.Nevertheless,thismethod
may not be applicable for polymers containing sensitive functional groups like
esters,suchas(meth)acrylatepolymers.

2.2 REVERSIBLEDEACTIVATIONRADICAL
POLYMERIZATION(RDRP)
Freeradicalpolymerizationisthemostcommonpolymerizationmethodapplied
intheindustryfortheproductionofpolymers,sinceitisthemosteconomically
favorable approach to produce large volumes. One advantage is the facile
reactionconditionsthatcanbeemployedonavarietyofmonomers,withoutany
specific demands for high purity. However, due to the high concentration of
radicals formed during the reaction, many chaintransfer and termination
reactionstakeplace,resultinginpoorcontroloverthepolymerization.Toobtain
morecomplexandwelldefinedpolymers,itiscrucialtobeabletopredetermine
themolarmass,themolarmassdispersity(M),andthechainendfunctionality.
Therefore,polymerizationmethodsthatsuppresschaintransferandtermination
reactionsarerequired.Inalivingpolymerizationsystem,noirreversibletransfer
or termination reactions occur. The initiation is fast and quantitative and the
reaction will continue until all the monomers are consumed. Reversible
deactivationradicalpolymerization(RDRP)techniquesalmostfollowtheconcept
ofatruelivingsystem;however,thesemethodsarediscouragedtobereferredto
aslivingbyIUPAC.31Inaddition,RDRPwaspreviouslycalledcontrolledradical
polymerization(CRP)buttheterminologyRDRPisnowbeingencouraged.

The RDRP methods can be divided into nitroxide mediated polymerization

(NMP),32, 33 atom transfer radical polymerization (ATRP)3436, and reversible
addition fragmentation chain transfer (RAFT) polymerization37, 38. NMP and
ATRParebasedonadynamicequilibriumbetweenalargemajorityofdormant
speciesandonlyafewactivespecies,keepingtheradicalconcentrationlow,see
Scheme1.InRAFTpolymerization,theequilibriumisbasedonreversiblechain
transfer.NMPwasthefirstmethodtosuccessfullyscavengeradicalsbyutilizing
anitroxideleavinggroupthatreversiblyterminatethepropagatingspecies.RAFT
polymerization relies on a chaintransfer agent that captures and releases

Introduction

propagating radicals reversibly. ATRP, discussed in more detail in the next

section, is based on the transfer of an atom between a transitionmetal catalyst
complex and the propagating chain. The RDRP methods diverge in their
applicability for different monomer systems, and all have their advantages and
disadvantages.

Scheme1.ThedynamicequilibriumpresentinRDRPtechniques.

2.2.1

Atomtransferradicalpolymerization(ATRP)

ATRPisthemoststudiedRDRPmethodowingtoitsversatilityandcompatibility
withavarietyofmonomers,renderingthesynthesisoffunctionalpolymerswith
welldefined compositions possible.39 In 1995, ATRP was independently
discovered by Sawamoto et al.34 and Wang and Matyjaszewski35, 36. ATRP
originates from the atom transfer radical addition (ATRA)40, which is a
modificationoftheKharaschadditionreaction41.Thereversibleredoxprocessin
ATRP involves the atom transfer of a halogen atom between the active and the
dormantchain,catalyzedbyatransitionmetal/ligandcomplex.Intheactivation
process, this complex abstracts the halide from the dormant chain, forming an
activechainbearingaradical.Theactivespeciescantheneitheraddamonomer
in a propagating step or react with the oxidized metal complex via back
transferringofthehalogenatomtothepropagatingchainend,whichdeactivates
the radical. To achieve proper control, it is crucial that the initiation is fast and
quantitative and that the reversible deactivation occurs rapidly. However, it is
impossibletoachieveatrulylivingsystem,andterminationreactionsalsooccur,
principally via radical coupling and disproportionation. Yet, just a few
propagating chains undergo termination during the initial, nonstationary stage
of the polymerization. During this stage, the concentration of the deactivator
increases, shifting the equilibrium towards the dormant side, and thereby
inhibiting the termination reactions. This phenomenon is called the persistent
radicaleffect.42

Introduction

2.2.1.1 ComponentsofATRP
AnATRPsystemisgenerallycomposedofamonomer,aninitiator,andacatalyst
based on a transition metal/ligand complex. The choice of monomer determines
which initiator and catalyst as well as temperature and solvent that will be
utilized.43 Monomers that successfully have been polymerized via ATRP are
styrenics,35, 44 (meth)acrylates,4547 meth(acrylamides),48, 49 and acrylonitriles,50, 51
which all are effective in stabilizing the propagating radical.43, 52 ATRP is also
tolerant to several functional groups such as epoxides,5355 hydroxyl groups,
amines, and cyanides.43 Vinylpyridines can be polymerized if a strongly
coordinating ligand is employed, suppressing the monomers ability to
coordinate to the transition metal. Conversely, acidic monomers cannot be
polymerized via an ordinary ATRP system due to protonation of the ligand.43
However,Janaetal.haverecentlyreportedaunimolecularligandinitiatordual
functionalsystemthatrendersATRPof(meth)acrylicacidspossible.56

The initiator determines the number of propagating chains, and hence also the
DP.Arapidinitiationandnegligibletransferandterminationreactionsresultin
that the number of propagating chains is equal to the initial initiator
concentration;thus,themolarmassorDPcanbeestimatedaccordingtoEq.1

monomer0 conv.

(1)
DP
initiator0

The initiator is commonly composed of an alkyl halide, where the halide most
frequentlyisabromideorchloride.Thehomolyticcleavageofthelabilebondon
theinitiatorresultsinafreeradicalthatcaninitiatethepolymerization.Thebond
dissociation energy for bromide halides is lower than for chloride halides,
suggesting that bromide halides are more efficient. It can be beneficial to utilize
aninitiatorthatresemblesthemonomerinstructure,e.g.abenzylichalideforthe
polymerizationofstyrene,butitisnotnecessary.Tertiaryalkylhalidesarebetter
at stabilizing the radical than secondary alkyl halides, resulting in a faster
initiationforthetertiarycompound.43

The catalyst has a central role in ATRP, since it determines the equilibrium
between the active and dormant species. Ideally, the catalyst should be very
selectiveforatomtransferandnotparticipateinotherreactions;furthermore,the
deactivation should be extremely rapid. The transition metal must have two
accessibleoxidationstatesandaffinitytothehalogenatom,andtheligandshould

Introduction

complextothemetalrelativelystrongly.43Themostfrequentlyutilizedtransition
metal is copper, due to its low cost and applicability to several different
monomers. Many other metals have also been employed: titanium, chromium,
molybdenum,rhenium,iron,ruthenium,osmium,rhodium,nickel,palladium,43,
57andcobalt58.Thecatalyticactivityandselectivityisstronglyliganddependent,
since it controls the redox potential of the metal center. Another important role
for the ligand is to solubilize the metal in the organic media. Commonly, the
ligands are based on nitrogen or phosphorus. Nitrogenbased ligands are
especiallyapplicabletocoppermediatedsystems.39,43,52

ATRP can be performed in bulk or in solution. Various organic solvents have

been employed for different monomers, and it is especially essential if the
polymer is insoluble in the monomer. The structure of the catalyst may be
affected by different solvent, resulting in different reaction rates. ATRP can be
performed in aqueous medium,59, 60 which is of interest both from an
environmental as well as industrial perspective. Polar media has shown to
enhance the reaction rate since it can promote the solubility of the catalyst,59, 61
which has resulted in the development of an alternative mechanism,6264
comparedwiththeoriginalmechanismpresentedbyMatyjaszewskietal.52.Both
mechanismswillbediscussedinthenextsection.

2.2.1.2 SuggestedmechanismofATRP
Infreeradicalpolymerization,thepolymerizationoccursinthreesteps:initiation,
propagation, and termination. In ATRP, mainly initiation and propagation take
placesincetheterminationreactionsaresuppressed.Themechanism,presented
inScheme2,isexemplifiedwithcopper(I)ascatalyst.Theinitiationinvolvesthe
homolytic cleavage of the alkyl halide (RX), transferring the halogen radical
atom to the activator Cu(I)X/L, forming the radical R and the deactivator
Cu(II)X2/L,whereLrepresenttheligand.TheATRPequilibriumrateconstantof
the initiation is denoted as Keq. The active species can react with either a
monomer or the deactivator by backtransfer of the halogen in the reversible
redox reaction. The latter reaction must be favored, and the rate constant of
deactivation (kdeact) should be higher than the propagation rate constant (kp), to
achieve a controlled polymerization.52 In the initial stage of the polymerization,
equalamountsofradicalsandCu(II)areformed,whichresultsinsimilarratesof
activationanddeactivation.Duetothepersistentradicaleffectthatoccursinthe
early stage of the polymerization, the concentration of the Cu(II)X2/L complex
increases and shifts the equilibrium to the dormant side, maintaining the

Introduction

concentrationoftheactivespecieslow.39,43Ifappropriateconditionsareobtained,
the few termination reactions that occur in the initial stage of the reaction, with
therateconstantkt,willnothaveansignificantimpacttothesystem.43

Scheme2.ThesuggestedmechanismforcoppermediatedATRPinaproticsolvents.

The ATRP process occurs with a homolytic innersphere electrontransfer

mechanism.62 The alternative mechanism, the heterolytic outersphere single
electrontransfermediatedlivingradicalpolymerization(SETLRP),wasreported
byPercecetal.,6264andisclaimedtobevalidwhenpolarsolvents,e.g.,waterand
alcohols, polar aprotic solvents, or ionic liquids, are employed. In SETLRP, the
Cu(I)X/L species disproportionate spontaneously to Cu(0) and Cu(II)X2/L.
Accordingly,theCu(I)X/LspeciesisinactivemeanwhiletheelectrondonorCu(0)
is extremely reactive. The deactivator Cu(II)X2/L is suggested to be formed only
due to disproportionation, making the persistent radical effect unnecessary, i.e.,
terminationreactionsareessentiallyabsent.
2.2.1.3 KineticsofATRP
The kinetics of the ATRP mechanism can be derived by assuming that the
initiation is fast and quantitative and that termination reactions are absent;
consequently, the concentration of radicals will be constant. The rate of
polymerization, Rp, is dependent on the apparent rate constant, kpapp, and the
concentrationofthemonomer[M],andhence,Rpisoffirstorderwithrespectto

10

Introduction

the[M],activator[Cu(I)X],andinitiator[PX],whileitisofnegativelyfirstorder
withrespecttothedeactivatorconcentration[Cu(II)X],seeEq.2.However,dueto
thepersistentradicaleffect,somedeactivatorsareformedintheinitialperiodof
thereaction,makingtheactualkineticsmorecomplicated.

PX Cu(I)X M

(2)
R k app M k P M k K
p

eq

Cu(II)X 2

where K

eq

P Cu(II)X
2
kact

PXCu(I)X
kdeact

(3)

According to Eq. 2, an increased initiator concentration, resulting in a higher

number of propagating radicals and lower DPtarget, will increase the
polymerization rate.65 If not all initiators initiate, the initiator efficiency (IE) will
belessthan1,andthemolarmassoftheformedpolymerwillbehigherthanthe
DPtarget.TheIEcanbeestimatedby

DPtarget M monomer conv. M initiator M theo

(4)
IE

Mn
Mn

where Mn is the obtained by size exclusion chromatography (SEC). The IE has

shown to gradually increase with reaction time for methacrylate systems, when
ethyl 2bromoisobuturate (EBiB) is utilized as the initiator and anisole as the
solvent, implying that the initiation do not only occur at the initial stage of the
polymerization.65,66TheIEcanbeincreasedbyemployingasolventthatsolubilize
the deactivator complex better, increasing the deactivation rate. Accordingly,
acetoneandDMFwereshowntoyieldhigherIEthananisole.66

The transfer and termination reactions, which can be complicated to completely

avoid, can be suppressed by reducing the DPtarget and limit the conversion, i.e.,
aimforshorterpolymerchains.65Therateofpropagationissignificantlyreduced
athighconversionsasthemonomerconcentrationdecreases(Eq.2).Therateof
the side reactions, on the other hand, is not as affected by the monomer
concentrationandcantherebybeessentiallyunchanged.43

11

2.2.2

Introduction

Activatorsregeneratedbyelectrontransfer(ARGET)
ATRP

Although ATRP has many advantages in comparison with conventional radical

polymerization,itsuffersfromsomedrawbacks.Therequirementofarelatively
large amount of the transition metal catalyst, which subsequently requires
purification of the final product, complicates and increases the industrial
productions costs. Furthermore, residual copper traces may color the product,
and can further cause severe problems in some application, e.g., biological
systems,duetoitstoxicity.Anotherdisadvantageisthehighsensitivitytowards
oxygen,whichneedstoberemovedbythoroughdegassing,furthercomplicating
andincreasingthepriceofthereactionprocess.Tocircumventthesedrawbacks,
Matyjaszewski and coworkers67 developed a new approach to conduct ATRP:
activators regenerated by electron transfer (ARGET) ATRP. ARGET ATRP is
basedontheregenerationoftheactivespeciesCu(I)fromthedeactivatorCu(II)
bytheutilizationofareducingagent,seeScheme3.Thesystemiscomposedofa
monomer,aninitiator,thetransitionmetalinitsinactiveform:Cu(II)X2,aligand,
andareducingagent.Owingtothereducingagent,theoxidativelystableCu(II)
complex is continuously reduced to Cu(I) throughout the polymerization,
significantlyreducingtheamountofcoppertoonlyafewppm.

Scheme3.ThemechanismofARGETATRP.67

Ascorbic acid (AsAc) is frequently utilized as an environmentally friendly

reducing agent. AsAc is a strong reducing agent, so to avoid a too high
concentration of radicals, which would reduce the control over the
polymerization, the solubility in the reaction medium can be limited by
employing a heterogeneous system with for example anisole as solvent.68 Two

12

Introduction

other not as strongly reducing agents that can be utilized are sodium ascorbate
(NaAsc), the salt of AsAc, as well as tin(II) 2ethylhexanoate (Sn(EH)2).67, 69 The
beautyofemployingareducingagentinARGETATRPisthatthereactioncanbe
conductedinthepresenceoflimitedamountsofair,sincethereducingagentalso
scavengeoxygen.Thereby,thedifficultywithtediousdeoxygenationprocedures
is reduced or avoided. Moreover, Matyjaszewski and coworkers recently
presentedanaqueousARGETATRPsystem,wheretheadditionofahalidesalt,
e.g. NaCl, promoted an increased concentration of deactivators to improve the
controloverthepolymerization.70

2.3 CLICKCHEMISTRYPOLYMERCONJUGATION
REACTIONS
TheclickconceptthatwasintroducedbySharplessandcoworkers71in2001was
firstly intended for organic chemistry, but it has also had a great impact on
polymer chemistry and the synthesis of macromolecules with welldefined
architecturesandfunctionalities.72Therequirementsofaclickreactionarethatit
mustgiveveryhighyields,bemodular,wideinscope,andorthogonal,andmust
alsoproceedbyasinglereactiontrajectory.However,nottoomanyreactionsin
polymerchemistrycanbereferredtoasatrueclickreaction,andthetermclick
is commonly misused. Therefore, BarnerKowollik et al. introduced a modified
definition adapted to polymer chemistry, including other parameters such as
equimolarity and largescale purification. Polymerlinking reactions that do not
fulfillthesecriteriaarenotclickreactionsbut(sometimesefficient)conjugation
processes.73 Examples of reactions that can be classified as click reactions are
thiolenereactions,7476heteroDielsAlder(HDA)chemistry,7779andazidealkyne
cycloaddition80.

2.3.1

Copper(I)catalyzedazidealkynecycloaddition(CuAAC)

The most frequently utilized click reaction is the copper(I)catalyzed azide

alkyne cycloaddition,81, 82 which is a modification of the classical Huisgen 1,3
dipolar cycloaddition between alkynes and azides83. The 1,4cycloaddition
betweenanazideandalkyne,catalyzedbyCu(I),formingthe1,2,3triazolering,
is presented in Scheme 4. A common Cusystem to employ is the Cu(II)SO4
combinedwithNaAscthatreducesCu(II)intoCu(I),butothersystemsutilizing
e.g.,Cu(I)BrorCu(I)Ialsoexist.84

13

Introduction

Scheme4.The1,4cycloadditioncatalyzedbyCu(I)formingthe1,2,3triazole.

2.4 GRAFTINGOFCELLULOSEVIAWELLCONTROLLED
POLYMERIZATIONREACTIONS
As mentioned before, an approach to expand the utilization of cellulose is by
grafting polymers onto the cellulose surface. However, to understand and to
tailor the surface properties for a given application, a deeper and more
fundamental knowledge about chemical modifications, such as grafting, is
required. If cellulose is to be applied for more sophisticated applications, e.g.,
superhydrophobic,85stimuliresponsive,8688orantibacterialsurfaces,30,89sensors,90,
91 and biomedical applications,88, 9295 the demands on understanding well
controlledreactions,suchasRDRP,arehighlysignificant.

To obtain a controlled polymerization when grafting polymers from a surface,

surfaceinitiated (SI) ATRP, NMP, and RAFT polymerization, can be employed.
Among these methods SIATRP is the most studied one.13, 88, 96 In SIATRP
systems,asacrificialinitiatorcanbeemployedtocontrolthegraftlength,forming
a free polymer in the solution, as mentioned above. The sacrificial initiator also
keeps the concentration of radicals low, since the overall concentration of
dormantspeciesonthesurfaceistoolowtoachieveacontrolledpolymerization.
However, from a processing point of view, the sacrificial initiator can be a
disadvantagesincethefreelyformedpolymerhastoberemoved.Thus,another
useful approach to finetune the SIATRP can be by adding the deactivator, i.e.,
Cu(II), to the solution, shifting the dynamic equilibrium towards the dormant
sidewithouttheformationoffreepolymer.16,88,97

RAFT and ATRP are frequently utilized when grafting polymers from cellulose
substrates.1214 When SIRAFT polymerization is employed, pretreatment of
cellulose with NaOH, to increase the surface area, has shown to be crucial to
obtainsufficientgraftingefficiency.21ThefirstSIATRPfromcellulosefilterpaper
was reported in 2002 by CarlmarkandMalmstrm.19 Since then, several reports
on the graftingfrom approach of various cellulose substrates employing ATRP

14

Introduction

have been described.98101 A problem correlated with SIATRP from cellulose is

that it can occasionally be problematic to remove the copper catalyst, which
mightresultincoloredproductsdespitethoroughwashing.14However,thiscan
be circumvented by utilizing ARGET ATRP. ARGET ATRP has proven to be a
very efficient tool when grafting polymers from cellulose substrates.26, 98, 102104
ARGETATRPhasbeenemployedforgraftingofnanotubes,withoutthepresence
of a sacrificial initiator, showing that the molar mass could be controlled by
varying the reaction time.105 Furthermore, SIARGET ATRP has been performed
from a silicon wafer without the requirement for any deoxygenation,69 which
mostcertainlycanincreaseitscommercialsignificance.

ATRP and RAFT polymerization are frequently utilized to produce the pre
polymerfortheensuinggraftingtoreaction.14Agreatadvantageofemployinga
RDRPisthepreservedendgroupfunctionality.ForanATRPsystem,theactive
endgroup, which commonly has a bromine or chlorine functionality, can be
transformedintoanazidemoiety.39,80Anazideoralkynefunctionalitycanalsobe
incorporated into the ATRP initiator prior to the polymerization,106 forming
functionalized prepolymers that can be grafted by conjugatation via CuAAC to
an alkyne or azidefunctional surface. Cellulose substrates have been modified
by employing efficient conjugation reactions such as CuAAC,106108 thiolene
chemistry,109 and HDA chemistry110, 111. The assumed lower grafting efficiency
connectedtothegraftingtoproceduremaybeenhancedbyutilizingthesehighly
efficientconjugationreactions.

2.5 CHARACTERIZATIONOFMODIFIEDCELLULOSE
SUBSTRATES
A persistent challenge when modifying solid cellulose substrates is to actually
knowthecharacteristicsofthegraftedsurfaces,i.e.,polymergraftcharacteristics,
polymer distribution, degree of substitution (DS), initiator content, and grafting
density. Several surface characterization methods exist, such as: Fourier
transformation infrared (FTIR) spectroscopy, contact angle (CA) measurement,
fieldemission scanning electron microscopy (FESEM), atomic force microscopy
(AFM),Xrayphotoelectronspectroscopy(XPS),andellipsometry.However,the
inherentsurfaceroughnessofcellulosesubstrates,suchasfilterpaper,combined
with its porosity renders cellulose a tricky substrate to analyze properly.
Comparatively,flatsurfacessuchassiliconandgoldwafersaremoreconvenient
substrates to characterize, especially with methods like XPS and ellipsometry.

15

Introduction

Withthelatter,itispossibletodeterminethethicknessofthinpolymerlayerson
smooth surfaces, but not on cellulose substrates due to its roughness. On the
contrary, XPS analysis, which can provide the elemental composition on the
surface, can be utilized on cellulose;18, 112 however, it is difficult to obtain
quantitative information about modified cellulose substrates due to the
inhomogeneoussurface,butthesuccessofthemodificationcanbeconfirmedby
thecomparisonofspectrafromdifferentsurfaces.113

2.5.1

HighresolutionFTIRmicroscopy(FTIRM)

Anadvantageousmethodtoemployforcharacterizationofgraftedsubstratesis
highresolution FTIR microscopy (FTIRM) imaging.110, 111, 114, 115 It combines the
benefits of IR spectroscopy and microscopy, yielding information about the
chemical composition on the surface combined with the surface topography.
Thereby,thespatialdistributionofthegraftedpolymercontentcanbevisualized.
A focal plane array detector spatially resolves the incoming beam of the ATR
crystal, acquiring 4096 FTIR spectra over an area of 32 32 m. The
measurement only takes a few minutes and can be achieved without any
requirements of special sample preparation. FTIRM has proven to be a highly
applicable technique for the characterization of modified cellulose surfaces,
allowing foranalysis ofsingle cellulose fibers.110, 111, 114, 115 The topography of the
cellulosefiberscanbeobtainedbyintegrationofthecelluloseabsorptionintensity
from the FTIR spectra from 950 to 1200 cm1, which originates from the CO
vibrationincellulose.Iftheintensityofacharacteristicpolymersignalisutilized,
e.g.,between1700and1760cm1thatcorrespondstothestretchingvibrationofa
carbonylbond,thespatialdistributionofthepolymercontentonthefibercanbe
visualized.ThisispresentedinFigure3,wherethecorrespondingregionsofthe
spectraresultintwoFTIRMmicrographsofasinglecellulosefiber,respectively.
Noteworthy, the micrographs correspond to the same fiber, but with different
intensityscalesofthecorrespondingregions.

16

Introduction

Figure 3. The characteristic carbonyl (polymer) and cellulose region as a single FTIR
spectrum(top)andasFTIRmicrographs(bottom),where4096FTIRspectraareacquired
overanareaof3232mofaPMMAgraftedfilterpaper.Themicrographscorrespondto
thesamefiber,butwithdifferentintensityscalesofthecorrespondingregions.

17

Experimental

3.EXPERIMENTAL
3.1 MATERIALS
Bromoisobutyryl bromide (BiB, 98 %), 2bromoethanol (95 %), copper(II)
bromide (Cu(II)Br2, 99 %), 4dimethylaminopyridine (DMAP, 99 %), oxalyl
chloride(98%),N,N,N,N,Npentamethyldiethylenetriamine(PMDETA,99%),
3(trimethylsilyl)propargyl alcohol (99 %), and Whatman no. 1 filter paper were
purchased from Sigma Aldrich. Ascorbic acid (AsAc, 99 %), sodium bisulfate
(NaHSO4), and sodium carbonate (Na2CO3) were purchased from Fluka.
Triethylamine(TEA)andsuccinicanhydride(99%)werepurchasedfromMerck.
Tetrabutylammonium fluoride trihydrate (TBAF 3H2O), copper sulfate
pentahydrate(CuSO4 5H2O),sodiumazide(NaN3),sodiumascorbate(NaAsc),
and 1,4dithiothreitol (DTT, 99 %) were purchased from ABCR. Methyl
methacrylate(MMA,99%,SigmaAldrich),styrene(St,99%,Fluka),andglycidyl
methacrylate (GMA, 97 %, Fluka), were passed through a column of activated
neutral aluminum oxide (Al2O3, Sigma Aldrich) prior to use in order to remove
theinhibitor.

3.2 INSTRUMENTATION
HNMRspectrawererecordedonaBrukerAvance400MHzNMRinstrument,
usingCDCl3assolvent.Thesolventresidualpeakwasusedasinternalstandard.
1

TheCP/MAS 13CNMRspectrawererecordedinaBrukerAvanceIIIAQS400SB
instrumentoperatingat9.4T.Thefilterpaperwaswettedwithdeionizedwater
to 4060% water content and packed uniformly in a zirconium oxide rotor.
Recording spectra on wet rather than dry samples gives a higher apparent
resolution.116 All measurements were made at 295 (1) K with a MAS rate of 10
kHz. A 4mm double airbearing probe was used. Acquisition was performed

18

Experimental

using a CP pulse sequence, i.e., a 2.95 microseconds proton 90 pulse and a 800
microsecondsramped(10050%)fallingcontactpulse,witha2.5secondsdelay
between repetitions. A SPINAL64 pulse sequence was used for 1H decoupling.
TheHartmannHahnmatchingprocedureisbasedonglycine.Thechemicalshift
scale was calibrated to the TMS ((CH3)4Si) scale by assigning the data point of
maximumintensityintheglycinecarbonylsignaltoashiftof176.03ppm.Atotal
of 4096 transients were recorded on each sample, giving an acquisition time of
approximately 3 h. The software for spectral fitting was developed at Innventia
AB and is based on a LevenbergMarquardt algorithm.117 All computations are
basedonintegratedsignalintensitiesasobtainedfromthespectralfitting.118

Size exclusion chromatography (SEC) using THF (1.0 mL min1) as the mobile
phase(inpaperI,II,andII)wasperformedat35CusingaViscotekTDAmodel
301 equipped with two T5000 columns with porous styrene divinylbenzene
copolymer(300mmL7.8mmID,exclusionlimitMWpolystyrene:400,000,000
Da) from Malvern (UK), a VE 2500 GPC autosampler, a VE 1121 GPC solvent
pump, and a VE 5710 GPC degasser from Viscotek Corp. (the Netherlands). A
conventional calibration method was created using narrow linear polystyrene
standards.Correctionsfortheflowratefluctuationsweremadebyusingtoluene
as an internal standard. Viscotek OmniSEC version 4.0 software was used to
processdata.

SEC measurements were also performed using THF (1.0 mL min1 ) at 35 C (in
paper IV) on a Polymer Laboratories PLGPC 50 Plus Integrated System,
comprisinganautosampler,aPLgel5mbeadsizeguardcolumn(507.5mm)
followedbythreePLgel5mMixedCcolumns(3007.5mm)andadifferential
refractiveindexdetector.TheSECsystemwascalibratedusinglinearpoly(methyl
methacrylate) standards ranging from 700 to 2,000,000 gmol1 (MarkHouwink
parametersK=12.8105dLg1,=0.69).119

SECmeasurementswereperformedusingDMF(0.2mLmin1)with0.01MLiBr
as the mobile phase at 50 C on a TOSOH EcoSEC HLC8320GPC system
equipped with an EcoSEC RI detector and three columns (PSS PFG 5m;
Microguard,100,and300)(MWresolvingrange:300to100,000Da)fromPSS
GmbH. A conventional calibration method was created using narrow linear
poly(methylmethacrylate)standards.Correctionsforflowratefluctuationswere
madeusingtolueneasaninternalstandard.PSSWinGPCUnitysoftwareversion
7.2wasusedtoprocessdata.

19

Experimental

InfraredspectrawererecordedonaPerkinElmerSpectrum2000FTIRequipped
with a MKII Golden GateTM, Single Reflection ATR System (from Specac Ltd,
London,UK).TheATRcrystalwasaMKIIheatedDiamond45ATRTopPlate.

Fieldemissionscanningelectronmicroscope(FESEM)imageswererecordedon
aHitachiS4800FESEM.Thesamplesweremountedonasubstratewithcarbon
tape and coated 3 s of a carbon coater (Cressington 108carbon/A) and
subsequently2x4nmofagold/palladiumsputtercoater(Cressington208HR).

ACary100UV/VISspectrophotometer(Varian,PaloAlto,CA,USA)wasusedto
recordtheabsorbanceincreaseat412nm.Thecellulosesubstratefromwhichthe
polymer had been cleavedoff was immersed in 20 mL of a 3.0 mM DTNB
phosphatebuffersolution,pH7.0,for30mintomakesurethatallthiolsonthe
surface wereaccessible.1mL of the solution was characterized employinga3.0
mM solution of DTNB medium as a reference (1 mL). Prior to the DTNB
treatment,eachsubstratewasweighed(seeSampleweightinTable2),inorderto
assesstheinitiatorcontent.

FTIRmicroscopy(FTIRM)imagingmeasurementsofthecellulosesampleshave
beenperformedusingaBrukerFTIRmicroscopeHYPERION3000coupledtoa
researchspectrometerVERTEX80.TheHYPERION3000microscopeisequipped
with two types ofdetectors:a single element MCTdetector (Mercury Cadmium
Telluride) for the conventional mapping approach and a multielement FPA
detector (Focal Plane Array) for imaging. The multielement FPAdetector
consistsof6464elements.Thisfactallowsforthesimultaneousacquisitionof
4096spectracoveringasampleareaof3232m(forATRdetection).Forpost
processing, baseline correction and atmospheric compensation were used. With
theFPAdetectorincombinationwiththe20GermaniumATRlens,atheoretical
lateralresolutionof0.25m2perpixelisachieved.

Xray photoelectron spectroscopy (XPS) measurements were performed using a

KAlpha XPS spectrometer (ThermoFisher Scientific, East Grinstead, UK). Data
acquisition and processing using the Thermo Avantage software is described
elsewhere.120 All samples were analyzed using a microfocused, monochromated
AlKXraysource(400mspotsize).TheKAlphachargecompensationsystem
was employed during analysis, using electrons of 8 eV energy, and lowenergy
argonionstopreventanylocalizedchargebuildup.Thespectrawerefittedwith
one or more Voigt profiles (BE uncertainty: +0.2eV) and Scofield sensitivity
factors wereapplied forquantification.121 All spectra were referenced to the C1s

20

Experimental

peak assumed to originate from surfacehydrocarbon contamination at 285.0 eV

binding energy controlled by means of the wellknown photoelectron peaks of
metallicCu,Ag,andAu,respectively.

Contactanglemeasurementswereperformedat50%relativehumidityand23C
and conducted on a KSV instruments CAM 200 equipped with a Basler A602f
camera, using 5 L droplets of deionized water. The water contact angles were
determinedusingtheCAMsoftware.

3.3 INITIATORSYNTHESES
InitiatorssuitableforARGETATRPweredesignedandsynthesizedwiththeaim
to also hold certain functionalities to enable ensuing reactions; e.g., a disulfide
containing initiator for immobilization onto cellulose, prior to grafting, was
produced, rendering postcleavage of the polymer grafts from the surface
possible.Furthermore,byintroducingalkynefunctionalitytoanATRPinitiator,
the freely formed polymer will bear this functionality, and can thereby be
employed in a subsequent conjugation reaction when grafting to a surface.
Noteworthy,alldetailsregardingtheexperimentalreactionscanbefoundinthe
correspondingarticles.

3.3.1

Synthesisofdisulfidecontainingsacrificialinitiator

Byreacting2,2dithiodiethanolwithbromoisobutyrylbromide(BiB)for3hat
ambienttemperature,thedisulfidecontainingsacrificialinitiatorOHdiSBrwas
synthesized,seeScheme5andpaperII.26

Scheme5.ThesynthesisofthedisulfidecontainingsacrificialinitiatorOHdiSBr.

21

3.3.2

Experimental

Synthesisofdisulfidecontaininginitiatorfor
immobilizationontocellulosesubstrates

The disulfidecontaining sacrificial initiator OhdiSBr was reacted with succinic

anhydridefor18hatambienttemperaturetointroduceacarboxylicacidmoiety
thatsubsequentlywastransformedintoanacidchloride,utilizingoxalylchloride
for3hatambienttemperature,formingCldiSBr,seeScheme6.The 1HNMRof
CldiSBrispresentedinFigure9andpaperII.26

Scheme6.ThesynthesisofthedisulfidecontaininginitiatorCldiSBrforimmobilization
ontocellulose.

3.3.3

Synthesisofsilaneprotectedalkynefunctionalsacrificial
initiator

3(Trimethylsilyl)propargyl alcohol and BiB were reacted for 18 h at ambient

temperaturetoformthesilaneprotectedalkynefunctionalsacrificialinitiatorSi
AlkBr,seeScheme7andpaperIV.115

22

Experimental

Scheme 7. The synthesis of the silaneprotected alkynefunctional sacrificial initiator Si

AlkBr.

3.3.4

Synthesisofbrominefunctionalinitiatorfor
immobilizationontocellulosesubstrates

A brominefunctional initiator was produced by reacting 2bromoethanol and

succinic anhydride for 18 h at ambient temperature. The carboxylic acid was
subsequently reacted with oxalyl chloride for 3 h at ambient temperature,
formingClRBr(R=CO(CH2)2COO(CH2)2),seeScheme8andpaperIV.115

Scheme 8. The synthesis of the brominefunctional initiator ClRBr for immobilization

ontocellulose.

3.4 IMMOBILIZATIONOFINITIATORSONTOCELLULOSE
Whatmanno.1filterpapersofvarioussizes(2x3cm,1x1cm,or=4cm)were
washed with ethanol, acetone, and THF and ultrasonicated for 2 min in each
solvent, prior to the immobilization of the initiator. The available hydroxyl
groups on the surface were converted into ARGET ATRP initiators by the
reactionwithaninitiatorholdingeitheranacidbromideoracidchloridemoiety:

23

Experimental

BiB,CldiSBr,orClRBr.Thereactionswereallowedtoproceedfor0.2518hin
THF at ambient temperature on a shaking device. Scheme 9 shows the
immobilization of ClRBr and the posttransformation of the bromines into
azidesemployingNaN3(seealsopaperIV).115Scheme10depictsBiB(asinpaperI
and III)102, 114 and CldiSBr (as in paper II and IV)26, 115 immobilized onto the
cellulosesubstrate.

Scheme9.ImmobilizationofbrominefunctionalinitiatorClRBrontocelluloseandpost
transformationofthebrominesintoazides.

3.5 GRAFTINGOFVARIOUSMONOMERSFROM
CELLULOSEVIAARGETATRP
ThegeneralpolymerizationsystememployedwhengraftingMMA(inpaperI,II,
III,andIV),26,102,114,115styrene(inpaperI),102orGMA(inpaperI)102frominitiator
functionalizedcelluloseconsistedofasacrificialinitiator(EBiB,OHdiSBr,orSi
AlkBr),PMDETA,Cu(II)Br2,AsAcorNaAsc,andanisole,inaninertatmosphere,
see Scheme 10 for further details. Different ratios of initiator to monomer were
utilizedobtaindifferentDPtarget,andtheotheremployedratioswere:[MMA]:[I]:
[Cu(II)Br2]:[PMDETA]:[AsAc/NaAsc]=DPtarget :1:0.1:1:1,exceptforPGMA
where the ratio of AsAc was 0.5. The reaction was monitored by 1H NMR and
terminated when the desired conversion was reached or after a predetermined
time. The polymer was precipitated and the grafted cellulose substrate was
thoroughlywashed.

24

Experimental

Scheme 10. The surfaceinitiated ARGET ATRP of MMA, St, or GMA from initiator
functionalizedcellulosesubstrate(CelBiBorCeldiSBr)inparalleltothepolymerization
initiatedfromasacrificialinitiator(EBiB,OHdiSBR,orSiAlkBr).

In addition, grafting of MMA from BiBfunctionalized filter paper (2 3 cm)

without any deoxygenation was also investigated (unpublished results). The
same ratios as above were employed, except that the amount of AsAc was
changed for some polymerization systems. The reaction took place in either a
roundbottomflaskcapsuledwitharubberseptumorinaglassjarwithascrew
lid,bothwithandwithouttheadditionofsolvent.Experimentswiththeaddition
ofasmallamountofH2O(0.1mLto25gMMA)tothebulkreactionswerealso
performed.

3.6 CLEAVAGEOFPMMAGRAFTSFROMMODIFIED
CELLULOSE
The PMMA grafts, which had been grafted from the cellulose substrate
functionalized with the disulfidecontaining initiator, were cleaved off by
employing 1,4dithiothreitol (DTT) for five days at ambient temperature, see
Scheme11andpaperII.26,115

25

Experimental

Scheme11.CleavageofgraftsfromPMMAmodifiedcellulosesubstrate.

3.7 GRAFTINGOFALKYNEFUNCTIONALPMMATO
CELLULOSEVIACUAAC
ThePMMApolymerSiAlkPMMAxBr(wherexdenotestheDPcalculatedfrom
1HNMR),formedfromthesacrificialinitiatorSiAlkBrinparalleltothegrafting
fromcellulose,wasutilizedastheprepolymerforthegraftingtoreaction.Priorto
thegraftingreaction,thesilaneprotectedPMMAhastobedeprotected.

3.7.1

ActivationofalkynefunctionalPMMA

The silaneprotected PMMA was deprotected by subjecting it to

tetrabutylammoniumfluoridetrihydrate(TBAF3H2O)underinertatmosphere,
seeScheme12andpaperIV.115

26

Experimental

Scheme12.DeprotectionofsilaneprotectedPMMA,formingAlkPMMAxBr.

3.7.2

Graftingtocellulose

The graftingto reaction was conducted by immersing the azidefunctionalized

cellulose substrate into a solution containing the alkynefunctional PMMA,
coppersulfatepentahydrate(Cu(II)SO45H2O),NaAsc,asmallamountofH2O,
andDMF,employinganinertatmosphere,seeScheme13andpaperIV.115

Scheme 13. The grafting of alkynefunctional PMMA to an azidefunctionalized cellulose

substrateviaCuAAC.

27

ResultsandDiscussion

4.RESULTSANDDISCUSSION
Celluloseisafascinatingnaturalresourceinmanyperspectives.Bymodifyingthe
available hydroxyl groups on cellulose via grafting of polymer, the applicability
ofcellulosecanbeenhanced.Totrulytailorthesurfacecharacteristics,itiscrucial
to obtain knowledge about the grafting properties; furthermore, certain control
over the reaction mechanism is essential. However, due to the inherent surface
roughness of cellulose substrates, such as filter paper, it is challenging to
characterizethegraftedsubstratequantitatively.Nevertheless,tobeabletoapply
themodificationindustrially,simpleandnottooharshreactionconditionsarea
prerequisite. Therefore, the development of straightforward surfaceinitiated
ARGETATRPgraftingsystems,withlowamountofcoppercombinedwithlow
sensitivitytowardsoxygen,canbeofgreatimportance.

4.1 GRAFTINGOFVARIOUSMONOMERSFROM
CELLULOSEVIAARGETATRP
ARGET ATRP was employed for surfaceinitiated polymerization of cellulose
substrates, utilizing the various monomers: MMA, St, and GMA. Commonly,
finetuning of ATRP systems for different monomers is required for the
polymerizationtosucceed,butonlyminoradjustmentstothereactionconditions
for these three rather different monomers were performed. The changes in
between the systems were the reaction temperature as well as the choice of
reducing agent (see Scheme 10). Furthermore, the grafting procedure is
performed straightforwardly by just immersing the initiatorfunctionalized
substrateinthereactionmixture,followedbyafewminutesofpurgingwithinert
gas. The graft length was controlled by employing a sacrificial initiator, also
allowing for the monitoring of the kinetics by 1H NMR and SEC. Noteworthy,
parallel grafting experiments were conducted and quenched after a

28

ResultsandDiscussion

predeterminedtime,sincethewithdrawalofaliquotsmayaffectthekinetics.The
unbound polymer, freely formed from the sacrificial initiator, was visually
colorless after precipitation, without the requirement for removal of the Cu salt
by passing the polymer solution through an Al3O2 column; nevertheless, small
amounts of Cu can be remaining. Therefore, the polymer was purified from
copperwhenbeingemployedinsubsequentreactions.

The free polymer formed simultaneously in the solution showed firstorder

kinetics with respect to monomer conversion up to at least 20 % monomer
conversion for all three systems; e.g., see Figure 4 for the kinetic plot of the
PMMA system, targeting two different DPs. For the PS system, a distinct
induction period in the beginning of the reaction, when the Cu(II) species is
transformedtoCu(I)species,couldbeobserved.ForthePMMAandPGMA
systems this effect was not as clearly observed, which can be due to that the
stronger reducing agent AsAc was employed instead of NaAsc as for PS.
Moreover, the propagation rate constant (kp) is much larger for MMA than for
styrene.39,43

Figure 4. Kinetic plot for ARGET ATRP of PMMA. Experimental conditions: T = 40 C,

anisole(50wt%), [MMA]:[EBiB]:[Cu(II)Br2]:[PMDETA]:[AsAc]=400:1:0.1:1:1)and
[MMA]:[EBiB]:[Cu(II)Br2]:[PMDETA]:[AsAc]=800:1:0.1:1:1).102

Figure 5 illustrates the molar mass and dispersity of crude samples of PMMA
(DPtarget = 800) as a function of monomer conversion. At low conversions, the
molarmassesobtainedfromSECarehigherthanthetheoreticalvaluescalculated
from 1HNMR(seeEq.4),suggestingthattheinitiatorefficiencyisbelow1.The
incomplete initiation and the fact that the endgroup of a PMMA chain has an

29

ResultsandDiscussion

activation rate constant (kact) that is approximately eight times higher compared
withkactofEBiB,66,122, 123seeScheme2andEq.3,explainswhythemolarmassis
higher at low monomer conversion. At higher monomer conversions, the molar
massislowerthanthetheoreticalvalue,whichwepreviouslyexplainedtobedue
to that the surface propagation contributes to the consumption of monomers to
largeextent,whenaimingforhigherDPtarget.102However,atthattime,wedidnot
know that on the cellulose substrate employed (filter paper: 2 3 cm)
approximately1.1molinitiatorsarepresent26(discussedindetailinsection4.3).
In the same system, the DPtarget of 800 with a monomer amount of 10 g
corresponds to 125 mol of EBiB; thus, the sacrificial initiator is in large excess
comparedwiththeinitiatoronthesurface.Therefore,themonomerconsumedby
the cellulose substrate cannot be the only explanation, also suggesting the
occurrence of transfer reactions,such as intraand intermolecularchaintransfer
as well as transfer to monomer or solvent. Transfer reaction results in an
increased number of total chains. The chain transfer to polymer results in
branching124, 125,whichdecreasesthehydrodynamicvolumeofthepolymer,and
therebyloweringtheobtainedMnsincetheSECseparatesmoleculesaccordingto
thehydrodynamicvolume.125

Figure5.Molarmassanddispersity(PDI)ofPMMAasafunctionofmonomerconversion.
The continuous line represents the theoretical values that were calculated from the
monomerconversiondeterminedby 1HNMR.Experimentalconditions:T=40C,anisole
(50wt%),[MMA]:[EBiB]:[Cu(II)Br2]:[PMDETA]:[AcAs]=800:1:0.1:1:1.102

Another possibility can be that as the reaction proceeds, the initiator efficiency
increases as reported previously,65, 66 forming more propagating species which
will lower the molar mass. Matyjaszewski et al. have reported the same

30

ResultsandDiscussion

phenomenonseeninFigure5forMMAwithEBiBasaninitiator,alsosuggesting
thatthereasonistransferreactionsandslowerinitiation.126Aschematicgraphof
how the different features affect the molar mass as a function of the monomer
conversionispresentedinFigure6.Nevertheless,thesamedeviationofMnfrom
MtheowasobservedforPSandPGMA,butthedifferenceathigherconversionwas
not as pronounced as for the PMMA system.102 Figure 5 also demonstrates that
the M (named here as PDI) slightly decreases with increasing monomer
conversion, which is contradictive to the presence of chaintransfer reactions
whichwouldincreasethedispersity.125

Figure6.AschematicgraphtoillustratehowMnvariesasafunctionoftheconversion,for
differentreactionfeaturesinthepolymerizationsystem.127

The cellulose substrates grafted with PMMA, PS, or PGMA were characterized
withFTIRtoverifythesuccessfulgrafting.Itcouldbeconcludedthattheamount
of polymer successively increased with monomer conversion. As an example,
Figure 7 depicts the increase in the carbonyl region for the PMMAgrafted
cellulose substrates with increasing reaction time. However, it is important to
keep in mind that the method is semiquantitative, since the spectra are
normalized against the noise arising from the ATR crystal (23001950 cm1).
Furthermore,whenanalyzingaroughsubstratesuchascellulosefilterpaper,the
absorbance can vary slightly depending on which point on the surface that is
beingexamined.Thiseffectcanalsobeduetothatthepolymerlayermaynotbe
completely homogenous. Nevertheless, FTIR is a versatile method to prove a
successful grafting, but it does not give the spatial distribution of the polymer
graftsonthesurface.

31

ResultsandDiscussion

Figure 7. FTIR spectra of PMMAgrafted cellulose at different reaction times (DPtarget =

800), showing the increase of carbonyl peak at 1732 cm1 as well as the bound water in
cellulose(approx.16001700cm1).102

Todeterminethespatialdistributionofthepolymercontentonthesurface,high
resolution FTIRM was employed. Figure 8 depicts the FTIRM micrographs of
thegraftedcellulosesubstrateswithincreasinggraftlengthforPMMAx(wherex
denotestheDPcalculatedfrom1HNMR).Thesixupperimagescorrespondtothe
same substrates as in Figure 7, except that the substrate modified for 0.5 h is
excluded. As can be seen, the polymer distribution is relatively uniform,
especially as the graft length increases. However, a tendency to form smaller
regions with higher polymer concentration can also be observed. These smaller
inhomogeneities may be a result of the surface roughness. Still, FTIRM was
proventobeaveryusefulmethodforthecharacterizationofcellulosesubstrates.

32

ResultsandDiscussion

Figure8.FalsecolorhighresolutionFTIRmicrographs(4cm1spectralresolutionwitha
0.25m2theoreticalspatialpixelresolutionandanopticalresolutionofcloseto1m)of
initiatorfunctionalizedcellulose(withBiB)andPMMAxgraftedcellulose(wherexdenotes
theDPcalculatedfrom1HNMR),displayingthecarbonylregionbyintegrationoftheC=O
stretchingvibration(between17001760cm1).Regionswithdarkbluecolorrepresentlow
intensityandpinkcolordepictshighintensityregions.114

The hydrophobicity of the cellulose surface was investigated utilizing CA

measurements.TheCAisaffectedbythechemicalcompositionofthesurfaceas
well as the surface roughness. Due to the inherent surface roughness of filter
paper, it is difficult to determine absolute values; hence, the CAs are only
approximations. An applied water droplet is immediately absorbed by an
unmodified filter paper due to the hydrophilic character of cellulose. Upon the
grafting of a hydrophobic polymer, the CA is significantly increased, even for
cellulosesubstrateswithshorterpolymergrafts;e.g.,aDPofaround50resultsin
CAs of 1093 for PMMAgrafted and 1373 for PSgrafted cellulose. In fact,
shorter polymer chains may result in a higher CA due to a rougher surface,128
since longer polymer grafts tend to smoothen the surface (see Figure 10b in
section4.2),whichisalsocorroboratedbytheFTIRMresultsthatsuggestamore
homogeneous topography for longer polymer grafts. The CAs of the cellulose
substratesgraftedwithhigherDPs,e.g.,DP=384forPMMAandDP=288forPS,

33

ResultsandDiscussion

were essentially the same as for those with shorter grafts: 1122 and 1323,
respectively.

4.2 SELECTIVECLEAVAGEOFPOLYMERGRAFTS
An initiator, employed for immobilization onto cellulose prior to the grafting
reaction,wasdesignedwithadisulfidelinker(Scheme6)toallowforcleavageof
polymer grafts, as well as for an estimation of the initiator content. Mild
conditions of the cleavage reaction were a prerequisite, in order to avoid
degradationofasensitivesubstratelikecellulose,andalsotobeabletoperform
the subsequent surface analysis. The 1H NMR of the initiator CldiSBr is
presentedinFigure9.Theinitiatorwasimmobilizedfor0.25,0.50,1.0,and15hat
ambient temperature, prior to the grafting of MMA via ARGET ATRP. A
sacrificial initiator (OHdiSBr) was employed to be able to compare the
characteristics of the grafted polymers with the free polymer. The grafted
substrates were subjected to DTT to cleave the disulfide bond at ambient
temperature for five days (see Scheme 11). FTIR analyses of the cleaved
substrates showed that most polymer chains were cleaved off after only 18 h,
suggesting that the disulfide bonds are readily accessible. However, to obtain
complete cleavage, which is crucial for the following analysis, longer reaction
timescombinedwithalargeramountofDTTwererequired.

Figure 9. 1H NMR spectrum of the disulfidecontaining initiator CldiSBr employed for

immobilizationontocelluloseinCDCl3.

Theamountoftheobtainedpolymergraftswasinsufficientforprecipitation,why
crude samples were analyzed by SEC. The molar masses of the free and the
cleaved polymers are in good agreement Table 1 suggesting that the
polymerization occurs at similar rate from the surface as from the sacrificial
initiator,corroboratingthehypothesisthatgraftscanbetailoredbyemployinga

34

ResultsandDiscussion

sacrificial initiator. The free polymers have slightly higher molar masses which
are probably due to removal of low molarmass molecules during precipitation,
resultinginanoverallhigheraveragemolarmassandlowerM.

Table1.Propertiesofthefreepolymerandthecleavedgrafts,DPtarget=800.

Freepolymer

Sample
a

M
nb

b
M

Cleavedgrafts

Mnb

Mb

PMMA240

20900

1.14

19000c

1.21c

PMMA432

47000

1.18

41200c

1.22c

a PMMAx where x represents the DP calculated from the conversion obtained from 1H
NMR.bObtainedfromTHFSEC(PSstandards).cSECofacrudesample.

FESEM was employed to study the surface topography of the modified

substrates. The initiatorfunctionalized cellulose substrate displays the typical
fine structure of an unmodified cellulose substrate,Figure 10a. On the contrary,
the PMMAgrafted cellulose substrate in Figure 10b gives rise to a smoother
surface.AftercleavageofthePMMAgrafts,thefinestructureofcellulosecanbe
perceived again (Figure 10c), indicating that the grafts have been successfully
removed. The initiatorfunctionalized and DTTtreated cellulose structures are
very similar to the unmodified substrate, establishing that both treatments are
essentiallynondestructive.

Figure 10. FESEM micrographs of cellulose substrate a) initiatorfunctionalized, b)

PMMAgrafted,andc)aftercleavage,magnified10000x.26

4.3 ASSESSINGINITIATORCONTENT
After the reduction of the disulfide bonds, thiol moieties are present on the
surface, which can readily be quantified by Ellmans reagent (5,5dithiobis2
nitrobenzoicacid(DTNB)).129132ThereactionbetweenDTNBandathiolgenerates
thechromophore5thio2nitrobenzoicacid(TNB),whichabsorbsstronglyat412

35

ResultsandDiscussion

nm,providingforthepossibilitytoassesstheinitiatorcontentofthesubstratevia
UV analysis. The measured absorbance was utilized to calculate the number of
moles of thiols present on the substrate, see Table 2. To evaluate the initiator
content, the number of moles of thiols was normalized to the sample weight
(Table 2), resulting in a value of approximately 21 mol initiators per gram of
cellulose. As a comparison, the initiator content of silica nanoparticles with
various sizes has been reported to be in the range of 35 to 260 mol/g,28, 133
suggestingthatthevaluesarereasonable.Tofurtherverifytheversatilityofthis
method,microcrystallinecellulose(MCC)withanaveragediameterof20m
was utilized as an additional substrate. The initiator content was found to be
roughly twice as high as for filter papers, see Table 2. Comparatively, silica
particles in the same size as MCC, where the OHgroups were reacted with a
monofunctional silyl chloride to immobilize the initiator, have initiator contents
of135mol/g134and260mol/g27.

Theinitiatordensityofthefilterpaperwasestimatedbyemployingthespecific
surface area of cellulose, which is 0.59 m2/g according to BET measurements
reported in the literature.135 Thus, the number of moles initiator per square
centimeterofcellulosecanbeassessed,seeTable2.

The results in Table 2 also demonstrate that the immobilization of the initiator
onto the surface is a fast reaction when a large surplus of the immobilized
initiator was utilized: 1.33 mmol of CldiSBr to approximately 1 mol reacted
hydroxyl groups. After 30 min of immobilization, the initiator content on the
surfacewasessentiallythesameasafter15h.

Table2.DataassessedfromUVanalysisofthecleavedcellulosesubstrates.
Immob.
[h]

Abs.
(=412nm)

nthiols
[mol]

Sample
weight
[mg]

Initiator
content
[mol/g]

Initiator
densityb
[nmol/cm2]

Initiator0.25

0.25

0.6530.003

1.0050.004

53.9

18.60.1

3.4

Initiator0.5

0.50

0.6860.002

1.0550.003

51.2

20.60.1

3.5

Initiator1.0

1.0

0.6810.003

1.0480.005

52.0

20.20.1

3.5

PMMA240

15

0.6850.001

1.0530.001

51.1

20.60.1

3.5

PMMA432

15

0.7010.005

1.0780.008

51.3

21.00.2

3.6

MCC

3.5

0.6610.003

1.0170.004

25.6

39.70.2

Samplea

Initiatory where y represent the immobilization time of the initiator. b Calculation based
onthespecificsurfaceareaofcellulosefilterpaper:0.59m2/g.135
a

36

ResultsandDiscussion

Todeterminethenumberofavailablehydroxylgrouponfilterpaper,solidstate
NMR (CP/MAS 13C NMR) was employed, suggesting that filter paper has7.1 (
0.4)%ofavailableOHgroupswhenitisswelledinwater.136Themolarmassof
the AGU of cellulose (C6H10O5) is 162.2 g/mol. Thus, 1.0 g of cellulose contains
18.5mmolofhydroxylgroups,where1.31mmoloftheseareactive,accordingto
theNMRanalysis.Uponimmobilizationoftheinitiatorontocellulose,THFwas
employedasasolvent;thus,thecelluloseisnotasswollenasinwater,resulting
in fewer available hydroxyl groups. However, if the higher value of active OH
groupsisutilized, the initiator content of approximately 20 mol/g corresponds
to1.5%oftheavailablehydroxylgroupshavingreacted.

4.4 COMPARISONBETWEENGRAFTINGFROMAND
GRAFTINGTOCELLULOSE
The graftingfrom and the graftingto approaches both have their pros and cons,
but the general comprehension is that the surfaceinitiated polymerization, i.e.,
thegraftingfromreaction,resultsinahighergraftingdensity.12, 13, 16However,to
the best of our knowledge, a comparative study investigating this has not been
conducteduntilnow.115Thedifferenceingraftingefficiencywhengraftingfrom
celluloseviaARGETATRPandgraftingtocelluloseviaCuAACwasevaluated
byFTIRMandXPS.Thegraftingfromreactionwasperformedinparalleltothe
insitu polymerization from a sacrificial initiator with a protected alkyne
functionality.Owingtothealkynefunctionalinitiator,thefreepolymer,bearing
this functionality, can subsequently be utilized in the graftingto reaction via
conjugation to an azidefunctionalized cellulose substrate. Thus, the polymers
graftedfromandtothesurfacewereessentiallyidentical,intermsofmolarmass
anddispersity.Thiswasfurthervalidatedbyemployingthedisulfidecontaining
initiator for immobilization onto the cellulose surface, rendering cleavage and
ensuingcharacterizationofthegraftedpolymerspossible.SeeScheme14forthe
schematicsyntheticpathway.

37

ResultsandDiscussion

Scheme 14. The schematic synthetic pathway of the grafting strategy, where the freely
formed PMMA in the graftingfrom reaction was employed as the prepolymer in the
graftingtoreactionafterthedeprotectionoftheprotectedalkynefunctionalinitiator.115

4.4.1 Graftingfromandgraftingtocellulose
The grafting from cellulose and the insitu formation of the free polymer were
performedbyARGETATRPofMMA,targetingthefinalDPof1200(Scheme10).
Fourpolymerizationswereconductedat50Ctodifferentconversions:11,39,51,
and80%,inordertoobtaindifferentgraftlengths.Thesilaneprotectedalkyne
functionalinitiatorSiAlkBr,seeScheme7,wasutilizedasasacrificialinitiator.
ThefreepolymerSiAlkPMMAxBr(wherexdenotestheDPcalculatedfrom 1H
NMR)wasprecipitatedandcharacterizedwithSECtoverifythatwellcontrolled
reactions were obtained, see Table 3. The slightly higher dispersity (M) for Si
AlkPMMA960Brcanbeexplainedbythehighconversion,whichprobablyledto
a higher degree of termination, compared to the other reactions; still, the M is
below1.3.

38

ResultsandDiscussion

Table 3. Characteristics of the free polymers and the cleaved polymer grafts obtained in
thegraftingfromreactions.
Freepolymers

Cleavedpolymergrafts

Namea

p
(%)

M
(g/mol)

M
(g/mol)

Md

Namea

Mnd
(g/mol)

Md

SiAlkPMMA132Br

11

13100

21000

1.07

SHPMMA132Br

23200

1.08

SiAlkPMMA468Br

39

47500

53300

1.09

SHPMMA468Br

45600

1.10

SiAlkPMMA612Br

51

61200

69400

1.12

SHPMMA612Br

66700

1.23

SiAlkPMMA960Br

80

96600

100800

1.26

SHPMMA960Br

87400

1.31

theoc

nd

PMMAx where x represents the DP calculated from the conversion obtained from 1H
NMR. b Conversioncalculatedfrom 1HNMR. c Mtheo =DPtargetpMMMA+MSiAlkBrbased
on1HNMRconversion.dObtainedfromTHFSEC(PMMAstandards).
a

ThePMMAgrafts(SHPMMAxBr)werecleavedoffthesurface(Scheme11),and
subsequently precipitated and isolated by centrifugation, due to very small
obtainedamounts(afewmg).ThedriedpolymerwascharacterizedbySEC,and
the results compared to those of the free polymer formed from the sacrificial
initiator,seeTable3.Ascanbeseen,themolarmassesandthedispersitieswere
ingoodagreement,whichalsohasbeensuggestedbeothers,18,2628proposingthat
thegraftlengthcanbetailoredbytheutilizationofasacrificialinitiator.

The silaneprotecting group of the free polymers (SiAlkPMMAxBr) was

removed utilizing TBAF, resulting in the alkynefunctional polymers Alk
PMMAxBr(Scheme12).Thepolymerswereprecipitatedandcharacterizedwith
SEC,seeTable4.Themolarmassesforthesepreformedgraftsforthegraftingto
reaction were in the same range as the cleaved grafts from the graftingfrom
surfaces, presented in Table 3, which are of utmost importance to obtain a
systematiccomparisonofthegraftingtechniques.

ToconjugatethesepolymersontocellulosesubstratesviaCuAAC,theinitiatorCl
RBr was first immobilized onto cellulose prior to the transformation of the
brominestoazides,formingazidefunctionalizedcellulose:CelAz,seeScheme9.
The same conditions were employed as when immobilizing CldiSBr to the
surface, most likely resulting in the same amount of initiator on the cellulose
substrate. The graftingtoreaction wasperformed by utilizing Cu(II)SO4 5H2O
andNaAscinDMF(Scheme13);furthermore,asmallamountofH2Owasadded
to the solution to facilitate the dissolution of the catalyst. The polymer
concentrationwaskeptconstant(1.5mM)toobtainthesamenumberofmolesof

39

ResultsandDiscussion

alkyneendgroupsforthefourdifferentpolymerlengths(Table4).Theresulting
cellulose substrates CelAzPMMAxBr were thoroughly rinsed and
ultrasonicated to remove any polymer residues that were not covalently
conjugatedtothesubstrate.

Table 4. The polymer characteristics after deprotection of the silaneprotecting group of

thefreepolymers.
Prepolymer
Namea

Mnb
(g/mol)

Mb

AlkPMMA132Br

18500

1.07

AlkPMMA468Br

51800

1.07

AlkPMMA612Br

66700

1.06

AlkPMMA960Br

89400

1.26

PMMAx where x represents the DP calculated from the conversion obtained from 1H
NMR.bObtainedfromTHFSEC(PMMAstandards).

4.4.2

XPSanalysisofmodifiedcellulosesubstrates

ThemodifiedcellulosesubstrateswereanalyzedbyXPStoconfirmthesuccessful
reactions. In Figure 11A, the C 1s spectra of pure Whatman no. 1 filter paper is
depicted,showingmainlythethreecharacteristicspeaks:theCHandCCbonds
at 285.0 eV, the CO bond of alcohol (COH) and ether (COC) groups at 286.8
eV,and theOCO bondof acetals (and/or C=O) bonds at288.3eV.However,a
fourth peak at 289.5 eV can often be detected, corresponding to oxidation and
impurities of cellulose.112 Upon immobilization of the initiator CldiSBr the
atomic percentages of CC and CH bonds increase, and the peak at 289.4 eV,
corresponding to the ester bonds137 (OC=O) that have been introduced to the
substrate, is also enhanced, see Figure 11B. Additionally, the successful grafting
ofPMMAfromthecellulosesurfacescanalsobeconfirmed,asthecharacteristic
polymer peaks at 285.0 (CC and CH) and 289.4 (OC=O) eV significantly
increase,whichisseeninFigure11Cand11DfortheCeldiSPMMA132Brandfor
CeldiSPMMA960Br,respectively.Comparatively,uponcleavageofthepolymer
graft, the characteristic polymer peaks at 285.0 and 289.3 eV have clearly
decreased,confirmingthedetachmentofthegrafts,seeFigure11E.

40

ResultsandDiscussion

Figure 11. C 1s XPS spectra for the cellulose substrates modified via the graftingfrom
approach: (A) Pure cellulose, (B) CeldiSBr, (C) CeldiSPMMA132Br, (D) CeldiS
PMMA132Br,and(E)CelSH132.Thespectrawerenormalizedtothepeakwiththehighest
intensity.115

XPS was also performed on the cellulose substrates modified via the graftingto
approach.TheC1sspectrainFigure12showthatthepeakcorrespondingtoO
C=O is enhanced upon immobilization of the initiator ClRBr and the post
transformationofthebrominesintoazides(Figure12B),asfortheimmobilization
of the initiator CldiSBr for the graftingfrom reaction (Figure 11B). Figures 12C
and 12D depict the spectra after the conjugation reaction between the substrate
CelAzandthepolymersAlkPMMA132BrandAlkPMMA960Br,respectively.As
canbeseen,thecharacteristicpolymerpeaksat285.0and289.3eVareincreased,
confirming that the polymers have been grafted to the initiatorfunctionalized
cellulose substrate. However, the spectrum shows a high intensity of the signal
attributedtotheCObondsfromthecellulosesubstrateforCelAzPMMA132Br,
suggestingthatthecoverageofthepolymergraftsareratherinhomogeneousand
low. In comparison, for CelAzPMMA960Br the polymer signal becomes higher
thanthecellulosesignal,suggestingamorehomogeneouspolymerlayer.

41

ResultsandDiscussion

Figure 12. C 1s XPS spectra for the cellulose substrates modified via the graftingto
approach: (A) Pure cellulose, (B) CelAz, (C) CelAzPMMA132Br, and (D) CelAz
PMMA132Br.Thespectrawerenormalizedtothepeakwiththehighestintensity.115

Theratiobetweenthecharacteristiccellulosesignal(CO)andtheestersignal(O
C=O)acquiredfromXPSispresentedinTable5.Theexpectedtheoreticalratioof
1, given by the structure of the repeating unit MMA (CO/OC=O = 1/1),
corresponds to that only the polymer layer is being measured. As can be seen,
uponimmobilizationoftheinitiatorsCeldiSBrandCelAztheratiosaregreatly
decreasedcomparedtothepurecellulosesubstrate.AsPMMAisgraftedfromthe
substrate,thisratioisfurtherreducedwithincreasinggraftlength.Theratioof1.9
for CeldiSPMMA132Br suggested that the graftedpolymer chains do not cover
thecellulosesurfacecompletely.Forthelongerpolymergrafts(CeldiSPMMA468
BrandCeldiSPMMA960Br)theratiois1.2,implyingthatthecellulosesubstrate
has not influenced the measurement significantly and mainly the polymer layer
wasanalyzed.

Uponcleavage,thecellulose/polymerratio(Table5)wasincreasedandthevalues
areinthesamerangeasfortheinitiatorfunctionalizedsurfaceCeldiSBr,clearly

42

ResultsandDiscussion

proving that the polymer grafts have been cleaved off the substrates. Yet, the
slightlylowerratioforCelSH960maysuggestthepresenceofpolymericresidues.

ForthecellulosesubstratesgraftedviatheCuAAC,theratiosarenotaslowasfor
thegraftingfromsubstrates,i.e.notonlythepolymerlayerwasmeasuredbutalso
the cellulose substrate to certain extent. For CelAzPMMA132Br, the ratio is
almost twice as large as for CelAzPMMA960Br (Table 5), suggesting that the
polymer coverage is larger for the substrate with the longer grafts than for the
shortergrafts.TheratioofCelAzPMMA468Brisinbetweentheratiooftheother
grafted substrates. Thus, according to XPS, the polymer content varies slightly
betweenthesubstratesgraftedviathegraftingtoapproach.

Table 5. The ratios between the characteristic peaks of cellulose (CO) and PMMA (O
C=O),asobtainedbyXPSanalysis.
Modification

Graftingfrom

Name

CO/OC=O

Purecellulose

CeldiSI

14

CeldiSPMMA132Br

1.9

CeldiSPMMA468Br

1.2

CeldiSPMMA960Br

1.2

Aftercleavage

CelSH132

23

CelSH468

22

CelSH960

16

Graftingto

CelAz

16

CelAzPMMA132Br

2.6

CelAzPMMA468Br

1.8

CelAzPMMA960Br

1.5

80

43

4.4.3

ResultsandDiscussion

FTIRMofmodifiedcellulosesubstrates

The modified substrates were characterized with FTIRM to determine the

differences in the spatial distribution of the polymer content on the cellulose
fibers. Figure 13 depicts the FTIR micrographs of the cellulose substrates after
modificationviathegraftingfromapproach(Figure13A),afterthecleavageofthe
polymer grafts (Figure 13B), and after modification via the graftingto method
(Figure 13C). The same intensity scales for the cellulose region, 0 to 52, and the
carbonyl signal, 0.3 to 1.5, are employed for all the micrographs to ensure
comparability.ThemicrographsofCeldiSPMMAxBrinFigure13Aclearlyshow
an increased polymer signal with increasing monomer conversion, confirming
that the cellulose substrates were grafted with different graft lengths; hence,
different polymeric amounts on the cellulose substrates were attained. As the
conversion increases above 11 %, the polymer becomes more evenly distributed
over the whole fiber; however, the polymer grafts are not completelyuniformly
distributed.

The detachment of the polymer grafts from the grafted cellulose substrates was
confirmed by FTIRM. The polymer signals present in Figure 13A have
disappearedforthecleavedsubstratesCelSHx,seeFigure13B.However,forCel
diSPMMAxBr there appears to be a minor polymeric residue on the cellulose
substrate,whichalsotheXPSresultssuggest,seeTable5.

The micrographs of the cellulose substrates CelAzPMMAxBr modified via the

graftingtoapproacharepresentedinFigure13C,confirmingthattheconjugation
reaction occurred. However, the increased graft length of the prepolymer does
notresultinanincreasedcontentofpolymeronthesurfaceastheintensityofthe
carbonylsignalsisessentiallyidenticalforthefoursubstrates.Although,forCel
AzPMMA960Br, having the longest grafts, a slightly thicker and more evenly
distributedpolymerlayerwasobtainedcomparedtotheothergraftedsubstrates.
Thisindicatesthatthesurfacewiththeshortestchainshashighergraftingdensity
compared to the substrates with the longer grafts, since the total amount of
graftedpolymeronthesurfacesissimilarforallsurfaces.Thereactivesitesonthe
surfaceareprobablynotasshieldedwhenpolymerswithshortergraftlengthsare
used compared to when larger polymers are utilized. The higher accessibility
probably yields a better diffusion of the chain ends to the reactive sites on the
surface. As a comparison, the graftingfrom technique clearly results in an
increasedamountofpolymerwithincreasinggraftlength,Figure13A.Themuch
smaller monomer units, in comparison to polymer grafts, have a much better

44

ResultsandDiscussion

accessibilitytothereactivesitesonthesurfacethroughoutthereaction;thus,the
sterichindrancebecomesmuchlowerwhengraftingfromthesurface,resultingin
higher grafting efficiency. Accordingly, the obtained results suggest that the
graftingfromapproachissuperioroverthegraftingtotechnique,withrespectto
controllingthepolymercontentonthesurface.Allthesame,theresultsarevalid
under these conditions and it may be hard to generalize them to other grafting
systems,i.e.,thereactionmethodologyandthesubstrateemployedcanhavean
impact. However, the obtained result support the suggested theory with higher
graftingefficiencyforthegraftingfromreactioncomparedtothegraftingto.

45

ResultsandDiscussion

Figure13.FalsecolorhighresolutionFTIRmicrographs(4cm1spectralresolutionwitha
0.25m2theoreticalspatialpixelresolutionandanopticalresolutionofcloseto1m)of
(A)CeldiSPMMAxBrmodifiedviathegraftingfromapproach,(B)CelSHxaftercleavage
ofthegraftedpolymers,and(C)CelAzPMMAxBrmodifiedviathegraftingtoapproach,
displayingthecelluloseregionbyintegrationoftheCOvibrations(between9501200cm
1) and the carbonyl region by integration of the C=O stretching vibration (between 1700
1760 cm1). Regions with dark blue color represent low intensity and pink color depicts
high intensity regions. The images corresponding to the same sample (e.g. CeldiS
PMMA132Br)representthesamefiberregion(3232m).115

46

ResultsandDiscussion

4.5 TOWARDSINDUSTRIALGRAFTINGOFCELLULOSE
ARGET ATRP has proven to be an efficient and straightforward approach to
employ when grafting cellulose. Moreover, the low amounts of the copper
catalyst that is required result in that the free polymer formed in solution is
colorless after precipitation, see Figure 14A, without the demand for tedious
removal of copper. The grafted cellulose substrates are also visually free from
coppertracesafterthoroughwashing.Tofurtherdemonstratetheadvantagesof
ARGET ATRP, with the ambition to enable its applicability in the industry, the
polymerization was performed without any deoxygenation and with simple
reaction setups. The reactions were performed either in flasks sealed with a
septum or in conventional crme jars with screw lids, the latter exemplified in
Figure 14B. All the reactants were simply added to the reaction vessel before
sealing the system; besides, the vessel was almost completely filled with the
reaction mixture to keep the volume of free air low. The polymerizations were
performed in anisole or in bulk, where the latter can be preferable form an
industrial point of view. The various polymerization systems, employing BiB
functionalized cellulose and EBiB as a sacrificial initiator, are shown in Table 6.
Thefirstpolymerization(PMMA208),performedinanisole,showedthatevenwith
the presence of limited amounts of air, ARGET ATRP can be performed in a
controlled manner, see Table 6. The exclusion of anisole resulted in a polymer
(PMMA160) with slightly higher dispersity, but still with retained control (M <
1.3).WhenalargeexcessofAsActoCuBr2wasutilized,thepolymerizationrate
increased significantly. The formed PMMA glass (Figure 14B) was difficult to
dissolve, resulting in that the conversion could not be trustworthy measured.
However,itwaspossibletorunSEC(seeTable6,samplePMMAEx),showingthat
the reaction was not as wellcontrolled. The molar mass is higher than the
theoreticalmaximumof80300g/mol,suggestingthattheinitiatorefficiencywas
poorandthatterminationviaradicalcouplingmayhaveoccurred(seeFigure6),
also giving rise to a broad dispersity. However, a shorter reaction time might
reducetheterminationreactions,establishingbettercontroloverthesystem.

In addition, to facilitate the solubility of the CuBr2 and AsAc when performing
the reaction in bulk, a small amount of H2O was added; thus, the reaction rate
was greatly increased, see Table 6 for the reaction times and conversions. The
additionof0.1mLwaterresultedinaconversionof67%afteronly2.2handa
broadMof2.42.Whenthewateramountwasdecreasedto0.05mL,noreaction
was observed after 2.2 h, but after 15 h the conversion was as high as 89 %.

47

ResultsandDiscussion

Despiteahigherconversion,thereactionresultedinapolymerwithlowerM (<
2.0),suggestingaslightlymorecontrolledreactionwithloweramountofH2O.

AB

Figure 14. The image of A) precipitated PMMA after ARGET ATRP without copper
removalandB)ARGETATRPpolymerizationperformedinacrmejar.

Table6.ARGETATRPsystemsperformedwithoutdeoxygenation.
Samplea
PMMA208
+cellulose

Systemb

[AsAc]/
[CuBr2]

Time
(h)

pc
(%)

Mtheod
(g/mol)

Mne
(g/mol)

Me

26

26

21000

27900

1.10

10

22

20

16200

23800

1.22

80

22

137800

2.06

10

2.2h

67

53900

88000

2.42

10

15h

89

71500

105000

1.93

20gMMA
8mlAnisole
25mLFlask

PMMA160
+cellulose

25gMMA
Bulk
25mLFlask

PMMAEx
+cellulose

25gMMA
Bulk
30mLCrmeJar

PMMA536
nocellulose

25gMMA
0.1mLH2O
25mlFlask

PMMA712
+cellulose

25gMMA
0.05LH2O
30mLCrmeJar

PMMAx where x represents the DP calculated from the conversion obtained from 1H
NMR. b System: [MMA]:[EBiB]:[Cu(II)Br2]:[PMDETA] = 800:1:0.1:1, 40 C. c Conversion
calculatedfrom1HNMR.dMtheo=DPtargetpMMMA+MEBiBbasedon1HNMRconversion.e
ObtainedfromDMFSEC(PMMAstandards).
a

48

ResultsandDiscussion

FTIRmeasurementsverifiedthesuccessfulgraftingreactionandshowedthatthe
polymeric amount of PMMA208 and PMMA160 on filter paper was very similar,
whereas it was much larger for PMMA712 and even larger for PMMAEx. For
PMMA536withthehigherwateramount,nocellulosesubstratewasadded.

Toconclude,furtherdevelopmentstoimprovethestraightforwardsystemsneed
to be conducted, however, the first trial that were performed suggested that
ARGET ATRP can indeed be an interesting method to employ industrially.
Noteworthy, from an industrial point of view, simple and straightforward
systemscanbemoreimportanttoachievethanwellcontrolledreactions.

49

Conclusions

5.CONCLUSIONS
To expand the application area of cellulose and to meet the demand for new
environmentally friendly materials, modification of cellulose is a prerequisite.
The focus of this study has therefore been to achieve valid fundamental
knowledge about the cellulose modification via wellcontrolled grafting
processes.Moreover,experimentshavebeenconductedwiththeaimtofacilitate
theemploymentofARGETATRPindustrially.

Cellulose has successfully been grafted via surfaceinitiated ARGET ATRP of

variousmonomers:MMA,St,andGMA,confirmedbyFTIR.CAmeasurements
suggested that the length of the polymer grafts does not significantly affect the
value of the contact angles, and even short graft lengths greatly enhance the
hydrophobicityofcellulose.

Highresolution FTIRM imaging was demonstrated to be a very useful method

for studying the spatial distribution of the polymer content on the cellulose
substrate. The polymer content increased with increasing graft length, and the
distribution of the polymer on the cellulose fiber was shown to be rather
homogenous,eventhoughsomesmallerareascontainedmorepolymer.

An initiator with a cleavable disulfide linker was successfully synthesized and

immobilizedontocellulose,renderingtheensuingcleavageofthepolymergrafts
possible. The molar masses and dispersities of the grafts were comparable to
valuesofthefreepolymersformedinparalleltothegrafting,suggestingthatthe
polymerization from the surface and in the solution proceeded with similar
kinetics, confirming that the grafts can be tailored by utilizing a sacrificial
initiator. Moreover, FESEM results confirmed that the cleavage was
accomplishedinanondestructivemanner,keepingthecellulosesubstrateintact,
rendering the characterization of the initiator content possible by employing
Ellmansreagent.Thus,theinitiatorcontent(inmol/gcellulose)onfilterpaper

50

Conclusions

as well as on MCC was efficiently assessed, also demonstrating that the

immobilization of the initiator to the surface is a fast reaction. The number of
active OHgroups of waterswelled cellulose was also determined by solidstate
NMR.

The two grafting techniques, graftingfrom via ARGET ATRP and graftingto via
CuAAC,weresystematicallycomparedbyensuringthatthegraftlengthswerein
the same range for the two methods. The successful grafting via ARGET ATRP
and CuACC was confirmed by XPS and FTIRM analyses. Under the selected
condition, it was verified that the graftingfrom technique is superior to the
graftingto approach with respect to controlling the polymeric amount on the
surface.Atthesametime,itisimportanttonotethatthepresentresultsshould
notbegeneralizedtoallgraftingtovs.graftingfromcomparisons.

ARGETATRPhastheadvantagesofrequiringonlysmallamountsofthecopper
catalystandnodeoxygenationstep;yet,providingforwellcontrolledreactions.
The straightforward system was performed with reduced requirements of
advancedreactionsvesselsandoforganicsolvents.Furthermore,thereactionrate
wasincreasedbytheadditionofasmallamountofwatertothebulksystemof
the waterinsoluble monomer, aiding the dissolution of the copper complex.
TheseadvantagescanrenderARGETATRPtoanindustriallyacceptablemethod.

51

Futurework

6.FUTUREWORK
Grafting of polymers has the potential to be an applicable method for the
modificationofcellulose,withthepurposeofutilizingcelluloseinawiderrange
of products, including more advanced applications. To facilitate the industrial
scaleup, certain improvements of the reaction conditions can be of importance,
such as the immobilization of reactive sites prior to the grafting. A milder
immobilization reaction, compared to the employment of an acid halide, that
preferablecanbeperformedinwaterissomethingtostriveforandtoinvestigate
morethoroughly,aswellastheARGETATRPgraftingsystem,wheremoretrials
andfinetuningneedtobeperformed.

Modifiedcelluloseis,asdiscussed,acomplicatedsubstratetocharacterizedueto
the surface roughness. Therefore, it could be significant to perform the grafting
and cleavage of polymer grafts via the disulfide linker from wellstudied, less
complex,andflatsubstrateslikesiliconwafers.Moreover,thecomparativestudy
of the graftingfrom and graftingto methods could also be interesting to
investigatewhenemployingthesetypesofsurfaces.

The versatility of surface modification can be explored by introducing more

specific functionalities to the cellulose substrates, aiming for the employment of
cellulose in more advanced applications, such as sensors and biomedical
applications.

It is also worth to investigate the production of (bio)composite materials with

modified and tailored cellulose fibers as fillers, aiming towards largescale
productionofbettermaterialscontaininglesspetroleumbasedcomponents.

52

Acknowledgements

7.ACKNOWLEDGEMENTS
Firstofall,IwanttoexpressmysinceregratitudetomysupervisorProf.EvaMalmstrm
foracceptingmeasherPh.D.student.Thankyouforyourendlesssupportandforalways
taking your time despite your fullybooked calendar. Your passion about science has
alwaysinspiredmeandhelpedme.Ialsoappreciateyourfriendship,theniceatmosphere
youcreateinYmpgruppen,andallthepleasantsummerdinners.Mysecondsupervisor
Ass. Prof. Anna Carlmark Malkoch is sincerely acknowledged for all the help and
encourage shehas given me throughout the years. Your positive energyandfriendliness
canbrighten upabaddayinthelab.Thanksalsoforsharingthe hotelroomwithme in
DenverandforlaughingatallthecrmesthatIhadbroughtwithme.Dr.Emmastmark
isalsogreatlythankedforhersupervisionofmyfirstyearsandforallthehelpafterthat.
You are a genuinely friendly person and devoted to whatever you are working with.
ThanksalsofortheinterpretationoftheNMRforestofisosorbide.Dr.LindaFogelstrm
isacknowledgedforallhersupervision,eversinceIwasamasterstudent.Youhavereally
taughtmemuch,especiallyhowreportsshallbewritten,andcorrected!Youhavebeena
significantsupportduringmytimeasaPh.D.student(especiallythelastweeks).Thanks
foryoursweetfriendship,yourthoughtfulness,andforalwaysbeinginsuchagoodmood.
Prof.AndersHultisthankedforcreatingthegreatworkingatmosphereinYtgruppen
andforunderstandingtheimportanceofahighEQvs.ahighIQ.Prof.MatsJohanssonis
acknowledgedforscientificdiscussionsandforhisenthusiasmaboutwinningovermein
Wordfeud.Ass.Prof.MichaelMalkochisthankedforyourgreatknowledgeaboutorganic
chemistry,andthecoffeemachine.
Wilhelm Beckers Jubileumsfond and the Swedish Research Council (Vetenskapsrdet)
are greatly acknowledged for financial support. The VINN Excellence Centre BiMaC
Innovationisthankedforcontributingtoscientificknowledgeanddiscussions,allowingfor
the opportunity to find new collaborations. The Karlsruhe House of Young Scientists
(KHYS)andKTHtravelgrantsarethankedforfinancingmyKITvisit.KTHTravelgrants
arealsoacknowledgedforfinancingconferencetrips.
Prof.ChristopherBarnerKowollikisacknowledgedforlettingmeworkinhisgroup,for
allthesupportanddiscussions,andfortheveryfruitfulcollaborations.Mycoauthorsand
friendsAnja,Thomas,andVanessaaregreatlythankedfortheireffortandfriendliness.I
would also like to acknowledge Michael (and Ronja), Corinna, Elise, Kim, Jan, Bernhard,
Lukas, Natalie, Andrew, Guillaume, Christiane, Elena, Alex H, Alex Q, Anna, Kristina,

53

Acknowledgements

Nicolas, Mathias, zcan, and all the other people in the Macroarc group for making my
KAvisitnotonlyscientificallyproductivebutalsosofabulousandfun.Jawohl!
Assoc.Prof.TomasLarsson,atInnventiaandWWSC,issincerelythankedforhelpwith
solidstateNMRmeasurementsandvaluablediscussions.
AllformerandpresentfriendsandmembersofYtgruppenarethankedforcreatinga
greatteamspiritandsupportiveclimatecombinedwithalotoffunat,andafter,work.I
will really miss this amazing working place! Thanks to Linn for being an extraordinary
friend,forthesongwriting,andforlovingvallekenasmuchasme;SaraO.foryourdear
friendship,foryouknowwhat,andforourcozytapasnights;Yvonneforyourkindness,
allthelaughter,andforturningmeintoatrueFriluftsnrd;Janforbeingsweeterthan
sugar, for how you express your love, and for all gosigos; Robert for all the hugging,
yourfunnystories,andforbeingtrulyawesome;Camillaforbeingsosweetandfriendly
and for all the fun pptpresentations; Pontus for everything you trusted me with (SEC,
forskarskolan), for being sexysmart, and for our great future plans; Hanna L. for
provingthatyoucanbebothblondandsmartandforallthedancinginthelab,Maribel
for being so lovely and for the SwedishSpanish wordexchange that I will not mention
here; Lina E. for having the guts of following your heart and for the great time we had;
Markusforourrawbuttenderhumor,ournicechats,andforyourspecialkickingskills;
Kim for our Pershagenconnection, for appreciating my modesty, and for flexing your
twins, Christian for being my excellent master student, for talking more and faster than
me, and for your social skills; Emma L. for all the time we spent with the SEC and for
eating, and enjoying, the white part of the clementine; Carl for the closetodeathby
laughterexperienceintheelevatorandforallthegreat recipes;Assyaforbeingasweet,
funny, and very wood girl, and for letting me know that you actually can be angry
sometimes;AlirezaforbeingagreatroommateandforbeingthethoughtfulAlibubu;
Tingforliterallyflushingdownmyproblemsinthetoiletandforsayingsomanyfunny
things; Martin for coming back to KTH and for being positive and happy all the time;
Kristina for your smiling and for understanding the fun about finding a horse in the
storageroomforbikes;Marieforbeingsmartandforlovinghearingmesaysacrebleu;
Emelie for being neat and for taking over my legendary fume hood; Mauro for poring
sugar on my already sweet cinnamon buns; Hui for lending me her fume hood the last
weeks; Daniel for introducing me to the wonderful world of ATRP; Pelle for the nice
collaboration; Helena almost a member of Ytgruppen for helping me with the
calibrationcurves;StacyforhelpingmewithEllmansregent;Petraforbeingsonice,calm,
andcool;SaraK.forheroccasionallybutverypleasantvisits;Niklasforyourcharacteristic
click sounds; Mange for being Mange; Kattis for the nicely coated metal roof you left
behind;Josefinaforpavingthewayformyproject;Susanaforjoiningthehiking;Oliverfor
helping me with computer issues; Carmen for you enthusiasm, and Eric for the nice
Spanish breakfast. Former members and diploma and project workers are also thanked,
especially,Amanda,AnnaA.,Axel,Chung,Dahlia,HannaLa.,Jocke,Jesper,andTobias,
forcontributingtothegreatatmosphere.TheformerandpresentPFpeopleBella,Kristin,
Jonas,andShamsarethankedforyourimportantandpleasantpresencehere.
Allseniors,employees,andfriendsatthedepartmentofFiberandPolymerTechnology
are acknowledged, especially Prof. Lars W., Assoc. Prof. Anna F. W., Inger, Inga, Mia,

54

Acknowledgements

Bosse,Simon,MikaelaH.,AnnaS.,Louise,Dimitri,AndreasF.,Nicholas,Caroline,Emil,
PontusO.,AndersH.,KarinO.,Sofia,Jens,Anas,Nina,Lidija,JennyU.,ThomasB.,Emma
S.,MichaelaS.,Fritjof,Torbjrn,PerL.,andJoby.
Mngatackgrventillminaunderbaravnneruteidenstoravidavrldenfrattni
alltidfinnsdrfrmig.lskadeViveka,vadvorelivetutanvragemytligapromenader,
allt tedrickande och alla loppisfynd?! Dtrist! Lisa, min kraste partypingla, tack fr allt
roligtochmysvihaftochfrattdusddefrettillminkrlektillhavet!Ellimammas
lilla hjrtegull vi har upplevt mnga stadier i livet tillsammans, tack fr att du alltid
funnitsvidminsidaivttochtorrt.Lina,minbarndomsvn,duharbetyttmycketunder
min uppvxt och det gr du fortfarande, tack fr allt! Frida, tack fr att vi kan dela alla
fantastiskaochroligaminnenfrnenavdebstaupplevelsernajaghaft.sa,tackfratt
dufrgylldeminafrsta4.5rpKTHmedallabrasamarbetenochalltkul.StisTomas,
tackbl.a.fralltmysmedkoppisocharkis.TackgoastepapiHenrikochfavoritbarnet
Adrianafralltroligtvihaftunderochefterforskarskolan.Tackventillejnmndamen
ickeglmdavnner!
Stort tack gr till min lilla men fantastiska familj och slkt. Bsta mamma och pappa,
tackfrerondligakrlek,fralltstdochfrattniskmmerbortmigprttstt.Min
krasysterLindatackasfralltkrleksgnabbandesgenomren,fralltkulvihaftochfr
attdurminbstavn.Utanerhadeinteminvrldvaritsfantastisksomdenridag.Jag
lskarer!TackventillLindasbstabihangAndreasfrdinhumorochfrdugjortmig
till kattmoster. Tack farfar fr att du r en sdan fantastisk, rolig och trevlig kta
gentleman.Siv,jaguppskattarverkligenattjagharfttlraknnadig.Brje,tackfrdin
vrme och vnlighet. Mormor, morfar, farmor och Rut jag saknar er tack fr all er
krlekunderminuppvxt!
Sistmeninteminst,jagharmycketatttackaforskarskolanfrRickard,jagrsglad
attvitrffades.Dugrmigsgladochlycklig!!!Tackfrattdursunderbarpallastt
ochvis,frallaskratt,frattdukanfmigattkopplaav(vilketrenstorbedrift)samtfr
allt kul som du vill gra ihop med mig! Ngon gng ska vara den frsta, s varfr inte
hrJaglskardig!!!

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