SURFACEMODIFICATIONOFCELLULOSEBY

COVALENTGRAFTINGANDPHYSICAL
ADSORPTION

LinnCarlsson
DoctoralThesis

AKADEMISKAVHANDLING

sommedtillstndavKungligaTekniskahgskolaniStockholmframlggs
tilloffentliggranskningfravlggandeavtekniskdoktorsexamenfredagen
den 21:a februari 2014, kl. 10:00 i Kollegiesalen, Brinellvgen 8, KTH,
Stockholm. Avhandlingen frsvaras p engelska. Fakultetsopponent:
Professor Mohamed Naceur Belgacem, Ecole Internationale du Papier, de
la communication imprime et des biomatriaux, Grenoble INP Pagora,
France.

Copyright2014LinnCarlsson
Allrightsreserved

PaperI
PaperII
PaperIII
PaperV

2012AmericanChemicalSociety
2012TheRoyalSocietyofChemistry
2013AmericanChemicalSociety
2012TheRoyalSocietyofChemistry

TRITACHEReport2014:2
ISSN16541081
ISBN9789175019871

ABSTRACT
The interest in new environmentally friendly cellulosebased products
has increased tremendously over the last years. At the same time the
Swedish forest industry faces new challenges in its strive to increase the
utilization of cellulose fibers in highvalue endproducts. The aim of this
study was to expand the toolbox for surface modification of cellulose by
employing covalent surfaceinitiated (SI) polymerizations or by physical
adsorptionofpolymers.
SIringopening polymerization (ROP) of caprolactone (CL) was
performed from filter paper (FP) and high surface area nanopaper (NP).
Larger amounts of polycaprolactone (PCL) were grafted from NP,
compared to FP, owing to the higher amount of available initiating
hydroxyl groups. Furthermore, the mechanical properties of PCL were
improvedbythegraftingofFPandNP,ascomparedtopurePCL.
Itischallengingtocharacterizeapolymergraftedfromasurface.Hence,
quartz crystal microbalance with dissipation (QCMD) was employed to
investigateSIROPinrealtimefromacellulosemodelsurface.
Furthermore,itwasshownbycolloidalprobeAFMthatincreasedlength
of grafted PCL, from cellulose microspheres, improved the interfacial
adhesiontoapurePCLsurface,suggestingthatchainentanglementshave
a significant impact on the interfacial properties. Increased temperature
andtimeincontactalsoimprovedtheadhesion.
Inordertoinvestigatethedegreeofsubstitution(DS)andthedegreeof
polymerization (DP), PCLgrafted hydrolyzed cellulose cotton linters
(HCCL)werestudiedbysolidstateNMR.ItwasfoundthatdespiteaDSof
only a few percent, the surface character changed considerably;
furthermore,the DS was virtuallyindependent of the DP. Toincrease the
amount of grafted polymer, ringopening metathesis polymerization
(ROMP) of norbornene was performed from FP. Short polymerization
timesandlowtemperaturesresultedinhighlygraftedsurfaces.
Alternatively, physical adsorption by electrostatic interactions was
employed to modify a cellulose model surface in the QCMD. Cationic
latexnanoparticlesofpoly(dimetylaminoethylmethacrylatecomethacrylic
acid)blockpoly(methyl methacrylate) were produced by reversible
additionfragmentation chaintransfer (RAFT)mediated surfactantfree
emulsionpolymerizationbypolymerizationinducedselfassembly(PISA).
This strategy does not require any organic solvents and could potentially
beintroducedinindustrialprocesses.

SAMMANFATTNING
Intresset fr nya miljvnliga cellulosabaserade produkter har kat
markantdesenasteren.Dettasamtidigtsomdensvenskaskogsindustrin
str infr nya utmaningar i sin strvan att ka anvndningen av
cellulosafibrerifrdladeprodukter.Syftetmeddennastudievarattutka
verktygsldan fr ytmodifiering av cellulosa via kovalent ytinitierade
polymerisationerellergenomfysikaliskadsorptionavpolymerer.
Ytinitierad ringppningspolymerisation av kaprolakton utfrdes frn
filterpapper (FP) och nanopapper (NP) med hg ytarea. NP gav strre
ympad mngd p grund av fler initierande hydroxylgrupper. De
mekaniska egenskaperna av polykaprolakton (PCL) frbttrades vid
ympningen frn FP och NP jmfrt med en ren PCL matris och
fuktadsorptionen reducerades avsevrt i jmfrelse med omodifierade FP
ellerNP.
Det r en stor utmaning att karakterisera ympade polymerer, drfr
utvecklades en metod dr ytinitieradROP frn en cellulosamodellyta
studerades med en kvartskristallmikrovg med dissipation (QCMD).
Atomkraftsmikroskopimedkolloidalsondvisadeattkadympningslngd
av PCL frbttrade vidhftningsfrmgan, vilket indikerar att
kedjeintrasslingarharensignifikantpverkanpgrnsskiktsegenskaperna.
kad temperatur och kontakttid resulterade ocks i kad
vidhftningsfrmga.
Frattutredainverkanavdenympadepolymerisationsgraden(DP)och
substitutionsgraden (DS) studerades PCLympade hydrolyserade
cellullosabomullslinters med fastfasNMR. Studierna visade att trots lg
substitutionsgrad (ngra f procent) s ndrades ytkaraktren signifikant
ochsubstitutionsgradenvarrelativtkonstantoberoendeavDP.
Fr att ka mngden ympad polymer utfrdes ringppnings
metatespolymerisation (ROMP) frn FP. Korta reaktionstider och lga
polymerisationstemperaturerresulteradeikraftigtympadeytor.
Fysikalisk adsorption genom elektrostatiska interaktioner anvndes fr
att modifiera en cellulosamodellyta i en QCMD. Katjoniska
latexnanopartiklar av sampolymeren poly(dimetylaminoetylmetakrylat
metakrylsyrametylmetakrylat) syntetiserades med reversibel additions
fragmenteringskedjeverfringsmedladtensidfriemulsionspolymerisation
genom polymerisationsinducerad sjlvorganisation. Denna strategi
krveringaorganiskalsningsmedelochharpotentialattkunnatillmpas
iindustriellaprocesser.

LISTOFPAPERS
Thisthesisisasummaryofthefollowingpapers:
I.

Facile Preparation Route for Nanostructured Composites: Surface

Initiated RingOpening Polymerization of Caprolactone from High
SurfaceAreaNanopaper,A.Boujemaoui,L.Carlsson,E.Malmstrm,
M. Lahcini, L. Berglund, H. Sehaqui, and A. Carlmark, ACS Applied
MaterialsandInterfaces2012,4,31913198

II. Surfaceinitiated ringopening polymerization from cellulose model

surfacesmonitoredbyaQuartzCrystalMicrobalance,L.Carlsson,S.
Utsel,L.Wgberg,E.Malmstrm,andA.Carlmark,SoftMatter2012,8,
512517

III. NanobiocompositesAdhesion:RoleofGraftLengthandTemperature
in a Hybrid Biomimetic Approach, N. Nordgren, L. Carlsson, H.
Blomberg, A. Carlmark, E. Malmstrm, and M. W. Rutland,
Biomacromolecules2013,14,10031009

IV. SolidStateNMRinvestigationofhydrolyzedcottonlintersgraftedby
surfaceinitiated ringopening polymerization of caprolactone, L.
Carlsson,P.T.Larsson,T.Ingverud,H.Blomberg,A.Carlmark,andE.
Malmstrm,Manuscript

V. Surfaceinitiated ringopening metathesis polymerisation from

cellulosefibres,L.Carlsson,E.Malmstrm,andA.Carlmark,Polymer
Chemistry2012,3,727733

VI. Modification of cellulose surfaces by cationic latex prepared by

RAFTmediatedsurfactantfreeemulsionpolymerizationL.Carlsson,
A. Fall, I. Chaduc, L. Wgberg, B. Charleux, E. Malmstrm, F.
DAgosto,M.Lansalot,andA.Carlmark,Manuscript

Mycontributiontotheappendedpapers:

I.
Part of the experimental work, analyses, and minor part of the
preparationofthemanuscript.
II.
A majority of the experimental work, analyses, and most of the
preparationofthemanuscript.
III.
Part of the experimental work, analyses, and minor part of the
preparationofthemanuscript.
IV.
Partoftheexperimentalwork,partoftheanalyses,andmostofthe
preparationofthemanuscript.
V.
All the experimental work and analyses, and most of the
preparationofthemanuscript.
VI.
Alltheexperimentalwork,amajorityoftheanalyses,andmostof
thepreparationofthemanuscript.

Scientificcontributionsnotincludedinthisthesis:
VII.
Aligned Cellulose Nanocrystals and Directed Nanoscale
DepositionofColloidalSpheres,G.Nystrm,A.Fall,L.Carlsson
andL.Wgberg,submitted

VIII.
Nanohybrid selfcrosslinked PDMA/silica hydrogels, L.
Carlsson, S. Rose, D.Hourdet, A.Marcellan, SoftMatter 2010, 6,
36193631

ABBREVIATIONS

AGU
AFM
AIBA
ATR
BCN
BET
CA
CCL
CL
CMC
CMS
CNC
CP/MAS
CNF
CTPPA
dL
M
DCM
DLS
DMAEMA
DMAP
DMF
DMSO
DP
DS
DSBM
DSSP
DSC
DVS
FESEM
FRP
FTIR
HCCL
MAA

anhydroglucoseunit
atomicforcemicroscopy
2,2azobis(2methylpropionamidine)
dihydrochloride
attenuatedtotalreflectance
bacterialcellulosenanofibers
BrunauerEmmettTeller
contactangle
cellulosecottonlinters
caprolactone
criticalmicelleconcentration
cellulosemicrosphere
cellulosenanocrystals
crosspolarizedmagicanglespinning
cellulosenanofibers
4cyano4thiothiopropylsulfanylthiocarbonyl
lateraldimension
molarmassdispersity
dichloromethane
dynamiclightscattering
N,Ndimethylaminoethylmethacrylate
4(dimethylamino)pyridine
N,Ndimethylformamide
dimethylsulfoxide
degreeofpolymerization
degreeofsubstitution
bulkmonomerdegreeofsubstitution
particlesurfacedegreeofsubstitution
differentialscanningcalorimetry
dynamicvaporsorption
fieldemissionscanningelectronmicroscopy
freeradicalpolymerization
Fouriertransforminfrared
hydrolyzedcellulosecottonlinters
methacrylicacid

MMA
NBE
NMMO
NMR
PdI
PEG
PET
PISA
PS
PVAm
QCM
RAFT
RDRP
RH
ROMP
ROP
Rq
RT
SEC
SI
Sn(Oct)2
SSA
TBD
Tc
TEM
TGA
Tg
Ti(OiPr)4
Ti(OnBu)4
UV
Xc

methylmethacrylate
norbornene
NmethylmorpholineNoxide
nuclearmagneticresonance
polydispersity(DLS)
poly(ethyleneglycol)
polyelectrolytetitration
polymerizationinducedselfassembly
polystyrene
poly(vinylamine)
quartzcrystalmicrobalance
reversibleadditionfragmentationchaintransfer
reversibledeactivationradicalpolymerization
relativehumidity
ringopeningmetathesispolymerization
ringopeningpolymerization
surfaceroughness
roomtemperature
sizeexclusionchromatography
surfaceinitiated
tin2ethylhexanoate
specificsurfacearea
1,5,7triazabicyclo[4.4.0]dec5ene
crystallizationtemperature
transmissionelectronmicroscopy
thermogravimetricanalysis
glasstransitiontemperature
titaniumipropoxide
titaniumnbutoxide
ultraviolet
degreeofcrystallinity

TABLEOFCONTENTS
1. PURPOSE OF THE STUDY

2. INTRODUCTION

2.1CELLULOSE.................................................................................................. 2
2.1.1 Structure of cellulose ......................................................................... 2
2.1.2 Cellulosic substrates .......................................................................... 4
2.1.3 Surface modification of cellulose....................................................... 6
2.2 RING-OPENING POLYMERIZATION TECHNIQUES ........................................... 9
2.2.1 Ring-opening polymerization (ROP) ................................................. 9
2.2.2 Ring-opening metathesis polymerization (ROMP) .......................... 12
2.3REVERSIBLE ADDITION-FRAGMENTATION CHAIN-TRANSFER (RAFT)
POLYMERIZATION ..................................................................................... 14
2.3.1 RAFT-mediated surfactant-free emulsion polymerization ............... 17
2.3.1.1 Polymer-induced self-assembly ....................................................... 19
2.4SURFACE MODIFICATION OF CELLULOSE BY COVALENT GRAFTING ............ 21
2.5SURFACE MODIFICATION OF CELLULOSE BY PHYSICAL ADSORPTION ......... 23
3. EXPERIMENTAL

26

3.1MATERIALS ............................................................................................... 26
3.2EXPERIMENTAL PROCEDURES .................................................................... 27
3.2.1 Cellulose surface modification by ring-opening polymerization ..... 27
3.2.2 Cellulose surface modification by ring-opening metathesis
polymerization ................................................................................. 28
3.2.3 Synthesis of cationic latex nanoparticles ......................................... 29
3.2.3.1 Aqueous RAFT polymerization of DMAEMA .................................. 29
3.2.3.2 RAFT-mediated surfactant-free emulsion polymerization of MMA . 30
3.2.3.3 Adsorption of cationic latex on cellulose model surfaces ................ 31
3.3CHARACTERIZATION METHODS ................................................................. 31
3.3.1 QCM-D ............................................................................................ 31
3.3.2 Colloidal probe AFM....................................................................... 32
3.3.3 Solid state CP/MAS 13C-NMR.......................................................... 32
4. RESULTS AND DISCUSSION

33

4.1CELLULOSE SURFACE MODIFICATION BY COVALENT GRAFTING ................ 33

4.1.1 Cellulose surface modification by ring-opening polymerization ..... 33
4.1.1.1 SI-ROP of -CL from FP and NP. Comparison between Sn(Oct)2 and
Ti(OnBu)4 ........................................................................................ 33

4.1.1.2 Monitor grafting of -CL from a cellulose model surface in QCM-D

......................................................................................................... 37
4.1.1.3 PCL-grafted cellulose microspheres Impact of graft length and
temperature on interfacial adhesion a study by colloidal probe by
AFM................................................................................................. 41
4.1.1.4 Solid state CP/MAS 13C-NMR investigation of HCCL grafted by SIROP of -CL .................................................................................... 45
4.1.2 Cellulose surface modification by ring-opening metathesis
polymerization (ROMP) .................................................................. 50
4.2MODIFICATION OF CELLULOSE SURFACES BY PHYSICAL ADSORPTION ....... 53
4.2.1 Synthesis of cationic latex nanoparticles......................................... 53
4.2.1.1 RAFT-mediated surfactant-free emulsion polymerization of MMA. 54
4.2.2 Adsorption of cationic latex on cellulose model surfaces................ 57
5. CONCLUSIONS

61

6. FUTURE WORK

63

7. ACKNOWLEDGEMENTS

65

8. REFERENCES

67

PURPOSEOFTHESTUDY

1. PURPOSEOFTHESTUDY
The interest in designing and developing new, more environmentally
friendly materials from cellulose has increased immensely in the last
years. Cellulose has several interesting properties, e.g., high stiffness
and low density compared to commonly employed glass fibers, but
cellulose is also highly hygroscopic, as a result of the large number of
hydroxyl groups. These can in turn be readily utilized for surface
modification; hence, the cellulose properties can be tailored and new
functionalities introduced, improving the compatibility with nonpolar
polymermatricesforexample.

The purpose of this study was to expand the toolbox for surface
modificationofcelluloseandtherebypossiblyincreasetheutilizationof
cellulosebased materials. Different techniques were employed to
achieve a better fundamental knowledge of surface modification by
polymers and its effect on the surface properties. Surface modification
hasbeenperformedbycovalentgraftingandphysisorptionofpolymers.
The polymers have been synthesized by controlled polymerization
techniques.

INTRODUCTION

2. INTRODUCTION

2.1 CELLULOSE
Celluloseisoneofourmostabundantpolymersonearth.Thepolymer
is renewable, biocompatible, biodegradable, and inexpensive, and has
bothinterestingphysicalandchemicalproperties.1,2Thecellulosefibers
havebothlowdensityandhighstrength.Themodulusofthecellulose
crystal is 138 GPa, which can be compared to steel with a modulus of
200 GPa.3 The production of cellulose is mainly performed in plants,
e.g.,flax,hempandjute.4However,therearealsoseveralothersources
of cellulose, e.g., wood, which has a dry content of 40 % cellulose.5 In
addition, wood contains significant amounts of lignin and different
typesofhemicelluloses.5Therefore,thecelluloseneedstobeisolatedby
separation from the other components prior to utilization. Bacteria,
algae,andfungicansynthesizecellulosewithhighpurity,crystallinity,
and very specific morphologies can be obtained.6 The total annual
productionofcelluloseisestimatedtobeover7.51010tons.1

2.1.1 Structureofcellulose
Cellulose is a linear, polydisperse biopolymer; exhibiting an advanced
hierarchical structure that can be attributed to the hydrogen bonds
betweenthehydroxylgroups.Thedegreeofpolymerization(DP)varies
between3001,700forwoodfibersand80010,000forcottonandother
plants,dependingonoriginandtreatmentofthecelluloserawmaterial.4

Thecellulosefibersarelocatedinthecellwallofplantsandarebuiltup
of aggregates of microfibrils, see Figure 1. The bundle of microfibrils
contains3040cellulosechainswithdifferentorientationsandisformed
by extended cellulose macromolecules that are organized in sheets
withbothcrystallineandamorphousregionswhicharestabilizedby
intraandintermolecularhydrogenbonding.4,7

INTRODUCTION

Figure1.Hierarchicalstructureofcellulose;fromthetreeonamacroscopicscale
down to the cellulose macromolecule on nanoscale with length (L) and lateral
dimension (dL).4, 7 The schematic picture is adopted from Isogai et al.7 and
Hansson8.

ThebiopolymerconsistsofDglucosylunitsthatarelinkedtogetherby
1,4glycosidic bonds. Each repeating unit in cellulose contains two
anhydroglucose units (AGU). The AGU, see Figure 2, has three
hydroxyl groups with a primary hydroxyl group at the carbon 6 (C6)
positionandtwosecondaryhydroxylgroupsattheC2andC3positions,
respectively. Every second repeating unit is rotated 180 in the plane.
Cellulose is highly hydrophilic owing to the numerous hydroxyl
groups;however,thestronginterandintramolecularbondingrenders
celluloseinsolubleinwater.Theexceptionalmechanicalpropertiesand
the lack of a melting point can also be ascribed to these hydrogen
bonds.9
OH
6
OH
4
O
1 O
5
HO 3
O
2
2
n
HO 3
5
1 O
4
O
OH
6
OH

Figure 2. Numbering of the carbon atoms in a repeating unit of cellulose (two

AGU)ofthecellulosechain.

INTRODUCTION

2.1.2 Cellulosicsubstrates
Cellulosecanbedividedintogroupsdependingonitscrystalstructure.
The naturally occurring cellulose is denoted celluloseI where the
polymer chains are organized in a parallel arrangement. However, by
treatmentofcelluloseI,themostthermallystablestructure,celluloseII,
isobtainedbychangeoftheorganizationofthemacromolecularchains
to an antiparallel arrangement. The transformation can be performed
by conc. alkali aqueous solution or by regeneration from solutions or
semistablederivatives.RegeneratedcellulosehasaDPof250500.The
viscous process was developed over 100 years ago to regenerate
cellulosic fibers.4 This technique has been employed to produce fibers,
films, membranes, sponges, and spheres. However, the method suffers
from major disadvantages since it requires hazardous chemicals and
onlyhighlypurepulpscanbeutilized.Animportantbreakthroughfor
theregeneratedfiberswastheLyocellprocesswherethecellulosefibers
successfullyweredissolvedinNmethylmorpholineNoxide(NMMO)
andthereafterspun,formingregeneratedfibers.10Inthisprocess,almost
allemployedsolventscanberecycledandtheenvironmentalimpactis
low. By employing the Lyocell process, Wgberg et al.11, 12 have
developed cellulose model surfaces. These surfaces are smooth, have
goodstabilityindifferentsolventsandthethicknessofthefilmscanbe
tuned, rendering the surfaces suitable for highresolution techniques,
suchasatomicforcemicroscopy(AFM)andquartzcrystalmicrobalance
withdissipation(QCMD).13

The nanocelluloses are produced by disintegration of the wood fibers,

smaller fibrils can be liberated which increases the available surface
area.14 For a summary of the characteristics for the most common
nanocelluloses,seeTable1.MicrographscanbeobservedinFigure3.

Figure 3. TEM images of a) CNF,15 b) CNC,16 and c) SEM image of BNC.14

Reprintedwithpermissionfrom(Klemm,D.etal.,Angew.Chem.,Int.Ed.201150
p.54385466).Copyright(2011)GermanChemicalSociety.

INTRODUCTION

Table1.CC

INTRODUCTION

CNFandtheothernanocellulosesarealreadycommercializedinseveral
products,e.g.,absorbentmaterialinhygieneproducts,foodadditives,
cosmetics,andpharmaceuticals.17CNFhaverecentlybeenemployedfor
producingnanofoams,18,19hydrogels,20nanopapers,21,22andaerogels23.
Cellulose cotton linters (CCL) are short (26mm), slightly curled,
cylindrically shaped fibers with widths of 1727m.24 Furthermore,
CCL possess higher crystallinity and smaller lateral dimensions of the
microfibrilscomparedtocellulosefromwoodfibers.4HighqualityCCL
are utilized to produce Whatman #1 filter paper which has a high
cellulosecontent(>98%)andacrystallinityof68%.25

2.1.3 Surfacemodificationofcellulose
The first patent that reported surface modification of cellulose isdated
tothe1870s.Thefiberswerereactedwithnitrosulfuricacid(amixture
of nitric and sulfuric acid) to form cellulose nitrate, and by adding a
plasticizer, the first cellulosebased material, celluloid, was produced.4
In recent years, the interest and utilization of cellulose fibers have
increased tremendously with the aim to create new and sustainable
materials developed from biobased resources.4,6,14,26,27 It is possible to
obtainrenewablecompositeswithlowerdensityandcostcomparingto
other fillers or if reinforcements, such as glass or carbon fibers, are
employed. Moreover, a cellulosebased composite can be recyclable.
Nanocelluloseswithhighcrystallinityareofparticularinterestowingto
their high stiffness that can reinforce polymer matrices. The extent of
amorphousdomainsisdependingonthepretreatmentofthefibers.The
amorphouspartsenhancetheflexibility.9

Cellulose can be applicable in many products; recent publications

discuss a wide range of exciting areas, e.g., inexpensive electronics,2830
paperbased medical diagnostics,3133 functional clothes,34, 35 and
membranes36,37. However, it is a challenge to incorporate and disperse
celluloseduetotheincompatibilityofthepolarcellulosewithnonpolar
polymermatrices.Goodcompatibilityisessentialtodrawbenefitsfrom
thefibersasreinforcement.Furthermore,thehydrophiliccharacterwill
most probably lead to moisture adsorption and swelling of the
composite.However,theavailablehydroxylgroupsoncellulosecanbe
employed for modifications as they can act as chemical handles. The
number of available hydroxyl groups can be tuned by different
6

INTRODUCTION

pretreatment methods. For example, with mercerization, i.e., treatment

with a strong base followed by neutralization, the amount of hydroxyl
groups is increased by breaking the hydrogen bonds, resulting in
swellingofthecellulosestructureand,thus,increasedsurfaceareaand
strengthisachieved.Still,itshouldbetakenintoconsiderationthatthe
mechanical properties of cellulose may be affected upon breakage of
intermolecularhydrogenbonds.4

Surface modification of cellulose can be performed by physical

treatmentssuchassolventexchange,physicochemicalmodificationsby
corona or plasma discharges, laser, UV or irradiation, or physical
adsorption. Chemical, i.e., covalent, modification is performed by
attachment of small molecules or polymers.26,27,3844 The different types
ofmodificationscanalsobecombined.
Traditionally, surface modification of cellulose by small molecules has
beenthemostutilizedtechniquetointroducevariousfunctionalitieson
thesurface.Anhydrides,isocyanates,organometallics,sulfates,andacid
chlorides are examples of molecules that successfully have been
employed to obtain functional groups on the fiber surface.6, 26, 27, 38, 4547
Celluloseestersandethersarethemostcommonexamplesofcellulose
derivatives. The water or organosoluble derivatives are obtained by
substitutionofthehydroxylgroups.Celluloseacetate,themostcommon
ester, is produced by reaction with acetic anhydride in the presence of
sulfuric acid as catalyst. Cellulose esters have thermoplastic properties
whichareinfluencedbythecarbonnumberoftheacylresidues.Water
soluble cellulose ethers are formed by alkaline treatment and
subsequentsubstitutionofanalkylhalideoradditiontoanoxirane.4

Freeradicalpolymerization(FRP)ofvinylmonomershavesuccessfully
beenperformedfromthecellulosebackbone.Theinitiatingradicalscan
beformedbyhydrogenabstraction(chaintransfer),byemployingredox
systems or by utilizing substituents that can form radicals or
polymerize.48,49 However, due to poor control it is impossible to tailor
themolecularstructureorthemolarmassbyFRP.Otherdrawbackscan
be the possible occurrence of chain scission of the cellulose backbone,
which may influence the strength of the final material50, as well as
unattachedpolymerformedinthebulk51.
Modification of cellulose by grafting polymer chains from its surface
enables alteration of both the physical and chemical properties and
7

INTRODUCTION

could potentially introduce other functionalities.4144, 5254 The two most

commonly employed grafting techniques are graftingfrom and
graftingto, see Figure 4. In the graftingfrommethod the polymer is
formed by propagation of monomer from initiating species (reactive
centers) on the surface, i.e., surfaceinitiated (SI) polymerization. In
ordertofullycharacterizethepropertiesofthegraftedpolymerchains,
cleavageofthechainsandsubsequentisolationisnecessary.Thiscanbe
performedbyacidhydrolysis,whichdecomposescellulose,leavingthe
polymer grafts intact. Nevertheless, this method cannot be applied for
polymerscontaininghydrolyticallysensitivegroups.44,55Tocharacterize
the grafted polymer without cleaving it from the surface is a great
challenge;therefore,thegraftingtotechniquecanbepreferable.

Figure 4. Schematic illustration of the graftingfrom and the graftingto

technique.

In the graftingto technique, preformed polymers, with an active

chainendthatcanattachcovalentlywithreactivecenterspresentonthe
cellulose surface. Recently, polymers with two active chainends have
been reported, which enables further post modification of the grafted
preformed polymer.1, 6 An advantage by employing the graftingto
technique is the possibility of characterizing the preformed polymers,
molar mass and the molarmass dispersity (M) prior to the surface
attachment. However, previous studies have shown that covalent
8

INTRODUCTION

surfacemodificationbygraftingfromenableshighergraftingdensities
duetolessstericalhindranceofmonomerscomparedtowhenlargeand
bulky prepolymers are coupled to the surface.1, 42, 52, 53 Nevertheless,
therearesomereportsintheliteraturewheresimilargraftingdensities
havebeenobtainedbythegraftingtoapproach.5658

2.2 RINGOPENINGPOLYMERIZATIONTECHNIQUES
Ringopening polymerization (ROP) and ringopening metathesis
polymerization (ROMP) are two techniques that are suitable for SI
polymerizations.59 These techniques are widely utilized for
polymerization of cyclic monomers. The polymerization mechanism
involves three reaction steps: initiation, propagation, and termination.
Theemployedinitiatorvariesdependingonthetechniqueappliedand
the ringopening of the cyclic monomer occurs during the propagation
stepinpresenceofacatalyst.Undesiredterminationmayoccurbyinter
or intramolecular chain transfers. Intermolecular chain transfers occur
between different chains whereas intramolecular chain transfers (back
biting) occurs within the polymer chain, forming cyclic oligomers. The
chain transfer reactions will give rise to deviation from the targeted
degreeofpolymerization(DP)andincreasetheM.

2.2.1 Ringopeningpolymerization(ROP)
ROP, developed in the 1930s by Carothers et al.60, providing
macromolecules with welldefined endgroups and high molar mass.
Sincethen,numerouscyclicmonomerssuchaslactones,lactides,cyclic
carbonates,siloxanes,andethershavebeenpolymerizedemployingthis
technique.61 The ease of polymerization of the cyclic monomers can be
attributedtobothkineticandthermodynamicfactors.Thepresenceofa
heteroatom(oxygen,nitrogen,sulfur,etc.)intheringfacilitatesthering
opening via a nucleophilic or electrophilic attack of the initiator.
Moreover, the reactivity of the monomers can be attributed to the ring
size, i.e., thermodynamic stability decreases reactivity due to
unwillingnesstochangestate.62
Poly(caprolactone) (PCL) is an aliphatic polyester, and its physical,
mechanicalandthermalpropertiesaredependentonthemolarmass.63
PCLpossessesadvantagessuchasgoodmiscibilitywithotherpolymers,
biodegradability and biocompatibility. The utilized catalyst system
9

INTRODUCTION

determines whether an anionic, a cationic, monomeractivated or

coordinationinsertion mechanism occurs.63 Several different catalytic
systems have been explored; metalbased, organic or enzymatic.6366
Three examples of catalysts are: the metalbased stannous 2
ethylhexanoate (Sn(Oct)2), titanium nbutoxide (Ti(OnBu)4), and the
organic1,5,7triazabicyclo[4.4.0]dec5ene(TBD).

Preinitiation

OH

O O
Sn
O
O

O
Sn
O

tin 2-ethylhexanoate

O
+

OR

Oct-Sn-O-R

HO

Oct-H

(Sn(Oct)2)
O

Coordination
O
Sn
O

Initiation

Oct-Sn-OR

OR

+ O

Insertion
O
O O
Sn OR
O

-CL

O
O Sn
O

R-O

Oct-Sn-OR
O

Propagation

O
O- Sn

R-O

1. n e-CL
2. H

R-O

O
+ HO Sn
O

poly(caprolactone)
PCL

Scheme 1. ROP of CL by coordinationinsertion mechanism employing

Sn(Oct)2ascatalystandanalcoholinitiator(ROH).

The most commonly utilized catalyst is Sn(Oct)2, owing to its excellent

performance, good thermostability, low cost, reasonably low toxicity,
and approval in food and drug applications (FDA approved).67 The
proposed mechanism for Sn(Oct)2 is coordinationinsertion reaction, as
presented in Scheme 1. The initiation is divided into two steps
formation of a metal oxide alkoxide (OctSnOR) from the catalyst
(Sn(Oct)2) and the initiator (ROH) which subsequently initiates the
polymerization of monomer by the coordinationinsertion mechanism
throughcoordinationofthemonomertothecatalystandinsertionofthe
monomerintoametaloxygenbondofthecatalyst.Themetalalkoxide
remains as the active center throughout all the polymerization.
However,therearesomedrawbacksofthiscatalystsystemintraand
intermoleculartransesterificationreactionsmayoccurwhichwillleadto
broadermolarmassdispersitiesanddeviationsfromthetargetedmolar
mass.Theextentoftheundesiredterminationreactionsisdependenton
the temperature and the monomer conversion.68 Another drawback is
the difficulty in removing the catalyst, and the presence of tin in
biomedical or food applications is highly undesirable; therefore, other
catalystsystemsareofprimeimportance.Hence,inrecentyears,alotof
10

INTRODUCTION

research has been conducted to find new, more environmentally

friendly and less toxic catalysts for ROP.63,65,66,69,70 This has resulted in
developmentofbothnewmetalbased71andorganiccatalysts65forROP.
In 2010, Prssinen et al.72 utilized titanium ipropoxide (Ti(OiPr)4) and
titaniumnbutoxide(Ti(OnBu)4),forROPinairatmosphereatelevated
temperatures, 70140 C. The chemical structure of Ti(OnBu)4 is
presentedinFigure5.Anadvantagewiththosecatalystsisthenontoxic
degradationproducts,titaniumoxideandalcohol,whichareapproved
for internal use in humans.72 They report openair systems requiring
higher temperatures (140 C) for efficient initiation attributed to
decreasing water content. However, after initiation the reaction
temperature could be decreased slightly over the melting temperature
for PCL (~60 C).73 Noteworthy, M was quite high and the values
variedfrom1.52,however,by 1HNMRitwasconfirmedthatthePCL
wasonlyformedfromoneofthearmsinthecatalyst.

ROP has also been performed by employment of enzymatic catalysts

which enables mild reaction conditions.66 Several different catalyst
systems, employing amino acids and small organic molecules for ROP
of cyclic lactones, have also been reported as successful.63, 70, 74, 75
Furthermore, Hedrick et al.76 have developed efficient organocatalysts
that enable polymerization at room temperature with good accordance
between theoretical and experimental molar mass, and narrow molar
mass dispersities. An example is 1,5,7triazabicyclo[4.4.0]dec5ene
(TBD),whichpolymerizesbythedualactivationmechanism,including
bothmonomerandinitiatorinatransitionstatewiththecatalyst.76

n-Bu

O
n-Bu

(Sn(Oct)2)

n-Bu

Ti

Sn

tin 2-ethylhexanoate

n-Bu

titanium n-butoxide
(Ti(On-Bu)4)

Figure5.DifferentcatalystsemployedforROP.

N
H

1,5,7-triazabicyclo[4.4.0]dec-5-ene
(TBD)

SIROP has been widely utilized for surface modification of different

substrates,e.g.,silicaandgoldsurfacesbyselfassembledmonolayers,77
clay minerals,78 nanoparticles of silica and cadmium sulfide,79
magnetite,80 and a wide range of different cellulosic substrates,43 and
morerecently,inionicliquids75.
11

INTRODUCTION

2.2.2 Ringopeningmetathesispolymerization(ROMP)
ROMP has had a large impact in both organic and polymer chemistry
for olefin metathesis over the last decade.8183 The polymerization
techniqueisachaingrowthprocesswheremono,biorpolycyclicrings
areopenedandconvertedintoapolymericmaterial.81In1957,Eleuterio
etal.84atDuPontwerethefirsttopatentthistechnique.In1960,Truettet
al.85
reported
the
first
polymerization
of
norbornene
(bicyclo[2.2.1]heptane) (NBE) by ROMP. The ringopening mechanism
ofnorbornenewasconfirmedbyDallAstaetal.88,89inthebeginningof
the1970s.ThemonomerandpolymerstructurecanbeseeninFigure6.
ROMPisahighlyinterestingpolymerizationtechniquesincehighmolar
masspolymerswithnarrowmolarmassdispersitiescanbeobtainedin
short reaction times and under mild reaction conditions. Moreover,
preserved double bonds in the polymer backbone enable facile post
modification.

P
Cl
Ru
Cl

Ph

Grubbs' 1st generation

catalyst

n
norbornene
(NBE)

polynorbornene
(PNBE)

Figure6.Molecularstructureofnorbornene(NBE),andtherepeatingunitofthe
correspondingpolymerpoly(norbornene)(PNBE).TopolymerizeNBE,Grubbs
1stgenerationcatalystisoftenutilized.

Initially,ROMPrequiredstringentreactionconditionsincludingtheuse
of highly pure reagents and the total exclusion of water, oxygen and
otherfunctionalgroups.However,owingtotheNoblePrizelaureatesin
Chemistryin2005Schrock86andGrubbs87andtheirdevelopmentof
less sensitive catalysts for ROMP, the interest for the polymerization
techniquehasincreasedremarkablyduetotheincreasedstabilityofthe
catalysts and, thus, a wider range of polymerizable monomers with
functional groups etc.81, 88 Grubbs developed ruthenium alkyl carbene
12

INTRODUCTION

thatareefficientinitiatorswithhighactivityforpolymerizationofNBE
and substituted NBEs.89 In addition to organic systems, these catalysts
canalsobeemployedinaqueoussystemsformetathesis.90

TheROMPmechanismofNBEisbasedonolefinmetathesiswherethe
ringopening occurs at the most stable site of the monomer, i.e., the
doublebond,seeScheme2.

Initiation:
coordination

LnM

[2+2]
Ln M

R
metal
alkyldiene

LnM

LnM

metallacyclobutane

Propagation:

m
R

LnM

LnM

Ln M

R
m+2

Termination:
R

Ln M

X=Y

MLn=X

m+2

m+2

Scheme2.SchematicoverviewoftheROMPprocess.

Thecriticalstepuponpropagationistheformationoftheintermediate
metallocyclobutane by coordination of the NBE by the catalytic metal
center of the carbene complex, followed by [2+2] cycloaddition where
the propagating species is formed. The metal atom separates from the
olefin bond by a cycloreversion.82 Commonly, transvinylene units are
formed during ROMP of NBE when Grubbs catalysts are employed.
Undesiredsecondarymetathesisreactionsleadtoterminationandoccur
by intra or intermolecular chain transfer, yielding polymers with
broadermolarmassdispersitiesandilldefinedendgroups.Theextent
of the termination reactions is dependent on many parameters, e.g.,
bulkiness of the monomer, temperature, monomer concentration, and
solvent.83

The pioneer work of SIROMP from a gold surface by the ruthenium

based Grubbs 1st generation catalyst was performed by Grubbs etal.91
in1999.Thereafter,numeroussubstrateshavebeensurfacemodifiedby
SIROMP, e.g., silicon wafers,92 quartz,93 Wang resins,94 silica
nanoparticles,95carbonnanotubes,96gold,97clay,98andcellulose99.

13

INTRODUCTION

2.3 REVERSIBLEADDITIONFRAGMENTATIONCHAIN
TRANSFER(RAFT)POLYMERIZATION
During the last years, much work has been conducted in the field of
polymersynthesiswiththeaimtodesignwelldefinedmacromolecular
structures with narrow M and endgroup functionalities.100 Tailored
polymers can be synthesized by reversibledeactivation radical
polymerization (RDRP) techniques. The most commonly employed
RDRPtechniquesincludesnitroxidemediatedpolymerization(NMP),101
atom transfer radical polymerization (ATRP),100, 102 and reversible
additionfragmentation chain transfer (RAFT)103, 104. Among those
techniques,RAFTisthemostrecentlydevelopedandprobablythemost
versatile.105, 106 The RAFT technique has versatility for numerous
different monomers and polymerization can be conducted in a wide
range of reaction media, organic solution, aqueous solution, or in
dispersed phase.107, 108 Therefore, this technique has been extensively
employed for controlled polymerization of both, hydrophilic and
hydrophobic monomers.104, 106, 108, 109 Moreover, a good control of the
macromolecular structure was achieved and, as the RAFT chainend
was preserved to a large extent, facile postfunctionalization could be
performedofthepolymers.100,106,107InareviewonRAFT,Moadetal.104,
morethan700publicationsfromthemiddleof2009untilthebeginning
of 2012 was cited, which demonstrate the intense ongoing research in
thisfield.

RAFT polymerization includes the same steps as classical free radical

polymerization (FRP): initiation, propagation and termination.
However,inaRAFTsystemtheterminationreactionsaresuppressedby
fastchaintransfer.Thepolymerizationstartsfromradicalinitiatorsthat
are activated in a classical manner, either by heating, redox,
photochemistry,UVorgammairradiation.Theadditionofanexternal
sourceofradicalsisrequiredtoinitiatepolymerizationandmaintainthe
rate of polymerization.105 However, RAFT polymerization is a more
sophisticatedtechniquecomparedtoFRPandthecontrolisprovidedby
degenerative(i.e.,thermodynamicallyneutral)chaintransfer,involving
transfer of an atom or a group from a covalently bond and dormant
species (i.e., the chain transfer agent, RAFTagent) to the active chain
end.TheRAFTagent,seeFigure7,iscomposedofanactivatinggroup
Z and a good free radical leaving group, R. The RAFT agent
14

INTRODUCTION

provides control of the polymerization and should be present in large

excesstotheinitiator103,104,110tosuppressirreversibleterminationofthe
active,propagatingchains.102,103,109
S
S
R

Figure 7. An example of a RAFT agent, the thiocarbonylthio chain transfer

agent.105

The mechanism of RAFT polymerization employing the

thiocarbonylthio RAFTagent is presented in Scheme 3. In the initial
step,afreeradical,I,isformedwhichpropagateswithmonomerunits,
M.Thisisfollowedbythepreequilibriumstepwhichoccursassoonas
the RAFTagent reacts with the radical in the propagating oligomer,
(Pn).TheradicalpositionisthentransferredtotheRAFTagent,forming
a relatively stable (dormant) specie. Further, the radical is either trans
ferredbacktothepropagatingoligomer,whichenablespropagation,or
totheRgroup.Inthiscase,theRgroupwillactasaninitiator,andstart
adding monomer units (Pm), until it goes back to the dormant side by
reactingwiththeRAFTagent.Thisprocessisfastwhichisvitalforthe
controland,hence,themainequilibriumshouldbereachedearlyinthe
process.TherateconstantsarestronglydependentontheZgroup.The
thiocarbonylthio groups are highly efficient RAFT agents, which is of
highimportancetoobtainagoodcontrolofthepolymerization.

15

INTRODUCTION

Initiation
Initiator

M
ki

I
kd

M
kp

M
kp

P1

Pn

Initialization/pre-equilibrium
S

Pn
M

kadd

Pn

k-add

kp

kb

k-b

Pn

S + R

Reninitiation
M
kiR

P1

M
kp

M
kp

Pm

Main equilibrium
S

Pm

Pn

kaddP
k-addP

kp

Pm

Z
kt

kaddP

Pn

k-addP

Pm

S + Pn
M

Termination
Pn + P m

kp

Dead polymer

Scheme 3. Mechanism of RAFT polymerization by employing the

thiocarbonylthioRAFTagent.

The versatility of the RAFT technique has permitted a wide range of

monomers for polymerization, for instance, acrylates, methacrylates,
and vinyl acetate.104, 111, 112 However, the environmental consciousness
has increased and in this context, water is the preferred reaction
medium not only due to economic reasons but also for environmental
and health aspects.106 Hence, polymerization of watersoluble
monomers,suchasN,Ndimethylaminoethylmethacrylate(DMAEMA),
has gained significant attention. The structure of the monomer,
DMAEMA, and corresponding polymer PDMAEMA are shown in
Figure8.
n

DMAEMA

PDMAEMA

Figure 8. Molecular structure of N,Ndimethyl aminoethylmethacrylate

(DMAEMA) and the repeating unit of the corresponding polymer,
P(DMAEMA).

16

INTRODUCTION

The polymer is both thermo and pHresponsive. Stimuliresponsive

polymers can change conformation, properties and interactions in
response to external stimuli, e.g., switching from hydrophilic to
hydrophobic.113Themolarmassofthepolymerinfluencetheresponsive
properties.114 Hence, they are interesting for a wide range of
applications.115 PDMAEMA has been employed in biological
applications, for antibacterial activity,116,117 gene delivery,118 as well as
other fields, e.g., wastewater treatment,119 and paints120. It is the polar
tertiary amine sidechain group that offers water solubility and, if
desired, can be charged either when below its pKa value (close to 7.5,
slightly chain length dependent)114 or irreversibly charged by
quaternization. However, there are few earlier investigations available
whereDMAEMAhasbeenpolymerizedinaqueousmediabyATRP121,
122orbyRAFT123.

Surfaceinitiated RAFT (SIRAFT) has been performed from numerous

surfaces,forinstance,goldnanoparticles,124silicananoparticles,125silicon
wafers,126proteins,127andvariouscellulosesurfaces52,55,128,129.

2.3.1 RAFTmediated
polymerization

surfactantfree

emulsion

RAFT polymerization, enables development and design of new,

advanced and tailored macromolecular architectures, both for homo
and block copolymers.100 Amphiphilic block copolymers, composed of
bothahydrophilicandahydrophobicblock,130132arehighlyinteresting
in applications such as compatibilizers. However, the synthesis of
amphiphilic block copolymers is demanding due to the difference in
polaritybetweentheblockswhichtypicallycausesatleasttwo(ormore)
steps, including thorough purification. The synthesis of block
copolymerscanbeperformedbyvariousmethods;twoexamplescanbe
seeninFigure9.

17

INTRODUCTION

Figure9.Synthesisofblockcopolymersinatwostepprocessbya)bycoupling
twopreformedmacromolecularchainstogetherorb)firstformingablockwith
living chainends that can be employed to initiate the growth of the second
block.

Previously, the RDRP techniques have primarily been performed in

organic solvents or bulk. However, the interest in the field of aqueous
dispersions has increased tremendously.133,134 All the RDRP techniques
have successfully been employed in dispersion.135 RAFT has thus far
been the most successful technique for waterborne systems.134, 136 By
employing dispersed systems, nanoparticles (d=20nm10m) with
differentmorphologies(coreshellparticles,hollowparticlesorcomplex
multilayerstructures)areformedwhichmaybeinterestingforvarious
applications,seeFigure10.133

Figure10.P(MAAcoPEOMA)bpolystyreneamphiphilicblockcopolymerself
assemblies.137Reprintedwithpermissionfrom(Zhang,W.etal.,Macromolecules
2012,45,p.40754084).Copyright(2012)AmericanChemicalSociety.

Classicalemulsionpolymerizationhasbeenemployedtoalargeextent
inindustrysincevolatileorganicsolventscanbeavoided,awiderange
of monomers can be utilized and this technique enables processing at
high solid content without any influence on the viscosity.134 The
technique requires employment of an organosoluble monomer, a
watersoluble initiator and a surfactant. The three regimes of emulsion
polymerizationaredemonstratedinScheme4.
18

INTRODUCTION

Interval I: Initially, an emulsion polymerization system consists of a

dispersion of monomers in an aqueous phase. The initiation always
takesplaceintheaqueousphase.Thereafter,twodifferentmechanisms
mayoccur,micellarnucleationorhomogeneousnucleation,depending
oftheconcentrationofthesurfactant.Themonomerisentrappedinthe
micelles if the concentration of surfactant is above the critical micelle
concentration (CMC). During the nucleation, particles are formed
whereinthepolymerizationwillproceed.
IntervalII:Duringthesecondinterval,thepolymerizationisproceeding
intheparticles.Thegrowingparticlesareconstantlyfedwithmonomer
by diffusion from the droplets through the aqueous phase into the
particles.Theparticlesareincreasinginsizeduringthepolymerization.
However, the number of particles and the polymerization rate are
constant throughout the process. When the monomer droplets are
consumed,thethirdintervalstarts.
Interval III: The residual monomers in the particle and in the aqueous
phase are consumed. At the end of interval III, the polymerization is
terminated.

Scheme 4. Schematic illustration of intervals in an emulsion polymerization,

adoptedfromZhang.138

2.3.1.1 Polymerinducedselfassembly
More recently, the development of RAFTmediated emulsion
polymerization has led to the aqueous synthesis of amphiphilic block
copolymers,whichselfassembletoformpolymerparticlesaccordingto
the polymerizationinduced selfassembly (PISA) strategy as originally
describedbyHawkettetal.139141ThePISAprocesshassuccessfullybeen
employed for all three RDRP techniques.134, 140 In the RAFTmediated
19

INTRODUCTION

PISAprocess,itiscrucialtochooseasuitableRAFTagentthatprovides
good control over formation of both blocks when synthesizing block
copolymers.107 Recently, new RAFT agents have been developed that
can be employed for polymerization of both hydrophilic and
hydrophobicmonomers,wherethefirstformedhydrophilicpolymeris
utilized as a macroRAFT for formation of the second hydrophobic
block.133ThemacroRAFTisactingasanelectrostericsurfactantasitboth
functionalizes the surface of the particles and controls the particle
growth, see Scheme 5. No additional low molarmass surfactant is
required, which is highly advantageous since the low molar mass
surfactants have an undesired impact on the latex stability under
freezingconditionsanddiffusionuponfilmformation.142

Scheme5.AnoverviewofthePISAprocess.AdaptedfromChaduc.143

InFigure11,thestructureofathiocarbonylthioRAFTagent,4cyano4
thiothiopropylsulfanylthiocarbonyl (CTPPA)142 is shown, which is
obtained by reacting the radical initiator, 4,4Azobis(4cyanovaleric
acid) with bis(propylsulfanylthiocarbonyl) disulfide according to the
literature.144, 145 CTPPA permits polymerization in water despites its
insolubilityinwater,asitissolubleinmanyhydrophilicmonomers.142,
146151
20

INTRODUCTION

O
S

OH
CN

CTPPA

Figure11. The RAFT agent, 4cyano4thiothiopropylsulfanylthiocarbonyl

(CTPPA).

Previously,thefirstdevelopedmacroRAFTagentswerepresynthesized
before being employed in water (i.e., a twopot process). However,
DAgostoetal.148recentlyperformedPISAaccordingtoatwostep,one
pot procedure. The synthesis of the hydrophilic macroRAFT is
performed in water up to full monomer conversion and directly
followedbyadditionofthehydrophobicmonomerinthesamereactor
andbytheformationofthepolymerparticles,withoutpresenceofany
additional molecular surfactant. This simple, robust and ecofriendly
strategy has successfully been applied to various hydrophilic
monomers,e.g.,acrylicacid,146methacrylicacid(MAA),152andamixture
of MAA and poly(ethylene oxide) methyl ether methacrylate.137, 149, 150
Various hydrophobic monomers such as styrenics and (meth)acrylics
have been employed to synthesize the hydrophobic core, leading to
numerous compositions of amphiphilic block copolymers. In addition,
different morphologies have been obtained,137, 150 similarly to the post
polymerization selfassembly of amphiphilic block copolymers
conducted at very low concentrations (< 1 wt %)153. The PISA strategy
permits to combine the advantages of RAFT and emulsion
polymerization under conventional aqueous emulsion polymerization
conditions to synthesize amphiphilic block copolymers with various
morphologies.

2.4 SURFACE MODIFICATION OF CELLULOSE BY

COVALENTGRAFTING
SI polymerizations have successfully been applied when surface
modifying cellulose, both by employing the RDRP techniques and
ROP.4244, 52 The RDRP techniques provide possibilities for designing
advanced macromolecular architectures both for homo and block
copolymers.100, 107, 154 However, a drawback when employing RDRP
techniquesfor SI polymerization is therequirementforimmobilization
oftheinitiatorpriortopolymerization.
21

INTRODUCTION

ThepreinitiatingstepcanbecircumventedbyinsteademployingROP,
since this polymerization can be initiated from the hydroxyl groups
already present in the cellulose structure.43 This technique has been
widely utilized for numerous cellulose substrates: solid fibers and
fibrils, dissolved celluloses, and cellulosic derivatives, employing
heterogeneous and homogeneous systems as well as graftingto and
graftingfrom.6, 38, 4547 Furthermore, more environmentally friendly SI
ROPsystemshavebeenconductedbyemployingenzymes.43

HafrnandCordovaperformedpioneeringworkinthefieldofSIROP
from cellulose surfaces, e.g., cotton and filter paper (FP), using an
organic catalyst.155 Belgacem et al.156 reported surface modification of
CNC and bleached soft wood kraft pulp in a three step process where
one chainend of preformed PCL was reacted with phenyl isocyanate
and the other with 2,4toluene diisocyanate. The difunctionalized PCL
wassubsequentlyattachedtocelluloseinamixtureofdichloromethane
(DCM) and anhydrous toluene in a graftingto process. Despite low
amounts of grafted PCL, the surface energy of the resulting
biocomposite changed considerably. Hult etal. were the first to report
SIROPfromCNF,resultinginPCLgCNFthatcouldbedispersedinan
organic solvent which is not possible for unmodified CNF.157 Dufresne
and Dubois et al.158 have also reported improved dispersity of PCLg
CNC in pure PCL prepared by extrusion. They found a significant
differenceinthermomechanicalperformanceandrheologicalbehaviors
between the PCLgCNC compared to the unmodified CNC.
Furthermore, Dufresne et al.159 have reported grafting of fatty acids or
polymers onto CNC. The grafted CNC were successfully dispersed in
polymermatrices,e.g.,PCL,polyethylene,andPLA160byextrusion.

Hult etal.161 utilized PCLgCNF to produce bilayer laminates together

with pure PCL. By dynamic mechanical analysis (DMA) it could be
concluded that the graft lengths had a large influence on the final
propertiesintermsoftoughnessoftheinterfaceandthepeelingenergy,
whichwasascribedtotheincreasedentanglementsoccurringforlonger
polymergrafts.MalmstrmandRutlandetal.162employedthecolloidal
probetechniquebyatomicforcemicroscopy(AFM)tostudythefriction
forces between cellulose microspheres (CMS) with or without grafted
PCL, to achieve an asymmetric system (CMS/PCLgCMS) or a
symmetric system (PCLgCMS/PCLgCMS). This study showed that
22

INTRODUCTION

the interfacial adhesion was improved for the symmetric system as a

resultofPCLentanglements.Furthermore,measurementsperformedat
highertemperatures,increasedthemobilityofPCL,thus,theadhesion
wasimproved.162

The graftingto technique can also be employed for covalent surface

modification of cellulose. This approach has been examined for
attachment of small molecules, such as isocyanates, acid chlorides,
maleic or succinic anhydrides, or click functionalities to the cellulose,
which subsequently enabled attachment of endfunctionalized
polymers.1, 6, 38, 41, 45, 47 Different click chemistries can be utilized, the
most studied one being the copper (I)catalyzed 1,3dipolar
cycloaddition of alkynes and azides (CuAAC), but thiolene chemistry
has also frequently been applied.1,27,163 Click reactions are considered
tobeselectivereactionsproceedingwithhighyieldandintheabsence
of byproducts.164 In addition, the reactions are orthogonal, modular,
wideinscope,andperformedundermildreactionconditions.
Recently, click chemistry in water was conducted from alkyne or
alkene groups attached to carboxymethylated cellulose which was
adsorbed onto a cellulose substrate.165, 166 Grafting of cellulose with
(PCL) by click chemistry has been reported by several groups.167169
Graftingto in ionic liquids170172 and employment of bifunctional
couplingagents1,6hasalsobeenreported.

2.5 SURFACE MODIFICATION OF CELLULOSE BY

PHYSICALADSORPTION
Polymers with charges can be adsorbed to an oppositely charged
surface by electrostatic interactions. The driving force is the release of
counter ions, e.g., gain in entropy upon adsorption. Physical surface
modification can often be performed under mild reaction conditions,
commonly in water, which is interesting from an environmental view
point.2 The pulp and paper industry has employed cationic
polyelectrolytesfordecadestosurfacemodifyfiberstoimprovesizing,
paperstrength,retentionandcreepproperties.173Thisisfeasibledueto
the slightly negative charge of native wood fibers. The nanocelluloses
(CNC and CNF) can obtain further negative charges, e.g., sulfate or
carboxylicgroupsduetopretreatmentsduringtheirproduction.7,14Itis
of prime importance that the interactions between the physically
23

INTRODUCTION

adsorbedpolymerandthesurfacearesufficientlystrongsotheinterface
is stable under conditions exposed to, such as wide temperature and
pHranges,differentsaltconcentrationsaswellasdifferentsolvents.
Amphiphilicblockcopolymers,140,174aresuitableforphysicaladsorption
to cellulose if one of the blocks are composed of a polymer that can
anchortheentireblockcopolymertothesurface,i.e.,ifthehydrophilic
block is charged, or composed of a hemicellulose or another polymer
whichhasanaturalhighaffinityforcellulose.
Oneexampleofahydrophilicblockwhicheasilyadsorbstonegatively
charged
cellulose
is
quaternized
poly(dimethyl
aminoethylmethacrylate) (PDMAEMA), which is a cationic
polyelectrolyte.Seppletal.175reportedphysicaladsorptionbetweena
cationic block copolymer of P(ethylene oxide)bP(DMAEMA) and
paper sheets which improved the paper strength. Surface modification
of paper sheets by adsorption of amphiphilic block copolymers
consisting of hydrophobicallymodified water soluble methacrylate
copolymers with one block of P(DMAEMA) generated paper sheets
with increased hydrophobicity.176 By utilizing RDRP techniques, tailor
made block copolymers between quaternized PDMAEMA and another
functional block can be obtained. For example, surface modification of
cellulose by amphiphilic block copolymers with PDMAEMA as
hydrophilic block and various hydrophobic blocks, e.g., polystyrene,131
or polybutadiene177 have successfully been performed. Several other
studies have utilized the same concept with different compositions for
physicaladsorptiontocellulose,suchaspolystyrenebpoly(Nmethyl4
vinylpyridiniumiodide)178andpoly(Nisopropylacrylamide)bpoly(3
acrylamidopropyl)trimethylammoniumchloride.179Physicaladsorption
tocellulosebyamphiphilicblockcopolymersconsistingofquaternized
PDMAEMAandPCLformedbyROPhasalsobeeninvestigated.130All
thesephysicalsurfacemodificationswereperformedinwater.
Severalotheraqueoussystemsforsurfacemodificationofcellulosehave
beeninvestigated.Belgacemetal.180performedanonestepinsitumini
emulsion polymerization of butyl methacrylate in presence of CNC. A
cationicsurfactantwasutilizedtoformmicellesforpolymerizationand
alsotoenableelectrostaticinteractionbetweenthelatexparticlesandthe
CNC. Films with good optical properties were presented as a result of
the well dispersed modified CNC. In another study, the same group
24

INTRODUCTION

surfacemodified CNF54 by alkyl ketene dimers (AKD), without

stabilizer, in presence of a cationic surfactant, and subsequently paper
sheetswereprepared.ByemployingmodifiedCNF,themechanicaland
barrierpropertiesweresignificantlyimprovedcomparedtounmodified
CNF. Another benefit was the increased hydrophobicity of the paper,
despiteadditionofsmallamountsofmodifiedCNF.

25

EXPERIMENTAL

3. EXPERIMENTAL

3.1 MATERIALS
Detailed information about employed chemicals can be found in the
correspondingpapers.
Filterpaper(FP)Whatmanno.1FPwasutilizedinpapersIandV.The
substrateswerecutintopieces2.53cm2andwashedinmethanoland
acetoneanddriedinvacuumovenat50Cfor24hpriortouse.
Nanopaper(NP)TheNP,utilizedinpaperI,wasproducedaccording
toSehaquietal.22Anaqueoussuspensionofcellulosenanofibrils(CNF)
was prepared by enzymatic pretreatment followed by high shear
mechanical treatment in a microfluidizer according to the literature.21
The high surface area NP was prepared from a 0.1 % CNF suspension
(300mg dry CNF) by vacuum filtration (0.65m membrane). The
filtratewassolventexchangedtomethanolandplacedinacriticalpoint
dryer chamber (Autosamdri815, Tousimis, USA), and liquid carbon
dioxidewasinjectedintothechamberunderapressureofca.50barfor
solventexchange.ThechamberwasthenbroughtabovetheCO2critical
point conditions to approx. 100 bar and 36 C. The chamber was then
depressurized,andCO2evaporatedtoformaporousCNFNP.

Cellulosemicrospheres(CMS)TheCMS,inpaperIII,wereproduced
from regenerated cellulose by the viscose process by Kanebo (Japan).
The diameters were 1015 m. Prior to use, the CMS were dried in
vacuumovenat50Cfor24h.

Hydrolyzed cellulose cotton linters (HCCL) In paper IV, cellulose

cotton linters (CCL) were hydrolyzed according to a procedure
developed by Larsson et al.181 Prior to the grafting, the HCCL was
solventexchangedinamultistepprocess,accordingtoKhnkeetal.182
Initially, the water was replaced by acetone followed by npentane,
repeatedtentimesforeachsolvent,respectively.TheHCCLweredried
underArovernight.

26

EXPERIMENTAL

CellulosemodelsurfaceInpapersIIandVI,cellulosemodelsurfaces
were utilized. The QCM silica crystals with an active surface of
sputteredsilica(50nmthickness)wererinsedinwaterandethanoland
cleaned in a plasma cleaner. Thereafter, the crystal was immersed to a
PVAm solution (0.01 g L1, pH 7.4). The cellulose fibers (0.25 g) were
added to a 100 mL glass beaker and dissolved in NMMO (12.5g,
50wt% solution in water) at 120 C until all the fibers were dissolved
(approx.1h).Thereafter37.5gofDMSOwasaddeddropwisetodilute
thesolution.Adropofthedissolvedcellulosewasspincoatedontothe
PVAm coated QCM crystals and regenerated by exposure to MilliQ
water. The obtained cellulose model surface was assumed to have a
thicknessof3040nmaccordingtoearlierreports.11

3.2 EXPERIMENTALPROCEDURES
3.2.1 Cellulose surface
polymerization

modification

by

ringopening

SIROP of CL from various solid cellulose substrates has been

performed (papers I IV). Herein, a short description of the
experimental procedures will follow. Detailed experimental setups,
procedures and characterization data can be found in the appended
papers/manuscripts.

Table2.OverviewofemployedreactionconditionsforgraftingreactionsbySI
ROPofCLfromcelluloseinpaperIIV.
Paper Cellulose
Catalyst
Sacrif. Solv.b
T
Atmosph.
t
(C)
substrate
init.a
(h)
I
Yes

120
Inert
0.81
NP
Sn(Oct)2

Yes

120
Inert
0.40.8
FP
Sn(Oct)2

120
Air
19.329
NP
Ti(OnBu)4

120
Air
12.522
FP
Ti(OnBu)4
II
Inert
0.53
TBD

RTc
Cellulose
model
surface
III
CMS
Sn(Oct)2
Yes
tol.c 110
Inert
13
IV
HCCL
Sn(Oct)2
Yes
tol.c
90
Inert
514.5
aBenzylalcoholwasemployedassacrificialinitiator.DPtarget=600.bsolvent:
toluene.croomtemperature.

27

EXPERIMENTAL

To purify PCLgrafted cellulose from ungrafted PCL, the precipitated

mixture was Soxhlet extracted in THF overnight and thereafter re
precipitatedinmethanolseparately.ThefreePCLandthePCLmodified
celluloseweredriedindividuallypriortocharacterization.
SIROP from cellulose model surfaces (paper II) A solution of CL
anddriedTBD(0.5mol%and1mol%)wasultrasonicatedandfiltered
(45m Teflon filter) prior to adsorption measurements in the QCMD
performed at 25 C. The experimental setup can be seen in Figure 12
andpaperII.

Figure12.ReactionsetupforperformingSIROPofCLfromacellulosemodel
surfaceintheQCM.

3.2.2 Cellulose surface modification

metathesispolymerization

by

ringopening

The surface modification by ROMP from FP was performed in three

steps, see Scheme 6. Initially, the FP was functionalized by attaching a
norborn2ene5carboxylic acid chloride, step i, which was prepared
according to literature.96 The resultingnorborn2ene functionalized FP
was catalystfunctionalized by addition of Grubbs first generation
catalyst,stepii.TheSIpolymerizationofNBEwasconductedfromthe
catalystfunctionalizedFP,stepii.Thepolymerizationwasconductedat
threedifferenttemperatures,RT,0Cor78Candfordifferentreaction
timesvaryingfrom1minto1h.

28

EXPERIMENTAL

Scheme 6. Reaction scheme for the surfaceinitiated ringopening metathesis

polymerization (SIROMP) from FP of NBE. i) triethylamine/4
(dimethylamino)pyridine/THF,RT;ii)heptane,RT;iii)DCM,RT,0C,or78C.

ThegraftedcellulosesurfaceswereextensivelywashedwithbothDCM
andMeOHincombinationwithultrasonication.

3.2.3 Synthesisofcationiclatexnanoparticles
Cationicamphiphiliclatexparticlesweredesignedandsynthesizedfor
surface modification of cellulose. A twostep process was developed
whereamphiphilicblockcopolymers,withachargedhydrophilicblock,
composed of cationic P(DMAEMAcoMAA) and a hydrophobic block,
PMMA,weredeveloped.

3.2.3.1 AqueousRAFTpolymerizationofDMAEMA
Aqueous RAFT polymerization of DMAEMA was performed at 70 C,
pH7, in presence of the RAFT agent 4cyano4thiothiopropylsulfanyl
thiocarbonyl (CTPPA) and the watersoluble initiator 2,2azobis(2
methylpropionamidine) dihydrochloride (AIBA). However, it was
found that approximately 10% of DMAEMA repeating units
hydrolyzedintomethacrylicacid(MAA)duringpolymerization.Hence
a copolymer of cationic poly(DMAEMAcoMAA) was formed,
confirmed by 1HNMR spectroscopy. A schematic overview of the
synthesiscanbeseeninScheme7.Thedetailedexperimentalprocedure
canbefoundinpaperVI.

29

EXPERIMENTAL

O
S
O

S
S

HO

CN

S
nS
O
O
O
HO
m

CN

CTPPA
NH Cl

OH

AIBA, water
pH 7, 70 C

DMAEMA

Cl
NH
P(DMAEMA-co-MAA)

Scheme7.ThesynthesisofcationicP(DMAEMAcoMAA)obtainedbyaqueous
RAFTpolymerizationofDMAEMA.

3.2.3.2

RAFTmediated surfactantfree emulsion polymerization

ofMMA

Amphiphilic block copolymers, composed of cationic P(DMAEMAco

MAA)macroRAFTasthehydrophilicandchargedblockandPMMAas
the hydrophobic block were prepared by employing the PISA process,
seeScheme8.Theemulsionpolymerizationwasperformedat70C,pH
6, in presence of the cationic macroRAFT P(DMAEMAcoMAA) and
AIBA.FourdifferentDPweretargetedforthePMMAblock,seeTable3.
S

O
HO

CN
O

O
HO

S
nS
O

Cl
NH

O
O
OH

CN

MMA
AIBA, water
pH 6, 70 C

P(DMAEMA-co-MAA)

HO

pS

O
O

Cl
NH

P(DMAEMA-co-MAA)-b-PMMA

Scheme 8. The synthesis of cationic P(DMAEMAcoMAA)bPMMA obtained

by RAFTmediated surfactant free emulsion polymerization of MMA. Cationic
P(DMAEMAcoMAA),seeScheme7wasemployedasmacroRAFT.

Table 3. Experimental conditions of performed RAFTmediated surfactantfree

emulsionpolymerizationofMMA.
Entry
[macroRAFT]
DPnb
tc
conv.d
e
a
(mMH2O)
(min)
(%)
(%)c
Latex1
15
176
90
90
25
Latex2
7.3
353
80
83
20
Latex3
3.7
705
90
86
20
Latex4
1.9
1410
90
80
17
aConcentrationofmacroRAFT.bTargetedDPofMMA.cReactiontime.
dMonomerconversiondeterminedbygravimetry.eSolidcontent.

30

EXPERIMENTAL

3.2.3.3

Adsorptionofcationiclatexoncellulosemodelsurfaces

Priortomeasurements,waterdispersionsoflatexinMilliQwaterwere
prepared (100 mg L1). The adsorption in the QCMD was performed
with a continuous flow of fresh latex dispersion until a stable baseline
was obtained indicating that saturation had been reached. The
adsorption was followed by a rinsing step to ensure that the adsorbed
latexeswereattachedtothesurface.

3.3 CHARACTERIZATIONMETHODS
Detailedinformationaboutthegeneralinstrumentsandcharacterization
techniques can be found in the individual papers. However a short
description about some more advanced characterization methods and
toolswillfollow.

3.3.1 QCMD
The QCMD was employed as a flowthrough reactor to measure the
changeinresonancefrequencyofthecrystal,correspondingtoachange
in mass attached to the surface. Measurements were performed with
continuous flow of reaction solution, 0.215mLmin1 (paper II) and
0.15mLmin1(paperVI),respectively.Toconvertachangeinfrequency
intoachangeinattachedmassperareaunit,mA,theSauerbreymodel183
wasused:

[3]

where C = the sensitivity constant of 0.177 (mg (m2Hz)1), f = the

changeinresonancefrequency(Hz),n=theovertonenumber.

Thetheoreticaldefinitionofthedissipation,D,canbeseenbelowandis
ameasureoftheviscoelasticpropertiesoftheattachedcompounds.184

Where

[4]

Energy dissipated during one oscillation period,

Energystoredintheoscillatingsystem.

31

EXPERIMENTAL

3.3.2 ColloidalprobeAFM
Adhesion and friction measurements by the colloidal probe technique
were performed using a MultiMode Picoforce AFM with a Nanscope
IIIacontroller.APCLgraftedcellulosemicrosphere(CMS)wasattached
to the end of a cantilever using a tiny amount of epoxy resin. The
adhesion was measured between the upper functionalized cellulose
probe (PCL graft of Mw = 55kg mol1) and a lower sphere of either a
neatCMSorPCLgCMSafterbeinginsurfacecontactatvaryingtimes
at a constant applied load. Typical force and friction measurements
were conducted in air (20 C, 40 C, and 60 C). To ensure
reproducibility, all measurements were repeated using different
substrates for all the conditions. Further details can be found in paper
III.

3.3.3 SolidstateCP/MAS13CNMR
SolidstateCrossPolarizationMagicAngleSpinningCarbon13Nuclear
MagneticResonance (CP/MAS 13CNMR) spectra were recordedwith a
BrukerAvance III AQS 400 SB instrument operating at 9.4 T. The
monomerbulkdegreeofsubstitutionwasestimatedfromtherecorded
CP/MAS 13CNMRspectrabyspectralintegration.Furtherdetailsabout
thecalculationofthedegreeofsubstitution(DS)ofthepolymergrafted
HCCLcanbefoundinpaperIV.

32

RESULTSANDDISCUSSION

4. RESULTSANDDISCUSSION
The work in this thesis has been conducted to expand the toolbox for
surfacemodificationofcellulosebypolymers.Thefirstpartofthisstudy
investigated surface modification by covalent grafting. SI
polymerizationviaROPofCLfromdifferentcellulosesubstrateswere
performed(paperIIV).Furthermore,SIROMPwasconductedfroma
cellulose surface (paper V). The last part of this thesis investigates
surface modification by physical adsorption where cationic latex
nanoparticles were designed, synthesized and developed for
electrostaticinteractions/adsorptionwithcellulose(paperVI).

4.1 CELLULOSE
SURFACE
COVALENTGRAFTING
4.1.1 Cellulose surface
polymerization

MODIFICATION

modification

by

BY

ringopening

Herein, results from papers I IV will be presented and discussed

where SIROP of CL was conducted from various solid cellulose
substrates,andsubsequentlycharacterized.

4.1.1.1

SIROP of CL from FP and NP. Comparison between

Sn(Oct)2andTi(OnBu)4

SIROPofCLwasexaminedusingtwodifferentcellulosicsubstrates,
high surface area nanopaper (NP)22 and conventional filter paper (FP),
respectively. SIROP from FP has been studied earlier,154, 182 thus, the
substrate is suitable for comparisons with the novel NP. In this study,
two different catalysts were examined and compared; the commonly
employed Sn(Oct)2 and Ti(OnBu)4 that more recently, successfully was
investigated for ROP of CL in air72. The less demanding
polymerization conditions facilitate the experimental performance and
are more interesting from an industrial viewpoint. The grafting
reactionswerecarriedouttolowandhighconversions,seeTable4.

33

RESULTSANDDISCUSSION

Table 4. SIROPconductedfrom NP and FP. Characterization of freePCL and

the weight percent of grafted PCL in grafted papers. The sample names are
basedonthecellulosicsubstrate,FPorNP,andtheemployedcatalystTi(OnBu)4
or Sn(Oct)2 and finally the weight percentage of grafted PCL, see Paper I for
furtherdetails.

Sample
FPTi33
FPTi50
NPTi50
NPTi64
FPSn2
FPSn3
NPSn61
NPSn79
FPbe
NPbe

Reaction
time
(h)
12.5
22.0
19.3
29.0
0.4
0.8
0.8
1.0
22.0
29.0

Conv.a
(%)
33
78
32
70
35
77
45
81
1
2

Mn,thb

Mnc

(gmol1)

(gmol1)

16300
38600
15800
34600
16500
36300
21200
38100

10700
25800
15000
27900
15700
36700
20300
39400

M
1.16
2.0
1.15
1.45
1.16
1.43
1.13
1.6

Grafted
PCLd
(%)
33
50
50
64
2
3
61
79
4
8

Conversion (conv.) determined by 1H NMR. b Estimated from conv. by 1H

NMR. c Molar mass of free PCL determined by CHCl3SEC. d Percentage of
graftedPCLinthegraftedcellulosesubstratemeasuredbyweightdifferenceof
thesubstratebeforeandaftergrafting.eBlankreaction(nocatalyst).

InTable4,itcanbeseenthatthemolarmassincreaseswithconversion.
The M is broad for higher conversions when Ti(OnBu)4 was utilized
which may be ascribed to the more frequently occurring
transesterification reactions at elevated temperatures and higher
conversions63. The grafted amount of PCL is significantly higher when
using NP compared to FP. This can be attributed to the larger surface
area of NPi.e. more available, initiating hydroxyl groups compared to
the FP. The grafting reactions performed from NP by employing the
Sn(Oct)2catalystresultedinthehighestgraftingamounts.However,by
utilizing FP,the lowest amount of PCL was obtained when employing
the same catalyst, Sn(Oct)2. This may be explained by shorter reaction
time compared to Ti(OnBu)4 and less available hydroxyl groups
compared to NP. The same trend is not observed for Ti(OnBu)4 where
significantamountsofPCLareobtainedbothfromNPandFP,although
smaller amounts from FP. The results may be elucidated by the
difference in atmospheres the synthesis employing Sn(Oct)2 was
performedinaninertatmosphereandtheTi(OnBu)4inairatmosphere.
34

RESULTSANDDISCUSSION

Furthermore,thepolymerizationsperformedwiththeTibasedcatalyst
areconsiderablyslowerandthusthesubstratesaresubjectedtoelevated
temperaturesforlongertimes,whichmayleadtoanincreasednumber
of transesterification reactions; subsequently this may lead to
disintegrationofthecellulosesubstrate.Thiswillleadtoanincreasein
number of hydroxyl groups available for initiation during the grafting
reaction. A slight swelling in the structure was observed for NP with
highamountsofgraftedPCL.
Characterization by ATRFTIR is highly applicable to evaluate surface
modification owing to its simplicity, speed and the fact that the
technique is nondestructive; therefore, it is commonly employed to
monitorchangesintheamountofsurfaceboundpolymerasaneffectof
monomer conversion. Neat cellulose does not contain any carbonyl
groupsbutPCLcontainsonegroupperrepeatingunitwhichgivesrise
toasignalaround1730cm1.Theintensityofthissignalincreasesforthe
cellulosesubstratesgraftedwithhigheramountsofPCL,seeFigure13.
Moreover,theintensityofthesignalfromthestretchofhydroxylgroups
(~3300cm1) decreases with increased amount of PCL indicating that
hydroxylgroupsareconsumedduringgrafting.

Figure13. FTIRspectraofgraftedNPandFP(enlargementoftheregions1800
1600 cm1 and 3600 3000 cm1, top) and full spectra of reference PCL and
referencecellulose(bottom).

By DSC, it was found that the degree of crystallinity (Xc) and the
crystallizationtemperature(Tc)increasedforhigheramountgrafted(i.e.
higher conversion) PCL which is in accordance with observations by
35

RESULTSANDDISCUSSION

Hult et al.161. Furthermore, FESEM was employed to investigate and

compare samples of unmodified NP and FP to samples grafted with
variousamountsofPCL,seeFigure14.Additionally,theporosity,pore
size and specific surface area (SSA) were determined by BET, see
Table5. The SEM images showed that the PCLgrafting resulted in a
smoothening of the surface, which is in accordance with the results
obtainedbyBETmeasurements,showingthattheporosityandtheSSA
decreasedforthegraftedsamples.Interestingly,thisshowsthatthepore
sizeofananofibernetworkcanbesuccessfullycontrolledbytheamount
ofgraftedpolymer.

Figure14.FESEMimagesofunmodifiedFP(A),NP(D)andPCLgraftedFP(B,
C),andPCLgraftedNP(E,F).Pleasenote;therearethreeordersofmagnitude
difference between the micrographs of unmodified FP (5 30 m), and
NP(520nm).
Table5.BETspecificsurfacearea,poresize,density,andporosityofthegrafted
cellulosesubstrates.
Sample
Specificsurface
Poresize(nm)
Density
Porosity
area(m2g1)
(kgm3)
(%)
a
FPb
0.55
c
550
62
FPTi50
0.39
c
670
47
refNPb
304
35.8
380
74
NPTi50
52
31.8
600
52
NPTi64
28
28.1
685
47
aFPblanksample(seeTable4). bUnmodifiedNP. cOutofmeasurementofthe
equipment.

36

RESULTSANDDISCUSSION

The mechanical properties of the biocomposites were studied byDMA

at room temperature. The glass transition temperature (Tg) of PCL is
approximately60Cwhichexplainstherelativelylowstoragemodulus
obtained for PCL, 225 MPa. A significant decrease of several orders of
magnitudes in storage modulus was noticed from 60C, attributed to
the melting of the crystalline domains in PCL. However, the grafted
samples have considerably higher values; FPTi50 and NPTi50 have
storagemoduliof700MPaand800MPa,respectively.Thehighmoduli
areretainedatelevatedtemperaturesandcanbeattributedtotheintra
and intermolecular hydrogen bonds in cellulose. Hence, the stiffening
effectofthenanofibernetworkwasclearlyconfirmed.
Unmodifiedcellulosefibersarehighlyhygroscopicandinacomposite,
the mechanical performance is considerably reduced when exposed to
moisture. Consequently, the moisture uptake for PCLgrafted cellulose
is very relevant. Moisture uptake was studied by dynamic vapor
sorption (DVS); experiments were performed at three different
humidities(25,50and80%RH).ItwasfoundthattheNPTi50(50wt
% grafted PCL) had 60 % lower moisture uptake, compared to
unmodified NP, at the highest relative humidity (80 %). Noteworthy,
the water uptake is higher for the unmodified NP at all evaluated
humidities.

4.1.1.2

Monitorgraftingof CLfromacellulosemodelsurfacein
QCMD

This study was conducted to increase the understanding of SI

polymerizationfromcellulosesubstrate,whichischallengingduetothe
lackofsuitablecharacterizationtechniquesforthegraftedpolymerand
the grafted substrate. A deeper knowledge is of particular interest for
polyesters, such as PCL, since selective cleavage by hydrolysis of the
ester linkage between the surface and the grafted polymer chain is
difficult.42, 43 Herein, the QCMD technique was employed to monitor
the insitu SIROP of CL from a cellulose model surface. The SI
polymerization was performed in bulk and catalyzed by the organic
catalyst 1,5,7triazabicyclo[4.4.0]dec5ene (TBD) at room temperature.
InFigure15,itisshownhowthepolymerizationsgaverisetoachange
infrequencyasafunctionofreactiontime.TheSIpolymerizationsfrom
thecellulosemodelsurfaceswereperformedwithtwodifferentcatalyst
concentrations, a) 1 mol% (black line) and 0.5 mol% (grey line).
37

RESULTSANDDISCUSSION

Furthermore, the SI polymerization was studied from both a cellulose

model surface (black line) and a reference gold surface (grey line)
utilizing 1 mol% catalyst, see Figure 15b. The gold surface has no
hydroxyl groups to initiate ROP, and thus, utilized as a reference. All
the measurements were performed under continuous flow. The CL
was pumped into the system under argon atmosphere until a stable
baseline was obtained, thereafter the reaction solution (CL and TBD)
wasintroducedandaninstantdecreaseinfrequencywasnoticedwhich
can be ascribed to an undesired bulk polymerization taking place,
despite the absence of sacrificial initiator. However, to solely monitor
thegraftedPCL;theexperimentwasperformedinthreecycles30min
with thorough rinsing in between the cycles, see Figure 15, which
permittedanestimationoftheaccumulatedamountofgraftedPCL.

Figure 15. ROP of CL with TBD as catalyst insitu in the QCMD. (a) Two
different catalyst concentrations, 0.5mol% and 1mol%, were used
respectively,(b)1mol%TBD,employinggoldasareferencesurface(greyline)
andacellulosemodelsurface(blackline).

The three consecutive cycles shows that reinitiation is possible after

eachcycleandthatmostofthechainendsremainactivesincethemass
increase is approximately the same for each step. However, a slight
decrease was noticed for the third cycle; see Figure 15 and Table 6.
Calculations, by employing the Sauerbrey model, were performed to
assess the grafted amounts, see Table6. The higher catalyst
concentration (1mol%) increased the amount of grafted PCL as
compared to when 0.5mol% of catalyst was utilized, but not the
anticipated doubling of the amount of polymer. Hence, there is a non
linear relationship between grafted amounts of PCL in relation to the
investigatedcatalystconcentrations.

38

RESULTSANDDISCUSSION

Table6.Accumulatedincreaseinmassforeachcycleispresentedforthegold
surface and for the two different cellulose surfaces with different amounts of
catalystinthereactionmixture.
Surface
Cycle1(mgm2) Cycle2(mgm2)
Cycle3(mgm2)
Gold(ref.)
1.4
2.7
4.4
Cellulose,
13.9
26.9
37.5
0.5mol%TBD
Cellulose,
17.2
31.7
44.4
1mol%TBD

Inanattempttobetterunderstandtheeffectofthebulkpolymerization,
thedecreaseinfrequencyforthegoldsurfacewasestimatedtoonlybe
attributed to the polymerization in the bulk. However, gold is a high
energy surface which may explain the small amounts of physically
adsorbedPCLorimmobilizedmonomer.Nevertheless,itconfirmedthat
a SI polymerization occurred from the cellulose model surfaces. The
higher concentration (1 mol%) of TBD also increased the formation of
bulkpolymer,whichcanbeseeninFigure15bytheimmediatedecrease
infrequencyafterintroducingthereactionsolutioninthesystem.This
mostlikelyisattributedtoTBDundergoingunwantedsidereactionsas
reported by Hedrick et al.185. However, this nonlinearity may also be
explained by decreased accessibility of the chain ends due to steric
hindranceasthepolymerchainsaregrowing.TBDneedstoactivatethe
hydroxylgroupsonthesurface,andpossiblytheaccessibilityreachesa
maximumwhichcanbeanotherreasonwhythegraftedamountisnot
directlyproportionaltothecatalystamount.Alreadyatrelativelyshort
graftlengths,consequencesduetosterichindrancemaybenoticed.This
is in accordance with an earlier study where it was reported that the
numberofgrowingchainsdecreasedasthefilmthicknessincreasedfor
SIATRP from a silicon wafer.186 A similar behavior could be expected
forSIROP.

It is also seen from the QCMD analyses that the dissipation is

increasingbetweentheconsecutivecycles,indicatingthattheamountof
grafted polymer increased for every performed cycle, see Table 7. The
obtained dissipation values are in good accordance to other studied
systems where polymers have been attached to a QCM substrate.188,189
Theratiobetweenthenormalizeddissipationandfrequencycanalsobe
seen in Table 7, showing a change in viscoelastic behaviors between
eachconsecutivecycle.Adecreasingtrendforeachcyclewasobserved
39

RESULTSANDDISCUSSION

whichcouldbeattributedtotheformationofamorecompactpolymer
layerandmayalsoindicatethatthepolymerstartstocrystallizeonthe
surfacewhenthePCLchainshavereachedacriticalmolarmass.

Table7.Dissipationaftereachcycle(D)andthedissipationnormalizedagainst
thefrequency(D/f)aftereachcycleforbothcatalystconcentrations1mol%
TBDand0.5mol%,respectively.

Da
Db
D/fax106/Hz1
D/fbx106/Hz1
Cycle1
6.6
5.4
0.068
0.064
Cycle2
11.5
7.3
0.064
0.048
Cycle3
12.6
9.5
0.051
0.045
a1mol%TBD,cellulose.b0.5mol%TBD,cellulose

Thepolymerformedinbulkwasisolatedandcharacterizedby1HNMR
spectroscopy.Themonomerconversionaftereachcyclewassimilarfor
the formed bulk polymer. Interestingly, the bulk polymerization was
four times faster for the higher catalyst concentration which can be
compared to the SI polymerization which only was 1.2 times faster
when twice the amount of catalyst was employed. This may also be
attributed to the behavior of the catalyst during polymerization, as
discussedpreviouslyfortheSIpolymerizationabove.

In Figure 16, AFM images and contact angles (CA) are shown for the
cellulose model surfaces before and after grafting of PCL and it can
clearly be seen that the surface topography has changed The fibrillar
like surface prior to grafting has changed to a smoother surface after
grafting.Thisisalsoreflectedbythesurfaceroughness,(Rq),thelower
the value the smoother the surface. Hence, Rq is decreasing with
increased amount of grafted PCL. Furthermore, the CAs, presented in
Figure 16, show that PCL grafted cellulose model surfaces have
considerably higher CA compared to the unmodified cellulose model
surface. This can be attributed to the nonpolar character of PCL
compared to cellulose. The CA is both affected of the chemical
composition of the surface as well as the surface roughness. However,
theCAsforthePCLmodifiedcellulosemodelsurfacesaresimilarwhich
may be explained by the similar composition in the outermost layer
wherebothsurfacesarecompletelycoveredwithPCL.

40

RESULTSANDDISCUSSION

Figure 16. Contact angle measurements (mean values are presented below the
images) and AFM height (upper) and AFM phase (lower) images of QCM
crystals with cellulose model surfaces before and after grafting of PCL. The
AFMimagesare2x2m,theheightimageshaveazrangeof100nmandthe
phase is 90. The roughness, (Rq), of the different surfaces is shown under the
images.Experimentswereperformedat50%RHand23C.

4.1.1.3

PCLgrafted cellulose microspheres Impact of graft

length and temperature on interfacial adhesion a study
bycolloidalprobebyAFM

The aim of this study was to investigate the impact of polymer graft
lengthsontheadhesion,whichisofsignificantinterestwhendesigning
aheterogeneousmaterialasabiocomposite.Themodelsystem,studied
at a nanoscopic level by the colloidal probe technique, allows direct
quantification of surface interactions. In this investigation, cellulose
microspheres(CMS)havebeengraftedwithdifferentlengthsofPCLvia
41

RESULTSANDDISCUSSION

SIROP.ThisstudywasacontinuationofaninitialworkbyMalmstrm
etal.162whereitwasconcludedthatPCLgraftingoncelluloseimproved
the adhesion significantly especially for the symmetric system, PCLg
CMS/PCLgCMS. The AFM cantilever tip was functionalized with a
CMS(bothunmodifiedandPCLgrafted)allowinginvestigationsofthe
interface between two CMS. Two different systems; an asymmetric
system(CMS/PCLgCMS)andasymmetricsystem(PCLgCMS/PCLg
CMS) were examined. Furthermore, the impact of graft length and
temperature was elucidated. The adhesion measurements were also
performedatdifferenttimesofcontact.

The CMS were grafted with PCL via SIROP of CL in presence of a

sacrificial initiator. After Soxhlet extraction, the PCL and the PCLg
CMS were characterized. The molar mass of the free PCL was
determinedforthesamples.Samplee,seeTable8,wassynthesizedand
utilizedinapreviouslypublishedstudy.162

Table 8. Sample denotation for PCLgrafted cellulose microspheres (PCLg

CMS)andcorrespondingmolarmassesandmolarmassdispersities(M)offree
PCL formed from sacrificial initiator simultaneously by SIROP of CL from
CMS.DPtarget=600forallperformedsyntheses.
Samples
Mw(kgmol1)a
CMS

PCL9kgCMS
9
PCL21kgCMS
21
PCL34kgCMS
34
PCL55kgCMS
55
aDeterminedbyTHFSECwithpolystyrenestandards.

1.2
1.3
1.5
1.9

By ATRFTIR spectroscopy, the carbonyl signal at 1730cm1 confirmed

the presence of PCL, an increased intensity in signal was observed for
highergraftedamounts,seeFigure17.

42

RESULTSANDDISCUSSION

Figure 17. ATRFTIR spectra: (a) neat CMS; CMS surfacegrafted with PCL of;
(b) PCL9kgCMS; (c) PCL21kgCMS; (d) PCL34kgCMS; (e) PCL55kgCMS. The
molecular weights refer to the corresponding values obtained from polymers
formedinbulk(obtainedbySEC).

The adhesion was studied with a PCL55kgCMS (Sample e) probe

attached to the cantilever. As anticipated, the interaction is dependent
onthegraftlengthascanbeseenintheforcedistanceprofilepresented
inFigure18.
The interaction between the PCLmodified probe and the unmodified
CMSreflectsaforceminimumwithasharpjumptozeroforce.Thiscan
be attributed to the instability when the cantilever spring constant
overcomes the adhesion force between the two surfaces. This force
minimum (pulloff force) is useful for composite design as a relative
measure between different materials. When symmetrical systems are
studied, i.e. adhesion between two PCLgrafted CMS, the increasing
graftlengthwillincreasetheadhesionduetotheincreasedsurfacearea
availableforinteractions,suchasentanglements,tooccur.

43

RESULTSANDDISCUSSION

Figure18. Normalized force profiles upon retraction between a CMS grafted

with PCL (Mw=55 kg mol1, Sample e in Table 8.) and (a) neat CMS; CMS
surfacegrafted with PCL of; (b) PCL9kgCMS; (c) PCL21kgCMS; (d) PCL34kg
CMS;(e)PCL55kgCMS.Themolecularweightsrefertothebulkvaluesobtained
bySEC.

By integration of the force curves in Figure 18 (the area is defined as

force curve at negative loads) the total work of adhesion can be
calculated. By studying the work of adhesion as a function of time in
contactat60C,whichisclosetothemeltingtemperatureofPCL,itcan
clearly be seen that the adhesion in a symmetric system is higher,
probably due to the higher chain mobility of the PCL. The work of
adhesion is increasing with longer PCL chains and time in contact.
However,SamplebshowsasimilarbehaviorasunmodifiedCMSwhich
may be explained by the insufficient graft length to create
entanglementsandinterpenetration.

Themaximumpulloffdistance,i.e.thesurfaceseparationatwhichfinal
detachment occurs, for Sample ae was studied at three different
temperatures(25C,40Cand60C),seeFigure19.Thismeasurement
elucidatestherelationshipbetweenthemolecularweightthresholdand
temperature. For measurements performed at 25C, the significant
difference in the interaction between the distances disappears between
Thesamplescandd,correspondingtomolarmassesbetween2134kg
mol1,visualizedbythebluearrowinFigure19.However,byincreasing
the temperature, it can be seen that the required molar mass is lower
which is to be expected due to the increasing mobility at elevated
44

RESULTSANDDISCUSSION

temperatures. The threshold is between921 kg mol1, see the orange

arrowinFigure19.

Figure19.Maximumpulloffdistance(nm)asafunctionofmolecularweight(g
mol1) at 25 C, 40 C, and 60 C after being in contact for 100 s. Inset shows
schematic of the macromolecular induced adhesion mechanism. The molecular
weightthresholdsareindicatedbythebluearrow(25C)andtheorangearrow
(40and60C).

Thelateral,slidingfrictionalforcesarealsoimportantinabiocomposite,
providing information about structural changes. This colloidal probe
AFM study showed that the results obtained for the frictional
measurementscorrelatewiththeobtainedresultsfornormalforces.The
results elucidate the benefits of the grafted layer and increased
temperature which improves the interfacial adhesion, both in terms of
normal and frictional forces which is of great interest regarding
integrationandstabilityforcomposites.

4.1.1.4

Solid state CP/MAS 13CNMR investigation of HCCL

graftedbySIROPofCL

The aim of this study was to investigate the impact of monomer

conversion on the degree of polymerization (DP) and degree of
substitution (DS), by employing solid state CP/MAS 13CNMR. Herein,
SIROPofCLwasperformedfromhydrolyzedcellulosecottonlinters
(HCCL).PCLgHCCLswithdifferentlengthsofPCLwerepreparedto
elucidate if the polymer chains continued to grow with increasing
45

RESULTSANDDISCUSSION

monomer conversion, or if more chains were initiated. The grafting

reactions were performed in bulk and a sacrificial initiator was added.
TheresultingfreeformingPCLwascharacterizedbothbysolution 1H
NMRandSEC,seeTable9.Bielaetal.68havereportedacorrectionfactor
for the molar mass of PCL with regard to the value obtained by
employing a SEC calibration with PS standards. This allows the
determination of molar masses closer to the true values. The corrected
molar masses were assessed, and were found to be in rather good
agreementwiththemolarmassesdeterminedby1HNMR,seeTable9.

Table9.ResultsfromcharacterizationoffreePCLproducedbyROPof CLat
90CandDPtarget=600.
Sample
MWtheoa
MWb
DPb
Mnc
DPSECc
M
1
1

1
(gmol )
(gmol )
(gmol )
PCL20gHCCL
19200
2400
20
1900
15
1.18
PCL31gHCCL
39200
3600
31
2600
22
1.26
PCL35gHCCL
31400
4100
35
2700
23
1.31
PCL39gHCCL
53600
4600
51
4200
36
1.35
PCL64gHCCL
55300
6500
64
5100
43
1.38
a Theoretical molar mass based on conversion by 1HNMR. b Estimated from
endgroup analysis by 1HNMR. c Molecular weights and corresponding DPs
obtainedbySECandcorrectedaccordingtoBielaetal.68

Areference 13CNMRspectrumforHCCLwithassignedcarbonsignals
is shown in Figure 20. Based on analyses by CP/MAS13CNMR, it was
foundthatapproximately3%ofthesurfacehydroxylgroupsinHCCL
wereavailableforsurfacemodification.Inaddition,thismethodcanbe
utilized to determine the bulkmonomer degree of substitution (DSBM)
bymeasuringthespectralintegralsrecordedonPCLgHCCL.

46

RESULTSANDDISCUSSION

Figure 20. 13CNMR spectrum with assigned carbon signals from the AGU in
HCCL.ThenumberingofthecarbonsintheAGUispresentedinFigure2.

TheCP/MAS13CNMRspectraofunmodifiedHCCL,PCLgHCCL,and
pure PCL are shown in Figure 21. The shifts of the carbonyl group at
~170 ppm, OCH2 at ~64ppm, and CH2 at 40 20 ppm are
characteristicforPCL.Inthespectrumforthegraftedsample(PCL64g
HCCL),thecharacteristicsignalsoriginatingbothfromHCCLandPCL
arepresent,confirmingthesuccessfulgrafting.Itwasassumedthatthe
intensityinsignalsfromalltheatomsinthedrysampleswereequaland
homogeneouslydistributedinthedetectedvolume.

Figure21.CP/MAS 13CNMRspectraofPCL(top),PCL64gHCCL(middle)and
HCCL(bottom).

47

RESULTSANDDISCUSSION

The DSSP, i.e. the number of grafting sites, was estimated utilizing the
DSBMandDP.TheDPvaluesweredeterminedeitherbySECorbyend
group analysis of 1HNMR spectra (Table 9). Further details about
assumptions and employed equations can be found in paper IV. In
Table 10, the integral value (Ip) determined by CP/MAS 13CNMR and
the corresponding DSSP can be found for the PCLgrafted HCCLs with
fivedifferentgraftlengths.DSSPwasdeterminedbyseparatelyutilizing
the DP achieved by SEC or 1HNMR. The DP values from these two
techniques deviate slightly but exhibit a linear relationship, see paper
IV. Therefore, a similar trend for DP versus DSSP was anticipated, see
Figure22.

Table10.IntegralvaluesbyCP/MAS 13CNMR,Ip,andpolymerparticlesurface
degree of substitution (DSSP) for PCLgHCCL of different graft lengths. DPs
determinedbySECand1HNMR.
Sample
PCL20gHCCL
PCL31gHCCL
PCL35gHCCL
PCL39gHCCL
PCL64gHCCL

Ip
0.086
0.133
0.129
0.222
0.352

DSSP(SEC)
0.046
0.048
0.045
0.049
0.065

DSSP(1HNMR)
0.034
0.034
0.029
0.044
0.050

Figure 22. Degree of surface substitution (DSSP) of the PCLgHCCLs versus

degreeofpolymerization(DP)offreeformingPCL.

48

RESULTSANDDISCUSSION

Figure22showsthatDSSPwasroughlyconstantandindependentofthe
DP of the grafted chains, suggesting that as the monomer conversion
increasesnoadditionalchainswereformed.Itisalsonoticeablethatthe
DSSP was very low for all the PCLgHCCL samples. Despite the low
number of available hydroxyl groups for surface modification and the
thin layer of grafted polymer, the surface properties changed
considerably.

AlthoughallthesamplesexhibitedrelativelylowDSSP,largedifferences
can be seen in ATRFTIR spectra recorded on the neat HCCL,
homopolymer of PCL and the PCLgrafted HCCL, as shown in Figure
23.However,onlyPCL64gHCCLisshowninFigure23a,sinceitisonly
the carbonyl region of the IR spectra that is strongly influenced by the
different graft lengths. All the PCLgrafted HCCL are presented in
Figure 23b, and the increased intensity of the carbonyl signal confirms
theincreasingDPofthegraftedpolymer.

Figure23.(a)ATRFTIRoffreeformedPCL(dottedline),HCCL(greyline)and
the PCLgHCCL (black solid line), (b) Enlargement of the carbonyl region for
threegraftedsampleswithvariedlengthofthegraftsandHCCLasreference.

This study elucidated that low degree of surface substitution was

obtained and the number of grafting sites was practically constant for
thefivedifferentsamples;thus,theincreasedamountofpolymeronthe
surface was confirmed to be a result of an increasing length of the
polymer chains. Nevertheless, surface characterization by other
techniques, e.g., ATRFTIR, displayed a significant difference between
thevariousPCLgHCCLs(Figure23).

49

RESULTSANDDISCUSSION

4.1.2 Cellulose surface modification by ringopening

metathesispolymerization(ROMP)
The aim of this study was to investigate whether SIROMP could be
employed to surfacemodify cellulose, since this has never before been
reported. This method is highly interesting since a large amount of
polymercanbeobtainedatshortreactiontimesandlowpolymerization
temperature.97,187,188HereinSIROMPofnorbornene(NBE)fromGrubbs
1stgeneration catalystfunctionalized FP was performed at three
different temperatures: room temperature (RT), 0C, and, 78C.
Furthermore, the reaction times were also varied, see Table 11. A
reference sample (Sample 1 in Table11) was utilized to investigate the
effect of catalyst functionalization that was performed prior to the
polymerization.Ablanksample(Sample2inTable11)consistingofan
unmodifiedFPwithoutanycatalystattachedtothesurfacewasexposed
tothemonomersolutionundersimilarconditionsasSample4inTable
11.

Table11.SIROMPreactionconditions,resultingcontactangles(CA)and
weightincrease(i.e.amountofgraftedPNBE)ofthegraftedFP.
Weightincreaseafter
graftinga
(%)
b
1
N/A
N/A
N/A
N/A
2c
RT
30
N/A
N/A
3
RT
1
1183
26
4
RT
30
1136
161
5
RT
60
1234
128
6
0
1
1122
35
7
0
30
1236
76
8
0
60
1146
95
9
78
1
1074
3
10
78
30
1293
23
11
78
60
1256
13
aMeanvalueoftwodoublesamples,bReferencesample:catalystfunctionalized
cellulose.cBlanksamplewithoutanycatalystattached.

Sample

T
(C)

Time
(min)

CA
()

TheSIROMPofNBEfromFPshowedthatdespiteshortreactiontimes
and low polymerization temperatures the surface properties changed
considerably, which is a significant feature for this polymerization
50

RESULTSANDDISCUSSION

technique.Theweightincreaseafterpolymerizationisremarkablyhigh;
some selected samples are shown in Table 11. The samples grafted for
longertimesshowahigherweightincrease.Interestingly,certainseries
had a higher weight increase after 30min compared to 60min,
especially for polymerizations performed at RT. This can possibly be
explained by slight delamination of samples grafted for longer times
where PNBE and/or PNBE/cellulose disintegrate from the FP, as a
consequence of the depolymerization mechanism and secondary
metathesis reactions that increase with time, due to decreasing
concentration of monomer and temperature.81 Furthermore, the
hydrogenbondsincellulosemayalsobeaffectedinthedenselygrafted
samples owing to increased amount of polymer which may break the
intermolecularhydrogenbonds.
Alreadyafter1minofpolymerizationat78C,ahydrophobiccharacter
was obtained, Sample 9 in Table 11. PNBE is much more hydrophobic
than cellulose, which explains the stable CA for the SIpolymerized
samples. No trend was observed by varying temperature and reaction
timewhichpossiblycanbeexplainedbytheinherentsurfaceroughness
of the FP and the large amount of grafted PNBE. Grafting of the FP
causes two competing effects: it increases the hydrophobic character
owing to the PNBEgrafting which gives rise to higher CAs.
Concurrently, the polymer grafting simultaneously smoothen surface
roughness of the FP, resulting in decreased CAs. The effect of grafting
onthephysicalstructurecanbeseeninFigure24,wherecameraimages
ofamildlygraftedFPiscomparedwithadenselygraftedsample.

Figure 24. Norbornenepolymerized filter paper for (a) 1 min at 0 C

(correspondingtoSample6inTable11),and(b)5hatroomtemperature.

The FESEM images, see Figure 25, show that the surface topography
has changed considerably upon SIROMP. The fine structure of the
51

RESULTSANDDISCUSSION

cellulose fibers are covered with PNBE which gives rise to a smoother
surface,alreadyafter1minofpolymerization.

Figure 25. FESEM images of (a) unmodified cellulose and two filter papers
graftedatroomtemperaturefor(b)1minuteand(Sample3inTable11)and(c)
1hour(Sample7inTable11)with5000xmagnification.

FTRaman spectroscopy showed that grafted samples gave rise to a

signal ascribed to the C=C stretch (1665 cm1) from the polymer
backbonewhichisnotpresentinunmodifiedcellulose,seeFigure26.

Figure 26. FTRamanspectraofcellulosepolymerizedwithnorborneneat0C

for1minandfor1h,respectively(Sample8and12inTable11).Anunmodified
filter paper (cellulose) is shown as a reference (black dashed line) as well as
polynorbornene(blackdottedline).

The intensity of the signal increased for longer reaction times, see
Figure27.ThesignalsfromtheCHstretch,at2950cm1and2865cm1,
originating from the alkyl groups are only present in PNBEgrafted
samples.Thereferencesampleandblanksamplegavesimilarsignalsas
obtainedforunmodifiedFP.

52

RESULTSANDDISCUSSION

Figure27.FTRamanspectraoftheC=Cregionat1665cm1:(a)FPgraftedwith
PNBE at 0 C for different reaction times and, (b) FP grafted with PNBE at
differenttemperaturesfor1h.

The thermal degradation of the PNBEmodified cellulose was studied

by thermogravimetric analysis (TGA) in nitrogen atmosphere and
comparedtopurePNBEandcellulose.Thecompositesdecomposedin
twostepswhichconfirmedthepresenceofbothcelluloseandPNBE.It
can be concluded that the SIROMP successfully can be employed to
modify cellulose at short reaction times and reaction temperatures
varyingfrom78CuptoRT.

4.2 MODIFICATION OF CELLULOSE SURFACES BY

PHYSICALADSORPTION
4.2.1 Synthesisofcationiclatexnanoparticles
Surface modification by physical adsorption of for instance
polyelectrolytes, is a highly versatile method to tailor the properties of
the surface. It can often be performed under mild conditions in water,
whichisdesirableregardingenvironmentalconcerns.2,189,190Adsorption
ofpolyelectrolytesisalreadyestablishedforsurfacemodificationwithin
the pulp and paper industry. Furthermore, cellulose fibers are most
frequently dispersed in water; hence there is a prerequisite of solvent
exchange to organic solvents for covalent modifications. This concept,
wellinvestigated with respect to polymer attachment to cellulose, is
bothverytediousandcostly.Therefore,thesynthesisanddevelopment
of amphiphilic block copolymers with chargeable atoms or functional
groups that possibly can be attached to cellulose through physical
adsorptionareofgreatinterest.
53

RESULTSANDDISCUSSION

In this work, cationic amphiphilic latex nanoparticles were designed

and synthesized. The employed RAFT agent, CTPPA, has previously
been utilized successfully in several studies137, 142, 146152, 191, 192 to form
amphiphilicblockcopolymersinaqueoussolutions.133,137,140146,185,186The
hydrophilic block in the final polymer, e.g., the macroRAFT, stabilized
the formation of particles in the emulsion polymerization. Hence, the
synthesis was performed in absence of any additional low molarmass
surfactant, which cause poor latex stability under freezing conditions
and migration in the films due to the presence of noncovalently
attachedsmallmolecules.142

4.2.1.1

RAFTmediated surfactantfree emulsion polymerization

ofMMA

The macroRAFT consisting of cationic P(DMAEMAcoMAA) was

employed for the RAFTmediated surfactantfree emulsion
polymerization of MMA, see Figure 28. Table 3 presents the
experimental conditions employed for polymerizations of methyl
methacryate (MMA). Four different molar masses of the hydrophobic
block were targeted by varying the initial amount of macroRAFT and
keepingtheamountofMMAconstant.Thereby,thesolidcontentvaried
from17to25wt%.

Figure28.SchematicillustrationofthePISAsystem.Formationofcationiclatex
nanoparticlesofP(DMAEMAcoMAA)bPMMA.

54

RESULTSANDDISCUSSION

Highmonomerconversionswereobtainedaftershortreactiontimesfor
all performed polymerizations, see Figure29a. A slightly lower
conversion was obtained for Latex 4 (entry 4, Table 3) which has the
highest targeted molar mass. Asfor the macroRAFT, it was difficult to
monitor the evolution of molar masses with conversion due to the
insolubility of the amphiphilic block copolymers at low MMA
conversions owing to the dominating nature of the insoluble
macroRAFT. However, the block copolymers were soluble in DMF at
higher monomer conversions of MMA and the SEC traces for the final
samplescanbefoundinFigure29b,showingthathighermolarmasses
wereobtainedwithincreasedtargetedDP.

Figure29.(a)EvolutionofmonomerconversionversustimeforRAFTemulsion
polymerizationsofMMAfromgravimetricanalysisand(b)SECtracesoffinal
latex,fordifferenttargetedDP.

ThevaluesofthemolecularweightsfromtheSECmeasurementscanbe
foundinTable12,andascanbeseentheyareconsiderablyhigherthan
thetargetedmolarmass.Thereareseveralpossibleexplanationstothis
discrepancy, e.g., the cationic latex nanoparticles consisting of
P(DMAEMAcoMAA)bPMMA are different from the linear PMMA
that was employed for calibration of the SEC instrument. Moreover, it
maybeattributedtothehydrolysissensitivenessofthetrithiocarbonate
chain end of P(DMAEMAcoMAA)+Cl which has also been reported
previously for a similar charged methacrylate, PMAA.146, 147 The
hydrolysis may give rise to chain transfer reactions which will affect
both the molar mass and the molar mass dispersity. The particle sizes
withthecorrespondingpolydispersitydeterminedbyDLSaswellasthe
charges measured by polyelectrolyte titration (PET) can be found in
Table12.

55

RESULTSANDDISCUSSION

Table12.CharacterizationoflatexesbySEC,TEM,DLS,andPET.Thenumber
ofparticlespervolume,Np,basedonTEMobservations.
Entry

Mn
(kg
mol1)a

Ma

Dhb

PdIb

(nm)

Dnc

Np

Charge

(nm)

(L1water)d

(meq/g)e

Latex1
59 1.2
50 0.08
285 8.701015
30.4
Latex2
116 1.4
68 0.05
446 2.241015
17.3
12.6
Latex3
240 1.4
98 0.03
776 4.181014
5.0
Latex4
380 1.8
146 0.01
12211 1.051014
a Obtained by DMFSEC employing PMMA calibration. b Obtained by DLS.
c Obtained by TEM. d Calculated from numberaverage diameter obtained by
TEM.eMeasuredbyPETinMilliQwater.

TheDLSmeasurementsshowthatparticlesizeincreasedwiththemolar
mass of the PMMA block and that narrow size distribution was
obtained. Further analyses by cryoTEM (Figure 30) indicate that
spherical latex particles, reasonably uniform in size, were effectively
formedduringthePISAprocess.Moreover,bytargetingahigherdegree
of polymerization of the hydrophobic core, the size of the particles
increases which was in accordance with the results obtained by both
DLS and SEC. The size of the particles measured by TEM was smaller
since only the hydrophobic core was visible while DLS results refer to
thehydrodynamicradius.Thesmallparticlesizesobtained,andallthe
abovedatawereconsistentwiththeselfassemblyofblockcopolymers
and confirmed a posteriori that the RAFT of DMAEMA performed in
water at pH7 was effectively controlled. The potentials and the PET
measurements both showed that all the latexes were cationically
charged despite the presence of PMAA. Furthermore, the PET
measurements elucidated that the charge per gram material decreased
as expected since the larger particles contain an increasing amount of
nonchargedPMMA.

56

RESULTSANDDISCUSSION

Figure 30. TEM images of the final cationic P(DMAEMAcoMAA)bPMMA

latexes,obtainedbyRAFTmediatedsurfactantfreeemulsionpolymerization.

4.2.2 Adsorptionofcationiclatexoncellulosemodelsurfaces
Adsorption was investigated in the QCMD to evaluate the affinity
between the cationic P(DMAEMAcoMAA)bPMMA latex and a
cellulose model surface. The significant decrease in frequency verified
theadsorptionofthecationiclatexestothenegativelychargedcellulose,
see Figure31. As anticipated, the frequency was decreasing with
increasing molar mass of the PMMA block in the cationic latex.
Furthermore, the charge density, as confirmed by PET measurements
(see Table 12), decreasedwith increasing molar mass of the uncharged
hydrophobicblock.

Figure31.AdsorptionofP(DMAEMAcoMAA)bPMMAlatexesonacellulose
modelsurfaceinaQCMD.Thesolidlinescorrespondtothefrequencyandthe
dottedlinestothedissipationforthefourdifferentsamples.Theconcentration
of the latex dispersion, prepared for the adsorption measurements, was
100mgL1.

57

RESULTSANDDISCUSSION

The initial adsorption kinetics for the Latex 2 and Latex 3 are similar
whereasLatex1possessesaslowerkinetics.Consideringthedifference,
inparticleconcentration,seeTable12,thesizeofthehydrophobiccore
and the change in the charged corona, it is reasonable that initial
adsorptionoftheLatex2andLatex3issimilar.Latex4,consistingofthe
largest particles, was expected to have the slowest adsorption which
was confirmed by experimental measurements. However, as the
adsorbed amount increases, the interaction within the adsorbed layer
will also affect the adsorption kinetics as the saturation adsorption is
reached. Furthermore, the higher charge of Latex 1, see Table 13, can
also explain the adsorption behavior of this species. In Figure 31 it is
shown that there is a small initial increase in frequency and also a
decreaseinthedissipationindicatingdeswellingofthecelluloseasalso
reportedearlier.

Table 13. Adsorbed mass per area, mA, of cationic P(DMAEMAcoMAA)b

PMMA latexes (Latex 14) on the cellulose model surfaces, dissipation after
adsorptionand,thedissipationnormalizedagainstfrequency.
Entry
Latex1
Latex2
Latex3
Latex4

mA(mgm2)
4.25
14.98
21.77
39.12

D106
3.06
1.32
11.30
25.67

D/f(106Hz1)
0.127
0.016
0.092
0.177

BystudyingtheAFMimagesinFigure32aditcanclearlybeseenthat
large amounts of latex was adsorbed to the cellulose model surfaces,
whichisinaccordancewiththelargedecreaseinfrequencyobservedin
theQCMDmeasurements.Furthermore,itcanbedetectedbyAFMthat
thesurfacesarenearlycompletelycoveredwithlatexparticles.
In order to examine the wetting properties of the surfaces, CA
measurements on latex saturated cellulose model surfaces were
performed. The CAs varied between 64 and 71 (Table 14) which are
significantly higher than 25, the CA for the neat cellulose model
surfacesadsorbedonasmoothsilicaQCMcrystal.

58

RESULTSANDDISCUSSION

Figure 32. AFM images of adsorbed cationic P(DMAEMAcoMAA)bPMMA

latexesoncellulosemodelsurfacesformedonQCMcrystalsandinsertpictures
showingthecontactangles.Thefourimagesinthetop(ad)showthesurfaces
after adsorption of latex (100 mg L1) and the four images in the bottom (eh)
werecollectedafterannealingat160Cfor2h.

59

RESULTSANDDISCUSSION

The cellulose model surfaces with adsorbed latex were heated (160 C
for 2 h) to increase the mobility of the polymer chains of the particles.
Thus, the charged hydrophilic polymer could move to the negatively
chargedcellulosemodelsurfaceandthehydrophobiccoreorienttothe
hydrophobicairsolidinterface.Thereorganizationmaystrengthenthe
interfaceandincreasethehydrophobicityoftheoutermostlayerofthe
surface. Upon heattreatment, the PMMA hydrophobic core was
exposedwhichincreasedthecontactanglesto9398(Table14).The
AFM images (Figure 32 eh) show that the heights of the particles
decreasedafterannealing.Thiswasanticipatedsincethemobilityofthe
polymer chains increased above the glass transition temperature of
PMMA,themaincomponentinthelatex.Theaverageroughnessvalues
oftheentiresurfacecanbefoundinTable14.Asanticipated,theheated
surfaces have a lower roughness than the nonheated surfaces which
confirms that the particles annealed to some extent during the heat
treatment.

Table 14. Contact angle and roughness measured over the entire surface on
cellulose model surface after adsorption of cationic P(DMAEMAcoMAA)b
PMMAlatexesbeforeandafterheating().
Entry
Cellulosemodelsurface

CA()
251

CA(),

Rq

Rq,

Latex1

664

932

14

4.6

Latex2

712

933

12

4.9

Latex3
Latex4

672
646

952
981

14
32

4.2
11.0

As the cellulose model surfaces were fully covered with latex

nanoparticles, it was impossible to distinguish individual particles.
Therefore,acontrolexperimentwasperformedemployingsilicawafers
which is a smoother surface compared to the cellulose model surfaces
andapplyingshorteradsorptiontimes.Furtherdetailscanbefoundin
paper VI. Lower particle coverage was obtained which both can be
ascribedtothesurfaceroughnessandalsototheadsorptiontime.

60

CONCLUSIONS

5. CONCLUSIONS
Inthisthesis,adeeperunderstandingofsurfacemodificationofvarious
types of cellulose substrates through graftingfrom and physical
adsorptionhasbeenaccomplished.Thepolymersemployedforsurface
modification were synthesized by different polymerization techniques
(ROP,ROMP,RAFT,andemulsionpolymerization).

SIROP from cellulose substrates with high surface area gave rise to
higheramountsofgraftedpolymercomparedtofilterpaper,explained
by the increased number of available, initiating hydroxyl groups. The
biocomposite formed insitu showed improved mechanical properties
compared to pure PCL material and the surface modification reduced
themoistureuptakeconsiderablycomparedtounmodifiedcellulose.

New methodologies havebeen developed to improve the fundamental

understanding for SI polymerizations. For the first time, SIROP was
successfully performed from a cellulose model surface and the SI
polymerizationcouldbemonitoredinrealtimeinaQCMD.

BytheAFMcolloidalprobeexperimentitwasshownthattheinterfacial
adhesion between pure PCL and cellulose was significantly improved
by polymer grafting. The interfacial adhesion was found to increase
with the grafted chain length which can be attributed to formation of
chain entanglements. Increasing temperature and time in contact, also
contributedtobetteradhesion.Furthermore,thecorrelationbetweenthe
degree of substitution (DS) and degree of polymerization (DP) was
examined by solid state 13CNMR spectroscopy. It was shown that the
DS was relatively constant, independently of DP, which corroborated
that the length of the grafted polymer increased with increasing
monomer conversion. Despite the low DS the surface properties
changedconsiderably.

SIROP results in low amounts of grafted polymer on the cellulose

substrate.Forsomeapplicationsitmaybevaluable,orevennecessary,
to have more polymer on the surface. To achieve such a material, SI
ROMP of NBE was performed. Remarkably high amounts of polymer
61

CONCLUSIONS

were obtained already after very short reaction times and at low
polymerization temperature. Weight increases by up to 150% were
observed after grafting and the hydrophobicity was considerably
enhanced.

ThefeasibilityofROPishamperedbythesensitivitytotraceamountsof
water. Additionally, from an industrial point of view it may be more
attractive,andversatile,tohaveapreformedpolymerinwatersolution
whichforinstancecanbeaddeddirectlytothepulp,butstillproviding
the final cellulosebased material with the desired properties. Inspired
bythis,surfacemodificationofcellulosewasalsoperformedbyphysical
adsorption. The PISA process provided narrow sizedistributed,
sphericalcationicparticleswithoutemployinganyadditionallowmolar
masssurfactant.Theparticlesizecouldbetunedbytargetingdifferent
DPs of the hydrophobic block. Adsorption measurements in the QCM
showedthatthecationiclatexparticleshaveahighaffinitytocellulose.
The cellulose model surface turned hydrophobic after the adsorption,
and after heat treatment the particles reorganized and the hydro
phobicityincreased.

62

FUTUREWORK

6. FUTUREWORK
Inthisthesis,mainlymodelsystemshavebeeninvestigated.Howeverit
would be interesting to apply the acquired knowledge for designing a
biocompositewithtailoredproperties,andtocharacterizeandevaluate
its properties at nano/micro/macroscopic level employing the
techniquesdevelopedthroughoutthiswork.

Given the findings in this thesis, there is no doubt that surface

modification by SIROP can be successfully performed from different
cellulosesurfaces.However,itwouldbeinterestingtoinvestigatewhy
there is such a pronounced difference between the theoretical molar
mass(calculatedbasedonmonomerconversion)andthemolarmassof
the polymer formed from the sacrificial initiator, in parallel to the
grafting reactions. It may be attributed to residual water or a non
negligible number of initiating hydroxyl groups on the cellulose
substrateoracombinationthereof.Itcanalsopossiblybeattributedto
transesterification reactions and decreased activity of the chain ends,
possiblyduetocyclization.Herein,adeeperknowledgewouldincrease
theunderstandingforthisgraftingprocess.

SIROMPresultsinsignificantlylargeramountsofgraftedpolymerthan
SIROP. SIROMP requires a preactivation of the surface by the
attachment of Grubbs catalyst. It would be interesting to elucidate
whetherthisprocesswouldprovidemoreactivechainsonthesurfaceor
longer chains, compared to conventional SIROP. Furthermore, it may
be interesting to examine, and study other SI polymerizations by the
CP/MAS 13CNMR technique, in particular SIROMP due to the high
yieldofgraftedpolymerstoexaminethecorrelationbetweenDSandDP
andcomparetotheresultsobtainedforSIROP.

Although it may be a challenge to cleave the densely grafted PNBE

formedbySIROMPfromthecellulosesurface,itwouldbevaluableto
develop a method to characterize the grafted polymer. More
information about the grafted PNBE may be required in order to
accomplish a successful posttreatment which can be performed from
the double bonds in the structure. Furthermore, other monomers with
63

FUTUREWORK

reactive groups that enable further postfunctionalization could

potentially be evaluated for SIROMP from cellulose. SIROMP in
aqueous systems would be of great interest since nanocelluloses are
providedinwaterdispersions.

Cationic amphiphilic latex nanoparticles were successfully developed.

InthisworkthehydrophobicblockconsistedofPMMAwhichhasaTg
wellaboveroomtemperature.Itisworthtoinvestigateemploymentof
other hydrophobic monomers for synthesis of cationic latex
nanoparticles. Thereby, properties of the final material can be tailored.
PolymerswithlowerTgsareofparticularinterestowingtotheirability
toformfilms.Furthermore,performingthePISAprocessinpresenceof
nanocelluloses may be an interesting approach to produce a
biocompositeinsitu.

64

ACKNOWLEDGEMENTS

7. ACKNOWLEDGEMENTS
In my opinion, this work is not only a doctoral thesis, but also my
journey and adventure the last 4.5 years of my life. This would have
been impossible without help, support and love from a lot of people I
metalongtheway.Youhaveall,inonewayoranother,contributedto
this thesis. Without you, this work (and my journey) would not have
beenthesame.Thankyou!

There would not have been any journey without the funding. The
Swedish Research Council Formas and Wallenberg Wood Science
Centeraregratefullyacknowledgedforfinancialsupportovertheyears.
SvenskFranska Stiftelsen is warmly thanked for generously having
supportedmetwicewhichhasenabledmystaysinLyon.

IwouldlikeexpressmysinceregratitudetomysupervisorsAssoc.Prof.
Anna Carlmark and Prof. Eva Malmstrm for enthusiastic having
guided me through this journey by inspiration, scientific skills, and
passion,especiallywhenthingswerenoteasy.Ithasbeenatruehonor
and pleasure to work with both of you. Your confidence and support,
havegivenmetheopportunitytodevelopanddiscovernewhorizons.I
would also like to thank you for your thoughtfulness about me as a
person.

A part of the work presented in this thesis was performed in LCCP at

CPE Lyon. My deepest gratitude to Prof. Bernadette Charleux for
accepted me visiting her laboratory. Ph.D. Muriel Lansalot and Ph.D.
FranckDAgostoarealsowarmlythankedforthe8monthsyouguided
me through the exiting field of RAFT and emulsion polymerizations.
ThankyouPierreYvesDugasandOlivierBoyronforassistancewiththe
cryoTEM and SEC analyzes, respectively. Merci toute lquipe du
LCPP.anemaquefaitduplaisirdepasserdutempsavecvous.

Thiswork,andmyjourney,wouldhavebeenverylonelyandfarfrom
as interesting as it has been with all my collaborations. I acknowledge
all my coauthors for excellent collaborations, Prof. Lars Wgberg,
Assoc. Prof. Tomas Larsson, Prof. Mark Rutland, Prof. Lars Berglund,
65

ACKNOWLEDGEMENTS

Prof. Mohammed Lachini, Simon Utsel, Andreas Fall, Assya

Boujemaoui,NiklasNordgren,HoussineSehaqui,GustavNystrm,and
HannaBlomberg.

MyjourneyasaPh.D.studentatthedivisionactuallystartedwhenProf.
Anders Hult recruited me to the group, as diploma worker, in Oskars
backe. Anders is thanked for never having forgotten that it was a
mistaketonotrecruitmeasPh.D.student(forMichael)andforhaving
recommended me for my current position. Prof. Mats Johansson is
thanked for all the wordfeud games, for always being positive and
helpful.Assoc.Prof.MichaelMalkoch is thankedfor being considerate
and curios about everything. Ph.D. Linda Fogelstrm is thanked for
alwaysbeingagreatsupport.

Daily life as a Ph.D. student is filled of successes and challenges

(probably more often the lastmentioned). Any success would not be
worthlivingifthereisnoonetosharethehappinesswith,aswellasthe
badmoments.Allformerandpresentcolleaguesandfriendsatdivision
of Coating technology are thanked for being absolutely lovely. Thank
you for all your invaluable help, support, all the laughs and tears! All
othercolleaguesandfriends,seniorsandotheremployees,especiallyat
WWSCandFiberTechnologyarethankedforthisgreattime.Mia,Inga,
Ramiro,Karin,Kjell,Bosse,Mona,andIngerareallthankedforallyou
helpforadministrativeandcomputerassistance.

During shorter or longer periods of time on my journey, I have had

company of some fantastic students with inquiring minds. Thank you
everybody for having enlighten my life during my Ph.D. studies.
Helena,Surinthra(Janne),Assya,Malin,Fredrik,Stina,Emilia,Marcus,
Oskar,Susanne,andTobiasYouarethebest!

Butinanyjourney,themostimportantthingistonotgetlost.Iwould
liketothankallmystarsandfriendsallovertheworldthatbyshining
bright in the sky, always indicate the right direction. Thank you to all
myfriendsoutsideKTHforremindingmethattheworldislargerthanI
thinksometimes.

Finally,Iwouldliketodedicatethisworktomyfamilyforalwaysbeing
therewheneverIneedyou.
66

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