Cellulose Derivatives: Synthesis, Properties And Applications

LIST OF ORIGINAL PUBLICATIONSIM. Granström, J. Kavakka, A. King, J. Majoinen, V. Mäkelä, J. Helaja, S. Hietala, T.Virtanen, S-L. Maunu, D. S. Argyropoulos, I. Kilpeläinen: Tosylation and acylationof cellulose in 1-allyl-3-methylimidazolium chloride, Cellulose, 2008, 15, 481-488.IIM. Granström, A. Olszewska, V. Mäkelä, S. Heikkinen, I. Kilpeläinen: A newprotection group strategy for cellulose in an ionic liquid: simultaneous protection oftwo sites to yield 2,6-di-O-substituted mono-p-methoxytrityl cellulose, TetrahedronLetters, 2009, 50, 1744-1747.IIIM. Granström, J. Majoinen, J. Kavakka, M. Heikkilä, M. Kemell, I. Kilpeläinen:Effect of self-assembly via π-stacking to morphology and crystallinity on tritylatedcellulose, Materials Letters, 2009, 63, 473-476.IVM. Granström, M. Havimo, M. Heikkilä, I. Kilpeläinen: Synthesis, characterisationand application of novel self-assembled comb-like liquid crystalline biphenylcellulose as UV absorber for paper, Journal of Materials Chemistry, 2009, 19, 639644.VM. Granström, M. Pääkkö, H. Jin, E. Kolehmainen, I. Kilpeläinen, O. Ikkala:Sustainable approach as an alternative preparation method for purely bio-based highlywater repellent cellulose materials, 2009, submitted.8

SO3HCNTCP-MAS lucopyranose azolium bromide1-allyl-3-methylimidazolium chloride1-allyl-3-methylimidazolium acetatebacterial celluloseBuchwald-Hartwig cross-coupling1-butyl-2,3-dimethylimidazolium chloride1-butyl-3-methylimidazolium bromide1-butyl-3-methylimidazolium chloride1-butyl-3-methylimidazolium acetate1-butyl-3-methylimidazolium tetrafluorophosphate1-butyl-3-methylimidazolium hexafluorophosphate1-butyl-3-methylimidazolium thioisocyanatecarbazole carbonyl oxyamineN,N ecellulose formiatecarboxymethyl cellulose1-hexyl-3-methylimidazolium chloride1-octyl-3-methylimidazolium chloridechloro sulphonic acidcarbon nanotubecross-polarisation magic angle spinning solid state nuclear magneticresonance spectroscopycarbon ecyclic voltammetrydonor-acceptor pairN,N-dicyclohexylcarbodiimidediethylamineN,N m chloride1,3-dimethyl-2-imidazolidinone/lithium chloridedimethylformamide sulphurtrioxide complexdimethylsulfoxide/tetra-n-butylammonium fluoridedegree of polymerisationdegree of substitutionethylenediamine1-ethyl-3-(3 midazolium aluminiumtetrachloride1-ethyl-3-methylimidazolium tetrafluoroborate1-ethyl-3-methylimidazolium zolium um chloride1-ethyl-3-methylimidazolium nitrite1-ethyl-3-methylimidazolium nitrate9

lium acetatetriethylamineferric sodium tartratephosphoric acid(hydroxylpropyl)celluloseheteronuclear single quantum coherenceionic liquidinfrared spectroscopyindium tin oxidepotassium tert-butoxideLangmuir-Blodgettliquid crystalmatrix assisted laser desorption/ionisation-time of flight massspectrometrymicrocrystalline cellulose1,3-dimethylimidazolium dimethylphosphatemethoxymethyl chloridemedium pressure liquid chromatography1-naphtyl-3-methylimidazolium N-methylmorpholine-N-oxidenuclear magnetic resonance1-methyl-2-pyrrolidinone/lithium chloridepolyanilineparaformaldehydepolarising optical microscopyroom temperature ionic liquidself-assembled monolayersugarcane bagassesize exclusion chromatographyscanning electron microscopytetra-n-butylammonium fluoridetransmission electron microscopytrifluoroacetic acidthermogravimetric analysisthin layer chromatographytrityl chlorideultraviolet-visible spectroscopywide-angle X-ray scatteringpowder X-ray diffractometerzinc chloride10

- Imagination is more important thanknowledge Albert Einstein (1879-1955)1. IntroductionCellulose is the most abundant polymer on Earth, which makes it also the most commonorganic compound. Annual cellulose synthesis by plants is close to 1012 tons.1 Plants containapproximately 33% cellulose whereas wood contains around 50 per cent and cotton contains90%. Most of the cellulose is utilised as a raw material in paper production. This equates toapproximately 108 tons of pulp produced annually.2 From this, only 4 million tons are usedfor further chemical processing annually.3 It is quite clear from these values that only a verysmall fraction of cellulose is used for the production of commodity materials and chemicals.This fact was the starting point of our research into understanding, designing, synthesisingand finding new alternative applications for this well known but underused biomaterial.1.1 Structure and reactivity of celluloseThe chemical and physical properties of cellulose can only be properly understood byacquiring knowledge of the chemical nature of the cellulose molecule in addition to itsstructure and morphology in the solid state.4 A profound understanding of the structuralproperties of native cellulose is a requirement to understand the effects of differentsubstituents on the chemical and physical properties of cellulose and its derivatives.4 Whenconsidering macromolecules of any kind, three structural levels must be distinguished:1) The molecular levelOn this level the cellulose is treated as a single macromolecule. At the molecularlevel the following concepts are considered: chemical constitution, molecularmass, molecular mass distribution, the presence of reactive sites and potentialintramolecular interactions.11

2) The supramolecular levelThis is one step further up from the molecular level and considers cellulosemolecules as interacting with other cellulose chains in the form of packing andmutual ordering of the macromolecules to form larger structures. At thesupramolecular level the following concepts are of importance: aggregation of themolecular chains to form elementary crystals and fibrils, the degree of orderwithin and around the fibrils and fibrillar orientation with respect to the fibre axis.3) The morphological levelThis level covers structural entities formed by cellulose molecules. As thestructures get larger, they may become very complex. On the morphological level,the existence of distinct cell wall layers in native cellulose fibres or in skin-corestructures in man-made cellulosic fibres are investigated. Presence of voids orinterfibrillar interstices is also studied.In this study, the focus is on those levels that emphasise the molecular and thesupramolecular level, with considerations about the morphology of the compounds.1.1.1Cellulose molecule at the molecular levelPayen was the first to determine the elemental composition of cellulose as early as in 1838.5He found that cellulose contains 44 to 45% carbon, 6 to 6.5% hydrogen and the restconsisting of oxygen. Based on these data, the empirical formula was deduced to be C6H10O5.However, the actual macromolecular structure of cellulose was still unclear. Haworthproposed a chain-like macromolecular structure in the late 1920s, whereas Staudingerdelivered the final proof of the highly polymer nature of the cellulose molecule.6,7,8Cellulose is a linear and fairly rigid homopolymer consisting of D-anhydroglucopyranoseunits (AGU). These units are linked together by β-(1 4) glycosidic bonds formed betweenC-1 and C-4 of adjacent glucose moieties (Figure 1).1 In the solid state, AGU units are rotatedby 180 with respect to each other due to the constraints of β-linkage. Each of the AGU unitshas three hydroxyl (OH) groups at C-2, C-3 and C-6 positions. Terminal groups at the eitherend of the cellulose molecule are quite different in nature from each other. The C-1 OH atone end of the molecule is an aldehyde group with reducing activity. Aldehyde groups form a12

pyranose ring through an intramolecular hemiacetal form. In contrast, the C-4 OH on theother end of the chain is an alcoholborne OH constituent and thus is called the non-reducingend. It has been known from the infrared spectroscopy (IR), X-ray crystallography andnuclear magnetic resonance (NMR) investigations, that the AGU ring exists in the pyranosering form and that this adopts the 4C1-chair formation which constitutes the lowest energyconformation for D-glucopyranose.9,10,11,12,13,14,15,164OHHHOHOH OHHH6H5 HOO4HOHOH OH3 HH21HHOHH OHO1HOO180OHOOHHHOHHHOH OHHOHHnFigure 1. Molecular structure of cellulose representing the cellobiose unit as a repeating unitshowing reducing (right) and non-reducing (left) end-groups. When considering only one ofthese glucopyranose structures, repeated anhydroglucopyranose units (AGU) are rotated 180 with respect to each other.7The chain length of the cellulose polymer varies depending on the cellulose source.4 Forexample, naturally occurring vascular plant cellulose has a degree of polymerisation (DP)higher than 10 000.4 The value of DP is greatly dependent on the method of isolation andtherefore, the cellulose used in practise has an average DP of between 800-3000.4Microcrystalline cellulose (MCC) used in the present study is pure and highly crystallinecellulose that has been produced by acid hydrolysis and has DP values in a range of 300-600.In its commonly used form, isolated cellulose is always polydisperse. It is like nearly allpolymers, a mixture of molecules that has the same basic composition but differs in the chainlength. Therefore, the molecular mass and the DP of cellulose can only be considered asaverage values.The chemical character and reactivity of cellulose is determined by the presence of threeequatorially positioned OH groups in the AGU, one primary and two secondary groups.1 Inaddition, the β-glycosidic linkages of cellulose are susceptible to hydrolytic attack.1 The13

hydroxyl groups do not only play a role in the typical reactions of primary and secondaryalcohols that are carried out on cellulose, but also play an important role in the solubility ofcellulose.1 Cellulose is insoluble in common organic solvents and in water.1 This is due to thefact that the hydroxyl groups are responsible for the extensive hydrogen bonding networkforming both, intra- and intermolecular hydrogen bonding as shown in figure 2.4 In order todissolve cellulose, the prevailing hydrogen bonding network must be broken.There are two possible mechanisms by which the OH groups in the cellulose molecule formhydrogen bonds. One is by the interaction between suitably positioned OH groups in thesame molecule (intramolecular). These are located between C2-OH and C6-OH groups andC3-OH with endocyclic oxygen (Figure 2a, i and ii). The other mechanism occurs whenneighbouring cellulose chains (intermolecular) interact via their C3-OH and C6-OH groups(Figure 2, iii). Intramolecular hydrogen bonds between the hydroxyl group at the C-3 andoxygen of the pyranose ring were first described in the 1960s by Liang and Marchessault, andBlackwell et al. who claimed the existence of a second ‘pair’ of intramolecular hydrogenbonds between the C-6 and C-2 of the neighbouring AGUs.17,18a)HO64ii5HO HO123OH OOOOOHiHb)OH645O3HOHO 2 HO1OOOHOiiiO46HH5HO3HO 21OH OOOOOHHFigure 2. Cellulose structures showing a) the intramolecular hydrogen bonding between C2OH and C6-OH (i), and C3-OH with endocyclic oxygen (ii); and b) the intermolecularhydrogen bonding between C3-OH and C6-OH (iii) (supramolecular structure).14

Cellulose is regarded as a semi-flexible polymer. The relative stiffness and rigidity of thecellulose molecule is mainly due to the intramolecular hydrogen bonding. This property isreflected in its high viscosity in solution, a high tendency to crystallise, and its ability to formfibrillar strands. The chain stiffness property is further favoured by the β-glucosidic linkagethat bestows the linear form of the chain. The chair conformation of the pyranose ring alsocontributes to chain stiffness. This is in contrast to the α-glucosidic bonds of starch.1.1.2Supramolecular structure of celluloseCellulose chains have a strong tendency to aggregate and to form highly ordered structuresand structural entities. The highly regular constitution of the cellulose molecule, the stiffnessof the molecular chain and the extensive hydrogen bonding capacity favour molecularalignment and aggregation. Despite this knowledge, the detailed structure of this hydrogenbond network is still an ongoing subject for discussion.The history of the supramolecular structure of cellulose, started as early as 1913 whenNishikawa and Ono discovered the structure of fibrous cellulose by the well-defined X-raydiffraction patterns.19,20 This finding led to the conclusion that individual cellulose moleculestend to arrange themselves in a highly organised manner leading to a ‘paracrystalline’ state.In the first decades of the past century, chemists believed that cellulose was an oligomeric,possibly ring-like glucane of up to approximately 100 glucose units. Therefore, it wasassumed that the micelles consisted of crystalline aggregates of such oligomers.4 This wasfirst proposed in 1865 by the biologists Naegeli and Schwendener for natural reticulumsubstrates, such as cellulose.4 Based on these findings, and the theories of Staudinger on themacromolecular structure, scientists developed the ‘fringed fibrillar’ model of the structure,which is still the prevailing accepted theory of the supramolecular structure (Figure 3).2115

Figure 3. Fringed fibril model of the supramolecular structure of cellulose.21 The latticeworkrepresents the highly ordered (crystalline) region whereas elongated lines represent the lowordered (amorphous) regions.The supramolecular model of cellulose is based on the organisation of cellulose chains into aparallel arrangements of crystallites and crystallite strands, which are the basic elements ofthe fibres.4 The intermolecular hydrogen bonding between C6-OH and C3-OH of adjacentchains are considered to be the major contributors to the structure of cellulose, and isregarded as the predominant factor responsible for uniformal packing.22 In turn, theconsistency of the interchain interactions is governed by the high spatial regularity andavailability of the hydroxyl groups. The order of molecules in a cellulose fibre is far fromuniform throughout the whole structure, and so it can be assumed that there exists regionswithin the structure, that have varying amounts of order. Today experimental evidencedescribes a two-phase model, which clearly divides the supramolecular structure into tworegions: low ordered (amorphous) and highly ordered (crystalline) excluding the mediumordered regions completely.21 In the present study, this fringed fibril model is used as a basicconcept to describe the hierarchy of cellulose derivatives formed by self-assembly, and in thecontext of their crystallinity.16

The degree of crystallinity of cellulose and its derivatives can be measured by different X-raytechniques such as by wide-angle X-ray scattering (WAXS) and by powder X-raydiffractometry (XRD).23 Moreover, solid state NMR methods have proved to be a valuabletools in the determination of the crystallinity of cellulose.24,25Cellulose exists in several polymorph (classes I, II, III, IV) that differ in their unit celldimensions (Table 1).4 The combination of X-ray diffraction with model building and alsowith conformational analyses in the 1970s provided the current model for the structures ofcellulose polymorphs, in particular those for cellulose I (native cellulose) and cellulose II(recrystallised cellulose).22,26,27,28,29Table 1. Unit cell dimensions of cellulose polymorphs I, II, III and IV.1,4aa-axis (Å)b-axis (Å)c-axis (Å)γ (deg)aPolymorph7.858.1710.3496.4Cellulose I9.087.9210.34117.3Cellulose II9.97.7410.3122Cellulose III7.98.1110.390Cellulose IVγ lattice angleNative cellulose has a polymorph structure of cellulose I that exists in two crystalline forms:Iα (in algae and bacteria) and Iβ (in higher plants).30,31,32 In cellulose I, a sheetlike structure isstabilised by intermolecular hydrogen bonds. These bonds are parallel to the pyranose ringsand the staggered stacking of the sheets by distances equivalent to half-glucose rings alongthe cellulose chain axis is common in both crystalline forms. The difference between the twoallomorphs in native cellulose lies in the mode of staggering: continuous staggering occurs incellulose Iα, and alternating staggering occurs in cellulose Iβ.33,34,35When cellulose I is treated with a strongly alkaline solution or regenerated from a suitablesolvent, such as ionic liquid (IL) in the present study, it adopts the different crystal structurepolymorph of cellulose II. The X-ray structure of cellulose II reveals that its unit cell consistsof two antiparallel chains (Figure 4).3617

Figure 4. Schematic presentation of the 3D network of hydrogen bonds between origin (‘up’)and center (‘down’) chains.36In the cellulose II polymorph, the backbones of these two chains have the same conformation,but they differ in the conformation of their hydroxylmethyl groups (Figure 5).28 These groupsare near the gt conformation for the glycosyl residues located at the origin (‘up’ chain) of thecell.36 In contrast, the center chain hydroxylmethyl moieties adopt the tg conformation(‘down’ chain).36 The le

In this study, the aim was to investigate and explore the versatility of cellulose as a starting . 3.5 Synthesis of cellulose-based precursors for noncovalent and covalent interactions with carbon nanotubes and fullerenes 81 3.6 Buchwald-Hartwig cross-coupling 88 3.7 Synthesis of 6-(4-aminophenyl)aminocellulose as a precursor for (polyaniline .