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Literature Review of Cellulose Acetylation

Puu-0.4100 Advanced Biomaterial Chemistry and Technology course report

Wang Lei 1/11/2013

The aim of this paper is to have a review of acetylation of cellulose. In total eleven papers are reviewed and summarized in this paper. Different acetylation methods are discussed and compared. Acetylation processes follow the first-order kinetic law. There are two distinguished reaction mechanisms: when there is a diluent, cellulose undergoes acetylation without changing its morphology; otherwise cellulose morphology is disturbed. The crystalline structure of cellulose nanocrystal is preserved after acetylation. Acetylated cellulose exhibited an increased solubility and dispersion in various solvents. Acetylated MFC films have good gas barrier properties, but poor water vapor transfer rate.

1. Introduction
Natural cellulose fiber is one of the most abundant and low-cost renewable raw materials. Meanwhile people are actively searching for alternatives for fossil based packaging materials. That is why cellulose, especially nano-scaled cellulose, has attracted a lot of attention due to its appealing intrinsic properties such as nano-scaled dimensions, high surface area, unique morphology, low density, and mechanical strength, as well as the fact that they are biodegradable[6]. In packaging polymer material, it is important to have strong mechanical properties and to provide good control of mass transfer between food and the environment. A lot of research focuses on isolation and modification of nanocellulose and utilize it as reinforcement in polymers, so that it can be competitive with conventional packaging materials. Despite all the great potential of nanocelluloses mentioned above, the difficulty of dispersing highly polar cellulose fiber in non-aqueous medium or polymers is one of the main challenges. The difficulty of uniformly dispersing nano-sized materials in liquids is mainly because of their high surface energy. Moreover due to the hydroxyl group located on surface of cellulose, the surface is hydrophilic. In order to decrease the hydrophilic characteristics of the fibers and improve the surface adhesion between the continuous and dispersed phases, chemical modifications of the cellulose are needed [4; 8]. Acetylation is one of the most commonly used modification methods. In acetylation reactions, OH group of cellulose is substituted with acetyl group; therefore the hydrophilic property is modified to more hydrophobic. Meanwhile moderate acetylation does not change the original crystalline structure of cellulose, so the desired properties are also preserved. [6; 7]

2. Acetylation methods
Depending on the purpose of the research, acetylation methods can be different. Table 1 lists the reaction characteristics of 8 papers among those I reviewed [1-8]. As we can see, most of the research used acetic anhydride as reactant; catalysts such as H2SO4 and HClO4 are used in most cases, since it can increase the reaction speed; temperature is also a variable for reaction. Both homogeneous and heterogeneous processes are used. Table 1 [1-8] Acetylation reaction characteristics
Raw material 1 2 3 4 5 6 7 8 30-40% acetylated cellulose Animal cellulose Cellulose Cellulose Cellulose Cellulose nanocrystal Microfibril Cellulose Kenaf fiber reactant and solvent acetic anhydride /acetic chlorine acetic anhydride acetic anhydride/AMIMCl acetic anhydride Tritylchloride/pyridine/ac etic anhydride pyridine/acetic anhydride acetic anhydride pyridine/acetic anhydride catalyst withHCLO4/H2SO4/ ZnCl2.../without H2SO4 no 0,1 vol% and 0.4 vol% H2SO4 pyridine pyridine no pyridine T 100/ R.T 60 80/100 30 90 80 70 100 hetergeneous/ homogeneous Homogeneous Both Homogeneous Hetergeneous Homogeneous Homogeneous Hetergeneous Homogeneous

After the reaction, successful acetylation can be indicated from FTIR with the appearance of new peak at around 1746 cm-1 which indicates formed ester groups and the decrease in the intensity of peaks at 3342cm 1 which is assigned to OH stretching of the cellulose after the modification. [3; 4; 6; 7] The following conclusions can be drawn from the reaction: Higher temperature results in higher degree of substitution (DS). But when temperature is too high, cellulose starts to degrade. [1;9] DS increases when reaction time extends. [1;9] Uncatalyzed reaction is more selective for primary hydroxyl group. [1] Catalyst such as H2SO4, HClO4 can boost the reaction and lower the selectivity. ZnCl2 does not affect the reaction so much. [1] One commercial way to produce cellulose acetate is to use ketene as a reactant. The manufacture of cellulose acetate by direct addition of ketene is patented as Nightingale. Samples reacted with ketene with an acetyl content up to 17% preserved their fibrous structure with only slight degradation. The ketene acetylation was accompanied by an objectionable polymerization of ketene which produced brownish coloration of the sample. The color could be removed by hot alcohol. [10] The mechanism of ketene accelerate acetylation reaction can be explained so that ketene can generate acetic anhydride under the presence of water and acetic acid [11].

Moreover, there is a possibility that ketene can react directly with carbohydrates [11].

Weili Wu et al. also conducted cellulose acetylation with acetic anhydride and iodine as catalyst, and then compared acetylated cellulose with original cellulose. The conclusions are similar with other acetylation processes. [9] I think in the future, a study can be conducted on comparing iodine as a catalyst with conventional acid.

3. Heterogeneous and homogeneous cellulose acetylation

Depending on the purpose of the research, there can be homogeneous and heterogeneous acetylation processes. Most of the modifications use heterogeneous reactions, so that the core of the cellulose is preserved; and also because of a lack of good cellulose solvents. However, homogenous reaction can create more options to induce novel functional groups, also open new avenues for the design of products, and offer opportunity to control the total degree of substitution (DS) value. To date, a number of solvent systems have been found, such as DMAc/LiCl, DMF/N2O4, NMNO, and DMSO/TBAF and some molten salt hydrates, such as LiClO4*3H2O, and LiSCN*2H2O. However, limitations remain, such as toxicity, cost, difficulty for solvent recovery, or instability in the above processing [3]. Heterogeneous acetylation is realized by modifying cellulose with acetic anhydride without swelling cellulose, which means that the reaction starts from the surface of cellulose. In many cases, only surface modification of cellulose is needed so that the morphological structure and mechanical properties of cellulose will be preserved. Giovoma et al. conducted a study on heterogeneous acetylation by using only acetic acid/acetic anhydride reacting with cellulose under mild reaction conditions (30 ). They pointed out that the heterogeneous acetylation reactions follow the first-order kinetic law. The SEM image showed surface damage only occurred at high degrees of substitution, which is very important for the applications in composites. Structure and morphological changes should be avoided. [4] Ionic liquids are a class of emerging novel solvents for cellulose. It is considered a green solvent due to its low vapor pressure which makes it easy to recycle. Jin Wu et al. conducted a study on homogeneous acetylation process with ionic liquid 1-allyl-3 methylimidazoliumchloride (AMIMCl). They found out that ionic liquids can boost acetylation reaction without a catalyst. There are more options to control the degree of substitution [3].

4. Properties that are affected by acetylation

Crystallinity The acetylated cellulose presents a lower degree of crystallinity compared with that of the original cellulose due to the substitution of the hydroxyl groups by acetyl groups, which weakens the inter- and intra-molecular hydrogen bonds of cellulose [9]. Dispersibility Acetylated cellulose nanocrystal (ACN) has improved dispersion ability in 6 tested solvents include water, dichloromethane, acetone, toluene, tetrahydrofuran (THF) and DMF due to the weakened intra- and intermolecular bonds [6]. Mehdi et al. pointed out in their paper that acetylated nanofibers are very stable and well dispersed in both acetone and ethanol for 2 months [8]. Wettability and polarity Water has a higher affinity for cellulose nanocrystal (CN) than ACN. Acetylation changes the surface of fibers from hydrophilic to more hydrophobic. As a result, water wettability decreases [6, 9]. Thermal properties The decomposition temperature of ACN was around 15 C higher than CN, which can be explained by the replacement of hydroxyl groups with the more stable acetyl groups. This means that ACN has a better thermal stability than the original cellulose nanocrystals, which is an advantage for the improvement of thermal performance of the nanocomposites [6, 9]. Size distribution of nanofibers and acetylated nanofibers The average size of distribution for acetylated nanofibers was improved. The overall average size is smaller due to degradation of cellulose [8]. Mechanical properties The Youngs modulus and tensile strength of the tested acetylated bacterial nanofibril cellulose are lower than that of the original bacterial cellulose due to the lower degree of crystallinity and the less dense network structure. However, the difference is insignificant, which means acetylated cellulose is still suitable for reinforcement in composites [9].

5. Acetylation relative reaction rate and kinetics

It is of fundamental importance to have knowledge on relative reaction rates between different hydroxyl groups. However, uneven penetration of reaction agents to amorphous and crystalline region makes the studying of reaction rate very difficult. Carl J. et al conducted a study of reaction rate by using cellulose acetate which contains 3040% of acetyl because they are soluble in acetic acid. They observed that the primary hydroxyls acetylated more rapidly than the secondary. When the amount of primary hydroxyls was plotted against secondary hydroxyls on log-log base, it is a fairly straight line. Acetylation is a second-order reaction which depends on concentrations of the hydroxyl and the anhydride. To make it simpler, the concentration of the anhydride is not taken as a variable by assuming it does not affect the relative rates of different hydroxyl groups. Then the esterification reaction can be simplified to a concurrent firstorder reaction [1]. Let x and y be the number of primary and secondary hydroxyls respectively. So we can derive the rate equation as follows: d x = K1 * x * d t and d y = K2 * y * d t Hence, d x / x= k1/k2 * d y / y By integration, log x= k1/ k2 log y + c (1)

Equation (1) is a correlation between the reaction rate of the primary and the secondary hydroxyl. k1/ k2 is the relative reaction rate. By conducting experiments under different conditions, with/without catalyst, different temperature and different reactant, conclusions were drawn that without catalyst, acetylation is more selective for primary alcohol; but the reaction is very slow. With catalyst, the primary OH only reacts two times faster than the secondary group. [1] Much later, Giovanna et al also studied acetylation kinetics. The difference is that he tried to concentrate on the heterogeneous acetylation processes. During his research, mild acetylation condition (30 ) was applied and two different concentrations of acid catalyst were used. By plotting the acetylation degree (r) along with different reaction times, the plotted curve represented also a first-order kinetic law. (2) where r is the plateau value (t = ; and the term (r + A) is the initial r value (t = 0), i.e., the r value of the unmodified fibers. Equation (2) very satisfactorily fits the experimental results [4].

6. Cellulose acetylation mechanisms

There are two heterogeneous acetylation mechanisms that can be distinguished depending on whether a non-swelling diluent is used or not. The first method is called fibrous process, where diluents such as toluene, benzene or amyl acetate are used as reaction medium. In fibrous process, cellulose triacetate (CTA) generated from the reaction remains insoluble and there is a direct conversion of cellulose into solid CTA without change in the gross morphology of the fibers. The other method is named homogeneous process in Jeans paper where there is no diluent; CTA is solubilized in reaction medium as it is produced. However, this method is not totally homogeneous in the descriptive sense of the word; it is essentially a heterogeneous acetylation which ends up in a homogeneous product (i.e., the CTA solution). In this situation, cellulose morphology is disturbed before its total acetylation and dissolution. [2] Sassi et al. conducted a study on the course of acetylation of cellulose microcrystal and native cellulose fragments at ultra-structural level, under both homogenous and fibrous processes. They found out that in both the homogeneous and the fibrous acetylation process, the cellulose crystals appear to be acetylated on their surface, which means acetylation does not lead to a crystalline swelling. In case of fibrous acetylation, the cellulose acetate stays where it was produced and surrounds the unreacted core of cellulose crystals. In case of homogeneous acetylation, it was observed that the surface of cellulose chains undergo continuous stripping as they become acetylated. This will lead to a reduction in the diameter of the crystal while the longitudinal dimension stays more or less constant. Because the sufficiently acetylated cellulose part will dissolve in acetylating medium, acetylated part is lifted from the surface of cellulose [2]. A schematic drawing of homogeneous acetylation process can be found in Figure 1. Chains that are sufficiently acetylated have become soluble in acetylating medium. Those still in the process of acetylation are lifted from crystal chain surface. The crystal is indented by a series of grooves that correspond to the missing cellulose chain. [2]

Figure 1 A schematic drawing of homogeneous acetylation process [2]

Ning Lin et al. also studied morphologies and crystalline properties of acetylated cellulose nanocrystalline (ACN). And they arrived at similar conclusion with Sassi that the rod-like shape of CN was preserved during the course of acetylation, but the size is decreased a bit. In addition, the outline of ACN is blurry. However, the crystalline characteristic is maintained. [6] Furthermore in the paper by Galina et al., they stated a different view of acetylation mechanism for microfibrill cellulose that the acetylation is not only happening on the surface of cellulose but also involves some bulky parts. It is proven by the fact that degree of substitution (DS), obtained by titration, and the degree of surface substitution (DSS), detected by XPS, are different. In their study, toluene and acetone are used to exchanging water out of cellulose solution. [7] Furthermore in Mehdis paper, they also suggested that cellulose acetylation involves swelling, so the acetylation happens not only on the surface but also the bulk part. But in their case, pyridine was used as catalyst. [8] To my understanding, when a diluent such as toluene or cellulose solvent such as ionic liquid are used, it opens cellulose structure or causes swelling of cellulose. In this case, the acetylation happens not only on the surface.

7. Regio-selective acetylation of cellulose

The solubility of cellulose acetate (CA) depends strongly on the distribution of acetylation in hydroxyl groups in the anhydroglucose units (AGU). Yoshisuke et al. pointed out that CA in solution is generally in a quasi-flexible chain state, which means that the chain stiffness is not a constant; it is between flexible and semi-flexible. The solubility and clustering in solutions are related to intra- and intermolecular hydrogen bond formation that would be controlled by both chain architecture and the surroundings. To study the influences of different hydroxyl group on cellulose acetate chain dynamics and solubility, it is important to control the sequence of different positions. The control can be achieved by regio-selective substitution of hydroxyl groups in cellulose. Three cellulose derivatives were prepared by the regio-selective substitution; 6-O- triphenylmethylcellulose (6TC); 2,3-di-O-acetyl-6-Otriphenylmethylcellulose (2,3Ac-6TC) and 2,3-di-O-acetylcellulose (2,3AcC ) regioselectively substituted cellulose deacetate. Figure 2 shows the scheme of preparation of these cellulose derivatives.

Figure 2 A schematic figure of preparation of cellulose derivatives. The 6TC chain was characterized by the architecture that every C-6 position hydroxyl in the chain was completely substituted by the hydrophobic triphenylmethyl group and that all the C-2,3 positions hydroxyls remained. On the other hand, 2,3Ac6TC was characterized by C-2 and -3 positions acetylated. Thus, 6TC and 2,3Ac6TC are expected not to form intermolecular hydrogen bonds, or not to induce any association, in polar solvents because of the lack of C-6 position hydroxyls. Intramolecular H-bonds are normally formed between C-3 position OH and neighboring O-5 ring oxygen or between C-2 OH and C-6 OH. The latter is the more important for the formation of intramolecular bonds [5]. Yoshisuke et al. found out that in in 6TC/DMSO system, there is one dynamical cluster and the size is at most 10 times larger than single chains. It was explained that to protect bulky trityl groups in C-6 position from precipitation in the hydrophilic DMSO atmosphere, a temporary hydrophilic cover is formed by many hydrophilic hydroxyls that exist at C-2 and -3 positions to cover the hydrophobic core. This hydrophobic interaction is a dynamic association that is not thermodynamically stable but a temporary buildup of 6TC [5].

8. Acetylated MFC and PLA/ACN composite film properties

As mentioned before, cellulose has potential to be applied in packaging materials. However, due to their hydrophilic surface, cellulose nanofillers cannot be homogeneously dispersed in other polymeric matrices. In many cases acetylation is used as modification for cellulose to increase the hydrophobicity and to improve cellulose surface properties. Following properties related with film applications are modified by acetylations:

Gas barrier properties of MFC film Both pure and partially acetylated MFC films fulfill gas barrier requirement due to the high crystallinity and densely packed cellulose microfibril. [7] Water vapor transfer rate (WVTR) It was expected that acetylation modification will reduce water vapor permeability because acetylation changes the cellulose surface from hydrophilic to hydrophobic. However both of them exhibit high WVTR compare to conventional packaging material. [7, 8] Mechanical properties of PLA/ACN nanocomposites Tensile strength increases until 6 wt% load level then decreases. All PLA/ ACN composites exhibited a dramatically increased Youngs modulus. Elongation decreases all the way because of the presence of rigid nanoctystals. It was suggested by Ning Lin et al., that with an appropriate amount of nanofabril, ACN can inhibit self-aggregation and promote dispersion in PLA matrix, thus acting as reinforcement. But when the amount of nanofiller exceeds a certain amount, ACN starts to aggregate and may damage the original PLA structure resulting in a decrease in strength and elongation properties. [6] Thermal properties of PLA/ ACN nanocomposites. When the ACN content was less than 2 wt%, the rigid nanocrystals dispersed homogeneously in the PLA matrix, it restricts the motion of amorphous and free domains with interactions between nanofillers and the matrix. This interaction causes a higher energy requirement for thermal transformation which means an increase in Tg,mid (glass transition point at midpoint) and heat capacity Cp. But when the amount of nanofillers is increased to 4-6%, the excess ACN affects the interactions between crystalline and amorphous domains, so it decreases Tg,mid and Cp. However, when a further increase in the amount of ACN causes self-aggregation it will restrain the motion of the amorphous domains and again increase Tg,mid and Cp. [6]

9. Conclusion and discussion

Natural fibers have a lot potential in polymer applications. However, due to their intrinsic drawbacks, modifications are normally required. Among all, acetylation is one of the most significant reactions for the derivatization and modification of cellulose. Iodine can act as a satisfying catalyst for acetylation. A further study could be conducted on comparing different catalysts. Acetylated cellulose exhibited increased solubility and dispersion in various solvents, which is stable for months. It also changes the surface of cellulose from hydrophilic to hydrophobic due to the substitution of OH group to acetyls. Acetylated nanocellulose generally preserves the good mechanical properties of nano-scaled fibers. Acetylation processes follows first-order kinetic law. There are two distinguished reaction mechanisms depending on whether a non-swelling diluent is used. When there is a diluent, cellulose undergoes acetylation without changing its morphology: in case of no diluent, morphology is disturbed before its total acetylation and dissolution. Acetylated MFC film has good gas barrier properties and shows better water vapor transfer rate result. But more research is needed to further conquer the high WVTR barrier. The crystalline structure of cellulose nanocrystals is preserved after acetylation. Acetylated cellulose nanocrystal can disperse homogeneously in PLA matrix up to 8 wt%. When it is 6 wt% the tensile strength of ACN/PLA composites was enhanced by 60% and Youngs modulus is 1.5 fold greater than that of PLA [6].

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