1-Allyl-3-methylimidazolium Chloride Room Temperature Ionic Liquid: A New and Powerful Nonderivatizing Solvent for Cellulose

A Critical review SUBMITTED TO THE INSTITUTE OF CHEMICAL TECHNOLOGY IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF TECHNOLOGY IN DEPARTMENT OF FIBRES AND TEXTILE PROCESSING TECHNOLOGY UNDER THE GUIDANCE OF

Prof.(Dr.) R.V Adivarekar

BY

Abhinav Nathany ( M. TECH - SEMESTER I) INSTITUTE OF CHEMICAL TECHNOLOGY, (Deemed to be University) MATUNGA, MUMBAI- 400 019

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Table of Contents
INDEX PAGE NO.

CHAPTER 1 : RESEARCH PAPER OVERVIEW 1.1 Materials 1.2 Synthesis of AMIMCl 1.3 Cellulose Dissolution in AMIMCl 1.4 Regeneration of Cellulose Film 1.5 Recycling of AMIMCl 1.6 Conclusion of the Research Paper

3 5 5 6 9 15 15

CHAPTER 2 : SUMMARY OF THE REVIEW

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CHAPTER 3 : REFERENCES

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CRITICAL REVIEW OF RESEARCH PAPER TITLE: 1-Allyl-3-methylimidazolium Chloride Room Temperature Ionic Liquid: A New and Powerful Nonderivatizing Solvent for Cellulose AUTHORS: Hao Zhang, Jin Wu, Jun Zhang, and Jiasong He Key Laboratory of Engineering Plastics, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China JOURNAL: Macromolecules 2005, 38, 8272-8277 1. RESEARCH PAPER OVERVIEW Before critically reviewing authors work, I would like to highlight some importance of cellulose processing using RTILs. Starting with dissolving pulp as a purified raw material, cellulose is converted by large-scale industrial processing into regenerated materials. Cellulose materials are the most abundant in nature, and they are renewable, biodegradable and biocompatible. However, because of their stiff molecules and close chain packing via numerous intermolecular and intramolecular hydrogen bonds, it is extremely difficult to dissolve cellulose in water and most common organic solvents. Therefore, the multistep and polluting viscose process has long occupied the leading position in the regenerated cellulose industry. With increasing governmental regulations in industries, the need to implement green processes for preventing the pollution is becoming important and acting as a strong driving force to discover effective solvents for cellulose. Since the 1970s, novel solvents for cellulose have been sought and among them, the NMMO/H2O system is the solely industrialized for manufacturing regenerated cellulose
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fibers and films.[1] However, the NMMO/H2O system has some disadvantages associated with its use, such as the demand for high temperature to dissolve, the degradation of cellulose, the side reactions of the solvent itself without an antioxidant, and its high cost as well. Room temperature ionic liquids (ILs), which are considered as desirable green solvents, have been used to replace the organic solvent in a wide range due to their advantages such as width of liquid range, excellent dissolution ability, free from the effect of vapor pressure, and ease of recycling. Furthermore, ILs may be easily modified through changing the structure of cations or anions, which will broaden their application fields. Recently, ILs has been used to dissolve native cellulose as shown in Figure 1.

Figure 1. RTIL process for regenerated cellulose fibres In the above mentioned paper, the authors have done an excellent work regarding environmental protection by using room temperature ionic liquids (RTILs), which are considered as desirable green solvents, to dissolve native cellulose. A new and highly efficient direct solvent, 1-allyl-3-methylimidazolium chloride (AMIMCl), have been synthesized for the dissolution and regeneration of cellulose. The cellulose samples without any pre-treatment were readily dissolved in AMIMCl.

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The authors have investigated the structure and properties of the regenerated cellulose materials. The regenerated cellulose materials prepared by coagulation in water exhibited a good mechanical property. Because of its thermo-stable and non-volatile nature, AMIMCl was easily recycled. Therefore, the authors have developed a novel and non-polluting process for the manufacture of regenerated cellulose materials using AMIMCl. 1.1 Materials The authors have used microcrystalline cellulose (MCC), dissolved pulp, and cotton linters as cellulose samples in their study. They have measured the viscosity-average degree of polymerization (DP) of these three cellulose materials 220, 650, and 1600, respectively by Ubbelodh viscometer in CUEN (cupriethylenediamine hydroxide solution). They have also measured the viscosity-average degree of polymerization (DP) of regenerated cellulose films. 1.2 Synthesis of AMIMCl In previous researches the author Jun Zhang et al. have synthesized AMIMCl to carry out homogeneous esterification of cellulose.[2] 1-Methylimidazole (400 mL) and allyl chloride (800 mL) at a molar ratio 1:1.25 were added to a round-bottomed flask fitted with a reflux condenser for 8 h at 55C with stirring. The unreacted chemical reagents and other impurities, such as water, were removed by vacuum distillation. The chemical structure of AMIMCl is shown in Figure 2.

Figure 2. Chemical structure of AMIMCl The authors have measured refractive index of AMIMCl with Abbes refractometer is 1.5465. A Zahner IM6e electrochemical workstation (made in Germany) was used to measure the conductivity of AMIMCl. The cell constant was calibrated with aqueous 0.01 M KCl at 25C, and the cell constant was 1.60 cm-1.

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The results show that in comparison with other imidazolium chloride ionic liquids, such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-ethyl-3methylimidazolium chloride (EMIMCl), the synthesis of AMIMCl was more readily carried out. The conversion ratio of 1-Methylimidazole reached almost 100% after 6 h. This was a result of the relatively high reactivity of allyl chloride. However, the AMIMCl obtained was slightly amber. There can be other synthesis routes that include solvent and halide free pathways, microwave or sono-chemical methods to obtain a clearer AMIMCl because type of impurities in the ILs depends on the method of their synthesis.[3,4] The TGA curve of AMIMCl showed that the onset temperature of degradation was about 273C, which was slightly higher than BMIMCl (254 C). More interestingly, AMIMCl showed a lower melting point at ca. 17 C and a considerably lower viscosity of 685 mPas at 30C, in contrast with BMIMCl, which has a melting point of 65 C and a viscosity of 11000 mPas at 30C. This is due to an allyl group on the N-position. There can be details in the form of graph for more understanding. Also, they have not considered other parameters like density and surface tension because for [AMIM]+ series, increasing the alkyl chain length decreases the densities and surface tension values.[5] 1.3 Cellulose Dissolution in AMIMCl The authors have carried out optical microscopic observation with a Leica DMLPMP30 microscope fitted with a hot stage and a multicolour digital camera. They have also measured the viscosity of the solvent and of the solution with a parallel plate rheometer (DSR200, Rheometric Scientific) at 80C. spectrometer at 90C. The results show that at room temperature, AMIMCl only swelled cellulose but could not dissolve it. However, cellulose dissolved readily in AMIMCl at 60 C with stirring. With increasing temperature, cellulose dissolved more rapidly. Dissolving
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C NMR measurement of the

cellulose solution in AMIMCl (8 wt % of MCC) was performed on a Bruker DMX 300

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process of cellulose in AMIMCl at 80 C was real time monitored by PLM and shown in Figure 3.

Figure 3. PLM images of cellulose (pulp) dissolution in AMIMCl at different time: (A) 0, (B) 10, (C) 15, (D) 17.5, (E) 25 and (F) 30 min It is interestingly observed that cellulose with a degree of polymerization as high as 650 dissolved in AMIMCl within 30 min. However, remarkable swelling was not observed in the dissolution. It was also observed that, at initial stage, the dissolution occurred very rapidly. Then dissolution rate is decreased, which might be the result of more perfect crystalline structure in residual cellulose fibrils and increased viscosity of cellulose solution. Despite this, at 80 C, a cellulose/AMIMCl solution of 5 wt % concentration was obtained only within 30 min. The viscosity of the solution strongly depended on the concentration of cellulose. The values of viscosity of 4% and 8% cellulose solutions (dissolved pulp) in AMIMCl at 80 C were 110 and 1480 Pa s, respectively. With increasing dissolution temperature and time, higher concentrations of cellulose solution with higher viscosities were prepared in AMIMCl. The authors have also investigated that a solution containing up to 14.5 wt % cellulose (dissolved pulp) in AMIMCl was also formed as a clear and viscous solution after a little longer dissolution time at 80 C. Furthermore, 8.0 wt % cotton linter was also interestingly dissolved in AMIMCl at 80 C, although it was difficult to be dissolved in some other solvents.
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From the industrial point of view, it is important that cellulose samples without any pre-treatment or activation should dissolved in AMIMCl rapidly above 60C. There can be use of microwave oven to significantly improve the dissolution rates by heating.[6]
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C NMR spectrum of cellulose (MCC) dissolved in AMIMCl is shown in Figure 4. The

signals of the carbon atoms C1-C6 are well-resolved, and therefore, AMIMCl can be considered as a truly solvent, in which cellulose could be molecularly dispersed.

Figure 4. 13C NMR spectrum of cellulose (MCC) in AMIMCl solution at 90o C The authors have also studied the influence of temperature on the dissolution of cellulose in AMIMCl, by measuring the effect of temperature on the conductivity of AMIMICl (Figure 5). It was clearly observed that with increasing temperature, the conductivity increases. They also noted that there is a slope change at about 43 C, which possibly indicates a critical temperature. This may be due to the dissociation of ion pair or hydrogen bonding of AMIMCl above 43 C leading to a significant increase in the diffusion rate of ions which lead to the abrupt increase of conductivity.

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Figure 5. Temperature dependence of the conductivity for AMIMCl The authors found that a clear cellulose solution with light amber colour was obtained after the complete dissolution. When cooled to room temperature, AMIMCl/cellulose solution remained in its liquid state with a little increased viscosity. Interestingly, no recrystallization of the cellulose solution occurred, which was commonly observed in the BMIMCl/Cellulose system. Furthermore, neither crystallization nor precipitation of the cellulose/AMIMCl solution occurred after keeping the solutions at room temperature for more than 3 months. Dissolution of cellulose in AMIMCl is attributed to their ability to break the extensive network of hydrogen bonds existing in cellulose. The authors have recommended Swatloski et al.[7] work to speculate the possible dissolution mechanism of cellulose in AMIMCl as shown in Scheme 1.

Scheme 1. Possible Dissolution Mechanism of Cellulose in AMIMCl According to the scheme, it can be speculated that above the critical temperature, the ion pairs in AMIMCl dissociated to individual Cl- and [AMIM]+ ions. Then the free Cl- ions get associated with the cellulose hydroxyl proton, and the free cations complex with the cellulose hydroxyl oxygen, which disrupted hydrogen bonding in cellulose and led to the dissolution of cellulose. However, the authors have suggested NMR and Raman spectroscopy to clearly understand the mechanism of dissolving cellulose in AMIMCl. 1.4 Regeneration of Cellulose Film The authors have cut cellulose samples into small pieces and dried them at 70 C for 3 h in a vacuum oven before use. They have taken known weight of cellulose sample to disperse it into 20 mL of AMIMCl in a flask, and the mixture was heated and stirred until cellulose samples were completely dissolved.
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Finally, a transparent cellulose solution with about 4% polymer concentration was obtained. The thickness of the cellulose solution was controlled to within 0.5 mm, otherwise, the dried regenerated cellulose films became curly. The regenerated cellulose gel was washed with running distilled water and dried at 60C in a vacuum oven. After removing AMIMCl and drying completely, a transparent cellulose film was obtained. The cellulose fiber regenerated from AMIMCl was prepared easily either by wet spinning or dry jet-wet spinning process and coagulated with water. Characterization of Regenerated Cellulose Film: WAXD: The regenerated cellulose films were cut into strips of 10 mm long and 15 mm

wide for the measurement of X-ray diffraction patterns. The X-ray diffraction patterns with Cu K radiation ( = 1.5406 ) at 40 kV and 30 mA were recorded in the range of 2) 5-40 with an X-ray diffraction diffractometer (D/MAX-2500, Rigaku Denki, Japan).
FTIR: The natural cellulose was ground into powder for infrared (IR) measurement.

The IR spectra were recorded with a Fourier transform IR (FT-IR) spectrometer (FT-IR 2000, PE).
SEM: The dry regenerated cellulose films were frozen in liquid nitrogen, fractured, and

vacuum-dried. The free surface (side in direct contact with the coagulant) and the fracture surface of the films were coated with gold and observed and photographed with a Hitachi S-530 scanning electron microscope. Properties of Regenerated Cellulose Film: Tensile strength (b) of the regenerated cellulose films was measured by using a universal testing machine (Instron 1122, UK) at a crosshead speed of 5 mm min-1. The size of the samples was 50 mm long and 10 mm wide, and a gauge length of 30 mm was used. All the strength data were collected under the same conditions, such as temperature and air humidity. The authors have prepared a series of regenerated cellulose (RC) films from cotton (C) and pulp (P) and coded them. They have also regenerated cellulose dissolved with
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recovered ILs (ReIL). The conditions for dissolving cellulose, codes of regenerated cellulose, and materials of RC films are presented in Table 1.

Table 1. Sample codes of regenerated cellulose films and their dissolution conditions The authors have recorded FTIR spectra of cellulose before and after regeneration of cellulose as shown in Figure 6. They found that the two spectra are quite similar, and no new peaks appear in the regenerated sample, indicating no chemical reaction occurred during the dissolution and coagulation processes of the cellulose. In other words, AMIMCl was a direct solvent for cellulose. There can also be the record of the FTIR spectra of other cellulose samples ReRC-P for better analysis in case of recovered AMIMCl.

Figure 6. FTIR spectra of original cellulose and regenerated cellulose: (A) original cellulose (pulp); (B) regenerated cellulose from AMIMCl/pulp cellulose section (RCP100)

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The authors have also recorded X-ray diffraction patterns of the cellulose films before and after regeneration of cellulose as shown in Figure 7. They found that the transformation from cellulose I to cellulose II occurred after the dissolution and regeneration in AMIMCl. But, compared to the original cellulose, the intensity of diffraction peaks of regenerated cellulose films reduced significantly. In other words, the crystallinity of regenerated cellulose films was lower than the original cellulose. It can be concluded that, in the dissolution process, IL rapidly broke intermolecular and intramolecular hydrogen bonds and destroyed the original crystalline form.

Figure 7. WAXD patterns of original cellulose and regenerated cellulose: (A) original cellulose (pulp); (B) regenerated cellulose from AMIMCl/pulp cellulose solution (RCP100); (C) regenerated cellulose from recovered AMIMCl/pulp cellulose solution (ReRC-P). The authors have also recorded SEM micrograms of the regenerated cellulose films as shown in Figure 8. It can be seen that the free surface and fracture surface of the regenerated films display uniformity from the interior to the surface, indicating a dense texture. There can be use of magnification (300x) in the SEM or can have the latest FESEM (JSM6700F) for a better vision.[8]

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Figure 8. SEM photographs of the free surface and fracture surface of the regenerated cellulose films: (A, C) free surface and fracture of regenerated cellulose from AMIMCl/pulp cellulose solution (RC-P130); (B, D) free surface and fracture of regenerated cellulose from recovered AMIMCl/pulp cellulose solution (ReRC-P). The authors have analyzed the degree of polymerization (DP) of the regenerated cellulose materials. The dependence of the DP of the regenerated cellulose on the temperature is shown in Figure 9. In the temperature range from 110 to 130 C, the DP did not change appreciably in ca. 40 min.

Figure 9. Degree of polymerization of regenerated cellulose from AMIMCl/pulp cellulose solutions prepared at different temperatures. Cellulose: pulp; dissolution time:

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40 min. Open symbol: regenerated cellulose from recovered AMIMCl/pulp cellulose solution. The dependence of the DP of the regenerated cellulose on the temperature is shown in Figure 10. The DP of a cotton sample with a higher DP is reduced with dissolving time at 110C. When the recycled AMIMCl was used as the solvent, the DP of the regenerated cellulose also showed a similar decrease trend.

Figure 10. Degree of polymerization of regenerated cellulose from AMIMCl/cotton cellulose solutions prepared at different times. Cellulose: cotton; dissolution temperature: 110C. Open symbol: regenerated cellulose from recovered AMIMCl/cotton cellulose solution. The regenerated cellulose film exhibited a good mechanical property. The tensile strength of the regenerated cellulose film with a DP of 480 was as high as 138 MPa. There can be more details of tensile strength in the form of table or graph. There can be consideration of other mechanical properties like elongation. There can be discusson about the physical factors (e.g. nozzle and air-gap dimensions, draw-down ratio, take-up speed) and dope characteristics (cellulose DP and concentration, temperature, modifiers) which influence the shaping process and
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the final fibers properties in a dry jet-wet spinning process.[1] 1.5 Recycling of AMIMCl The authors have claimed that the residual ILs in the coagulation bath can be recovered by simply reducing the pressure and subsequently distilling to remove water i.e. evaporation of the water from the precipitation liquid. The purity of the IL was determined by 1H NMR spectroscopy. It should be noted that the presence of residual water in RTILs was found to reduce the solubility of cellulose significantly, probably by forming competing hydrogen bonds to the macromolecular chains of cellulose. thoroughly. However, the authors have neither provided any experimental detail nor have cited any reference about it. Also, the authors have not mentioned the instrument used for 1H NMR spectroscopy. The authors have recommended, Swatloski et al.[7] work about recycling of BMIMCl by using aqueous biphasic systems (ABS) for AMIMCl also. They found that AMIMCl was also effectively concentrated from a dilute aqueous solution and have been almost completely recovered. But, they have not recommended other methods like pervaporation, reverse osmosis and salting out to recover the ionic liquid.[9] Also, the authors have not provided any details about the AMIMCl recovery. 1.6 Conclusion of the Research Paper

[3]

Therefore, before dissolving cellulose, it is needed to remove water from RTILs

A novel ionic liquid, 1-allyl-3-methylimidazolium chloride (AMIMCl), was found to be a powerful direct solvent, non-derivatizing single-component solvent for the dissolution and regeneration of cellulose by homogeneous esterification.

The untreated or inactivated cellulose, such as cotton and dissolved pulp were readily dissolved in AMIMCl. The regenerated cellulose materials prepared by coagulation in water exhibited a good mechanical property. On the basis of the fact that AMIMCl is thermo-stable and non-volatile, and can be easily prepared and recycled, this process of dissolution and regeneration of cellulose
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seems to be a promising green process for the preparation of regenerated cellulose materials and can overcome the inherent environmental problems of waste (toxic) gases in the current industrial processes for cellophane and viscose rayon.

The properties of fibers spun from recycled AMIMCl remain intact even after a number of process cycles. It can be concluded that AMIMCl enhance the efficiency of cellulose processing.

In all, industrial implementation of AMIMCl in industry is attractive. However, the present investigation is still in the preliminary stage, and further study is required. 2. SUMMARY OF THE REVIEW

The authors have synthesized novel RTIL, but in order to meet the requirement for clean manufacturing and effective cost-decreasing, it is needed to develop techniques together with corresponding facilities for large-scale production of RTILs, and the integration of producing processes of RTILs with other industrial processes.

They should have mentioned the characteristics and other standard parameters of the chemicals they have taken for the synthesis of AMIMCl. They should have used other methods of synthesizing the AMIMCl that include solvent and halide free pathways, microwave or sono-chemical methods, to obtain it in pure form because type of impurities in the ILs depends on the method of their synthesis. It should be noted that, these RTILs are cheaper than most well-known RTILs obtained by anion-exchange reactions using imidazolium halide salts as starting materials.

In their use as solvent in cellulose industry, the safety to human health should be evaluated, because of possible trace residual RTILs in the final regenerated cellulose materials and cellulose derivatives.

From the industrial point of view, it is important that cellulose samples without any pretreatment or activation should dissolved in AMIMCl rapidly above 60 C. The authors should have use microwave oven to significantly improve the dissolution rates by heating. ILs are heated with exceptional efficiency by microwaves.

For regenerated cellulose fibers spun from AMIMCl solutions, further investigation on their condensed structure like crystallinity, orientation and textile-related physical properties like tensile properties, dye ability, and moisture absorption is needed.

The authors have not discussed about the physical factors (e.g. nozzle and air-gap dimensions, draw-down ratio, take-up speed) and dope characteristics (cellulose DP and
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concentration, temperature, modifiers) which influence the shaping process and the final fibers properties in a dry jet-wet spinning process.

The authors have recovered the AMIMCl by evaporation and aqueous biphasic systems (ABS). This, however, would consume large amount of energy. Therefore, further efforts are required to develop effective methods like pervaporation, reverse osmosis and salting out to recover the ionic liquid.

There is a need for optimization of cellulose processing in the aspects of dissolution, spinning, coagulation, reaction, precipitation and AMIMCl recycling. Thus the critical review of this paper should be considered to throw more light into the research activity made by authors. The topic has more research potential if my reviews are considered. 3. REFERENCES [1] Fink, H. P.; Weigel, P.; Purz, H. J.; Ganster, J. Prog. Polym.Sci. 2001, 26, 14731524. [2] Ren Q Wu J Zhang J He JS Guo ML. Synthesis of 1-allyl3-methyle mazolium-based room temperature ionic liquid and preliminary study of its dissolving cellulose. Acta Polym Sin. 2003 (3): 448-451 [3] Ren, R. X. Green synthesis of ionic liquids for green chemistry. In Ionic Liquids as Green Solvents: Progress and Prospects; American Chemical Society: Washington, DC, 2003; Vol. 856, pp 70-81. [4] Varma, R. S. Expeditious synthesis of ionic liquids using ultrasound and microwave irradiation. In Ionic Liquids as Green Solvents: Progress and Prospects; American Chemical Society: Washington, DC, 2003; Vol. 856, pp 82-92. [5] Huddleston, J. G.; Visser, A. E.; Reichert, W. M.; Willauer, H. D.; Broker, G. A.; Rogers, R. D. Green Chem. 2001, 3, 156-164. [6] Varma, R. S.; Namboodiri, V. V. Chem. Commun. 2001, 643-644. [7] Swatloski, R. P.; Spear, S. K.; Holbrey, J. D.; Rogers, R. D. J. Am. Chem. Soc. 2002, 124, 4974-4975. [8] Xuejing Wang; Huiquan Li; Yan Cao, Qing Tang Bioresource Technology 102 (2011) 79597965 [9] Gutowski, K. E.; Broker, G. A.; Willauer, H. D.; Huddleston, J. G.; Swatloski, R. P.; Holbrey, J. D.; Rogers, R. D. J. Am.Chem. Soc. 2003, 125, 6632-6633
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