Reactive Extrusion for In-situ Chemical Modification of Cellulose

Reactive Extrusion for In-situ Chemical Modification of Cellulose with De-Octenyl succinic anhydride (DDSA) in presence of

Ionic liquid Magdi Elamin Gibril,

College of Material Science and Engineering, Donghua University, Shanghai 201620, China

E-mail: [email protected]

Magdi E. Gibril, Li Xin Da, Li Huan, Li hai Feng, Zhang Yue, Zhong Xuan and Yu Muhuo

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, China; Fax: 86-21-67792707

Correspondence should be addressed E-mail: [email protected] Abstract:

Modification of microcrystalline cellulose by means of DDSA through the reactive extrusion process was preformed. The process was carried out by twin screw extruder in the presence of ionic liquids (IL), 1-butyl-3-methylimidazolium chloride [Bmim]Cl. The suitable composition for cellulose/IL mixture and optimum conditions for extrusion process were determined. Degree of substitution (DS) for modified cellulose was found to be in the range of 0.100- 0.284. In order to study the chemical structure and the physical properties of the modified cellulose, characterization was done by FT-IR, solid-state CP/MAS 13CNMR, and theromgravimetric analysis. FT-IR data were found to have a new peak in contrast to original reactant which clearly indicated the presence of a chemical group. CP/MAS 13CNMR analysis approved the existence of succinylation between cellulose and DDSA. The TGA analysis showed that the thermal stability of modified cellulose was decreased upon increasing of the degree of substitution (DS) or the increasing of the amount of DDSA in the samples.

Keywords: Cellulose; Reactive extrusion; ionic liquid; modification; DDSA.

1. Introduction

Cellulose is considered to be the most abundant renewable polymer on Earth [1]. It consists of a linear homopolysaccharide composed of ß-D-glucopyranose units linked together by ß-1-4-linkages [2]. Each monomer bears three hydroxyl groups, therefore these hydroxyl groups have an ability to form hydrogen bonds play a major role in directing the crystalline packing and also governing the physical properties of cellulose [16]. Cellulose is high crystalline this is refer to the extensive hydrogen bond network which make it insoluble in water and most conventional organic solvents. Chemical modification implies the substitution of free hydroxyl groups in the polymer with functional groups, yielding different cellulose derivatives, which have important applications in our daily life such as in textile, pharmaceutical, beauty, food and packaging industries [3, 4]Cellulose does not modifying thermally through melting process [5], because of decomposition temperature is less than melting temperature.

Ionic liquids (ILs) currently, have widely applications in the field of cellulose dissolution and modifications, especially with Succinic anhydride to produce cellulose succinylated [6-11]. Modification of cellulose with cyclic anhydrides such Succinic anhydride does not yield such a byproduct. Moreover, the reaction results in a pendant carboxylic moiety attached to the cellulose via a covalent ester bond, providing a site upon which further reactive chemistry is possible [12]. There is many study succinoylation of cellulose in ILs with Succinic anhydride with different degrees of substitution (DS) was done with or without catalyst [13-16].

Alkenyl-succination is cyclic dicarboxylic acid which apply to modifying the polysaccharides by substitution reactions. The application of DDSA in modification of polysaccharides was patented by Caldwell and Wurzburg in 1953 [17] when they were invented a simple and economical method to prepare polysaccharides with amphiphilic property. The structural formula of the alkenylsuccinates is shown in Figure 1.

Magdi Elamin Gibril et al. / International Journal of Engineering Science and Technology (IJEST)

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Figure 1Chemical structure of De-Octenyl succinic anhydride (DDSA).

The R group may be alkyl, alkenyl, aralkyl or aralkenyl, and can contain 5-18 carbon lipophilic chain. This alklly succiniate it has been use to esterify the polysaccharides such like for modification can be starch, gelatinized or un-gelatinized, from sources including corn, tapioca, potato, wheat, sago, rice and waxy maize; as well as modified or thin-boiling starches and starch derivatives; and also cellulose and hemi-cellulose[17]. The alkenylsuccination changes properties of native polysaccharides, such as pasting properties [18], emulsifying properties [19] and digestibility. Alkenyl succinic polysaccharides (starch) are widely used emulsifiers in a variety of oil-in-water emulsions in food, pharmaceutical and industrial areas[20].

Despite the vide-spread use of DDSA in starch. There has not been any report of utilizing DDSA to modify cellulose. DDSA-modified cellulose it consider as DDSA-modified starch which were potentially used for food application if it contains <3% DDSA by weight. The long chain of methylene groups of DDSA could improve some cellulose properties. Alkenyl Succinic Anhydride has been use with cellulose as sizing agent in modification of paper surface to increase the water resistance; this application was patented at 1963 by Wurzburg and Mazzarella [21]. Also it has been applied in recycling cellulose fibers.

Extrusion technology is a high-temperature, short-time process with the advantage of high versatility and absence of effluents. This overcomes the problems of conventional methods because it uses reduced amounts of reagents. Moreover it reduces the time of modification process[22]. Reactive extrusion is an extrusion-conducted process which allows the chemical and/or the structural modification of polymers. This technology is mainly used to control polymers' rheology in order to functionalize and compatibilize polymers blends. It is generally flexible and can avoid long and costly development of new polymers. Twin screw extruders are particularly suitable for the reactive extrusion process due to the excellent mixing properties [23].

In current studies, the mixture of cellulose, IL and succinic anhydride or DDSA were prepared in order to adapt the feeding process. The main function of IL in this process is to dissolve cellulose and guarantee that the cellulose modification could be performed in a homogeneous medium beside to act as a plasticizer.

The aim of present work is to study the possibility of applying reactive extrusion process for mixture of microcrystalline cellulose, IL and DDSA by using twin extruder in the absence of any catalyst. Further studies will be carried out in order to characterize the modified cellulose by means of FT-IR, 13CNMR, XRD and TGA.

2. Experimental Section 2.1 Materials:

Microcrystalline cellulose [degree of polymerization~220] and succinic anhydride were supplied by shanghai Honest CHEM. CO., LTD. The degree of polymerization of MCC is determined according to the literature by Gericke et al. [24]. Ionic liquid (1-butyl-3-methylimidazolium chloride) [Bmim] Cl, was provided by Shanghai Chengjie Chemical industry Co., Ltd Shanghai, China. And DDSA provided by Shanghai Honest CHEM. CO., LTD Shanghai, China.

2.2 Preparation of the extrusion mixture: The cellulose MCC was dried at 750C for 10 hours in vacuum oven, the dried cellulose was mixed with ILs and DDSA in different ratio as is it shown in Table 1, by use universal grinder for 2 - 4 seconds. Mixing process has been applied in isolation from the moist air to avoid absorption of moisture by ILs and cellulose together i.e. to avoid side reactions during the modification.


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Table 1. The formulation of cellulose modification with De-Octenyl-succinic anhydride (DDSA).

Sample Cellulose (MCC) ILs DDSA Code (C: ILs: DDSA)

1 100 400 25 (C1:P4: DDSA 0.25)

2 100 400 50 (C1:P4: DDSA 0.50)

3 100 400 75 (C1:P4: DDSA 0.75)

4 100 400 100 (C1:P4: DDSA 1)

2.3 Extrusion: The mixtures were extruded by twin screw extruder EUROLAB-16 XL, made in German with specifications like; diameter 16 mm and length/ratio is 40/1, The mixture were feed into contestant rate under conditions; temperature was set as it shown in Table 2 , and the rotation rate of the screw was set at 65rpm.

Table 2 The temperature setup of twin screw extruder heating zones for cellulose modification with DDSA.

Zone1 Zone 2 Zone 3 Zone 4 Zone 5 Zone 6 Zone 7 Zone 8 Zone 9 Zone 10 110 120 140 150 160 160 160 160 160 150 0C

2.4 Purification of samples: The extruded materials were precipitated in water to remove ILs and solid was filtered subjected to extraction process by acetone for 6 to 10 hours to remove unreacted Succinic anhydride and byproduct (if any). Drying was done at 50 °C for 24 hours in a vacuum oven.

2.5 Reaction of cellulose with De-Octenyl succinic anhydride (DDSA): The succinoylation of cellulose with DDSA was carried out through reactive extrusion process by using IL ([BMIM]CL) in absent of catalyst to esterifies the hydroxyl groups of cellulose. DDSA generally is reacts with cellulose or others carbohydrate to produce monoester and the Figure 2 shows the reaction mechanism.

Figure 2, Shows the reaction mechanism of cellulose MCC with De-Octenyl succinic anhydride (DDSA).

3. Characterization of the succinylated cellulose

The chemical structure of the cellulose MCC and modified cellulose was investigated by:

1- Degree of substitution (DS): The determination of the degree of substitution (DS) was conducted by saponification method which reported[25].

2- FT-IR spectra analysis:


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FT-IR curve were recorded were recorded with FTIR spectrophotometer (Nicolet 8700 IR), the scan of each sample was recorded from 4000 to 400 cm-1 at a resolution of 2 cm-1 in the transmission mode.

3- X-ray diffraction analysis: X-ray diffraction data were obtained using a Rigaku Ultima3 X-ray instrument and the microcrystalline cellulose and extruded microcrystalline with ILs samples were prepared by powder. Ni-filtered CuKα radiation (λ=1.54060 Å) generated at a voltage of 40 kV and current of 40 mA was utilized, and a scan speed of 5o /min from 2θ 5 o to 45 o was used.

4- Solid-state CP/MAS 13CNMR spectroscopy analysis. The solid-state CP/MAS 13CNMR curves were recorded on a Bruker DRX-400 spectrometer at the frequency of 100 MHz for carbons. The spinning rate and the contact time were 5.0 kHz and 5.0 ms, respectively.

5- Theromgravimetric analysis (TGA). Thermal stability of modified cellulose was performed using theromgravimetric analysis (TGA) on a simultaneous thermal analyzer (Netzsch TG209F1). The sample weighed between 5 and 10 mg. The scans were run from room temperature to 400 0C at rate of 100C/min under nitrogen flow.

4. Results and Discussion

4.1 Determination of the Degree of Substitution (DS)

The degree of substitution of modified cellulose was determined by saponification method as cited in literature [26], 0.05 g sample and 10 mL KOH (in ethanol solution) with concentration 0.1mol/L, were placed in a 250 mL conical flask, at 60 0C with magnetic stirring for 0.5 h. the content were cooled and 3 -4 drops of phenolphthalein were added as indicator. This solution was titrated against 0.1 mol/L standard HCL (isopropyl alcohol) until the pink color disappeared. The DS was calculated by using the following two equations:

[WSA = 100 X C (V0 - V)/ (1000 X 2m)]

[DS = (162 X WSA) / (1 - WSA) ]

(1)

(2)

Whereas WSA is the succinic anhydride content in sample, m is the mass of sample (g);

C is standard HCl concentration in (mol/L);

V0 is the Blank consumption HCl-isopropyl alcohol solution volume (mL);

V is the sample consumption HCl-isopropyl alcohol solution volume (mL);

4.1.1 Effect of reagents amount on degree of substitution (DS)

The modification of microcrystalline cellulose with De-Octenyl succinic anhydride (DDSA) was carried out with different cellulose/DDSA ratios. The reagents amounts (concentration) were adjusted it were shown in Error! Reference source not found.. All samples were shown that the DS increased with the increase of reagent amounts in same processing conditions.

Table 3 the effect of DDSA amount on the degree of substitution.

Reagent Sample no. MCC: reagent DS

DDSA 1 1:0.25 0.100

2 1:0.50 0.143

3 1:0.75 0.244

4 1:1 0.284


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4.2 FT-IR analysis for cellulose succinylated by (DDSA)

Figure . show the FT-IR spectra of microcrystalline cellulose (spectrum a) and DDSA-succinylated cellulose samples 4 (spectrum b) The absorbance peaks at 3343, 2904, 1641, 1371, 1171, and 1051 cm-1 seen in spectrum (spectrum a) are associated with native cellulose; whereas the a strong band at 3343 cm-1corresponds to the O-H stretching, and that at 2904 cm-1 originates from the C-H stretching. The band at 1641 cm-1 is attributed to the bending mode of the absorbed water. The peak at 1371 cm-1 is corresponds to the O-H bending. The absorption band at 1171 cm-1 originates from the C-O antisymmetric bridge stretching. A strong peak at 1051 cm-1 arises from the C-O-C pyranose ring skeletal vibration [27].

In comparison with cellulose succiniate (DDSA) sample 4 (spectrum b) in Figure , some characteristics peaks of DDSA were found which were located at1726 cm-1 which corresponding to the stretch ester carbonyl group C=O cellulose of carbonyl group from DDSA [28], and1569 cm1 which attribute to the asymmetric stretch of vibration of carboxylate RCOO [29]. All these results confirmed that DDSA had been reacted into the cellulose backbone. Additionally, the C-H stretching vibration centered on 2921 cm-1 was increased in intensity from the CH contribute to the carbon chain of the ester [30]. From the spectrum evidence, it was concluded that DDSA had been reacted into the cellulose backbone.

4000 3500 3000 2500 2000 1500 10000

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a

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Figure 3 FT-IR spectra of unmodified cellulose (spectrum a) and succinylated cellulose sample 4 (spectrum b) which was prepared by (1Cell:

1DDSA).

In addition, the effects of DDSA amounts (concentrations) on the extent of succinylation were also investigated by the peaks intensity of succinylated cellulose samples, and their spectra are given in Figure Error! No text of

specified style in document..


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(d)sample 4 (c)sample 3 (b)sample 2 (a)sample 1

a

Figure Error! No text of specified style in document. FT-IR spectra of different succinylated cellulose; sample 1 (spectrum a), sample 2

(spectrum b), sample 3 (spectrum c) and sample 4 (spectrum d), which were prepared by (1cellulose: 0.25 DDSA), (1cellulose: 0.50 DDSA), (1cellulose: 0.75 DDSA) and (1cellulose: 1 DDSA), respectively.

4.3 XRD for Cellulose Succinylate by DDSA

The x-ray spectrum a of unmodified cellulose in Figure , shows the characteristic peaks of cellulose-I crystalline (spectrum a) structure at 14.98°, 16.48°, 22.66° and 34.2°. While, the modified cellulose DDSA; sample 4 (spectrum b) the peak at 22.66° is retain and notably decreasing, indicating the crystalline structure of cellulose was effect by the modification. Also the new peak which was appeared at 20.14 which characteristic of cellulose-II crystalline structure.


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0 10 20 30 40 50 60

2

sample 4 (DDSA) pure cellulose

a

b

Figure 5 X-ray diffraction curves of unmodified cellulose (spectrum a) and sample 4 succinylated cellulose which was prepared by (1cellulose: 1 DDSA).

In Figure 6 the diffractogram of all cellulose succinylated (DDSA) samples were show that the intensity peak at 22.66° is retained and notably displayed, this peaks decrease with the increase of amounts of succinic anhydride i.e. it has relationship with the DS. However, the intensity of this peak decreases with an increase in DS. This indicates that the amorphous regions of cellulose were partially succinylated; however, as the DS increased there may have been some succinylation in the crystalline regions causing a reduction in crystallinity.

The highlights of X-ray diffractograms for samples in

Table Error! No text of specified style in document., shows the effects of DDSA amounts (concentration), on the degree crystallinity succinylate cellulose.


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60 50 40 30 20 10

3200

6400

9600

12800

16000

sample 4

sample 3

sample 2

sample 1

2 ()

inte

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Figure 6 X-ray diffraction curves of different succinylated cellulose; sample 1 (spectrum a), sample 2 (spectrum b), sample 3 (spectrum c) and sample 4 (spectrum d), which were prepared by (1cellulose: 0.25 DDSA), (1cellulose: 0.50 DDSA), (1cellulose: 0.75 DDSA) and

(1cellulose: 1 DDSA), respectively.

Table Error! No text of specified style in document. Summarizes of Diffraction angle and crystallinity of succinylated cellulose with DDSA

Sample Cellulose I Cellulose II crystallinity

Peak I (°) Peak II (°) Peak III (°) New peak Xc (%)

1 14.608 16.351 22.503 20.18 38.07 2 14.732 16.44 22.567 20.20 41.02 3 14.735 16.262 22.505 20.00 40.78 4 14.732 16.300 22.569 20.14 42.00

Pure MCC 14.98 16.48 22.66 - 80.76

4.4 CP/MAS 13CNMR for Cellulose Succinylate by DDSA

The succinylation reaction of cellulose was also characterized by CP/MAS 13C-NMR spectroscopy. Figure shows the CP/MAS 13C-NMR spectra of native cellulose (spectrum a) and modified cellulose with DDSA, sample 1 (spectrum b), sample 2(spectrum c), sample 3(Spectrum d) and sample 4 (spectrum e). In the two spectra of native cellulose spectrum a, and sample 4 spectrum e, the noticeable signals in the region between 50 to 110 ppm are mostly attributed to the different carbons of cellulose. The resonance line at 106.0 ppm is assigned to the C-1. The peaks at 89.8 and 85.2 ppm are related to the C-4 of crystalline cellulose and disordered cellulose, respectively.

Whereas for modified cellulose samples, a trend has seen in the signal to C-6, namely, the signal at 65.8 ppm is attributed to the crystalline cellulose and the peak at 63.1 ppm is assigned to disordered or crystal surfaces cellulose. In this region there were also two peaks at 73.5 and 75.6 ppm which belong to the C-2−C-5. In addition, the two representative peaks at 173.8 and 27.5 ppm in spectra b, which belong to CO and CH3 in succinoyl groups, indicated the occurrence of succinylation reaction. On the other hand, the intensity of the signals at 89.7 ppm for crystalline C-4 and 65.9 ppm for crystalline C-6 decreased sharply in spectra of all


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samples, which reveals that the crystalline structure of the cellulose was disrupted and the succinylation reaction was occurs.

200 150 100 50 0

ppm

MCC sample 1 sample 2 sample 3 sample 4

carboxylmethylene

a

b

c

d

e

Figure 7 CNMR curves of unmodified cellulose (spectrum a) and succinylated cellulose; sample 1(spectrum b), sample 2 (spectrum c), sample 3 (spectrum d) and sample 4 (spectrum e), which were prepared by (1cellulose:

0.25 DDSA), (1cellulose: 0.50 DDSA), (1cellulose: 0.75 DDSA) and (1cellulose: 1 DDSA) respectively

4.5 Thermal analysis for Cellulose Succinylate by DDSA

Unmodified cellulose and succinylated cellulose with DDSA samples were subjected to thermal analysis studied by TGA under temperature range from room temperature to 600 °C at the rate 10 °C/min under nitrogen flow, to investigate the effective of succinylation BY DDSA in the thermal properties of cellulose. Figure shows the TGA of unmodified cellulose (spectrum a) and succinylated cellulose samples 4 (spectrum b). As it can be seen from the curve of the unmodified cellulose (spectrum a) shows two stages of weight loss. The first stage starts from 30 °C to 110 °C with weight loss of about 2.5% which may be related to the loss of absorbed water. The second stage starts at 221.7 °C and continues up to 379.7 0C with weight loss 79.59% which is happened due to the cellulose degradation. The stage of weight loss of succinylated cellulose samples 4 (spectrum b) starts at 292°C, and continues to 301 °C, with weight loss 22 %.


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b

wei

ght(

%)

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MCC:DDSA(1:1) MCC pure

a

Figure 8 TGA curves of unmodified cellulose (spectrum a) and cellulose Succiniate sample 4 (spectrum b) which was prepared by

(1cellulose: 1 DDSA).

In addition, the weight loss of others succinylated cellulose sample 1, sample 2 and sample 3 starts at 246, 242 and 232 °C, and continues to 298, 302 and 296 °C, with weight loss 24, 16 and 14 %, respectively as it shown in figure .9.


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MCC:DDSA(1:0.25) MCC:DDSA(1:0.50) MCC:DDSA(1:0.75) MCC:DDSA(1:1)

Figure 9 TGA curves of different succinylated cellulose sample 1, sample 2, sample 3 and sample 4, which were prepared by (1cellulose:

0.25 DDSA), (1cellulose: 0.50 DDSA), (1cellulose: 0.75 DDSA) and (1cellulose:1 DDSA), respectively.

5. Conclusion

The application of extrusion/reactive extrusion process for microcrystalline cellulose modification has been found to be quite promising; it may be the best alternative to replace the conventional methods for cellulose modification because of environmental and economical consideration. In the present study, the modification of MCC was successfully established with DDSA through reactive extrusion with the assistance of [Bmim]Cl using twin-screw extruder. The modified cellulose has shown different DS. FT-IR and XRD have confirmed the formation of cellulose II by extrusion process. Solid-state CP/MAS 13CNMR spectroscopy has confirmed the occurrence of succinylation at C-6, C-2, and C-3 positions in cellulose. TGA has shown that, the thermal stability of modified cellulose was found to be lower than that of the native cellulose, and also the thermal stability decreased with the increase of DDSA amount.

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Reactive Extrusion for In-situ Chemical Modification of Cellulose

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