Manufacturing & Characterization of Cellulose Acetate Film from Oil

IJSTE - International Journal of Science Technology & Engineering | Volume 4 | Issue 8 | February 2018 ISSN (online): 2349-784X Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent &

Triacetin as Plasticizer

Rica Fitri Yunita Darwin Yunus Nasution P.G. Student Lecturer Department of Mathematics & Natural Science Department of Mathematics & Natural Science Universitas Sumatera Utara Universitas Sumatera Utara

Marpongahtun Lecturer Department of Mathematics & Natural Science Universitas Sumatera Utara

Abstract

A research has been done on the production of cellulose acetate films from oil palm logs (Elaeis guinensis Jack) with chloroform as solvent and triacetin as plasticizer. Cellulose from oil palm sawdust obtained by alkalization process with addition of 2% NaOH. The bleaching process was carried out with addition 2% of NaOCl, 8 drops of glacial CH3COOH and heated at 60-70°C while stirring for 1 hour. The obtained residue was added with 0.05 N HNO3 and heated at 70°C for 1 hour. The obtained cellulose is synthesized to cellulose acetate by the addition of glacial acetic acid as an activator to allow the esterification reaction to proceed smoothly. The acetylation process was carried out by addition of catalyst acetic anhydride acid and H2SO4. The obtained cellulose acetate was formed into a cellulose acetate film with a chloroform solvent and a variation amount of plasticizer triacetin 0 mL, 0.5 mL, 1 mL, and 1.5 mL. Functional group analysis was determined by FT-IR and showed the presence groups of -OH, C-H, C-O for cellulose and groups of -OH, C-H, C-O, C=O for cellulose acetate and cellulose acetate film. The mechanical analysis was determined by tensile test and showed cellulose acetate added with triacetin (1.8:1.5 (w / v)) having an optimum yield of 156,701 MPa, strain 0.0269 and Young's Modulus 3725.4 MPa. Thermal degradation analysis with TGA ie good heat stability occurred at temperature 294,25oC and residual mass 1,9%. Morphological analysis with SEM is at 1000 times enlargement, the distribution of pore film spread evenly, has a smooth surface, pores are small and homogeneous. Keywords: cellulose acetate, chloroform, film, oil palm logs, triacetin ______

I. INTRODUCTION

Oil palm is one of Indonesia's flagship commodities that are growing rapidly, especially in Sumatra and Kalimantan. Indonesian Plantation statistics states that the area of oil palm in 2017 reaches 12,307,677 Ha [1]. Oil palm plantations in Indonesia are expected to continue to rise, as it is a potential producer of vegetable oils. This industry produces a very large amount of solid waste. Out of several types of solid waste generated such as logs (KKS), empty oil palm bunches (TKKS), coir, mud, palm shells, etc. Oil palm logs is one of the abundant plantation waste that has not been optimally utilized so that it has no economic value. In the constant dry state, the components contained in the KKS were cellulose (30.77%), pentose (20.05%), lignin (17.22%), hemicellulose (16.81%), water (12.05 %), ash (2.25%) and SiO2 (0.84%) [2]. Cellulose is a polysaccharide made of d-glucose linked together by β-1,4-glycosidic bonds and is a crude raw material that promises to produce important chemicals, including cellulose-ethanol, hydrocarbons, and starting materials for polymer production [3,4,5]. Currently, the derivatives of cellulose have been widely used in waste treatment, oil recovery, papermaking, textiles, food additives and pharmaceutical applications. Cellulose acetate, one of the most important derivatives of cellulose is more important in industry and it is estimated that 1.5 billion pounds annually are produced globally [6]. Cellulose acetate is a cellulose derived compound obtained by esterification using acetic anhydride as reagents. Cellulose acetate is one type of polymer that is widely used for industry. Cellulose acetate is generally distinguished into two types: cellulose triacetate (primary cellulose acetate) and cellulose diacetate (secondary cellulose acetate). Primary cellulose acetate is made through the reaction of cellulose esterification (acetylation) with acetic anhydride as reactant, whereas secondary cellulose acetate is made by hydrolyzing cellulose acetate primer. Cellulose acetate has extensive industrial applications such as coatings, cigarette filters, textile fibers, consumer products, filtration membranes, composites, laminates, and medical and pharmaceutical products [7,8].

Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent & Triacetin as Plasticizer (IJSTE/ Volume 4 / Issue 8 / 019)

To improve the processing power of cellulose acetate films, triacetin and diacetin were tested as plasticizers due to their eco- friendly, low toxicity and faster biodegradability compared to conventional phthalates [9]. The addition of triacetin and diacetin made the process of melting cellulose acetate and tensile test results showed good effect as a plasticizer. Therefore, the authors intend to make cellulose acetate film isolated from KKS using chloroform as solvent and triacetin as plasticizer which can then be applied to membrane, filter, packaging, etc. In addition, it is expected to produce better and economically valued cellulose acetate films that will be tested for functional, mechanical, morphological, and thermal analysis by FTIR, tensile test, SEM. and TGA.

II. EXPERIMENTAL ARRANGEMENT

Preparation of Oil palm Powder Oil palm logs for samples is oil palm that has been non-productive and aged 20-25 years. Sampling was taken from the oil palm plantation in Kuta Cane, Aceh province. Samples (KKS) were radically differentiated on the outside, middle and core. Samples used in this study taken from the center of the stem, then dried in open air for 30 days. The specimens were then dried until a constant weight was obtained [10]. Crushed and sieved with an 80 mesh siever making it into small particles.

Isolation of Cellulose from Oil palm Powders Oil palm Powder (KKS) 50 g put into a Beaker glass and aquadest 500 mL added. KKS were dispersed in distilled water and the suspension was stirred for 2 h at 50ºC and filtered, and this procedure was repeated once more. The residue was dispersed in a 100 ml of 2% NaOH solution and the suspension was stirred for 2 h at 80ºC, filtered and washed with water. This alkaline treatment is repeated once more and the fibres were dried at 50ºC for 24 h. The result of the alkali treatment of KKS was mixed with 250 mL of NaOCl 5% and 8 drops of glacial acetic acid while stirred by using magnetic stirrer and heated with temperature 70oC for 1 h. Furthermore, it is filtered and washed until the filtrate is neutral. Then 0.05 N of HNO3 added , stirred and heated at temperature 70°C for 1 h. Then filtered and washed until the filtrate is neutral. Then dried with oven at temperature 60oC for 1 h [11].

Acetylation of Cellulose Cellulose 2 g was added with glacial acetic acid 50 mL and stirred using a magnetic stirrer for 30 min at temperature 50°C. Then 0.32 mL of H2SO4 and 18 mL of glacial acetic acid added and then stirred for 25 min. Then it is acetylated with acetic anhydride 64 mL, stirring for 30 min at temperature 50oC. The mixture was allowed to stand for 14 h at room temperature, followed by filtration. Into the filtrate, water is added set by drop to form of precipitate. The precipitate obtained is separated from the solution, then washed to neutral and then dried at temperature 70°C for 2 h [12].

Film Cellulose Acetate of KKS Synthesis Cellulose acetate 1.8 g was dissolved with solvent 50 mL chloroform stirred using a magnetic stirrer for 2h. Then triacetin were added (0.5, 1, and 1.5 mL). The solution is stirred until it’s homogenous for 24 h. The homogeneous polymer solution is then left until no more air bubbles. Polymer solutions that do not contain air bubbles are moulded on glass plates whose edges have been duct tape to adjust the film thickness. Then the film is evaporated by left in the open air with 24 h evaporation time.

III. RESULTS & DISCUSSION

Synthesis of Cellulose Acetate Glacial acetic acid as an activator is required for the esterification so the reaction could proceed smoothly. Immersion in acetic acid aims to obtain a large surface area of cellulose fiber and reduce the intramolecular bond of hydrogen thereby facilitating the diffusion of acetic anhydride as an esterification reagent into cellulose fibers. The esterification process is intended to substitute a cellulose hydroxyl group with an acetyl group to form cellulose acetate. Acetic acid anhydride will be protonated in the presence of sulfuric acids to produce carbonium ions. The formed carbonium ion will react with cellulose to form cellulose acetate. The reaction of cellulose acetate synthesis from cellulose can be seen in fig.1.

Cellulose Cellulose Acetate Fig. 1: Reaction of Cellulose Acetate Synthesis from Cellulose

Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent & Triacetin as Plasticizer (IJSTE/ Volume 4 / Issue 8 / 019)

The esterification process lasts until the material is perfectly dissolved. The esterification reaction is an exothermic reaction so the temperature should be kept low, in order to avoid degradation of the cellulose chain and avoid evaporation. When all OH groups on cellulose are replaced by acetyl groups of acetic anhydride, the excess of acetic acid anhydride will affect the decrease of the yield of cellulose acetate [13]. Some factors affect the yield of cellulose acetate, including the type and moisture content of the raw materials used, the ratio of cellulose: acetic acid, temperature and time of acetylation process and others [14]

Characterization Functional Groups Analysis with FT-IR

CA 30 C

20 % T

0 3500 3000 2500 2000 1500 1000 500 wave number (cm-1)

Fig. 2: FT-IR spectrum of Cellulose & Cellulose Acetate

-1 -1 Cellulose from oil palm log powder has OH streching bond at wave peak 3410,15 cm , C-H streching 2900,94 cm , -CH2 deformation at 1427 cm-1, C-O-C stretching at 1165 cm-1, C-C stretching at 1057 cm-1 and C-H deformation at 895 cm-1. The absorbance rate at 1620 cm-1 to 1057 cm-1 was normalized with respect to the cellulose peak at 895 cm-1, assuming an unnecessary amount of cellulose was removed during the bleaching process [15]. The sample residue after bleaching is more exposed to acid attack in the acid treatment process because more lignin is removed. Therefore, the amorphous region is dissolved by acid attack and the lignin peak ratio to cellulose increases due to the decrease in cellulose content which causes a decrease in absorption peak at a change of 895 cm-1 (C-H deformation) glucose ring [16]. Increased lignin content has an effect on the characteristics of cellulose and the resulting film. High purity cellulose can produce cellulose acetate with good quality. cellulose purity level is indicated by the high value of α-cellulose and the presence of a characteristic peak on the IR spectrum of cellulose . The main functional group in pure cellulose is the hydroxy group (O-H), since cellulose is the long chain of β glucose [14]. While the FTIR spectra of cellulose acetate have C = O ester bonds at wave numbers 1751,36 cm-1, C-O at wave number 1234,44 cm-1. It also appears to decrease the intensity of tape absorption at 3500 cm-1 wave numbers, which is related to the axial vibration of the OH bond, in respect of the non-acetylation material [17,18].

70 CA CA+TA(0.5mL) CA+TA(1.0mL) 60 CA+TA(1.5mL)

% T 30

0 3000 2500 2000 1500 1000 500 wave number (cm-1)

Fig. 3: FTIR Spectrum of Film Cellulose Acetate

Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent & Triacetin as Plasticizer (IJSTE/ Volume 4 / Issue 8 / 019)

When compounds are mixed, physical bonds and chemical interactions are reflected by changes in characteristic IR spectra peaks [19]. Fig 4.6 shows the IR spectra of triacetin and cellulose acetate films with/without triacetin. As triacetin content increases, the bands at 1226.73 cm-1 gradually shift to the band 1234.44 cm-1, indicating that the alkoxyl groups of triacetin and cellulose acetate molecules are enhanced. The gel theory [20,21] considers that plasticizers take effect by breaking polymer– polymer interactions (e.g. hydrogen bonds and Van der Waals or ionic forces). Accord-ing to the molecular structure of triacetin and cellulose acetate, the primary inter- and intra-molecule forces in unplasticized and plas-ticized films are regarded as Van der Waals’ force. Consequently, shifts of above-mentioned peaks should arise from the new intermolecular Van der Waals’ force between triacetin and cellulose acetate molecules. This new interaction replaced the respective molecular forces which originally belonged to triacetin and cellulose acetate themselves. The gradually increasing interaction simultaneously weakened the original molecular forces [22]. Analysis of Mechanical Properties of Cellulose Acetate film Table – 1 Test data on mechanical properties of Cellulose Acetate film Film Composition (b/v) Stress (MPa) Strain Modulus Young’s (MPa) CA + TA (1,8:0) 76,561 0,026 1933,6 CA + TA (1,8:0,5) 61,894 0,0148 2164,3 CA + TA (1,8:1,0) 159,578 0,0186 4289,8 CA + TA (1,8:1,5) 156,701 0,0296 3725,4 From Table 1. above, it is seen that the most optimum elongation is in the film CA + TA (1.8: 1.5 (b / v)) that is 0,0296. From the results of the tensile strength test it is seen that triacetin variation as plastizer produces the best value because it can increase tensile strength and modulus of young's from the resulting cellulose acetate film. However, the addition of 0-1,5 mL triacetin in the process of making cellulose acetate film has an effect of increasing tensile strength and young's modulus. This is because triacetin and cellulose acetate can be mixed perfectly (homogeneous).

8 CA 1.6x10 CA+TA(0.5mL) CA+TA(1.0mL) 8 1.4x10 CA+TA(1.5mL)

1.2x108

1.0x108

(Pa)

8.0x107

Stress 6.0x107

4.0x107

2.0x107

0.0 0.000 0.005 0.010 0.015 0.020 0.025 0.030

Strain (%)

Fig. 3: Stress-Strain Graph of Film Cellulose Acetate with Triacetin as Plastisizer

Thermal Degradation Analysis Using TGA

100 CA CA+TA(0.5mL) CA+TA(1.0mL) 80 CA+TA(1.5mL)

% W

0 0 50 100 150 200 250 300 350 400 450 500 550 Temperature (oC)

Fig. 4: TGA curve of Film Cellulose Acetate

Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent & Triacetin as Plasticizer (IJSTE/ Volume 4 / Issue 8 / 019)

The TGA curve of cellulose acetate film (CA) shows an initial weight loss at temperatures below 100°C caused by water evaporation. The decomposition of cellulose acetate films beginning at 235oC-381oC can be attributed to the degradation of acetate from hemicellulose and lignin, which is confirmed by the weight loss on the TGA curve [24] with a residual mass of 0.3% of the initial weight. Although there is still lignin and hemicellulose in the cellulose acetate composition, some of these elements are easily removed by hydrolysis and dissolution in the reaction medium during the acetylation process [25]. On the TGA curve of the cellulose acetate film (CA: TA (0.5 mL), CA: TA (1 mL) CA: TA (1.5 mL)) the thermal stability of the triacetin decreases significantly (seen from the onset and peak value) After mixing with cellulose acetate ie from 53.5oC to 177.5oC (37.6% by weight), 57.8oC to 208.91oC (48.6% by weight), and 39.3oC to 118.9oC (9 , 44% by weight) with an initial residual mass of 1.9% by weight. This is due to the evaporation of triacetin associated with the destruction of molecular forces, so that the thermal stability of triacetin changes with its interaction with cellulose acetate molecules. Most of the triacetin molecular forces are replaced by interactions with cellulose acetate molecules when these two components are mixed. Triacetin in the film evaporates at a lower temperature, which can be concluded that triacetin intermolecular forces have higher stability than interaction with cellulose acetate [22]. In addition, the increased triacetin collected in the amorphous region is rich in plasticizer due to crystallization [25]. The molecular strength of triacetin should be much more remarkable within the amorphous region, which may cause the characteristic value of the triacetin to increase [26]. Morphological Analysis Using SEM

Fig. 5: Morphology Film Analysis of Cellulose Acetate magnification 1000x

The formation of the film could caused by the process of making the film by phase inversion, where the phase inversion occurs solvent evaporation in open air so as to encourage the surface of the film to form pores [27]. The producing process of cellulose acetate film with the addition of chloroform can improve the stability of the solution and avoid phase separation so as to affect the characteristics of the resulting cellulose film. The morphology of the cellulose acetate film shown in Figure 4.9 clearly shows that the cellulose acetate film without the triacetin plasticizer is coarser with the presence of white particles. However, cellulose acetate films with triacetin plasticizers produce different textures. This is characterized by the addition of triacetin from 0.5 mL, 1 mL and 1.5 mL seen that the more triacetin added showed a lower roughness. Thus indicating that plastization can effectively encourage intuitive homogenization in the resulting film [22].

IV. CONCLUSION

Cellulose acetate film from oil palm powder synthesis result has been successfully done by blending method by using chloroform solvent and triacetin plastisizer. The success of this synthesis is evidenced by FT-IR data. Cellulose acetate film with chloroform solvent and triacetin plastisizer with 1.5 mL triacetin variation is the best result. Cellulose acetate film with addition of plasticizer (1.8: 1.5 (w / v)) has Young's modulus and tensile strength of 3,725 MPa and 156,701 MPa where there is a greater increase than cellulose acetate film without using triacetin plastisizer. Good heat stability at 294.25oC with a residual time of 1.9%. The morphology of cellulose acetate film with chloroform solvent and triacetin plastisizer of 1.5 mL triacetin variation showed that cellulose acetate was evenly dispersed

Manufacturing & Characterization of Cellulose Acetate Film from Oil Palm Logs (Elaeis Guinensis Jack) with Chloroform as Solvent & Triacetin as Plasticizer (IJSTE/ Volume 4 / Issue 8 / 019)

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