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TUGAS

TEKNOLOGI KOMPOSIT
Muhammad Hendra Sahputra Ginting, S.T., M.T

Oleh:
Jecklyn Gultom (170405112)
Ridho Sitinjak (170405120)
Hotmauli Aruan (170405121)
Orlando Oloan Hidari Tan (170405128)
Fachreni Dwi Putri (170405139)

DEPARTEMEN TEKNIK KIMIA


FAKULTAS TEKNIK
UNIVERSITAS SUMATERA UTARA
MEDAN
2020
Judul : Synthesis of Bioplastic-based Renewable Cellulose Acetate from Teak Wood
(Tectona grandis) Biowaste Using Glycerol-Chitosan Plasticizer
Jurnal : ORIENTAL JOURNAL OF CHEMISTRY
Volume dan Halaman : Volume 34 No. (4), halaman 1810-1816
Tahun : 2018
Penulis : Baiti Rohmawati, Fatin Atikah Nata Sya’idah, Rhismayanti, Dante Alighiri
dan Willy Tirza Eden
Reviewer : 1. Jecklyn Gultom/170405112
2. Ridho Sitinjak/170405120
3. Hotmauli Aruan/170405121
4. Orlando Oloan Hidari Tan/170405128
5. Fachreni Dwi Putri/170405139
Tanggal : 06 Juni 2020

Tujuan Penelitian:
Penelitian ini bertujuan untuk mengetahui metode yang paling efektif dan efisien untuk
memanfaatkan selulosa dari limbah bioselulosa kayu jati menjadi bioplastik dan untuk
menganalisis karakteristik bioplastik yang dihasilkan. Limbah kayu dalam penelitian ini
dipasok oleh industri mebel di Jepara yang telah dibuang dan dibakar.

Metode Penelitian:
Secara garis besar, penelitian ini terbagi atas dua tahapan. Tahapan pertama adalah
tahapan proses, dimana tahapan ini berlangsung dari pre treatment terhadap bahan baku yang
akan digunakan, dalam hal ini adalah limbah kayu yang di dapatkan dari industri mebel
hingga aktivasi selulosa yang di dapatkan dari bahan baku tersebut. Tahapan yang kedua
adalah tahapan analisis, yang meliputi karakterisasi produk hingga uji degradasi produk
bioplastik yang dihasilkan dari penelitian. Kemudian, data yang diperoleh dari uji degradasi
bioplastik dianalisis menggunakan uji-t (P <0,05). Data dianalisis menggunakan uji Chi-
square dengan P = 0,05.

Langkah Penelitian:
Langkah pertama yang dilakuan dalam penelitian ini adalah pre treatment terhadap bahan
baku yang digunakan, yaitu limbah kayu yang di dapatkan dari industri mebel. Limbah kayu
tersebut dicuci dan di keringkan sampai 24 jam. Kemudian limbah kayu tersebut diekstraksi
menggunkan campuran larutan heksana dan etanol dengan metode refluks selama 6 jam
sebelum akhirnya difiltrasi dan dihidrolisis menggunakan asam sulfat.
Selanjutnya, limbah kayu yang telah dihidrolisis diisolasi selulosanya dengan multitahap
menggunakan metode pulping. Setelahnya, selulosa yang didapat disintesis menjadi selulosa
asetat melalui tahapan aktivasi dan asetilasi.
Selulosa asetat yang didapat kemudian disintesis menjadi bioplastik. Produk akhir
bioplastik tersebut kemudian dikarakterisasi, dianalisis gugus fungsinya menggunakan alat
Fourier Transfer Infra Red (FTIR), dianalisis mikrostrukturnya dengan alat Scanning
Electron Microscope (SEM), diuji kemampuan degradasinya, dan dianalisis sifat mekaniknya
menggunakan metode ASTM D638. Terakhir, data yang diperoleh dari uji degradasi
dianalisis menggunakan uji-t dan data dianalisis menggunakan uji Chi-square.

Hasil Penelitian:
Pada jurnal ini, hasil karakterisasi bioplastik yang dihasilkan yaitu:
1. Analisis Gugus Fungsi Bioplastik
Dengan menggunakan spektroskopi FTIR, menunjukkan bahwa serbuk kayu jati
memiliki konten selulosa yang dibuktikan dengan adanya gugus –OH dalam pita absorben
pada 3435,59 cm-1. Spektra FTIR dari serbuk kayu pretreatment mengidentifikasi adanya
selulosa pada pita penyerap 3408,28 cm-1, di mana lembah lebih tajam. Setelah selulosa
diisolasi, pita penyerap dalam 3349.78 cm-1 area semakin jelas. Kemungkinan besar selulosa
dari serbuk kayu jati telah terisolasi. Ini juga didukung oleh kehadiran gugus tertentu selain
gugus hidroksil, seperti kelompok metilen (CH2) di 2901,48 cm-1 yang merupakan getaran C-
H, dan grup –O yang bersatu dengan selulosa muncul dalam pita penyerapan 1319,85 cm-
1
dan 1372.75 cm-1.
Spektra FTIR pada selulosa asetat bila dibandingkan dengan spektra FTIR selulosa,
gugus hidroksil pada selulosa lebih tajam daripada kelompok hidroksil pada selulosa
asetat. Ini membuktikan bahwa adanya gugus hidroksil asetilat. Spektra FTIR selulosa asetat
juga membuktikan bahwa proses asetilasi tidak mematahkan struktur utama selulosa, karena
masih menunjukkan keberadaan kelompok spesifik selulosa, seperti C-H dalam 2905,49 cm-
1, grup -O- pada 1318,98 cm-1 dan 1373,21 cm-1.
2. Analisis SEM
Analisis SEM pada perbesaran 1000x dan 5000x menunjukkan bahwa permukaan serbuk
kayu jati memanjang dalam bentuk fibril. Ini merupakan bentuk permukaan selulosa. Karena
itu, dari hasil uji SEM ini, dapat dilihat bahwa ada kandungan selulosa dalam bubuk kayu
jati. Struktur selulosa seperti tali bengkok yang diikat satu sama lain di antara hidrogen liner
dengan fibril yang berdiameter berbeda. Fibril pada selulosa asetat lebih teratur daripada
fibril dalam selulosa. Itu berarti selulosa asetat memiliki karakter plastik. Bioplastik yang
terdiri dari selulosa asetat, kitosan dan gliserol memiliki permukaan yang lebih halus
dibandingkan dengan selulosa dan selulosa asetat. Hal itu karena gliserol telah menutupi
permukaan bioplastik. Kehadiran pori-pori dalam bioplastik akan membuat bioplastik dapat
berinteraksi dengan mikroba sehingga akan mempengaruhi laju degradasi bioplastik di tanah.
3. Analisis Degradasi Bioplastik
Uji biodegradasi dilakukan dengan metode penguburan dalam campuran tanah dengan
kompos. Uji degradasi membuktikan bahwa bioplastik lebih mudah terdegradasi daripada
plastik konvensional yang mana tidak dapat terurai secara hayati. Bioplastik ini mudah
terdegradasi karena bentuk polimer amorf sehingga mikroorganisme di dalam tanah bisa
menyerang molekul bioplastik.
4. Sifat Mekanik
Hasil tes mekanik dilakukan untuk mengukur kekuatan tarik dan perpanjangan dari tiga
sampel bioplastik menunjukkan bahwa bioplastik dengan penambahan gliserol akan
menurunkan daya tarik kekuatan tetapi meningkatkan perpanjangan putus. Gugus fungsi
rantai selulosa adalah gugus hidroksil yang dapat berinteraksi dengan kelompok -O, -N, dan -
S, membentuk ikatan hidrogen dimana ikatan hidrogen lebih panjang dari ikatan kovalen
tetapi ikatan itu lebih lemah. Karena itu, selain gliserol, ada juga interaksi antara ikatan
hidrogen di selulosa dan gliserol. Selain itu, dengan tambahan gliserol dapat meningkatkan
fleksibilitas bioplastik dan meningkatkan mobilitas molekul sehingga bioplastik memiliki
perpanjangan elongasi yang lebih elastis dan lebih besar.

Kelebihan Penelitian :
1. Plastik biodegradable yang dihasilkan berdasarkan selulosa asetat sangat bagus karena
dapat terurai di tanah atau air dalam beberapa tahun, juga dapat didaur ulang atau dibakar
tanpa residu.
2. Prosedur percobaan yang tertulis sudah jelas dan lengkap. Dimana kondisi operasi dan
tahapan yang dilakukan juga sudah dituliskan dengan runut, mulai dari pretreatment
bahan baku, isolasi selulosa, sintesis selulosa asetat, sintesis bioplastik, hingga
karakterisasi bioplastiknya.
3. Penjelasan mengenasi hasil karakterisasi FTIR sudah dipaparkan dengan baik dengan
bahasa yang mudah dimengerti, seperti karakterisasi FTIR bubuk kayu jati mentah
menunjukkan memungkinkannya akan terdapat kandungan selulosa, begitu juga dengan
pretreatment dari bubuk kayu jati, selulosa dari bubuk kayu jati dan selulosa asetat.
Penjelasan mengenai hasil karakterisasi SEM sudah dipaparkan dengan sangat jelas
mengenai morfologi yang diuji dengan menampilkan hasil SEM pada perbesaran yang
berbeda yaitu pada perbesaran 1000x dan 5000x. Penjelasan mengenai penghitungan
tingkat substitusi selulosa asetat (DS), analisis degradasi bioplastik, dan sifat mekanik
bioplastik telah menjelaskan dengan baik kualifikasi bioplastik yang dihasilkan.

Kekurangan Penelitian:
1. Tidak adanya analisis kadar air, yang mana hal ini dapat berhubungan dengan daya
simpan bahan, dimana jika kadar air tinggi, akan menyebabkan bahan menjadi rusak dan
tidak tahan lama. Sehingga dengan adanya analisis kadar air dapat diketahui daya simpan
dari bioplastik yang dihasilkan.
2. Tidak adanya analisis daya serap air, yang mana dengan adanya analisis ini dapat
diketahui apakah terjadi ikatan dalam polimer serta tingkatan atau keteraturan ikatan
dalam polimer yang dihasilkan melalui adanya penambahan berat polimer setelah
mengalami penggembungan.

Kesimpulan:
Isolasi selulosa dari kayu jati dilakukan dengan tiga langkah proses yang efektif seperti
metode pretreatment dengan heksana, etanol, dan asam sulfat. Kemudian, selulosa yang
diperoleh diisolasi menggunakan asam nitrat, natrium hidroksida, natrium sulfit dan
pemutihan dengan kalsium hipoklorit. Selulosa asetat berhasil disintesis dengan hasil 45,88%
dengan menggunakan asetat anhidrida, toluena sebagai pelarut, dan asam sulfat sebagai
katalis. Selulosa asetat bereaksi dengan asam asetat dan gliserol menjadi bioplastik. Produk
yang disintesis dikarakterisasi dengan menggunakan FT-IR dan SEM. Perilaku mekanik
dievaluasi oleh ASTM D638. Dengan demikian, persiapan sukses bioplastik akan
memberikan peluang yang menjanjikan untuk memilih residu pertanian sebagai kandidat
yang kuat dan kompetitif untuk pemanfaatan industri.

Pada segi penulisan, artikel telah memenuhi kaidah kebahasaan pada umumnya, mudah
untuk dipahami. Judul yang digunakan spesifik dan memberikan gambaran yang jelas
mengenai penelitian yang dilaksanakan, pemilihan kata juga sudah baik dan tepat.
ISSN: 0970-020 X
ORIENTAL JOURNAL OF CHEMISTRY CODEN: OJCHEG
An International Open Free Access, Peer Reviewed Research Journal
2018, Vol. 34, No.(4):
Pg. 1810-1816
www.orientjchem.org

Synthesis of Bioplastic-based Renewable Cellulose Acetate


from Teak Wood (Tectona grandis) Biowaste Using
Glycerol-Chitosan Plasticizer
Baiti Rohmawati1*, Fatin Atikah Nata Sya’idah1, Rhismayanti2,
Dante Alighiri1 and Willy Tirza Eden1

1
Chemistry Department, Faculty of Mathematics and Natural Sciences, Universitas Negeri Semarang,
Indonesia.
2
Biology Department, Faculty of Mathematics and Natural Sciences, Universitas Negeri Semarang,
Indonesia.
*Corresponding author E-mail: baitirohmawati6@gmail.com

http://dx.doi.org/10.13005/ojc/3404014

(Received: July 07, 2018; Accepted: July 31, 2018)

ABSTRACT

Cellulose acetate was synthesized from cellulose which was isolated from teak wood
(Tectona grandis) biowaste. The isolation process used an isolation method using nitric acid, sodium
hydroxide, sodium sulfite and bleaching with calcium hypochlorite. Cellulose acetate was synthesized
with acetic anhydride, toluene as a solvent, and sulphuric acid as a catalyst. Cellulose acetate
reacted with acetic acid as a catalyst and glycerol-chitosan as a plasticizer. This product yielded a
bioplastic. The synthesized products were characterized by using FTIR and SEM. The bioplastic’s
mechanical properties were evaluated by ASTM D638 method. Based on the results of FTIR analysis,
this result was successfully performed. This condition was shown by the sharpness of the hydroxyl
group of cellulose acetate than the hydroxyl group in the cellulose and wood powder. The optimum
result of bioplastic was obtained by composition of cellulose acetate: acetic acid: chitosan: glycerol is
0.8 g: 15 mL: 0,4 g: 1 mL.

Keyword: Bioplastic, Tectona grandis, Cellulose acetate, Glycerol, Chitosan, Plasticizer.

INTRODUCTION resources (such plants) has got increasing attention,


Biodegradable polymers expand the range especially in EU countries2 and the use of renewable
of waste management alternative over conventional resources has been revitalized 3-5 . If properly
plastics, and this is supported by the Life Cycle managed, this would reduce their environmental
Assessment1. In recent years, the production of impact upon disposal 2 and, also, it would be
biodegradable materials from renewable natural technically and economically practicable6.

This is an Open Access article licensed under a Creative Commons Attribution-Non Commercial-Share Alike
4.0 International License (https://creativecommons.org/licenses/by-nc-sa/4.0/), which permits unrestricted
Non Commercial use, distribution and reproduction in any medium, provided the original work is properly cited.
Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1811

Plastics are considered to be the most moldability, and di-electric strength 19,20. Natural
widely used polymers in our daily life especially in plastic is produced in a fluid form and, therefore, it is
packaging applications. The annual production of shaped easily and does not require a large amount
petroleum-based plastics exceeded 300 million tons of energy. This is compared with the conventional
in 20157. In fact, 34 million tons of plastic wastes are plastic which is usually stored as granules and needs
generated each year throughout the world, and 93% a massive amount of energy so that it can be shaped
of them are disposed of in landfills and oceans8. To by mo lding, injection, or extrusion21.
save fossil fuels, reduce CO emission and plastic
wastes, there is found a bioplastic. Bioplastics can Based on this explanation, this research
be defined as plastics made of biomass such as aims to find out the most effective and efficient
corn, sugarcane, and wood. method to utilize cellulose from cellulose biowaste
of teak wood become a bioplastic and to analyze the
Bioplastics are derived from agricultural characteristics of produced bioplastic. Wood waste
resources and biomass feedstock that are renewable in this research supplied by the furniture industry in
and therefore comply with materials that are Jepara which had been thrown away and burned
eco-effcient and sustainable9,10. It has been reported away.
that the worldwide production capacity of bioplastics
will increase from 0.36 Mt in 2007 to 3.45 Mt in 2020. EXPERIMENTAL
Among the biopolymer matrices being utilized for the
production of bioplastics, cellulose is considered to Materials
be used as the raw material11. Teak wood in the experiments was supplied
by the furniture industry in Jepara District, Central
Cellulose is the major constituent of all Java Province, Indonesia. Teak wood was washed
plant materials12. Cellulose can be found in the to remove its impurities. Chitosan in the experiment
teak wood (Tectona grandis) sawdust. In general, was purchased in CV Chimultiguna with 98% purity.
the composition of wood is 50% (w/w) cellulose, The reagents and chemicals using in our study were
15–30% (w/w) hemicellulose, 15–35% (w/w) lignin, such as hexane, ethanol, NaOH, HNO3, H2SO4,
and 5–30% (w/w) ash13. NaOCl, Na2SO3, glycerol, acetic acid, water, and
compost. The chemicals were purchased from
To improve the quality of bioplastics, Merck.
cellulose is acetylated to be a cellulose acetate.
Cellulose acetate is typically made from wood Pretreatment of raw material
pulp through reaction with acetic acid and acetic The sawdust was washed several times
anhydride in the presence of sulfuric acid to form with water and then dried at 60°C for 24 hours.
cellulose triacetate14-16. Cellulose acetate presents 300 g of the dried powder was extracted with a
a high glass transition temperature and cannot be hexane and ethanol mixture with ratio 2: 1 and
melt-processed as a raw material because of its
refluxed for 6 h then allowed to cool and filtered.
thermal properties. For this reason, plasticizers
Then, the residue was hydrolyzed using sulfuric acid
are usually added to cellulose acetate. These
p.a. 2.2% with a temperature of 121oC22.
substances allow the melting of the polymers without
thermal degradation and reduce the rigidity17,18
Cellulose isolation use the multistage pulping method
The processed sawdust was mixed with
Biodegradable plastics, based on cellulose
400 mL of 3.5% nitric acid. The mixture was immersed
acetate, were studied and the produced plastic
in a water bath for 2 h at 90°C. Furthermore, the
decomposed in soil or water within a few years. obtained residue was washed with distilled water.
However, the material can be recycled, also, The residue is immersed into 300 mL of sodium
or burned without residue1. There were studies hydroxide and sodium sulfite solution each 2%
of the important properties of cellulose acetate w/v at 50°C for 1 hour. Then, the residue was filtered
including mechanical strength, impact resistance, and washed. The residue was bleached by 200 mL
transparency, colorability, fabricating versatility, of water and 3.5% w/v sodium hypochlorite mixture
Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1812

(water ratio and 3.5% sodium hypochlorite solution as 0.804 grams and added 15 ml of vinegar solution
is 1: 1), then it was boiled for 10 min. filtered and 0.665 M. it was added with 0.4 g of chitosan and
washed. The obtained residue from the filtration was 1 mL of glycerol and stirred for 15 minutes. After the
heated at 80°C in the 200 mL of sodium hydroxide mixture was homogeny, it was shaped by a casting
17.5 w/v for 30 min. then filtered and washed. The method. In this method, the biopolymer sample
obtained residue is cellulose22. was shaped with a glass plate. The mold was flat
and then dried with an oven at 600C for 1 hour. The
The obtained cellulose was dried in the experiment was repeated by varying the volume of
oven at 600C for 1 hour. Pure dry cellulose was stored glycerol addition.
in a desiccator for bioplastic synthesis.
Bioplastic characterization
Cellulose acetate synthesis In this study, several tests were performed
Cellulose activation to study the characteristics of varied bioplastics. The
4 grams of cellulose was refluxed with characteristic tests include the analysis of functional
100 ml of 3 M acetic acid and 5 ml of concentrated group analysis, pore structure analysis, degradation
sulfuric acid 98% (v/v). Then, it was heated at 400C ability of bioplastic, and mechanical properties of
for 3 hours. The resulted precipitate is separated from bioplastic.
the filtrate by filtration, then it was dried in an oven at
60°C and weighed until its mass was constant then Functional group analysis
it was deposited in the exciter. Functional group analysis performed by
using FTIR Spectrometer Frontier instrument which
Cellulose acetylation can identify functional groups in a material through
4 gram activated cellulose was refluxed typical IR uptake. Analysis using FTIR is done in the
with 10 ml acetic anhydride, 5 ml toluene, and 5 range 300 - 4000 cm-1.
ml of concentrated sulfuric acid 98% (v/v). The
mixture was heated at 40°C for 8 hours. The product Scanning electron microscope (SEM) analysis
was cooled, and the precipitate was filtered. The SEM is a method of characterization and
remained toluene was evaporated, and the rest of the research of the pore structure of an object. This SEM
other reagents were cleaned by wash the precipitate analysis can be performed on the teak wood powder
several times with water. The precipitate was dried surface, cellulose surface, cellulose acetate surface,
with an oven at 60°C to a constant weight. and bioplastic.

Cellulose acetate substitution degree calculation Degradation ability of bioplastic


1) Dried cellulose acetate 0,5 g was added by Bioplastic degradation tests were performed
50 mL of water (pH is arranged until 7)
by burying all three bioplastic samples for 30 days.
2) 25 ml 0.5 N NaOH was added and heated
The percentage loss of mass from bioplastics will
while stirring until the precipitate dissolved
be known through this analysis. We can determine
and homogeneous then the solution was
percent loss of mass of the three bioplastic samples
cooled.
through the equation
3) The mixture was titrated with 0.02 N HCl until
the pH returns 7. The DS value was calculated (2)
with the titration formula as follows24
with:
(1) Wi: bioplastic mass before degradation
With: Wf: bioplastic mass after degradation
W : weight of cellulose ester
MW : molecular weight of bound substituent at Mechanical properties of bioplastic
cellulose A mechanical test was performed to
measure the tensile strength and elongation of the
Bioplastic synthesis three bioplastic samples. The used method was
Dry cellulose acetate was weighed as much ASTM D638.
Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1813

Data Analysis Technique


Obtained data from the bioplastic
degradation test were analyzed using a t-test
(P <0.05). The data were analyzed using the Chi-
square test with P = 0.05.

RESULT AND DISCUSSION

Bioplastic’s functional group analysis


FTIR spectra from teak wood powder,
pretreatment wood powder, cellulose, and cellulose
acetate to know every step of the research. (d)
Fig. 1. FTIR spectra a) Teak wood powder, b) pretreatment
wood powder, c) cellulose, d) cellulose acetate

Structure of compound from teak wood


powder, pretreatment teak dust, cellulose, and
cellulose acetate confirmed using FTIR spectroscopy.
This was done to see the success of cellulose isolation
process from Tectona grandis teak wood waste. In
Fig.1.a, the results show that on raw teak powder, it
was probably to have cellulose content, which was
proved by the presence of typical cellulose groups,
-OH, in absorbent bands at 3435.59 cm-1. In Fig.1.b,
(a)
after pretreatment of teakwood dust, cellulose began
to appear. It was identified in absorbent bands
3408.28 cm-1, where the valleys were sharper. After
being isolated, the absorbent bands in the 3349.78
cm-1 area was increasingly apparent (Fig. 1.c). Most
likely the cellulose from teakwood powder had been
isolated. This was also supported by the presence of
specific groups of cellulose other than the hydroxyl
group, such as the methylene group (CH2) in the
2901.48 cm-1 absorption band which was a C-H
stretch vibration, and the -O- groups that assemble
cellulose appeared in the absorption band 1319.85
cm-1 and 1372.75 cm-1.
(b) The FTIR Cellulose acetate spectra were
depicted in Fig. 1.d. When compared to the cellulose
FTIR spectra, the hydroxyl group on the cellulose
was sharper than the hydroxyl group on cellulose
acetate. This proved that there was an acetylated
hydroxyl group. Not all hydroxyl groups could be
acetylated, so the degree of substitution (DS) needs
to be calculated. The FTIR cellulose acetate spectra
also proved that the acetylation process did not
break the main structure of cellulose, still indicating
the presence of cellulose-specific groups, such
C-H in 2905.49 cm -1 absorptions, group -O- in
(c) 1318.98 cm-1 and 1373.21 cm-1.
Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1814

Scanning electron microscope (SEM) analysis diagonally from one fibril to another. The arrangement
of such fibrillation units was similar to the arrangement
of cellulose fibrillar in soft cotton23.

Figure 4a showed that cellulose acetate


fibrils were more regular than fibrils in cellulose
(Fig. 3a). It also means that the produced cellulose
acetate has a plastic character. The cellulose acetate
pores were shown in Fig. 4b. These pores showed a
modification of cellulose with acetyl groups.
(a) (b)
Fig. 2. SEM micrographs teak wood powder surface
structure at magnification (a) 1000 x and (b) 5000x

Figure 2a showed that the surface of teak


wood sawdust was elongated in the form of fibrils. This
form was the surface form of cellulose. Therefore,
from the results of this SEM test, it could be seen that
there was cellulose content in teak wood powder.

(a) (b)
Fig. 5. SEM micrographs bioplastic surface structure
at magnification (a) 1000x and (b) 5000x

Figure 5a and 5b showed that the bioplastic


which was composed of cellulose acetate, chitosan
and glycerol had a smoother surface when compared
to cellulose and cellulose acetate. It occurred
because glycerol had covered the surface of the
(a) (b) bioplastic. The presence of pores in bioplastics
Fig. 3. SEM micrographs cellulose surface structure suggested that bioplastics were able to interact with
at magnification (a)1000x and (b) 5000x microbes so that it would affect the rate of bioplastic
In Fig. 3b, it was seen that cellulose structures degradation in the soil.
like twisted ropes tied to each other between hydrogen
liners. Fibrils were a collection of cellulosic molecules Cellulose acetate degree of substitution (DS)
and contained regular and less regular parts23. Fibrils calculation
did not have the same diameter, as shown in Fig. 3a The degree of substitution (DS) value
showing different fibrils. In the figure also showed shows the average substitution rate of each glucose
that the visible fibrillar bundle consisted of fibrils with
unit in the polysaccharide. If all of the hydroxyl groups
various diameters and single molecules directed
in each unit of glucose is esterified, the DS value
is 3. The higher the DS value, the properties of the
plastic of the cellulose ester is higher24.

During acetylation of free hydroxyl


groups at C2, C3 and C6 atoms in cellulose may be
substituted with acetyl groups. Therefore, in theory,
the maximum DS value is 3. Substitution occurs
because of the addition-elimination mechanism.
(a) (b)
Fig. 4. SEM micrographs cellulose acetate surface Three free hydroxyls (-OH) groups have
structure at magnification (a) 1000x and (b) 5000x different reactivity. The -OH group of C6 atoms is
Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1815

more reactive and more rapidly acetylated than -OH method for characterizing the biodegradation of a
groups in C2 and C3 atoms due to steric hindrances. polymer is to determine the mass loss of the polymer
If the -OH group of C2 and C3 atoms are compared, material. In this study, 3 pieces of bioplastic samples
then the -OH group at C2 is more reactive. This is were analyzed for their ability of biodegradation. The
because the -OH group at C2 is closer to hemiacetal time required to analyze bioplastic biodegradation
and more acidic than the -OH group of C3 atoms. capability was 30 days. The observed results of the
three mass of bioplastics before and after degradation
The value of this cellulose acetate DS could be were based on Table 1,
well measured using a titration method on esters whose
esterification process24. Based on the titration method, Bioplastic was reduced by an average mass
cellulose acetate with method 1 had a DS value 1,4. of 44.12% after being buried in the soil-compost
mixture for 30 days. This proved that bioplastics were
Bioplastic degradation analysis easier to degrade than conventional plastics which
The biodegradation test was carried out were non-biodegradable. This bioplastic was easily
by the method buried in soil mix with compost. The degraded due to the amorphous form of a polymer
addition of compost was useful for accelerating the so that microorganisms in the soil could attack the
decay of bioplastic samples. The simplest quantitative bioplastic molecules.

Table 1: Observation Result of Before and After Bioplastic’s Mass

Bioplastic Initial mass Mass after Mass loss


(gram) degradation (gram) (%)

Cellulose acetate + Chitosan + Glycerol (1) 0,340 0,149 56,17


Cellulose acetate + Chitosan + Glycerol (2) 0,350 0,231 34,00
Cellulose acetate + Chitosan + Glycerol (3) 0,320 0,185 42,18

Mechanical properties of bioplastic cellulose chain functional group is a hydroxyl group


A mechanical test was performed to which can interact with the -O, -N, and -S groups,
measure the tensile strength and elongation of the forming hydrogen bonds where the hydrogen bond
three of the bioplastic samples. The method used is longer than the covalent bond but the bond is
was ASTM D638. The results of the three bioplastic weaker. Therefore, in addition to glycerol, there
was an interaction between the hydrogen bonds in
mechanical tests were shown in Figure 6.
cellulose and glycerol. Besides, with the addition of
Figure 6 showed that bioplastic with the glycerol may increase the flexibility of bioplastics
addition of glycerol would decrease the tensile and increase molecular mobility so that bioplastics
strength but increase the breaking elongation. The get more elastic and greater breaking elongation.

Fig. 6. Mechanical properties of 3 bioplastic samples


Rohmawati et al., Orient. J. Chem., Vol. 34(4), 1810-1816 (2018) 1816

CONCLUSION using FT-IR and SEM. The mechanic behavior was


evaluated by ASTM D638. Thus, the successful
The isolation of cellulose from teak wood preparation of bioplastic would provide a promising
by an effective three-step process like pretreatment opportunity to select the agricultural residues as
method with hexane, ethanol, and sulphuric acid. a potent and competitive candidate for industrial
Then, the obtained cellulose was isolated using nitric utilization.
acid, sodium hydroxide, sodium sulfite and bleaching
with calcium hypochlorite. Cellulose acetate was Acknowledgment
synthesized successfully with the yield of 45.88%
by using acetic anhydride, toluene as a solvent, and The authors gratefully acknowledge the
sulphuric acid as a catalyst. Cellulose acetate reacted financial assistance supported by Kementerian
with acetic acid and glycerol became a bioplastic. Riset, Teknologi, dan Pendidikan Tinggi on Program
The synthesized products were characterized by Kreativitas Mahasiswa (PKM) program.

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