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e-mail: euis.hermiati@lipi.go.id
Abstract
Lignin from lignocellulosic biomass is a potential biopolymer for wood adhesive. The aims of this study were to
characterize lignin isolated from the black liquor of oil palm empty fruit bunch fiber pretreated with steam explosion in
alkaline conditions and to examine the bond quality of aqueous polymer isocyanate (API) adhesive prepared from
lignin, natural rubber latex (NRL), and polyvinyl alcohol (PVA) as base polymers with isocyanate crosslinkers. Lignin
was precipitated from the black liquor by adding hydrochloric acid; then the precipitate was separated by filtration,
thoroughly washed with water up to pH 2 and pH 5, and dried. The isolated lignin was characterized by ultimate
analysis, UV spectroscopy, FT-IR spectroscopy, and thermal analysis. Three-layer plywood samples were prepared, and
the bond strengths of the plywood samples were determined in dry conditions and after cyclic boiling. The lignin
isolates with different pH values did not have significantly different chemical and thermal properties. Both lignin
isolates had similar C, H, and O contents, identical functional groups in the FTIR spectra, similar absorption in the UV
spectra, and high decomposition temperatures. The base polymers composition that could produce API adhesive for
exterior applications was NRL/PVA/lignin (4/4/2). The use of more lignin in the adhesive formulation decreased the
bond strength of the plywood.
Abstrak
Sifat lignin dari tandan kosong kelapa sawit dan aplikasinya sebagai perekat kayu lapis. Lignin dari biomassa
lignoselulosa merupakan biopolimer potensial untuk perekat kayu. Tujuan penelitian ini adalah untuk mengenali sifat
lignin yang diisolasi dari lindi hitam sisa pretreatment steam explosion alkalis serat tandan kosong kelapa sawit, dan
untuk menguji daya rekat perekat aqueous polymer isocyanatae (API) yang dibuat dari lignin, lateks karet alam (LKA)
dan polivinil alkohol (PVA) sebagai polimer dasar dengan senyawa isosianat sebagai crosslinker. Lignin diendapkan
dari lindi hitam dengan menambahkan asam klorida, setelah itu endapan dipisahkan dari larutan dengan penyaringan,
dicuci dengan air sampai pH 2 dan pH 5, dan dikeringkan. Isolat lignin dikarakterisasi dengan analisis ultimat,
spektroskopi UV, spektroskopi FT-IR, dan analisis termal. Kayu lapis (tiga lapisan) dibuat dari vinir kayu meranti
(depan dan belakang) dan sengon (tengah) dan keteguhan rekatnya diuji pada kondisi kering dan setelah melalui
perebusan berulang. Isolat lignin dengan pH yang berbeda tidak memberikan pengaruh nyata terhadap sifat kimia dan
sifat termalnya. Kedua isolat lignin mempunyai kadar C, H, dan O yang mirip, gugus fungsi yang identik pada spektra
FTIR, serapan yang mirip pada spektra UV, dan suhu dekomposisi yang tinggi. Komposisi polimer dasar yang dapat
menghasilkan perekat API untuk aplikasi eksterior adalah LKA/PVA/lignin (4/4/2). Penggunaan lignin yang lebih
banyak menurunkan keteguhan rekat kayu lapis.
Keywords: adhesive, lignin, natural rubber latex, oil palm empty fruit bunch, plywood
1. Introduction
Lignin is the second largest biomass available after
cellulose, which is rich in phenolic compounds. Lignin
can be obtained by direct isolation from plants or by
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Risanto, et al.
2. Methods
Materials. Black liquor was obtained from the Research
Center for Chemistry, Indonesian Institute of Sciences,
Serpong, Tangerang Selatan, which resulted from the
pretreatment of OPEFB using steam explosion with
alkaline (NaOH), having a total solid content of 4.65.1%. Natural rubber latex was purchased from Balai
Penelitian Perkebunan Sembawa, South Sumatera. The
concentrated latex (61-62% total solid content) was
diluted with water to 50 and 60% total solid content.
The PVA, purchased from a local market in Bogor, was
dissolved in warm water to reach 15% total solid
content. The isocyanate crosslinking agent and other
chemicals were purchased from domestic chemical
suppliers in Bogor and Jakarta. Veneers of meranti
(Shorea sp.) and albizzia (Paraserianthes falcataria)
used for the preparation of plywood were obtained from
East Kalimantan and West Java, respectively.
Lignin isolation from black liquor. This process
aimed to separate the lignin from the black liquor. The
black liquor was run through a filter paper to separate
the insoluble materials from the liquor. Hydrochloric
acid (2N) was then added into the black liquor with
continuous stirring until the pH of the black liquor
solution reached 2 to precipitate the lignin. The lignin
suspension was kept for eight hours to complete the
precipitation. The precipitate was then separated by
vacuum filtration, washed twice with distilled water,
and dried at 45 C for 24 hours. Some precipitates were
washed several times with distilled water until the pH of
August 2014 | Vol. 18 | No. 2
Properties of Lignin from Oil Palm Empty Fruit Bunch and Its
H N
+ +1
2
2
(2)
69
Formula
NRLa
PVAb
Ligninc
A1
100
A2
80
20
A3
60
40
A4
50
50
A5
40
60
B1
100
B2
80
20
B3
60
40
B4
50
50
B5
40
60
C1
50
50
C2
40
40
20
C3
30
30
40
C4
25
25
50
C5
20
20
60
70
Risanto, et al.
Lignin
Isolate
pH 2
0.99
Lignin
Isolate
pH 5
0.82
50.48
6.55
41.02
0.81
0.08
5.06
3.05
50.71
6.59
40.98
0.75
0.15
4.69
3.04
Lignin (%):
AIL
ASL
93.43
1.81
93.67
1.88
Analysis Parameters
Black
Liquor
40.40
51.23
4.1
Properties of Lignin from Oil Palm Empty Fruit Bunch and Its
71
Figure 2. FT-IR Spectra of Black Liquor, Lignin Isolate pH 2, and Lignin Isolate pH 5
72
Risanto, et al.
Table 3. FT-IR Absorption Bands and Assignments for Black Liquor, Lignin Isolate pH 2, and Lignin Isolate pH 5
Band (cm-1)
[25,27]
3450-3400
Assignments [23,26]
2966
2942
1703
2920
1703
2940-2820
1715-1710
1591
1635
1508
1641
1506
1605-1600
1515-1505
1454
1460
1458
1470-1460
1421
1327
1220
1425
1328
1217
1430-1425
1330-1325
1220
1120
1118
1118
1115
1043
1043
1041
1085-1030
867
894
896
875-850
(a)
100
Lignin pH 5
Lignin pH 2
Black Liquor
Weight (%)
80
100
(b)
60
40
Lignin pH 5
Lignin pH 2
Black Liquor
50
20
-50
0
200
400
600
Temperature (C)
800
50
100
150
200
Temperature (C)
Figure 3. TGA (a) and DSC (b) Curves of Black Liquor, Lignin Isolate pH 2, and Lignin Isolate pH 5
Makara J. Technol.
Properties of Lignin from Oil Palm Empty Fruit Bunch and Its
73
Table 4. Shear Strength of Plywood After the Dry and Cyclic Boiling Tests
Formula
NRLa
PVAb
Ligninc
A1
A2
A3
A4
A5
B1
B2
B3
B4
B5
C1
C2
C3
C4
C5
100
80
60
50
40
100
80
60
50
40
50
40
30
25
20
50
40
30
25
20
0
20
40
50
60
0
20
40
50
60
0
20
40
50
60
Makara J. Technol.
74
Risanto, et al.
4. Conclusions
Lignin isolated from steam explosion alkaline
pretreatment of OPEFB has similar properties as that
isolated through kraft and soda pulping of OPEFB. The
lignin isolates from OPEFB with different pH values
did not have significantly different chemical and
thermal properties. Both lignin isolates had similar C,
H, and O contents; identical functional groups in the
FT-IR spectra; similar absorption in the UV spectra;
and high decomposition temperatures. Lignin can be
used as a component of base polymers for API
adhesive. The base polymers composition that could
produce an API adhesive for exterior applications is
NRL/PVA/lignin (4/4/2). The use of more lignin in the
adhesive formulation decreased the bond strength of the
plywood. Further studies are needed in order to better
understand the bonding mechanism between the base
polymers used and the isocyanate crosslinker.
Acknowledgements
The authors would like to acknowledge the Ministry of
Research and Technology of the Republic of Indonesia
for funding this research through SINas 2013 project
entitled Pengolahan limbah biomassa industri sawit
untuk produksi bioetanol generasi 2 dan ko produk,
under contract No. KP-2013-1392.
The authors also would like to thank Mr. Fazhar Akbar
for his assistance in the bond strength analysis, as well
as Mr. Sudarmanto and Mr. Rd. Budi Permana Laksana
for their assistance in sample preparations.
Makara J. Technol.
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