LIGNIN

Part 2: Heterogenitas Lignin

Oleh:
Deded Sarip Nawawi

DIVISI KIMIA HASIL HUTAN

DEPARTEMEN HASIL HUTAN
FAKULTAS KEHUTANAN INSTITUT PERTANIAN BOGOR
 Heterogeneity of Lignin Structure

In the woody plant, lignin is a heterogenic substances

subjected to:

 Different classes
(e.g. Hardwood vs Softwood lignin)
 Different species
 Reaction wood
(e.g. Compression wood vs Tension wood lignin)
 Different wood tissue
(e.g. Vessel vs Fibers cell lignin)
LIGNIN COMPOSITION

Tipe Cincin Aromatik

(Monomer)

β-O-4 Linkage
(Arylglycerol-β -aryl ether)
 SOFTWOOD LIGNIN

◼ Kadar lignin kayu softwood > kayu hardwood

◼ Kadar lignin terlarut asam softwood sangat kecil (< 1%)

◼ Lignin kayu daun jarum lebih homogen yang terutama OCH3

disusun oleh guaiacyl (±90%), dan sisanya p-hidroksifenil
O

◼ Kadar p-hidroksifenil > kayu hardwood

◼ Lignin kayu softwood lebih bersifat “condensed”

◼ Kelimpahan ikatan β-O-4 lignin softwood < kayu hardwood

◼ Ikatan karbon-karbon lebih tinggi dibanding hardwood

O
HARDWOOD LIGNIN

◼ Kadar lignin hardwood < softwood

◼ Lignin terlarut asam pada hardwood > softwood

◼ Struktur lignin hardwood bersifat heterogen yang OCH3

disusun oleh unit guaiasil dan siringil O

◼ Komposisi lignin : nisbah Siringil/Guaiasil (nisbah S/G)

◼ Lignin hardwood bersifat “Less condensed”

◼ Hardwood lignin memiliki kelimpahan struktur β-O-4 >

softwood H3CO OCH3
◼ Ikatan carbon-carbon lignin hardwood < softwood O
Characteristics of Lignin
in Different Wood Species

A cid soluble lignin/Lignin content

50 Klason lignin 0.25
A cid soluble lignin
A SL/total lignin 0.2

Lignin content (w t%)

40
0.15

(w /w )
Softwood contains very 30
0.1
small acid soluble lignin 20
0.05

Lower Klason lignin → 10 0

Higher acid-soluble lignin 0 -0.05

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sam ple N o.

Yield of nitrobenzene oxidation products

50
H +H A V +V A S+SA
Lower lignin content
40
→ Higher S/G ratio
30
(m ol%)
Higher S/G ratio →
20
Higher methoxyl
content 10

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21
Sam ple N o.

Softwood Hardwood
more methoxyl group in lignin
LIGNIN CHARACTERISTICS OF
REACTION WOOD
LIGNIN CHARACTERISTICS IN REACTION WOOD

180o (Opposite wood)

180o
120o 240o

0o SOFTWOOD
60o 300o

0o (Compression wood)

180o (Tension wood)

180o
120o 240o
0o
HARDWOOD
60o 300o

0o (Opposite wood)
 Compression Wood Lignin (Softwood)

Opposite wood part ◼ Compression wood has a higher lignin content than
opposite wood

◼ Compression wood contains higher p-Hydroxyphenyl

unit than opposite wood

Compression wood part

Tension Wood Lignin (Hardwood)

Tension wood part

◼ Tension wood has lower lignin content than opposite
wood

◼ Tension wood has higher S/G ratio than opposite wood

◼ Tension wood contains higher acid soluble lignin than

opposite wood
Opposite wood part
LIGNIN CHARACTERISTICS IN WOOD TISSUE

◼ Lignin concentration is higher in middle lamella and lower in

cell wall of fibers

◼ Tracheid is mainly composed by guaiacyl lignin

◼ Middle lamella and vessel contain mostly guaiacyl unit

◼ Fibers and ray cell predominantly contain syringyl unit

 Distribusi Komponen Kimia Kayu
Composition (%)

Primary cell
S1 wall
Middle
Lignin lamella
Hemicellulose
S2
Cellulose

Lumen cell
S3

S1 S2 S3

Secondary wall

Compound middle lamella

LIGNIN DISTRIBUTION (in spruce wood)

Location Volume of Concentration

tissue (%) of Lignin (%)

Early S 87 23
Wood ML 9 50
CC 4 85
Late S 94 22
Wood ML 4 60
CC 2 100
HUBUNGAN KARAKTERISTIK LIGNIN DENGAN
SIFAT DAN PENGOLAHAN KAYU

• Mempengaruhi sifat kimia polimer lignin

e.g. High S/G ratio → Less condensed lignin structure

• Memperngaruhi reaktifitas polimer lignin

e.g. High S/G ratio → High Reactivity

• Mempengaruhi ketahanan kayu terhadap faktor perusak biologis

e.g. High S/G ratio → easier to biodegradation
Low S/G ratio → more resistance to biodegradation
Hubungan Sifat Kimia Lignin dengan Sifat Kayu

more lignin Klason less lignin Klason

less syringyl more syringyl

less b-O-4 more b-O-4
more condensed less condensed
Less ASL High ASL

Worse Pulp-Ability Better Pulp-Ability

More resistance to biodegradation Easier to biodegradation
LIGNIN CARBOHYDRATE COMPLEX (LCC)

◼ Adanya asosiasi antara lignin dan karbohidrat diduga kuat karena

adanya ikatan kimia antara kedua senyawa tersebut.

◼ Asosiasi antara lignin dan karbohidrat merupakan hal penting,

terutama berkaitan dengan isolasi lignin dari kayu yang harus
dilakukan secara selektif

◼ Belum ada cara untuk mengisolasi komponen-komponen tersebut

secara murni.

◼ lignin secara kimiawi paling tidak berikatan dengan hemicellulose,

walaupun ada indikasi juga ikatan antara lignin dengan selulosa.

◼ Ada 3 jenis ikatan LCC yang diusulkan, yaitu ikatan benzyl ester,
benzyl ether, dan phenyl glycosidic.
THREE TYPE OF LCC
(Mostly frequently suggested)
STRUCTURAL MODEL LCC / LPC

C L C L

C
L

L C L C L C

L C
STRUCTURAL MODEL LCC / LPC

L C L

C L C

L C L