1 Chemistry and Structure of Lignin 11

1.3 The Chemistry of Lignin

1.3.1 Lignin Structural Architecture

Lignin is an amorphous aromatic polymer with a very complex chemical structure. It

contains three primary precursors which are different in proportion depending on
their sources. These precursors (p-hydroxyphenyl (H), guaiacyl (G) and syringyl (S)
units) are linked together by different functional groups. The frequency of these func-
tional groups is what results in the structural variation of various lignins. Chemically,
lignin is a phenolic polymer that differs according to plant. It has also been reported
that some lignin are linear oligomers with no defined primary structure. However,
they can be viewed as a representative random phenyl-propanoid (C9) polyphenols,
usually linked by acylglycerol ether bonds between phenolic para-coumaryl alcohols,
coniferyl alcohol and sinapyl alcohol units (Fig. 1.8) [51–53]. Effective processing of
lignin into required components requires a good knowledge of the structural architec-
ture of lignin. Although the structure of lignin differs greatly according to plant,
source, extraction and location, the basic structure of lignin is the same and is the key
to lignin modification. In simple terms, lignin can be viewed as consisting of phenyl-
propane units with an oxygen atom at the p-position (as OH or O–C) and with or
without methoxyl groups in the o-positions to the oxygen atom. In some cases, the
o-positions is C-substituted or O-substituted with constituents other than methoxyl.
Some other possibilities in the lignin structure are substitution of other aromatic units
in the ring positions. In some cases, a situation arises where either a few percentage
of the building blocks not being phenylpropane units are missing or side chains are
shortened or replaced by a quinoid group. The coupling between each of the basic
units (H, G and S) includes β–O–4, β–5, β–1 etc. Alternatively, these linkages exist as
members of a series of characteristic end groups (e.g. cinnamaldehyde units) [54].
The general structure of lignin usually shows eight different motifs for interunit
linkages but not all the lignin monomeric units can take part in all coupling modes.
The basic condition that determines the coupling of the units is β-position of the
monolignol species. This results in the formation of five motifs, namely aryl glycerol-
β-aryl ethers (β-O-4′ motif), phenylcoumarans (β-5′), pinoresinols (β-β′), diphenyle-
thane dimers (β-1′) and spirodienones (SD). On the other hand, dilignols and some
higher oligomers prefer to couple at positions 4 and 5, giving rise to two motifs,
namely diaryl ethers (4-O-5′ motif) and biphenyls (5–5′ motif). It is only possible to
couple these oligomers by the formation of dibenzodioxocine units which also gives
results in the eighth motif (5,5′- α, β-O-4′ motif) (Fig. 1.8). β–O–4 (β-aryl ether) link-
age is the most frequent inter-unit linkage in lignin. It is an important linkage in lignin
because it is easily cleaved chemically and thus providing a basis for lignin related
industrial processes, such as chemical pulping. All other linkages (β–5, β–β, 5–5,
5–O–4 and β–1) are very resistant to chemical degradation [17]. These linkages of
lignin are what give the plant cell walls many physicochemical properties and biologi-
cal activities such as their rigidity and pathogen defence. They provide useful infor-
mation on the production of other biopolymers from lignin. A good example is the use
of phenolic groups in the lignin structure to produce phenol formaldehyde resins.