336
Chapter 19 · Plastics from Nature - Biopolymers
19
conditions yields sebacic acid (1,10-decandicarboxylic acid) from ricinoleic acid (7 Sect. 2.2.7).
Ozonolysis of oleic acid produces azelaic acid
(1,9-non-anedicarboxylic acid) (7 Sect. 4.2.1).
Both diacids are produced in industrial processes
and are mainly used in producing special polyamides which are not made by petrochemical
routes. Another ricinoleic acid cleavage product,
10-undecenoic acid, can be converted into an aminocarboxylic acid by formal addition of an amino
group at the end of the chain (7 Sect. 4.2.2.6):
11-aminoundecanoic acid. This acid is already
being converted on a commercial scale into the
biopolyamide nylon-11 (Rilsan®), the carbon content of which thus consists 100% of renewable raw
materials.
The formation of biobased polyesters with the
dicarboxylic acids described above also requires
biogenic polyols as alcohol components. Glycerol
(7 Chap. 5), for example, is suitable for the production of branched polyesters. Smaller amounts
of glycerol are used for the production of polyester resins. Glycerol can also be used to produce
a wide variety of downstream products that can
also be used in plastics that are otherwise petrochemically based, and are therefore biogenic in
principle (e.g. epichlorohydrin, propanediols or
acrylic acid).
additionally carries a methylene unit on C2, and
fumaric or maleic acid. All three can also be produced from carbohydrates and are suitable as
acid components for biopolyesters and biopolyamides.
The double unsaturated muconic acid can
also be produced from glucose by specific microorganisms. By hydrogenation of muconic acid,
adipic acid is obtained, which in principle is
biogenic. Adipic acid is of particular technical
importance for the production of polyamides,
such as nylon-6,6, but also for certain polyesters.
Another dicarboxylic acid based on renewable raw materials is 2,5-furandicarboxylic
acid (FDCA). It can be produced from
5-hydroxymethylfurfural, a potential platform
chemical accessible from carbohydrates, e.g. by
dehydration of glucose (7 Chap. 6). FDCA is
a heteroaromatic dicarboxylic acid which can
potentially replace the most essential aromatic
dicarboxylic acid to date, terephthalic acid, in
fibers and beverage bottles. FDCA is not petrochemically produced and is therefore not a direct
substitute for an already established polymer
component.
Linear dicarboxylic acids are also accessible from oleochemicals (. Fig. 19.13). Oxidation at elevated temperature under basic
. Fig. 19.12 Biogenic
dicarboxylic acids from
conversions of sugars
HO
O
OH
O
HO
O
OH
O
HO
O
OH
O
HO
O
OH
O
HO
O
O
OH
O
HO
O
OH
O
Succinic acid
Itaconic acid
Fumaric acid
Maleic acid
Muconic acid
Furandicarboxylic acid
FDCA
Chapter 19 · Plastics from Nature - Biopolymers
19
conditions yields sebacic acid (1,10-decandicarboxylic acid) from ricinoleic acid (7 Sect. 2.2.7).
Ozonolysis of oleic acid produces azelaic acid
(1,9-non-anedicarboxylic acid) (7 Sect. 4.2.1).
Both diacids are produced in industrial processes
and are mainly used in producing special polyamides which are not made by petrochemical
routes. Another ricinoleic acid cleavage product,
10-undecenoic acid, can be converted into an aminocarboxylic acid by formal addition of an amino
group at the end of the chain (7 Sect. 4.2.2.6):
11-aminoundecanoic acid. This acid is already
being converted on a commercial scale into the
biopolyamide nylon-11 (Rilsan®), the carbon content of which thus consists 100% of renewable raw
materials.
The formation of biobased polyesters with the
dicarboxylic acids described above also requires
biogenic polyols as alcohol components. Glycerol
(7 Chap. 5), for example, is suitable for the production of branched polyesters. Smaller amounts
of glycerol are used for the production of polyester resins. Glycerol can also be used to produce
a wide variety of downstream products that can
also be used in plastics that are otherwise petrochemically based, and are therefore biogenic in
principle (e.g. epichlorohydrin, propanediols or
acrylic acid).
additionally carries a methylene unit on C2, and
fumaric or maleic acid. All three can also be produced from carbohydrates and are suitable as
acid components for biopolyesters and biopolyamides.
The double unsaturated muconic acid can
also be produced from glucose by specific microorganisms. By hydrogenation of muconic acid,
adipic acid is obtained, which in principle is
biogenic. Adipic acid is of particular technical
importance for the production of polyamides,
such as nylon-6,6, but also for certain polyesters.
Another dicarboxylic acid based on renewable raw materials is 2,5-furandicarboxylic
acid (FDCA). It can be produced from
5-hydroxymethylfurfural, a potential platform
chemical accessible from carbohydrates, e.g. by
dehydration of glucose (7 Chap. 6). FDCA is
a heteroaromatic dicarboxylic acid which can
potentially replace the most essential aromatic
dicarboxylic acid to date, terephthalic acid, in
fibers and beverage bottles. FDCA is not petrochemically produced and is therefore not a direct
substitute for an already established polymer
component.
Linear dicarboxylic acids are also accessible from oleochemicals (. Fig. 19.13). Oxidation at elevated temperature under basic
. Fig. 19.12 Biogenic
dicarboxylic acids from
conversions of sugars
HO
O
OH
O
HO
O
OH
O
HO
O
OH
O
HO
O
OH
O
HO
O
O
OH
O
HO
O
OH
O
Succinic acid
Itaconic acid
Fumaric acid
Maleic acid
Muconic acid
Furandicarboxylic acid
FDCA