bioplasticsMAGAZINE_1205

Polyurethanes / Elastomers
CO 2
C
CH 3
H 3
C H 3
C O
O
O
C
C
C CH 2
H 3
C CH 2
H 3
C CH 2
H 3
C
O
O O
Limonene
C
+ H 2
N
O
O
H 3
C
OH
O
C
O
NH
Limonene
dicarbonate
O
C
C
O
C
H 3
C
OH
H 2
bioplastics MAGAZINE [05/12] Vol. 7 41
NH
NIPU
limonene, is commercially used as component of epoxy
resins. The FMF research has succeeded in reacting terpene
oxides quantitatively with carbon dioxide, thus producing
novel and cost-effective families of terpene carbonates.
This chemical carbon dioxide fixation is highly effective.
Around 34 wt-% carbon dioxide is incorporated into limonene
dicarbonate! As a function of their stereoisomer compostion,
limonene dicarbonates can be obtained as viscous liquid
or white crystalline solid. The limonene dicarbonate reacts
with a great variety of amines, producing multifunctional
urethanes. Reaction with amines and amino-alcohols affords
cycloaliphatic polyols useful as intermediates in conventional
PU synthesis. As a chain extender of oligomeric polyamines
and amino-alcohols limonene dicarbonate incorporates
hard limonene segments into flexible curing agents. This
approach has been used to produce new families of reactive
prepolymers which can be functionalized in numerous
ways. Upon curing with polyamines, e.g. using bio-based
diamines or novel aminoamides derived from citric acid,
100% renewable and even 100% citrus-based NIPU are
made available. In contrast to the rather soft soybean-oilbased
NIPU, the mechanical properties of limonene-NIPU
can be varied over a very wide range from highly rigid and
stiff to rubbery and ultrasoft. Applications include casting
resins, rubbers, thermoplastic elastomers, foams, coatings,
sealants and adhesives. As illustrated using the example of
limonene, this NIPU strategy can be applied to a very large
variety of terpenes. Terpene carbonates are also attractive
as components and non-toxic solvents for numerous other
applications, going well beyond the scope of bio-based NIPU.
www.fmf.uni-freiburg.de
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