Biobased resins and plastics
Dr. Arie van der Bent
Sustainable Chemistry & Technology
Agrotechnology & Food Innovations
Outline
„
Carbohydrate-based building blocks for plastics
„
Modified vegetable oils and fatty acids for resins
& plastics
Carbohydrate-based building
blocks for plastics
Dr. Daan van Es
Dr. Jacco van Haveren
Renewable building blocks for plastics
„
Multiple projects performed as participant of the Dutch
Polymer Institute
„
General objectives
z
z
„
Demonstrate the feasibility of sustainable, renewable resources as
alternative feedstock for (co)monomers for engineering plastics
Explore the unique chemical and structural features of produced
plastics (collaboration with Technical University Eindhoven)
Target plastics
z
Polyesters, polyamides, polycarbonates & polyurethanes
Specific replacement target
„
‘Rigid’ dicarboxylic acid terephthalic acid
z
z
„
monomer for polyethyleneterephthalate
2006 monomer production > 30 Mt
Renewable ‘homologue’: 2,5 furandicarboxylic
acids
z
z
2nd place in USDA top 10 of most promising
agrochemicals
ROOC
No commercial route yet
O
COOR
What’s new?
„
„
Most renewable monomers have been synthesized
decades ago
And have been polymerized with many other monomers
BUT
„
„
„
Chemistry is outdated and often not economically feasible
Only rudimentary property analyses were performed
Data on industrial applicability of produced plastics is
generally lacking
Promises & challenges of biobased monomers
+
+
-
Renewable
‘High energy’ heteroatom functionality already
present
Elimination of ‘superfluous’ heteroatom
functionality is often required
Difficult to achieve extreme purity of monomer,
required for HMW polymers
Carbohydrate-based monomers studied at
AFSG
Dianhydrohexitols (DAH)
HO
HO
O
HO
O
O
O
O
O
OH
OH
isomannide
OH
isosorbide
isoidide
Furan (di)acids and derivatives
HOOC
O
COOH
HOOC
O
R2
O
COOH
H2N
O
O
R1
2,5-FDA
DFDA
DFFA-iPr
NH2
Possible routes to 2,5-FDA (esters)
„
Via furfural from pentoses like xylose
„
Via hydroxymethylfurfural (HMF) from hexoses
like fructose
„
In practice: two chemical pathways converge
Synthesis of furan based monomers
„
Furan based platform chemicals
Pentoses
Rice hulls,
O
CHO
furfural
O
COOMe
methyl-2-furoate
corn cobs,…
O
NH2
furfurylamine
Synthesis of furan based monomers
„
Furan based platform chemicals
O
Pentoses
Rice hulls,
CHO
furfural
O
COOMe
methyl-2-furoate
corn cobs,…
O
D-fructose
(inulin)
HO
O
H
HMF
O
NH2
furfurylamine
Synthesis of furan based monomers
Dimethyl-2,5-FDA; via Hachihama/Moldenhauer
1)
„
O
HCl (g), ZnCl2
p-formaldehyde
COOMe
ClH2C
CHCl3
O
COOMe
ROOC
isolated yield 30%
significant formation of isolable crystalline by-product (acetal):
MeOOC
O
O
O
O
O
COOMe
COOR
Synthesis of furan based monomers
2)
ClH2C
O
COOMe
HNO3 (c)
HOOC
O
COOMe + HOOC
O
COOH
or HMF (=intermediate)
„
Oxidation in HNO3 (c) is very effective; 60°C, 4-6h.
„
Product mixture is white amorphous precipitate (isolated yield 60%)
„
Approx. 80/20 monoester/diacid; diacid increases with temperature and
reaction time
„
Several intermediates were isolated in (approx. 5% yield each)
Synthesis of furan based monomers
3)
HOOC
O
COOMe + HOOC
O
COOH
SOCl2/MeOH
-20°C
„
100 g high purity (>99.8%) crystals produced
„
m.p. (DSC) = 113.00°C (Lit. 110-115)
MeOOC
O
COOMe
Synthesis of furan based monomers
„
furan-2,5-dicarboxylic acid
dimethyl ester
MeOOC
„
13C-NMR
„
DEPT-135
O
COOMe
(CDCl3)
Synthesis of furan based monomers
„
Alternative routes developed avoiding the (irritant & allergenic)
5-chloromethyl-furan intermediate (based on Moldenhauer et al.)
O
„
a)
H2SO4
O
COOMe
MeOOC
p-formaldehyde
O
O
O
COOMe
HNO3 (c)
HOOC
O
O
COOH + HOOC
COOMe
HNO3 (c)
„
b)
O
H2SO4
HCOOH
COOMe
p-formaldehyde
HCOOCH2
O
COOMe
HOH2C
O
COOMe
Conclusions & outlook part I
„
„
„
‘Old school chemistry’ successfully reproduced
Hands on expertise with this chemistry increases
Tasks within DPI now shift
z
z
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Detailed assessment of material properties by
TU Eindhoven
Optimisation of the chemistry
Synthesis of new analogues
Modified vegetable oils and fatty
acids for resins & plastics
Dr. Rolf Blaauw
Dr. Jacco van Haveren
Contents
„
Introduction on vegetable oils & fatty acids
„
Dimer fatty acid based 2K epoxy resin
Natural fats and oils - Market figures
„
More than 120 million tonnes/year worldwide
(about 30 x less than petroleum)
z
z
z
„
80% vegetable, 20% animal
80% food, 20% technical applications
12 million tons as raw material for oleochemicals industry
Two product groups:
1. Base chemicals: fatty acids, methyl esters, fatty alcohols (and
glycerine)
2. Derivatives
Fatty acid & derivatives use (US 2000)
In 1000 tonnes
Others
Exports
Personal Care
Paper
286
Rubber
Foods
Emulsion
Polymers
Fabric
Softeners
132
114
121
Industrial
Lubricants
Plastics
Coatings & Cleaners
Adhesives
Total: 1.2 million
tonnes
SOURCE: Oleochemicals as feedstock for the Biorefinery, Joe Bozell, NREL, August
2004
Chemical structure of fatty acids and oils
„
Oils and fats are triglycerides of fatty acids
O
O
O
O
O
O
Soybean oil:
„
„
Even number of C-atoms
Differences in:
z
z
z
carbon chain length
number of unsaturated (-CH=CH-) bonds
side chain functional groups (e.g. -OH)
C-16:0 (10%)
C-18:1 (25%)
C-18:2 (55%)
other
(10%)
Industrial oleochemistry
„
Commercial fatty acid transformations:
z
z
96% at COOH group
only 4% at side chain
O
OH
Oleic acid
Opportunities for new side chain modifications
Non-food R&D on FAs and oils at A&F
„
Binders:
z
z
z
z
z
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„
high-solid alkyd resins
alkyd emulsions
latex systems based on
poly(hydroxyalkanoates)
paper coatings; sizing agents
emission free floor coverings
powder coatings based on
renewable monomers
Solvents:
z
„
reactive diluents
Additives:
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z
z
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„
alternative cross-linkers for
powder coatings
cobalt free drying catalysts
phthalate free plasticisers
surface active agents
Biolubricants
Dimer fatty acid based 2K epoxy resin
„
Epoxy resins:
z
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„
Our epoxy resin:
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„
Prepared from harmful starting materials: epichlorohydrin and bisphenol A
Curing (crosslinking) with polyamines
Epoxidised vegetable oil (e.g. ELO, ESO)
Curing with polyacids derived from fatty acids
Product properties:
z
z
z
Flexible, rubber-like
Water resistant
Base system is transparent, low in colour
Dimer fatty acid based 2K epoxy resin
„
Component 1: epoxidized vegetable oil (e.g. ELO, ESO)
O
O
O
O
O
O
O
O
O
O
O
ELO
O
„
Component 2: dimerized fatty acid derivative
O
OH
OH
O
Dimer fatty acid
COOH groups poorly
reactive towards
epoxy groups of ELO
→ increase reactivity
Dimer fatty acid based 2K epoxy resin
Increase reactivity by introducing activated COOH
groups, e.g. α,β-unsaturated: -C=C-COOH
OH
Dimer fatty diol
OH
O
O
O
100°C, 2 - 3 h
O
O
OH
Dimer fatty dimaleate
O
O
O
O
OH
Dimer fatty acid based 2K epoxy resin
„
Curing time:
z
„
ranges from 30 h at room temperature to <2 minutes at 150°C
Very little yellowing
O
2
„
Strong and elastic
„
No solvent required
HO
+
O
O
O
O
O
HO
O
O
O
O
O
O
O
O
O
OH
OH
Dimer fatty acid based 2K epoxy resin
OH
O
O
O
O
OH
O
O
2
O
O
O
OH
1
OH
O
O
O
O
O
O
O
O O
O
O
HO
1: Tg = --20°C
2: Tg = 45°C
O
O O
OH
O
O
HO
O
O
O
HO
O
3
3: Tg =
8°C
Dimer fatty acid based 2K epoxy resin
Increase reactivity of dimer fatty acids by introducing citric
acid
O
O
OH
CAA
=
O
Citric acid
anhydride
OH
Dimer fatty diol
CAA
20°C, 15 min.
O
O
OH
COOH
O
OH
O
OH
COOH
Dimer fatty dicitrate
O
O
OH
O
OH
OH
Dimer fatty acid based 2K epoxy resin
„
Preparation of citric acid mono-esters:
O
O
O
OH
O
HO
O
O
+
OH
O
O
O
OR
AcOH
HO
Acetic anhydride
O
OH
OH
Citric acid
R = H or Ac
O
O
R'
AcOH
O
OH
OH
O
O
O
OH
O
+
O
O
OH
HO
O
R'
R'
OH
(fatty alcohol)
O
OR
O
O
OH
OH
Dimer fatty acid based 2K epoxy resin
„
Properties of thermosets based on epoxidized linseed oil and dimer fatty
acid based hardener A.
Samples (1 mm thick) were treated at 150°C for 15 minutes:
E-
Tensile
Elongation
modulus
strength
at break
[°C]
[MPa]
[MPa]
[%]
A1
16
8
4.6
55
A1 + 1% kat.
20
10
9.1
43
A2
–18
5
0.4
38
A3
11
9
4.4
63
A4
11
4
25
57
Hardener A
Tg
Conclusion & outlook part II
„
Functional fatty acids are versatile building blocks for many
products and applications
„
Although oleochemistry is a well-established field, there are
still plenty of opportunities for innovative technologies and
new raw materials.