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New bio-based
polymers:
Ambitions and
progress at CRODA
Biobased Performance Materials SymposiumWageningen, 15 June 2011
Hans Ridderikhoff
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Agenda
Introduction Croda and oleochemical products forpolymers
Examples of new oleochemical developments for:
Polymer modification by phase separation E.g. in TPE modification
Dimer diamine as new polymer building block
E.g. as epoxy curative
Future development
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A global supplier of natural based, speciality chemicals
Founded in Yorkshire, England in 1925 to manufacture lanolin from wool
grease
Sales ~1000 M GBP
Around 3,000 employees
> 40 sales and marketing offices in 36 countries
> 20 production sites in all the regions of the world
Innovation centres in all major regions
Acquired in 2006
The world of Croda
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Croda Business structure
Croda
Consumer Care Industrial Specialities
Coatings & Polymers Plastic Additives Lubricants Geo Technologies Process Additives Homecare
Personal Care Health Care Crop Care
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High performance oleochemicals
Seed crushing
Oil refinery
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High performance oleochemicals
Natural oils & fats
Splitting &refining
Glycerine
Water
Fatty acid
Amidation Polymerisation Esterification Saponification
Isostearicacid
Dimer acids &trimer acids
Amides Esters Soaps
Hydrogenation
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Oleochemicals in polymers
Use the fatty acid, e.g. alkyd resins, polyamides
Derivatisation of fatty acids
Alcohol functionality
Epoxy functionality
Dimer fatty acids
Dimer fatty alcohol
Polyols based on dimer technology
Many more
Oleochemical technology in polymer applications:
Polyamide hotmelt adhesives
Epoxy coatings Polyurethane foams
Polyurethane dispersions
Radcure
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Dimerised fatty acids - Properties
O=C
HO
Large hydrocarbon part (C36)Hydrophobic
Hydrolytic resistance of derivatives
Affinity for non-polar matrices and surfaces
Irregular non-crystalline structureFlexibility
Low Tg
Flow, wetting
Di-functional constituent for:Polyamides
Polyesters
Polyurethanes
Epoxies
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Different forms of dimer fatty acid
technology
HOOC
HO
HO---- ----- OHE--E
Dimer acidPRIPOL
Dimer diolPRIPOL
Polyesters polyolsmade with dimer acid(or dimer diol)PRIPLAST
n
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Benefits of dimer technology as
Polymer backbone
PRIPOL Dimer fatty acid (or diol) used for flexibility and hydrophobicity Inclusion of dimer acid (or derivatives) improves mould flow
fully made from natural oils and fats = 100 % renewable carbon
PRIPLAST Dimer polyesters can be used to make block copolymers
Properties of hard segment not compromised
Adding hydrophobicity and impact strength
Hydrolytic, thermo-oxidative, UV stability
Very versatile technology
Contains high % Carbon of renewable origin (mostly >80%)
Bio-based, renewable resource Reduce use of fossil resources
Plants absorbed CO2 to grow
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Examples of new oleochemical
developments for:
Polymer modification by phase
separation
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Polymer modification with dimer
technology
Dimer acid makes it suitable for flexibilisation because of its low Tg andlow polarity
Dimer acid too small as soft segment (Mw 580) for phase separation
Polyesters based on dimerised fatty acids allow incorporation of larger mol
wt soft segments
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Modification of rigid polymers with soft
segments: flexibilization
crystalline
or high-Tg
amorphous
hard
segments
low-Tg
amorphous
soft
segments
this copolymer is able to respond to bending forces through its
flexible links
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-100
-50
0
50
100
150
200
250
0 20 40 60 80
concentration dimer acid/diol [%]
temperatu
re[C]
dimer acid Pripol 1009
dimer acid P1006
dimer diol P2033
melting
crystallisation
glass transition
Modification of PBT with dimer fatty
acids: melting / crystallisation
Reduction in
glass transition
Melting pointcompromised
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Modification of rigid polymers with
apolar soft segments
A special way of impactmodification
Crystalline or
high-Tg amorphous
hard segments
Large low-Tg amorphous soft segments flock together, driven by
polarity difference, forming large domains that provide impact strength.
Copolymer, chemically linked, therefore no stability issues.
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Electron microscopySEM of COPA cryogenically fractured / plasma etched
Continuous hard
phase (PA12)
Low-Tg
amorphous
(dimer) soft
segments, as
rubbery second
phase
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Modification of PBT with dimer
polyester:Unique Thermo-mechanical Properties
Random Dimer-75
-25
25
75
125
175
225
Tempe
rature[C]
Rubber Melt Glass
Blocky Dimer esterPTMEG
Wide application window: low Tg and high Tm
Potentially beneficial in automotive and cabling sectors
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Properties of dimerate COPE v
Industry standards
Dimerate Polycap PTMEG
Hardness / Shore
D
65 64 60
Tensile Strength
[kg/cm2]
280 267 284
Elongation at
break [%]
353 364 466
Conclusion: Dimerate based COPE maintains its good
mechanical properties
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Hydrolysis resistance of COPARetention of solution viscosity with time
(immersion in 95 C water )
20
30
40
50
60
70
80
90
100
110
0 2 4 6 8 10Time [days]
Retention
ofviscosity
[%]
Dimerate 1
Dimerate 3
Polycaprolactone
PTMEG
Conclusion: Much improved hydrolysis resistance,
especially relative to standard polyester soft segment
Th id i bili f
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Thermo-oxidative stability of
COPA retention of solution viscosity with time(exposure to 140 C)
10
20
30
40
50
60
70
80
90
100
110
120130
0 2 4 6
Time [days]
Retentiono
fviscosity
[%]
Dimerate 4
Dimerate 3
Polycaprolactone
PTMEG
Conclusion: Much improved thermo-oxidative stability,
especially relative to standard polyether soft segment
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Polymer modification with dimer
technology
Blocky COPE / COPA elastomers with PRIPLAST dimer polyester as softsegment
phase separated structure for wide application window (Tm Tg)
Combination of good low temperature flexibility AND structural integrity at
high temperature
Enhanced toughness through morphological control
Low moisture uptake and excellent hydrolytic stability
Modification through phase separation allows formany new applications
e.g. toughening of materials
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Examples of new oleochemical
developments for:
Dimer diamine as new polymer
building block
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Different forms of dimer fatty acid
technology
HOOC
HO
Dimer acidPRIPOL
Dimer diolPRIPOL
Dimer diaminePRIAMINE H2N NH2 New !
10 years
30 years
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Different forms of dimer fatty acid
technology
HOOC
HO
Dimer acidPRIPOL
Dimer diolPRIPOL
Dimer diaminePRIAMINE H2N NH2 250 mPa.s
2500 mPa.s
7000 mPA.s
Typical viscosity RT
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Amine functionalised dimers
Amine functional dimer/trimer as curing agent, cross-linker or buildingblock
Generic Benefits:
Very low viscosity no solvent dilutions required
Flexibility, low Tg
Hydrophobic nature / water barrier properties
No ether-linkages UV & oxidative stability
100% renewable carbon
NH2H2N
H2N
NH2H2N
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Dimer Di Amine (DDA) range
Priamine Colour
Di-functional
content Suggested application
Gardner %
Dev 5 1 99 Engineering Plastics
Dev 4 3 99
Polyamide hot melts &
sealants
Dev 3 8 92 Poly urea, adhesivesDev 1 10 75 Epoxy curative
Data are typicals, to be confirmed.
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Increasing Solids in Liquid Epoxy
Coating Formulations (Epikote 828)
Epoxy coating formulation comprising Epikote 828, curing agent and solvent.
Solvent mixture used is xylene / butanol in a 4:1 ratio
0
500
1000
1500
2000
2500
3000
50% 60% 70% 80% 90% 100%
Solid content (%)
Dyn.visc.
25C(mPa.s
)
V125 type polyamide
V125/P1071 50/50
Priamine1071
Target viscosity 500 mPa.s
At 500 mPa.s:
V125 type Polyamide:
83% solids
Priamine 1071:93% solids
60% less solvents!
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Improving impact resistance
Epikote 828 / hardener blend after 1 wk cure @25C
0
25
50
75
100125
150
175
200
0 10 20 30 50 80 100
Modifying Ancamide 3201 with PRIAMINE 1071 (%wt)
Impactresistance(cm.kg)
direct impact @ 25C indirect impact @ 25C indirect impact @ 4C indirect impact @ -25C
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Priamine as epoxy curative
Low viscosity: allowing for high solid formulations
Provides very high impact resistance
Suitable for adjusting flexibility versus hardness
to improve crack resistance performance
A-polar / hydrophobic
Low water absorption, so excellent anti-corrosion properties
Excellent compatibility with apolar materials such as resins, additives and/or diluents
Provides good early water resistance properties
Excellent chemical resistance
Biobased modifier with 100 % renewable Carbon
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The Future
Development of many more highperformance, biobased polymers
Bi b d i l
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Biobased raw materialsNew possibilities for sustainable polymers
Biobased raw materials already a strong performance for many years
Croda Gouda >150 years !
Biobased products can have at least similar performance or in many cases
even outperform petrochemical derived materials
Biobased / renewable raw materials nice premium.
Croda has a long and successful history in biobased naturally derived products
for use in many consumer & industrial applications and will continue its
innovation in biobased solutions to meet or exceed customers demands nowand in the future.
Bi b d i l
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Biobased raw materialsNew possibilities for sustainable polymers
Much more product derivatisations and application development possible fordevelopment of high performing biobased polymers such as:
Polycarbonate
Acrylates
Polyesters, like PET, PBT and PEN
Polyurethane and PUDs
Polyurea
Polyamide
Polylactic
Etc.
To accomplish this, we wish to cooperate as much as possible with Innovative industry partners in this field Universities & institutes
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THANK YOU!
Contacts:
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