New bio-based

polymers:
Ambitions and
progress at CRODA
Biobased Performance Materials Symposium
Wageningen, 15 June 2011
Hans Ridderikhoff
Agenda
 Introduction Croda and oleochemical products for
polymers

 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
 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…

Croda Business structure
Croda
Consumer Care Industrial Specialities

• Coatings & Polymers
• Plastic Additives
• Lubricants
• Geo Technologies
• Process Additives
• Homecare

• Personal Care
• Health Care
• Crop Care
High performance oleochemicals
Seed crushing
Oil refinery
High performance oleochemicals
Natural oils & fats
Splitting &
refining
Glycerine
Water
Fatty acid
Amidation Polymerisation Esterification Saponification
Isostearic
acid
Dimer acids &
trimer acids
Amides Esters Soaps
Hydrogenation
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

Dimerised fatty acids - Properties
C=O
OH
O=C
HO
Large hydrocarbon part (C36)
•Hydrophobic
•Hydrolytic resistance of derivatives
•Affinity for non-polar matrices and surfaces
Irregular non-crystalline structure
•Flexibility
•Low Tg
•Flow, wetting
Di-functional constituent for:
•Polyamides
•Polyesters
•Polyurethanes
•Epoxies
Different forms of dimer fatty acid
technology
HOOC COOH
HO OH
HO---- ----- OH E--E
Dimer acid
PRIPOL



Dimer diol
PRIPOL



Polyesters polyols
made with dimer acid
(or dimer diol)
PRIPLAST

n
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 CO
2
to grow


Examples of new oleochemical
developments for:


Polymer modification by phase
separation
Polymer modification with dimer
technology
 Dimer acid makes it suitable for flexibilisation because of it’s low Tg and
low 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


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
-100
-50
0
50
100
150
200
250
0 20 40 60 80
concentration dimer acid/diol [%]
t
e
m
p
e
r
a
t
u
r
e

[
°
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 point
compromised
Modification of rigid polymers with
apolar soft segments
A special way of impact
modification
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.
Electron microscopy
SEM of COPA – cryogenically fractured / plasma etched

Continuous hard
phase (PA12)

Low-Tg
amorphous
(dimer) soft
segments, as
rubbery second
phase
Modification of PBT with dimer
polyester:
Unique Thermo-mechanical Properties
Random Dimer
-75
-25
25
75
125
175
225
T
e
m
p
e
r
a
t
u
r
e

[
°
C
]
Rubber Melt Glass
Blocky Dimer ester PTMEG
 Wide application window: low Tg and high Tm
 Potentially beneficial in automotive and cabling sectors
Properties of dimerate COPE v
Industry standards
Dimerate Polycap PTMEG
Hardness / Shore
D
65 64 60
Tensile Strength
[kg/cm
2
]
280 267 284
Elongation at
break [%]
353 364 466
Conclusion: Dimerate based COPE maintains it’s good
mechanical properties
Hydrolysis resistance of COPA
Retention 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 10
Time [days]
R
e
t
e
n
t
i
o
n

o
f

v
i
s
c
o
s
i
t
y

[
%
]
Dimerate 1
Dimerate 3
Polycaprolactone
PTMEG
Conclusion: Much improved hydrolysis resistance,
especially relative to standard polyester soft segment
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
120
130
0 2 4 6
Time [days]
R
e
t
e
n
t
i
o
n

o
f

v
i
s
c
o
s
i
t
y

[
%
]
Dimerate 4
Dimerate 3
Polycaprolactone
PTMEG
Conclusion: Much improved thermo-oxidative stability,
especially relative to standard polyether soft segment
Polymer modification with dimer
technology
 Blocky COPE / COPA elastomers with PRIPLAST dimer polyester as soft
segment
 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

Examples of new oleochemical
developments for:


Dimer diamine as new polymer
building block
Different forms of dimer fatty acid
technology
HOOC COOH
HO OH
Dimer acid
PRIPOL



Dimer diol
PRIPOL



Dimer diamine
PRIAMINE

H
2
N NH
2
New !
10 years
30 years
Different forms of dimer fatty acid
technology
HOOC COOH
HO OH
Dimer acid
PRIPOL



Dimer diol
PRIPOL



Dimer diamine
PRIAMINE

H
2
N NH
2

250 mPa.s
2500 mPa.s
7000 mPA.s
Typical viscosity RT
Amine functionalised dimers

 Amine functional dimer/trimer as curing agent, cross-linker or building
block

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
NH2 H2N
H2N
NH2 H2N
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, adhesives

Dev 1 10 75 Epoxy curative
Data are typicals, to be confirmed.
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 (%)
D
y
n
.

v
i
s
c
.

2
5
C

(
m
P
a
.
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!
Improving impact resistance
Epikote 828 / hardener blend after 1 wk cure @25°C
0
25
50
75
100
125
150
175
200
0 10 20 30 50 80 100
Modifying Ancamide 3201 with PRIAMINE 1071 (%wt)
I
m
p
a
c
t

r
e
s
i
s
t
a
n
c
e

(
c
m
.
k
g
)
direct impact @ 25°C indirect impact @ 25°C indirect impact @ 4°C indirect impact @ -25°C
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

The Future

Development of many more high
performance, biobased polymers
Biobased raw materials
New 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 now
and in the future.


Biobased raw materials
New possibilities for sustainable polymers

 Much more product derivatisations and application development possible for
development of high performing biobased polymers such as:
 Polycarbonate
 Acrylates
 Polyesters, like PET, PBT and PEN
 Polyurethane and PUD’s
 Polyurea
 Polyamide
 Polylactic
 Etc.

 To accomplish this, we wish to cooperate as much as possible with
 Innovative industry partners in this field
 Universities & institutes

THANK YOU!



Contacts:
Hans.ridderikhoff@croda.com
Angela.smits@croda.com