presentation hans ridderikhoff - bpm symposium 15-06-2011 secured

7/27/2019 Presentation Hans Ridderikhoff - BPM Symposium 15-06-2011 Secured

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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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technology

HOOC

HO

Dimer acidPRIPOL

Dimer diolPRIPOL

Dimer diaminePRIAMINE H2N NH2 New !

10 years

30 years


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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:

[email protected]

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presentation hans ridderikhoff - bpm symposium 15-06-2011 secured

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