Levulinic acid and

derivatives: sustainable

solutions for

today and tomorrow

R. Parton 3 FIIBN) GHENT

MAY 10TH 2017

T a b le o f c o n te n ts

> L e v u lin ic a c id a n d a ppro a c h to b rin g it in the m a rke t

> GF B a ppro a c h a n d pro d u c ts

T e c h n o lo g y : T h e R e a c tio n

> A m ira c le

> e a s y in la b n o t s o e a s y in pla n t

DR OP IN OR NEW BIOBASED BUILDING BLOCKS?

NEW BUILDING BLOCKS: LEVULINIC ACID

DR OP-IN:

COMPET E ON PR ICE

NEW BB:

IMPR OVED PER FOR MANCE

Levulinic acid: essential building block for a Green

Future

MAKING LEVULINIC ACID

HAPPEN

LEVULINIC ACID

NEW VALUE OR DROP-IN?

Drop in: plant trees

Which chemicals from biomass:

New biochemicals: built a new value chain = plant seeds

Financial risk mitigation :

o Clarity on

market size

price elasticity

Saving & using existing assets base

Economy of scale (introduction) considerations

Drop-in

But !!

Drop-in competes on price

Pro’s

› Known markets and properties

› Market development forecasts

› Downstream production established

Con’s

› Competing price

› Bio-label main differentiator

Con’s

› Properties not know

› Application development needed

› Higher initial investment and risk

Pro’s

› Competition on functionality

› Bio-label added feature

› New business opportunities

› Later phase at large scale

compete on price

New building blocks

compete on functionality

New building blocks can be the

Sequia’s of the FUTURE

LEVULINICACID: WILL IT BE A SEQUIAOF THE FUTURE????

GFB CHOICE:

ADDED VALUE TO ENTER THE MARKET

1 4

F o c u s e d a n d d e d ic a te d to m a rke t le v u lin ic a c id s in c e 2008

2008

FOUNDATIONMis s io n : B rin g ing le v u lin ic

a c id to th e m a rke t b y

te ch n o logy in n o v a tio n

2014

ORGANISATIONK e y p e rs o n n e l fro m g lo b a l

le a d e rs e n fo rc e G F B io che m ic a ls

to fu rthe r d e v e lo p th e te ch n o log ie s

2016

GFBIOCHEMICAL

S AMERICASAc q u is itio n o f S e g e tis

a s s e ts , IP a n d

tra d e m a rks

2009

FACILITYL e a s e C a s e rta p la n t to

d e v e lo p a n d d e m o

b re a k thro ugh te ch n o log ie s

2015

LEVULINIC ACID DEMO

PLANTN o v e l te ch n o log ie s im p le m e n te d

Ca p a c ity 1 ,2 00 M T

2017

COMMERCIALISATI

ON LEVULINIC ACID

& DERIVATIVEST o ll M a n u fa c tu rin g

2013

NEW FUNDSN e w in v e s to r a n d

re b ra n d in g G re e n

F u tu re to

GF B io che m ic a ls

2020-2022

LARGE SCALE PRODUCTION

FACILITY

Gro w th s tra te g y : b y a c q u is itio n s o f d e riv a tiv e te c h n o lo g ie s a n d p a rtn e rs h ip s w ith m a jo r c o m p a n ie s

Pro b le m fo r a l l b io m a s s b a s e d p ro d u c ts :

CAPEX h u rd le

&

Gro w th ra te v s c h o ic e o f s ize

How to bring a new building block to the market?

• Market development via toll manufacturing

• Afterwards Investments in CAPEX:

* Picture from

teecraze.com

Levulinic acid

Biobased Building Block

GFB:

Ketal platform

GVL platform

Personal Care

Industrial Cleaners

Household

Cleaners

Coatings & Adhesive

Strippers

FragrancesAgrochemicals

Asustainable multifunctional 1st order derivative of LAwith large potential and

broad application across a range of market segmentsApplication

Air care

Fragrance Concentrates

Vanillin

Value

Inherently low odor

Help keep vanillin in waxy formulation

Compatible with soy waxes

Enables more intense aroma without

discoloration

Application

Industrial degreasers

Industrial hand soap

Value

Replacement for d-limonene

Effective dirt and grease removal

Improved clarity without glycol ethers

Pleasing aesthetics of personal care

Application

Laundry concentrates

Specialty hard surface

cleaners

Wipes and pads (skin

contact)

Value

LGK as a coupling agent to

replace glycol ethers

Low VOC alternative

Application

Coatings, Ink, Gum,

Adhesive, and Graffiti

Removal

Value

LPK is an excellent

solvent for resins.

Low VOC

alternative

Application

Skin care

Makeup removers

Value

Increased active loading

Simplified formulation

Brings an attractive light, dry

emolliency to formulations

Excellent, natural-based

makeup remover that is gentle

on the skin

Application

Emulsifiable Concentrate

Value

Enhanced delivery to target

site

Solubilize multiple actives

Polar solvent

Low toxicity

Low volatility

High solubility

LA KETALS

Levulinic acid, esters and ketals for personal care

› Levulinic acid:

› Offers perfuming, skin conditioning and pH regulation

› Levulinic esters

› Appreciated as fragrance ingredients

› Levulinic ketals:

› Dissolve a wide range of actives

› Bring difficult ingredients into formulations

› Enable high water loading for moisturizing formulations

› Broad compatibility

› Light, dry emolliency

› Biodegradable

2 2

High solvency and dispersing power

Solubility of Active Ingredients (in wt%) by Application Area FC1100 FC1200

Suncare

Sunscreen

Avobenzone 20% 30%

Oxybenzone 20% 30%

Skincare

Bioavailability Enhancer Tetrahydropiperine 20% 20%

Anti-Acne

Anti-Aging

Benzoyl Peroxide 5%

Salicylic Acid 15% 11%

Resveratrol 1% 0.50%

Retinoic Acid (all-trans) 0.50%

Ulbiquinone (Co-enzyme Q10) 20%

Dimethylmethoxy Chomanol 2.50% 2.50%

Skin Whitening Tetrahydrodiferuloylmethane 20% 5%

› B rin gs d iffic u lt in g re d ie n ts in to fo rm u la tio n ,

e n a b ling h ighe r c o n c e n tra tio n s o f a c tiv e s

› D is s o lv e s a w id e ra nge o f a c tiv e s

23

Broad solubility gives formulation flexibility: oils

Oil Soluble with what % FC1100? Soluble with what % FC1200?

Stearyl alcohol 50 50

Stearic acid 50 50

Castor oil 50 50

Beeswax 50 50

C12-15 alkyl benzoate 50 50

Isopropyl myristate 50 50

Isopropyl palmitate 50 50

Caprylic/capric triglyceride 50 50

Mineral oil -- 50

Octyl methoxycinnamate 50 50

Cyclomethicone -- 50

Avocado oil 10 50

Sunflower oil 10 50

Almond oil 10 50

Squalene -- 50

Isododecane -- 50

Caprylyl methicone -- 50

24

Broad solubility gives formulation flexibility: water, solvent & alcohol

Ingredient Soluble with FC1100 Soluble with FC1200

Ethanol Infinite Infinite

Isopropanol Infinite Infinite

Water Infinite 3-5%

Hydroalcohol Infinite Infinite

25

Bring difficult ingredients into formulations: polymers

Polymer Wt. % in FC1100 Wt. % in FC1200

nitrocellulose Y Y

cellulose acetate butyrate 14 ≥25

acrylate/octylacrylamide copolymer ~5 ~1

PMMA 1 >10

Increased active loading

Simplified formulation

Simplified raw material inventory

Dissolve crystalline actives & polymers

High solubility limit

Broad substitution range

26

Versatile match-makers

EXPAND SOLUBILITY RANGE

OF ETHANOL

EXPAND SOLUBILITY RANGE

OF WATER

BRING WATER

INTO ANHYDROUS SYSTEMS

27

Actives more tolerant to water with FC1100 than with ethanol

Ethanol

FC1100

2 8

O ppo rtu n itie s to u s e o u r S e ge tis pro d u c t lin e

› Single formulation ingredient to replace many specialized ingredients

› Troubleshooting ingredient that allows formulators to expand the range of actives & increase actives concentration

› Robust formulation latitude

› Compatible with many starting formulations

› Incorporates water into anhydrous systems

› Expands solubility of ethanol, w/ clarity

› Compliment to natural formulations to reduce greasiness

› Dry, silky after-feel

Improved performance

Simplified formulation and inventory

Easy to use

Innovative ingredient combinations

Improved skin feel in natural formulations

› Superior grease-cutting and soil removal

› High Stability in multi-component systems

› Low skin irritation & sensitization

› Good substantivity and skin feel

Levulinic Ketals in household and industrial cleaners

D-limonene replacement by Levulinic Ketals

› Powerful at neutral pH, easy handling

› Safe and Non-sensitizing

› No flash or VOC

› Renewable and bio-degradable

Levulinic ketals outperforms bio-based alternatives

Key

1 Soluble

2 Almost Soluble

3 Slight Solubility

4 Swollen

5 Little Swelling

6 No Visible Effect

Glycol ether DBE D-limoneneSoy methyl

estersSV218

Paraloid B-72 (acrylic) 1 1 4 5 1

Paraloid B-82 (acrylic) 1 1 3 6 1

Desmocoll 176 (TPU) 1 2 5 4 2

CAP-482-0.5 (cellulose acetate) 1 1 6 6 1

DER-661 (epoxy) 1 1 5 5 1

EPON 1001F (epoxy) 1 1 5 3 1

UCAR PKHH (phenoxy) 2 1 6 6 1

Polyvinyl Acetate 1 1 6 6 1

Solubility observations were made after 1.0 g resin and 9.0 g solvent were agitated for 24 hours at room

temperature.

Paint strippers & brush cleaners, Graffiti-, Gum, rosin, & tar-, Adhesive

removers

Method Detergent: 4 times more concentrated than traditional

2X concentrated detergents

Strong solvency and performance in acidic environments

Approved as food additives

LevulinicKetals polyols

› Allows reduced isocyanate/catalyst content

› Less plasticized by hydrocarbon blowing agents

› No residual unsaturation

› Highly compatible

Levulinic-Ketal polyols are produced by reacting ketal monomers with a variety of

initiators and, optionally, co-monomers:

> The special levulinate ketal monomer creates rigidity and can be used to fine tune

flexibility in polyols and polyurethanes and therefore properties.

Levulinic-Ketal Polyol Technology: Many Design

Variables

34

O

O

EtO

O

OH+

O

O

O

O

O Hy

catalyst

I OH

n I

nheat

AB monomer

F o a m T yp e Applic a tio n E x a m p le sL e v u lin ic K e ta l

P o ly o l a d v a n ta g e s

R ig id F o a m s

› Gap-filling s e a la n t

fo a m s fo r c o n s tru c tio n

› R o o fin g in s u la tio n

b o a rd

› W a ll in s u la tio n

› Applia n c e in s u la tio n

› Au to m o tiv e in te rio rs

Im pro v e d m o d u lu s

V is c o e la s tic

F o a m s

› B e d d in g

› F u rn itu re , s e a tin g

R e d u c e d is o c y a n a te

u s a g e

> L -K e ta l po ly o ls o ffe r b e tte r pe rfo rm a n c e a n d m o re

v e rs a tility v e rs u s o the r b io -b a s e d a lte rn a tiv e s (s e e d -o il

po ly o ls like c a s to r o il)

Le v u l in ic K e ta l P o ly o ls fo r P o ly u re th a n e F o a m A p p l ic a tio n s

> Am o rpho u s> N o prehe a tin g re q u ire d to m e lt

> N o pha s e tra n s itio n s re la te d to so ft se gm e n t

> S tiffe r tha n po ly e the r po ly o ls , w h ich e n a b le s> R e d u c e d is o c y a n a te co n te n t

> L o w e r po ly m e r cro s s lin k d e n s ity

> S y n e rg is tic e ffe c ts w ith o the r po ly o l te chn o log ie s

Levulinic acid Ketals

plasticizers› Good hardness efficiency

› Phthalate-Free formulations with

low fusion temperatures

› Rapid dry blend time

› Lower volatility then other

plasticizers

› Improve processing of phthalate

alternatives

Levulinic Ketals are excellent performing phthalate-free, bio-based

plasticizers

Replace the phthalic anhyride core with

levulinic ketal core

> In Ketal plasticizers the core is a

biobased levulinic ketal

> The plasticizer properties can be

modified in a similar way through

choice of (biobased) R groups

> Plasticizers rely on a phthalic

anhydride core; this is

modified to meet

performance requirements

SG0159x SG0158x SGP9200

Hardness Efficiency Excellent Good Excellent

Fusion Temperature Average Excellent Excellent

Volatility Good Good Good

Color stability Excellent Average Excellent

Non-polar Extraction Average Good Excellent

> SG0159x: Primary plasticizer for all flooring types.

> SG0158x: Performance plasticizer for sheet flooring and VCT/LVT

with HEXAMOLL® DINCH® and DOTP

> SGP9200: Best combination --- low gelation temperature with

excellent efficiency, volatility, and superior non-polar extraction. For

all flooring types

Phthalate-free, Bio-based Plasticizers

Un iq u e p ro p e rty p ro fi le s to f le x PV C a n d f le x PLA w ith Le v u l in ic Ke ta ls

F le x ib le P L A

w ith L e v u lin ic

K e ta l pla s tic iz e r

F le x ib le P L A

w ith

co m pe titiv e

pla s tic iz e r(s tre s s

w h ite n in g w h e n b e n t)

Ex c e l le n t c o m p a tib i l i ty w ith

h y d ro p h i l ic b io p o ly m e rs

0

10

20

30

40

50

60

70

80

90

100

DINP DINCH Segetis BBP DOP

% E

xtra

cte

d i

n H

exa

ne

60 phr PVC Formulation60 phr plasticizer, 2 phr Ferro SP175 in GEON 121A; % mass loss is

normalized to plasticizer loading (assumes all mass loss is plasticizer)

> K e ta l p la s tic ize r h a s lo w c o m pa tib ility

w ith po ly e thy le n e lo w m igra tio n in to

P E a n d o th e r hy d ropho b ic po ly m e rs

Lo w M ig ra tio n in to N o n p o la r

Me d ia

C o m p le x v is c o s ity o f

p la s tic ize d PLA fo rm u la tio n s a t

1 5 0g rC

> T ra n s m is s io n >90% w ith L e v u lin ic

K e ta l p la s tic ize r

> L o w e rs th e P ro c e s s in g T e m pe ra tu re

o f P L A

BEN EF IT S T O FLOOR ING

Ph th a la te -fre e P V C fo rm u la tio n s w ith e x c e lle n t p e rfo rm a n c e

> V in y l S he e t

• Fast gelation: high throughput

• Low gelation temperature: lower energy

• Low volatility: better plasticizer utilitization

• Excellent heat-aged stability: good color retention

> V in y l T ile

• Fast dry blend time: high throughput

• Low gelation temperature: lower energy

• Excellent heat-aged stability: good color retention

Levulinic acid

Gamma

valerolactone

Platform

=

Next platform to

be developed

Unique from LA

NOT unique from LA

methylene-γ-valerolactone(monomer)

5-methyl-2-alkyl pyrrolidone(monomer)

Hydroxypropionic acid(monomer)

Adipic acid(monomer)

Caprolactam(monomer)

LEVULINIC ACID

2-methyl THF(solvent, fuel oxygenate)

Acrylic acid(monomer)

5-amino Levulinic acid(herbicide)

Acetyl Acrylic acid(monomer)

Methyl ethyl ketone(solvent)

Diphenolic Acid(Bisphenol A substitute)

Succinic acid(monomer)

Methyl vinyl ketone(monomer)

BIOMASS

Glucose

Cellulose

1,4-pentanediol(Polyester precursor)

Levulinate esters(biodiesel additive)

MOLECULE TREE

LA-ketals(plasticizer/solvent)

γ-valerolactone(solvent)

42

SUMMARY

> Levulinic acid

• Huge potential to make numerous chemicals to develop biobased chemical industry

• CAPEX and OPEX comparable or lower to lignocellulosic fermentation products

> GFB

• First to bring lignocellulosic levulinic acid in the market

• Commercialize levulinate ketal platform with applications as coupling agent, solvent, plasticizer, polyol, ….

• Develop & commercialize gamma-valerolactone platform

Levulinic acid: Road to a flourishing

bioeconomy

58

60

62

64

66

68

70

72

74

Shor

e A

Hard

ness

Plasticizer - 60 phr in PVC

ALL LEVULINATEKETAL PRODUCTS HAVE GOOD HARDNESS EFFICIENCY

60 phr plasticizer, 2 phr Ferro SP175 in GEON 121A (paste resin), cured 10 min. @ 200 °CShore A 15-sec hardness, 245 mil film thickness

•SGP9200 is more efficient than DOP

•SG0159x is as efficient as DINP

•SG0158x is equivalent to phthalate-alternatives

SG0159X IS MORE EFFECTIVE THAN DOTP AND DINP IN FILLED TILE FORMULATIONS

50 phr plasticizer in GG2095 (suspension resin) with 40 phr CaCO3, 3 phr ESO (except SG0159x), 0.25 phr stearic acid, 2.5 phr Mark 1221Cured 10 min. @ 160 °C

Potential to reduce plasticizer usage

40

50

60

70

80

90

100

Gel T

empe

ratu

re ( C

)

Plasticizer - 60 phr in PVC

PHTHALATE-FREE FLOORING FORMULATIONS WITH FASTER THROUGHPUT AND LOWER ENERGY

60 phr plasticizer, 2 phr Ferro SP175 in GEON 121A (paste resin)Gel bar (gradient temperature bar) test, 6 mil drawdowns, recorded after 1 minute

HEXAMOLL® DINCH ® is registered to BASF

For sheet:low gel & fusion temperature

For tile: rapid blend time and lower fusion temperature

All three Segetis products show low gel temperature.

Similar to DINP

Fast-fusers

LEVULINATE KETAL BASED FAST FUSERS ENABLE DINP PERFORMANCE IN NON-PHTHALATE FORMULATIONS

HEXAMOLL® DINCH ® is registered to BASF

60 phr plasticizer, 2 phr Ferro SP175 in GEON 121A (paste resin)Gel bar (gradient temperature bar) test, 6 mil drawdowns, recorded after 1 minute

Segetis fast fusers bring gel points of DINCH and DOTP into DINP regime

SG0158x shows the same performance as SGP9200

DINP/BBP range

Improve processing of DINCH and DOTP without sacrificing•Hardness•Color

SGP9200 IS ADVANTAGED IN VISCOSITY STABILITY COMPARED TO OTHER FAST FUSERS

60 phr plasticizer, 2 phr Ferro SP175 in GEON 121A (paste resin)Brookfield viscosity at 21 °C.DPGDB = dipropylene glycol dibenzoate

Benefits of fast-fusing with less viscosity build

Good storage stability of plastisolsfor sheet vinyl

MAKING LEVULINIC ACID HAPPEN

Problem for all biomass based products:

CAPEX hurdle

&

Growth rate vs choice of size