Post on 11-Apr-2018
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