Upload
others
View
4
Download
0
Embed Size (px)
Citation preview
INNOVATION FROM RENEWABLE RESOURCES AT L’OREAL:
EXPANDING THE CHEMIST’S TOOLBOX
Julien HITCE, PhDProcess Innovation & Development - L’Oréal Advanced Research
25.8 Billions € (2016)
Countries
People
International brands
205 Products sold every second
140
82 900
32
1st WORLDWIDE COSMETIC GROUP
In R&I teams3 870
Hair dyeFraganceMake up Hair care Skincare& Hygiene
ALL BEAUTY NEEDS
4
IGCW2017 – Innovation from Renewable Resources
I N N OVAT I N GSUSTAINABLY
DEVELOPPINGSUSTAINABLY
P RO D U C I N GSUSTAINABLY
L I V I N GSUSTAINABLY
5
IGCW2017 – Innovation from Renewable Resources
INNOVATINGSUSTAINABLY
BY 2020, WE WILL INNOVATE
SO THAT 100% OF OUR
PRODUCTS HAVE AN
ENVIRONMENTAL
OR SOCIAL BENEFIT.
6
IGCW2017 – Innovation from Renewable Resources
INNOVATINGSUSTAINABLY
� the new formula REDUCES THE
ENVIRONMENTAL FOOTPRINT
� the new formula uses RENEWABLE raw
materials SUSTAINABLY SOURCED or derived
from GREEN CHEMISTRY
� the new product has an ENVIRONMENTAL or
SOCIAL POSITIVE IMPACT
� the new packaging has an IMPROVED
environmental profile
7
IGCW2017 – Innovation from Renewable Resources
ENVIRONMENTAL IMPACTPARTICULARFOCUS ON WATER
+ CO2 + H2O
O2+ +
IMPROVING THE % OF BIODEGRADABILITY
LOWERING THE WATER FOOTPRINT
https://www.youtube.com/watch?v=h6MYI5JFDGo L’Oréal assessment of Water Footprint
renewable
obtained from an eco-respectful process
demonstrating a favorable
environmental impact
L’Oréal commitment to Green Chemistry
http://youtu.be/QOi3ja1TaDo
GREEN CHEMISTRY3 PILLARS ENCOMPASSINGTHE 12 PRINCIPLES
IGCW2017 – Innovation from Renewable Resources
9
IGCW2017 – Innovation from Renewable Resources
GREEN CHEMISTRYSAFE& INNOVATIVEPRODUCTS ON THE MARKET
54% (2016) by volume of our Raw Materials from renewable origin:
1400 Raw Materials
290 Botanical species
60 Countries
RENEWABLE RAW MATERIALS IN OUR
PORTFOLIO
IGCW2017 – Innovation from Renewable Resources
Innovative products originating from POLYSACCHARIDES
such as pectines and carrageenans
RENEWABLE INGREDIENTS DEVELOPMENT
IGCW2017 – Innovation from Renewable Resources
Science for a Sustainable Society Symposium,
McGillIGCW2017 – Innovation from Renewable Resources
CANDIDATE SELECTED, DEVELOPPED and MARKETED
as a NEW ANTIAGING active
PROXYLANE TM
O OH
OH
OHOH
CH3
CH3
O
O
O
OHOHOH
O
CH3 O
OHOHOH
OH
CH3+H2O90°C
(D-xylose)
H2O
cat. reductionbase
⌧⌧⌧⌧ Sustainable Starting Material Xylose from Beech Wood
⌧ Green Process=> efficient synthesis (2 steps), use of water as solvent, use of catalysis
⌧⌧⌧⌧ Ecofriendly Compound: biodegradable (software BIOWIN), no bioaccumulation
(software KIOWIN) and no ecotoxicity (software ECOSAR)
PROXYLANE TM
Synthesis of Pro-Xylane TM: A new biologically active C-glycoside in aqueous media M. Dalko-Csiba and al. Biorg. Med Chem. Letters , 2009, 19 (3),
pp. 845-849.
L’Oreal Patent : WO2002051828
MANUFACTURING Footprint ///
[[[[iLiLiLiL]]]] Raw Material Origin
[H2O][H2O][H2O][H2O] Water consumption
[eFA] Aqueous Waste Valorization
[sIOS] Organic Waste Valorization
[eC] Manufacturing Carbon Footprint
ECO-DESIGN Footprint ///
[eVS] Synthetic Pathway Efficiency
[eF] E-factor
[rMP] Renewable Origin of RM
[ieMP] Raw Material Environmental Impact
[ieD] Waste Environmental Impact
L. Leseurre et al., Green Chemistry, 2014, 16, 1139-1148
Made in CHIMEX EcoFootPrint
Science for a Sustainable Society Symposium,
McGillIGCW2017 – Innovation from Renewable Resources
ProXylane™
6 month clinical study (versus placebo):
Effect on :- overall skin strength- tone- elasticity - smoothness and homogeneity
In vivo results
ProXylane™ at 10%
Currently marketed in a wide range of skincare products
Eur. J. Dermatol. 2008, 18, 297Eur. J. Dermatol. 2008, 18, 36
15
IGCW2017 – Innovation from Renewable Resources
GREEN CHEMISTRYA CATALYST FOR INNOVATION
16
IGCW2017 – Innovation from Renewable Resources
FROM BIOMASS TO INNOVATIVE COSMETIC INGREDIENTSADDING VALUE THROUGH SPECIFICALLY OPTIMIZED
TRANSFORMATIONS
Carbohydrates
Adjustingthe properties of
polymers throughreactive extrusion
Polyphenols
Exploringstructural diversitythrough tailoredtransformations
Noprotecting
group
Eco-friendlysolvents (Bio)catalysis
Straightforwardroutes
Processintensification
Favorable environ. profile
17
IGCW2017 – Innovation from Renewable Resources
POLYPHENOLS: BIOLOGICAL ACTIVITY
O
O
OH
OH
OHOH
OHO
OH
OH
OH
O
OH
OH
OHOH
OH
OH
O
OH
OH
OH
O. V. Zillich et al., Int. J. Cosmet. Sci. 2015, 37, 455J. Sœur et al., Free Radicals Biol. Med. 2015, 78, 213ANTI-OXIDANT PROPERTIES
oxidativestress photo-induced
ageing
lipidperoxidation
MMP activation
degradation of structural
components in skin
UV exposure
ROS
Resveratrol Myricetin
Epigallocatechingallate
18
IGCW2017 – Innovation from Renewable Resources
INSPIRATION FROMNATURE
RESVERATROL
OH
OH
OH
VERSATILITY FROMCHEMISTRY
+
OLEFIN METATHESISOLEFIN METATHESIS
Assembling a diversity of renewable aromaticmoieties to generate symmetrical or non-symmetrical
Resveratrol analogues
J. Hitce, M. Crutizat, C. Bourdon, A. Vivès, X. Marat, M. DalkoGreen Chem. 2015, 17, 3756
BIOCARBOXYLATIONBIOCARBOXYLATION
Incorporating an additional carboxyl function to modify the substitution pattern of Resveratrol and
analogues
K. Plasch, V. Resch, J. Hitce, J. Popłoński, K. Faber, S. M. GlueckAdv. Synth. Catal. 2017, 359, 959
HOW TO GENERATE STRUCTURAL DIVERSITY?
Y. Chauvin R. H. GrubbsR. R. Schrock
Nobel Prize – Chemistry – 2005
19
IGCW2017 – Innovation from Renewable Resources
GREEN CHEMISTRY
Botanicalextract
Pure, naturalbuilding-block
High value product
RO
Essential oil PhenylpropenoidSymmetrical,
functionalized stilbene
OR
RO
ISOLATE TRANSFORM
DIRECT TRANSFORMATION
© I. Walter, L’Oréal R&I
Optimizingoverall
efficiency
R1O
OR1
R2O
OR2
Me
R1O
R2O
Ru
PCy3PhCl
Cl
NN MesMes
down to 0.01 mol%
90°Csolvent-free
2-10 min
� up to > 98% conversion
� up to 95% isolated yield
� extremely fast
� practical lab procedure
� multi-gram scale
Catalyticprocess
Renewablebuildingblocks
Solventfree
Green Chemistryprinciples
J. C. WarnerP. T. Anastas
Item #5 Item #7
Directtransform.
Item #8Item #9
Flashmetathesis
TAILOR-MADE METHODOLOGY
20
IGCW2017 – Innovation from Renewable Resources
ACCESS TO STRUCTURAL DIVERSITYOPENINGNEW PERSPECTIVES
New compounds
tested
DevelopingScience
OH
MeO
OH
OMe
AcO
MeO
OAc
OMe
MeO
OMe
OH
OMe
MeO AcO
MeO
OH
OMeMeO
OH
OMe
MeO
OMe
MeO
OMe
MeOHO
OH
OHRESVERATROL
92% yield
92% yield 84% yield 95% yield
50% yield 18% yield 42% yield
21
IGCW2017 – Innovation from Renewable Resources
INSPIRATION FROMNATURE
RESVERATROL
OH
OH
OH
VERSATILITY FROMCHEMISTRY
+
OLEFIN METATHESISOLEFIN METATHESIS
Assembling a diversity of renewable aromaticmoieties to generate symmetrical or non-symmetrical
Resveratrol analogues
J. Hitce, M. Crutizat, C. Bourdon, A. Vivès, X. Marat, M. DalkoGreen Chem. 2015, 17, 3756
BIOCARBOXYLATIONBIOCARBOXYLATION
Incorporating an additional carboxyl function to modify the substitution pattern of Resveratrol and
analogues
K. Plasch, V. Resch, J. Hitce, J. Popłoński, K. Faber, S. M. GlueckAdv. Synth. Catal. 2017, 359, 959
HOW TO GENERATE STRUCTURAL DIVERSITY?
IGCW2017 – Innovation from Renewable Resources
BIOCATALYSISEXPANDINGTHE CHEMIST’S TOOLBOX
MOLECULAR BIOLOGY MICROBIOLOGY
SYNTHETICCHEMISTRY
Pr K. FaberUniversity of GrazAustria
Pr K. FaberUniversity of GrazAustria
Enzymes Designed by Nature and Improved for Chemistry
OrganicChemistry
300 microbial strainsbacteria, fungi and extremophiles
23
IGCW2017 – Innovation from Renewable Resources
BIOCATALYZEDCARBOXYLATIONOF PHENOLS
Aspergillus oryzae2,3-DHBA decarboxylase
Rhizobium sp.2,6-DHBA decarboxylase
Trichosporon moniliiformeSA decarboxylase
� Nature’s detoxification pathway
� Alternative to Kolbe-Schmidt reaction
� KHCO3 as C1 source
� Mild conditions (pressure, temperature)
� Water as major solvent
OH
R
OH
CO2H
ROrg. Lett. 2012, 14, 1974J. Biotechnol. 2013, 168, 264
RSC Adv. 2014, 4, 9679
OH
OH
OH
OH
OH
OH
OH
OH
OH OH
97% conv.95% isolated yield
77% conv.45% isolated yield
97% conv.66% isolated yield
What about more complexphenol substrates?
24
IGCW2017 – Innovation from Renewable Resources
OH
OH
OH
OH
OH
OH
CO2H
RESVERATROL: OPTIMIZEDCONDITIONS
94%isolated yield
Resveratrol
substrate (mM)co-solvent
co-solvent amountenzyme preparation
enzyme amountbicarbonate stoech.
75mMMeOH20% v/vwhole cells10mg/mL2M
Organicco-solvent
KHCO3stoechiometry
Catalystloading
Substrateconcentration
15 solvents tested10-30% v/v
10-100mM
0.5-3M
0.5-30mg/mL
Perfectregio-
selectivity
J. Hitce, K. Faber et al., Adv. Synth. Catal. 2017, 359, 959
25
IGCW2017 – Innovation from Renewable Resources
FROM BIOMASS TO INNOVATIVE COSMETIC INGREDIENTSADDING VALUE THROUGH SPECIFICALLY OPTIMIZED
TRANSFORMATIONS
Carbohydrates
Adjustingthe properties of
polymers throughreactive extrusion
Polyphenols
Exploringstructural diversitythrough tailoredtransformations
Noprotecting
group
Eco-friendlysolvents (Bio)catalysis
Straightforwardroutes
Processintensification
Favorable environ. profile
26
IGCW2017 – Innovation from Renewable Resources
POLYSACCHARIDES BUILDING-BLOCKS
Sugarsin
Nature
Sugarsin
Cosmetics
Energy storageStructure
componentsSignalling
Biological pathways
Active ingredientsFilm-formers
Rheologymodifiers
� viscosity
� solubility
� molecular weight
� functional groups
Multiplefunctions
Diverseformulae
Fine-tuningphys.-chem.properties
� etc.
27
IGCW2017 – Innovation from Renewable Resources
EXTRUSION: REVISITINGPOLYSACCHARIDES
FROM BIOMASS TO INNOVATIVE COSMETIC INGREDIENTSINTENSIFICATION
ECO-DESIGN
SAFETY
VERSATILITY
extrusion
starting materials
product
tunable screws
REACTIVE EXTRUSIONREACTIVE EXTRUSIONREACTIVE EXTRUSION
Heat and shear forces transferred to the neat mixture to induce chemical reactions
� Polymer grafting
� Polymer fragmentation
� Polymerization from monomers
� Polymer cross-linking
ChemoselectivityPolydispersityControl of size
Controlled fragmentation of polysaccharides to adjust their phys.-chem. properties
CASE STUDY
V. D. Miladinov, M. Hanna, Ind. Crop. Prod. 2000, 11, 51A. A. Vaidya et al., Carbohyd .Polym. 2016, 36, 1238
28
IGCW2017 – Innovation from Renewable Resources
ETHYLCELLULOSEFILM-FORMER
Hydrophobically-modified cellulose derivatives used as film-former.
Need to increase w/w% concentration in formula withoutimpacting viscosity
R = H or CH2CH3
Mn ~ 5-6 kDa
Mw ~ 18-20 kDa
Mn ~ 18 kDa
Mw ~ 52 kDa
commercially available
Viscosity
pristine fragmented
22 000 cP ~ 150 cP
Gelling point
pristine fragmented
15-20 %w/w 35-40 %w/w
20 %w/w in octyldodecanol (22°C) in octyldodecanol (20°C)
NaHSO4�H2O(4 %w/w)
170°C
RECHERCHE & INNOVATION29
IGCW2017 – Innovation from Renewable Resources
High MW linearHyaluronic AcidHigh MW linearHyaluronic AcidHigh MW linearHyaluronic Acid
O
OH OH
O *m O
OO
*
AlginateAlginateAlginate
O
OH OH
Om
O
OO
O
NH
O
O
OH OH
*
*
λ-carreghenaneλ-carreghenaneλ-carreghenane
PROCESS VERSATILITY
From lab scaleto pilot plant
From lab scaleto pilot plant
From lab scaleto pilot plant
O
O O
O
OH
O
OSO3-
O
OH OSO3- SO3-
OH
*
*
m
MW Viscosity
(2% in water)
pristine 700 kDa 710 cP
fragmented 480 kDa 290 cP
aq. HCl
Similar behaviour for all tested polysaccharides
Optimization of rheological properties: viscositydecreased through fragmentation by reactive extrusion
RECHERCHE & INNOVATION30
IGCW2017 – Innovation from Renewable Resources
SUSTAINABLEINNOVATIONEXPANDINGTHE CHEMIST’S TOOLBOX
PUSHING THE LIMITS OF TECHNOLOGIES BY EXPANDING OR REVISITING
THEIR SCOPE AND ADAPTING THEM TO OUR CONTEXT AND AP PLICATIONS
++++====Need for a solution
Ingredientoptimization
► better performance► optimal phys.-chem. Properties► structural diversity, novelty
Green&
straightforwardtransformations
► diversity of techniques► practical procedures► no organic solvent
Renewable, sustainably
sourced startingmaterials
► biopolymers► plant metabolites► plant extracts► biomasses
RECHERCHE & INNOVATION31
IGCW2017 – Innovation from Renewable Resources
GREEN CHEM. FOR SUSTAINABLEINNOVATIONTAKEHOME MESSAGES
� Green Chemistry at every stage: from design to manufacturing
� Method development gives access to versatile and efficient tools
� Starting materials from renewable origin to reach sophisticated structures and/or properties
� Products that are not only green but also that display performance
� High ambition sustainability objectives translate into scientific/technical challenges and recognition