innovation from renewable resources at l’oreal: …

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


INNOVATINGSUSTAINABLY

BY 2020, WE WILL INNOVATE

SO THAT 100% OF OUR

PRODUCTS HAVE AN

ENVIRONMENTAL

OR SOCIAL BENEFIT.

6


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


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


9


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


Innovative products originating from POLYSACCHARIDES

such as pectines and carrageenans

RENEWABLE INGREDIENTS DEVELOPMENT


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


GREEN CHEMISTRYA CATALYST FOR INNOVATION

16


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


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


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


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


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


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?


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


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



What about more complexphenol substrates?

24


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


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


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


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


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


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



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



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



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

innovation from renewable resources at l’oreal: …

Documents