Presentation at the ESPP conference Phosphorus stewardship in industrial applications, Brussels, 01-12-2016 European Sustainable Phosphorus Platform (ESPP) www.phosphorusplatform.eu Sustainable management of nutrients is crucial for agriculture, food, industry, water and the environment. ESPP brings together companies and stakeholders to address the Phosphorus Challenge and its opportunities for the circular economy. Countries: Austria AT Belgium BE Bulgaria BG Cyprus CY Czech Republic CZ Germany DE Denmark DK Estonia EE Spain ES Finland FI France FR Greece EL Hungary HU Ireland IE Italy IT Lithuania LT Luxembourg LU Latvia LV Malta MT Netherlands NL Poland PL Portugal PT Romania RO Sweden SE Slovenia SI Slovakia SK United Kingdom UK Switzerland CH Phosphorus: Fosfor Fosfor Fòsfòr Фосфор Fosfor Фосфор Fosfor Fosfor Фосфор Фосфор Fosforas Fosfors Fuosfuors Fosfor Ffуsfforws Fosfar Fosfaras Fosfaar Fosforus Φωσφορος Ֆոսֆոր Fosfor Fosfor Фосфор Фосфор ফসফরাস فسفر ફૉસ્ફરસનો फास्फोरस Fosfor Fosfori Foszfor Фосфор Фосфор Паликандур Fosfor Fosfor Фосфор Фосфор Фосфор Фосфор Fosfor فوسفور Fosfor Fosforoa ფოსფორი [fūsfūr] זרחן Fosfru Lìn リン 인 ฟอสฟอรัส Photpho 磷 Posporo Fosfor Pūtūtae-whetū Fosforus ഫോസ്ഫറസ് பொஸ்பரசு Fosofo Fosforase Posfori Fósforo Phusphuru Fosforimi Fosforo Fosforon Pesticium

1. Public
Dr. Wolfgang Wanzke
BU Additives
Sustainability Manager
24.11.2016
Sustainability in the
Phosphorus Value Chain
P-BASED FLAME
RETARDANTS AND
FIRE RETARDED PLASTICS

2. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
Clariant at a Glance
A global player in the specialty chemicals business
2
TOTAL SALES IN 2015
5.807 Mio CHF Employees 2015: approx. 17.000
CARE CHEMICALS CATALYSIS NATURAL RESOURCES PLASTICS & COATINGS
Strong commitment to sustainability:

3. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
Clariant in the P Value Chain
o Leading supplier of P-based flame retardants
for engineering plastics and coatings
o Uses a few thousand tons of elemental
phosphorus and intermediate products
based on P4 per year
o Flame retardant portfolio was developed to
more sustainable products in several steps
Our vision on sustainable FRs:
Phosphorus based flame retardants produced
from recycled P with renewable energy, as part
of a future circular P-economy
Public, Sustainability in the P Value Chain3

4. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
FR Portfolio Development@Clariant
Step 1: Halogen-Phase-out
4
• Situation 1990ies: heterogeneous product mix based on Phosphorus and/or Chlorine
based products
• Decision 1995 (when the business still was with Hoechst AG): phase–out of
all halogenated Flame Retardants:
• TCEP, TCPP
• Chlorinated Phosphate-Oligomers
• Chlorinated paraffines
CH2
CH3
CH3
CH2
Cl
CH2Cl
CH3
P
O
O
O
O
Cl
P O
ONH4
O
n
P
O
CH2CH2 C
O
OCH2CH2OHHO
CH3
P
P
P
P
P
P P
P
P
P
P
P
P
P
P
P
ClH
Cl
H
HCl
Cl
H
H
H H H
HHHH
ClCH2CH2O P
O
OCH2CH2Cl
OCH2CH2Cl
O
O
P O
O
O
P
S S

5. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
Looking for the “Ideal Flame Retardant”
5
Ideal FR
Maintain properties of polymer
• minimal interference with polymer structure
• applicable in various polymers
• colorless
Maintain properties over polymer lifetime
• no migration in polymer / no leaching
• low impact on mechanical properties
Stable and safe processing
• no vapor pressure or volatility
• thermal stability
• low water solubility
Halogen-free and safe FR
• no bioavailability
• no physiological activity
• sustainable
Basic Needs
• FR Performance
• Cost Performance
• Legal Compliance

6. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
FR Portfolio Development@Clariant
Step 2: Development of new sustainable P-FR-s – organic Phosphinates
6
• Exploration of Phosphinate Chemistry based on well available raw materials yellow
phosphorus[1] and sodium hypophosphite[2]
P
O
H
H
NaO P
O
R
X
OH
Disubstituted Phosphinic Acids
[1] Weferling, N., Sicken, M. and Hörold, S., Phosphorus, Sulfur and Silicon 177 (2002) 1757-1761
[2] Hill, M., Bauer, H., Krause, W., WO2009/010188
P
O
R
H
NaO
PP
P
P
- H2
RCl NaOH+ +
[PTC]
Radical initiated Alkylation

7. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
7
P
O
H
H
NaO P
O
CH2
CH3
CH2
CH3
NaO
Al P
O
CH2
CH3
CH2
CH3
O
3
Zn P
O
CH2
CH3
CH2
CH3
O
Diethyl Phosphinic Acid
Aluminium Salt (DEPAL)
Sodium Hypophosphite
Ethylation
Precipitation
Diethyl Phosphinic Acid
Sodium Salt
Diethyl Phosphinic Acid
Zinc Salt (DEPZN)
2
FR Portfolio Development@Clariant
Step3: Commercialization of Diethylphosphinic acid derivatives

8. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
FR Portfolio Development@Clariant
Step 4: Development of tailor made synergistic blends/recipes
8
• Exolit OP in combination with N-
synergists and Stabilizers is an
important building block for the
compounding industry
• Exolit OP 1240, Exolit OP 1260
for Polyesters
• Exolit OP 1230, Exolit OP 1311,
Exolit OP 1312, Exolit OP 1314,
for Polyamides

9. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
How Sustainable is our Portfolio ?
A new system of evaluation
Public, Sustainability in the P Value Chain9
CONTINUOUS
IMPROVEMENT
SCREENING PROMOTION/
LABELLING
THE PORTFOLIO VALUE PROGRAM SYSTEM
Main Components
CriteriaCatalogue
Products Meeting
Clariant
Sustainability
Definition
Product
Portfolio
Sustainability
Screening
CSI R&D
Screening for
Innovation
Pipeline
EcoTain+
Selected
Products
Product Portfolio
Improvement
Roadmap
STAKEHOLDER AND THIRD PARTY INVOLVEMENT AND VERIFICATION
INTERNAL TRAINING AND COMMUNICATION

10. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
10
The Assessment Process
TWO “LENSES” ARE USED TO LOOK AT PRODUCT SUSTAINABILITY
Absolute
Sustainability Risks &
Benefits
Sustainability
Performance against
the Market
• 36 criteria are applied following corporate guidelines and a criteria glossary
• Team effort with a maximum of product knowledge at the table and data mining
• 26 environmental criteria, 4 economical and 6 social
• The full life cycle of the products is addressed

11. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
The PVP System Rating Scale
The Clariant Portfolio Value Program System11

12. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
FR Portfolio Development@Clariant
Step 5: PVP assessment and portfolio optimization
12
• Main FR Products have achieved the EcoTain®-Label:
• Exolit OP 1230 (Aluminium diethyl phosphinate)
• Exolit AP 422 (Ammonium Polyphosphate)
• Some FR grades with needs for improvements regarding sustainability
• e.g. Synergistic blends containing Zinc Borate (Category 2 reproductive toxicant)
Replacement of Zinc Borate by non-classified products
as part of a sustainability roadmap
Development of new “P-P-Synergism”
Exolit OP 1400

13. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
External Proof Points – e. g. Green Screen®
Public, Sustainability in the P Value Chain13
DfE to GreenScreen Translations Final Benchmark Scores
Antimony Trioxide (1309-64-4) 1 = Avoid - chemical of high concern
Melamine Cyanurate (CAS# 37640-57-6)] 1 = Avoid - chemical of high concern
N-alkoxy Hindered Amine Rx Products (CAS#191680-81-6) 1 = Avoid - chemical of high concern
Phosphonate Oligomer (CAS#68664-06-2) 1 = Avoid - chemical of high concern
Zinc Borate 1332-07-6, 138265-88-0 1 = Avoid - chemical of high concern
Aluminum diethylphosphinate (CAS#225789-38-8) 2 = Use but search for safer alternatives
Aluminum Hydroxide (CAS#21645-51-2) 2 = Use but search for safer alternatives
Melamine Polyphosphate (CAS#15541-60-3) 2 = Use but search for safer alternatives
Poly[phosphonate-co-carbonate] (CAS# 77226-90-5) 2 = Use but search for safer alternatives
Resorcinol Bis-Diphenylphosphate (CAS#125997-21-9) 2 = Use but search for safer alternatives
Red Phosphorus (CAS# 7723-14-0) 2 = Use but search for safer alternatives
Substituted Amine Phosphate mixture (CAS# 66034-17-1) 2 = Use but search for safer alternatives
Triphenyl Phosphate (CAS#115-86-6)] 2 = Use but search for safer alternatives
Ammonium Polyphosphate (CAS # 68333-79-9)] 3 = Use but still opportunity for improvement
Magnesium Hydroxide (CAS # 1309-42-8)] 3 = Use but still opportunity for improvement
Polyphosphonate (CAS#68664-06-2) 3 = Use but still opportunity for improvement
Bisphenol A Bis-(diphenyl phosphate) (CAS#181028-79-5 and 5945-
33-5) (BAPP)
U = not enough data for assessment
Phosphoric acid, mixed esters with [1,1'-bisphenyl-4,4'-diol] and phenol;
BPBP (CAS#1003300-73-9)]
U = not enough data for assessment
4 = Prefer - safer chemical
Data gaps filled ! Aluminium diethylphosphinate is now benchmark 3 !
Recent
Update

14. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
More Life Cycle Data – e. g. ENFIRO Project
Public, Sustainability in the P Value Chain14
Impact assessment
studies
• Life cycle
assessment
• Life cycle costing
• Social life cycle
assessment
Technological
assessment
• Application
• Fire performance
•Leaching and air
emission
Risk assessment
• Hazard
•Environment
•Human health
• Exposure
FR Material Product

15. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
End of Life Scenarios - Recyclability
Public, Sustainability in the P Value Chain15
PA 66 39,3 39,3
PA 6 10 10
Glass fibre HP3610 30 30
Stab. 1098/168* 0,2/0,2 0,2/0,2
Licowax E 0,3 0,3
Exolit OP 1312 20
Exolit OP 1400 20

16. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
End of Life Scenarios - Incineration
Public, Sustainability in the P Value Chain16
Waste incineration
Mixed
plastics
Domestic
waste
Mech. & biol.
Treatment:
“High caloric
fraction”
AlPO48 %
24 %
28 %
Off-gas
0,1%
AlPO4
Ashes
8 %AlPO2R
Slag
52 %
60 %
AlPO4
AlPO4

17. Dr. Wolfgang Wanzke, BU Additives, Sustainability Manager, 24.11.2016
Conclusion
Phosphorus based flame retardants like the presented phosphinates or
ammonium polyphosphate
 have a very favorable sustainability profile as shown by internal and external
investigations covering the life cycle of these products and flame retarded
plastics made thereof
 Remaining life cycle issues are the
- high energy consumption and the
- green house gas emissions caused by the production of elemental P
 Both problems can be mitigated or solved, once phosphorus can be sourced
from recycled phosphates and produced by using renewable energy
Public, Sustainability in the P Value Chain17