ISP Polyclar PVPP History

2. Agenda Company & PVPP History of ISP History of PVPP Product Production PVPP Function / Key Effects in Wine Safety Regulations, Certificates, Approvals

3. History of ISP ISP, a premier specialty chemical company, serving 500+ specialty chemicals to 6000+ customers from 67 locations and 3,300 employees worldwide. 1842-1941: Privately Held: Business was founded in 1842 as a photographic supply house. After a series of acquisitions and reorganizations, the business was renamed General Aniline & Film Corporation (GAF), a subsidiary of the German Chemical concern IG Farben. 1942-1965: Government Run: In 1942, the US government seized control of 98% of GAF under the Trading with the Enemies Act.

4. History of ISP (cont�d) 1965-1989: Publicly Held: In 1965, GAF stock held by the US government was sold. GAF grew through diversification and expansion. Between 1980 and 1982 GAF divested many of its non-chemical and non-roofing businesses. 1989-2003: Largely Private: In 1989, management took GAF private. In 1991, GAF held an IPO for common stock of ISP, its Specialty Chemicals business. ISP common stock was listed on the New York Stock Exchange until 2003 when the company went private again.

5. History of ISP (cont�d)

6. History of Polyclar PVPP 1939 Patent for synthesis of PVP filed by Reppe 1950s and 1960s Brewing scientists discover polyphenol adsorption capability of PVP Solubility of PVP an obstacle for wider application in beverage industry 1968-1970 ISP is first patent holder on crosslinking PVP and first to market with PVPP Polyclar AT launched to the market

7. History of Polyclar PVPP (cont�d) 1965-1989 Polyclar approval in most European countries for beer Launch: Polyclar 10, specialised grade for single use application Launch: Polyclar R (later Super R), specialised grade for regeneration purpose Polyclar approval by OIV (1980s) Launch: Polyclar V & VT, specialised grades for wine application Patent on ultrasonic and post-treatment of PVPP to improve filtration characteristics 1990s Global spread of Polyclar PVPP applications in various beverage applications Development of a pyrolysis-GC method to proof absence of PVPP in treated beverages by Cheng and Malawer, ISP

8. History of Polyclar PVPP (cont�d) 2000 Launch: Polyclar Brewbrite, improved wort settling combined with brewhouse stabilisation Launch: Polyclar Plus, combined protein and polyphenol stabilisation 2005 Start up of second Polyclar plant in Texas City 2006 Launch: Polyclar XG, micronised PVPP for membrane filter application in brewing 2008 Launch: Polyclar Granule for beer application, low dust and easy wetting PVPP granules

9. History of Polyclar PVPP (cont�d) 2009 Launch: Polyclar WINE (granule) for wine application, low dust and easy wetting PVPP granules 2010 Development of a titration based method to measure pinking & browning potential Development of further Polyclar granulated blends for preventative and curative must and wine treatments

10. Marl, Germany

11. Calvert, Kentucky

12. Texas City, Texas

13. Polyvinylpyrrolidone � the �building block� Polyvinylpyrrolidone (PVP) is an analogue of the amino acid proline ? strong affinity to complex haze-producing polyphenols and precursors of colour and off-flavours, such as adstringency

14. Production of Polyclar PVPP Chemically crosslinked polymer of poly (vinylpyrrolidone) manufactured at Calvert City (Kentucky, USA) and Texas City(Texas, USA) Linear polymer chains grow by a free radical mechanism in the presence of high monomer concentration Localized flux, creates physical chain entanglement and chemical crosslinking (by interaction with crosslinking agent and chain branch points) Macroradicals become trapped and, due to generation of osmotic pressure, rupture yielding high concentration of new radicals Resulting material has low swollen volume

15. Outline of manufacturing process PVPP

16. Crosslinking agents Ethylidenevinylpyrrolidone (ISP)

17. PVPP manufacturing process

18. Crosslinked PVP (PVPP)

19. EM photo of Polyclar PVPPEM photo: 400x / 1000x

20. Polyphenol adsorption by Polyclar PVPP Adsorbs tannoids & haze polyphenols Interaction based on p-orbital overlap, H-bonding and polar and hydrophobic interactions More possible binding sites than proteins - thus PVPP is favoured by beer polyphenols

21. Key function Polyclar PVPP in wine

22. Polyclar PVPP health and safety Hazard identification: No known hazards Eye contact: Possible irritation Handling and storage: Avoid breathing dust Personal protection: Dust mask when dusting cannot be avoided Skin irritation: Not a primary irritant Toxicity: No effect level greater than 10% of total diet

23. Safety of PVPP PVPP has a long history of use in pharmaceutical, medical, agricultural, and food industries Extensive studies to demonstrate human & animal safety PVPP is chemically inert & lacks biological activity PVPP cannot bioaccumulate: crosslinked polymer cannot cross cell membranes hydrophilicity prevents concentration in adipose tissue

24. Approvals & certificates PVPP is a highly regulated product in a highly regulated market. Safety first. Compliant to FDA regulations Food Chemical Codex (FCC) OIV regulations German beer purity law (Reinheitsgebot) New (2010) Japanese standards of food additives Note: Polyclar currently the only approved product!

25. Approvals & certificates (cont�d) According to EU Directive 95/2/EC (on food additives other than colours and sweeteners) EC Regulation No 1622/2000 (laying down rules on � establishing a community code of oenological practices and processes) EC Regulation No. 1935/2004 (materials and articles intended to come in food contact) EC Opinion of the Scientific Committee on Food on the safety of N-vinyl-2-pyrrolidone residues in PVPP when used as food additives (April 17th 2001) Fully aligned with HACCP principles

26. Approvals & certificates (cont�d) Certified ISO 9001:2000 for Calvert City and Texas City plant on Design, development, manufacture and supply of solvents, intermediates and polymers including Marketing, sales, customer service, purchasing, corporate quality insurance and logistics Certified ISO 14001:2004

27. Approvals & certificates (cont�d) PVPP is a highly regulated product in a highly regulated market. Safety first. Toxicity tests carried out to gain approvals Acute oral toxicity 28-day feeding study (rat & dog) 90-day feeding study (rat) 180-day feeding study (dog) Teratogenicity Pharmacokinetics Ecotoxicity Bioaccumulation Toxicity to marine dwelling organisms

28. Approvals & certificates (cont�d) Other available certificates and statements Free from plasticisers (DEHP, NPE, PAH, �) No use of heavy metal catalysts No GMO PVPP produced in GMP environment Halal & Kosher (regular Rabby visits required)

29. OIV compliance requirements

30. Polyclar PVPP A highly regulated product, produced and marketed by specialists. ISP was first to market with PVPP and leading above regulative work for registration and approval ISP holds a track record of four decades of meeting above specifications, regulations and quality principles and can provide comprehensive traceability of all PVPP produced at either of the two existing PVPP plants

31. Polyclar PVPP (cont�d) A highly regulated product, produced and marketed by specialists. Polyclar is a true processing aid: insoluble (not partly insoluble like other polyphenol complexing reagents) completely removable (not like enzymes, that remain in beverage) physically interacting (hydrogen bonding, no chemical reaction) Polyclar is marketed by highly technical sales teams with a strong background in the respective markets brewers, wine-maker, food technicians, chemists who understand needs of customers and requirements of markets

32. PVPP � A safe product from ISP