1. Presented at SPE International Polyolefins Conference February 28, 2012 Houston, TX Kasinath Nayak, Ph. D.

2.  Why Stabilize Polyolefins? »Need for a viable stabilizer  ETHANOX 330 »Chemical Identity »Compatibility with Polymer matrix Supporting Extraction Data »Test Data Extrusion Study »Case Studies/Applications PE Pipe PP Raffia Film »Conclusions »Extrusion Studies Summary Outline 2

3.  Degradation resulting in »Loss of physical properties and performance »Discoloration: yellowing, pinking, and black specks  Objectives of stabilization »Extraction resistance »Processing stability »Color prevention »Long term heat aging (LTHA) stability Why Stabilize Polyolefins? Extractability of additives can have a profound negative effect on polyolefin stability, physical properties and resistance to color change 3

4. ROO · RH RO· OH· R· RH ROOH O2O2 RH ROH/H 2 O impurity O 2, τ, Δ Δ Auto-catalytic oxidation reaction: 1 radical becomes 3 after 1 cycle Auto-Oxidation Cycle and How to prevent 4 Radical Scavenger Antioxidants interrupt the oxidative cycles by removing the peroxy radicals and preventing the formation of hydroperoxides. Hydroperoxide Decomposer

5. Chemical/Trade NameChemical StructureMol. WtBenefits 1,3,5-trimethyl-2,4,6-tris(3,5-di-t- butyl-4-hydroxybenzyl)benzene, CAS#1709-70-2: ETHANOX 330 775 Melt processing/LTHA, Low extractability Tetrakismethylene(3,5-di-t-butyl- 4-hydroxyhydrocinnamate; CAS# 6683-19-8; ETHANOX 310 1178 Melt processing/LTHA 1,3,5-tris(3,5-di-t-butyl-4- hydroxybenzyl)isocyanurate; CAS#27676-62-6; ETHANOX 314 784 Melt processing/LTHA, Good gas-fading resistance Octadecyl 3-(3’5’-di-t-butyl- 4’hydroxyphenyl)propionate; CAS#2082-79-3; ETHANOX 376 531 Melt processing Primary Antioxidants 5

6. Chemical name: 1,3,5-trimethyl-2,4,6-tris (3,5- di-tert-butyl-4-hydroxybenzyl)benzene Mol. Wt.: 775.2; CAS #: 1709-70-2 Melting Point: 244°C  High MW Crystalline Powder  Electrically neutral  Superior Processing Stabilizer  No imparted odor/taste  Provides long-term stability  Good benefits in filled and  Biologically inert flame-retardant applications  Extremely low extractability  Reduced water-carryover PROS 6 ETHANOX 330

7.  ETHANOX 330 antioxidant (1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) benzene (CAS reg. No. 1709-70-2):  Permitted for use in Adjuvants per FDA 21 CFR 178.2010 for indirect food contact applications:  For Use only:  At levels not to exceed 0.5% by weight of polymers except nylon resins identified in sect.177.1500 of this chapter.  At levels not to exceed 1% by weight of nylon resins identified in Sec. 177.1500 of this chapter.  Global Compliances  EU, Japan, and other Asia-Pacific Countries 7 ETHANOX 330: Regulatory Compliances

8.  Hydrolysis of the ester groups of Irganox 1010 in de-ionized water and resulting migration from PP films were demonstrated via HPLC  ETHANOX 330 lacks these ester linkages thus exhibiting superior resistance to hydrolysis Ref: M. Bertoldo and F. Ciardelli, Polymer 45(2004) 8751-8759 ETHANOX 330 8 Irganox 1010 Extraction Resistance: Hindered Phenolic Antioxidants

9. Ref.: Norman Allen et. al. Poly. Deg. & Stab. (1990) 145-157 No Loss of ETHANOX 330 occurred, showing negligible degree of extractability SurfaceBore Extruded Pipe (OD=63mm) containing 0.1% Radio-labeled ETHANOX 330, aged @ 60°C for 3 months 9 Extraction Resistance of ETHANOX 330 in MDPE Pipe

10.  MDPE Pipe formulations »I. 0.1% ETHANOX 330 +0.3%Cyassorb 531+0.1%Chimassorb 944+0.2%Irgalite Blue +0.2%TiO 2 »II. 0.1% Irganox 1010 +0.3%Cyassorb 531+0.1%Chimassorb 944+0.2%Irgalite Blue +0.2%TiO 2  Pipe Dimension  Outer Diameter = 66mm  Thickness of cross-section = 6mm  Environmental Conditions  Exposed to air for 9 months  Exposed water at ambient temperature for 9 months  Exposed to water and oven-aged @ 60°C for 3 Months  Oxidative Induction Time (OIT)  Accelerated aging test done 200°C per ASTM D3895-07 10 Environmental Depletion of Antioxidants in MDPE

11. Exposed to AIR for 9 Months Exposed to water at RT for 9 Months Exposed to water & oven-aged @ 60 °C for 3 Months % Oxidative Induction Time (OIT) Retention 11

12. 25 mil Plaques in Boiling water 0 200 400 600 800 1000 1200 1400 1600 Hours to Failure Ethanox 330Ethanox 310Ethanox 330/DSTDPEthanox 310/DSTDP 0 Day 7 Days Formulations: 1 st Set:PP Homopolymer (3dg/min) containing Aox(600)/DHT4A(250ppm) 2 nd Set: PP Homopolymer(3dg/min) containing Aox(600)/DSTDP(600ppm)/DHT-4A(250ppm) Ethanox 330 is shown to have more resistance to boiling water 12 Effect of Boiling Water on Antioxidant Activity in 3rd Gen Polypropylene

13. OIT @ 180°C 0 5 10 15 20 25 30 OIT in Minutes Un-agedAged 14 Days @ 105°C Aged 7 Days in boiling water Aged 14 Days in boiling water Ethanox 330Ethanox 310 © Copyright 2012 Albemarle Corporation - Strictly confidential - Proprietary information of Albemarle. 13 Effect of Oven-Aging and Boiling Water on OIT: LLDPE Polymer

14. Multi-Pass Ext. @ 260°C/30 rpm flat profile 0 2 4 6 8 10 1st Pass3rd Pass5th Pass Extrusion Pass MFI,g/10 min E-330 E-310 E-314 Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm Melt Flow Index per ASTM D 1238-10 ETHANOX 330 (E-330) outperforms both ETHANOX 310 (E-310) and ETHANOX 314 (E- 314) in maintaining melt flow stability. 14 Stability Test: Polypropylene Homopolymer

15. Multi-Pass Ext.@288°C/30 rpm flat Profile 0 5 10 15 20 25 30 35 1st Pass3rd Pass5th Pass Extrusion Pass MFI, g/10min E-330 E-310 E-314 Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm Multiple extrusion passes at higher temperature resulted in similar trend in melt flow rates, but much greater differences were seen between Ethanox 330 and other two antioxidants. 15 Stability Test (continued)

16. Effect of Temperature on Melt Stability 0 5 10 15 20 25 12345 Extruder Zone 4 (Die) Temperature in °C MFI, g/10min Ethanox 310 Ethanox 314 Ethanox 330 260°C 275°C 290°C 305°C 310°C Formulations: Phenolic Antioxidant/Cal. St. @ 1500ppm/500ppm Ethanox 330 and Ethanox 314 are fairly equal in maintaining melt flow stability up to 290°C, but Ethanox 330 exhibited better melt-flow stability at temperatures above 290°C. 16 Stability Test (continued): Single Pass Extrusion Test

17.  Base Resin: ExxonMobil’s HDPE ( D ~ 0.954g/cc, and MI ~ 0.5dg/min)  Base Additive Package: Phenolic/Phosphite/Hydrotalcite @1500ppm/750ppm/500ppm  Enhanced Additive Package: Phenolic/Phosphite/Hydrotalcite/AM-1/DS-1/HN-1/N-1 @ 1500/750/500/1000/1500/500/500 ppm  Compounding:  Initial Extrusion: by Haake TW100 Twin Screw Extruder (180/200/200/200°C) @ 30 RPM  Molding: Compression molded plaques (0.05 inc or 50 mil) Ref: Proceeding of International Polyolefin Conference (2010), Houston, TX 17 Case Study-I: PE Pipe

18. 0 50 100 150 200 250 BaseBase + Thioester OIT, min E-330 SeriesE-314 SeriesE-310 Series Enhanced Additive Package 18 Relative OITs of Various AOx based formulations

19. Effect of Extractive Media @ 60 Deg C/7Days on OIT 19 Effect of Extractive Media on OIT

20. 20 Hydrostatic Pressure Test (ISO 1167- 73): PE 100 Pipe PE100 (Density = 0.96/MFI=0.37 @5kg/190°C); and extruded Pipe of 20 mm OD & 2mm wall thickness containing Phenolic/Phosphite/Cal St.(1000/1000/1000ppm)/Carbon black(2.5%) with Brass or PVDF fittings Ethanox 330 is ~20% better than Irganox 1010 under hydrostatic pressure (static) test. Lifetimes of PE-100 Pipe at 110 0 C 0500100015002000250030003500 E-330/I-168 Brass I-1010/I-168 Brass E-330/I-168 PVDF I-1010/I-168 PVDF Hours to Failure 0.95 MPa 1.41 MPa

21.  ETHANOX 330 outperforms both ETHANOX 310 and ETHANOX 314 in maintaining least loss in Oxygen Induction Time (OIT) after extraction in de-ionized water and chlorinated water.  Hydrostatic Pressure Tests (Static) showed  ETHANOX 330 is approx. 10 – 20% better than Irganox-1010.  Special ALBlend Packages with thioesters and amines are shown to exhibit exceptional OITs, thus showing promises for HDPE pipe applications to extend the life expectancy beyond 100 years.  Hence, ETHANOX 330 is an antioxidant of choice for polyolefin water pipe applications because of its resistance to hydrolysis and water extraction. 21 Case Study-I: Outcome

22. Objective:  Reduce the yellowness index color  Improve the line speed (reduce water carry over) during film extrusion of raffia grade polypropylene  Lower overall treat cost 22 Case Study-II: Improving Color/Line Speed in Raffia Grade Polypropylene

23. 23 Water Carry Over Test

24. 24 Effect of Antioxidants on Water Carry Over In a Homopolymer PP

25.  Four ALBlend samples vs. a Specific Customer formulation were tested  ALBlend A20: E330/E368/Cal. St. @ 1600 ppm  ALBlend B20: E330/E368/Cal. St. @ 1700 ppm  ALBlend C20: E330/E368/Cal. St. @ 1650 ppm  ALBlend D20: E330/E368/DHT-4A/Cal. St. @ 1500 ppm  Current formulation  Test Data  Yellowness index  Melt flow index  Line speed (Water Carry Over) 25 Case Study-II: Experimental Details

26. 26 Multiple Extrusion and Water Carryover Data Better line speed, better color and comparable melt flow stability Current Formulation ALBlend A20 ALBlend B20 ALBlend C20 ALBlend D20 Line Speed 105110115120125130 Avg. ft/min

27.  ALBlend containing ETHANOX 330 was chosen for optimum performance:  Reduced yellowness index color from 4.19 to 2.04 after the 5 th pass.  Improved line speed from 113 ft/min to 122 ft/min. 27 Case Study-II: Outcome

28.  Extraction Resistance  ETHANOX 330 exhibits superior hydrolytic stability resulting in excellent extraction resistance when in contact with extracting media  Processing Stability:  ETHANOX 330 shows better performance in maintaining melt flow stability  Oxidative Induction Time (OIT) Retention:  ETHANOX 330 exhibits better OIT retention  Resistance to Hydrostatic Pressure:  ETHANOX 330 outperforms in hydrostatic pressure test  Lower Water Carryover:  Formulations based on ETHANOX 330 result in low color and higher line speed 28 Conclusions

29. For more information regarding Albemarle’s antioxidants, please visit www.ethanox.com.www.ethanox.com 29 ETHANOX 330: Add less, get more value