1. New Stabilization Package for Controlled Rheology Polypropylene Fibers (Benchmarked against Phenol & Phenol-free Systems) SPE International Polyolefins Conference 2012 J. Mara 1, H.-J. Kwon 2, J.-D. Kim 2, J. Bayer 3 & K. Keck 2 1 Songwon International Americas; USA 2 Songwon Industrial, South Korea 3 Songwon International, Switzerland

2. Introduction to Auto-oxidation of Polyolefins Degradation of Polypropylene (PP) Classification of PP Fibers (by Songwon)  Stabilization Requirements for PP Fibers  Stabilization Strategies for PP Fibers  Technical Benchmarking vs. Phenol-containing & Phenol-free Systems  Summary Contents SPE International Polyolefins Conference 2012

3. Peroxy Radical Hydroperoxide Alkyl Radical Alkoxy Radical Hydroxy Radical Polymer None Radicalic Products Oxygen Heat Shear UV Metal Ion (Mn + ) Heat UV Simplified Auto-Oxidation Cycle of Polyolefins Introduction

4. Concepts to Counter Auto-Oxidation of Polyolefins Free Radical Scavenging Phenolic Antioxidant + → + Aminic Antioxidant + → + Peroxide Decomposition Phosphite Antioxidant + → + Thioester Antioxidant + → + OH B A C OO* O*O* B A C OOH NHNH R OO* *N*N R OOH P OR RO OOH P OR O RO OR OH S RR OOH S R O R S R O R O OH S R O R OOHIntroduction SPE International Polyolefins Conference

5. Peroxy Radical Hydroperoxide Alkyl Radical Alkoxy Radical Hydroxy Radical Polymer Oxygen Heat Shear UV Metal Ion (Mn + ) Heat UV Radical Scavenging HALS, Amine ? Radical Scavenging HALS, Amine, AO Radical Scavenging HALS, Amine, AO Auto-Oxidation Mechanism Thermo-Oxidation Peroxide Decomposition Phosphite, Thioester SPE International Polyolefins Conference 2012 Introduction

6. PP is an unstable substrate Industrially unsuitable w/o stabilizers Undergoes uncontrolled thermo-oxidative degradation w/o stabilizers Polymerization, processing, & service life conditions can vary … Degradation of Polypropylene SPE International Polyolefins Conference 2012

7. PP will undergo different Degradation Mechanisms: Processing/Conversion: Concentration [ROO*] < Concentration [R*] MW decreases; [Mw/Mn] narrows Disproportioning of Alkyl Radicals (formation of c=c) Storage/Service Life: Concentration [ROO*] >> Concentration [R*] MW decreases; [Mw/Mn] broadens Formation of Carbonyl Groups Different & Contradicting Stabilizer Reqirements Degradation of Polypropylene SPE International Polyolefins Conference 2012

8. Classification of Polypropylene Fiber PP fiber grades are supplied over a range of MW’s depending upon processing & conversion characteristics as well as required properties of the application. Songwon classifies PP fiber grades by the conversion technology & by the presence (or absence) of peroxides for controlled degradation (Controlled Rheology). Monofilament & Tape grades have low MFI’s which need to be maintained during compounding & conversion. Meltblown & Spunbond grades have MFI’s that must be tailored in a post reactor operation via the use of peroxides (CR grades). Bulk continuous filament & Staple grades are available as either reactor grades or CR grades. SPE International Polyolefins Conference 2012

9. Classification of Polypropylene Fibers SPE International Polyolefins Conference 2012 Reference:E.P. Moore; Polypropylene Handbook; Hanser Publishers (1996) Monofilament Slit Tape Staple Fiber Continuous Filament Spunbond Meltblown - 1500 Reactor grade Narrow Normal to narrow Normal to broad Normal

10. Classification of Polypropylene Fibers SPE International Polyolefins Conference 2012 Reference:E.P. Moore; Polypropylene Handbook; Hanser Publishers (1996) Monofilament Slit Tape Staple Fiber Continuous Filament Spunbond Meltblown - 1500 Can be cracked Reactor grade Narrow Normal to narrow Normal to broad Normal

11. Classification of Polypropylene Fibers SPE International Polyolefins Conference 2012 Reference:E.P. Moore; Polypropylene Handbook; Hanser Publishers (1996) Monofilament Slit Tape Staple Fiber Continuous Filament Spunbond Meltblown Typically cracked - 1500 Can be cracked Reactor grade Narrow Normal to narrow Normal to broad Normal 1-Step CR 2-Step CR

12. Standard Post Reactor Extrusion SPE International Polyolefins Conference 2012 Stabiliser & Peroxide Addition for CR-PP WW Peroxide (mainly liquid) Stabiliser Single Additive, OPS or masterfluff Loss-in-weight feeder (Individual) additive streams Polyolefin bulk feed Polymer main stream High shear extruder Pelletizing & Storage Silo or discharge hopper P Storage tank Pump

13. Separate Addition during Extrusion SPE International Polyolefins Conference 2012 Stabiliser & Peroxide Addition for CR-PP WW Peroxide (mainly liquid) Stabiliser Single Additive, OPS or masterfluff Loss-in-weight feeder Stabiliser stream (later) Polyolefin bulk feed Polymer main stream High shear extruder Pelletizing & Storage Silo or discharge hopper P Storage tank Pump Peroxide stream (first)

14. Stabilization Requirements of PP Fibers SPE International Polyolefins Conference 2012 Excellent MW protection during compounding & conversion –Principle reason for addition of processing stabilizer No interaction with peroxides (CR grades) –Peroxide interaction leads to strong antagonism w/processing stabilizer Low initial color following compounding Low color development following conversion Low gas fade during conversion & storage –Potentially negatively affected by primary AO Adequate storage stability (optional) Outdoor UV stability (optional) –Easily adjustable by choice of HAS Other (registrations, cost, industrial availability)

15. Stabilization Requirements of PP Fibers Stabilization Requirements of PP Fibers Performance requirements for PP fiber stabilization packages vary with the conversion technology & the need for CR grades. An overview of the importance of the various requirements for the different PP fiber grades is given below: SPE International Polyolefins Conference 2012

16. February 26 th - February 29 th, 2012 Stabilization Strategies for PP Fibers SPE International Polyolefins Conference 2012 3 Alternatives for PP Fibers

17. SPE International Polyolefins Conference 2012 Selection Guide for PP Fiber Grades Recommendations are grouped around the conversion technology & corresponding importance of stabilizer requirements as captured in previous slide.

18. Songnox 3016 Characteristics Songnox 3016 Characteristics New AO package for color critical applications, including: –PP Fiber (Bulk Continuous Filament – Reactor & CR; Staple – Reactor & CR; & Spunbond applications) –Polyolefin Film applications (Not covered today) –Polyolefin Tape applications (Not covered today) –Thin Walled Injection Molding (TWIM) applications (Not covered today) Provides an excellent balance between Processing Stability & Low Peroxide interaction. The interaction with peroxide is significantly reduced compared to Phenol containing systems (i.e., Songnox 321B) & Phenol-free systems, including: –Irgastab FS 533 (Composition: FS042 + I-168 + C-2020) [1:10:3] –Irgastab FS 102 (Composition: FS042 + I-168 + T-622) [1:2:1] –Irgastab FS 410 (Composition: FS042 + C-944) [1:1] Performance data in PP homopolymer (gas phase) / MFI (230 C/2.16 kg) ~4 to 6 [dg/min] follows… SPE International Polyolefins Conference 2012

19. Substrate:PP homopolymer (gasphase) MFI 230/2.16 ~ 4 to 6 [dg/min] Compounding: N 2, 190 – 215 o C, TS Criterion: MFI after compounding Stabilisation:500 ppm Ca-stearate + 1000 ppm stabiliser Additivation:490 ppm PO-4 [2,5-Bis(t.-butylperoxy)-2,5-dimethylhexane] Stabilizer Interaction with Peroxide in CR-PP No additive Songnox 3016 GR Songnox 321B Irgastab FS 102 Irgastab FS 410 Irgastab FS 533 SPE International Polyolefins Conference 2012

20. Substrate:PP homopolymer (gasphase) MFI 230/2.16 ~ 4 to 6 [dg/min] Compounding: N 2, 190 – 215 o C, TS Exposure: 5hr at 60 o C under 5% NO x gas (KS K 0454) Stabilisation:500 ppm Ca-stearate + 1000 ppm stabiliser Additivation:490 ppm PO-4 [2,5-Bis(t.-butylperoxy)-2,5-dimethylhexane] Criterion: Delta YI Low Gas Fading in CR-PP Songnox 3016 GR Songnox 321B Irgastab FS 102 Irgastab FS 410 Irgastab FS 533 SPE International Polyolefins Conference 2012

21. Substrate:PP homopolymer (gasphase) MFI 230/2.16 ~ 4 to 6 [dg/min] Compounding: N 2, 190 – 215 o C, TS Stabilisation:500 ppm Ca-stearate + 1000 ppm stabiliser Additivation:490 ppm PO-4 [2,5-Bis(t.-butylperoxy)-2,5-dimethylhexane] Criterion: YI after compounding Low Initial Color in CR-PP Songnox 3016 GR Songnox 321B Irgastab FS 102 Irgastab FS 410 Irgastab FS 533 SPE International Polyolefins Conference 2012

22. Substrate:PP homopolymer (gasphase) MFI 230/2.16 ~ 4 to 6 [dg/min] Compounding: N 2, 190 – 215 o C, TS Stabilisation:500 ppm Ca-stearate + 1000 ppm stabiliser Additivation:490 ppm PO-4 [2,5-Bis(t.-butylperoxy)-2,5-dimethylhexane] Criterion: YI after multiple extursion Pass 1 ~ 5 Low Color Development during Processing Songnox 3016 GR Songnox 321B Irgastab FS 102 Irgastab FS 410 Irgastab FS 533 SPE International Polyolefins Conference 2012

23. Stabilisation of Controlled Rheology Polypropylene Methodology  Radar chart  Relative scale:5 Best (outside) 4 3 Intermediate 2 1 Worst (inside, center) SPE International Polyolefins Conference 2012

24. Stabilisation of Controlled Rheology Polypropylene SPE International Polyolefins Conference 2012

25. Stabilisation of Controlled Rheology Polypropylene Unstabilised Controlled Rheology PP SPE International Polyolefins Conference 2012

26.  Formulation:  Stabilisation Strategy:  Positioning: General Phenol Stabilizer System A  A [Songnox 317B] Composition: 3 parts SN1680 + 1 part SN1076  [Phenolic AO + Phosphite] synergism  Standard phenolic AO  Standard phosphite  Partially optimised composition & ratio  Standard AO package from IM or extrusion SPE International Polyolefins Conference 2012

27. Stabilisation of Controlled Rheology Polypropylene A [Songnox 317B] 1000 ppm SPE International Polyolefins Conference 2012

28.  Formulation:  Stabilisation Strategy:  Positioning: General Phenol Stabilizer System B  B [Songnox-321B] Composition: 2 parts SN1680 + 1 part SN3114  [Phenolic AO + Phosphite] synergism  Phenolic AO with reduced color formation  Partially optimised composition & ratio  Improved processing stability SPE International Polyolefins Conference 2012

29. Stabilisation of Controlled Rheology Polypropylene A [Songnox 317B] 1000 ppm B [Songnox 321B] 1000 ppm SPE International Polyolefins Conference 2012

30.  Formulation:  Stabilisation Strategy:  Positioning: Phenol-Free Stabiliser System C  C [Hydroxylamine + HAS / FS 410]  Elimination of phenolic AO (color source)  Processing stability based only on hydroxylamine  No synergistic effect  Conversion independant of service life  Hyperactive processing stabiliser SPE International Polyolefins Conference 2012

31. Stabilisation of Controlled Rheology Polypropylene A [Songnox 317B] 1000 ppm B [Songnox 321B] 1000 ppm C [FS 410] 1000 ppm SPE International Polyolefins Conference 2012

32.  Formulation:  Stabilisation Strategy:  Positioning: Phenol-Free Stabiliser System D,E  D [Hydroxylamine + Phosphite + HAS / FS 102]  E [Low hydroxylamine + Phosphite + HAS / FS 533]  Elimination of phenolic AO (colour source)  ‘‘Kinetic’’ balance Processing vs. Peroxide  Synergistic effect  Conversion independant of Service Life  C System formulated with low level of hyperactive processing stabiliser SPE International Polyolefins Conference 2012

33. Stabilisation of Controlled Rheology Polypropylene A [Songnox 317B] 1000 ppm B [Songnox 321B] 1000 ppm C [FS 410] 1000 ppm D [FS 102] 1000 ppm E [FS 533] 1000 ppm SPE International Polyolefins Conference 2012

34.  Formulation:  Stabilisation Strategy:  Positioning: New Color Critical Stabiliser System  F [Songnox 3016 GR]  Elimination of phenolic AO (colour source)  ‘‘Kinetic’’ balance Processing vs. Peroxide  Synergistic effect  Conversion independant of Service Life  No hyperactive processing stabiliser SPE International Polyolefins Conference 2012

35. Stabilisation of Controlled Rheology Polypropylene A [Songnox 317B] 1000 ppm B [Songnox 321B] 1000 ppm C [FS 410] 1000 ppm D [FS 102] 1000 ppm E [FS 533] 1000 ppm F [Songnox 3016] 1000 ppm SPE International Polyolefins Conference 2012

36. Summary PP in general must be stabilized during compounding, processing, storage, and service life. The stabilization of CR-PP during compounding and conversion is rather complex. While efficient protection of the PP is easily achievable via stabilizers with high molar activity & reaction kinetics, peroxides may also be added in order to degrade the PP in a controlled manner, yielding grades with lower MW & narrower MWD’s. In this work, we introduced a powerful new AO package for CR-PP that provides excellent balance between processing stability, color suppression, and low peroxide interaction. While the scope of today’s presentation was limited to CR-PP fiber applications, the technology is also applicable to other applications such as TWIM where low peroxide interaction and low color development are critical.

37. SPE International Polyolefins Conference 2012