Polyolefin Stabilization: Overview of Chemistry & Effects

Transcription

1 Polyolefin Stabilization: verview of Chemistry & Effects R.E. King III; Ph.D. Senior Technology Manager Plastic Additives Business Unit Applications & Technology Center BASF Corporation 500 White Plains Road Tarrytown Y rick.king@basf.com ctober 20-22, 2015 The Woodlands, TX

2 pening Remark: Even after all these years Polyolefins are still quite interesting Elevator Speech: Even though polyolefins have been around for >70 years, and have a relatively simply structure, the properties of this diverse material still provides a very nice opportunity for the cost effective replacement of other materials, such as wood, metal, glass as well as other types of thermoplastic polymers Polypropylene Polyethylene gas phase; slurry phase; bulk phase; zn-pp; m-pp; homopolymer; random copolymer; impact copolymer; R R.E. King III; BASF Corporation gas phase; liquid phase; slurry phase; zn-lldpe; Zr; CGCT m-lldpe; m-hdpe, Cr-HDPE; Ti-HDPE HMW-HDPE; UHMW-HDPE; plastomers; elastomers; tubular; autoclave; short chains; long chains; Variables that provide design flexibility.. Catalyst / Co-Catalyst Monomer / Co-Monomer Polymerization Process Additive / Co-Additive Selection Targets for End-Use Application -2-

3 Generalized Polymerization Scenario Possible Additive Addition Points Possible Additive Addition Points = * * * V 1 V 2 V 3 V 4 V 5 * * * Reactor Flash Deactivate Drying Storage Concentrates Value Chain "Dry Blended Fluff" "Base Stabilized Pellets" Compounders "Fully Formulated Pellets" verall Goal: Keep the Designed Molecular Architecture Intact R.E. King III; BASF Corporation -3-

4 -4- Target: Continue to be A Powerful Partner Focusing on Material Replacement & ew Markets Paper Cardboard Glass Wood Cotton Cast Iron Stone HMW HDPE PP Copo LDPE/EVA PP Homo PP onwoven HMW HDPE HDPE Material Replacement is one of the more exciting Innovation areas

5 -5- Target: Continue to be A Powerful Partner Being part of the Plastics Industry via Innovation Products Antioxidants/process stabilizers Light Stabilizers rganic & Inorganic Colorants Functional Pigments Halogen Free Flame Retardants Polymer Modifiers Markets & Industries Automotive Agriculture Building & Construction Electrical & Electronics Textiles & Fibers Packaging & Consumer Goods Substrates Polyolefins Elastomers Engineering Plastics Polyurethanes Styrenics PVC Applications Woven & onwoven Fibers Thin & Thick Films Sheets & Membranes Pipes & Profile Extrusion Injection/Blow Molding Rotomolding Snapshot of required competencies to deliver Innovation

6 -6- Innovation in Plastics in orth America: Substrates & Applications Markets & Industries Market & Industry facing approach Membranes Water Pipe Gas Pipe Building & Construction Interior Exterior Under the Hood Automotive Processability Clarity Rotomolded Artificial Turf Carpet onwovens Packaging & Consumer Goods Textiles & Fibers Significant innovation happens via Material Replacement pportunities

7 -7- Quick Review: Let s Hit the Basics Stabilization of Polyolefins Q. Why Do I eed to Use Stabilizers? A. Stabilizers Used to Maintain the Polymer's riginal Strength, Flexibility, Toughness; etc. Properties eed to be Maintained to Meet End Use Applications that have Performance Targets Useful to Split Performance Targets (Economics) Low End: Mid-Range: High End: on-durable Goods Use it for a While Durable Goods

8 Processability, Durability & Aesthetics ften a matter of perspective R.E. King III; III; BASF Corporation 249th ACS ational Meeting -8-

9 -9- Defining Key Measures Elements that constitute a Good Product Physical Properties Polymer Selection Molecular Weight / Molecular Weight Distribution Aesthetic Properties Polymer Selection (clarity; gloss; modulus; etc.) Initial Color / Color Maintenance over time Melt Processability Selection of Appropriate Melt Processing Stabilizers Long Term Thermal Stability Selection of Appropriate Thermal Stabilizer System Weatherability Selection of Appropriate UV Stabilizer System

10 -10- Quick verview on Antioxidants & Process Stabilizers Chemistry vs. Effects

11 -11- Polymer Auto-oxidation Cycle A polymer is born, and then meets reality Polymer Polymer Energy; Shear; Melt Processing; Catalyst Residues R Alkyl Radical R Alkoxy Radical H Hydroxy Radical R Peroxy Radical RH Hydroperoxide xygen R + H Cycle II R + RH Cycle I R Energy (UV Light, Heat) Catalyst Residues Path of Degradation Polymer

12 -12- Effective Temperatures for Stabilizers How do each of the components contribute? Hindered Amine Long Term Thermal Stability (o Melt Processing Stability) Hindered Phenol Long Term Thermal Stability Melt Processing Stability Thiosynergist (& Phenol) Long Term Thermal Stability (o Melt Processing Stability) Phosphite Hydroxylamine alpha-tocopherol (Vitamin E) (o Long Term Thermal Stability) Melt Processing Stability Temperature ( C)

13 Representative Commercial Phenolic A s Similar Warheads, but different appendages H CH 2 CH 2 C CH 2 4 C H CH 2 CH 2 C C 18 H H H H H CH 2 P Ca 2+ H 1330 H H (CH 2 ) 2 C H 1425 C 2 H 5 H H CH 3 H H S CH 3 C 8 H 17 BHT S C 8 H H 3114 H CH 2 CH 2 C H H MD-1024 R.E. King III; BASF Corporation 2 H CH 2 CH 2 C (CH 2 ) 2 -] 2 -S Vitamin E H 431 H 1135 H 565 SC 8 H 17 SC 8 H

14 Phenolic Antioxidants: Powerful Chemistry Scavenge xygen Centered Radicals H H H R + R disp. - RH 1 2 R R + R rearrange C R H 3 R C R C R 5 R RH 6 C R C R rearrange C R C R 4 2x C R H e = 440 nm Bis-Quinonemethide R.E. King III; BASF Corporation -14-

15 -15- Decomposition of Hydroperoxides Relative Easy Significant egative Implications R-H Heat Light Ti(III) Cu(II) R- + H R- + H - R- + H + Ti(IV) R- + H + + Cu(I)

16 -16- Phosphites Decompose Hydroperoxides via xidation of Phosphite to Phosphate (R) 3 P + R'H Phosphite P(III) (R) 3 P= + R'H Phosphate P(V) (R) 3 P= + R'H o Reaction Relative rates of reaction for various R groups: alkyl > aryl > sterically hindered aryl P.P Klemchuk, Antioxidants in Ullmann s Encyclopedia of Industrial Chemistry, VCH Publishers, Deerfeild Beach, FL, 91 (1985)

17 Representative Commercial Phosphites Two flagship products then lots of specialties Larger Volume / Semi-Commodity Intermediate Volume / Semi-Specialty P C 9 H 19 ] 3 -P P P P Irgafos Weston 399 (TPP) Irgafos 126 Sandostab PEPQ 2 Smaller Volume / Specialty (introduced in mid-1990 s - recent) H CH 3 Irgafos 38 P C 2 H 5 2 P C 8 H 17 ADK STAB HP 10 P F Ethanox 398 P CH 2 CH 2 P P 3 Irgafos 12 Doverphos S-9228 H 37 C 18 P P C 18 H 37 Weston 618/619 P P P C 13 H 27 C 13 H 27 P C 3 H 7 P C 13 H 27 C 13 H 27 R.E. King III; BASF Corporation ADK STAB PEP 36 Ultranox 641 ADK STAB 260 Doverphos

18 -18- Antioxidants in Action Inhibited Auto-oxidation Cycle Polymer R + H Cycle II Energy; Shear; Melt Processing; Catalyst Residues R + RH Cycle I R Alkyl Radical R Alkoxy Radical H Hydroxy Radical R Peroxy Radical RH Hydroperoxide xygen R Phenolic As react with oxygen centered radicals to yield less active products (RH and H 2 0) Path of Degradation Phosphites react with hydroperoxides to yield inactive products (RH) Phenolic As react with oxygen centered radicals to yield less active products (RH and H 2 0) Path of Stabilization

19 Additive Concentration vs. Performance Finding the right balance of cost & performance (Antioxidant/Phosphite) Stabilizer Blend / Loading Titration Study in LLDPE Melt Index Data at 2.16 kg / 190 C 1000 ppm 1076/1000 ppm ppm ppm 1076/1500 ppm ppm 1076/750 ppm ppm ppm 1076/2000 ppm 168 Multiple solutions to properly stabilize film grade LLDPE 500 ppm 1076/1000 ppm ppm 1076/500 ppm ppm 1076 Blank Polymer R.E. King III; BASF Corporation dgrams/min First Pass Fifth Pass -19-

20 -20- ew Challenges and ew Directions Effectiveness, Efficiency, Applications, EHS/PS&R Antioxidants & Process Stabilizers More efficient melt processing stabilization More effective melt processing stabilization; e.g. elevated temps Improved compatibility of additives (solubility; diffusion; temp) Long term thermal stability at elevated temperatures (less volatility) Extraction resistant in applications requiring long term durability Certified Customer Specific Blends (analyze one additive vs. many) User friendliness at the production facility (less dust, easy flow; melt) More efficient packaging and delivery Global PS&R Issues & pportunities Migration resistance for sensitive applications Reduced additive loadings while maintaining adequate performance Good outlook on PBT (persistence, bioaccumulation, tox profile) Moving away from animal sources of raw materials (Kosher, Halal) Moving away from concerns with endocrine / estrogen mimics

21 -21- ew Challenges and ew Directions Effectiveness, Efficiency, Applications, EHS/PS&R Example 1: Improved Processability Approach: Identify Market eed Combine Technologies Measure Performance Verify Value Proposition Validate with Customer

22 Performance Concentration vs. Performance Finding the right balance of cost & performance Stable Polymer Powerful Additives Easy Processing Lower Temperatures Brief Residence Times Less Shear Diminishing Returns Stronger Radical Scavenger Insufficient Amount The Zone Unstable Polymer Weaker Additives Difficult Processing Higher Temperatures Long Residence Times High Shear R.E. King III; BASF Corporation Additive Loading -22-

23 ew Directions for Antioxidants More efficient Inhibition of Auto-oxidation Cycle Polymer Energy; Shear; Melt Processing; Catalyst Residues Carbon Centered Radical Traps Improve Efficiency of Traditional Stabilizers R + H Cycle II R + RH Cycle I xygen R Phenolic As react with free radicals to yield inactive products (RH and H 2 0) R.E. King III; BASF Corporation Path of Degradation Phosphites react with hydroperoxides to yield inactive products (RH) Phenolic As react with oxygen centered radicals Path of Stabilization -23-

24 -24- Improved Processability Stabilizer Systems Slurry Phase zn-pp Homopolymer ISP-1E 33% reduction vs ppm I-1010/I ppm IPS-1E gave very good performance vs 1500 ppm of traditional A-1010/PS-168 Blend 1500 ppm of traditional A-1010/PS-168 Blend provides adequate melt flow control for this grade

25 -25- Improved Processability Stabilizer Systems Slurry Phase zn-pp Homopolymer ISP-1E 33% reduction vs ppm I-1010/I ppm IPS-1E gave similar performance vs ppm of traditional A-1010/PS-168 Blend 1500 ppm of traditional A-1010/PS-168 Blend provides adequate good color maintenance

26 -26- Quick verview on Light Stabilizers & UV Stabilization Chemistry vs. Effects

27 Durability During Weathering Impact of Electromagnetic Radiation Conditions Wavelength [nm] UVB UVA Photo-degradation Measure performance by Xenon weathering Visible Coloration & Filtering Measure performance by spectral properties & colorimetry IR IR Heat transfer Measure performance by oven aging & calorimetry UV Absorbers HALS Pigments Colorants IR Absorber IR Reflector IR non-absorber R.E. King III; BASF Corporation -27-

28 Damaging Effect of Ultraviolet Radiation via Photo-xidative Degradation Polymer Partially Deactivated Catalyst Residues R UV Light (~ nm) RH R + H Polymer Polymer R R + RH + H 2 R.E. King III; BASF Corporation

29 Early Approach to UV Stabilization Representative UV Absorbers H light H C 8 H 17 C 8 H 17 H light + H CH 3 CH 3 Governed by Lambert-Beer Equation: Absorbance = Molar Absorptivity Concentration Path Length Calvert and Pitts: Photochemistry, Wiley, ew York, 1967, p.534. Heller and Blattmann: Pur. Appl. Chem. 1973, 36, 141. Kramer: Angew. Makromol. Chem. 1990, 183, 67. R.E. King III; BASF Corporation -29-

30 Abs Ultraviolet Spectra: Various Benzotriazoles ote: Blue Shifting / Red Shifting of Absorption TIUVI 234 TIUVI 328 TIUVI 326 TIUVI 327 TIUVI P (nm) R.E. King III; BASF Corporation 20 mg/l in EtAc -30-

31 -31- Hindered Amine Stabilizers UV Stabilization via Free Radical Scavenging R R R R [xidation] R* = -H -CH 3 -R** R* R [H + ] R X R= + RH R + TE: An acidified hindered amine cannot easily enter into the free radical scavenging cycle R* H -H and -R Hindered Amine Stabilizers (HAS) fit most needs regarding light stability, but can be alkaline (basic) -R type HAS enter the UV stabilization cycle quickly, and are not alkaline, in comparison to -H & -R type HAS

32 -32- R.E. King III; BASF Corporation Representative Hindered Amine Stabilizers Similar Warheads, but different appendages H H H (CH 2 ) 6 n R R H R R ] 2 - CH 3 C 4 H 9 R = n H H H H (CH 2 ) 6 n C C (CH 2 ) 8 C 8 H 17 H 17 C 8 R = C 4 H 9 C 4 H 9 H H R R H R H H H H H n R

33 -33- UV Stability can be a Function of Location Radiation Intensity is non-linear

34 Photo-xidative Degradation Prevented: Via Appropriate Selection of UV Stabilization Polymer Partially Deactivated Catalyst Residues Hindered Amine Light Stabilizers R Polymer UV Light (~ nm) RH R UV Absorbers UV Quenchers ***HALS: Low Temperature Free Radical Scavengers*** R + H R + RH + H 2 Polymer Hindered Amine Light Stabilizers - R.E. King III; BASF Corporation Hindered Amine Light Stabilizers -34-

35 -35- ew Challenges and ew Directions Effectiveness, Efficiency, Applications, EHS/PS&R UV Stabilization More efficient UV stabilization More effective UV stabilization Enabling polyolefins to displace conventional building materials UV stabilization systems that providing improved durability/longer life Extraction resistant in applications requiring long term durability Chemically resistant UV for Ag films (greenhouse, silage, much) Reduce negative additive interactions Global PS&R Issues & pportunities Migration resistance for sensitive applications Reduced additive loadings while maintaining adequate performance Good outlook on PBT (persistence, bioaccumulation, tox profile) Moving away from animal sources of raw materials (Kosher, Halal)

36 -36- ew Challenges and ew Directions Effectiveness, Efficiency, Applications, EHS/PS&R Example 2: Enhanced Durability Approach: Identify Market eed Develop Technology Measure Performance Verify Value Proposition Validate with Customer

37 -37- High performance light stabilizers -H, -R, R-HALS provide a distinct advantage Hindered Amine Chemistry R Markets & Industries R R R R* = - H - CH 3 - R** - R R* [H + ] [xidation] R R X R= + RH R + R* H TE: An acidified hindered amine cannot easily enter into the free radical scavenging cycle High performance light stabilizers via -H, -R, R-HALS

38 Innovation Focus: Develop ew Blends & Systems Grow Plastics in Building & Construction Representative Project Focus Areas: TP Roofing Membranes HDPE Roofing Tiles LMDPE Geomembranes HDPE Water Pipe & Gas Pipe PEX Pipe & Tubing Polypropylene Siding (Thick Section Thin) Polycarbonate Glazing Wood Plastic Composite Decking High Melt Strength PP Window Profiles R.E. July 17, King 2015 III; BASF Corporation Also working with: BASF Construction Industry Team BASF Center for Building Excellence n the radar: Testing orms; e.g., ASTM Your Connection to Innovation

39 Volume Polymer Parallel Growth: Polymers & Stabilizers Facilitated by technology / demanding applications Melt Phase HP-LDPE Solution Phase Slurry Phase zn-pp Cr-HDPE zn-pe A: BHT; TPP UV: LMW Absorbers Bulk Phase Gas Phase zn-pp zn-pe All Process Types m-pp m-pe A: Hyperactives UV: HPT UVA s -R HALS A: HMW & Specialty Phenolics & Phosphites UV: HMW Absorbers Hindered Amines (HALS) R.E. King III; BASF Corporation -39-

40 -40- Acknowledgments FlexP 2015 rganizing Committee BASF Corporation (for permission to present) All the folks who contributed to the advancement Marybeth Ryan (for the Molecular Structures) You, and your attention regarding today s presentation