![Why do polyolefin properties deteriorate during recycling?
• Most polyolefin grades are made for short lived consumer applications and are
not stabilized for recycling
• Additional AO is needed to protect the inherent properties of the polymer during
the recycling step – Damage done to the polymer at this stage cannot be
corrected later!
Source: Fraunhofer Institute for Structural Durability and System Reliability LBF: www.lbf.fraunhofer.de
Property Virgin Polyolefin Recyclate Consequences
Carbonyl groups [mmol/kg] <2 10 - >100 Initiator sites for accelerated oxidation and photo oxidation
Acidic groups [mmol/kg] <1 10 - 100 Accelerated oxidative degradation
Double bonds [mmol/kg] 10 5 - 200 Accelerated oxidative degradation, higher sensitivity for cross
linking (gel formation) in PE, discolouration from conjugated
double bonds
Metal impurities [ppm] <50 50 - >2000 Oxidation catalysts
Baerlocher | Sustainable Plastics May 2023](https://image.slidesharecdn.com/elaynasimmons-230516042106-6d7a36e5/85/SUPPORTING-SUSTAINABLE-PLASTICS-THROUGH-ADDITIVES-16-320.jpg)
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- 1. Elayna Simmons Technical Specialist SpecialAdditives North America Baerlocher Supporting Sustainable Plastics Through Additives May 8th 2023, Sustainable Plastics Conference, LA Baerlocher | Sustainable Plastics May 2023
- 2. Baerlocher | SustainablePlastics May 2023 Overview • Recycling Goals vs Reality • Mechanical Recycling of Polyolefins • Stabilization Basics • Baeropol RST Stabilizer Blends • Case Studies – Stabilizing PCR for Blow Molded Bottles • Conclusions and Baerlocher Info
- 3. Recycling Plastics – Goalsvs Reality
- 4. Baerlocher | SustainablePlastics May 2023 How does Recycling Fit into Sustainability?
- 5.
- 6. Baerlocher | SustainablePlastics May 2023 Ellen MacArthur Foundation Data
- 7.
- 8. Is Plastic Recyclinga Myth?
- 9.
- 10. No, But it isdifficult
- 11. Polyethylene (HDPE, LDPE,LLDPE) • ↑ Degradation • ↑ Crosslinking • ↑ Viscosity • ↑ Difficulty in processing • ↑ Undesired physical properties Baerlocher | Sustainable Plastics May 2023 Polymer Degradation During Recycling
- 12. Sources of Prodegradantsand Contamination in PCR and PIR Baerlocher | Sustainable Plastics May 2023 • Dirt • Former contents of the package • Wash water/detergent • Incompatible resins (e.g. PVC in HDPE) • Exposure to the environment • Poor quality resin • Time between heat histories No Stabilization Melt Flow
- 13. • Color • Tasteand Odor • Loss of mechanical properties • Gels • Reduced lifetime • Inconsistent parts and process • Inability to regrind/recycle Effect of Polymer Degradation and Contamination Baerlocher | Sustainable Plastics May 2023
- 14. PCR Resin Properties– Making a Product Baerlocher | Sustainable Plastics May 2023 Side reactions Change in Melt Flow Sag, Swell, Poor Processing Control Process Variation Poor Quality, Downtime
- 15.
- 16. Why do polyolefinproperties deteriorate during recycling? • Most polyolefin grades are made for short lived consumer applications and are not stabilized for recycling • Additional AO is needed to protect the inherent properties of the polymer during the recycling step – Damage done to the polymer at this stage cannot be corrected later! Source: Fraunhofer Institute for Structural Durability and System Reliability LBF: www.lbf.fraunhofer.de Property Virgin Polyolefin Recyclate Consequences Carbonyl groups [mmol/kg] <2 10 - >100 Initiator sites for accelerated oxidation and photo oxidation Acidic groups [mmol/kg] <1 10 - 100 Accelerated oxidative degradation Double bonds [mmol/kg] 10 5 - 200 Accelerated oxidative degradation, higher sensitivity for cross linking (gel formation) in PE, discolouration from conjugated double bonds Metal impurities [ppm] <50 50 - >2000 Oxidation catalysts Baerlocher | Sustainable Plastics May 2023
- 17. Thermo-Oxidation Cycle Oxygen POO• POOH PO• P• Polymer Heat Shear Light Time Catalyst Residues Contaminants (inPCR) •OH Polymer Polymer D Baerlocher | Sustainable Plastics May 2023
- 18. Thermo-Oxidation Cycle Oxygen POO• POOH PO• P• Polymer Heat Shear Light Time Catalyst Residues Contaminants (inPCR) •OH Polymer Polymer D Antacids Primary AO Secondary AO Baerlocher | Sustainable Plastics May 2023
- 19. Polymer stabilization isa well-established concept Standard Stabilization Background •Destroys catalyst residuals and buffers the polymer and thus protects antioxidants Antacid • Destroys hydroperoxides in the melt that result from oxidation and therefore protects the phenol Secondary AO •Gives long term stability and helps determine the lifetime of the resin Primary AO Baerlocher | Sustainable Plastics May 2023
- 20.
- 21. RST (Resin StabilizationTechnology) Baeropol T-Blends • Complete stabilizer package with synergistic RST technology Traditional stabilizer blends Baeropol RST Baeropol T-Blends Baerlocher | Sustainable Plastics May 2023
- 22. • Twin screwextrusion • High temperatures • Extrude, pelletize, repeat • 5x multipass to see degradation Baerlocher | Sustainable Plastics May 2023 Multipass Extrusion Testing • Test properties: • Melt index/melt flow • Oxidation induction time • Rheology • Color Looking for stability over multiple passes
- 23. • Stabilizing thepolymer means preventing degradation • Resulting in virtually no change in the polymer architecture • ❌ Degradation • ❌ Crosslinking • ❌ Change in viscosity • ✓ Easier processability Baerlocher | Sustainable Plastics May 2023 Melt Index Stability Melt Flow Various T-Blend Stabilizers at 0.3% Loading No Stabilization
- 24. Baerlocher | SustainablePlastics May 2023 OIT: indicator of long-term oxidative stability Oxidation Induction Time Improvement ❌ Poorly stabilized ❌ No remaining active antioxidant
- 25. Case Studies: BlowMolding Bottles with HDPE PCR
- 26. Baerlocher | SustainablePlastics May 2023 Mixed Color Co-Polymer PCR Mono-layer bottles made from 100% PCR • Unstabilized PCR • PCR with Baeropol T-1111 • PCR with Traditional B-Blend Case Studies Summary Natural Clear HDPE PCR Mono-layer bottles made from blends of Virgin and HDPE PCR • Unstabilized PCR • PCR with Baeropol T-1111 • 50/50 blends PCR and Virgin Natural Clear HDPE PCR Mono-layer and Tri-layer bottles 100% PCR when used • Unstabilized PCR • PCR with Baeropol T-1111 • PCR in core layer only • 100% PCR bottles • Comparison of many PCRs
- 27. Blow Molding Bottleswith Mixed Color Co-Polymer PCR
- 28. Baerlocher | SustainablePlastics May 2023 • Bottles made from 100% PCR • Lower grade HDPE PCR – mixed color co-polymer feedstock • Compounded with and without stabilizer blend • Blow molding trial at FGH with Boston Round Bottle • Physical properties tested Mixed Color Co-Polymer PCR Case Study
- 29. PCR Degradation ResultsIn Parison Problems Side reactions Change in Melt Flow Sag, Swell, Poor Parison Control Process Variation Poor Quality, Downtime 29 | Looking for consistency in bottle properties
- 30. Mixed Color Co-PolymerPCR Case Study – Wall Thickness Baerlocher | Sustainable Plastics May 2023 • T-1111 stabilized PCR resulted in bottles with profile closest to initial PCR • ↓ Degradation • ↓ Crosslinking • ↓ Change in viscosity • ✓ More consistency in final part
- 31. Baerlocher | SustainablePlastics May 2023 Mixed Color Co-Polymer PCR Case Study – Bottle Weight • T-1111 stabilized PCR resulted in bottle weight closest to initial PCR • ↓ Degradation • ↓ Crosslinking • ↓ Change in viscosity • ✓ More consistency • ✓ More consistency in final part
- 32. Baerlocher | SustainablePlastics May 2023 Mixed Color Co-Polymer PCR Case Study – Top Load • T-1111 stabilized PCR resulted in top load results closest to initial PCR • ↓ Degradation • ↓ Crosslinking • ↓ Change in viscosity • ✓ More consistency • ✓ More consistency in final part • ✓ Better physical properties
- 33. Blow Molding Bottleswith Natural Color HDPE PCR
- 34. Baerlocher | SustainablePlastics May 2023 • Higher grade HDPE PCR – dairy grade resin feedstock • PCR compounded with and without stabilizer blend • Bottles made from blends of Virgin HDPE and PCR • Blow molding trial at Bekum with F-style Bottle • Physical properties tested Natural Clear HDPE PCR Case Study
- 35. Blending PCR withVirgin Resin
- 36. Baerlocher | SustainablePlastics May 2023 The Problem with Blending PCR with Virgin Blending Virgin with PCR does not help melt index
- 37. Addition of T-Blendsto PCR – Melt Stability Baerlocher | Sustainable Plastics May 2023 Addition of T-Blend improves MI • ↓ Degradation • ↓ Crosslinking • ↓ Change in viscosity • ✓ More consistency Making a bottle: • Better physical properties?
- 38. Baerlocher | SustainablePlastics May 2023 Reminder: Virgin Material Does Not Have Good OIT Blending Virgin with PCR does not help OIT
- 39. Baerlocher | SustainablePlastics May 2023 Addition of T-Blends to PCR – Oxidative Stability Must add more AO to improve OIT and long term stability • ↓ Degradation • ↓ Crosslinking • ↓ Change in viscosity • ✓ More consistency Making a bottle: • Better physical properties?
- 40.
- 41. Natural Clear HDPEPCR Case Study – Wall Thickness Baerlocher | Sustainable Plastics May 2023 1 10
- 42. Natural Clear HDPEPCR Case Study – Top Load Testing Baerlocher | Sustainable Plastics May 2023 • Comparison between bottles made at optimized processing conditions (350g) • Stabilization improved crush properties
- 43.
- 44. Baerlocher | SustainablePlastics May 2023 • Higher grade HDPE PCR used in Multilayer tests • PCR compounded with and without stabilizer blend • Blow molding trial at W Muller GmbH • Other PCRs available in Europe tested • Physical properties tested Multilayer PCR/Virgin Case Study
- 45. Baerlocher | SustainablePlastics May 2023 Multilayer PCR/Virgin Case Study – Melt Pressure • Parison control is essential in making a consistently good bottle • Lower variance means more control and consistency
- 46. Multilayer PCR/Virgin CaseStudy – Top Load Baerlocher | Sustainable Plastics May 2023 • Stabilized PCR performed better in single layer and 3- layer bottles • Even when PCR is in the middle layer or a lower % of the overall bottle construction, stabilization is necessary
- 47. Summary of CaseStudies • Three separate studies, all with different PCR and on different equipment, confirm added value from stabilization: ✓ Improved stability by improving melt stability ✓ Reduced parison variation in blow molding case studies ✓ Reduced loss from waste ✓ Strengthened mechanical properties Baerlocher | Sustainable Plastics May 2023
- 48. A Note fromW Muller
- 49. Baerlocher | SustainablePlastics May 2023 • PCR is an amalgamation • ↑ Lot-to-lot variation • ↑ Variation between distributors
- 50.
- 51. Baerlocher | SustainablePlastics May 2023 Conclusions • Recycling polyolefins is a growing challenge for North America with higher demand for the use of PCR in finished products and varying quality in PCR • Stabilization shows promising results in real world applications • Stabilizers can improve PCR resin stability for processability, physical properties, and quality of final product compared to unstabilized PCR • By improving PCR quality, we are contributing to the overall sustainability of plastic! Symbols from: https://en.wikipedia.org/wiki/Recycling
- 52.
- 53. Global Footprint -Diverse Capabilities Germany UK Italy I Italy II San Morino Turkey Brazil Peru USA I & II Argentina Korea China India Malaysia 53 |
- 54. Baerlocher | SustainablePlastics May 2023 Baerlocher | Company | Global Partner ▪Your global partner for additives ▪Baerlocher Group of Companies serves local customer needs with innovative / customer tailored solutions. • Global leader in PVC additives: Leader in Ca-based solutions • Global metal soaps specialist • Customer focused blend solutions • Global footprint of 1200 employees representing a trusted and reliable partner • 200 years of experience
- 55. Special Additives Products Lubricants Baerolub Stabilizers Baeropol RST Metal Soaps Calcium Soaps Zinc Soaps Aluminum Soaps Magnesium Soaps Alkali Soaps Non Polymer Powdered MetalRubber VSA Hydrophobe Grease Recycling Solutions Baerolub AID Baerlocher | Sustainable Plastics May 2023
- 56. Baerlocher Philosophy: Teach- Learn - Collaborate . Sales Marketing Technical Capabilities Innovation •Global, Across Circular Economy •Aligned with Brand Owners’ Recycling Goals! •Industry Engagement (APR, Summits, Trade Shows, Webinars) •Tailored Solutions •Applications Expertise •Technical Field Support •Applications Lab •Creating Solutions That Advance Plastics Recycling 56 |
- 57. Elayna Simmons 5890 HighlandRidge Dr Cincinnati, OH 45232 513-508-6352 simmons.elayna@baerlocher.com Baerlocher USA