Estabilización del polietileno reciclado

posconsumo
Roberto Nunez
New Business Development Director
Baerlocher USA
[email protected] I 01- 513-808-0342
June 8-9, 2022, Mexico City
Overview

• Baerlocher Introduction

• Mechanical Recycling of Polyolefins

• Stabilization Basics

• Considerations using Baerlocher’s T-blends

• Film and blow molding applications

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 and trusted
partner for BAEROPOL solutions
• About 1200 employees worldwide representing
a trusted and reliable partner
• 190 years of experience
 Manufacturing Companies: Countries

Germany Italy I San Morino Brazil USA I & II Korea India

UK Italy II Turkey Peru Argentina China Malaysia
Specialty Additives Products

Baerolub
Calcium Alkali
Coatings Soaps Soaps

Hydrophobe
Baeropol
Lubricants Metal
Soaps
Non
Stabilizers Polymer Zinc Aluminum
Soaps Soaps

Powdered
Metal Rubber Magnesium
RST Soaps

Recycling
VSA
Baerlocher capabilities for mechanical recycling

Sales •Global, Across Different Entry Points

•Aligned with Brand Owners’ Needs
Marketing •Industry engagement (APR, Forums,
webinars)

.
Technical •Tailored Solutions
•Specific Applications
Capabilities •Field Support

Innovation •Incorporating Other Solutions

Mechanical Recycling of
Polyolefins
Basic types of Mechanical Recycling

▪ Circular economy: Taking ▪ Downcycling: Taking ▪ Upcycling: Taking lower

recyclate and reforming higher quality recyclate quality recyclate and
it into an equal value and creating lower value creating higher value
object products products

Symbols from: https://en.wikipedia.org/wiki/Recycling

Sources of Prodegradants and Contamination in PCR and PIR

▪ Analysis of PCR and PIR typically shows that the resin is:
▪ 1 poorly stabilized
▪ 2 is contaminated
▪ Sources of prodegradants and contamination
▪Dirt
▪Former contents of the package
▪Wash water/detergent
▪Incompatible resins (i.e. PVC in HDPE)
▪The age of the resins/exposure to the environment
▪Poor quality resin
▪Multilayer packaging
Effect of Polymer Degradation and Contamination

▪ Color
▪ Taste and Odor
▪ Loss of mechanical properties
▪ Gels
▪ Reduced lifetime
▪ Inconsistent parts and process
▪ Inability to regrind/recycle
Example Cycle for Circular Economy
via Mechanical Recycling

▪ Example of post consumer circular

economy for rigid packaging

▪Other recycle stream vary from the

shown process

▪ Stabilizers can be introduced in these

steps to help improve the recycling
process, to improve resin stability, and
allow the cycle to be more robust

https://plasticsrecycling.org/
Stabilization
 Why do polyolefin properties deteriorate during recycling?

▪ Most polyolefin grades are made for short lived consumer applications and are
thereby 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!
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

Source: Fraunhofer Institute for Structural Durability and System Reliability LBF: www.lbf.fraunhofer.de
 Stabilization of Polyolefins is Complicated

"Stabilization“: Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc. 2002
Thermo-Oxidation Cycle

Heat
Shear Oxygen
Light
Time
Polymer P• POO•
Catalyst Residues
Contaminants Polymer
(in PCR)

PO• •OH
D

POOH Polymer
Standard Stabilization Background

▪ Polymer stabilization is a well-established concept

Secondary AO
• Destroys catalyst • Gives long term
residuals and stability and helps
• Destroys
buffers the polymer hydroperoxides in the
determine the
and thus protects melt that result from lifetime of the resin
antioxidants oxidation and
therefore protects
Antacid the phenol Primary AO
Antacids

▪ Antacids are alkaline additives added to polymers with the purpose of neutralizing acidic
species:
▪Catalyst residues – Ziegler Natta Catalyst in polyolefins
▪Neutralizes acidic contaminants in PCR
▪Protects antioxidants from degradation
▪Help to buffer the polymer to prevent side reactions with antioxidants
Ca(OH)2
CaO
MgO
Mg(OH)2
ZnO
Metal Soap Hydrotalcite Metal Oxides/Hydroxides
Metal Corrosion

▪ Acidic contamination in PCR such as food, unclean wash water, PVC can cause severe damage
to both the resin and tooling equipment

HDPE PCR Properly stabilized

contaminated with HDPE PCR with
fraction of a % PVC antacid

Brass sheet with polymer pressed at 260 C for 90 minutes

Secondary Antioxidants

▪ Secondary Antioxidants react in the melt phase with hydroperoxides to prevent the
formation of free radicals:
▪Elimination of free radicals prevents the initiation of degradation
▪Fewer free radicals prevents the consumption of primary antioxidants
▪ Secondary antioxidants preserve the primary antioxidant to allow for long term
stabilization at room temperature
Primary Antioxidants

▪ Primary Antioxidants react in the solid or melt phase with free radicals to terminate
the degradation cycle:
▪Elimination of free radicals prevents stops degradation
▪Stopped degradation allows for longer shelf life, better color, better odor,
retention of mechanical properties

▪ Primary antioxidants protect the polymer to allow for long term stabilization at
room temperature
Thermo-Oxidation Cycle

Heat
Shear Oxygen
Light
Time
Polymer P• POO•
Catalyst Residues
Contaminants Polymer
(in PCR)

Antacids
PO• •OH Primary AO
D

Secondary AO POOH Polymer

Baeropol T-blends
Baeropol T blends

• Baeropol T-Blends are complete stabilizer

packages with synergistic RST technology, providing
and easy-to-use product that caters to recyclers, Traditional
stabilizer
compounders, and converters blends

Baeropol
T-Blends
Baeropol
RST
Addition of T-Blends to PCR (Melt Stability)

• Unstabilized PCR has poor

stability during multi-pass
extrusion

• When degraded, polyolefins

(HDPE, LLDPE, LDPE, PP) can
experience irreversible changes
to their structure, causing
changes to its melt flow

• Addition of T-Blend stabilizers

result in essentially no change to
melt flow, even after multiple
passes at high temperatures
Addition of T-Blends to PCR (Oxidative Induction Time)

• OIT: indicator of long-term

oxidative stability

• PCR/PIR often insufficiently

stabilized beyond the initial cycle

• Baeropol T-Blends support

oxidative stability over multiple
cycles
Polyolefin applications and PCR

Final Attributes Commercial PCR offering Challenges

application needed offering
Stretch film Toughness (dart, LLDPE/LDPE Avangard 150 Gels can cause
puncture) blends tears
Shrink film Needs orientation LDPE Avangard 100 Clarity, melt fracture
for optimal
shrinkage
Cast film clarity 3 MI LLDPE Die build up

Blow molding Impact and 0.3 – 0.7 MI Envision 9607 – Find PCR with
processability LNO consistent MI
(stable parison)
PP Injection Balance impact Typically, injection Mostly PIR – 3/1 Amount of PP PCR
molding rigidity molding 10-15 or ratio available
25-35 MFR non Typically black Typically mix with
food contact HDPE
 Things to consider when running production trials with T- blends

Definition of trial success What exactly are we trying to improve? Gels? YI? Increase in
productivity?
Baseline/control performance Its critical to use the same lot materials to have a good
baseline
Trial conditions vs control Its key to keep the same processing temperatures of the
different zones
Material needed Output x 0.3% loadings plus at least 20 minutes transition time
Feeding rates Maintain your standard feeding rates, even if torque is lowered.

Processing conditions: temperatures, filters, other Use the same filters than the control.

Equipment considerations Gravimetric feeder preferred, ideal into the throat

PCR Testing on site What are the typical measurements? Density ? MI or MFR?
SDS We will provide documentation
Baeropol RST in Blown Film
Gel Formation and Process Stability

• Degradation causes material to create gels and irregularities

• Oxidized black specks

Degradation
• Side reactions from heat, shear, residues

• Builds up in the recycle stream

Crosslinks • Requires high levels of filtration
and Gels

• Process issues (bubble instability, poor filtration, downtime)

• Poor visual and mechanical properties
Issues • Limits recycle and regrind usage
Gel Semi-Quantification by Melt Filtration on a High Pressure Capillary Rheometer

Melt filter
Measuring nozzle

Measuring nozzle: Ø = 1mm; l = 30mm

Melt filter: 14µm (25µ for industrial recyclate)
Measuring temperature: 265ºC
Shear rate: ca 300 1/s
Effects of Gels/Degradation on Melt Filtration

• Measurements on a high-
pressure capillary rheometer

• Pressure builds up as
contaminants are collected

• Build-up is slow for a virgin

LDPE homopolymer
Effects of Gels/Degradation on Melt Filtration (14 µm filter)

• As resin is put through multiple

extrusion cycles, gels accumulate

• Pressure builds at a faster rate

• Results in poor reprocessability,

increased downtime, and limited
opportunities for recycled resins

Time (sec)
Effects of Gels/Degradation on Melt Filtration (14 µm filter)

Unstabilized w/ Baeropol T-1214

Time (sec) Time (sec)

Gel Prevention in LDPE, LLDPE PCR

• Customer using PCR in shrink, stretch, and

construction film applications

• Baeropol T-1214 reduced gels by over 40% in

LLDPE, 80% in LDPE

• Supplemented the benefits of mechanical

recycling solutions by eliminating hard-to-filter
degradants
Effects of Recycling on HDPE-
Extrusion Blow Molding
Extrusion Blow Molding

▪ This trial examines the effects of introducing Baeropol T-Blends to

HDPE PCR for use in extrusion blow molding applications

▪ Baeropol T-Blends 1111 TX and 1214 TX were compared to a

typical binary antioxidant blend in a reprocessed PCR HDPE
How changes in melt strength affects mechanical & processing properties

▪ Variations in melt flow affect parison sag

Sag, Swell,
Side Change in Process Poor Quality,
Poor Parison
reactions Melt Flow Variation Downtime
Control

“Tear-dropping” results in more flash

Addition of T-Blends to PCR (Melt Stability)

▪ As melt flow is stabilized, processes are more

repeatable

▪ An unstabilized material can result in higher

levels of sag and flash (left) compared to the
same resin stabilized with T-Blends (right)

▪ These changes can negatively affect wall

thickness and mechanical properties
 Changes in Part Weight

▪ As PCR is reused, it is susceptible

to changes in melt flow if not
properly stabilized

▪ Baeropol T-Blends help keep your

recyclate consistent

✓ Protects quality and accuracy

by providing unparalleled
stability

✓ Helps prevent unnecessary

process changes
Part Variation

▪ Changes in melt behavior can have

adverse effects
✓ Warpage
✓ Excess flash

▪ Enhanced stability provided by

Baeropol T-1111 supports part quality
and reproducibility

0.30% Binary Blend 0.30% T-1111 TX

 Improved Product Performance

▪ With Baeropol T-Blends,

there’s no need to
compromise:

✓ Keeps properties
elevated, cycle after
cycle

✓ Outperforms traditional
stabilizer blends
Conclusions
Conclusions

▪ Recycling polyolefins is a growing challenge for North America

▪ Recycling, Downcycling, and Upcycling are all ways to prevent polymers from
becoming waste
▪ Stabilizers can assist with any of these forms of recycling
▪ To properly recycle a resin, the recyclate must be handled properly including:
cleaning, sorting, appropriate extrusion conditions, and adding stabilizers
▪ Stabilizers are only one part of the overall recycling solution
 Your Company
Logo

Baerlocher will use its technical, manufacturing, and market

expertise with additives to preserve polymer properties of
virgin and recycled materials.
These solutions will enable to increase the PCR content and
value, advancing the circular economy.

How can we help?