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The SPE Library contains thousands of papers, presentations, journal briefs and recorded webinars from the best minds in the Plastics Industry. Spanning almost two decades, this collection of published research and development work in polymer science and plastics technology is a wealth of knowledge and information for anyone involved in plastics.

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Conference Proceedings

Influence of Additive Type and Mixing Protocol on the Properties of LDPE-PA6-blends for Films
Christoph Burgstaller, February 2020

Current discussions about the use plastics and the waste generated have generated great interest in plastics recycling. While this question is relatively easy to answer for monomaterials, for multilayer or composite materials there is always the question if this can work. On the other hand, to produce high quality flexible packaging, there is the need for multilayer films to protect the packed food and increase the shelf life. To have a closer look at the recyclability for such multilayer films, we wanted to take a closer look at a simple LDPE-PA6-material to see how the materials properties of this mixture can be improved. Therefore, the aim of this work was to compare the effects of compatibilisation with a pre-fabricated additive and the in-situ generation of a similar additive in the melt for LDPE-PA6-blends and to investigate the effect of mixing protocol (i.e. compounding vs. dry-blending) of the pre-fabricated additive on the resulting properties of reprocessed LDPE-PA6 films. We found, that it is possible to compatibilize LDPE-PA6-blends via the addition of maleic anhydride based compatibilizers, regardless of fabrication approach. This effect can be seen from the morphology of the samples as well as from mechanical properties. Also, the reprocessing of films from LDPE and PA6 with reasonable properties is possible when adding a compatibilizer. The best, i.e. the most balanced properties can be found when the compatibilizer is melt compounded, as this gives the best distribution. These results show that it is possible to reuse multilayer materials when considering the blend components and properly selecting a compatibilizer.

Stabilization of Polymers for a More Circular Economy
Robert Sherman, February 2020

Polyethylene and polypropylene are two of the most easily recycled polymers. Recycling polyolefins can result in downcycling to simple functional polymers, true recycling for reuse in the intended application, or upcycling of the polymer into higher quality products. To take advantage of the available feedstock, and improve its utilization, stabilizers are can be added to allow the polymer to retain its original physical properties. A variety of customer based case studies on recycling and upcycling will be covered showing how additives allow for improvements in the recycle stream.

Antioxidant Solutions for Plastics Recycling
Hartmut Siebert MSc, February 2020

Circular economy and plastics recycling require a Polyolefin stabilization that protects the polymer during the whole cycle in the recycling process. AddWorks LXR 568, Hostanox O310 and Hycite 713 are high performance additives that protects the polymer during processing and heat exposure as well as during the washing step. Antioxidant solutions as AddWorks PKG 906 circle helps the converter and recycler to provide heat and process stability and replenish antioxidants that had been consumed during the recycling process.

New Color Removal Technology for Recycled Polyolefins
Warren Ebenezer, February 2020

The application development labs of SI Group recently invented a highly innovative technology that enables significant reduction in color of discolored polyolefins in industrial or post-consumer recycled streams. This very effective bleach-out phenomena takes place in the polymer melt in a processing extruder upon addition of a new additive system that is a subject to this presentation. The new system is composed of solid-state components and can be fabricated in a powdery form or as a non dusting formulated one-pack. The system does not change the taste and oder properties of polymers and is safe from both the manufacturing and consumer perspective.

Toughness, Stiffness and Transparency Control of PO Containing Nanofibrils (Paper)
Jinchuan Zhao, February 2020

In this paper, we demonstrate how a small amount of nanofibrils can enhance the toughness, stiffness, and transparency of polyolefins. We have studied two different kinds of toughening rubbery nanofibrils and stiffening hard nanofibrils depending on the kind of the material used for the nanofibrils, and we have observed that the properties of the nanofibril composites with these fibers were very different. It was observed that the rubber nanofibrils with ~200 nm diameter and an L/D ratio over 200 well dispersed in the PO matrix exhibited numerous outstanding properties, such as elasticity, ductility, toughness, and impact strength. It is commonly well-known that 15-25% rubber content must be compounded into the polymer matrix, to induce brittle-to-ductile transition. But with nanofibril rubbers, only 1% was needed to achieve the brittle-to-ductile transition. These results indicate that the dispersed rubber nanofibrils are much more effective than the conventional spherical rubbery phases in toughening of polyolefins. This has another significant implication that the ductility can be improved without any sacrifice to the stiffness, unlike the case of using a large amount of rubber over 15%. In other words, the toughening of polyolefins can be achieved with less than 1% nanofibril rubber without losing the stiffness. The increased stiffness with added nanofibrils was also studied. When PET or PBT nanofibrils were added in the PO matrix, the nanofibril composites exhibited a much higher stiffness. Unlike the case of using a brittle matrix such as PS or PLA, the increase in the ductility-related properties was marginal in the relatively ductile matrix such as PP or PE. The transparency change of PO materials with included nanofibrils was also studied. Like in the case of Sorbitol, the added nanofibrils decreased the crystal size significantly, to make the PO materials more transparent. But when the nanofiber content was large, then the transparency was decreased because of the large number of nanofibrils. As the nanofibril content decreased, the transparency was significantly improved.

Toughness, Stiffness and Transparency Control of PO Containing Nanofibrils (Presentation)
Jinchuan Zhao, February 2020

In this paper, we demonstrate how a small amount of nanofibrils can enhance the toughness, stiffness, and transparency of polyolefins. We have studied two different kinds of toughening rubbery nanofibrils and stiffening hard nanofibrils depending on the kind of the material used for the nanofibrils, and we have observed that the properties of the nanofibril composites with these fibers were very different. It was observed that the rubber nanofibrils with ~200 nm diameter and an L/D ratio over 200 well dispersed in the PO matrix exhibited numerous outstanding properties, such as elasticity, ductility, toughness, and impact strength. It is commonly well-known that 15-25% rubber content must be compounded into the polymer matrix, to induce brittle-to-ductile transition. But with nanofibril rubbers, only 1% was needed to achieve the brittle-to-ductile transition. These results indicate that the dispersed rubber nanofibrils are much more effective than the conventional spherical rubbery phases in toughening of polyolefins. This has another significant implication that the ductility can be improved without any sacrifice to the stiffness, unlike the case of using a large amount of rubber over 15%. In other words, the toughening of polyolefins can be achieved with less than 1% nanofibril rubber without losing the stiffness. The increased stiffness with added nanofibrils was also studied. When PET or PBT nanofibrils were added in the PO matrix, the nanofibril composites exhibited a much higher stiffness. Unlike the case of using a brittle matrix such as PS or PLA, the increase in the ductility-related properties was marginal in the relatively ductile matrix such as PP or PE. The transparency change of PO materials with included nanofibrils was also studied. Like in the case of Sorbitol, the added nanofibrils decreased the crystal size significantly, to make the PO materials more transparent. But when the nanofiber content was large, then the transparency was decreased because of the large number of nanofibrils. As the nanofibril content decreased, the transparency was significantly improved.

Improved Polypropylene Stabilization with New Catalyst Neutralizers
Donald Beuke, February 2020

For many decades’ metallic oxides, metallic stearates have been used to scavenge acids from the 1st – 4th generation TiCl4 catalysts spanning 1955-1995. Metallic oxides and stearates form Lewis Acids which reduce antioxidant efficiency resulting in polymer degradation. New line of Stabiace hydrotalcites improve oxidation stability of polypropylene proven by OIT, MFR and tensile properties. Mitsui’s trade secret ZR Series provides same performance of Stabiace HT with addition of much less color and further reduction in PP oxidation proven by FTIR. Three polypropylene take-a ways: 1. Quality: New Stabiace HT improves the oxidation stability and physical properties. 2. Quality + Performance: Mitsui ZR Series no yellow color and 50-60% increase in antioxidant retention, increased OIT and up to 80 % less polyolefin degradation per FTIR analysis from 1-5 extruder passes at 250c. 3. Recycle and sustainability: Because the PP has much less multi-pass extruder oxidation; quality, recyclability, sustainability, odor and VOC reduction may be improved.

Deformulation & Failure Analysis of Apparently Similar Polymers Using Multiple Modes of Pyrolysis-GC (Paper)
Rojin Belganeh, February 2020

Polymeric products are often complex and frequently include components from several sources and suppliers. The formulation details of the polymer parts are often not known to the manufacturer. Companies in later stages in the supply chain may have even less information on components in the final formulations. Therefore, the same part number at a point in the supply chain can result in a polymer part that is not made with the same formulation, yet the apparent polymer properties may seem to be equivalent. After usage by a company or customer, a failure analysis may be required to determine the chemical details of the item. In this work, Pyrolysis-GC/MS is used in multiple modes to characterize a set of polymer parts that seem approximately similar. The results reveal significant differences in chemical composition. Similar results can be used to monitor the chemistry and part quality at the manufacturing point in the supply chain to reduce future variability in parts failure. After usage, the same techniques can be used to understand the chemistry differences and the possible reasons for the failure. This presentation demonstrates the capabilities of the Pyrolysis technique with Gas Chromatography-Mass Spectrometry. Multiple pyrolyzer modes, such as Evolved Gas Analysis (EGA), flash Pyrolysis, and Heart Cutting (HC) analyses will be performed to characterize the differences between the rubber samples.

Deformulation & Failure Analysis of Apparently Similar Polymers Using Multiple Modes of Pyrolysis-GC (Presentation)
Rojin Belganeh, February 2020

Polymeric products are often complex and frequently include components from several sources and suppliers. The formulation details of the polymer parts are often not known to the manufacturer. Companies in later stages in the supply chain may have even less information on components in the final formulations. Therefore, the same part number at a point in the supply chain can result in a polymer part that is not made with the same formulation, yet the apparent polymer properties may seem to be equivalent. After usage by a company or customer, a failure analysis may be required to determine the chemical details of the item. In this work, Pyrolysis-GC/MS is used in multiple modes to characterize a set of polymer parts that seem approximately similar. The results reveal significant differences in chemical composition. Similar results can be used to monitor the chemistry and part quality at the manufacturing point in the supply chain to reduce future variability in parts failure. After usage, the same techniques can be used to understand the chemistry differences and the possible reasons for the failure. This presentation demonstrates the capabilities of the Pyrolysis technique with Gas Chromatography-Mass Spectrometry. Multiple pyrolyzer modes, such as Evolved Gas Analysis (EGA), flash Pyrolysis, and Heart Cutting (HC) analyses will be performed to characterize the differences between the rubber samples.

Novel Methylated and N-Alkoxy Hindered Amine Stabilizers For Polyolefins
Rob Lorenzini, February 2020

Herein, two novel hindered amine stabilizers (HAS) are formally introduced to the North American Polyolefin market. The first, a methylated oligomeric HAS, is demonstrated in the artificial and natural weathering, as well as long-term heat aging, of various polyolefin films and thin sections. Particular attention is paid to data generated in the presence of acidic species and pesticides, showing how methylated HAS resist deactivation and therefore improve polyolefin article service lives better than their more basic N-H HAS analogues. The second, an oligomeric n-alkoxy HALS, shows clear performance benefits in the presence of acidic species over methylated HALS. These two materials are recommended for use in plasticulture, artificial turf, and halogenated flame retardant applications, among others.

Using Polymer Stabilizers to Accelerate Plastics into a Sustainable and Circular Economy (Paper)
Danielle Neu, February 2020

Today, various plastics utilized in single-use and disposable applications generate significant amount of wastes which negatively impact the environment. By applying proper technologies, however, these plastics can be repurposed to reduce their environmental footprint and impact on society. Additionally, providing plastics with a second long term life can positively contribute to the circular economy. This paper will discuss how polymer stabilizer technology and application can be used to enable the recycling and repurposing of polyolefins by maintaining their desirable properties.

Using Polymer Stabilizers to Accelerate Plastics into a Sustainable and Circular Economy (Presentation)
Danielle Neu, February 2020

Today, various plastics utilized in single-use and disposable applications generate significant amount of wastes which negatively impact the environment. By applying proper technologies, however, these plastics can be repurposed to reduce their environmental footprint and impact on society. Additionally, providing plastics with a second long term life can positively contribute to the circular economy. This paper will discuss how polymer stabilizer technology and application can be used to enable the recycling and repurposing of polyolefins by maintaining their desirable properties.

The Importance of Chemical Stabilization in Recycled Material for Corrugated and Conduit Polyolefin
Ian Query, February 2020

Much attention has been given to stabilization packages for polyolefin pressure pipes over the past couple decades, however corrugated and conduit pipes have generally been ignored with respect to more robust stabilization packages. Certain groups such as the Florida Department of Transportation and the American Association of State Highway and Transportation Officials (AASHTO) have set rules establishing oxidative resistance in HDPE corrugated pipes, but few others have followed this example. A discussion of the simplicity and importance of pipe resin stabilization as well as examples from stabilized pipes will be covered.

The Importance of Chemical Stabilization in Recycled Material for Corrugated and Conduit Polyolefin
Ian Query, February 2020

Much attention has been given to stabilization packages for polyolefin pressure pipes over the past couple decades, however corrugated and conduit pipes have generally been ignored with respect to more robust stabilization packages. Certain groups such as the Florida Department of Transportation and the American Association of State Highway and Transportation Officials (AASHTO) have set rules establishing oxidative resistance in HDPE corrugated pipes, but few others have followed this example. A discussion of the simplicity and importance of pipe resin stabilization as well as examples from stabilized pipes will be covered.

LyondellBasell Advancing Catalyst Technology and Sustainability
Stephen Davis, February 2020

Use of plastics and particularly polyolefins is increasing rapidly globally due to their low environmental footprint, their versatility and durability, and competitiveness in use cost. The polyolefin industry is continuously evolving in response to global megatrends of population and environment, particularly in response to regulatory and consumer preferences regarding reduction of single-use plastics. In this presentation we will provide an update regarding polyolefin markets, a view regarding sustainability trends in polyolefin applications, and recent developments in the area of catalysts for PP which are improving product performance and plant operations. Innovation in process design and catalysis, combined with operational excellence, is driving LyondellBasell's unique technology portfolio to deliver differential performance, creating value for the user and positioning them for long term success in response to a constantly changing environment.

2-PHENYL INDOLE.TiCl3. A Modifier and a Propylene Polymerization Catalyst (Paper)
Gregory Arzoumanidis, February 2020

Several nitrogen-containing ligands have been tested as internal modifiers of the Amoco CD commercial catalyst for propylene polymerization, among them 2-phenyl indole. The ligand forms an indolenine complex with TiCl4 at room temp. with a hydrogen and a double bond migration, from the 2-3 to the 1-2 position of the indole framework. Chemical and analytical evidence indicates that the Indolenine.TiCl4 complex coordinates exclusively on the 110 lateral cut of MgCl2, which has two open coordination sites on each Mg (1). During catalyst activation at above 105oC the complex undergoes ortho-metallation (2). To our knowledge, this is the first example so far in Ziegler-Natta catalysis of an organometallic complex, (a polymerization catalyst itself), coordinating on the MgCl2 support. Reaction with Et3Al (3) reduces the titanium to Ti(III) and the double bond migrades back to the 2-3 position. Titanium looses all the chlorides with formation of a single Ti-Et bond. The organotitanium complex occupies now only a single coordination site on Mg. The second coordination site on this Mg atom becomes now available for additional TiCl4 coordination! Indeed, fresh TiCl4 attaches on the newly created vacant coordination sites (4) boosting substantially catalyst activity (up to 100%, especially in the gas phase), with retention or even improvement of polymer extractables. There are now two types of active sites on the catalyst system: a. Originating from the complex, and b. From the TiCl4. Both polymerization sites are activated with Et3Al. These transformations occur only on the 110 lateral cut of MgCl2, which constitutes about 15% of the total surface area. The other 85% is represented by the 106 cut, which may be occupied by standard modifiers (phthalates, diethers, succinates, etc.), and by TiCl4 dimers or oligomers.

2-PHENYL INDOLE.TiCl3. A Modifier and a Propylene Polymerization Catalyst (Presentation)
Gregory Arzoumanidis, February 2020

Several nitrogen-containing ligands have been tested as internal modifiers of the Amoco CD commercial catalyst for propylene polymerization, among them 2-phenyl indole. The ligand forms an indolenine complex with TiCl4 at room temp. with a hydrogen and a double bond migration, from the 2-3 to the 1-2 position of the indole framework. Chemical and analytical evidence indicates that the Indolenine.TiCl4 complex coordinates exclusively on the 110 lateral cut of MgCl2, which has two open coordination sites on each Mg (1). During catalyst activation at above 105oC the complex undergoes ortho-metallation (2). To our knowledge, this is the first example so far in Ziegler-Natta catalysis of an organometallic complex, (a polymerization catalyst itself), coordinating on the MgCl2 support. Reaction with Et3Al (3) reduces the titanium to Ti(III) and the double bond migrades back to the 2-3 position. Titanium looses all the chlorides with formation of a single Ti-Et bond. The organotitanium complex occupies now only a single coordination site on Mg. The second coordination site on this Mg atom becomes now available for additional TiCl4 coordination! Indeed, fresh TiCl4 attaches on the newly created vacant coordination sites (4) boosting substantially catalyst activity (up to 100%, especially in the gas phase), with retention or even improvement of polymer extractables. There are now two types of active sites on the catalyst system: a. Originating from the complex, and b. From the TiCl4. Both polymerization sites are activated with Et3Al. These transformations occur only on the 110 lateral cut of MgCl2, which constitutes about 15% of the total surface area. The other 85% is represented by the 106 cut, which may be occupied by standard modifiers (phthalates, diethers, succinates, etc.), and by TiCl4 dimers or oligomers.

Automated High Throughput in Silico Reaction Screening for Design of Enhanced Reactivity (Paper)
Thomas Mustard, February 2020

First-principles simulation has become a reliable tool for the prediction of structures, chemical mechanisms, and reaction energetics for the fundamental steps in homogeneous catalysis. Details of reaction coordinates for competing pathways can be elucidated to provide the fundamental understanding of observed catalytic activity, selectivity, and specificity. Such predictive capability raises the possibility for computational discovery and design of new single-site catalysts with enhanced properties. Unfortunately, this is an arduous process that requires meticulous maintenance, specialized training, and accounting of hundreds of files and properties. To democratize the fundamental understanding, design, and discovery of novel catalysts, an automated reaction workflow has been developed. This suite of tools, with minimal user input, automates catalyst enumeration, reaction coordinate mapping, ab initio computation of ground and transition states, and property calculations. Being agnostic to the chemistry of interest, several homogeneous catalysis examples are presented.

Automated High Throughput in Silico Reaction Screening for Design of Enhanced Reactivity (Presentation)
Thomas Mustard, February 2020

First-principles simulation has become a reliable tool for the prediction of structures, chemical mechanisms, and reaction energetics for the fundamental steps in homogeneous catalysis. Details of reaction coordinates for competing pathways can be elucidated to provide the fundamental understanding of observed catalytic activity, selectivity, and specificity. Such predictive capability raises the possibility for computational discovery and design of new single-site catalysts with enhanced properties. Unfortunately, this is an arduous process that requires meticulous maintenance, specialized training, and accounting of hundreds of files and properties. To democratize the fundamental understanding, design, and discovery of novel catalysts, an automated reaction workflow has been developed. This suite of tools, with minimal user input, automates catalyst enumeration, reaction coordinate mapping, ab initio computation of ground and transition states, and property calculations. Being agnostic to the chemistry of interest, several homogeneous catalysis examples are presented.

Polypropylene Catalyst and Process Technology- Advancing Sustainability
Amaia Montoya, February 2020

Grace as an independent catalyst producer and UNIPOL® Polypropylene Process Technology licensor is committed to bring to market innovations that address current and future polyolefins products and PP process needs and to advance societal sustainability goals. Polypropylene catalysts that enable advanced products are of key importance to deliver environmentally friendly solutions across applications. This paper showcases how catalyst innovation is enabling PP product sustainability in areas such as interpolymer substitution and application development.










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