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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

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.

Ionic Liquids - Next Generation Polyolefin Cocatalysts (Paper)
Peter Hanik, February 2020

The discovery of the first ionic liquid is disputed. The first known ionic liquid may have been ethanolammonium nitrate discovered in 1888 by S. Gabriel and J. Weiner. Ethylammonium nitrate was reported in 1914 by Paul Walden. In the 1970s and 1980s, ionic liquids based on alkyl-substituted imidazolium and pyridinium cations, with halide or tetrahalogenoaluminate anions, were developed. Our recent work has focused on halometallate ionic liquids. This class of ionic liquids has recently seen commercial application in catalysis and as solvents. This paper/presentation will discuss recent developments using halometallate ionic liquids to replace alkyl aluminum compounds in polyolefin catalysis. Our work targeted lower Al:Ti ratios combined with superior coordination with the metal complex to provide an opportunity for increased catalyst activity, molecular weight control, molecular weight distribution control, comonomer incorporation and improved safety. In experiments polymerizing 1-hexene the ionic liquids we developed have shown higher activity and higher molecular weight at the same Al/Ti ratio. In addition, the ionic liquids developed are not pyrophoric and non-volatile. Experiments polymerizing ethylene have shown higher molecular weight and narrower molecular weight distribution at the same Al/Ti ratio. Future work planned for continued development is shared.

Ionic Liquids - Next Generation Polyolefin Cocatalysts (Presentation)
Peter Hanik, February 2020

The discovery of the first ionic liquid is disputed. The first known ionic liquid may have been ethanolammonium nitrate discovered in 1888 by S. Gabriel and J. Weiner. Ethylammonium nitrate was reported in 1914 by Paul Walden. In the 1970s and 1980s, ionic liquids based on alkyl-substituted imidazolium and pyridinium cations, with halide or tetrahalogenoaluminate anions, were developed. Our recent work has focused on halometallate ionic liquids. This class of ionic liquids has recently seen commercial application in catalysis and as solvents. This paper/presentation will discuss recent developments using halometallate ionic liquids to replace alkyl aluminum compounds in polyolefin catalysis. Our work targeted lower Al:Ti ratios combined with superior coordination with the metal complex to provide an opportunity for increased catalyst activity, molecular weight control, molecular weight distribution control, comonomer incorporation and improved safety. In experiments polymerizing 1-hexene the ionic liquids we developed have shown higher activity and higher molecular weight at the same Al/Ti ratio. In addition, the ionic liquids developed are not pyrophoric and non-volatile. Experiments polymerizing ethylene have shown higher molecular weight and narrower molecular weight distribution at the same Al/Ti ratio. Future work planned for continued development is shared.

Recent Advancements in Incorporating Post-consumer Recycled PE for Packaging Applications
Yongchao Zeng, February 2020

Dow is committed to advance the circular economy by delivering innovative solutions to close resource loops in key markets. This presentation showcases how Dow’s leading technologies and new product development can enhance recycled polyethylene utilization. In particular, brand owners of consumer products are calling for sustainable packaging solutions, including the incorporation of post-consumer recycled (PCR) plastics. Polyethylene PCR usually suffers from compromised abuse, aesthetic, and taste & odor properties due to polymer contaminants, inorganic impurities, moisture, and thermal oxidation and degradation products. Creating and opening up the PCR market demand innovative material science solutions to compatibilize, strengthen, and recover the lost performance that is typical with PCR incorporation. We will present Dow’s recent advancements towards the enhancement of polyethylene PCR utilization.

SKGC, Solution Provider for Sustainable and Functional Flexible Multilayer Packaging
Doh-Yeon Park, February 2020

On a global scope, the growth of flexible packaging industry is abundantly cleardue to several drivers including the change of lifestyle, the expansion of E-commerce. Surge in demand for smarter, longer storable, more luxury, and greener flexible packaging requires a bundle of multi-faceted functionalities of polymer materials. SK Global Chemical (SKGC) envisions to be ‘Solution Provider for Sustainable and Functional Flexible Multilayer Packaging’. In this presentation, SKGC’s current and upcoming product portfolio for a comprehensive multilayer packaging structure from coating & structural layer to barrier & seal will be introduced. The continuing efforts for providing technical solutions for meeting customer’s needs will be also discussed.

Are We Ready for EPP’s Expanding Market Based on Rapidly Decreasing EPP Price?
Chul Park, February 2020

The expanded polypropylene (EPP) bead foam market is expanding rapidly because of the decreased EPP prices all over the world starting from China. All the polypropylene (PP) resin manufacturers, the EPP bead manufacturers, the steam chest molders, and the final EPP users are changing their business strategies accordingly. Due to the lowered price of EPP and due to the EPP’s outstanding performance in energy absorption, resilience, fracture strength, durability, chemical resistance, thermal insulation properties, acoustic properties, rigidity, and recyclability/sustainability, numerous new applications of EPP have been developed in various industries. Furthermore, many expandable polystyrene (EPS) products, such as sports helmet and packaging materials, have been actively replaced by the EPP products. Compared to the EPS, the EPP’s performance is much better other than the initial stiffness for the same density products. The EPP’s raw material cost is at least 30% lower than that of the EPS, but the EPP bead’s price used to be 3 times as high as the EPS price because of the earlier patent. After the patent expiration in 2015, many EPP bead manufacturing companies have been supplying quality beads in the market and, therefore, the EPP price has become now less than 2 times of the EPS price. It is expected that the EPP price will converge to the EPS price or even go below because of the expanding EPP supply. However, the EPP products’ outstanding performance and the decreasing EPP price will continue to promote the invention and development of new EPP products, and the EPP market will continue to grow for the next decade. Therefore, despite the decreased EPP price, the EPP business and market will be great because of the increased demand of the EPP products. It appears that the increased EPP resin manufacturers will be a temporary solution to the current changes. Because of the large-volume of the EPP beads, unlike the unexpanded low-volume EPS beads, the transportation cost from the EPP resin manufacturer site to the steam-chest molder site is very high. Consequently, most steam chest molders will locate a micro-pelletizer (an extruder) and an EPP bead foam autoclave at an affordable price. The EPP products’ costs will be decreased and thereby the EPP products’ prices will be decreased. Reliable EPP equipment manufacturers are demanded.

Celanese Ateva® ExtruBond EVA & LDPE Resins for Flexible Packing Applications
Nagarjuna Palyam, February 2020

ExtruBond™ technology is the Celanese latest material innovation for Ethylene Vinyl Acetate (EVA) copolymers and Low Density Polyethylene (LDPE) resins with high adhesion to substrates in the extrusion coating process. Using a laboratory set up designed to model the extrusion coating of EVA onto polymer films, we coated both conventional and high-adhesion EVA copolymers onto corona-treated polyester films, and measured the force required to separate EVA from the substrate. The peel force required to separate the improved EVA from the polyester substrate was approximately six times greater than the peel force measured with conventional EVA. The technology is validated on commercial-scale extrusion coating line as well, where we observed three-fold greater peel force for new EVA material compared to control EVA material. Large increases in adhesion were also recorded when corona-treated films were chemically primed, and the EVA extradite curtain was ozone treated. This innovative material solution delivers not only strong substrate bond strength but also improved line speeds during the extrusion coating process.

Processing-Property Relationships for Polyethylene Blown Films Using Six Factor Statistical Modeling
Mubashir Qamar Ansari, February 2020

The most important target for blown film production is to achieve high throughput without compromising film quality. This is achieved by proper selection of resin, equipment, and fabrication conditions. In this work, the effect of blown film fabrication conditions on mechanical and optical properties of LLDPE and 80/20 LLDPE/LDPE films was studied. Haze, instrument dart impact (IDI), tear (machine and transverse direction) and tensile (machine and cross direction) properties of the films were examined as a function of six processing parameters: frost line height (FLH), die temperature, throughput, film thickness, blow up ratio (BUR), and die gap. Each process condition was varied on two levels to elucidate primary factor effects. This paper discusses which blown film fabrication conditions significantly influence film properties.








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