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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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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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
In 2017, the Montgomery County Food Bank (MCFB) and Dow partnered to create the Produce Rescue Center. The MCFB supports 65+ partner agencies in Montgomery County, TX. The Produce Rescue Center seeks to increase the amount of fresh produce that reaches people in need serviced through the partner agencies. In this presentation we will highlight the impact and accomplishments from the Produce Rescue Center and the role plastic packaging plays in this success. We will also discuss next steps for the project to complete a circular economy model for plastics packaging.
Thermoplastic elastomers (TPEs) are widely used in electronics, clothing, adhesives and automotive components due to their high processability and flexibility. ABA triblock copolymers, in which A represents glassy endblocks and B the rubbery midblock, are commercially available TPEs. The most commonly used triblock copolymer TPEs contain glassy polystyrene endblocks and rubbery polydiene midblocks. However, commercial TPEs are derived from petroleum. The manufacturing and disposal of petroleum-derived products have undesired environmental impacts, which promotes development of TPEs from sustainable sources. Vegetable oils and their fatty acid derivatives are attractive alternatives to petroleum due to their abundancy and low cost. Our group has previously reported replacing polydienes in commercial TPEs with sustainable polyacrylates derived from fatty acids. However, polymers with bulky constituents, such as the long alkyl side-chains of fatty acid-derived polymers, typically exhibit poor mechanical performance due to lack of entanglements in the rubbery matrix. To improve the mechanical properties, a transient network was incorporated into the fatty-acid derived midblock through hydrogen bonding. Specifically, triblock copolymers containing polystyrene endblocks and a midblock composed of a random copolymer of poly(lauryl acrylate) (derived from lauric acid) and acrylamide (which undergoes hydrogen bonding) were synthesized. Quantitative FTIR analysis confirmed the formation of a transient network. The polymers exhibits disordered spherical morphologies, desirable for application as TPEs. Rheological measurement revealed the order-disorder transition temperature reduced with increasing acrylamide content, beneficial for high temperature melting process. Importantly, triblock copolymers with hydrogen bonding in the matrix exhibited significantly higher modulus, strain at break, and tensile strength as compared to comparable polymers in the absence of hydrogen bonding.
The global production and use of plastics (especially polyolefins) continues to grow and is expected to double to nearly 800 million metric tons per year by 2040. The use of plastics has resulted in convenience and reduced overall energy consumption, though we are also beginning to recognize challenges due to the mismanagement of plastic waste. Public concern over issues such as ocean plastics, along with the emergence of the concept of the circular economy, has resulted in commitments by some consumer packaged goods (CPG) companies to use recyclable packaging and to use more recycled plastic in their packaging. Mechanical recycling is an established approach that provides an opportunity to better manage waste plastics by creating value from otherwise worthless waste. The increasing demand for recycled content should increase the recycled plastic price further, resulting in an increase in the global plastics recycling rate from the current level of approximately 12%. We will provide an overview of mechanical recycling technologies while also highlighting some of the technical limitations that prevent immediate widespread incorporation of recycled polyolefins into new packaging and other high value products. We will also discuss potential approaches to overcoming these technical challenges and the role of the REMADE Institute in these developments. In addition, we will discuss how mechanical recycling will be a critical first step in many of the chemical recycling approaches that are beginning to emerge.
The global production and use of plastics (especially polyolefins) continues to grow and is expected to double to nearly 800 million metric tons per year by 2040. The use of plastics has resulted in convenience and reduced overall energy consumption, though we are also beginning to recognize challenges due to the mismanagement of plastic waste. Public concern over issues such as ocean plastics, along with the emergence of the concept of the circular economy, has resulted in commitments by some consumer packaged goods (CPG) companies to use recyclable packaging and to use more recycled plastic in their packaging. Mechanical recycling is an established approach that provides an opportunity to better manage waste plastics by creating value from otherwise worthless waste. The increasing demand for recycled content should increase the recycled plastic price further, resulting in an increase in the global plastics recycling rate from the current level of approximately 12%. We will provide an overview of mechanical recycling technologies while also highlighting some of the technical limitations that prevent immediate widespread incorporation of recycled polyolefins into new packaging and other high value products. We will also discuss potential approaches to overcoming these technical challenges and the role of the REMADE Institute in these developments. In addition, we will discuss how mechanical recycling will be a critical first step in many of the chemical recycling approaches that are beginning to emerge.
Major environmental challenges associated with petrochemical plastics need to be addressed via a) reduction of environmental contamination through enhanced recyclability at the end of service life and b) the supply of low cost renewable feedstock for plastics production. In particular, there is a large need for innovative plastics that are readily recyclable to lower environmental hazards and the renewable feedstocks for these plastics must be made widely and cheaply available. We have developed two aspects of advances to enable widespread production of such innovative plastics. On one front, we will develop various pretreatment, fractionation and metabolic engineering technologies to enable the efficient conversion of lignocellulosic biomass or lignin waste to PHA for bioplastics. On the other front, we have tailored lignin chemistry and designed lignin-based composite material both with enhanced performance and with controlled degradability at the end of service time. These innovative technologies produce desirable lignin-based plastics in the context of biorefinery design, in a manner that adds value for a lignocellulosic biorefinery. The overall impact could significantly enhance environmental sustainability by replacing the non-degradable plastics and enabling lignocellulosic bioproduction.
Polymerization reaction engineering (PRE) combines fundamentals of chemical engineering (transport phenomena, reaction engineering, and thermodynamics) and polymer science (chemistry, physics, and characterization) to create mathematical models that describe polymerization reactors from micro- to macroscale under different polymerization mechanisms and conditions. This powerful integrated approach helps scale up experimental results from laboratory to pilot plant, and finally to industrial scale. PRE is also essential to optimize the operation of existing reactors and design new polymerization processes. Polyolefins are made with comonomers that contain only carbon and hydrogen atoms. Their simplicity, however, is only apparent. Polyolefins have a wide range of applications (domestic appliances, automotive and aeronautical parts, and biomedical devices, just to mention a few) because their simple monomers (ethylene, propylene, 1-butene, 1-hexene, and 1-octene) can be combined in numerous ways to produce polymers with a variety of microstructures that give rise to their versatile properties. From a product development point of view, polyolefin microstructure is influenced by complex phenomena that takes place during the polymerization at different scales in the reactor, which is the realm of PRE technology. Olefin polymerization processes are among the most complex in the polymer industry. They require catalysts of different types, employ several reactor configurations, and comprise phenomena that range from microscale (polymerization kinetics at the active sites) to meso- (inter- and intraparticle mass and heat transfer resistances, and thermodynamic equilibrium), and macroscale (reactor residence time distribution, fluid dynamics, and thermodynamic equilibrium). All these phenomena combine to determine the microstructure, and consequently the application properties, of polyolefins. In this presentation, I will show how the integrated, multi-scale approach provided by the PRE approach can be used to understand polyolefins made in variety of processes and catalyst types.
The details of two complimentary patent pending inventions are described along with the actions taken to reduce them both to practice. A new modular disk die that uses very thin disks incorporating a doubly opposed melt distribution system capable of up to about 160 nano-layers using up to 12 different materials has been made. Included with the die is a new “dry” water quench system that has made blown film from a die with high clarity and sparkle without the usual cascading water mess. This system was tested successfully for downward blown film with a partial scale up for upward blown film. Further work is now taking place with both inventions to bring them both to commercial reality.
The details of two complimentary patent pending inventions are described along with the actions taken to reduce them both to practice. A new modular disk die that uses very thin disks incorporating a doubly opposed melt distribution system capable of up to about 160 nano-layers using up to 12 different materials has been made. Included with the die is a new “dry” water quench system that has made blown film from a die with high clarity and sparkle without the usual cascading water mess. This system was tested successfully for downward blown film with a partial scale up for upward blown film. Further work is now taking place with both inventions to bring them both to commercial reality.
Sulzer Chemtech is a product division of Sulzer, headquartered in Winterthur, Switzerland, and is active in the field of process engineering. Since several decades is active in the development and supply of process solutions for mixing, reaction, devolatilization and upgrading for different polymers. One of the key technologies from Sulzer in the polymer field is the, so call, DEVO, a devolatilization/degassing technology able to remove unreacted monomer, solvent or impurities from a polymer stream. In the recent years, Sulzer develop devolatization technology applications in the fields of polyolefins. When devolatilizing residual monomers, solvents or impurities, technologies based on static mixing may offer several potential. First of all, Devolatilization it determines polymer quality, applicability and value, moreover Sulzer technology, exhibiting low shear, gentle heating, optimized volume usage and absence of heavy rotating equipment, significant energy savings may be realized while maintaining or even improving product quality. Additionally, maintenance costs are typically lower as well. The Sulzer Polymer technology are presented with focus on the different aspects of the devolatilization technology. Polyolefins based case studies are discussed and each case that bring to an industrial application is analyzed starting from the experimental work carried out on pilot scale were Sulzer verify the technology on the customer material in the R&D test center in Switzerland.
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