Ethylene–Styrene Copolymers

Viscoelastic, Mechanical, and Glasstomeric Properties of Precision Polyolefins Containing a Phenyl Branch at Every Five Carbons

“…Although styrene (S) polymerizes readily through most chain-growth strategies, it is challenging to copolymerize with other prominent olefin monomers, such as ethylene (E), due to the high discrepancy in comonomer reactivity . Ethylene–styrene (ES) copolymers have historically garnered interest due to the large range of material properties possible from combining two ubiquitous yet markedly different homopolymers. − Although traditional Ziegler–Natta catalysts were unsuccessful at ES copolymerizations, the advent of metallocene single-site or molecular catalysts successfully made ES copolymers with varying degrees of control. − The reactivity difference of E and S still presents challenges with homopolymer formation, nonuniform comonomer distribution, necessity for high S content in the feed, and the well-defined yet often complex catalyst systems. In the late 1990s, the Dow Chemical Company patented INSITE technology, which are constrained-geometry catalysts that allowed for superior control over a variety of E copolymerizations, even with S. ,,− The coined ES Interpolymers (ESIs) were introduced with a broad distribution of E and S composition fidelity and a multitude of potential applications.…”

“…Ethylene–styrene (ES) copolymers have historically garnered interest due to the large range of material properties possible from combining two ubiquitous yet markedly different homopolymers. − Although traditional Ziegler–Natta catalysts were unsuccessful at ES copolymerizations, the advent of metallocene single-site or molecular catalysts successfully made ES copolymers with varying degrees of control. − The reactivity difference of E and S still presents challenges with homopolymer formation, nonuniform comonomer distribution, necessity for high S content in the feed, and the well-defined yet often complex catalyst systems. In the late 1990s, the Dow Chemical Company patented INSITE technology, which are constrained-geometry catalysts that allowed for superior control over a variety of E copolymerizations, even with S. ,,− The coined ES Interpolymers (ESIs) were introduced with a broad distribution of E and S composition fidelity and a multitude of potential applications. Varying the S composition allowed for a wide range of tunable polymer properties such as glass transition temperature ( T g ), melting behavior, tensile properties, and dynamic mechanical response in addition to many other thorough investigations pioneered by Hiltner and Baer in collaboration with the Dow Chemical Company. ,,− General trends in material properties were elucidated as the incorporation of S within the ESIs increased.…”

“…In the late 1990s, the Dow Chemical Company patented INSITE technology, which are constrained-geometry catalysts that allowed for superior control over a variety of E copolymerizations, even with S. ,,− The coined ES Interpolymers (ESIs) were introduced with a broad distribution of E and S composition fidelity and a multitude of potential applications. Varying the S composition allowed for a wide range of tunable polymer properties such as glass transition temperature ( T g ), melting behavior, tensile properties, and dynamic mechanical response in addition to many other thorough investigations pioneered by Hiltner and Baer in collaboration with the Dow Chemical Company. ,,− General trends in material properties were elucidated as the incorporation of S within the ESIs increased. For example, crystallinity is sequestered once the S content exceeds ∼42% w/w S. As the S content is further increased above ∼42% w/w, the T g value of the ESI also gradually increases and reaches ambient values (∼25 °C) at ∼70% w/w S .…”

“…Varying the S composition allowed for a wide range of tunable polymer properties such as glass transition temperature ( T g ), melting behavior, tensile properties, and dynamic mechanical response in addition to many other thorough investigations pioneered by Hiltner and Baer in collaboration with the Dow Chemical Company. ,,− General trends in material properties were elucidated as the incorporation of S within the ESIs increased. For example, crystallinity is sequestered once the S content exceeds ∼42% w/w S. As the S content is further increased above ∼42% w/w, the T g value of the ESI also gradually increases and reaches ambient values (∼25 °C) at ∼70% w/w S . ESIs with this high level of S content (termed “Type S”) were coined with the name “glasstomers” due to their unique strain rate sensitivity.…”

Copolymerization of Ethene with Styrene Derivatives, Vinyl Ketone, and Vinylcyclohexane Using a (Phosphine−sulfonate)palladium(II) System: Unusual Functionality and Solvent Tolerance

“…The copolymers of ethene with styrene are of great current interest because of their anticipated high viscoelasticity, compatibility with other commodity polymers, and excellent mechanical properties. , Early transition-metal-based systems are known to catalyze this copolymerization, but these cannot tolerate an oxygen functionality on the styrenic monomer and protic solvents cannot be employed for the reaction. , Late-transition-metal polymerization systems are known for the polymerization of some monomers with oxygen functionalities. , However, few – have been shown to be effective for copolymerization of ethene with styrene; insertion of styrene typically leads to chain termination through β-H elimination. Herein, we describe the first well-defined system for the copolymerization of ethene with a variety of styrene derivatives, including those with oxygen functionalities.…”