Tacticity, Regio and Stereoregularity

Talarico, Giovanni; Rosa, Claudio De; Auriemma, Finizia

doi:10.1007/978-3-030-12903-3_1

Cited by 6 publications

(4 citation statements)

References 119 publications

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“…The α‐olefins polymerization catalyzed by transition metals (TM) is an extraordinary catalytic process characterized by three main facets: stereoselectivity, 1–3 regioselectivity, 4,5 and the propagation/termination reaction rates 6–8 …”

Section: Introductionmentioning

confidence: 99%

Predicting the propene stereoselectivity on transition metal catalysts: A daunting task for density functional theory

D'Anania,

Romano,

Barone

et al. 2024

J Comput Chem

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Thanks to recent developments in hardware and software, quantum chemical methods are increasingly used for interpreting the complex mechanisms underlying polymerization reaction by homogeneous catalysis. Unfortunately, the dimensions of even the smallest realistic models are too large to permit the use of state‐of‐the‐art composite wave function methods. Under these circumstances, density functional theory still offers the best compromise between cost and accuracy. However, comprehensive benchmarks of different functionals are not yet available for this important research field. The main aim of the present paper is to fill this gap by performing an unbiased comparison of several density functionals and continuum solvent models for the stereo‐control in the propylene polymerization on prototypical catalysts inducing different reaction mechanisms. While it was not possible to define a unique computational protocol providing the best results in all the situations, the B3PW91 functional in conjunction with D3 empirical dispersions and the solvent model density solvent model performs remarkably well for three out of the four investigated catalysts. Under such circumstances, it is recommended to compare the results delivered by different models when approaching additional classes of catalysts.

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Section: Introductionmentioning

confidence: 99%

Predicting the propene stereoselectivity on transition metal catalysts: A daunting task for density functional theory

D'Anania,

Romano,

Barone

et al. 2024

J Comput Chem

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“…Polyolefins can be regarded as the most important class of polymeric materials produced by industries, accounting for more than half of the total weight of the globally produced polymers ( Olabisi, 2016 ; Sauter et al, 2017 ; Talarico et al, 2019 ). Indeed, they are well-suited for a broad spectrum of applications that cover practically every aspect of our everyday lives ( Hutley and Ouederni, 2016 ).…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights on 1-butene polymerization catalyzed by homogeneous single-site catalysts: a DFT computational study

D’Anania,

De Rosa,

Talarico

2024

Front. Chem.

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Isotactic poly (1-butene) (iPB) is an interesting semi-crystalline thermoplastic material characterized by notable physical and mechanical attributes encompassing superior creep and stress resistance, elevated toughness, stiffness, and thermal endurance. These distinctive features position iPB as a viable candidate for specific applications; however, its widespread utilization is hindered by certain inherent limitations. Indeed, iPB manifests an intricate polymorphic behavior, and the gradual and spontaneous transition of the kinetically favored form II to the thermodynamically favored form I during aging introduces alterations to the material’s properties. Despite its potential, the attainment of iPB with an exceedingly high molecular mass remains elusive, particularly when employing homogeneous catalysts renowned for their efficacy in propene polymerization. In this study we analyze the mechanistic aspects governing 1-butene polymerization by using DFT calculations modelling the regioselectivity of 1-butene insertions and the termination reactions occurring after primary (1,2) and secondary (2,1) insertions. Finally, the isomerization pathways leading to the formation of 4,1 units in iPB samples synthesized by homogenous catalysts is also discussed. All these aspects, furnish a mechanistic picture of the main drawbacks of an “old” but still interesting material.

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“…Polypropylene (PP) stands out as the foremost commodity plastic globally, commanding an annual market value exceeding $100 billion. Its widespread use is attributed to remarkable mechanical strength, excellent chemical resistance, and facile processability, making it indispensable in diverse sectors such as packaging, household goods, medical devices, and automotive industries [ 1 , 2 , 3 ]. Despite its pivotal role, PP, derived entirely from non-degradable petroleum, raises environmental concerns due to its persistent nature.…”

Section: Introductionmentioning

confidence: 99%

Enhancing Mechanical Performance of High-Lignin-Filled Polypropylene via Reactive Extrusion

Wang,

You,

et al. 2024

Polymers

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Polypropylene (PP) is one of the most extensively used commodity plastics. In terms of eco-friendliness, it is worth considering preparing high-lignin-filled PP. This study explores the incorporation of high lignin content, derived from acetic acid lignin (AAL) and Kraft lignin (KL), into PP through twin-screw extrusion and injection molding. The challenge lies in maintaining mechanical performance. A compatibilizer—specifically, maleic anhydride-grafted polypropylene (MAPP)—is employed to enhance lignin–PP compatibility by chemically bonding with lignin and physically associating with the PP phase. Results indicate that KL maintains better dispersity than AAL. Compatibilizers with a high maleic anhydride (MA) level (≥0.8 wt.%) and moderate melt flow index (MFI) in the range of 60–100 g 10 min⁻¹ prove favorable in constructing a reinforced PP/KL network. Optimizing with 40 wt.% lignin content and 10 parts per hundred (pph) of compatibilizer yields blends with mechanical performance comparable to neat PP, exhibiting a notable increase in modulus and heat deflection temperature (HDT). Furthermore, utilizing PP/lignin blends can lead to a 20% reduction in expenses and approximately 40% reduction in PP-induced greenhouse gas (GHG) emissions. This approach not only reduces PP costs but also adds value to lignin utilization in a sustainable and cost-effective manner.

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Tacticity, Regio and Stereoregularity

Cited by 6 publications

References 119 publications

Predicting the propene stereoselectivity on transition metal catalysts: A daunting task for density functional theory

Predicting the propene stereoselectivity on transition metal catalysts: A daunting task for density functional theory

Mechanistic insights on 1-butene polymerization catalyzed by homogeneous single-site catalysts: a DFT computational study

Enhancing Mechanical Performance of High-Lignin-Filled Polypropylene via Reactive Extrusion

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