A Novel Ziegler–Natta-Type Catalytic System—TiCl4/2,2′-Dimethoxy-1,1′-Binaphthalene/Et3Al2Cl3/Bu2Mg for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solvent-Free Processing

Серенко, О. А.; Бузин, М. И.; Тuskaev, Vladislav А.; Гагиева, С. Ч.; Kolosov, Nikolay A.; Kurmaev, Dmitrii A.; Savel’eva, T. F.; Golubev, Evgenii K.; Zubkevich, Sergey V.; Васильев, В. Г.; Никифорова, Г. Г.; Korlyukov, Alexander A.; Булычев, Б. М.

doi:10.3390/polym10111281

Cited by 8 publications

(7 citation statements)

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“…These values are equal to the ultimate mechanical properties reported by using a homogeneous Cat. 1 /MAO catalytic system and far superior than any other heterogeneous catalytic system reported for the synthesis of solid-state processable UHMWPE. ,,,, …”

Section: Resultsmentioning

confidence: 95%

“…2 The so far reported heterogeneous Ziegler−Natta type catalytic system reached up to 2.5 GPa in terms of tensile strength and 136 GPa for tensile modulus with the highest activity. 26 Borealis AG, Austria, together with Rastogi and Romano also patented a modified Ziegler−Natta catalyst for solid-state processable UHMWPE. 18 Tuskaev et al reported the highest values of 2.8 and 145 GPa in terms of tensile strength and tensile modulus, respectively, for heterogeneous catalytic systems.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Tuskaev et al . reported the highest values of 2.8 and 145 GPa in terms of tensile strength and tensile modulus, respectively, for heterogeneous catalytic systems. ,− Ronca et al . achieved a tensile strength of 2.7 GPa with a tensile modulus of 170 GPa by using nanoparticles with the highest activity of 682 kg PE /(mol Cat ·h·bar) (Table ; entry 3) .…”

Section: Resultsmentioning

confidence: 99%

“…1/MAO catalytic system and far superior than any other heterogeneous catalytic system reported for the synthesis of solid-state processable UHMWPE. 10,17,19,23,26 Figure 12 shows the 13 C CPMAS and SPMAS of the nascent and 300× drawn sample of heterogeneous dis-UHMWPE. The signal of the crystalline region for both nascent and drawn dis-UHMWPE in 13 C CPMAS spectra is the same.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The resulting polymer should be suitable for uniaxial and biaxial solid-state processing and is expected to match the mechanical properties of the homogeneous catalysis counterpart. Although the synthesis of UHMWPE using a heterogeneous catalytic system is not new, ,− the low entangled state that can lead to properties equivalent to those of the homogeneous catalytic system has not been reported yet. Below, experimental findings for the synthesis of UHMWPE using heterogeneous catalytic systems are recalled.…”

Section: Introductionmentioning

confidence: 99%

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Unprecedented Mechanical Properties in Linear UHMWPE Using a Heterogeneous Catalytic System

et al. 2022

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Several homogeneous postmetallocene complexes are known to produce weakly entangled ultrahigh-molecular-weight polyethylene (disentangled UHMWPE) under controlled polymerization conditions leading to ultimate mechanical properties. Major challenges in using a homogeneous catalyst system exist such as reactor fouling and uncontrolled polymer morphology, which could be addressed by heterogenization of the single-site complex. In such a scenario, a heterogeneous catalytic system that can synthesize ultrahigh-molecular-weight polyethylene with a reduced number of entanglements, to an extent that the mechanical properties are equivalent to those obtained using a postmetallocene catalyst in a homogeneous condition, remains a challenge. Herein, a magnesium chloride based in situ formed activator/support, MgCl x /Et n Al y (2-ethyl-1-hexoxide) z , is employed with a highly active bis[N-(3-tert-butylsalicylidene)pentafluoroanilinato] titanium(IV) dichloride (Cat. 1) for the synthesis of ultrahigh-molecular-weight polyethylene with a reduced number of entanglements. A novel route is adopted to make a nano-support that allows tailoring of the entangled state and control over the resultant morphology without reactor fouling and wall sheeting, thus providing the feasibility of pursuing the polymerization via a continuous process. The synthesized nascent polymer shows the formation of single crystals of linear UHMWPE, identifying the fold surface and crystal thickness and suggesting a low entangled state. The topological differences with the commercial entangled sample are identified by chain diffusion from the noncrystalline to crystalline region via solid-state NMR, following melting kinetics via DSC, and transformation of the nonequilibrium melt into the equilibrium state via rheology. Thus, the obtained disentangled crystals can be compressed in the solid state, without melting, to an extent that the macroscopic forces can be transferred to the molecular level. This allows the desired chain orientation for securing the ultimate tensile modulus (>200 N/tex) and tensile strength (>4.0 N/tex) in the synthesized low entangled linear polyethylene having a weight average molar mass exceeding a million grams per mole. These mechanical properties are equivalent to those perceived using a homogeneous catalytic system and are the first of their kind reported in a polymer synthesized using a heterogeneous catalytic system.

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Section: Resultsmentioning

confidence: 95%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Unprecedented Mechanical Properties in Linear UHMWPE Using a Heterogeneous Catalytic System

et al. 2022

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Solid‐State Processing of Nascent Disentangled UHMWPE Reactor Powders Mixed with Carbon Nanoparticles

Lebedev,

Tikunova,

Golubev

et al. 2024

Macromolecular Symposia

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Aspects of solid‐state processing of nascent disentangled ultra‐high‐molecular‐weight polyethylene (UHMWPE) powders of different syntheses mixed with electrically conductive carbon nanoparticles (NPs) of various types are studied. Effect of multiple parameters of the processing procedures on the electrophysical characteristics of the composite samples is investigated. Such parameters include time of preliminary ultrasonication (US) of NPs, time of US of UHMWPE/NPs mixtures, molding time, temperature, and pressure, deformation degree, etc. It is observed that by selecting optimal values of such parameters it is possible to obtain samples of composites with an extremely segregated structure made of the NPs, with NPs distributed evenly on the surfaces of the compacted UHMWPE powder particles. This ensures high levels of conductivity at very low values of NPs content. The segregated structure is retained when the composites are strengthened using the solid‐state uniaxial shear deformation process. While conductivity of most of the composites filled with various types of NPs monotonously decreases with the deformation ratio, conductivity of the composites filled with exceptionally long double‐walled carbon nanotubes is maintained. The processed oriented composites are also characterized by high EMR shielding properties, as well as interesting temperature dependencies of the electrical conductivity.

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Highly active titanium(IV) dichloride FI catalysts bearing a diallylamino group for the synthesis of disentangled UHMWPE

Oleynik

Shundrina

2020

Polymers for Advanced Techs

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A family of 16 salicylaldarylimine titanium(IV) dichloride complexes bearing diallylamino group, namely {2‐[3‐ or 4‐(CH2CHCH2)2NC6H4NCH]‐6‐R1‐4‐R2‐C6H2O}2TiCl2 (R1 = t‐Bu, CMe2(Ph); R2 = H, Me, OMe, t‐Bu) have been used for polymerization of ethylene in the presence of methylaluminoxane. The effects of reaction conditions on the polymerization were examined in detail. All the pre‐catalyst are highly active (up to 14.0 × 106 g(PE) mol(Ti)−1 −1 h−1) for ethylene polymerization at 30°С to 60°С with the activities and MM correlating with the R1‐substituent type and position of NAll2‐group: CMe2(Ph) > t‐Bu and meta‐NAll2 > para‐NAll2 for any R2. Highly linear polyethylenes (Tm's as high as 141.0°С) can be obtained with high molecular weights in the range 0.70 to 4.10 × 106 g mol−1 with disentangled morphology, suitable for technologically more advanced and greeny way to produce high‐modulus high‐strength fibers of ultrahigh molecular weight polyethylene via solid‐state (solvent‐free) deformation processing.

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A Novel Ziegler–Natta-Type Catalytic System—TiCl4/2,2′-Dimethoxy-1,1′-Binaphthalene/Et3Al2Cl3/Bu2Mg for Production of Ultrahigh Molecular Weight Polyethylene Nascent Reactor Powders, Suitable for Solvent-Free Processing

Cited by 8 publications

References 37 publications

Unprecedented Mechanical Properties in Linear UHMWPE Using a Heterogeneous Catalytic System

Unprecedented Mechanical Properties in Linear UHMWPE Using a Heterogeneous Catalytic System

Solid‐State Processing of Nascent Disentangled UHMWPE Reactor Powders Mixed with Carbon Nanoparticles

Highly active titanium(IV) dichloride FI catalysts bearing a diallylamino group for the synthesis of disentangled UHMWPE

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