All Polyethylene Compositions Based on Ultrahigh Molecular Weight Polyethylene Synthesized Over Binary Catalyst Including Zirconocenes of Various Designs

Tatiana M. Ushakova; Elena E. Starchak; Sergey S. Gostev; Sergey S. Gusarov; Igor I. Arutyunov; Vadim G. Krasheninnikov; Aleksandr Z. Voskoboynikov; Ludmila A. Novokshonova

doi:10.1007/s10118-025-3420-9

Your Location：

Home >

Browse articles >

All Polyethylene Compositions Based on Ultrahigh Molecular Weight Polyethylene Synthesized Over Binary Catalyst Including Zirconocenes of Various Designs

RESEARCH ARTICLE | Updated：2025-10-11

- All Polyethylene Compositions Based on Ultrahigh Molecular Weight Polyethylene Synthesized Over Binary Catalyst Including Zirconocenes of Various Designs
- Chinese Journal of Polymer Science Vol. 43, Pages: 1-8(2025)
- Affiliations：
  
  a.N.N. Semenov Federal Research Center for Chemical Physics Russian Academy of Sciences, 119991 Moscow, Russian Federation
  b.Federal State Budget Educational Institution of Higher Education «MIREA – Russian Technological University», 119571 Moscow, Russian Federation
  c.Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation
- Author bio：
  
  star2004i341@rambler.ru
- Funds：
- DOI：10.1007/s10118-025-3420-9
  CLC：
- Received：12 May 2025，
  
  Accepted：02 August 2025，
  
  Published Online：11 October 2025，
  
  Published：05 November 2025
- Accepted：
Scan QR Code
Ushakova, T. M.; Starchak, E. E.; Gostev, S. S.; Gusarov, S. S.; Arutyunov, I. I.; Krasheninnikov, V. G.; Voskoboynikov, A. Z.; Novokshonova, L. A. All polyethylene compositions based on ultrahigh molecular weight polyethylene synthesized over binary catalyst including zirconocenes of various designs. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-025-3420-9

Tatiana M. Ushakova, Elena E. Starchak, Sergey S. Gostev, et al. All Polyethylene Compositions Based on Ultrahigh Molecular Weight Polyethylene Synthesized Over Binary Catalyst Including Zirconocenes of Various Designs[J/OL]. Chinese journal of polymer science, 2025, 431-8.
Ushakova, T. M.; Starchak, E. E.; Gostev, S. S.; Gusarov, S. S.; Arutyunov, I. I.; Krasheninnikov, V. G.; Voskoboynikov, A. Z.; Novokshonova, L. A. All polyethylene compositions based on ultrahigh molecular weight polyethylene synthesized over binary catalyst including zirconocenes of various designs. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-025-3420-9 DOI：

Tatiana M. Ushakova, Elena E. Starchak, Sergey S. Gostev, et al. All Polyethylene Compositions Based on Ultrahigh Molecular Weight Polyethylene Synthesized Over Binary Catalyst Including Zirconocenes of Various Designs[J/OL]. Chinese journal of polymer science, 2025, 431-8. DOI： 10.1007/s10118-025-3420-9.

摘要

Abstract

Single-step ethylene polymerization over a binary catalyst

including zirconocene precatalysts of various designs

has been studied to obtain polymer compositions based on ultrahigh-molecular-weight polyethylene (UHMWPE) and low-molecular-weight HDPE (LMWPE) directly in synthesis. Zirconocenes

rac

-(CH

)

SiInd

ZrCl

(

Zr-1

) and

rac

-(C

)CpIndZrCl

(

Zr-2

) activated with methylaluminoxane (MAO) were used as the components of the binary catalyst. It has been shown that the use of

Zr-1

/MAO and

Zr-2

/MAO in ethylene polymerization at 30 °C leads to the production of UHMWPE with

=1000 kg·mol

–1

and LMWPE with

=18 kg·mol

–1

respectively. Reactor polymer compositions (RPC) with LMWPE fraction contents ranging from 9 wt% to 42 wt% were obtained when a molar fraction of

Zr-2

in the binary catalyst (

Zr-1

Zr-2

)/MAO varied in the range from 0.3 to 0.85. A study of the molecular weight characteristics of RPC showed that it has a wide bimodal molecular weight distribution (MWD) and includes UHMWPE (

=1000 kg·mol

–1

) and LMWPE (

=18 kg·mol

–1

) fractions. The degree of crystallinity of the polymer products was determined using the DSC method. The tensile properties and melt indices of the materials were studied depending on the LMWPE fraction content in the polymer composition. UHMWPE/LMWPE compositions with high tensile properties and fluidity at a load of 5 kg were obtained.

关键词

Keywords

references

Patel, K.; Chikkali, S. H.; Sivaram, S. Ultrahigh molecular weight polyethylene: catalysis, structure, properties, processing and applications. Prog. Polym. Sci. 2020 , 109 , 101290..

[Liang, P.; Chen, Y.; Ren, C.; Chen, M.; Jiang, B.; Wang, J.; Yang, Y.; Li, W. Efficient synthesis of low-polydispersity UHMWPE by elevating active sites on anchored POSS molecules. Eng. Chem. Res . 2020 , 19964..

[Kurtz, S.M. Ultra-high molecular weight polyethylene in total joint replacement. in the UHMWPE Handbook , Elsevier Academic Press: San Diego, CA, 2004 , p. 1−6..

[Wu, B.; Cai, Y.; Zhao, X.; Ye, L. Fabrication of well-miscible and highly enhanced polyethylene/ultrahigh molecular weight polyethylene blends by facile construction of interfacial intermolecular entanglement. Polym. Test . 2021 , 93 . 106973..

Kurtz, S.; Muratoglu, O.; Evans, M.; Edidin, A. Advances in the processing, sterilization, and crosslinking of ultra-high molecular weight polyethylene for total joint arthroplasty. Biomater. 1999 , 20 , 1659−1688..

Ahmad, M.; Wahit, M. U.; Kadir, M. R. A.; Dahlan, K. Z. M.; Jawaid, M. Thermal and mechanical properties of ultrahigh molecular weight polyethylene/high-density polyethylene/polyethylene glycol blends. J. Polym. Eng. 2013 , 33 , 599−614..

Okularczyk W. Experimental investigations of guide rings made of UHMWPE and PTFE composite in water hydraulic systems. Arch. Civ. Mech. Eng. 2007 , 7 , 167−176..

Feng, Y.; Gao, Y.; Chen, J.; Jiang, J.; Yin, X.; He, G.; Zeng, Y.; Kuang, Q.; Qu, J. Properties of compression molded ultra-high molecular weight polyethylene products pretreated by eccentric rotor extrusion. Polym. Int. 2019 , 68 , 862−870..

Chen, K.; Cui, Y.; Wang, S.; Xue, P.; Yang, Q.; Jia, M. Characterization of plasticizing process of single screw extruder with grooved melting zone. J. Polym. Res. 2020 , 27 , 70..

Chen, Y.; Nie, X.; Zou, H.; Liang, M.; Liu, P. Structure and tensile properties change of LDPE/UHMWPE blends via solid state shear milling. J. Appl. Pol. Sci. 2013 , 130 , 2487−2493..

Gonzalez, J.; Rosales, C.; Gonzalez, M.; Leon, N.; Escalona, R.; Rojas, H. Rheological and mechanical properties of blends of LDPE with high contents of UHMWPE wastes. J. Appl. Polym. Sci. 2017 , 134 , 44996..

[Stürzеl, M.; Mihаn, S.; Mülhаuрt, R. From multisite polymerization catalysis to sustainable materials and all-polyolefin composites. Сhеm. Rеv . 2016, 116 , 1398–1433..

Bakshi, A. K.; Ghosh, A. K. Processability and physico-mechanical properties of ultrahigh-molecular-weight polyethylene using low-molecular-weight olefin wax. Polym. Eng. Sci. 2022 , 62 , 2335−2350..

Lim, K. L. K.; Ishak, Z. A. M.; Ishiaku, U. S.; Fuad, A. M. Y.; Yusof, A. H.; Czigany, T.; Pukanszky, B.; Ogunniyi, D. S. High-density polyethylene/ultrahigh-molecular-weight polyethylene blend. I. The processing, thermal, and mechanical properties. J. Appl. Polym. Sci. 2005 , 97 , 413−425..

[S. Liu, L.; Chen, J. Y.; Cao, Y. Effect of solid paraffin on the integrity of welded interfaces and properties of ultra-high molecular weight polyethylene. Polym. Sci. Ser. A. 2015, 57, 168–176..

[Ferreira, E. H. C.; Fechine, G. J. M. Healing phenomenon adapted to understand the miscibility of polymer blends: An approach based on the deformation mechanism. J. Appl. Polym. Sci . 2020 , 49604..

Krishnaswamy, R. K.; Yang, Q. ; Fernandez-Ballester, L.; Kornfield, J. A. Effect of the distribution of short-chain branches on crystallization kinetics and mechanical properties of high-density polyethylene. Macromolecules. 2008 , 41 , 1693−1704..

Kessner, U.; Kaschta, J.; Stadler, F. J.; Le Duff, C. S.; Drooghaag, X.; Munstedt, H. Thermorheological behavior of various short- and long-chain branched polyethylenes and their correlations with the molecular structure. Macromolecules. 2010 , 43 , 7341−7350..

Boscoletto, A. B.; Franco, R.; Scapin, M.; Tavan, M. An investigation on rheological and impact behaviour of high density and ultra high molecular weight polyethylene mixtures. Eur. Polym. J. 1997 , 33 , 97−105..

Ruff, M.; Paulik, C. Controlling polyolefin properties by in-reactor blending: 2. particle design. Macromol. React. Eng. 2013 , 7 , 71−83..

Lafleur, S.; Berthoud, R.; Ensinck, R.; Cordier, A.; Cremer, G. De.; Philippaerts, A.; Bastiaansen, K.; Margossian, T.; Severn, J. R. Tailored bimodal ultra-high molecular weight polyethylene particles. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56 , 1645−1656..

Ruff, M.; Lang, C.; Paulik, R. W. Controlling polyolefin properties by in-reactor blending: 3. mechanical properties. Macromol. React. Eng. 2013 , 7 , 328−343..

Zuo, J.; Zhu, Y.; Liu, S.; Jiang, Z.; Zhao, J. Preparation of HDPE/UHMWPE/MMWPE blends by two-step processing and properties of blown films. Polym. Bull. 2007 , 58 , 711−722..

Ahmadi, M.; Jamjah, R.; Nekoomanesh, M.; Zohuri, G. H.; Arabi, H. ZieglerNatta/metallocene hybrid catalyst for ethylene polymerization. Macromol. React. Eng. 2007 , 1 , 604−610..

[Severn, J. R.; Chadwick, J. C.; Duchateau, R.; Friderichs, N. “Bound but not gagged” immobilizing single-site α -olefin polymerization catalysts. Chem. Rev . 2005, 105 , 4073−4147..

Soares, J. B. P.; Kim, J. D. Copolymerization of ethylene and α-olefins with combined metallocene catalysts. I. A formal criterion for molecular weight bimodality. J. Polym. Sci., Part A: Polym. Chem. 2000 , 38 , 1408−1416..

D’agnillo, L.; Soares, J. B. P.; Penlidis, A. Controlling molecular weight distributions of polyethylene by combining soluble metallocene/MAO catalysts. J. Polym. Sci. Part A: Polym. Chem. 1998 , 36 , 831−840..

Liu, J.; Rytter, E. Bimodal Polyethylenes obtained with a dual-site metallocene catalyst system. effect of trimethylaluminium addition. Macromol. Rapid Commun. 2001 , 22 , 952−956..

Stürzel, M.; Thomann, M.; Enders, Y.; Muelhaupt, R. Graphene supported dual-site catalysts for preparing self-reinforcing polyethylene reactor blends containing UHMWPE nanoplatelets and in situ UHMWPE shish-kebab nanofibers. Macromolecules 2014 , 47 , 4979−4986..

Sturzel, M.; Hees, T.; Enders, M.; Thomann, Y.; Blattmann, H.; Mulhaupt, R. Nanostructured polyethylene reactor blends with tailored trimodal molar mass distributions as melt-processable all-polymer composites. Macromolecules 2016 , 49 , 8048−8060..

Ushakova, T. M.; Starchak, E. E.; Gostev, S. S.; Grinev, V. G.; Krasheninnikov, V. G.; Gorenberg, A. Ya.; Novokshonova, L. A. All -polyethylene compositions based on ultrahigh molecula r weight polyethylene: Synthesis and properties. J. Appl. Polym. Sci. 2020 , 137 , 49121..

Ushakova, T.; Gostev, S.; Starchak, E.; Krasheninnikov, V.; Grynev, V.; Kudinova, O.; Novokshonova, L. All-polyethylene compositions of ultrahigh molecular weight polyethylene synthesized in one-step ethylene polymerization with combination of zirconocene and iron-based catalysts. Iran. Polym. J. 2023 , 32 , 523−531..

Gostev, S.; Starchak, E.; Ushakova, T.; Grinev, V.; Krasheninnikov, V.; Gorenberg, A.; Vtyurina, D.; Ladygina, T.; Novokshonova L. Modifying effect of polyethylene fractions of different molecular weights on the morphology and properties of reactor polymer compositions based on ultrahigh molecular weight Polyethylene. Polym. Sc. A 2023 , 65 , 386−395..

Peifer, B.; Bruce Welch, M.; Alt, H. Synthese und charakterisierung von bis(fluorenyl)komplexen des zirconiums und hafniums und deren anwendung bei der katalytischen olefinpolymerisation. J. Organ. Chem. 1997 , 544 , 115−119..

[Neira-Valázquez, M.; Rodríguez-Hernández. M. Polymer molecular weight measurement. Handbook of Polymer Synthesis, Characterization and Processing . J ohn Wiley & Sons, 2013, 355−366..

Bodorodea, F.; Collignon, A.; Brookes A. Characterization of polyethylene in dibutoxymethane by high-temperature gel permeation chromatography with triple detection. Int. J. Polym. Anal. Character. 2015 , 20 , 316−322..

[Ehrenstein, G. W.; Riedel, G.; Trawiel, P. Dynamic mechanical analysis (DMA). Thermal analysis of plastics . Carl Hanser Verlag, Munich. 2004, p. 236−299..

Ushakova, T. M.; Starchak, E. E.; Krasheninnikov, V. G.; Grinev, V. G.; Ladygina, T. A.; Novokshonova, L. A. Influence of Copolymer Fraction composition in ultrahigh molecular weight polyethylene blends with ethylene/1-Hexene copolymers on material physical and tensile properties. J. Appl. Pol. Sci. 2014 , 131 , 40151..

Alt, H. G.; Koppl, A. Effect of the nature of metallocene complexes of group IV metals on their performance in catalytic ethylene and propylene polymerization. Chem. Rev. 2000 , 100 , 1205−1221..

[Kim, J. D.; Soar es, J. B.P. Copolymerization of ethylene and α-olefins with combined metallocene catalysts. II. Mathematical modeling of polymerization with single metallocene catalysts. J. Polym. Sci., Part A: Polym. Chem . 2000 , 38 , 1417−1426..

Kim, J. D.; Soares, J. B. P. Copolymerization of ethylene and α-olefins with combined metallocene catalysts. III. Production of polyolefins with controlled microstructures. J. Polym. Sci., Part A: Polym. Chem. 2000 , 38 , 1427−1432..

Trainor A.; Haward R. N.; Hay J. N. The effect of density on the properties of high molecular weight polyethylenes. J. Polym. Sci. Polym. Phys. Ed. 1977 , 15 , 1077−1088..

Adhikari R.; Godehardt R.; Lebek W.; Michler G. H. Blends of high density polyethylene and ethylene/1-octene copolymers: Structure and properties. J. Appl. Polym. Sci. 2007 , 103 , 1887−1893..

Seguela, R. Critical review of the molecular topology of semicrystalline polymers: the origin and assessment of intercrystalline tie molecules and chain entanglements. J. Polym. Sci. B Polym. Phys. 2005 , 43 , 1729−1748..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Sunlight-induced Permanent Hair Dyeing

Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene

Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Access to High-Molecular-Weight Polyethylenes through High Temperature Ethylene Polymerization Catalysed by Ethylene-Bridged ansa-(3-R-Cyclopentadienyl)(Fluorenyl) Zirconocene Complexes

Related Author

Ting Zhang

Bo Liang

Jian-Hua Zhang

Lei Yang

Jun-Fei Hu

Yi-Wen Li

Giovanni Ricci

Benedetta Palucci

Related Institution

School of Emergent Soft Matter, South China University of Technology

School of Materials Science and Engineering, Hubei University of Automotive Technology

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University

Centro per l'Integrazione della Strumentazione Scientifica dell'Università di Pisa (C.I.S.U.P.), Università di Pisa,- Pisa

Università di Pisa, Dipartimento di Chimica e Chimica Industriale, Via Moruzzi 13,- Pisa

⁰