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US-12617880-B2 - Compounds for use in catalyst compositions for the production of polyolefins

US12617880B2US 12617880 B2US12617880 B2US 12617880B2US-12617880-B2

Abstract

The present invention relates to compounds according to formula I, wherein: R1 is a cyclopentadienyl moiety or a moiety comprising a cyclopentadienyl ring structure; R2 is a moiety M(R5) 2 or MR5, wherein M is a metal selected from hafnium, titanium or zirconium, and R5 is F, Cl, I, Br or an alkyl-moiety comprising 1 to 10 carbon atoms, preferably methyl, benzyl, butadiene or pentadiene; R3 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms; R4 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms, or a halogen; wherein if R3 is H, R4 is a moiety other than H, and if R4 is H, R3 is a moiety other than H; each R6 is individually selected from H, a halogen, an alkyl moiety, an aryl moiety, a halogen-substituted alkyl moiety, a halogen-substitute d aryl moiety, an alkoxy moiety, a siloxy-moiety, or a nitrogen-containing moiety, preferably H. Such compounds may be used in a catalyst system for olefin polymerisation, particularly ethylene copolymerisation, providing at least one of a high catalyst activity, a high comonomer incorporation, and/or a high molecular weight polymer.

Inventors

  • Jaiprakash Brijlal Sainani
  • Oleg SAMSONOV
  • Pavel KULYABIN
  • Georgy GORYUNOV
  • Andrey YASHIN
  • Akhilesh Tanwar
  • Nicolaas Hendrika Friederichs
  • Alexander Voskoboynikov
  • Dmitry Uborsky
  • Kankan Bhaumik
  • Vincenzo Busico
  • ANTONIO VITTORIA
  • Roberta Cipullo
  • Bogdan Guzeev

Assignees

  • SABIC GLOBAL TECHNOLOGIES B.V.

Dates

Publication Date
20260505
Application Date
20200904
Priority Date
20190910

Claims (11)

  1. 1 . A compound according to formula: wherein: R2 is a moiety M(R5) 2 or MR5, wherein M is a metal selected from hafnium, titanium or zirconium, and R5 is F, Cl, I, Br or an alkyl-moiety comprising 1 to 10 carbon atoms; R3 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms; R4 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms, or a halogen; wherein if R3 is H, R4 is a moiety other than H, and if R4 is H, R3 is a moiety other than H; each R6 is individually selected from H, a halogen, an alkyl moiety, an aryl moiety, a halogen-substituted alkyl moiety, a halogen-substituted aryl moiety, an alkoxy moiety, a siloxy-moiety, or a nitrogen-containing moiety.
  2. 2 . The compound according to claim 1 , wherein the compound is a compound according to formula: wherein: R2 is a moiety M(R5) 2 or MR5, wherein M is a metal selected from hafnium, titanium or zirconium, and R5 is F, Cl, I, Br or an alkyl-moiety comprising 1 to 10 carbon atoms; R3 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms; R4 is H, an alkyl or aryl moiety comprising 1 to 10 carbon atoms, or a moiety comprising N or O and 1 to 15 carbon atoms, or a halogen; wherein if R3 is H, R4 is a moiety other than H, and if R4 is H, R3 is a moiety other than H.
  3. 3 . The compound according to claim 1 , wherein R2 is selected from ZrCl 2 , TiCl 2 , HfCl 2 , Zr(CH 3 ) 2 , Ti(CH 3 ) 2 , or Hf(CH 3 ) 2 .
  4. 4 . The compound according to claim 1 , wherein each R3 and R4 individually is selected from fluorine, a methyl moiety, a phenyl moiety, a t-butyl moiety, a methoxy moiety, or a 9-carbazole moiety.
  5. 5 . The compound according to claim 1 , wherein the compound is supported onto a polymeric support, a clay material, or an inorganic oxide.
  6. 6 . A catalyst composition comprising the compound according to claim 1 , wherein the composition further comprises an activator.
  7. 7 . A catalyst composition comprising the compound according to claim 1 , wherein the catalyst composition further comprises a main group organometallic compound.
  8. 8 . A catalyst composition comprising the compound according to claim 1 , wherein the catalyst composition further comprises a compound containing at least one active hydrogen.
  9. 9 . A process for the polymerization of olefins, wherein the process is a homopolymerization process of ethylene or propylene, or a copolymerization process of ethylene or propylene with one or more comonomer(s) in the presence of the catalyst composition according to claim 6 .
  10. 10 . The process according to claim 9 , wherein the process is a copolymerization process of ethylene with one or more comonomer(s), wherein the comonomer(s) are selected from 1-butene, 1-hexene, 1-octene, norbornene, vinyl-cyclohexane, styrene, and 4-methyl-1-pentene.
  11. 11 . A polymer comprising the compound of claim 1 .

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a National Stage application of PCT/EP2020/074839, filed Sep. 4, 2020, which claims the benefit of European Application No. 19196373.5, filed Sep. 10, 2019, both of which are incorporated by reference in their entirety herein. The present invention relates to compounds that are suitable for use as single-site type catalyst for the production of polyolefins, in particular for the production of ethylene-based polymers. The compounds display in a polymerisation of ethylene a high reactivity towards comonomers such as α-olefins, and allow for the production of ethylene-based copolymers having a high molecular weight. Copolymers of ethylene and other olefins find widespread commercial application. For instance, medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), polyolefin plastomers (POP), polyolefin elastomers (POE), and even ethylene-propylene-diene terpolymers (EPDM) are polymers that are typically produced using ethylene and other olefinic comonomers, using a transition metal-based catalyst. In commercial applications, the molecular weights of these polymers, expressed as the weight-averaged molecular weight (Mw) are typically above 10 kg/mol, more typically above 50 kg/mol, but also may be above 100 kg/mol, for such polymers to be of significant commercial importance. In addition, the industrially important bimodal high-density polyethylene (HDPE) is used in certain high-demanding applications, for instance in pressure pipes. This bimodal HDPE comprises a low molecular weight homopolymer of ethylene, and a high molecular weight ethylene-based copolymer. The high molecular weight copolymer fraction in such bimodal HDPE typically has an Mw of above 100 kg/mol, and for specific applications, the Mw of the copolymer may even need to be above 300 kg/mol or even above 500 kg/mol. Also, the ultra-high molecular weight polyethylene (UHMwPE), with Mw of above 1000 kg/mol is often commercialised as a copolymer of ethylene and a small amount of comonomer, for example in applications that require very high impact resistance or low creep in fiber applications. Hence, it is important to develop compounds that are suitable as catalysts to produce high molecular weight ethylene-based polymers. In an industrial production process for the production of ethylene-based polymers, it is highly advantageous that the applied catalyst displays a high reactivity for the comonomer. It is well known in the art that the reactivity of α-olefins compared to ethylene decreases upon increase of the size of the α-olefin. In the context of the present invention, suitable α-olefins for use as comonomer in ethylene polymerisation reactions may for example be propylene, 1-butene, 1-hexene and 1-octene. For instance, the reactivity in copolymerisations with ethylene is understood to decrease from propylene>1-butene>1-hexene>1-octene, as published for example by Krentsel et al. in Polymers and Copolymers of Higher Alpha-Olefins, Carl Hanser Verlag, München, 1997, and by McDaniel et al. in Macromolecules, 2010(43), p. 8836-8852. As pointed out by Kissin in Transition Metal catalysed Polymerizations, Alkenes and Dienes, Quirck, R. P. (ed.), Harwood Academic Publishers, New York, 1983, part B, p. 597-615, this lower reactivity of the comonomer compared to ethylene is mainly due to steric crowding close to the reactive olefin bond. This may be understood to demonstrate why branched olefins, such as for instance 3-methyl-butene-1, 4-methyl-pentene-1, vinyl cyclohexane or iso-butene are in general more difficult to incorporate compared to for instance propylene or 1-butene. If the reactivity of the comonomer is low, one needs to apply relatively high concentrations of the comonomer during the polymerisation process in order to incorporate significant, desirable amounts in the copolymer. Such high concentrations are undesirable in industrial processes because the unreacted monomer needs to be separated from the polymer and subsequently recycled, which is an energy-intensive process, especially for comonomers with relatively high boiling points. In addition, in for example fluidised-bed gas-phase polymerisation processes, high amounts of liquid comonomers in the reactor can be detrimental to the fluidisation of the reactor contents. Therefore, especially when copolymerising ethylene with higher α-olefins or sterically encumbered olefins, catalysts are needed that display a high reactivity towards such comonomers. Further, in the preparation of copolymers of ethylene and α-olefins, it is understood that the Mw of the obtained copolymers tends to decrease upon increasing the α-olefin content of the copolymer, which for example has been published by Friederichs et al., J. Mol. Cat. A: Chemical, 242 (2005), p. 91-104. The combination of high comonomer incorporation and high molecular weight is therefore a challenging target for developing commercially available catalysts. N