EP4676988A1 - Process for polymerisation of olefins - Google Patents

Process for polymerisation of olefins

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Publication number
EP4676988A1
EP4676988A1 EP24707868.6A EP24707868A EP4676988A1 EP 4676988 A1 EP4676988 A1 EP 4676988A1 EP 24707868 A EP24707868 A EP 24707868A EP 4676988 A1 EP4676988 A1 EP 4676988A1
Authority
EP
European Patent Office
Prior art keywords
fraction
process according
moiety
cocatalyst
indenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24707868.6A
Other languages
German (de)
French (fr)
Inventor
Yahya Banat
Lidong LI
Nasser Abdullah ALSAIF
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
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SABIC Global Technologies BV
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Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP4676988A1 publication Critical patent/EP4676988A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/02—Anti-static agent incorporated into the catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer

Definitions

  • the present invention relates to a process for the polymerisation of olefins.
  • Polymers produced from olefins are well known to be of the most versatile polymeric materials available. Capable of being produced in an economic way at high and consistent product quality, and, by variation of amongst others polymerisation conditions and raw material formulations, in a wide array of grades each satisfying certain application needs, suitable for use in the production of a multitude of articles.
  • Particular polymers produced from olefins include polyethylenes and polypropylenes.
  • Polyethylenes or polypropylenes may be homopolymers of ethylene or propylene, respectively, of may be copolymers.
  • Polyethylene copolymers may for example be produced using further monomers, referred to as comonomers, including a-olefins, particularly a-olefins having 3 to 10 carbon atoms.
  • Such a-olefin comprising 3 to 10 carbon atoms may for example be selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
  • Particularly appropriate compounds to be used as comonomer are 1-butene, 1-hexene and 1-octene.
  • Polypropylene copolymers may for example be produced using further monomers, referred to as comonomers, including ethylene or a-olefins comprising 4 to 10 carbon atoms.
  • Such a-olefin comprising 4 to 10 carbon atoms may for example be selected from 1-butene, 1-pentene, 1- hexene, 1-octene, and 4-methyl- 1-pentene.
  • Particularly appropriate compounds to be used as comonomer are ethylene, 1-butene, and 1-hexene.
  • a particular aspect of olefin polymerisation that has its reflection on the nature of the polymer that is produced, and the efficiency of the polymerisation process, is the catalytic system that is used in the polymerisation.
  • a particular family of catalysts that may be suitable for the production of polyethylenes via catalytic polymerisation processes are the so-called single-site catalysts, a well-known group of species of which are the catalysts referred to as metallocene catalysts. Whilst such catalysts are broadly applied in the manufacture of polyethylene products, there continue to be a desire to develop catalyst systems that allow for the production of polyethylenes having desired polymer properties such as a desired density, molecular weight distribution (M w /M n ), and a high molecular weight M w , whilst polymerisation may be performed at high productivity of polymer per quantity of supplied catalyst, at high monomer conversion rate, and where the occurrence of reactor fouling due to excessive heat generation is prevented.
  • Z is a moiety selected from ZrX2, HfX2, or TiX2, wherein X is selected from the group of halogens, alkyls, aryls and aralkyls;
  • R2 is a bridging moiety containing at least one sp2 hybridised carbon atom, preferably R2 is a substituted or unsubstituted methylene, 1 ,2-phenylene or 2,2’-biphenylene moiety; and
  • each R1, RT, R3, R3’, R4, R4’, R5 and R5’ are hydrogen or a hydrocarbon moiety comprising 1-20 carbon atoms; wherein the cocatalyst is an organoaluminium compound; and wherein the antistatic agent is an antistatic composition comprising:
  • the metallocene compound may be selected from [ortho-bis(4-phenyl-2- indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)- benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2- indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2,2'-bis(2-indenyl)biphenyl]zirconiumdichloride and [2,2'-bis(2- indenyl)biphenyl]hafniumdichloride, preferably the metallocene compound is [2,2’-bis(2- indenyl)biphenyl]zirconium
  • X is a monovalent anionic group, selected from the group consisting of halogens, a C1-C20 hydrocarbyl group or a C1-C20 alkoxy group, preferably X is a methyl group, Cl, Br or I, most preferably methyl or Cl.
  • Z is a moiety selected from ZrCI 2 , HfCI 2 and TiCI 2 .
  • the cocatalyst may be an organoaluminium compound or a noncoordinating anionic compound, preferably the cocatalyst is a compound selected from methylaluminoxane, perfluorphenylborane, triethylammonium tetrakis(pentafluorphenyl)borate, triphenylcarbenium tetrakis(pentafluorphenyl)borate, trimethylsilyl tetrakis(pentafluorphenyl)borate, 1-pentafluorphenyl-1 ,4-dihydroboratabenzene, tributylammonium-1 ,4-bis(pentafluorphenyl)boratabenzene, and triphenylcarbenium-1- methylboratabenzene, more preferably the cocatalyst is methylaluminoxane.
  • the antistatic composition preferably comprises > 50.0 and ⁇ 95.0 wt% of the hydrocarbon fraction (a), more preferably > 50.0 and ⁇ 85.0 wt%, even more preferably > 50.0 and ⁇ 75.0 wt%, yet even more preferably > 50.0 and ⁇ 70.0 wt% with regard to the total weight of the antistatic composition.
  • the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms.
  • the hydrocarbon fraction (a) consists of a mixture of hydrocarbons having a boiling point of > -20°C and ⁇ 190°C.
  • the mixture of hydrocarbons may comprise n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof.
  • the mixture of hydrocarbons may comprise > 75.0 wt% of saturated hydrocarbons, preferably > 80.0 wt%, more preferably > 85.0 wt%, even more preferably > 90.0 wt%, yet even more preferably > 95.0 wt%, with regard to the total weight of the mixture of hydrocarbons.
  • the antistatic composition preferably comprises ⁇ 10.0 wt% of the fraction of benzenesulfonic acid derivatives, more preferably > 0.5 and ⁇ 10.0 wt%, even more preferably > 1.0 and ⁇ 7.5 wt%, yet even more preferably > 2.5 and ⁇ 7.5 wt%, with regard to the total weight of the antistatic composition.
  • the fraction of benzenesulfonic acid derivatives (b) may for example comprise 4-alkyl benzenesulfonic acid compounds.
  • fraction of benzenesulfonic acid derivatives (b) may for example comprise or consist of compounds of formula (II), or mixtures thereof: formula (II) wherein R1 is an alkyl moiety comprising > 10 and ⁇ 13 carbon atoms.
  • the compounds of formula (II) comprise a benzenesulfonic acid moiety and an alkyl moiety comprising > 10 and ⁇ 13 carbon atoms, wherein the alkyl moiety is bound to the benzene moiety of the benzenesulfonic acid moiety at the 4 position and the sulfonic acid moiety at the 1 position. It is preferred that the alkyl moiety is bound to the benzene moiety via a secondary carbon atom of the alkyl moiety.
  • the compounds of formula (II) are compounds of formula (HI): formula (III) wherein each of R2 and R3 individually is a hydrocarbon moiety comprising > 1 and ⁇ 11 carbon atoms, and wherein the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12.
  • each of R2 and R3 individually is an alkyl moiety comprising > 1 and ⁇ 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12.
  • each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and ⁇ 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12.
  • the antistatic composition preferably comprises ⁇ 2.5 wt% of the fraction of quaternary ammonium compounds (c), with regard to the total weight of the antistatic composition, more preferably > 0.1 and ⁇ 2.5 wt%, even more preferably > 0.5 and ⁇ 2.5 wt%, yet even more preferably > 1.0 and ⁇ 2.5 wt%.
  • the fraction of quaternary ammonium compounds (c) preferably comprises quaternary ammonium compounds comprising a cation moiety and an anion moiety.
  • fraction of quaternary ammonium compounds (c) preferably comprises or consists of compounds comprising cation moieties of formula (IV), or mixtures thereof:
  • the fraction of quaternary ammonium compounds (c) preferably comprises or consists of compounds comprising anion moieties selected from nitrite, chloride, fluoride, hydroxide, and carbonate, preferably nitrite.
  • the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V): formula (V) wherein R5 is selected from NO2; Cl; F; OH and !
  • each of R1 and R2 are the same and selected from methyl, ethyl, propyl or butyl moieties, preferably both R1 and R2 are methyl moieties; and wherein each of R3 and R4 individually is an alkyl moiety comprising > 8 and ⁇ 18 carbon atoms.
  • the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2; each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and ⁇ 18 carbon atoms.
  • the antistatic composition in a preferable embodiment, may for example comprise
  • the antistatic composition in a further preferable embodiment, may for example comprise
  • hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and ⁇ 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof.
  • the antistatic composition in a further preferable embodiment, may for example comprise
  • fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and ⁇ 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12.
  • the antistatic composition in a further preferable embodiment, may for example comprise
  • the antistatic composition may for example comprise
  • hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and ⁇ 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof; and wherein the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and ⁇ 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12.
  • the antistatic composition may for example comprise
  • the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and ⁇ 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof; and wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2 each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and ⁇ 18 carbon atoms.
  • the antistatic composition may for example comprise
  • the antistatic composition may for example comprise
  • the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and ⁇ 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof;
  • the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and ⁇ 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and ⁇ 12; and wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2 each of R1 and R2 is
  • the support material may for example be selected from silica, alumina, magnesia, titania, zirconia, clay, zeolite, polystyrene, polyethylene, polypropylene, polyvinylchloride, polycarbonate, polyketone, polyvinylalcohol, polymethyl methacrylate, cellulose, and graphite, preferably the support material is silica.
  • the support material is a porous support material, preferably a porous silica. More preferably, the support material has an average particle size of 1 to 120 pm, more preferably 20 to 80 pm, even more preferably 40 to 50 pm.
  • the pore volume of the support preferably is > 0.5 and ⁇ 3.0 cm 3 /g.
  • the surface area of the support material is > 50 and ⁇ 500 m 2 /g.
  • the silica that may be employed as support in for the catalyst system preferably is dehydrated prior to use in preparation of the catalyst system. It is preferred that the supported material is a silica having a particle size of from 10 to 120 pm, a pore volume of > 0.5 and ⁇ 3.0 cm 3 /g, and a surface area of > 50 and ⁇ 500 m 2 /g, as determined in accordance with ISO 9276-2 (2014).
  • the catalyst system according to the invention may for example be produced using a process involving the steps of: (i) adding, in a reaction vessel, the support material, preferably wherein the support material is pre-dehydrated, to a quantity of an organic hydrocarbon liquid, preferably toluene, and stirring to form a suspension;
  • step (iii) after step (iii) but prior to step (v), an additional quantity of the cocatalyst aid is added to the reaction mixture obtained from (iii).
  • each of the steps (i), (ii) and (iv) are performed at a temperature of ⁇ 60°C, preferably of ⁇ 50°C, more preferably of > 10°C and ⁇ 30°C, and that the heat treatment in steps (iii) and (v) is performed at a temperature of > 80°C and ⁇ 120°C.
  • the organic hydrocarbon liquid may for example be selected from heptane, hexane, isopentane and toluene, preferably the hydrocarbon solvent is toluene. It is preferred that the organic hydrocarbon liquid used in each of the steps of the process is the same, most preferable toluene.
  • the invention also relates to a catalyst system according to the invention, wherein the catalyst system is prepared according to the process according to the invention.
  • the invention will now be illustrated by the following non-limiting examples. A number of synthesis experiments of catalyst systems were conducted, as well as a number of polymerisation experiments.
  • the support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
  • the supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296.
  • the support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
  • the supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296.
  • Table 3 Material formulations for catalyst systems synthesised according to Method B
  • the support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
  • the suspension was maintained at 95°C for another 1 hour. Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder.
  • the supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296.
  • Table 4 Material formulations for catalyst systems synthesised according to Method C
  • a 3-litre autoclave reactor equipped with a heating/cooling control unit and a mechanical stirring system was baked at 150°C under a nitrogen flow for 2 hours and then cooled down to 30°C.
  • the support was pre-dehydrated at 600°C for 4 hours. 150 g of the pre-dehydrated support was charged to the reactor, followed by the addition of 750 ml of toluene at room temperature, and stirred to form a suspension.
  • the antistatic agent I cocatalyst aid mixture was added to the autoclave reactor directly after the 4 hour heat treatment as described above.
  • the reaction mixture in the autoclave reactor was kept at 95°C for 1 further hour, under stirring.
  • the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder.
  • the supported catalyst systems contained 0.18 wt% of Zr and 14.0 wt% of Al.
  • the supported catalyst system contained 0.18 wt% of Zr and 14.0 wt% of Al.
  • a 1.6 stainless steel reactor vessel equipped with a helical stirrer and a heating/cooling control unit was heated to 110°C at a nitrogen flow of 100 g/h for 2 hours. After that, the reactor was pressure purged with nitrogen, followed by a purge with ethylene. This purging cycle was repeated three times.
  • the reactor was then cooled to 88°C under ethylene pressurised to 1000 kPa. After venting, 4 ml of scavenger A0 was added via a cocatalyst injection pump. Nitrogen was introduced to maintain a nitrogen pressure of 800 kPa. Ethylene was then introduced into the reactor under control of mass flow parameters to maintain an ethylene pressure in the reactor of 1000 kPa.
  • the reactor was kept at a constant temperature of 87°C and at a constant ethylene pressure of 2.17 MPa. Ethylene and 1-hexene were used as the reactants for polymerisation. These materials are supplied as a make-up stream. 60 ppm by wt of the continuity aid agent A1 was added to the make-up stream before charging into the reactor.
  • the catalyst system composition in solid form was injected directly into the reaction zone of the fluidised bed reactor using purified nitrogen as carrier gas.
  • the injection rate was adjusted to maintain a constant polymerisation rate of about 10 kg/h.
  • the produced polymer was discharged from the reactor semi-continuously via a series of valves into a fixed volume chamber.
  • the so obtained product was purged to remove any volatile hydrocarbons, and was then treated with humidified nitrogen to deactivate any trace quantities of residual catalyst composition.
  • Table 7 Catalyst systems and feeds used, and polymer properties from experiments F.
  • melt mass-flow rate was determined according to ISO 1133-1 (2011) at 190°C and 21.6 kg load.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to a process for the polymerisation of olefins, the process involving reacting olefins in the presence of a catalyst system wherein the catalyst system comprises a support material carrying: a. a metallocene compound; b. a cocatalyst; and c. an antistatic agent; wherein the metallocene compound is a compound according to formula (I) wherein: - Z is a moiety selected from ZrX2, HfX2, or TiX2, wherein X is selected from the group of halogens, alkyls, aryls and aralkyls; - R2 is a bridging moiety containing at least one sp2 hybridised carbon atom, preferably R2 is a substituted or unsubstituted methylene, 1,2-phenylene or 2,2'-biphenylene moiety; and - each R1, R1', R3, R3', R4, R4', R5 and R5' are hydrogen or a hydrocarbon moiety comprising 1-20 carbon atoms; wherein the cocatalyst is an organoaluminium compound; and wherein the antistatic agent is an antistatic composition comprising: (a) a hydrocarbon fraction; (b) a fraction of benzenesulfonic acid derivatives; and (c) a fraction of quaternary ammonium compounds. Such process allows for the manufacturing of olefin polymers at high productivity and yield, whilst reducing the reactor fouling.

Description

Process for polymerisation of olefins.
[0001] The present invention relates to a process for the polymerisation of olefins.
[0002] Polymers produced from olefins are well known to be of the most versatile polymeric materials available. Capable of being produced in an economic way at high and consistent product quality, and, by variation of amongst others polymerisation conditions and raw material formulations, in a wide array of grades each satisfying certain application needs, suitable for use in the production of a multitude of articles.
[0003] Particular polymers produced from olefins include polyethylenes and polypropylenes. Polyethylenes or polypropylenes may be homopolymers of ethylene or propylene, respectively, of may be copolymers. Polyethylene copolymers may for example be produced using further monomers, referred to as comonomers, including a-olefins, particularly a-olefins having 3 to 10 carbon atoms. Such a-olefin comprising 3 to 10 carbon atoms may for example be selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Particularly appropriate compounds to be used as comonomer are 1-butene, 1-hexene and 1-octene. Polypropylene copolymers may for example be produced using further monomers, referred to as comonomers, including ethylene or a-olefins comprising 4 to 10 carbon atoms. Such a-olefin comprising 4 to 10 carbon atoms may for example be selected from 1-butene, 1-pentene, 1- hexene, 1-octene, and 4-methyl- 1-pentene. Particularly appropriate compounds to be used as comonomer are ethylene, 1-butene, and 1-hexene.
[0004] A particular aspect of olefin polymerisation that has its reflection on the nature of the polymer that is produced, and the efficiency of the polymerisation process, is the catalytic system that is used in the polymerisation.
[0005] A particular family of catalysts that may be suitable for the production of polyethylenes via catalytic polymerisation processes are the so-called single-site catalysts, a well-known group of species of which are the catalysts referred to as metallocene catalysts. Whilst such catalysts are broadly applied in the manufacture of polyethylene products, there continue to be a desire to develop catalyst systems that allow for the production of polyethylenes having desired polymer properties such as a desired density, molecular weight distribution (Mw/Mn), and a high molecular weight Mw, whilst polymerisation may be performed at high productivity of polymer per quantity of supplied catalyst, at high monomer conversion rate, and where the occurrence of reactor fouling due to excessive heat generation is prevented.
[0006] This is now achieved by a process for the polymerisation of olefins, the process involving reacting olefins in the presence of a catalyst system wherein the catalyst system comprises a support material carrying: a. a metallocene compound; b. a cocatalyst; and c. an antistatic agent; wherein the metallocene compound is a compound according to formula (I): wherein:
• Z is a moiety selected from ZrX2, HfX2, or TiX2, wherein X is selected from the group of halogens, alkyls, aryls and aralkyls;
• R2 is a bridging moiety containing at least one sp2 hybridised carbon atom, preferably R2 is a substituted or unsubstituted methylene, 1 ,2-phenylene or 2,2’-biphenylene moiety; and
• each R1, RT, R3, R3’, R4, R4’, R5 and R5’ are hydrogen or a hydrocarbon moiety comprising 1-20 carbon atoms; wherein the cocatalyst is an organoaluminium compound; and wherein the antistatic agent is an antistatic composition comprising:
(a) a hydrocarbon fraction;
(b) a fraction of benzenesulfonic acid derivatives; and (c) a fraction of quaternary ammonium compounds.
[0007] For example, the metallocene compound may be selected from [ortho-bis(4-phenyl-2- indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)- benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2- indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2,2'-bis(2-indenyl)biphenyl]zirconiumdichloride and [2,2'-bis(2- indenyl)biphenyl]hafniumdichloride, preferably the metallocene compound is [2,2’-bis(2- indenyl)biphenyl]zirconium dichloride.
[0008] It is preferred that in the metallocene compound, X is a monovalent anionic group, selected from the group consisting of halogens, a C1-C20 hydrocarbyl group or a C1-C20 alkoxy group, preferably X is a methyl group, Cl, Br or I, most preferably methyl or Cl.
[0009] It is also preferred that in the metallocene compound, Z is a moiety selected from ZrCI2, HfCI2 and TiCI2.
[0010] For example, the cocatalyst may be an organoaluminium compound or a noncoordinating anionic compound, preferably the cocatalyst is a compound selected from methylaluminoxane, perfluorphenylborane, triethylammonium tetrakis(pentafluorphenyl)borate, triphenylcarbenium tetrakis(pentafluorphenyl)borate, trimethylsilyl tetrakis(pentafluorphenyl)borate, 1-pentafluorphenyl-1 ,4-dihydroboratabenzene, tributylammonium-1 ,4-bis(pentafluorphenyl)boratabenzene, and triphenylcarbenium-1- methylboratabenzene, more preferably the cocatalyst is methylaluminoxane.
[0011] The antistatic composition preferably comprises > 50.0 and < 95.0 wt% of the hydrocarbon fraction (a), more preferably > 50.0 and < 85.0 wt%, even more preferably > 50.0 and < 75.0 wt%, yet even more preferably > 50.0 and < 70.0 wt% with regard to the total weight of the antistatic composition. Preferably, the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms. Preferably, the hydrocarbon fraction (a) consists of a mixture of hydrocarbons having a boiling point of > -20°C and < 190°C. The mixture of hydrocarbons may comprise n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof. The mixture of hydrocarbons may comprise > 75.0 wt% of saturated hydrocarbons, preferably > 80.0 wt%, more preferably > 85.0 wt%, even more preferably > 90.0 wt%, yet even more preferably > 95.0 wt%, with regard to the total weight of the mixture of hydrocarbons. [0012] The antistatic composition preferably comprises < 10.0 wt% of the fraction of benzenesulfonic acid derivatives, more preferably > 0.5 and < 10.0 wt%, even more preferably > 1.0 and < 7.5 wt%, yet even more preferably > 2.5 and < 7.5 wt%, with regard to the total weight of the antistatic composition. The fraction of benzenesulfonic acid derivatives (b) may for example comprise 4-alkyl benzenesulfonic acid compounds.
[0013] The fraction of benzenesulfonic acid derivatives (b) may for example comprise or consist of compounds of formula (II), or mixtures thereof: formula (II) wherein R1 is an alkyl moiety comprising > 10 and < 13 carbon atoms.
[0014] Preferably, the compounds of formula (II) comprise a benzenesulfonic acid moiety and an alkyl moiety comprising > 10 and < 13 carbon atoms, wherein the alkyl moiety is bound to the benzene moiety of the benzenesulfonic acid moiety at the 4 position and the sulfonic acid moiety at the 1 position. It is preferred that the alkyl moiety is bound to the benzene moiety via a secondary carbon atom of the alkyl moiety.
[0015] In a preferred embodiment, the compounds of formula (II) are compounds of formula (HI): formula (III) wherein each of R2 and R3 individually is a hydrocarbon moiety comprising > 1 and < 11 carbon atoms, and wherein the sum of carbon atoms of R2 and R3 together is > 9 and < 12. Preferably, each of R2 and R3 individually is an alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12. More preferably, each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12.
[0016] The antistatic composition preferably comprises < 2.5 wt% of the fraction of quaternary ammonium compounds (c), with regard to the total weight of the antistatic composition, more preferably > 0.1 and < 2.5 wt%, even more preferably > 0.5 and < 2.5 wt%, yet even more preferably > 1.0 and < 2.5 wt%.
[0017] The fraction of quaternary ammonium compounds (c) preferably comprises quaternary ammonium compounds comprising a cation moiety and an anion moiety.
[0018] The fraction of quaternary ammonium compounds (c) preferably comprises or consists of compounds comprising cation moieties of formula (IV), or mixtures thereof:
R2
R1 — N+ — R3
R4 formula (IV) wherein each of R1 and R2 are the same and selected from methyl, ethyl, propyl or butyl moieties, preferably both R1 and R2 are methyl moieties; and wherein each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0019] The fraction of quaternary ammonium compounds (c) preferably comprises or consists of compounds comprising anion moieties selected from nitrite, chloride, fluoride, hydroxide, and carbonate, preferably nitrite. [0020] Preferably, the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V): formula (V) wherein R5 is selected from NO2; Cl; F; OH and ! (CC>32 , preferably NO2; and wherein each of R1 and R2 are the same and selected from methyl, ethyl, propyl or butyl moieties, preferably both R1 and R2 are methyl moieties; and wherein each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0021] Particularly preferably, the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2; each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0022] The antistatic composition, in a preferable embodiment, may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition.
[0023] The antistatic composition, in a further preferable embodiment, may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and < 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof.
[0024] The antistatic composition, in a further preferable embodiment, may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12.
[0025] The antistatic composition, in a further preferable embodiment, may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2; each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0026] Particularly, the antistatic composition may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and < 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof; and wherein the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12.
[0027] Further particularly, the antistatic composition may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and < 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof; and wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2 each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0028] Further particularly, the antistatic composition may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (II), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12; and wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2 each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms. [0029] Even further particularly, the antistatic composition may for example comprise
(a) > 50.0 and < 95.0 wt%, preferably > 50.0 and < 75.0 wt% of the hydrocarbon fraction;
(b) > 0.5 and < 10.0 wt% of the fraction of benzenesulfonic acid derivatives; and
(c) > 0.1 and < 2.5 wt% of the fraction of quaternary ammonium compounds with regard to the total weight of the antistatic composition; wherein the hydrocarbon fraction (a) consists of a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > -20°C and < 190°C, and preferably comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof; wherein the fraction of benzenesulfonic acid derivatives (b) comprises or consists of compounds of formula (III), or mixtures thereof, wherein each of R2 and R3 individually is a straight chain alkyl moiety comprising > 1 and < 11 carbon atoms, and the sum of carbon atoms of R2 and R3 together is > 9 and < 12; and wherein the fraction of quaternary ammonium compounds (c) comprises or consists of compounds according to formula (V), wherein R5 is NO2 each of R1 and R2 is methyl, and each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
[0030] In the catalyst system of the present invention, the support material may for example be selected from silica, alumina, magnesia, titania, zirconia, clay, zeolite, polystyrene, polyethylene, polypropylene, polyvinylchloride, polycarbonate, polyketone, polyvinylalcohol, polymethyl methacrylate, cellulose, and graphite, preferably the support material is silica. Preferably, the support material is a porous support material, preferably a porous silica. More preferably, the support material has an average particle size of 1 to 120 pm, more preferably 20 to 80 pm, even more preferably 40 to 50 pm. The pore volume of the support preferably is > 0.5 and < 3.0 cm3/g. Preferably, the surface area of the support material is > 50 and < 500 m2/g. The silica that may be employed as support in for the catalyst system preferably is dehydrated prior to use in preparation of the catalyst system. It is preferred that the supported material is a silica having a particle size of from 10 to 120 pm, a pore volume of > 0.5 and < 3.0 cm3/g, and a surface area of > 50 and < 500 m2/g, as determined in accordance with ISO 9276-2 (2014).
[0031] The catalyst system according to the invention may for example be produced using a process involving the steps of: (i) adding, in a reaction vessel, the support material, preferably wherein the support material is pre-dehydrated, to a quantity of an organic hydrocarbon liquid, preferably toluene, and stirring to form a suspension;
(ii) preparing, in a separate vessel, an activated metallocene by mixing the metallocene with the cocatalyst in a quantity of an organic hydrocarbon liquid, preferably toluene;
(iii) adding the mixture comprising the activated metallocene obtained under (ii) to the suspension obtained under (i), and subjecting the obtained reaction mixture to a heat treatment, preferably at a temperature of > 80°C, more preferably of > 80°C and < 120°C, and preferably for a period of > 2.5 hours, more preferably for a period of > 2.5 and < 6.0 hours;
(iv) mixing, in a further separate vessel, the cocatalyst aid and the antistatic agent in a quantity of an organic hydrocarbon liquid, preferably toluene;
(v) adding the mixture obtained in (iv) to the reaction mixture obtained from (iii), and subjecting the obtained reaction mixture to a heat treatment, preferably at a temperature of > 80°C, more preferably of > 80°C and < 120°C, for a period of > 0.5 and < 2.0 hours; and
(vi) drying the reaction product obtained from (v).
[0032] Preferably, after step (iii) but prior to step (v), an additional quantity of the cocatalyst aid is added to the reaction mixture obtained from (iii).
[0033] It is preferred that each of the steps (i), (ii) and (iv) are performed at a temperature of < 60°C, preferably of < 50°C, more preferably of > 10°C and < 30°C, and that the heat treatment in steps (iii) and (v) is performed at a temperature of > 80°C and < 120°C.
[0034] The organic hydrocarbon liquid may for example be selected from heptane, hexane, isopentane and toluene, preferably the hydrocarbon solvent is toluene. It is preferred that the organic hydrocarbon liquid used in each of the steps of the process is the same, most preferable toluene.
[0035] In a particular embodiment, the invention also relates to a catalyst system according to the invention, wherein the catalyst system is prepared according to the process according to the invention. [0036] The invention will now be illustrated by the following non-limiting examples. A number of synthesis experiments of catalyst systems were conducted, as well as a number of polymerisation experiments.
Handling of Materials
[0037] During the conduct of the experiments, all materials were handled in a nitrogen atmosphere using either Schlenk techniques or a nitrogen-filled glove box. Nitrogen and isopentane were dried through a bed of molecular sieves. All other solvents were first dried over molecular sieves and sodium/potassium amalgam. In preparation of the catalyst systems, the temperatures were controlled to within 0.5°C of the set temperature in a silicon oil bath with stirring. During ethylene polymerisation experiments, a scavenger AO was used which was prepared by dilution of commercial product AXION PA 4276, obtainable from Lanxess, in hexane by 1.6 times. A continuity aid agent A1 was used in certain fluidized bed ethylene polymerisation experiments that was prepared by dilution of AXION PA4276 by 25 times in isopentane. Chimassorb 944 was dried under vacuum at 80°C for 12 hours.
Materials used
[0038] In the table 1 below, the materials that were used in the experiments are listed.
Table 1 : Materials
Synthesis of Catalyst Systems, Method A
[0039] A number of supported metallocene catalyst systems were prepared according to the below method. The quantities and type of each of the materials used in the synthesis are presented in table 2, unless otherwise specified below.
[0040] The support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
[0041] In a 25 ml vial, 0.035 g of the metallocene was activated by mixing it with 12.5 ml of a 10 wt% solution of the cocatalyst in toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere. The activated metallocene was then added to the suspension.
[0042] In another 25 ml vial, given amounts of cocatalyst aid and antistatic agent were mixed in 10 ml of toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere, and then also added to the suspension.
[0043] Subsequently, the suspension was heated to 95°C, and maintained at that temperature for 5 hours. Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder. The supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296.
Table 2: Material formulations for catalyst systems synthesised according to Method A
Synthesis of Catalyst Systems, Method B
[0044] A number of supported metallocene catalyst systems were prepared according to the below method. The quantities and type of each of the materials used in the synthesis are presented in table 3, unless otherwise specified below.
[0045] The support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
[0046] In a 25 ml vial, 0.035 g of the metallocene was activated by mixing it with 12.5 ml of a 10 wt% solution of the cocatalyst in toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere. The activated metallocene was then added to the suspension.
[0047] The suspension was then heated to 95°C and maintained at that temperature for 4 hours.
[0048] In another 25 ml vial, given amounts of cocatalyst aid and antistatic agent were mixed in 10 ml of toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere, and then also added to the suspension that was still at 95°C.
[0049] Subsequently, the suspension was maintained at 95°C for another 1 hour. Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder. The supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296. Table 3: Material formulations for catalyst systems synthesised according to Method B
Synthesis of Catalyst Systems, Method C
[0050] A number of supported metallocene catalyst systems were prepared according to the below method. The quantities and type of each of the materials used in the synthesis are presented in table 4, unless otherwise specified below.
[0051] The support was pre-dehydrated at 600°C for 4 hours. 2.5 g of the pre-dehydrated support was charged into a 100 ml two-neck Schlenk flask in a glovebox under nitrogen atmosphere, followed by the addition of 15 ml of toluene at room temperature. After shaking, a suspension was obtained.
[0052] In a 25 ml vial, 0.035 g of the metallocene was activated by mixing it with 12.5 ml of a 10 wt% solution of the cocatalyst in toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere. The activated metallocene was then added to the suspension.
[0053] The suspension was then heated to 95°C and maintained at that temperature for 4 hours. Subsequently, 0.0074 g of the cocatalyst aid in 10 ml of toluene was added to the suspension at 95°C and kept at 95°C for another 10 min.
[0054] In another 25 ml vial, given amounts of cocatalyst aid and antistatic agent as in table 4 were mixed in 10 ml of toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere, and then also added to the suspension that was still at 95°C.
[0055] Subsequently, the suspension was maintained at 95°C for another 1 hour. Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder. The supported catalyst systems contained 0.16 wt% of Zr and 14.0 wt% of Al, which translates to a molar ratio of Al to Zr of ca. 296. Table 4: Material formulations for catalyst systems synthesised according to Method C
Synthesis of Catalyst Systems, Method D
[0056] A number of supported metallocene catalyst systems were prepared according to the below method. The quantities and type of each of the materials used in the synthesis are presented in table 5, unless otherwise specified below.
[0057] A 3-litre autoclave reactor equipped with a heating/cooling control unit and a mechanical stirring system was baked at 150°C under a nitrogen flow for 2 hours and then cooled down to 30°C.
[0058] The support was pre-dehydrated at 600°C for 4 hours. 150 g of the pre-dehydrated support was charged to the reactor, followed by the addition of 750 ml of toluene at room temperature, and stirred to form a suspension.
[0059] 2.065 g of the metallocene was activated by mixing it with 737 ml of a 10 wt% solution of the cocatalyst in toluene, at 50°C for 30 min. The activated metallocene was then added to the reactor with stirring.
[0060] The suspension was then heated to 95°C and maintained at that temperature for 4 hours.
[0061] In a 250 ml vial, given amounts of cocatalyst aid and antistatic agent as in table 5 were mixed in 100 ml of toluene, at room temperature for 10 min in the glovebox, also under nitrogen atmosphere, to form an antistatic agent I cocatalyst aid mixture.
[0062] In the examples D1 and D3, the antistatic agent I cocatalyst aid mixture was added to the autoclave reactor directly after the 4 hour heat treatment as described above. The reaction mixture in the autoclave reactor was kept at 95°C for 1 further hour, under stirring. [0063] Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder. The supported catalyst systems contained 0.18 wt% of Zr and 14.0 wt% of Al.
[0064] In the examples D2 and D4, 0.44 g of cocatalyst aid in 50 ml of toluene was charged into the reactor directly after the 4 hour heat treatment as described above, and kept at 95°C for 10 min under stirring. Then, the antistatic agent I cocatalyst aid mixture was added to the autoclave reactor. The reaction mixture in the autoclave reactor was kept at 95°C for 1 further hour, under stirring.
[0065] Thereafter, the product was dried at 75°C under vacuum to obtain the supported catalyst system, which was isolated as a free-flowing powder. The supported catalyst systems contained 0.18 wt% of Zr and 14.0 wt% of Al.
Table 5: Material formulations for catalyst systems synthesised according to Method D
Examples E: Polymer synthesis experiments - batch
[0066] Using the catalyst systems produced according to the methods A through D above, a set of polymerisation experiments was conducted at batch reactor scale.
[0067] A 1.6 stainless steel reactor vessel equipped with a helical stirrer and a heating/cooling control unit was heated to 110°C at a nitrogen flow of 100 g/h for 2 hours. After that, the reactor was pressure purged with nitrogen, followed by a purge with ethylene. This purging cycle was repeated three times.
[0068] The reactor was then cooled to 88°C under ethylene pressurised to 1000 kPa. After venting, 4 ml of scavenger A0 was added via a cocatalyst injection pump. Nitrogen was introduced to maintain a nitrogen pressure of 800 kPa. Ethylene was then introduced into the reactor under control of mass flow parameters to maintain an ethylene pressure in the reactor of 1000 kPa.
[0069] Upon reaching a stable level of temperature and pressure, 30 mg of the catalyst system as specified for each polymerisation example in the table 6 below was injected via a catalyst injection pump, and the reaction started. After 1 hour, the ethylene supply was discontinued, and the reactor was cooled to 40°C. The reactor was opened after venting. The polyethylene product that was obtained was collected to a sample tray, and dried at ambient temperature under atmospheric pressure.
[0070] The results of the batch polymerisation experiments E are presented in the table 6 below.
Table 6: Catalyst systems used and polymerisation results from experiments E.
[0071] In the reaction of experiment E1 , certain sheeting and lump formation occurred in the reactor. No sheeting and lump formation occurred in the experiments E2-E18.
[0072] It can be observed that when using the catalyst system according to the present invention, a desirably high yield of polyethylene and productivity can be observed, whilst avoiding sheeting and lump formation in the reactor. Furthermore, it can be observed that the addition of the antistatic agent during the synthesis of the catalyst system as per the present invention, i.e. after first subjecting the suspension of silica and activated metallocene to heat for a certain period, affects the productivity in polyethylene synthesis. Examples F: Polymer synthesis experiments - fluidized bed polymerisation
[0073] The supported catalyst systems produced in experiments D1-D4 were tested in a continuous gas phase fluidised bed reactor having an internal diameter of 45 cm and a reaction zone height of 140 cm. the bed of polymer particles in the reaction zone was kept in a fluidised state by supplying a recycle gas stream that acts as fluidising medium as well as as a heat dissipating agent for absorbing the exothermal heat generated within the reaction zone.
[0074] The reactor was kept at a constant temperature of 87°C and at a constant ethylene pressure of 2.17 MPa. Ethylene and 1-hexene were used as the reactants for polymerisation. These materials are supplied as a make-up stream. 60 ppm by wt of the continuity aid agent A1 was added to the make-up stream before charging into the reactor.
[0075] The catalyst system composition in solid form was injected directly into the reaction zone of the fluidised bed reactor using purified nitrogen as carrier gas. The injection rate was adjusted to maintain a constant polymerisation rate of about 10 kg/h. the produced polymer was discharged from the reactor semi-continuously via a series of valves into a fixed volume chamber. The so obtained product was purged to remove any volatile hydrocarbons, and was then treated with humidified nitrogen to deactivate any trace quantities of residual catalyst composition.
[0076] In the table 7 below, the specifications of the catalyst and the feed used in the experiments F1-F4, and the properties of the polymers that were obtained are presented.
Table 7: Catalyst systems and feeds used, and polymer properties from experiments F.
The determination of the polymer properties of the products of the experiments F1-F4 was performed using the following methods:
• The residual ash content was determined in accordance with ISO 3451-1 (2019), at 600°C for 4 hours.
• The melt mass-flow rate was determined according to ISO 1133-1 (2011) at 190°C and 21.6 kg load.
• The density was determined in accordance with ISO 1183-1 (2019).
• The bulk density was determined in accordance with ASTM D1895- 96 (2010). • The average particle size was determined as D5o in accordance with ISO 13320 (2009).
• The fraction of fines was determined in accordance with the method of ASTM D1921 (2006), as the wt% of material passing through a 125 pm sieve.

Claims

Claims
1. Process for the polymerisation of olefins, the process involving reacting olefins in the presence of a catalyst system wherein the catalyst system comprises a support material carrying: a. a metallocene compound; b. a cocatalyst; and c. an antistatic agent; wherein the metallocene compound is a compound according to formula (I): wherein:
• Z is a moiety selected from ZrX2, HfX2, or TiX2, wherein X is selected from the group of halogens, alkyls, aryls and aralkyls;
• R2 is a bridging moiety containing at least one sp2 hybridised carbon atom, preferably R2 is a substituted or unsubstituted methylene, 1 ,2-phenylene or 2,2’-biphenylene moiety; and
• each R1, R1’, R3, R3’, R4, R4’, R5 and R5’ are hydrogen or a hydrocarbon moiety comprising 1-20 carbon atoms; wherein the cocatalyst is an organoaluminium compound; and wherein the antistatic agent is an antistatic composition comprising:
(a) a hydrocarbon fraction;
(b) a fraction of benzenesulfonic acid derivatives; and (c) a fraction of quaternary ammonium compounds.
2. Process according to claim 1, wherein the metallocene compound is selected from [ortho- bis(4-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)- benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho- bis(2-indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)- benzene]zirconiumdichloride, [2,2'-bis(2-indenyl)biphenyl]zirconiumdichloride and [2,2 - bis(2-indenyl)biphenyl]hafniumdichloride, preferably the metallocene compound is [2,2’- bis(2-indenyl)biphenyl]zirconium dichloride.
3. Process according to claim 1 , wherein X is a monovalent anionic group, selected from the group consisting of halogens, a C1-C20 hydrocarbyl group or a C1-C20 alkoxy group, preferably wherein X is a methyl group, Cl, Br or I, most preferably methyl or Cl.
4. Process according to any one of claims 1 or 3, wherein Z is a moiety selected from ZrCI2, HfCI2 and TiCI2.
5. Process according to any one of claims 1-4, wherein the cocatalyst is methylaluminoxane.
6. Process according to any one of claims 1-5, wherein the hydrocarbon fraction is a mixture of hydrocarbons comprising 4 to 11 carbon atoms, preferably having a boiling point of > - 20°C and < 190°C, more preferably wherein the hydrocarbon fraction is a mixture of hydrocarbons comprising n-alkanes, isoalkanes, cyclic hydrocarbons, or mixtures thereof.
7. Process according to any one of claims 1-6, wherein the fraction of benzenesulfonic acid derivatives comprises or consists of compounds of formula (II), or mixtures thereof: formula (II) wherein R1 is an alkyl moiety comprising > 10 and < 13 carbon atoms.
8. Process according to any one of claims 1-7, wherein the antistatic composition comprises
< 10.0 wt% of benzenesulfonic acid derivatives, preferably > 0.5 and < 10.0 wt%, with regard to the total weight of the antistatic composition.
9. Process according to any one of claims 1-8, wherein the fraction of quaternary ammonium compounds comprises or consists of compounds according to formula (V):
R2
R1 - N - R3 ■ R5
R4 formula (V) wherein R5 is selected from NO2", C , F OH and ! (CO3 2 , preferably NO2 and wherein each of R1 and R2 are the same and selected from methyl, ethyl, propyl or butyl moieties, preferably both R1 and R2 are methyl moieties; and wherein each of R3 and R4 individually is an alkyl moiety comprising > 8 and < 18 carbon atoms.
10. Process according to any one of claims 1-9, wherein the antistatic composition comprises
< 2.5 wt% of the fraction of quaternary ammonium compounds, preferably > 0.1 and < 2.5 wt%, with regard to the total weight of the antistatic composition.
11. Process according to any one of claims 1-10, wherein the support material is selected from silica, alumina, magnesia, titania, zirconia, clay, zeolite, polystyrene, polyethylene, polypropylene, polyvinylchloride, polycarbonate, polyketone, polyvinylalcohol, polymethyl methacrylate, cellulose, and graphite, preferably wherein the support material is silica.
12. Process according to any one of claims 1-11 , wherein the olefins are one or more selected from ethylene, propylene, 1 -butene, 1 -hexene, and 1 -octene, preferably wherein the process is a polymerisation process of ethylene alone or as a mixture with 1 -butene, 1- hexene or 1 -octene.
13. Process according to any one of claims 1-12, wherein the catalyst system is produced via a the process involving the steps of:
(i) adding, in a reaction vessel, the support material, preferably wherein the support material is pre-dehydrated, to a quantity of an organic hydrocarbon liquid, preferably toluene, and stirring to form a suspension;
(ii) preparing, in a separate vessel, an activated metallocene by mixing the metallocene with the cocatalyst in a quantity of an organic hydrocarbon liquid, preferably toluene;
(iii) adding the mixture comprising the activated metallocene obtained under (ii) to the suspension obtained under (i), and subjecting the obtained reaction mixture to a heat treatment, preferably at a temperature of > 80°C, more preferably of > 80°C and < 120°C, and preferably for a period of > 2.5 hours, more preferably for a period of > 2.5 and < 6.0 hours;
(iv) mixing, in a further separate vessel, a cocatalyst aid and the antistatic agent in a quantity of an organic hydrocarbon liquid, preferably toluene;
(v) adding the mixture obtained in (iv) to the reaction mixture obtained from (iii), and subjecting the obtained reaction mixture to a heat treatment, preferably at a temperature of > 80°C, more preferably of > 80°C and < 120°C, for a period of > 0.5 and < 2.0 hours; and
(vi) drying the reaction product obtained from (v); preferably wherein after step (iii) but prior to step (v), an additional quantity of the cocatalyst aid is added to the reaction mixture obtained from (iii).
14. Process according to claim 13, wherein each of the steps (i), (ii) and (iv) are performed at a temperature of < 60°C, preferably of < 50°C, more preferably of > 10°C and < 30°C, and wherein the heat treatment in steps (iii) and (v) is performed at a temperature of > 80°C and < 120°C.
15. Process according to any one of claims 1-14, wherein the process is a gas-phase process, preferably a fluidised-bed gas-phase polymerisation process, preferably wherein the polymerisation is performed at a temperature of > 70°C and < 100°C, and at a pressure of > 1.0 and < 3.0 MPa.
EP24707868.6A 2023-03-10 2024-03-04 Process for polymerisation of olefins Pending EP4676988A1 (en)

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PCT/EP2024/055634 WO2024188700A1 (en) 2023-03-10 2024-03-04 Process for polymerisation of olefins.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0445110A (en) * 1990-06-12 1992-02-14 Japan Synthetic Rubber Co Ltd Production of ethylenic copolymer
US8987389B2 (en) * 2010-07-30 2015-03-24 Total Research & Technology Feluy Process for preparing polyolefins and use of antifouling agents therein
JP5667949B2 (en) * 2011-09-08 2015-02-12 日本ポリエチレン株式会社 Method for polymerizing olefins with improved polymer particle properties
EP3155025B1 (en) * 2014-06-12 2018-03-14 Total Research & Technology Feluy Process for preparing a polyethylene in at least one continuously stirred tank reactor

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