WO2017093129A1 - Procédé de préparation d'un procatalyseur pour la polymérisation d'oléfines - Google Patents

Procédé de préparation d'un procatalyseur pour la polymérisation d'oléfines Download PDF

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WO2017093129A1
WO2017093129A1 PCT/EP2016/078769 EP2016078769W WO2017093129A1 WO 2017093129 A1 WO2017093129 A1 WO 2017093129A1 EP 2016078769 W EP2016078769 W EP 2016078769W WO 2017093129 A1 WO2017093129 A1 WO 2017093129A1
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intermediate product
compound
tetravalent titanium
aryl
alkyl
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PCT/EP2016/078769
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English (en)
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Bandar Abdullah ALMOHAMMADI
Inaamul Haq SIDDIQUI
Sudhakar R PADMANABHAN
Akhlaq Moman
Ahmad Abdullah ALSHAIBAN
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Sabic Global Technologies B.V.
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Publication of WO2017093129A1 publication Critical patent/WO2017093129A1/fr

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    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • 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
    • C08F2410/06—Catalyst characterized by its size

Definitions

  • the present invention is related to a method for producing a olefin polymerization catalyst component, which method comprises the steps of halogenating a magnesium compound of the formula MgR'R" wherein R' is an alkoxide or aryloxide group and wherein R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an internal electron donor.
  • Such catalyst systems are generally referred to as "Ziegler-Natta" catalysts comprising a transition metal-containing solid catalyst compound (also typically referred to as a procatalyst); an organometallic compound (also typically referred to as a co-catalyst) and optionally one or more electron donor compounds (e.g. external electron donors).
  • a transition metal-containing solid catalyst compound also typically referred to as a procatalyst
  • an organometallic compound also typically referred to as a co-catalyst
  • electron donor compounds e.g. external electron donors
  • Such a process is for example known from US 4,414,132 and US 4,535,068 wherein a magnesium compound, such as magnesium diethoxide is reacted with a titanium halide compound in the presence of a halohydrocarbon and e.g. ethyl benzoate or p-methyl toluate as internal donor and moreover an acid halide, such as benzoyl chloride.
  • a magnesium compound such as magnesium diethoxide
  • a titanium halide compound in the presence of a halohydrocarbon and e.g. ethyl benzoate or p-methyl toluate as internal donor and moreover an acid halide, such as benzoyl chloride.
  • a disadvantage of said methods is that benzoyl chloride is a toxic compound and should be avoided.
  • said method does not sufficiently allow the tuning of the procatalyst in such a manner that the properties of the resulting product may be tuned.
  • the present invention relates to a method for producing an olefin polymerization catalyst component, which method comprises the steps of: (a) halogenating a magnesium compound of the formula MgR'R" wherein R' is an alkoxide or aryloxide group and wherein R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an activator; to form a first intermediate product; (b) contacting the first intermediate product with a mixture of a tetravalent titanium halide and an internal electron donor, wherein step (b) comprises two sub steps (b1 ) and (b2):
  • each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon
  • each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms;
  • R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • N is
  • step (b) comprises two sub steps (b1 ) and (b2): (b1 ) contacting the first intermediate product with a mixture of a tetravalent titanium halide and an internal electron donor; to obtain a second intermediate product; and (b2) contacting the second intermediate product with a tetravalent titanium halide to obtain a third intermediate product; and wherein step (c) is: (c) washing the third intermediate product with an inert hydrocarbon liquid to obtain a procatalyst.
  • the activator is a monoester, preferably a benzoate ester, more preferably ethylbenzoate.
  • the internal donor is represented by a compound according to the formula A: ;
  • each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon
  • R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.
  • R 7 is a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof.
  • R 7 is not hydrogen.
  • the internal donor is represented by a compound according to the formula B:
  • each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms;
  • R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • N is
  • the magnesium compound is a dialkoxymagnesium compound, preferably diethoxymagnesium.
  • the tetravalent titanium compound is a titanium tetrahalide, preferably TiCU and/or wherein the same tetravalent titanium compound is used in each of the steps.
  • the halohydrocarbon is chlorobenzene.
  • the inert hydrocarbon liquid is an alkane, preferably isopentane or n-heptane.
  • the activator is ethylbenzoate, wherein the internal donor is 4- [benzoyl(methyl)amino]pentan-2-yl benzoate (AB), wherein the magnesium compound is diethoxymagnesium, wherein the tetravalent titanium compound for each step is TiCU, wherein the halohydrocarbon is chlorobenzene, wherein the inert hydrocarbon liquid is an alkane.
  • the internal donor is 4- [benzoyl(methyl)amino]pentan-2-yl benzoate (AB)
  • the magnesium compound is diethoxymagnesium
  • the tetravalent titanium compound for each step is TiCU
  • the halohydrocarbon is chlorobenzene
  • the inert hydrocarbon liquid is an alkane.
  • the activator is ethylbenzoate, wherein the internal donor is ethyl (4- ((ethoxycarbonyl)oxy)pentan-2-yl)(methyl)carbamate (AB-OEt), wherein the magnesium compound is diethoxymagnesium, wherein the tetravalent titanium compound for each step is TiCU, wherein the halohydrocarbon is chlorobenzene, wherein the inert hydrocarbon liquid is an alkane.
  • the internal donor is ethyl (4- ((ethoxycarbonyl)oxy)pentan-2-yl)(methyl)carbamate (AB-OEt)
  • the magnesium compound is diethoxymagnesium
  • the tetravalent titanium compound for each step is TiCU
  • the halohydrocarbon is chlorobenzene
  • the inert hydrocarbon liquid is an alkane.
  • inter donor or "internal electron donor” or “ID” as used in the present description means: an electron-donating compound containing one or more atoms of oxygen (O) and/or nitrogen (N). This ID is used as a reactant in the preparation of a solid procatalyst.
  • activator as used in the present description means: an electron-donating compound containing one or more atoms of oxygen (O) and/or nitrogen (N) which is used to during the synthesis of the procatalyst prior to or simultaneous with the addition of an internal donor.
  • activator as used in the present description means: an electron-donating compound containing one or more atoms of oxygen (O) and/or nitrogen (N) which is used to during the synthesis of the procatalyst prior to or simultaneous with the addition of an internal donor.
  • external donor or “external electron donor” or “ED” as used in the present description means: an electron-donating compound used as a reactant in the polymerisation of olefins.
  • An ED is a compound added independent of the procatalyst.
  • catalyst as used in the present description have the same meaning: a component of a catalyst composition (also called “catalyst component” in this description) generally comprising a solid support, a transition metal-containing catalytic species and optionally one or more internal donor.
  • halide as used in the present description means: an ion selected from the group of: fluoride (F-), chloride (CI-), bromide (Br-) or iodide (I-).
  • alkoxide or “alkoxy” as used in the present description means: a functional group or side- chain obtained from a alkyl alcohol. It consist of an alkyl bonded to a negatively charged oxygen atom, "alkyl” as used in the present description means: an alkyl group being a functional group or side-chain consisting of carbon and hydrogen atoms having only single bonds. An alkyl group may be straight or branched and may be un-substituted or substituted. An alkyl group may also comprise alkenyl or alkylaryl groups.
  • aryloxide or aryloxy or “phenoxy” as used in the present description means: a functional group or side-chain obtained from an aryl alcohol. It consist of an aryl bonded to a negatively charged oxygen atom, "aryl” as used in the present description means: an aryl group being a functional group or side-chain derived from an aromatic ring. An aryl group and may be un-substituted or substituted with straight or branched hydrocarbyl groups. An aryl group also encloses alkaryl groups wherein one or more hydrogen atoms on the aromatic ring have been replaced by alkyl groups.
  • Mw weight-average molecular weight
  • Mn number average molecular weight
  • Mw and Mn are determined by GPC using a Waters 150 °C gel permeation chromatograph (GPC) combined with a Viscotek 100 differential viscosimeter; the chromatograms were run at 140 °C using 1 ,2,4- trichlorobenzene as a solvent; the refractive index detector was used to collect the signal for molecular weights.
  • XS or "xylene soluble fraction” or “CXS” or “cold soluble xylene fraction” as used in the present description means: the weight percentage (wt.%) of soluble xylene in the isolated polymer, measured according to ASTM D 5492-10.
  • d50 as used in the present description means: the Particle Size Distribution D50 or median diameter or medium value of the particle size distribution and is measured using Malvern SCIROCCO 2000 laser scattering detector according to ASTM D4464-15.
  • production rate or yield as used in the present description means: the amount of kilograms of polymer produced per gram of procatalyst consumed in the polymerization reactor per hour, unless stated otherwise.
  • any R group is "independently selected from” this means that when several of the same R groups are present in a molecule they may have the same meaning of they may not have the same meaning.
  • R2M wherein R is independently selected from ethyl or methyl, both R groups may be ethyl, both R groups may be methyl or one R group may be ethyl and the other R group may be methyl.
  • the present invention relates to a method which comprises the steps of:
  • step (b) contacting the first intermediate product with a mixture of a tetravalent titanium halide and an internal electron donor; wherein step (b) comprises two sub steps (b1 ) and (b2):
  • each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon
  • each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • an activator preferably a monoester activator
  • internal donor preferably according to Formula A or B
  • an activator during step (a) and an internal donor during step (b) eliminates the need to add an acid halide, such as benzoyl chloride, during step (b) thereby making the process more environmentally friendly and more safe and allows the process to be carried out on a larger scale.
  • an acid halide such as benzoyl chloride
  • Step (a) relates to halogenating a magnesium compound of the formula MgR'R" wherein R' is an alkoxide or aryloxide group and wherein R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an activator; to form a first intermediate product.
  • magnesium compounds of the formula MgR'R" wherein R' is an alkoxide or aryloxide group and wherein R" is an alkoxide or aryloxide group or halogen are disclosed in US 4,535,068, column 4, lines 1 1 -34 and in US 4,414,132 column 2, lines 33- 50 which sections are incorporated by reference.
  • R' may comprise between 1 and 20 carbon atoms.
  • R" may comprise between 1 and 20 carbon atoms.
  • Suitable examples of tetravalent titanium compounds are disclosed in US 4,535,068, column 4, lines 53-58 and in US 4,414,132 column 3, lines 3-8 which sections are incorporated by reference.
  • the tetravalent titanium compound is a titanium tetrahalide, preferably TiCU.
  • halohydrocarbon Suitable examples of the halohydrocarbon are disclosed in US 4,535,068, column 4, line 59 - column 5, line 9 and in US 4,414,132 column 3, lines 10-25 which sections are incorporated by reference.
  • the halohydrocarbon is an aromatic halohydrocarbon, such as (di)chlorobenzene.
  • the halohydrocarbon is chlorobenzene.
  • an inert diluent or solvent may also be present. The same inert solvents as used in step (c) may also be used here.
  • the ratio between the amount of titanium compound and halohydrocarbon may for example between 25:75 and 75:25, such as between 60:40 and 40:60 or even 50:50 (all in v/v).
  • the halogenation of magnesium is preferably carried out in such a manner that magnesium halide is formed in which the atomic ratio of halogen to magnesium is at least 1.2, preferably at least 1.5.
  • the molar ratio of the magnesium compound and the titanium compound during step (a) are in an embodiment between 0.005 : 1 and 2: 1 , preferably between 0.01 : 1 to 1 :1.
  • the activator is a monoester, preferably a benzoate ester, more preferably ethylbenzoate. More monoesters are discussed in WO 2014/1 18164, page 7, line 28 to page 8 lines 26, which section is incorporated by reference.
  • the amount of the activator may be such that the content of the activator in the procatalyst is between 1 and 7 wt.%, such as between 2 and 5 wt.% based on the procatalyst weight.
  • the molar ratio of activator to magnesium compound during step (a) may for example between 0.05: 1 and 0.5 : 1 , preferably between 0.1 : 1 and 0.3 : 1 , more preferably between 0.1 : 1 and 0.3 : 1.
  • Step (a) may be carried out at temperatures ranging e.g. between 60 °C to 140 °C, preferably between 80 °C to 120 °C, more preferably between 100 °C to 120 °C, such as 1 10 °C.
  • the starting compounds are first mixed at room temperature, e.g. 25 °C, and subsequently heated.
  • Step (a) may be carried out for a duration of between 0.1 and 6 hours, preferably between 0.5 and 3.5 hours, such as between 0.5 and 1.0 hour.
  • step (a) preferably an additional step is carried out, being step (a'): step (a') filtrating the reaction mixture obtained in step (a) to obtain a solid product, being the first intermediate reaction product.
  • the retentate is the first intermediate reaction product.
  • the filtrate may be discarded.
  • filtrating step (a') may also involve decanting.
  • Step (b) relates to contacting the first intermediate product with a tetravalent titanium halide and an internal electron donor. There are several embodiments to this step that will be discussed below.
  • Suitable examples of tetravalent titanium compounds are disclosed in US 4,535,068, column 4, lines 53-58 and in US 4,414,132 column 3, lines 3-8 which sections are incorporated by reference.
  • the same tetravalent titanium compound is used in each of the steps (a) and (b). Examples are: dialkoxy-titanium dihalides, alkoxy-titanium trihalides, phenoxy- titanium trihalides and titanium tetrahalides.
  • the tetravalent titanium compound is a titanium tetrahalide, preferably TiCU.
  • TiCU is used in each of the steps (a) and (b).
  • Suitable examples of the halohydrocarbon are disclosed in US 4,535,068, column 4, line 59 - column 5, line 9 and in US 4,414,132 column 3, lines 10-25 which sections are incorporated by reference.
  • the halohydrocarbon is an aromatic halohydrocarbon, such as (di)chlorobenzene.
  • the halohydrocarbon is chlorobenzene.
  • the ratio between the amount of titanium compound and halohydrocarbon may for example between 25:75 and 75:25, such as between 60:40 and 40:60 or even 50:50 (all in v/v).
  • the titanation treatments increase the content of titanium in the solid catalyst.
  • the final molar ratio of tetravalent titanium to magnesium in the procatalyst obtained is between 0.005 to 3.0, preferably from 0.02 to 1 .0.
  • the final tetravalent titanium content is between 1 .5 and 5.5 wt.%, preferably between 2.0 and 4.5 wt.% based on the procatalyst weight.
  • Step (b) may be carried out at temperatures ranging e.g. between 60 °C to 140 °C, preferably between 80 °C to 120 °C, more preferably between 100 °C to 120 °C, such as 1 10 °C.
  • Steps (b), or (b1 ) or (b2) may be carried out for a duration of between 0.1 and 6 hours, preferably between 0.25 and 2 hours, for example 0.3 to 1.0 hour, such as 0.5 hours.
  • step (b) (or afters both of steps (b1 ) and (b2) preferably an additional step is carried out, being respectively step (b')/(b1 ')/(b2'):
  • step (b') filtrating the reaction mixture obtained in step (b) to obtain a solid product, being the second intermediate reaction product.
  • the retentate is the second intermediate reaction product.
  • the filtrate may be discarded.
  • step (b1 ') filtrating the reaction mixture obtained in step (b1 ) to obtain a solid product, being the second intermediate reaction product.
  • the retentate is the second intermediate reaction product.
  • the filtrate may be discarded.
  • step (b2') filtrating the reaction mixture obtained in step (b2) to obtain a solid product, being the third intermediate reaction product.
  • the retentate is the third intermediate reaction product.
  • the filtrate may be discarded. Instead of a filtrating step, this step may also involve decanting.
  • no acyl halide preferably no benzoyl chloride is used during step b).
  • the internal donor is represented by a compound according to formula A wherein each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms; R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms; R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms; N is
  • the internal donor is represented by a compound according to formula B wherein each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms; R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms; R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably
  • R 81 , R 82 R 83 R 84 R 85 and R 86 of Formula B are independently selected from a group consisting of hydrogen, C1-C10 straight and branched alkyl; C3-Cio cycloalkyl; C6-C10 aryl; and C7-Cio alkaryl and aralkyi group.
  • R 81 and R 82 are each a hydrogen atom and R 83 R 84 , R 85 and R 86 are independently selected from a group consisting of C1-C10 straight and branched alkyl; C3-C10 cycloalkyl; C6-C10 aryl; and C7-C10 alkaryl and aralkyi group, preferably from C1-C10 straight and branched alkyl and more preferably from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl group.
  • R 83 and R 84 and one of R 85 and R 86 when one of R 83 and R 84 and one of R 85 and R 86 has at least one carbon atom, then the other one of R 83 and R 84 and of R 85 and R 86 is each a hydrogen atom.
  • R 87 is selected from a group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl, benzyl, substituted benzyl and halophenyl group.
  • R 80 is a aliphatic hydrocarbyl group or an aromatic hydrocarbyl group. R 80 may be substituted on unsubstituted.
  • R 80 is an aliphatic hydrocarbyl group, it may be selected from the group consisting of aliphatic substituted and unsubstituted hydrocarbyls having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. More preferably, R 80 is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, t-butyl, pentyl or hexyl. Most preferably, R 80 is ethyl. In case R 80 is an aromatic hydrocarbyl group, it may be phenyl or substituted phenyl or any other aromatic group having from 6 to 20 carbon atoms.
  • Step (b) comprises two sub steps (b1 ) and (b2): (b1 ) contacting the first intermediate product with a mixture of a tetravalent titanium halide and an internal electron donor; to obtain a second intermediate product; and (b2) contacting the second intermediate product with a tetravalent titanium halide to obtain a third intermediate product.
  • the internal donor is added in a single addition during step (b1 ).
  • This invention comprises in step (a) halogenation of magnesium, the addition of an activator and a 1 st titanation, in step (b1 ) the addition of a ID and a 2 nd titanation and in step (b2) a 3 rd titanation.
  • Step (c) relates to the work up.
  • a procatalyst prepared according to this invention produces a polymer having a regular molecular weight distribution and a relatively low value for xylene solubles.
  • Step (c) relates to washing the intermediate product obtained with an inert hydrocarbon liquid.
  • the washing of step (c) may be carried out with one or more washing cycles.
  • each washing cycle the solid intermediate product is contacted with an amount of intern hydrocarbon liquid and mixed.
  • an amount of intern hydrocarbon liquid and mixed For example, two, three, four, five, six or seven washing cycles may be carried out.
  • the amount of liquid added during each washing cycle may be determined by the person skilled in the art.
  • the liquid may be different or the same during each washing cycle, preferably the same.
  • the amount of liquid may be different or the same during each washing cycle, preferably the same.
  • step (c) may be carried out at a temperature of between room temperature and 100 °C, preferably between room temperature and 60 °C.
  • the temperature during step (c) may be constant or may be decreased, e.g. from 60 °C to 25 °C, in several steps. For example when 5 washing cycles are carried out, the temperature may be decreased with each cycle.
  • the temperature may be determined by the temperature of the liquid to be added or by external cooling or heating.
  • the inert hydrocarbon liquid is an alkane, such as n-pentane, isopentane, n-hexane, n-heptane, iso-octane, preferably isopentane.
  • alkane such as n-pentane, isopentane, n-hexane, n-heptane, iso-octane, preferably isopentane.
  • toluene may also be used.
  • This inert hydrocarbon liquid is used to wash the solid intermediate product obtained. During this washing any unreacted material, including physically absorbed halohydrocarbon may be removed.
  • step (c) preferably an additional step is carried out, being step (c'): step (c') filtrating the reaction mixture obtained in step (c) to obtain a solid product, being the procatalyst.
  • the retentate is the procatalyst.
  • the filtrate may be discarded. Instead of a filtrating step, this step may also involve decanting.
  • the procatalyst can be used as such wetted by the solvent or suspended in solvent or it can be first dried, preferably partly dried, for storage.
  • step (c') preferably an additional step is carried out, being step (c"): step (c") drying the solid product obtained in step (c').
  • This step may for example be carried out by conventional dryings means, such as a flow of an inert gas, e.g. dry nitrogen, during a certain period of time, e.g. between 0.5 and 10 hours, e.g. between 1 and 3 hours, such as 2 hours. Drying can e.g.
  • the procatalyst obtained can be used as dried or suspended in mineral oil for storage. Several embodiments of the present invention are shown below.
  • the present invention relates to a method for producing an olefin polymerization procatalyst, which method comprises the following steps:
  • the present invention relates to a method for producing an olefin polymerization procatalyst, which method comprises the following steps:
  • the present invention relates to a method for producing an olefin polymerization procatalyst, which method comprises the following steps: (a) halogenating diethoxymagnesium with TiCU in the presence of chlorobenzene, and ethylbenzoate; to form a first intermediate product; (b1 ) contacting the first intermediate product with a mixture of TiCU and AB to obtain a second intermediate product; and (b2) contacting the second intermediate product with TiCU to obtain a third intermediate product; and (c) washing the third intermediate product with an alkane, such as n-heptane or isopentane, to obtain a procatalyst.
  • an alkane such as n-heptane or isopentane
  • the present invention relates to a method for producing an olefin polymerization procatalyst, which method comprises the following steps: (a) halogenating diethoxymagnesium with TiCU in the presence of chlorobenzene, and ethylbenzoate; to form a first intermediate product; (b1 ) contacting the first intermediate product with a mixture of TiCU and AB-OEt to obtain a second intermediate product; and (b2) contacting the second intermediate product with TiCU to obtain a third intermediate product; and (c) washing the third intermediate product with an alkane, such as n-heptane or isopentane, to obtain a procatalyst.
  • an alkane such as n-heptane or isopentane
  • a procatalyst prepared according to this first embodiment produces a polymer having a regular molecular weight distribution and a relatively low value for xylene solubles.
  • Synthesis examples 1 and 5 are prepared according to the present invention, having a single addition of the internal donor.
  • Synthesis Examples 2 and 6 are prepared according to a method according to the clauses (see below) not according to the present claims, having a dual (50%/50%) addition of the internal donor.
  • the temperature of the process is reduced from 1 10 °C to 96 °C.
  • the ratio of titanium tetrachloride to chlorobenzene is amended from 40:60 v/v to 50:50 v/v.
  • Comparative Synthesis Example 8 * is according to a prior art method wherein only one electron donor is used.
  • Table 1 shows in the first column the number of the synthesis example, in the second column the designation of the procatalyst, in the third column the activator as well as the amount thereof (between brackets), in the fourth column the reaction temperature in first three steps, in the fifth column the internal donor as well as the amount thereof (between brackets), in the sixth column the d50 value in microns of the procatalyst particles obtained, in the seventh through the eleventh column the percentage of respectively magnesium, titanium, the internal donor, the activator and the alkoxide of the magnesium alkoxide starting product are shown. These different procatalysts were used in the polymerization of propylene.
  • Table 2 shows in the first column the number of the polymerization example, in the second column the designation of the procatalyst, in the third column productivity for the production of PP (in kilogram per gram catalyst), in the fourth column the bulk density (in kilogram per cubic meter), in the fifth column the weight average molecular weight (M w ), (in grams per mole), in the sixth column the number average molecular weight (M n ), (in grams per mole), in the seventh column molecular weight distribution (M w /M n ), in the eighth column the percentage of xylene solubles, in the ninth and tenth column the melting temperature (T m ) and crystallization temperature (T c ) respectively (in degrees Celsius) and in the eleventh column the crystallinity percentage.
  • T m melting temperature
  • T c crystallization temperature
  • Step a halogenation of magnesium and 1 st titanation
  • Step b1 addition of ID and 2 nd titanation
  • Step a halogenation of magnesium and 1 st titanation in presence of an activator
  • Step b1 1 st addition of internal donor and 2 nd titanation
  • Step b2 2 nd addition of internal donor and 3 rd titanation
  • Step c work up
  • the filtrate was discarded and the solid was retained in the flask and subsequently, the contents of the flask were washed 5 times with 100 mL of heptane starting at a temperature of 60 °C.
  • the solid product was stirred for 5 minutes per wash prior to filtration in which the filtrate was discarded and the solid was retained in the flask.
  • the temperature was gradually reduced from 60 °C to 25 °C during the washings.
  • the solid product obtained was dried using a nitrogen purge at a temperature of 25°C for a period of 2 hours.
  • the specifications of this procatalyst are provided in Table 1.
  • Synthesis Example 3 was carried out in the same way as Synthesis Example 1 , except the reaction temperature was maintained at a temperature of 96 °C instead of a temperature of 1 10 °C for each of the steps 1 ), 2), 3) and 4). The specifications of this procatalyst are provided in Table 1 .
  • Synthesis Example 4 Preparation of Procatalvst D
  • Synthesis Example 4 was carried out in the same way as Synthesis Example 1 , except that the ratio of the mixture of TiCU and chlorobenzene was 50:50 by volume instead of 40:60 by volume.
  • the specifications of this procatalyst are provided in Table 1.
  • Synthesis Example 5 Preparation of Procatalvst E
  • Synthesis Example 5 was carried out in the same way as Synthesis Example 1 , except that during step 2 a solution of 1318 mg of internal donor 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (AB) in 2 mL of CB was used instead of a solution of 1058 mg of internal donor ethyl (4-((ethoxycarbonyl)oxy)pentan-2-yl)(methyl)carbamate (AB-OEt) in 2 mL of CB.
  • AB benzoyl(methyl)amino]pentan-2-yl benzoate
  • Synthesis Example 6 was carried out in the same way as Synthesis Example 2, except that during step 2 and step 3 a solution of 659 mg of internal donor 4- [benzoyl(methyl)amino]pentan-2-yl benzoate (AB) in 2 mL of CB was used instead of a solution of 529 mg of internal donor ethyl (4-((ethoxycarbonyl)oxy)pentan-2- yl)(methyl)carbamate (AB-OEt) in 2 mL of CB.
  • Synthesis Example 7 # Preparation of Procatalyst G # [according to a method in the clauses (below) - not according to the claimsl
  • Synthesis Example 7 was carried out in the same way as Synthesis Example 2, except that during step 2 and step 3 a solution of 1058 mg of internal donor 4- [benzoyl(methyl)amino]pentan-2-yl benzoate (AB) in 2 mL of CB was used instead of a solution of 1058 mg of internal donor ethyl (4-((ethoxycarbonyl)oxy)pentan-2- yl)(methyl)carbamate (AB-OEt) in 2 mL of CB.
  • AB benzoyl(methyl)amino]pentan-2-yl benzoate
  • Step 1 * halogenation of magnesium and 1 st titanation in presence of activator
  • Liquid pool propylene polymerization was carried out in a one gallon bench scale reactor.
  • the method of polymerization involved baking the polymerization reactor at a temperature of 1 10°C for a period of 60 minutes, then applying three high pressure (15 bar) nitrogen purges at a temperature 1 10°C, then lowering the reactor temperature to 30°C whilst purging the reactor with nitrogen. Then the reactor was purged three times with 50 g of propylene for each purge. Then 1.375 kg of liquid propylene was introduced to the reactor followed by the addition of 200 psig hydrogen to the reactor from an 75 mL stainless steel cylinder.
  • the reactor temperature was then raised to 62°C with a stirring speed of 500 rpm and 0.25 mmol of the external electron donor, cyclohexylmethyldimethoxysilane, was injected into the reactor. Then, 2.0 mmol of a co-catalyst, triethylaluminium was injected in the reactor. Then the procatalyst, corresponding to 0.01 mmol Ti, was injected into the reactor. The reactor temperature was then raised to 67°C and the stirring speed increased to 1500 rpm and polymerization was carried out for a period of 1 hour. After this period had expired, the propylene in the reactor was vented and product polypropylene was collected. The yield was determined after allowing the product to dry. Polymerization and product analysis results are given in Table 2.
  • Polymerization Example 4 Using Procatalyst D Polymerization Example 1 was repeated except that procatalyst D was used in the process. Polymerization and product analysis results are given in Table 2.
  • procatalyst H * a procatalyst according to the prior art
  • procatalyst A a procatalyst according to the present invention
  • a method for producing a olefin polymerization catalyst component which method comprises the steps of:
  • step (b) washing the second intermediate product with an inert hydrocarbon liquid.
  • step (b2) contacting the second intermediate product with a tetravalent titanium halide to obtain a third intermediate product; and wherein step (c) is:
  • step (b) comprises two sub steps (b1 ) and (b2):
  • step (b2) contacting the second intermediate product with a mixture of a tetravalent titanium halide and a second portion of an internal electron donor; to obtain a third intermediate product; and wherein step (c) is:
  • each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 7 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon
  • each R 8 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms
  • R 1 , R 2 R 3 R 4 R 5 , and R 6 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • R 7 is a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms
  • N is nitrogen atom
  • O oxygen atom
  • C is carbon atom; most
  • each R 80 group is independently a linear, branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 30 carbon atoms;
  • R 81 , R 82 , R 83 , R 84 , R 85 , and R 86 are each independently selected from hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • R 87 is a hydrogen or a linear, branched or cyclic hydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyi, alkoxycarbonyl or alkylaryl groups, and one or more combinations thereof, preferably having from 1 to 20 carbon atoms;
  • N is
  • magnesium compound is a dialkoxymagnesium compound, preferably diethoxymagnesium.
  • tetravalent titanium compound is a titanium tetrahalide, preferably TiCU and/or wherein the same tetravalent titanium compound is used in each of the steps.
  • inert hydrocarbon liquid is an alkane, preferably n-heptane or isopentane.
  • the activator is ethylbenzoate, wherein the internal donor is 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (AB), wherein the magnesium compound is diethoxymagnesium, wherein the tetravalent titanium compound for each step is TiCU, wherein the halohydrocarbon is chlorobenzene, wherein the inert hydrocarbon liquid is an alkane.
  • the activator is ethylbenzoate
  • the internal donor is 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (AB)
  • the magnesium compound is diethoxymagnesium
  • the tetravalent titanium compound for each step is TiCU
  • the halohydrocarbon is chlorobenzene
  • the inert hydrocarbon liquid is an alkane.
  • the activator is ethylbenzoate, wherein the internal donor is ethyl (4-((ethoxycarbonyl)oxy)pentan-2-yl)(methyl)carbamate (AB-OEt), wherein the magnesium compound is diethoxymagnesium, wherein the tetravalent titanium compound for each step is TiCU, wherein the halohydrocarbon is chlorobenzene, wherein the inert hydrocarbon liquid is an alkane.
  • the activator is ethylbenzoate
  • the internal donor is 4-[benzoyl(methyl)amino]pentan-2-yl benzoate (AB) and wherein the first portion and the second portion are each half (50%/50%) of the total amount of internal donor added
  • the magnesium compound is diethoxymagnesium
  • the tetravalent titanium compound for each step is TiCU
  • the halohydrocarbon is chlorobenzene
  • the inert hydrocarbon liquid is an alkane.
  • the activator is ethylbenzoate, wherein the internal donor is ethyl (4-((ethoxycarbonyl)oxy)pentan-2-yl)(methyl)carbamate (AB-OEt) and wherein the first portion and the second portion are each half (50%/50%) of the total amount of internal donor added, wherein the magnesium compound is diethoxymagnesium, wherein the tetravalent titanium compound for each step is TiCU, wherein the halohydrocarbon is chlorobenzene, wherein the inert hydrocarbon liquid is an alkane.

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Abstract

La présente invention concerne un procédé de production d'un élément catalyseur de polymérisation d'oléfines, lequel procédé comprend les étapes suivantes : (a) l'halogénation d'un composé de magnésium de formule MgR'R" où R' est un groupe alkoxyde ou aryloxyde et où R" représente un groupe alkoxyde ou aryloxyde ou halogène, avec un halogénure de titane tétravalent en présence d'un hydrocarbure halogéné et d'un activateur ; pour former un premier produit intermédiaire ; (b) la mise en contact du produit intermédiaire avec un mélange d'un halogénure de titane tétravalent et d'un donneur d'électrons interne ; l'étape (b) comprenant deux sous-étapes (b1) et (b2), à savoir : (b1) la mise en contact du premier produit intermédiaire avec un mélange d'un halogénure de titane tétravalent et d'un donneur d'électrons interne ; pour obtenir un deuxième produit intermédiaire; et (b2) la mise en contact du deuxième produit intermédiaire avec un halogénure de titane tétravalent pour obtenir un troisième produit intermédiaire ; et (c) le lavage du troisième produit intermédiaire à l'aide d'un liquide d'hydrocarbure inerte. Grâce à ce procédé nouveau et inventif, les propriétés du polymère observé au moyen du procatalyseur obtenu peuvent être ajustées.
PCT/EP2016/078769 2015-12-02 2016-11-25 Procédé de préparation d'un procatalyseur pour la polymérisation d'oléfines WO2017093129A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414132A (en) 1979-05-17 1983-11-08 Shell Oil Company Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions
US4535068A (en) 1983-09-20 1985-08-13 Shell Oil Company Olefin polymerization catalyst compositions and polymerization process
US4771024A (en) * 1986-02-28 1988-09-13 Shell Oil Company Olefin polymerization catalyst composition
WO2011106500A1 (fr) * 2010-02-26 2011-09-01 Dow Global Technologies Llc Donneur d'électrons interne ester d'amide et procédé correspondant
WO2014118164A1 (fr) 2013-01-31 2014-08-07 Saudi Basic Industries Corporation Composition de catalyseur pour la polymérisation d'oléfines
WO2015185490A1 (fr) * 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyseur pour la polymérisation d'oléfines comprenant un monoester et un donneur interne de type amidobenzoate
WO2015185489A1 (fr) * 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyseur pour la polymérisation d'oléfines

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414132A (en) 1979-05-17 1983-11-08 Shell Oil Company Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions
US4535068A (en) 1983-09-20 1985-08-13 Shell Oil Company Olefin polymerization catalyst compositions and polymerization process
US4771024A (en) * 1986-02-28 1988-09-13 Shell Oil Company Olefin polymerization catalyst composition
WO2011106500A1 (fr) * 2010-02-26 2011-09-01 Dow Global Technologies Llc Donneur d'électrons interne ester d'amide et procédé correspondant
WO2014118164A1 (fr) 2013-01-31 2014-08-07 Saudi Basic Industries Corporation Composition de catalyseur pour la polymérisation d'oléfines
WO2015185490A1 (fr) * 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyseur pour la polymérisation d'oléfines comprenant un monoester et un donneur interne de type amidobenzoate
WO2015185489A1 (fr) * 2014-06-02 2015-12-10 Sabic Global Technologies B.V. Procatalyseur pour la polymérisation d'oléfines

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