WO2016184884A1 - Catalyst components for the polymerization of olefins - Google Patents

Catalyst components for the polymerization of olefins Download PDF

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Publication number
WO2016184884A1
WO2016184884A1 PCT/EP2016/061078 EP2016061078W WO2016184884A1 WO 2016184884 A1 WO2016184884 A1 WO 2016184884A1 EP 2016061078 W EP2016061078 W EP 2016061078W WO 2016184884 A1 WO2016184884 A1 WO 2016184884A1
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Prior art keywords
amino
ethoxycarbonyl
groups
catalyst component
methyl
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French (fr)
Inventor
Alessandro Mignogna
Igor KASHULIN
Giampiero Morini
Ilya Nifant'ev
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Basell Poliolefine Italia SRL
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Basell Poliolefine Italia SRL
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Priority to CN201680026686.9A priority Critical patent/CN107580607B/en
Priority to ES16725438T priority patent/ES2746290T3/en
Priority to JP2017558544A priority patent/JP6404497B2/en
Priority to KR1020177034969A priority patent/KR101895565B1/en
Priority to RU2017140819A priority patent/RU2667539C1/en
Priority to EP16725438.2A priority patent/EP3298048B1/en
Priority to BR112017023776-8A priority patent/BR112017023776B1/en
Priority to US15/574,807 priority patent/US10221256B2/en
Publication of WO2016184884A1 publication Critical patent/WO2016184884A1/en
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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
    • 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
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F4/643—Component covered by group C08F4/64 with a metal or compound covered by group C08F4/44 other than an organo-aluminium compound
    • C08F4/6432—Component of C08F4/64 containing at least two different metals
    • C08F4/6435—Component of C08F4/64 containing at least two different metals containing magnesium
    • 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
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/15—Isotactic

Definitions

  • the present disclosure relates to catalyst components for the polymerization of olefins, in particular propylene, comprising a Mg dihalide based support on which are supported Ti atoms and an electron donor compound containing an ester and a carbamate function.
  • the present disclosure further relates to the catalysts obtained from said components and to their use in processes for the polymerization of olefins in particular propylene.
  • Catalyst components for the stereospecific polymerization of olefins have been disclosed in the art.
  • Concerning the polymerization of propylene Ziegler-Natta catalysts are used which, in general terms, comprise a solid catalyst component, constituted by a magnesium dihalide on which are supported a titanium compound and an internal electron donor compound, used in combination with an Al-alkyl compound.
  • an external donor for example an alkoxysilane
  • Esters of phthalic acid, particularly diisobutylphthalate are used as internal donors in catalyst preparations. The phthalates are used as internal donors in combination with alkylalkoxysilanes as external donor.
  • This catalyst system gives good performances in terms of activity, isotacticity and xylene insolubility.
  • Some of the tested catalysts contain donors structures having contemporaneously amido groups and ester groups.
  • WO2011/106494 describes substituted amide ester deriving from aliphatic 1,3-amino alcohol. The catalysts generated by these structures have not entirely satisfactory performances.
  • R groups are hydrogen or a Ci-C2o hydrocarbon radicals, optionally containing a heteroatom selected from halogen, P, S, N,0 and Si, which can be fused together to form one or more cycles
  • m is a number satisfying the valences of Z and n is an integer ranging from 1 to 10
  • R 1 and R 4 are selected from C Qs hydrocarbon groups, optionally containing a heteroatom selected from halogen, P, S, ⁇ , ⁇ ; and R 3 group is hydrogen or R 4 groups.
  • Z is selected from C and Si.
  • Z is carbon.
  • only C and Si can be linked directly to the ester oxygen and/or the carbamic nitrogen of formula (I).
  • the (ZR 2 m ) n group of formula (I) can be selected from the group consisting of aliphatic, alicyclic and aromatic bivalent radicals, optionally substituted with Q-Q5 hydrocarbon groups and/or with heteroatoms selected from halogen, P, S, N, O and Si, in which n ranges from 1 to 6 atoms and especially from 1 to 4.
  • the (ZR 2 m ) n group is an aliphatic or alicyclic bridging group in which n ranges from 1-6 carbon atoms.
  • bridging groups are methyliden, ethane- 1,2-diyl, butane-2,3-diyl, pentane-2,4-diyl, 2,2-diisobutylpropane-l,3-diyl, cyclohexane-l,2-diyl, cyclopentane -1,2-diyl.
  • the bridging group pentane-2,4-diyl being the most preferred.
  • Another class of preferred bridging group is the one based on cyclic aromatic groups which through the carbon ring atoms can link the two oxygen of formula (I).
  • cyclic aromatic groups which through the carbon ring atoms can link the two oxygen of formula (I).
  • particularly preferred are the phenyl groups, optionally substituted with halogens or Ci-C2o alkyl radicals, bridging the oxygen atoms in position 1,2 or 1,3 or 1,4 and the naphthalene groups, optionally substituted bridging the oxygen groups in position 1,2 or 2,3 or 1,8.
  • Preferred structures of formula (II) are those in which at least two of the R 5 -R 7 groups are different from hydrogen. More preferably, the aromatic ring of formula (II) is substituted in position 3,5 and/or 6. In all these cases, R 5 -R 8 groups are preferably selected from C Cs alkyl groups. Particularly preferred is the substitution in position 3 and/or 6 with a primary alkyl group especially methyl, and in position 4 and/or 5 with a tertiary alkyl group especially tert-butyl.
  • aromatic bridging groups are 1 ,2-phenylene, 3-methyl-l,2- phenylene, 4-chloro-l,2-phenylene, 4-(ieri-butyl)-l,2-phenylene, 3,6-dimethyl-l,2-phenylene, 3,5-dimethyl- 1 ,2-phenylene, 5-(ie/ -butyl)-3-methyl- 1 ,2-phenylene, 3,5-diisopropyl- 1 ,2- phenylene. 5-(ieri-butyl)-3-methyl-l,2-phenylene is the most preferred.
  • the R 1 groups are independently selected from Q-Q5 alkyl groups, C6-C 14 aryl groups, C3-C 15 cycloalkyl groups, and C7-Q5 arylalkyl or alkylaryl groups; the same applies to R groups in formula (I) which can additionally be hydrogen. More preferably, the R 1 groups aryl or alkylaryl groups in particular phenyl groups preferably substituted with halogen and/or Q-Cs alkyl groups.
  • the R 3 group is independently selected from hydrogen or Ci-Cw alkyl groups and even more preferably from hydrogen or C Cs alkyl groups in particular methyl.
  • the R 4 group is preferably selected from Ci-Cw alkyl groups and even more preferably from Q-Cs alkyl groups in particular ethyl.
  • R groups are phenyl groups optionally substituted with halogen and/or Q-Cs alkyl groups
  • R 3 is hydrogen or Ci-C 2 o hydrocarbon group
  • R 4 is a Ci-Cw alkyl group.
  • R 3 is hydrogen or methyl
  • R 4 is a Q-C5 alkyl group.
  • the final amount of electron donor compound in the solid catalyst component ranges from 1 to 25% by weight preferably in the range from 3 to 20% by weight.
  • the compounds falling in formula (I) and (II) can be generally prepared by reacting an aminoalcohol HO-A-NRH with a suitable chloroformate. Then the monocarbamate- monoalcohol is reacted with a suitable acyl chloride. Both steps are carried out in presence of a base.
  • the amount of Ti atoms is preferably higher than 2.5%wt more preferably higher than 3.0% with respect to the total weight of said catalyst component.
  • the catalyst components of the disclosure comprise, in addition to the above electron donors, Ti, Mg and halogen.
  • the catalyst components comprise a titanium compound, having at least a Ti-halogen bond and the above mentioned electron donor compounds supported on a Mg halide.
  • the magnesium halide is preferably MgCl 2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts.
  • Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis.
  • magnesium dihalides in active form used as support or co- support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
  • the preferred titanium compounds used in the catalyst component of the present disclosure are TiCl 4 and TiCl 3 ; furthermore, also Ti-haloalcoholates of formula Ti(OR) m - y X y can be used, where m is the valence of titanium, y is a number between 1 and m-1, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
  • the preparation of the solid catalyst component can be carried out according to several methods.
  • One method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to USP 4,220,554) and an excess of TiCl 4 in the presence of the electron donor compounds at a temperature of about 80 to 120°C.
  • the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) m _ y X y , where m is the valence of titanium and y is a number between 1 and m, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCi 2 *pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
  • the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648.
  • the so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5.
  • the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (about 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours.
  • the treatment with TiCl 4 can be carried out one or more times.
  • the electron donor compound is preferably added during the treatment with TiCl 4 .
  • the preparation of catalyst components in spherical form are described for example in European Patent Applications EP-A-395083, EP-A- 553805, EP-A-553806, EPA601525 and W098/44009.
  • the solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) may range between 20 and 500 m /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between
  • the porosity (Hg method) due to pores with radius up to 10.000A ° may range from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cm 3 /g.
  • the solid catalyst component has an average particle size ranging from 5 to 120 ⁇ and more preferably from 10 to 100 ⁇ .
  • the desired electron donor compounds can be added as such or, in an alternative way, it can be obtained in situ by using an appropriate precursor capable to be transformed in the desired electron donor compound by means, for example, of available chemical reactions.
  • the final amount of the electron donor compound of formula (I) is such that its molar ratio with respect to the Ti atoms is from 0.01 to 2, preferably from 0.05 to 1.5.
  • the solid catalyst components according to the present disclosure are converted into catalysts for the polymerization of olefins by reacting them with organo aluminum compounds according to available methods.
  • the alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt 2 Cl and Al 2 Et 3 Cl 3 , possibly in mixture with the above cited trialkylaluminums.
  • the external electron-donor compounds can include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6, 6-tetramethylpiperidine and ketones.
  • Another class of preferred external donor compounds is that of silicon compounds of formula (R 7 ) a (R 8 ) b Si(OR 9 ) c , where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R 7 , R 8 , and R 9 , are radicals with 1-18 carbon atoms optionally containing heteroatoms.
  • Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, N,N- diethylaminotriethoxysilane.
  • C donor methylcyclohexyldimethoxysilane
  • D donor dicyclopentyldimethoxysilane
  • Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t- butyltrimethoxysilane and thexyltrimethoxysilane.
  • the electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
  • the catalyst components of the present disclosure particularly when used in the polymerization of propylene in association with an aluminum alkyl compound and an alkyl alkoxysilane are able to produce polypropylene, under the polymerization conditions set forth in the experimental section, with an activity higher than 40 Kg/gcat preferably higher than 50 Kg/gcat and a xylene insolubility at 25°C higher than 96%, preferably higher than 97 and more preferably higher than 98%.
  • the polymerization process can be carried out according to available techniques for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.
  • the polymerization may be carried out at temperature of from 20 to 120°C, preferably of from 40 to 80°C.
  • the operating pressure may range between 0.5 and 5 MPa, preferably between 1 and 4 MPa.
  • the operating pressure ranges between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
  • the content of electron donor has been carried out via gas-chromatography.
  • the solid component was dissolved in acidic water.
  • the solution was extracted with ethyl acetate, an internal standard was added, and a sample of the organic phase was analyzed in a gas chromatograph, to determine the amount of donor present at the starting catalyst compound.
  • the melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).
  • adduct A An initial amount of micro spheroidal MgCl 2 2.8C 2 H 5 OH was prepared according to the method described in Example 2 of WO98/44009, but operating on larger scale. This adduct is called adduct A.
  • the solid adduct A was then subject to thermal dealcoholation at increasing temperatures from 30 to 130°C and operating in nitrogen current until reaching an alcohol content of 1.9 moles per mol of MgCl 2 .
  • This partially dealcoholated adduct is called adduct B.
  • the non- reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for three hours. Then the polymer was weighed and fractionated with o-xylene to determine the amount of the xylene insoluble (X.I.) fraction.
  • the internal donor used in the comparative example 1 has been prepared according to US2015/0259448.
  • T1CI 4 Into a 500 cm round bottom flask, equipped with mechanical stirrer, cooler and thermometer 250 cm of T1CI 4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, the internal donor of synthetic example 1 and 10.0 g of the spherical adduct A were sequentially added into the flask. The amount of charged internal donor was such to charge a Mg/donor molar ratio of 6. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh T1CI 4 was added to reach the initial liquid volume again.

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Abstract

A solid catalyst component for the polymerization of olefins comprising Mg, Ti and a an electron donor of formula (I) where independently, Z is a bridging group, the R2 groups, equal to or different from each other, are hydrogen or a C1-C20 hydrocarbon radicals, m is a number satisfying the valences of Z and n is an integer ranging from 1 to 10, R1 and R4 are selected from C1-C15 hydrocarbon groups, optionally containing a heteroatom selected from halogen, P, S, N,O; and R3 group, is hydrogen or R4 groups. The catalyst system based on the solid catalyst component is endowed with high activity and stereospecificity.

Description

TITLE
CATALYST COMPONENTS FOR THE POLYMERIZATION OF OLEFINS
FIELD OF THE INVENTION
[0001] The present disclosure relates to catalyst components for the polymerization of olefins, in particular propylene, comprising a Mg dihalide based support on which are supported Ti atoms and an electron donor compound containing an ester and a carbamate function. The present disclosure further relates to the catalysts obtained from said components and to their use in processes for the polymerization of olefins in particular propylene.
BACKGROUND OF THE INVENTION
[0002] Catalyst components for the stereospecific polymerization of olefins have been disclosed in the art. Concerning the polymerization of propylene, Ziegler-Natta catalysts are used which, in general terms, comprise a solid catalyst component, constituted by a magnesium dihalide on which are supported a titanium compound and an internal electron donor compound, used in combination with an Al-alkyl compound. Conventionally however, when a higher crystallinity of the polymer is desired, also an external donor (for example an alkoxysilane) is needed in order to obtain higher isotacticity. Esters of phthalic acid, particularly diisobutylphthalate, are used as internal donors in catalyst preparations. The phthalates are used as internal donors in combination with alkylalkoxysilanes as external donor. This catalyst system gives good performances in terms of activity, isotacticity and xylene insolubility.
[0003] One of the problems associated with the use of this catalyst system is that the phthalates have recently raised some concerns which caused some compounds within this class to be classified as source of heavy health problems.
[0004] Consequently, research activities have been devoted to discover alternative classes of internal donors for use in the preparation of catalyst components for propylene polymerization.
[0005] Some of the tested catalysts contain donors structures having contemporaneously amido groups and ester groups. WO2011/106494 describes substituted amide ester deriving from aliphatic 1,3-amino alcohol. The catalysts generated by these structures have not entirely satisfactory performances.
SUMMARY OF THE INVENTION
[0006] Surprisingly, the applicant has found that a class of donors containing both a carbamate and ester function within a specific structure deriving from amino alcohol generates catalysts showing a good balance of activity and stereospecificity.
[0007] Accordingly, it is an object of the present disclosure a catalyst component for the polymerization of olefins comprising Mg, Ti and an electron donor of formula (I)
Figure imgf000003_0001
(I)
where independently, Z is selected from C, Si, Ge, O, N, S or P with the proviso that the atoms O, S, and N are not directly linked to either the ester oxygen or the carbamic nitrogen of the formula (I), the R groups, equal to or different from each other, are hydrogen or a Ci-C2o hydrocarbon radicals, optionally containing a heteroatom selected from halogen, P, S, N,0 and Si, which can be fused together to form one or more cycles, m is a number satisfying the valences of Z and n is an integer ranging from 1 to 10, R1 and R4 are selected from C Qs hydrocarbon groups, optionally containing a heteroatom selected from halogen, P, S, Ν,Ο; and R3 group is hydrogen or R4 groups.
DETAILED DESCRIPTION OF THE INVENTION
[0008] Preferably, Z is selected from C and Si. In a more preferred embodiment, Z is carbon. Preferably, only C and Si can be linked directly to the ester oxygen and/or the carbamic nitrogen of formula (I). [0009] In a particular embodiment, the (ZR2 m)n group of formula (I) can be selected from the group consisting of aliphatic, alicyclic and aromatic bivalent radicals, optionally substituted with Q-Q5 hydrocarbon groups and/or with heteroatoms selected from halogen, P, S, N, O and Si, in which n ranges from 1 to 6 atoms and especially from 1 to 4.
[0010] In a particularly preferred embodiment, the (ZR2 m)n group is an aliphatic or alicyclic bridging group in which n ranges from 1-6 carbon atoms. Examples of bridging groups are methyliden, ethane- 1,2-diyl, butane-2,3-diyl, pentane-2,4-diyl, 2,2-diisobutylpropane-l,3-diyl, cyclohexane-l,2-diyl, cyclopentane -1,2-diyl. The bridging group pentane-2,4-diyl being the most preferred.
[0011] Another class of preferred bridging group is the one based on cyclic aromatic groups which through the carbon ring atoms can link the two oxygen of formula (I). Among them, particularly preferred are the phenyl groups, optionally substituted with halogens or Ci-C2o alkyl radicals, bridging the oxygen atoms in position 1,2 or 1,3 or 1,4 and the naphthalene groups, optionally substituted bridging the oxygen groups in position 1,2 or 2,3 or 1,8.
[0012] Particularly preferred internal donor structures are those of formula (II) below
Figure imgf000004_0001
(Π)
[0013] Preferred structures of formula (II) are those in which at least two of the R 5 -R 7 groups are different from hydrogen. More preferably, the aromatic ring of formula (II) is substituted in position 3,5 and/or 6. In all these cases, R 5 -R 8 groups are preferably selected from C Cs alkyl groups. Particularly preferred is the substitution in position 3 and/or 6 with a primary alkyl group especially methyl, and in position 4 and/or 5 with a tertiary alkyl group especially tert-butyl.
[0014] Specific examples of aromatic bridging groups are 1 ,2-phenylene, 3-methyl-l,2- phenylene, 4-chloro-l,2-phenylene, 4-(ieri-butyl)-l,2-phenylene, 3,6-dimethyl-l,2-phenylene, 3,5-dimethyl- 1 ,2-phenylene, 5-(ie/ -butyl)-3-methyl- 1 ,2-phenylene, 3,5-diisopropyl- 1 ,2- phenylene. 5-(ieri-butyl)-3-methyl-l,2-phenylene is the most preferred.
[0015] Preferably, in the formulae (I) and (II) the R1 groups are independently selected from Q-Q5 alkyl groups, C6-C14 aryl groups, C3-C15 cycloalkyl groups, and C7-Q5 arylalkyl or alkylaryl groups; the same applies to R groups in formula (I) which can additionally be hydrogen. More preferably, the R1 groups aryl or alkylaryl groups in particular phenyl groups preferably substituted with halogen and/or Q-Cs alkyl groups.
[0016] Preferably the R3 group is independently selected from hydrogen or Ci-Cw alkyl groups and even more preferably from hydrogen or C Cs alkyl groups in particular methyl.
[0017] The R4 group is preferably selected from Ci-Cw alkyl groups and even more preferably from Q-Cs alkyl groups in particular ethyl.
[0018] Particularly preferred are the structures of formula (III) below
Figure imgf000005_0001
(III)
in which R groups are phenyl groups optionally substituted with halogen and/or Q-Cs alkyl groups, R3 is hydrogen or Ci-C2o hydrocarbon group, and R4 is a Ci-Cw alkyl group. Preferably, R3 is hydrogen or methyl and R4 is a Q-C5 alkyl group. These structures may exist in different configurations that may imply the presence of mixture of stereoisomers in variable proportions although the syn form may often be preponderant. In particular, the ratio syn/anti may range from 2: 1 to 10: 1. As a specific example, we report that for certain structures of formula (III) the ratio syn/anti ranges from 7: 1 to 10: 1.
[0019] Preferably, the final amount of electron donor compound in the solid catalyst component ranges from 1 to 25% by weight preferably in the range from 3 to 20% by weight.
[0020] Non limiting examples of structures of formulas (I) are the following:
4-((butoxycarbonyl)(methyl)amino)pentan-2-yl 3-chlorobenzoate, 4-
((butoxycarbonyl)(methyl)amino)pentan-2-yl 4-chlorobenzoate, 4- ((ethoxycarbonyl)(ethyl)amino)pentan-2-yl 3-chlorobenzoate, 4-
((ethoxycarbonyl)(ethyl)amino)pentan-2-yl 4-chlorobenzoate, 4-
((ethoxycarbonyl)(ethyl)amino)pentan-2-yl 4-propylbenzoate, 4-
((ethoxycarbonyl)(ethyl)amino)pentan-2-yl benzoate, 4-((ethoxycarbonyl)(methyl)amino)-3- methylpentan-2-yl 3-chlorobenzoate, 4-((ethoxycarbonyl)(methyl)amino)-3-methylpentan-2-yl 4-propylbenzoate, 4-((ethoxycarbonyl)(methyl)amino)-3-methylpentan-2-yl benzoate, 4- ((ethoxycarbonyl)(methyl)amino)pentan-2-yl 3-chlorobenzoate, 4-
((ethoxycarbonyl)(methyl)amino)pentan-2-yl 3-methylbutanoate, 4-
((ethoxycarbonyl)(methyl)amino)pentan-2-yl 4-chlorobenzoate, 4-
((ethoxycarbonyl)(methyl)amino)pentan-2-yl 4-propylbenzoate, 4-
((ethoxycarbonyl)(methyl)amino)pentan-2-yl acetate, 4-((ethoxycarbonyl)(methyl)amino)pentan- 2-yl benzoate, 4-((ethoxycarbonyl)(methyl)amino)pentan-2-yl pivalate, 4- ((ethoxycarbonyl)amino)pentan-2-yl 3-chlorobenzoate, 4-((ethoxycarbonyl)amino)pentan-2-yl 4- chlorobenzoate, 4-((ethoxycarbonyl)amino)pentan-2-yl 4-propylbenzoate, 4-
((ethoxycarbonyl)amino)pentan-2-yl benzoate, 4-((methoxycarbonyl)(methyl)amino)pentan-2-yl benzoate, 4-(benzyl(ethoxycarbonyl)amino)pentan-2-yl 3-chlorobenzoate, 4-
(benzyl(ethoxycarbonyl)amino)pentan-2-yl 4-chlorobenzoate, 4-
(benzyl(ethoxycarbonyl)amino)pentan-2-yl 4-propylbenzoate, 4-
(benzyl(ethoxycarbonyl)amino)pentan-2-yl benzoate, 4-(methyl(propoxycarbonyl)amino)pentan- 2-yl 4-propylbenzoate, (9-(((ethoxycarbonyl)(methyl)arnino)methyl)-9H-fluoren-9-yl)methyl 3- chlorobenzoate, (9-(((ethoxycarbonyl)(methyl)amino)methyl)-9H-fluoren-9-yl)methyl 4- chlorobenzoate, (9-(((ethoxycarbonyl)(methyl)amino)methyl)-9H-fluoren-9-yl)methyl 4- propylbenzoate, (9-(((ethoxycarbonyl)(methyl)amino)methyl)-9H-fluoren-9-yl)methyl benzoate, 2-(((ethoxycarbonyl)(methyl)amino)methyl)-2-isobutyl-4-methylpentyl benzoate, 2-
(((ethoxycarbonyl)(methyl)amino)methyl)-2-isopropyl-3-methylbutyl 4-propylbenzoate, 2- (((ethoxycarbonyl)(methyl)amino)methyl)-2-isopropyl-5-methylhexyl 3-chlorobenzoate, 2- (((ethoxycarbonyl)(methyl)amino)methyl)-2-isopropyl-5-methylhexyl 4-propylbenzoate, 2- (((ethoxycarbonyl)(methyl)amino)methyl)phenyl 4-chlorobenzoate, 2-
(((ethoxycarbonyl)(methyl)amino)methyl)phenyl 4-propylbenzoate, 2-
(((ethoxycarbonyl)(methyl)amino)methyl)phenyl benzoate, 2-(l-
((ethoxycarbonyl)(methyl)amino)ethyl)phenyl 4-chlorobenzoate, 3- (ethoxycarbonyl)(methyl)amino)-2,2-dimethylpropyl 3-chlorobenzoate, 3-
(ethoxycarbonyl)(methyl)amino)-2,2-dimethylpropyl 4-propylbenzoate, 3-
(ethoxycarbonyl)(methyl)amino)-2,2-dimethylpropyl benzoate, 3-
(ethoxycarbonyl)(methyl)amino)propyl 3-chlorobenzoate, 3-
(ethoxycarbonyl)(methyl)amino)propyl 4-chlorobenzoate, 3-
(ethoxycarbonyl)(methyl)amino)propyl 4-propylbenzoate, 3-
(ethoxycarbonyl)(methyl)amino)propyl benzoate, 4-(tert-butyl)-2-(l-
(ethoxycarbonyl)(methyl)amino)ethyl)-6-methylphenyl 4-propylbenzoate, 2-
(ethoxycarbonyl)(methyl)amino)- 1 ,2-diphenylethyl 4-propylbenzoate, 2-
(ethoxycarbonyl)(methyl)amino)ethyl 4-propylbenzoate, 2-
(ethoxycarbonyl)(methyl)amino)ethyl benzoate, 2-((ethoxycarbonyl)(methyl)amino)propyl 4- propylbenzoate, 3-(((ethoxycarbonyl)(methyl)amino)methyl)-2-isopropyl-4-methylpentyl 4- propylbenzoate, 3-((ethoxycarbonyl)(ethyl)amino)butan-2-yl 4-propylbenzoate, 4- (ethoxycarbonyl)(methyl)amino)-2,5-dimethylhexan-3-yl 4-propylbenzoate, 4-
(ethoxycarbonyl)amino)-2,5-dimethylhexan-3-yl 4-propylbenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)phenyl 3-chlorobenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)phenyl 4-chlorobenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)phenyl 4-propylbenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)phenyl acetate, 2-((ethoxycarbonyl)(ethyl)amino)phenyl benzoate, 2-((ethoxycarbonyl)(ethyl)amino)phenyl pivalate, 2-
(ethoxycarbonyl)(methyl)amino)phenyl 3-chlorobenzoate, 2-
(ethoxycarbonyl)(methyl)amino)phenyl 4-chlorobenzoate, 2-
(ethoxycarbonyl)(methyl)amino)phenyl 4-propylbenzoate, 2-
(ethoxycarbonyl)(methyl)amino)phenyl acetate, 2-((ethoxycarbonyl)(methyl)amino)phenyl benzoate, 2-((ethoxycarbonyl)(methyl)amino)phenyl pivalate, 2-((ethoxycarbonyl)amino)phenyl 3-chlorobenzoate, 2-((ethoxycarbonyl)amino)phenyl 4-chlorobenzoate, 2-
(ethoxycarbonyl)amino)phenyl 4-propylbenzoate, 2-((ethoxycarbonyl)amino)phenyl acetate, 2- (ethoxycarbonyl)amino)phenyl benzoate, 2-((ethoxycarbonyl)amino)phenyl pivalate, 2- (ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 3-chlorobenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 4-chlorobenzoate, 2-
(ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 4-propylbenzoate, 2- ((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl acetate, 2-((ethoxycarbonyl)(ethyl)amino)-6- methylphenyl benzoate, 2-((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl pivalate, 2- ((ethoxycarbonyl)(methyl)amino)-6-methylphenyl 3-chlorobenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-6-methylphenyl 4-chlorobenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-6-methylphenyl 4-propylbenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-6-methylphenyl acetate, 2-((ethoxycarbonyl)(methyl)amino)- 6-methylphenyl benzoate, 2-((ethoxycarbonyl)(methyl)amino)-6-methylphenyl pivalate, 2- ((ethoxycarbonyl)amino)-6-methylphenyl 3-chlorobenzoate, 2-((ethoxycarbonyl)amino)-6- methylphenyl 4-chlorobenzoate, 2-((ethoxycarbonyl)amino)-6-methylphenyl 4-propylbenzoate, 2-((ethoxycarbonyl)amino)-6-methylphenyl acetate, 2-((ethoxycarbonyl)amino)-6-methylphenyl benzoate, 2-((ethoxycarbonyl)amino)-6-methylphenyl pivalate, 2-
((ethoxycarbonyl)(ethyl)amino)-4,6-dimethylphenyl 3-chlorobenzoate, 2-
((ethoxycarbonyl)(ethyl)amino)-4,6-dimethylphenyl 4-chlorobenzoate, 2-
((ethoxycarbonyl)(ethyl)amino)-4,6-dimethylphenyl 4-propylbenzoate, 2-
((ethoxycarbonyl)(ethyl)amino)-4,6-dimethylphenyl acetate, 2-((ethoxycarbonyl)(ethyl)amino)- 4,6-dimethylphenyl benzoate, 2-((ethoxycarbonyl)(ethyl)amino)-4,6-dimethylphenyl pivalate, 2- ((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl 3-chlorobenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl 4-chlorobenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl 4-propylbenzoate, 2-
((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl acetate, 2-
((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl benzoate, 2-
((ethoxycarbonyl)(methyl)amino)-4,6-dimethylphenyl pivalate, 2-((ethoxycarbonyl)amino)-4,6- dimethylphenyl 3-chlorobenzoate, 2-((ethoxycarbonyl)amino)-4,6-dimethylphenyl 4- chlorobenzoate, 2-((ethoxycarbonyl)amino)-4,6-dimethylphenyl 4-propylbenzoate, 2- ((ethoxycarbonyl)amino)-4,6-dimethylphenyl acetate, 2-((ethoxycarbonyl)amino)-4,6- dimethylphenyl benzoate, 2-((ethoxycarbonyl)amino)-4,6-dimethylphenyl pivalate, 4-(tert- butyl)-2-((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 3-chlorobenzoate, 4-(tert-butyl)-2- ((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 4-chlorobenzoate, 4-(tert-butyl)-2-
((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl 4-propylbenzoate, 4-(tert-butyl)-2-
((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl acetate, 4-(tert-butyl)-2-
((ethoxycarbonyl)(ethyl)amino)-6-methylphenyl benzoate, 4-(tert-butyl)-2- ethoxycarbonyl" (ethyl)amino)-6-methylphenyl pivalate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl 3-chlorobenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl 4-chlorobenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl 4-propylbenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl acetate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl benzoate, 4-(tert-butyl) -2- ethoxycarbonyl" (methyl)amino)-6-methylphenyl pivalate, 4-(tert-butyl) -2- ethoxycarbonyl" amino)-6-methylphenyl 3-chlorobenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" amino)-6-methylphenyl 4-chlorobenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" amino)-6-methylphenyl 4-propylbenzoate, 4-(tert-butyl) -2- ethoxycarbonyl" amino)-6-methylphenyl acetate, 4-(tert-butyl)-2-((ethoxycarbonyl)amino) -6- methylphenyl benzoate, 4-(tert-butyl)-2-((ethoxycarbonyl)amino)-6-methylphenyl pivalate, 2- benzyl(ethoxycarbonyl)amino)-4-(tert-butyl)-6-methylphenyl 3-chlorobenzoate, 2- benzyl(ethoxycarbonyl)amino)-4-(tert-butyl)-6-methylphenyl 4-chlorobenzoate, 2- benzyl(ethoxycarbonyl)amino)-4-(tert-butyl)-6-methylphenyl 4-propylbenzoate, 2- benzyl(ethoxycarbonyl)amino)-4-(tert-butyl)-6-methylphenyl benzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(isobutyl)amino)-6-methylphenyl 3-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(isobutyl)amino)-6-methylphenyl 4-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(isobutyl)amino)-6-methylphenyl 4-propylbenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(isobutyl)amino)-6-methylphenyl benzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(phenyl)amino)-6-methylphenyl 3-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(phenyl)amino)-6-methylphenyl 4-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(phenyl)amino)-6-methylphenyl 4-propylbenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(phenyl)amino)-6-methylphenyl benzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl 3-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl 4-chlorobenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl 4-propylbenzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl acetate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl benzoate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(ethyl)amino)phenyl pivalate, 4- (tert-butyl) -2-
(ethoxycarbonyl)(methyl)amino)phenyl 3-chlorobenzoate, 4- (tert-butyl) -2- (ethoxycarbonyl)(methyl)amino)phenyl 4-chlorobenzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)(methyl)amino)phenyl 4-propylbenzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)(methyl)amino)phenyl acetate, 4-(tert-butyl) -2-
(ethoxycarbonyl)(methyl)amino)phenyl benzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)(methyl)amino)phenyl pivalate, 4-(tert-butyl) -2-
(ethoxycarbonyl)amino)phenyl 3-chlorobenzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)amino)phenyl 4-chlorobenzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)amino)phenyl 4-propylbenzoate, 4-(tert-butyl) -2-
(ethoxycarbonyl)amino)phenyl acetate, 4-(tert-butyl)-2-((ethoxycarbonyl)amino)j benzoate, 4-(tert-butyl)-2-((ethoxycarbonyl)amino)] pivalate, 1-
(ethoxycarbonyl)amino)naphthalen-2-yl benzoate, 2- (ethoxycarbonyl)(methyl)amino)naphthalen- 1-yl 3- chlorobenzoate, 2- (ethoxycarbonyl)(methyl)amino)naphthalen- 1-yl 4- chlorobenzoate, 2- (ethoxycarbonyl)(methyl)amino)naphthalen- 1-yl 4-propylbenzoate, 2- (ethoxycarbonyl)(methyl)amino)naphthalen- 1-yl benzoate, 2- (ethoxycarbonyl)amino)naphthalen- 1-yl 3- chlorobenzoate, 2- (ethoxycarbonyl)amino)naphthalen- 1-yl 4- chlorobenzoate, 2- (ethoxycarbonyl)amino)naphthalen- 1-yl 4-propylbenzoate, 2- (ethoxycarbonyl)amino)naphthalen- 1-yl benzoate, 3- (ethoxycarbonyl)(methyl)amino)naphthalen-2-yl 4-chlorobenzoate, 3- (ethoxycarbonyl)amino)naphthalen-2-yl 4-chlorobenzoate, 3- (ethoxycarbonyl)amino)naphthalen-2-yl benzoate, 8- (ethoxycarbonyl)(methyl)amino)naphthalen- 1-yl 4-propylbenzoate, 8-
(ethoxycarbonyl)amino)naphthalen- 1-yl 4-chlorobenzoate, 8- (ethoxycarbonyl)amino)naphthalen- 1-yl benzoate, 4-((ethoxycarbonyl)(propyl)amino)pentan-2- yl 4-methylbenzoate, 4-(butyl(ethoxycarbonyl)amino)pentan-2-yl benzoate, 4- butyl(ethoxycarbonyl)amino)pentan-2-yl 4-methylbenzoate, 4- butyl(ethoxycarbonyl)amino)pentan-2-yl 4-chlorobenzoate, 4- butyl(ethoxycarbonyl)amino)pentan-2-yl 4-fluorobenzoate, 4-((ethoxycarbonyl)(4- fluorophenyl)amino)pentan-2-yl 4-propylbenzoate, 4-(butyl(ethoxycarbonyl)amino)pentan-2-yl
3 -methylbutanoate . [0021] The compounds falling in formula (I) and (II) can be generally prepared by reacting an aminoalcohol HO-A-NRH with a suitable chloroformate. Then the monocarbamate- monoalcohol is reacted with a suitable acyl chloride. Both steps are carried out in presence of a base.
[0022] In solid catalyst component of the disclosure the amount of Ti atoms is preferably higher than 2.5%wt more preferably higher than 3.0% with respect to the total weight of said catalyst component.
[0023] As explained above, the catalyst components of the disclosure comprise, in addition to the above electron donors, Ti, Mg and halogen. In particular, the catalyst components comprise a titanium compound, having at least a Ti-halogen bond and the above mentioned electron donor compounds supported on a Mg halide. The magnesium halide is preferably MgCl2 in active form which is widely known from the patent literature as a support for Ziegler-Natta catalysts. Patents USP 4,298,718 and USP 4,495,338 were the first to describe the use of these compounds in Ziegler-Natta catalysis. It is known from these patents that the magnesium dihalides in active form used as support or co- support in components of catalysts for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line that appears in the spectrum of the non-active halide is diminished in intensity and is replaced by a halo whose maximum intensity is displaced towards lower angles relative to that of the more intense line.
[0024] The preferred titanium compounds used in the catalyst component of the present disclosure are TiCl4 and TiCl3; furthermore, also Ti-haloalcoholates of formula Ti(OR)m-yXy can be used, where m is the valence of titanium, y is a number between 1 and m-1, X is halogen and R is a hydrocarbon radical having from 1 to 10 carbon atoms.
[0025] The preparation of the solid catalyst component can be carried out according to several methods. One method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to USP 4,220,554) and an excess of TiCl4 in the presence of the electron donor compounds at a temperature of about 80 to 120°C.
[0026] According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR)m_yXy, where m is the valence of titanium and y is a number between 1 and m, preferably TiCl4, with a magnesium chloride deriving from an adduct of formula MgCi2*pROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130°C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130°C) so as to obtain an adduct in which the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl4 (about 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiCl4 can be carried out one or more times. The electron donor compound is preferably added during the treatment with TiCl4. The preparation of catalyst components in spherical form are described for example in European Patent Applications EP-A-395083, EP-A- 553805, EP-A-553806, EPA601525 and W098/44009.
[0027] The solid catalyst components obtained according to the above method show a surface area (by B.E.T. method) may range between 20 and 500 m /g and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between
0.2 and 0.6 cm 3 /g. The porosity (Hg method) due to pores with radius up to 10.000A ° may range from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cm 3 /g.
[0028] The solid catalyst component has an average particle size ranging from 5 to 120 μιη and more preferably from 10 to 100 μιη.
[0029] In any of these preparation methods the desired electron donor compounds can be added as such or, in an alternative way, it can be obtained in situ by using an appropriate precursor capable to be transformed in the desired electron donor compound by means, for example, of available chemical reactions.
[0030] Regardless of the preparation method used, the final amount of the electron donor compound of formula (I) is such that its molar ratio with respect to the Ti atoms is from 0.01 to 2, preferably from 0.05 to 1.5. [0031] The solid catalyst components according to the present disclosure are converted into catalysts for the polymerization of olefins by reacting them with organo aluminum compounds according to available methods.
[0032] In particular, it is an object of the present disclosure a catalyst for the polymerization of olefins CH2=CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, comprising the product obtained by contacting:
(i) the solid catalyst component as disclosed above and
(ii) an alkylaluminum compound and optionally,
(iii) an external electron donor compound.
[0033] The alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, possibly in mixture with the above cited trialkylaluminums.
[0034] The external electron-donor compounds can include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6, 6-tetramethylpiperidine and ketones.
[0035] Another class of preferred external donor compounds is that of silicon compounds of formula (R7)a(R8)bSi(OR9)c, where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R7, R8, and R9, are radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R7 and Rg is selected from branched alkyl, cycloalkyl or aryl groups with 3- 10 carbon atoms optionally containing heteroatoms and R9 is a C Cio alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)t-butyldimethoxysilane, (2- ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2- ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoro-n-propyl)dimethoxysilane, N,N- diethylaminotriethoxysilane. Moreover, are also preferred the silicon compounds in which a is 0, c is 3, Re is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and Rg is methyl. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t- butyltrimethoxysilane and thexyltrimethoxysilane.
[0036] The electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100.
[0037] As explained, the catalyst components of the present disclosure, particularly when used in the polymerization of propylene in association with an aluminum alkyl compound and an alkyl alkoxysilane are able to produce polypropylene, under the polymerization conditions set forth in the experimental section, with an activity higher than 40 Kg/gcat preferably higher than 50 Kg/gcat and a xylene insolubility at 25°C higher than 96%, preferably higher than 97 and more preferably higher than 98%.
[0038] Therefore, it constitutes a further object of the present disclosure a process for the (co)polymerization of olefins CH2=CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of a catalyst comprising the product of the reaction between:
(i) the solid catalyst component of the disclosure;
(ii) an alkylaluminum compound and,
(iii) optionally an electron-donor compound (external donor).
[0039] The polymerization process can be carried out according to available techniques for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.
[0040] The polymerization may be carried out at temperature of from 20 to 120°C, preferably of from 40 to 80°C. When the polymerization is carried out in gas-phase the operating pressure may range between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In the bulk polymerization the operating pressure ranges between 1 and 8 MPa, preferably between 1.5 and 5 MPa.
[0041] The following examples are given in order to further illustrate the disclosure without being intended as limiting it. [0042] CHARACTERIZATIONS
[0043] Determination of X.I.
2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomed flask provided with a cooler and a reflux condenser and kept under nitrogen. The obtained mixture was heated to 135°C and was kept under stirring for about 60 minutes. The final solution was allowed to cool to 25°C under continuous stirring, and the insoluble polymer was then filtered. The filtrate was then evaporated in a nitrogen flow at 140°C to reach a constant weight. The content of said xylene- soluble fraction is expressed as a percentage of the original 2.5 grams and then, by difference, the X.I. %.
[0044] Determination of donors.
The content of electron donor has been carried out via gas-chromatography. The solid component was dissolved in acidic water. The solution was extracted with ethyl acetate, an internal standard was added, and a sample of the organic phase was analyzed in a gas chromatograph, to determine the amount of donor present at the starting catalyst compound.
[0045] Melt flow rate (MFR)
The melt flow rate MIL of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).
[0046] EXAMPLES
[0047] General procedure for preparation of the spherical adducts
[0048] Procedure for preparation of the spherical adducts A and B
An initial amount of micro spheroidal MgCl2 2.8C2H5OH was prepared according to the method described in Example 2 of WO98/44009, but operating on larger scale. This adduct is called adduct A. The solid adduct A was then subject to thermal dealcoholation at increasing temperatures from 30 to 130°C and operating in nitrogen current until reaching an alcohol content of 1.9 moles per mol of MgCl2. This partially dealcoholated adduct is called adduct B.
[0049] General procedure for the polymerization of propylene
A 4-litre steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostating jacket, was purged with nitrogen flow at 70°C for one hour. Then, at 30°C under propylene flow, were charged in sequence with 75 mL of anhydrous hexane, 0.76 g of AlEt3, the external electron donor indicated in Table 1 (if used) and 0.006÷0.010 g of solid catalyst component. The autoclave was closed; subsequently 2.0 NL of hydrogen (1,5NL if C donor is used as ED) were added. Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C in five minutes and the polymerization was carried out at this temperature for two hours. At the end of the polymerization, the non- reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for three hours. Then the polymer was weighed and fractionated with o-xylene to determine the amount of the xylene insoluble (X.I.) fraction.
Donor synthesis
The internal donors used in the examples 1-12 have been prepared using the following synthetic route:
reflux, -H20
Figure imgf000016_0001
see: J. Braz. Chem. Soc.
Vol. 15, No. 6, 971 -975, 2004
The internal donor used in the comparative example 1 has been prepared according to US2015/0259448.
[0050] EXAMPLES 1-12 and Comp. Ex.1
Preparation of Solid Catalyst Component and polymerization
Into a 500 cm round bottom flask, equipped with mechanical stirrer, cooler and thermometer 250 cm of T1CI4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, the internal donor of synthetic example 1 and 10.0 g of the spherical adduct A were sequentially added into the flask. The amount of charged internal donor was such to charge a Mg/donor molar ratio of 6. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh T1CI4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times (6 x 100 cm 3 ) in temperature gradient down to 60°C and one time (100 cm 3 ) at room temperature. The obtained solid was then dried under vacuum. The so obtained solid catalyst components were tested in polymerization of propylene, using the procedure described above. The results are listed in Table 1.
[0051] EXAMPLE 13
Preparation of Solid Catalyst Component and polymerization
Into a 500 cm round bottom flask, equipped with mechanical stirrer, cooler and thermometer 250 cm of TiCl4 were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, 10.0 g of the spherical adduct B were sequentially added into the flask. The temperature was raised to 120°C and maintained for 1 hour. The internal donor is charged when the internal temperature reaches 40°C. The amount of charged internal donor was such to charge a Mg/donor molar ratio of 8.. After 1 hour at 120°C stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 120°C. After the supernatant was removed, additional fresh T1CI4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 30 minutes. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. After the supernatant was removed, additional fresh T1CI4 was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 15 minutes. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The obtained solid was washed four times with anhydrous heptane (4 x
100 cm 3 ) at 90°C and two times with anhydrous iso-hexane (2 x 100 cm 3 ) at 25°C then dried under vacuum. The so obtained solid catalyst components were tested in polymerization of propylene, using the procedure described above. The results are listed in Table 1.
TABLE 1
Figure imgf000018_0001
Figure imgf000019_0001
Ex. Catalyst compostion Polymerization
Internal Donor Ti Activity XI MIL
ED
Structure / Name %wt %wt kg/g %wt g/10'
Comp. .0. 3.8 4
Ex 1
4-(N o-benzylbenzamido)£pentano 1 .4 D 34 96.2 2.2 -2-yl benzoate
0 0
C 80 98.8 0.3
13 n.d. 3.4
No ED 90 95.5 1.7
4-((ethoxycarbonyl)(methyl)amino)pentan-2-yl 4- propylbenzoate, syn/anti 8:2
ED: External Donor.
D: dicyclopentyldimethoxysilane
C : methylcyclohexyldimethoxysilane
nd: not determined

Claims

A solid catalyst component for the polymerization of olefins comprising Mg, Ti and electron donor of formula (I)
Figure imgf000021_0001
(I)
where independently, Z is selected from C, Si, Ge, O, N, S or P with the proviso that the atoms O, S, and N are not directly linked to either the ester oxygen or the carbamic nitrogen of the formula (I), the R groups, equal to or different from each other, are hydrogen or a Ci-C2o hydrocarbon radicals, optionally containing a heteroatom selected from halogen, P, S, N,0 and Si, which can be fused together to form one or more cycles, m is a number satisfying the valences of Z and n is an integer ranging from 1 to 10, R1 and R4 are selected from C Qs hydrocarbon groups, optionally containing a heteroatom selected from halogen, P, S, N,0; and R3 group, is hydrogen or R4 groups.
2. The catalyst component according to claim 1 in which the (ZR m)n group of formula (I) is selected from the group consisting of aliphatic, alicyclic and aromatic bivalent radicals, optionally substituted with Q-Q5 hydrocarbon groups and/or with heteroatoms selected from halogen, P, S, N, O and Si, in which n ranges from 1 to 6 atoms.
3. The catalyst component according to claim 2 in which the (ZR m)n group is an aliphatic or alicyclic bridging group in which n ranges from 1-6 carbon atoms.
4. The catalyst component according to claim 1 in which R groups are selected from aryl and alkylaryl groups.
5. The catalyst component according to claim 4 in which R1 groups are selected from phenyl groups.
6. The catalyst component according to claim 5 in which the phenyl groups are substituted with halogen and/or Q-Cs alkyl groups.
7. The catalyst component according to claim 1 in which R groups are independently selected from hydrogen or C Qo alkyl groups.
8. The catalyst component according to claim 7 in which R groups are independently selected from C Cs alkyl groups.
9. The catalyst component according to claim 1 in which the R4 groups are selected from Q- Cio alkyl groups.
10. The catalyst component according to claim 9 in which the R4 groups are selected from Q- C5 alkyl groups.
11. The catalyst component according to claim 1 in which the electron donor is selected from those of formula (III)
Figure imgf000022_0001
in which in which R groups are phenyl groups optionally substituted with halogen and/or C C5 alkyl groups, R3 is hydrogen or C C2o hydrocarbon group, and R4 is a Ci-Cw alkyl group.
12. The catalyst component according to claim 11 in which R3 is hydrogen or methyl and R4 is a C C5 alkyl group.
13. Catalyst for the polymerization of olefins comprising the product of the reaction between:
(i) the solid catalyst component according to any of the preceding claims and
(ii) an alkylaluminum compound and optionally,
(iii) an external electron donor compound.
14. The catalyst according to claim 13 further comprising an external electron donor compound.
15. A process for the (co)polymerization of olefins CH2=CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of a catalyst system comprising the product of the reaction between: i. the solid catalyst component according to any of the proceeding claims;
ii. an alkylaluminum compound and,
iii. optionally an external donor compound.
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