EP4713375A1 - Catalyst components for the polymerization of olefins - Google Patents
Catalyst components for the polymerization of olefinsInfo
- Publication number
- EP4713375A1 EP4713375A1 EP24724285.2A EP24724285A EP4713375A1 EP 4713375 A1 EP4713375 A1 EP 4713375A1 EP 24724285 A EP24724285 A EP 24724285A EP 4713375 A1 EP4713375 A1 EP 4713375A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst component
- component according
- groups
- polymerization
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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 functional group.
- 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 carbamic groups and ester groups.
- PCT Publication No. W02021/001232 describes 1,2-amino esters derivatives including one carbamate group and one ester function.
- the catalysts generated by these structures have generally acceptable performances but it would be desirable to improve it.
- a catalyst component for the polymerization of olefins comprising Mg, Ti and an electron donor of formula (I) where the R 1 and R 5 groups, equal to or different from each other, are selected from C1-C15 hydrocarbon groups, R 2 group is selected from C3-C10 alkyl groups or C7-C10 arylalkyl groups, R 3 is hydrogen or C1-C20 hydrocarbon group and R 4 is selected from a C7-C20 halogen substituted arylalkyl group.
- hydrocarbon group also include the possible presence, in addition to carbon and hydrogen, in groups R 1 to R 5 as defined above of a heteroatom selected from halogen, P, S, N,0 and Si.
- alkyl group also include, if not separately specified, arylalkyl groups with the same carbon atom range deriving from alkyl groups by replacement of a hydrogen atom with an aryl group.
- R 1 is a C1-C10 alkyl group or arylalkyl group, more preferably a Ci-Cs alkyl group. More preferably the alkyl group is a primary alkyl group.
- R 2 is selected from C3-C10 primary alkyl or primary C7-C10 arylalkyl groups.
- R 3 can be hydrogen or a C1-C15 alkyl group, more preferably R 3 is selected from hydrogen.
- R 4 is preferably selected from halogen substituted C7-C20 arylalkyl groups, especially from primary C7-C20 arylalkyl groups. In a preferred aspect, R 4 is selected from halogen substituted C7-C15 arylalkyl groups.
- Preferred arylalkyl groups are 4-chlorobenzyl, 3 -chlorobenzyl, 2- chlorobenzyl, 3, 4-di chlorobenzyl, 4-fluorobenzyl, 3 -fluorobenzyl, 2-fluorobenzyl, 3,4- difluorobenzyl, 4-bromobenzyl, 3 -bromobenzyl, 3,4-dibromobenzyl, 4-iodobenzyl, 2-iodobenzyl, 3-iodobenzyl, 3, 4-iodobenzyl, l-(4-chlorophenyl)ethyl, l-(3-chlorophenyl)ethyl, l-(3,4- dichlorophenyl)ethyl, l-(4-chlorophenyl)propyl, l-(3-chlorophenyl)propyl, l-(3,4- dichlorophenyl)propy
- the halogen substituent is preferably positioned on the aromatic ring of the arylalkyl group.
- the aromatic rings may be substituted with one or more halogen atoms.
- each isolated or condensed aromatic ring is substituted with a number of halogens ranging from 1 to 2.
- any position can be substituted. Preferred positions are meta and/or para with this latter being especially preferred.
- Preferred halogens are Br, Cl and F with Cl being the most preferred.
- the aromatic moiety of the arylalkyl groups may also be substituted with C1-C10 alkyl group, more preferably a Ci-Cs alkyl groups.
- R 5 is a C1-C10 alkyl group, more preferably a Ci-Cs alkyl group. More preferably, the alkyl group is a primary alkyl group.
- Preferred structures of formula (I) are those in which R 1 and R 5 are independently a Ci- C10 alkyl group, R 2 is selected from C2-C10 alkyl or C7-C10 arylalkyl groups, R 3 is hydrogen and R 4 is a halogen substituted benzyl 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.
- Non-limiting examples of structures of formulas (I) are the following:.
- the amount of Ti atoms is preferably higher than 2%wt more preferably higher than 2.5% 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 MgCh in active form which is described 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 cosupport 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 TiCh and TiCh; furthermore, also Ti-haloalcoholates of formula Ti(0R 6 )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 6 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 TiCh 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 7 ) m-y X y , where m is the valence of titanium and y is a number between 1 and m, preferably TiCh, with a magnesium chloride deriving from an adduct of formula MgC12*pR 8 OH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R 8 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 TiCh (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 TiCh can be carried out one or more times.
- the electron donor compound is preferably added during the treatment with TiCk
- 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 2 /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.
- the solid catalyst component has an average particle size ranging from 5 to 120 pm and more preferably from 10 to 100 pm.
- 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 ranges from 0.01 : 1 to 2: 1, preferably from 0.05:1 to 1.5:1.
- the solid catalyst components according to the present disclosure are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum 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 AlEt2Cl and AhEtsCh, possibly in mixture with the above cited trialkylaluminums.
- the external electron-donor compounds can include silicon compounds, ethers, esters, amines, and heterocyclic compounds.
- Another class of preferred external donor compounds (iii) is that of silicon compounds of formula (R 9 ) a (R 10 )bSi(OR 11 ) 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 9 , R 10 , and R 11 , 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-trifhioro-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 a polymerization activity higher than 35 kg P oi/g ca t preferably higher than 40 kg po i/g ca t and a xylene insolubility at 25°C higher than 96%wt, preferably higher than 97%wt.
- 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).
- microspheroidal MgCh 2.8C2H5OH was prepared according to the method described in Example 2 of W098/44009, but operating on larger scale.
- the temperature was raised to 70°C in five minutes and the polymerization was carried out at this temperature for two hours.
- 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.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23173320 | 2023-05-15 | ||
| PCT/EP2024/063028 WO2024235894A1 (en) | 2023-05-15 | 2024-05-13 | Catalyst components for the polymerization of olefins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4713375A1 true EP4713375A1 (en) | 2026-03-25 |
Family
ID=86382705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP24724285.2A Pending EP4713375A1 (en) | 2023-05-15 | 2024-05-13 | Catalyst components for the polymerization of olefins |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP4713375A1 (en) |
| JP (1) | JP2026513612A (en) |
| CN (1) | CN121127504B (en) |
| WO (1) | WO2024235894A1 (en) |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL162661B (en) | 1968-11-21 | 1980-01-15 | Montedison Spa | PROCESS FOR PREPARING A CATALYST FOR THE POLYMERIZATION OF OLEFINS-1. |
| YU35844B (en) | 1968-11-25 | 1981-08-31 | Montedison Spa | Process for obtaining catalysts for the polymerization of olefines |
| GB1603724A (en) | 1977-05-25 | 1981-11-25 | Montedison Spa | Components and catalysts for the polymerisation of alpha-olefins |
| IT1096661B (en) | 1978-06-13 | 1985-08-26 | Montedison Spa | PROCEDURE FOR THE PREPARATION OF SOLID SPHEROIDAL PRODUCTS AT AMBIENT TEMPERATURE |
| IT1098272B (en) | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| IT1230134B (en) | 1989-04-28 | 1991-10-14 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| IT1262935B (en) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1262934B (en) | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1256648B (en) | 1992-12-11 | 1995-12-12 | Montecatini Tecnologie Srl | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| IL127230A (en) | 1997-03-29 | 2004-07-25 | Montell Technology Company Bv | Magnesium dichloride-alcohol adducts, process for their preparation and catalyst components obtained therefrom |
| DE10358824A1 (en) * | 2003-12-16 | 2005-07-21 | Bayer Healthcare Ag | Antibacterial macrocycles with substituted biphenyl |
| US8288606B2 (en) * | 2005-03-08 | 2012-10-16 | Ineos Usa Llc | Propylene polymer catalyst donor component |
| EP3298048B1 (en) * | 2015-05-19 | 2019-07-03 | Basell Poliolefine Italia S.r.l. | Catalyst components for the polymerization of olefins |
| ES2834436T3 (en) * | 2016-11-18 | 2021-06-17 | Basell Poliolefine Italia Srl | Catalyst components for olefin polymerization |
| WO2018161854A1 (en) * | 2017-03-10 | 2018-09-13 | 北京利和知信科技有限公司 | Solid catalyst component for use in olefin polymerisation, catalyst, and application thereof |
| US11834515B2 (en) * | 2017-10-11 | 2023-12-05 | Cornell University | Macrocyclic compounds as proteasome inhibitors |
| ES2980461T3 (en) | 2019-07-03 | 2024-10-01 | Basell Poliolefine Italia Srl | Catalytic components for olefin polymerization |
| WO2024107076A1 (en) * | 2022-11-14 | 2024-05-23 | Public Joint Stock Company "Sibur Holding" (Pjsc "Sibur Holding") | Procatalyst for olefin polymerization, method for preparation thereof |
-
2024
- 2024-05-13 JP JP2025560550A patent/JP2026513612A/en active Pending
- 2024-05-13 EP EP24724285.2A patent/EP4713375A1/en active Pending
- 2024-05-13 WO PCT/EP2024/063028 patent/WO2024235894A1/en not_active Ceased
- 2024-05-13 CN CN202480029048.7A patent/CN121127504B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN121127504A (en) | 2025-12-12 |
| CN121127504B (en) | 2026-06-30 |
| WO2024235894A1 (en) | 2024-11-21 |
| JP2026513612A (en) | 2026-04-28 |
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