Catalyst components for the polymerization of olefins

Abstract

A solid catalyst component for the polymerization of olefins comprising Mg, Ti, Cl and at least one electron donor compound, said solid catalyst component being a reaction product obtained by contacting a Mg compound and a Ti compound having at least a Ti-halogen bond with an electron donor selected from specific diphenol derivatives.

Description

Technical Field

[0001] This invention relates to catalyst components for the polymerization of olefins, particularly propylene, comprising a magnesium dihalide-based support and an electron donor, wherein the magnesium dihalide-based support is supported with Ti atoms, and the electron donor is selected from a specific class of bisphenol derivatives. The invention also relates to catalysts obtained from said components and their use in the polymerization processes of olefins, particularly propylene. Background Technology

[0002] Catalyst components for the stereodirectional polymerization of olefins are widely known in the art. For propylene polymerization, the most developed family of catalysts belongs to the Ziegler-Natta class, and generally comprises a solid catalyst component used in combination with an alkylaluminum compound, consisting of a magnesium dihalide supported on a titanium compound and an internal electron donor compound. However, when higher crystallinity of the polymer is required, an external donor (e.g., an alkoxysilane) is often needed to achieve higher isotactic regularity. One preferred type of internal donor is composed of phthalic acid esters, with diisobutyl phthalate being the most commonly used. Phthalic acid esters are combined with alkylalkoxysilanes as external donors to serve as internal donors. This catalyst system exhibits good performance in terms of activity, isotacticity, and xylene insolubility. One of the problems associated with the use of this catalyst system is that phthalic acid esters have recently attracted attention due to medical problems related to their use, and some compounds in this class have been classified as sources of serious health problems. Therefore, research activities are dedicated to discovering alternative classes of internal donors for preparing catalyst components for propylene polymerization. WO 2014 / 184171 is a bisphenol derivative in which the two hydroxyl groups of the bisphenol can be substituted with different functional groups, such as ethers, esters, urethanes, and carbonates. While catalyst components including such donors generally exhibit good performance, it is noted that it is difficult to simultaneously obtain both very high polymerization activity and high stereospecificity, as evidenced by high xylene insolubility values. Summary of the Invention

[0003] The applicant has surprisingly discovered that when the structure of prior art diphenol derivatives is modified with specific types of functional groups, electron donor compounds capable of producing solid catalyst components that simultaneously exhibit very high activity and high stereospecificity can be obtained.

[0004] This article discloses a solid catalyst composition for olefin polymerization comprising Mg, Ti, Cl and at least one electron donor compound, said catalyst composition being obtained by contacting a Mg compound and a Ti compound having at least a Ti-halogen bond with a bisphenol derivative of formula (I) as a reaction product.

[0005]

[0006] Where X is a chlorinated phenyl group, and Y is selected from hydrogen or R. 1 The R groups may be the same or different from each other, and are selected from hydrogen, halogens, and C1-C. 15 The hydrocarbon group, optionally containing heteroatoms selected from halogens, P, S, N, O, and Si, can fused together to form one or more rings, and R 1 It is a C1-C5 aliphatic group. Detailed Implementation

[0007] Preferably, in the bisphenol of formula (I), at least one of the R groups on the benzene ring is different from hydrogen and is selected from halogens or C1-C. 15 The R groups are hydrocarbon groups, and more preferably, at least two of them are different from hydrogen. In a preferred embodiment, at least three, particularly at least four, R groups are different from hydrogen. In a specific embodiment, six of the R groups are different from hydrogen. Preferably, the two benzene rings of the diphenol structure of formula (I) have the same substitution pattern. Therefore, when the number of R groups different from hydrogen is even (about 2, 4, 6, etc.), they are equally distributed in number and position on the two benzene rings. The R groups different from hydrogen are preferably selected from C1-C1. 15 Hydrocarbon groups, especially those selected from C1-C 10 Alkyl group. Preferably, the R group, which is different from hydrogen, is a straight-chain or branched C1-C5 alkyl group. Among straight-chain alkyl groups, methyl is preferred, while tert-butyl is preferred as a branched alkyl group.

[0008] R 1 The group is preferably selected from hydrogen or straight-chain C1-C5 alkyl groups, such as methyl, ethyl, and propyl. Hydrogen and methyl are preferred.

[0009] The chlorinated phenyl group denoted as X may contain one or more chlorine atoms. Preferably, the phenyl group is monosubstituted with chlorine.

[0010] Preferably, the chlorine atom is in the ortho position; a particularly preferred combination is when R 1 When it is hydrogen and chlorine is in the ortho position.

[0011] When two or more chlorines are present, at least one is in the ortho position; the others are preferably in the meta and / or para position. The meta position is preferred. Preferably, only two chlorines are present. In addition to chlorine substitution, the phenyl group may also contain C1-C5 alkyl substituents.

[0012] Non-limiting examples of the structure of formula (I) are as follows: 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2-chlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 2-chlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2-chlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,3-chlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 2,3-dichlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[ 1,1'-biphenyl]-2-yl 2,3-dichlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,3-chlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,4-dichlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 3,4-dichlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,4-chlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,4-chlorobenzoate, 6'-hydroxy-2',3' ',5,6-Tetramethyl-[1,1'-biphenyl]-2-yl 2,5-chlorobenzoate, 2',3',5,6-Tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 2,5-dichlorobenzoate, 6'-ethoxy-2',3',5,6-Tetramethyl-[1,1'-biphenyl]-2-yl 2,5-chlorobenzoate, 6'-methoxy-2',3',5,6-Tetramethyl-[1,1'-biphenyl]-2-yl 2,5-dichlorobenzoate, 6'-ethoxy-2',3',5,6-Tetramethyl-[1,1'-biphenyl]-2-yl 2,4-chlorobenzoate, 2',3',5,6-Tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate Esters, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4-chlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4,6-trichlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4,6-trichlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4,6-trichlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-Biphenyl]-2-yl 2,4,6-trichlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 3,5-dichlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,5-chlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,5-chlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3,5-dichlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,6-chlorobenzoate, 2',3',5,6- Tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 2,6-dichlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,6-chlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,6-dichlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 6'-methyl 2',3',5,6-Tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 6'-ethoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 2',3',5,6-tetramethyl-6'-propoxy-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 2'-hydroxy-[1,1'-biphenyl]-2-yl 2-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3- 2'-Chlorobenzoate, 2'-hydroxy-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate, 2'-ethoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate, 2'-hydroxy-[1,1'-biphenyl]-2-yl 3,4-dichlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 2-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3,4-dichlorobenzoate, 2'-hydroxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-hydroxy-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3 ...2,4-dichlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 4-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-methoxy-[1,1'-biphenyl]-2-yl 3-chlorobenzoate, 2'-1'-Biphenyl]-2-yl-4-chlorobenzoate, 2'-ethoxy-[1,1'-biphenyl]-2-yl-2-chlorobenzoate, 2'-ethoxy-[1,1'-biphenyl]-2-yl-4-chlorobenzoate, 2'-methoxy-[1,1'-binaphthyl]-2-yl-3-chlorobenzoate, 2'-methoxy-[1,1'-binaphthyl]-2-yl-2-chlorobenzoate, 2'-hydroxy-[1,1'-binaphthyl]-2-yl-3-chlorobenzoate, 2'-hydroxy-[1,1'-binaphthyl]-2-yl-2-chlorobenzoate, 2'-ethoxy-[1,1'-binaphthyl]-2-yl-3-chlorobenzoate, 2'-ethoxy-[1,1'-binaphthyl]-2-yl-2-chlorobenzoate, 2'-ethoxy-[1,1'-binaphthyl]- 2-yl-4-chlorobenzoate, 2'-hydroxy-5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthyl]-2-yl-3,4-dichlorobenzoate, 2'-hydroxy-5',6-dimethyl-[1,1'-biphenyl]-2-yl-2-chlorobenzoate, 2'-hydroxy-5',6-dimethyl-[1,1'-biphenyl]-2-yl-3-chlorobenzoate, 2'-hydroxy-5,5',6,6',7,7',8,8'-octahydro-[1,1'-binaphthyl]-2-yl-2,3-dichlorobenzoate, 2'-hydroxy-6,6'-dimethyl-[1,1'-biphenyl]-2-yl-2-chlorobenzoate, 2'-methoxy-6,6'-dimethyl-[1,1'-biphenyl]-2-yl-3-chlorobenzoate.

[0013] The compound falling into formula (I) can be added as is during catalyst preparation, or alternatively, added as a precursor, which can be converted into the compound of formula (I) due to reaction with other catalyst components. In addition to the compound of formula (I) described above, the solid catalyst component may also contain other donors. While there is no limitation on the type of other donor, it is preferred to select those that may be halogenated or C1-C on the benzene ring. 15 Those esters of benzoic acid with hydrocarbon-substituted groups.

[0014] As described above, in addition to the aforementioned electron donors, the catalyst components described herein may contain Ti, Mg, and halogens. Specifically, the catalyst components comprise titanium compounds having at least Ti-halogen bonds and the aforementioned electron donor compounds supported on magnesium halides. Magnesium halides are preferably MgCl2, an active form widely known from patent literature as a support for Ziegler-Natta catalysts. The use of these compounds in Ziegler-Natta catalysis was first described in patents USP 4,298,718 and USP 4,495,338. It is known from these patents that the active form of magnesium dihalides used as a support or co-support in the components of catalysts for olefin polymerization is characterized by X-ray spectroscopy, wherein the intensity of the strongest diffraction line appearing in the spectrum of the inactive halide decreases and is replaced by the halogen, and the maximum intensity of the halogen shifts to a lower angle relative to the maximum intensity of the stronger line.

[0015] Preferred titanium compounds for preparing the catalyst components disclosed herein are TiCl4 and TiCl3; alternatively, Ti(OR) can also be used. m-y X y Ti-halools, where m is the valence of titanium, y is a number from 1 to m-1, X is a halogen, and R is a hydrocarbon group having 1 to 10 carbon atoms.

[0016] The solid catalyst component described in this application may contain Ti atoms in an amount greater than 2.5% wt, more preferably greater than 3.0% relative to the total weight of the catalyst component. Particularly preferred is an amount of titanium of 2.5% to 8%.

[0017] The preparation of solid catalyst components can be carried out by several methods. One method involves the reaction of magnesium alkoxide or magnesium chlorohydrin (particularly chlorohydrins prepared according to USP 4,220,554) with excess TiCl4 in the presence of an electron donor compound at a temperature of about 80°C to 120°C.

[0018] According to a preferred method, the solid catalyst component can be prepared by using the formula Ti(OR). m-y X yThe adduct is prepared by reacting a titanium compound with magnesium chloride derived from the formula MgCl2·pROH, wherein m is the valence of titanium and y is a number between 1 and m, preferably TiCl4, and p is a number between 0.1 and 6, preferably 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms. The adduct can be suitably prepared in a spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring at the melting temperature of the adduct (100-130 °C). The emulsion is then rapidly quenched, causing the adduct to solidify into spherical particles. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The adduct thus obtained can be reacted directly with the Ti compound, or it can be pre-treated with thermally controlled alcohol removal (80-130 °C) to obtain an adduct in which the molar number of alcohol is typically less than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (de-alcoholized or as is) in cold TiCl4 (typically 0°C); the mixture is then heated to 80-130°C and held at that temperature for 0.5-2 hours. The TiCl4 treatment can be performed once or multiple times. In a preferred embodiment, the electron donor compound is added during the first treatment with TiCl4 in an amount such that the Mg / donor ratio is 2 to 15, preferably 4 to 10. If additional donors are present, they are preferably added separately. In particular, it is preferred to add additional donors during the first treatment with TiCl4, and more preferably during the second treatment with TiCl4, the donor of formula (I). The preparation of the spherical catalyst components is described, for example, in European patent applications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525 and WO98 / 44009.

[0019] The solid catalyst components obtained by the above method showed surface areas (by the BET method) of 20 and 500 m². 2 Between / g, preferably between 50 and 400m 2 Between / g, the total porosity (by BET method) is higher than 0.2cm. 3 / g, preferably at 0.2 and 0.6cm 3 Between / g. From a radius up to The porosity caused by the pores (Hg method) is typically 0.3 to 1.5 cm⁻¹. 3 / g, preferably 0.45 to 1cm 3 / g.

[0020] The solid catalyst component has an average particle size ranging from 5 to 120 μm, and more preferably from 10 μm to 100 μm.

[0021] Regardless of the preparation method used, the final amount of the electron donor compound of formula (I) is such that its molar ratio to Ti atoms is 0.01:1 to 2:1, preferably 0.05:1 to 1.2:1.

[0022] Solid catalyst components can be converted into catalysts for olefin polymerization by reacting them with organoaluminum compounds according to known methods.

[0023] In particular, a catalyst for the polymerization of olefins CH2=CHR is provided, wherein R is hydrogen or a hydrocarbon group having 1-12 carbon atoms, said catalyst comprising a product obtained by contacting the following substances:

[0024] (i) and the above solid catalyst components and

[0025] (ii) Alkyl aluminum compounds and optionally...

[0026] (iii) External electron donor compounds.

[0027] The alkyl-Al compound (ii) is preferably selected from trialkylaluminum compounds, such as triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum. Alkylaluminum halides, alkylaluminum hydrides, or alkylaluminum sesquichlorides, such as AlEt2Cl and Al2Et3Cl3, may also be used, possibly in combination with the aforementioned trialkylaluminum compounds.

[0028] Suitable external electron donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds, and especially 2,2,6,6-tetramethylpiperidine and ketones.

[0029] Another preferred type of external donor compound is formula (R7). a (R8) b Si(OR9) c The silicon compound wherein 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 groups having 1 to 18 carbon atoms, optionally containing heteroatoms. Particularly preferred are silicon compounds wherein a is 1, b is 1, c is 2, at least one of R7 and R8 is selected from branched alkyl, cycloalkyl, or aryl groups having 3 to 10 carbon atoms, optionally containing heteroatoms, and R9 is C1-C9. 10Alkyl groups, particularly methyl groups. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C-donor), diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane (D-donor), diisopropyldimethoxysilane, (2-ethylpiperidinyl)tert-butyldimethoxysilane, (2-ethylpiperidinyl)tert-hexyldimethoxysilane, (3,3,3-trifluoropropyl)(2-ethylpiperidinyl)dimethoxysilane, methyl(3,3,3-trifluoropropyl)dimethoxysilane, and N,N-diethylaminotriethoxysilane. Furthermore, silicon compounds in which a is 0, c is 3, R8 is optionally a branched alkyl or cycloalkyl group containing a heteroatom, and R9 is methyl are also preferred. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0030] The amount of electron donor compound (iii) used is such that the molar ratio between the organoaluminum compound and the electron donor compound (iii) is 0.1:1 to 500:1, preferably 1:1 to 300:1, and more preferably 3:1 to 100:1.

[0031] Therefore, a process for the (co)polymerization of the olefin CH2=CHR is also described, wherein R is hydrogen or a hydrocarbon group having 1-12 carbon atoms, the process being carried out in the presence of a catalyst comprising the reaction products between:

[0032] (i) Solid catalyst components as described above;

[0033] (ii) Alkyl aluminum compounds and,

[0034] (iii) Optional electron donor compound (external donor).

[0035] The polymerization process can be carried out using known techniques, such as slurry polymerization using inert hydrocarbon solvents as diluents, or bulk polymerization using liquid monomers (e.g., propylene) as the reaction medium. Alternatively, the polymerization process can be carried out in the gas phase in one or more fluidized or mechanically stirred bed reactors.

[0036] Polymerization is typically carried out at temperatures between 20 and 120°C, preferably between 40 and 80°C. When polymerization is carried out in the gas phase, the operating pressure can be between 0.5 and 5 MPa, preferably between 1 and 4 MPa. In bulk polymerization, the operating pressure can be between 1 and 8 MPa, preferably between 1.5 and 5 MPa.

[0037] As already mentioned, the catalyst of the present invention can simultaneously provide very high activity (more than 70 kg polymer / g catalyst), wherein the isotactic index (XI%) exceeds 97.5%, which is not achievable with existing structures.

[0038] The following embodiments are given to illustrate the invention but not to limit it.

[0039] Example

[0040] Characterization

[0041] Measurement of XI

[0042] 2.5 g of the polymer and 250 ml of o-xylene were placed in a round-bottom flask equipped with a condenser and a reflux condenser, and kept under nitrogen atmosphere. The resulting mixture was heated to 135 °C and maintained with stirring for about 60 minutes. The final solution was cooled to 25 °C with continuous stirring, and then the insoluble polymer was filtered off. The filtrate was then evaporated at 140 °C under a nitrogen stream to constant weight. The content of the xylene-soluble fraction is expressed as a percentage of the initial 2.5 g, and then XI is obtained by subtraction.

[0043] Melt flow rate (MFR)

[0044] The melt flow rate (MIL) of the polymer was determined according to ISO 1133 (230°C, 2.16 kg).

[0045] Comparative Example 1: Synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-ylbenzoate

[0046] Step 1: Synthesis of 2-(tert-butyl)-3,4-dimethylphenol

[0047] Under nitrogen atmosphere, 100 g (0.82 mol) of 3,4-dimethylphenol, 267 mL (3 eq.) of 2-chloro-2-methylpropane, and 1.3 mL (3% mol.) of sulfuric acid were added to a 1 L round-bottom flask. The mixture was then refluxed until GC showed the reaction was complete (10 h). The flask was then cooled to room temperature, and 400 mL of water was added with 300 mL of toluene while stirring. The organic layer was separated and washed with water (2 × 150 mL), NaHCO3 (aq), and again with water. The toluene solution was used directly for the next step.

[0048] Step 2: Synthesis of 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-[1,1'-biphenyl]-2,2'-diol

[0049] The toluene solution of 2-(tert-butyl)-3,4-dimethylphenol from the previous step was charged into a 1 L round-bottom flask containing Cu(I)Cl (4.9 g, 6% mol), N,N,N',N'-tetramethylethylenediamine (11.1 mL, 9% mol), and water (1.8 mL, 12% mol). Air was bubbled through a porous glass frit into the mixture at room temperature with stirring until GC indicated completion (7 hours). Acidic water was added with stirring, and the organic layer was separated, washed with water to neutral pH, dehydrated with Na₂SO₄, and the solvent was distilled off to give 138 g of solid (93% yield in two steps).

[0050] Step 3: Synthesis of 5,5',6,6'-tetramethyl-[1,1'-biphenyl]-2,2'-diol

[0051] Under nitrogen atmosphere, 138 g (0.39 mol) of 3,3'-di-tert-butyl-5,5',6,6'-tetramethyl-[1,1'-biphenyl]-2,2'-diol, obtained in the previous step, was loaded together with toluene (390 mL, 1 mol / L) into a 1 L round-bottom flask equipped with a mechanical stirrer. The flask was then cooled to 0 °C, and AlCl3 (52 g, 1 eq) was added in portions. The slurry was stirred at room temperature until GC indicated the reaction was complete (50 min), then cooled in an ice / water bath, and 200 mL of 4M HCl was added. The slurry was filtered through a sintered glass funnel and washed thoroughly with water (500 mL × 3), NaHCO3 (aq), and isohexane (300 mL × 2). The wet solid was dried under vacuum at 80 °C overnight to give 90 g of GC-grade pure white solid (96% yield).

[0052] Step 4: Synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-ylbenzoate

[0053] Under nitrogen atmosphere, 10 g (0.041 mol) of 5,5',6,6'-tetramethyl-[1,1'-biphenyl]-2,2'-diol, along with toluene (200 mL, 0.2 mol / L), TiCl4 (4.8 mL, 1.2 eq), and benzoyl chloride (5 mL, 1.05 eq), were placed in a 500 mL round-bottom flask equipped with a mechanical stirrer. After stirring at room temperature for 6 hours, the resulting deep red powder was filtered under nitrogen atmosphere and washed with toluene (2 × 100 mL). The powder was then treated with acidic water / ether under vigorous stirring until the red color disappeared. The organic layer was separated, washed with water to neutral pH, dehydrated with Na2SO4, and the solvent was distilled off to give 13 g of a pale yellow viscous oil (99% GC purity, 91% yield).

[0054] Example 1 of the Invention: Synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl-2-chlorobenzoate become

[0055] The synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2-chlorobenzoate was the same as that of Comparative Example 1, except that 2-chlorobenzoyl chloride was used instead of benzoyl chloride in step four.

[0056] Example 2 of the invention: 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,3-dichlorobenzoate Synthesis

[0057] The synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,3-dichlorobenzoate was the same as that of Comparative Example 1, except that 2,3-dichlorobenzoyl chloride was used instead of benzoyl chloride in step four.

[0058] Example 3 of the invention: 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate Synthesis

[0059] The synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 2,4-dichlorobenzoate was the same as that of Comparative Example 1, except that 2,4-dichlorobenzoyl chloride was used instead of benzoyl chloride.

[0060] Example 4 of the Invention: 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate synthesis

[0061] Step 1: Synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl-3-chlorobenzoate

[0062] The synthesis of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate was the same as that of Comparative Example 1, except that 3-chlorobenzoyl chloride was used instead of benzoyl chloride in step four.

[0063] Step 2: Synthesis of 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl-3-chlorobenzoate

[0064] 12 g (0.032 mol) of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate was mixed with THF (150 mL, 0.2 mol / L) and methyl iodoforme (5.9 mL, 3 eq) under nitrogen atmosphere in a 500 mL round-bottom flask equipped with a mechanical stirrer. The mixture was then cooled to 0 °C in an ice / water bath, and NaH (1.1 mol, 1.1 eq) was added in portions. After 3 hours at room temperature, the mixture was quenched with acidic water with stirring and extracted with diethyl ether. The organic layer was separated, washed with water to neutral pH, dehydrated with Na2SO4, and the solvent was distilled off to give 12.1 g of a viscous oily substance, which was crystallized from 24 mL of diisopropyl ether to give 8.6 g of pure product (70% yield).

[0065] Example 5 of the Invention: 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate synthesis

[0066] The synthesis of 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate is the same as in Example 4 of the invention, except that in the second step, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 4-chlorobenzoate is used instead of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate.

[0067] Synthesis of 2,6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-ylbenzoate (Comparative Example)

[0068] The synthesis of 6'-methoxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-ylbenzoate is the same as in Example 4 of the invention, except that in the second step, 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-ylbenzoate is used instead of 6'-hydroxy-2',3',5,6-tetramethyl-[1,1'-biphenyl]-2-yl 3-chlorobenzoate.

[0069] General procedure for preparing spherical adducts

[0070] The initial amount of microspheres of MgCl2·2.8C2H5OH was prepared according to the method described in Example 2 of WO98 / 44009, but the scale was relatively large.

[0071] Procedure for preparing solid catalyst components using donors from Comparative Example 1 and Examples 1-3 of the present invention.

[0072] 250 mL of TiCl4 was introduced into a 500 mL round-bottom flask equipped with a mechanical stirrer, cooler, and thermometer at room temperature under a nitrogen atmosphere. After cooling to 0 °C, ethyl benzoate and 10.0 g of a spherical adduct (prepared as described above) were added sequentially to the flask while stirring. The amount of ethyl benzoate added was such that the Mg / EB molar ratio was 6. The temperature was raised to 40 °C, and an internal donor was added. The amount of internal donor added was such that the Mg / donor molar ratio was 6. The temperature was then raised to 100 °C and held for 2 hours. After this, stirring was stopped, the solid product was allowed to settle, and the supernatant was siphoned off at 100 °C. After removing the supernatant, fresh TiCl4 was added again to bring the initial liquid volume back up. The mixture was then heated at 120 °C and held at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle, and the supernatant was siphoned off.

[0073] The solid was washed six times (6 × 100 mL) with anhydrous hexane, the temperature gradient was reduced to 60 °C, and then washed once at room temperature (100 mL). The obtained solid was then dried under vacuum and analyzed.

[0074] Procedure for preparing solid catalyst components using donors from Comparative Example 2 and Examples 4-5 of the present invention.

[0075] 250 mL of TiCl4 was introduced into a 500 mL round-bottom flask equipped with a mechanical stirrer, cooler, and thermometer at room temperature under a nitrogen atmosphere. After cooling to 0 °C, the internal donor and 10.0 g of the spherical adduct (prepared as described above) were added sequentially to the flask while stirring. The amount of internal donor added was such that the Mg / donor molar ratio was 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 was siphoned off at 100 °C. After removing the supernatant, additional fresh TiCl4 was added to return to the initial liquid volume. The mixture was then heated at 120 °C and maintained at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle, and the supernatant was siphoned off.

[0076] The solid was washed six times (6 × 100 mL) with anhydrous hexane, the temperature gradient was reduced to 60 °C, and then washed once at room temperature (100 mL). The obtained solid was then dried under vacuum and analyzed.

[0077] General procedures for propylene polymerization

[0078] A 4-liter steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feed system, monomer feed line, and thermostatic jacket was purged with nitrogen at 70°C for one hour. Then, at 30°C, under a propylene stream, 75 mL of anhydrous hexane, 0.76 g of AlEt3, the external electron donor shown in Table 1 (if used), and 0.006 ÷ 0.010 g of solid catalyst components were added sequentially. The autoclave was shut off; subsequently, 2.0 NL of hydrogen was added. Then, under stirring, 1.2 kg of liquid propylene was fed. The temperature was raised to 70°C over five minutes and polymerization was carried out at this temperature for two hours. At the end of polymerization, unreacted propylene was removed; the polymer was recovered and dried under vacuum at 70°C for three hours. The polymer was then weighed and fractionated with o-xylene to determine the amount of xylene-insoluble (XI) fraction.

[0079] Embodiments 1-5 and Comparative Examples 1-2

[0080] Catalyst components were prepared according to the above procedure using the donors prepared in Comparative Examples 1-2 and Examples 1-4 of the present invention. They were tested in the polymerization of propylene using the above polymerization procedure. The results are listed in Table 1.

[0081] Table 1.

[0082]

[0083] ED: External donor.

[0084] D: Dicyclopentyldimethoxysilane

Claims

1. A solid catalyst component for olefin polymerization, comprising Mg, Ti, Cl and at least one electron donor compound, said solid catalyst component being a reaction product obtained by contacting a Mg compound and a Ti compound having at least a Ti-halogen bond with an electron donor selected from a bisphenol derivative of formula (I). (I) Where X is (i) a phenyl substituted with one chlorine atom; or (ii) a phenyl substituted with two chlorine atoms, one of which is in the ortho position and the other in the meta position; and Y is selected from hydrogen or R. 1 The R groups may be the same or different from each other, and are selected from hydrogen, halogens, and C1-C. 15 The hydrocarbon group, optionally containing heteroatoms selected from halogens, P, S, N, O, and Si, can fused together to form one or more rings, and R 1 It is a C1-C5 aliphatic group.

2. The catalyst component according to claim 1, wherein R 1 The group is selected from hydrogen or straight-chain C1-C5 alkyl.

3. The catalyst component according to claim 2, wherein R 1 The group is hydrogen or methyl.

4. The catalyst component according to claim 1, wherein X is a phenyl group (i) substituted with a chlorine atom.

5. The catalyst component according to claim 4, wherein the chlorine atom is in the ortho position.

6. The catalyst component according to claim 3 or 5, wherein R 1 It is hydrogen and the chlorine atom is in the adjacent position.

7. The catalyst component according to claim 1, wherein X is a phenyl group (ii) substituted with two chlorine atoms.

8. The catalyst component according to claim 1, wherein at least one of the R groups is different from hydrogen and is selected from halogens or C1-C4 groups. 15 Hydrocarbon group.

9. The catalyst component according to claim 8, wherein at least four of the R groups are different from hydrogen.

10. The catalyst component according to claim 5, wherein the R group, which is different from hydrogen, is selected from C1-C6. 10 alkyl.

11. The catalyst component according to claim 1, further comprising an additional electron-donating compound, said additional electron-donating compound being selected from those possibly bonded to a halogen or C1-C2 bond on the benzene ring. 15 Esters of benzoic acid with hydrocarbon-substituted groups.

12. A catalyst for the polymerization of olefins CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1-12 carbon atoms, said catalyst comprising a product obtained by contacting the following: (i) the solid catalyst component according to any one of claims 1-11; (ii) Alkyl aluminum compounds and optionally, (iii) External electron donor compounds.

13. The catalyst according to claim 12, wherein the external electron donor compound is selected from formula (R7). a (R8) b Si(OR9) c The silicon compound wherein 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 groups having 1 to 18 carbon atoms, optionally containing heteroatoms.

14. A process for the polymerization of the olefin CH2=CHR, wherein R is hydrogen or a hydrocarbon group having 1-12 carbon atoms, said process being carried out in the presence of a catalyst according to any one of claims 12-13.

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