CN101759816A - Method for preparing a catalyst component for olefinic polymerization, and a catalyst component thereof - Google Patents

Abstract

The present invention provides a method for preparing a catalyst component for olefin polymerization and the catalyst component thereof, which comprises the following reaction steps: (1) adding magnesium halide as shown in general formula (I) MgCl ₂ .nROH The compound is added to a titanium compound or a mixture of a titanium compound and an inert solvent at -30°C to 0°C to form a solution; (2) Heat the above solution, add electron donor compound a at -30°C to 20°C, and add electron donor compound a at 40°C to Add electron donor compound b at 80°C, and finally raise the temperature to 80°C to 130°C, then add titanium compound for one or more treatments, and finally wash with an inert solvent to obtain a solid catalyst component. The electron donor compound a is selected from diesters The electron donor compound b is selected from 1,3-diether compounds, wherein the electron donor compound b is 0.01 to 0.5 moles per mole of magnesium; the electron donor compound a and the electron donor compound The molar ratio of b is 0.1-0.4.

Description

Process for the preparation of catalyst components for olefin polymerization and catalyst components thereof

technical field

The present invention relates to a preparation method of a catalyst component for olefin polymerization and its catalyst component, more specifically to a catalyst component comprising a spherical adduct, a titanium compound and at least two electron donor compounds. Preparation method and its catalyst components.

technical background

It is well known that solid titanium catalyst components based on magnesium, titanium, halogen and electron donors can be used in the polymerization of _CH2 =CHR olefins, especially in the polymerization of α-olefins with 3 carbon atoms or more Polymers with higher yield and higher stereoregularity can be obtained, in which the electron donor compound is one of the essential components in the catalyst component, and with the development of the internal electron donor compound, polyolefin catalysts have continuously ground replacement. So far, many patents have disclosed various internal electron donor compounds suitable for the preparation of Ziegler-Natta catalysts, and catalysts for olefin polymerization containing these internal electron donor compounds.

These internal electron donor compounds mainly include: phthalate electron donor compounds described in European Patent EP0045977, 1,3-diether compounds described in European Patent EP0361493, EP0728724, Chinese patent CN1105671A described 1,3-diketone compounds, special substituted malonate compounds described in Chinese patents CN1236732, CN1236733, CN1236734, CN1292800, succinate compounds described in PCT international application WO0063261, and PCT international application WO0055215 β-substituted glutarate compounds, cyano ester compounds described in Chinese patent CN1242780, diamine electron donor compounds described in Chinese patent CN1087918, maleic acid di Electron donor compounds of esters, and a special polyol ester compound described in Chinese patents CN1436766A and CN1436796A.

Due to the use of different internal electron donor compounds, the prepared catalysts have different characteristics, for example, some catalysts have higher activity, and some catalysts have better hydrogen tuning sensitivity, but in general, for the use of a single internal electron donor The catalyst of the electron body compound has a narrow molecular weight distribution of the prepared polymer, which affects the processing performance of the resin. For example, the 1,3-diether compounds described in European patents EP0361493 and EP0728724, when using this type of compound as an internal electron donor, can improve the activity of the catalyst and improve the isotacticity of the polymer, and even save the external When the electron donor component is used, high yield and high isotactic polymers can still be obtained. However, the molecular weight distribution obtained by this type of catalyst is narrow, and the processability of the polymer is poor, which limits the application of the polymer.

In the prior art, people usually use the method of adding various internal electron donor compounds during the catalyst preparation process to improve the overall performance of the catalyst. As disclosed in the Chinese patent CN1268957A, in the preparation process of the catalyst, two electron donor compounds are used, one is selected from the ether compound containing two or more ether bonds, and the other is selected from the monocarboxylic acid or polycarboxylic acid of ester compounds. The obtained catalyst has high activity, and the prepared polypropylene has a high xylene-insoluble content and low crystallinity, and is suitable for preparing double-oriented polypropylene film BOPP. As proposed in WO03/002617, in the catalyst preparation process, first add a small amount of monofunctional compounds, such as ethyl benzoate, and then add another electron donor compound in the subsequent preparation process, the monofunctional group in the catalyst obtained The content of the compound is very small or even undetectable. However, the obtained catalyst activity and melt flow index have been greatly improved. Although the above methods have improved the catalyst to some extent, they are still unsatisfactory in terms of broadening the molecular weight distribution of the polymer.

Patent No. CN1803863A discloses that in the catalyst preparation process, adding a 1,3-diether electron donor compound and adding a dibasic ester compound with a special structure can prepare catalyst components and catalysts with excellent comprehensive performance. For olefin polymerization, especially propylene polymerization, polymers with wide molecular weight distribution can be obtained, but the catalyst activity and fluidity still need to be further improved.

The inventors found in the research process that during the preparation of the spherical catalyst component, a dibasic ester electron donor compound with a special structure was added while adding the above-mentioned 1,3-diether electron donor compound, Simultaneously controlling the molar ratio and the adding sequence of the two electron donor compounds can prepare a spherical catalyst component with excellent comprehensive performance. It is worth pointing out that this catalyst shows high activity when used in the polymerization of olefins, especially propylene, while the molecular weight distribution of the polymer is significantly improved.

Contents of the invention

The invention provides a kind of preparation method for the catalyst component of olefin polymerization, it comprises following reaction steps:

(1) adding the magnesium halide adduct represented by the general formula (I) MgCl ₂ .nROH to a titanium compound or a mixture of a titanium compound and an inert solvent at -30°C to 0°C to form a solution;

(2) Heat the above solution, add electron donor compound a at -30°C to 20°C, add electron donor compound b at 40°C to 80°C, and finally raise the temperature to 80°C to 130°C, and then add titanium compound for treatment once or multiple times, and finally wash with an inert solvent to obtain a solid catalyst component;

In step (1), in the general formula (I), R is a C ₁ -C ₄ alkyl group, and n is 1.5-3.5;

The general formula of the titanium compound described in step (1) and step (2) is TiX _m (OR) _4-m , where R is a hydrocarbon group with 1 to 20 carbon atoms, X is a halogen, and m=1 ~4.

In step (2), the electron donor compound a is selected from diester compounds as shown in general formula (II):

In the formula, R' and _R1 are the same or different, and are selected from substituted or unsubstituted linear or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aromatic group, C ₇ -C ₂₀ alkaryl group, C ₇ -C ₂₀ aralkyl group, C ₂ -C ₁₀ alkenyl group, C ₁₀ -C ₂₀ fused ring aryl group; A is a divalent carbon chain length of 1-10 Linking group, which is selected from aliphatic, alicyclic and aromatic divalent groups, the carbon in the divalent linking group can have C ₁ -C ₂₀ selected from linear or branched alkyl, Substituents of cycloalkyl, aryl, alkaryl, aralkyl, alkenyl, fused ring aryl, ester, and two or more substituents can be connected to form saturated or unsaturated monocyclic or polycyclic ;

In step (2), the electron donor compound b is selected from 1,3-diether compounds of general formula (III),

(III)

Wherein R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI are the same or different, selected from hydrogen, halogen atom, straight or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ ring Alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl, and R ^VII and R ^VIII can be the same or different, selected from straight chain Or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl ; The groups of R ^I -R ^VI can be bonded to form a ring;

Calculated per mole of magnesium, the electron donor compound b is 0.01-0.5 moles, preferably 0.06-0.3 moles; the molar ratio of the electron donor compound a and the electron donor compound b is 0.1-0.4.

In the above-mentioned diester compounds represented by the general formula (II), preferably A is a divalent linking group with a chain length of 2 carbon atoms, and R' is selected from substituted or unsubstituted C ₆ -C ₂₀ aromatic radical, alkaryl or aralkyl.

In a more preferred embodiment, the diester compound of the general formula (II) includes a diester compound represented by the following general formula (IV):

In the formula:

R ₁ is C ₁ -C ₂₀ unsubstituted or halogen-substituted alkyl, or C ₆ -C ₂₀ unsubstituted or halogen-substituted aryl or alkaryl;

R _2-5 are the same or different, and are hydrogen or C _1-4 linear or branched alkyl;

R ^1-5 are the same or different, hydrogen, halogen, C ₁ -C ₁₀ unsubstituted or halogen substituted alkyl, or C ₆ -C ₂₀ unsubstituted or halogen substituted aryl or alkaryl or aralkyl base.

The aforementioned halogen is preferably selected from F, Cl, Br.

Among the above-mentioned compounds of general formula (IV), R ₁ is preferably C ₂ -C ₁₀ linear or branched chain alkyl C ₆ -C ₂₀ alkaryl. More preferably _R is _C2 - _C6 linear or branched alkyl such as ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, etc. .

Among the above-mentioned compounds of general formula (IV), preferably R ^1-5 are the same or different, and are hydrogen or C ₁ -C ₆ linear or branched alkyl or halogenated alkyl, such as methyl, ethyl , propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, etc.

Examples of specific dibasic ester compounds include:

Ethyl 3-benzoyloxybutyrate, ethyl 2-methyl-3-benzoyloxybutyrate, ethyl 2-ethyl-3-benzoyloxybutyrate, 2-n-propane Ethyl-3-benzoyloxybutyrate, ethyl 2-allyl-3-benzoyloxybutyrate, ethyl 2-isopropyl-3-benzoyloxybutyrate, 2-n-Butyl-3-benzoyloxy ethyl butyrate, 2-isobutyl-3-benzoyloxy ethyl butyrate, 2-tert-butyl-3-benzoyloxy butyrate ethyl 2-benzyl-3-benzoyloxybutanoate, ethyl 2,2-dimethyl-3-benzoyloxybutyrate, 3-benzoyloxyvaleric acid Ethyl ester, 2-methyl-3-benzoyloxyethyl valerate, 2-ethyl-3-benzoyloxyethyl valerate, 2-n-propyl-3-benzoyloxy Ethyl valerate, ethyl 2-allyl-3-benzoyloxyvalerate, ethyl 2-isopropyl-3-benzoyloxyvalerate, 2-n-butyl-3-benzene Formyloxyethyl valerate, 2-isobutyl-3-benzoyloxyethyl valerate, 2-tert-butyl-3-benzoyloxyethyl valerate, 2-benzyl- 3-Benzoyloxyethyl valerate, 2,2-dimethyl-3-benzoyloxyethyl valerate, 3-benzoyloxyhexanoic acid ethyl ester, 2-methyl-3 -Ethyl benzoyloxyhexanoate, ethyl 2-ethyl-3-benzoyloxyhexanoate, ethyl 2-n-propyl-3-benzoyloxyhexanoate, 2-allyl Ethyl-3-benzoyloxyhexanoate, ethyl 2-isopropyl-3-benzoyloxyhexanoate, ethyl 2-n-butyl-3-benzoyloxyhexanoate, 2-Isobutyl-3-benzoyloxyhexanoic acid ethyl ester, 2-tert-butyl-3-benzoyloxyhexanoic acid ethyl ester, 2-benzyl-3-benzoyloxyhexanoic acid Ethyl ester, isopropyl 3-benzoyloxybutyrate, isopropyl 2-methyl-3-benzoyloxybutyrate, isopropyl 2-ethyl-3-benzoyloxybutyrate Esters, Isopropyl 2-n-Propyl-3-benzoyloxybutyrate, Isopropyl 2-allyl-3-benzoyloxybutyrate, 2-Isopropyl-3-Benzene Isopropyl acyloxybutyrate, isopropyl 2-n-butyl-3-benzoyloxybutyrate, isopropyl 2-isobutyl-3-benzoyloxybutyrate, 2-tert Butyl-3-benzoyloxybutyrate isopropyl, 2-benzyl-3-benzoyloxybutyrate isopropyl, 2,2-dimethyl-3-benzoyloxybutyrate Isopropyl Butyrate, Isobutyl 3-Benzoyloxybutyrate, Isobutyl 2-Methyl-3-Benzoyloxybutyrate, 2-Ethyl-3-Benzoyloxybutyrate Isobutyl ester, 2-n-propyl-3-benzoyloxybutyric acid isobutyl ester, 2-allyl-3-benzoyloxybutyric acid isobutyl ester, 2-isopropyl-3- Isobutyl benzoyloxybutyrate, isobutyl 2-n-butyl-3-benzoyloxybutyrate, isobutyl 2-isobutyl-3-benzoyloxybutyrate, 2 - Isobutyl-tert-butyl-3-benzoyloxybutyrate, isobutyl 2-benzyl-3-benzoyloxybutyrate, 2,2-dimethyl-3-benzoyloxy Isobutyl Butyrate, Methyl 3-Benzoylbutyrate, Methyl 2-Methyl-3-Benzoylbutyrate, 2-Ethyl-3-Benzoyloxybutyrate Methyl ester, methyl 2-n-propyl-3-benzoyloxybutyrate, methyl 2-allyl-3-benzoyloxybutyrate, 2-isopropyl-3-benzoyl Methyl oxybutyrate, methyl 2-n-butyl-3-benzoyloxybutyrate, methyl 2-isobutyl-3-benzoyloxybutyrate, 2-tert-butyl-3 - methyl benzoyloxybutyrate, methyl 2-benzyl-3-benzoyloxybutyrate, methyl 2,2-dimethyl-3-benzoyloxybutyrate. Ethyl 3-cinnamoyloxybutyrate, ethyl 2-methyl-3-cinnamoyloxybutyrate, ethyl 2-ethyl-3-cinnamoyloxybutyrate, 2-n-propyl-3 -Ethyl cinnamoyloxybutyrate, ethyl 2-allyl-3-cinnamoyloxybutyrate, ethyl 2-isopropyl-3-cinnamoyloxybutyrate, 2-n-butyl- Ethyl 3-cinnamoyloxybutyrate, ethyl 2-isobutyl-3-cinnamoyloxybutyrate, ethyl 2-tert-butyl-3-cinnamoyloxybutyrate, 2-benzyl- Ethyl 3-cinnamoyloxybutyrate, ethyl 2,2-dimethyl-3-cinnamoyloxybutyrate, ethyl 3-cinnamoyloxyvalerate, 2-methyl-3-cinnamoyl Ethyl Oxyvalerate, Ethyl 2-Ethyl-3-cinnamoyloxyvalerate, Ethyl 2-n-Propyl-3-cinnamoyloxyvalerate, 2-Allyl-3-cinnamoyl Ethyl oxyvalerate, ethyl 2-isopropyl-3-cinnamoyloxyvalerate, ethyl 2-n-butyl-3-cinnamoyloxyvalerate, 2-isobutyl-3-cinnamon Ethyl acyloxyvalerate, ethyl 2-tert-butyl-3-cinnamoyloxyvalerate, ethyl 2-benzyl-3-cinnamoyloxyvalerate, 2,2-dimethyl-3 -Ethyl cinnamoyloxyvalerate, ethyl 3-cinnamoyloxyhexanoate, ethyl 2-methyl-3-cinnamoyloxyhexanoate, 2-ethyl-3-cinnamoyloxyhexanoate Ethyl ester, ethyl 2-n-propyl-3-cinnamoyloxyhexanoate, ethyl 2-allyl-3-cinnamoyloxyhexanoate, 2-isopropyl-3-cinnamoyloxyhexanoate ethyl 2-n-butyl-3-cinnamoyloxyhexanoate, ethyl 2-isobutyl-3-cinnamoyloxyhexanoate, 2-tert-butyl-3-cinnamoyloxy Ethyl hexanoate, ethyl 2-benzyl-3-cinnamoyloxyhexanoate, ethyl 2,2-dimethyl-3-cinnamoyloxyhexanoate, isopropyl 3-cinnamoyloxybutyrate Esters, Isopropyl 2-Methyl-3-cinnamoyloxybutyrate, Isopropyl 2-Ethyl-3-cinnamoyloxybutyrate, 2-n-Propyl-3-cinnamoyloxybutyrate Isopropyl ester, Isopropyl 2-allyl-3-cinnamoyloxybutyrate, Isopropyl 2-isopropyl-3-cinnamoyloxybutyrate, 2-n-Butyl-3-cinnamoyl Isopropyl oxybutyrate, isopropyl 2-isobutyl-3-cinnamoyloxybutyrate, isopropyl 2-tert-butyl-3-cinnamoyloxybutyrate, 2-benzyl-3 - Isopropyl cinnamoyloxybutyrate, 2,2-Dimethyl-3-isopropyl cinnamoyloxybutyrate, isobutyl 3-cinnamoyloxybutyrate, 2-methyl-3- Isobutyl cinnamoyloxybutyrate, isobutyl 2-ethyl-3-cinnamoyloxybutyrate, isobutyl 2-n-propyl-3-cinnamoyloxybutyrate, 2-allyl -isobutyl 3-cinnamoyloxybutyrate, isobutyl 2-isopropyl-3-cinnamoyloxybutyrate, isobutyl 2-n-butyl-3-cinnamoyloxybutyrate, 2 -isobutyl-3-cinnamoyloxybutyrate, isobutyl 2-tert-butyl-3-cinnamoyloxybutyrate, isobutyl 2-benzyl-3-cinnamoyloxybutyrate Esters, 2,2-Dimethyl-3-cinnamoyloxybutyrate isobutyl, 3-cinnamoyloxybutyrate methyl ester, 2-methyl-3-cinnamoyloxy methyl 2-ethyl-3-cinnamoyloxybutyrate, methyl 2-n-propyl-3-cinnamoyloxybutyrate, 2-allyl-3-cinnamoyloxy methyl butyrate, methyl 2-isopropyl-3-cinnamoyloxybutyrate, methyl 2-n-butyl-3-cinnamoyloxybutyrate, 2-isobutyl-3-cinnamoyl Methyl oxybutyrate, methyl 2-tert-butyl-3-cinnamoyloxybutyrate, methyl 2-benzyl-3-cinnamoyloxybutyrate, 2,2-dimethyl-3- Methyl Cinnamoyloxybutyrate, Ethyl 3-Acetoxybutyrate.

The above-mentioned dibasic ester compound can be synthesized by various reactions, wherein the alcohol ester compound of the corresponding general formula (V) is esterified with the acyl compound containing R' in the presence of the corresponding acid or acid chloride to obtain the corresponding Diester compounds.

Wherein R' and R ₁ are defined with the general formula (II).

The compound of the general formula (V) can generally be obtained by reduction of the corresponding ketoester compound, and there are many synthetic methods of the ketoester compound, among which the β-ketoester compound can be obtained by condensing a carboxylic acid ester.

Wherein the electron donor compound b is selected from 1,3-diether compounds of general formula (III);

Wherein R ^I , R ^II , R ^III , R ^IV , R ^V and R ^VI are the same or different, selected from hydrogen, halogen atom, straight or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ ring Alkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl, and R ^VII and R ^VIII can be the same or different, selected from straight chain Or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl ; The groups of R ^I -R ^VI can be bonded to form a ring.

The 1,3-diether compounds preferably have the following structure (VI):

Further preferably, the 1,3-diether compound is selected from compounds represented by the general formula (VII):

R in the above general formula (VI) or (VII) is the same or different, selected from hydrogen, halogen atoms, straight or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ - One of C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, C ₇ -C ₂₀ aralkyl;

Wherein R ₁ is the same or different, selected from hydrogen, halogen atoms, straight or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C One of ₂₀ alkaryl and C ₇ -C ₂₀ aralkyl;

Wherein R ₂ is the same or different, selected from straight or branched C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, C ₇ -C ₂₀ alkaryl, One of C ₇ -C ₂₀ aralkyl groups.

Examples of said 1,3-diether compounds are:

2-(2-Ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane , 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2- Cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane Methoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1- Naphthyl)-1,3-dimethoxypropane, 2-(2-fluorophenyl)-1,3-dimethoxypropane, 2-(1-decalinyl)-1,3-dimethoxypropane Methoxypropane, 2-(p-tert-butylphenyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2- Dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane , 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2- Methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1 , 3-dimethoxypropane, 2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3- Dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxy Propane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3 -Dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane , 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3- Dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2, 2-Dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl- 1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxy propane, 2-benzyl-2-sec-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl- 2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl -1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene , 1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5 -Tetraphenylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene, 1,1-bis(methoxymethyl)- 3,4-dicyclopentylcyclopentadiene, 1,1-bis(methoxymethyl)indene, 1,1-bis(methoxymethyl)-2,3-dimethoxyindene, 1,1-bis(methoxymethyl)-4,5,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,7-dimethylindene, 1,1-bis(methoxymethyl)-3,6-dimethylindene, 1,1-bis( Methoxymethyl)-4-phenylindene, 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1-bis(methoxymethyl)- 4-cyclohexylindene, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene, 1,1-bis(methoxymethyl)-7- Trimethylsilylindene, 1,1-bis(methoxymethyl)-7-trifluoromethylindene, 1,1-bis(methoxymethyl)-4,7-dimethyl- 4,5,6,7-tetrahydroindene, 1,1-bis(methoxymethyl)-7-methylindene, 1,1-bis(methoxymethyl)-7-cyclopentylindene , 1,1-bis(methoxymethyl)-7-isopropylindene, 1,1-bis(methoxymethyl)-7-cyclohexylindene, 1,1-bis(methoxymethyl) Base)-7-tert-butylindene, 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene, 1,1-bis(methoxymethyl)- 7-phenylindene, 1,1-bis(methoxymethyl)-2-phenylindene, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl) )-2,3,6,7-tetramethylfluorene, 9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene, 9,9-bis( Methoxymethyl)-2,3 phenylpropane, 9,9-bis(methoxymethyl)-2,3,6,7-diphenylpropane, 9,9-bis(methoxymethyl) base)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-dichlorofluorene, 9,9-bis(methoxymethyl)-2,7 -Dicyclopentylfluorene, 9,9-bis(methoxymethyl)-1,8-difluorofluorene, 9,9-bis(methoxymethyl)-1,2,3,4-tetrafluorofluorene Hydrofluorene, 9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene, 9 , 9-bis(methoxymethyl)-4-tert-butylfluorene, 1,1-bis(1′-butoxyethyl)-cyclopentadiene, 1,1-bis(1′- Isopropoxy-n-propyl)cyclopentadiene, 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene , 1,1-bis(α-methoxybenzyl)indene, 1,1-bis(phenoxymethyl)-indene, 1,1-bis(1′-methoxyethyl)-5, 6-dichloroindene, 1,1-bis(phenoxymethyl)-3,6-dicycloethylindene, 1-methoxymethyl-1-(1′-methoxyethyl)- 7-tert-butylindene, 1,1-bis[2-(2'methoxypropyl)]-2-methylindene, 9,9-bis(α-methoxyphenyl)fluorene, 9, 9-bis(1′-isopropoxy-n-butyl)-4,5-diphenylfluorene, 9,9-bis(1′-methoxyethyl)fluorene, 9-(methoxymethyl Base)-9-(1′-methoxyethyl)-2,3,6,7-tetrafluorofluorene, 9-(methoxymethyl)-9-pentyloxymethylfluorene, 9-( Methoxymethyl)-9-ethoxymethylfluorene, 9-(methoxymethyl)-9-(1′-methoxyethyl)fluorene, 9-(methoxymethyl)- 9-[2-(2'methoxypropyl)]fluorene, 1,1-bis-(methoxymethyl)-2,5-cyclohexadiene, 1,1-bis-(methoxy Methyl)benzonaphthalene, 7,7-bis-(methoxymethyl)2,5-norbornadiene, 9,9-bis-(methoxymethyl)-1,4-methanedihydro Naphthalene, 9,9-bis-(methoxymethyl)-9,10-dihydroanthracene, 1,1-bis-(methoxymethyl)-1,2-dihydroanthracene, 4,4- Bis-(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene, 4,4-bis-(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene, 5,5-bis-(methoxymethyl)-1,3,6-cycloheptatriene.

The above-mentioned 1,3-diether compounds of the present invention are disclosed in Chinese patents CN1020448C and CN1141285A, the relevant content of which is incorporated herein as a reference.

The titanium compound described in the preparation method of the present invention has at least one Ti-halogen bond, and its general formula is: TiX _m (OR) _4-m , where R is an alkyl group of C ₁ to C ₂₀ , preferably n-butyl Base/isobutyl, 2-ethylhexyl, n-octyl and phenyl; X is halogen, m is 1-4. The specific titanium compound can be titanium tetrahalide, especially titanium tetrachloride; trichloroalkoxyorgano titanium, especially trichlorobutoxy and trichlorophenoxy titanium; tetraalkoxy titanium, especially tetrabutyl Titanium oxide, titanium tetraethoxide.

In the preparation method of the present invention, first, a MgCl ₂ .nROH adduct is loaded with the reaction product of the above-mentioned titanium compound and the two electron donor compounds a and b, wherein the MgCl ₂ .nROH adduct is The adduct of magnesium dichloride and alcohol is preferably spherical particles, wherein n is 1.5-3.5; R is an alkyl group with 1-4 carbons, and the alcohols are ethanol, propanol, isopropanol, butanol, isopropanol, butanol, isooctyl alcohol, etc. The relevant preparation steps can be carried out with reference to the methods disclosed in Chinese patents CN1036011C and CN1330086A, and the disclosed relevant content is hereby incorporated by reference in the present invention.

The specific preparation method of MgCl ₂ .nROH adducts: mix anhydrous magnesium halide and alcohol, heat up and react to form a magnesium halide alcoholate melt, the reaction temperature is 90-140°C, and undergo high-shearing in the dispersion medium Then put it into a cooled inert medium to form spherical magnesium halide alcoholate particles, and obtain a spherical carrier after washing and drying. High shear can be obtained by conventional methods, such as high-speed stirring method (such as CN1330086), spray method (such as US6020279), and high-gravity rotating bed (such as CN1580136A) and emulsifier method (CN1463990A). The dispersant system uses hydrocarbon inert solvents, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooling medium is selected from pentane, hexane, heptane, petroleum ether, raffinate and the like.

The solid catalyst component of the present invention is converted into a catalyst for olefin polymerization by reacting with an organoaluminum compound according to known methods.

In particular, the present invention also provides a catalyst for the polymerization of olefins, especially α-olefins CH ₂ =CHR, wherein R is hydrogen or an alkyl group of 1 to 12 carbon atoms, the catalyst comprising the reaction between the following substances product:

(1), a catalyst component obtained by the catalyst component preparation method of the present invention

(2), an alkylaluminum compound, and optionally

(3), one or more electron donor compounds (external electron donors)

The alkyl aluminum compound is preferably a compound with the general formula AlR _n X _3-n , wherein R is hydrogen or an alkyl group with 1 to 20 carbon atoms, especially an alkyl group, an aralkyl group, an aryl group, etc.; X is a halogen, Especially chlorine and bromine; n is a number 0<n≦3. The alkylaluminum compounds described in the present invention include: trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum and other trialkylaluminums; monohydrogen diethylaluminum, monohydrogen diisobutyl Alkylaluminum hydrides such as aluminum; diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride and other alkylaluminum chlorides, among which triethylaluminum and Triisobutylaluminum.

The amount of aluminum alkyl used is: wherein the molar ratio of aluminum to titanium in the solid component (1) is 5-5000, preferably 20-500.

The external electron donor compound is preferably an organosilicon compound. Its general formula is RnSi(OR') _4-n , in which 0<n≤3, in which R and R' are the same or different kinds of alkyl, cycloalkyl, aryl, haloalkyl, etc., R It may also be a halogen or a hydrogen atom. The organosilicon compound described in the present invention includes trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane , methyl tert-butyldimethoxysilane, diphenoxydimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxy ylsilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-tri Fluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane and the like.

The amount of the external electron donor (3) is: the molar ratio of the organoaluminum compound to the external electron donor compound is 0.1-500, preferably 1-300, more preferably 3-100.

The polymerization of olefins is carried out according to known methods, operating in the liquid phase of liquid monomers or solutions of monomers in inert solvents, or in the gas phase, or by combined polymerization processes in the gas-liquid phase. The polymerization temperature is generally 0°C to 150°C, preferably 60°C to 100°C. The polymerization reaction pressure is normal pressure or higher.

Detailed ways

The following examples are given in order to illustrate the present invention, but not to limit the present invention.

Test Methods:

1. Polymer molecular weight and molecular weight distribution MWD (MWD=Mw/Mn): adopt gel permeation chromatography method, use PL-GPC220 to measure at 150 ℃ with trichlorobenzene as solvent (standard sample: polystyrene, flow rate: 1.0 ml/min, column: 3xPlgel 10um M1xED-B 300x7.5nm).

2. Polymer isotacticity II is measured by heptane extraction method (heptane boiling extraction for 6 hours): two grams of dry polymer samples are placed in an extractor and extracted with boiling heptane for 6 hours, then The ratio of the polymer weight (g) to 2 obtained by drying the residue to constant weight is the isotacticity.

3. Melt index MFI is determined according to ASTM D1238-99.

Example 1

Catalyst component preparation

In the reactor fully replaced by high-purity nitrogen, add 100ml of TiCl ₄ , cool down to -20°C, and add 7.0g of magnesium chloride and ethanol adduct spherical carrier at -20°C (for the preparation method, refer to Example 1 in CN1330086A), Add 0.7 mmol of ethyl 3-benzoyloxybutyrate, rise to 0°C within 1 hour, continue to increase the temperature to 20°C within 2 hours, continue to increase the temperature to 40°C within 1 hour, add 9,9 - 6 mmol of bis(methylmethoxy)fluorene, raised to 100° C. in 1 hour, maintained for 2 hours, and drained the filtrate. Add 100ml of TiCl ₄ , raise the temperature to 120°C in 1 hour, maintain it for 2 hours, and drain the filtrate. Add 60 ml of hexane, wash 3 times in boiling state, then add 60 ml of hexane, wash 2 times at normal temperature, discharge, vacuum dry to obtain spherical catalyst component.

Propylene polymerization:

A stainless steel reaction kettle with a volume of 5L, after being fully replaced by gaseous propylene, _{2.5mmol of} AlEt, 0.1mmol of methylcyclohexyldimethoxysilane (CHMMS), 8-10mg of the spherical catalyst component prepared in the above examples and 1.8 NL of hydrogen gas was injected into 2.3 L of liquid propylene, the temperature was raised to 70° C., polymerized for 1 hour, the temperature was lowered, and the pressure was released to obtain polypropylene. The results are shown in Table 1.

Example 2:

Catalyst component preparation is the same as embodiment 1, just replace ethyl 3-benzoyloxybutyrate with 3-benzoyloxybutyrate isobutyl, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane was used instead of 9,9-bis(methylmethoxy)fluorene.

Propylene polymerization: same as Example 1, to obtain polypropylene. The results are shown in Table 1.

Example 3:

The catalyst synthesis was the same as in Example 1, except that the amount of ethyl 3-benzoyloxybutyrate was changed from 0.7 mmol to 2.0 mmol.

Propylene polymerization: same as Example 1, to obtain polypropylene. The results are shown in Table 1.

Example 4:

The catalyst component was prepared as in Example 1, except that ethyl 3-benzoyloxybutyrate was replaced with ethyl 2-methyl-3-benzoyloxyvalerate.

Propylene polymerization was the same as in Example 1 to obtain polypropylene. The results are shown in Table 1.

Example 5:

In the reactor fully replaced by high-purity nitrogen, add 100ml of TiCl ₄ , cool down to -20°C, and add 7.0g of magnesium chloride and ethanol adduct spherical carrier at -20°C (for the preparation method, refer to Example 1 in CN1330086A), Rise to 0°C within 1 hour, add and continue to raise the temperature to 20°C within 2 hours, add 1 mmol 2-methyl-3-benzoyloxyethyl valerate, continue to raise the temperature to 40°C within 1 hour, Add 6 mmol of 9,9-bis(methylmethoxy)fluorene, raise the temperature to 100° C. for 1 hour, maintain it for 2 hours, and drain the filtrate. Add 100ml of TiCl ₄ , raise the temperature to 120°C in 1 hour, maintain it for 2 hours, and drain the filtrate. Add 60ml of hexane, wash 3 times in boiling state, then add 60ml of hexane, wash 2 times at normal temperature, discharge, vacuum dry to obtain spherical catalyst component

Propylene polymerization was the same as in Example 1 to obtain polypropylene. The results are shown in Table 1.

Comparative example 1

The preparation of the catalyst components was the same as in Example 1, except that the propylene polymerization was the same as in Example 1 without adding ethyl 3-benzoyloxybutyrate to obtain polypropylene. The results are shown in Table 1.

Comparative example 2

The preparation of the catalyst components was the same as in Example 2, except that propylene polymerization without adding 3-benzoyloxybutyrate isobutyl was the same as in Example 1 to obtain polypropylene. The results are shown in Table 1.

Table 1 Catalyst polymerization result

catalyst Polymerization activity KgPP/gcat MFIg/10min II% Mw/Mn BDg/ml Example 1 62 7.2 97.8 7.2 0.50 Example 2 61 6.8 98.1 6.8 0.49 Example 3 60 6.8 98.5 8.4 0.49 Example 4 65 7.3 97.7 7.9 0.50 Example 5 68 7.6 97.6 8.2 0.49 Comparative example 1 65 7.0 98.2 4.5 0.49 Comparative example 2 59 6.5 97.9 4.3 0.49

As can be seen from the data of the embodiment of table 1 and the comparative example, use two kinds of electron donor compounds in the present invention, control the mol ratio and the addition order of the addition amount of two kinds of electron donor compounds simultaneously, obtain catalyst with very high The activity of the obtained polymer is higher, the melt index, isotactic index, etc. have no obvious changes, while the molecular weight distribution is significantly improved.

Claims (10)

1. preparation method who is used for the catalyst component of olefinic polyreaction, it comprises following reactions steps:

(1) will be as general formula (I) MgCl ₂.nROH the adduct of magnesium halides shown in joins in the mixture of-30 ℃～0 ℃ titanium compound or titanium compound and inert solvent, forms solution;

(2) with above-mentioned solution heating,-30 ℃～20 ℃ add the electron donor compound a, and 40 ℃～80 ℃ add the electron donor compound b, are warmed up to 80 ℃～130 ℃ at last, add titanium compound then and handle one or many, obtain ingredient of solid catalyst with the inert solvent washing at last;

In step (1), in the described general formula (I), R is C ₁～C ₄Alkyl, n is 1.5～3.5;

General formula at the titanium compound described in step (1) and the step (2) is TiX _m(OR) _4-m, R is that carbonatoms is 1～20 alkyl in the formula, X is a halogen, m=1～4.

In step (2), described electron donor compound a is selected from two ester compounds shown in general formula (II):

R ' and R in the formula ₁Group is identical or inequality, is selected from the C of replacement or unsubstituted straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀Aralkyl, C ₂-C ₁₀Alkylene, C ₁₀-C ₂₀Fused ring aryl; A is that carbon chain length is the divalent linker of 1-10, and it is selected from aliphatics, alicyclic and aromatic divalent group, can have C on the carbon in the described divalent linker ₁-C ₂₀Be selected from alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkylene, the fused ring aryl of straight chain or branching, the substituting group of ester group, and two or more substituting group can be connected to form saturated or undersaturated monocycle or many rings;

In step (2), described electron donor compound b is selected from 1 of general formula (III), the 3-diether compound,

R wherein ^I, R ^II, R ^III, R ^IV, R ^VAnd R ^VIIdentical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀A kind of in the aralkyl, and R ^VIIAnd R ^VIIICan be identical or different, be selected from the C of straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀A kind of in the aralkyl; R ^I-R ^VIGroup between can be keyed to ring;

In every mole of magnesium, the electron donor compound b is 0.01～0.5 mole; The mol ratio of electron donor compound a and electron donor compound b is 0.1～0.4.

2. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 1, in the diester compound of its formula of (II), A is that chain length is the divalent linker of 1～6 carbon atom, there is C in optional area on the carbon atom in this divalent linker ₁-C ₁₀The alkyl of straight or branched, C ₃-C ₁₀Cycloalkyl, C ₆-C ₁₀Aryl, C ₂-C ₁₀Alkylene, C ₇-C ₁₀Alkaryl or aralkyl.

3. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 1, in the diester compound of its formula of (II), R ' and R ₁Group is identical or inequality, is selected from the C of replacement or unsubstituted straight or branched ₁-C ₁₀Alkyl, C ₆-C ₁₀Aryl or alkaryl or aralkyl.

4. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 1, in the diester compound of its formula of (II), R ' is selected from C ₆-C ₁₀Aryl or alkaryl or aralkyl.

5. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 1, its formula of (II) comprises the dibasic ester compound shown in the following general formula (IV):

In the general formula (IV), R ₁Be C ₁-C ₂₀Unsubstituted or the halogen alkyl or the C that replace ₆-C ₂₀Unsubstituted or halogen replaces aryl or alkaryl;

R _2-5Identical or different, be hydrogen or C _1-4The alkyl of straight or branched;

R ^1-5Identical or different, be hydrogen, halogen, C ₁-C ₁₀Unsubstituted or halogen replaces alkyl or C ₆-C ₂₀Unsubstituted or halogen replaces aryl or alkaryl or aralkyl;

Above-mentioned halogen is selected from F, Cl or Br.

6. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 5, in the wherein said general formula (IV), R ₁Be C ₂-C ₁₀The alkyl or the C of straight or branched ₆-C ₂₀Alkaryl.

7. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 5, in the wherein said general formula (IV), R ₁Be C ₂-C ₆The alkyl of straight or branched.

8. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 5, in the wherein said general formula (IV), R ^1-5Identical or different, be hydrogen or C ₁-C ₆The alkyl or the halogenated alkyl of straight or branched.

9. the preparation method who is used for the catalyst component of olefinic polyreaction according to claim 1, it is described 1 to it is characterized in that described electron donor compound b is selected from shown in general formula (VI), the 3-diether compound:

R is identical or inequality in the general formula (VI), is selected from the C of hydrogen, halogen atom, straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀A kind of in the aralkyl;

R wherein ₁Identical or inequality, be selected from the C of hydrogen, halogen atom, straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀A kind of in the aralkyl;

R wherein ₂Identical or inequality, be selected from the C of straight or branched ₁-C ₂₀Alkyl, C ₃-C ₂₀Cycloalkyl, C ₆-C ₂₀Aryl, C ₇-C ₂₀Alkaryl, C ₇-C ₂₀A kind of in the aralkyl.

10. a kind of catalyst component that is used for olefinic polyreaction that makes according to the described preparation method of arbitrary claim in the claim 1～9.