阅读说明：本技术 一种烷氧基镁颗粒、及其制备方法和应用 (Alkoxy magnesium particle, and preparation method and application thereof ) 是由 徐秀东 谭忠 周奇龙 张锐 李凤奎 于金华 宋维玮 尹珊珊 于 2019-10-28 设计创作，主要内容包括：本发明提供了一种烷氧基镁颗粒,包括镁化合物和磷；所述烷氧基镁颗粒中磷的含量为0.01-2.00wt％。本发明的烷氧基镁颗粒通过使包括组分：镁粉、含羟基类化合物、卤化剂和磷酸酯类化合物的原料反应得到。本发明选用少量的含卤物质的混合物为卤化剂,通过在反应过程中加入酚类化合物和磷酸酯类化合物时,使得反应更容易控制,颗粒形态保持的更好。本发明制备的烷氧基镁颗粒特别适用于制备烯烃聚合催化剂中,得到的催化剂活性高,得到的聚合物堆积密度大,颗粒形态好,且分布均匀,适用于气相工艺生产烯烃的装置。(The invention provides alkoxy magnesium particles, which comprise a magnesium compound and phosphorus; the content of phosphorus in the alkoxy magnesium particles is 0.01-2.00 wt%. The magnesium alkoxide particles of the present invention are prepared by reacting a mixture comprising the components: magnesium powder, hydroxyl-containing compounds, halogenating agents and phosphate compounds. According to the invention, a small amount of mixture of halogen-containing substances is selected as a halogenating agent, and when phenolic compounds and phosphate compounds are added in the reaction process, the reaction is easier to control, and the particle morphology is better maintained. The alkoxy magnesium particles prepared by the invention are particularly suitable for preparing olefin polymerization catalysts, the obtained catalysts have high activity, the obtained polymers have large bulk density, good particle shape and uniform distribution, and the alkoxy magnesium particles are suitable for devices for producing olefins by gas phase processes.)

1. An alkoxy magnesium particle comprising a magnesium compound and phosphorus; preferably, the phosphorus content of the magnesium alkoxide particles is 0.001 to 2.00 wt%, preferably 0.01 to 1.00 wt%, more preferably 0.01 to 0.40 wt%.

2. Magnesium alkoxide particles according to claim 1, wherein the magnesium compound has the general formula Mg (OR1) (OR 2); wherein R1 and R2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, preferably from the group consisting of substituted or unsubstituted C1-C10 straight or branched chain alkyl, C6-C10 aryl, C7-C10 aralkyl and C7-C10 alkaryl.

3. Magnesium alkoxide particles according to claim 1 or2, wherein R1 and/or R2 are selected from the group consisting of C6-C10 aryl and C7-C10 alkaryl; preferably, the content of the phenoxide group in the alkoxy magnesium particles is 0.001 to 10 wt%, preferably 0.01 to 8 wt%, more preferably 0.1 to 3 wt%.

4. A process for the preparation of magnesium alkoxide particles as claimed in any one of claims 1 to 3 which comprises the steps of: reacting magnesium powder, a hydroxyl-containing compound, a halogenating agent and a phosphate compound to obtain alkoxy magnesium particles; preferably, the hydroxyl-containing compound comprises R1OH and R2OH, wherein R1 and R2 are the same or different and are respectively and independently selected from substituted or unsubstituted C1-C20 alkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, preferably selected from substituted or unsubstituted C1-C10 straight or branched chain alkyl, C6-C10 aryl, C7-C10 aralkyl and C7-C10 alkaryl; more preferably, the hydroxyl group-containing compound includes an alcohol compound and a phenol compound.

5. The method for producing alkoxymagnesium particles according to claim 4, wherein the phenolic compound is at least one of monophenol and polyphenol, preferably at least one of monophenol, bisphenyl monophenol and bisphenyl polyphenol, more preferably at least one selected from catechol, resorcinol, hydroquinone, pyrogallol, 1, 2, 4-benzenetriol, 1, 2, 5-benzenetriol, 1, 3, 5-benzenetriol, α -naphthol, β -naphthol, γ -naphthol, 1, 2-naphthalenediol, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 1, 8-naphthalenediol, 1, 9-naphthalenediol, naphthalenediol and their homologues, and particularly preferably at least one selected from catechol, pyrogallol, catechol, and their homologues, At least one of 1, 2, 3-benzenetriol, alpha-naphthol, and beta-naphthol; and/or the weight ratio of the phenolic compound to the magnesium powder is (0.001-5) to 1, preferably (0.005-2) to 1.

6. The method for preparing alkoxy magnesium particles according to claim 4 or 5, wherein the phosphate compound is selected from phosphate compounds represented by formula I:

in the formula I, R¹、R²And R³The same or different, each independently selected from hydrogen and C₁-C₂₀Substituted or unsubstituted alkyl of, C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aromatic group of (a); preferably, R¹、R²And R³Each independently selected from hydrogen and C₁-C₁₂Alkyl or haloalkyl of, C₃-C₁₀Cycloalkyl or halocycloalkyl of, C₆-C₁₀Aryl or haloaryl of (C)₇-C₁₀And C is an alkylaryl or haloalkylaryl group₇-C₁₀Aralkyl or haloaralkyl groups of (a); more preferably, the phosphate ester compound is selected from phosphoric acid, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monobutyl phosphate, triethyl phosphate, and triethyl phosphatePentyl ester, monohexyl phosphate, heptyl phosphate, monooctyl phosphate, monoponyl phosphate, monodecyl phosphate, monophenyl phosphate, xylyl phosphate, diethylphenyl phosphate, dipropyl phosphate, diisopropylphenyl phosphate, dimethoxyphenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, dinonyl phosphate, didecyl phosphate, diphenyl phosphate, xylyl phosphate, diethylphenyl phosphate, dipropyl phosphate, diisopropylphenyl phosphate, dimethoxyphenyl phosphate, phenyldimethyl phosphate, tolyldibutyl phosphate, tolyldimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenylxylyl phosphate, phenyldiisopropylphenyl phosphate, p-tolyldibutyl phosphate, At least one of m-tolyl dibutyl phosphate, p-cumyl dimethyl phosphate, p-cumyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate, and o-tolyl p-di-tert-butylphenyl phosphate; and/or the weight ratio of the phosphate compound to the magnesium powder is (0.001-5) to 1, preferably (0.05-2) to 1.

7. A method for producing alkoxymagnesium particles according to any one of claims 4 to 6, characterized in that the alcoholic compound comprises a linear or branched mono-or polyol, preferably C₁-C₁₀More preferably a mixture of ethanol and isooctyl alcohol; and/or the molar ratio of the alcohol compound to the magnesium powder is (2-50):1, preferably (2.5-18): 1.

8. The method for producing alkoxy magnesium particles according to any one of claims 4 to 7, wherein the halogenating agent is an elemental halogen and/or an inorganic halide, preferably at least one selected from the group consisting of elemental iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide, and alkoxy magnesium halide, more preferably at least one selected from the group consisting of elemental iodine, magnesium iodide, magnesium chloride, and alkoxy magnesium halide, and particularly preferably a mixture of elemental iodine and magnesium chloride; and/or the molar ratio of the halogenating agent to the magnesium powder is (0.0002-0.2):1, preferably (0.0025-0.05):1, calculated as halogen atoms.

9. A method for producing alkoxy magnesium particles according to any one of claims 4 to 8, wherein the raw material further comprises a dispersing agent, preferably an inert organic solvent, more preferably at least one selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene, xylene, and derivatives thereof.

10. A ziegler-natta catalyst component comprising the reaction product of:

A) magnesium alkoxide particles as defined in any one of claims 1 to 3 or as prepared by the process of any one of claims 4 to 9;

B) a titanium-containing halide;

C) an electron donor compound.

11. The catalyst component according to claim 10, wherein the electron donor compound is a carboxylic acid ester electron donor compound, preferably selected from benzoic acid monoesters or phthalic acid ester compounds as shown in formula II,

in the formula II, R₁And R₂Is independently selected from C₁-C₈Substituted or unsubstituted alkyl of, C₃-C₁₀Substituted or unsubstituted cycloalkyl or C₆-C₂₀Substituted or unsubstituted aromatic group of (a); r₃-R₆Each independently selected from hydrogen, halogen, C₁-C₄Substituted or unsubstituted alkyl or C₁-C₄Substituted or unsubstituted alkoxy of, preferably, R₃-R₆At least three inMore preferably, the carboxylate electron donor compound is at least one selected from the group consisting of di-n-butyl phthalate, diisobutyl phthalate, diethyl phthalate, dipentyl phthalate, dioctyl phthalate, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate and isobutyl benzoate.

12. The catalyst component according to claim 10 or 11, characterized in that the molar ratio of the titanium-containing halide to the magnesium alkoxide particles is (0.5-100) to 1, preferably (1-50) to 1; and/or the molar ratio of the electron donor compound to the alkoxy magnesium particles is (0.005-10): 1, preferably (0.01-2): 1.

13. A catalyst for the polymerization of olefins comprising the reaction product of:

a) the catalyst component of any one of claims 10 to 12;

b) an organoaluminum compound;

c) optionally, an external electron donor compound.

14. The catalyst according to claim 13, characterized in that the molar ratio of aluminium in the organoaluminium compound to titanium in the catalyst component is (5-5000):1, preferably (20-1000):1, more preferably (50-500): 1; the molar ratio of aluminum in the organic aluminum compound to the external electron donor compound is (0-500):1, preferably (1-300):1, and more preferably (3-100): 1.

15. A process for the polymerization of olefins comprising contacting under olefin polymerization conditions one or more olefins, at least one of which is represented by the general formula CH, with the catalyst component of any one of claims 10 to 12 or the catalyst of claim 13 or 14₂Wherein R is hydrogen and C₁-C₆Any one of the alkyl groups of (1).

Technical Field

The invention relates to alkoxy magnesium particles for olefin polymerization, a preparation method and application thereof, a catalyst component for olefin polymerization and a catalyst, belonging to the field of olefin polymerization catalysts.

Background

With the increasing demand for polyolefins, the demand for olefin polymerization catalysts is increasing, and the most widespread catalysts at present are magnesium chloride supported ziegler-natta catalysts. The preparation method of the catalyst disclosed in Chinese patents CN85100997A and CN 1453298A and the like generally comprises the steps of preparing a solid catalyst component from magnesium, titanium, halogen and an electron-donating organic compound. However, it is not a catalyst that can satisfy various requirements in terms of various properties such as suitable particle size and shape, uniform particle distribution, minimization of fine particles and high bulk density, etc., and high catalyst activity and stereoregularity. In the components disclosed in U.S. Pat. No. 4,973,973 and EP0728769 for olefin polymerization catalysts, a special compound containing two ether groups is used as an electron donor, and the catalysts have high activity and high isotactic index. Then WO98/56830, WO98/56834, WO01/57099, WO01/63231 and WO00/55215 disclose special aliphatic dibasic carboxylic ester compounds, such as succinate, malonate, glutarate and the like, as polyolefin catalysts of electron donors, and the use of the electron donor compounds can not only improve the activity of the catalysts, but also obviously widen the molecular weight distribution of the obtained propylene polymer. However, the activity of these catalysts decays relatively rapidly.

At present, a supported catalyst taking alkoxy magnesium as a carrier can have more excellent performances, and is commonly used for developing high-end polypropylene products, and the preparation of the catalyst needs to prepare the alkoxy magnesium carrier with excellent performances firstly.

It is a very valuable task to prepare a magnesium alkoxide support in a good particulate form and which exhibits excellent properties in olefin polymerization catalysts.

Disclosure of Invention

The present inventors have conducted intensive studies on the production of spherical fine-particle alkoxymagnesium by direct reaction of metallic magnesium with alcohol against the drawbacks of the prior art, and have prepared alkoxymagnesium particles containing phosphorus by adding a phenolic compound and a phosphate compound having a certain structure as specific raw materials and using a halogen simple substance and/or an inorganic halide as a halogenating agent in the preparation process. The results show that the alkoxy magnesium particles are more uniformly distributed, the prepared catalyst has slow polymerization activity decay during polymerization, and the polymer particles have good shapes and excellent flowability.

According to an aspect of the present invention, there is provided an alkoxy magnesium particle comprising a magnesium compound and phosphorus; preferably, the phosphorus content of the magnesium alkoxide particles is 0.01 to 2 wt%.

According to some embodiments of the invention, the magnesium compound has the general formula Mg (OR1) (OR 2); wherein R1 and R2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, preferably from the group consisting of substituted or unsubstituted C1-C10 straight or branched chain alkyl, C6-C10 aryl, C7-C10 aralkyl and C7-C10 alkaryl.

According to a preferred embodiment of the present invention, R1 and R2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl and C7-C20 aralkyl, preferably selected from the group consisting of substituted or unsubstituted C1-C10 straight or branched chain alkyl and C7-C10 aralkyl, more preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylbutyl, 2-ethylhexyl, 4-methyl sec-pentyl, 3, 5-trimethylpentyl, 1-ethyl 2-methylpentyl, benzyl, 2-phenylethyl and 1-phenylpropyl, further preferably ethyl and isooctyl.

In the above embodiment, the R1 and R2 may be bonded to form a ring, preferably a benzene ring or a naphthalene ring. The hydrogens on the phenyl and naphthyl rings may optionally be substituted with other alkyl or hydroxy groups.

According to a preferred embodiment of the present invention, R1 and R2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted C6-C20 aryl and C7-C20 alkaryl, preferably C6-C10 aryl and C7-C10 alkaryl, more preferably from the group consisting of phenyl, hydroxy-substituted phenyl, naphthyl and hydroxy-substituted naphthyl, even more preferably from the group consisting of o-hydroxyphenyl, 2, 3-dihydroxyphenyl, 2-dihydroxyphenyl and naphthyl.

According to a preferred embodiment of the present invention, R1 and R2 are different and R1 is selected from substituted or unsubstituted C1-C20 alkyl and C7-C20 aralkyl, preferably from substituted or unsubstituted C1-C10 straight or branched chain alkyl and C7-C10 aralkyl, more preferably from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylbutyl, 2-ethylhexyl, 4-methyl sec-pentyl, 3, 5-trimethylpentyl, 1-ethyl 2-methylpentyl, benzyl, 2-phenylethyl and 1-phenylpropyl; r2 is selected from substituted or unsubstituted C6-C20 aryl and C7-C20 alkaryl, preferably C6-C10 aryl and C7-C10 alkaryl, more preferably from phenyl, hydroxy-substituted phenyl, naphthyl and hydroxy-substituted naphthyl, further preferably from o-hydroxyphenyl, 2, 3-dihydroxyphenyl, 2-dihydroxyphenyl and naphthyl.

According to some embodiments of the invention, R1 and/or R2 is selected from the group consisting of C6-C10 aryl and C7-C10 alkaryl; preferably selected from the group consisting of phenyl, hydroxy-substituted phenyl, naphthyl and hydroxy-substituted naphthyl, and more preferably selected from the group consisting of o-hydroxyphenyl, 2, 3-dihydroxyphenyl, 2-dihydroxyphenyl and naphthyl.

According to a preferred embodiment of the present invention, the content of the phenoxide group in the alkoxy magnesium particles is 0.001 to 10 wt%, preferably 0.01 to 8 wt%, more preferably 0.1 to 3 wt%.

According to another aspect of the present invention, there is provided a method for producing the above-mentioned magnesium alkoxide particle, comprising the steps of: the alkoxy magnesium particles are obtained by the reaction of magnesium powder, hydroxyl-containing compounds, halogenating agents and phosphate compounds.

According to a preferred embodiment of the present invention, the hydroxyl group-containing compound comprises R1OH and R2OH, wherein R1 and R2 are the same or different and are each independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, C6-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, preferably selected from the group consisting of substituted or unsubstituted C1-C10 straight or branched chain alkyl, C6-C10 aryl, C7-C10 aralkyl, and C7-C10 alkaryl. The choice of R1 and R2 is the same as above.

According to a preferred embodiment of the present invention, the hydroxyl group-containing compound includes an alcohol compound and a phenol compound.

According to a preferred embodiment of the present invention, the phenolic compound is at least one of monophenol or polyphenol, preferably a compound of a single benzene ring or a double benzene ring, more preferably at least one of monophenyl polyphenol, double benzene ring monophenol and double benzene ring polyphenol.

In some specific embodiments, the phenolic compound is selected from at least one of catechol, resorcinol, hydroquinone, pyrogallol, 1, 2, 4-benzenetriol, 1, 2, 5-benzenetriol, 1, 3, 5-benzenetriol, α -naphthol, β -naphthol, γ -naphthol, 1, 2-naphthalenediol, 1, 3-naphthalenediol, 1, 4-naphthalenediol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 1, 8-naphthalenediol, 1, 9-naphthalenediol, and their homologs, and particularly preferably at least one of catechol, pyrogallol, 1, 2, 3-benzenetriol, α -naphthol, and β -naphthol.

According to some embodiments of the invention, the phosphate compound is selected from the group consisting of phosphate compounds represented by formula I:

in the formula I, R¹、R²And R³The same or different, each independently selected from hydrogen and C₁-C₂₀Substituted or unsubstituted alkyl of, C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aromatic group of (a); preferably, R¹、R²And R³Each independently selected from hydrogen and C₁-C₁₂Alkyl or haloalkyl of, C₃-C₁₀Cycloalkyl or halocycloalkyl of, C₆-C₁₀Aryl or haloaryl of (C)₇-C₁₀And C is an alkylaryl or haloalkylaryl group₇-C₁₀Aralkyl or haloaralkyl groups of (a); more preferably, R¹、R²And R³Each independently selected from hydrogen and C₁-C₆Alkyl or haloalkyl of, C₃-C₆Cycloalkyl or halocycloalkyl of, C₆-C₁₀Aryl or haloaryl of (C)₇-C₁₀And C is an alkylaryl or haloalkylaryl group₇-C₁₀Aralkyl or haloaralkyl groups of (a).

In some specific embodiments, the phosphate ester compound is selected from the group consisting of phosphoric acid, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, triisopropylphenyl phosphate, trimethoxyphenyl phosphate, monomethyl phosphate, monoethyl phosphate, monopropyl phosphate, monobutyl phosphate, monopentyl phosphate, monohexyl phosphate, monoeeptyl phosphate, monooctyl phosphate, monopropyl phosphate, monodecyl phosphate, monophenyl phosphate, xylyl phosphate, diethylphenyl phosphate, dipropyl phosphate, diisopropylphenyl phosphate, dimethoxyphenyl phosphate, dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, At least one of dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, dinonyl phosphate, didecyl phosphate, diphenyl phosphate, ditolyl phosphate, diethylphenyl phosphate, dipropyl phenyl phosphate, diisopropylphenyl phosphate, dimethoxyphenyl phosphate, phenyl dimethyl phosphate, tolyl dibutyl phosphate, isopropylphenyl dimethyl phosphate, isopropylphenyl diethyl phosphate, isopropylphenyl dibutyl phosphate, phenyl ditolyl phosphate, phenyl diisopropylphenyl phosphate, p-tolyl dibutyl phosphate, m-tolyl dibutyl phosphate, p-isopropylphenyl dimethyl phosphate, p-isopropylphenyl diethyl phosphate, p-tert-butylphenyl dimethyl phosphate and o-tolyl p-di-tert-butylphenyl phosphate.

According to a preferred embodiment of the invention, the weight ratio of the phenolic compound to the magnesium powder is (0.001-5) to 1, preferably (0.005-2) to 1.

According to some embodiments of the present invention, the weight ratio of the phosphate compound to the magnesium powder is (0.001-5) to 1, preferably (0.05-2) to 1.

The magnesium powder used in the present invention may be in any form, for example, in the form of granules, ribbons, or powders, when the reactivity is good. In order to ensure that the average particle size of the produced magnesium alkoxide is kept at 10 to 80 μm and the particle morphology is excellent, it is required that the average particle size of the magnesium powder is preferably spherical particles of 360 μm or less, more preferably, 100-300 μm, so that relatively uniform reaction performance can be maintained. The surface of the magnesium powder is not particularly limited, and a coating such as a hydroxide is formed on the surface of the magnesium powder supported, which slows down the reaction, and therefore, a magnesium powder having no coating such as a hydroxide on the surface is preferred.

According to a preferred embodiment of the invention, the alcoholic compound comprises a linear or branched mono-or polyol, preferably C₁-C₁₀Mixtures of alcohols of (a).

Specific examples of the alcohol according to some embodiments of the present invention include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-nonanol, 2-decanol, 2-ethylbutanol, 2-ethylhexanol, 4-methyl-2-pentanol, 3, 5-trimethylpentanol, 4-methyl-3-heptanol, benzyl alcohol, 2-phenylethanol, 1-phenyl-1-propanol, ethylene glycol, and glycerol, and the like.

In some specific embodiments, the alcohol compound is preferably a mixture of ethanol and isooctanol, wherein ethanol is 80-99 wt% and isooctanol is 1-20 wt%. In the present invention, the water content of the alcohol is not particularly limited, and in order to obtain good performance of the magnesium alkoxide, it is required that the water content is as small as possible. The water content in the alcohol is generally controlled to be below 1000ppm, and preferably below 200 ppm.

According to a preferred embodiment of the invention, the molar ratio of the alcohol compound to the magnesium powder is (2-50) to 1, preferably (2.5-18) to 1.

According to some embodiments of the present invention, the halogenating agent is an elemental halogen and/or an inorganic halide, preferably at least one selected from elemental iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, and alkoxy magnesium halide, more preferably at least one selected from elemental iodine, magnesium iodide, magnesium chloride, and alkoxy magnesium halide, and particularly preferably a mixture of elemental iodine and magnesium chloride. The iodine simple substance and the magnesium chloride can be respectively added into the reaction system, and can also be partially or completely mixed together and added into the reaction system.

According to a preferred embodiment of the present invention, the molar ratio of the halogenating agent to magnesium powder is (0.0002-0.2) to 1, preferably (0.0025-0.05) to 1, in terms of halogen atoms. The inventors have found that the amount of halogen atom added affects the particle morphology and particle size of the final magnesium alkoxide. When the amount of the halogen atom used is too small, the particle morphology of the resulting magnesium alkoxide is extremely poor; if the amount of the halogen atom used is too large, not only the cost for producing the magnesium alkoxide increases, but also the particle size of the magnesium alkoxide is not uniform and the reaction is difficult to control.

According to a preferred embodiment of the present invention, the component further comprises a dispersant, which is preferably an inert organic solvent, more preferably at least one selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene, xylene and derivatives thereof. The invention uses inert organic solvent to disperse materials, and the inert organic solvent can not only dilute the materials and make the materials be stirred well, but also eliminate partial static electricity, which has certain effect on protecting the particle form of the product.

According to some embodiments of the invention, the order of addition of the components in the reaction may be determined as desired. Specifically, the method of adding the phenolic compound and the halogenating agent is not particularly limited, and the phenolic compound and the halogenating agent may be added dissolved in an alcohol, may be added directly to magnesium powder and the alcohol in the form of a solid or a liquid, or may be prepared by a method of dropping an alcohol solution of the halogenating agent while heating the magnesium powder and the alcohol solution.

All reactions of the present invention are carried out under an inert gas atmosphere, such as argon, nitrogen, with nitrogen being preferred for the present invention.

The magnesium powder, the alcohol compound, the phenol compound, the phosphate compound, the halogenating agent and the inert solvent may be added at once at the beginning or may be added in portions. The divided charging of the raw materials can prevent instantaneous generation of a large amount of hydrogen and the generation of droplets of alcohol or halogen due to the instantaneous generation of a large amount of hydrogen, and such a charging method is preferable from the viewpoint of safety. The number of divisions can be determined depending on the scale of the reaction tank and the amounts of the respective materials.

The reaction temperature of the invention can be carried out at 0 ℃ to the reflux temperature of the reaction system, the reflux temperature can be changed by slight change of the reaction pressure, and the reaction can be carried out faster as the reaction temperature is selected higher. The reaction temperature may also be varied during the reaction, and the particle size and particle morphology may be varied by selection of the reaction temperature. The preferred reaction temperature in the present invention is the reflux temperature of the reaction system.

The degree of progress of the reaction is judged by observing the amount of hydrogen discharged from the reaction, and the reaction time is usually 2 to 30 hours.

According to an embodiment of the invention, the reaction product is dried or suspended in a dispersant.

After the reaction, the product can be washed with an alcohol and/or a mixture of alcohols to produce magnesium alkoxide; or washing with organic solvent used in the reaction process; the washing may be optionally carried out, and the manner and the number of washing treatments are not particularly limited.

According to another aspect of the present invention there is provided a Ziegler-Natta catalyst component comprising the reaction product of:

A) the aforementioned magnesium alkoxide particles;

B) a titanium-containing halide;

C) an electron donor compound.

According to some embodiments of the present invention, the electron donor compound is a carboxylic acid ester electron donor compound, preferably selected from benzoic acid monoesters or phthalic acid ester compounds represented by formula II,

in the formula II, R₁And R₂Is independently selected from C₁-C₈Substituted or unsubstituted alkyl of, C₃-C₁₀Substituted or unsubstituted cycloalkyl or C₆-C₂₀Substituted or unsubstituted aromatic group of (a); r₃-R₆Independently selected from hydrogen, halogen, C₁-C₄Substituted or unsubstituted alkyl or C₁-C₄Substituted or unsubstituted alkoxy of, preferably, R₃-R₆At least three of them are hydrogen, and more preferably, the carboxylate electron donor compound is at least one selected from the group consisting of di-n-butyl phthalate, diisobutyl phthalate, diethyl phthalate, dipentyl phthalate, dioctyl phthalate, methyl benzoate, ethyl benzoate, propyl benzoate, isopropyl benzoate, butyl benzoate and isobutyl benzoate.

And/or the molar ratio of the electron donor compound to the alkoxy magnesium particles is (0.005-10) to 1, preferably (0.01-2) to 1.

According to a preferred embodiment of the invention, the titanium-containing halide comprises a compound of the formula TiX_m(OR₇)_4-mWherein X is halogen, preferably chlorine, bromine or iodine; r₇Is C₁-C₂₀M is an integer of 0 to 4.

In some specific embodiments, the titanium-containing halide preferably comprises at least one of a titanium tetrahalide, an alkoxy titanium trihalide, a dialkoxy titanium trihalide, and a trialkoxy titanium halide; more preferably, it comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxyide, titanium tetrabutoxide, titanium monochlorotriethoxyide, titanium dichlorodiethoxylate and titanium trichloroethoxylate. According to one embodiment of the invention, the titanium compound is preferably titanium tetrachloride.

According to an embodiment of the invention, the molar ratio of titanium-containing halide to magnesium alkoxide particles is (0.5-100) to 1, preferably (1-50) to 1.

According to an embodiment of the present invention, the Ziegler-Natta catalyst component is prepared at a reaction temperature of from-40 to 200 ℃, preferably from-20 to 150 ℃ and for a reaction time of from 1min to 20h, preferably from 5min to 8 h.

According to another aspect of the present invention, there is provided a catalyst for the polymerization of olefins comprising the reaction product of:

a) the foregoing catalyst components;

b) an organoaluminum compound;

c) optionally, an external electron donor compound.

According to the embodiment of the present invention, the alkyl aluminum compound is not particularly limited, and an alkyl aluminum compound that is generally used in the art and can be used in a ziegler-natta type catalyst may be selected.

The aluminum alkyl compounds suitable for use in the present invention are preferably of the formula AlR'_n′X′_3-n′The alkyl aluminum compound is shown in the specification, wherein R' is selected from hydrogen and C₁-C₂₀Alkyl and C₆-C₂₀Aryl of (a); x 'is halogen, and n' is an integer of 1 to 3.

In some specific embodiments, as a specific example of the alkylaluminum compound, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride can be selected.

According to some embodiments of the present invention, the molar ratio of aluminum in the organoaluminum compound to titanium in the catalyst component is (5-5000) to 1, preferably (20-1000) to 1, and more preferably (50-500) to 1.

According to a specific embodiment of the present invention, said component c is an optional external electron donor compound, meaning that the external electron donor compound may or may not be present in the catalyst system for olefin polymerization. According to a preferred embodiment of the present invention, the external electron donor compound is not particularly limited, and an external electron donor compound that can be used in a ziegler-natta type catalyst, which is generally used in the art, may be selected.

The external electron donor compounds suitable for use in the present invention are preferably of the general formula R⁴ _pR⁵ _qSi(OR⁶)_4-p-qAn organosilicon compound represented by the formula (I), wherein R⁴And R⁵Independently selected from halogen, hydrogen atom, C₁-C₂₀Alkyl of (C)₃-C₂₀Cycloalkyl of, C₆-C₂₀Aryl and C₁-C₂₀Any one of the haloalkyl groups of (1), R⁶Is selected from C₁-C₂₀Alkyl of (C)₃-C₂₀Cycloalkyl of, C₆-C₂₀Aryl and C₁-C₂₀Any one of the haloalkyl groups of (a); p and q are each an integer of 0 to 3, and p + q < 4.

In some specific examples, as specific examples of the organosilicon compound, at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1, 1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1, 1, 1-trifluoro-2-propyl) -methyldimethoxysilane, etc., preferably at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane and diphenyldimethoxysilane.

According to an embodiment of the present invention, the molar ratio of aluminum to the external electron donor compound in the organoaluminum compound is (0-500) to 1, preferably (1-300) to 1, and more preferably (3-100) to 1.

According to a further aspect of the present invention there is provided an olefin polymerisation process comprising contacting under olefin polymerisation conditions one or more olefins, at least one of which is represented by the general formula CH, with the aforesaid catalyst component or catalyst₂Wherein R is hydrogen and C₁-C₆Any one of the alkyl groups of (1).

The olefin polymerization method can be used for olefin homopolymerization and can also be used for copolymerizing a plurality of olefins. Said general formula CH₂Specific examples of α -olefins represented by ═ CHR are ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene, and more preferably, the general formula CH₂The olefin represented by ═ CHR is at least one selected from the group consisting of ethylene, propylene and 1-butene.

According to the olefin polymerization process of the present invention, the olefin polymerization conditions are not particularly limited, and the conditions conventional in the art may be selected; the amount of the catalyst to be used is not particularly limited, and the amount of each catalyst to be used in the olefin polymerization of the prior art can be selected.

According to a preferred embodiment of the invention, the olefin polymerization conditions are: the temperature is 0-150 ℃, preferably 60-130 ℃; the time is 0.1 to 5 hours, preferably 0.5 to 4 hours; the pressure is 0.01-10MPa, preferably 0.5-5 MPa.

According to the invention, a small amount of mixture of halogen-containing substances is selected as the halogenating agent, so that the reaction is easier to control and the particle morphology is better maintained when the phenolic compound and the phosphate ester compound are added in the reaction process.

The alkoxy magnesium particles prepared by the invention are particularly suitable for preparing olefin polymerization catalysts, the obtained catalysts have high activity, the obtained polymers have large bulk density, good particle shape and uniform distribution, and the alkoxy magnesium particles are suitable for devices for producing olefins by gas phase processes.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.

It should be noted that in the following examples and comparative examples, the evaluation and test methods are as follows:

1. the titanium atom content in the olefin polymerization catalyst component was measured using a 721 spectrophotometer;

2. melt Index (MI) measurements of the polymers were determined using an XRZ-00 melt index apparatus according to the method specified in GB/T3682-2000.

3. The particle size and particle size distribution of the dialkoxy magnesium and the catalyst were measured by a Malvern Mastersizer TM 2000 n-hexane dispersant laser diffraction method, wherein SPAN ═ D90-D10)/D50.

4. Determination of the content of phenoloxy groups in the magnesium alkoxide particles: the obtained sample was dissolved by adding a 1N hydrochloric acid solution thereto and stirring for 24 hours, and the phenolic compound was quantified by gas chromatography and then calculated.

5. The phosphorus content of the magnesium alkoxide particles was determined using gas chromatography.

6. The test method of the polymer Isotactic Index (II) is as follows: after a 2 gram sample of the dried polymer was placed in an extractor and extracted with boiling heptane for 6 hours, the residue was dried to constant weight and the isotacticity was calculated by the following formula:

the isotacticity II is equal to the mass of the polymer after extraction/2 × 100%.

7. The Bulk Density (BD) of the polymer was determined by the method of the weight of the bulk solid per unit volume.

Examples 1 to 13 and comparative examples 1 to 2

Preparation of magnesium alkoxide particles: in the reactor with a stirrer, a reflux condenser, a thermometer and a burette were installed. After sufficient replacement with nitrogen, 260ml of ethanol having a water content of less than 200ppm and 20ml of isooctyl alcohol having a water content of less than 200ppm were fed to the reactor, and 1.5g of elemental iodine and 1.0g of magnesium chloride were added to dissolve them. Then 32g of magnesium powder (less than 300 mu m), a certain amount of phenolic compounds and phosphate compounds and 100ml of toluene are added in 6 times for reaction. After stirring, the temperature is raised until the reflux temperature of the reaction system is reached, and the reaction is carried out until the reaction is completed, namely, no hydrogen is discharged. Then washing, separating and drying are carried out. The specific amounts of the respective raw materials added and the results are shown in tables 1 and 2.

The prepared magnesium alkoxide particles were used for preparing a solid catalyst component: in a 300mL reaction vessel repeatedly purged with high purity nitrogen, 10mL of toluene and 90mL of titanium tetrachloride were added, the temperature was reduced to-15 ℃ and a suspension prepared from 10g of the obtained magnesium alkoxide particles, 50mL of toluene and 1.2mL of a carboxylic acid ester (which is exemplified by di-n-butyl phthalate DNBP, but not limited thereto) was added, followed by slowly raising the temperature to 120 ℃ and maintaining the temperature for 2 hours, and then the liquid was subjected to pressure filtration. Then adding a mixed solution of 30mL of titanium tetrachloride and 120mL of toluene, heating to 110 ℃, dropwise adding 1.5mL of DNBP, stirring for 1 hour, and performing pressure filtration on the liquid; then adding a mixed solution of 120mL of titanium tetrachloride and 30mL of toluene, heating to 110 ℃, stirring for 1 hour, treating for 2 times in this way, filtering out the liquid, washing the obtained solid with 150mL of hexane for 4 times at 60 ℃, filtering out the liquid, and drying to obtain solid powder, namely the solid catalyst component. The specific data are shown in tables 1 and 2.

Polymerization of propylene: in a 5-liter autoclave, purged with a nitrogen stream at 70 ℃ for 1 hour, then 5mL of a hexane solution of triethylaluminum (concentration of triethylaluminum 0.5mmol/m1), 1mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration of CHMMS 0.10mmol/m1), 10mL of anhydrous hexane, and 10mg of the solid catalyst component were introduced at room temperature into the nitrogen stream. The autoclave was closed and 1.0L or 4.5L (under standard conditions) of hydrogen and 2.0L of liquid propylene were introduced; the temperature was raised to 70 ℃ over 10 minutes with stirring. After polymerization at 70 ℃ for 1 to 3 hours, the stirring was stopped, the unpolymerized propylene monomer was removed, and the polymer was collected and tested. The specific data are shown in tables 1 and 2.

TABLE 1 data Table for examples 1-9

TABLE 2 data tables for examples 10-13 and comparative examples 1-2

As can be seen from the data in tables 1 and 2, when the catalyst of the invention is used for propylene polymerization, the polymerization activity is high, the attenuation is slow, the hydrogen regulation sensitivity is good, the bulk density of the obtained polymer is high, the fluidity is better, and the catalyst is beneficial to the long-term stable application on a large propylene polymerization device. The catalyst has wide application prospect.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.