WO2016074243A1 - Polyolefin resin composition and preparation method therefor - Google Patents

Abstract

Provided are a polyolefin resin and a preparation method therefor. The preparation method for the polyolefin resin comprises olefin monomers undergoing a polymerisation reaction in the presence of an olefin polymerisation catalyst component and a cocatalyst, the olefin polymerisation component containing halloysite, a transition metal component, a non-transition metal component and the cocatalyst. When the transition metal component is a titanium tetrahalide and/or a titanium alkoxide, the non-transition metal component is a magnesium-containing compound. When the transition metal component is a metallocene compound and/or a non-metallocene compound, the non-transition metal component is an aluminium-containing compound. When the transition metal component is mixture of a titanium tetrahalide and/or a titanium alkoxide and a metallocene compound and/or a non-metallocene compound, the non-transition metal component is a mixture of a magnesium-containing compound and an aluminium-containing compound. The polyolefin composition prepared via the present method has a relatively high melt strength and relatively high mechanical properties.

Description

Polyolefin resin composition and preparation method thereof Technical field

The present invention relates to a process for producing a polyolefin resin composition and a polyolefin resin composition prepared by the process.

Background technique

Polyolefin resin is a general term for a class of general-purpose plastics represented by polyethylene and polypropylene. It has excellent comprehensive performance and wide application fields, and has occupied a huge market share. The innovation in composition and structure of olefin polymerization catalysts is one of the main driving forces for regulating the composition and properties of polyolefin resins and promoting the performance improvement of polyolefins. Since the German chemist Zielger and the Italian chemist Natta jointly initiated the olefin coordination polymerization in the 1950s, olefin polymerization catalysts have gradually developed three types of catalysts including Zielger-Natta catalysts, metallocene catalysts and non-metallocene catalysts.

Although olefin polymerization catalysts with new structures and new properties have been discovered and applied to polyolefin high performance research, some high performance polyolefin resins with broad application prospects still lack effective catalytic polymerization preparation methods. For example, long-chain branched polypropylene (HMS-PP) with high melt strength has broad application prospects in applications such as blow molding and foaming. However, there is currently no effective catalyst system and polymerization method that can be directly used in the polymerization vessel. Preparation of HMS-PP. For example, the polypropylene in-cylinder alloy represented by impact copolymer polypropylene (hiPP) has great potential in the fields of automobiles, equipment and durable consumer goods, but polypropylene and ethylene-propylene rubber are present in the alloy resin in the polypropylene kettle. The problem of low interfacial adhesion and unstable phase separation scale makes the alloy resin in the polypropylene kettle have low melt strength and poor mechanical properties, which seriously affects its performance.

Halloysite is a clay mineral, a multi-walled, hollow nanotube formed by a silicate sheet composed of a siloxane tetrahedron and an aluminoxy octahedron in a 1:1 structure, having an inner diameter of 10-20 nm. The outer diameter is 10-100 nm and the length is 0.5-40 microns. Due to its rich source, low cost and easy availability, halloysite has attracted the attention of academia and industry, and is used in the fields of catalytic materials, reinforcing materials and porous materials. For example, the preparation method and properties of polypropylene-based high-content halloysite nanotube composites (Deng Chengye, Huang Hanxiong, Journal of Chemical Industry, 2013, 64(10): 3824-3830) discloses that the halloysite nanotube HNTs are placed in a vacuum. Drying is carried out in a dry box, and then the dried HNTs and PP and PP-g-MAH and the antioxidant are uniformly blended. Although the method can improve the melt strength of the polyolefin resin to some extent and improve its mechanical properties, the melt strength of the polyolefin resin is difficult to ensure that the halloysite is uniformly distributed in the polyolefin resin. The range of improvement in mechanical properties is limited.

Summary of the invention

The object of the present invention is to overcome the defects of low melt strength and poor mechanical strength of a polyolefin resin prepared by the existing method, and to provide a novel preparation method of the polyolefin resin composition and the preparation method prepared by the method. Polyolefin resin composition.

Specifically, the first preparation method of the polyolefin resin composition provided by the present invention comprises carrying out polymerization of an olefin monomer in the presence of an olefin polymerization catalyst component and a cocatalyst, wherein the olefin polymerization catalyst component contains angstrom Rock, transition metal component and non-transition metal component;

The transition metal component is titanium tetrahalide and/or titanium alkoxide, and the non-transition metal component is a magnesium-containing compound; or

The transition metal component is a metallocene compound in a metallocene catalyst and/or a nonmetallocene compound in a non-metallocene catalyst, and the non-transition metal component is an aluminum-containing compound; or

The transition metal component is a mixture of titanium tetrahalide and/or titanium alkoxide with a metallocene compound in a metallocene catalyst and/or a non-metallocene compound in a non-metallocene catalyst, and the non-transition metal component It is a mixture of a magnesium-containing compound and an aluminum-containing compound.

The second preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) Coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain an olefin polymerization catalyst component:

(3) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.

The third preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with the first aluminum-containing compound at 0-90 ° C for 1-20 hours to obtain activated halloysite;

(2) reacting the transition metal component with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component which is a metallocene compound in the metallocene catalyst and/or Or a non-metallocene compound in a non-metallocene catalyst;

(3) reacting the activated halloysite with the activated catalyst component at 0-100 ° C for 1-10 hours to obtain an olefin polymerization catalyst component;

(4) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.

The fourth preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain a catalyst component containing halloysite;

(3) reacting the halloysite-containing catalyst component with the first aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated halloysite-containing catalyst component;

(4) reacting the metallocene compound in the metallocene catalyst and/or the non-metallocene compound in the non-metallocene catalyst with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component;

(5) reacting the activated halloysite-containing catalyst component with the activated catalyst component at 0 to 110 ° C for 1 to 10 hours to obtain an olefin polymerization catalyst component;

(6) Polymerization is carried out in the presence of an olefin monomer in the olefin polymerization catalyst component and a cocatalyst.

Further, the present invention provides a polyolefin resin composition prepared by the above method.

The inventors of the present invention have found through intensive studies that when the halloysite-containing olefin polymerization catalyst provided by the present invention is used for the preparation of a polyolefin resin, the obtained polyolefin resin composition has high melt strength and mechanical strength. It is speculated that the reason may be due to the doping of halloysite into the olefin polymerization catalyst system, which can not only use the polymerization to uniformly disperse halloysite in the polyolefin resin at the nanometer scale, and realize the halloysite and polyolefin resin. Nanocomposite, but also able to utilize the halloysite nanotubes to present a large inner diameter and length of the tube Suitable characteristics form physical cross-linking points, inhibit molecular chain movement of polyolefin resin, improve melt strength of polyolefin resin and improve phase interfacial action in multi-phase polyolefin resin system, thereby improving melt strength and mechanics of polyolefin resin performance.

Other features and advantages of the invention will be described in detail in the detailed description which follows.

detailed description

Specific embodiments of the present invention will be described in detail below. It is to be understood that the specific embodiments described herein are merely illustrative and not restrictive.

The first preparation method of the polyolefin resin composition provided by the present invention comprises carrying out polymerization of an olefin monomer in the presence of an olefin polymerization catalyst component and a cocatalyst, wherein the olefin polymerization catalyst component contains halloysite, a transition metal component and a non-transition metal component;

The transition metal component is titanium tetrahalide and/or titanium alkoxide, and the non-transition metal component is a magnesium-containing compound; or

The transition metal component is a metallocene compound in a metallocene catalyst and/or a nonmetallocene compound in a non-metallocene catalyst, and the non-transition metal component is an aluminum-containing compound; or

The transition metal component is a mixture of titanium tetrahalide and/or titanium alkoxide with a metallocene compound in a metallocene catalyst and/or a non-metallocene compound in a non-metallocene catalyst, and the non-transition metal component It is a mixture of a magnesium-containing compound and an aluminum-containing compound.

The content of the various components in the olefin polymerization catalyst component of the present invention is not particularly limited, and for example, the content of the halloysite may be 0.5 to 90 by weight based on the total weight of the olefin polymerization catalyst component. %, the total content of metal elements in the transition metal component and the non-transition metal component may be 2 to 80% by weight; preferably, the halloysite is based on the total weight of the olefin polymerization catalyst component The content is from 1 to 50% by weight, and the total content of the metal elements in the transition metal component and the non-transition metal component is from 5 to 60% by weight.

Further, when the non-transition metal component is a magnesium-containing compound, the content of the transition metal element in the transition metal component may be 0.5 to 10% by weight based on the total weight of the olefin polymerization catalyst component. Preferably, it is 1-5% by weight; the non-transition metal component in the non-transition metal component may be included in an amount of 2 to 30% by weight, preferably 5 to 20% by weight.

When the non-transition metal component is an aluminum-containing compound, the content of the transition metal element in the transition metal component may be 0.01 to 5% by weight, based on the total weight of the olefin polymerization catalyst component, preferably 0.05 to 2.5% by weight; the content of the non-transition metal element in the non-transition metal component may be 2 to 40% by weight, preferably 5 to 25% by weight.

When the non-transition metal component is a mixture of a magnesium-containing compound and an aluminum-containing compound, the transition metal component may have a transition metal element content of 0.25 based on the total weight of the olefin polymerization catalyst component. 15% by weight, preferably 0.5 to 5% by weight; the non-transition metal component in the non-transition metal component may be contained in an amount of 5 to 50% by weight, preferably 7.5 to 40% by weight.

The halloysite may be natural halloysite or may be modified halloysite, for example, halloysite and/or organically modified halloysite, ie, the halloysite may be natural angstrom At least one of a sulphate, a halloysite, and an organically modified halloysite. Wherein, as described above, the natural halloysite is a multi-walled, hollow nanotube formed by the silicate sheet layer composed of a silicon oxytetrahedron and an aluminoxy octahedron in a 1:1 structure, and has an inner diameter of 10- 20 nm, outer diameter 10-100 nm, length 0.5-40 micron. The altered halloysite is obtained by heat-treating natural halloysite at 50-900 ° C, preferably at 100-600 ° C, for 0.5-48 hours, preferably for 2-10 hours. Place The organically modified halloysite is obtained by modifying natural halloysite and/or halloysite with at least one of an organosilicon compound, a titanium compound, and an organic compound containing no silicon or titanium and having a double bond at the end. .

The natural halloysite and meta-allogite contain a hydroxyl group, and the organically modified halloysite passes through a hydroxyl group in natural halloysite and/or halloysite, an organosilicon compound, a titanium compound, and no silicon and titanium. The functional groups capable of reacting with a hydroxyl group in the organic compound having a double bond at the terminal are chemically bonded together, and specific reaction conditions are well known to those skilled in the art, and are not described herein. It should be noted that when the organosilicon compound, the titanium compound, and the organic compound containing no silicon and titanium and having a double bond at the end do not contain a functional group capable of reacting with a hydroxyl group, the halloysite may be first performed. Modifying to introduce a functional group capable of reacting with at least one of the organosilicon compound, the titanium compound, and the organic compound having no double bond at the end and having no silicon or titanium in the halloysite. It is well known to the skilled person and will not be described here. Wherein the organosilicon compound has the formula R ¹ R ² SiR ³ ₂ , wherein R ¹ is a halogen atom, a vinyl group, an amino group, a C ₁ -C ₅ aminoalkyl group, an epoxy group, a methacryl group An oxy group, a fluorenyl group, a C ₁ -C ₅ alkoxy group, a ureido group or an alkyl group having an α-olefin double bond of the formula -(CH ₂ ) _m1 COOCH(CH ₃ )=CH ₂ , m1 is 1- An integer of 18, R ² is a halogen atom, a C ₁ -C ₅ alkoxy group or an alkyl group of the formula -(CH ₂ ) _{m 2} -CH ₃ , m 2 is an integer of 0-2, and R ³ is a halogen atom, C ₁ -C ₅ alkoxy or acetoxy. The organosilicon compound is particularly preferably γ-methacryloxypropyltrimethoxysilane and/or γ-aminopropyltriethoxysilane from the viewpoint of availability of raw materials. The titanium compound has the formula R ⁴ _p Ti(OR ⁵ ) _4-p , wherein R ⁴ and R ⁵ are C ₁ -C ₄ alkyl groups, and p is an integer of 0-3. The titanium compound is particularly preferably at least one of tetrabutyl titanate, titanium triethoxytitanium, methyltrimethoxytitanium, and tetraethyl titanate from the viewpoint of availability of raw materials. The organic compound containing no silicon and titanium and having a double bond at the end has the formula R ⁶ R ⁷ CH=CH ₂ , wherein R ⁶ is an acid chloride group, a carboxyl group, an epoxy group or an ester group, and R ⁷ is C ₁ -C ₂₀ alkylene group or a C with an ester group, an oxygen atom or a carboxyl group ₁ -C ₂₀ alkylidene. From the viewpoint of availability of raw materials, the organic compound having no silicon and titanium and having a double bond at the end is HOOC(CH ₂ ) ₄ CH=CH ₂ , HOOC(CH ₂ ) ₇ CH=CH ₂ and At least one of HOOC(CH ₂ ) ₉ CH=CH ₂ .

The types of the titanium tetrahalide and the titanium alkoxide can be conventionally selected in the art. For example, the titanium tetrahalide is TiCl ₄ may be TiCl _4, at least one of _4, TiBr ₄ and TiI particularly preferred. The alkoxy group in the alkoxide titanium may be a substituted or unsubstituted C ₁ -C ₅ alkoxy group, wherein the substituent is usually a halogen atom. Specifically, examples of the titanium alkoxide include, but are not limited to, Ti(OEt)Cl ₃ , Ti(OEt) ₂ Cl ₂ , Ti(OEt) ₃ Cl, Ti(OEt) _4, and Ti(OBu) ₄ . At least one.

The kind of the metallocene compound in the metallocene catalyst may be a conventional choice in the art, and for example, may be a metallocene compound of the formula: (I):

(Cp ^I -B _e -Cp ^II )M'R ⁸ _a R ⁹ _b (I)

Wherein M' is Ti, Zr, Hf, V, Fe, Y, Sc or a lanthanide metal; Cp ^I and Cp ^II are each independently H, C ₁ -C ₅ alkyl, substituted or unsubstituted ring a pentadienyl, substituted or unsubstituted C ₆ -C ₁₈ aryl group, and the substituent is a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ cycloalkyl group and a C ₆ -C ₁₈ aryl group At least one of the groups; R ⁸ and R ⁹ are each independently H, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group, a C ₆ -C ₂₀ aryl group, a band a C ₇ -C ₂₀ aryl group having a C ₁ -C ₁₅ alkyl group, a C ₁ -C ₈ acyloxy group, an allyl group or a C ₁ -C ₁₅ silane group, each of a and b being independently 0- An integer of 2, and a+b=2; B is an alkyl bridge or a silane bridge, preferably a -C(R ¹⁰ R ¹¹ )-alkyl bridge or a -Si(R ¹² R ¹³ )-silane bridge, wherein R ¹⁰ -R ¹³ are each independently H, C ₁ -C ₄ alkyl or C ₆ -C ₁₀ aryl; and e is an integer from 1 to 3. Specifically, examples of the metallocene compound in the metallocene catalyst include, but are not limited to, C ₂ H ₄ (Ind) ₂ ZrCl ₂ , C ₂ H ₄ (H ₄ Ind) ₂ ZrCl ₂ , Me ₂ Si (Ind) ₂ ZrCl ₂ , Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ , Me ₂ Si(Me ₄ Cp) ₂ ZrCl ₂ , Me ₂ Si(Flu) ₂ ZrCl ₂ , Me ₂ Si(2- Me-4-Naph-Ind) ₂ at least one of ZrCl ₂ and Ph ₂ Si(Ind) ₂ ZrCl ₂ , Me is a methyl group, Ph is a phenyl group, Cp is a cyclopentadienyl group, and Ind is a fluorenyl group. H ₄ Ind is 4,5,6,7-tetrahydroanthracene, Flu is an anthracenyl group, and Naph is a naphthyl group.

The kind of the non-metallocene compound in the non-metallocene catalyst may be a conventional choice in the art, and for example, may be a non-metallocene compound of the formula: (II):

Wherein M is selected from Zr, Ti, V or Hf, and R ₁ , R ₂ and R ₃ are each independently H, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group, C An aryl group of _6- C _{20 ,} an aryl group having a C ₁ -C ₆ alkyl group, an aryl group having a C ₃ -C ₁₈ cycloalkyl group, an aryl group having a C ₆ -C ₁₈ aryl group a C ₁ -C ₈ acyloxy group, an allyl group or a C ₁ -C ₁₅ silane group, X is F, Cl, Br or I, and n is 2. Specifically, examples of the non-metallocene compound in the non-metallocene catalyst include, but are not limited to, bis[N-(3-tert-butyl salicylidene)anilino]zirconium dichloride, and two [N-( 3-methyl salicylidene)anilino]zirconium dichloride, bis[N-(3-isopropylsalicylidene)anilino]zirconium dichloride and bis[N-(3-adamantyl) At least one of -5-methyl salicylidene)anilino]zirconium dichloride.

The magnesium-containing compound may be any of various magnesium-containing compounds which can be used in an olefin polymerization catalyst, and may be, for example, a magnesium halide of the formula MgX ¹ ₂ or a Grignard reagent of the formula RMgX ² or both. a mixture of people. In MgX ¹ ₂ , X ¹ is F, Cl, Br or I; in RMgX ² , R is a C ₁ -C ₁₀ alkyl group, and X ² is F, Cl, Br or I. Specifically, examples of the magnesium-containing compound include, but are not limited to, at least one of magnesium chloride, magnesium bromide, magnesium isopropoxide chloride, and n-butoxymagnesium chloride. The magnesium-containing compound is preferably magnesium chloride from the viewpoint of availability of raw materials.

The aluminum-containing compound may be an existing aluminum-containing compound which can be used for an olefin polymerization catalyst, and for example, may be an aluminum-containing compound of the formula Al(OR') _q R" _{3 - q} , wherein R 'and R' are each independently a C ₂ -C ₁₀ alkyl group, 0 ≤ q ≤ 3. Specifically, examples of the aluminum-containing compound include, but are not limited to, at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, methyl aluminoxane, and the like.

In the olefin polymerization catalyst component, when the non-transition metal component is a magnesium-containing compound or a mixture of a magnesium-containing compound and an aluminum-containing compound (that is, the non-transition metal component contains a magnesium-containing compound), The olefin polymerization catalyst component preferably further contains an internal electron donor compound, which can enhance the catalytic activity of the catalyst and can improve the isotacticity and crystallinity of the polyolefin resin. The amount of the internal electron donor compound may be conventionally selected in the art. For example, the molar ratio of the internal electron donor compound to the magnesium element in the olefin polymerization catalyst component may be 0.05-0.6:1, preferably 0.1-0.4:1. Further, the kind of the internal electron donor compound may also be a conventional choice in the art, and for example, may be at least one of a diether compound, a carboxylate compound, an alcohol ester, a ketone, an amine, and a silane, and particularly preferably Diether compound and / or carboxylate compound.

Specifically, examples of the diether compound include, but are not limited to, 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxy group. Propane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2- Phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-di Methoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-di Cyclohexyl-1,3-dimethoxy Propane, 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-dimethyl Oxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl- 2-cyclohexyl-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-dimethoxypropane, 2,2-diisobutyl-1,3-dimethyl Oxypropane, 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-isopropyl-2-isopentyl-1,3-dimethoxy Propane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl- 2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-secondary-butyl -1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethyl Oxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9 One or more of 9-bis(methoxymethyloxime), particularly preferably 9,9-bis(methoxymethyloxime).

Examples of the carboxylic acid ester compound include, but are not limited to, diethyl succinate, dibutyl succinate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate. Ester, di-n-octyl phthalate, diisooctyl phthalate, ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, triethyl trimellitate One or more of tributyl trimellitate is particularly preferably dibutyl phthalate and/or diisobutyl phthalate.

The olefin polymerization catalyst component provided by the present invention can be produced by various existing methods. According to a specific embodiment of the present invention, when the non-transition metal component is a magnesium-containing compound, the olefin polymerization catalyst component is prepared by a method comprising the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) The magnesium complex of the halloysite is coordinated with titanium tetrahalide and/or titanium alkoxide.

The amount of the halloysite and the magnesium-containing compound to be used in the step (1) is not particularly limited. For example, the weight ratio of the amount of the halloysite to the amount of the magnesium-containing compound may be 1:0.5-99. It is preferably 1:0.5-35.

As described above, the reaction temperature of the halloysite and the magnesium-containing compound is 30 to 150 ° C, and the reaction time is 1 to 50 hours. Preferably, the reaction temperature of the halloysite and the magnesium-containing compound is 40 to 130 ° C, and the reaction time is 4 to 20 hours.

The reaction between the halloysite and the magnesium-containing compound is preferably carried out in an organic solvent, which enables the reaction to proceed more smoothly. The type of the organic solvent may be any of various existing inert materials which can be used as a reaction medium, for example, may be a C ₅ - C ₁₀ alkane, an aromatic hydrocarbon, a cycloalkane, a C ₂ - C ₁₂ ether, and a tetrahydrofuran. At least one of them is preferably n-hexane, cyclohexane, heptane, decane, ethanol, isobutanol, isooctanol, tetrahydrofuran, methyl ether, diethyl ether, n-propyl ether, diisopropyl ether, n-butyl ether, iso At least one of butyl ether, diisoamyl ether, benzene, toluene, xylene, chlorobenzene, and the like. Further, the organic solvent is usually used in an amount such that the concentration of halloysite may be from 1 to 500 g/L, preferably from 2 to 50 g/L.

The manner in which the magnesium complex of the halloysite is coordinated with the titanium tetrahalide and/or the titanium alkoxide is not particularly limited. For example, the angstrom may be firstly cooled at a low temperature (0-40 ° C). The magnesium complex of Lost is mixed with titanium tetrahalide and/or titanium alkoxide, and then The temperature is raised to a high temperature (80-130 ° C) for 1-10 hours. Preferably, the manner of coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide comprises first combining the magnesium complex of the halloysite with a portion of titanium tetrahalide and/or A part of the titanium alkoxide is reacted at -20 ° C to 0 ° C for 0.5-2 hours, and then the temperature is raised to 80-130 ° C for 1-4 hours, followed by solid-liquid separation of the reaction product, and the obtained solid product is The remaining portion of titanium tetrahalide and/or the remaining portion of titanium alkoxide is reacted at 80-130 ° C for 1-4 hours. More preferably, the manner of coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide comprises first combining the magnesium complex of the halloysite with a portion of titanium tetrahalide and/or Or a part of titanium alkoxide is reacted at -20 ° C to -10 ° C for 0.5-1.5 hours, and then the temperature is raised to 100-125 ° C for 1.5-2.5 hours, followed by solid-liquid separation of the reaction product, and the obtained solid The product is reacted with the remainder of the titanium tetrahalide and/or the remainder of the titanium alkoxide at 100-125 ° C for 1.5-2.5 hours. Further, when the reaction of the step (1) is carried out in the presence of an organic solvent, the product obtained in the step (1) is present in the form of a solution, and the coordination reaction of the step (2) can directly directly apply the magnesium containing halloysite. The solution of the composite is added dropwise to the titanium tetrahalide and/or the titanium alkoxide, or the titanium tetrahalide and/or the titanium alkoxide are directly added to the solution of the magnesium complex containing the halloysite, wherein the dropping is used. The time may be 0.5-4 hours; if the reaction of the step (1) is carried out in the absence of an organic solvent, or after the step (1) has been dried, the external reaction of the step (2) may be The magnesium complex of halloysite is dispersed in a solution containing titanium tetrahalide and/or titanium alkoxide.

The amount of the magnesium-containing compound, a part of titanium tetrahalide, a part of titanium alkoxide, another part of titanium tetrahalide, and another part of titanium alkoxide is not particularly limited. When the magnesium-containing compound is a magnesium halide of the formula MgX ¹ ₂ , the total amount of the titanium tetrahalide and the titanium alkoxide used in the first loading may be from 10 to 60:1, and the molar ratio of the magnesium-containing compound may be from 10 to 60:1. Preferably, it is 10-30:1 (ie, the total amount of the part of the titanium tetrahalide and a part of the titanium alkoxide is from 10 to 60:1, preferably from 10 to 30:1); The molar ratio of the total amount of titanium tetrahalide and titanium alkoxide used to the secondary load to the magnesium-containing compound may be from 10 to 60:1, preferably from 10 to 30:1 (i.e., the remaining portion of titanium tetrahalide and the remainder) The molar ratio of the total amount of titanium alkoxide to the magnesium-containing compound is from 10 to 60:1, preferably from 10 to 30:1. When the magnesium-containing compound is a Grignard reagent of the formula RMgX ² , the total amount of the titanium tetrahalide and the titanium alkoxide used in the first loading may be from 1 to 100:1, and the molar ratio of the magnesium-containing compound may be from 1 to 100:1. Preferably, it is from 1 to 20:1 (ie, the total amount of the part of the titanium tetrahalide and a part of the titanium alkoxide is from 10 to 100:1, preferably from 1 to 20:1); The molar ratio of the total amount of titanium tetrahalide and titanium alkoxide used in the secondary loading to the magnesium-containing compound may be from 1 to 100:1, preferably from 1 to 20:1 (i.e., the remaining portion of titanium tetrahalide and the remainder) The molar ratio of the total amount of titanium alkoxide to the magnesium-containing compound is from 1 to 100:1, preferably from 1 to 20:1.

The portion of the titanium tetrahalide and titanium tetrahalide another portion that can be prepared in various olefin polymerization catalyst with a titanium tetrahalide conventionally used, for example, may be TiCl _4, TiBr ₄ and at least one of TiI _4. In addition, the portion of the titanium alkoxide and the other portion of the titanium alkoxide may also be various titanium alkoxides conventionally used in the preparation of an olefin polymerization catalyst, for example, Ti(OEt)Cl ₃ , Ti(OEt At least one of ₂ Cl ₂ , Ti(OEt) ₃ Cl, Ti(OEt) ₄ and Ti(OBu) ₄ .

According to the present invention, the method of solid-liquid separation of the reaction product of the halloysite magnesium complex with a part of titanium tetrahalide and/or a part of titanium alkoxide may be a variety of existing solid phase and liquid phase. The method of separation, such as suction filtration, pressure filtration or centrifugation, is preferably pressure filtration. The conditions of the press filtration of the present invention are not particularly limited, and the separation of the solid phase and the liquid phase is carried out as fully as possible.

The preparation method of the olefin polymerization catalyst component provided by the present invention preferably further comprises reacting the magnesium complex of the halloysite with a part of titanium tetrahalide and/or a part of titanium alkoxide at -20 ° C to 0 ° C for 0.5- After 2 hours and at 80-130 ° C for 1-4 hours Before, the internal electron donor is added to the reaction system, so that the obtained olefin polymerization catalyst component further contains an internal electron donor compound, thereby improving the catalytic activity of the catalyst and improving the isotacticity and crystallinity of the polyolefin resin. . The specific kind of the internal electron donor compound has been described above in the section on the olefin polymerization catalyst component, and will not be described herein. Further, the amount of the internal electron donor compound may be a conventional choice in the art. For example, the molar ratio of the internal electron donor compound to the magnesium complex of the halloysite may be 0.05-0.6: 1, preferably from 0.1 to 0.4:1.

According to another embodiment of the present invention, when the non-transition metal component is an aluminum-containing compound, the olefin polymerization catalyst component is prepared according to the method comprising the following steps:

(1) reacting halloysite with the first aluminum-containing compound at 0-90 ° C for 1-20 hours to obtain activated halloysite;

(2) reacting the transition metal component with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component which is a metallocene compound in the metallocene catalyst and/or Or a non-metallocene compound in a non-metallocene catalyst;

(3) reacting the activated halloysite with the activated catalyst component at 0-100 ° C for 1-10 hours.

The temperature of the reaction in the step (1) is 0 to 90 ° C, preferably 70 to 90 ° C; and the reaction time is 1 to 20 hours, preferably 4 to 10 hours. The temperature of the reaction in the step (2) is 0 to 90 ° C, preferably 0 to 10 ° C; and the reaction time is 1 to 20 hours, preferably 2 to 4 hours. In the step (3), the temperature of the reaction is 0-100 ° C, preferably 60-90 ° C; the reaction time is 1-10 hours, preferably 4-10 hours.

The amount of each substance in the step (1), the step (2), and the step (3) of the present invention is not particularly limited. For example, in the step (1), the weight ratio of the halloysite to the first aluminum-containing compound may be from 1:0.1 to 20, preferably from 1:0.1 to 10, more preferably from 1:0.5 to 2. In the step (2), the weight ratio of the transition metal component to the second aluminum-containing compound may be from 1:1 to 5,000, preferably from 1:1 to 1000, more preferably from 1:50 to 120. In the step (3), the weight ratio of the activated halloysite to the activated catalyst component may be from 1:0.5 to 50, preferably from 1:1 to 20, more preferably from 1:1 to 5.

The first aluminum-containing compound and the second aluminum-containing compound may each be an aluminum-containing compound conventionally used in an olefin polymerization catalyst, for example, the first aluminum-containing compound and the second aluminum-containing compound are each independently a compound of the formula (OR ') _q R _"3-q of the aluminum-containing compound, wherein, R' and R" are each independently C ₂ -C ₁₀ alkyl is, 0≤q≤3. Specifically, the first aluminum-containing compound and the second aluminum-containing compound are each independently at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, methyl aluminoxane, and the like.

The reaction between the halloysite and the first aluminum-containing compound and the reaction between the transition metal component and the second aluminum-containing compound are preferably carried out in an organic solvent, which enables the reaction to proceed more smoothly. The type of the organic solvent may be any of various existing inert materials which can be used as a reaction medium, for example, may be a C ₅ - C ₁₀ alkane, an aromatic hydrocarbon, a cycloalkane, a C ₂ - C ₁₂ ether, and a tetrahydrofuran. At least one of them is preferably n-hexane, cyclohexane, heptane, decane, ethanol, isobutanol, isooctanol, tetrahydrofuran, methyl ether, diethyl ether, n-propyl ether, diisopropyl ether, n-butyl ether, iso At least one of butyl ether, diisoamyl ether, benzene, toluene, xylene, chlorobenzene, and the like. Further, the organic solvent is usually used in an amount such that the concentration of halloysite may be from 1 to 500 g/L, preferably from 2 to 50 g/L.

Further, the specific kind of the metallocene compound in the metallocene catalyst and the non-metallocene compound in the non-metallocene catalyst have been described in the above section regarding the olefin polymerization catalyst component, and will not be described herein.

According to another embodiment of the present invention, when the non-transition metal component is a mixture of a magnesium-containing compound and an aluminum-containing compound, the olefin polymerization catalyst component is prepared according to the method comprising the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain a catalyst component containing halloysite;

(3) reacting the halloysite-containing catalyst component with the first aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated halloysite-containing catalyst component;

(4) reacting the metallocene compound in the metallocene catalyst and/or the non-metallocene compound in the non-metallocene catalyst with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component;

(5) reacting the activated halloysite-containing catalyst component with the activated catalyst component at 0 to 110 ° C for 1 to 10 hours.

Wherein, the kind and amount of the reaction raw materials involved in the reaction described in the step (1) and the step (2) and the specific reaction conditions are the same as the above-mentioned olefin polymerization catalyst group containing the magnesium compound as the non-transition metal component. The type and amount of the reaction raw materials involved in the steps (1) and (2) in the preparation method of the fraction are the same as the specific reaction conditions, and are not described herein.

The temperature of the reaction in the step (3) is from 0 to 90 ° C, preferably from 70 to 90 ° C; and the reaction time is from 1 to 20 hours, preferably from 4 to 10 hours. The temperature of the reaction in the step (4) is 0 to 90 ° C, preferably 0 to 20 ° C; and the reaction time is 1 to 20 hours, preferably 2 to 6 hours. The temperature of the reaction in the step (5) is from 0 to 110 ° C, preferably from 80 to 100 ° C; and the reaction time is from 1 to 10 hours, preferably from 2 to 6 hours.

The first aluminum-containing compound and the second aluminum-containing compound may each be an aluminum-containing compound conventionally used in an olefin polymerization catalyst, for example, the first aluminum-containing compound and the second aluminum-containing compound are each independently a compound of the formula (OR ') _q R _"3-q of the aluminum-containing compound, wherein, R' and R" are each independently C ₂ -C ₁₀ alkyl is, 0≤q≤3. Specifically, the first aluminum-containing compound and the second aluminum-containing compound are each independently at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, methyl aluminoxane, and the like.

The reaction described in the step (3) and the step (4) is preferably carried out in an organic solvent, which enables the reaction to proceed more smoothly. The type of the organic solvent may be any of various existing inert materials which can be used as a reaction medium, for example, may be a C ₅ - C ₁₀ alkane, an aromatic hydrocarbon, a cycloalkane, a C ₂ - C ₁₂ ether, and a tetrahydrofuran. At least one of them is preferably n-hexane, cyclohexane, heptane, decane, ethanol, isobutanol, isooctanol, tetrahydrofuran, methyl ether, diethyl ether, n-propyl ether, diisopropyl ether, n-butyl ether, iso At least one of butyl ether, diisoamyl ether, benzene, toluene, xylene, chlorobenzene, and the like. In addition, the amount of the organic solvent used can be generally selected in the art and will not be described herein.

In the step (3), the weight ratio of the halloysite-containing catalyst component to the first aluminum-containing compound may be from 1:0.1 to 20, preferably from 1:0.5 to 1.5. In the step (4), the weight ratio of the total amount of the metallocene compound and the nonmetallocene compound to the amount of the second aluminum-containing compound may be from 1:1 to 1000, preferably from 1:30 to 60. In the step (5), the weight ratio of the activated catalyst component to the activated halloysite-containing catalyst component may be from 1:0.1 to 20, preferably from 1:0.5 to 2.

Further, the specific kind of the metallocene compound in the metallocene catalyst and the non-metallocene compound in the non-metallocene catalyst have been described above in the section on the olefin polymerization catalyst component, and will not be described herein.

The type of the co-catalyst is not particularly limited in the present invention, and may be a conventional Ziegler-Natta catalyst capable of forming a Tiegler-Natta catalyst with titanium tetrahalide and/or titanium alkoxide, capable of forming a metallocene catalyst with a metallocene compound or capable of The substance constituting the non-metallocene catalyst with the non-metallocene compound may be, for example, an aluminum alkyl and/or an aluminum alkoxide, and specifically may be trimethyl aluminum, triethyl aluminum or triiso At least one of butyl aluminum, methyl aluminoxane, and the like. Further, the molar ratio of the aluminum element in the cocatalyst to the transition metal element in the olefin polymerization catalyst component may be from 1 to 5000:1, preferably from 10 to 2000:1.

The amount of the olefin polymerization catalyst component to be used in the present invention is not particularly limited. For example, the olefin polymerization catalyst component may be used in an amount such that the content of halloysite in the obtained polyolefin resin is 0.0001 to 25% by weight, preferably. It is 0.001 to 10% by weight. It should be noted that when the halloysite is metamorphic halloysite and/or organically modified halloysite, the above content of halloysite refers to the content of halloysite and/or organically modified halloysite.

The main improvement of the preparation method of the polyolefin resin composition provided by the present invention is that a new ocene polymerization catalyst containing halloysite is used, and the kind of the olefin monomer and the specific reaction conditions can be in the art. Regular selection.

Specifically, the olefin monomer may be ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-octene, isoprene, divinylbenzene, or the like. At least one of them. The polyolefin resin may be an olefin homopolymer or an olefin copolymer. When the polyolefin resin is an olefin copolymer, the content of the comonomer in the olefin monomer may be a conventional choice in the art and will not be described herein.

The conditions of the polymerization reaction in the present invention are not particularly limited, and generally include a polymerization temperature of 30 to 90 ° C, preferably 40 to 80 ° C; a polymerization pressure of 1-10 atmospheres, preferably 1 to 7 atmospheres; The polymerization time may be from 0.05 to 10 hours, preferably from 0.05 to 2 hours. In the present invention, the polymerization pressure refers to gauge pressure. Further, the polymerization reaction may be a slurry polymerization reaction or a bulk polymerization reaction. When the polymerization is a slurry polymerization, the polymerization should also be carried out in the presence of an organic solvent. The organic solvent may be a C ₅ -C ₁₀ alkane or a C ₆ -C ₈ aromatic hydrocarbon, wherein the C ₅ -C ₁₀ alkane is preferably at least one of heptane, n-hexane and cyclohexane. The C ₆ -C ₈ aromatic hydrocarbon is preferably toluene. In addition, the amount of the organic solvent used may be a conventional choice in the art and will not be described herein.

According to the method for producing a polyolefin resin composition provided by the present invention, the polymerization reaction can also be carried out in the presence of an external electron donor compound. The kind of the external electron donor compound may be a conventional choice in the art, and for example, may be a compound of the formula R ¹ ' _4-d Si(R ² ') _d wherein R ¹ ' and R ² ' are each Independently an alkyl group, a cycloalkyl group or an aryl group, 1 ≤ d ≤ 3. Specifically, examples of the external electron donor compound include, but are not limited to, dimethyldimethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, diphenyldimethoxysilane, At least one of diphenyldiethoxysilane and methylcyclohexenedimethoxysilane. Further, the molar ratio of the external electron donor compound to the aluminum element in the cocatalyst may be from 0.001 to 1 :1, preferably from 0.01 to 1:1, more preferably from 0.05 to 0.5:1.

The second preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain an olefin polymerization catalyst component;

(3) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.

Among them, the kind and amount of the reaction raw materials involved in each step and the reaction conditions have been described above, and will not be described herein.

The third preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with the first aluminum-containing compound at 0-90 ° C for 1-20 hours to obtain activated halloysite;

(2) reacting the transition metal component with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component which is a metallocene compound in the metallocene catalyst and/or Or a non-metallocene compound in a non-metallocene catalyst;

(3) reacting the activated halloysite with the activated catalyst component at 0-100 ° C for 1-10 hours to obtain an olefin polymerization catalyst component;

(4) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.

Among them, the kind and amount of the reaction raw materials involved in each step and the reaction conditions have been described above, and will not be described herein.

The fourth preparation method of the polyolefin resin composition provided by the present invention comprises the following steps:

(1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

(2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain a catalyst component containing halloysite;

(3) reacting the halloysite-containing catalyst component with the first aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated halloysite-containing catalyst component;

(4) reacting the metallocene compound in the metallocene catalyst and/or the non-metallocene compound in the non-metallocene catalyst with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component;

(5) reacting the activated halloysite-containing catalyst component with the activated catalyst component at 0 to 110 ° C for 1 to 10 hours to obtain an olefin polymerization catalyst component;

(6) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.

Among them, the kind and amount of the reaction raw materials involved in each step and the reaction conditions have been described above, and will not be described herein.

Further, the present invention provides a polyolefin resin composition prepared by the above method.

The invention will be described in detail below by way of examples.

In the following examples and comparative examples:

The content of the transition metal element in the olefin polymerization catalyst component is determined by ultraviolet spectrophotometry.

The content of magnesium element in the olefin polymerization catalyst component is determined by titration method, as follows: 50 mg of the catalyst is taken, and the catalyst is dissolved in 10 mL of sulfuric acid solution under nitrogen protection, heated to boiling for 10 minutes, and then filtered to remove insoluble matter, followed by filtration. The titration was carried out with EDTA at a concentration of 0.01 mol·L ^-1 . The chrome black T was used as an indicator during the titration. When the color of the catalyst-containing solution turned blue-violet, it was the end point of the titration, and the amount of EDTA in the whole titration process was counted. In the case of V (mL), the content of the magnesium element = (0.01 × V ÷ 10) × 24.3 ÷ (50 × 10 ^-3 ).

The content of aluminum in the olefin catalyst component is determined by titration, as follows: 5 mL of the above test solution is taken in a 250 mL Erlenmeyer flask, and 20 mL of EDTA standard solution is accurately added, 1-2 drops of xylenol orange, and 8 mol is added dropwise. /L NH ₃ ·H ₂ O, the solution just turns red, then add 3mol/L HCl solution to make the solution yellow, then heat it on the electric stove for 10min, cool it to room temperature with running water, add 200g/L six times. 10 mL of methyltetramine solution was adjusted with 3 mol/L HCl solution to make the solution yellow, and the pH was controlled to 4-5. Add 1 drop of xylenol orange indicator, and titrate the solution with Zn standard solution to become orange, which is the end point. The content of aluminum is: (C _EDTA V _EDTA - C _Zn V _Zn ) × 0.53963.

The content of titanium and zirconium in the olefin polymerization catalyst component is measured by a spectrophotometer, as follows: taking 50 mg of the catalyst, dissolving the catalyst in 10 mL of sulfuric acid solution under nitrogen protection, heating to boiling for 10 minutes, and then filtering to remove insoluble Then, the absorbance of the solution at a fixed wavelength (measured by titanium at 410 nm, zirconium at 666 nm) is measured by a spectrophotometer, and titanium or zirconium is obtained by comparison with the absorbance of the standard curve at 410 nm or 666 nm. The concentration of the element, and further the content of titanium or zirconium element in the olefin polymerization catalyst.

The content of halloysite in the olefin polymerization catalyst and the polyolefin resin composition was measured by a thermogravimetric analysis method.

Example 1

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 4.0 g of anhydrous magnesium chloride MgCl ₂ and 13.0 mL of isooctanol were dispersed in 90 mL of decane, and heated to 130 ° C to form a transparent solution, which was reacted at 130 ° C for 1.0 hour to obtain a magnesium chloride alcoholate. Then, the above magnesium chloride alkoxide was added dropwise to a suspension of 1.0 g of halloysite and 20 mL of decane, and the mixture was reacted at 60 ° C for 4.0 hours under constant temperature to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite described in the step 1 was dropwise added to 200 mL of titanium tetrachloride at -20 ° C for 1 hour, and then reacted at -20 ° C for 1.0 hour under constant temperature. Then slowly warming to 120 ° C, adding 0.2 mL of diisobutyl phthalate (the molar ratio of magnesium to the magnesium complex of diisobutyl phthalate and halloysite is 0.15:1), after which The reaction was carried out at 120 ° C for 1.5 hours under constant temperature. After completion of the reaction, the liquid was filtered off, 240 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours. Finally, it was washed 5 times with hexane, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C1. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C1 was 18.0%, the mass percentage of the transition metal element Ti was 1.68%, and the mass percentage of the metal element magnesium was 12%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 600 ° C for 4 hours to obtain 8.1 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

In a vacuum state, the gaseous propylene monomer was charged into the reaction vessel, and then 50 mL of hexane, 3 mL of a heptane solution containing 5.5 mmol of triethylaluminum, and G of 0.55 mmol of diphenyldimethoxysilane were sequentially added. 3mL of the alkane solution and 20mg of the olefin polymerization catalyst component C1, and the pressure in the reaction vessel is controlled at 5.0 atmospheres, the reaction temperature is controlled at 60 ° C, and the polymerization reaction is carried out for 0.5 hours. After the completion of the polymerization, the acidification is added to terminate the polymerization reaction, and then respectively, respectively. The mixture was washed three times with deionized water and ethanol, and finally vacuum dried at 60 ° C to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.02% by weight.

2 propylene copolymerization:

In a vacuum state, a mixed gas of propylene and ethylene (molar ratio of propylene to ethylene of 95 _: 5) was charged into the reaction vessel, and then 100 mL of hexane, 1 mL of heptane containing 1.8 mmol of triethylaluminum, and the like were sequentially added. 0.1 mmol of dimethyldiphenylsilane in heptane solution and 20 mg of olefin polymerization catalyst component C1, and the pressure in the reactor was controlled at 5 atm, the temperature was controlled at 60 ° C, and the polymerization was carried out for 1.0 hour. Thereafter, the polymerization reaction was terminated by adding acidified ethanol, and then washed three times with deionized water and ethanol, respectively, and finally vacuum dried at 60 ° C to obtain a copolymerized polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.016% by weight.

Comparative example 1

This comparative example is used to explain the reference olefin polymerization catalyst component, a process for preparing the same, and a polyolefin resin composition and a process for the preparation thereof.

The olefin polymerization catalyst component and the polyolefin resin composition were prepared in the same manner as in Example 1, except that the halloysite in the comparative example was not added during the preparation of the olefin polymerization catalyst component, but directly and obtained. Polypropylene resin and copolymerized polypropylene resin are blended, the specific steps are as follows:

(1) Preparation method of olefin polymerization catalyst component:

1 4.0 g of anhydrous magnesium chloride MgCl ₂ and 13.0 mL of isooctanol were dispersed in 90 mL of decane, and heated to 130 ° C to form a transparent solution, which was reacted at 130 ° C for 1.0 hour to obtain a magnesium chloride alcoholate. Then, the above magnesium chloride alkoxide was added dropwise to a suspension of 20 mL of decane, and the mixture was reacted at 60 ° C for 4.0 hours under constant temperature to obtain a magnesium complex.

2 The magnesium complex described in the step 1 was dropwise added to 200 mL of titanium tetrachloride at -20 ° C for 1 hour, and then reacted at -20 ° C for 1.0 hour. Then slowly warming to 120 ° C, adding 0.2 mL of diisobutyl phthalate (the molar ratio of magnesium to the magnesium complex of diisobutyl phthalate and halloysite is 0.15:1), after which The reaction was carried out at 120 ° C for 1.5 hours under constant temperature. After completion of the reaction, the liquid was filtered off, 240 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours. Finally, it was washed 5 times with hexane, and after drying, a reference olefin polymerization catalyst component was obtained, which was designated as DC1. It was found that the mass percentage of the transition metal element Ti in the reference olefin polymerization catalyst component DC1 was 2.33%, and the mass percentage of the metal element magnesium was 18%.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

In a vacuum state, the gaseous propylene monomer was charged into the reaction vessel, and then 50 mL of hexane, 3 mL of a heptane solution containing 5.5 mmol of triethylaluminum, and G of 0.55 mmol of diphenyldimethoxysilane were sequentially added. 3 mL of the alkane solution and 20 mg of the reference olefin polymerization catalyst component DC1, and the pressure in the reaction vessel was controlled at 5.0 atmospheres, the reaction temperature was controlled at 60 ° C, the polymerization reaction was carried out for 0.5 hours, and the polymerization was terminated by adding acidified ethanol after the completion of the polymerization. Then, it was washed three times with deionized water and ethanol, respectively, and finally vacuum dried at 60 ° C to obtain a homopolypropylene resin. Then, the above homopolypropylene resin was uniformly mixed with 1.0 g of halloysite to obtain a homopolypropylene resin composition of halloysite. The content of halloysite in the halloysite-containing homopolypropylene resin composition was found to be 5.0% by weight.

2 propylene copolymerization:

In a vacuum state, a mixture of propylene and ethylene (molar ratio of propylene to ethylene of 95:5) is charged into the reaction vessel, and then Add 100 mL of hexane, 1 mL of heptane containing 1.8 mmol of triethylaluminum, 1 mL of heptane solution containing 0.1 mmol of dimethyldiphenylsilane, and 20 mg of the reference olefin polymerization catalyst component DC1, and the reaction kettle The pressure inside was controlled at 5 atmospheres, the temperature was controlled at 60 ° C, and the polymerization was carried out for 1.0 hour. After the completion of the polymerization, the acidification was terminated by adding acidified ethanol, and then washed with deionized water and ethanol three times, respectively, and finally dried at 60 ° C under vacuum. , a copolymerized polypropylene resin was obtained. Then, the above copolymer polypropylene resin was uniformly mixed with 1.0 g of halloysite to obtain a copolymerized polypropylene resin composition of halloysite. The content of halloysite in the halloysite-containing copolymerized polypropylene resin composition was found to be 4.5% by weight.

Comparative example 2

This comparative example is used to explain the reference olefin polymerization catalyst component, a process for preparing the same, and a polyolefin resin composition and a process for the preparation thereof.

The olefin polymerization catalyst component and the polyolefin resin composition were prepared according to the method of Example 1, except that no halloysite was added during the preparation of the olefin polymerization catalyst component and during the preparation of the polyolefin resin composition. A homopolypropylene resin composition containing no halloysite and a copolymerized polypropylene resin composition containing no halloysite were obtained.

Example 2

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.0 g of anhydrous magnesium chloride MgCl ₂ and 12.5 mL of ethanol were dispersed in 50 mL of decane, and heated to 110 ° C to form a transparent solution, which was reacted at 110 ° C for 2.0 hours to obtain a magnesium chloride alcoholate. Then, the magnesium chloride alcoholate was added dropwise to a suspension of 1.0 g of halloysite and 50 mL of decane, and reacted at 110 ° C for 4.0 hours under constant temperature to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite described in the step 1 was dropwise added to 120 mL of titanium tetrachloride at -20 ° C for 1 hour, and then reacted at -20 ° C for 1.0 hour. Then slowly warming to 120 ° C, adding 2.0 grams of 9,9-bis(methoxymethyl) fluorene (the magnesium complex of the 9,9-bis(methoxymethyl) fluorene and halloysite magnesium complex The molar ratio was 0.10:1), followed by constant temperature reaction at 120 ° C for 1.5 hours. After completion of the reaction, the liquid was filtered off, 150 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours under constant temperature. Finally, it was washed 5 times with hexane, and after drying, a component containing a halloysite olefin polymerization catalyst was obtained, which was designated as C2. It has been found that the mass percentage of halloysite in the olefin polymerization catalyst component C2 is 26%, the mass percentage of the transition metal element Ti is 2.82%, and the mass percentage of the metal element magnesium is 12.5%, 9, The mass percentage of 9-bis(methoxymethyl)anthracene was 10.2%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

In a vacuum state, 450 g of liquid propylene was charged into the reaction vessel, and then 0.25 mol of triethylaluminum, 0.005 g of hydrogen, and 35 mg of the olefin polymerization catalyst component C2 were sequentially added, and the pressure in the autoclave was controlled at 5.0 atm. The temperature is controlled at 70 ° C, The polymerization reaction was carried out for 1.0 hour. After the completion of the polymerization, the gas in the reaction vessel was vented and discharged to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was measured to be 0.0046% by weight.

2 propylene copolymerization:

In a vacuum, a mixture of propylene and ethylene (molar ratio of propylene to ethylene of 99:1) was charged into the reaction vessel, and then 100 mL of hexane and 45 mg of the olefin polymerization catalyst component C2 were sequentially added, and the reaction kettle was placed. The pressure inside is controlled at 6.0 atmospheres, the temperature is controlled at 50 ° C, and the polymerization is carried out for 1.0 hour. After the polymerization is completed, acidification is added to terminate the polymerization reaction, and then washed with deionized water and ethanol three times, respectively, and finally dried at 60 ° C under vacuum. A copolymerized polypropylene resin composition was obtained. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.18% by weight.

Example 3

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.0 g of anhydrous magnesium chloride MgCl ₂ and 2.8 mL of isooctanol were dispersed in 50 mL of decane, and heated to 130 ° C to form a transparent solution, which was reacted at 130 ° C for 4.0 hours to obtain a magnesium chloride alcoholate. Then, the above magnesium chloride alkoxide was added dropwise to a suspension of 0.5 g of halloysite and 10 mL of decane, and the mixture was reacted at 60 ° C for 10.0 hours under constant temperature to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite described in the step 1 was dropwise added to 125 mL of titanium tetrachloride at -10 ° C for 2 hours, and then reacted at -10 ° C for 1.0 hour. Then, the temperature was slowly raised to 120 ° C, and 0.1 mL of ethyl benzoate (the molar ratio of magnesium to the magnesium complex of ethyl benzoate and halloysite was 0.20:1) was added, followed by constant temperature reaction at 120 ° C for 2.0 hours. After the reaction was completed, the liquid was filtered off, 120 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours under constant temperature. Finally, it was washed 5 times with hexane, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C3. It has been found that the mass percentage of halloysite in the olefin polymerization catalyst component C3 is 12%, the mass percentage of the transition metal element Ti is 2%, and the mass percentage of the metal element magnesium is 18%, benzoic acid. The ethyl ester has a mass percentage of 5%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 300 ° C for 4 hours to obtain 8.3 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C3 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was measured to be 0.016% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C3 to obtain a copolymerized polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was determined to be 0.20% by weight.

Example 4

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 1.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 mL of isooctanol were dispersed in 20 mL of decane, and heated to 110 ° C to form a transparent solution, which was reacted at 110 ° C for 6.0 hours to obtain an alcoholate of magnesium chloride. Then, the above-mentioned magnesium chloride alcoholate was added dropwise to a suspension of 1.5 g of halloysite and 100 mL of decane, and the mixture was reacted at 90 ° C for 10.0 hours under constant temperature to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite described in the step 1 was dropwise added to 50 mL of titanium tetrachloride at -20 ° C for 1 hour, and then reacted at -20 ° C for 1.0 hour. Then, the temperature was slowly raised to 110 ° C, and then the reaction was kept at 110 ° C for 2.0 hours. After the completion of the reaction, the liquid was filtered off, and 60 mL of titanium tetrachloride was again added thereto, and the reaction was carried out at 120 ° C for 2.0 hours under constant temperature. Finally, it was washed 5 times with hexane, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C4. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C4 was 49%, the mass percentage of the transition metal element Ti was 2.56%, and the mass percentage of the metal element magnesium was 5.8%.

Wherein, the halloysite used in the step 1 is halloysite modified with γ-methacryloxypropyltrimethoxysilane, which is prepared according to the following method:

10 g of halloysite was dispersed in 500 mL of ethanol to form a suspension, and 12 g of γ-methacryloxypropyltrimethoxysilane was added to the suspension, and reacted at 80 ° C for 4.0 hours, followed by filtration, using ethanol. It was washed three times and further dried under vacuum at 80 ° C for 20.0 hours to obtain halloysite modified with γ-methacryloxypropyltrimethoxysilane.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C4 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.020% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C4 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was found to be 0.12% by weight.

Example 5

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 mL of isooctanol were dispersed in 50 mL of decane, and heated to 130 ° C to form a transparent solution, which was reacted at 130 ° C for 4.0 hours to obtain the magnesium chloride alcoholate. Then, the above magnesium chloride alcoholate was added dropwise to a suspension of 3.0 g of halloysite and 100 mL of decane, and the mixture was reacted at 60 ° C for 20.0 hours under constant temperature to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite described in the step 1 was dropwise added to 100 mL of titanium tetrachloride at -20 ° C for 1 hour, and then reacted at -20 ° C for 1.0 hour under constant temperature. Then slowly warming to 60 ° C, adding 0.1 g of 9,9-bis(methoxymethyl) fluorene (the magnesium complex of the 9,9-bis(methoxymethyl) fluorene and halloysite magnesium complex The molar ratio was 0.05:1), and then the temperature was gradually raised to 120 ° C, and the reaction was carried out at a constant temperature for 1.5 hours. After the completion of the reaction, the liquid was filtered off, 120 mL of titanium tetrachloride was further added, and the reaction was carried out at 120 ° C for 2.0 hours under constant temperature. Finally, it was washed 5 times with hexane, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C5. It has been found that the mass percentage of halloysite in the olefin polymerization catalyst component C5 is 50%, the mass percentage of the transition metal element Ti is 1.5%, and the mass percentage of the metal element magnesium is 10%, 9, The mass percentage of 9-bis(methoxymethyl)anthracene was 2.0%.

Among them, the halloysite used in the step 1 is halloysite modified with γ-aminopropyltriethoxysilane, which is prepared according to the following method:

10 g of halloysite was dispersed in 500 mL of ethanol to form a suspension, and 5 g of γ-aminopropyltriethoxysilane was added to the suspension, which was reacted at 80 ° C for 4.0 hours, filtered, and washed three times with ethanol, and then It was dried under vacuum at 80 ° C for 20.0 hours to obtain halloysite modified with γ-aminopropyltriethoxysilane.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C5 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.009% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C5 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was determined to be 0.20% by weight.

Example 6

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 Disperse 10.0 g of halloysite in 100 mL of tetrahydrofuran to obtain a suspension of halloysite. Then, 50 mL of a tetrahydrofuran solution containing 0.10 mol of C ₄ H ₉ MgCl was added dropwise to the suspension of the above halloysite, and the reaction was refluxed at 80 ° C for 20.0 hours. After the reaction was completed, it was washed 5 times with tetrahydrofuran, and dried to obtain halloysite. Magnesium complex.

2 5.0 g of the magnesium complex of the halloysite was dispersed in 10 mL of titanium tetrachloride at 20 ° C, and the mixture was heated to 120 ° C for 2.0 hours. After the reaction was completed, it was filtered, washed with hexane 5 times, and dried to obtain The olefin polymerization catalyst component is designated as C6. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C6 was 60%, the mass percentage of the transition metal element Ti was 1.10%, and the mass percentage of the metal element magnesium was 3.50%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 600 ° C for 4 hours to obtain 8.1 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C6 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.011% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C6 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.18% by weight.

Example 7

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 Disperse 10.0 g of halloysite in 50 mL of diethyl ether to obtain a suspension of halloysite. Then, a solution of 0.05 mol of C ₄ H ₉ MgBr in 50 mL of diethyl ether was added dropwise to the suspension of the above halloysite, and the reaction was refluxed at 40 ° C for 20.0 hours under constant temperature. After the reaction was completed, it was washed 5 times with diethyl ether to obtain halloysite after drying. Magnesium complex.

2 Take 5.0 g of the magnesium complex of the halloysite dispersed in 20 mL of titanium tetrachloride at 20 ° C, and slowly raise the temperature to 80 ° C for 2.0 hours. After the reaction is completed, filter, wash with hexane 5 times, and obtain after drying. A component comprising an halloysite olefin polymerization catalyst, designated C7. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C7 was 65%, the mass percentage of the transition metal element Ti was 1.20%, and the mass percentage of the metal element magnesium was 3.60%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 600 ° C for 4 hours to obtain 8.1 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C7 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.011% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 1, except that the olefin polymerization catalyst component C1 was replaced with the same weight part of the olefin polymerization catalyst component C7 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was found to be 0.12% by weight.

Example 8

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.5 g of halloysite was dispersed in 50 mL of n-butyl ether to obtain a suspension of halloysite. Then, 50 mL of n-butyl ether solution containing 0.05 mol of C ₄ H ₉ MgBr was added dropwise to the suspension of the above halloysite, and the reaction was refluxed at 40 ° C for 20.0 hours under constant temperature. After the reaction was completed, it was washed 5 times with n-butyl ether, and dried. A magnesium complex of halloysite is obtained.

2 Take 5.0 g of the magnesium complex of the halloysite disperse in 40 mL of titanium tetrachloride at 20 ° C, and heat up to 120 ° C for 2.0 hours. After the reaction is completed, filter, wash with hexane 5 times, and obtain olefin after drying. The catalyst component was polymerized and designated as C8. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C8 was 58%, the mass percentage of the transition metal element Ti was 1.36%, and the mass percentage of the metal element magnesium was 3.18%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 600 ° C for 4 hours to obtain 8.1 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The gaseous propylene monomer was charged into the reaction vessel under vacuum, and then 100 mL of heptane, 5.5 mmol of triethylaluminum, 0.55 mmol of methyltrimethoxysilane, and 30 mg of the olefin polymerization catalyst component C8 were sequentially added, and The pressure in the reactor was controlled at 7.0 atmospheres, the reaction temperature was controlled at 60 ° C, and the polymerization was carried out for 0.5 hours. After the completion of the polymerization, the acidification was terminated by adding acidified ethanol, and then washed three times with deionized water and ethanol, respectively, and finally at 60 ° C. Vacuum drying gave a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.068% by weight.

2 propylene copolymerization:

In a vacuum, a mixture of propylene and ethylene (molar ratio of propylene to ethylene of 100:1) was charged into the reaction vessel, and then 100 mL of hexane, 1.8 mmol of triethylaluminum, and 0.18 mmol of dimethyldiphenyl were sequentially added. Base silane and 20 mg of olefin polymerization catalyst component C8, and control the pressure in the reactor at 5.0 atmospheres, the temperature is controlled at 60 ° C, and the polymerization reaction is 1.0 hour. After the polymerization is completed, acidified ethanol is added to terminate the polymerization reaction, and then used separately. Deionized water and ethanol were each washed three times, and finally vacuum dried at 60 ° C to obtain a copolymerized polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was determined to be 0.061% by weight.

Example 9

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 5.0 g of halloysite was dispersed in 50 mL of diethyl ether to obtain a suspension of halloysite. Then, a solution of 0.20 mol of C ₃ H ₇ Mgl in 50 mL of diethyl ether was added dropwise to the diethyl ether suspension of the above halloysite, and the reaction was refluxed at 40 ° C for 48.0 hours under constant temperature. After the reaction was completed, it was washed 5 times with diethyl ether, and dried to obtain Elo. Stone magnesium complex.

2 Disperse 5.0 g of the magnesium complex of the halloysite in 100 mL of titanium tetrachloride at 0 ° C, and raise the temperature to 120 ° C to react 2.0 times. At the time of completion of the reaction, it was filtered, and washed with hexane five times. After drying, an olefin polymerization catalyst component was obtained, which was designated as C9. It was found that the mass percentage of halloysite in the olefin polymerization catalyst component C9 was 62%, the mass percentage of the transition metal element Ti was 0.98%, and the mass percentage of the metal element magnesium was 3.50%.

Wherein, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 600 ° C for 12 hours to obtain 8.05 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 8, except that the olefin polymerization catalyst component C8 was replaced with the same weight part of the olefin polymerization catalyst component C9 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.008% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 8, except that the olefin polymerization catalyst component C8 was replaced with the same weight part of the olefin polymerization catalyst component C9 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was found to be 0.09% by weight.

Example 10

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 5.0 g of halloysite was dispersed in 50 mL of toluene to obtain a suspension of halloysite. Then, 30 mL of a toluene solution containing 0.05 mol of methylaluminoxane was added dropwise to the suspension of the above halloysite, and the reaction was carried out at 90 ° C for 10.0 hours, and then washed with toluene 5 times, and dried to obtain an aluminum complex of halloysite. .

2 0.05 g of the transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 40 mL of a toluene solution containing 0.1 mol of methylaluminoxane at 0 ° C, and reacted at 0 ° C for 2.0 hours, and then added dropwise with 5.0 g of halloysite. The aluminum complex was reacted in 50 mL of a toluene suspension at 60 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C10. The mass percentage of halloysite in the olefin polymerization catalyst component C10 was 70%, the mass percentage of the zirconium element was 0.08%, and the mass percentage of the aluminum element was 9.87%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 ethylene homopolymerization:

The ethylene monomer was charged into the reaction vessel under vacuum, and then 100 ml of toluene, 1.6 mL of a toluene solution containing 0.8 mmol of methylaluminoxane and 20 mg of an olefin polymerization catalyst component C10 were successively added, and the pressure in the reaction vessel was measured. Controlled at 5.0 atmospheres, the reaction temperature is controlled at 50 ° C, polymerization is 1.0 hour, after the completion of the polymerization, acidification of ethanol is added to terminate the polymerization, and then deionized separately. Water and ethanol were each washed three times, and finally vacuum dried at 60 ° C to obtain a homopolyethylene resin composition. The content of halloysite in the homopolyethylene resin composition was measured to be 0.14% by weight.

2 propylene copolymerization:

In a vacuum state, a mixture of propylene and ethylene (molar ratio of propylene to ethylene of 95:5) was charged into the reaction vessel, and then 100 mL of toluene, a toluene solution containing 2.1 mmol of methylaluminoxane, 3.0 mL, and 30 were sequentially added. Mg of olefin polymerization catalyst C10, and the pressure in the reactor was controlled at 5.0 atmospheres, the temperature was controlled at 50 ° C, and the polymerization was carried out for 0.5 hours. After the completion of the polymerization, acidification was added to terminate the polymerization, and then each was washed with deionized water and ethanol. Three times, finally, it was vacuum dried at 60 ° C to obtain a copolymerized polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.13% by weight.

Comparative example 3

This comparative example is used to explain the reference olefin polymerization catalyst component, a process for preparing the same, and a polyolefin resin composition and a process for the preparation thereof.

The olefin polymerization catalyst component and the polyolefin resin composition were prepared in the same manner as in Example 10 except that no halloysite was added during the preparation of the olefin polymerization catalyst component and during the preparation of the polyolefin resin composition. A homopolypropylene resin composition containing no halloysite and a copolymerized polypropylene resin composition containing no halloysite were obtained.

Example 11

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.5 g of halloysite was dispersed in 50 mL of toluene to obtain a suspension of halloysite. Then, 40 mL of a toluene solution containing 0.10 mol of methylaluminoxane was added dropwise to the suspension of the above halloysite, and reacted at 90 ° C for 10.0 hours, and then washed with toluene 5 times, and dried to obtain an aluminum complex of halloysite. .

2 0.10 g of transition metal compound rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl ₂ (where rac- represents racemic, the same below) was added to 0 ° C of toluene containing 0.2 mol of methylaluminoxane The solution was reacted at 40 ° C for 4.0 hours in 40 mL of a solution, and then added dropwise to 50 mL of a toluene suspension containing an aluminum complex of 5.0 g of halloysite, and reacted at 60 ° C for 10.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, an halloysite-containing olefin polymerization catalyst component was obtained, which was designated as C11. The mass percentage of halloysite in the olefin polymerization catalyst component C11 was determined to be 64%, the mass percentage of the zirconium element was 0.46%, and the mass percentage of the aluminum element was 7.80%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin:

1 ethylene homopolymerization:

The ethylene homopolymerization reaction was carried out in the same manner as in Example 10 except that the olefin polymerization catalyst component C10 was replaced with the same weight part of the olefin polymerization catalyst component C11 to obtain a homopolyethylene resin composition. Tested in a homopolyethylene resin composition The content of halloysite is 0.12% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 10 except that the olefin polymerization catalyst component C10 was replaced with the same weight part of the olefin polymerization catalyst component C11 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.10% by weight.

Example 12

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 3.0 g of halloysite was dispersed in 30 mL of toluene to obtain a suspension of halloysite. Then, 30 mL of a toluene solution containing 0.1 mol of methylaluminoxane was added dropwise to the suspension of the above halloysite, and reacted at 90 ° C for 5.0 hours, and then washed with toluene 5 times, and dried to obtain an aluminum complex of halloysite. .

2 0.15 g of the transition metal compound Me ₂ C(Cp)(Flu)ZrCl _{2 was} added to 40 mL of a toluene solution containing 0.25 mol of methylaluminoxane at 0 ° C, reacted at 0 ° C for 4.0 hours, and then added dropwise containing 5.0 g. The toluene suspension of the aluminum complex of halloysite was reacted at 50 ° C for 4.0 hours in 50 mL of a toluene suspension. After completion of the reaction, it was washed 5 times with toluene, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C12. The mass percentage of halloysite in the olefin polymerization catalyst component C12 was 62%, the mass percentage of the zirconium element was 0.22%, and the mass percentage of the aluminum element was 9.12%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

In a vacuum state, the gaseous propylene monomer was charged into the reaction vessel, and then 100 mL of toluene, 3.0 mL of a toluene solution containing 3.2 mmol of methylaluminoxane, and 30 mg of an olefin polymerization catalyst component C12 were sequentially added, and the reaction vessel was placed in the reaction vessel. The pressure is controlled at 3.0 atmospheres, the reaction temperature is controlled at 50 ° C, and the polymerization reaction is carried out for 0.1 hour. After the completion of the polymerization, the polymerization reaction is terminated by adding acidified ethanol, and then washed three times with deionized water and ethanol, respectively, and finally dried at 60 ° C under vacuum. A homopolypropylene resin composition was obtained. The content of halloysite in the homopolypropylene resin composition was found to be 0.66% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 10 except that the olefin polymerization catalyst component C10 was replaced with the same weight part of the olefin polymerization catalyst component C12 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was found to be 0.22% by weight.

Example 13

This embodiment is for explaining the olefin polymerization catalyst component provided by the present invention, a preparation method thereof, and a polyolefin resin composition and the same Preparation.

(1) Preparation method of olefin polymerization catalyst component:

1 5.0 g of halloysite was dispersed in 50 mL of toluene to obtain a suspension of halloysite. Then, 30 mL of a toluene solution containing 0.1 mol of methylaluminoxane was added dropwise to the suspension of the above halloysite, and reacted at 90 ° C for 4.0 hours, and then washed with toluene 5 times, and dried to obtain an aluminum complex of halloysite. .

2 0.2 g of the transition metal compound bis[N-(3-tert-butylsalilinyl)anilino]zirconium dichloride was added to 40 mL of a toluene solution containing 0.20 mol of methylaluminoxane at 0 ° C at 0 ° C. The reaction was carried out for 4.0 hours, and then added dropwise to 50 mL of a toluene suspension containing an aluminum complex of 5.0 g of halloysite, and reacted at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C13. It was examined that the mass percentage of halloysite in the olefin polymerization catalyst component C13 was 65%, the mass percentage of zirconium element was 0.5%, and the mass percentage of aluminum element was 8.5%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 ethylene homopolymerization:

The ethylene homopolymerization reaction was carried out in the same manner as in Example 10 except that the olefin polymerization catalyst component C10 was replaced with the same weight part of the olefin polymerization catalyst component C13 to obtain a homopolyethylene resin composition. The content of halloysite in the homopolyethylene resin composition was measured to be 0.11% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 10 except that the olefin polymerization catalyst component C10 was replaced with the same weight part of the olefin polymerization catalyst component C13 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was found to be 0.09% by weight.

Example 14

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 mL of isooctanol were dispersed in 20 mL of decane, and heated to 110 ° C to form a transparent solution, which was reacted at 110 ° C for 4.0 hours to obtain a magnesium chloride alcoholate. Then, the above magnesium chloride alkoxide was added dropwise to a suspension of 3.0 g of halloysite and 100 mL of decane, and the mixture was reacted at 90 ° C for 12.0 hours to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite in step 1 was added dropwise to 60 mL of titanium tetrachloride at -20 ° C for 2 hours, followed by constant temperature reaction at -20 ° C for 1.0 hour. Slowly warming to 110 ° C, adding 0.1 ml of diisobutyl phthalate (the molar ratio of magnesium to the magnesium complex of diisobutyl phthalate and halloysite is 0.15:1), and then The reaction was carried out at 110 ° C for 2.0 hours under constant temperature. After completion of the reaction, the liquid was filtered off, 60 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a catalyst component containing halloysite.

3 5.0 g of the halloysite-containing catalyst component was dispersed in 50 mL of toluene, and then 30 mL of a toluene solution containing 0.05 mol of methylaluminoxane was added, and the reaction was carried out at 90 ° C for 10.0 hours, followed by washing with toluene 5 times. The activated halloysite-containing catalyst component is obtained after drying.

4 0.15 g of the transition metal compound rac-Me ₂ Si(2-Me-4-PhInd) ₂ ZrCl _{2 was} added to 40 mL of a toluene solution containing 0.10 mol of methylaluminoxane, and then reacted at 0 ° C for 4.0 hours to obtain activation. Catalyst component solution.

5 The activated catalyst component solution described in the step 4 was dropwise added to 50 mL of a toluene suspension containing 5.0 g of the activated halloysite-containing catalyst component prepared in the step 3, and reacted at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C14. It has been found that the mass percentage of halloysite in the olefin polymerization catalyst component C14 is 42%, the mass percentage of titanium element is 1.18%, the mass percentage of magnesium element is 2.56%, and the mass of zirconium element is 100%. The content of the fraction is 0.10%, and the mass percentage of the aluminum element is 6.58%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 12 except that the olefin polymerization catalyst component C12 was replaced with the same weight part of the olefin polymerization catalyst component C14 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.08% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 12 except that the olefin polymerization catalyst component C12 was replaced with the same weight part of the olefin polymerization catalyst component C14 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was measured to be 0.11% by weight.

Example 15

This embodiment is for explaining the olefin polymerization catalyst component and the preparation method thereof, and the polyolefin resin composition and the preparation method thereof provided by the present invention.

(1) Preparation method of olefin polymerization catalyst component:

1 2.0 g of anhydrous magnesium chloride MgCl ₂ and 5.5 mL of isooctanol were dispersed in 20 mL of decane, and heated to 110 ° C to form a transparent solution, which was reacted at 110 ° C for 4.0 hours to obtain a magnesium chloride alcoholate. Then, the above magnesium chloride alkoxide was added dropwise to a suspension of 3.0 g of halloysite and 100 mL of decane, and the mixture was reacted at 90 ° C for 12.0 hours to obtain a magnesium complex of halloysite.

2 The magnesium complex of halloysite in step 1 was added dropwise to 60 mL of titanium tetrachloride at -20 ° C for 1 hour, followed by constant temperature reaction at -20 ° C for 1.0 hour. Slowly warming to 60 ° C, adding 2.0 grams of 9,9-bis(methoxymethyl) fluorene (the magnesium complex of the 9,9-bis(methoxymethyl) fluorene and halloysite magnesium complex The molar ratio was 0.20:1), and then the reaction was carried out at 110 ° C for 2.0 hours. After the completion of the reaction, the liquid was filtered off, 60 mL of titanium tetrachloride was again added, and the reaction was carried out at 120 ° C for 2.0 hours. Finally, it was washed 3 to 6 times with hexane, and dried to obtain a catalyst component containing halloysite.

3 5.0 g of the halloysite-containing catalyst component was dispersed in 50 mL of toluene, and then 30 mL of a toluene solution containing 0.1 mol of methylaluminoxane was added, and the reaction was carried out at 90 ° C for 4.0 hours, followed by washing with toluene 5 times, and after drying. An activated halloysite-containing catalyst component is obtained.

4 0.10 g of a transition metal compound Et(Ind) ₂ ZrCl _{2 was} added to 40 mL of a toluene solution containing 0.10 mol of methylaluminoxane, followed by a reaction at 20 ° C for 4.0 hours to obtain an activated catalyst component solution.

5 The activated catalyst component solution described in the step 4 was dropwise added to 50 mL of a toluene suspension containing 5.0 g of the activated halloysite-containing catalyst component prepared in the step 3, and reacted at 90 ° C for 4.0 hours. After completion of the reaction, it was washed 5 times with toluene, and after drying, an olefin polymerization catalyst component was obtained, which was designated as C15. It has been found that the mass percentage of halloysite in the olefin polymerization catalyst component C15 is 50%, the mass percentage of titanium element is 1.78%, the mass percentage of magnesium element is 3.20%, and the mass of zirconium element is 100%. The content of the fraction was 0.15%, the mass percentage of the aluminum element was 10.02%, and the mass percentage of the 9,9-bis(methoxymethyl)anthracene was 5.60%.

Among them, the halloysite in the step 1 is changed into halloysite, and the preparation method is as follows: 10 g of natural halloysite mineral is calcined at 100 ° C for 12 hours to obtain 8.6 g of halloysite.

(2) Preparation method of polyolefin resin composition:

1 propylene homopolymerization:

The propylene homopolymerization reaction was carried out in the same manner as in Example 12 except that the olefin polymerization catalyst component C12 was replaced with the same weight part of the olefin polymerization catalyst component C15 to obtain a homopolypropylene resin composition. The content of halloysite in the homopolypropylene resin composition was determined to be 0.05% by weight.

2 propylene copolymerization:

The propylene copolymerization reaction was carried out in the same manner as in Example 12 except that the olefin polymerization catalyst component C12 was replaced with the same weight part of the olefin polymerization catalyst component C15 to obtain a copolymer polypropylene resin composition. The content of halloysite in the copolymerized polypropylene resin composition was determined to be 0.07% by weight.

Test case

Test examples are used to demonstrate the performance of olefin polymers.

(1) Test of melt strength:

The experimental setup for determining the melt strength consisted of a single screw extruder equipped with a capillary tube and a Gottfert Rheotens melt strength meter. First, the melt of the alloy composition in the polypropylene kettle to be tested is extruded from the die of the extruder, and then the obtained extruded melt beam spline is mounted on the balance beam in opposite directions of movement. Roller traction. The force applied when the melt beam is stretched is a function of the speed and time of the rolls. The roller is uniformly accelerated to rotate until the melt beam breaks, and the force received when the melt beam is broken is defined as the melt strength. The results obtained are shown in Table 1.

(2) Mechanical properties test:

The tensile strength was measured in accordance with the method specified in ASTM D 638, and the results are shown in Table 1.

The impact strength was measured in accordance with the method specified in ASTM D256A, and the results are shown in Table 1.

Table 1

As can be seen from the results of Table 1, when the halloysite-containing olefin polymerization catalyst provided by the present invention is used for the preparation of a polyolefin resin, the obtained polyolefin resin has high melt strength and mechanical strength.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solutions of the present invention within the scope of the technical idea of the present invention. These simple variants All fall within the scope of protection of the present invention.

It should be further noted that the specific technical features described in the above specific embodiments may be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not be further described in various possible combinations.

In addition, any combination of various embodiments of the invention may be made as long as it does not deviate from the idea of the invention, and it should be regarded as the disclosure of the invention.

Claims (29)

1. A process for producing a polyolefin resin composition, which comprises polymerizing an olefin monomer in the presence of an olefin polymerization catalyst component and a cocatalyst, characterized in that the olefin polymerization catalyst component contains halloysite, a transition metal component and a non-transition metal component;

   The transition metal component is titanium tetrahalide and/or titanium alkoxide, and the non-transition metal component is a magnesium-containing compound; or

   The transition metal component is a metallocene compound in a metallocene catalyst and/or a nonmetallocene compound in a non-metallocene catalyst, and the non-transition metal component is an aluminum-containing compound; or

   The transition metal component is a mixture of titanium tetrahalide and/or titanium alkoxide with a metallocene compound in a metallocene catalyst and/or a non-metallocene compound in a non-metallocene catalyst, and the non-transition metal component It is a mixture of a magnesium-containing compound and an aluminum-containing compound.
2. The method according to claim 1, wherein said halloysite is contained in an amount of from 0.5 to 90% by weight based on the total mass of said olefin polymerization catalyst component, said transition metal component and non-transition metal group The total content of the metal elements in the fraction is from 2 to 80% by weight; preferably, the content of the halloysite is from 1 to 50% by weight based on the total weight of the olefin polymerization catalyst component, the transition metal group The total content of metal elements in the divided and non-transition metal components is from 5 to 60% by weight.
3. The method according to claim 1 or 2, wherein when the non-transition metal component is a magnesium-containing compound, a transition metal in the transition metal component is based on the total weight of the olefin polymerization catalyst component The content of the element is 0.5-10% by weight, and the content of the non-transition metal element in the non-transition metal component is 2-30% by weight;

   When the non-transition metal component is an aluminum-containing compound, the content of the transition metal element in the transition metal component is 0.01 to 5% by weight based on the total weight of the olefin polymerization catalyst component, the non- The content of the non-transition metal element in the transition metal component is 2-40% by weight;

   When the non-transition metal component is a mixture of a magnesium-containing compound and an aluminum-containing compound, the content of the transition metal element in the transition metal component is 0.25-15 based on the total weight of the olefin polymerization catalyst component. The content of the non-transition metal element in the non-transition metal component is 5 to 50% by weight.
4. The method according to any one of the preceding claims, wherein the halloysite is at least one of natural halloysite, halloysite and organically modified halloysite; Natural halloysite is obtained by heat treatment at 50-900 ° C for 0.5-48 hours; the organic modified halloysite is made of organosilicon compound, titanium compound and silicon-free and titanium-free natural halloysite and/or halloysite And at least one of the organic compounds having a double bond at the end is modified.
5. The method according to claim 4, wherein said organosilicon compound has the formula R ¹ R ² SiR ³ ₂ , and R ¹ is a halogen atom, a vinyl group, an amino group, a C ₁ - C ₅ aminoalkyl group, or a ring. Oxyl, methacryloxy, fluorenyl, C ₁ -C ₅ alkoxy, ureido or alpha-olefin-containing double bond of the formula -(CH ₂ ) _m1 COOCH(CH ₃ )=CH ₂ Alkyl, m1 is an integer from 1 to 18, R ² is a halogen atom, a C ₁ -C ₅ alkoxy group or an alkyl group of the formula -(CH ₂ ) _{m 2} -CH ₃ , and m 2 is an integer of 0-2 R ³ is a halogen atom, a C ₁ -C ₅ alkoxy group or an acetoxy group; preferably, the organosilicon compound is γ-methacryloxypropyltrimethoxysilane and/or γ-ammonia Propyltriethoxysilane;

   The titanium compound has the formula R ⁴ _p Ti(OR ⁵ ) _4-p , R ⁴ and R ⁵ are C ₁ -C ₄ alkyl groups, and p is an integer of 0-3; preferably, the titanium compound Is at least one of tetrabutyl titanate, titanium triethoxytitanium, methyltrimethoxytitanium, and tetraethyltitanate;

   The organic compound containing no silicon and titanium and having a double bond at the end has the formula R ⁶ R ⁷ CH=CH ₂ , R ⁶ is an acid chloride group, a carboxyl group, an epoxy group or an ester group, and R ⁷ is a C ₁ group. An alkylene group of -C ₂₀ or a C ₁ -C ₂₀ alkylene group having an ester group, an oxygen atom or a carboxyl group; preferably, the structural formula of the organic compound containing no silicon and titanium and having a double bond at the end It is at least one of HOOC(CH ₂ ) ₄ CH=CH ₂ , HOOC(CH ₂ ) ₇ CH=CH ₂ and HOOC(CH ₂ ) ₉ CH=CH ₂ .
6. The method according to any one of the preceding claims, wherein the titanium tetrahalide is at least one of TiCl ₄ , TiBr ₄ and Til ₄ ; the titanium alkoxide is Ti(OEt)Cl ₃ , Ti (OEt) at least one of ₂ Cl ₂ , Ti(OEt) ₃ Cl, Ti(OEt) ₄ and Ti(OBu) ₄ .
7. The method according to any one of the preceding claims, wherein the metallocene compound has a general formula of the metallocene catalyst as shown in formula (I):

   (Cp ^I -B _c -Cp ^II )M'R ⁸ _a R ⁹ _b Formula (I)

   Wherein M' is Ti, Zr, Hf, V, Fe, Y, Sc or a lanthanide metal; Cp ^I and Cp ^II are each independently H, C ₁ -C ₅ alkyl, substituted or unsubstituted ring a pentadienyl, substituted or unsubstituted C ₆ -C ₁₈ aryl group, and the substituent is a C ₁ -C ₆ alkyl group, a C ₃ -C ₁₈ cycloalkyl group and a C ₆ -C ₁₈ aryl group At least one of the groups; R ⁸ and R ⁹ are each independently H, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group, a C ₆ -C ₂₀ aryl group, a band a C ₇ -C ₂₀ aryl group having a C ₁ -C ₁₅ alkyl group, a C ₁ -C ₈ acyloxy group, an allyl group or a C ₁ -C ₁₅ silane group, each of a and b being independently 0- An integer of 2, and a+b=2; B is a -C(R ¹⁰ R ¹¹ )-alkyl bridge or a -Si(R ¹² R ¹³ )-silyl bridge, wherein R ¹⁰ -R ¹³ are each independently H, C ₁ -C ₄ alkyl or C ₆ -C ₁₀ aryl; e is an integer from 1 to 3;

   Preferably, the metallocene compound in the metallocene catalyst is C ₂ H ₄ (Ind) ₂ ZrCl ₂ , C ₂ H ₄ (H ₄ Ind) ₂ ZrCl ₂ , Me ₂ Si(Ind) ₂ ZrCl ₂ , Me ₂ Si(2-Me-4-Ph-Ind) ₂ ZrCl ₂ , Me ₂ Si(Me ₄ Cp) ₂ ZrCl ₂ , Me ₂ Si(Flu) ₂ ZrCl ₂ , Me ₂ Si(2-Me-4-Naph- Ind) ₂ at least one of ZrCl ₂ and Ph ₂ Si(Ind) ₂ ZrCl ₂ , Me is a methyl group, Ph is a phenyl group, Cp is a cyclopentadienyl group, Ind is a fluorenyl group, and H ₄ Ind is 4. 5,6,7-tetrahydroanthracene, Flu is a fluorenyl group, and Naph is a naphthyl group.
8. The method according to any one of the preceding claims, wherein the non-metallocene compound has a general formula of formula (II):

   

   Wherein M is selected from Zr, Ti, V or Hf, and R ₁ , R ₂ and R ₃ are each independently H, a halogen atom, a C ₁ -C ₈ alkyl group, a C ₁ -C ₈ alkoxy group, C An aryl group of _6- C _{20 ,} an aryl group having a C ₁ -C ₆ alkyl group, an aryl group having a C ₃ -C ₁₈ cycloalkyl group, an aryl group having a C ₆ -C ₁₈ aryl group , C ₁ -C ₈ acyloxy, allyl or C ₁ -C ₁₅ silane group, X is F, Cl, Br or I, n is 2;

   Preferably, the non-metallocene compound in the non-metallocene catalyst is bis[N-(3-tert-butyl-salicylidene)anilino]zirconium dichloride, bis[N-(3-methyl hydrazine) Yanji) Anilino]zirconium dichloride, bis[N-(3-isopropylsalicylidene)anilino]zirconium dichloride and bis[N-(3-adamantyl-5-methyl) At least one of salicyl)aniline-zirconium dichloride.
9. The method according to any one of the preceding claims, wherein the magnesium-containing compound is a magnesium halide of the general formula MgX ¹ ₂ and/or a Grignard reagent of the formula RMgX ² ; in MgX ¹ ₂ , X ¹ is F, Cl, Br or I; in RMgX ² , R is a C ₁ -C ₁₀ alkyl group, and X ² is F, Cl, Br or I; preferably, the aluminum-containing compound has the formula Al (OR') _q R"' _3-q , R' and R" are each independently a C ₂ -C ₁₀ alkyl group, and 0 ≤ q ≤ 3.
10. The method according to any one of the preceding claims, wherein, when the non-transition metal component contains a magnesium-containing compound, the olefin polymerization catalyst component further contains an internal electron donor compound; preferably, the inner The electron donor compound is a diether compound and/or a carboxylate compound.
11. The method according to any one of the preceding claims, wherein the polymerization reaction is carried out in the presence of an external electron donor; preferably, the molar ratio of the external electron donor compound to the aluminum element in the cocatalyst may It is 0.001-1:1.
12. The method according to any of the preceding claims, wherein the cocatalyst is an aluminum alkyl and/or an aluminum alkoxide.
13. The method according to any one of claims 1 to 12, wherein, when the non-transition metal component is a magnesium-containing compound, the olefin polymerization catalyst is prepared according to a method comprising the following steps:

    (1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

    (2) The magnesium complex of the halloysite is coordinated with titanium tetrahalide and/or titanium alkoxide.
14. The method according to claim 13, wherein the weight ratio of the halloysite to the amount of the magnesium-containing compound in the step (1) is from 1:0.5 to 99, preferably from 1:0.5 to 35.
15. The method according to claim 13 or 14, wherein the coordination reaction is carried out by first mixing the magnesium complex of the halloysite with a part of titanium tetrahalide and/or a part of titanium alkoxide and at -20 The reaction is carried out at ° C to 0 ° C for 0.5-2 hours, and then the temperature is raised to 80-130 ° C for 1-4 hours, followed by solid-liquid separation of the reaction product, and the obtained solid product and the remaining portion of titanium tetrahalide and / or The remaining portion of titanium alkoxide is reacted at 80-130 ° C for 1-4 hours.
16. The method according to claim 15, wherein said portion of titanium tetrahalide and the remaining portion of titanium tetrahalide are each independently at least one of TiCl ₄ , TiBr ₄ and Til ₄ ; preferably, said portion of alkoxy groups The titanium and the remaining portion of the titanium alkoxide are each independently at least one of Ti(OEt)Cl ₃ , Ti(OEt) ₂ Cl ₂ , Ti(OEt) ₃ Cl, Ti(OEt) ₄ and Ti(OBu) ₄ . .
17. The method according to claim 15 or 16, wherein the method for producing the olefin polymerization catalyst further comprises subjecting the magnesium complex of the halloysite with a portion of titanium tetrahalide and/or a portion of titanium alkoxide at -20 The internal electron donor compound is added to the reaction system after the reaction at ° C to 0 ° C for 0.5-2 hours and before the reaction at 80-130 ° C for 1-4 hours; preferably, the internal electron donor compound is a diether compound And / or carboxylate compounds.
18. The method according to any one of claims 1 to 12, wherein, when the non-transition metal component is an aluminum-containing compound, the olefin polymerization catalyst is prepared according to a method comprising the following steps:

    (1) reacting halloysite with the first aluminum-containing compound at 0-90 ° C for 1-20 hours to obtain activated halloysite;

    (2) reacting the transition metal component with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component which is a metallocene compound in the metallocene catalyst and/or Or a non-metallocene compound in a non-metallocene catalyst;

    (3) reacting the activated halloysite with the activated catalyst component at 0-100 ° C for 1-10 hours.
19. The method according to claim 18, wherein the weight ratio of the halloysite to the first aluminum-containing compound is 1:0.1-20; preferably, the weight ratio of the transition metal component to the second aluminum-containing compound Is 1:1 to 5000; preferably, the weight ratio of the activated halloysite to the activated catalyst component is 1:1 to 20; preferably, the first aluminum-containing compound and the second aluminum-containing compound are each Independently of the aluminum-containing compound of the formula Al(OR') _q R" _3-q , R' and R" are each independently a C ₂ -C ₁₀ alkyl group, 0 ≤ q ≤ 3.
20. The method according to any one of claims 1 to 12, wherein when the non-transition metal component is a mixture of a magnesium-containing compound and an aluminum-containing compound, the olefin polymerization catalyst is prepared according to a method comprising the following steps :

    (1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

    (2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain a catalyst component containing halloysite;

    (3) reacting the halloysite-containing catalyst component with the first aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated halloysite-containing catalyst component;

    (4) reacting the metallocene compound in the metallocene catalyst and/or the non-metallocene compound in the non-metallocene catalyst with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component;

    (5) reacting the activated halloysite-containing catalyst component with the activated catalyst component at 0 to 110 ° C for 1 to 10 hours.
21. The method according to claim 20, wherein the weight ratio of said halloysite to said magnesium-containing compound in step (1) is from 1:0.5 to 99, preferably from 1:0.5 to 35.
22. The method according to claim 20 or 21, wherein the coordination reaction is carried out by first mixing the magnesium complex of the halloysite with a portion of titanium tetrahalide and/or another portion of titanium alkoxide and at - The reaction is carried out at 20 ° C to 0 ° C for 0.5-2 hours, and then the temperature is raised to 80-130 ° C for 1-4 hours, followed by solid-liquid separation of the reaction product, and the obtained solid product and the remaining portion of titanium tetrahalide and / or the remaining portion of titanium alkoxide is reacted at 80-130 ° C for 1-4 hours.
23. The method according to claim 22, wherein said portion of titanium tetrahalide and the remaining portion of titanium tetrahalide are each independently at least one of TiCl ₄ , TiBr ₄ and Til ₄ ; said portion of alkoxide titanium and remaining The partial alkoxytitanium is each independently at least one of Ti(OEt)Cl ₃ , Ti(OEt) ₂ Cl ₂ , Ti(OEt) ₃ Cl, Ti(OEt) ₄ and Ti(OBu) ₄ .
24. The method according to claim 22 or 23, wherein the method for producing the olefin polymerization catalyst further comprises subjecting the magnesium complex of the halloysite with a portion of titanium tetrahalide and/or a portion of titanium alkoxide at -20 The internal electron donor compound is added to the reaction system after the reaction at ° C to 0 ° C for 0.5-2 hours and before the reaction at 80-130 ° C for 1-4 hours; preferably, the internal electron donor compound is a diether compound And / or carboxylate compounds.
25. The method according to any one of claims 20 to 24, wherein a weight ratio of the amount of the halloysite-containing catalyst component to the amount of the first aluminum-containing compound is 1:0.1 to 20; The weight ratio of the total amount of the metallocene compound and the non-metallocene compound to the amount of the second aluminum-containing compound is from 1:1 to 1000; preferably, the activated catalyst component and the activated The weight ratio of the halloysite-containing catalyst component is 1:0.1-20; preferably, the first aluminum-containing compound and the second aluminum-containing compound are each independently of the formula Al(OR') _q R" ₃ The aluminum-containing compound of _-q , each of R' and R" is independently a C ₂ -C ₁₀ alkyl group, and 0 ≤ q ≤ 3.
26. A method for preparing a polyolefin resin composition, the method comprising the steps of:

    (1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

    (2) coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain an olefin polymerization catalyst component;

    (3) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.
27. A method for preparing a polyolefin resin composition, the method comprising the steps of:

    (1) reacting halloysite with the first aluminum-containing compound at 0-90 ° C for 1-20 hours to obtain activated halloysite;

    (2) reacting the transition metal component with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component which is a metallocene compound in the metallocene catalyst and/or Or a non-metallocene compound in a non-metallocene catalyst;

    (3) reacting the activated halloysite with the activated catalyst component at 0-100 ° C for 1-10 hours to obtain an olefin polymerization catalyst component;

    (4) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.
28. A method for preparing a polyolefin resin composition, the method comprising the steps of:

    (1) reacting halloysite with a magnesium-containing compound at 30-150 ° C for 1-50 hours to obtain a magnesium complex of halloysite;

    (2) Coordinating the magnesium complex of the halloysite with titanium tetrahalide and/or titanium alkoxide to obtain a catalyst containing halloysite Agent component;

    (3) reacting the halloysite-containing catalyst component with the first aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated halloysite-containing catalyst component;

    (4) reacting the metallocene compound in the metallocene catalyst and/or the non-metallocene compound in the non-metallocene catalyst with the second aluminum-containing compound at 0 to 90 ° C for 1 to 20 hours to obtain an activated catalyst component;

    (5) reacting the activated halloysite-containing catalyst component with the activated catalyst component at 0 to 110 ° C for 1 to 10 hours to obtain an olefin polymerization catalyst component;

    (6) The olefin monomer is subjected to a polymerization reaction in the presence of the olefin polymerization catalyst component and a cocatalyst.
29. A polyolefin resin composition prepared by the method according to any one of claims 1-28.