CN104448551A

CN104448551A - Polypropylene in-reactor alloy composition and preparation method thereof

Info

Publication number: CN104448551A
Application number: CN201410648753.3A
Authority: CN
Inventors: 董金勇; 牛慧; 秦亚伟; 王宁
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2014-11-14
Filing date: 2014-11-14
Publication date: 2015-03-25
Anticipated expiration: 2034-11-14
Also published as: CN104448551B

Abstract

The invention provides a polypropylene in-reactor alloy composition and a preparation method thereof. The method for preparing the polypropylene in-reactor alloy composition comprises the following steps: carrying out a polymerization reaction on propylene in the presence of olefin polymerization catalyst components and promoters, and introducing ethylene and alpha-olefin into the polymerization reaction system to continuously carry out a polymerization reaction, wherein the olefin polymerization catalyst components comprise halloysite, a transition metal component and a non-transition metal component; when the transition metal component is titanium tetrahalide and/or titanium alkoxide, the non-transition metal component is a magnesium-containing compound; when the transition metal component is a metallocene compound and/or non-metallocene compound, the non-transition metal component is an aluminum-containing compound; and when the transition metal component is a mixture of titanium tetrahalide and/or titanium alkoxide and the metallocene compound and/or non-metallocene compound, the non-transition metal component is a mixture of the magnesium-containing compound and the aluminum-containing compound. The polypropylene in-reactor alloy composition has high melt strength and mechanical property.

Description

Alloy composite and preparation method thereof in a kind of polypropylene

Technical field

Alloy composite in the preparation method that the present invention relates to alloy composite in a kind of polypropylene and the polypropylene prepared by the method.

Background technology

In polypropylene, alloy is polymerized under the existence of olefin polymerization catalysis by propylene to form porous polypropylene particle, ethene is passed into again afterwards and alpha-olefin comonomer carries out copolyreaction in polymerization system, the copolyreaction of these two kinds of monomers is carried out in above-mentioned porous polypropylene particle, is formed in the space that the elastocopolymer of generation is filled in porous polypropylene particle.The innovation of olefin polymerization catalysis on the Nomenclature Composition and Structure of Complexes is one of main drive that in the composition of alloy and character in regulation and control polypropylene, promotion polypropylene, alloy property promotes.Since the 1950's, Germanization scholar Zielger started olefin coordination polymerization jointly with the scholar Natta that Italianizes, olefin polymerization catalysis has developed the three major types catalyzer comprising Zielger-Natta catalyzer, metallocene catalyst and non-metallocene catalyst gradually.

Although the olefin polymerization catalysis with new texture and new capability is constantly found and is applied in polypropylene in the research of alloy high performance, in some high-performance polypropylene stills with wide application prospect, alloy still lacks effective catalyzed polymerization preparation means.Such as, in the polypropylene being representative with impact copolymer polypropylene (hiPP), alloy is huge at automobile, plant and instrument and durable consumer goods field application potential, but there is the problems such as interfacial adhesion between polypropylene and ethylene-propylene rubber(EPR) phase is low, the yardstick that is separated is unstable in polypropylene in alloy resin, thus make that the melt strength of alloy resin in described polypropylene is low and mechanical property is poor, have a strong impact on its use properties.

Halloysite is a kind of clay mineral, the many walls, the hollow nanotube that are curled into according to the silicate lamella that 1:1 structure forms by silicon-oxy tetrahedron and alumina octahedral, and its internal diameter is 10-20 nanometer, and external diameter is 10-100 nanometer, and length is 0.5-40 micron.Halloysite because having abundance, the feature such as cheap and easy to get and enjoy the concern of academia and industry member, and is applied in the fields such as catalytic material, supporting material and porous material.

Summary of the invention

The object of the invention is the lower and defect that mechanical strength is poor of melt strength in order to overcome alloy in existing polypropylene, and alloy composite in the preparation method that alloy composite in new polypropylene is provided and the polypropylene prepared by described method.

Particularly, in polypropylene provided by the invention, the first preparation method of alloy composite comprises and makes propylene carry out the first polyreaction under the existence of olefin polymerization catalyst components and promotor, then in polymerization reaction system, ethene is passed into and alpha-olefin carries out the second polyreaction, wherein, described olefin polymerization catalyst components contains halloysite, transition metal component and nontransition metal component;

Described transition metal component is titanium tetrahalide and/or titan-alkoxide, and described nontransition metal component is magnesium-containing compound; Or,

Described transition metal component is the metallocene compound in metallocene catalyst and/or the non-metallocene compound in non-metallocene catalyst, and described nontransition metal component is aluminum contained compound; Or,

Described transition metal component is the mixture of the metallocene compound in titanium tetrahalide and/or titan-alkoxide and metallocene catalyst and/or the non-metallocene compound in non-metallocene catalyst, and described nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound.

In polypropylene provided by the invention, the second preparation method of alloy resin composition comprises:

(1) halloysite and magnesium-containing compound are reacted 1-50 hour at 30-150 DEG C, obtain the magnesium mixture of halloysite;

(2) the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide are carried out coordination reaction, obtain olefin polymerization catalyst components;

(3) make propylene carry out the first polyreaction under the existence of described olefin polymerization catalyst components and promotor, then in polymerization reaction system, pass into ethene and alpha-olefin carries out the second polyreaction.

In polypropylene provided by the invention, the third preparation method of alloy resin composition comprises:

(1) halloysite and the first aluminum contained compound are reacted 1-20 hour at 0-90 DEG C, obtain the halloysite activated;

(2) transition metal component and the second aluminum contained compound are reacted 1-20 hour at 0-90 DEG C, obtain the catalyst component activated, described transition metal component is the metallocene compound in metallocene catalyst and/or the non-metallocene compound in non-metallocene catalyst;

(3) catalyst component of the halloysite of described activation and described activation is reacted 1-10 hour at 0-100 DEG C, obtain olefin polymerization catalyst components;

(4) make propylene carry out the first polyreaction under the existence of described olefin polymerization catalyst components and promotor, then in polymerization reaction system, pass into ethene and alpha-olefin carries out the second polyreaction.

In polypropylene provided by the invention, the 4th kind of preparation method of alloy resin composition comprises:

(2) the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide are carried out coordination reaction, obtain the catalyst component containing halloysite;

(3) the described catalyst component containing halloysite and the first aluminum contained compound are reacted 1-20 hour at 0-90 DEG C, obtain the catalyst component containing halloysite activated;

(4) metallocene compound in metallocene catalyst and/or the non-metallocene compound in non-metallocene catalyst and the second aluminum contained compound are reacted 1-20 hour at 0-90 DEG C, obtain the catalyst component activated;

(5) at 0-110 DEG C, react 1-10 hour containing the catalyst component of halloysite and the catalyst component of described activation by described activation, obtain olefin polymerization catalyst components;

(6) make propylene carry out the first polyreaction under the existence of described olefin polymerization catalyst components and promotor, then in polymerization reaction system, pass into ethene and alpha-olefin carries out the second polyreaction.

In addition, present invention also offers alloy composite in the polypropylene prepared by aforesaid method.

The present inventor finds after further investigation, and by the olefin polymerization catalysis containing halloysite provided by the invention for the preparation of in polypropylene during alloy, in the polypropylene obtained, alloy composite has higher melt strength and mechanical strength.Infer its reason, may be due to: halloysite is doped in catalytic systems for polymerization of olefins, polymerization not only can be utilized to be dispersed in polypropylene in alloy by halloysite with nanoscale, realize the nano combined of alloy in halloysite and polypropylene, but also the bore that halloysite nanotubes can be utilized to present is large, the features such as suitable length form physics cross-linking set, suppress the molecular chain movement of alloy in polypropylene, improve the melt strength of alloy in polypropylene and improve its phase interface effect, and then improve melt strength and the mechanical property of alloy in polypropylene.

Other features and advantages of the present invention are described in detail in embodiment part subsequently.

Embodiment

Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.

In polypropylene provided by the invention, the first preparation method of alloy composite comprises and makes propylene carry out the first polyreaction under the existence of olefin polymerization catalyst components and promotor, then in polymerization reaction system, ethene is passed into and alpha-olefin carries out the second polyreaction, wherein, described olefin polymerization catalyst components contains halloysite, transition metal component and nontransition metal component;

The content of the present invention to composition various in described olefin polymerization catalyst components is not particularly limited, such as, with the gross weight of described olefin polymerization catalyst components for benchmark, the content of described halloysite can be 0.5-90 % by weight, and in described transition metal component and nontransition metal component, the total content of metallic element can be 2-80 % by weight; Preferably, with the gross weight of described olefin polymerization catalyst components for benchmark, the content of described halloysite is 1-50 % by weight, and in described transition metal component and nontransition metal component, the total content of metallic element is 5-60 % by weight.

Further, when described nontransition metal component is magnesium-containing compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal can be 0.5-10 % by weight, is preferably 1-5 % by weight; In described nontransition metal component, the content of non-transition metal elements can be 2-30 % by weight, is preferably 5-20 % by weight.

When described nontransition metal component is aluminum contained compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal can be 0.01-5 % by weight, is preferably 0.05-2.5 % by weight; In described nontransition metal component, the content of non-transition metal elements can be 2-40 % by weight, is preferably 5-25 % by weight.

When described nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal can be 0.25-15 % by weight, is preferably 0.5-5 % by weight; In described nontransition metal component, the content of non-transition metal elements can be 5-50 % by weight, is preferably 7.5-40 % by weight.

Described halloysite can be natural halloysite, also can be the halloysite after modification, and such as, metahalloysite and/or organically-modified halloysite, that is, described halloysite can be at least one in natural halloysite, metahalloysite and organically-modified halloysite.Wherein, as mentioned above, many walls, hollow nanotube that described natural halloysite is curled into according to the silicate lamella that 1:1 structure forms by silicon-oxy tetrahedron and alumina octahedral, its internal diameter is 10-20 nanometer, external diameter is 10-100 nanometer, and length is 0.5-40 micron.Described metahalloysite by by natural halloysite 50-900 DEG C, preferably at 100-600 DEG C thermal treatment 0.5-48 hour, preferably thermal treatment 2-10 hour obtain.Described organically-modified halloysite is by obtaining natural halloysite and/or metahalloysite silicoorganic compound, titanium compound and not siliceous and titanium and end with at least one modification in the organic compound of double bond.

Hydroxyl is contained in described natural halloysite and metahalloysite, and described organically-modified halloysite by the hydroxyl in natural halloysite and/or metahalloysite and silicoorganic compound, titanium compound and not siliceous and titanium and end with can be bonded together with functional group's chemistry of hydroxyl reaction and obtaining in the organic compound of double bond, concrete reaction conditions is known to the skilled person, and therefore not to repeat here.It should be noted that, when during described silicoorganic compound, titanium compound and not siliceous and titanium and end are with the organic compound of double bond containing can functional group with hydroxyl reaction time, first described halloysite can be carried out modification with introduce in halloysite can with described silicoorganic compound, titanium compound and not siliceous and titanium and the end functional group with at least one radical reaction in the organic compound of double bond, as well known to those skilled in the art to this, therefore not to repeat here.Wherein, the general formula of described silicoorganic compound is R ¹r ²siR ³ ₂, wherein, R ¹for halogen atom, vinyl, amino, C ₁-C ₅aminoalkyl, epoxy group(ing), methacryloxy, sulfydryl, C ₁-C ₅alkoxyl group, urea groups or general formula be-(CH ₂) _m1cOOCH (CH ₃)=CH ₂containing the alkyl of alpha-olefin double bond, m1 is the integer of 1-18, R ²for halogen atom, C ₁-C ₅alkoxyl group or general formula be-(CH ₂) _m2-CH ₃alkyl, m2 is the integer of 0-2, R ³for halogen atom, C ₁-C ₅alkoxyl group or acetoxyl group.From the angle that raw material is ready availability, described silicoorganic compound are particularly preferably γ-methacryloxypropyl trimethoxy silane and/or γ-aminopropyl triethoxysilane.The general formula of described titanium compound is R ⁴ _pti (OR ⁵) _4-p, wherein, R ⁴and R ⁵for C ₁-C ₄alkyl, p is the integer of 0-3.From the ready availability angle of raw material, described titanium compound is particularly preferably at least one in tetrabutyl titanate, methyl triethoxy titanium, methyl trimethoxy oxygen base titanium and tetraethyl titanate.Described not siliceous and titanium and end is R with the general formula of the organic compound of double bond ⁶r ⁷cH=CH ₂, wherein, R ⁶for acid chloride group, carboxyl, epoxy group(ing) or ester group, R ⁷for C ₁-C ₂₀alkylidene group or C with ester group, Sauerstoffatom or carboxyl ₁-C ₂₀alkylidene.From the angle that raw material is ready availability, described not siliceous and titanium and end is HOOC (CH with the organic compound structure formula of double bond ₂) ₄cH=CH ₂, HOOC (CH ₂) ₇cH=CH ₂with HOOC (CH ₂) ₉cH=CH ₂in at least one.

The kind of described titanium tetrahalide and titan-alkoxide can be all the routine selection of this area.Such as, described titanium tetrahalide can be TiCl ₄, TiBr ₄and TiI ₄in at least one, be particularly preferably TiCl ₄.Alkoxyl group in described titan-alkoxide can be substituted or non-substituted C ₁-C ₅alkoxyl group, wherein, substituting group is generally halogen atom.Particularly, the example of described titan-alkoxide includes but not limited to Ti (OEt) Cl ₃, Ti (OEt) ₂cl ₂, Ti (OEt) ₃cl, Ti (OEt) ₄with Ti (OBu) ₄in at least one.

The kind of the metallocene compound in described metallocene catalyst can be the routine selection of this area, such as, can be the metallocene compound of general formula as shown in formula I:

(Cp ⁱ-B _e-Cp ^iI) M ' R ⁸ _ar ⁹ _bformula (I)

Wherein, M ' is Ti, Zr, Hf, V, Fe, Y, Sc or lanthanide series metal; Cp ⁱand Cp ^iIbe H, C independently of one another ₁-C ₅alkyl, replacement or non-substituted cyclopentadienyl, replacement or non-substituted C ₆-C ₁₈aryl, and substituting group is C ₁-C ₆alkyl, C ₃-C ₁₈cycloalkyl and C ₆-C ₁₈aryl at least one; R ⁸and R ⁹be H, halogen atom, C independently of one another ₁-C ₈alkyl, C ₁-C ₈alkoxyl group, C ₆-C ₂₀aryl, with C ₁-C ₁₅the C of alkyl ₇-C ₂₀aryl, C ₁-C ₈acyloxy, allyl group or C ₁-C ₁₅silylation, a, b are the integer of 0-2 independently of one another, and a+b=2; B is alkyl bridge or silylation bridge, is preferably-C (R ¹⁰r ¹¹)-alkyl bridge or-Si (R ¹²r ¹³)-silylation bridge, wherein, R ¹⁰-R ¹³be H, C independently of one another ₁-C ₄alkyl or C ₆-C ₁₀aryl; E is the integer of 1-3.Particularly, the example of the metallocene compound in described metallocene catalyst includes but not limited to: C ₂h ₄(Ind) ₂zrCl ₂, C ₂h ₄(H ₄ind) ₂zrCl ₂, Me ₂si (Ind) ₂zrCl ₂, Me ₂si (2-Me-4-Ph-Ind) ₂zrCl ₂, Me ₂si (Me ₄cp) ₂zrCl ₂, Me ₂si (Flu) ₂zrCl ₂, Me ₂si (2-Me-4-Naph-Ind) ₂zrCl ₂and Ph ₂si (Ind) ₂zrCl ₂in at least one, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl, and Ind is indenyl, H ₄ind is 4,5,6,7-tetrahydro-indenes, and Flu is fluorenyl, and Naph is naphthyl.

In described non-metallocene catalyst, the kind of non-metallocene compound can be that the routine of this area is selected, such as, and can for general formula be such as formula the non-metallocene compound shown in (II):

formula (II)

Wherein, M is selected from Zr, Ti, V or Hf, R ₁, R ₂and R ₃be H, halogen atom, C independently of one another ₁-C ₈alkyl, C ₁-C ₈alkoxyl group, C ₆-C ₂₀aryl, with C ₁-C ₆alkyl aryl, with C ₃-C ₁₈cycloalkyl aryl, with C ₆-C ₁₈aryl, the C of aromatic base ₁-C ₈acyloxy, allyl group or C ₁-C ₁₅silylation, X is F, Cl, Br or I, and n is 2.Particularly, the example of the non-metallocene compound in described non-metallocene catalyst includes but not limited to: at least one in two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride, two [N-(3-methyl salicylidene) anilino] zirconium dichloride, two [N-(3-sec.-propyl salicylidene) anilino] zirconium dichloride and two [N-(3-adamantyl-5-methyl salicylidene) anilino] zirconium dichloride.

Described magnesium-containing compound can be the existing various compound containing magnesium that can be used in olefin polymerization catalysis, such as, can be MgX for general formula ¹ ₂magnesium halide or general formula be RMgX ²grignard reagent or both mixture above.At MgX ¹ ₂in, X ¹for F, Cl, Br or I; At RMgX ²in, R is C ₁-C ₁₀alkyl, X ²for F, Cl, Br or I.Particularly, the example of described magnesium-containing compound includes but not limited to: at least one in magnesium chloride, magnesium bromide, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium.From the angle that raw material is ready availability, described magnesium-containing compound is preferably magnesium chloride.

Described aluminum contained compound can be the existing various compound containing aluminium that can be used in olefin polymerization catalysis, such as, can be Al (OR ') for general formula _qr " _3-qaluminum contained compound, wherein, R ' and R " are C independently of one another ₂-C ₁₀alkyl, 0≤q≤3.Particularly, the example of described aluminum contained compound includes but not limited to: at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, methylaluminoxane etc.

In described olefin polymerization catalyst components, when described nontransition metal component be magnesium-containing compound or the mixture (namely described nontransition metal component contains magnesium-containing compound) for magnesium-containing compound and aluminum contained compound time, described olefin polymerization catalyst components is also preferably containing internal electron donor compound, the catalytic activity of catalyzer can be improved like this, and degree of isotacticity and the crystallinity of polyolefin resin can be improved.The consumption of described internal electron donor compound can be that the routine of this area is selected, and such as, described internal electron donor compound can be 0.05-0.6:1 with the mol ratio of magnesium elements in described olefin polymerization catalyst components, preferably 0.1-0.4:1.In addition, the kind of described internal electron donor compound also can be the routine selection of this area, such as, can be at least one in diether compounds, carbonate, alcohol ester, ketone, amine and silane, be particularly preferably diether compounds and/or carbonate.

Particularly, the example of described diether compound includes but not limited to: 2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-butyl-1,3-Propanal dimethyl acetal, 2-sec-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-1,3-Propanal dimethyl acetal, 2-phenyl-1,3-Propanal dimethyl acetal, 2-(2-phenylethyl)-1,3-Propanal dimethyl acetal, 2-(2-cyclohexyl-ethyl)-1,3-Propanal dimethyl acetal, 2-(p-chloro-phenyl-)-1,3-Propanal dimethyl acetal, 2-(diphenyl methyl)-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-bicyclopentyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1,3-Propanal dimethyl acetal, two (2-cyclohexyl-ethyl)-1, the 3-Propanal dimethyl acetal of 2,2-, 2-methyl-2-isobutyl--1,3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2,2-two (cyclohexyl methyl)-1,3-Propanal dimethyl acetal, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-(1-methyl butyl)-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-phenyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-benzyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclopentyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-sec.-propyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-the second month in a season-butyl-1,3-Propanal dimethyl acetal, one or more in 2-cyclohexyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal and 9,9-bis-(methoxymethyl fluorenes), are particularly preferably 9,9-bis-(methoxymethyl fluorenes).

The example of described carbonate includes but not limited to: one or more in diethyl succinate, dibutyl succinate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dinoctyl phthalate, dimixo-octyl phthalate, ethyl benzoate, ethyl anisate, ethyl p-ethoxybenzoate, triethyl trimellitate and tributyl trimellitate, is particularly preferably dibutyl phthalate and/or diisobutyl phthalate.

Olefin polymerization catalyst components provided by the invention can be prepared by existing various method.According to a kind of embodiment of the present invention, when described nontransition metal component is magnesium-containing compound, described olefin polymerization catalyst components is prepared by the method comprised the following steps:

(2) the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide are carried out coordination reaction.

The consumption of the present invention to halloysite described in step (1) and magnesium-containing compound is not particularly limited, and such as, the weight ratio of the consumption of described halloysite and the consumption of described magnesium-containing compound can be 1:0.5-99, is preferably 1:0.5-35.

As mentioned above, the temperature of reaction of described halloysite and magnesium-containing compound is 30-150 DEG C, and the reaction times is 1-50 hour.Preferably, the temperature of reaction of described halloysite and magnesium-containing compound is 40-130 DEG C, and the reaction times is 4-20 hour.

Reaction between described halloysite and magnesium-containing compound is preferably carried out in organic solvent, and reaction can be made like this to carry out more reposefully.The kind of described organic solvent can be the existing various inert substance that can be used as reaction media, such as, can be C ₅-C ₁₀alkane, aromatic hydrocarbon, naphthenic hydrocarbon, C ₂-C ₁₂ether and tetrahydrofuran (THF) at least one, be preferably at least one in normal hexane, hexanaphthene, heptane, decane, ethanol, isopropylcarbinol, isooctyl alcohol, tetrahydrofuran (THF), methyl ether, ether, positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl ether, benzene,toluene,xylene, chlorobenzene etc.In addition, the consumption of described organic solvent makes the concentration of halloysite can be 1-500g/L usually, is preferably 2-50g/L.

The present invention is not particularly limited the mode of the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide being carried out coordination reaction, such as, first under low temperature (0-40 DEG C), the magnesium mixture of halloysite can be mixed with titanium tetrahalide and/or titan-alkoxide, and then react 1-10 hour under temperature being risen to high temperature (80-130 DEG C).Preferably, the mode of the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide being carried out coordination reaction comprises first reacts the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide to 0.5-2 hour at-20 DEG C at 0 DEG C, and then temperature is risen to 80-130 DEG C of reaction 1-4 hour, then by reaction product solid-liquid separation, and the solid product obtained and remainder titanium tetrahalide and/or remainder titan-alkoxide are reacted 1-4 hour at 80-130 DEG C.More preferably, the mode of the magnesium mixture of described halloysite and titanium tetrahalide and/or titan-alkoxide being carried out coordination reaction comprises first reacts the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide to 0.5-1.5 hour at-20 DEG C to-10 DEG C, and then temperature is risen to 100-125 DEG C of reaction 1.5-2.5 hour, then by reaction product solid-liquid separation, and the solid product obtained and remainder titanium tetrahalide and/or remainder titan-alkoxide are reacted 1.5-2.5 hour at 100-125 DEG C.In addition, when the reaction of step (1) is carried out in presence of organic solvent, the product that step (1) obtains exists as a solution, so the solution of the magnesium mixture containing halloysite then can directly be added dropwise in titanium tetrahalide and/or titan-alkoxide by the coordination reaction of step (2), or directly titanium tetrahalide and/or titan-alkoxide are added dropwise in the solution of the magnesium mixture containing halloysite, wherein, dripping the time used can be 0.5-4 hour; When if the reaction of step (1) is carried out under the existence of organic solvent-free or step (1) reacted after that product is dry, so the magnesium mixture of halloysite then can be scattered in the solution containing titanium tetrahalide and/or titan-alkoxide by the coordination reaction of step (2).

The consumption of the present invention to described magnesium-containing compound, a part of titanium tetrahalide, a part of titan-alkoxide, another part titanium tetrahalide and another part titan-alkoxide is not particularly limited.When described magnesium-containing compound be general formula is the magnesium halide of MgX12, first time load titanium tetrahalide used and total consumption of titan-alkoxide and the mol ratio of magnesium-containing compound can be 10-60:1, be preferably 10-30:1 (namely, total consumption of described a part of titanium tetrahalide and a part of titan-alkoxide and the mol ratio of magnesium-containing compound are 10-60:1, are preferably 10-30:1); Second time load titanium tetrahalide used and total consumption of titan-alkoxide and the mol ratio of magnesium-containing compound can be 10-60:1, be preferably 10-30:1 (namely, total consumption of described remainder titanium tetrahalide and remainder titan-alkoxide and the mol ratio of magnesium-containing compound are 10-60:1, are preferably 10-30:1).Be RMgX when described magnesium-containing compound is general formula ²grignard reagent time, first time load titanium tetrahalide used and total consumption of titan-alkoxide and the mol ratio of magnesium-containing compound can be 1-100:1, be preferably 1-20:1 (namely, total consumption of described a part of titanium tetrahalide and a part of titan-alkoxide and the mol ratio of magnesium-containing compound are 10-100:1, are preferably 1-20:1); Second time load titanium tetrahalide used and total consumption of titan-alkoxide and the mol ratio of magnesium-containing compound can be 1-100:1, be preferably 1-20:1 (namely, total consumption of described remainder titanium tetrahalide and remainder titan-alkoxide and the mol ratio of magnesium-containing compound are 1-100:1, are preferably 1-20:1).

Described a part of titanium tetrahalide and another part titanium tetrahalide can, for preparing the conventional various titanium tetrahalides used in olefin polymerization catalysis process, such as, can be all TiCl ₄, TiBr ₄and TiI ₄in at least one.In addition, described a part of titan-alkoxide and another part titan-alkoxide can, for preparing the conventional various titan-alkoxides used in olefin polymerization catalysis process, such as, can be all also Ti (OEt) Cl ₃, Ti (OEt) ₂cl ₂, Ti (OEt) ₃cl, Ti (OEt) ₄with Ti (OBu) ₄in at least one.

According to the present invention, the method of the magnesium mixture of described halloysite and the reaction product of a part of titanium tetrahalide and/or a part of titan-alkoxide being carried out solid-liquid separation can be the existing various method that can realize solid phase and liquid phase separation, such as suction filtration, press filtration or centrifugation, be preferably press filtration.The condition of the present invention to press filtration is not particularly limited, and is as the criterion with being separated of liquid phase to realize solid phase as far as possible fully.

After the preparation method of olefin polymerization catalyst components provided by the invention is also preferably included in and the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide reacted 0.5-2 hour at-20 DEG C to 0 DEG C and react 1-4 hour at 80-130 DEG C before, internal electron donor is added in reaction system, can make like this in the olefin polymerization catalyst components obtained also containing internal electron donor compound, thus improve the catalytic activity of catalyzer, and improve degree of isotacticity and the crystallinity of polyolefin resin.The concrete kind of described internal electron donor compound is hereinbefore about described by olefin polymerization catalyst components part has, and therefore not to repeat here.In addition, the consumption of described internal electron donor compound can be the routine selection of this area, and such as, in the magnesium mixture of described internal electron donor compound and described halloysite, the mol ratio of magnesium elements can be 0.05-0.6:1, is preferably 0.1-0.4:1.

According to another kind of embodiment of the present invention, when described nontransition metal component is aluminum contained compound, described olefin polymerization catalyst components prepares according to the method comprised the following steps:

(3) catalyst component of the halloysite of described activation and described activation is reacted 1-10 hour at 0-100 DEG C.

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

The present invention is not particularly limited the consumption of each material in step (1), step (2) and step (3).Such as, in step (1), the weight ratio of described halloysite and the first aluminum contained compound can be 1:0.1-20, is preferably 1:0.1-10, is more preferably 1:0.5-2.In step (2), the weight ratio of described transition metal component and the second aluminum contained compound can be 1:1-5000, is preferably 1:1-1000, is more preferably 1:50-120.In step (3), the weight ratio of the halloysite of described activation and the catalyst component of described activation can be 1:0.5-50, is preferably 1:1-20, is more preferably 1:1-5.

Described first aluminum contained compound and the second aluminum contained compound can be all the conventional aluminum contained compound used in olefin polymerization catalysis, and such as, described first aluminum contained compound and the second aluminum contained compound are independently of one another for general formula is Al (OR ') _qr " _3-qaluminum contained compound, wherein, R ' and R " are C independently of one another ₂-C ₁₀alkyl, 0≤q≤3.Particularly, described first aluminum contained compound and the second aluminum contained compound are at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, methylaluminoxane etc. independently of one another.

Reaction between the reaction of described halloysite and the first aluminum contained compound and described transition metal component and second contain after calorize is preferably carried out in organic solvent, and reaction can be made like this to carry out more reposefully.The kind of described organic solvent can be the existing various inert substance that can be used as reaction media, such as, can be C ₅-C ₁₀alkane, aromatic hydrocarbon, naphthenic hydrocarbon, C ₂-C ₁₂ether and tetrahydrofuran (THF) at least one, be preferably at least one in normal hexane, hexanaphthene, heptane, decane, ethanol, isopropylcarbinol, isooctyl alcohol, tetrahydrofuran (THF), methyl ether, ether, positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl ether, benzene,toluene,xylene, chlorobenzene etc.In addition, the consumption of described organic solvent makes the concentration of halloysite can be 1-500g/L usually, is preferably 2-50g/L.

In addition, the concrete kind of the metallocene compound in described metallocene catalyst and the non-metallocene compound in non-metallocene catalyst is hereinbefore about described by olefin polymerization catalyst components part has, and therefore not to repeat here.

According to another kind of embodiment of the present invention, when described nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound, described olefin polymerization catalyst components prepares according to the method comprised the following steps:

(5) at 0-110 DEG C, 1-10 hour is reacted containing the catalyst component of halloysite and the catalyst component of described activation by described activation.

Wherein, the kind of the reaction raw materials that step (1) relates to the reaction described in step (2) and consumption and concrete reaction conditions are all that in the preparation method of the olefin polymerization catalyst components of nontransition metal component, step (1) is identical with consumption and concrete reaction conditions with the kind of the reaction raw materials that step (2) relates to magnesium-containing compound with what above mention, and therefore not to repeat here.

In step (3), the temperature of reaction is 0-90 DEG C, is preferably 70-90 DEG C; The time of reaction is 1-20 hour, is preferably 4-10 hour.In step (4), the temperature of reaction is 0-90 DEG C, is preferably 0-20 DEG C; The time of reaction is 1-20 hour, is preferably 2-6 hour.In step (5), the temperature of reaction is 0-110 DEG C, is preferably 80-100 DEG C; The time of reaction is 1-10 hour, is preferably 2-6 hour.

Step (3) and the reaction described in step (4) are preferably carried out in organic solvent, and reaction can be made like this to carry out more reposefully.The kind of described organic solvent can be the existing various inert substance that can be used as reaction media, such as, can be C ₅-C ₁₀alkane, aromatic hydrocarbon, naphthenic hydrocarbon, C ₂-C ₁₂ether and tetrahydrofuran (THF) at least one, be preferably at least one in normal hexane, hexanaphthene, heptane, decane, ethanol, isopropylcarbinol, isooctyl alcohol, tetrahydrofuran (THF), methyl ether, ether, positive propyl ether, isopropyl ether, n-butyl ether, ethyl isobutyl ether, isoamyl ether, benzene,toluene,xylene, chlorobenzene etc.In addition, the consumption of described organic solvent can be the routine selection of this area usually, and therefore not to repeat here.

In step (3), described can be 1:0.1-20 containing the consumption of catalyst component of halloysite and the weight ratio of the consumption of described first aluminum contained compound, is preferably 1:0.5-1.5.In step (4), the weight ratio of total consumption of described metallocene compound and non-metallocene compound and the consumption of described second aluminum contained compound can be 1:1-1000, is preferably 1:30-60.In step (5), the weight ratio of the catalyst component of described activation and the catalyst component containing halloysite of described activation can be 1:0.1-20, is preferably 1:0.5-2.

The kind of the present invention to described promotor is not particularly limited, variously can form Ziegler-Natta catalyst, can metallocene catalyst be formed with metallocene compound or the material of non-metallocene catalyst can be formed with non-metallocene compound with titanium tetrahalide and/or titan-alkoxide for existing, can be such as aluminum alkyls and/or aluminum alkoxide, be specifically as follows at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, methylaluminoxane etc.In addition, the mol ratio of the transition metal in the aluminium element in described promotor and described olefin polymerization catalyst components can be 1-5000:1, is preferably 10-2000:1.

The consumption of the present invention to described olefin polymerization catalysis is not particularly limited, and such as, the consumption of described olefin polymerization catalysis can make the content of halloysite in alloy in the polypropylene that obtains be 0.0005-5 % by weight usually, is preferably 0.01-2.0 % by weight.It should be noted that, when halloysite is metahalloysite and/or organically-modified halloysite, the above-mentioned content of halloysite refers to the content of metahalloysite and/or organically-modified halloysite.

In polypropylene provided by the invention, the main improvements of the preparation method of alloy are to have employed a kind of olefin polymerization catalysis containing halloysite newly, and the concrete kind of reaction raw materials and proportioning and reaction conditions can be all the routine selection of this area.

Particularly, described alpha-olefin can be the monoolefine of existing various double bond in molecular chain end, such as, can be at least one in propylene, 1-butylene, 1-amylene, 1-hexene and 1-octene.In addition, in the second polymerization process, with the gross weight of described ethene and alpha-olefin for benchmark, the consumption of described ethene can be 1-99 % by weight, is preferably 20-50 % by weight; The consumption of described alpha-olefin can be 1-99 % by weight, is preferably 50-80 % by weight.In described first polymerization process, in the consumption of propylene and the second polymerization process, the weight ratio of total consumption of ethene and alpha-olefin can be 0.2-100:1, is preferably 0.5-10:1.

The condition of the present invention to described first polyreaction and the second polyreaction is not particularly limited.Such as, it can be 30-90 DEG C that the condition of described first polyreaction generally includes temperature of reaction, is preferably 40-80 DEG C, is more preferably 60-75 DEG C; Reaction times can be 0.05-10 hour, is preferably 0.1-2 hour, is more preferably 0.1-0.5 hour.In addition, when the propylene passed in the first polyreaction is propylene steam, it can be 0-40 normal atmosphere that the condition of described first polyreaction also comprises reaction pressure, is preferably 1-35 normal atmosphere, is more preferably 5-10 normal atmosphere.It can be 60-120 DEG C that the condition of described second polyreaction generally includes temperature of reaction, is preferably 75-95 DEG C, is more preferably 80-90 DEG C; Reaction times can be 0.1-10 hour, is preferably 0.1-2 hour, is more preferably 0.2-0.5 hour.In addition, it can be 0-15 normal atmosphere that the condition of the second polyreaction also comprises reaction pressure, is preferably 0.2-10 normal atmosphere, is more preferably 4-6 normal atmosphere.In the present invention, described pressure all refers to gauge pressure.In addition, described first polyreaction and/or the second polyreaction are preferably carried out in the presence of hydrogen gas.In the first polymerization process, relative to the propylene of 100 weight parts, the consumption of described hydrogen can be 0.001-0.5 weight part, is preferably 0.005-0.1 weight part; In the second polymerization process, relative to the described ethene of 100 weight parts and the gross weight of alpha-olefin, the consumption of described hydrogen can be 0.001-5 weight part, is preferably 0.02-0.15 weight part.

Described first polyreaction and the second polyreaction can be slurry polymerization, also can be bulk polymerization.When described polyreaction is slurry polymerization, described polyreaction also should be carried out in presence of organic solvent.Described organic solvent can be C ₅-C ₁₀alkane or C ₆-C ₈aromatic hydrocarbon, wherein, described C ₅-C ₁₀alkane be preferably at least one in heptane, normal hexane and hexanaphthene, described C ₆-C ₈aromatic hydrocarbon be preferably toluene.The consumption of described organic solvent can be the routine selection of this area, and therefore not to repeat here.

In addition, described first polyreaction can also be carried out under the existence of external electron donor.The kind of described external donor compound can be the routine selection of this area, such as, can be R for general formula ¹' _4-dsi (R ²') _dcompound, wherein, R ¹' and R ²' be alkyl, cycloalkyl or aryl independently of one another, 1≤d≤3.Particularly, the example of described external donor compound includes but not limited to: at least one in dimethyldimethoxysil,ne, trimethylmethoxysilane, methyltrimethoxy silane, dimethoxydiphenylsilane, diphenyl diethoxy silane and tetrahydrotoluene dimethoxysilane.In described external donor compound and described promotor, the mol ratio of aluminium element can be 0.001-1:1, is preferably 0.01-1:1, is more preferably 0.05-0.5:1.

In polypropylene provided by the invention, the second preparation method of alloy composite comprises:

Wherein, described by the kind of the reaction raw materials that each step relates to and consumption and reaction conditions have had hereinbefore, therefore not to repeat here.

In polypropylene provided by the invention, the third preparation method of alloy composite comprises:

In polypropylene provided by the invention, the 4th kind of preparation method of alloy composite comprises:

Present invention also offers alloy composite in the polypropylene that prepared by aforesaid method.

Below will be described the present invention by embodiment.

In following examples and comparative example:

In olefin polymerization catalyst components, the content of transition metal adopts ultraviolet spectrophotometry to measure.

In olefin polymerization catalyst components, the content of magnesium elements adopts volumetry to measure, specific as follows: to get 50mg catalyzer, under nitrogen protection; catalyzer is dissolved in 10mL sulphuric acid soln; be heated to boiling 10 minutes, then cross and filter insolubles, then adopt concentration to be 0.01molL ^-1eDTA carry out titration, adopt eriochrome black T as indicator in titration process, titration end point is when the color of the solution containing catalyzer becomes bluish voilet, the consumption of whole titration process EDTA is counted V (mL), then content=(0.01 × V ÷ 10) × 24.3 ÷ (50 × 10 of magnesium elements ^-3).

In alkene catalyst component, the content of aluminium element adopts titration measuring, specific as follows: pipette the above-mentioned liquid to be measured of 5mL in 250mL Erlenmeyer flask, accurately add 20mL EDTA standardized solution, xylenol orange 1-2 drips, and drips 8mol/L NH ₃h ₂o makes solution just become red, then the HCl solution dripping 3mol/L makes solution be yellow, then heated and boiled 10min on electrothermal oven, be cooled to room temperature with flowing water, add 200g/L hexamethylenetetramine solution 10mL, regulate with the HCl solution of 3mol/L, solution is made to be yellow, control pH=4-5.Add xylenol orange indicator 1, become orange with Zn standardized solution volumetric soiutions, be terminal.Aluminium element content is: (C _eDTAv _eDTA-C _znv _zn) × 0.53963.

In olefin polymerization catalyst components, the content of titanium and zr element adopts spectrophotometer to record, specific as follows: to get 50mg catalyzer, under nitrogen protection, catalyzer is dissolved in 10mL sulphuric acid soln, be heated to boiling 10 minutes, then cross and filter insolubles, then (410nm place surveys titanium elements at fixed wave length to adopt spectrophotometer to record this solution, 666nm place survey zr element) absorbancy, and by the concentration of titanium or zr element can be obtained in the comparison of 410nm or 666nm place absorbancy with typical curve, and and then calculate the content of titanium or zr element in olefin polymerization catalysis.

In olefin polymerization catalysis and polyolefine resin composition, the content of halloysite adopts thermogravimetic analysis (TGA) method to measure.

Embodiment 1

This embodiment is for illustration of alloy composite and preparation method thereof in olefin polymerization catalyst components provided by the invention and preparation method thereof and polypropylene.

(1) preparation method of olefin polymerization catalyst components:

1. by 2.0g Magnesium Chloride Anhydrous MgCl ₂be scattered in 20mL decane with 5.5mL isooctyl alcohol, be heated to 110 DEG C, form clear solution, react 4.0 hours at 110 DEG C, obtain magnesium chloride alcohol adduct.Then be added dropwise in the suspension of 3.0g halloysite and 100mL decane by above-mentioned magnesium chloride alcohol adduct, isothermal reaction 12.0 hours at 90 DEG C, obtains the magnesium mixture of halloysite.

2. be added dropwise in the 60mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, isothermal reaction 1.0 hours at-20 DEG C afterwards.Slowly be warming up to 60 DEG C, add 2.0 gram 9,9-bis-(methoxymethyl) fluorenes (described 9, in the magnesium mixture of 9-bis-(methoxymethyl) fluorenes and halloysite, the mol ratio of magnesium elements is 0.20:1), then isothermal reaction 2.0 hours at 110 DEG C, react rear filtering liquid, again added 60mL titanium tetrachloride, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 3-6 time, after drying, obtain the catalyst component containing halloysite.

3. 5.0 grams of catalyst components containing halloysite are scattered in 50mL toluene, then the toluene solution 30mL containing 0.1mol methylaluminoxane is added, react 4.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the catalyst component containing halloysite activated.

4. by 0.10 gram of transistion metal compound Et (Ind) ₂zrCl ₂add in the toluene solution 40mL containing 0.10mol methylaluminoxane, then react 4.0 hours at 20 DEG C, obtain the catalyst component solution activated.

5. the catalyst component solution of activation 4. described for step is added dropwise to and 3. prepares in the toluene suspension 50mL of the catalyst component containing halloysite of gained activation containing 5.0 grams of described steps, react 4.0 hours at 90 DEG C.After having reacted, by toluene wash 5 times, obtain olefin polymerization catalyst components after drying, be designated as C1.After testing, in this olefin polymerization catalyst components C1, the mass percentage of halloysite is 50%, the mass percentage of titanium elements is 1.78%, the mass percentage of magnesium elements is 3.20%, the mass percentage of zr element is 0.15%, the mass percentage of aluminium element is the mass percentage of 10.02%, 9,9-bis-(methoxymethyl) fluorenes is 5.60%.

Wherein, step 1. described in halloysite be metahalloysite, its preparation method is as follows: get 10 grams of natural halloysite mineral substance and calcine 12 hours at 100 DEG C, obtain 8.6 grams of metahalloysites.

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, propylene steam monomer is filled with in reactor, then add 100mL hexane, 5.5mmol triethyl aluminum and 30 milligrams of olefin polymerization catalyst components C1 successively, and reacting kettle inner pressure is controlled at 7.0 normal atmosphere, temperature of reaction is controlled react 0.5 hour at 60 DEG C.Then stop being filled with propylene steam monomer, under vacuum state, liquid in reactor is extracted, the gas mixture (mol ratio of ethene and propylene is 1:2) of ethene and propylene is passed into again in reactor, then reacting kettle inner pressure is controlled at 5.0 normal atmosphere, temperature of reaction is controlled at 80 DEG C, continue reaction 0.2 hour, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J1 in the polypropylene containing halloysite, wherein the content of halloysite is 0.85 % by weight.

Comparative example 1

This comparative example is for illustration of alloy composite and preparation method thereof in the olefin polymerization catalyst components and preparation method thereof of reference and polypropylene.

Alloy composite in olefin polymerization catalyst components and polypropylene is prepared according to the method for embodiment 1, unlike, in the preparation process of olefin polymerization catalyst components and in polypropylene alloy composite preparation process in all do not add halloysite, obtain not containing halloysite polypropylene in alloy composite DJ1.

Embodiment 2

(1) preparation method of olefin polymerization catalyst components:

2. be added dropwise in the 60mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 2 hours, isothermal reaction 1.0 hours at-20 DEG C afterwards.Slowly be warming up to 110 DEG C, add 0.5 gram 9,9-bis-(methoxymethyl) fluorenes (described 9, in the magnesium mixture of 9-bis-(methoxymethyl) fluorenes and halloysite, the mol ratio of magnesium elements is 0.15:1), then isothermal reaction 2.0 hours at 110 DEG C, react rear filtering liquid, again added 60mL titanium tetrachloride, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 5 times, after drying, obtain the catalyst component containing halloysite.

3. 5.0 grams of catalyst components containing halloysite are scattered in 50mL toluene, then the toluene solution 30mL containing 0.05mol methylaluminoxane is added, react 10.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the catalyst component containing halloysite activated.

4. by 0.15 gram of transistion metal compound rac-Me ₂si (2-Me-4-PhInd) ₂zrCl ₂(wherein, rac-represents racemization, lower same) adds in the toluene solution 40mL containing 0.10mol methylaluminoxane, then reacts 4.0 hours at 0 DEG C, obtains the catalyst component solution activated.

5. the catalyst component solution of activation 4. described for step is added dropwise to and 3. prepares in the toluene suspension 50mL of the catalyst component containing halloysite of gained activation containing 5.0 grams of described steps, react 4.0 hours at 90 DEG C.After having reacted, by toluene wash 5 times, obtain olefin polymerization catalyst components after drying, be designated as C2.After testing, in this olefin polymerization catalyst components C2, the mass percentage of halloysite is 42%, the mass percentage of titanium elements is 1.18%, the mass percentage of magnesium elements is 2.56%, the mass percentage of zr element is 0.10%, the mass percentage of aluminium element is the mass percentage of 6.58%, 9,9-bis-(methoxymethyl) fluorenes is 6.4%.

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, 500 grams of propylene liquid monomers are added in reactor, at 30 DEG C, then add 0.25mol triethyl aluminum, 20 milligrams of olefin polymerization catalyst components C2 and 0.2g hydrogen successively, then temperature of reaction is risen to 70 DEG C of reactions 0.2 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.05g hydrogen of 20g ethene and 60g propylene, then temperature of reaction is controlled to continue reaction 0.2 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J2 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0034 % by weight.

Embodiment 3

(1) preparation method of olefin polymerization catalyst components:

1. by 4.0g Magnesium Chloride Anhydrous MgCl ₂be scattered in 90mL decane with 13.0mL isooctyl alcohol, be heated to 130 DEG C, form clear solution, react 1.0 hours at 130 DEG C, obtain magnesium chloride alcohol adduct.Then be added dropwise in the suspension of 1.0g halloysite and 20mL decane by above-mentioned magnesium chloride alcohol adduct, isothermal reaction 4.0 hours at 60 DEG C, obtains the magnesium mixture of halloysite.

2. be added dropwise in the 200mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, isothermal reaction 1.0 hours at-20 DEG C afterwards.Slowly be warming up to 120 DEG C, add 0.2mL diisobutyl phthalate (in the magnesium mixture of described diisobutyl phthalate and halloysite, the mol ratio of magnesium elements is 0.15:1), then isothermal reaction 1.5 hours at 120 DEG C, react rear filtering liquid, again add 60mL titanium tetrachloride, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 5 times, obtain olefin polymerization catalyst components after drying, be designated as C3.After testing, in this olefin polymerization catalyst components C3, the mass percentage of halloysite is 18.0%, and the mass percentage of titanium elements is 1.68%, and the mass percentage of magnesium elements is 12%.

Wherein, step 1. described in halloysite be metahalloysite, its preparation method is as follows: get 10 grams of natural halloysite mineral substance and calcine 4 hours at 600 DEG C, obtain 8.1 grams of metahalloysites.

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, 450 grams of propylene liquid monomers are added in reactor, then at 30 DEG C, add 0.25mol triethyl aluminum, 0.052mol dimethyl diphenyl silane, 20 milligrams of olefin polymerization catalyst components C3 and 0.2g hydrogen successively, then temperature of reaction is risen to 60 DEG C of reactions 0.2 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.03g hydrogen of 20g ethene and 60g propylene, then temperature of reaction is controlled to continue reaction 0.2 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J3 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0055 % by weight.

Embodiment 4

(1) preparation method of olefin polymerization catalyst components:

Prepare olefin polymerization catalyst components according to the method for embodiment 2, obtain olefin polymerization catalyst components C2.

(2) preparation method of alloy in polypropylene:

Under vacuum conditions, 450 grams of propylene liquid monomers are added in reactor, at 30 DEG C, then add 0.25mol triethyl aluminum, 20 milligrams of olefin polymerization catalyst components C2 and 0.1g hydrogen successively, then temperature of reaction is risen to 75 DEG C of reactions 0.2 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.03g hydrogen of 20g ethene and 60g propylene, then temperature of reaction is controlled to continue reaction 0.2 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J4 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0075 % by weight.

Embodiment 5

(1) preparation method of olefin polymerization catalyst components:

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, 450 grams of propylene liquid monomers are added in reactor, at 30 DEG C, then add 0.25mol triethyl aluminum, 20 milligrams of olefin polymerization catalyst components C2 and 0.2g hydrogen successively, then temperature of reaction is risen to 70 DEG C of reactions 0.5 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.03g hydrogen of 20g ethene and 60g propylene, then temperature of reaction is controlled to continue reaction 0.2 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J5 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0043 % by weight.

Embodiment 6

(1) preparation method of olefin polymerization catalyst components:

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, 450 grams of propylene liquid monomers are added in reactor, at 30 DEG C, then add 0.25mol triethyl aluminum, 20 milligrams of olefin polymerization catalyst components C2 and 0.1g hydrogen successively, then temperature of reaction is risen to 70 DEG C of reactions 0.1 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.03g hydrogen of 20g ethene and 40g1-butylene, then temperature of reaction is controlled to continue reaction 0.2 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J6 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0071 % by weight.

Comparative example 2

Alloy composite in olefin polymerization catalyst components and polypropylene is prepared according to the method for embodiment 6, unlike, in the preparation process of olefin polymerization catalyst components and in polypropylene alloy composite preparation process in all do not add halloysite, obtain not containing halloysite polypropylene in alloy composite DJ2.

Embodiment 7

(1) preparation method of olefin polymerization catalyst components:

1. natural for 2.5g halloysite is scattered in 50mL n-butyl ether, obtains the suspension of halloysite.Then by the C containing 0.05mol ₄h ₉the n-butyl ether solution 50mL of MgCl is added dropwise in the suspension of described halloysite, constant temperature back flow reaction 20.0 hours at 40 DEG C, after having reacted, uses n-butyl ether to wash 5 times, obtains the magnesium mixture of halloysite after drying.

2. the magnesium mixture of step 1. described halloysite is scattered in the 20mL titanium tetrachloride of 20 DEG C, then 9 of 1.0g are added, 9-bis-(methoxymethyl) fluorenes (described 9, in the magnesium mixture of 9-bis-(methoxymethyl) fluorenes and halloysite, the mol ratio of magnesium elements is 0.20:1), react 2 hours at again temperature slowly being risen to 80 DEG C, use hexanes wash 5 times after having reacted, obtain olefin polymerization catalyst components after drying, be designated as C4.After testing, in this olefin polymerization catalyst components C4, the mass percentage of halloysite is 60%, and the mass percentage of titanium elements is 1.56%, and the mass percentage of magnesium elements is 3.44%.

(2) preparation method of alloy composite in polypropylene:

Under vacuum conditions, 450 grams of propylene liquid monomers are added in reactor, at 30 DEG C, then add 0.25mol triethyl aluminum, 20 milligrams of olefin polymerization catalyst components C4 and 0.2g hydrogen successively, then temperature of reaction is risen to 70 DEG C of reactions 0.5 hour.Then by emptying for the propylene monomer of the remnants in reactor and cool the temperature to 50 DEG C, then in reactor, pass into gas mixture and the 0.03g hydrogen of 10g ethene and 40g propylene, then temperature of reaction is controlled to continue reaction 0.5 hour at 90 DEG C, after having reacted, add acidic ethanol and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, finally obtain alloy composite J7 in the polypropylene containing halloysite, wherein the content of halloysite is 0.0072 % by weight.

Embodiment 8

(1) preparation method of olefin polymerization catalyst components:

1. get 2.5 grams of halloysites to be scattered in 50mL toluene, obtain the suspension of halloysite.Then the toluene solution 40mL containing 0.10mol methylaluminoxane is added dropwise in the suspension of above-mentioned halloysite, reacts 10.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the aluminium mixture of halloysite.

2. by 0.10 gram of transistion metal compound rac-Me ₂si (2-Me-4-PhInd) ₂zrCl ₂add 0 DEG C containing 0.2mol methylaluminoxane toluene solution 40mL in, at 0 DEG C react 4.0 hours, then drop in the toluene suspension 50mL of the aluminium mixture containing 5.0 grams of halloysites, at 60 DEG C react 10.0 hours.After having reacted, by toluene wash 5 times, obtain the olefin polymerization catalyst components containing halloysite after drying, be designated as C5.After testing, in this olefin polymerization catalyst components C5, the mass percentage of halloysite is 64%, and the mass percentage of zr element is 0.46%, and the mass percentage of aluminium element is 7.80%.

(2) preparation method of alloy composite in polypropylene:

Alloy composite in polypropylene is prepared according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C5 of olefin polymerization catalyst components C1 identical weight part substitutes, and obtain alloy composite J8 in the polypropylene containing halloysite, wherein the content of halloysite is 0.020 % by weight.

Test case

Test case is for illustration of the test of alloy combination physical performance in polypropylene.

(1) test of melt strength:

Determine that the experimental installation of melt strength is made up of the single screw extrusion machine and GottfertRheotens melt strength determinator being furnished with kapillary.First alloy composite melt in the polypropylene of melt strength to be measured is extruded from extruding dies, then the melt extrusion bundle batten the obtained roller that two direction of motion be contained on balance beam are contrary is drawn.When melt bundle is stretched stressed be the function of roll speed and time.Roller evenly accelerates to rotate, until the fracture of melt bundle, when being ruptured by melt bundle, suffered power is defined as melt strength.Acquired results is as shown in table 1.

(2) Mechanics Performance Testing:

Tensile strength measures according to the method specified in ASTM D638, and result is as shown in table 1.

Shock strength measures according to the method specified in ASTM D256A, and result is as shown in table 1.

Table 1

From the results shown in Table 1, by the olefin polymerization catalysis containing halloysite provided by the invention for the preparation of in polypropylene during alloy, in the polypropylene obtained, alloy composite has higher melt strength and mechanical strength.

More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.

It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.

In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.

Claims

1. the preparation method of alloy composite in a polypropylene, the method comprises makes propylene carry out the first polyreaction under the existence of olefin polymerization catalyst components and promotor, then in polymerization reaction system, ethene is passed into and alpha-olefin carries out the second polyreaction, it is characterized in that, described olefin polymerization catalyst components contains halloysite, transition metal component and nontransition metal component;

2. method according to claim 1, wherein, with the gross weight of described olefin polymerization catalyst components for benchmark, the content of described halloysite is 0.5-90 % by weight, and in described transition metal component and nontransition metal component, the total content of metallic element is 2-80 % by weight; Preferably, with the gross weight of described olefin polymerization catalyst components for benchmark, the content of described halloysite is 1-50 % by weight, and in described transition metal component and nontransition metal component, the total content of metallic element is 5-60 % by weight.

3. method according to claim 2, wherein, when described nontransition metal component is magnesium-containing compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal is 0.5-10 % by weight, and in described nontransition metal component, the content of non-transition metal elements is 2-30 % by weight;

When described nontransition metal component is aluminum contained compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal is 0.01-5 % by weight, and in described nontransition metal component, the content of non-transition metal elements is 2-40 % by weight;

When described nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound, with the gross weight of described olefin polymerization catalyst components for benchmark, in described transition metal component, the content of transition metal is 0.25-15 % by weight, and in described nontransition metal component, the content of non-transition metal elements is 5-50 % by weight.

4. according to the method in claim 1-3 described in any one, wherein, described halloysite is at least one in natural halloysite, metahalloysite and organically-modified halloysite; Described metahalloysite is by obtaining natural halloysite thermal treatment 0.5-48 hour at 50-900 DEG C; Described organically-modified halloysite is by obtaining natural halloysite and/or metahalloysite silicoorganic compound, titanium compound and not siliceous and titanium and end with at least one modification in the organic compound of double bond.

5. method according to claim 4, wherein, the general formula of described silicoorganic compound is R ¹r ²siR ³ ₂, R ¹for halogen atom, vinyl, amino, C ₁-C ₅aminoalkyl, epoxy group(ing), methacryloxy, sulfydryl, C ₁-C ₅alkoxyl group, urea groups or general formula be-(CH ₂) _m1cOOCH (CH ₃)=CH ₂containing the alkyl of alpha-olefin double bond, m1 is the integer of 1-18, R ²for halogen atom, C ₁-C ₅alkoxyl group or general formula be-(CH ₂) _m2-CH ₃alkyl, m2 is the integer of 0-2, R ³for halogen atom, C ₁-C ₅alkoxyl group or acetoxyl group; Preferably, described silicoorganic compound are γ-methacryloxypropyl trimethoxy silane and/or γ-aminopropyl triethoxysilane;

The general formula of described titanium compound is R ⁴ _pti (OR ⁵) _4-p, R ⁴and R ⁵for C ₁-C ₄alkyl, p is the integer of 0-3; Preferably, described titanium compound is at least one in tetrabutyl titanate, methyl triethoxy titanium, methyl trimethoxy oxygen base titanium and tetraethyl titanate;

Described not siliceous and titanium and end is R with the general formula of the organic compound of double bond ⁶r ⁷cH=CH ₂, R ⁶for acid chloride group, carboxyl, epoxy group(ing) or ester group, R ⁷for C ₁-C ₂₀alkylidene group or C with ester group, Sauerstoffatom or carboxyl ₁-C ₂₀alkylidene; Preferably, described not siliceous and titanium and end is HOOC (CH with the structural formula of the organic compound of double bond ₂) ₄cH=CH ₂, HOOC (CH ₂) ₇cH=CH ₂with HOOC (CH ₂) ₉cH=CH ₂in at least one.

6. according to the method in claim 1-3 described in any one, wherein, described titanium tetrahalide is TiCl ₄, TiBr ₄and TiI ₄in at least one; Described titan-alkoxide is Ti (OEt) Cl ₃, Ti (OEt) ₂cl ₂, Ti (OEt) ₃cl, Ti (OEt) ₄with Ti (OBu) ₄in at least one.

7. according to the method in claim 1-3 described in any one, wherein, in described metallocene catalyst the general formula of metallocene compound as shown in formula I:

(Cp ⁱ-B _e-Cp ^iI) M ' R ⁸ _ar ⁹ _bformula (I)

Wherein, M ' is Ti, Zr, Hf, V, Fe, Y, Sc or lanthanide series metal; Cp ⁱand Cp ^iIbe H, C independently of one another ₁-C ₅alkyl, replacement or non-substituted cyclopentadienyl, replacement or non-substituted C ₆-C ₁₈aryl, and substituting group is C ₁-C ₆alkyl, C ₃-C ₁₈cycloalkyl and C ₆-C ₁₈aryl at least one; R ⁸and R ⁹be H, halogen atom, C independently of one another ₁-C ₈alkyl, C ₁-C ₈alkoxyl group, C ₆-C ₂₀aryl, with C ₁-C ₁₅the C of alkyl ₇-C ₂₀aryl, C ₁-C ₈acyloxy, allyl group or C ₁-C ₁₅silylation, a, b are the integer of 0-2 independently of one another, and a+b=2; B is-C (R ¹⁰r ¹¹)-alkyl bridge or-Si (R ¹²r ¹³)-silylation bridge, wherein, R ¹⁰-R ¹³be H, C independently of one another ₁-C ₄alkyl or C ₆-C ₁₀aryl; E is the integer of 1-3;

Preferably, the metallocene compound in described metallocene catalyst is C ₂h ₄(Ind) ₂zrCl ₂, C ₂h ₄(H ₄ind) ₂zrCl ₂, Me ₂si (Ind) ₂zrCl ₂, Me ₂si (2-Me-4-Ph-Ind) ₂zrCl ₂, Me ₂si (Me ₄cp) ₂zrCl ₂, Me ₂si (Flu) ₂zrCl ₂, Me ₂si (2-Me-4-Naph-Ind) ₂zrCl ₂and Ph ₂si (Ind) ₂zrCl ₂in at least one, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl, and Ind is indenyl, H ₄ind is 4,5,6,7-tetrahydro-indenes, and Flu is fluorenyl, and Naph is naphthyl.

8. according to the method in claim 1-3 described in any one, wherein, in described non-metallocene catalyst the general formula of non-metallocene compound such as formula shown in (II):

Wherein, M is selected from Zr, Ti, V or Hf, R ₁, R ₂and R ₃be H, halogen atom, C independently of one another ₁-C ₈alkyl, C ₁-C ₈alkoxyl group, C ₆-C ₂₀aryl, with C ₁-C ₆alkyl aryl, with C ₃-C ₁₈cycloalkyl aryl, with C ₆-C ₁₈aryl, the C of aromatic base ₁-C ₈acyloxy, allyl group or C ₁-C ₁₅silylation, X is F, Cl, Br or I, and n is 2;

Preferably, the non-metallocene compound in described non-metallocene catalyst is at least one in two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride, two [N-(3-methyl salicylidene) anilino] zirconium dichloride, two [N-(3-sec.-propyl salicylidene) anilino] zirconium dichloride and two [N-(3-adamantyl-5-methyl salicylidene) anilino] zirconium dichloride.

9. according to the method in claim 1-3 described in any one, wherein, described magnesium-containing compound is general formula is MgX ¹ ₂magnesium halide and/or general formula be RMgX ²grignard reagent; At MgX ¹ ₂in, X ¹for F, Cl, Br or I; At RMgX ²in, R is C ₁-C ₁₀alkyl, X ²for F, Cl, Br or I; Preferably, the general formula of described aluminum contained compound is Al (OR ') _qr " _3-q, R ' and R " is C independently of one another ₂-C ₁₀alkyl, 0≤q≤3.

10., according to the method in claim 1-3 described in any one, wherein, when described nontransition metal component contains magnesium-containing compound, described olefin polymerization catalyst components is also containing internal electron donor compound; Preferably, described internal electron donor compound is diether compounds and/or carbonate.

11. according to the method in claim 1-3 described in any one, and wherein, described promotor is aluminum alkyls and/or aluminum alkoxide.

12. according to the method in claim 1-3 described in any one, and wherein, it is 30-90 DEG C that the condition of described first polyreaction comprises temperature of reaction, and the reaction times is 0.05-10 hour; Preferably, it is 60-120 DEG C that the condition of described second polyreaction comprises temperature of reaction, and the reaction times is 0.1-10 hour.

13. according to the method in claim 1-3 described in any one, and wherein, when described nontransition metal component is magnesium-containing compound, described olefin polymerization catalysis prepares according to the method comprised the following steps:

14. methods according to claim 13, wherein, described in step (1), the weight ratio of the consumption of halloysite and the consumption of described magnesium-containing compound is 1:0.5-99, is preferably 1:0.5-35.

15. methods according to claim 13, wherein, the mode of described coordination reaction be first by the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide is mixed be incorporated in-20 DEG C to 0 DEG C at react 0.5-2 hour, and then temperature is risen to 80-130 DEG C of reaction 1-4 hour, then by reaction product solid-liquid separation, and the solid product obtained and remainder titanium tetrahalide and/or remainder titan-alkoxide are reacted 1-4 hour at 80-130 DEG C.

16. methods according to claim 15, wherein, described a part of titanium tetrahalide and remainder titanium tetrahalide are TiCl independently of one another ₄, TiBr ₄and TiI ₄in at least one; Preferably, described a part of titan-alkoxide and remainder titan-alkoxide are Ti (OEt) Cl independently of one another ₃, Ti (OEt) ₂cl ₂, Ti (OEt) ₃cl, Ti (OEt) ₄with Ti (OBu) ₄in at least one.

17. methods according to claim 15 or 16, wherein, react 1-4 hour at 80-130 DEG C before, in reaction system, internal electron donor compound is added after the preparation method of described olefin polymerization catalysis is also included in and the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide reacted 0.5-2 hour at-20 DEG C to 0 DEG C; Preferably, described internal electron donor compound is diether compounds and/or carbonate.

18. according to the method in claim 1-3 described in any one, and wherein, when described nontransition metal component is aluminum contained compound, described olefin polymerization catalysis prepares according to the method comprised the following steps:

19. methods according to claim 18, wherein, the weight ratio of described halloysite and the first aluminum contained compound is 1:0.1-20; Preferably, the weight ratio of described transition metal component and the second aluminum contained compound is 1:1-5000; Preferably, the weight ratio of the halloysite of described activation and the catalyst component of described activation is 1:1-20; Preferably, described first aluminum contained compound and the second aluminum contained compound are independently of one another for general formula is Al (OR ') _qr " _3-qaluminum contained compound, R ' and R " are C independently of one another ₂-C ₁₀alkyl, 0≤q≤3.

20. according to the method in claim 1-3 described in any one, and wherein, when described nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound, described olefin polymerization catalysis prepares according to the method comprised the following steps:

21. methods according to claim 20, wherein, described in step (1), the weight ratio of the consumption of halloysite and the consumption of described magnesium-containing compound is 1:0.5-99, is preferably 1:0.5-35.

22. methods according to claim 21, wherein, the mode of described coordination reaction be first by the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or another part titan-alkoxide is mixed be incorporated in-20 DEG C to 0 DEG C at react 0.5-2 hour, and then temperature is risen to 80-130 DEG C of reaction 1-4 hour, then by reaction product solid-liquid separation, and the solid product obtained and remainder titanium tetrahalide and/or remainder titan-alkoxide are reacted 1-4 hour at 80-130 DEG C.

23. methods according to claim 22, wherein, described a part of titanium tetrahalide and remainder titanium tetrahalide are TiCl independently of one another ₄, TiBr ₄and TiI ₄in at least one; Described a part of titan-alkoxide and remainder titan-alkoxide are Ti (OEt) Cl independently of one another ₃, Ti (OEt) ₂cl ₂, Ti (OEt) ₃cl, Ti (OEt) ₄with Ti (OBu) ₄in at least one.

24. methods according to claim 22 or 23, wherein, react 1-4 hour at 80-130 DEG C before, in reaction system, internal electron donor compound is added after the preparation method of described olefin polymerization catalysis is also included in and the magnesium mixture of described halloysite and a part of titanium tetrahalide and/or a part of titan-alkoxide reacted 0.5-2 hour at-20 DEG C to 0 DEG C; Preferably, described internal electron donor compound is diether compounds and/or carbonate.

25. methods according to claim 20, wherein, described is 1:0.1-20 containing the consumption of catalyst component of halloysite and the weight ratio of the consumption of described first aluminum contained compound; Preferably, the weight ratio of total consumption of described metallocene compound and non-metallocene compound and the consumption of described second aluminum contained compound is 1:1-1000; Preferably, the weight ratio of the catalyst component of described activation and the catalyst component containing halloysite of described activation is 1:0.1-20; Preferably, described first aluminum contained compound and the second aluminum contained compound are independently of one another for general formula is Al (OR ') _qr " _3-qaluminum contained compound, R ' and R " are C independently of one another ₂-C ₁₀alkyl, 0≤q≤3.

The preparation method of alloy composite in 26. 1 kinds of polypropylenes, the method comprises the following steps:

The preparation method of alloy composite in 27. 1 kinds of polypropylenes, the method comprises the following steps:

The preparation method of alloy composite in 28. 1 kinds of polypropylenes, the method comprises the following steps:

Alloy composite in 29. polypropylenes prepared by the method in claim 1-28 described in any one.