CN104448063A - Components and preparation method of catalyst for polymerization of olefin as well as catalyst for polymerization of olefin and application of catalyst for polymerization of olefin - Google Patents

Components and preparation method of catalyst for polymerization of olefin as well as catalyst for polymerization of olefin and application of catalyst for polymerization of olefin Download PDF

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CN104448063A
CN104448063A CN201410647435.5A CN201410647435A CN104448063A CN 104448063 A CN104448063 A CN 104448063A CN 201410647435 A CN201410647435 A CN 201410647435A CN 104448063 A CN104448063 A CN 104448063A
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halloysite
compound
olefin polymerization
polymerization catalyst
catalyst components
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董金勇
秦亚伟
王宁
牛慧
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Abstract

The invention provides components and a preparation method of a catalyst for polymerization of olefin as well as the catalyst for polymerization of olefin and an application of the catalyst for polymerization of olefin. The catalyst for polymerization of olefin comprises the components of the catalyst for polymerization of olefin and a co-catalyst, wherein the components of the catalyst for polymerization of olefin comprise halloysite, a transition metal component and a non-transition metal component, wherein 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 a 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 the non-metallocene compound, the non-transition metal component is a mixture of the magnesium-containing compound and the aluminum-containing compound. When the halloysite-containing catalyst for polymerization of olefin is used in the polymerization reaction of olefin, obtained polyolefin has higher melt strength and mechanical property.

Description

A kind of olefin polymerization catalyst components and preparation method thereof and olefin polymerization catalysis and application thereof
Technical field
The present invention relates to a kind of olefin polymerization catalyst components, the preparation method of described olefin polymerization catalyst components, the olefin polymerization catalyst components prepared by the method, olefin polymerization catalysis containing described olefin polymerization catalyst components and the application of described olefin polymerization catalysis in olefinic polyreaction.
Background technology
The innovation of olefin polymerization catalysis on the Nomenclature Composition and Structure of Complexes is one of main drive of promoting of the regulation and control composition of polyolefin resin and character, promotion polyolefin properties.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 be applied in the research of polyolefine high performance, some High performance polyolefin resins with wide application prospect still lack effective catalyzed polymerization preparation means.Such as, the long-chain branching polypropylene (HMS-PP) with high fondant-strength has broad application prospects in the Application Areas such as blowing, foaming, but there is no effective catalyst system at present and polymerization process directly can prepare HMS-PP in polymeric kettle.And for example, 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.Such as, the preparation method of polypropylene-base high-content halloysite nanotubes matrix material and performance (Deng Chengye, Huang Hanxiong, Journal of Chemical Industry and Engineering, 2013,64 (10): 3824-3830) disclose and halloysite nanotubes HNTs is put into vacuum drying oven carry out drying, then by HNTs and PP of drying and PP-g-MAH and oxidation inhibitor evenly blended.Although adopt the method can improve the melt strength of polyolefin resin to a certain extent and improve its mechanical property, but because Blending Processes is difficult to ensure that halloysite is evenly distributed in polyolefin resin, the therefore melt strength of polyolefin resin and the limited extent of mechanical property raising.
Summary of the invention
The object of the invention is to overcome the lower and defect that mechanical strength is poor of the melt strength of polyolefin resin adopting existing method to prepare, and the preparation method of a kind of new olefin polymerization catalyst components, described olefin polymerization catalyst components, the olefin polymerization catalyst components prepared by the method, olefin polymerization catalysis containing described olefin polymerization catalyst components and the application of described olefin polymerization catalysis in olefinic polyreaction are provided.
Particularly, olefin polymerization catalyst components provided by the invention 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.
The first preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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.
The second preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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.
The third preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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 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, 1-10 hour is reacted containing the catalyst component of halloysite and the catalyst component of described activation by described activation.
Present invention also offers the olefin polymerization catalyst components prepared by aforesaid method.
Present invention also offers a kind of olefin polymerization catalysis, wherein, described olefin polymerization catalysis contains above-mentioned olefin polymerization catalyst components and promotor.
In addition, present invention also offers the application of described olefin polymerization catalysis in olefinic polyreaction.
The present inventor finds after further investigation, and when the olefin polymerization catalysis containing halloysite provided by the invention is used for olefinic polyreaction, the polyolefin resin obtained 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 polyolefin resin by halloysite with nanoscale, realize the nano combined of halloysite and polyolefin resin, 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 polyolefin resin, improve the melt strength of polyolefin resin and the phase interface effect improved in phase polyolefin resin system, and then improve melt strength and the mechanical property of polyolefin resin.In addition, the olefin polymerization catalysis containing halloysite provided by the invention may be used for preparing alloy resin in olefin homo, olefin copolymer and polypropylene, has prospects for commercial application.
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.
Olefin polymerization catalyst components provided by the invention contains halloysite, transition metal component and nontransition metal component, and wherein, 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.
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):
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.
According to olefin polymerization catalyst components provided by the invention, 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.
The first preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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.
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.
According to the preparation method of olefin polymerization catalyst components provided by the invention, 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 joining in the solution that the magnesium mixture of halloysite then can be scattered in containing titanium tetrahalide and/or titan-alkoxide by outer 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.Be MgX when described magnesium-containing compound is general formula 1 2magnesium halide time, 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.
According to the preparation method of olefin polymerization catalyst components provided by the invention, after the method 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 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.
The second preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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.
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 having in olefin polymerization catalyst components part, and therefore not to repeat here.
The third preparation method of olefin polymerization catalyst components provided by the invention comprises the following steps:
(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 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, 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.
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 " be the alkyl of C2-C10 independently of one another, 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.
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.
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 having in olefin polymerization catalyst components part, and therefore not to repeat here.
Present invention also offers the olefin polymerization catalyst components prepared by aforesaid method.
Olefin polymerization catalysis provided by the invention contains above-mentioned olefin polymerization catalyst components and/or the olefin polymerization catalyst components that prepared by aforesaid method and promotor.
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.
In addition, present invention also offers the application of described olefin polymerization catalysis in olefinic polyreaction.
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 olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(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. drop in the 200mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, then isothermal reaction 1.0 hours at-20 DEG C.Then 120 DEG C are slowly warming up to, 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), isothermal reaction 1.5 hours at 120 DEG C afterwards, react rear filtering liquid, again add 240mL 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 C1.After testing, in this olefin polymerization catalyst components C1, the mass percentage of halloysite is 18.0%, and the mass percentage of transition metal Ti is 1.68%, and the mass percentage of metallic element magnesium 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 polyolefine resin composition:
1. propylene homo:
Under vacuum conditions, propylene steam monomer is filled with in reactor, then 50mL hexane is added successively, containing the n-heptane solution 3mL of the triethyl aluminum of 5.5mmol, containing n-heptane solution 3mL and 20 milligram of olefin polymerization catalyst components C1 of 0.55mmol dimethoxydiphenylsilane, and by the pressure-controlling in reactor at 5.0 normal atmosphere, temperature of reaction controls at 60 DEG C, polyreaction 0.5 hour, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtain homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.02 % by weight.
2. copolymerization of propylene:
Under vacuum conditions, the gas mixture (mol ratio of propylene and ethene is 95:5) of propylene and ethene is filled with in reactor, then 100mL hexane is added successively, containing the heptane 1mL of 1.8mmol triethyl aluminum, containing n-heptane solution 1mL and 20 milligram of olefin polymerization catalyst components C1 of 0.1mmol dimethyl diphenyl silane, and by the pressure-controlling in reactor at 5 normal atmosphere, temperature controls at 60 DEG C, polyreaction 1.0 hours, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtain acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.016 % by weight.
Comparative example 1
This comparative example is for illustration of the olefin polymerization catalyst components and preparation method thereof and polyolefine resin composition and preparation method thereof of reference.
Olefin polymerization catalyst components and polyolefine resin composition is prepared according to the method for embodiment 1, unlike, halloysite in this comparative example does not add in the preparation process of olefin polymerization catalyst components, but directly carry out blended with the homo-polypropylene resin obtained and acrylic resin copolymer, concrete steps are as follows:
(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 20mL decane by above-mentioned magnesium chloride alcohol adduct, at 60 DEG C, isothermal reaction 4.0 hours, obtains magnesium mixture.
2. by step 1. described magnesium mixture drop in the 200mL titanium tetrachloride of-20 DEG C, time for adding is 1 hour, then isothermal reaction 1.0 hours at-20 DEG C.Then 120 DEG C are slowly warming up to, 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), isothermal reaction 1.5 hours at 120 DEG C afterwards, react rear filtering liquid, again add 240mL titanium tetrachloride, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 5 times, obtain the olefin polymerization catalyst components of reference after drying, be designated as DC1.After testing, in the olefin polymerization catalyst components DC1 of this reference, the mass percentage of transition metal Ti is 2.33%, and the mass percentage of metallic element magnesium is 18%.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Under vacuum conditions, propylene steam monomer is filled with in reactor, then 50mL hexane is added successively, containing the n-heptane solution 3mL of the triethyl aluminum of 5.5mmol, containing the olefin polymerization catalyst components DC1 of n-heptane solution 3mL and the 20 milligram reference of 0.55mmol dimethoxydiphenylsilane, and by the pressure-controlling in reactor at 5.0 normal atmosphere, temperature of reaction controls at 60 DEG C, polyreaction 0.5 hour, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtain homo-polypropylene resin.Then above-mentioned homo-polypropylene resin is mixed with 1.0g halloysite, obtain the homo-polypropylene resin combination of halloysite.After testing, should be 5.0 % by weight containing the content of halloysite in the homo-polypropylene resin combination of halloysite.
2. copolymerization of propylene:
Under vacuum conditions, the gas mixture (mol ratio of propylene and ethene is 95:5) of propylene and ethene is filled with in reactor, then 100mL hexane is added successively, containing the heptane 1mL of 1.8mmol triethyl aluminum, containing the olefin polymerization catalyst components DC1 of n-heptane solution 1mL and the 20 milligram reference of 0.1mmol dimethyl diphenyl silane, and by the pressure-controlling in reactor at 5 normal atmosphere, temperature controls at 60 DEG C, polyreaction 1.0 hours, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtain acrylic resin copolymer.Then above-mentioned acrylic resin copolymer is mixed with 1.0g halloysite, obtain the acrylic resin copolymer composition of halloysite.After testing, should be 4.5 % by weight containing the content of halloysite in the acrylic resin copolymer composition of halloysite.
Comparative example 2
This comparative example is for illustration of the olefin polymerization catalyst components and preparation method thereof and polyolefine resin composition and preparation method thereof of reference.
Olefin polymerization catalyst components and polyolefine resin composition is prepared according to the method for embodiment 1, unlike, in the preparation process of olefin polymerization catalyst components and in the preparation process of polyolefine resin composition, all do not add halloysite, obtain not containing the homo-polypropylene resin combination of halloysite and not containing the acrylic resin copolymer composition of halloysite.
Embodiment 2
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. by 2.0g Magnesium Chloride Anhydrous MgCl 2be scattered in 50mL decane with 12.5mL ethanol, be heated to 110 DEG C, form clear solution, react 2.0 hours at 110 DEG C, obtain magnesium chloride alcohol adduct.Then be added dropwise in the suspension of 1.0g halloysite and 50mL decane by described magnesium chloride alcohol adduct, isothermal reaction 4.0 hours at 110 DEG C, obtains the magnesium mixture of halloysite.
2. drop in the 120mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, then isothermal reaction 1.0 hours at-20 DEG C.Then 120 DEG C are slowly warming up to, 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 0.10:1), isothermal reaction 1.5 hours at 120 DEG C afterwards, react rear filtering liquid, again added 150mL titanium tetrachloride, isothermal reaction 2.0 hours at 120 DEG C.Finally, with hexanes wash 5 times, obtain after drying, containing halloysite olefin polymerization catalyst components, being designated as C2.After testing, in this olefin polymerization catalyst components C2, the mass percentage of halloysite is 26%, the mass percentage of transition metal Ti is 2.82%, the mass percentage of metallic element magnesium is 12.5%, the mass percentage of 9,9-bis-(methoxymethyl) fluorenes is 10.2%.
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 polyolefine resin composition:
1. propylene homo:
Under vacuum state, 450 grams of propylene liquids are added in reactor, then 0.25mol triethyl aluminum, 0.005 gram of hydrogen and 35 milligrams of olefin polymerization catalyst components C2 are added successively, and reacting kettle inner pressure being controlled at 5.0 normal atmosphere, temperature of reaction controls at 70 DEG C, polyreaction 1.0 hours, after being polymerized, by gas emptying in reactor, discharging, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.0046 % by weight.
2. copolymerization of propylene:
Under vacuum conditions, the gas mixture (mol ratio of propylene and ethene is 99:1) of propylene and ethene is filled with in reactor, then 100mL hexane and 45 milligrams of olefin polymerization catalyst components C2 are added successively, and by the pressure-controlling in reactor at 6.0 normal atmosphere, temperature controls at 50 DEG C, polyreaction 1.0 hours, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.18 % by weight.
Embodiment 3
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. by 2.0g Magnesium Chloride Anhydrous MgCl 2be scattered in 50mL decane with 2.8mL isooctyl alcohol, be heated to 130 DEG C, form clear solution, react 4.0 hours at 130 DEG C, obtain magnesium chloride alcohol adduct.Then be added dropwise in the suspension of 0.5g halloysite and 10mL decane by above-mentioned magnesium chloride alcohol adduct, isothermal reaction 10.0 hours at 60 DEG C, obtains the magnesium mixture of halloysite.
2. drop in the 125mL titanium tetrachloride of-10 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 2 hours, then isothermal reaction 1.0 hours at-10 DEG C.Then 120 DEG C are slowly warming up to, add 0.1mL ethyl benzoate (in the magnesium mixture of described ethyl benzoate and halloysite, the mol ratio of magnesium elements is 0.20:1), isothermal reaction 2.0 hours at 120 DEG C afterwards, react rear filtering liquid, again add 120mL 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 12%, and the mass percentage of transition metal Ti is 2%, and the mass percentage of metallic element magnesium is 18%, and ethyl benzoate mass percentage is 5%.
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 300 DEG C, obtain 8.3 grams of metahalloysites.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C3 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.016 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C3 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.20 % by weight.
Embodiment 4
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. by 1.0g Magnesium Chloride Anhydrous MgCl 2be scattered in 20mL decane with 5.5mL isooctyl alcohol, be heated to 110 DEG C, form clear solution, react 6.0 hours at 110 DEG C, obtain the alcohol adduct of magnesium chloride.Then be added dropwise to by the alcohol adduct of above-mentioned magnesium chloride in the suspension of 1.5g halloysite and 100mL decane, isothermal reaction 10.0 hours at 90 DEG C, obtains the magnesium mixture of halloysite.
2. drop in the 50mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, then isothermal reaction 1.0 hours at-20 DEG C.Then be slowly warming up to 110 DEG C, then isothermal reaction 2.0 hours at 110 DEG C, has reacted rear filtering liquid, has again added 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 C4.After testing, in this olefin polymerization catalyst components C4, the mass percentage of halloysite is 49%, and the mass percentage of transition metal Ti is 2.56%, and the mass percentage of metallic element magnesium is 5.8%.
Wherein, step 1. halloysite used is the halloysite through γ-methacryloxypropyl trimethoxy silane modification, and it prepares by the following method:
10 grams of halloysites are scattered in 500mL ethanol and form suspension, 12 grams of γ-methacryloxypropyl trimethoxy silane are added in this suspension, react at 80 DEG C after 4.0 hours and filter, by washing with alcohol three times, vacuum-drying 20.0 hours at 80 DEG C again, obtains the halloysite through γ-methacryloxypropyl trimethoxy silane modification.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C4 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.020 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C4 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.12 % by weight.
Embodiment 5
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. by 2.0g Magnesium Chloride Anhydrous MgCl 2be scattered in 50mL decane with 5.5mL isooctyl alcohol, be heated to 130 DEG C, form clear solution, react 4.0 hours at 130 DEG C, obtain described 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 20.0 hours at 60 DEG C, obtains the magnesium mixture of halloysite.
2. drop in the 100mL titanium tetrachloride of-20 DEG C by the magnesium mixture of step 1. described halloysite, time for adding is 1 hour, then isothermal reaction 1.0 hours at-20 DEG C.Then 60 DEG C are slowly warming up to, add 0.1 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 0.05:1), then continue slowly to be warming up to 120 DEG C, isothermal reaction 1.5 hours, reacted rear filtering liquid, again add 120mL 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 C5.After testing, in this olefin polymerization catalyst components C5, the mass percentage of halloysite is 50%, and the mass percentage of transition metal Ti is 1.5%, and the mass percentage of metallic element magnesium is 10%, the mass percentage of 9,9-bis-(methoxymethyl) fluorenes is 2.0%.
Wherein, step 1. halloysite used is the halloysite through γ-aminopropyl triethoxysilane modification, and it prepares by the following method:
10 grams of halloysites are scattered in 500mL ethanol and form suspension, 5 grams of γ-aminopropyl triethoxysilanes are added in this suspension, react at 80 DEG C after 4.0 hours and filter, by washing with alcohol three times, vacuum-drying 20.0 hours at 80 DEG C again, obtains the halloysite through γ-aminopropyl triethoxysilane modification.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C5 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.009 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C5 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.20 % by weight.
Embodiment 6
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. 10.0 grams of halloysites are scattered in 100mL tetrahydrofuran (THF), obtain the suspension of halloysite.Then will containing 0.10molC 4h 9the tetrahydrofuran solution 50mL of MgCl is added dropwise in the suspension of above-mentioned halloysite, back flow reaction 20.0 hours at 80 DEG C, after having reacted, uses tetrahydrofuran (THF) to wash 5 times, obtains the magnesium mixture of halloysite after drying.
2. be scattered in by the magnesium mixture of 5.0 grams of described halloysites in the 10mL titanium tetrachloride at 20 DEG C, react 2.0 hours at being warming up to 120 DEG C, after having reacted, filter, hexanes wash 5 times, obtains olefin polymerization catalyst components after drying, is designated as C6.After testing, in this olefin polymerization catalyst components C6, the mass percentage of halloysite is 60%, and the mass percentage of transition metal Ti is 1.10%, and the mass percentage of metallic element magnesium is 3.50%.
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 polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C6 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.011 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C6 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.18 % by weight.
Embodiment 7
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. 10.0 grams of halloysites are scattered in 50mL ether, obtain the suspension of halloysite.Then will containing 0.05molC 4h 9the 50mL diethyl ether solution of MgBr is added dropwise in the suspension of above-mentioned halloysite, constant temperature back flow reaction 20.0 hours at 40 DEG C, after having reacted, uses washed with diethylether 5 times, obtains the magnesium mixture of halloysite after drying.
2. the magnesium mixture getting 5.0 grams of described halloysites is scattered in the 20mL titanium tetrachloride of 20 DEG C, reacts 2.0 hours at being slowly warming up to 80 DEG C, after having reacted, filters, hexanes wash 5 times, obtains, containing halloysite olefin polymerization catalyst components, being designated as C7 after drying.After testing, in this olefin polymerization catalyst components C7, the mass percentage of halloysite is 65%, and the mass percentage of transition metal Ti is 1.20%, and the mass percentage of metallic element magnesium is 3.60%.
Wherein, step 1. described in halloysite be metahalloysite, its preparation method is as follows: get 10 grams of natural halloysite mineral substance and calcine 4 hours at 600 DEG C, obtain 8.1 grams of metahalloysites.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C7 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.011 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 1, unlike, the olefin polymerization catalyst components C7 of olefin polymerization catalyst components C1 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.12 % by weight.
Embodiment 8
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. 2.5 grams of halloysites are scattered in 50mL n-butyl ether, obtain the suspension of halloysite.Then will containing 0.05molC 4h 9the 50mL n-butyl ether solution of MgBr is added dropwise in the suspension of above-mentioned 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 getting 5.0 grams of described halloysites is scattered in the 40mL titanium tetrachloride of 20 DEG C, reacts 2.0 hours at being warming up to 120 DEG C, and after having reacted, filter, hexanes wash 5 times, obtains olefin polymerization catalyst components after drying, be designated as C8.After testing, in this olefin polymerization catalyst components C8, the mass percentage of halloysite is 58%, and the mass percentage of transition metal Ti is 1.36%, and the mass percentage of metallic element magnesium is 3.18%.
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 polyolefine resin composition:
1. propylene homo:
Under vacuum conditions, propylene steam monomer is filled with in reactor, then 100mL heptane, 5.5mmol triethyl aluminum, 0.55mmol methyltrimethoxy silane and 30 milligrams of olefin polymerization catalyst components C8 are added successively, and reacting kettle inner pressure is controlled at 7.0 normal atmosphere, temperature of reaction controls at 60 DEG C, polyreaction 0.5 hour, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.068 % by weight.
2. copolymerization of propylene:
Under vacuum conditions, propylene and ethene gas mixture (mol ratio of propylene and ethene is 100:1) are filled with in reactor, then 100mL hexane is added successively, 1.8mmol triethyl aluminum, 0.18mmol dimethyl diphenyl silane and 20 milligrams are containing olefin polymerization catalyst components C8, and by the pressure-controlling in reactor at 5.0 normal atmosphere, temperature controls at 60 DEG C, polyreaction 1.0 hours, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtain acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.061 % by weight.
Embodiment 9
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. 5.0 grams of halloysites are scattered in 50mL ether, obtain the suspension of halloysite.Then will containing 0.20molC 3h 7the 50mL diethyl ether solution of MgI is added dropwise in the ether suspension of above-mentioned halloysite, constant temperature back flow reaction 48.0 hours at 40 DEG C, after having reacted, uses washed with diethylether 5 times, obtains the magnesium mixture of halloysite after drying.
2. be scattered in the 100mL titanium tetrachloride of 0 DEG C by the magnesium mixture of 5.0 grams of described halloysites, react 2.0 hours at being warming up to 120 DEG C, after having reacted, filter, hexanes wash 5 times, obtains olefin polymerization catalyst components after drying, is designated as C9.After testing, in this olefin polymerization catalyst components C9, the mass percentage of halloysite is 62%, and the mass percentage of transition metal Ti is 0.98%, and the mass percentage of metallic element magnesium is 3.50%.
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 600 DEG C, obtain 8.05 grams of metahalloysites.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 8, unlike, the olefin polymerization catalyst components C9 of olefin polymerization catalyst components C8 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.008 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 8, unlike, the olefin polymerization catalyst components C9 of olefin polymerization catalyst components C8 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.09 % by weight.
Embodiment 10
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. get 5.0 grams of halloysites to be scattered in 50mL toluene, obtain the suspension of halloysite.Then the toluene solution 30mL containing 0.05mol 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 0.05 gram of transistion metal compound Et (Ind) 2zrCl 2add 0 DEG C containing 0.1mol methylaluminoxane toluene solution 40mL in, at 0 DEG C react 2.0 hours, be then added dropwise in the toluene suspension 50mL of the aluminium mixture containing 5.0 grams of halloysites, at 60 DEG C react 4.0 hours.After having reacted, by toluene wash 5 times, obtain olefin polymerization catalyst components after drying, be designated as C10.After testing, in this olefin polymerization catalyst components C10, the mass percentage of halloysite is 70%, and the mass percentage of zr element is 0.08%, and the mass percentage of aluminium element is 9.87%.
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 polyolefine resin composition:
1. ethylene homo:
Under vacuum conditions, vinyl monomer is filled with in reactor, then 100ml toluene, toluene solution 1.6mL and 20 milligram of olefin polymerization catalyst components C10 containing 0.8mmol methylaluminoxane is added successively, and reacting kettle inner pressure is controlled at 5.0 normal atmosphere, temperature of reaction controls at 50 DEG C, polyreaction 1.0 hours, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtains homopolymerisation polyethylene resin combination.After testing, in homopolymerisation polyethylene resin combination, the content of halloysite is 0.14 % by weight.
2. copolymerization of propylene:
Under vacuum conditions, propylene and ethene gas mixture (mol ratio of propylene and ethene is 95:5) are filled with in reactor, then 100mL toluene, toluene solution 3.0mL and 30 milligram of olefin polymerization catalysis C10 containing 2.1mmol methylaluminoxane is added successively, and by the pressure-controlling in reactor at 5.0 normal atmosphere, temperature controls at 50 DEG C, polyreaction 0.5 hour, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.13 % by weight.
Comparative example 3
This comparative example is for illustration of the olefin polymerization catalyst components and preparation method thereof and polyolefine resin composition and preparation method thereof of reference.
Olefin polymerization catalyst components and polyolefine resin composition is prepared according to the method for embodiment 10, unlike, in the preparation process of olefin polymerization catalyst components and in the preparation process of polyolefine resin composition, all do not add halloysite, obtain not containing the homo-polypropylene resin combination of halloysite and not containing the acrylic resin copolymer composition of halloysite.
Embodiment 11
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(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 2(wherein, rac-represents racemization, lower with) add 0 DEG C containing 0.2mol methylaluminoxane toluene solution 40mL in, at 0 DEG C react 4.0 hours, then be added dropwise in the toluene suspension 50mL of the aluminium mixture containing 5.0 grams of halloysites, react 10.0 hours at 60 DEG C.After having reacted, by toluene wash 5 times, obtain the olefin polymerization catalyst components containing halloysite after drying, be designated as C11.After testing, in this olefin polymerization catalyst components C11, 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%.
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 polyolefin resin:
1. ethylene homo:
Ethylene homo reaction is carried out according to the method for embodiment 10, unlike, the olefin polymerization catalyst components C11 of olefin polymerization catalyst components C10 identical weight part is substituted, obtains homopolymerisation polyethylene resin combination.After testing, in homopolymerisation polyethylene resin combination, the content of halloysite is 0.12 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 10, unlike, the olefin polymerization catalyst components C11 of olefin polymerization catalyst components C10 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.10 % by weight.
Embodiment 12
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. get 3.0 grams of halloysites to be scattered in 30mL toluene, obtain the suspension of halloysite.Then the toluene solution 30mL containing 0.1mol methylaluminoxane is added dropwise in the suspension of above-mentioned halloysite, reacts 5.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the aluminium mixture of halloysite.
2. by 0.15 gram of transistion metal compound Me 2c (Cp) (Flu) ZrCl 2add 0 DEG C containing 0.25mol methylaluminoxane toluene solution 40mL in, at 0 DEG C react 4.0 hours, be then added dropwise in the toluene suspension 50mL of the aluminium mixture containing 5.0 grams of halloysites, at 60 DEG C react 4.0 hours.After having reacted, by toluene wash 5 times, obtain olefin polymerization catalyst components after drying, be designated as C12.After testing, in this olefin polymerization catalyst components C12, the mass percentage of halloysite is 62%, and the mass percentage of zr element is 0.22%, and the mass percentage of aluminium element is 9.12%.
Wherein, step 1. described in halloysite be metahalloysite, its preparation method is as follows: get 10 grams of natural halloysite mineral substance and calcine 12 hours at 100 DEG C, obtain 8.6 grams of metahalloysites.
(2) preparation method of polyolefine resin composition:
1. propylene homo:
Under vacuum conditions, propylene steam monomer is filled with in reactor, then 100mL toluene, toluene solution 3.0mL and 30 milligram of olefin polymerization catalyst components C12 containing 3.2mmol methylaluminoxane is added successively, and reacting kettle inner pressure is controlled at 3.0 normal atmosphere, temperature of reaction controls at 50 DEG C, polyreaction 0.1 hour, add acidic ethanol after being polymerized and stop polyreaction, then 3 times are respectively washed with deionized water and ethanol respectively, last vacuum-drying at 60 DEG C, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.66 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 10, unlike, the olefin polymerization catalyst components C12 of olefin polymerization catalyst components C10 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.22 % by weight.
Embodiment 13
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(1) preparation method of olefin polymerization catalyst components:
1. get 5.0 grams of halloysites to be scattered in 50mL toluene, obtain the suspension of halloysite.Then the toluene solution 30mL containing 0.1mol methylaluminoxane is added dropwise in the suspension of above-mentioned halloysite, reacts 4.0 hours at 90 DEG C, then use toluene wash 5 times, after drying, obtain the aluminium mixture of halloysite.
2. 0.2 gram of transistion metal compound two [N-(3-tertiary butyl salicylidene) anilino] zirconium dichloride is added 0 DEG C containing 0.20mol methylaluminoxane toluene solution 40mL in, react 4.0 hours at 0 DEG C, then be added dropwise in the toluene suspension 50mL of the aluminium mixture containing 5.0 grams of halloysites, 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 C13.After testing, in this olefin polymerization catalyst components C13, the mass percentage of halloysite is 65%, and the mass percentage of zr element is 0.5%, and the mass percentage of aluminium element is 8.5%.
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 polyolefine resin composition:
1. ethylene homo:
Ethylene homo reaction is carried out according to the method for embodiment 10, unlike, the olefin polymerization catalyst components C13 of olefin polymerization catalyst components C10 identical weight part is substituted, obtains homopolymerisation polyethylene resin combination.After testing, in homopolymerisation polyethylene resin combination, the content of halloysite is 0.11 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 10, unlike, the olefin polymerization catalyst components C13 of olefin polymerization catalyst components C10 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.09 % by weight.
Embodiment 14
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(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 2 hours, isothermal reaction 1.0 hours at-20 DEG C afterwards.Slowly be warming up to 110 DEG C, add 0.1ml 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 2.0 hours at 110 DEG C, react rear filtering liquid, again add 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. the catalyst component containing halloysite described in 5.0 grams is 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 2add in the toluene solution 40mL containing 0.10mol methylaluminoxane, then react 4.0 hours at 0 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 C14.After testing, in this olefin polymerization catalyst components C14, the mass percentage of halloysite is 42%, and the mass percentage of titanium elements is 1.18%, and the mass percentage of magnesium elements is 2.56%, the mass percentage of zr element is 0.10%, and the mass percentage of aluminium element is 6.58%.
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 polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 12, unlike, the olefin polymerization catalyst components C14 of olefin polymerization catalyst components C12 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.08 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 12, unlike, the olefin polymerization catalyst components C14 of olefin polymerization catalyst components C12 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.11 % by weight.
Embodiment 15
This embodiment is for illustration of olefin polymerization catalyst components provided by the invention and preparation method thereof and polyolefine resin composition and preparation method thereof.
(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 C15.After testing, in this olefin polymerization catalyst components C15, 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 polyolefine resin composition:
1. propylene homo:
Propylene homo reaction is carried out according to the method for embodiment 12, unlike, the olefin polymerization catalyst components C15 of olefin polymerization catalyst components C12 identical weight part is substituted, obtains homo-polypropylene resin combination.After testing, in homo-polypropylene resin combination, the content of halloysite is 0.05 % by weight.
2. copolymerization of propylene:
Copolymerization of propylene reaction is carried out according to the method for embodiment 12, unlike, the olefin polymerization catalyst components C15 of olefin polymerization catalyst components C12 identical weight part is substituted, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition, the content of halloysite is 0.07 % by weight.
Test case
Test case is for illustration of the test of olefinic polymerization physical performance.
(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 for regulation in ASTM D 638, 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, when the olefin polymerization catalysis containing halloysite provided by the invention is used for olefinic polyreaction, the polyolefin resin obtained has higher melt strength and mechanical strength.In addition, the olefin polymerization catalysis containing halloysite provided by the invention may be used for preparing alloy resin in olefin homo, olefin copolymer and polypropylene, has prospects for commercial application.
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 (28)

1. an olefin polymerization catalyst components, is characterized in that, 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.
2. olefin polymerization catalyst components 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. olefin polymerization catalyst components 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 olefin polymerization catalyst components 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. olefin polymerization catalyst components 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 olefin polymerization catalyst components 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.
7. according to the olefin polymerization catalyst components 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.
8. according to the olefin polymerization catalyst components 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.
9., according to the olefin polymerization catalyst components 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.
10. a preparation method for olefin polymerization catalyst components, the method comprises the following steps:
(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.
11. preparation methods according to claim 10, 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.
12. preparation methods according to claim 10, 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.
13. preparation methods according to claim 12, 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.
14. according to the preparation method in claim 12-13 described in any one, wherein, react 1-4 hour at 80-130 DEG C before, in reaction system, internal electron donor compound is added after the method 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.
The preparation method of 15. 1 kinds of olefin polymerization catalyst components, the method comprises the following steps:
(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.
16. preparation methods according to claim 15, 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.
17. preparation methods according to claim 15 or 16, wherein, 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 18. 1 kinds of olefin polymerization catalyst components, the method comprises the following steps:
(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 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, 1-10 hour is reacted containing the catalyst component of halloysite and the catalyst component of described activation by described activation.
19. preparation methods according to claim 18, 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.
20. preparation methods according to claim 18, 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.
21. preparation methods according to claim 20, 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.
22. preparation methods according to claim 20 or 21, wherein, react 1-4 hour at 80-130 DEG C before, in reaction system, internal electron donor compound is added after the method 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.
23. according to the preparation method in claim 18-21 described in any one, and 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 mol 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.
24. preparation methods according to claim 23, wherein, 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.
25. olefin polymerization catalyst components prepared by the method in claim 10-24 described in any one.
26. 1 kinds of olefin polymerization catalysis, described olefin polymerization catalysis contains olefin polymerization catalyst components and promotor, it is characterized in that, described olefin polymerization catalyst components is the olefin polymerization catalyst components in claim 1-9 described in any one and/or the olefin polymerization catalyst components that prepared by the method in claim 10-24 described in any one.
27. olefin polymerization catalysis according to claim 26, wherein, described promotor is aluminum alkyls and/or aluminum alkoxide.
The application of olefin polymerization catalysis described in 28. claims 26 or 27 in olefinic polyreaction.
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