CN104448064B

CN104448064B - A kind of polyolefine resin composition and preparation method thereof

Info

Publication number: CN104448064B
Application number: CN201410649298.9A
Authority: CN
Inventors: 董金勇; 王宁; 秦亚伟; 牛慧
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2014-11-14
Filing date: 2014-11-14
Publication date: 2017-06-30
Anticipated expiration: 2034-11-14
Also published as: CN104448064A

Abstract

The invention provides a kind of vistanex and preparation method thereof.The preparation method of the vistanex includes making olefinic monomer carry out polymerisation in the presence of catalyst component for olefin polymerization and co-catalyst, and the catalyst component for olefin polymerization contains galapectite, transition metal component and nontransition metal component and co-catalyst；When the transition metal component is titanium tetrahalide and/or alkoxytitanium, the nontransition metal component is magnesium-containing compound；When the transition metal component is metallocene compound and/or non-metallocene compound, the nontransition metal component is aluminum contained compound；When the mixture that the transition metal component is titanium tetrahalide and/or alkoxytitanium and metallocene compound and/or non-metallocene compound, the nontransition metal component is the mixture of magnesium-containing compound and aluminum contained compound.The polyolefine resin composition that method provided by the present invention is prepared has melt strength and mechanical property higher.

Description

A kind of polyolefine resin composition and preparation method thereof

Technical field

The polyolefin prepared the present invention relates to a kind of preparation method of polyolefine resin composition and by the method Resin combination.

Background technology

Vistanex is the general designation of the class general-purpose plastics as representative with polyethylene and polypropylene, and its combination property is excellent Different, application field is wide, occupies the huge market share.Innovation of the olefin polymerization catalysis on the Nomenclature Composition and Structure of Complexes is poly- regulation and control One of the composition and property of olefin resin, the main drive for promoting polyolefin properties lifting.From the 1950's Germanization Since scholar Zielger has started olefin coordination polymerization jointly with the scholar Natta that Italianizes, olefin polymerization catalysis are gradually sent out The three major types catalyst including Zielger-Natta catalyst, metallocene catalyst and non-metallocene catalyst is put on display.

Although the olefin polymerization catalysis with new construction and new capability are constantly found and are applied to polyolefin high-performance In changing research, but some there is the High performance polyolefin resin of wide application prospect still to lack effective catalytic polymerization prepare hand Section.For example, the long-chain branching polypropylene (HMS-PP) with high fondant-strength blowing, foaming etc. application field have it is wide Application prospect, but there is no effective catalyst system and the polymerization HMS-PP directly can be prepared in polymeric kettle at present.And for example, Alloy is in automobile, instrument and equipment and durable consumer goods field in polypropylene with impact copolymer polypropylene (hiPP) as representative Application potential is huge, but exist in alloy resin in polypropylene interfacial adhesion between polypropylene and EP rubbers phase it is low, The problems such as phase separation yardstick is unstable so that the melt strength of alloy resin is low in the polypropylene and mechanical property compared with Difference, has had a strong impact on its performance.

Galapectite is a kind of clay mineral, by silicon-oxy tetrahedron and alumina octahedral according to 1:The silicic acid of 1 structure composition Duo Bi, middle empty nanotube that salt lamella is curled into, its internal diameter are 10-20 nanometers, and external diameter is 10-100 nanometers, and length is 0.5- 40 microns.Galapectite because with abundance, it is cheap and easy to get the features such as enjoy the concern of academia and industrial quarters, and be applied to In the fields such as catalysis material, supporting material and porous material.For example, polypropylene-base high content halloysite nanotubes composite Preparation method and performance (Deng Chengye, Huang Hanxiong, Journal of Chemical Industry and Engineering, 2013,64 (10):3824-3830) disclose galapectite Nanotube HNTs is dried in being put into vacuum drying chamber, then will be through dry HNTs and PP and PP-g-MAH and antioxidant Blending is uniform.Although can to a certain extent improve the melt strength of vistanex using the method and improve its mechanical property Can, but because Blending Processes are difficult to ensure that galapectite is evenly distributed in vistanex, therefore vistanex melt The limited extent that intensity and mechanical property are improved.

The content of the invention

The invention aims to overcome using existing method prepare vistanex melt strength it is relatively low and Mechanical strength poor defect, and the preparation method of new polyolefine resin composition is provided and is prepared by the method Polyolefine resin composition.

Specifically, the first preparation method for the polyolefine resin composition that the present invention is provided includes making olefinic monomer in alkene Polymerisation is carried out in the presence of polymerized hydrocarbon catalytic component and co-catalyst, wherein, the catalyst component for olefin polymerization contains There are galapectite, transition metal component and nontransition metal component；

The transition metal component is titanium tetrahalide and/or alkoxytitanium, and the nontransition metal component is containing magnesium Compound；Or,

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

The transition metal component is the metallocene compound in titanium tetrahalide and/or alkoxytitanium and metallocene catalyst And/or the mixture of the non-metallocene compound in non-metallocene catalyst, and the nontransition metal component is chemical combination containing magnesium The mixture of thing and aluminum contained compound.

Second preparation method of the polyolefine resin composition that the present invention is provided is comprised the following steps：

(1) galapectite and magnesium-containing compound are reacted 1-50 hours at 30-150 DEG C, obtains the magnesium compound of galapectite；

(2) the magnesium compound of the galapectite and titanium tetrahalide and/or alkoxytitanium are carried out into complexation reaction, obtains alkene Polymerization catalyst component；

(3) make olefinic monomer carries out polymerisation in the presence of the catalyst component for olefin polymerization and co-catalyst.

The third preparation method for the polyolefine resin composition that the present invention is provided is comprised the following steps：

(1) galapectite and the first aluminum contained compound are reacted 1-20 hours at 0-90 DEG C, the galapectite for being activated；

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

(3) galapectite of the activation is reacted 1-10 hours with the catalytic component of the activation at 0-100 DEG C, is obtained To catalyst component for olefin polymerization；

(4) make olefinic monomer carries out polymerisation in the presence of the catalyst component for olefin polymerization and co-catalyst.

4th kind of preparation method of the polyolefine resin composition that the present invention is provided is comprised the following steps：

(2) the magnesium compound of the galapectite and titanium tetrahalide and/or alkoxytitanium are carried out into complexation reaction, obtain containing angstrom The catalytic component of Lip river stone；

(3) catalytic component containing galapectite and the first aluminum contained compound are reacted 1-20 hours at 0-90 DEG C, The catalytic component containing galapectite for being activated；

(4) by the Nonmetallocene chemical combination in the metallocene compound and/or non-metallocene catalyst in metallocene catalyst Thing and the second aluminum contained compound react 1-20 hours at 0-90 DEG C, the catalytic component for being activated；

(5) catalytic component by the activation containing galapectite with the catalytic component of the activation at 0-110 DEG C Reaction 1-10 hours, obtains catalyst component for olefin polymerization；

(6) polymerisation is carried out in the presence of the catalyst component for olefin polymerization and co-catalyst in olefinic monomer.

Additionally, present invention also offers the polyolefine resin composition prepared by the above method.

The present inventor is by discovery after further investigation, the olefinic polymerization catalysis containing galapectite that the present invention is provided When agent is used to prepare vistanex, the polyolefine resin composition for obtaining has melt strength and mechanical strength higher.Push away Survey its reason, it may be possible to due to：Galapectite is doped into catalytic systems for polymerization of olefins, not only using polymerization by angstrom Lip river Stone is dispersed in vistanex with nanoscale, realizes that galapectite is nano combined with vistanex, and can also The bore that is enough presented using halloysite nanotubes is big, suitable length the features such as form physics crosslinking points, suppress polyolefin tree The molecular chain movement of fat, improves the melt strength of vistanex and improves the work of the boundary in phase polyolefin resin system With, and then improve the melt strength and mechanical property of vistanex.

Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.

Specific embodiment

Specific embodiment of the invention is described in detail below.It should be appreciated that described herein specific Implementation method is merely to illustrate and explain the present invention, and is not intended to limit the invention.

The first preparation method for the polyolefine resin composition that the present invention is provided includes making olefinic monomer in olefinic polymerization Polymerisation is carried out in the presence of catalytic component and co-catalyst, wherein, the catalyst component for olefin polymerization contains an angstrom Lip river Stone, transition metal component and nontransition metal component；

The present invention is not particularly limited to the content of various composition in the catalyst component for olefin polymerization, for example, with On the basis of the gross weight of the catalyst component for olefin polymerization, the content of the galapectite can be 0.5-90 weight %, described The total content of metallic element can be 2-80 weight % in transition metal component and nontransition metal component；Preferably, with described On the basis of the gross weight of catalyst component for olefin polymerization, the content of the galapectite is 1-50 weight %, the transition metal group It is 5-60 weight % to divide with the total content of metallic element in nontransition metal component.

Further, when the nontransition metal component is magnesium-containing compound, with the catalyst component for olefin polymerization Gross weight on the basis of, in the transition metal component content of transition metal can be 0.5-10 weight %, preferably 1-5 weight %；The content of non-transition metal elements can be 2-30 weight %, preferably 5-20 in the nontransition metal component Weight %.

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

When the mixture that the nontransition metal component is magnesium-containing compound and aluminum contained compound, with the olefinic polymerization On the basis of the gross weight of catalytic component, the content of transition metal can be 0.25-15 weights in the transition metal component Amount %, preferably 0.5-5 weight %；The content of non-transition metal elements can be 5-50 weights in the nontransition metal component Amount %, preferably 7.5-40 weight %.

The galapectite can be natural galapectite, or the galapectite after by being modified, for example, indianaite And/or organically-modified galapectite, i.e. the galapectite can be in natural galapectite, indianaite and organically-modified galapectite At least one.Wherein, as described above, the natural galapectite is according to 1 by silicon-oxy tetrahedron and alumina octahedral:1 structure Duo Bi, middle empty nanotube that the silicate lamella of composition is curled into, its internal diameter are 10-20 nanometers, and external diameter is 10-100 nanometers, Length is 0.5-40 microns.The indianaite by by natural galapectite at 50-900 DEG C, preferably at 100-600 DEG C at heat Reason 0.5-48 hours, preferably heat treatment are obtained for 2-10 hours.The organically-modified galapectite is by by natural galapectite and/or change In the organic compound of galapectite organo-silicon compound, titanium compound and not siliceous and titanium and end with double bond extremely A kind of few being modified obtains.

Contain hydroxyl in the natural galapectite and indianaite, and the organically-modified galapectite passes through natural galapectite And/or the hydroxyl in indianaite carries double bond with organo-silicon compound, titanium compound and not siliceous and titanium and end Can be bonded together with the chemical functional groups of hydroxyl reaction and obtained in organic compound, specific reaction condition is this area Known in technical staff, therefore not to repeat here.It should be noted that when the organo-silicon compound, titanium compound and not siliceous With titanium and end with double bond organic compound in do not contain can with the functional group of hydroxyl reaction when, can first will described in Galapectite is modified so that introduced in galapectite can be with the organo-silicon compound, titanium compound and not siliceous and titanium And the functional group of at least one radical reaction in organic compound of the end with double bond, it is public to this those skilled in the art Know, therefore not to repeat here.Wherein, the formula of the organo-silicon compound is R¹R²SiR³ ₂, wherein, R¹For halogen atom, vinyl, Amino, C₁-C₅Aminoalkyl, epoxy radicals, methacryloxy, sulfydryl, C₁-C₅Alkoxy, urea groups or formula for- (CH₂)_m1COOCH(CH₃)=CH₂The alkyl containing alpha-olefin double bond, m1 for 1-18 integer, R²It is halogen atom, C₁-C₅Alcoxyl Base or formula are-(CH₂)_m2-CH₃Alkyl, m2 for 0-2 integer, R³It is halogen atom, C₁-C₅Alkoxy or acetoxyl group. From the ready availability angle of raw material, the organo-silicon compound are particularly preferably γ-methacryloxypropyl trimethoxy Base silane and/or gamma-aminopropyl-triethoxy-silane.The formula of the titanium compound is R⁴ _pTi(OR⁵)_4-p, wherein, R⁴And R⁵For C₁-C₄Alkyl, p for 0-3 integer.From the ready availability angle of raw material, the titanium compound is particularly preferably the fourth of metatitanic acid four At least one in ester, methyl triethoxy titanium, methyl trimethoxy epoxide titanium and tetraethyl titanate.It is described not siliceous and titanium and last The formula of organic compound of the end with double bond is R⁶R⁷CH=CH₂, wherein, R⁶It is acid chloride group, carboxyl, epoxy radicals or ester group, R⁷ It is C₁-C₂₀Alkylidene or the C with ester group, oxygen atom or carboxyl₁-C₂₀Alkylidene.Go out from the ready availability angle of raw material Hair, the not siliceous and titanium and organic compound structure formula of the end with double bond is HOOC (CH₂)₄CH=CH₂、HOOC (CH₂)₇CH=CH₂With HOOC (CH₂)₉CH=CH₂In at least one.

The species of the titanium tetrahalide and alkoxytitanium can be the conventional selection of this area.For example, four halogenation Titanium can be TiCl₄、TiBr₄And TiI₄In at least one, particularly preferably TiCl₄.Alkoxy in the alkoxytitanium can Think substituted or non-substituted C₁-C₅Alkoxy, wherein, substitution base be usually halogen atom.Specifically, the alkoxytitanium Example includes but is not limited to Ti (OEt) Cl₃、Ti(OEt)₂Cl₂、Ti(OEt)₃Cl、Ti(OEt)₄With Ti (OBu)₄In at least one Kind.

The species of the metallocene compound in the metallocene catalyst can be the conventional selection of this area, for example, can Think metallocene compound of the formula as shown in formula (I)：

(Cp^I-B_e-Cp^II)M′R⁸ _aR⁹ _bFormula (I)

Wherein, M ' is Ti, Zr, Hf, V, Fe, Y, Sc or lanthanide series metal；Cp^IAnd Cp^IIIt is each independently H, C₁-C₅Alkane Base, substitution or non-substituted cyclopentadienyl group, substitution or non-substituted C₆-C₁₈Aryl, and substitution base be C₁-C₆Alkane Base, C₃-C₁₈Cycloalkyl and C₆-C₁₈Aryl at least one；R⁸And R⁹It is each independently H, halogen atom, C₁-C₈Alkane Base, C₁-C₈Alkoxy, C₆-C₂₀Aryl, with C₁-C₁₅The C of alkyl₇-C₂₀Aryl, C₁-C₈Acyloxy, pi-allyl or C₁-C₁₅Silylation, a, b are each independently the integer of 0-2, and a+b=2；B is alkyl bridge or silylation bridge, preferably-C (R¹⁰R¹¹)-alkyl bridge or-Si (R¹²R¹³)-silylation bridge, wherein, R¹⁰-R¹³It is each independently H, C₁-C₄Alkyl or C₆-C₁₀ Aryl；E is the integer of 1-3.Specifically, the example of the metallocene compound in the metallocene catalyst includes but does not limit In：C₂H₄(Ind)₂ZrCl₂、C₂H₄(H₄Ind)₂ZrCl₂、Me₂Si(Ind)₂ZrCl₂、Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂、 Me₂Si(Me₄Cp)₂ZrCl₂、Me₂Si(Flu)₂ZrCl₂、Me₂Si(2-Me-4-Naph-Ind)₂ZrCl₂And Ph₂Si(Ind)₂ZrCl₂In at least one, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl group, and Ind is indenyl, H₄Ind is 4,5,6,7- Tetrahydro indenes, Flu is fluorenyl, and Naph is naphthyl.

The species of non-metallocene compound can be the conventional selection of this area in the non-metallocene catalyst, for example, Can be non-metallocene compound of the formula as shown in formula (II)：

Formula (II)

Wherein, M is selected from Zr, Ti, V or Hf, R₁、R₂And R₃It is each independently H, halogen atom, C₁-C₈Alkyl, C₁-C₈'s Alkoxy, C₆-C₂₀Aryl, with C₁-C₆Alkyl aryl, with C₃-C₁₈Cycloalkyl aryl, with C₆-C₁₈Virtue The aryl of perfume base, C₁-C₈Acyloxy, pi-allyl or C₁-C₁₅Silylation, X be F, Cl, Br or I, n is 2.Specifically, it is described The example of the non-metallocene compound in non-metallocene catalyst is included but is not limited to：Two [N- (3- tert-butyl groups salicylidene) benzene Amido] zirconium dichloride, two [N- (3- methyl salicylidene) anilino-] zirconium dichlorides, two [N- (3- isopropyls salicylidene) benzene Amido] at least one in zirconium dichloride and two [N- (3- adamantyl -5- methyl salicylidene) anilino-] zirconium dichlorides.

The magnesium-containing compound can be the existing various compounds containing magnesium that can be used in olefin polymerization catalysis, For example, can be MgX for formula¹ ₂Magnesium halide or formula be RMgX²RMgBr or both of the above mixture. MgX¹ ₂In, X¹It is F, Cl, Br or I；In RMgX²In, R is C₁-C₁₀Alkyl, X²It is F, Cl, Br or I.Specifically, it is described containing magnesium The example of compound is included but is not limited to：In magnesium chloride, magnesium bromide, chlorination isopropoxy magnesium and chlorination n-butoxy magnesium at least It is a kind of.From the ready availability angle of raw material, the magnesium-containing compound is preferably magnesium chloride.

The aluminum contained compound can be the existing various compounds containing aluminium that can be used in olefin polymerization catalysis, For example, can be Al (OR ') for formula_qR″_3-qAluminum contained compound, wherein, R ' and R " are each independently C₂-C₁₀Alkyl, 0≤q≤3.Specifically, the example of the aluminum contained compound is included but is not limited to：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, At least one in MAO etc..

In the catalyst component for olefin polymerization, when the nontransition metal component is magnesium-containing compound or be containing magnesium During the mixture (i.e. described nontransition metal component contains magnesium-containing compound) of compound and aluminum contained compound, the olefinic polymerization Catalytic component further preferably contains internal electron donor compound, can so improve the catalysis activity of catalyst, and can improve The isotacticity and crystallinity of vistanex.The consumption of the internal electron donor compound can be the conventional selection of this area, For example, the internal electron donor compound can be 0.05- with the mol ratio of magnesium elements in the catalyst component for olefin polymerization 0.6：1, preferably 0.1-0.4：1.Additionally, the species of the internal electron donor compound can also be the conventional choosing of this area Select, for example, can be at least one in diether compounds, carboxylate compound, alcohol ester, ketone, amine and silane, particularly preferably Diether compounds and/or carboxylate compound.

Specifically, the example of the diether compound is included but is not limited to：2- (2- ethylhexyls) -1,3- dimethoxys Propane, 2- isopropyl -1,3- dimethoxy propanes, 2- butyl -1,3- dimethoxy propanes, 2- sec-butyl -1,3- dimethoxys Propane, 2- cyclohexyl -1,3- dimethoxy propanes, 2- phenyl -1,3- dimethoxy propanes, 2- (2- phenylethyls) -1,3- two Methoxy propane, 2- (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- (p- chlorphenyl) -1,3- dimethoxy propanes, 2- (diphenyl methyl) -1,3- dimethoxy propanes, 2,2- dicyclohexyl -1,3- dimethoxy propanes, 2,2- bicyclopentyl -1, 3- dimethoxy propanes, 2,2- diethyl -1,3- dimethoxy propanes, 2,2- dipropyl -1,3- dimethoxy propanes, 2,2- bis- Isopropyl -1,3- dimethoxy propanes, 2,2- dibutyl -1,3- dimethoxy propanes, 2- methyl-2-propyl -1,3- dimethoxies Base propane, 2- methyl -2- benzyl -1,3- dimethoxy propanes, 2- methyl -2- ethyl -1,3- dimethoxy propanes, 2- methyl - 2- isopropyl -1,3- dimethoxy propanes, 2- methyl -2- phenyl -1,3- dimethoxy propanes, 2- methyl -2- cyclohexyl -1,3- Dimethoxy propane, 2,2- double (2- cyclohexyl-ethyls) -1,3- dimethoxy propanes, 2- methyl -2- isobutyl group -1,3- dimethoxies Base propane, 2- methyl -2- (2- ethylhexyls) -1,3- dimethoxy propanes, 2,2- diisobutyl -1,3- dimethoxy propanes, Double (cyclohexyl methyl) -1 of 2,2- diphenyl -1,3- dimethoxy propanes, 2,2- dibenzyl -1,3- dimethoxy propanes, 2,2-, 3- dimethoxy propanes, 2- isobutyl group -2- isopropyl -1,3- dimethoxy propanes, 2- (1- methyl butyls) -2- isopropyl -1, 3- dimethoxy propanes, 2- isopropyl -2- isopentyl -1,3- dimethoxy propanes, 2- phenyl -2- isopropyl -1,3- dimethoxies Base propane, 2- phenyl -2- sec-butyl -1,3- dimethoxy propanes, 2- benzyl -2- isopropyl -1,3- dimethoxy propanes, 2- Cyclopenta -2- isopropyl -1,3- dimethoxy propanes, 2- cyclopenta -2- sec-butyl -1,3- dimethoxy propanes, 2- hexamethylenes Base -2- isopropyl -1,3- dimethoxy propanes, 2- cyclohexyl -2- sec-butyl -1,3- dimethoxy propanes, 2- isopropyls -2- Sec-butyl -1,3- dimethoxy propanes, 2- cyclohexyl -2- cyclohexyl methyl -1,3- dimethoxy propanes and the (methoxies of 9,9- bis- Ylmethyl fluorenes) in one or more, particularly preferably 9,9- bis- (methoxy fluorenes).

The example of the carboxylate compound is included but is not limited to：Diethyl succinate, dibutyl succinate, O-phthalic Diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, phthalic acid two Different monooctyl ester, ethyl benzoate, ethyl anisate, paraethoxybenxoic acid ethyl ester, triethyl trimellitate and inclined benzene One or more in three sour tributyls, particularly preferably dibutyl phthalate and/or diisobutyl phthalate.

The catalyst component for olefin polymerization that the present invention is provided can be prepared by existing various methods.According to this hair A kind of bright specific embodiment, when the nontransition metal component is magnesium-containing compound, the olefin polymerization catalysis group The method by comprising the following steps is divided to prepare：

(2) the magnesium compound of the galapectite and titanium tetrahalide and/or alkoxytitanium are carried out into complexation reaction.

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

As described above, the reaction temperature of the galapectite and magnesium-containing compound is 30-150 DEG C, the reaction time is that 1-50 is small When.Preferably, the reaction temperature of the galapectite and magnesium-containing compound is 40-130 DEG C, and the reaction time is 4-20 hours.

Reaction between the galapectite and magnesium-containing compound is preferably carried out in organic solvent, so enables to reaction More smoothly carry out.The species of the organic solvent can be the existing various inert substances that can act as reaction media, For example, can be C₅-C₁₀Alkane, aromatic hydrocarbon, cycloalkane, C₂-C₁₂Ether and tetrahydrofuran at least one, preferably just Hexane, hexamethylene, heptane, decane, ethanol, isobutanol, isooctanol, tetrahydrofuran, methyl ether, ether, positive propyl ether, isopropyl ether, just At least one in butyl ether, isobutyl ether, isoamyl ether, benzene,toluene,xylene, chlorobenzene etc..Additionally, the use of the organic solvent Amount generally allows that the concentration of galapectite is 1-500g/L, preferably 2-50g/L.

Side to the magnesium compound of the galapectite and titanium tetrahalide and/or alkoxytitanium to be carried out complexation reaction of the invention Formula is not particularly limited, for example, can first under low temperature (0-40 DEG C) by the magnesium compound of galapectite and titanium tetrahalide and/or Alkoxytitanium mixes, and is reacted 1-10 hours under temperature then is risen into high temperature (80-130 DEG C) again.Preferably, by the galapectite Magnesium compound and titanium tetrahalide and/or alkoxytitanium carry out the mode of complexation reaction and include first being combined the magnesium of the galapectite Thing reacts 0.5-2 hours with a part of titanium tetrahalide and/or a part of alkoxytitanium at -20 DEG C to 0 DEG C, then again by temperature 80-130 DEG C is risen to react 1-4 hours, then by product separation of solid and liquid, and the solid product that will be obtained and remainder four Halogenated titanium and/or remainder alkoxytitanium react 1-4 hours at 80-130 DEG C.It is highly preferred that by the magnesium of the galapectite Compound and titanium tetrahalide and/or alkoxytitanium carry out complexation reaction mode include first by the magnesium compound of the galapectite with A part of titanium tetrahalide and/or a part of alkoxytitanium react 0.5-1.5 hours at -20 DEG C to -10 DEG C, then again by temperature 100-125 DEG C is risen to react 1.5-2.5 hours, then by product separation of solid and liquid, and the solid product that will be obtained and residue Part titanium tetrahalide and/or remainder alkoxytitanium react 1.5-2.5 hours at 100-125 DEG C.Additionally, working as step (1) Reaction when carrying out in presence of organic solvent, the product that step (1) is obtained exists as a solution, then step (2) Complexation reaction then the solution of the magnesium compound containing galapectite directly can be added dropwise to titanium tetrahalide and/or alkoxytitanium In, or directly titanium tetrahalide and/or alkoxytitanium are added dropwise in the solution of the magnesium compound containing galapectite, wherein, drop Plus the time used can be 0.5-4 hours；If the reaction of step (1) when being carried out in the presence of organic solvent-free or Step (1) reacted after product is dried, then step (2) with it is outer reaction then can be by the magnesium compound of galapectite It is scattered in the solution containing titanium tetrahalide and/or alkoxytitanium.

The present invention is to the magnesium-containing compound, a part of titanium tetrahalide, a part of alkoxytitanium, another part titanium tetrahalide Consumption with another part alkoxytitanium is not particularly limited.When the magnesium-containing compound is that formula is MgX¹ ₂Magnesium halide When, load titanium tetrahalide used and total consumption of alkoxytitanium and the mol ratio of magnesium-containing compound can be 10-60 for the first time： 1, preferably 10-30：1 (that is, described a part of titanium tetrahalide and total consumption of a part of alkoxytitanium and rubbing for magnesium-containing compound You are than being 10-60：1, preferably 10-30：1)；Second loads total consumption of titanium tetrahalide used and alkoxytitanium and contains magnesium The mol ratio of compound can be 10-60：1, preferably 10-30：1 (that is, described remainder titanium tetrahalide and remainder alkane Total consumption of epoxide titanium is 10-60 with the mol ratio of magnesium-containing compound：1, preferably 10-30：1).When the magnesium-containing compound is Formula is RMgX²RMgBr when, total consumption and chemical combination containing magnesium of used titanium tetrahalide and alkoxytitanium are loaded for the first time The mol ratio of thing can be 1-100：1, preferably 1-20：1 (that is, described a part of titanium tetrahalide and a part of alkoxytitanium Total consumption is 10-100 with the mol ratio of magnesium-containing compound：1, preferably 1-20：1)；Second load titanium tetrahalide used and Total consumption of alkoxytitanium and the mol ratio of magnesium-containing compound can be 1-100：1, preferably 1-20：1 (that is, described remainder Total consumption of titanium tetrahalide and remainder alkoxytitanium is divided to be 1-100 with the mol ratio of magnesium-containing compound：1, preferably 1-20： 1)。

A part of titanium tetrahalide and another part titanium tetrahalide can be during preparing olefin polymerization catalysis Conventional use of various titanium tetrahalides, for example, can be TiCl₄、TiBr₄And TiI₄In at least one.Additionally, described one Point alkoxytitanium and another part alkoxytitanium also can be prepare it is conventional use of various during olefin polymerization catalysis Alkoxytitanium, for example, can be Ti (OEt) Cl₃、Ti(OEt)₂Cl₂、Ti(OEt)₃Cl、Ti(OEt)₄With Ti (OBu)₄In extremely Few one kind.

According to the present invention, by the magnesium compound of the galapectite and a part of titanium tetrahalide and/or a part of alkoxytitanium Product to carry out the method for separation of solid and liquid can be the existing various methods that can realize solid phase and liquid phase separation, for example Suction filtration, press filtration or centrifugation, preferably press filtration.The present invention is not particularly limited to the condition of press filtration, with as abundant as possible Realize that solid phase is separated with liquid phase and be defined.

The preparation method of the catalyst component for olefin polymerization that the present invention is provided further preferably is included in the magnesium of the galapectite Compound and a part of titanium tetrahalide and/or a part of alkoxytitanium at -20 DEG C to 0 DEG C after reaction 0.5-2 hours and Before being reacted 1-4 hours at 80-130 DEG C, to internal electron donor is added in reaction system, the alkene for so enabling to gathers Also contain internal electron donor compound in conjunction catalytic component, so as to improve the catalysis activity of catalyst, and improve polyolefin tree The isotacticity and crystallinity of fat.The specific species of the internal electron donor compound is hereinbefore about olefinic polymerization catalysis It is described in agent component Parts, therefore not to repeat here.Additionally, the consumption of the internal electron donor compound can be this area Conventional selection, for example, the internal electron donor compound can with the mol ratio of magnesium elements in the magnesium compound of the galapectite Think 0.05-0.6：1, preferably 0.1-0.4：1.

Another specific embodiment of the invention, when the nontransition metal component is aluminum contained compound, institute Catalyst component for olefin polymerization is stated to be prepared according to the method for comprising the following steps：

(3) galapectite of the activation is reacted 1-10 hours with the catalytic component of the activation at 0-100 DEG C.

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

To step (1), step (2) and in step (3), the consumption of each material is not particularly limited the present invention.For example, step Suddenly in (1), the weight ratio of the galapectite and the first aluminum contained compound can be 1：0.1-20, preferably 1：0.1-10, it is more excellent Elect 1 as：0.5-2.In step (2), the transition metal component can be 1 with the weight ratio of the second aluminum contained compound：1-5000, Preferably 1：1-1000, more preferably 1：50-120.In step (3), the catalyst of the galapectite of the activation and the activation The weight ratio of component can be 1：0.5-50, preferably 1：1-20, more preferably 1：1-5.

First aluminum contained compound and the second aluminum contained compound can be conventional use of in olefin polymerization catalysis Aluminum contained compound, for example, first aluminum contained compound and the second aluminum contained compound are each independently formula for Al (OR ')_qR″_3-qAluminum contained compound, wherein, R ' and R " are each independently C₂-C₁₀Alkyl, 0≤q≤3.Specifically, described first Aluminum contained compound and the second aluminum contained compound are each independently trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, MAO At least one in.

The reaction of the galapectite and the first aluminum contained compound and the transition metal component with second containing after calorize it Between reaction preferably carry out in organic solvent, so enable to reaction more smoothly carry out.The kind of the organic solvent Class can be the existing various inert substances that can act as reaction media, for example, can be C₅-C₁₀Alkane, aromatic hydrocarbon, ring Alkane, C₂-C₁₂Ether and tetrahydrofuran at least one, preferably n-hexane, hexamethylene, heptane, decane, ethanol, isobutyl Alcohol, isooctanol, tetrahydrofuran, methyl ether, ether, positive propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, isoamyl ether, benzene, toluene, two At least one in toluene, chlorobenzene etc..Additionally, the consumption of the organic solvent generally allows that the concentration of galapectite is 1- 500g/L, preferably 2-50g/L.

Additionally, the Nonmetallocene chemical combination in metallocene compound and non-metallocene catalyst in the metallocene catalyst , hereinbefore about being described in catalyst component for olefin polymerization part, therefore not to repeat here for the specific species of thing.

Another specific embodiment of the invention, when the nontransition metal component is for magnesium-containing compound and containing aluminium During the mixture of compound, the catalyst component for olefin polymerization is prepared according to the method for comprising the following steps：

(5) catalytic component by the activation containing galapectite with the catalytic component of the activation at 0-110 DEG C Reaction 1-10 hours.

Wherein, the species and consumption of the reaction raw materials that step (1) and the reaction described in step (2) are related to and specific anti- Answer condition with the preparation of the catalyst component for olefin polymerization with magnesium-containing compound as nontransition metal component mentioned hereinabove Step (1) is identical with consumption and specific reaction condition with the species of the reaction raw materials that step (2) is related in method, herein not Repeat.

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

Reaction described in step (3) and step (4) is preferably carried out in organic solvent, so enables to reaction more flat Quietly carry out.The species of the organic solvent can be the existing various inert substances that can act as reaction media, for example, can Think C₅-C₁₀Alkane, aromatic hydrocarbon, cycloalkane, C₂-C₁₂Ether and tetrahydrofuran at least one, preferably n-hexane, ring It is hexane, heptane, decane, ethanol, isobutanol, isooctanol, tetrahydrofuran, methyl ether, ether, positive propyl ether, isopropyl ether, n-butyl ether, different At least one in butyl ether, isoamyl ether, benzene,toluene,xylene, chlorobenzene etc..Additionally, the consumption of the organic solvent generally may be used Think the conventional selection of this area, therefore not to repeat here.

In step (3), the consumption of the catalytic component containing galapectite and the consumption of first aluminum contained compound Weight ratio can be 1：0.1-20, preferably 1：0.5-1.5.In step (4), the metallocene compound and Nonmetallocene chemical combination Total consumption of thing can be 1 with the weight ratio of the consumption of second aluminum contained compound：1-1000, preferably 1：30-60.Step (5) in, the catalytic component of the activation can be 1 with the weight ratio of the catalytic component containing galapectite of the activation： 0.1-20, preferably 1：0.5-2.

Additionally, the Nonmetallocene chemical combination in metallocene compound and non-metallocene catalyst in the metallocene catalyst The specific species of thing is hereinbefore described about catalyst component for olefin polymerization part, and therefore not to repeat here.

The present invention is not particularly limited to the species of the co-catalyst, can for it is existing it is various can be with four halogenations Titanium and/or alkoxytitanium composition Ziegler-Natta catalyst, can with metallocene compound constitute metallocene catalyst or The material of non-metallocene catalyst can be constituted with non-metallocene compound, for example, can be alkyl aluminum and/or aluminum alkoxide, tool Body can be at least one in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, MAO etc..Additionally, the co-catalysis The mol ratio of the transition metal in aluminium element in agent and the catalyst component for olefin polymerization can be 1-5000：1, it is excellent Elect 10-2000 as：1.

The present invention is not particularly limited to the consumption of the catalyst component for olefin polymerization, for example, the olefinic polymerization The consumption of catalytic component can generally make the content of galapectite in the vistanex for obtaining be 0.0001-25 weight %, excellent Elect 0.001-10 weight % as.It should be noted that when galapectite is indianaite and/or organically-modified galapectite, galapectite Above-mentioned content refer to indianaite and/or organically-modified galapectite content.

Main the theing improvement is that of the preparation method of the polyolefine resin composition that the present invention is provided employs one kind newly The olefin polymerization catalysis containing galapectite, and the species of olefinic monomer and specific reaction condition can be this area Conventional selection.

Specifically, the olefinic monomer can be pungent for ethene, propylene, 1- butylene, 2- butylene, 1- amylenes, 1- hexenes, 1- At least one in alkene, isoprene, divinylbenzene etc..The vistanex can be olefin homo, or Olefin copolymer.When the vistanex is olefin copolymer, the content of comonomer can be ability in olefinic monomer The conventional selection in domain, therefore not to repeat here.

The present invention is not particularly limited to the condition of the polymerisation, and it can be 30-90 to generally include polymerization temperature DEG C, preferably 40-80 DEG C；Polymerization pressure can be 1-10 atmospheric pressure, preferably 1-7 atmospheric pressure；Polymerization time can be 0.05-10 hours, preferably 0.05-2 hours.In the present invention, the polymerization pressure refers both to gauge pressure.Additionally, the polymerization is anti- It should be slurry polymerization, or bulk polymerization.It is described when the polymerisation is slurry polymerization Polymerisation should also be carried out in presence of organic solvent.The organic solvent can be C₅-C₁₀Alkane or C₆-C₈'s Aromatic hydrocarbon, wherein, the C₅-C₁₀Alkane be preferably at least one in heptane, n-hexane and hexamethylene, the C₆-C₈Virtue Fragrant hydrocarbon is preferably toluene.Additionally, the consumption of the organic solvent can be the conventional selection of this area, therefore not to repeat here.

The preparation method of the polyolefine resin composition provided according to the present invention, the polymerisation can also outside to electricity Carried out in the presence of donor compound.The species of the external donor compound can be the conventional selection of this area, for example, Can be R for formula¹′_4-dSi(R²′)_dCompound, wherein, R¹' and R²' it is each independently alkyl, cycloalkyl or aryl, 1 ≤d≤3.Specifically, the example of the external donor compound is included but is not limited to：Dimethyldimethoxysil,ne, front three Methoxylsilane, MTMS, dimethoxydiphenylsilane, diphenyl diethoxy silane and methyl cyclohexane At least one in alkene dimethoxysilane.Additionally, the external donor compound and aluminium element in the co-catalyst Mol ratio can be 0.001-1：1, preferably 0.01-1：1, more preferably 0.05-0.5：1.

Wherein, the species and consumption and reaction condition of the reaction raw materials that each step is related to hereinbefore have been retouched State, therefore not to repeat here.

(6) make olefinic monomer carries out polymerisation in the presence of the catalyst component for olefin polymerization and co-catalyst.

Below will the present invention will be described in detail by embodiment.

In following examples and comparative example：

The content of transition metal is measured using ultraviolet spectrophotometry in catalyst component for olefin polymerization.

The content of magnesium elements is measured using titration in catalyst component for olefin polymerization, specific as follows：50mg is taken to urge Agent, under nitrogen protection, catalyst is dissolved in 10mL sulfuric acid solutions, is heated to boiling 10 minutes, is then filtered to remove not Molten thing, it is 0.01molL then to use concentration^-1EDTA titrated, using eriochrome black T as indicator in titration process, when The color of the solution containing catalyst as titration end-point when being changed into bluish violet, V is calculated as by the consumption of whole titration process EDTA (mL), the then content of magnesium elements=÷ (50 × 10 of (0.01 × V ÷ 10) × 24.3^-3)。

The content of aluminium element uses titration measuring in alkene catalyst component, specific as follows：Pipette the above-mentioned prepare liquids of 5mL Accurate to add 20mL EDTA standard liquids in 250mL conical flasks, xylenol orange 1-2 drops are added dropwise 8mol/L NH₃·H₂O makes Solution becomes red just, then the HCl solution of 3mol/L is added dropwise makes solution in yellow, is then heated on electrothermal furnace and boiled 10min, room temperature is cooled to flowing water, adds 200g/L hexamethylenetetramine solution 10mL, is adjusted with the HCl solution of 3mol/L, Make solution in yellow, control pH=4-5.Add xylenol orange indicator 1 to drip, be changed into orange with Zn standard liquid volumetric soiutions, As terminal.Aluminium element content is：(C_EDTAV_EDTA-C_ZnV_Zn)×0.53963。

The content of titanium and zr element is measured using spectrophotometer in catalyst component for olefin polymerization, specific as follows：Take 50mg catalyst, under nitrogen protection, catalyst is dissolved in 10mL sulfuric acid solutions, is heated to boiling 10 minutes, is then filtered Insoluble matter is removed, then measure the solution using spectrophotometer (surveys titanium elements, zirconium is surveyed at 666nm in fixed wave length at 410nm Element) absorbance, and the comparison of absorbance is that can obtain titanium or zr element at 410nm or 666nm by with standard curve Concentration, and and then calculate the content of titanium or zr element in olefin polymerization catalysis.

The content of galapectite is carried out using thermogravimetic analysis (TGA) method in olefin polymerization catalysis and polyolefine resin composition Determine.

Embodiment 1

The embodiment is used to illustrate catalyst component for olefin polymerization of present invention offer and preparation method thereof and polyolefin Resin combination and preparation method thereof.

(1) preparation method of catalyst component for olefin polymerization：

1. by 4.0g anhydrous magnesium chlorides MgCl₂It is scattered in 90mL decane with 13.0mL isooctanol, is heated to 130 DEG C, shape Into clear solution, in being reacted 1.0 hours at 130 DEG C, chlorination magnesium alcoholate is obtained.Then above-mentioned chlorination magnesium alcoholate is added dropwise to In the suspension of 1.0g galapectites and 20mL decane, in isothermal reaction 4.0 hours at 60 DEG C, the magnesium compound of galapectite is obtained.

2. in the magnesium compound of the step 1. galapectite being dropped into -20 DEG C of 200mL titanium tetrachlorides, time for adding is 1 hour, then in isothermal reaction 1.0 hours at -20 DEG C.Then 120 DEG C are to slowly warm up to, 0.2mL phthalic acids two are added (diisobutyl phthalate is 0.15 with the mol ratio of magnesium elements in the magnesium compound of galapectite to isobutyl ester：1), afterwards In isothermal reaction 1.5 hours at 120 DEG C, liquid is filtered after the completion of reaction, 240mL titanium tetrachlorides are added again, in permanent at 120 DEG C Temperature reaction 2.0 hours.Finally, washed with hexane 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C1.After testing, The weight/mass percentage composition of galapectite is 18.0%, the quality percentage of transition metal Ti in catalyst component for olefin polymerization C1 Content is 1.68%, and the weight/mass percentage composition of metallic element magnesium is 12%.

Wherein, step 1. described in galapectite be indianaite, its preparation method is as follows：Take 10 grams of natural galapectite mineral Matter obtains 8.1 grams of indianaites in being calcined 4 hours at 600 DEG C.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Under vacuum conditions, propylene steam monomer is filled with reactor, then sequentially adds 50mL hexanes, contains The n-heptane solution 3mL of the triethyl aluminum of 5.5mmol, the n-heptane solution 3mL containing 0.55mmol dimethoxydiphenylsilanes and 20 milligrams of catalyst component for olefin polymerization C1, and by the Stress control in reactor in 5.0 atmospheric pressure, reaction temperature control exists 60 DEG C, polymerisation 0.5 hour, polymerization adds acidic ethanol to terminate polymerisation after completing, and deionized water is then used respectively Respectively washed with ethanol 3 times, be finally vacuum dried at 60 DEG C, obtain HOPP resin combination.After testing, homopolymerization poly- third The content of galapectite is 0.02 weight % in olefine resin composition.

2. propylene copolymerization：

Under vacuum conditions, by the gaseous mixture of propylene and ethene, (propylene is 95 with the mol ratio of ethene:5) it is filled with reactor In, then sequentially add 100mL hexanes, the heptane 1mL containing 1.8mmol triethyl aluminums, the silane of dimethyl diphenyl containing 0.1mmol N-heptane solution 1mL and 20 milligrams of catalyst component for olefin polymerization C1, and by the Stress control in reactor in 5 air Pressure, at 60 DEG C, polymerisation 1.0 hours, polymerization adds acidic ethanol to terminate polymerisation, Ran Houfen to temperature control after completing Not Yong respectively washing 3 times of deionized water and ethanol, be finally vacuum dried at 60 DEG C, obtain acrylic resin copolymer composition.Through Detection, the content of galapectite is 0.016 weight % in acrylic resin copolymer composition.

Comparative example 1

The comparative example is used to illustrate catalyst component for olefin polymerization of reference and preparation method thereof and vistanex group Compound and preparation method thereof.

Method according to embodiment 1 prepares catalyst component for olefin polymerization and polyolefine resin composition, unlike, Galapectite in the comparative example is added not in the preparation process of catalyst component for olefin polymerization, but directly with the homopolymerization for obtaining Acrylic resin and acrylic resin copolymer are blended, and are comprised the following steps that：

(1) preparation method of catalyst component for olefin polymerization：

1. by 4.0g anhydrous magnesium chlorides MgCl₂It is scattered in 90mL decane with 13.0mL isooctanol, is heated to 130 DEG C, shape Into clear solution, in being reacted 1.0 hours at 130 DEG C, chlorination magnesium alcoholate is obtained.Then above-mentioned chlorination magnesium alcoholate is added dropwise to In the suspension of 20mL decane, in isothermal reaction 4.0 hours at 60 DEG C, magnesium compound is obtained.

2. by step during 1. the magnesium compound drops to -20 DEG C of 200mL titanium tetrachlorides, time for adding is 1 hour, so After isothermal reaction 1.0 hours at -20 DEG C.Then 120 DEG C are to slowly warm up to, 0.2mL diisobutyl phthalates (institute is added It is 0.15 that diisobutyl phthalate is stated with the mol ratio of magnesium elements in the magnesium compound of galapectite：1), after at 120 DEG C Isothermal reaction 1.5 hours, filters liquid after the completion of reaction, 240mL titanium tetrachlorides are added again, in isothermal reaction 2.0 at 120 DEG C Hour.Finally, washed with hexane 5 times, the catalyst component for olefin polymerization of reference is obtained after drying, be designated as DC1.After testing, should The weight/mass percentage composition of transition metal Ti is 2.33%, metallic element magnesium in the catalyst component for olefin polymerization DC1 of reference Weight/mass percentage composition be 18%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Under vacuum conditions, propylene steam monomer is filled with reactor, then sequentially adds 50mL hexanes, contains The n-heptane solution 3mL of the triethyl aluminum of 5.5mmol, the n-heptane solution 3mL containing 0.55mmol dimethoxydiphenylsilanes and 20 milligrams of catalyst component for olefin polymerization DC1 of reference, and by the Stress control in reactor in 5.0 atmospheric pressure, reaction temperature At 60 DEG C, polymerisation 0.5 hour, polymerization adds acidic ethanol to terminate polymerisation after completing, and then uses respectively for degree control Respectively washing 3 times of deionized water and ethanol, are finally vacuum dried at 60 DEG C, obtain HOPP resin.Then will be above-mentioned equal Poly- acrylic resin is well mixed with 1.0g galapectites, obtains the HOPP resin combination of galapectite.After testing, this contains The content of galapectite is 5.0 weight % in the HOPP resin combination of galapectite.

2. propylene copolymerization：

Under vacuum conditions, by the gaseous mixture of propylene and ethene, (propylene is 95 with the mol ratio of ethene:5) it is filled with reactor In, then sequentially add 100mL hexanes, the heptane 1mL containing 1.8mmol triethyl aluminums, the silane of dimethyl diphenyl containing 0.1mmol N-heptane solution 1mL and 20 milligrams of catalyst component for olefin polymerization DC1 of reference, and by the Stress control in reactor 5 Individual atmospheric pressure, at 60 DEG C, polymerisation 1.0 hours, polymerization adds acidic ethanol to terminate polymerisation to temperature control after completing, Then finally it is vacuum dried at 60 DEG C with respectively washing 3 times of deionized water and ethanol respectively, obtains acrylic resin copolymer.So Above-mentioned acrylic resin copolymer is well mixed with 1.0g galapectites afterwards, obtains the acrylic resin copolymer composition of galapectite. After testing, the content for containing galapectite in the acrylic resin copolymer composition of galapectite is 4.5 weight %.

Comparative example 2

Method according to embodiment 1 prepares catalyst component for olefin polymerization and polyolefine resin composition, unlike, It is added without in the preparation process of catalyst component for olefin polymerization and in the preparation process of polyolefine resin composition angstrom Lip river stone, obtains the HOPP resin combination without galapectite and the acrylic resin copolymer combination without galapectite Thing.

Embodiment 2

(1) preparation method of catalyst component for olefin polymerization：

1. by 2.0g anhydrous magnesium chlorides MgCl₂It is scattered in 50mL decane with 12.5mL ethanol, is heated to 110 DEG C, is formed Clear solution, in being reacted 2.0 hours at 110 DEG C, obtains chlorination magnesium alcoholate.Then the chlorination magnesium alcoholate is added dropwise to In the suspension of 1.0g galapectites and 50mL decane, in isothermal reaction 4.0 hours at 110 DEG C, the magnesium compound of galapectite is obtained.

2. in the magnesium compound of the step 1. galapectite being dropped into -20 DEG C of 120mL titanium tetrachlorides, time for adding is 1 hour, then in isothermal reaction 1.0 hours at -20 DEG C.Then 120 DEG C are to slowly warm up to, 2.0 grams of (methoxyl groups of 9,9- bis- are added Methyl) ((methoxy) fluorenes of the 9,9- bis- is 0.10 with the mol ratio of magnesium elements in the magnesium compound of galapectite to fluorenes：1), After isothermal reaction 1.5 hours at 120 DEG C, liquid is filtered after the completion of reaction, again add 150mL titanium tetrachlorides, in 120 DEG C Lower isothermal reaction 2.0 hours.Finally, washed with hexane 5 times, catalyst component for olefin polymerization containing galapectite is obtained after drying, remembered It is C2.After testing, the weight/mass percentage composition of galapectite is 26%, transition metal Ti in catalyst component for olefin polymerization C2 Weight/mass percentage composition be 2.82%, the weight/mass percentage composition of metallic element magnesium is 12.5%, 9,9- bis- (methoxy) fluorenes Weight/mass percentage composition be 10.2%.

Wherein, step 1. described in galapectite be indianaite, its preparation method is as follows：Take 10 grams of natural galapectite mineral Matter obtains 8.6 grams of indianaites in being calcined 12 hours at 100 DEG C.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Under vacuum state, will during 450 grams of propylene liguids add reactors, then sequentially add 0.25mol triethyl aluminums, 0.005 gram of hydrogen and 35 milligrams of catalyst component for olefin polymerization C2, and by reacting kettle inner pressure control in 5.0 atmospheric pressure, Reaction temperature is controlled at 70 DEG C, and polymerisation 1.0 hours after the completion of polymerization, gas in reactor is vented, discharging, is obtained Poly- polypropylene resin composite.After testing, the content of galapectite is 0.0046 weight % in HOPP resin combination.

2. propylene copolymerization：

Under vacuum conditions, by the gaseous mixture of propylene and ethene, (propylene is 99 with the mol ratio of ethene:1) it is filled with reactor In, 100mL hexanes and 45 milligrams of catalyst component for olefin polymerization C2 are then sequentially added, and the Stress control in reactor is existed 6.0 atmospheric pressure, at 50 DEG C, polymerisation 1.0 hours adds acidic ethanol to terminate polymerization anti-to temperature control after the completion of polymerization Should, then finally it is vacuum dried at 60 DEG C with respectively washing 3 times of deionized water and ethanol respectively, obtain acrylic resin copolymer Composition.After testing, the content of galapectite is 0.18 weight % in acrylic resin copolymer composition.

Embodiment 3

(1) preparation method of catalyst component for olefin polymerization：

1. by 2.0g anhydrous magnesium chlorides MgCl₂It is scattered in 50mL decane with 2.8mL isooctanol, is heated to 130 DEG C, is formed Clear solution, in being reacted 4.0 hours at 130 DEG C, obtains chlorination magnesium alcoholate.Then above-mentioned chlorination magnesium alcoholate is added dropwise to In the suspension of 0.5g galapectites and 10mL decane, in isothermal reaction 10.0 hours at 60 DEG C, the magnesium compound of galapectite is obtained.

2. in the magnesium compound of the step 1. galapectite being dropped into -10 DEG C of 125mL titanium tetrachlorides, time for adding is 2 hours, then in isothermal reaction 1.0 hours at -10 DEG C.Then 120 DEG C are to slowly warm up to, 0.1mL ethyl benzoates (institute is added It is 0.20 that ethyl benzoate is stated with the mol ratio of magnesium elements in the magnesium compound of galapectite：1), after isothermal reaction at 120 DEG C 2.0 hours, liquid is filtered after the completion of reaction, 120mL titanium tetrachlorides are added again, in isothermal reaction 2.0 hours at 120 DEG C.Most Afterwards, washed with hexane 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C3.After testing, the olefin polymerization catalysis The weight/mass percentage composition of galapectite is 12% in component C3, and the weight/mass percentage composition of transition metal Ti is 2%, metallic element The weight/mass percentage composition of magnesium is 18%, and ethyl benzoate weight/mass percentage composition is 5%.

Wherein, step 1. described in galapectite be indianaite, its preparation method is as follows：Take 10 grams of natural galapectite mineral Matter obtains 8.3 grams of indianaites in being calcined 4 hours at 300 DEG C.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 1 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C3 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.016 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 1 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C3 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.20 weight % in resin combination.

Embodiment 4

(1) preparation method of catalyst component for olefin polymerization：

1. by 1.0g anhydrous magnesium chlorides MgCl₂It is scattered in 20mL decane with 5.5mL isooctanol, is heated to 110 DEG C, is formed Clear solution, in being reacted 6.0 hours at 110 DEG C, obtains the alcohol adduct of magnesium chloride.Then the alcohol adduct of above-mentioned magnesium chloride is added dropwise Enter in the suspension of 1.5g galapectites and 100mL decane, in isothermal reaction 10.0 hours at 90 DEG C, the magnesium for obtaining galapectite is combined Thing.

2. in the magnesium compound of the step 1. galapectite being dropped into -20 DEG C of 50mL titanium tetrachlorides, time for adding is 1 Hour, then in isothermal reaction 1.0 hours at -20 DEG C.Then 110 DEG C are to slowly warm up to, then in isothermal reaction at 110 DEG C 2.0 hours, liquid is filtered after the completion of reaction, 60mL titanium tetrachlorides are added again, in isothermal reaction 2.0 hours at 120 DEG C.Most Afterwards, washed with hexane 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C4.After testing, the olefin polymerization catalysis The weight/mass percentage composition of galapectite is 49% in component C4, and the weight/mass percentage composition of transition metal Ti is 2.56%, metal The weight/mass percentage composition of element magnesium is 5.8%.

Wherein, 1. galapectite used is the Ai Luo being modified through γ-methacryloxypropyl trimethoxy silane to step Stone, it is prepared by the following method：

10 grams of galapectites are scattered in 500mL ethanol and form suspension, to 12 grams of γ-methyl-props of addition in the suspension Alkene acryloxypropylethoxysilane trimethoxy silane, filters after being reacted 4.0 hours at 80 DEG C, is washed with ethanol three times, at 80 DEG C Vacuum drying 20.0 hours, obtains the galapectite being modified through γ-methacryloxypropyl trimethoxy silane.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 1 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C4 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.020 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 1 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C4 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.12 weight % in resin combination.

Embodiment 5

(1) preparation method of catalyst component for olefin polymerization：

1. by 2.0g anhydrous magnesium chlorides MgCl₂It is scattered in 50mL decane with 5.5mL isooctanol, is heated to 130 DEG C, is formed Clear solution, in being reacted 4.0 hours at 130 DEG C, obtains the chlorination magnesium alcoholate.Then above-mentioned chlorination magnesium alcoholate is added dropwise Enter in the suspension of 3.0g galapectites and 100mL decane, in isothermal reaction 20.0 hours at 60 DEG C, the magnesium for obtaining galapectite is combined Thing.

2. in the magnesium compound of the step 1. galapectite being dropped into -20 DEG C of 100mL titanium tetrachlorides, time for adding is 1 hour, then in isothermal reaction 1.0 hours at -20 DEG C.Then 60 DEG C are to slowly warm up to, 0.1 gram of (methoxyl group of 9,9- bis- is added Methyl) ((methoxy) fluorenes of the 9,9- bis- is 0.05 with the mol ratio of magnesium elements in the magnesium compound of galapectite to fluorenes：1), Then proceed to be to slowly warm up to 120 DEG C, isothermal reaction 1.5 hours filters liquid after the completion of reaction, 120mL tetrachloros are added again Change titanium, in isothermal reaction 2.0 hours at 120 DEG C.Finally, washed with hexane 5 times, olefin polymerization catalysis group is obtained after drying Point, it is designated as C5.After testing, the weight/mass percentage composition of galapectite is 50%, transition metal in catalyst component for olefin polymerization C5 The weight/mass percentage composition of element ti is 1.5%, and the weight/mass percentage composition of metallic element magnesium is 10%, 9,9- bis- (methoxies) The weight/mass percentage composition of fluorenes is 2.0%.

Wherein, 1. galapectite used is the galapectite being modified through gamma-aminopropyl-triethoxy-silane to step, and it is according to following Method is prepared：

10 grams of galapectites are scattered in 500mL ethanol and form suspension, to 5 grams of γ-aminopropyls of addition in the suspension Triethoxysilane, is filtered after being reacted 4.0 hours at 80 DEG C, is washed with ethanol three times, and 20.0 are vacuum dried at 80 DEG C Hour, obtain the galapectite being modified through gamma-aminopropyl-triethoxy-silane.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 1 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C5 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.009 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 1 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C5 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.20 weight % in resin combination.

Embodiment 6

(1) preparation method of catalyst component for olefin polymerization：

1. 10.0 grams of galapectites are scattered in 100mL tetrahydrofurans, obtain the suspension of galapectite.Then will contain 0.10molC₄H₉The tetrahydrofuran solution 50mL of MgCl is added dropwise in the suspension of above-mentioned galapectite, in back flow reaction at 80 DEG C 20.0 hours, after the completion of reaction, washed 5 times using tetrahydrofuran, the magnesium compound of galapectite is obtained after drying.

2. in the 10mL titanium tetrachlorides magnesium compound of 5.0 grams of galapectites being scattered at 20 DEG C, 120 DEG C are warming up to Lower reaction 2.0 hours, after the completion of reaction, filtering, hexane is washed 5 times, and catalyst component for olefin polymerization is obtained after drying, and is designated as C6.After testing, the weight/mass percentage composition of galapectite is 60% in catalyst component for olefin polymerization C6, transition metal Ti's Weight/mass percentage composition is 1.10%, and the weight/mass percentage composition of metallic element magnesium is 3.50%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 1 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C6 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.011 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 1 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C6 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.18 weight % in resin combination.

Embodiment 7

(1) preparation method of catalyst component for olefin polymerization：

1. 10.0 grams of galapectites are scattered in 50mL ether, obtain the suspension of galapectite.Then will contain 0.05molC₄H₉The 50mL diethyl ether solutions of MgBr are added dropwise in the suspension of above-mentioned galapectite, in constant temperature back flow reaction at 40 DEG C 20.0 hours, after the completion of reaction, washed 5 times using ether, the magnesium compound of galapectite is obtained after drying.

2. the magnesium compound for taking 5.0 grams of galapectites is scattered in 20 DEG C of 20mL titanium tetrachlorides, is to slowly warm up to 80 Reacted 2.0 hours at DEG C, after the completion of reaction, filtering, hexane is washed 5 times, and olefin polymerization catalysis containing galapectite are obtained after drying Component, is designated as C7.After testing, the weight/mass percentage composition of galapectite is 65% in catalyst component for olefin polymerization C7, transition gold The weight/mass percentage composition for belonging to element ti is 1.20%, and the weight/mass percentage composition of metallic element magnesium is 3.60%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 1 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C7 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.011 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 1 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C1 phases Substituted with the catalyst component for olefin polymerization C7 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.12 weight % in resin combination.

Embodiment 8

(1) preparation method of catalyst component for olefin polymerization：

1. 2.5 grams of galapectites are scattered in 50mL n-butyl ethers, obtain the suspension of galapectite.Then will contain 0.05molC₄H₉The 50mL n-butyl ether solution of MgBr is added dropwise in the suspension of above-mentioned galapectite, in constant temperature back flow reaction at 40 DEG C 20.0 hours, after the completion of reaction, washed 5 times using n-butyl ether, the magnesium compound of galapectite is obtained after drying.

2. the magnesium compound for taking 5.0 grams of galapectites is scattered in 20 DEG C of 40mL titanium tetrachlorides, is warming up at 120 DEG C Reaction 2.0 hours, after the completion of reaction, filtering, hexane is washed 5 times, and catalyst component for olefin polymerization is obtained after drying, and is designated as C8. After testing, the weight/mass percentage composition of galapectite is 58%, the matter of transition metal Ti in catalyst component for olefin polymerization C8 Amount percentage composition is 1.36%, and the weight/mass percentage composition of metallic element magnesium is 3.18%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Under vacuum conditions, propylene steam monomer is filled with reactor, then sequentially adds 100mL heptane, 5.5mmol Triethyl aluminum, 0.55mmol MTMSs and 30 milligrams of catalyst component for olefin polymerization C8, and by reactor In 7.0 atmospheric pressure, at 60 DEG C, polymerisation 0.5 hour adds acidifying second to Stress control after the completion of polymerization for reaction temperature control Alcohol terminates polymerisation, is then finally vacuum dried at 60 DEG C with respectively washing 3 times of deionized water and ethanol respectively, obtains Poly- polypropylene resin composite.After testing, the content of galapectite is 0.068 weight % in HOPP resin combination.

2. propylene copolymerization：

Under vacuum conditions, by propylene and ethene gaseous mixture, (propylene is 100 with the mol ratio of ethene:1) it is filled with reactor In, 100mL hexanes, 1.8mmol triethyl aluminums, 0.18mmol dimethyl diphenyls silane and 20 milligrams are then sequentially added containing alkene Polymerized hydrocarbon catalytic component C8, and by the Stress control in reactor in 5.0 atmospheric pressure, temperature control is at 60 DEG C, and polymerization is anti- Answer 1.0 hours, add acidic ethanol to terminate polymerisation after the completion of polymerization, then respectively with the respectively washing 3 of deionized water and ethanol It is secondary, finally it is vacuum dried at 60 DEG C, obtain acrylic resin copolymer composition.After testing, acrylic resin copolymer composition The content of middle galapectite is 0.061 weight %.

Embodiment 9

(1) preparation method of catalyst component for olefin polymerization：

1. 5.0 grams of galapectites are scattered in 50mL ether, obtain the suspension of galapectite.Then will contain 0.20molC₃H₇The 50mL diethyl ether solutions of MgI are added dropwise in the ether suspension of above-mentioned galapectite, anti-in constant temperature backflow at 40 DEG C Answer 48.0 hours, after the completion of reaction, washed 5 times using ether, the magnesium compound of galapectite is obtained after drying.

2. the magnesium compound of 5.0 grams of galapectites is scattered in 0 DEG C of 100mL titanium tetrachlorides, is warming up at 120 DEG C Reaction 2.0 hours, after the completion of reaction, filtering, hexane is washed 5 times, and catalyst component for olefin polymerization is obtained after drying, and is designated as C9. After testing, the weight/mass percentage composition of galapectite is 62%, the matter of transition metal Ti in catalyst component for olefin polymerization C9 Amount percentage composition is 0.98%, and the weight/mass percentage composition of metallic element magnesium is 3.50%.

Wherein, step 1. described in galapectite be indianaite, its preparation method is as follows：Take 10 grams of natural galapectite mineral Matter obtains 8.05 grams of indianaites in being calcined 12 hours at 600 DEG C.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 8 carries out propylene homo reaction, unlike, by catalyst component for olefin polymerization C8 phases Substituted with the catalyst component for olefin polymerization C9 of weight portion, obtain HOPP resin combination.After testing, HOPP The content of galapectite is 0.008 weight % in resin combination.

2. propylene copolymerization：

Method according to embodiment 8 carries out propylene copolyreaction, unlike, by catalyst component for olefin polymerization C8 phases Substituted with the catalyst component for olefin polymerization C9 of weight portion, obtain acrylic resin copolymer composition.After testing, COPP The content of galapectite is 0.09 weight % in resin combination.

Embodiment 10

(1) preparation method of catalyst component for olefin polymerization：

1. 5.0 grams of galapectites are taken to be scattered in 50mL toluene, the suspension of galapectite is obtained.Then 0.05mol first will be contained The toluene solution 30mL of base aikyiaiurnirsoxan beta is added dropwise in the suspension of above-mentioned galapectite, in reaction 10.0 hours, Ran Houyong at 90 DEG C Toluene is washed 5 times, and the aluminium compound of galapectite is obtained after drying.

2. by 0.05 gram of transistion metal compound Et (Ind)₂ZrCl₂Add 0 DEG C of the first containing 0.1mol MAOs In benzole soln 40mL, in being reacted 2.0 hours at 0 DEG C, then it is added dropwise to and is suspended containing 5.0 grams of toluene of the aluminium compound of galapectite In liquid 50mL, in reaction 4.0 hours at 60 DEG C.After the completion of reaction, washed with toluene 5 times, olefinic polymerization catalysis are obtained after drying Agent component, is designated as C10.After testing, the weight/mass percentage composition of galapectite is 70%, zirconium in catalyst component for olefin polymerization C10 The weight/mass percentage composition of element is 0.08%, and the weight/mass percentage composition of aluminium element is 9.87%.

(2) preparation method of polyolefine resin composition：

1. ethylene homo：

Under vacuum conditions, vinyl monomer is filled with reactor, then sequentially adds 100ml toluene, first containing 0.8mmol The toluene solution 1.6mL of base aikyiaiurnirsoxan beta and 20 milligrams of catalyst component for olefin polymerization C10, and reacting kettle inner pressure control is existed 5.0 atmospheric pressure, at 50 DEG C, polymerisation 1.0 hours adds acidic ethanol to terminate polymerization after the completion of polymerization for reaction temperature control Reaction, is then finally vacuum dried with respectively washing 3 times of deionized water and ethanol at 60 DEG C respectively, obtains homopolymerisation polyethylene tree Oil/fat composition.After testing, the content of galapectite is 0.14 weight % in homopolymerisation polyethylene resin combination.

2. propylene copolymerization：

Under vacuum conditions, by propylene and ethene gaseous mixture, (propylene is 95 with the mol ratio of ethene:5) it is filled with reactor In, then sequentially add 100mL toluene, urged containing the toluene solution 3.0mL of 2.1mmol MAOs and 30 milligrams of olefinic polymerizations Agent C10, and by the Stress control in reactor in 5.0 atmospheric pressure, temperature control at 50 DEG C, gather by polymerisation 0.5 hour Acidic ethanol is added to terminate polymerisation after the completion of conjunction, then respectively with respectively washing 3 times of deionized water and ethanol, finally at 60 DEG C Lower vacuum drying, obtains acrylic resin copolymer composition.After testing, in acrylic resin copolymer composition galapectite content It is 0.13 weight %.

Comparative example 3

Method according to embodiment 10 prepares catalyst component for olefin polymerization and polyolefine resin composition, different It is to be added without in the preparation process of catalyst component for olefin polymerization and in the preparation process of polyolefine resin composition Galapectite, obtains the HOPP resin combination without galapectite and the acrylic resin copolymer combination without galapectite Thing.

Embodiment 11

(1) preparation method of catalyst component for olefin polymerization：

1. 2.5 grams of galapectites are taken to be scattered in 50mL toluene, the suspension of galapectite is obtained.Then 0.10mol first will be contained The toluene solution 40mL of base aikyiaiurnirsoxan beta is added dropwise in the suspension of above-mentioned galapectite, in reaction 10.0 hours, Ran Houyong at 90 DEG C Toluene is washed 5 times, and the aluminium compound of galapectite is obtained after drying.

2. by 0.10 gram of transistion metal compound rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂(wherein, rac- is represented and disappeared In rotation, similarly hereinafter) adding 0 DEG C of the toluene solution 40mL containing 0.2mol MAOs, in reacting 4.0 hours at 0 DEG C, then In being added dropwise to containing 5.0 grams of toluene suspension 50mL of the aluminium compound of galapectite, in reaction 10.0 hours at 60 DEG C.React Cheng Hou, is washed 5 times with toluene, and the catalyst component for olefin polymerization containing galapectite is obtained after drying, and is designated as C11.After testing, the alkene The weight/mass percentage composition of galapectite is 64% in polymerized hydrocarbon catalytic component C11, and the weight/mass percentage composition of zr element is 0.46%, The weight/mass percentage composition of aluminium element is 7.80%.

(2) preparation method of vistanex：

1. ethylene homo：

Method according to embodiment 10 carries out ethylene homo reaction, unlike, catalyst component for olefin polymerization C10 is used The catalyst component for olefin polymerization C11 of identical weight part is substituted, and obtains homopolymerisation polyethylene resin combination.After testing, homopolymerization gathers The content of galapectite is 0.12 weight % in acetate resin composition.

2. propylene copolymerization：

Method according to embodiment 10 carries out propylene copolyreaction, unlike, catalyst component for olefin polymerization C10 is used The catalyst component for olefin polymerization C11 of identical weight part is substituted, and obtains acrylic resin copolymer composition.After testing, copolymerization gathers The content of galapectite is 0.10 weight % in propylene resin composition.

Embodiment 12

(1) preparation method of catalyst component for olefin polymerization：

1. 3.0 grams of galapectites are taken to be scattered in 30mL toluene, the suspension of galapectite is obtained.Then 0.1mol methyl will be contained The toluene solution 30mL of aikyiaiurnirsoxan beta is added dropwise in the suspension of above-mentioned galapectite, in being reacted 5.0 hours at 90 DEG C, then uses toluene Washing 5 times, obtains the aluminium compound of galapectite after drying.

2. by 0.15 gram of transistion metal compound Me₂C(Cp)(Flu)ZrCl₂Add 0 DEG C and contain 0.25mol methyl aluminas In the toluene solution 40mL of alkane, in being reacted 4.0 hours at 0 DEG C, then it is added dropwise to and contains 5.0 grams of first of the aluminium compound of galapectite In benzene suspension 50mL, in reaction 4.0 hours at 60 DEG C.After the completion of reaction, washed with toluene 5 times, alkene is obtained after drying and is gathered Catalytic component is closed, C12 is designated as.After testing, the weight/mass percentage composition of galapectite is in catalyst component for olefin polymerization C12 62%, the weight/mass percentage composition of zr element is 0.22%, and the weight/mass percentage composition of aluminium element is 9.12%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Under vacuum conditions, propylene steam monomer is filled with reactor, then sequentially adds 100mL toluene, contains The toluene solution 3.0mL of 3.2mmol MAOs and 30 milligrams of catalyst component for olefin polymerization C12, and by reactor internal pressure Power control is controlled at 50 DEG C in 3.0 atmospheric pressure, reaction temperature, and polymerisation 0.1 hour adds acidic ethanol after the completion of polymerization Terminate polymerisation, be then finally vacuum dried at 60 DEG C with respectively washing 3 times of deionized water and ethanol respectively, obtain homopolymerization Polypropylene resin composite.After testing, the content of galapectite is 0.66 weight % in HOPP resin combination.

2. propylene copolymerization：

Method according to embodiment 10 carries out propylene copolyreaction, unlike, catalyst component for olefin polymerization C10 is used The catalyst component for olefin polymerization C12 of identical weight part is substituted, and obtains acrylic resin copolymer composition.After testing, copolymerization gathers The content of galapectite is 0.22 weight % in propylene resin composition.

Embodiment 13

(1) preparation method of catalyst component for olefin polymerization：

1. 5.0 grams of galapectites are taken to be scattered in 50mL toluene, the suspension of galapectite is obtained.Then 0.1mol methyl will be contained The toluene solution 30mL of aikyiaiurnirsoxan beta is added dropwise in the suspension of above-mentioned galapectite, in being reacted 4.0 hours at 90 DEG C, then uses toluene Washing 5 times, obtains the aluminium compound of galapectite after drying.

2. 0.2 gram of transistion metal compound two [N- (3- tert-butyl groups salicylidene) anilino-] zirconium dichloride is added 0 DEG C The toluene solution 40mL containing 0.20mol MAOs in, at 0 DEG C react 4.0 hours, be then added dropwise to and contain 5.0 In the toluene suspension 50mL of the aluminium compound of gram galapectite, in being reacted 4.0 hours at 90 DEG C.After the completion of reaction, washed with toluene Wash 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C13.After testing, in catalyst component for olefin polymerization C13 angstrom The weight/mass percentage composition of Lip river stone is 65%, and the weight/mass percentage composition of zr element is 0.5%, and the weight/mass percentage composition of aluminium element is 8.5%.

(2) preparation method of polyolefine resin composition：

1. ethylene homo：

Method according to embodiment 10 carries out ethylene homo reaction, unlike, catalyst component for olefin polymerization C10 is used The catalyst component for olefin polymerization C13 of identical weight part is substituted, and obtains homopolymerisation polyethylene resin combination.After testing, homopolymerization gathers The content of galapectite is 0.11 weight % in acetate resin composition.

2. propylene copolymerization：

Method according to embodiment 10 carries out propylene copolyreaction, unlike, catalyst component for olefin polymerization C10 is used The catalyst component for olefin polymerization C13 of identical weight part is substituted, and obtains acrylic resin copolymer composition.After testing, copolymerization gathers The content of galapectite is 0.09 weight % in propylene resin composition.

Embodiment 14

(1) preparation method of catalyst component for olefin polymerization：

1. by 2.0g anhydrous magnesium chlorides MgCl₂It is scattered in 20mL decane with 5.5mL isooctanol, is heated to 110 DEG C, is formed Clear solution, in being reacted 4.0 hours at 110 DEG C, obtains chlorination magnesium alcoholate.Then above-mentioned chlorination magnesium alcoholate is added dropwise to In the suspension of 3.0g galapectites and 100mL decane, in isothermal reaction 12.0 hours at 90 DEG C, the magnesium for obtaining galapectite is combined Thing.

2. the magnesium compound of the step 1. galapectite is added dropwise in -20 DEG C of 60mL titanium tetrachlorides, time for adding is 2 Hour, after isothermal reaction 1.0 hours at -20 DEG C.110 DEG C are to slowly warm up to, 0.1ml diisobutyl phthalates are added (diisobutyl phthalate is 0.15 with the mol ratio of magnesium elements in the magnesium compound of galapectite：1), then in 110 Isothermal reaction 2.0 hours at DEG C, filter liquid after the completion of reaction, 60mL titanium tetrachlorides are added again, in isothermal reaction at 120 DEG C 2.0 hours.Finally, washed 3-6 times with hexane, the catalytic component containing galapectite is obtained after drying.

3. the catalytic component containing galapectite described in 5.0 grams is scattered in 50mL toluene, is subsequently adding first containing 0.05mol The toluene solution 30mL of base aikyiaiurnirsoxan beta, in being reacted 10.0 hours at 90 DEG C, is then washed 5 times with toluene, is activated after drying The catalytic component containing galapectite.

4. by 0.15 gram of transistion metal compound rac-Me₂Si(2-Me-4-PhInd)₂ZrCl₂Add and contain 0.10mol first In the toluene solution 40mL of base aikyiaiurnirsoxan beta, then in reaction 4.0 hours, the catalyst component solution for being activated at 0 DEG C.

5. the catalyst component solution of the 4. described activation of step is added dropwise to and 3. prepares gained containing 5.0 grams of steps In the toluene suspension 50mL of the catalytic component containing galapectite of activation, in reaction 4.0 hours at 90 DEG C.After the completion of reaction, Washed with toluene 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C14.After testing, the olefin polymerization catalysis group The weight/mass percentage composition for dividing galapectite in C14 is 42%, and the weight/mass percentage composition of titanium elements is 1.18%, the quality hundred of magnesium elements Content is divided to be 2.56%, the weight/mass percentage composition of zr element is 0.10%, the weight/mass percentage composition of aluminium element is 6.58%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 12 carries out propylene homo reaction, unlike, catalyst component for olefin polymerization C12 is used The catalyst component for olefin polymerization C14 of identical weight part is substituted, and obtains HOPP resin combination.After testing, homopolymerization gathers The content of galapectite is 0.08 weight % in propylene resin composition.

2. propylene copolymerization：

Method according to embodiment 12 carries out propylene copolyreaction, unlike, catalyst component for olefin polymerization C12 is used The catalyst component for olefin polymerization C14 of identical weight part is substituted, and obtains acrylic resin copolymer composition.After testing, copolymerization gathers The content of galapectite is 0.11 weight % in propylene resin composition.

Embodiment 15

(1) preparation method of catalyst component for olefin polymerization：

2. the magnesium compound of the step 1. galapectite is added dropwise in -20 DEG C of 60mL titanium tetrachlorides, time for adding is 1 Hour, after isothermal reaction 1.0 hours at -20 DEG C.60 DEG C are to slowly warm up to, 2.0 grams of 9,9- bis- (methoxy) are added ((methoxy) fluorenes of the 9,9- bis- is 0.20 with the mol ratio of magnesium elements in the magnesium compound of galapectite to fluorenes：1), Ran Houyu Isothermal reaction 2.0 hours at 110 DEG C, filter liquid after the completion of reaction, 60mL titanium tetrachlorides are added again, in constant temperature at 120 DEG C Reaction 2.0 hours.Finally, washed 3-6 times with hexane, the catalytic component containing galapectite is obtained after drying.

3. 5.0 grams of catalytic components containing galapectite are scattered in 50mL toluene, are subsequently adding aluminium methyl containing 0.1mol The toluene solution 30mL of oxygen alkane, at 90 DEG C react 4.0 hours, then wash with toluene 5 times, drying after activated containing angstrom The catalytic component of Lip river stone.

4. by 0.10 gram of transistion metal compound Et (Ind)₂ZrCl₂Add the toluene containing 0.10mol MAOs molten In liquid 40mL, then in reaction 4.0 hours, the catalyst component solution for being activated at 20 DEG C.

5. the catalyst component solution of the 4. described activation of step is added dropwise to and 3. prepares gained containing 5.0 grams of steps In the toluene suspension 50mL of the catalytic component containing galapectite of activation, in reaction 4.0 hours at 90 DEG C.After the completion of reaction, Washed with toluene 5 times, catalyst component for olefin polymerization is obtained after drying, be designated as C15.After testing, the olefin polymerization catalysis group The weight/mass percentage composition for dividing galapectite in C15 is 50%, and the weight/mass percentage composition of titanium elements is 1.78%, the quality hundred of magnesium elements Content is divided to be 3.20%, the weight/mass percentage composition of zr element is 0.15%, the weight/mass percentage composition of aluminium element is 10.02%, 9, The weight/mass percentage composition of 9- bis- (methoxy) fluorenes is 5.60%.

(2) preparation method of polyolefine resin composition：

1. propylene homo：

Method according to embodiment 12 carries out propylene homo reaction, unlike, catalyst component for olefin polymerization C12 is used The catalyst component for olefin polymerization C15 of identical weight part is substituted, and obtains HOPP resin combination.After testing, homopolymerization gathers The content of galapectite is 0.05 weight % in propylene resin composition.

2. propylene copolymerization：

Method according to embodiment 12 carries out propylene copolyreaction, unlike, catalyst component for olefin polymerization C12 is used The catalyst component for olefin polymerization C15 of identical weight part is substituted, and obtains acrylic resin copolymer composition.After testing, copolymerization gathers The content of galapectite is 0.07 weight % in propylene resin composition.

Test case

Test case is used to illustrate the test of olefinic polymerization physical performance.

(1) test of melt strength：

Determine that the experimental provision of melt strength is melted by the single screw extrusion machine equipped with capillary and Gottfert Rheotens Body intensity measuring device is constituted.Alloy composite melt in the polypropylene of melt strength to be measured is squeezed from extruding dies first Go out, the melt extrusion beam batten that then will be obtained is drawn with the opposite roller of two directions of motion on equalizer bar.Melt Institute's stress is the function of roll speed and time when beam is stretched.Roller uniformly accelerates to rotate, until the fracture of melt beam, by melt Beam power suffered when being broken is defined as melt strength.Acquired results are as shown in table 1.

(2) Mechanics Performance Testing：

Tensile strength is measured according to method specified in ASTM D 638, as a result as shown in table 1.

Impact strength is measured according to method specified in ASTM D256A, as a result as shown in table 1.

Table 1

From the results shown in Table 1, the olefin polymerization catalysis containing galapectite for the present invention being provided are poly- for preparing During olefin resin, the vistanex for obtaining has melt strength and mechanical strength higher.

The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.

It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.

Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims

1. a kind of preparation method of polyolefine resin composition, the method includes making olefinic monomer in catalyst component for olefin polymerization With polymerisation is carried out in the presence of co-catalyst, it is characterised in that the catalyst component for olefin polymerization contains galapectite, mistake Cross metal component and nontransition metal component；

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

The transition metal component be titanium tetrahalide and/or alkoxytitanium with metallocene catalyst in metallocene compound and/ Or the mixture of the non-metallocene compound in non-metallocene catalyst, and the nontransition metal component be magnesium-containing compound and The mixture of aluminum contained compound；

The formula of non-metallocene compound such as formula in the non-metallocene catalyst（II）It is shown：

Formula（II）

Wherein, M is selected from Zr, Ti, V or Hf, R₁、R₂And R₃It is each independently H, halogen atom, C₁-C₈Alkyl, C₁-C₈Alcoxyl Base, C₆-C₂₀Aryl, with C₁-C₆Alkyl aryl, with C₃-C₁₈Cycloalkyl aryl, with C₆-C₁₈Aromatic radical Aryl, C₁-C₈Acyloxy, pi-allyl or C₁-C₁₅Silylation, X be F, Cl, Br or I, n is 2.

2. method according to claim 1, wherein, on the basis of the gross weight of the catalyst component for olefin polymerization, institute The content of galapectite is stated for 0.5-90 weight %, metallic element always contains in the transition metal component and nontransition metal component It is 2-80 weight % to measure.

3. method according to claim 1, wherein, on the basis of the gross weight of the catalyst component for olefin polymerization, institute The content of galapectite is stated for 1-50 weight %, the total content of metallic element in the transition metal component and nontransition metal component It is 5-60 weight %.

4. method according to claim 2, wherein, when the nontransition metal component is aluminum contained compound, with described On the basis of the gross weight of catalyst component for olefin polymerization, the content of transition metal is 0.01-5 in the transition metal component Weight %, the content of non-transition metal elements is 2-40 weight % in the nontransition metal component；

When the mixture that the nontransition metal component is magnesium-containing compound and aluminum contained compound, with the olefinic polymerization catalysis On the basis of the gross weight of agent component, the content of transition metal is 0.25-15 weight % in the transition metal component, described The content of non-transition metal elements is 5-50 weight % in nontransition metal component.

5. the method according to any one in claim 1-4, wherein, the galapectite is natural galapectite, becomes angstrom Lip river At least one in stone and organically-modified galapectite；The indianaite is heat-treated by by natural galapectite at 50-900 DEG C Obtain within 0.5-48 hours；The organically-modified galapectite by by natural galapectite and/or indianaite organo-silicon compound, Titanium compound and not siliceous and titanium and at least one in organic compound of the end with double bond is modified obtains.

6. method according to claim 5, wherein, the formula of the organo-silicon compound is R¹R²SiR³ ₂, R¹For halogen is former Son, vinyl, amino, C₁-C₅Aminoalkyl, epoxy radicals, methacryloxy, sulfydryl, C₁-C₅Alkoxy, urea groups or logical Formula is-(CH₂)_m1COOCH(CH₃)=CH₂The alkyl containing alpha-olefin double bond, m1 for 1-18 integer, R²It is halogen atom, C₁-C₅'s Alkoxy or formula are-(CH₂)_m2-CH₃Alkyl, m2 for 0-2 integer, R³It is halogen atom, C₁-C₅Alkoxy or acetyl oxygen Base；

The formula of the titanium compound is R⁴ _pTi(OR⁵)_4-p, R⁴And R⁵It is C₁-C₄Alkyl, p for 0-3 integer；

The not siliceous and titanium and the formula of organic compound of the end with double bond is R⁶R⁷CH=CH₂, R⁶It is acid chloride group, carboxylic Base, epoxy radicals or ester group, R⁷It is C₁-C₂₀Alkylidene or the C with ester group, oxygen atom or carboxyl₁-C₂₀Alkylidene.

7. method according to claim 6, wherein, the organo-silicon compound are γ-methacryloxypropyl three Methoxy silane and/or gamma-aminopropyl-triethoxy-silane.

8. method according to claim 6, wherein, the titanium compound is butyl titanate, methyl triethoxy titanium, first At least one in base trimethoxy titanium and tetraethyl titanate.

9. method according to claim 6, wherein, described not siliceous and titanium and organic compound of the end with double bond Structural formula be HOOC (CH₂)₄CH=CH₂、HOOC(CH₂)₇CH=CH₂With HOOC (CH₂)₉CH=CH₂In at least one.

10. the method according to any one in claim 1-4, wherein, the titanium tetrahalide is TiCl₄、TiBr₄With TiI₄In at least one；The alkoxytitanium is Ti (OEt) Cl₃、Ti(OEt)₂Cl₂、Ti(OEt)₃Cl、Ti(OEt)₄And Ti (OBu)₄In at least one.

11. method according to any one in claim 1-4, wherein, metallocene chemical combination in the metallocene catalyst The formula of thing such as formula（Ⅰ）It is shown：

(Cp^I-B_e-Cp^II)M′R⁸ _aR⁹ _bFormula（I）

Wherein, M ' is Ti, Zr, Hf, V, Fe, Y, Sc or lanthanide series metal；Cp^IAnd Cp^IIIt is each independently H, C₁-C₅Alkyl, take Generation or non-substituted cyclopentadienyl group, replace or non-substituted C₆-C₁₈Aryl, and substitution base be C₁-C₆Alkyl, C₃- C₁₈Cycloalkyl and C₆-C₁₈Aryl at least one；R⁸And R⁹It is each independently H, halogen atom, C₁-C₈Alkyl, C₁- C₈Alkoxy, C₆-C₂₀Aryl, with C₁-C₁₅The C of alkyl₇-C₂₀Aryl, C₁-C₈Acyloxy, pi-allyl or C₁-C₁₅ Silylation, a, b are each independently the integer of 0-2, and a+b=2；B is-C (R¹⁰R¹¹)-alkyl bridge or-Si (R¹²R¹³)-silane Ji Qiao, wherein, R¹⁰-R¹³It is each independently H, C₁-C₄Alkyl or C₆-C₁₀Aryl；E is the integer of 1-3.

12. methods according to claim 11, wherein, the metallocene compound in the metallocene catalyst is C₂H₄ (Ind)₂ZrCl₂、C₂H₄(H₄Ind)₂ZrCl₂、Me₂Si(Ind)₂ZrCl₂、Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂、Me₂Si (Me₄Cp)₂ZrCl₂、Me₂Si(Flu)₂ZrCl₂、Me₂Si(2-Me-4-Naph-Ind)₂ZrCl₂And Ph₂Si(Ind)₂ZrCl₂In At least one, Me is methyl, and Ph is phenyl, and Cp is cyclopentadienyl group, and Ind is indenyl, H₄Ind is 4,5,6,7- tetrahydro indenes, Flu is fluorenyl, and Naph is naphthyl.

13. methods according to claim 1, wherein, the non-metallocene compound in the non-metallocene catalyst is two [N- (3- tert-butyl groups salicylidene) anilino-] zirconium dichloride, two [N- (3- methyl salicylidene) anilino-] zirconium dichlorides, two [N- (3- isopropyls salicylidene) anilino-] zirconium dichloride and two [N- (3- adamantyl -5- methyl salicylidene) anilino-s] At least one in zirconium dichloride.

14. method according to any one in claim 1-4, wherein, the magnesium-containing compound is that formula is MgX¹ ₂'s Magnesium halide and/or formula are RMgX²RMgBr；In MgX¹ ₂In, X¹It is F, Cl, Br or I；In RMgX²In, R is C₁-C₁₀'s Alkyl, X²It is F, Cl, Br or I.

15. method according to any one in claim 1-4, wherein, the formula of the aluminum contained compound is Al (OR ')_qR′′_3-q, R ' and R ' ' are each independently C₂-C₁₀Alkyl, 0≤q≤3.

16. method according to any one in claim 1-4, wherein, when the nontransition metal component is containing magnesium During the mixture of compound and aluminum contained compound, the catalyst component for olefin polymerization also contains internal electron donor compound.

17. methods according to claim 16, wherein, the internal electron donor compound is diether compounds and/or carboxylic Ester compound.

18. method according to any one in claim 1-4, wherein, the polymerisation is deposited external electron donor Under carry out.

19. methods according to claim 18, wherein, the external donor compound and in the co-catalyst aluminium unit The mol ratio of element is 0.001-1：1.

20. method according to any one in claim 1-4, wherein, the co-catalyst is alkyl aluminum and/or alcoxyl Base aluminium.

21. method according to any one in claim 1-4, wherein, when the nontransition metal component is containing calorize During compound, the olefin polymerization catalysis are prepared according to the method for comprising the following steps：

（1）Galapectite and the first aluminum contained compound are reacted 1-20 hours at 0-90 DEG C, the galapectite for being activated；

（2）Transition metal component and the second aluminum contained compound are reacted 1-20 hours at 0-90 DEG C, the catalyst for being activated Component, the transition metal component be metallocene catalyst in metallocene compound and/or non-metallocene catalyst in it is non- Metallocene compound；

（3）The galapectite of the activation is reacted 1-10 hours with the catalytic component of the activation at 0-100 DEG C.

22. methods according to claim 21, wherein, the weight ratio of the galapectite and the first aluminum contained compound is 1： 0.1-20。

23. methods according to claim 21, wherein, the weight ratio of the transition metal component and the second aluminum contained compound It is 1：1-5000.

24. methods according to claim 21, wherein, the weight of the galapectite of the activation and the catalytic component of activation Than being 1：1-20.

25. methods according to claim 21, wherein, first aluminum contained compound and the second aluminum contained compound are each only On the spot for formula is Al (OR ')_qR′′_3-qAluminum contained compound, R ' and R ' ' are each independently C₂-C₁₀Alkyl, 0≤q≤3.

26. method according to any one in claim 1-4, wherein, when the nontransition metal component is containing magnesium During the mixture of compound and aluminum contained compound, the olefin polymerization catalysis are prepared according to the method for comprising the following steps：

（1）Galapectite and magnesium-containing compound are reacted 1-50 hours at 30-150 DEG C, the magnesium compound of galapectite is obtained；

（2）The magnesium compound of the galapectite and titanium tetrahalide and/or alkoxytitanium are carried out into complexation reaction, is obtained containing galapectite Catalytic component；

（3）The catalytic component containing galapectite and the first aluminum contained compound are reacted 1-20 hours at 0-90 DEG C, is obtained The catalytic component containing galapectite of activation；

（4）By the non-metallocene compound in the metallocene compound and/or non-metallocene catalyst in metallocene catalyst with Second aluminum contained compound reacts 1-20 hours at 0-90 DEG C, the catalytic component for being activated；

（5）The catalytic component containing galapectite of the activation is reacted with the catalytic component of the activation at 0-110 DEG C 1-10 hours.

27. methods according to claim 26, wherein, step（1）Described in galapectite consumption and the chemical combination containing magnesium The weight ratio of the consumption of thing is 1：0.5-99.

28. methods according to claim 27, wherein, step（1）Described in galapectite consumption and the chemical combination containing magnesium The weight ratio of the consumption of thing is 1：0.5-35.

29. methods according to claim 26, wherein, the mode of the complexation reaction is first to answer the magnesium of the galapectite Compound mixes and reaction 0.5-2 hours at -20 DEG C to 0 DEG C with a part of titanium tetrahalide and/or another part alkoxytitanium, so Afterwards again by temperature rise to 80-130 DEG C react 1-4 hour, then by product separation of solid and liquid, and the solid product that will be obtained and Remainder titanium tetrahalide and/or remainder alkoxytitanium react 1-4 hours at 80-130 DEG C.

30. methods according to claim 29, wherein, a part of titanium tetrahalide and remainder titanium tetrahalide are each It independently is TiCl₄、TiBr₄And TiI₄In at least one；A part of alkoxytitanium and remainder alkoxytitanium are each It independently is Ti (OEt) Cl₃、Ti(OEt)₂Cl₂、Ti(OEt)₃Cl、Ti(OEt)₄With Ti (OBu)₄In at least one.

31. method according to claim 29 or 30, wherein, the preparation method of the olefin polymerization catalysis is additionally included in The magnesium compound of the galapectite is reacted with a part of titanium tetrahalide and/or a part of alkoxytitanium at -20 DEG C to 0 DEG C Before being reacted 1-4 hours after 0.5-2 hours and at 80-130 DEG C, to addition internal electron donor chemical combination in reaction system Thing.

32. methods according to claim 31, wherein, the internal electron donor compound is diether compounds and/or carboxylic Ester compound.

33. methods according to claim 26, wherein, the consumption of the catalytic component containing galapectite and described first The weight ratio of the consumption of aluminum contained compound is 1：0.1-20.

34. methods according to claim 26, wherein, total consumption of the metallocene compound and non-metallocene compound It is 1 with the weight ratio of the consumption of second aluminum contained compound：1-1000.

35. methods according to claim 26, wherein, the catalytic component of the activation is with the activation containing galapectite Catalytic component weight ratio be 1：0.1-20.

36. methods according to claim 26, wherein, first aluminum contained compound and the second aluminum contained compound are each only On the spot for formula is Al (OR ')_qR′′_3-qAluminum contained compound, R ' and R ' ' are each independently C₂-C₁₀Alkyl, 0≤q≤3.

A kind of 37. preparation methods of polyolefine resin composition, the method is comprised the following steps：

（3）The galapectite of the activation is reacted 1-10 hours with the catalytic component of the activation at 0-100 DEG C, alkene is obtained Polymerized hydrocarbon catalytic component；

（4）Make olefinic monomer that polymerisation is carried out in the presence of the catalyst component for olefin polymerization and co-catalyst；

Formula（II）

A kind of 38. preparation methods of polyolefine resin composition, the method is comprised the following steps：

（5）The catalytic component containing galapectite of the activation is reacted with the catalytic component of the activation at 0-110 DEG C 1-10 hours, obtain catalyst component for olefin polymerization；

（6）Make olefinic monomer that polymerisation is carried out in the presence of the catalyst component for olefin polymerization and co-catalyst；

Formula（II）

The polyolefine resin composition that 39. method as described in any one in claim 1-38 is prepared.