阅读说明：本技术 一种用于烯烃聚合的催化剂组分及其催化剂 (A kind of catalytic component and its catalyst for olefinic polymerization ) 是由 张锐 谭忠 周奇龙 徐秀东 于金华 宋维玮 李凤奎 尹珊珊 于 2018-05-21 设计创作，主要内容包括：本发明涉及一种用于烯烃聚合的催化剂组分及其催化剂。所述催化剂组分包含镁、钛、卤素、内给电子体化合物和助析出剂,其中,所述助析出剂包括如通式(I)所示的助析出剂a；通式(I)所示的助析出剂a包含如通式(I-a)和/或通式(I-b)所示的光学异构体,且通式(I-a)和/或通式(I-b)所示的光学异构体的含量大于90wt％。将本发明的催化剂用于烯烃聚合反应时,具有较高的活性和立体定向能力,制备的聚丙烯具有较窄的分子量分布,特别适用于制备窄分子量分布的丙烯聚合物。<Image he="603" wi="700" file="DDA0001667214570000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a kind of catalytic components and its catalyst for olefinic polymerization.The catalytic component includes magnesium, titanium, halogen, internal electron donor compound and precipitation additive, wherein the precipitation additive includes the precipitation additive a as shown in logical formula (I)；Precipitation additive a shown in logical formula (I) includes the optical isomer as shown in general formula (I-a) and/or general formula (I-b), and the content of optical isomer shown in general formula (I-a) and/or general formula (I-b) is greater than 90wt%.When catalyst of the invention is used for olefin polymerization, activity and stereotaxis ability with higher, the polypropylene of preparation have relatively narrow molecular weight distribution, the acrylic polymers particularly useful for making Narrow Molecular Weight Distribution.)

1. a kind of catalytic component for olefinic polymerization it includes magnesium, titanium, halogen, internal electron donor compound and helps precipitation Agent, wherein the precipitation additive includes at least one precipitation additive a as shown in logical formula (I)；

Wherein, R₁And R₂It is identical or different, it is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀Cycloalkanes Base, C₆-C₁₀Aryl or C₇-C₁₀Aralkyl；R₃And R₄It is identical or different, it is each independently selected from substituted or unsubstituted C₁- C₂₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₂₀Aryl or C₇-C₂₀Aralkyl；

Precipitation additive a shown in logical formula (I) includes the optical isomer as shown in general formula (I-a) and/or general formula (I-b), and logical The content of optical isomer shown in formula (I-a) and/or general formula (I-b) is greater than 90wt%, preferably greater than 95wt%, more preferably big In 98wt%；

2. catalytic component according to claim 1, which is characterized in that in logical formula (I), R₁And R₂It selects each independently From substituted or unsubstituted C₁-C₈Alkyl, C₃-C₈Naphthenic base or C₆-C₈Aryl；It is preferred that R₁And R₂It is each independently selected from Substituted or unsubstituted C₁-C₄Alkyl；R₃And R₄It is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀ Naphthenic base or C₆-C₁₀Aryl；It is preferred that R₃And R₄It is each independently selected from substituted or unsubstituted C₅-C₁₀Alkyl, cycloalkanes Base, aryl or aralkyl.

3. catalytic component according to claim 1 or 2, which is characterized in that the total weight based on catalytic component, it is described The content of precipitation additive a is lower than 1.0wt%, preferably shorter than 0.5wt%, more preferably less than 0.2wt%, most preferably less than 0.1wt%.

4. catalytic component described in any one of -3 according to claim 1, which is characterized in that the precipitation additive is optionally Including the precipitation additive b as shown in logical formula (II)；

Ti(OR₇)_nX_4-n (II)

Wherein, R₇Selected from C₁-C₁₀Alkyl or C₃-C₁₀Naphthenic base, X be halogen, 1≤n≤4, and n be integer.

5. catalytic component described in any one of -4 according to claim 1, which is characterized in that the internal electron donor chemical combination Object includes at least one 2,2- dialkyl -1,3- diformazan ether compound as shown in logical formula (III)；

Wherein, R₅And R₆It is identical or different, it is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀Cycloalkanes Base, C₆-C₁₀Aryl or C₇-C₁₀Alkaryl；It is preferred that R₅And R₆It is each independently selected from substituted or unsubstituted C₁-C₈Alkane Base, C₃-C₈Naphthenic base or C₆-C₈Aryl；More preferable R₅And R₆It is each independently selected from substituted or unsubstituted C₁-C₆Alkane Base or phenyl；R₅And R₆Optionally connection cyclization.

6. catalytic component described in any one of -5 according to claim 1, which is characterized in that based on the total of catalytic component Weight, the content of the titanium are 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%；The content of the magnesium is 10.0wt%-70.0wt%, preferably 15.0wt%-40.0wt%；The content of the halogen is 20.0wt%-90.0wt%, Preferably 30.0wt%-85.0wt%；The content of the internal electron donor compound is 2.0wt%-30.0wt%, preferably 3.0wt%-20.0wt%.

7. catalytic component described in any one of -6 according to claim 1, which is characterized in that the catalytic component includes Internal electron donor compound shown in the logical formula (III) of magnesium compound, titanium compound, at least one and at least one logical formula (I) institute The reaction product of the precipitation additive a shown；

Wherein, in terms of every mole of magnesium compound, the dosage of the precipitation additive a is 0.005-0.3 moles, preferably 0.01-0.05 Mole.

8. a kind of catalyst for olefinic polymerization, it includes following components:

Component 1, the catalytic component as described in any one of claim 1-7；

Component 2, alkyl aluminum compound；

And optionally component 3, external donor compound；

Wherein, the molar ratio of component 1 and component 2 is with titanium: aluminium is calculated as (5-5000): 1, preferably (20-1000): 1, more preferably (50-500):1。

9. a kind of pre-polymerized catalyst for olefinic polymerization comprising the catalysis as described in any one of claim 1-7 Agent component or catalyst as claimed in claim 8 and alkene carry out the resulting prepolymer of prepolymerization；Wherein, the prepolymer Pre-polymerization multiple is 5-1000g olefin polymer/g catalytic component, preferably 10-500g olefin polymer/g catalytic component； It is preferred that alkene used in prepolymerization is ethylene or propylene.

10. a kind of olefine polymerizing process, the alkene is in the catalytic component, such as described in any one of claim 1-7 It is polymerize under the action of catalyst according to any one of claims 8 or pre-polymerized catalyst as claimed in claim 9, the alkene General formula be CH₂=CHR, wherein R is hydrogen, C₁-C₆Alkyl or aryl.

Technical field

The invention belongs to catalyst technical fields, and in particular to a kind of catalytic component and its catalysis for olefinic polymerization Agent.

Background technique

It is using magnesium, titanium, halogen and electron donor as the ingredient of solid catalyst of basis, i.e., known in the field Ziegler-Natta catalyst can be used for CH2=CHR olefin polymerization, especially have 3 carbon or more Alpha-olefine polymerizing in available higher yields and higher stereospecificity polymer.Preparation method first is that first by chlorine Change magnesium and be prepared into homogeneous solution, then the active component of titaniferous is precipitated and loaded by crystallization.In solution modeling system, only help The presence of precipitation agent, is possible to obtain even-grained solids, precipitation additive generally use organic acid anhydride, organic acid, ketone, The classes compound such as ether, ester.

CN1020448 discloses Donor compound in one kind 1,3-, bis- ethers, and catalyst component obtained is used for alkene With high activity and good hydrogen response when polymerized hydrocarbon, the most significant feature of catalyst containing such compound is to be prepared into The weight of otefi pi polymer distribution arrived is very narrow.The polypropylene of Narrow Molecular Weight Distribution has many good qualities, such as anti-reflection not adding There is the preferable transparency in the case where agent, advantageously reduce the buckling deformation of product in the molding of high flow injection and improves product Impact property, and in flow process have broader newton platform area, viscosity with shear rate variation fluctuation it is smaller, Extrusion output is easier stability contorting, is particularly suitable for some forming methods for requiring low viscosity, high fluidity.When the object to polymer Reason-mechanical performance when such as bending strength, impact resistance and more demanding heat-resistant deformation performance, for example prepares fiber, thin-walled and height Rigid injection-molded item, it is necessary to be produced using the relatively narrow acrylic resin of molecular weight distribution.Especially in spinning application aspect, The stability of spinning nozzle pressure can be improved in the polypropylene of molecular weight narrow ditribution, it is ensured that the fineness for spraying silk is uniform.Therefore, narrow Polypropylene articles performance can be improved in the exploitation of molecular weight distribution polypropylene new product, expands application field, meets different field Demand to acrylic resin.

Currently, industrially preparing there are mainly three types of the polyacrylic methods of molecular weight narrow ditribution: being to pass through peroxide first Degradation obtains (so-called controllable rheology polypropylene), still, the cost of product is on the one hand increased using peroxide, is remained simultaneously Peroxide also easily cause final product generate taste and limit it in the application in certain fields.Followed by use metallocene Catalyst produces the polypropylene of Narrow Molecular Weight Distribution, molecular weight distribution 2.3-2.7.Since its oligomer obviously drops It is low, the peculiar smell generated in resin process can be not only reduced, material property is also significantly improved.But metallocene catalysis The supported cost of agent costly, and load after catalyst activity it is relatively low, limit its scope of application to a certain extent. It is finally point prepared using the Ziegler-Natta catalyst containing specific internal electron donor (1,3- diether compound) The polypropylene of son amount narrow ditribution, has many advantages, such as that at low cost, catalytic activity is high, therefore use the supported of high activity Ziegler-Natta catalyst preparation Narrow Molecular Weight Distribution polypropylene has broad application prospects.

CN106317274 and CN106317275, which is disclosed, uses diol ester as precipitation additive, and 1,3- diether is made interior to electricity The catalyst and preparation method of daughter, glycol ester content is 2-4%, high comprehensive performance, still, due to conduct in the catalyst The residual of the diol ester of precipitation additive in the catalyst " has neutralized " 1, the 3- diether as internal electron donor to a certain extent Feature leads to declines of 1, the 3- diether as internal electron donor in catalyst.

Although having done a large amount of research work in Ziegler-Natta catalyst field, for preparing higher performance It is required that Ziegler-Natta catalyst, it is still desirable to some new or improved method.Therefore, presently, there are the problem of be The content for being badly in need of researching and developing a kind of diol ester is extremely low, can be maximally maintained 1,3- diether compound as interior to electricity The catalytic component and its catalyst for olefinic polymerization of the most distinguishing feature of daughter.

Summary of the invention

The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide one kind to be used for olefinic polymerization Catalytic component and its catalyst.The present inventor has carried out extensively and profoundly in olefin polymerization catalysis technical field Experimental study, using isomers (R, R- configuration and/or S, the S- configurational isomer) content of particular optical configuration greater than 95% Diol ester has and effect is precipitated well, obtained catalyst particle shape is preferable, and the content of precipitation additive as precipitation additive a It is extremely low, it has been maximally maintained most distinguishing feature of 1, the 3- diformazan ether compound as internal electron donor in the catalyst, The polymer molecular weight distribution obtained is very narrow.

For this purpose, first aspect present invention provides a kind of catalytic component for olefinic polymerization, it includes magnesium, titanium, halogen Element, precipitation additive and internal electron donor compound, wherein the precipitation additive includes the precipitation additive a as shown in logical formula (I)；

Wherein, R₁And R₂It is identical or different, it is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀'s Naphthenic base, C₆-C₁₀Aryl or C₇-C₁₀Aralkyl, preferably R₁And R₂It is each independently selected from substituted or unsubstituted C₁-C₈ Alkyl, C₃-C₈Naphthenic base or C₆-C₈Aryl, more preferable R₁And R₂It is each independently selected from substituted or unsubstituted C₁-C₄ Alkyl, further preferred R₁And R₂It is respectively so independent that be selected from methyl, ethyl, n-propyl or isopropyl；R₃And R₄It is identical or not Together, it is each independently selected from substituted or unsubstituted C₁-C₂₀Alkyl, C₃-C₂₀Naphthenic base, C₆-C₂₀Aryl or C₇-C₂₀'s Aralkyl, preferably R₃And R₄It is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀Naphthenic base or C₆-C₁₀ Aryl, more preferable R₃And R₄It is each independently selected from substituted or unsubstituted C₅-C₁₀Alkyl, naphthenic base, aryl or aralkyl Base, further preferred R₃And R₄It is each independently selected from cyclopenta, cyclohexyl, phenyl, p-methylphenyl is right to ethylphenyl N-propyl phenyl, to n-butylphenyl.

Precipitation additive a shown in logical formula (I) includes the optical isomer as shown in general formula (I-a) and/or general formula (I-b), And the content of optical isomer shown in general formula (I-a) and/or general formula (I-b) is greater than 90wt%, preferably greater than 95wt%, it is more excellent Choosing is greater than 98wt%.

Heretofore described " substitution " refers to that the hydrogen on each group is replaced by halogen (miscellaneous) atom, alkyl or alkoxy；Main chain On carbon atom be exchanged for heteroatoms.

Precipitation additive a shown in formula of (I) of the present invention is diol-lipid compound, is contained there are two asymmetric carbon atom, Work as R₁And R₂Not identical and/or R₃And R₄When not identical, two asymmetric carbon atoms are different asymmetric carbon atom, lead to formula (I) institute The compound shown includes the R as shown in general formula (I-a), (I-b), (I-c), (I-d), R- configuration, S, S- configuration, R, S- structure Type, S, four optical isomers of R- configuration, wherein R, R- configuration and S, S- configuration, R, S- configuration and S, R- configuration are right each other respectively Reflect isomers, R, R- configuration and R, S- configuration or S, R- configuration, S, S- configuration and R, S- configuration or S, R- configuration are referred to as diastereomeric Isomers；Work as R₁And R₂Identical and R₃And R₄When identical, two asymmetric carbon atoms are identical asymmetric carbon atoms, R, S- configuration and S, R- configuration become a kind of identical configuration, and to R, R- configuration and S, S- configuration does not influence, and still mapping is different each other Structure body, while respectively and R, S- configuration are still diastereoisomer, leading to formula (I) compound represented, only there are three types of optical siomerisms Body.

Enantiomter shown in catalytic component according to the present invention, suitable general formula (I-a) and general formula (I-b) Combined example includes but is not limited to:

(R, R) -2,4-PD dibenzoate and (S, S) -2,4-PD dibenzoate, (R, R) -2,4- penta 2 Two p-methylbenzoic acid ester of alcohol and two p-methylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -2,4-PD two are to ethyl Benzoic ether and two p-ethylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -2,4-PD two are to n-propylbenzene formic acid esters (S, S) -2,4-PD two to n-propylbenzene formic acid esters, (R, R) -2,4-PD two to n-butylbenzoic acid ester and (S, S) -2,4-PD two is to n-butylbenzoic acid ester, (R, R) -3,5- heptandiol dibenzoate and (S, S) -3,5- heptandiol Dibenzoate, two p-methylbenzoic acid ester of (R, R) -3,5- heptandiol and two p-methylbenzoic acid of (S, S) -3,5- heptandiol Ester, two p-ethylbenzoic acid ester of (R, R) -3,5- heptandiol and two p-ethylbenzoic acid ester of (S, S) -3,5- heptandiol, (R, R) - 3,5- heptandiol two is to n-propylbenzene formic acid esters and (S, S) -3,5- heptandiol two to n-propylbenzene formic acid esters, (R, R) -3,5- heptan The enantiomter group that glycol two forms n-butylbenzoic acid ester and (S, S) -3,5- heptandiol two to n-butylbenzoic acid ester It is one or more groups of in conjunction.

It is preferably selected from (R, R) -2,4-PD dibenzoate and (S, S) -2,4-PD dibenzoate, (R, R) - Two p-methylbenzoic acid ester of 2,4-PD and two p-methylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -2,4-PD Two p-ethylbenzoic acid esters and two p-ethylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -2,4-PD two are to n-propyl Benzoic ether and (S, S) -2,4-PD two to n-propylbenzene formic acid esters, (R, R) -3,5- heptandiol dibenzoate and (S, S) -3,5- heptandiol dibenzoate, two p-methylbenzoic acid ester of (R, R) -3,5- heptandiol and (S, S) -3,5- heptandiol two P-methylbenzoic acid ester, two p-ethylbenzoic acid ester of (R, R) -3,5- heptandiol and (S, S) -3,5- heptandiol two are to ethylamino benzonitrile Acid esters, (R, R) -3,5- heptandiol two are to n-propylbenzene formic acid esters and (S, S) -3,5- heptandiol two to n-propylbenzene formic acid esters shape At enantiomter combination in it is one or more groups of.

Be most preferably selected from (R, R) -2,4-PD dibenzoate and (S, S) -2,4-PD dibenzoate, (R, R)-two p-methylbenzoic acid ester of 2,4-PD and two p-methylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -2,4- penta Two p-ethylbenzoic acid ester of glycol and two p-ethylbenzoic acid ester of (S, S) -2,4-PD, (R, R) -3,5- heptandiol hexichol first Acid esters and (S, S) -3,5- heptandiol dibenzoate, two p-methylbenzoic acid ester of (R, R) -3,5- heptandiol and (S, S) -3,5- Two p-methylbenzoic acid ester of heptandiol, two p-ethylbenzoic acid ester of (R, R) -3,5- heptandiol and (S, S) -3,5- heptandiol two are right It is one or more groups of in the enantiomter combination that ethylamino benzonitrile acid esters is formed.

Catalytic component according to the present invention, the total weight based on catalytic component, the content of the precipitation additive a Lower than 1.0wt%.

In some embodiments of the invention, based on the total weight of catalytic component, the content of the precipitation additive a is lower than 0.5wt%.

In some preferred embodiments of the invention, the total weight based on catalytic component, the precipitation additive a's contains Amount is lower than 0.2wt%.

In some further preferably embodiments of the invention, the total weight based on catalytic component is described to help precipitation The content of agent a is lower than 0.1wt%.

Catalytic component according to the present invention, the precipitation additive, which is optionally included, helps analysis as shown in logical formula (II) Agent b out；

Ti(OR₇)_nX_4-n (II)

Wherein, R₇Selected from C₁-C₁₀Alkyl or C₃-C₁₀Naphthenic base, X be halogen, 1≤n≤4, and n be integer.

In some embodiments of the invention, the precipitation additive b is selected from tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid four At least one of butyl ester and tetraisopropyl titanate, preferably butyl titanate.

Term " optionally " of the present invention, which refers to, to be contained or not contain, and is also referred to be added or is added without.

Catalytic component according to the present invention, the internal electron donor compound are selected from as shown in logical formula (III) 2,2- dialkyl -1,3- diformazan ether compound.

Wherein, R₅And R₆It is identical or different, it is each independently selected from substituted or unsubstituted C₁-C₁₀Alkyl, C₃-C₁₀'s Naphthenic base, C₆-C₁₀Aryl or C₇-C₁₀Alkaryl；It is preferred that R₅And R₆It is each independently selected from substituted or unsubstituted C₁-C₈ Alkyl, C₃-C₈Naphthenic base or C₆-C₈Aryl；More preferable R₅And R₆It is each independently selected from substituted or unsubstituted C₁-C₆ Alkyl；Further preferred R₅And R₆It is each independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, Tertiary butyl, n-pentyl, isopentyl, tertiary amyl, cyclopenta, cyclohexyl, phenyl.R₅And R₆Optionally connection cyclization.

The example of 2,2- dialkyl -1,3- diformazan ether compound shown in suitable logical formula (III) includes but is not limited to:

2,2'- diη-propyl -1,3- dimethyl ether, 2,2'- diisopropyl -1,3- dimethyl ether, 2,2'- di-n-butyl -1,3- Dimethyl ether, 2,2'- diisobutyl -1,3- dimethyl ether, bis- n-pentyl -1,3- dimethyl ether of 2,2'-, 2,2'- diisoamyl -1,3- two Methyl ether, 2,2'- di-n-hexyl -1,3- dimethyl ether, bis- isohesyl -1,3- diether of 2,2'-, 2- n-propyl -2- isopropyl -1,3- two Methyl ether, 2- n-propyl -2- normal-butyl -1,3- dimethyl ether, 2- n-propyl -2- isobutyl group -1,3- dimethyl ether, 2- n-propyl -2- are just Amyl -1,3- dimethyl ether, 2- n-propyl -2- isopentyl -1,3- dimethyl ether, 2- n-propyl -2- n-hexyl -1,3- dimethyl ether, 2- N-propyl -2- isohesyl -1,3- dimethyl ether, 2- isopropyl -2- normal-butyl -1,3- dimethyl ether, isobutyl group -1 2- isopropyl -2-, 3- dimethyl ether, 2- isopropyl -2- n-pentyl -1,3- dimethyl ether, 2- isopropyl -2- isopentyl -1,3- dimethyl ether, 2- isopropyl - 2- n-hexyl -1,3- dimethyl ether, 2- isopropyl -2- isohesyl -1,3- dimethyl ether, 2- normal-butyl -2- isobutyl group -1,3- diformazan Ether, 2- normal-butyl -2- n-pentyl -1,3- dimethyl ether, 2- normal-butyl -2- isopentyl -1,3- dimethyl ether, 2- normal-butyl -2- just oneself Base -1,3- dimethyl ether, 2- normal-butyl -2- isohesyl -1,3- dimethyl ether, 2- isobutyl group -2- n-pentyl -1,3- dimethyl ether, 2- are different Butyl -2- isopentyl -1,3- dimethyl ether, 2- isobutyl group -2- n-hexyl -1,3- dimethyl ether, 2- isobutyl group -2- isohesyl -1,3- Dimethyl ether, 2- n-pentyl -2- isopentyl -1,3- dimethyl ether, 2- n-pentyl -2- n-hexyl -1,3- dimethyl ether, 2- n-pentyl -2- Isohesyl -1,3- dimethyl ether, 2- isopentyl -2- n-hexyl -1,3- dimethyl ether, 2- isopentyl -2- isohesyl -1,3- dimethyl ether, One of 2- n-hexyl -2- isohesyl -1,3- dimethyl ether is a variety of.

It is preferably selected from 2,2'- diisopropyl -1,3- dimethyl ether, 2,2'- di-n-butyl -1,3- dimethyl ether, bis- isobutyl of 2,2'- Base -1,3- dimethyl ether, bis- n-pentyl -1,3- dimethyl ether of 2,2'-, 2,2'- diisoamyl -1,3- dimethyl ether, 2- n-propyl -2- are different Propyl -1,3- dimethyl ether, 2- n-propyl -2- isobutyl group -1,3- dimethyl ether, 2- n-propyl -2- isopentyl -1,3- dimethyl ether, 2- Isopropyl -2- normal-butyl -1,3- dimethyl ether, 2- isopropyl -2- isobutyl group -1,3- dimethyl ether, n-pentyl -1 2- isopropyl -2-, 3- dimethyl ether, 2- isopropyl -2- isopentyl -1,3- dimethyl ether, 2- isopropyl -2- isohesyl -1,3- dimethyl ether, 2- normal-butyl - 2- isobutyl group -1,3- dimethyl ether, 2- normal-butyl -2- isopentyl -1,3- dimethyl ether, 2- normal-butyl -2- isohesyl -1,3- diformazan Ether, 2- isobutyl group -2- n-pentyl -1,3- dimethyl ether, 2- isobutyl group -2- isopentyl -1,3- dimethyl ether, 2- isobutyl group -2- just oneself Base -1,3- dimethyl ether, 2- isobutyl group -2- isohesyl -1,3- dimethyl ether, one in 2- n-pentyl -2- isopentyl -1,3- dimethyl ether Kind is a variety of.

It is different to be most preferably selected from 2,2'- diisopropyl -1,3- dimethyl ether, 2,2'- diisobutyl -1,3- dimethyl ether, 2,2'- bis- Amyl -1,3- dimethyl ether, 2- isopropyl -2- isobutyl group -1,3- dimethyl ether, 2- isopropyl -2- n-pentyl -1,3- dimethyl ether, 2- Isopropyl -2- isopentyl -1,3- dimethyl ether, 2- isopropyl -2- isohesyl -1,3- dimethyl ether, n-pentyl -1 2- isobutyl group -2-, One of 3- dimethyl ether, 2- isobutyl group -2- isopentyl -1,3- dimethyl ether, 2- n-pentyl -2- isopentyl -1,3- dimethyl ether or It is a variety of.

The content of catalytic component according to the present invention, the total weight based on catalytic component, the titanium is 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%；The content of the magnesium is 10.0wt%-70.0wt%, preferably 15.0wt%-40.0wt%；The content of the halogen is 20.0wt%-90.0wt%, preferably 30.0wt%-85.0wt%； The content of the internal electron donor compound is 2.0wt%-30.0wt%, preferably 3.0wt%-20.0wt%.

Catalytic component according to the present invention, the catalytic component include magnesium compound, titanium compound, at least one The reaction product of precipitation additive a shown in internal electron donor compound shown in the logical formula (III) of kind and at least one logical formula (I). The dosage for being used to prepare the titanium compound of the catalytic component, magnesium compound and internal electron donor compound does not limit especially It is fixed, it can be the conventional amount used of this field.

In some embodiments of the invention, in terms of every mole of magnesium compound, the dosage of the precipitation additive a is 0.005- 0.3 mole, preferably 0.01-0.05；The molar ratio of the precipitation additive a and the internal electron donor compound is 0.05:1 to small In 0.8:1, preferably (0.1-0.7): 1.

In some embodiments of the invention, the precipitation additive for being used to prepare the catalytic component further includes precipitation additive B, in terms of every mole of precipitation additive a, the dosage of the precipitation additive b is 0.01-5 moles, preferably 0.5-3 moles.

The preparation method of catalyst component for olefin polymerization of the invention can prepare olefin catalytic by this field routine The method of agent component carries out.Such as the catalytic component for olefinic polymerization of the invention can be prepared by following methods.

Magnesium compound and alcohol compound are carried out in inert hydrocarbon solvent the first haptoreaction, obtained by method one, (1) Uniform magnesium compound alcohol adduct solution；(2) in the presence of precipitation additive, by the resulting homogeneous solution of step (1) and first Part titanium compound carries out the second haptoreaction, obtains the mixture precipitated containing solid；(3) by step (2) resulting mixture Third haptoreaction is carried out with first part's internal electron donor compound, obtains suspension；(4) suspension for obtaining step (3) Liquid is separated by solid-liquid separation, obtained solid intermediate product and second part titanium compound, second part internal electron donor compound The 4th haptoreaction is carried out, then is separated by solid-liquid separation, solid intermediate product is obtained；(5) it is produced among the solid for obtaining step (4) Object and Part III titanium compound carry out the 5th haptoreaction, then are separated by solid-liquid separation, and obtained solid product is molten using inertia Agent washing, it is dry, obtain final ingredient of solid catalyst.

The alcohol compound used in method one is selected from one of fatty alcohol, alicyclic ring alcohol or aromatic alcohol or a variety of；Its In, the fatty alcohol is selected from C₁-C₁₀Linear chain or branched chain fatty alcohol；The alicyclic ring alcohol is selected from C₃-C₁₂Alicyclic ring alcohol；The fragrance Alcohol is selected from C₆-C₂₀Aryl alcohol or C₇-C₂₀Aralkyl alcohol.

In some embodiments of the invention, alcohol compound is selected from ethyl alcohol, propyl alcohol, butanol, 2-Ethylhexyl Alcohol, benzene first One of alcohol, benzyl carbinol are a variety of, preferably 2-Ethylhexyl Alcohol.

The dosage of each ingredient used in method one, in terms of every mole of magnesium, the dosage of alcohol compound is 2-4 moles, excellent 2.5-3.5 moles is selected, in step (2), (4) and (5), the dosage of titanium compound is 1-40 moles, preferably 1.5-35 moles.

In method one, the first catalytic temperature is 30-150 DEG C, preferably 60-140 DEG C；First it is catalytic when Between be 0.5-10 hours, preferably 0.5-6 hours.Second catalytic temperature be -40 DEG C to 0 DEG C, preferably -30 DEG C to -20 DEG C, Second catalytic time was 3-5 hours, preferably 3.5-4.5 hours.The catalytic temperature of third is 20-120 DEG C, preferably 70-110℃；The third catalytic time is 0.5-6 hours, preferably 1-4 hours.4th catalytic temperature is 50-150 DEG C, preferably 80-120 DEG C；4th catalytic time was 1-6 hours, preferably 2.5-4.5 hours.5th catalytic temperature Degree is 50-150 DEG C, preferably 80-120 DEG C；Five catalytic times were 1-6 hours, preferably 2.5-4.5 hours.

Method two, (1) carry out magnesium compound and organic epoxy compound object, organic phosphorus compound in inert hydrocarbon solvent First haptoreaction obtains uniform magnesium compound solution；(2) in the presence of precipitation additive, step (1) is obtained uniform Solution and first part's titanium compound and first part's internal electron donor compound carry out the second haptoreaction, and it is heavy containing solid to obtain The suspension of starch；(3) suspension containing solid sediment that step (2) obtains is separated by solid-liquid separation, in obtained solid Between product A and second part titanium compound, second part internal electron donor compound carry out third haptoreaction, through being separated by solid-liquid separation Afterwards, solid intermediate product B is obtained；(4) the solid intermediate product B for obtaining step (3) and Part III titanium compound carry out the Four haptoreactions, after being separated by solid-liquid separation, obtained solid intermediate product C；Obtained solid intermediate product C again with titanium compound into Row haptoreaction is repeated 1-3 times, is separated by solid-liquid separation, and obtained solid product is washed using atent solvent, dry, is obtained most Whole ingredient of solid catalyst.

The organic epoxy compound object used in method two is selected from ethylene oxide, propylene oxide, epoxy butane, butadiene oxygen At least one of compound, butadiene double oxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether, preferably Epoxychloropropane.

The organic phosphorus compound used in method two is selected from the hydrocarbyl carbonate or halogenated hydrocarbons base ester of orthophosphoric acid or phosphorous acid, excellent Select orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate, Trimethyl phosphite, phosphorous triethylenetetraminehexaacetic acid At least one of ester, tributyl phosphite or phosphorous acid benzene methyl, more preferable orthophosphoric acid tributyl.

The dosage of each ingredient used in method two, in terms of every mole of magnesium, the dosage of organic epoxy compound object is 0.2-10 Mole, preferably 0.5-4.0 moles；The dosage of organic phosphorus compound is 0.1-3.0 moles, preferably 0.3-1.5, mole；In step (2) in-(4), the dosage of titanium compound is 3-40 moles, preferably 5-35 moles.

In method two, the first catalytic temperature is 0-80 DEG C, preferably 10-60 DEG C；First catalytic time It is 0.5-10 hours, preferably 0.5-6 hours.Second catalytic temperature is -40 DEG C to 0 DEG C, preferably -30 DEG C to -20 DEG C；The Two catalytic times were 3-5 hours, preferably 3.5-4.5 hours.The catalytic temperature of third is 50-150 DEG C, preferably 80-120℃；The third catalytic time is 1-6 hours, preferably 2.5-4.5 hours.4th catalytic temperature is 50- 150 DEG C, preferably 80-120 DEG C；4th catalytic time was 1-6 hours, preferably 2.5-4.5 hours.

Catalytic component according to the present invention, in above-mentioned preparation method, first part's internal electron donor compound with The molar ratio of second part internal electron donor compound is (0.1-10): 1, preferably (0.2-5): 1, more preferable (0.2-1): 1.

Catalytic component according to the present invention, in above two preparation method, the magnesium compound includes general formula (IV) one of compound represented, alcohol adduct shown in hydrate and logical formula (VI) shown in logical formula (V) or a variety of；

MgR₈R₉ (IV)

MgR₈R₉·qH₂O (V)

MgR₈R₉·pR₀OH (VI)

In logical formula (IV)-(VI), R₈And R₉It is identical or not identical, it is each independently selected from halogen, C₁-C₅Alkyl, hydrocarbon Oxygroup, halohydrocarbyl or halogenated oxyl；It is preferred that R₈And R₉Respectively halogen, the halogen be fluorine, chlorine, bromine or iodine, preferably chlorine or Bromine.

In logical formula (V), q 0.1-6.0, preferably 2.0-3.5；

In logical formula (VI), R₀Selected from C₁-C₁₈Alkyl, preferably C₁-C₅Alkyl；P is 0.1-6.0, preferably 2.0- 3.5。

In some preferred embodiments of the invention, the magnesium compound is selected from magnesium dichloride, magnesium dibromide, Benzene Chloride At least one of oxygroup magnesium, chlorination isopropoxy magnesium, chlorination butoxy magnesium.

In some preferred embodiments of the invention, the magnesium compound is anhydrous magnesium dichloride.

Catalytic component according to the present invention, in above-mentioned preparation method, the inert hydrocarbon solvent can be ability The hydrocarbon solvent of chemical action does not occur commonly with the magnesium compound for domain, such as in alkane, cycloalkane or aromatic hydrocarbon extremely Few one kind, preferably at least one of decane, benzene, toluene or dimethylbenzene, more preferably toluene.

Catalytic component according to the present invention, in above-mentioned preparation method, the titanium compound includes at least one logical Formula (VII) compound represented；

TiX_m(OR₁₀)_4-m (VII)

In logical formula (VII), R₁₀For C₁-C₂₀Alkyl, preferably C₁-C₅Alkyl；X is halogen；1≤m≤4 and m is Integer, such as 1,2,3 or 4.The halogen is chlorine, bromine or iodine.

In some preferred embodiments of the invention, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, tetraiodide At least one of titanium, tetraalkoxy titanium, three halogenated titanium of alkoxy, dialkoxy dihalide titanium, tri-alkoxy halogenated titanium.

In some preferred embodiments of the invention, the titanium compound is titanium tetrachloride.

Second aspect of the present invention provides a kind of catalyst for olefinic polymerization, and it includes following components:

Component 1, catalytic component as described in the first aspect of the invention；

Component 2, alkyl aluminum compound；

And optionally component 3, external donor compound.

Wherein, the molar ratio of component 1 and component 2 is with titanium: aluminium is calculated as (5-5000): 1, preferably (20-1000): 1, it is more excellent It is selected as (50-500): 1.

Catalyst according to the present invention, 2 alkyl aluminum compound of component can be common for field of olefin polymerisation The alkyl aluminum compound of the various co-catalysts that can be used as Ziegler-natta catalyst.

In some preferred embodiments of the invention, 2 alkyl aluminum compound of component includes at least one general formula (VIII) compound represented；

AlR'_n'X'_3-n' (VIII)

In logical formula (VIII), R' is selected from H, C₁-C₂₀Alkyl or C₆-C₂₀Aryl, X' is halogen, 1≤n'≤3 and n' For integer.

In some preferred embodiments of the invention, the alkyl aluminum compound be selected from trimethyl aluminium, triethyl aluminum, Triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, At least one of sesquialter ethylmercury chloride aluminium and ethyl aluminum dichloride.

Catalyst according to the present invention does not limit the type and content of the external donor compound especially It is fixed.3 external donor compound of component can be used as Ziegler-Natta type for field of olefin polymerisation is commonly various The external donor compound of the co-catalyst of catalyst.

In some preferred embodiments of the invention, the molar ratio of the component 3 and component 2 is with silicon: aluminium is calculated as 1: (0.1-500).In some preferred embodiments of the invention, the molar ratio of the component 3 and component 2 is with silicon: aluminium is calculated as 1:(1-300).In some further preferred embodiments of the invention, the molar ratio of the component 3 and component 2 is with silicon: aluminium It is calculated as 1:(3-100).

In some preferred embodiments of the invention, 3 external donor compound of component includes at least one logical Formula (IX) compound represented:

R¹"_m"R²"_n"Si(OR^3")_4-m"-n" (IX)

In logical formula (IX), R¹" and R²" it is identical or not identical, it is each independently selected from H, halogen, C₁-C₂₀Alkyl or halogen Substituted alkyl, C₃-C₂₀Naphthenic base or C₆-C₂₀Aryl；R³" it is selected from C₁-C₂₀Alkyl or halogenated alkyl, C₃-C₂₀Naphthenic base Or C₆-C₂₀Aryl；The integer that m " and n " is 0-3, and m "+n " < 4.

In some preferred embodiments of the invention, 3 external donor compound of component is selected from trimethyl first Oxysilane, trimethylethoxysilane, trimethylbenzene oxygroup triethyl group methoxy silane, triethyl-ethoxy-silicane alkane, diformazan Base dimethoxysilane, dimethyl diethoxysilane, ethylisopropyl base dimethoxysilane, propyl iso-propyl dimethoxy silicon Alkane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, isopropyl butyldimethoxysilane, two tertiary fourths Base dimethoxysilane, tertbutyl methyl dimethoxysilane, t-butylethyl dimethoxysilane, tert-butyl dimethylamine oxygen Base silane, ter /-butylisopropyl dimethoxysilane, tert-butyl butyldimethoxysilane, tert-butyl isobutyl group dimethoxy silicon Alkane, tert-butyl (sec-butyl) dimethoxysilane, t-butyl amyl dimethoxysilane, tert-butyl nonyl dimethoxysilane, Tert-butyl hexyl dimethoxysilane, tert-butyl heptyl dimethoxysilane, tert-butyl octyl dimethoxysilane, the tert-butyl last of the ten Heavenly stems Base dimethoxysilane, methyl-t-butyldimethoxysilane, Cyclohexyl Methyl Dimethoxysilane, cyclohexyl-ethyl dimethoxy Base silane, Cyclohexylpropyl dimethoxysilane, cyclohexyl isobutyl group dimethoxysilane, Dicyclohexyldimethoxysilane, Cyclohexyl t-butyldimethoxysilane, cyclopentyl-methyl dimethoxysilane, cyclopentyl ethyl dimethoxysilane, cyclopenta Propyldimethoxy-silane, cyclopenta t-butyldimethoxysilane, dicyclopentyl dimethoxyl silane, cyclopentyl cyclohexyl two Methoxy silane, bis- (2- methylcyclopentyl) dimethoxysilanes, dimethoxydiphenylsilane, diphenyl diethoxy silicon Alkane, phenyl triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyl trimethoxy silane, ethyl three Ethoxysilane, propyl trimethoxy silicane, isopropyltri-methoxysilane, butyl trimethoxy silane, butyl triethoxy Silane, trimethoxysilane, tert-butyl trimethoxy silane, sec-butyl trimethoxy silane, amyl trimethoxy silicon Alkane, isopentyl trimethoxy silane, cyclopentyl-trimethoxy-silane, cyclohexyl trimethoxy silane, diphenyl dimethoxy silicon Alkane, diphenyl diethoxy silane, phenyltrimethoxysila,e, phenyl triethoxysilane, n-propyl trimethoxy silane, second Alkenyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, four butoxy silanes, 2- ethyl piperidine base -2- tert-butyl Dimethoxysilane, (the fluoro- 2- propyl of 1,1,1- tri-) -2- ethyl piperidine base dimethoxysilane and (the fluoro- 2- third of 1,1,1- tri- At least one of base)-methyl dimethoxysilane.

In some further preferred embodiments of the invention, 3 external donor compound of component is selected from two rings Dicyclopentyldimetoxy silane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, cyclohexyl methyl dimethoxy At least one of silane, methyl-t-butyldimethoxysilane and tetramethoxy-silicane.

Third aspect present invention provides a kind of pre-polymerized catalyst for olefinic polymerization comprising such as the present invention first Catalytic component described in aspect or catalyst as described in respect of the second aspect of the invention and alkene carry out the resulting pre-polymerization of prepolymerization Object；Wherein, the pre-polymerization multiple of the prepolymer is 5-1000g olefin polymer/g catalytic component, preferably 10-500g alkene Polymer/g catalytic component；It is preferred that alkene used in prepolymerization is ethylene or propylene.

In some embodiments of the invention, the prepolymerized temperature is -20 to 80 DEG C, preferably 10-50 DEG C.

Fourth aspect present invention provides a kind of olefine polymerizing process, and the alkene is as described in the first aspect of the invention Catalytic component, catalyst as described in respect of the second aspect of the invention or pre-polymerized catalyst as described in the third aspect of the present invention It is polymerize under effect.The general formula of the alkene is CH₂=CHR, wherein R is hydrogen, C₁-C₆Alkyl or phenyl.

Olefine polymerizing process provided by the invention can be used for the homopolymerization of alkene, can be used for carrying out in a variety of alkene Combined polymerization.The alkene is selected from ethylene, propylene, 1- n-butene, 1- n-pentene, 1- n-hexylene, the positive octene of 1- and 4- methyl-1-pentene At least one of alkene.Preferably, the alkene can for ethylene, propylene, 1- n-butene, 4-methyl-1-pentene and 1- just oneself At least one of alkene.It is preferred that the alkene is propylene.

When preparing polyolefin, each component in catalyst of the present invention, i.e., catalytic component provided by the invention, work It can first be contacted before contacting olefinic monomer for the organo-aluminum compound and external donor compound of co-catalyst, In It is referred to as " pre-contact " or " pre- complexing " in the industry；Can also three components be added separately in olefinic monomer to carry out polymerizeing again it is anti- It answers, i.e., does not implement " pre-contact ".The olefine polymerizing process provided according to the present invention, each component is adopted in preferred alkenes polymerization catalyst With the method for " pre-contact ".The time of " pre-contact " be 0.1-30min, preferably 1-10 minutes；The temperature of " pre-contact " is -20 DEG C to 80 DEG C, preferably 10-50 DEG C.

Catalyst of the present invention is first carried out in the presence of a small amount of olefinic monomer a degree of prepolymerization obtain it is pre- Polymerization catalyst, then pre-polymerized catalyst is further contacted with olefinic monomer and is reacted to obtain olefin polymer.This skill Art is in the field of business to be referred to as " prepolymerization " technique, facilitates polymerization catalyst activity and raising of polymer bulk density etc..According to Olefine polymerizing process provided by the invention can use " prepolymerization " technique, can not also use " prepolymerization " technique, preferably adopt With " prepolymerization " technique.

Olefine polymerizing process according to the present invention, the polymerizing condition can be this field normal condition, the use of catalyst Amount can be the dosage of the various catalyst of the prior art.

The present invention is big by using isomers (R, R- configuration and/or S, S- configurational isomer) content of particular optical configuration In 95% diol ester as precipitation additive a, have and effect be precipitated well, obtained catalyst particle shape is preferable, precipitation additive Content it is extremely low, and be maximally maintained 1 in the catalyst, 3- diformazan ether compound is as the most aobvious of internal electron donor Work feature is very narrow to get the polymer molecular weight distribution arrived.

Specific embodiment

To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only Serve illustrative, it is not limited to application range of the invention.

As previously mentioned, residual quantity when glycol ester compounds are as precipitation additive in the prior art in the catalyst is higher, And the residual quantity of glycol ester compounds is higher, the effect of 1, the 3- diformazan ether compound in catalyst as internal electron donor is got over It is weak.In view of the above problems, the present inventor has found after study, in the preparation of olefin polymerization catalysis, using such as logical When the glycol ester compounds of configuration shown in formula (I-a) and/or (I-b) are as precipitation additive, glycol ester compounds in catalyst Content be lower than 0.5wt%, and use the configuration as shown in general formula (I-c) and/or (I-d) diol ester as precipitation additive when, urge The content of glycol ester compounds is higher than 3wt% in agent.Therefore, the present invention is by using such as general formula (I-a) and/or (I-b) institute Showing diol-lipid compound of the content of isomer greater than 95% of configuration as precipitation additive, obtained catalyst particle shape is preferable, And the content of precipitation additive is extremely low；Catalyst 1,3- diformazan ether compound in catalyst just can be maximally maintained in this way to make It is very narrow to get the polymer molecular weight distribution arrived for the most distinguishing feature of internal electron donor.The present invention is based on above-mentioned discovery It makes.

Test method used in the present invention is as follows:

(1) purity of precipitation additive a glycol ester compounds and the ratio of diastereoisomer use Waters, US Acquity UPLC Ultra Performance Liquid Chromatography instrument is measured；

(2) precipitation additive compound structure type uses Brukerdmx Nuclear Magnetic Resonance (300MHz, solvent C DCl3, internal standard TMS, measuring temperature 300K) it is determined；

(3) content of the glycol ester compounds in catalytic component: super using Waters, US Acquity UPLC High performance liquid chromatograph is measured；

(4) it melt index (MI): is measured according to GB/T3682-2000；

(5) acrylic polymers isotacticity index (II): measured using heptane extraction process: 2g dry polymer samples are put It is after being extracted 6 hours in extractor with boiling heptane, residue is dry to the resulting polymer weight (g) of constant weight and 2 (g) Ratio is isotacticity；

(6) active (Ac) is calculated: catalyst activity=(the polyolefin quality of preparation)/(catalyst solid constituent quality) kg/g；

(7) bulk density (BD) measures: will prepare resulting polymer powders in funnel from 10cm height freely falling body Into 100mL container, polymer powders weight is M g in weighing container, then polymer bulk density is M/100g/cm³；

(8) polymer molecular weight distribution MWD (MWD=Mw/Mn): PL-GPC220 is used, using trichloro-benzenes as solvent, 150 (standard specimen: polystyrene, flow velocity: 1.0mL/min, pillar: 3x Plgel10um MlxED-B 300x 7.5nm) is measured at DEG C.

In the present invention, using Ultra Performance Liquid Chromatography instrument, by adjusting the separation condition of liquid chromatogram, make R, R- configuration and The diol ester of the diol ester and R of S, S- configuration, S- configuration has different retention times, thus by R, R- configuration and S, S- configuration The same R of diol ester, the diol ester of S- configuration distinguishes.Specific separation condition are as follows:

(1) chromatographic column: ACQUITY UPLC BEH Shield RP18 (100mm × 2.1mm, 1.7 μm)；

(2) column temperature: 35 DEG C；

(3) mobile phase: 75% methanol, 25% ultrapure water；

(4) flow velocity 0.3mL/min；

(5) PDA Detection wavelength 229nm.

Under this condition, the diol ester retention time of R, R- configuration and S, S- configuration are identical and relatively short, R, S- configuration Diol ester retention time it is relatively long.Meanwhile it also can determine whether according to the nuclear magnetic resonance spectroscopy signal peak of diastereoisomer Configuration.