CN109096417A - A kind of catalyst and olefine polymerizing process for olefinic polymerization - Google Patents
A kind of catalyst and olefine polymerizing process for olefinic polymerization Download PDFInfo
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- CN109096417A CN109096417A CN201710475391.6A CN201710475391A CN109096417A CN 109096417 A CN109096417 A CN 109096417A CN 201710475391 A CN201710475391 A CN 201710475391A CN 109096417 A CN109096417 A CN 109096417A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6498—Catalysts containing a specific non-metal or metal-free compound organic containing another heteroatom
Abstract
The invention belongs to olefin polymerization catalysis fields, provide a kind of catalyst and olefine polymerizing process for olefinic polymerization.The catalyst includes the reaction product of following components: (1) ingredient of solid catalyst；(2) alkyl aluminum compound；(3) external donor compound, the external donor compound include two hydrocarbyloxysilane of oxyl phenyl carboxylic acid ester compounds and alkyl；Shown in the structure such as formula (II) of oxyl phenyl carboxylic acid's ester compounds, shown in the structure such as formula (III) of two hydrocarbyloxysilane of alkyl.Catalyst of the invention is matched by adjusting in the case where the total dosage of external electron donor is constant, can prepare the polymer of different performance.
Description
Technical field
The invention belongs to olefin polymerization catalysis fields, and in particular to a kind of catalyst for olefinic polymerization, Yi Jiyi
Kind olefine polymerizing process.
Background technique
It is well known that for the catalyst system in the polymerization reaction of ethylene, alpha-olefin and its mixture generally by three
Divide and constitute, specifically includes: (1) major catalyst (ingredient of solid catalyst), (2) co-catalyst (usually alkyl aluminum class compound)
(3) external donor compound being added when polymerizeing.
The stereoregular of polymer is controlled using one or more of External Electron Donor Compounds in polymerization process
Property and form.External electron donor can influence catalysis other than influencing the stereoregularity of polymer, toward contact to some extent
The activity of agent and hydrogen response etc., but the influence is often presented as there is positive effect in one aspect, in other aspects
Side effect can then be played.
Although can be used as external electron donor it has been known that there is multiple compounds to use, specific catalyst uses different
External electron donor may generate different polymer performances.Select suitable external electron donor can be with specific caltalyst
It is especially compatible, that is to say, that certain property of polymeric articles can be improved significantly by finding a kind of suitable external electron donor
Can, such as isotacticity, molecular weight distribution and hydrogen response, and other performance is not influenced or is influenced simultaneously very little.Therefore,
It was found that the external electron donor for special catalyst can to make polymer have fine comprehensive performance is necessary.
EP385765A describes a kind of catalyst system, and the system is neat by mixing with two kinds of silanes external electron donors
Ge Le-Natta catalyst is constituted, and a kind of specific external electron donor mixture is dicyclopentyl dimethoxyl silane and propyl three
Ethoxysilane.
US5,100,981A disclose a kind of catalyst system, and the system is mixed by major catalyst and two kinds of external electron donors
Object composition is closed, the external electron donor is Cyclohexyl Methyl Dimethoxysilane (CHMMS) and phenyl triethoxysilane.
JP19820199728 also illustrates a kind of catalyst system, which is mixed neat using two kinds of external electron donors
Ge Le-Natta catalyst is constituted, and mixed external electron donor can be methyl benzoate and tetraethoxysilane；
Using tetraethoxysilane as external electron donor in JP19820174495, JP19920331459, but resultant effect is bad.
CN02100896.5、CN02100900.7、CN03109781.2、CN03140565.7、CN
200410073623.8, CN200410073621.9 is described using polyalcohol ester type compound and adjacent benzene dicarboxylic acid esters chemical combination
Object compounding is the catalytic component of internal electron donor, when which is used for propylene polymerization, the external electron donor hydrocarbon that uses
Two hydrocarbyloxysilane of base is current industrial common external electron donor, such as CHMMS etc..Although CN03109781.2 is also used
Different external electron donors as a comparison, such as other than using CHMMS, has also used second, isobutyl dimethoxy silane, two
Cyclopenta dimethoxysilane (DCPMS), two (cyclobutylmethyl) dimethoxysilanes etc., but sent out from disclosed patent
Existing, the hydrogen response of this kind of catalyst system is poor.
As described above, the research of existing olefin polymerization catalysis is mainly around raising olefin polymerizating activity and polymerization
The expansion of the performances such as the steric regularity of object.However, these catalyst are difficult to control in the case where component is certain, by adjusting dosage
The performance (such as the polymer for preparing different isotacticities, melt index) of polymer processed, that is, be unable to satisfy different trade mark polyolefin
Production.For this reason, it is necessary to develop the new catalyst of one kind to solve the problems, such as this.
Summary of the invention
The present inventor is in research work it was unexpectedly observed that urging by the solid of internal electron donor of polyalcohol ester type compound
Oxyl phenyl carboxylic acid ester compounds are added in olefinic polymerization and compound work with two hydrocarbyloxysilane compound of alkyl for agent component
For external electron donor, by adjusting the ratio of compounding internal electron donor, under the conditions of same polymeric, can adjust polymer etc.
Advise index and melt index.Based on the discovery, the present invention is proposed.
The present invention provides a kind of catalyst for olefinic polymerization, which includes the reaction product of following components:
(1) ingredient of solid catalyst, which includes titanium, magnesium, chlorine and internal electron donor compound, described
Internal electron donor compound is diol-lipid compound shown in formula (I):
In formula (I), R1~R6、R1~R2nIt is identical or different, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkane
Base, C3~C20Naphthenic base, C6~C20Aryl, C7~C20Alkaryl, C7~C20Aralkyl or C2~C10Alkylene, but R1And R2No
It is hydrogen；
R3~R6And R1~R2nAt least one carbon atom and/or hydrogen atom are optionally exchanged for heteroatoms on group, described miscellaneous
Atom is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen, R3~R6And R1~R2nGroup optionally can be mutually cyclic；N be 1~10 it is whole
Number；
(2) alkyl aluminum compound；
(3) compound external donor compound, the compound external donor compound include oxyl phenyl carboxylic acid ester
Two hydrocarbyloxysilane of compound and alkyl；Wherein,
Shown in the structure such as formula (II) of the oxyl phenyl carboxylic acid ester compounds:
In formula (II), R1'、R2' identical or different, it each is selected from the C of substituted or unsubstituted linear chain or branched chain1~C20Alkane
Base, C3~C20Naphthenic base, C6~C20Aryl, C7~C20Aralkyl, C7~C20Alkaryl or C2~C10Alkylene；R3' selected from straight
The C of chain or branch1~C20Alkylidene, C3~C20Cycloalkylidene, C6~C20Arlydene or C2~C10Sub- alkylene；
Shown in the structure such as formula (III) of two hydrocarbyloxysilane of alkyl:
In formula (III), R1″、R2″、R3″、R4" it is identical or different, it each is selected from the C of linear chain or branched chain1~C20Alkyl, C3~
C20Naphthenic base, C6~C20Aryl or C7~C20Alkaryl；
In terms of the aluminium in every molar constituent (2), the dosage of the oxyl phenyl carboxylic acid ester compounds is 0.001~1.0
Mole, the content of two hydrocarbyloxysilane of alkyl is 0.001~1.0 mole, and oxyl phenyl carboxylic acid ester compounds and hydrocarbon
The molar ratio of two hydrocarbyloxysilane of base is 1 ︰, 100~100 ︰ 1,20~20 ︰ 1 of preferably 1 ︰.
The present invention also provides a kind of olefine polymerizing process, this method is included under olefin polymerization conditions, makes a kind of or more
Kind alkene is contacted with the catalyst, and the general formula of the alkene is CH2=CH-RV, R thereinVFor hydrogen or C1~C6's
Alkyl.
Compared with the conventional external electron donor such as C-donor, compounding external donor compound of the invention and diol ester
Class compound internal electron donor combines, and obtained catalyst passes through adjusting in the case where the total dosage of external electron donor is constant
Proportion, can prepare the polymer of different performance.
Specific embodiment
Specific embodiments of the present invention will be described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of catalyst for olefinic polymerization, which includes the reaction product of following components:
(1) ingredient of solid catalyst, which includes titanium, magnesium, chlorine and internal electron donor compound, described
Internal electron donor compound is diol-lipid compound shown in formula (I):
In formula (I), R1~R6、R1~R2nIt is identical or different, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkane
Base, C3~C20Naphthenic base, C6~C20Aryl, C7~C20Alkaryl, C7~C20Aralkyl or C2~C10Alkylene, but R1And R2No
It is hydrogen；
R3~R6And R1~R2nAt least one carbon atom and/or hydrogen atom are optionally exchanged for heteroatoms on group, described miscellaneous
Atom is selected from nitrogen, oxygen, sulphur, silicon, phosphorus or halogen, R3~R6And R1~R2nGroup optionally can be mutually cyclic；N be 1~10 it is whole
Number；
(2) alkyl aluminum compound；
(3) compound external donor compound, the compound external donor compound include oxyl phenyl carboxylic acid ester
Two hydrocarbyloxysilane of compound and alkyl；Wherein,
Shown in the structure such as formula (II) of the oxyl phenyl carboxylic acid ester compounds:
In formula (II), R1'、R2' identical or different, it each is selected from the C of substituted or unsubstituted linear chain or branched chain1~C20Alkane
Base, C3~C20Naphthenic base, C6~C20Aryl, C7~C20Aralkyl, C7~C20Alkaryl or C2~C10Alkylene；R3' selected from straight
The C of chain or branch1~C20Alkylidene, C3~C20Cycloalkylidene, C6~C20Arlydene or C2~C10Sub- alkylene；
Shown in the structure such as formula (III) of two hydrocarbyloxysilane of alkyl:
In formula (III), R1″、R2″、R3″、R4" it is identical or different, it each is selected from the C of linear chain or branched chain1~C20Alkyl, C3~
C20Naphthenic base, C6~C20Aryl or C7~C20Alkaryl.
In the present invention, the C of linear chain or branched chain1~C20Alkyl refers to C1~C20Straight chained alkyl, C3~C20Branched alkyl.
In the present invention, the C6~C20Aryl includes phenyl, xenyl, fused ring aryl (such as naphthalene) etc..
In the present invention, the C of linear chain or branched chain1~C20The specific example of alkylidene includes but is not limited to methylene, sub- second
Base, sub- n-propyl, isopropylidene, sub- normal-butyl, sub- sec-butyl, isobutylidene, sub- tert-butyl, sub- n-pentyl, isoamylidene, Asia
Tertiary pentyl, sub- neopentyl, sub- n-hexyl, sub- n-heptyl, sub- n-octyl, sub- positive decyl and sub- dodecyl.
In the present invention, R3' involved in " alkylidene ", " cycloalkylidene ", " arlydene ", " sub- alkylene " refer respectively to alkane
Hydrocarbon, cycloalkane, aromatic hydrocarbons, alkene lose the residue after two hydrogen atoms.For alkane, cycloalkane and alkene, two hydrogen
Atom can be two hydrogen atoms on same carbon atom, or two hydrogen atoms on different carbon atoms.For example, described
Ethylidene can be-CH2CH2Or-CH (CH3)-。
Preferably, in formula (II), R1' the C selected from linear chain or branched chain1~C10Alkyl or C2~C10Alkylene；R2' be selected from
The C of linear chain or branched chain1~C10Alkyl or C6~C12Aryl；R3' the C selected from linear chain or branched chain1~C10Alkylidene.
It is highly preferred that the oxyl phenyl carboxylic acid ester compounds are selected from methyl p-methoxybenzoate, to ethoxybenzene
Methyl formate, to propoxy benzoic acid methyl esters, to butoxybenzoic acid methyl esters, ethyl anisate, to methoxybenzene
Propyl formate, P-methoxybenzoic acid butyl ester, m-methoxybenzoic acid methyl esters, m-oxethyl methyl benzoate, propoxyl group benzene
Methyl formate, butoxybenzoic acid methyl esters, m-methoxybenzoic acid ethyl ester, m-methoxybenzoic acid propyl ester, meta-methoxy benzene
Butyl formate, methyl o-anisate, o-ethoxybenzoic acid methyl esters, adjacent propoxy benzoic acid methyl esters, adjacent butyl phenyl ether
Methyl formate, o-methoxybenzoic acid ethyl ester, o-methoxybenzoic acid propyl ester, butyl-o-methoxybenzoate, to methoxybenzene
Methyl acetate, to ethoxyphenylacetate, to propoxyl group methyl phenylacetate, p-butoxy phenylacetic acid methyl ester, to methoxybenzene
Ethyl acetate, homoanisic acid propyl ester, homoanisic acid butyl ester, meta-methoxy methyl phenylacetate, m-oxethyl benzene
Methyl acetate, propoxyl group methyl phenylacetate, butyl phenyl ether methyl acetate, meta-methoxy ethyl phenylacetate, meta-methoxy benzene
Propyl acetate, meta-methoxy butyl phenylacetate, O-methoxy methyl phenylacetate, O-ethoxyl methyl acetate, adjacent propoxyl group benzene
Methyl acetate, adjacent butyl phenyl ether methyl acetate, O-methoxy ethyl phenylacetate, O-methoxy propyl phenylacetate, O-methoxy benzene
Butyl acetate, to methoxybenzene methyl butyrate, to ethoxybenzene methyl butyrate, to propoxyl group benzenebutanoic acid methyl esters, to butyl phenyl ether
Methyl butyrate, to methoxybenzene ethyl butyrate, to methoxybenzene propyl butyrate, to methoxybenzene butyl butyrate, meta-methoxy benzene
Methyl butyrate, m-oxethyl benzenebutanoic acid methyl esters, propoxyl group benzenebutanoic acid methyl esters, butyl phenyl ether methyl butyrate, meta-methoxy benzene
Ethyl butyrate, meta-methoxy benzenebutanoic acid propyl ester, meta-methoxy benzenebutanoic acid butyl ester, O-methoxy benzenebutanoic acid methyl esters, O-ethoxyl
Methyl butyrate, adjacent propoxyl group benzenebutanoic acid methyl esters, adjacent butyl phenyl ether methyl butyrate, O-methoxy ethyl phenylbutyrate, O-methoxy benzene
Propyl butyrate, O-methoxy benzenebutanoic acid butyl ester, to phenoxy benzoic acid methyl esters, to phenoxy benzoic acid ethyl ester, to phenoxy group benzene
Propyl formate, to phenoxy benzoic acid butyl ester, to phenoxy group methyl phenylacetate, to phenoxy group ethyl phenylacetate, to phenoxy group benzene
Propyl acetate, to phenoxy group butyl phenylacetate, m-phenoxybenzoic acid methyl esters, m-phenoxybenzoic acid ethyl ester, m-phenoxy benzene
Propyl formate, m-phenoxybenzoic acid butyl ester, m-phenoxy methyl phenylacetate, m-phenoxy ethyl phenylacetate, m-phenoxy benzene
Propyl acetate, m-phenoxy butyl phenylacetate, adjacent phenoxy benzoic acid methyl esters, adjacent phenoxy benzoic acid ethyl ester, adjacent phenoxy group benzene
Propyl formate, adjacent phenoxy benzoic acid butyl ester, adjacent phenoxy group methyl phenylacetate, adjacent phenoxy group ethyl phenylacetate, adjacent phenoxy group benzene
Propyl acetate, adjacent phenoxy group butyl phenylacetate, P-methoxybenzoic acid vinyl acetate, m-methoxybenzoic acid vinyl acetate and adjacent methoxy
At least one of benzoate.
The oxyl phenyl carboxylic acid ester compounds can be prepared using conventional synthetic method in laboratory, can also
The method of chemical product purchasing, buys in the market by.
Preferably, in formula (III), R1″、R2″、R3″、R4" it each is selected from the C of linear chain or branched chain1~C20Alkyl or C3~
C20Naphthenic base.
Preferably, in formula (III), R1" and R2" identical, R3" and R4It is " identical or different.
It is highly preferred that two hydrocarbyloxysilane of alkyl is selected from Cyclohexylmethyldimethoxysilane, diisopropyl diformazan
Oxysilane, second, isobutyl dimethoxy silane, Dicyclohexyldimethoxysilane, dicyclopentyl dimethoxyl silane, methyl
Cyclohexyl diethoxy silane, diisopropyldiethoxysilane, diisobutyl diethoxy silane, dicyclohexyl diethoxy
Silane, bicyclopentyl diethoxy silane, methylcyclohexyl dipropoxy silane, diisopropyl dipropoxy silane, two isobutyls
Base dipropoxy silane, dicyclohexyl dipropoxy silane, bicyclopentyl dipropoxy silane, methylcyclohexyl dibutoxy silicon
Alkane, diisopropyl dibutoxy silane, diisobutyl dibutoxy silane, dicyclohexyl dibutoxy silane and bicyclopentyl two
At least one of butoxy silane.
In the present invention, in terms of the aluminium in every molar constituent (2), the dosage of the oxyl phenyl carboxylic acid ester compounds is
0.001~1.0 mole, the dosage of two hydrocarbyloxysilane of alkyl is 0.001~1.0 mole, and oxyl phenyl carboxylic acid's ester
The molar ratio of compound and two hydrocarbyloxysilane of alkyl is 1 ︰, 100~100 ︰ 1,20~20 ︰ 1 of preferably 1 ︰.
In formula (I), as n=1, shown in the specific structure of the internal electron donor compound such as formula (IV):
In the present invention, the internal electron donor compound is preferably selected from diol-lipid compound shown in formula (IV), and formula
(IV) in, R1~R6、R1~R2It is identical or not identical, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkyl, C3~C20
Naphthenic base, C6~C20Aryl, C7~C20Alkaryl or C7~C20Aralkyl.
In the present invention, the internal electron donor compound is further preferably selected from diol-lipid compound shown in formula (V):
In formula (V), R1~R6It is identical or not identical, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkyl, C3
~C20Naphthenic base, C6~C20Aryl, C7~C20Alkaryl or C7~C20Aralkyl；Multiple R' are identical or not identical, each are selected from
Hydrogen, halogen, linear chain or branched chain C1~C10Alkyl, C6~C12Aryl, C7~C10Alkaryl or C7~C10Aralkyl.
The non-limiting example of the internal electron donor compound includes: 2- isopropyl -2- isopentyl -1,3- propylene glycol
Dibenzoate, 2,4-PD dibenzoate, 3,5- heptandiol dibenzoate, 4- ethyl -3,5- heptandiol hexichol first
Bis- (benzoyloxy methyl) fluorenes of acid esters, 9,9- etc..
In component (1), in terms of every mole of magnesium, the content of the internal electron donor compound can be 0.01~5 mole.
In addition, the dihydric alcohol ester type compound is synthesized according to CN1436766A, disclosure of which is fully incorporated
The present invention is as reference.
According to the present invention, the component (1) includes that the reaction of magnesium chloride, titanium compound and internal electron donor compound produces
Object.
The general formula of the titanium compound is Ti (ORw)4-kXk, R thereinwFor C1~C20Alkyl, X Cl, Br or I, k
For 1~4 integer.
The titanium compound be preferably selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide,
At least one of one chlorine triethoxy titanium, one ethanolato-titanium of dichlorodiethyl oxygroup titanium and trichlorine, further preferably four chlorinations
Titanium.
According to the present invention, the ingredient of solid catalyst can be prepared by the following method: magnesium chloride is dissolved in by having
In the dicyandiamide solution of machine epoxide, organic phosphorus compound and inert diluent composition, closed after forming homogeneous solution with titanizing
Solids is precipitated in the presence of precipitation additive in object mixing；This solids use selected from formula (I) internal electron donor compound into
Row processing, is attached to it on solids, when necessary, then is handled solids with titanium tetrahalide and inert diluent,
Middle precipitation additive is one of organic acid anhydride, organic acid, ether, ketone or their mixture.Unless otherwise indicated, specifically may be used
With the preparation method of the ingredient of solid catalyst referring to disclosed in CN1436796A, CN1453298A, disclosure of which is complete
Portion is incorporated herein by reference.
In the present invention, the general formula of the alkyl aluminum compound of component (2) is AlR " '3, multiple R " ' are identical or different, each free
From C1~C8Alkyl, wherein one or two alkyl optionally replaces by chlorine.
The alkyl aluminum compound is preferably selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, Al
(n-C6H13)3、Al(n-C8H17)3And AlEt2At least one of Cl, further preferably triethyl aluminum.
According to the present invention, the molar ratio of the aluminium in component (2) and the titanium in component (1) can be 1~1000 ︰ 1.
It is required according to the difference to polymer performance, the polymerization that catalyst of the present invention is used directly for alkene is anti-
It answers；Prepolymerization first can also be carried out with alkene, generate pre-polymerized catalyst, then carry out polymerization reaction with alkene.
The present invention also provides a kind of olefine polymerizing process, this method is included under olefin polymerization conditions, makes a kind of or more
Kind alkene is contacted with the catalyst, and the general formula of the alkene is CH2=CH-RV, R thereinVFor hydrogen or C1~C6's
Alkyl.
The non-limiting example of the alkene includes: ethylene, propylene, butylene, amylene, hexene, octene, 4- methyl-1-pentene
Alkene.Preferably, the alkene is propylene and/or ethylene.
In addition, the alkene can carry out polymerization reaction in the presence of a small amount of alkadienes according to specific requirement.
In the present invention, the olefin polymerization can (monomer be dissolved in atent solvent by liquid monomer in liquid phase
In) or gas phase in carry out, or can also liquid and gas polymerization stage combine operation under carry out.Olefin polymerization can
To be carried out according to well known polymerization technique, for example, by using conventional technique such as slurry process, gas-phase fluidized-bed etc..
The olefin polymerization conditions include: that polymerization temperature is 0~150 DEG C, and preferably 60~90 DEG C, polymerization pressure is normal pressure
Or it is higher.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
(1) isotactic index of polymer is measured using normal heptane extraction process, concrete operation method are as follows: by the polymerization that 2g is dry
Object sample is placed in extractor, after being extracted 6 hours with boiling n-heptane, residue is dry to constant weight；Resulting polymer weight
The ratio that (g) is measured with 2 is isotactic index.
(2) it melt index: according to GB3682-2000, is measured under 230 DEG C, 2.16kg load.
Preparation example 1
This preparation example is used to illustrate the preparation method of internal electron donor compound 2,4-PD dibenzoate.
(1) preparation of 2,4-PD
The mixture of 10g 2,4- pentanedione and 30mL methanol is added drop-wise to 2.5g sodium borohydride, 0.1g at 0~10 DEG C
In the mixed solution of sodium hydroxide and 25mL water, finishes, solvent is removed under reduced pressure.With 40mL ethyl acetate continuous extraction 15h.It removes
Solvent is removed, column chromatography obtains colourless liquid 2,4- pentanediol, yield 90%.
(2) preparation of 2,4-PD dibenzoate
To 0.03mo1 2,30mL tetrahydrofuran and 0.09mol pyridine is added in 4- pentanediol, is added under stiring
0.075mol chlorobenzoyl chloride, is heated to reflux 4h.20mL saturated salt solution is added after cooling, is then extracted with ethyl acetate, it is anhydrous
Na2SO4It is dry, remove solvent.Column chromatographs to obtain colourless liquid 2,4- glycol dibenzoate, yield 95%.
1H NMR (δ, ppm, TMS): 1.3~1.4 (8H, m, methyl H)；2.0~2.1 (2H, m, methylene H)；5.2~
5.3 (2H, m, the methine H of ester group)；7.3~8.0 (10H, m, phenyl ring H).
Preparation example 2
This preparation example is used to illustrate the preparation method of component (1) ingredient of solid catalyst.
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chlorine are sequentially added
Propane 4mL, tributyl phosphate (TBP) 12.5mL are warming up to 50 DEG C, and maintain 2.5 hours under stirring, be completely dissolved solid,
Phthalic anhydride 1.4g is added, continues to 1 hour.Solution is cooled to -25 DEG C hereinafter, TiCl is added dropwise in 1 hour4
56mL is to slowly warm up to 80 DEG C, and solids is gradually precipitated in temperature-rise period, and 2, the 4- pentanediol hexichol first of preparation example 1 is added
Acid esters 6mmol is maintained temperature 1 hour, after filtering, toluene 70mL is added, washing is secondary, obtains solid sediment.Then to this
Toluene 60mL, TiCl is added in solid440mL is warming up to 100 DEG C, handles 2 hours, after venting filtrate, repeats the processing again
Step.Toluene 60mL is added, the washing of boiling state three times, adds hexane 60mL and obtains solid catalysis after boiling state washing is secondary
Agent component.
Examples 1 to 5
This implementation is for illustrating catalyst and olefine polymerizing process of the invention.
In 5 liters of autoclaves, is purged at 70 DEG C 1 hour using stream of nitrogen gas, then will be polymerize with gas-phase propene
Kettle is replaced 3 times, introduce under nitrogen protection 5mL triethyl aluminum hexane solution (concentration of triethyl aluminum be 0.5mmol/mL),
1mL compound the hexane solution (concentration of external electron donor be 0.1mmol/mL) of external electron donor, 10mL anhydrous hexane and 8~
The ingredient of solid catalyst of 12mg preparation example 2.Autoclave is closed, suitable hydrogen and 1.0~1.2kg liquid propene are introduced；It is stirring
It mixes and lower temperature in Fu is quickly risen to 70 DEG C.At 70 DEG C after polymerization reaction 1 hour, stop stirring, removes unpolymerized propylene list
Body, collected polymer are dried in vacuo 2 hours at 70 DEG C, so that polypropylene be made.Wherein, compounding external electron donor is adjacent first
P-methoxybenzoic acid methyl esters (MOA) and Cyclohexyl Methyl Dimethoxysilane (C-donor).The proportion of external electron donor, adds hydrogen amount,
The polymerization activity of catalyst and polyacrylic performance are as shown in table 1.
Embodiment 6~7
This implementation is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 5, the difference is that is be added when polymerization is that compounding is outer to electricity
Daughter is methyl o-anisate and dicyclopentyl dimethoxyl silane (D-donor), so that polypropylene be made.It is outer to give electricity
Daughter proportion, adds hydrogen amount, polymerization activity and polyacrylic performance are as shown in table 1.
Embodiment 8~10
This implementation is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 5, the difference is that is be added when polymerization is that compounding is outer to electricity
Daughter methyl p-methoxybenzoate (MPA) and Cyclohexyl Methyl Dimethoxysilane, so that polypropylene be made.External electron donor
Proportion, adds hydrogen amount, polymerization activity and polyacrylic performance are as shown in table 1.
Embodiment 11~13
This implementation is for illustrating catalyst and olefine polymerizing process of the invention.
Solid catalyst is prepared according to the method for embodiment 1 and carries out propylene polymerization, the difference is that be added when polymerization
It is compounding external electron donor ethyl anisate (EPA) and Cyclohexyl Methyl Dimethoxysilane, to be made poly- third
Alkene.External electron donor proportion, adds hydrogen amount, polymerization activity and polyacrylic performance are as shown in table 1.
Comparative example 1~5
The external electron donor of addition is only changed to the cyclohexyl methyl two of different amounts by the same Examples 1 to 5 of polymerization
Methoxy silane, so that polypropylene be made.External electron donor dosage adds hydrogen amount, polymerization activity and polyacrylic performance such as 1 institute of table
Show.
Comparative example 6~8
The external electron donor of addition is only changed to the bicyclopentyl diformazan of different amounts by the same Examples 1 to 5 of polymerization
Oxysilane, so that polypropylene be made.External electron donor dosage adds hydrogen amount, polymerization activity and polyacrylic performance such as 1 institute of table
Show.
Table 1
Note: MOA: methyl o-anisate
MPA: methyl p-methoxybenzoate
EPA: ethyl anisate
C or C-donor: Cyclohexylmethyldimethoxysilane
D or D-donor: dicyclopentyl dimethoxyl silane
It can be seen from Table 1 that conventional internal electron donor, even if its dosage is changed at double, polyacrylic above-mentioned two
A Parameters variation is not obvious, and is significantly just varied melt index, but isotactic refers in the case where adjustment hydrogen usage
Number is still basically unchanged；And catalyst of the invention is used, in the case where the total dosage of external electron donor is constant, by adjusting its group
The proportion divided can make the polyacrylic isotactic index of preparation and melt index that significant change occur, and it is different that this is conducive to exploitation
The polypropylene of the trade mark.
The embodiment of the present invention is described above, above description is exemplary, and non-exclusive, and also not
It is limited to disclosed embodiment.Without departing from the scope and spirit of illustrated embodiment, for the art
Many modifications and changes are obvious for those of ordinary skill.
Claims (10)
1. a kind of catalyst for olefinic polymerization, which is characterized in that the catalyst includes the reaction product of following components:
(1) ingredient of solid catalyst, the ingredient of solid catalyst include titanium, magnesium, chlorine and internal electron donor compound, it is described in give
Electron compound is diol-lipid compound shown in formula (I):
In formula (I), R1~R6、R1~R2nIt is identical or different, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkyl, C3
~C20Naphthenic base, C6~C20Aryl, C7~C20Alkaryl, C7~C20Aralkyl or C2~C10Alkylene, but R1And R2It is not hydrogen；
R3~R6And R1~R2nAt least one carbon atom and/or hydrogen atom are optionally exchanged for heteroatoms on group, and the hetero atom is selected from
Nitrogen, oxygen, sulphur, silicon, phosphorus or halogen, R3~R6And R1~R2nGroup optionally can be mutually cyclic；The integer that n is 1~10；
(2) alkyl aluminum compound；
(3) compound external donor compound, the compound external donor compound include that oxyl phenyl carboxylic acid is esterified conjunction
Two hydrocarbyloxysilane of object and alkyl；Wherein,
Shown in the structure such as formula (II) of the oxyl phenyl carboxylic acid ester compounds:
In formula (II), R1'、R2' identical or different, it each is selected from the C of substituted or unsubstituted linear chain or branched chain1~C20Alkyl, C3
~C20Naphthenic base, C6~C20Aryl, C7~C20Aralkyl, C7~C20Alkaryl or C2~C10Alkylene；R3' it is selected from straight chain or branch
The C of chain1~C20Alkylidene, C3~C20Cycloalkylidene, C6~C20Arlydene or C2~C10Sub- alkylene；
Shown in the structure such as formula (III) of two hydrocarbyloxysilane of alkyl:
In formula (III), R1”、R2”、R3”、R4" identical or different, it each is selected from the C of linear chain or branched chain1~C20Alkyl, C3~C20Ring
Alkyl, C6~C20Aryl or C7~C20Alkaryl；
In terms of the aluminium in every molar constituent (2), the dosage of the oxyl phenyl carboxylic acid ester compounds is 0.001~1.0 mole,
The dosage of two hydrocarbyloxysilane of alkyl is 0.001~1.0 mole, and oxyl phenyl carboxylic acid ester compounds and two hydrocarbon of alkyl
The molar ratio of oxysilane is 1 ︰, 100~100 ︰ 1,20~20 ︰ 1 of preferably 1 ︰.
2. the catalyst according to claim 1 for olefinic polymerization, wherein in formula (II), R1' it is selected from linear chain or branched chain
C1~C10Alkyl or C2~C10Alkylene；R2' the C selected from linear chain or branched chain1~C10Alkyl or C6~C12Aryl；R3'
C selected from linear chain or branched chain1~C10Alkylidene.
3. the catalyst according to claim 1 for olefinic polymerization, wherein the oxyl phenyl carboxylic acid ester compounds
Selected from methyl p-methoxybenzoate, paraethoxybenxoic acid methyl esters, to propoxy benzoic acid methyl esters, to butoxybenzoic acid first
Ester, ethyl anisate, P-methoxybenzoic acid propyl ester, P-methoxybenzoic acid butyl ester, m-methoxybenzoic acid first
Ester, m-oxethyl methyl benzoate, propoxy benzoic acid methyl esters, butoxybenzoic acid methyl esters, m-methoxybenzoic acid second
Ester, m-methoxybenzoic acid propyl ester, m-methoxybenzoic acid butyl ester, methyl o-anisate, o-ethoxybenzoic acid first
Ester, adjacent propoxy benzoic acid methyl esters, adjacent butoxybenzoic acid methyl esters, o-methoxybenzoic acid ethyl ester, o-methoxybenzoic acid third
Ester, butyl-o-methoxybenzoate, homoanisic acid methyl esters, to ethoxyphenylacetate, to propoxyl group phenylacetic acid first
Ester, p-butoxy phenylacetic acid methyl ester, homoanisic acid ethyl ester, homoanisic acid propyl ester, homoanisic acid fourth
Ester, meta-methoxy methyl phenylacetate, m-oxethyl methyl phenylacetate, propoxyl group methyl phenylacetate, butyl phenyl ether acetic acid first
Ester, meta-methoxy ethyl phenylacetate, meta-methoxy propyl phenylacetate, meta-methoxy butyl phenylacetate, O-methoxy phenylacetic acid first
Ester, O-ethoxyl methyl acetate, adjacent propoxyl group methyl phenylacetate, adjacent butyl phenyl ether methyl acetate, O-methoxy phenylacetic acid second
Ester, O-methoxy propyl phenylacetate, O-methoxy butyl phenylacetate, to methoxybenzene methyl butyrate, to ethoxybenzene butyric acid first
Ester, to propoxyl group benzenebutanoic acid methyl esters, to butyl phenyl ether methyl butyrate, to methoxybenzene ethyl butyrate, to methoxybenzene butyric acid third
Ester, to methoxybenzene butyl butyrate, meta-methoxy benzenebutanoic acid methyl esters, m-oxethyl benzenebutanoic acid methyl esters, propoxyl group benzenebutanoic acid first
Ester, butyl phenyl ether methyl butyrate, meta-methoxy ethyl phenylbutyrate, meta-methoxy benzenebutanoic acid propyl ester, meta-methoxy benzenebutanoic acid fourth
Ester, O-methoxy benzenebutanoic acid methyl esters, O-ethoxyl methyl butyrate, adjacent propoxyl group benzenebutanoic acid methyl esters, adjacent butyl phenyl ether butyric acid first
Ester, O-methoxy ethyl phenylbutyrate, O-methoxy benzenebutanoic acid propyl ester, O-methoxy benzenebutanoic acid butyl ester, to phenoxy benzoic acid first
Ester, to phenoxy benzoic acid ethyl ester, to phenoxy benzoic acid propyl ester, to phenoxy benzoic acid butyl ester, to phenoxy group phenylacetic acid first
Ester, to phenoxy group ethyl phenylacetate, to phenoxy group propyl phenylacetate, to phenoxy group butyl phenylacetate, m-phenoxybenzoic acid first
Ester, m-phenoxybenzoic acid ethyl ester, m-phenoxybenzoic acid propyl ester, m-phenoxybenzoic acid butyl ester, m-phenoxy phenylacetic acid first
Ester, m-phenoxy ethyl phenylacetate, m-phenoxy propyl phenylacetate, m-phenoxy butyl phenylacetate, adjacent phenoxy benzoic acid first
Ester, adjacent phenoxy benzoic acid ethyl ester, adjacent phenoxy benzoic acid propyl ester, adjacent phenoxy benzoic acid butyl ester, adjacent phenoxy group phenylacetic acid first
Ester, adjacent phenoxy group ethyl phenylacetate, adjacent phenoxy group propyl phenylacetate, adjacent phenoxy group butyl phenylacetate, P-methoxybenzoic acid second
At least one of enester, m-methoxybenzoic acid vinyl acetate and o-methoxybenzoic acid vinyl acetate.
4. the catalyst according to claim 1 for olefinic polymerization, wherein two hydrocarbyloxysilane of alkyl is selected from first
Butylcyclohexyl dimethoxysilane, diisopropyl dimethoxy silane, second, isobutyl dimethoxy silane, dicyclohexyl dimethoxy
It is base silane, dicyclopentyl dimethoxyl silane, methylcyclohexyl diethoxy silane, diisopropyldiethoxysilane, two different
Butyl diethoxy silane, dicyclohexyl diethoxy silane, bicyclopentyl diethoxy silane, methylcyclohexyl dipropoxy
Silane, diisopropyl dipropoxy silane, diisobutyl dipropoxy silane, dicyclohexyl dipropoxy silane, bicyclopentyl
Dipropoxy silane, methylcyclohexyl dibutoxy silane, diisopropyl dibutoxy silane, diisobutyl dibutoxy silicon
At least one of alkane, dicyclohexyl dibutoxy silane and bicyclopentyl dibutoxy silane.
5. the catalyst according to claim 1 for olefinic polymerization, wherein the internal electron donor compound is selected from formula
(IV) diol-lipid compound shown in:
In formula (IV), R1~R6、R1~R2It is identical or not identical, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkyl,
C3~C20Naphthenic base, C6~C20Aryl, C7~C20Alkaryl or C7~C20Aralkyl.
6. the catalyst according to claim 1 for olefinic polymerization, wherein the internal electron donor compound is selected from formula
(V) diol-lipid compound shown in:
In formula (V), R1~R6It is identical or not identical, each be selected from hydrogen, halogen, linear chain or branched chain C1~C20Alkyl, C3~C20
Naphthenic base, C6~C20Aryl, C7~C20Alkaryl or C7~C20Aralkyl；Multiple R' are identical or not identical, each are selected from hydrogen, halogen
The C of element, linear chain or branched chain1~C10Alkyl, C6~C12Aryl, C7~C10Alkaryl or C7~C10Aralkyl.
7. the catalyst according to claim 1 for olefinic polymerization, wherein the component (1) includes magnesium chloride, titanizing
Close the reaction product of object and internal electron donor compound；
The general formula of the titanium compound is Ti (ORw)4-kXk, R thereinwFor C1~C20Alkyl, X Cl, Br or I, k be 1~4
Integer；
Preferably, the titanium compound be selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide,
At least one of one chlorine triethoxy titanium, one ethanolato-titanium of dichlorodiethyl oxygroup titanium and trichlorine.
8. the catalyst according to claim 1 for olefinic polymerization, wherein the general formula of the alkyl aluminum compound is
AlR”'3, multiple R " ' are identical or different, each are selected from C1~C8Alkyl, wherein one or two alkyl optionally takes by chlorine
Generation；
Preferably, the alkyl aluminum compound is selected from triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, tri-n-hexyl aluminum, Al
(n-C6H13)3、Al(n-C8H17)3And AlEt2At least one of Cl.
9. a kind of olefine polymerizing process, which is characterized in that this method is included under olefin polymerization conditions, makes one or more alkene
It is contacted with the catalyst described in any one of claim 1~8, the general formula of the alkene is CH2=CH-RV, therein
RVFor hydrogen or C1~C6Alkyl.
10. olefine polymerizing process according to claim 9, wherein the alkene is propylene and/or ethylene.
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