CN109096418A - 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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- CN109096418A CN109096418A CN201710476058.7A CN201710476058A CN109096418A CN 109096418 A CN109096418 A CN 109096418A CN 201710476058 A CN201710476058 A CN 201710476058A CN 109096418 A CN109096418 A CN 109096418A
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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 (I) of oxyl phenyl carboxylic acid's ester compounds, shown in the structure such as formula (II) 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
Generally be made of three parts for the catalyst system of alkene homopolymerization or copolyreaction: (1) major catalyst (urge by solid
Agent component), (2) co-catalyst (for example, alkyl aluminum class compound) and (3) external donor compound.
Transition metal in major catalyst is usually titanium, zirconium or vanadium, and preferably titanium is (in practice it has been found that titanium is a kind of
Particularly excellent transition metal), the compound of these transition metal typically has halide or oxyhalide, or organises
It closes object (usually alkoxide, alcoholates or halogenohydrin salt).But the compound of transition metal usually seldom chooses organic compound.
Co-catalyst is usually made of the organic compound of the 1st~3 main group metal.Frequently with the compound of aluminium, but also
Developed the compound of boron, zinc and alkali metal.
Major catalyst can be prepared on more or less inert carrier, therefore main catalyst component can be solid-state.In addition,
Major catalyst can be complexed with internal electron donor compound and select type and/or activity to improve catalyst system solid.
External donor compound can be added in the course of the polymerization process, it is intended to the solid for improving final product selects type etc., from
And further increase the final performance of catalyst.
The stereoregular of polymer is controlled using one or more of External Electron Donor Compounds in polymerization process
Property and form are well known to those skilled in the art.External electron donor is other than influencing the stereoregularity of polymer, often
The performance of catalyst other aspects can be also influenced to some extent.Although kind compound can be used as outer to electricity there are many known
Daughter, but specific catalyst may generate different polymer performances using different external donor compounds.Choosing
Selecting suitable external electron donor can be especially compatible with specific catalyst, that is to say, that finds a kind of suitable outer electron
Body can improve the performance of polymeric articles some aspects significantly, consequently found that one group can make polymer for special catalyst
The external electron donor with outstanding properties is very favorable in some aspects.
EP19810106301 discloses a kind of highly active and stereoselectivity catalyst, solid group therein
Divide includes carrying halogenated titanium (TiCl4) and the electron donor compound selected from phthalate activated form halogenation
Magnesium.Co-catalyst used be wherein joined at least containing a Si-OR key (R represents alkyl) silicon compound (it is i.e. outer to
Electron compound) alkyl aluminum compound.
The research of existing olefin polymerization catalysis is mainly around the stereoregular for improving olefin polymerizating activity and polymer
The expansion of the performances such as degree, and be already available to the polymer of high regularity.However, these catalyst external electron donor type not
In the case where change, the performance for being difficult to control polymer to a certain extent by adjusting the dosage of external electron donor (such as is prepared
The polymer of different isotacticities, melt index), that is, it is unable to satisfy the production of different trade mark polyolefin.For this reason, it is necessary to develop one
New catalyst is planted to solve the problems, such as this.
Summary of the invention
The present inventor in research work it was unexpectedly observed that using carboxylic acid ester compound as internal electron donor, magnesium halide alcohol
It closes the ingredient of solid catalyst that object is carrier and oxyl phenyl carboxylic acid ester compounds and two hydrocarbon oxygen of alkyl is added in olefinic polymerization
Base silane compound is compound to be used as external electron donor, in the case where the total dosage of external electron donor is constant, by adjusting compound outer
Ratio between electron donor can adjust the isotactic index and melt index of polymer under the conditions of same polymeric.Based on the hair
It is existing, propose the present 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, the ingredient of solid catalyst include spherical magnesium halide alcohol polymer carrier and are supported on
Titanium compound and internal electron donor compound on carrier；
The internal electron donor compound is selected from unitary or polynary aliphatic carboxylic acid ester compounds and aromatic carboxylic acid esters
At least one of compound；
(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 (I) of the oxyl phenyl carboxylic acid ester compounds:
In formula (I), 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 (II) of two hydrocarbyloxysilane of alkyl:
In formula (II), R1”、R2”、R3”、R4" 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 dosage 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 carboxylate
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, the ingredient of solid catalyst include spherical magnesium halide alcohol polymer carrier and are supported on
Titanium compound and internal electron donor compound on carrier；
The internal electron donor compound is selected from unitary or polynary aliphatic carboxylic acid ester compounds and aromatic carboxylic acid esters
At least one of compound；
(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 (I) of the oxyl phenyl carboxylic acid ester compounds:
In formula (I), 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 (II) of two hydrocarbyloxysilane of alkyl:
In formula (II), R1”、R2”、R3”、R4" 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 (I), R'1C selected from linear chain or branched chain1~C10Alkyl or C2~C10Alkylene, R'2It is 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 (II), 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 (II), R1" and R2" identical, R3" and R4" 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 polymerization process
In, the compound outer Donor compound can be separately added into or be added simultaneously.
In component (1), the internal electron donor compound for example selected from benzoic ether, phthalic acid ester, malonate,
Succinate, glutarate etc..Under preferable case, the internal electron donor compound is selected from ethyl benzoate, phthalic acid
Diethylester, diisobutyl phthalate, n-butyl phthalate, diisooctyl phthalate, phthalic acid two
N-octyl, diethyl malonate, dibutyl malonate, 2,3- diisopropyl diethyl succinate, 2,3- diisopropyl succinic acid
Diisobutyl ester, 2,3- diisopropyl dibutyl succinate, 2,3- diisopropyl dimethyl succinate, 2,2- dimethyl succinate
Diisobutyl ester, 2- Ethyl-2-Methyl di-iso-octyl succinate, 2- Ethyl-2-Methyl diethyl succinate, diethylene adipate,
Dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, maleic acid n-butyl, naphthalene
Diethyl dicarboxylate, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, tributyl trimellitate, benzene-1,2,3-tricarboxylic acid triethyl, even benzene
At least one of three sour tributyls, four butyl ester of pyromellitic acid tetra-ethyl ester and pyromellitic acid.
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 component (1), the magnesium halide alcohol adduct carrier is ball type carrier.The general formula of magnesium halide alcohol adduct is represented by
MgX2P (ROH), wherein X Cl, Br or I, preferably I；R is C1~C18Alkyl, preferably C2~C4Straight chained alkyl；
P is 0.1~6.
The spherical magnesium halide alcohol polymer carrier can refer to CN1091748A, CN1330086A, CN101050245A,
The preparation method of US6020279A, CN1580136A and CN1463990A obtain, and disclosed related content is fully incorporated this hair
It is bright to be used as reference.
Specifically, the preparation method of the spherical magnesium halide alcohol polymer carrier can include: carry out magnesium halide and low-carbon alcohols
Mixing, temperature reaction generate magnesium halide alcohol adduct melt, and reaction temperature is 90~140 DEG C, make in a dispersion medium through high shear
It is put into after in cooling inert media, forms spherical magnesium halide alcohol polymer particle, obtain ball type carrier after washed, dry.
High shear forces can be used conventional method and obtain, as high-speed mixing method (for example, CN00109216.2), spray-on process (for example,
) and high-gravity rotating bed (for example, CN1580136A) and mulser method (for example, CN1463990A) etc. US6020279A.
Hydro carbons atent solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil can be used in dispersant system.Cooling inertia is situated between
Matter can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil.
The general formula of the titanium compound is Ti (ORw)4-kX'k, R thereinwFor C1~C20Alkyl, X' Cl, Br or I,
The integer that k is 1~4.
Preferably, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, tetraethoxy
At least one of titanium, a chlorine triethoxy titanium, one ethanolato-titanium of dichlorodiethyl oxygroup titanium and trichlorine.
In component (1), in terms of element ti/Mg, the molar ratio of the titanium compound and magnesium halide alcohol adduct can be 1 ︰ 0.5
~150.
According to one preferred embodiment, the ingredient of solid catalyst is made by method comprising the following steps:
1) -30 DEG C to 0 DEG C at a temperature of, titanium compound is mixed with spherical magnesium halide alcohol polymer carrier, is mixed
Object；
2) mixture is warming up to 80~130 DEG C, be added in temperature-rise period the internal electron donor compound into
Row reaction, is made solid sediment；
3) by solid sediment washing, drying, the ingredient of solid catalyst is made.Optionally, in step 3),
Before washing, solid sediment is handled with titanium compound.The processing can carry out one or many.Inertia used by washing is molten
Agent can be selected from one or more of hexane, heptane, octane, decane and toluene.
The general formula of the alkyl aluminum compound is AlR " '3, multiple R " ' are identical or different, each are selected from C1~C8Alkane
Base, wherein one or two alkyl are optionally replaced by chlorine.
Preferably, the alkyl aluminum compound be 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.
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 poly- of 2g drying
Object sample is closed to be placed in extractor, it is after being extracted 6 hours with boiling n-heptane, residue is dry to constant weight；Resulting polymer
Weight (g) and 2 ratio are isotactic index.
(2) it melt index: according to GB3682-2000, is measured under 230 DEG C, 2.16kg load.
Preparation example
This preparation example is used to illustrate the preparation of component (1) ingredient of solid catalyst.
In glass reaction bottle of the 300mL being sufficiently displaced from by high pure nitrogen with stirring, 100mL titanium tetrachloride is added,
- 20 DEG C are cooled to, 8g spherical shape chlorination magnesium alcoholate is added and (is made according to the method for CN1330086A embodiment 1, second in carrier
2.62) molar ratio of alcohol and magnesium chloride is.It is to slowly warm up to 110 DEG C stage by stage, phthalic acid is added in temperature-rise period
Dibutyl ester 3.9mmol obtains solid sediment after 110 DEG C of constant temperature 0.5h, filters off liquid, adds 100mL titanium tetrachloride every time
Processing twice, is then washed five times with hexane, solids containing titanium catalytic component A (major catalyst) is obtained after vacuum drying.
Examples 1 to 4
The present embodiment 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),
The hexane solution (concentration of external electron donor be 0.1mmol/mL) of the compound external electron donor of 1mL, 8mL anhydrous hexane and 8~
12mg solids containing titanium catalytic component A.Autoclave is closed, suitable hydrogen and the liquid propene of 1.0~1.2kg are introduced；It is stirring
Temperature in Fu is quickly risen to 70 DEG C down.At 70 DEG C after polymerization reaction 1 hour, stop stirring, remove unpolymerized propylene monomer,
Collected polymer is dried in vacuo 2 hours at 70 DEG C, so that polypropylene be made.Wherein, compounding external electron donor is to methoxyl group
Ethyl benzoate (EPA) and Cyclohexylmethyldimethoxysilane (C-donor).The proportion of external electron donor adds hydrogen amount, catalysis
Agent polymerization activity and Properties of Polypropylene are as shown in table 1.
Embodiment 5
The present embodiment is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 4, the difference is that by the compound outer to electricity of addition when polymerizeing
The hexane solution of daughter is adjusted to 2mL, so that polypropylene be made.External electron donor proportion, adds hydrogen amount, polymerization catalyst activity and
Polyacrylic performance is as shown in table 1.
Embodiment 6~9
The present embodiment is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 4, the difference is that the outer electron of the compounding being added when polymerization
Body is methyl p-methoxybenzoate (MPA) and Cyclohexylmethyldimethoxysilane (C-donor), so that polypropylene be made.
External electron donor proportion, adds hydrogen amount, polymerization catalyst activity and polyacrylic performance are as shown in table 1.
Embodiment 10~14
The present embodiment is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 4, the difference is that the outer electron of the compounding being added when polymerization
Body is methyl o-anisate (MOA) and Cyclohexylmethyldimethoxysilane (C-donor), so that polypropylene be made.
External electron donor proportion, adds hydrogen amount, polymerization catalyst activity and polyacrylic performance are as shown in table 1.
Embodiment 15~16
The present embodiment is for illustrating catalyst and olefine polymerizing process of the invention.
Propylene polymerization is carried out according to the method for Examples 1 to 4, the difference is that the outer electron of the compounding being added when polymerization
Body is methyl o-anisate (MOA) and dicyclopentyl dimethoxyl silane (D-donor), so that polypropylene be made.Outside
Electron donor proportion, adds hydrogen amount, polymerization catalyst activity and polyacrylic performance are as shown in table 1.
Comparative example 1~4
The external electron donor of addition is only changed to the cyclohexyl methyl two of different amounts by the same Examples 1 to 4 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 5~8
The external electron donor of addition is only changed to the bicyclopentyl diformazan of different amounts by the same Examples 1 to 4 of polymerization
Oxysilane (D-donor), so that polypropylene be made.External electron donor dosage adds hydrogen amount, polymerization activity and polyacrylic performance
As shown in table 1.
Table 1
Note: EPA: ethyl anisate
MPA: methyl p-methoxybenzoate
MOA: methyl o-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 tune is passed through in the case where the total dosage of external electron donor is constant using catalyst of the invention
The proportion of its whole component can make the polyacrylic isotactic index of preparation and melt index that significant change occur, this is conducive to out
The polypropylene for sending out the trade mark different.
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 is comprising spherical magnesium halide alcohol polymer carrier and is supported on carrier
On titanium compound and internal electron donor compound；
The internal electron donor compound is selected from unitary or polynary aliphatic carboxylic acid ester compounds and aromatic carboxylic acid esters chemical combination
At least one of object；
(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 (I) of the oxyl phenyl carboxylic acid ester compounds:
In formula (I), R'1、R'2It is 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 (II) of two hydrocarbyloxysilane of alkyl:
In formula (II), 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 (I), R'1Selected from linear chain or branched chain
C1~C10Alkyl or C2~C10Alkylene；R'2C selected from linear chain or branched chain1~C10Alkyl or C6~C12Aryl；R3' choosing
From the C of 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 benzene
Ethyl formate, diethyl phthalate, diisobutyl phthalate, n-butyl phthalate, phthalic acid two
Different monooctyl ester, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, 2,3- diisopropyl diethyl succinate,
2,3- diisopropyl di-iso-octyl succinate, 2,3- diisopropyl dibutyl succinate, 2,3- diisopropyl succinic acid diformazan
Ester, 2,2- dimethyl succinate diisobutyl ester, 2- Ethyl-2-Methyl di-iso-octyl succinate, 2- Ethyl-2-Methyl succinic acid two
It is ethyl ester, diethylene adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, suitable
Butene dioic acid di-n-butyl, naphthalene dicarboxylic acids diethylester, naphthalene dicarboxylic acids dibutyl ester, triethyl trimellitate, tributyl trimellitate,
At least one of benzene-1,2,3-tricarboxylic acid triethyl, four butyl ester of benzene-1,2,3-tricarboxylic acid tributyl, pyromellitic acid tetra-ethyl ester and pyromellitic acid.
6. the catalyst according to claim 1 for olefinic polymerization, wherein the general formula of magnesium halide alcohol adduct is MgX2·p
(ROH), X Cl, Br or I, preferably Cl, R C1~C18Alkyl, p be 0.1~6.
7. the catalyst according to claim 1 for olefinic polymerization, wherein the ingredient of solid catalyst is by including
The method of following steps is made:
1) -30 DEG C to 0 DEG C at a temperature of, titanium compound is mixed with spherical magnesium halide alcohol polymer carrier, obtains mixture；
2) mixture is warming up to 80~130 DEG C, the internal electron donor compound is added in temperature-rise period and carries out instead
It answers, solid sediment is made；
3) by solid sediment washing, drying, the ingredient of solid catalyst is made；
Optionally, in step 3), before washing, solid sediment is handled with titanium compound.
8. the catalyst according to claim 1 for olefinic polymerization, wherein the general formula of the titanium compound is Ti
(ORw)4-kX'k, 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.
9. 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.
10. a kind of olefine polymerizing process, which is characterized in that this method is included under olefin polymerization conditions, makes one or more alkene
Catalyst described in any one of hydrocarbon and claim 1~9 is contacted, and the general formula of the alkene is CH2=CH-RV, wherein
RVFor hydrogen or C1~C6Alkyl；
Preferably, the alkene is propylene and/or ethylene.
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|---|---|---|---|---|
| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
| CN101835812A (en) * | 2007-08-24 | 2010-09-15 | 陶氏环球技术公司 | Self-limiting catalyst system with controlled aluminum rto sca ratio and method |
| CN102558398A (en) * | 2010-12-30 | 2012-07-11 | 中国石油化工股份有限公司 | Method for preparing spherical magnesium chloride carrier |
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| CN1262693A (en) * | 1998-03-23 | 2000-08-09 | 蒙特尔技术有限公司 | Prepolymerized catalyst components for polymerization of olefins |
| US20030069372A1 (en) * | 2001-10-09 | 2003-04-10 | Formosa Plastics Corporation, U.S.A. | Olefin polymerization catalyst and process for preparing polyolefins with said catalyst |
| CN101835812A (en) * | 2007-08-24 | 2010-09-15 | 陶氏环球技术公司 | Self-limiting catalyst system with controlled aluminum rto sca ratio and method |
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