CN109280110A - For the ingredient of solid catalyst and olefin polymerization catalysis of olefinic polymerization and its application and ethylene copolymer - Google Patents
For the ingredient of solid catalyst and olefin polymerization catalysis of olefinic polymerization and its application and ethylene copolymer Download PDFInfo
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- CN109280110A CN109280110A CN201710592386.3A CN201710592386A CN109280110A CN 109280110 A CN109280110 A CN 109280110A CN 201710592386 A CN201710592386 A CN 201710592386A CN 109280110 A CN109280110 A CN 109280110A
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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
- C08F4/6493—Catalysts containing a specific non-metal or metal-free compound organic containing halogen
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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
Abstract
The invention belongs to olefin polymerization catalysis fields, and in particular to for the ingredient of solid catalyst and olefin polymerization catalysis of olefinic polymerization and its application and ethylene copolymer.The ingredient of solid catalyst includes magnesium, titanium, halogen and internal electron donor compound, and the internal electron donor compound includes at least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I), in formula (I), M1、M2、M3、M4、M5And M6It each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl group etc..Present invention proposition is used using the internal electron donor of ring three black false hellebore hydrocarbons and their derivates as olefin polymerization catalysis, compared with the ingredient of solid catalyst for not including three black false hellebore hydrocarbons and their derivates of ring, the present invention introduces three black false hellebore hydrocarbons and their derivates of ring in olefin polymerization catalysis can improve activity, hydrogen tune susceptibility and the copolymerization performance of catalyst simultaneously.
Description
Technical field
The invention belongs to olefin polymerization catalysis fields, and in particular to a kind of solid catalyst group for olefinic polymerization
Point, a kind of olefin polymerization catalysis and its application and a kind of ethylene copolymer.
Background technique
In the past 60 years, since technology continues to develop, the activity of Ziegler-Natta type olefin polymerization catalysis, hydrogen tune are quick
Sensitivity, copolymerization performance and its bulk density, melt index, molecular weight distribution, fine powder content, copolymerization units distribution that polymerize powder
Etc. parameters obtained significant optimization.But it is to be able to better adapt to industrial demand, it is more excellent to produce performance
Different product, then the above-mentioned parameter of such catalyst and its polymerization powder also needs to further increase.
In the prior art, certain electron donors are introduced into olefin polymerization catalysis can improve its hydrogen tune susceptibility, such as
CN1958620A, CN1743347A, CN102295717A and CN103772536A introduce respectively type siloxane electron donor,
Benzoic ether/carboxylate (or diether) that ortho alkoxy replaces compounds electron donor, benzoates electron donor.To catalysis
Other electron donor is introduced in agent can improve the copolymerization performance of catalyst, such as CN1726230A, CN1798774A and
CN101050248A introduce respectively alcohol, ketone, amine, amide, nitrile, alkoxy silane, fatty ether and aliphatic carboxylic acid esters etc. to
Electron.Further, it is also possible to Long carbon chain monoesters class/short carbon chain monoesters class electron donor of compounding be introduced into catalyst to improve
The activity of catalyst (as shown in CN102807638A).
Electron mentioned above can be improved the performance of olefin polymerization catalysis in one aspect, still,
Ziegler-Natta type olefin polymerization catalysis field, can improve catalyst activity, hydrogen tune susceptibility and copolymerization performance simultaneously
The less report of electron donor, and its versatility is bad；For example, the ethyl benzoate for slurry polyethylene catalyst can not answer
For gas-phase polythene catalyst.
If find one kind can improve simultaneously Ziegler-Natta type polyolefin catalyst activity, hydrogen tune susceptibility and
The special electron donor of copolymerization performance, and its performance is substantially better than electron donor well known in the art, can also be applied to a variety of
Catalyst, then such electron donor has substantial worth.
Summary of the invention
The present inventor in the course of the research surprisingly it has been found that: gather using three black false hellebore hydrocarbons and their derivates of ring as alkene
The internal electron donor for closing catalyst is introduced in ingredient of solid catalyst, and activity, the hydrogen tune that can be improved catalyst are sensitive
Degree and copolymerization performance.Based on the discovery, the present invention is proposed.
According to the first aspect of the invention, the present invention provides a kind of ingredients of solid catalyst for olefinic polymerization, should
Ingredient of solid catalyst includes magnesium, titanium, halogen and internal electron donor compound, and the internal electron donor compound includes formula (I)
At least one of shown three black false hellebore hydrocarbons and their derivates of ring:
In formula (I), M1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl
Base, halogen atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1-C10Alkyl, substituent group are selected from hydroxyl, ammonia
Base, aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from R1Or-OR2When, two
It is optionally mutually cyclic between a adjacent group.
According to the second aspect of the invention, the present invention provides a kind of olefin polymerization catalysis, include the anti-of following components
Answer product:
1) ingredient of solid catalyst described in；
2) organo-aluminum compound.
According to the third aspect of the invention we, the present invention provides the olefin polymerization catalysis in olefin polymerization
Using.
According to the fourth aspect of the invention, the present invention provides a kind of ethylene copolymer, which is described
In the presence of olefin polymerization catalysis, ethylene is made to close to obtain with alpha-olefin copolymer.
The present invention is proposed using the three black false hellebore hydrocarbons and their derivates of ring as Ziegler-Natta type olefinic polymerization catalysis
The internal electron donor of agent uses, and compared with the ingredient of solid catalyst for not including three black false hellebore hydrocarbons and their derivates of ring, the present invention exists
Introduced in olefin polymerization catalysis three black false hellebore hydrocarbons and their derivates of ring can improve simultaneously the activity of catalyst, hydrogen tune susceptibility and
Copolymerization 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.
According to the first aspect of the invention, the present invention provides a kind of ingredient of solid catalyst for olefinic polymerization, institutes
Stating ingredient of solid catalyst includes magnesium, titanium, halogen and internal electron donor compound, and the internal electron donor compound includes formula
(I) at least one of black false hellebore hydrocarbons and their derivates of ring three shown in:
In formula (I), M1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl
Base, halogen atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1-C10Alkyl, substituent group are selected from hydroxyl, ammonia
Base, aldehyde radical, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from R1Or-OR2When, two
It is optionally mutually cyclic between a adjacent group.
In the present invention, C1-C10Alkyl can be selected from C1-C10Alkyl, C3-C10Naphthenic base, C2-C10Alkenyl, C2-C10Alkynyl,
C6-C10Aryl and C7-C10Aryl alkyl etc..
C1-C10Alkyl refers to C1-C10Straight chained alkyl or C3-C10Branched alkyl, non-limiting example includes: first
Base, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, new penta
Base, n-hexyl, n-heptyl, n-octyl and positive decyl.
C3-C10The example of naphthenic base can include but is not limited to: cyclopropyl, cyclopenta, cyclohexyl, 4- methyl cyclohexane
Base, 4- ethylcyclohexyl, 4- n-propyl cyclohexyl and 4- normal-butyl cyclohexyl.
C6-C10The example of aryl can include but is not limited to: phenyl, naphthalene, 4- aminomethyl phenyl and 4- ethylphenyl.
C2-C10The example of alkenyl can include but is not limited to: vinyl and allyl.
C2-C10The example of alkynyl can include but is not limited to: acetenyl and propargyl.
C7-C10The example of aryl alkyl can include but is not limited to: phenyl methyl, phenylethyl, phenyl n-propyl, benzene
Base normal-butyl, phenyl t-butyl and propyloxy phenyl base.
In the present invention, " substituted C1-C10Alkyl " typically refer to " C1-C10Alkyl " on hydrogen atom (preferably one
Hydrogen atom) or carbon atom replaced by the substituent group.
The hetero atom refers to the three black false hellebore hydrocarbons and their derivates of other rings other than halogen atom, carbon atom and hydrogen atom
Molecular structure on the atom that generally comprises, such as O, N, S, P, Si and B etc..
Preferably, in formula (I), M1、M2、M3、M4、M5And M6It is identical or different, it is former each to be selected from hydroxyl, amino, aldehyde radical, halogen
Son ,-R1Or-OR2, and R1And R2It each is selected from by the substituted or unsubstituted C of halogen atom1-C10Alkyl.
Preferably, M1、M3And M5It is identical, M2、M4And M6It is identical, and it is above-mentioned two groups it is identical or different.
It is highly preferred that the three black false hellebore hydrocarbons and their derivates of ring are selected from least one of following compound:
Compound A:M1=M2=M3=M4=M5=M6=OCH3；
Compound B:M1=M2=M3=M4=M5=M6=OCH2CH3；
Compound C:M1=M2=M3=M4=M5=M6=OCH2CH2CH3；
Compound D:M1=M2=M3=M4=M5=M6=OCH (CH3)2；
Compound E:M1=M2=M3=M4=M5=M6=OCH2CH2CH2CH3；
Compound F:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH3；
Compound G:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH3；
Compound H:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2CH3；
Compound I:M1=M2=M3=M4=M5=M6=OH；
Compound J:M1=M3=M5=OCH3；M2=M4=M6=OH；
Compound K: M1=M3=M5=OCH3；M2=M4=M6=NH2；
Compound L: M1=M3=M5=OCH3；M2=M4=M6=Cl；
Compound M:M1=M3=M5=OCH3；M2=M4=M6=Br；
Compound N: M1=M3=M5=OCH3；M2=M4=M6=I；
Compound O:M1=M3=M5=OCH3；M2=M4=M6=CHO；
Compound P:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2Br；
Compound Q: M1=M3=M5=OH, M2=M4=M6=OCH2CH3。
According to the present invention, M1=M3=M5=X, M2=M4=M6(X, Y respectively indicate the above-mentioned M of the present invention to=Y1、M3、M5With
M2、M4、M6Selectable group, and X is different from Y) when, there may be following isomers for the three black false hellebore hydrocarbons and their derivates of ring:
M1=M4=M5=X, M2=M3=M6=Y.It should be noted that the isomers is also within the scope of the present invention.
In the present invention, the three black false hellebore hydrocarbons and their derivates of ring can be prepared one of as follows:
Method one: in the presence of acidic materials and optional halogenated hydrocarbons, by phenyl ring analog derivative A shown in formula (II) with
Formaldehyde or derivatives thereof is reacted, to obtain the three black false hellebore hydrocarbons and their derivates of ring；
Method two: in the presence of acidic materials, the condensation of phenyl ring analog derivative B shown in catalysis type (III), to obtain described
Three black false hellebore hydrocarbons and their derivates of ring；
Method three: in the presence of a lewis acid, in halogenated hydrocarbons, phenyl ring analog derivative A and first shown in catalysis type (II)
Aldehyde or derivatives thereof is reacted, to obtain the three black false hellebore hydrocarbons and their derivates of ring；
Wherein, to M7、M8、M9、M10Definition and M1~M6It is identical, details are not described herein.
The acidic materials can be selected from hydrochloric acid, perchloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, pyrosulfuric acid, sulfurous acid, phosphorus
Acid, pyrophosphoric acid, at least one of phosphorous acid, boric acid, formic acid, acetic acid, benzoic acid, trifluoroacetic acid, sulfonic acid and benzene sulfonic acid.
The halogenated hydrocarbons can be selected from carbon tetrachloride, chloroform, methylene chloride, bromomethane, monochlorethane, a chlorine third
Alkane, a chlorobutane, a chloropentane, a chlorohexane, bromic ether, 1,2- dichloroethanes, 1,3- dichloropropane, bis- neoprene of 1,4-
In alkane, 1,5- dichloropentane, 1,6- dichloro hexane, chlorocyclopentane, chlorocyclohexane, monochloro-benzene, dichloro-benzenes and bromobenzene
It is at least one.
The lewis acid can be selected from least one in boron trifluoride ether, ferric trichloride, alchlor and titanium tetrachloride
Kind.
The derivative of formaldehyde can be selected from paraformaldehyde, for example, metaformaldehyde.
In the above each method, the dosage of various raw materials is referred to routine techniques selection, and details are not described herein.
In the present invention, the ingredient of solid catalyst includes magnesium compound, titanium compound and internal electron donor compound
Reaction product.
The magnesium compound, titanium compound are the conventional selection in Ziegler-Natta type olefin polymerization catalysis.
Normally, the magnesium compound can be selected from the hydrate or alcohol adduct of magnesium halide, magnesium halide, alkyl magnesium and halogen
Change at least one of the derivative that the halogen atom (at least one) in magnesium molecular formula is replaced by alkoxy or halogenated alkoxy.
The general formula of the titanium compound is represented by Ti (OR)nX’4-n, wherein R C1-C8Alkyl, preferably C1-C8Alkane
Base, X ' are halogen atom, such as fluorine, chlorine or bromine, 0≤n≤4.
Preferably, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, purity titanium tetraethoxide, a chlorine triethoxy titanium, two
At least one of one ethanolato-titanium of chlorine diethoxy titanium, butyl titanate and trichlorine.
It is highly preferred that the titanium compound is titanium tetrachloride and/or butyl titanate.
According to one preferred embodiment, the ingredient of solid catalyst includes the titanizing being carried on magnesium halide
Close object and three black false hellebore hydrocarbons and their derivates of the ring.
In the present invention, the molar ratio of the three black false hellebore hydrocarbons and their derivates of ring and magnesium (or magnesium compound) is 0.001~
0.1 ︰ 1, preferably 0.002~0.05 ︰ 1.
In the present invention, in terms of every mole of magnesium, the dosage of the titanium compound can be 0.1~100mol.
The present invention is this, described in addition to the three black false hellebore hydrocarbons and their derivates of ring (hereinafter referred to as " internal electron donor a ")
Interior Donor compound also may include different from internal electron donor a other internal electron donors commonly used in the art it is (following
Referred to as internal electron donor b), the internal electron donor b can be selected from Organic Alcohol, organic acid, organic acid esters, organic acid halides, have
Machine acid anhydrides, ether, ketone, amine, phosphate, amide, carbonic ester, phenol, pyridine and high-molecular compound with polar group etc..Specifically
For, the internal electron donor b can be selected from methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetic acid n-octyl, benzene first
Sour methyl esters, ethyl benzoate, butyl benzoate, hexyl-benzoate, ethyl p-methyl benzoate, 2-methyl naphthoate, naphthoic acid second
Ester, methyl methacrylate, ethyl acrylate, butyl acrylate, ether, butyl ether, tetrahydrofuran, 2,2- dimethyl -1,3- two
Ethoxy propane, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isooctanol, octylame, triethylamine, acetone, butanone, cyclopentanone, 2-
Methyl-cyclopentanone, cyclohexanone, phenol, hydroquinone, organic epoxy compound object (such as ethylene oxide, propylene oxide, epoxy chloropropionate
Alkane, Hydrin, polyethylene oxide), organic phosphorus compound (such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate third
Ester, tributyl phosphate, triphenyl phosphate, tri hexyl phosphate), at least one of polymethyl methacrylate and polystyrene.
In the ingredient of solid catalyst, when containing the internal electron donor b, the internal electron donor b and titanium
Molar ratio can be 1000 ︰, 1~1 ︰ 1000.
In addition, the ingredient of solid catalyst can also include ultra-fine carrier, magnesium halide, halogenated titanium and interior electron chemical combination
The reaction product of object, wherein the partial size of the ultra-fine carrier is 0.01~10 micron, the optional self-alumina of the ultra-fine carrier,
At least one of active carbon, clay, silica, titanium dioxide, polystyrene and calcium carbonate.
Specifically, the ingredient of solid catalyst can be prepared using following methods:
Method 1
1) under conditions of magnesium halide activates, by magnesium halide, internal electron donor compound and optional titanium compound
Mixed grinding；
2) using excessive titanium compound that the product processing after mixed grinding is one or many；
3) treated, and product is washed to obtain the ingredient of solid catalyst with hydrocarbon solvent.
Method 2
1) in the presence of an inert solvent, magnesium halide is reacted with alcohol compound and internal electron donor compound；
2) it adds organosilicon compound and carries out haptoreaction；
3) step 2) system and titanium compound are subjected to haptoreaction；
4) it removes unreacted reactant and solvent, washing precipitate obtains the ingredient of solid catalyst；
In addition, the internal electron donor compound can also be after step 3) without being added in step 1).
Method 3
1) it dissolves magnesium halide, halogenated titanium and internal electron donor compound and is reacted, mother liquor is made；
2) ultra-fine carrier and the mother liquor are blended, slurry liquid is made；
3) the slurry liquid is spray-dried, obtains the ingredient of solid catalyst.
Arbitrary activator component of the organo-aluminum compound as the ingredient of solid catalyst can be used, it will be described
Titanium atom in ingredient of solid catalyst is reduced into the state that the alkene such as ethylene can be made effectively to polymerize, and the solid for obtaining prereduction is urged
Agent component.
Method 4
1) it in the presence of an inert solvent, by magnesium halide and organic epoxy compound object, organic phosphorus compound, Organic Alcohol and interior gives
Electron a is reacted；
2) by reaction solution obtained by step 1) and titanium compound and organosilicon compound haptoreaction, and high-temperature process；
3) unreacted reactant and solvent, washing precipitate are removed, the ingredient of solid catalyst is obtained.
Method 5
1) in the presence of an inert solvent, make magnesium halide and organic epoxy compound object, organic phosphorus compound and optionally organic
Alcohol is reacted, and organic acid compound anhydride (precipitation additive) is then added, and the reaction was continued, obtains solution；
2) by above-mentioned solution and titanium compound haptoreaction；
3) internal electron donor a and optional Organic Alcohol are added in the reaction system, is reacted；
4) unreacted reactant and solvent, washing precipitate are removed, the ingredient of solid catalyst is obtained.
Method 6
1) magnesium halide is reacted with organic epoxy compound object, organic phosphorus compound and Organic Alcohol；
2) by above-mentioned solution and titanium compound, organo-silicon compound haptoreaction；
3) internal electron donor compound is added in the reaction system, carries out haptoreaction；
4) unreacted reactant and solvent, washing precipitate are removed, the ingredient of solid catalyst is obtained.
Method 7
1) magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
2) make the suspension and optional organo-aluminum compound and internal electron donor compound haptoreaction, then remove
Unreacted reactant, and washed with atent solvent；
3) sediment in the presence of an inert solvent, obtaining step 2) and the titanium compound haptoreaction, are then removed
Unreacted reactant and solvent are removed, washing precipitate obtains the ingredient of solid catalyst.
In step 2), the organo-aluminum compound specifically can be selected from Al (CH3)3、Al(CH2CH3)3、 Al(i-Bu)3、Al
(n-C6H13)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、 AlCl1.5(CH2CH3)1.5、AlCl(CH2CH3)2、
AlCl2(CH2CH3) etc. alkyl aluminum compounds.In addition, the organo-aluminum compound is preferably Al (CH2CH3)3、Al(n-C6H13)3
With Al (i-Bu)3At least one of, further preferably Al (CH2CH3)3。
Method 8
1) magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
2) suspension and titanium compound are subjected to haptoreaction, then high temperature (such as 50 under low temperature (such as -5 DEG C or less)
DEG C or more) processing, unreacted reactant is then removed, and washed with atent solvent；
3) sediment in the presence of an inert solvent, obtaining step 2) connects with titanium compound and internal electron donor compound
Touching reaction, then removes unreacted reactant and solvent, washing precipitate, obtains the ingredient of solid catalyst.
Method 9
1) alkyl magnesium/alkoxyl magnesium/alkoxy magnesium compound is dispersed in atent solvent, obtains solution or suspension
Liquid；
2) it by the solution or suspension and titanium compound and internal electron donor compound haptoreaction, then removes not anti-
Object is answered, and is washed with atent solvent；
3) sediment in the presence of an inert solvent, obtaining step 2) and the titanium compound haptoreaction, are then removed
Unreacted reactant and solvent are removed, washing precipitate obtains the ingredient of solid catalyst.
Method 10
1) alkoxyl magnesium compound is reacted with titanium compound and internal electron donor compound, forms clear solution,
Add atent solvent dilution；
2) organo-aluminum compound is added into above-mentioned dilute solution, unreacted reactant and solvent, washing precipitating are removed after reaction
Object obtains the ingredient of solid catalyst.
Compound employed in above each preparation method belongs to the selection of this field routine, for example, organic epoxidation
Conjunction object, organic phosphorus compound, alcohol compound and organosilicon compound etc. can refer to the prior art and selected, herein not
Make particular determination.Selected atent solvent can be identical or different in each method, and can refer to the prior art and selected, example
Such as, the atent solvent is toluene and/or hexane.
In addition, method made above is description of illustrating in more detail to ingredient of solid catalyst of the present invention, but the present invention
It is not limited to these preparation methods.
According to the second aspect of the invention, the present invention provides a kind of olefin polymerization catalysis, include the anti-of following components
Answer product:
1) ingredient of solid catalyst described in；
2) organo-aluminum compound.
In the olefin polymerization catalysis, organo-aluminum compound is well known co-catalyst in olefin polymerization catalysis.Institute
The general formula for stating organo-aluminum compound is AlR 'dX’3-d, R ' is hydrogen or C in formulal-C20Alkyl, X ' are halogen atom, 0 < d≤3.Cl-
C20Alkyl is, for example, Cl-C20Alkyl, aralkyl or aryl.The machine aluminium compound is preferably selected from Al (CH3)3、Al
(CH2CH3)3、Al(i-Bu)3、AlH(CH2CH3)2、AlH(i-Bu)2、AlCl(CH2CH3)2、Al2Cl3(CH2CH3)3、AlCl
(CH2CH3)2、 AlCl2(CH2CH3), it is more preferably selected from Al (CH2CH3)3And/or Al (i-Bu)3。
Component 2) in aluminium and component 1) in the molar ratio of titanium can be 5 ︰, 1~500 ︰ 1,1~200 ︰ 1 of preferably 20 ︰.
According to the third aspect of the invention we, the present invention provides the olefin polymerization catalysis in olefin polymerization
Using.The olefin polymerization catalyst system is suitable for the homopolymerization of alkene or the combined polymerization of a variety of alkene.The alkene it is specific
Example includes: ethylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
Preferably, the alkene is ethylene and/or butylene.
In addition, the olefin polymerization catalysis is suitable for the olefin polymerization of various conditions, for example, the alkene is poly-
Closing reaction can carry out in liquid phase or gas phase, or can also carry out under the operation that liquid and gas polymerization stage combines.
The temperature of polymerization can be 0~150 DEG C, preferably 60~90 DEG C.
Liquid polymerization medium includes: iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, hydrogasoline, kerosene,
The atent solvents such as the aliphatic saturated hydrocarbons such as benzene,toluene,xylene or aromatic hydrocarbon.
In addition, making molecular weight regulator using hydrogen to adjust the molecular weight of final polymer.
According to the fourth aspect of the invention, the present invention provides a kind of ethylene copolymer, which is described
In the presence of olefin polymerization catalysis, ethylene is made to close to obtain with alpha-olefin copolymer.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
1, in catalyst system titanium elements relative weight percents: use spectrophotometry.
2, the composition of catalytic component: liquid nuclear-magnetism is used1H-NMR。
3, the measurement (MI) of melt index: according to ASTM D1238-99, load 2.16kg.
4, polymer powders copolymerization units content: liquid nuclear-magnetism is used13C-NMR,
5, in polymer powders hexane extractable content weight content: take it is dry after powder 20g, place it in container
In, it is extracted 2 hours at 50 DEG C with 300mL hexane, then extracts 20mL extracting solution, place it in the surface plate being precisely weighed
In, the surface plate being completely dried is weighed, and the thus gross mass of calculating hexane extractable content: the mass weight gain of surface plate is
m1(g), the weight percent for and thus calculating hexane extractable content is 75m1%.
The polymer powders are by the way that whole powder slurries obtained by following copolyreaction are transferred to standard round with nitrogen
In cylindrical container, it is dried to obtain under ventilation condition.Pressure refers both to absolute pressure in kettle.
Embodiment 1
(1) preparation of ingredient of solid catalyst a
In the reactor being sufficiently displaced from by high pure nitrogen, 6.0g ball type carrier MgCl is sequentially added2·
2.6C2H5OH, toluene 120mL, are cooled to -10 DEG C under stirring, be added dropwise 50mL triethyl aluminum hexane solution (triethyl aluminum:
1.2M) with 0.3g compound A, 60 DEG C are then heated to, and maintains reaction 3 hours.Stop stirring, stands, suspension is quickly
Layering extracts supernatant liquor, and sediment toluene and hexane successively wash for several times.120mL toluene is added, which is cooled to
0 DEG C, titanium tetrachloride 8mL is slowly added dropwise, is warming up to 60 DEG C later, reacts 2 hours.Stop stirring, stand, suspension divides quickly
Layer extracts supernatant liquor, after sediment washs twice with hexane, is transferred them in chromatography funnel by hexane, uses High Purity Nitrogen
Air-blowing is dry, obtains the solid spherical catalytic component a of good fluidity, and composition is shown in Table 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is
The triethyl aluminum of 1M adds the ingredient of solid catalyst (titanium containing 0.6mg) prepared by the above method, is warming up to 75 DEG C, leads to
Entering hydrogen makes pressure in kettle reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, polymerize 2 under the conditions of 85 DEG C
Hour, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is
The triethyl aluminum of 1M adds the ingredient of solid catalyst (titanium containing 0.6mg) prepared by the above method, is warming up to 75 DEG C, leads to
Entering hydrogen makes pressure in kettle reach 0.68MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, polymerize 2 under the conditions of 85 DEG C
Hour, polymerization result is shown in Table 2.
(3) copolymerization
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0ml concentration is
The triethyl aluminum of 1M adds the ingredient of solid catalyst (titanium containing 0.6mg) prepared by the above method, is warming up to 70 DEG C, leads to
Entering hydrogen makes pressure in kettle reach 0.28MPa, then is passed through ethylene/butylene gaseous mixture (molar ratio be 0.9 ︰ 0.1) and makes stagnation pressure in kettle
Reach 0.73MPa, polymerize 2 hours under the conditions of 80 DEG C, polymerization result is shown in Table 3.
Embodiment 2
(1) preparation of ingredient of solid catalyst b
In the reactor being sufficiently displaced from by high pure nitrogen, 6.0g ball type carrier MgCl is sequentially added2·
2.6C2H5OH, toluene 120mL, are cooled to -10 DEG C under stirring, be added dropwise 50mL triethyl aluminum hexane solution (triethyl aluminum:
After 1.2M), 1mL ethyl benzoate and 0.2g compound Q is added, then heats to 60 DEG C, and maintains reaction 3 hours.Stop
Stirring is stood, and suspension is layered quickly, extracts supernatant liquor, sediment toluene and hexane successively wash for several times.It is added
The system is cooled to 0 DEG C, titanium tetrachloride 8mL is slowly added dropwise by 120mL hexane, is warming up to 60 DEG C later, is reacted 2 hours.Stop
It only stirs, stands, suspension is layered quickly, supernatant liquor is extracted, after sediment washs twice with hexane, by hexane by its turn
It moves in chromatography funnel, is dried up with high pure nitrogen, obtain the solid spherical catalytic component b of good fluidity, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 1
(1) preparation of ingredient of solid catalyst D1
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g ball type carrier MgCl is sequentially added2·
3.0C2H5OH, hexane 150mL, are cooled to -10 DEG C under stirring, be added dropwise 60mL triethyl aluminum hexane solution (triethyl aluminum:
1.2M) with 1mL acetic acid n-octyl, 1mL ethyl benzoate, 50 DEG C are then raised temperature to, and maintains reaction 3 hours.Stop stirring, it is quiet
It sets, suspension is layered quickly, extracts supernatant liquor, sediment toluene and hexane successively wash for several times.150mL hexane is added,
The system is cooled to 0 DEG C, titanium tetrachloride 6mL is slowly added dropwise, is warming up to 60 DEG C later, is reacted 2 hours.Stop stirring, stand,
Suspension is layered quickly, is extracted supernatant liquor, after sediment washs twice with hexane, is transferred them to chromatography funnel by hexane
In, it is dried up with high pure nitrogen, obtains the solid spherical catalytic component D1 of good fluidity, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 3
(1) preparation of ingredient of solid catalyst c
By 4.0 grams of magnesium chlorides, 50mL toluene, 3.0mL epoxychloropropane, 9mL TRI N BUTYL PHOSPHATE, ethyl alcohol 4.4mL, 0.3g
Compound B is added in reaction kettle, under conditions of temperature is 70 DEG C, isothermal reaction 2 hours.The system is cooled to -10 DEG C,
Titanium tetrachloride 70mL is slowly added dropwise, 5mL tetraethoxy-silicane is then added, is gradually heated to 85 DEG C, constant temperature 1 hour.Stop stirring,
It standing, suspension is layered quickly, extracts supernatant liquor, and it is dry after toluene and hexane repeatedly wash, it obtains with good flow
Property ingredient of solid catalyst c, composition be shown in Table 1.
(2) homopolymerization is reacted
1. low hydrogen gas/ethylene ratio polymerization reaction
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is
The triethyl aluminum of 1M adds the ingredient of solid catalyst (titanium containing 0.6mg) prepared by the above method, is warming up to 70 DEG C, leads to
Entering hydrogen makes pressure in kettle reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa, polymerize 2 under the conditions of 80 DEG C
Hour, polymerization result is shown in Table 2.
2. the polymerization reaction of high hydrogen/ethylene ratio
Volume is the stainless steel cauldron of 2L, after high pure nitrogen is sufficiently displaced from, 1L hexane is added and 1.0mL concentration is
The triethyl aluminum of 1M adds the ingredient of solid catalyst (titanium containing 0.6mg) prepared by the above method, is warming up to 70 DEG C, leads to
Entering hydrogen makes pressure in kettle reach 0.58MPa, then being passed through ethylene makes stagnation pressure in kettle reach 0.73MPa, polymerize 2 under the conditions of 80 DEG C
Hour, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 4
(1) preparation of ingredient of solid catalyst d
4.0 grams of magnesium chlorides, 50mL toluene, 3.0mL epoxychloropropane, 9mL TRI N BUTYL PHOSPHATE, 4.4mL ethyl alcohol are added
Into reaction kettle, under conditions of temperature is 70 DEG C, react 2 hours.The system is cooled to -10 DEG C, four chlorinations are slowly added dropwise
Titanium 70mL is then added 5mL tetraethoxy-silicane, is gradually heated to 85 DEG C, constant temperature 1 hour.0.2g compound F is added, continues permanent
Temperature 1 hour.Stopping stirring, stands, suspension is layered quickly, extracts supernatant liquor, and it is dry after toluene and hexane repeatedly wash,
The ingredient of solid catalyst d with good fluidity is obtained, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 2
(1) preparation of ingredient of solid catalyst D2
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g magnesium chloride, 50mL toluene, 3.0mL are sequentially added
Epoxychloropropane, 9.0mL tri-n-butyl, ethyl alcohol 4.4mL, are warming up to 70 DEG C under stirring, when solid be completely dissolved to be formed it is uniform
It is reacted 2 hours at 70 DEG C after solution.The system is cooled to -10 DEG C, is slowly added dropwise into ethyl benzoate 4.0mL, constant temperature 10 divides
60mL titanium tetrachloride is added dropwise after clock.85 DEG C are to slowly warm up to, is reacted 2 hours.Stop stirring, stand, suspension is layered quickly, is taken out
Except supernatant liquor, washed four times with hexane.High pure nitrogen drying, obtains the ingredient of solid catalyst D2 of good fluidity, forms
It is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 5
(1) preparation of ingredient of solid catalyst e
4.0 grams of magnesium chlorides, 90mL toluene, 8.0mL epoxychloropropane, 16.0mL TRI N BUTYL PHOSPHATE are added to reaction kettle
It is interior, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react 2 hours, 3g phthalic anhydride is added, continue constant temperature 1
Hour, -40 DEG C are cooled to, titanium tetrachloride 70mL is added dropwise, is gradually heated to 95 DEG C, constant temperature 1 hour.0.3g compound B is added,
Continue constant temperature 1 hour.Mother liquor is filtered off, it is dry after toluene and hexane repeatedly wash, obtain having the solid of good fluidity to urge
Agent component e, composition are shown in Table 1.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 3
(1) preparation of ingredient of solid catalyst D3
4.0 grams of magnesium chlorides, 90mL toluene, 8.0mL epoxychloropropane, 16.0mL TRI N BUTYL PHOSPHATE are added to reaction kettle
It is interior, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react 2 hours, 3g phthalic anhydride is added, continue constant temperature 1
Hour, -40 DEG C are cooled to, titanium tetrachloride 70mL is added dropwise, is gradually heated to 95 DEG C, constant temperature 1 hour.Filter off mother liquor, through toluene and
Hexane is dry after repeatedly washing, and obtains the ingredient of solid catalyst D3 with good fluidity, and composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 6
(1) preparation of ingredient of solid catalyst f
4.0 grams of magnesium chlorides, 100mL toluene, 6.0mL epoxychloropropane, 12mL three iso-butyl ester of phosphoric acid are added to reaction kettle
It is interior, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react 2 hours.- 40 DEG C are cooled to, titanium tetrachloride is added dropwise
75mL is gradually heated to 85 DEG C, constant temperature 1 hour.System is cooled to 60 DEG C, 0.2g compound A and 1mL ethyl alcohol is added, gradually
85 DEG C are warming up to, is continued constant temperature 1 hour.Mother liquor is filtered off, is done after inert diluent toluene and organic solvent hexane repeatedly wash
It is dry, the ingredient of solid catalyst f with good fluidity is obtained, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 4
(1) preparation of ingredient of solid catalyst D4
4.0 grams of magnesium chlorides, 100mL toluene, 6.0mL epoxychloropropane, 12mL three iso-butyl ester of phosphoric acid are added to reaction kettle
It is interior, under conditions of speed of agitator 450rpm, temperature are 60 DEG C, react 2 hours.- 40 DEG C are cooled to, titanium tetrachloride is added dropwise
75mL is gradually heated to 85 DEG C, constant temperature 1 hour.System is cooled to 60 DEG C, 1mL ethyl alcohol is added, is gradually heated to 85 DEG C, after
Continuous constant temperature 1 hour.Mother liquor is filtered off, it is dry after toluene and hexane repeatedly wash, obtain the solid catalysis with good fluidity
Agent component D4, composition are shown in Table 1.
(2) polymerization reaction
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 7
(1) preparation of ingredient of solid catalyst g
It is blown to one by nitrogen and 1.5g TiCl is successively added in the 250mL there-necked flask of row4, the anhydrous MgCl of 4.4g2, 0.1g
Compound A and 100mL tetrahydrofuran, is warming up to 65 DEG C, at this temperature isothermal reaction 3h under stirring, be then cooled to 35 DEG C,
Obtain mother liquor.
Into another 250mL there-necked flask for blowing row by nitrogen be added 6g silica gel (Cabot Corporation TS-610,
Partial size is 0.02~0.1 micron), the mother liquor after cooling is added, is kept for 35 DEG C of temperature, after stirring 1h, after silica gel is blended
Mother liquor is spray-dried with spray dryer, spray condition: 180 DEG C of inlet temperature, 110 DEG C of outlet temperature, being obtained solid and is urged
Agent component g, composition are shown in Table 1.
(2) pre-reduction treatment
To one by nitrogen blow successively be added in the 250mL there-necked flask of row 100mL hexane, 5g ingredient of solid catalyst and
4mL tri-n-hexyl aluminum (1M), is warming up to 50 DEG C, at this temperature constant temperature 1h under stirring；Add 9mL aluminium diethyl monochloride
(1M) continues constant temperature 1h.Mother liquor is filtered off, dry after hexane repeatedly washs, the solid for obtaining the prereduction of good fluidity is urged
Agent component.
(2) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 8
(1) preparation of ingredient of solid catalyst h
Ingredient of solid catalyst is prepared according to the method for embodiment 7, the difference is that replacing implementing with 0.2g compound F
The compound A of example 7, so that ingredient of solid catalyst h be made, composition is shown in Table 1.
(2) pre-reduction treatment
With embodiment 7.
(3) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(4) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 5
(1) preparation of ingredient of solid catalyst D5
It is blown to one by nitrogen and 1.5g TiCl is successively added in the 250mL there-necked flask of row4, the anhydrous MgCl of 4.4g2With
100mL tetrahydrofuran is warming up to 65 DEG C, at this temperature isothermal reaction 3h under stirring, then is cooled to 35 DEG C, obtains mother liquor.
Into another 250mL there-necked flask for blowing row by nitrogen be added 6g silica gel (Cabot Corporation TS-610,
Partial size is 0.02~0.1 micron), the mother liquor after cooling is added, is kept for 35 DEG C of temperature, after stirring 1h, after silica gel is blended
Mother liquor is spray-dried with spray dryer, spray condition: 195 DEG C of inlet temperature, 110 DEG C of outlet temperature, being obtained solid and is urged
Agent component D5, composition are shown in Table 1.
(2) pre-reduction treatment
With embodiment 7.
(3) homopolymerization is reacted
With embodiment 1, polymerization result is shown in Table 2.
(4) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 9
(1) preparation of ingredient of solid catalyst i
4.8 grams of magnesium chlorides, 30mL decane, 20mL isooctanol, 0.2g compound B are added in reaction kettle, in stirring speed
Rate 300rpm and temperature are reacted 3 hours under conditions of being 130 DEG C, and system is cooled to 50 DEG C, 3.5mL tetraethoxy-silicane is added,
Continue stirring 2 hours.The system is cooled to room temperature, is slowly dropped into 0 DEG C of 200mL titanium tetrachloride, is added dropwise to complete
Constant temperature 1h afterwards.System is gradually heated to 110 DEG C, constant temperature 2 hours.Stop stirring, stands, suspension is layered quickly, in abstraction
Layer clear liquid, it is dry after toluene and hexane repeatedly wash, the ingredient of solid catalyst i with good fluidity is obtained, is formed
It is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 10
(1) preparation of ingredient of solid catalyst j
4.8 grams of magnesium chlorides, 30mL decane, 20mL isooctanol are added in reaction kettle, in stirring rate 300rpm and temperature
Degree reacts 3 hours under conditions of being 130 DEG C.System is cooled to 50 DEG C, 3.5mL tetraethoxy-silicane is added, it is small to continue stirring 2
When, which is cooled to room temperature, is slowly dropped into the 200mL titanium tetrachloride for having fallen to 0 DEG C, rear constant temperature is added dropwise to complete
1h.System is gradually heated to 110 DEG C, constant temperature 1 hour.0.2g compound A is added, continues constant temperature 1 hour.Stop stirring, it is quiet
It sets, suspension is layered quickly, extracts supernatant liquor, and it is dry after toluene and hexane repeatedly wash, it obtains with good fluidity
Ingredient of solid catalyst j, composition be shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 6
(1) preparation of ingredient of solid catalyst D6
4.8 grams of magnesium chlorides, 30mL decane, 20mL isooctanol are added in reaction kettle, in stirring rate 300rpm and temperature
Degree reacts 3 hours under conditions of being 130 degree.System is cooled to 50 DEG C, 3.5mL tetraethoxy-silicane is added, it is small to continue stirring 2
When.The system is cooled to room temperature, is slowly dropped into the 200mL titanium tetrachloride for having fallen to 0 DEG C, rear constant temperature is added dropwise to complete
1h.System is gradually heated to 110 DEG C, constant temperature 1 hour, 0.2mL 1 is added, 2- 1,2-dimethoxy benzene continues constant temperature 1 hour.Stop
It only stirring, stands, suspension is layered quickly, extracts supernatant liquor, and it is dry after toluene and hexane repeatedly wash, it obtains having good
The ingredient of solid catalyst D6 of good mobility, composition are shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Embodiment 11
(1) preparation of ingredient of solid catalyst k
By 10g Mg (OEt)2, 55mL toluene be added in reaction kettle, formed under conditions of stirring rate 300rpm outstanding
Supernatant liquid.System is cooled to 0 DEG C, 30mL titanium tetrachloride and 0.2g compound M is slowly successively added, is slowly risen after being added dropwise to complete
Temperature is to 90 DEG C, constant temperature 1.5 hours.Stop stirring, stand, suspension is layered quickly, extracts supernatant liquor.Add 60mL toluene
With 30mL titanium tetrachloride, it is warming up to 90 DEG C, constant temperature 2 hours.Stop stirring, stand, extracts supernatant liquor.It is more through toluene, hexane
It is dry after secondary washing, the ingredient of solid catalyst k with good fluidity is obtained, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
Comparative example 7
(1) preparation of ingredient of solid catalyst D7
By 10g Mg (OEt)2, 55mL toluene be added in reaction kettle, formed under conditions of stirring rate 300rpm outstanding
Supernatant liquid.System is cooled to 0 DEG C, 30mL titanium tetrachloride and 1mL ethyl benzoate is slowly successively added, after being added dropwise to complete slowly
It is warming up to 90 DEG C, constant temperature 1.5 hours.Stop stirring, stand, suspension is layered quickly, extracts supernatant liquor.Add 60mL first
Benzene and 30mL titanium tetrachloride are warming up to 90 DEG C, constant temperature 2 hours.Stop stirring, stand, extracts supernatant liquor.Through toluene, hexane
It is repeatedly dry after washing, the ingredient of solid catalyst D7 with good fluidity is obtained, composition is shown in Table 1.
(2) homopolymerization is reacted
With embodiment 3, polymerization result is shown in Table 2.
(3) copolymerization
With embodiment 1, polymerization result is shown in Table 3.
The composition of 1 ingredient of solid catalyst of table
* note: not comprising the ethoxy group in three black false hellebore hydrocarbons and their derivates of ring.
The activity and hydrogen tune susceptibility of 2 catalyst of table
As shown in Table 2, under the polymerizing condition of low hydrogen second ratio, catalyst activity and the powder melting of the embodiment of the present invention refer to
Number is slightly above comparative example, and under the polymerizing condition of higher hydrogen second ratio, the catalyst activity and powder of the embodiment of the present invention melt
Index is all remarkably higher than comparative example, this feature is very beneficial for industrial production.Specifically, being particularly conducive to slurry polymerization processes
In bimodal products production and gas-phase polymerization process in high melting means product production.It follows that three black false hellebore hydrocarbon of ring and its spreading out
Biology can be improved catalyst activity and hydrogen tune susceptibility.
Copolymerization units content and hexane extractable content in 3 powder of table
As shown in Table 3, when the copolymerization units content of embodiment is slightly above comparative example, hexane extractable content is obviously inclined
It is low.It follows that copolymerization units contained by the lower-molecular-weight component of powder of the embodiment of the present invention are less for compared with comparative example, and
Copolymerization units contained by medium/high molecular weight component are more.It follows that three black false hellebore hydrocarbons and their derivates of ring improve being total to for catalyst
Poly- performance, this is conducive to the raising of product comprehensive performance.
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 ingredient of solid catalyst for olefinic polymerization, which is characterized in that the ingredient of solid catalyst include magnesium,
Titanium, halogen and internal electron donor compound, the internal electron donor compound include three black false hellebore hydrocarbon of ring and its derivative shown in formula (I)
At least one of object:
In formula (I), M1、M2、M3、M4、M5And M6It is identical or different, it each is selected from hydrogen, hydroxyl, amino, aldehyde radical, carboxyl, acyl group, halogen
Atom ,-R1Or-OR2, wherein R1And R2Respectively substituted or unsubstituted C1-C10Alkyl, substituent group are selected from hydroxyl, amino, aldehyde
Base, carboxyl, acyl group, halogen atom, alkoxy or hetero atom；
As two group M adjacent on phenyl ring1And M2Or M3And M4Or M5And M6It each is selected from R1Or-OR2When, two phases
It is optionally mutually cyclic between adjacent group.
2. ingredient of solid catalyst according to claim 1, wherein in formula (I), M1、M2、M3、M4、M5And M6It is identical or not
Together, hydroxyl, amino, aldehyde radical, halogen atom ,-R each are selected from1Or-OR2, and R1And R2It each is selected from and is replaced or do not taken by halogen atom
The C in generation1-C10Alkyl.
3. ingredient of solid catalyst according to claim 1, wherein the three black false hellebore hydrocarbons and their derivates of ring are selected from following
At least one of compound:
Compound A:M1=M2=M3=M4=M5=M6=OCH3；
Compound B:M1=M2=M3=M4=M5=M6=OCH2CH3；
Compound C:M1=M2=M3=M4=M5=M6=OCH2CH2CH3；
Compound D:M1=M2=M3=M4=M5=M6=OCH (CH3)2；
Compound E:M1=M2=M3=M4=M5=M6=OCH2CH2CH2CH3；
Compound F:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH3；
Compound G:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH3；
Compound H:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2CH3；
Compound I:M1=M2=M3=M4=M5=M6=OH；
Compound J:M1=M3=M5=OCH3；M2=M4=M6=OH；
Compound K: M1=M3=M5=OCH3；M2=M4=M6=NH2；
Compound L: M1=M3=M5=OCH3；M2=M4=M6=Cl；
Compound M:M1=M3=M5=OCH3；M2=M4=M6=Br；
Compound N: M1=M3=M5=OCH3；M2=M4=M6=I；
Compound O:M1=M3=M5=OCH3；M2=M4=M6=CHO；
Compound P:M1=M3=M5=OCH3；M2=M4=M6=OCH2CH2CH2Br；
Compound Q: M1=M3=M5=OH, M2=M4=M6=OCH2CH3。
4. ingredient of solid catalyst according to claim 1, wherein the ingredient of solid catalyst includes to be carried on halogenation
Three black false hellebore hydrocarbons and their derivates of titanium compound and the ring on magnesium.
5. ingredient of solid catalyst according to claim 1 or 4, wherein the three black false hellebore hydrocarbons and their derivates of ring and magnesium
Molar ratio be 0.001~0.1 ︰ 1, preferably 0.002~0.05 ︰ 1.
6. ingredient of solid catalyst according to claim 4, wherein the general formula of the titanium compound is Ti (OR)nX’4-n,
R is C in formula1-C8Alkyl, X ' are halogen atom, 0≤n≤4；
Preferably, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichloro two
At least one of one ethanolato-titanium of ethanolato-titanium, butyl titanate and trichlorine.
7. a kind of olefin polymerization catalysis, which is characterized in that the olefin polymerization catalysis includes the reaction product of following components:
1) ingredient of solid catalyst described in any one of claim 1-6；
2) organo-aluminum compound.
8. olefin polymerization catalysis according to claim 7, wherein aluminium and the solid in the organo-aluminum compound
The molar ratio of titanium in catalytic component is 5 ︰, 1~500 ︰ 1,1~200 ︰ 1 of preferably 20 ︰.
9. application of the olefin polymerization catalysis described in claim 7 or 8 in olefin polymerization.
10. a kind of ethylene copolymer, which is characterized in that the ethylene copolymer is that the olefinic polymerization described in claim 7 or 8 is urged
In the presence of agent, ethylene is made to close to obtain with alpha-olefin copolymer.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710592386.3A CN109280110B (en) | 2017-07-19 | 2017-07-19 | Solid catalyst component for olefin polymerization, olefin polymerization catalyst, application thereof and ethylene copolymer |
| KR1020207002897A KR102336976B1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotiberatrylene and derivatives thereof |
| CN201880002860.5A CN109526217B (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof |
| JP2020502696A JP7038797B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst containing cyclotribellatrilen and its derivatives |
| PCT/CN2018/096248 WO2019015638A1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| BR112020001201-7A BR112020001201B1 (en) | 2017-07-19 | 2018-07-19 | ZIEGLER-NATTA CATALYST SYSTEM FOR OLEFIN POLYMERIZATION, SOLID CATALYST COMPONENT FOR OLEFIN POLYMERIZATION AND OLEFIN POLYMERIZATION PROCESS |
| RU2020103744A RU2740916C1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerisation catalyst comprising cyclotriveratrilene and derivatives thereof |
| US16/631,482 US11401356B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| EP18835679.4A EP3656754A4 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
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| CN110734510A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives |
| CN113004452A (en) * | 2021-04-27 | 2021-06-22 | 辛集市旭远新材料科技有限公司 | Impact-resistant polypropylene and preparation method thereof |
| CN114478861A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application |
| CN114478854A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization, preparation method thereof, catalyst, method for preparing ultrahigh molecular weight polyolefin and application |
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| CN110734510A (en) * | 2018-07-19 | 2020-01-31 | 中国石油化工股份有限公司 | Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives |
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| CN115677884A (en) * | 2021-07-30 | 2023-02-03 | 上海立得催化剂有限公司 | Process for preparing main component of catalyst for olefin polymerization |
| CN115677884B (en) * | 2021-07-30 | 2023-12-12 | 上海立得催化剂有限公司 | Process for preparing a bulk component for an olefin polymerization catalyst |
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