CN109280108A - Ingredient of solid catalyst and catalyst system and olefine polymerizing process for olefinic polymerization - Google Patents
Ingredient of solid catalyst and catalyst system and olefine polymerizing process for olefinic polymerization Download PDFInfo
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- CN109280108A CN109280108A CN201710592384.4A CN201710592384A CN109280108A CN 109280108 A CN109280108 A CN 109280108A CN 201710592384 A CN201710592384 A CN 201710592384A CN 109280108 A CN109280108 A CN 109280108A
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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
- C08F110/02—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
- C08F210/02—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
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
Abstract
The present invention relates to olefin polymerization catalysis fields, and in particular to a kind of ingredient of solid catalyst and catalyst system and olefine polymerizing process for olefinic polymerization, the ingredient of solid catalyst include the reaction product of following components: 1) magnesium halide alcohol adduct；2) titanium compound；3) internal electron donor compound；Optionally 4) organo-aluminum compound, the interior Donor compound include at least one of three black false hellebore hydrocarbons and their derivates of ring shown in formula (I).Ingredient of solid catalyst of the invention improves the polymerization activity, hydrogen response and copolymerization performance of polyolefin catalyst by introducing three black false hellebore hydrocarbon compound of ring as internal electron donor.
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, catalyst system and a kind of olefine polymerizing process for olefinic polymerization.
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.
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: using three black false hellebore hydrocarbons and their derivates of ring as with halogenation
Magnesium alcoholate be carrier polyolefin catalyst internal electron donor in use, its polymerization activity that can either improve catalyst and
Hydrogen tune susceptibility, and the copolymerization performance of catalyst can be improved.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 the reaction product of following components:
1) magnesium halide alcohol adduct；
2) titanium compound；
3) internal electron donor compound；
Optionally, 4) organo-aluminum compound；
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 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 terms of every mole of magnesium, the dosage of the three black false hellebore hydrocarbon compound of ring is at least 0.001mol, preferably 0.001~
0.1mol。
According to the second aspect of the invention, the present invention provides a kind of catalyst system for olefinic polymerization, the catalysis
Agent system includes the reaction product of following components:
Component I: above-mentioned ingredient of solid catalyst；
Component II: organo-aluminum compound；
The general formula of the organo-aluminum compound is AlR3 dX3 3-d, wherein R3For hydrogen or Cl-C20Alkyl, X3For halogen atom, 0 <
d≤3。
According to the third aspect of the invention we, the present invention provides a kind of olefine polymerizing process, this method comprises: poly- in alkene
Under the conditions of conjunction, contact one or more alkene with above-mentioned catalyst system.
In ingredient of solid catalyst of the invention, three black false hellebore hydrocarbon compound of ring is introduced as internal electron donor, is not only mentioned
The high polymerization activity of polyolefin catalyst, hydrogen response, also improve the copolymerization performance of catalyst.
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 ingredients of solid catalyst for olefinic polymerization, should
Ingredient of solid catalyst includes the reaction product of following components:
1) magnesium halide alcohol adduct；
2) titanium compound；
3) internal electron donor compound；
Optionally, 4) organo-aluminum compound；
In the present invention, the internal electron donor compound include formula (I) shown in three black false hellebore hydrocarbons and their derivates of ring extremely
Few one kind:
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-C10Aralkyl 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- methylcyclohexyl,
4- ethylcyclohexyl, 4- n-propyl cyclohexyl and 4- normal-butyl cyclohexyl.
C6-C10The example of aryl can include but is not limited to: phenyl, 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 aralkyl can include but is not limited to: phenyl methyl, phenylethyl, phenyl n-propyl, phenyl are just
Butyl, phenyl t-butyl and propyloxy phenyl base.
In the present invention, " substituted C1-C10Alkyl " refer to " C1-C10Alkyl " on a hydrogen atom (preferably hydrogen original
Son) 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 hydrocarbon compound of ring is 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=OCH2CH3；M2=M4=M6=OH.
In addition, working as M1=M3=M5=X, M2=M4=M6(X, Y respectively indicate the above-mentioned M of the present invention to=Y1、M3、M5And M2、M4、
M6Selectable group, and X is different from Y) when, there may be following isomers: M for the three black false hellebore hydrocarbons and their derivates of ring1=M4
=M5=X, M2=M3=M6=Y.However the isomers is also within the scope of the present invention.
In the present invention, the three black false hellebore hydrocarbon compound of ring can be prepared one of as follows:
Method 1: 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 hydrocarbon compound of ring；
Method 2: in the presence of acidic materials, phenyl ring analog derivative B shown in catalysis type (III) carries out condensation reaction, thus
To the three black false hellebore hydrocarbon compound of ring；
Method 3: in the presence of a lewis acid, in halogenated hydrocarbons, phenyl ring analog derivative A and formaldehyde shown in catalysis type (II)
Or derivatives thereof reacted, to obtain the three black false hellebore hydrocarbon compound 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, hydrobromic acid, hydroiodic acid, sulfuric acid, pyrosulfuric acid, sulfurous acid, phosphoric acid, burnt phosphorus
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, repeats no more herein.
According to the present invention, in terms of every mole of magnesium, the dosage of the three black false hellebore hydrocarbon compound of ring is at least 0.001mol,
Preferably 0.001~0.1mol, more preferably 0.002~0.05mol.
In addition, the interior Donor compound can also be different from the three black false hellebore hydrocarbon compound of ring (referred to as containing other
For the internal electron donor b commonly used in the art of " internal electron donor a "), internal electron donor b for example can be selected from Organic Alcohol, have
Machine acid, organic acid esters, organic acid halides, organic acid anhydride, ether, ketone, amine, phosphate, amide, carbonic ester, phenol, pyridine and have pole
The high-molecular compound etc. of property group.
Preferably, the internal electron donor b is being selected from methyl acetate, ethyl acetate, propyl acetate, butyl acetate, acetic acid just
Monooctyl ester, methyl benzoate, ethyl benzoate, butyl benzoate, hexyl-benzoate, ethyl p-methyl benzoate, 2-methyl naphthoate,
Naphthoic acid ethyl ester, methyl methacrylate, ethyl acrylate, butyl acrylate, ether, butyl ether, tetrahydrofuran, 2,2- diformazan
Base -1,3- di ethyl propyl ether, methanol, ethyl alcohol, propyl alcohol, isopropanol, butanol, isooctanol, octylame, triethylamine, acetone, butanone,
Cyclopentanone, 2- methyl-cyclopentanone, cyclohexanone, phenol, hydroquinone, ethylene oxide, propylene oxide, epoxychloropropane, tricresyl phosphate
Methyl esters, triethyl phosphate, tricresyl phosphate propyl ester, tributyl phosphate, triphenyl phosphate, tri hexyl phosphate, polymethyl methacrylate,
At least one of polystyrene, Hydrin and polyethylene oxide.
According to the present invention, the magnesium halide alcohol adduct carrier is ball type carrier.The general formula of magnesium halide alcohol adduct is represented by
MgX2M (ROH), X Cl, Br or I, preferably Cl；R is C1~C6Alkyl, m are 2.5~4.0.
Specifically, the preparation method of the magnesium halide alcohol adduct carrier can include: magnesium halide and low-carbon alcohols are mixed,
Temperature reaction generates magnesium halide alcohol adduct melt, and reaction temperature is 110~130 DEG C, in a dispersion medium after high shear forces
It is put into cooling inert media, forms spherical magnesium halide alcohol polymer particle, obtain ball type carrier after washed, dry.Dispersion
Hydro carbons atent solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil can be used in agent system.Cooling inert media can
Selected from pentane, hexane, heptane, petroleum ether, raffinate oil.
In addition, the preparation method that the magnesium halide alcohol adduct carrier can refer to CN1091748A obtains, it is disclosed related
Content is all incorporated herein by reference.
According to the present invention, the titanium compound can be the conventional selection of this field, and general formula is represented by Ti (OR2)nX2 4-n, R therein2For C1~C8Alkyl, preferably C1~C8Alkyl；X2For Cl, Br or I, the integer that 0≤n≤4 are 1~4；
The specific example of the titanium compound includes: TiCl4、TiBr4、TiI4、Ti(OC2H5)Cl3、 Ti(OCH3)Cl3、Ti
(OC4H9)Cl3、Ti(OC2H5)Br3、Ti(OC2H5)2Cl2、Ti(OCH3)2Cl2、 Ti(OCH3)2I2、Ti(OC2H5)3Cl、Ti
(OCH3)3Cl、Ti(OC2H5)3I、Ti(OC2H5)4、Ti(OC3H7)4With Ti (OC4H9)4。
Under preferable case, the titanium compound is selected from TiCl4、Ti(OC2H5)Cl3、Ti(OCH3)Cl3、 Ti(OC4H9)Cl3
With Ti (OC4H9)4At least one of, more preferably TiCl4。
In the present invention, in terms of every mole of magnesium, the dosage of the titanium compound is usually 0.1~100mol, preferably 1~
50mol。
Component 4) organo-aluminum compound general formula be AlR1 aX1 bHc, R in formula1For C1-C14Alkyl, X1For halogen atom, preferably
Fluorine, chlorine, bromine, a, b, c are the number of 0-3, and a+b+c=3.
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. meet the alkyl aluminum compound of formula above carbon atom number.
In addition, the organo-aluminum compound is preferably Al (CH2CH3)3、Al(n-C6H13)3With Al (i-Bu)3In at least one
Kind, further preferably Al (CH2CH3)3。
In terms of every mole of magnesium, the dosage of the organo-aluminum compound can be 0~5mol, preferably 0~3mol.
In the present invention, the method that the ingredient of solid catalyst can refer to CN102807638A is prepared.
In the present invention, the ingredient of solid catalyst is by the way that first the magnesium halide alcohol adduct is dispersed in atent solvent
Suspension is made, add more than reactant composition carry out haptoreaction made from.
Preferably, which is prepared one of by the following method:
Method one:
1) magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
2) by the suspension and optional organo-aluminum compound, the internal electron donor compound haptoreaction, then
Unreacted reactant is removed, 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 is removed, and is washed with atent solvent, the ingredient of solid catalyst is obtained；
Method two:
1) magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
2) it by the suspension and organo-aluminum compound and optional internal electron donor b 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) connects with the titanium compound and internal electron donor a
Touching reaction, then removes unreacted reactant, and washed with atent solvent, obtains the ingredient of solid catalyst；
Method three:
1) magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
2) by the suspension and titanium compound haptoreaction, unreacted reactant is then removed, and is washed with atent solvent；
3) sediment and titanium compound and the internal electron donor chemical combination in the presence of an inert solvent, obtaining step 2)
Then object haptoreaction removes unreacted reactant and solvent, obtains the ingredient of solid catalyst.
Method one can specifically include:
S1: the magnesium halide alcohol adduct is dispersed in atent solvent, suspension is obtained；
S2: -20 DEG C to 20 DEG C at a temperature of, to the suspension be added optional organo-aluminum compound, it is described in
Electron a and optional electron donor b；
S3: being warming up to 50~85 DEG C, reacts 0.5~5 hour under agitation, is then allowed to stand layering, and abstraction upper layer is clear
Liquid, sediment are washed with atent solvent；
S4: being added atent solvent and titanium compound, reacts 0.5~5 hour, is then allowed to stand in stirring condition at 50~85 DEG C
Layering extracts supernatant liquor, and sediment is washed with atent solvent, so that the ingredient of solid catalyst be made.
Method two can specifically include:
S1: magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
S2: -20 DEG C to 20 DEG C at a temperature of, organo-aluminum compound and optional interior electron is added to the suspension
Body b；
S3: being warming up to 50~85 DEG C, reacts 0.5~5 hour under agitation, is then allowed to stand layering, and abstraction upper layer is clear
Liquid, sediment are washed with atent solvent；
S4: being added atent solvent, titanium compound and electron donor a, small in stirring condition reaction 0.5~5 at 50~85 DEG C
When, it is then allowed to stand layering, extracts supernatant liquor, sediment is washed with atent solvent, so that the ingredient of solid catalyst be made.
Method three can specifically include:
S1: magnesium halide alcohol adduct is dispersed in atent solvent, obtains suspension；
S2: -20 DEG C to 20 DEG C at a temperature of, to the suspension be added titanium compound；
S3: being warming up to 50~85 DEG C, reacts 0.5~5 hour under agitation, is then allowed to stand layering, and abstraction upper layer is clear
Liquid, sediment are washed with atent solvent；
S4: being added atent solvent, titanium compound, internal electron donor a and optional internal electron donor b, 50~85 DEG C in
Stirring condition reacts 0.5~5 hour, is then allowed to stand layering, extracts supernatant liquor, sediment is washed with atent solvent, to make
Obtain the ingredient of solid catalyst.
In method two and method three, S4 can be carried out stage by stage, and each stage is separately added into different reactive components and carries out instead
It answers.
The atent solvent that above each step is mentioned can be identical or different, and can refer to the prior art and selected, this
This is not particularly limited in invention.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 catalyst system for olefinic polymerization, the catalysis
Agent system includes the reaction product of following components:
Component I: above-mentioned ingredient of solid catalyst；
Component II: organo-aluminum compound.
In component II, the organo-aluminum compound is co-catalyst.
The general formula of the organo-aluminum compound is AlR3 dX3 3-d, wherein R3For hydrogen or Cl-C20Alkyl, X3For halogen atom, and
0<d≤3。
Under preferable case, the organo-aluminum compound is selected from triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, three just pungent
At least one of one aluminium ethide of base aluminium, aluminium diethyl monochloride and dichloro.
According to the present invention, the molar ratio of the titanium in component I and the aluminium in component II can be 1 ︰, 5~1 ︰ 500, preferably
1 ︰, 20~1 ︰ 200.
According to the third aspect of the invention we, the present invention provides a kind of olefine polymerizing process, this method comprises: poly- in alkene
Under the conditions of conjunction, contact one or more alkene with the catalyst system.
Catalyst system of the invention can be used for the homopolymerization of ethylene, it can also be used to the combined polymerization of ethylene and alpha-olefin.
The specific example of the alkene includes: ethylene, butylene, amylene, hexene, octene, 4-methyl-1-pentene.
Preferably, the alkene is ethylene and/or butylene.
In addition, the catalyst system is suitable for the olefin polymerization of various conditions, for example, the olefinic polymerization is anti-
It can should carry out, or can also be carried out under the operation that liquid and gas polymerization stage combines in liquid phase or gas phase.Polymerization
Temperature can be 0~150 DEG C, preferably 60~90 DEG C.
Medium used by liquid phase polymerization can be selected from iso-butane, hexane, heptane, hexamethylene, naphtha, raffinate oil, add
The atent solvents such as the aliphatic saturated hydrocarbons such as hydrogen gasoline, kerosene, benzene,toluene,xylene or aromatic hydrocarbon, preferably toluene, n-hexane or
Hexamethylene.
In addition, making molecular weight regulator using hydrogen to adjust the molecular weight of final polymer.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
1, in catalytic component titanium elements relative weight percents: use spectrophotometry；
2, the composition of catalytic component: liquid nuclear-magnetism is used1H-NMR；
3, melt index (MI): according to ASTM D1238-99, load 2.16kg is determined at 190 DEG C；
4, it copolymerization units content in polymer powders: is determined using liquid nuclear-magnetism 13C-NMR；
5, in polymer powders hexane extractable content weight percent: resulting whole powder slurries nitrogen will be polymerize
It is transferred in standard cylindrical container, is thoroughly dried in ventilation condition, obtain blocky powder, vertically cut the blocky powder of gained
20g is placed it in container after crushing, is extracted 2 hours at 50 DEG C with 300mL hexane, 20mL extracting solution is then extracted, by it
It is placed in the surface plate being precisely weighed, the surface plate being completely dried is weighed, the mass weight gain of surface plate is m1G, and by
This calculates that the weight percent of hexane extractable content is 75m1%.
The polymer powders are that the whole powder slurries as obtained by will polymerize with nitrogen are transferred to standard cylindrical container
It is interior, it is dried to obtain under ventilation condition.In following embodiment and comparative example, the molar ratio of gaseous mixture are as follows: ethylene/butylene=
0.90/0.10, it is obtained before copolyreaction by being configured in distribution tank.In addition, the pressure in the kettle mentioned is absolute pressure
Power.
Preparation example 1-3 is used to illustrate the preparation method of the three black false hellebore hydrocarbon compound of ring.
Preparation example 1
Under condition of ice bath, 1,2- 1,2-dimethoxy benzene (1.0g) is added drop-wise to formalin (4mL/38%)/0.1mL tri-
It in the mixture of chloromethanes/concentrated hydrochloric acid (6mL), is reacted, after 30 minutes, solution becomes starchiness, continues stirring 4 at room temperature
Hour.Solid is collected by filtration, ice water washing thoroughly obtains 0.5g formula (IV) compound represented A after drying.
Preparation example 2
3- ethyoxyl -4- (2- allyloxy) benzyl alcohol (5g) is dissolved in 30mL methanol, is added dropwise under ice bath and stirring
18h is stirred at room temperature under nitrogen protection in 65% perchloric acid 15mL.Enough methylene chloride are added into reaction product, for molten
Solve sediment.Organic phase is washed with water to neutral (eliminating whole perchloric acid), dry, is then spin-dried for organic solvent, obtains compound Q
Precursor 2g.Nitrogen protection and stirring under, 2g compound Q precursor is dissolved in Isosorbide-5-Nitrae-dioxane 10mL, then be added ethyl alcohol and
Pt/C catalyst.65% perchloric acid 10mL is added dropwise, in 60 degree of constant temperature 20h.Reaction product is filtered to remove catalyst, successively
It is washed using 1,4- dioxane and methylene chloride.Organic phase is sufficiently washed with water, dry, concentration, compound Q will be analysed gradually
Out, 1g such as formula (V) compound represented Q is obtained after suction filtration.
Preparation example 3
1,2- neighbour's benzene diethyl ether (3.3g) and metaformaldehyde (0.63g) are dissolved in dry methylene chloride (30mL), ice
The lower stirring of bath, is slowly dropped into boron trifluoride ether (4.25g), after being added dropwise, removes ice-water bath, stirs 3h under room temperature, TLC with
Track reacts until the reaction is complete, stops reaction, and mixture is washed with water 3 times, separates organic layer, be spin-dried for organic solvent, obtain oil
Shape object is added a small amount of acetone and dissolves grease, then a large amount of methanol are added thereto, and being statically placed in refrigerator makes it that white be precipitated admittedly
Body.It filters, thoroughly after drying, obtains 1.5g formula (VI) compound represented B.
Embodiment 1-3 is for illustrating ingredient of solid catalyst of the invention, catalyst system and olefine polymerizing process.
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) the compound A prepared with 0.3g preparation example 1, then heats to 60 DEG C, 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.120mL toluene is added,
The system is cooled to 0 DEG C, titanium tetrachloride 8mL 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 a of good fluidity, 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 a (titanium containing 0.6mg) prepared by the above method, is warming up to 75 DEG C,
Being passed through hydrogen makes pressure in kettle reach 0.28MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, gathers under the conditions of 85 DEG C
It closes 2 hours, 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 a (titanium containing 0.6mg) prepared by the above method, is warming up to 75 DEG C,
Being passed through hydrogen makes pressure in kettle reach 0.68MPa, then being passed through ethylene makes stagnation pressure in kettle reach 1.03MPa, gathers under the conditions of 85 DEG C
It closes 2 hours, 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 a (titanium containing 0.6mg) prepared by the above method, is warming up to 70 DEG C,
Being passed through hydrogen makes pressure in kettle reach 0.28MPa, then be passed through ethylene/butylene gaseous mixture (molar ratio be 0.9 ︰ 0.1) make it is total in kettle
Pressure reaches 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), the compound Q of 1mL ethyl benzoate and the preparation of 0.2g preparation example 2 is added, then heats to 60 DEG C, and maintain
Reaction 3 hours.Stop stirring, stand, suspension is layered quickly, extracts supernatant liquor, sediment toluene and hexane are successively washed
It washs for several times.120mL hexane is added, which is cooled to 0 DEG C, titanium tetrachloride 8mL is slowly added dropwise, is warming up to 60 DEG C later, instead
It answers 2 hours.Stop stirring, stand, suspension is layered quickly, is extracted supernatant liquor, after sediment washs twice with hexane, is passed through
Hexane transfers them in chromatography funnel, is dried up with high pure nitrogen, obtains 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.
Embodiment 3
(1) preparation of ingredient of solid catalyst c
In the reactor being sufficiently displaced from by high pure nitrogen, 5.0g ball type carrier MgCl is sequentially added2·
3.0C2H5OH, toluene 120mL are cooled to -5 DEG C under stirring, 80mL titanium tetrachloride is added dropwise, and then raise temperature to 40 DEG C, and 0.3g is added
Compound B prepared by preparation example 3, then heats to 85 DEG C, and maintains reaction 2 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 30mL is slowly added dropwise, is warming up to 85 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 c of 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.
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, toluene 100mL, are cooled to -10 DEG C under stirring, be added dropwise 35mL triethyl aluminum hexane solution (triethyl aluminum:
1.2M), 50 DEG C are then heated to, and maintains reaction 3 hours.Stop stirring, stand, suspension is layered quickly, and abstraction upper layer is clear
Liquid, sediment toluene and hexane successively wash for several times.150mL hexane is added, which is cooled to 0 DEG C, is slowly added dropwise four
Titanium chloride 6mL is warming up to 60 DEG C later, reacts 2 hours.Stopping stirring, stands, suspension is layered quickly, supernatant liquor is extracted,
After sediment washs twice with hexane, is transferred them in chromatography funnel by hexane, dried up with high pure nitrogen, obtain mobility
Good solid spherical catalytic component D1, 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 2
(1) preparation of ingredient of solid catalyst D2
It is prepared according to the method for CN102807638A specification embodiment 2:
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 D2 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 3
(1) preparation of ingredient of solid catalyst D3
In the reactor being sufficiently displaced from by high pure nitrogen, 4.0g ball type carrier MgCl is sequentially added2·
3.0C2H5OH, toluene 100mL are cooled to -10 DEG C under stirring, 60mL titanium tetrachloride is added dropwise, and then raise temperature to 40 DEG C, and 2mL is added
Ethyl benzoate is continuously heating to 85 DEG C, and maintains reaction 3 hours.Stop stirring, stands, suspension is layered quickly, in abstraction
Layer clear liquid, sediment toluene and hexane successively wash for several times.150mL hexane is added, which is cooled to 0 DEG C, slowly drips
Add titanium tetrachloride 30mL, be warming up to 85 DEG C later, reacts 2 hours.Stop stirring, stand, suspension is layered quickly, extracts upper layer
Clear liquid after sediment washs twice with hexane, is transferred them in chromatography funnel by hexane, is dried up, obtained with high pure nitrogen
The solid spherical catalytic component D3 of good fluidity, 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.
Table 1
* note: the ethoxy group not comprising three black false hellebore hydrocarbons and their derivates of ring.
Table 2
As shown in Table 2, under the polymerizing condition of low hydrogen second ratio, the catalyst activity of embodiment is slightly above comparative example；And
Under the polymerizing condition of higher hydrogen second ratio, the catalyst activity of the embodiment of the present invention is significantly higher than comparative example.In addition, embodiment is urged
Agent has better hydrogen tune susceptibility.This feature is conducive to the production of the bimodal products in slurry polymerization processes and gas phase is poly-
Close the production of high melting means product in technique.It follows that three black false hellebore hydrocarbons and their derivates of ring can be improved catalyst activity and
Hydrogen tune susceptibility.
Table 3
| Number | Copolymerization units content (mol%) | Hexane extractable content (wt%) |
| Embodiment 1 | 2.7 | 3.8 |
| Embodiment 2 | 2.7 | 4.3 |
| Embodiment 3 | 2.7 | 3.6 |
| Comparative example 1 | 2.3 | 6.0 |
| Comparative example 2 | 2.2 | 5.1 |
| Comparative example 3 | 2.3 | 4.4 |
As shown in Table 3, in the case where gaseous mixture ratio is ethylene/butylene=0.90/0.10 (mol/mol), compared with right
For ratio, the copolymerization units content of the embodiment of the present invention is higher and hexane extractable content is lower.It follows that compared with right
For ratio, copolymerization units contained by the lower-molecular-weight component of powder of the embodiment of the present invention are less, and contained by medium/high molecular weight component
Copolymerization units are more.Therefore, three black false hellebore hydrocarbons and their derivates of ring improve the copolymerization performance of catalyst, and it is comprehensive that this is conducive to product
The raising of 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 includes with the following group
The reaction product divided:
1) magnesium halide alcohol adduct；
2) titanium compound；
3) internal electron donor compound；
Optionally, 4) organo-aluminum compound；
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 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；
The general formula of the organo-aluminum compound is AlR1 aX1 bHc, R in formula1For C1-C14Alkyl, X1For halogen atom, preferably fluorine, chlorine,
Bromine, a, b, c are the integer of 0-3, and a+b+c=3；
In terms of every mole of magnesium, the dosage of the three black false hellebore hydrocarbon compound of ring is at least 0.001mol, preferably 0.001~
0.1mol。
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 hydrocarbon compound of ring is selected from followingization
Close at least one of object:
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=OCH2CH3；M2=M4=M6=OH.
4. ingredient of solid catalyst according to claim 1, wherein the general formula of the magnesium halide alcohol adduct is MgX2·m
(ROH), X Cl, Br or I, preferably Cl；R is C1~C6Alkyl, m are 2.5~4.0.
5. ingredient of solid catalyst according to claim 1, wherein the general formula of the titanium compound is Ti (OR2)nX2 4-n,
R therein2For C1~C8Alkyl, preferably C1~C8Alkyl；X2For Cl, Br or I, the integer that 0≤n≤4 are 1~4.
6. ingredient of solid catalyst according to claim 5, wherein the titanium compound is selected from TiCl4、Ti(OC2H5)
Cl3、Ti(OCH3)Cl3、Ti(OC4H9)Cl3With Ti (OC4H9)4At least one of.
7. ingredient of solid catalyst according to claim 1, wherein in terms of every mole of magnesium, the dosage of the titanium compound
For 0.1~100mol, preferably 1~50mol.
8. ingredient of solid catalyst according to claim 1, wherein in terms of every mole of magnesium, the organo-aluminum compound
Dosage is 0~5mol.
9. a kind of catalyst system for olefinic polymerization, which is characterized in that the catalyst system includes the reaction of following components
Product:
Component I: the ingredient of solid catalyst as described in any one of claim 1~8；
Component II: organo-aluminum compound；
The general formula of the organo-aluminum compound is AlR3 dX3 3-d, wherein R3For hydrogen or Cl-C20Alkyl, X3For halogen atom, 0 < d≤3.
10. a kind of olefine polymerizing process, which is characterized in that this method comprises: making a kind of or more under the conditions of olefin polymerization
Kind alkene is contacted with catalyst system as claimed in claim 9.
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| CN201710592384.4A CN109280108B (en) | 2017-07-19 | 2017-07-19 | Solid catalyst component and catalyst system for olefin polymerization and olefin polymerization process |
| 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 |
| EP18835679.4A EP3656754A4 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| 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 |
| US16/631,482 US11401356B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| RU2020103744A RU2740916C1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerisation catalyst comprising cyclotriveratrilene and derivatives thereof |
| PCT/CN2018/096248 WO2019015638A1 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst comprising cyclotriveratrylene and derivatives thereof |
| JP2020502696A JP7038797B2 (en) | 2017-07-19 | 2018-07-19 | Olefin polymerization catalyst containing cyclotribellatrilen and its derivatives |
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| US6255419B1 (en) * | 1997-02-07 | 2001-07-03 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and process for producing olefin polymers |
| CN103509218A (en) * | 2012-06-18 | 2014-01-15 | 中国石油化工股份有限公司 | Components of catalyst used for olefin polymerization and preparation method thereof |
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| US6255419B1 (en) * | 1997-02-07 | 2001-07-03 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and process for producing olefin polymers |
| CN1272851A (en) * | 1998-06-16 | 2000-11-08 | 三井化学株式会社 | Catalyst for olefin polymerization and method of polymerizing olefin |
| CN103509218A (en) * | 2012-06-18 | 2014-01-15 | 中国石油化工股份有限公司 | Components of catalyst used for olefin polymerization and preparation method 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 |
| CN110734510B (en) * | 2018-07-19 | 2022-02-08 | 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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