CN108864337A - A method of carbon monoxide-olefin polymeric and olefinic polymerization for olefinic polymerization - Google Patents
A method of carbon monoxide-olefin polymeric and olefinic polymerization for olefinic polymerization Download PDFInfo
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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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F295/00—Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer
Abstract
The present invention relates to the catalyst field of olefinic polymerization, a kind of method of the carbon monoxide-olefin polymeric for olefinic polymerization and olefinic polymerization is provided, which includes：(1) first olefin polymerization catalysis (A), in metal complex shown in general formula I, formula, R1~R5, R7~R11It is identical or different, it is selected from hydrogen, alkyl or halogen；M is group IVA metal, and X is identical or different, is selected from halogen, alkyl, oxyl；L is the VIth A race element；(2) second olefin polymerization catalysis (B), in metal complex shown in general formula II, formula, R1And R4It is identical or different, it is selected from C1‑C30Alkyl or C1‑C30Miscellaneous alkyl；R2And R3It is identical or different, it is selected from hydrogen, chlorine, C1‑C20Alkyl, contain heteroatomic organic group；M is group VIII metal；(3) chain shuttling agent；(4) co-catalyst.The catalyst can realize copolymerization at relatively high temperatures.
Description
Technical field
The present invention relates to the catalyst fields of olefinic polymerization, more particularly, to a kind of catalyst for olefinic polymerization
Composition and the method for olefinic polymerization.
Background technique
The polymer of block type structure usually has more excellent compared with random copolymerization object and blend for a long time
Property.For example, the triblock copolymer (SBS) and their hydrogenation transformed object (SEBS) of styrene and butadiene are with excellent
Heat resistance and elasticity.With thermoplastic elastomer (TPE) (TPE), famous block copolymer is due to having " soft " in polymer chain
Or the crystallizable part of elastic segment connection " firmly ".When temperature reaches the glass transition temperature of fusing point or " hard " section, these
Polymer demonstrates flexibility the characteristic of material.In higher temperature, these polymer become runny, show thermoplasticity spy
Property.The existing method for being used to prepare block copolymer includes anionic polymerisation and controlled free radical polymerization.But these are prepared
The method of block copolymer needs continuously to add monomer and intermittently operated, and can be used for the monomeric species of above method polymerization
It is relatively fewer.For example, during the anionic polymerisation of styrene and butadiene is to form SBS based block copolymer, each
Polymer chain needs the initiator of stoichiometric(al) amount and obtained polymer has very narrow molecular weight distribution mw/mn, excellent
Select 1.0 to 1.3.In addition, anion and free radical polymerization are relatively slow, its industrialization development is influenced.
It is desirable to realize preferably control catalytic process production block copolymer, that is, every kind in the course of the polymerization process
Catalyst or initiator molecule can form more than one polymer molecule.Additionally, it is desirable that can from single monomer, such as ethylene,
It produces to have and has both high-crystallinity and indefiniteness block or segment segmented copolymer.
In the past researcher be already indicated above some homogeneous coordination polymerization catalysts can by during polymerization inhibit chain turn
It moves and the polymer with block structure is made.For example, in polymerization process, by reducing chain-transferring agent to the greatest extent and reducing reaction temperature
Degree, controls β-hydrogen migration or chain tra nsfer prepares block polymer.Under the above conditions, it is believed that the sequence addition of different monomers can be led
Cause to be formed the polymer of sequence or segment with different monomers content.Some embodiments of above-mentioned carbon monoxide-olefin polymeric and method
It is described in Angew.Chem.Int.Ed., 2002,41,2236-2257 and the US2003/ of Coates, Hustad and Reinartz
In 0114623.
Known in the art is by turning using certain alkyl metal cpds and other compound such as hydrogen as chain
Agent is moved to interrupt the chain growth in olefinic polymerization.In addition, alkyl aluminum compound would generally be selected as net in olefin polymerization process
Agent or co-catalyst.In Macromolecules, 2000,33,9192-9199, it was recently reported that by by certain trialkylaluminiums
Compound is used in combination as chain-transferring agent with certain pairs of zirconocene catalysts compositions, generates while comprising a small amount of complete
The polypropylene block polymers of the polymer of structure chain segment are found with vertical structure and trackless.Liu's and Rytter
Macromolecules in 2003,3026-3034 articles, is also reported trimethyl aluminium chain-transferring agent with similar catalyst group
Close catalysis ethylene and 1- hervene copolymer.
It reports in US 6,380,341 and US 6,169,151, by using " vertical structure " metallocene catalyst, passes through
Catalyst aggregation features of mutually conversion performance differential responses rate etc. between two kinds of spatial configurations form " block-wise " structure
Olefin polymer.
It is well known that alpha-diimine nickel and palladium catalyst can form more (height during polymerization by " chain tra nsfer "
Branching) polymer.The example of this Type of Collective is disclosed in Chem.Rev., 2000,100,1169-1203,
Macromol.Chem.Phys., 2004,205,897-906 etc..The polymer of this long chain branching can also by such as 1- and
Bis- (indenyl) zirconium complexes that 2- t-butyldimethylsilyloxy base replaces and methyl alumoxane cocatalyst catalysis ethylene are equal
It is poly- to be made.The example of this Type of Collective is disclosed in J.Mol.Catal.A:Chem.,1995,102,59-65；Macromolecules,
1988,21,617-622；J.Mol.Catal.A:Chem.,2002,185,57-64,J.Am.Chem.Soc.,1995,117,
In 6414-6415.
Existing article report realizes chain under diethyl zinc effect with metallocene catalyst using diimine nickel metal at present
Shuttle polymerization reacts (Macromolecules 2009,42,1834-1837), but polymerization temperature is lower, and only 20 DEG C.It is existing
The ethylene polymerization activity of alpha-diimine Raney nickel at high temperature is very low, and the molecular weight with polymerisation temperature of prepared polyethylene mentions
High and decline rapidly, original late transition metal catalyst is unable to satisfy the requirement of existing gas phase, solwution method ethylene polymerization plants.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of catalyst combinations for olefinic polymerization
Object and the method for olefinic polymerization, catalyst A used and catalyst B can be achieved keep at relatively high temperatures higher ethylene and
C3~C16Alpha-olefin or cycloolefin copolymer close activity, and resulting polymers molecular weight is higher, and molecular weight distribution is relatively narrow, wears in chain
Block shaped polymer can be prepared under shuttle agent effect, and comonomer C can be passed through3~C16Alpha-olefin or cycloolefin selection and dosage
Control, control the structure and crystal property of resulting polymers.
To achieve the goals above, the present invention provides a kind of carbon monoxide-olefin polymeric for olefinic polymerization, the catalyst group
Closing object is the mixture or reaction product for including following ingredients：
(1) first olefin polymerization catalysis (A), selected from least one of metal complex shown in general formula I：
In general formula I, R1~R5, R7~R11It is identical or different, it is each independently selected from hydrogen, alkyl or halogen, and optionally,
R1With R4Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；M is group IVA metal, and X is identical or different, is selected from halogen
Element, alkyl, oxyl；L is the VIth A race element；
(2) second olefin polymerization catalysis (B), selected from least one of metal complex shown in general formula II：
In general formula II, R1And R4It is identical or different, it is each independently selected from C1-C30Alkyl or C1-C30Miscellaneous alkyl；R2
And R3It is identical or different, it is each independently selected from hydrogen, chlorine, C1-C20Alkyl, contain heteroatomic organic group, and optionally, R2
And R3Mutually cyclization；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl, acid group or amido；N is full
The integer of sufficient M valence state；
(3) chain shuttling agent；
(4) co-catalyst.
The carbon monoxide-olefin polymeric provided according to the present invention, it is preferable that (1) first olefin polymerization catalysis (A) is selected from general formula
At least one of metal complex shown in I：
In general formula I, R1~R5, R7~R11It is identical or different, it is each independently selected from hydrogen, C1~C20Aliphatic group, C6~
C30Aryl radical or halogen, and optionally, R1With R4Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；M is selected from
Titanium, zirconium or hafnium, X is identical or different, is selected from halogen, C1~C20Saturated hydrocarbyl, C2~C20Unsaturated alkyl or C1~C20's
Oxyl；L is selected from O or S element；
(2) second olefin polymerization catalysis (B), selected from least one of metal complex shown in general formula III：
In general formula III, R1And R4It is identical or different, it is each independently selected from C1-C20Alkyl or C1-C20Miscellaneous alkyl；R5
~R8It is identical or different, it is each independently selected from hydrogen, chlorine, C1-C15Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulphur,
Phosphorus, silicon, germanium or tin atom non-ring compound group, and optionally, R5~R8It is mutually cyclic two-by-two；M is group VIII metal；X phase
It is same or different, it is selected from halogen, alkyl or oxyl；N is the integer for meeting M valence state；
(3) chain shuttling agent；
(4) co-catalyst.
The carbon monoxide-olefin polymeric provided according to the present invention, it is preferable that first olefin polymerization catalysis (A) is selected from general formula
At least one of metal complex shown in IV,
In general formula IV, R1~R5, R7, R9, R11It is identical or different, it is each independently selected from hydrogen, C1~C20Aliphatic group,
C6~C30Aryl radical or halogen, and optionally, R1With R4Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；X is
Halogen, M are titanium, zirconium or hafnium；
Second olefin polymerization catalysis (B) is selected from least one of metal complex shown in general formula V,
In general formula V, R11-R20It is identical or different, it is each independently selected from hydrogen, C1-C10Saturated hydrocarbyl, C2-C10Insatiable hunger
With alkyl, C1-C10Alkoxy and halogen；Further preferably it is selected from hydrogen, C1~C6Alkyl, C2~C6Alkenyl, C1~C6's
Alkoxy or halogen；X is halogen, and M is nickel or palladium.
C in the present invention1~C20Aliphatic group refer to C1~C20Alkane or C1~C20Cycloalkane；C1~C20Alkane
Refer to C1~C20Straight chained alkyl or C3-C20Branched alkyl.C in the present invention1~C10Saturated hydrocarbyl refer to C1~C10It is straight
Alkyl group or C3-C10Branched alkyl, non-limiting example includes：It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, secondary
Butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
In the present invention, first olefin polymerization catalysis (A) can be prepared by a conventional method to obtain, such as bibliography
Organometallics,1998,17,2152-2154；Macromolecules, 1998,31,7588-7597；
J.Mol.Catal.A 2009,303,102-109.Related content disclosed in aforementioned documents is all incorporated herein by reference,
Details are not described herein.
The polymerization activity of the carbon monoxide-olefin polymeric provided according to the present invention, second olefin polymerization catalysis (B) is lower than
First olefin polymerization catalysis (A).In general formula V, M can be for example nickel, iron, cobalt, palladium etc., preferably nickel；X is selected from halogen.
Preferably, at least one of second olefin polymerization catalysis (B) metal complex chosen from the followings；General formula
In V, R17-R20It is hydrogen, M is nickel,
Complex 1：R11=R13=R14=R16=Me, R12=R15=H, X=Br；
Complex 2：R11=R13=R14=R16=Et, R12=R15=H, X=Br；
Complex 3：R11=R13=R14=R16=iPr, R12=R15=H, X=Br；
Complex 4：R11=R12=R13=R14=R15=R16=Me, X=Br；
Complex 5：R11=R13=R14=R16=Me, R12=R15=Br, X=Br；
Complex 6：R11=R13=R14=R16=Me, R12=R15=Et, X=Br；
Complex 7：R11=R13=R14=R16=Et, R12=R15=Me, X=Br；
Complex 8：R11=R13=R14=R16=Et, R12=R15=Br, X=Br；
Complex 9：R11=R13=R14=R16=F, R12=R15=H, X=Br；
Complex 10：R11=R13=R14=R16=Cl, R12=R15=H, X=Br；
Complex 11：R11=R13=R14=R16=Br, R12=R15=H, X=Br；
Complex 12：R11=R13=R14=R16=Me, R12=R15=H, X=Cl；
Complex 13：R11=R13=R14=R16=Et, R12=R15=H, X=Cl；
Complex 14：R11=R13=R14=R16=iPr, R12=R15=H, X=Cl；
Complex 15：R11=R12=R13=R14=R15=R16=Me, X=Cl；
Complex 16：R11=R13=R14=R16=Me, R12=R15=Br, X=Cl；
Complex 17：R11=R13=R14=R16=Me, R12=R15=Et, X=Cl；
Complex 18：R11=R13=R14=R16=Et, R12=R15=Me, X=Cl；
Complex 19：R11=R13=R14=R16=Et, R12=R15=Br, X=Cl；
Complex 20：R11=R13=R14=R16=F, R12=R15=H, X=Cl；
Complex 21：R11=R13=R14=R16=Cl, R12=R15=H, X=Cl；
Complex 22：R11=R13=R14=R16=Br, R12=R15=H, X=Cl.
In the present invention, second alkene catalyst (B) can refer to document Macromolecules, and 2009,42,7789-
Complex preparation method disclosed in 7796 obtains, and disclosed related content is all incorporated herein by reference, herein not
It repeats again.
The carbon monoxide-olefin polymeric provided according to the present invention, it is preferable that first olefin polymerization catalysis (A) and the second alkene
The molar ratio of polymerized hydrocarbon catalyst (B) is 1:100~100:1, preferably 10:90~90:10.
The carbon monoxide-olefin polymeric provided according to the present invention, the chain shuttling agent can refer in existing chain shuttle polymerization reaction
It is selected；Preferably, the chain shuttling agent, which is selected from, contains at least one C1-C20The IA of alkyl, II A, IB, the metallization of II B race
Object or complex compound are closed, is more preferably selected from containing C1-C12The aluminium compound of alkyl contains C1-C12The gallium compound of alkyl contains
C1-C12The zinc compound of alkyl；The alkyl is preferably alkyl.
It is further preferred that the chain shuttling agent is selected from least one of trialkylaluminium, dialkyl group zinc and trialkyl gallium,
It is more preferably selected from triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, zinc methide, diethyl
At least one of base zinc and trimethyl gallium.
The carbon monoxide-olefin polymeric provided according to the present invention, the olefin polymerization catalysis are used in combination with co-catalyst, energy
Make the olefin polymerization catalysis that there is higher activity.The co-catalyst can be selected from lewis acid, for instance, it is preferred that institute
The co-catalyst stated is selected from C1-C30The III A compounds of group that alkyl replaces, is more preferably selected from alkylaluminoxane, aryl borane and virtue
At least one of ylboronic acid salt；Further preferably selected from methylaluminoxane, modified methylaluminoxane, triarylborane and four virtues
At least one of ylboronic acid salt.
The carbon monoxide-olefin polymeric provided according to the present invention, it is preferable that aluminium and first alkene in the co-catalyst
The molar ratio of polymerization catalyst (A) and the second olefin polymerization catalysis (B) summation is (10-20000):1 or the co-catalyst
In boron and the molar ratio of first olefin polymerization catalysis (A) and the second olefin polymerization catalysis (B) summation be (0.01-
50):1。
Preferably, first olefin polymerization catalysis (A) and the second olefin polymerization catalysis (B) summation are worn with the chain
The molar ratio of shuttle agent is 1:1~1:20000, preferably 1:1~1:1000.
Carbon monoxide-olefin polymeric of the present invention is used for olefin polymerization.In the polymerization, two kinds of different activities catalysis
Can be prepared in conjunction with the components such as olefin polymerization catalysis and the chain shuttling agent of agent composition include the different segment of performance block
Copolymer.
The present invention also provides a kind of method of olefinic polymerization, this method includes：By the carbon monoxide-olefin polymeric and monomer
Contact carries out copolymerization.
The method provided according to the present invention, it is preferable that the monomer is selected from ethylene, C3~C16Alpha-olefin and C3~C16's
At least one of cycloolefin.
The C3~C16Alpha-olefin or the example of cycloolefin include：Propylene, 1- butylene, 1- amylene, decene, cyclopentene,
Norbornene, 5- methyl -2- norbornene, 1,5- hexadiene etc..
Preferably, alkene described in the method for olefinic polymerization is ethylene or ethylene and C3~C16Alpha-olefin or cyclenes
The combination of hydrocarbon (comonomer).In addition, the dosage of the comonomer can be according to the block copolymer of preparation in practical applications
Required fusing point is adjusted, and details are not described herein.
The method according to the invention, the polymerization reaction are with continuous polymerization, and the preferably mode of continuous solution polymerization carries out
Polymerization reaction.Wherein by catalytic component, one or more shuttling agents, monomer and optional solvent, auxiliary agent, cleanser and
Polymerization reaction auxiliary agent is continuously supplied into reactor, and continuously removes polymerizate in the reaction vessel.The present invention is to institute
The selection for stating solvent in polymerisation in solution is not particularly limited, and can be the conventional selection in olefin polymerization, for example, toluene.
In one embodiment, it is preferable that the condition of the polymerization reaction includes：Temperature is -20~150 DEG C, preferably
It is 20~100 DEG C, more preferably 40~100 DEG C；Pressure is 0.1~10MPa, preferably 0.1~5MPa.
Using above-mentioned polymeric reaction condition, especially using the successive soln of two or more active polymerizing catalyst components
Polymerization.Allow using increased temperature of reactor, this causes multi-block polymer or fragments polymer with high efficiency production.
The reaction condition of uniform plug flow type can be used.
Under the conditions of continuous solution polymerization, compared with chain growth, the shuttle from chain shuttling agent to catalyst becomes excellent
Point, and multi-block polymer of the invention, especially linear polyblock polymer are formed with high efficiency.
Olefine polymerizing process of the invention belongs to the reaction of chain shuttle polymerization, the carbon monoxide-olefin polymeric at high temperature (such as 60
DEG C) polymerization activity still with higher.In the course of the polymerization process, living chain can be in two different catalysis by the chain shuttling agent
The activity of agent (the i.e. described first olefin polymerization catalysis A and the second olefin polymerization catalysis B) is intermediate alternately to be increased, and is then generated
Block copolymer.Prepared high molecular weight fragments polymer (multi-block polymer), it include density or it is other chemistry or
Different two or more of physical property, preferably three or more segments.The polymer has less than 5.0, and preferably smaller than 4.0
Molecular weight distribution Mw/Mn.Molecular weight distribution (the M of the block copolymerw/Mn) 5 are preferably smaller than, more preferably less than 4.
Technical solution of the present invention bring beneficial effect is：In carbon monoxide-olefin polymeric of the invention, the olefinic polymerization
Catalyst can realize ethylene or ethylene and alpha-olefin or cycloolefin (altogether in higher temperature (such as 60 DEG C) and chain shuttling agent cooperation
Polycondensation monomer) copolymerization, be made block polymer under conditions of, the molecular weight of polymer is higher, and molecular weight distribution is relatively narrow, this
The method of invention can also be by the selection of comonomer and the control of dosage, to prepare the block copolymer of different crystal properties.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although being described in embodiment of the invention preferred
Embodiment, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by embodiments set forth herein
System.
The characterization of polymer molecular weight (Mw) and molecular weight distribution (Mw/Mn)：
Molecular weight and its distribution are measured by gel permeation chromatography (GPC), and instrument uses Waters Alliance GPCV
2000, solvent is 1,2,4- trichloro-benzenes, sample concentration lmg/ml, solvent flow rate 1.0ml/min；Measuring temperature is 150 DEG C.
Each sample is surveyed secondary.
The carbon monoxide-olefin polymeric and olefine polymerizing process that the following examples are intended to illustrate the invention.
Embodiment 1
First olefin polymerization catalysis A1【Shown in its structure such as formula (1), synthesis process is shown in document
Organometallics,1998,17,2152-2154】。
Second olefin polymerization catalysis B1【Shown in its structure such as formula (2), synthesis process is shown in document
Macromolecules,2009,42,7789-7796】。
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A1 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 2
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A1 (toluene solution that 6ml concentration is 1.0mM) and catalyst B1 (toluene solution that 4ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 3
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A1 (toluene solution that 2ml concentration is 1.0mM) and catalyst B1 (toluene solution that 8ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Comparative example 1
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) it is added by syringe.Catalyst A1 is added by syringe again, and (5ml concentration is the first of 1.0mM
Benzole soln) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM), continue to be passed through ethylene, pressure is risen to and maintained
1.0MPa, 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Comparative example 2
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) it is added by syringe.Catalyst A1 is added by syringe again, and (6ml concentration is the first of 1.0mM
Benzole soln) and catalyst B1 (toluene solution that 4ml concentration is 1.0mM), continue to be passed through ethylene, pressure is risen to and maintained
1.0MPa, 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Comparative example 3
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) it is added by syringe.Catalyst A1 is added by syringe again, and (2ml concentration is the first of 1.0mM
Benzole soln) and catalyst B1 (toluene solution that 8ml concentration is 1.0mM), continue to be passed through ethylene, pressure is risen to and maintained
1.0MPa, 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Comparative example 4
First olefin polymerization catalysis A1 is added without the second olefin polymerization catalysis B1 with embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (3.2ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (0.5ml concentration be) pass through syringe addition.Pass through note again
Catalyst A1 (toluene solution that 5ml concentration is 1.0mM) is added in emitter, continues to be passed through ethylene, pressure is risen to and maintained
1.0MPa, 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Comparative example 5
Second olefin polymerization catalysis B1 is added without the first olefin polymerization catalysis A1 with embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (3.2ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (0.5ml concentration be) pass through syringe addition.Pass through note again
Catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added in emitter, continues to be passed through ethylene, pressure is risen to and maintained
1.0MPa, 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 4
First olefin polymerization catalysis A1 with embodiment 1,
Shown in the structure such as formula (3) of second olefin polymerization catalysis B2,
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A1 (toluene solution that 5ml concentration is 1.0mM) and catalyst B2 (toluene solution that 5ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 5
First olefin polymerization catalysis A2【Shown in its structure such as formula (4), synthesis process is shown in document
Macromolecules, 1998,31,7588-7597】.
Second olefin polymerization catalysis B1 with embodiment 1,
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A2 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 6
First olefin polymerization catalysis A3【Shown in its structure such as formula (5), synthesis process is shown in document
Macromolecules, 1998,31,7588-7597】,
Second olefin polymerization catalysis B1 with embodiment 1,
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A3 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 7
First olefin polymerization catalysis A4【Shown in its structure such as formula (6), synthesis process is shown in document J.Mol.Catal.A
2009,303,102-109】,
Second olefin polymerization catalysis B1 with embodiment 1,
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (6.5ml concentration is 1.53M's by co-catalyst
Methylaluminoxane toluene solution) and the DEZ DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Pass through injection again
Catalyst A4 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added in device,
Continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cools down, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 8
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is Ph3CB(C6F5)4Four (pentafluorophenyl group) borates, shuttling agent are diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (10ml concentration is 1.0mM's by co-catalyst
Ph3CB(C6F5)4Four (pentafluorophenyl group) borate toluene solutions, the triisobutylaluminum toluene solution that 5ml concentration is 1.0M) and DEZ
(toluene solution that 1ml concentration is 1.5M) is added by syringe.Catalyst A1 is added by syringe again, and (5ml concentration is
The toluene solution of 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM), continue to be passed through ethylene, pressure is risen to
And 1.0MPa is maintained, and 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 9
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A1 (toluene solution that 8ml concentration is 1.0mM) and catalyst B1, (2ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 10
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A1 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1, (5ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 11
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A1 (toluene solution that 2ml concentration is 1.0mM) and catalyst B1, (8ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Comparative example 6
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) it is added by syringe.Catalyst A1 is added by syringe again, and (5ml concentration is
The toluene solution of 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM), continue to be passed through ethylene, pressure is risen to
And 1.0MPa is maintained, and 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Comparative example 7
First olefin polymerization catalysis A1 is added without the second olefin polymerization catalysis B1 with embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 10ml decene, co-catalyst (3.2ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 0.5ml concentration is 1.5M) added by syringe
Enter.Catalyst A1 (toluene solution that 5ml concentration is 1.0mM) is added by syringe again, continues to be passed through ethylene, pressure is risen to
And 1.0MPa is maintained, and 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Comparative example 8
Second olefin polymerization catalysis B1 is added without the first olefin polymerization catalysis A1 with embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 10ml decene, co-catalyst (3.2ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 0.5ml concentration is 1.5M) added by syringe
Enter.Catalyst B1 (toluene solution that 5ml concentration is 1.0mM) is added by syringe again, continues to be passed through ethylene, pressure is risen to
And 1.0MPa is maintained, and 60 DEG C of polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 12
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by the 20ml norbornene (norbornene of 5.0M
Toluene solution), (1ml concentration is 1.5M's by co-catalyst (the methylaluminoxane toluene solution that 6.5ml concentration is 1.53M) and DEZ
DEZ toluene solution) it is added by syringe.Catalyst A1 (toluene solution that 2ml concentration is 1.0mM) is added by syringe again
With catalyst B1 the toluene solution of 1.0mM (8ml concentration be), continue to be passed through ethylene, pressure rises to and maintained 1.0MPa, 60 DEG C
Polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 13
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by the 20ml norbornene (norbornene of 5.0M
Toluene solution), (1ml concentration is 1.5M's by co-catalyst (the methylaluminoxane toluene solution that 6.5ml concentration is 1.53M) and DEZ
DEZ toluene solution) it is added by syringe.Catalyst A1 (toluene solution that 5ml concentration is 1.0mM) is added by syringe again
With catalyst B1 the toluene solution of 1.0mM (5ml concentration be), continue to be passed through ethylene, pressure rises to and maintained 1.0MPa, 60 DEG C
Polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 14
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by the 20ml norbornene (norbornene of 5.0M
Toluene solution), (1ml concentration is 1.5M's by co-catalyst (the methylaluminoxane toluene solution that 6.5ml concentration is 1.53M) and DEZ
DEZ toluene solution) it is added by syringe.Catalyst A1 (toluene solution that 8ml concentration is 1.0mM) is added by syringe again
With catalyst B1 the toluene solution of 1.0mM (2ml concentration be), continue to be passed through ethylene, pressure rises to and maintained 1.0MPa, 60 DEG C
Polymerization reaction 30min, cooling, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
Comparative example 9
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is methylaluminoxane, is added without shuttling agent.
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by the 20ml norbornene (norbornene of 5.0M
Toluene solution), the co-catalyst methylaluminoxane toluene solution of 1.53M (6.5ml concentration be) pass through syringe addition.Pass through again
(5ml concentration is that the toluene of 1.0mM is molten by syringe addition catalyst A1 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1
Liquid), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collected polymer claims
Weight.
Specific polymerization result is listed in Table 2 below.
Embodiment 15
First olefin polymerization catalysis A1 is with embodiment 1, and the second olefin polymerization catalysis B2 is the same as embodiment 4.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A1 (toluene solution that 5ml concentration is 1.0mM) and catalyst B2, (5ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 16
First olefin polymerization catalysis A2 is with embodiment 5, and the second olefin polymerization catalysis B1 is the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A2 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1, (5ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 17
First olefin polymerization catalysis A3 is with embodiment 6, and the second olefin polymerization catalysis B1 is the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A3 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1, (5ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 2 below.
Embodiment 18
First olefin polymerization catalysis A4 is with embodiment 7, and the second olefin polymerization catalysis B1 is the same as embodiment 1.
Co-catalyst is methylaluminoxane, and shuttling agent is diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, by 20ml decene, co-catalyst (6.5ml concentration
For the methylaluminoxane toluene solution of 1.53M) and DEZ (the DEZ toluene solution that 1ml concentration is 1.5M) pass through syringe be added.
By syringe addition catalyst A4 (toluene solution that 5ml concentration is 1.0mM) and catalyst B1, (5ml concentration is 1.0mM's again
Toluene solution), continue to be passed through ethylene, pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, cool down, collects polymerization
Object, weighing.
Specific polymerization result is listed in Table 1 below.
Embodiment 19
First olefin polymerization catalysis A1, the second olefin polymerization catalysis B1 are the same as embodiment 1.
Co-catalyst is Ph3CB(C6F5)4Four (pentafluorophenyl group) borates, shuttling agent are diethyl zinc (DEZ).
The stainless steel polymerization autoclave of 1L is vacuumized and is replaced with nitrogen, the process is repeated twice, then vacuumizes again,
Under ethylene environment, 500 milliliters of toluene solvants are added, with the addition of toluene, (1ml concentration is by 20ml decene, co-catalyst
The Ph of 1.0mM3CB(C6F5)4Four (pentafluorophenyl group) borate toluene solutions), triisobutyl aluminium (5ml concentration be 1.0M toluene
Solution) and the DEZ toluene solution of 1.5M (1ml concentration be) pass through syringe addition.Catalyst A1 is added by syringe again
(toluene solution that 5ml concentration is 1.0mM) and catalyst B1 (toluene solution that 5ml concentration is 1.0mM), continues to be passed through ethylene,
Pressure is risen to and maintained 1.0MPa, 60 DEG C of polymerization reaction 30min, is cooled down, collected polymer, weighing.
Specific polymerization result is listed in Table 2 below.
1 ethylene homo of table closes result
2 ethylene of table and C3-C16Alpha-olefin or cycloolefin copolymer close result
"-" expression is not tested in table 1.
It can be seen from table 1 and 2 with comparative example (catalyst A1 and catalyst B1 is used, but chain shuttling agent is not added)
It compares, is significantly lower than comparative example using the molecular weight distribution of resulting polymers in the embodiment of inventive catalyst composition.Only
Using the comparative example of catalyst A, the polymer molecular weight obtained under the same conditions is smaller, using only the comparative example of catalyst B,
Obtained polymer molecular weight is larger, and the polymer molecular weight distribution Mw/Mn of embodiment 1~19 is smaller, illustrates that working as use includes
It when the composition of catalyst A and catalyst B, is copolymerized under chain shuttling agent effect, forms block polymer, and be not pair
In ratio be used alone catalyst A, B preparation polymer mixture, otherwise in embodiment 1~19 resulting polymers Mw/
Mn should be much larger than 4.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.
Claims (10)
1. a kind of carbon monoxide-olefin polymeric for olefinic polymerization, which is characterized in that the carbon monoxide-olefin polymeric be include following each group
The mixture or reaction product divided：
(1) first olefin polymerization catalysis (A), selected from least one of metal complex shown in general formula I：
In general formula I, R1~R5, R7~R11It is identical or different, it is each independently selected from hydrogen, alkyl or halogen, and optionally, R1With R4
Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；M be group IVA metal, X is identical or different, selected from halogen, alkyl,
Oxyl；L is the VIth A race element；
(2) second olefin polymerization catalysis (B), selected from least one of metal complex shown in general formula II：
In general formula II, R1And R4It is identical or different, it is each independently selected from C1-C30Alkyl or C1-C30Miscellaneous alkyl；R2And R3Phase
It is same or different, it is each independently selected from hydrogen, chlorine, C1-C20Alkyl, contain heteroatomic organic group, and optionally, R2And R3Phase
Mutually cyclization；M is group VIII metal；X is identical or different, is selected from halogen, alkyl, oxyl, acid group or amido；N is to meet M valence state
Integer；
(3) chain shuttling agent；
(4) co-catalyst.
2. carbon monoxide-olefin polymeric according to claim 1, wherein
(1) first olefin polymerization catalysis (A), selected from least one of metal complex shown in general formula I：
In general formula I, R1~R5, R7~R11It is identical or different, it is each independently selected from hydrogen, C1~C20Aliphatic group, C6~C30's
Aryl radical or halogen, and optionally, R1With R4Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；M is selected from titanium, zirconium
Or hafnium, X is identical or different, is selected from halogen, C1~C20Saturated hydrocarbyl, C2~C20Unsaturated alkyl or C1~C20Hydrocarbon oxygen
Base；L is selected from O or S element；
(2) second olefin polymerization catalysis (B), selected from least one of metal complex shown in general formula III：
In general formula III, R1And R4It is identical or different, it is each independently selected from C1-C20Alkyl or C1-C20Miscellaneous alkyl；R5~R8
It is identical or different, it is each independently selected from hydrogen, chlorine, C1-C15Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulphur, phosphorus,
The non-ring compound group of silicon, germanium or tin atom, and optionally, R5~R8It is mutually cyclic two-by-two；M is group VIII metal；X is identical
Or it is different, it is selected from halogen, alkyl or oxyl；N is the integer for meeting M valence state；
(3) chain shuttling agent；
(4) co-catalyst.
3. carbon monoxide-olefin polymeric according to claim 2, wherein first olefin polymerization catalysis (A) is selected from general formula
At least one of metal complex shown in IV,
In general formula IV, R1~R5, R7, R9, R11It is identical or different, it is each independently selected from hydrogen, C1~C20Aliphatic group, C6~
C30Aryl radical or halogen, and optionally, R1With R4Be connected to each other cyclization and/or R2With R5Be connected to each other cyclization；X is halogen
Element, M are titanium, zirconium or hafnium；
Second olefin polymerization catalysis (B) is selected from least one of metal complex shown in general formula V,
In general formula V, R11-R20It is identical or different, it is each independently selected from hydrogen, C1-C10Saturated hydrocarbyl, C2-C10Unsaturated hydrocarbons
Base, C1-C10Alkoxy and halogen；It is preferably selected from hydrogen, C1~C6Alkyl, C2~C6Alkenyl, C1~C6Alkoxy or halogen
Element；X is halogen, and M is nickel or palladium.
4. carbon monoxide-olefin polymeric according to claim 3, wherein second olefin polymerization catalysis (B) is selected from as follows
At least one of metal complex；In general formula V, R17-R20It is hydrogen, M is nickel,
Complex 1：R11=R13=R14=R16=Me, R12=R15=H, X=Br；
Complex 2：R11=R13=R14=R16=Et, R12=R15=H, X=Br；
Complex 3：R11=R13=R14=R16=iPr, R12=R15=H, X=Br；
Complex 4：R11=R12=R13=R14=R15=R16=Me, X=Br；
Complex 5：R11=R13=R14=R16=Me, R12=R15=Br, X=Br；
Complex 6：R11=R13=R14=R16=Me, R12=R15=Et, X=Br；
Complex 7：R11=R13=R14=R16=Et, R12=R15=Me, X=Br；
Complex 8：R11=R13=R14=R16=Et, R12=R15=Br, X=Br；
Complex 9：R11=R13=R14=R16=F, R12=R15=H, X=Br；
Complex 10：R11=R13=R14=R16=Cl, R12=R15=H, X=Br；
Complex 11：R11=R13=R14=R16=Br, R12=R15=H, X=Br；
Complex 12：R11=R13=R14=R16=Me, R12=R15=H, X=Cl；
Complex 13：R11=R13=R14=R16=Et, R12=R15=H, X=Cl；
Complex 14：R11=R13=R14=R16=iPr, R12=R15=H, X=Cl；
Complex 15：R11=R12=R13=R14=R15=R16=Me, X=Cl；
Complex 16：R11=R13=R14=R16=Me, R12=R15=Br, X=Cl；
Complex 17：R11=R13=R14=R16=Me, R12=R15=Et, X=Cl；
Complex 18：R11=R13=R14=R16=Et, R12=R15=Me, X=Cl；
Complex 19：R11=R13=R14=R16=Et, R12=R15=Br, X=Cl；
Complex 20：R11=R13=R14=R16=F, R12=R15=H, X=Cl；
Complex 21：R11=R13=R14=R16=Cl, R12=R15=H, X=Cl；
Complex 22：R11=R13=R14=R16=Br, R12=R15=H, X=Cl.
5. carbon monoxide-olefin polymeric according to claim 1, wherein first olefin polymerization catalysis (A) and the second alkene
The molar ratio of polymerized hydrocarbon catalyst (B) is 1:100~100:1, preferably 10:90~90:10.
6. carbon monoxide-olefin polymeric according to any one of claims 1-5, wherein the chain shuttling agent is selected from containing at least
One C1-C20The IA of alkyl, II A, IB, II B race metallic compound or complex compound, are preferably selected from containing C1-C12The calorize of alkyl
It closes object, contain C1-C12The gallium compound of alkyl contains C1-C12The zinc compound of alkyl；The alkyl is preferably alkyl；
The chain shuttling agent is preferably selected from least one of trialkylaluminium, dialkyl group zinc and trialkyl gallium, is more preferably selected from three
Aluminium ethide, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, zinc methide, diethyl zinc and trimethyl
At least one of gallium.
7. carbon monoxide-olefin polymeric according to any one of claims 1-5, wherein the co-catalyst is selected from C1-C30
The III A compounds of group that alkyl replaces, is preferably selected from least one of alkylaluminoxane, aryl borane and aromatic yl acid salt；More
It is preferably selected from least one of methylaluminoxane, modified methylaluminoxane, triarylborane and four aromatic yl acid salts.
8. carbon monoxide-olefin polymeric according to claim 1, wherein the aluminium and first alkene in the co-catalyst are poly-
The molar ratio for closing catalyst (A) and the second olefin polymerization catalysis (B) summation is (10-20000):1 or the co-catalyst in
Boron and the molar ratio of first olefin polymerization catalysis (A) and the second olefin polymerization catalysis (B) summation be (0.01-
50):1；
Mole of first olefin polymerization catalysis (A) and the second olefin polymerization catalysis (B) summation and the chain shuttling agent
Than being 1:1~1:20000, preferably 1:1~1:1000.
9. a kind of method of olefinic polymerization, which is characterized in that this method includes：It is urged of any of claims 1-8
Agent composition and monomer contact carry out copolymerization.
10. according to the method described in claim 9, wherein, the monomer is selected from ethylene, C3~C16Alpha-olefin and C3~C16's
At least one of cycloolefin；The condition of the polymerization reaction includes：Temperature is -20~150 DEG C, and pressure is 0.1~10MPa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022024549A1 (en) * | 2020-07-31 | 2022-02-03 | ポリプラスチックス株式会社 | Method for producing cycloolefin copolymer |
| WO2022070958A1 (en) * | 2020-10-02 | 2022-04-07 | ポリプラスチックス株式会社 | Method for producing cycloolefin copolymer |
| CN114853964A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and method for producing the same |
| CN115109189A (en) * | 2022-06-15 | 2022-09-27 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
| CN115246896A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Double/multi-metal catalyst and preparation method and application thereof |
| CN115246893A (en) * | 2021-04-28 | 2022-10-28 | 中国石油化工股份有限公司 | Catalyst composition for preparing bimodal polyolefin and preparation method and application thereof |
| CN116023537A (en) * | 2021-10-26 | 2023-04-28 | 中国石油化工股份有限公司 | Catalyst composition for olefin polymerization and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954005A (en) * | 2004-03-17 | 2007-04-25 | 陶氏环球技术公司 | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
| CN101531725A (en) * | 2009-04-08 | 2009-09-16 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene |
| CN101812145A (en) * | 2009-04-08 | 2010-08-25 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene |
-
2017
- 2017-05-12 CN CN201710335588.XA patent/CN108864337B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1954005A (en) * | 2004-03-17 | 2007-04-25 | 陶氏环球技术公司 | Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation |
| CN101531725A (en) * | 2009-04-08 | 2009-09-16 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene |
| CN101812145A (en) * | 2009-04-08 | 2010-08-25 | 中山大学 | Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene |
Non-Patent Citations (2)
| Title |
|---|
| FENG-SHOU LIU ET AL.: "Thermostable R-Diimine Nickel(II) Catalyst for Ethylene Polymerization:", 《MACROMOLECULES》 * |
| XIAO ANGUO ET AL.: "Study the Influences of ZnEt2 on Ethylene Chain Transfer Polymerization", 《ADVANCED MATERIALS RESEARCH》 * |
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| WO2022024549A1 (en) * | 2020-07-31 | 2022-02-03 | ポリプラスチックス株式会社 | Method for producing cycloolefin copolymer |
| WO2022070958A1 (en) * | 2020-10-02 | 2022-04-07 | ポリプラスチックス株式会社 | Method for producing cycloolefin copolymer |
| JP2022060008A (en) * | 2020-10-02 | 2022-04-14 | ポリプラスチックス株式会社 | Method for producing cycloolefin copolymer |
| JP7073467B2 (en) | 2020-10-02 | 2022-05-23 | ポリプラスチックス株式会社 | Method for Producing Cyclic Olefin Copolymer |
| CN114853964A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and method for producing the same |
| CN114853964B (en) * | 2021-02-04 | 2023-12-22 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and process for producing the same |
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