CN105482001B - A kind of carbon monoxide-olefin polymeric for vinyl polymerization - Google Patents
A kind of carbon monoxide-olefin polymeric for vinyl polymerization Download PDFInfo
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- CN105482001B CN105482001B CN201410479683.3A CN201410479683A CN105482001B CN 105482001 B CN105482001 B CN 105482001B CN 201410479683 A CN201410479683 A CN 201410479683A CN 105482001 B CN105482001 B CN 105482001B
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Abstract
The present invention relates to a kind of carbon monoxide-olefin polymeric for vinyl polymerization, to form the polymer product with peculiar physical properties.The invention further relates to the region comprising two or more different physical characteristics or the polymer product of fragment (block).The carbon monoxide-olefin polymeric includes the mixture or reaction product of following material：First olefin polymerization catalysis (A)；Second olefin polymerization catalysis (B), under equivalent polymerization conditions, its prepare polymer from by polymer phase prepared by catalyst (A) than with different chemically or physically features；And chain shuttling agent.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymeric for vinyl polymerization, to form the polymerization with peculiar physical properties
Thing product.The invention further relates to the region comprising two or more different physical characteristics or the polymerization produce of fragment (block)
Thing.
Background technology
The polymer of block type structure usually has more excellent compared with random copolymerization compound and blend for a long time
Property.For example, the triblock copolymer of styrene and butadiene (SBS) and their hydrogenation transformed object (SEBS) are with excellent
Heat resistance and elasticity.With thermoplastic elastomer (TPE) (TPE), famous block copolymer in polymer chain due to having " soft "
Or elastic " firmly " the crystallizable part of fragment connection.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 turn into 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 available 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 copolymers, each
Polymer chain needs the initiator of stoichiometric(al) amount and resulting polymer has very narrow molecular weight distribution mw/mn, excellent
Select 1.0 to 1.3.In addition, anion and radical polymerization are relatively slow, its industrialization development is influenceed.
It is desirable to realize preferably control catalytic process production block copolymer, i.e. every kind of 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 ethene,
Segmented copolymer of the production with have both high-crystallinity and indefiniteness block or fragment.
Researcher was already indicated above some homogeneous coordination polymerization catalysts and can turned by suppressing chain during polymerization in the past
Move and the polymer with block structure is made.For example, in polymerization process, by reducing chain-transferring agent as far as possible and reducing reaction temperature
Degree, β-hydrogen migration or chain tra nsfer is controlled to prepare block polymer.Under these conditions, it is believed that the order addition meeting of different monomers
Result in the polymer of sequence or fragment with different monomers content.Some of above-mentioned carbon monoxide-olefin polymeric and method are implemented
Example is described in Coates, Hustad and Reinartz Angew.Chem.Int.Ed., 2002,41,2236-2257 and US-A-
In 2003/0114623.
Known in the art is to turn by using some alkyl metal cpds and other compounds such as hydrogen as chain
Agent is moved to interrupt the chain in olefinic polymerization to increase.In addition, alkyl aluminum compound would generally be selected as net in olefin polymerization process
Agent or cocatalyst.In Macromolecules, 2000,33,9192-9199, it was recently reported that by by some trialkylaluminiums
Compound is used in combination with some zirconocene catalysts compositions in pairs, generated while comprising a small amount of complete as chain-transferring agent
The polypropylene block polymers of the polymer of structure chain fragment are found with vertical structure and trackless.Liu's and Rytter
Macromolecules, in 2003,3026-3034 articles, also report trimethyl aluminium chain-transferring agent with similar catalyst group
Close catalysis ethene and 1- hervene copolymers.
Report in USP6,380,341 and 6,169,151, by using " vertical structure " metallocene catalyst, urged by this
Agent aggregation features of mutually conversion performance differential responses speed etc. between two kinds of spatial configurations form the alkene of " block-wise " structure
Hydrocarbon polymer.
It is well known that alpha-diimine nickel and palladium catalyst can form branched (height during polymerization by " chain tra nsfer "
It is branched) 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
Double (indenyl) zirconium complexs of 2- t-butyldimethylsilyloxies base substitution and MAO cocatalyst catalysis ethene 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.
Having article report at present uses diimine nickel metal to realize chain under diethyl zinc effect with metallocene catalyst
Shuttle polymerization reacts (Macromolecules 2009,42,1834-1837), but polymerization temperature is relatively low, 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 carries
It is high and decline rapidly.And existing ethene gas-phase polymerization technological requirement polymerization temperature is more than 85 DEG C, vinyl solution polymerization technique will
It is 150-250 DEG C to seek polymerization temperature, and original late transition metal catalyst can not meet existing gas phase, solwution method ethylene polymerization plants
Requirement.Catalyst A and catalyst B provided by the invention can keep higher ethylene polymerization activity at relatively high temperatures, and
Resulting polymers molecular weight is higher, and molecular weight distribution is narrower, and block shaped polymer can be prepared under chain shuttling agent effect.
The content of the invention
It is (more to form block polymer it is an object of the invention to provide a kind of carbon monoxide-olefin polymeric for vinyl polymerization
Block polymer).The polymer is excellent wherein comprising different two or more of one or more chemically or physically characteristics
Fragment or the block of more than three is selected, said composition includes the mixture or reaction product of following material：
(1) first olefin polymerization catalysis (A),
Heretofore described catalyst (A) includes following non-metallocene compound, refers to the gold shown in formula 1 or 2
Metal complex：
Formula 1
In formula 1, R1Selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical, R2-R6It is identical
Or it is different, it is hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20Aryl radical, it is described
Any hydrogen or carbon atom are optionally substituted by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hetero atom on alkyl；
M is the transition metal of IV B races in the periodic table of elements, and X is in halogen, alkyl, oxyl, acid group and amido
One kind, when n is two or more, multiple X groups are identical or different；M and n is 1-3 integer, and m+n=4；
Formula 2
In formula 2, M is the transition metal of IV B races in the periodic table of elements；N is 1-30 integer, when m is two or more,
Multiple X groups are identical or different；M is the integer for meeting M valence states；
The one kind of X in halogen, alkyl, oxyl, acid group and amido；
R1-R8It is identical or different, it is hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20's
Aryl radical, any hydrogen or carbon atom on the alkyl are optionally miscellaneous by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin
Atom substitutes；
R9-R10It is identical or different, selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical；
R1-R10In two or more groups optionally mutually bonded cyclization；
Y is a bridge joint group, is C1-C20Aliphatic group or C6-C20Aryl radical, any hydrogen on the alkyl
Or carbon atom is optionally substituted by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hetero atom；
(2) second olefin polymerization catalysis (B), under equivalent polymerization conditions, its prepare polymer with by catalyst (A)
The polymer phase of preparation is than with different chemically or physically features.Catalyst (B) of the present invention meets formula 3：
Formula 3
In formula 3, R1And R4It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；R2And R3Be respectively selected from hydrogen atom, chlorine atom,
C1-C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, the organic group of germanium or tin atom；And R2And R3
It is optionally mutually cyclic；M is VIII race's metal；
Existing n X is identical or different, selected from halogen, alkyl, oxyl, acid group or amido；N is meet M valence states whole
Number；
At least one of catalyst (A) or catalyst (B) can be by chain tra nsfers, or are incorporated to the alkene being formed in situ again
Belong to polymer chain and form branched polymer；With
(3) chain shuttling agent.
It is preferred that said composition includes the mixture or reaction product of following material：
(1) first olefin polymerization catalysis (A), it can form highly crystalline Alathon by vinyl polymerization；Its
Formula is as shown in formula 1 or formula 2, in formula 1, R1Selected from C1-C20Aliphatic group or C6-C30Aryl radical, R2-
R6Selected from hydrogen atom, halogen atom or C1-C20Aliphatic group；M is selected from titanium, zirconium or hafnium；X is selected from halogen or alkyl；M and n is 2；
In formula 2, M is selected from titanium, zirconium or hafnium；N is 1-10 integer；R1-R8Selected from hydrogen atom, halogen atom or C1-C20Aliphatic group；
R9-R10Selected from C1-C20Fat or aryl radical；X is selected from halogen or alkyl；Y is a bridge joint group, selected from C1-C20Fat
Fat alkyl or C6-C20Aryl radical.
(2) second olefin polymerization catalysis (B), it can be by chain tra nsfer, or is incorporated to the olefinic being formed in situ again and gathers
Compound chain forms branched polymer；Catalyst (B) is complex of the structure as shown in formula 4：
Formula 4
In formula 4, R9And R10It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；R5-R8It is respectively selected from hydrogen atom, chlorine atom, C1-
C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulphur, phosphorus, silicon, the organic group of germanium or tin atom；And R5-R8Appoint
Selection of land is mutually cyclic；M is VIII race's metal；Existing n X is identical or different, selected from halogen, alkyl, oxyl；N is to meet M valencys
The integer of state；With
(3) chain shuttling agent.
In another embodiment of the invention, there is provided a kind of method for preparing block polymer, methods described are included in
Ethene is contacted with composition under addition polymerization conditions, the composition includes the mixture or reaction product of following material：
(1) first olefin polymerization catalysis (A)；
(2) second olefin polymerization catalysis (B), under equivalent polymerization conditions, its prepare polymer with by catalyst (A)
The polymer phase of preparation is than with different chemically or physically features.At least one in catalyst (A) or catalyst (B) can
By chain tra nsfer, or the ethylenic polymer chain being formed in situ is incorporated to again and forms branched polymer；With
(3) chain shuttling agent.
Catalyst (B) more preferably complex of the self-structure as shown in formula 5：
Formula 5
In formula 5：R1And R2For alkyl or halogen, X is halogen, and M is nickel or palladium.
Catalyst (B) is most preferably from following complex in the present invention：
1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；2：R1=R3=R4=R6=Et, R2=R5=H, X=
Br；3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；4：R1=R2=R3=R4=R5=R6=Me, X=Br；5：R1
=R3=R4=R6=Me, R2=R5=Br, X=Br；6:R1=R3=R4=R6=Me, R2=R5=Et, X=Br7：R1=R3=
R4=R6=Et, R2=R5=Me, X=Br；8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；9：R1=R3=R4=R6
=Me, R2=R5=H, X=Cl；10：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；11：R1=R3=R4=R6=
IPr, R2=R5=H, X=Cl；12：R1=R2=R3=R4=R5=R6=Me, X=Cl；13：R1=R3=R4=R6=Me, R2
=R5=Br, X=Cl；14：R1=R3=R4=R6=Me, R2=R5=Et, X=Cl；
15：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；16：R1=R3=R4=R6=Et, R2=R5=Br, X
=Cl；
Suitable chain shuttling agent includes containing at least one C1-20The IA of alkyl, II A, IB or the metallic compound of II B races
Or complex compound, preferably comprise C1-12Aluminium, gallium or the zinc compound of alkyl.Preferable alkyl is alkyl, more preferably linear or branched
C2-8Alkyl.The chain shuttling agent of the present invention most preferably with is trialkylaluminium and dialkyl zinc compounds, especially triethyl group
Aluminium, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triethyl-gallium and diethyl zinc.Other is suitable
Chain shuttling agent include reaction product or the mixture combined to form by above-mentioned metallic compound and secondary amine or hydroxy compounds, institute
State amido in secondary amine or hydroxy compounds or hydroxyl summation is less than alkyl summation in above-mentioned metallic compound.The secondary amine or
Hydroxy compounds especially HMDS, 2- hydroxymethylpyridines, two (n-pentyl) amine, 2,6- bis- (tert-butyl group) phenol,
Ethyl (1- naphthyls) amine or 2,6- diphenyl phenol.It is it is preferred that anti-using the secondary amine or hydroxy compounds and metallic compound of sufficient amount
Should so that each metallic atom comprises only an alkyl in the reaction product.In above-mentioned reaction product, the present invention is most preferably for
What it is as chain shuttling agent is octyl aluminum two (double (trimethyl silyl) acid amides), the double (dimethyl (tert-butyl group) of isopropyl aluminium
Monosilane oxide, aluminium ethide two (double (trimethyl silyl) acid amides), zinc ethyl (2,6- diphenyl benzenes phenates).
The present invention can be by with reference to cocatalyst, preferred cationic forming cocatalysts or lewis acid or its combination
Thing, foregoing catalyst (A) and (B) are activated to form effective carbon monoxide-olefin polymeric.In preferable scheme, in order to which chain is worn
Shuttle and use chain shuttling agent as the cocatalyst component of carbon monoxide-olefin polymeric.
It is required, by being combined with the cocatalyst of cation form, such as the previous known and IV B races metal network in this area
Some cocatalyst that compound is used together, make metal complex have catalytic activity.Suitable cation shape used herein
State cocatalyst includes neutral lewis acid, such as C1-30III A compounds of group of alkyl substitution, preferably trialkyl aluminium, trialkyl
Boron compound and its there is in each alkyl or halohydrocarbyl halo (including perhalogeno) derivative of 1 to 10 carbon, more
It is preferred that fluoridized triarylboron, most preferably three (pentafluorophenyl group) borines.
Cation forming cocatalysts and lewis acidic conjugate, especially C1-4Alkyl aluminum compound and C1-20Alkyl
The conjugate of haloboronated thing preferably three (phenyl-pentafluoride base) borine.Above-mentioned Lewis acid mixture and aikyiaiurnirsoxan beta oligomer
The conjugate of further conjugate, and single lewis acid, especially three (pentafluorophenyl group) borines and aikyiaiurnirsoxan beta oligomer can
For use as activating cocatalysts.
It in the present invention, can include that the Bronsted of proton can be contributed as the ionic formses compound of cocatalyst
The cation of acid, and compatible, noncoordinating anion A-.Preferable anion is those the moon comprising single co-ordination complex
Ion, the co-ordination complex include electrically charged metal or metalloid core, and wherein anion can be balanced when two components
The electric charge for the active catalyst species (metal cation) being likely to form during mixing.In addition, the anion should be unstable
, it is sufficient to substituted with olefinic, diolefins and acetylene series unsaturated compound or other neutral Lewis bases such as ether or nitrile.Close
Suitable metal includes but is not limited to lead, gold and platinum.Suitable nonmetallic including but not limited to boron, phosphorus and silicon.
It is preferred that above-mentioned cocatalyst can be represented by general formula：
(L*-H)g +(A)G-
Wherein：
L*It is neutral Lewis base；
(L*-H)+It is L*Conjugate Bronsted acid；
AG-It is with g-Noncoordinating, the compatible anion of electric charge；With
G is 1 to 3 integer.
More preferably AG-Meet chemical formula：[M’Q4]-；
Wherein：
M ' is+3 positive oxidation state boron or aluminium；With
Each existing Q independently selected from hydride, dialkylamido, halide, alkyl, oxyl, chloro alkyl,
Chloro oxyl and silylhydrocarbyl (including perhalogeno alkyl, full halogenated hydrocarbon epoxide and the perhalogenated monosilane of halogen substitution
Base alkyl), the Q has at most 20 carbon.
In a preferred scheme, g 1.That is, ion balance has single negative electrical charge i.e. A-.Including boron
Preparation of the activating cocatalysts to catalyst of the present invention be particularly useful, it can be represented by general formula：
(L*-H)+(BQ4)-
Wherein：
L*It is as defined in previous；
B is+3 positive oxidation state boron；With
Q is alkyl, oxyl, fluorination alkyl, fluorination oxyl or silyl fluoride base alkyl, and it is non-with most 20
Hydrogen atom.
Preferable Louis's alkali salt is ammonium salt, more preferably comprising one or more C12-40The trialkyl ammonium salts of alkyl.It is optimal
The each existing Q of choosing is fluoro aryl, especially phenyl-pentafluoride base.
In the preparation of the improved catalyst of the present invention, may be used as the example of the boron compound of activating cocatalysts is：
The ammonium salt of three substituents is such as：Trimethyl ammonium four (phenyl-pentafluoride base) borate, triethyl ammonium four (phenyl-pentafluoride base)
Borate, tripropyl ammonium four (phenyl-pentafluoride base) borate, three (normal-butyl) ammonium four (phenyl-pentafluoride base) borates, N, N- diformazans
Base aniline four (phenyl-pentafluoride base) borate, DMA normal-butyl three (phenyl-pentafluoride base) borate, N, N- diformazans
Base aniline benzyl three (phenyl-pentafluoride base) borate, DMA four (4- (t-butyldimethylsilyl) -2,3,
5,6- tetrafluoro phenyl) borate, DMA four (4- (triisopropylsilyl) -2,3,5,6- tetrafluoro phenyl) boron
Hydrochlorate, N, N- diethylanilines four (phenyl-pentafluoride base) borate, dimethyl stearyl ammonium four (phenyl-pentafluoride base) borate.
Dialkyl ammonium salt is such as：Two-(isopropyl) ammonium four (phenyl-pentafluoride base) borates, (five fluorine of methyl octadecyl ammonium four
For phenyl) borate, the pungent dodecyl ammonium four of methyl (phenyl-pentafluoride base) borate and the (phenyl-pentafluoride of hexatriacontane base ammonium four
Base) borate.
Trisubstituted phosphonium salt is such as：Triphenylphosphine four (pentafluorophenyl group) borate, methyl hexatriacontane base phosphine (pentafluorophenyl group)
Borate and three (2,6- 3,5-dimethylphenyl) phosphine four (pentafluorophenyl group) borates.
The mol ratio of the catalyst/cocatalyst used is preferably 1：10,000 to 100：1, more preferably 1：5000 to 10：
1, most preferably 1：1000 to 1：1.When aikyiaiurnirsoxan beta is used as activating cocatalysts in itself, largely using aikyiaiurnirsoxan beta, typically with mole
On the basis of be at least 100 times of metal complex dosage.When three (pentafluorophenyl group) borines are as activating cocatalysts, used
Three (pentafluorophenyl group) borines and the mol ratio of metal complex be 0.5:1 to 10:1, more preferably 1:1 to 6:1, most preferably 1:1
To 5:1.Other activating cocatalysts are typically used with amount about equimolar with metal complex.
In composition of the present invention, the mol ratio of the catalyst (A) and catalyst (B) is 1:100~100:
1, catalyst (A) is 1 with the summation of catalyst (B) and the mol ratio of chain shuttling agent:1~1:1000, preferably 1:1~1:200.
Used catalyst of the present invention is to carry out polymerisation with continuous polymerization, the preferably mode of continuous solution polymerization.Wherein
Catalytic component, one or more shuttling agents, monomer and optional solvent, auxiliary agent, cleanser and polymerisation auxiliary agent are connected
Conversion zone is fed to continuously, and continuously removes polymerizate there.
Carbon monoxide-olefin polymeric can be advantageously used in high pressure, solution, slurry or gas phase polymerization process.Gather for solution
For conjunction method, it is desirable to using dispersed system of the catalytic component in liquid diluent, wherein being used
Polymeric reaction condition under polymer be soluble.The solution polymerization process of the novel polymer of the present invention is prepared, is especially connected
Continuous solution polymerization process is preferably between 70 DEG C to 250 DEG C, more preferably between 80 DEG C to 210 DEG C, and most preferably 80 to
Carried out at a temperature of between 150 DEG C.High pressure method is typically under the pressure at a temperature of 100 DEG C to 400 DEG C and more than 50MPa
Carry out.Slurry method typically essentially becomes using inert hydrocarbon diluent and from 0 DEG C to caused polymer and dissolves in inertia
Temperature under the temperature of polymerisation medium.Preferable temperature is from 30 DEG C to 115 DEG C, more preferably from 60 in slurry polymerization
DEG C to 115 DEG C, most preferably up to 100 DEG C.The general range of pressure is from normal pressure (100kPa) to 500psi (3.4MPa).
In all above methods, preferably using continuously or substantially continuous polymerizing condition.It is anti-using above-mentioned polymerization
Answer condition, especially use the continuous solution polymerization method of two or more active polymerizing catalyst materials.Allow using increase
Temperature of reactor, this causes multi-block polymer or fragments polymer with high efficiency production.Uniform plug flow can be used
The reaction condition of type.
The above method is taken to form block polymer, especially multi-block polymer, preferably linear polyblock polymer
The form of successive soln method.Using non-interchangeable multiple catalyst, i.e. these catalyst have different chemical property.
Under the conditions of continuous solution polymerization, compared with chain increases, the shuttle from chain shuttling agent to catalyst turns into advantage, and with height
Efficiency forms multi-block polymer of the invention, especially linear polyblock polymer.
In another embodiment of the present invention, there is provided a kind of HMW fragments polymer from ethene preparation is (more
Block polymer), it includes density or different two or more of other chemically or physically properties, preferably more than three
Fragment.It is preferred that the block polymer is ethene or Noblen or ethene and C3-8Alpha-olefin copolymer.The polymer
With less than 4.0, preferably smaller than 2.8 molecular weight distribution mw/mn.
In yet another embodiment of the present invention, there is provided the functional derivative of above-mentioned fragment or multi-block polymer.
In further embodiment of the invention, there is provided a kind of polymeric blends, including：(1) organic or inorganic
The copolymer of the homopolymer and/or ethene or propylene of polymer, optimal ethylene or propylene and copolymerizable comonomer, and (2)
Of the invention or HMW multi-block polymer prepared according to the methods of the invention.In a desired embodiment,
Component (1) is the matrix polymer for including high density polyethylene (HDPE) or isotactic polypropylene, and component (2) is the more block polymerizations of elastomer
Thing.In a preferred scheme, component (2) is included in being mingled with for the matrix polymer that is formed during component (1) and (2) mix
Thing.
In addition, the polymer of the present invention can preferably have the second of 130J/g or smaller heat of fusion, at least 50 weight %
Alkene content (i.e.-CH2-CH2Polymer segments), less than -25 DEG C, more preferably less than -30 DEG C of glass transition temperature Tg。
In addition, the polymer of the present invention can have 0.01 to 2000 grams/10 minutes, preferably from 0.01 to 1000 gram/10
Minute, more preferably from 0.01 to 500 gram/the melt index I of 10 minutes2.Required, polymer of the invention can have 1,
000 gram/mol to 5,000,000 gram/mol, preferably from 1000 grams/mol to 1,000,000 gram/mol, more preferably from
10000 grams/mol to 800,000 grams/mol of molecular weight Mw.The density of the polymer of the present invention can 0.80 arrive 0.99g/
cm3With preferably for being from 0.85g/cm for the polymer comprising ethene3To 0.97g/cm3。
In the present invention, catalyst A and B are used in conjunction with as composition, and any of which is used alone and cannot get block
Polymer.Compared compared with document, catalyst B of the invention still has greater activity at high temperature, can be at high temperature with catalysis
Agent A collective effect catalyzed ethylene polymerizations, obtain the block polymer of special construction.
Embodiment
The following specific embodiment of the present invention and its to combine be especially desirably, and in order to which attached right after providing will
The detailed content asked is described herein following embodiment.
The sign of polymer molecular weight (Mw) and molecular weight distribution (Mw/Mn)：Molecular weight and its distribution are by gel infiltration color
(GPC) measure is composed, instrument uses Waters Alliance GPCV 2000, and solvent is 1,2,4- trichloro-benzenes, and sample concentration is
Lmg/ml, solvent flow rate 1.0ml/min；Measurement temperature is 150 DEG C.Each sample is surveyed secondary.
Embodiment 1
Catalyst (A1) is double-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride【(L1)2ZrCl2, its
Chinese patent CN101173011, embodiment 6 are shown in synthesis, and its structure sees below formula】.
Catalyst (B1) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
In 1 liter of stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 500 milliliters of toluene
Solvent, with the addition of toluene, by cocatalyst (2ml concentration is 1.53M methylaluminoxane toluene solution) and DEZ, (1ml is dense
Spend the DEZ toluene solutions for 1.5M) added by syringe.Adding catalyst A1 by syringe again, (5ml concentration is 1.0mM
Toluene solution) and catalyst B1 (5ml concentration be 1.0mM toluene solution), pressure is risen to and maintains 1.0MPa, 90 DEG C are poly-
Reaction 30min is closed, cooling, collected polymer, is weighed.
Specific polymerization result is listed in Table 1 below.
Embodiment 2
Catalyst (A1) is double-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride.
Catalyst (B2) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is listed in Table 1 below with embodiment 1, specific polymerization result.
Embodiment 3
Catalyst (A2) is double-[N- (3- phenyl-salicylidene) aniline] zirconium dichloride.
Catalyst (B1) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is listed in Table 1 below with embodiment 1, specific polymerization result.
Embodiment 4
Catalyst (A3) such as following formula (Chinese patent CN1769310, embodiment 2 are shown in synthesis)
Catalyst (B3) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is listed in Table 1 below with embodiment 1, specific polymerization result.
Embodiment 5
Catalyst (A4) such as following formula (Chinese patent CN1769310, embodiment 1 are shown in synthesis)
Catalyst (B4) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
In addition to polymerizing condition is 110 DEG C of polymerisation 30min, other courses of reaction are the same as embodiment 1.Specific polymerization result row
In table 1.
Embodiment 6
Catalyst (A1) is double-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride
Catalyst (B1) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
In 1 liter of stainless steel polymerization autoclave, with nitrogen and ethene, respectively displacement three times, then adds 500 milliliters of toluene
Solvent, with the addition of toluene, by cocatalyst, (1ml concentration is 1.0mM DMA four (pentafluorophenyl group) boric acid
Salt toluene solution) and DEZ (1ml concentration be 1.5M toluene solution) added by syringe.Added and be catalyzed by syringe again
(5ml concentration is 1.0mM toluene solution, and 1- hexenes by agent A1 (5ml concentration is 1.0mM toluene solution) and catalyst B1
10ml, pressure is risen to and maintains 1.0MPa, 90 DEG C of polymerisation 30min, cooling, collected polymer, weighed.
Specific polymerization result is listed in Table 1 below.
Embodiment 7
Catalyst (A2) is double-[N- (3- phenyl-salicylidene) aniline] zirconium dichloride.
Catalyst (B1) is：
Cocatalyst is DMA four (pentafluorophenyl group) borate, and shuttling agent is diethyl zinc (DEZ).
In addition to no addition 1- hexenes, other courses of reaction are the same as embodiment 6.Specific polymerization result is listed in Table 1 below.
Embodiment 8
Catalyst (A2) is double-[N- (3- phenyl-salicylidene) aniline] zirconium dichloride.
Catalyst (B3) is：
Cocatalyst is DMA four (pentafluorophenyl group) borate, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is listed in Table 1 below with embodiment 7, specific polymerization result.
Comparative example 1
Catalyst (A1) is double-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride
Catalyst (B5) is：
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is listed in Table 1 below with embodiment 1, specific polymerization result.
Comparative example 2
Catalyst is A1 pairs-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride.
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is with embodiment 1, using only double-[N- (the 3- tert-butyl groups-salicylidene) cyclohexylamine] zirconium dichloride
As catalyst, specific polymerization result is listed in Table 1 below.
Comparative example 3
Catalyst is that B1 brominations [11,12- (9,10- dihydro -9,10- ethylenes anthracene) two (contracting 2,6- diisopropyl anilines)] are closed
Nickel (II).
Cocatalyst is MAO, and shuttling agent is diethyl zinc (DEZ).
Polymerization process is with embodiment 1, using only bromination [11,12- (9,10- dihydro -9,10- ethylene anthracene) two (contracting 2,6- bis-
Isopropyl aniline)] close nickel (II) be used as catalyst, specific polymerization result is listed in Table 1 below.
The vinyl polymerization result of table 1
"-" represents not tested in table 1.
As can be seen from Table 1, (catalyst A1 and catalyst B5 is used, but catalyst B5 structure is different from comparative example 1
The present invention) compare, still there is higher polymerization activity, gained polymerization under the high temperature conditions using the carbon monoxide-olefin polymeric of the present invention
The molecular weight of thing is apparently higher than comparative example 1.Catalyst A1, the polymer molecule obtained under the same conditions is used only in comparative example 2
Amount is smaller, and catalyst B1 is used only in comparative example 3, and obtained polymer molecular weight is larger, the polymer molecular weight of embodiment 1~8
Distribution Mw/Mn is smaller, illustrates when using the composition for including catalyst A and catalyst B, to form under chain shuttling agent effect
The mixture of homopolymer prepared by catalyst A1, B1 is used alone in block polymer, rather than comparative example 2 and 3, otherwise embodiment
The Mw/Mn of resulting polymers should be much larger than 4 in 1~8.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (22)
1. a kind of carbon monoxide-olefin polymeric for vinyl polymerization, include the mixture or reaction product of following material：
1) the first olefin polymerization catalysis (A), it is the metal complex shown in formula 1：
In formula 1, R1Selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical, R2-R5For hydrogen, R6For
C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20Aryl radical, any hydrogen or carbon atom are optional on described alkyl
Ground is substituted by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hetero atom；
M is the transition metal of IV B races in the periodic table of elements, and X is halogen, and when n is two or more, multiple X groups are identical or not
Together；M and n is 1-3 integer, and m+n=4；
2) the second olefin polymerization catalysis (B), the complex selected from structure as shown in formula 5：
In formula 5：R1-R6For alkyl or halogen, X is halogen；With
3) chain shuttling agent.
2. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that in formula 1；M is selected from titanium, zirconium or hafnium；M and
N is 2.
3. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the catalyst (B) is selected from following cooperation
Thing：
1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；4：R1=R2=R3=R4=R5=R6=Me, X=Br；
5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；6:R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
9：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；10：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
11：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；12：R1=R2=R3=R4=R5=R6=Me, X=Cl；
13：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；14：R1=R3=R4=R6=Me, R2=R5=Et, X=
Cl；
15：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；16：R1=R3=R4=R6=Et, R2=R5=Br, X=
Cl。
4. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the chain shuttling agent be trialkylaluminium and/or
Dialkyl zinc compounds.
5. carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the chain shuttling agent is triethyl aluminum, three different
At least one of propyl group aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triethyl-gallium and diethyl zinc.
6. according to the carbon monoxide-olefin polymeric any one of claim 1-5, it is characterised in that the catalyst (A) is with urging
The mol ratio of agent (B) is 1:100~100:1, catalyst (A) is with the summation of catalyst (B) and the mol ratio of chain shuttling agent
1:1~1:1000.
7. carbon monoxide-olefin polymeric according to claim 6, it is characterised in that the summation of catalyst (A) and catalyst (B) with
The mol ratio of chain shuttling agent is 1:1~1:200.
8. a kind of carbon monoxide-olefin polymeric for vinyl polymerization, include the mixture or reaction product of following material：
1) the first olefin polymerization catalysis (A), it is the metal complex shown in formula 2：
In formula 2, M is the transition metal of IV B races in the periodic table of elements；N is 1-30 integer, when m is two or more, multiple X
Group is identical or different；M is the integer for meeting M valence states；
The one kind of X in halogen, alkyl, oxyl, acid group and amido；
R1-R8It is identical or different, it is hydrogen atom, halogen atom, C1-C20Aliphatic group, C3-C20Cyclic hydrocarbon radical or C6-C20Fragrance
Alkyl, any hydrogen or carbon atom on the alkyl are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hetero atom
Substitution；
R9-R10It is identical or different, selected from substituted or unsubstituted C1-C20Aliphatic group or C6-C30Aryl radical；
R1-R10In two or more groups optionally mutually bonded cyclization；
Y is a bridge joint group, is C1-C20Aliphatic group or C6-C20Aryl radical, any hydrogen or carbon on the alkyl
Atom is optionally substituted by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hetero atom；
2) the second olefin polymerization catalysis (B), the complex selected from structure as shown in formula 5：
In formula 5：R1-R6For alkyl or halogen, X is halogen；With
3) chain shuttling agent.
9. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that in formula 2, M is selected from titanium, zirconium or hafnium；N is 1-
10 integer；R1-R8Selected from hydrogen atom, halogen atom or C1-C20Aliphatic group；R9-R10Selected from C1-C20Fat or aromatic hydrocarbon
Base；X is selected from halogen or alkyl；Y is a bridge joint group, selected from C1-C20Aliphatic group or C6-C20Aryl radical.
10. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that the catalyst (B) is selected from following match somebody with somebody
Compound：
1：R1=R3=R4=R6=Me, R2=R5=H, X=Br；2：R1=R3=R4=R6=Et, R2=R5=H, X=Br；
3：R1=R3=R4=R6=iPr, R2=R5=H, X=Br；4：R1=R2=R3=R4=R5=R6=Me, X=Br；
5：R1=R3=R4=R6=Me, R2=R5=Br, X=Br；6:R1=R3=R4=R6=Me, R2=R5=Et, X=Br；
7：R1=R3=R4=R6=Et, R2=R5=Me, X=Br；8：R1=R3=R4=R6=Et, R2=R5=Br, X=Br；
9：R1=R3=R4=R6=Me, R2=R5=H, X=Cl；10：R1=R3=R4=R6=Et, R2=R5=H, X=Cl；
11：R1=R3=R4=R6=iPr, R2=R5=H, X=Cl；12：R1=R2=R3=R4=R5=R6=Me, X=Cl；
13：R1=R3=R4=R6=Me, R2=R5=Br, X=Cl；14：R1=R3=R4=R6=Me, R2=R5=Et, X=
Cl；
15：R1=R3=R4=R6=Et, R2=R5=Me, X=Cl；16：R1=R3=R4=R6=Et, R2=R5=Br, X=
Cl。
11. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that the chain shuttling agent be trialkylaluminium and/or
Dialkyl zinc compounds.
12. carbon monoxide-olefin polymeric according to claim 8, it is characterised in that the chain shuttling agent is triethyl aluminum, three different
At least one of propyl group aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triethyl-gallium and diethyl zinc.
13. according to the carbon monoxide-olefin polymeric any one of claim 8-12, it is characterised in that the catalyst (A) with
The mol ratio of catalyst (B) is 1:100~100:1, catalyst (A) and the summation of catalyst (B) and the mol ratio of chain shuttling agent
For 1:1~1:1000.
14. carbon monoxide-olefin polymeric according to claim 13, it is characterised in that the summation of catalyst (A) and catalyst (B)
Mol ratio with chain shuttling agent is 1:1~1:200.
15. a kind of catalytic polymerization, its usage right requires the carbon monoxide-olefin polymeric described in any one of 1 to 7 or 8-14.
16. according to the method for claim 15, it is characterised in that described to be polymerized to continuous polymerization.
17. according to the method for claim 15, it is characterised in that the polymerization is carried out in a manner of continuous solution polymerization.
18. according to the method for claim 15, it is characterised in that polymerized monomer is ethene or C3-8Alpha-olefin.
19. according to any one methods described in claim 15-18, it is characterised in that obtain block polymer after polymerization.
20. according to the method for claim 19, it is characterised in that the block polymer be ethene or Noblen or
Ethene and C3-8Alpha-olefin copolymer.
21. according to the method for claim 20, it is characterised in that the polymer has the molecular weight distribution less than 4.0
Mw/Mn。
22. according to the method for claim 20, it is characterised in that the polymer has the molecular weight distribution less than 2.8
Mw/Mn。
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