CN105482001A - Catalyst composition for polymerization of ethylene - Google Patents
Catalyst composition for polymerization of ethylene Download PDFInfo
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Abstract
The invention relates to a catalyst composition for polymerization of ethylene so as to form polymer products with unique physical properties. The invention further relates to a polymer product comprising two or more regions or fragments (blocks) with different physical properties. The catalyst composition comprises mixtures or reaction products of following substances: a first olefinic polymerization catalyst (A), a second olefinic polymerization catalyst (B) and a chain shuttling agent, wherein under equivalent polymerization conditions, compared with polymers prepared from the catalyst (A), polymers prepared from the second olefinic polymerization catalyst (B) have different chemical characteristics or physical characteristics.
Description
Technical field
The present invention relates to a kind of catalyst composition for vinyl polymerization, to form the polymer product with peculiar physical properties.The invention still further relates to the polymer product of region or the fragment (block) comprising two or more different physical characteristics.
Background technology
Polymkeric substance and the random copolymerization compound of block type structure are compared with blend and are usually had more excellent character for a long time.Such as, the triblock copolymer (SBS) of vinylbenzene and divinyl and their hydrogenation transformed object (SEBS) have excellent thermotolerance and elasticity.With thermoplastic elastomer (TPE), famous segmented copolymer owing to having " soft " or elasticity fragment connection " hard " crystallizable part in polymer chain.When temperature reaches the second-order transition temperature of fusing point or " firmly " section, these polymers exhibit go out the characteristic of resilient material.In higher temperature, these polymkeric substance become runny, demonstrate thermoplastic characteristics.The existing method for the preparation of segmented copolymer comprises anionoid polymerization and controlled free radical polymerization.But these methods preparing segmented copolymer need to add monomer and periodical operation continuously, and the monomeric species that can be used for aforesaid method polymerization is relatively less.Such as, in the anionoid polymerization of vinylbenzene and divinyl to be formed in the process of SBS based block copolymer, each polymer chain needs the initiator of stoichiometric(al) amount and the polymkeric substance obtained has very narrow molecular weight distribution mw/mn, and preferably 1.0 to 1.3.In addition, negatively charged ion is relative with radical polymerization slowly, affects its industrialization development.
People wish that can realize better controlling catalytic process produces segmented copolymer, that is, often kind of catalyzer or initiator molecule can form more than one polymer molecule in the course of the polymerization process.In addition, wishing can from single monomer, as ethene, produce have that have both high-crystallinity with indefiniteness block or fragment segmented copolymer.
Researchist had pointed out that some homogeneous phase coordination polymerization catalysts can have the polymkeric substance of block structure by suppressing chain tra nsfer to obtain between polymerization period in the past.Such as, in polymerization process, by reducing chain-transfer agent and reduce temperature of reaction as far as possible, control β-hydrogen transference or chain tra nsfer prepare block polymer.Under these conditions, think that the order interpolation of different monomers can cause being formed and has the sequence of different monomers content or the polymkeric substance of fragment.Some embodiments of above-mentioned catalyst composition and method are described in the Angew.Chem.Int.Ed. of Coates, Hustad and Reinartz, in 2002,41,2236-2257 and US-A-2003/0114623.
Known in the art is chainpropagation by utilizing some alkyl metal cpd and other compound to interrupt in olefinic polymerization as chain-transfer agent as hydrogen.In addition, alkylaluminium cpd usually can be selected as scavenging agent or cocatalyst at olefin polymerization process.At Macromolecules, 2000,33, in 9192-9199, report by using some trialkyl aluminium compound as chain-transfer agent, be combined with some paired zirconocene catalysts composition, generate and comprise the polypropylene block polymers that a small amount of isotaxy and trackless found the polymkeric substance of structure chain fragment simultaneously.In the Macromolecules of Liu and Rytter, 2003,3026-3034 article, also report trimethyl aluminium chain-transfer agent with similar catalyst combination catalyzed ethylene and 1-hervene copolymer.
At USP6,380,341 and 6,169, reporting in 151, by using " vertical structure " metallocene catalyst, forming the olefin polymer of " block-wise " structure by this catalyzer mutual aggregation features changing performance differential responses speed etc. between two kinds of steric configurations.
As everyone knows, alpha-diimine nickel and palladium catalyst form the polymkeric substance of branched (highly branched) between polymerization period by " chain tra nsfer ".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 polymkeric substance of this long chain branching also can by two (indenyl) zirconium complex of replacing as 1-and 2-t-butyldimethylsilyloxy base and the homopolymerization of methylaluminoxane cocatalyst catalyzed ethylene obtained.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., in 1995,117,6414-6415.
Existing article report adopts diimine nickel metal under zinc ethyl effect, to realize chain shuttle polymerization reaction (Macromolecules2009,42,1834-1837) with metallocene catalyst at present, but polymerization temperature is lower, is only 20 DEG C.Existing alpha-diimine nickel catalyzator ethylene polymerization activity is at high temperature very low, and prepared poly molecular weight with polymerisation temperature improves and declines rapidly.And existing ethene gas-phase polymerization processing requirement polymerization temperature is more than 85 DEG C, vinyl solution polymerization technique requires that polymerization temperature is 150-250 DEG C, and original late transition metal catalyst cannot meet the requirement of existing gas phase, solution method ethylene polymerization plants.Catalyst A provided by the invention and catalyst B all can keep higher ethylene polymerization activity at relatively high temperatures, and resulting polymers molecular weight is higher, and molecular weight distribution is narrower, can prepare block-wise polymkeric substance under chain shuttling agent effect.
Summary of the invention
The object of this invention is to provide a kind of catalyst composition for vinyl polymerization, to form block polymer (multi-block polymer).Described polymkeric substance comprises one or more chemistry or different two or more of physical property wherein, preferably the fragment of more than three or block, and said composition comprises mixture or the reaction product of following material:
(1) first olefin polymerization catalysis (A),
Catalyzer described in the present invention (A) comprises following non-metallocene compound, refers to the metal complexes shown in general formula 1 or 2:
In general formula 1, R
1be selected from substituted or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, on described alkyl, arbitrary hydrogen or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
M is the transition metal of IV B race in the periodic table of elements, and X is selected from the one in halogen, alkyl,-oxyl, acid group and amido, and when n is two or more, multiple X group is identical or different; M and n is the integer of 1-3, and m+n=4;
In general formula 2, M is the transition metal of IV B race in the periodic table of elements; N is the integer of 1-30, and when m is two or more, multiple X group is identical or different; M is the integer meeting M valence state;
X is selected from the one in halogen, alkyl,-oxyl, acid group and amido;
R
1-R
8identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, the arbitrary hydrogen on described alkyl or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
R
9-R
10identical or different, be selected from substituted or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical;
R
1-R
10in two or more groups be optionally mutually keyed to ring;
Y is a bridge joint group, is C
1-C
20aliphatic group or C
6-C
20aryl radical, the arbitrary hydrogen on described alkyl or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
(2) second olefin polymerization catalysis (B), under equivalent polymerization conditions, its polymkeric substance prepared and the polymer phase prepared by catalyzer (A) are than having different chemistry or physical features.Catalyzer of the present invention (B) meets general formula 3:
In general formula 3, R
1and R
4be selected from C respectively
1-C
30alkyl or assorted alkyl; R
2and R
3be selected from hydrogen atom, chlorine atom, C respectively
1-C
20alkyl, heterocyclic compound group, organic group containing oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2and R
3optionally be in ring; M is VIII race's metal;
N the X existed is identical or different, is selected from halogen, alkyl,-oxyl, acid group or amido; N is the integer meeting M valence state;
At least one in catalyzer (A) or catalyzer (B) can pass through chain tra nsfer, or is incorporated to the ethylenic polymer chain formation branched polymer formed on the spot again; With
(3) chain shuttling agent.
Preferred said composition comprises mixture or the reaction product of following material:
(1) first olefin polymerization catalysis (A), it can pass through vinyl polymerization height of formation crystalline ethylene homopolymer; Its general formula as shown in general formula 1 or general formula 2, in general formula 1, R
1be selected from C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; M is selected from titanium, zirconium or hafnium; X is selected from halogen or alkyl; M and n is 2; In general formula 2, M is selected from titanium, zirconium or hafnium; N is the integer of 1-10; R
1-R
8be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; R
9-R
10be selected from C
1-C
20fat or aryl radical; X is selected from halogen or alkyl; Y is a bridge joint group, is selected from C
1-C
20aliphatic group or C
6-C
20aryl radical.
(2) second olefin polymerization catalysis (B), it can pass through chain tra nsfer, or is incorporated to the ethylenic polymer chain formation branched polymer formed on the spot again; Catalyzer (B) is the title complex of structure as shown in general formula 4:
In general formula 4, R
9and R
10be selected from C respectively
1-C
30alkyl or assorted alkyl; R
5-R
8be selected from hydrogen atom, chlorine atom, C respectively
1-C
20alkyl, heterocyclic compound group, organic group containing oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
5-R
8optionally be in ring; M is VIII race's metal; N the X existed is identical or different, is selected from halogen, alkyl,-oxyl; N is the integer meeting M valence state; With
(4) chain shuttling agent.
In another one embodiment of the present invention, provide a kind of method preparing block polymer, described method is included under addition polymerization conditions and is contacted with composition by ethene, and described composition comprises mixture or the reaction product of following material:
(1) first olefin polymerization catalysis (A);
(2) second olefin polymerization catalysis (B), under equivalent polymerization conditions, its polymkeric substance prepared and the polymer phase prepared by catalyzer (A) are than having different chemistry or physical features.At least one in catalyzer (A) or catalyzer (B) can pass through chain tra nsfer, or is incorporated to the ethylenic polymer chain formation branched polymer formed on the spot again; With
(3) chain shuttling agent.
Catalyzer (B) is the title complex of self-structure as shown in general formula 5 more preferably:
In general formula 5: R
1and R
2for alkyl or halogen, X is halogen, and M is nickel or palladium.
In the present invention, catalyzer (B) is most preferably from following title complex:
1：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝H，X＝Br；2：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝H，X＝Br；3：R
1＝R
3＝R
4＝R
6＝iPr，R
2＝R
5＝H，X＝Br；4：R
1＝R
2＝R
3＝R
4＝R
5＝R
6＝Me，X＝Br；5：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Br，X＝Br；6:R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Et，X＝Br7：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Me，X＝Br；8：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Br，X＝Br；9：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝H，X＝Cl；10：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝H，X＝Cl；11：R
1＝R
3＝R
4＝R
6＝iPr，R
2＝R
5＝H，X＝Cl；12：R
1＝R
2＝R
3＝R
4＝R
5＝R
6＝Me，X＝Cl；13：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Br，X＝Cl；14：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Et，X＝Cl；15：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Me，X＝Cl；16：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Br，X＝Cl；
Suitable chain shuttling agent comprises containing at least one C
1-20iA, II A, IB of alkyl or the metallic compound of II B race or complex compound, preferably containing C
1-12the aluminium of alkyl, gallium or zn cpds.Preferred alkyl is alkyl, more preferably the C of linear or branching
2-8alkyl.The chain shuttling agent that the present invention most preferably uses is trialkylaluminium and dialkyl zinc compounds, especially triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triethyl-gallium and zinc ethyl.Suitable chain shuttling agent in addition comprises and is combined by above-mentioned metallic compound the reaction product or mixture that are formed with secondary amine or oxy-compound, and the amido in described secondary amine or oxy-compound or hydroxyl summation are less than the alkyl summation in above-mentioned metallic compound.Described secondary amine or oxy-compound be hexamethyldisilazane, 2-4-hydroxymethylpiperidine, two (n-pentyl) amine, 2,6-bis-(tertiary butyl) phenol, ethyl (1-naphthyl) amine or 2,6-diphenylphenol especially.The secondary amine of preferred use q.s or the reaction of oxy-compound metallizing thing, make each atoms metal in the reaction product only contain an alkyl.In above-mentioned reaction product, most preferably octyl aluminum two (two (trimethyl silyl) acid amides), sec.-propyl aluminium two (dimethyl (tertiary butyl) silicomethane oxide compound, aluminium triethyl two (two (trimethyl silyl) acid amides), zinc ethyl (2,6-diphenylphenol salt) for the present invention as chain shuttling agent.
The present invention can by conjunction with cocatalyst, preferred cationic forming cocatalysts or Lewis acid or its binding substances, by aforesaid catalyzer (A) and (B) activation to form effective catalyst composition.In preferred scheme, in order to chain shuttles back and forth and as the cocatalyst component of catalyst composition and usage chain shuttling agent.
Required, by being combined with the cocatalyst of positively charged ion form, as some cocatalyst used together with IV B race metal complex that this area is previously known, make metal complex have catalytic activity.Suitable cation forming cocatalysts used herein comprises neutral Lewis acid, as C
1-30the III A compounds of group that alkyl replaces, preferred trialkyl aluminium, trialkyl boron compound and its there is halo (the comprising perhalogeno) derivative of 1 to 10 carbon in each alkyl or halo alkyl, more preferably fluoridized triarylboron, most preferably three (pentafluorophenyl group) borine.
Cation forming cocatalysts and lewis acidic binding substances, especially C
1-4alkylaluminium cpd and C
1-20the binding substances of preferred three (phenyl-pentafluoride base) borine of the haloboronated thing of alkyl.The further binding substances of above-mentioned Lewis acid mixture and aikyiaiurnirsoxan beta oligopolymer, and single Lewis acid, especially the binding substances of three (pentafluorophenyl group) borines and aikyiaiurnirsoxan beta oligopolymer can be used as activating cocatalysts.
In the present invention, the ionic forms compound that can be used as cocatalyst comprises the positively charged ion of the Bronsted acid can contributing proton, and negatively charged ion A that is compatible, non-coordinated
-.Preferred negatively charged ion is those negatively charged ion comprising single co-ordination complex, described co-ordination complex comprises charged metal or metalloid core, and wherein negatively charged ion can balance the electric charge of the active catalyst species (metallic cation) that may be formed when two component mixing.In addition, described negatively charged ion should be unstable, be enough to olefinic, the replacing with the unsaturated compound of acetylene series or other neutral Lewis base such as ether or nitrile of diolefinic.Suitable metal is including, but not limited to plumbous, golden and platinum.Suitable nonmetally include, but are not limited to boron, phosphorus and silicon.
Preferably above-mentioned cocatalyst can be represented by following general formula:
(L
*-H)
g +(A)
g－
Wherein:
L
*it is neutral Lewis base;
(L
*-H)
+l
*conjugate Bronsted acid;
A
g-that there is g
-the non-coordinated of electric charge, compatible negatively charged ion; With
G is the integer of 1 to 3.
More preferably A
g-meet chemical formula: [M ' Q
4]
-;
Wherein:
M ' is positive oxidation state boron or the aluminium of+3; With
The Q of each existence is independently selected from the silylhydrocarbyl (comprising perhalogeno alkyl, perhalogeno-oxyl and perhalogenated monosilane base alkyl) of hydride, dialkylamido, halogenide, alkyl,-oxyl, chloro alkyl, chloro-oxyl and halogen substiuted, and described Q has 20 carbon at the most.
In a preferred scheme, g is 1.That is, counterion has single negative charge and A
-.The preparation of activating cocatalysts to catalyzer of the present invention comprising boron is particularly useful, and it can be represented by following general formula:
(L
*-H)
+(BQ
4)
-
Wherein:
L
*define as previous;
B is the positive oxidation state boron of+3; With
Q is alkyl,-oxyl, fluoridize alkyl, fluoridize-oxyl or silyl fluoride base alkyl, and it has 20 non-hydrogen atoms at the most.
Preferred Louis's alkali salt is ammonium salt, more preferably comprises one or more C
12-40the trialkyl ammonium salts of alkyl.Most preferably the Q of each existence is fluoro aryl, especially phenyl-pentafluoride base.
In the preparation of the catalyzer of the present invention's improvement, the example that can be used as the boron compound of activating cocatalysts be:
Three substituent ammonium salts are 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) borate, N, accelerine four (phenyl-pentafluoride base) borate, N, accelerine normal-butyl three (phenyl-pentafluoride base) borate, N, accelerine benzyl three (phenyl-pentafluoride base) borate, N, accelerine four (4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluoro phenyl) borate, N, accelerine four (4-(triisopropyl silyl)-2, 3, 5, 6-tetrafluoro phenyl) borate, N, N-Diethyl Aniline four (phenyl-pentafluoride base) borate, dimethyl stearyl ammonium four (phenyl-pentafluoride base) borate.
Dialkyl ammonium salt is as two-(sec.-propyl) ammonium four (phenyl-pentafluoride base) borates, methyl octadecyl ammonium four (phenyl-pentafluoride base) borate, methyl pungent dodecyl ammonium four (phenyl-pentafluoride base) borate and hexatriacontane base ammonium four (phenyl-pentafluoride base) borate.
Trisubstituted phosphonium salt is as triphenylphosphine four (pentafluorophenyl group) borate, methyl hexatriacontane base phosphine (pentafluorophenyl group) borate and three (2,6-3,5-dimethylphenyl) phosphine four (pentafluorophenyl group) borate.
The mol ratio of the catalyzer/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 itself is as activating cocatalysts, use aikyiaiurnirsoxan beta in a large number, generally with mole for benchmark be at least 100 times of metal complex consumption.When three (pentafluorophenyl group) borine is as activating cocatalysts, three (pentafluorophenyl group) borines used and the mol ratio of metal complex are 0.5:1 to 10:1, more preferably 1:1 to 6:1, most preferably 1:1 to 5:1.Other activating cocatalysts generally uses with about and the equimolar amount of metal complex.
In composition of the present invention, described catalyzer (A) is 1:100 ~ 100:1 with the mol ratio of catalyzer (B), catalyzer (A) is 1:1 ~ 1:1000 with the summation of catalyzer (B) and the mol ratio of chain shuttling agent, preferred 1:1 ~ 1:200.
Used catalyst of the present invention is with successive polymerization, and the mode of preferred continuous solution polymerization carries out polyreaction.Wherein catalyst component, one or more shuttling agents, monomer and optional solvent, auxiliary agent, scavenging agent and polyreaction auxiliary agent are fed to conversion zone continuously, and continuous print removes polymerisate there.
Advantageously catalyst composition can be used in high pressure, solution, slurry or gas phase polymerization process.For solution polymerization process, desirably use the dispersed system of catalyst component in liquid diluent, wherein under used polymeric reaction condition, polymkeric substance is soluble.Prepare the solution polymerization process of novel polymer of the present invention, especially continuous solution polymerization method is preferably between 70 DEG C to 250 DEG C, more preferably between 80 DEG C to 210 DEG C, and carries out at temperature most preferably between 80 to 150 DEG C.High pressure method normally carries out at the temperature of 100 DEG C to 400 DEG C He more than under the pressure of 50MPa.Slurry method generally uses inert hydrocarbon diluent and substantially becomes temperature under the temperature dissolving in inert polymerisation medium from 0 DEG C to produced polymkeric substance.In slurry polymerization, preferred temperature is from 30 DEG C to 115 DEG C, more preferably from 60 DEG C to 115 DEG C, and most preferably at the most 100 DEG C.The general range of pressure is from normal pressure (100kPa) to 500psi (3.4MPa).
In all aforesaid methods, preferably use continuously or continuous print polymerizing condition substantially.Utilize above-mentioned polymeric reaction condition, especially use the continuous solution polymerization method of two or more active polymerizing catalyst materials.Allow to use the temperature of reactor increased, this causes multi-block polymer or fragments polymer with high efficiency production.The reaction conditions of all even plug flow type can be used.
Aforesaid method is taked to form block polymer, especially multi-block polymer, the form of the successive soln method of preferred linear polyblock polymkeric substance.Use non-interchangeable multiple catalyst, namely these catalyzer have different chemical property.Under continuous solution polymerization condition, compared with chainpropagation, the shuttle from chain shuttling agent to catalyzer becomes advantage, and forms multi-block polymer of the present invention, especially linear polyblock polymkeric substance with high-level efficiency.
In another embodiment of the invention, a kind of high molecular fragments polymer (multi-block polymer) from ethylene making is provided, it comprises density or other chemistry or different two or more of physical properties, the preferably fragment of more than three.Preferred described block polymer is ethene or alfon or ethene and C
3-8the multipolymer of alpha-olefin.This polymkeric substance has and is less than 4.0, is preferably less than the molecular weight distribution mw/mn of 2.8.
In yet another embodiment of the present invention, the functional derivative of above-mentioned fragment or multi-block polymer is provided.
In the present invention further embodiment, a kind of polymeric blends is provided, comprise: (1) organic or inorganic polymkeric substance, the homopolymer of optimal ethylene or propylene and/or ethene or propylene and can the multipolymer of comonomer of copolymerization, and the high molecular multi-block polymer that (2) are of the present invention or prepared according to the methods of the invention.In desired embodiment, component (1) is the matrix polymer comprising high density polyethylene(HDPE) or isotatic polypropylene, and component (2) is elastomerics multi-block polymer.In a preferred version, component (2) is included in the inclusion of the matrix polymer formed between component (1) and (2) mixing period.
In addition, polymkeric substance of the present invention preferably can have the melting heat of 130J/g or less, the ethylene content (i.e.-CH of at least 50 % by weight
2-CH
2polymer segments), be less than-25 DEG C, be more preferably less than the second-order transition temperature T of-30 DEG C
g.
In addition, polymkeric substance of the present invention can have 0.01 to 2000 grams/10 minutes, preferably from 0.01 to 1000 grams/10 minutes, more preferably from the melting index I of 0.01 to 500 grams/10 minutes
2.Required, polymkeric substance of the present 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 the molecular weight Mw of 10000 grams/mol to 800,000 gram/mol.The density of polymkeric substance of the present invention can be 0.80 to 0.99g/cm
3with preferred be from 0.85g/cm for the polymkeric substance comprising ethene
3to 0.97g/cm
3.
In the present invention, catalyst A and B use jointly as composition, are used alone wherein any one and can not get block polymer.Compare with existing document, catalyst B of the present invention at high temperature still has greater activity, at high temperature with catalyst A acting in conjunction catalyzed ethylene polymerization, can obtain the block polymer of special construction.
Embodiment
Following specific embodiment of the present invention and its combination are especially wished, and in order to provide the detailed content of appended claim to describe following embodiment at this.
The sign of polymericular weight (Mw) and molecular weight distribution (Mw/Mn): molecular weight and distributing is measured by gel permeation chromatography (GPC), instrument adopts WatersAllianceGPCV2000, solvent is 1,2,4-trichlorobenzene, sample concentration is lmg/ml, and solvent flow rate is 1.0ml/min; Measuring tempeature is 150 DEG C.Secondary surveyed by each sample.
Embodiment 1
Catalyzer (A1) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride [(L1)
2zrCl
2, its synthesis is shown in Chinese patent CN101173011, embodiment 6, and its structure is shown in following formula].
Catalyzer (B1) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
In the stainless steel polymermaking autoclave of 1 liter, three times are respectively replaced with nitrogen and ethene, then 500 milliliters of toluene solvants are added, along with adding of toluene, cocatalyst (2ml concentration is the methylaluminoxane toluene solution of 1.53M) and DEZ (1ml concentration is the DEZ toluene solution of 1.5M) are added by syringe.Catalyst A 1 (5ml concentration is the toluene solution of 1.0mM) and catalyst B 1 (5ml concentration is the toluene solution of 1.0mM) is added again by syringe, pressure is risen to and maintains 1.0MPa, 90 DEG C of polyreaction 30min, cooling, collected polymer, weighs.
Concrete polymerization result is listed in table 1.
Embodiment 2
Catalyzer (A1) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride.
Catalyzer (B2) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 1, and concrete polymerization result is listed in table 1.
Embodiment 3
Catalyzer (A2) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride.
Catalyzer (B1) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 1, and concrete polymerization result is listed in table 1.
Embodiment 4
Catalyzer (A3) is as shown in the formula (Chinese patent CN1769310 is shown in synthesis, embodiment 2)
Catalyzer (B3) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 1, and concrete polymerization result is listed in table 1.
Embodiment 5
Catalyzer (A4) is as shown in the formula (Chinese patent CN1769310 is shown in synthesis, embodiment 1)
Catalyzer (B4) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Except polymerizing condition is 110 DEG C of polyreaction 30min, other reaction process is with embodiment 1.Concrete polymerization result is listed in table 1.
Embodiment 6
Catalyzer (A1) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride
Catalyzer (B1) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
In the stainless steel polymermaking autoclave of 1 liter, three times are respectively replaced with nitrogen and ethene, then 500 milliliters of toluene solvants are added, along with adding of toluene, cocatalyst (1ml concentration is DMA four (pentafluorophenyl group) the borate toluene solution of 1.0mM) and DEZ (1ml concentration is the toluene solution of 1.5M) are added by syringe.(5ml concentration is the toluene solution of 1.0mM, and 1-hexene 10ml, is risen to by pressure and maintains 1.0MPa to add catalyst A 1 (5ml concentration is the toluene solution of 1.0mM) and catalyst B 1 by syringe again, 90 DEG C of polyreaction 30min, cooling, collected polymer, weighs.
Concrete polymerization result is listed in table 1.
Embodiment 7
Catalyzer (A2) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride.
Catalyzer (B1) is:
Cocatalyst is DMA four (pentafluorophenyl group) borate, and shuttling agent is zinc ethyl (DEZ).
Except not adding 1-hexene, other reaction process is with embodiment 6.Concrete polymerization result is listed in table 1.
Embodiment 8
Catalyzer (A2) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride.
Catalyzer (B3) is:
Cocatalyst is DMA four (pentafluorophenyl group) borate, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 7, and concrete polymerization result is listed in table 1.
Comparative example 1
Catalyzer (A1) is two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride
Catalyzer (B5) is:
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 1, and concrete polymerization result is listed in table 1.
Comparative example 2
Catalyzer is A1 pair-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride.
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process with embodiment 1, only use two-[N-(the 3-tertiary butyl-salicylidene) hexahydroaniline] zirconium dichloride is as catalyzer, concrete polymerization result is listed in table 1.
Comparative example 3
Catalyzer is that B1 bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,6-DIPAs)] closes nickel (II).
Cocatalyst is methylaluminoxane, and shuttling agent is zinc ethyl (DEZ).
Polymerization process is with embodiment 1, and only use bromination [11,12-(9,10-dihydro-9,10-ethylene anthracene) two (contracting 2,6-DIPAs)] to close nickel (II) as catalyzer, concrete polymerization result is listed in table 1.
Table 1 vinyl polymerization result
In table 1, "-" expression is not tested.
As can be seen from Table 1, (catalyst A 1 and catalyst B 5 is used with comparative example 1, but the structure of catalyst B 5 is different from the present invention) compare, use catalyst composition of the present invention still to have higher polymerization activity under the high temperature conditions, the molecular weight of resulting polymers is apparently higher than comparative example 1.Comparative example 2 only uses catalyst A 1, the polymericular weight obtained under the same conditions is less, comparative example 3 only uses catalyst B 1, the polymericular weight obtained is larger, the molecular weight distribution Mw/Mn of embodiment 1 ~ 8 is less, illustrate when use comprises the composition of catalyst A and catalyst B, block polymer is defined under chain shuttling agent effect, but not be used alone catalyst A 1 in comparative example 2 and 3, the mixture of homopolymer prepared by B1, otherwise in embodiment 1 ~ 8, the Mw/Mn of resulting polymers should much larger than 4.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1., for a catalyst composition for vinyl polymerization, comprise mixture or the reaction product of following material:
1) the first olefin polymerization catalysis (A), the metal complexes for shown in general formula 1 or 2:
In general formula 1, R
1be selected from substituted or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, on described alkyl, arbitrary hydrogen or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
M is the transition metal of IV B race in the periodic table of elements, and X is selected from the one in halogen, alkyl,-oxyl, acid group and amido, and when n is two or more, multiple X group is identical or different; M and n is the integer of 1-3, and m+n=4;
In general formula 2, M is the transition metal of IV B race in the periodic table of elements; N is the integer of 1-30, and when m is two or more, multiple X group is identical or different; M is the integer meeting M valence state;
X is selected from the one in halogen, alkyl,-oxyl, acid group and amido;
R
1-R
8identical or different, be hydrogen atom, halogen atom, C
1-C
20aliphatic group, C
3-C
20cyclic hydrocarbon radical or C
6-C
20aryl radical, the arbitrary hydrogen on described alkyl or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
R
9-R
10identical or different, be selected from substituted or unsubstituted C
1-C
20aliphatic group or C
6-C
30aryl radical;
R
1-R
10in two or more groups be optionally mutually keyed to ring;
Y is a bridge joint group, is C
1-C
20aliphatic group or C
6-C
20aryl radical, the arbitrary hydrogen on described alkyl or carbon atom are optionally by halogen atom, oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin hybrid atom MCM-41;
2) the second olefin polymerization catalysis (B), the metal complexes for shown in general formula 3:
In general formula 3, R
1and R
4be selected from C respectively
1-C
30alkyl or assorted alkyl; R
2and R
3be selected from hydrogen atom, chlorine atom, C respectively
1-C
20alkyl, heterocyclic compound group, organic group containing oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
2and R
3optionally be in ring; M is VIII race's metal;
N the X existed is identical or different, is selected from halogen, alkyl,-oxyl, acid group or amido; N is the integer meeting M valence state; With
3) chain shuttling agent.
2. catalyst composition according to claim 1, is characterized in that, said composition comprises mixture or the reaction product of following material:
(1) first olefin polymerization catalysis (A), its general formula as shown in general formula 1 or general formula 2, in general formula 1, R
1be selected from C
1-C
20aliphatic group or C
6-C
30aryl radical, R
2-R
6be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; M is selected from titanium, zirconium or hafnium; X is selected from halogen or alkyl; M and n is 2; In general formula 2, M is selected from titanium, zirconium or hafnium; N is the integer of 1-10; R
1-R
8be selected from hydrogen atom, halogen atom or C
1-C
20aliphatic group; R
9-R
10be selected from C
1-C
20fat or aryl radical; X is selected from halogen or alkyl; Y is a bridge joint group, is selected from C
1-C
20aliphatic group or C
6-C
20aryl radical.
(2) second olefin polymerization catalysis (B), it is the title complex of structure as shown in general formula 4:
In general formula 4, R
9and R
10be selected from C respectively
1-C
30alkyl or assorted alkyl; R
5-R
8be selected from hydrogen atom, chlorine atom, C respectively
1-C
20alkyl, heterocyclic compound group, organic group containing oxygen, nitrogen, boron, sulphur, phosphorus, silicon, germanium or tin atom; And R
5-R
8optionally be in ring; M is VIII race's metal; N the X existed is identical or different, is selected from halogen, alkyl,-oxyl; N is the integer meeting M valence state; With
(3) chain shuttling agent.
3. catalyst composition according to claim 2, is characterized in that, described catalyzer (B) is selected from the title complex of structure as shown in general formula 5:
In general formula 5: R
1-R
6for alkyl or halogen, X is halogen, and M is nickel or palladium.
4. catalyst composition according to claim 3, is characterized in that, described catalyzer (B) is selected from following title complex:
1：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝H，X＝Br；2：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝H，X＝Br；3：R
1＝R
3＝R
4＝R
6＝iPr，R
2＝R
5＝H，X＝Br；4：R
1＝R
2＝R
3＝R
4＝R
5＝R
6＝Me，X＝Br；5：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Br，X＝Br；6:R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Et，X＝Br；7：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Me，X＝Br；8：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Br，X＝Br；9：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝H，X＝Cl；10：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝H，X＝Cl；11：R
1＝R
3＝R
4＝R
6＝iPr，R
2＝R
5＝H，X＝Cl；12：R
1＝R
2＝R
3＝R
4＝R
5＝R
6＝Me，X＝Cl；13：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Br，X＝Cl；14：R
1＝R
3＝R
4＝R
6＝Me，R
2＝R
5＝Et，X＝Cl；15：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Me，X＝Cl；16：R
1＝R
3＝R
4＝R
6＝Et，R
2＝R
5＝Br，X＝Cl。
5. the catalyst composition according to any one of claim 1-4, it is characterized in that, described chain shuttling agent is trialkylaluminium and/or dialkyl zinc compounds, at least one in preferred triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, triethyl-gallium and zinc ethyl.
6. the catalyst composition according to any one of claim 1-5, it is characterized in that, described catalyzer (A) is 1:100 ~ 100:1 with the mol ratio of catalyzer (B), catalyzer (A) is 1:1 ~ 1:1000 with the summation of catalyzer (B) and the mol ratio of chain shuttling agent, preferred 1:1 ~ 1:200.
7. a catalytic polymerization, it uses the catalyst composition described in any one of claim 1 to 6, is preferably successive polymerization, more preferably carries out in the mode of continuous solution polymerization.
8. catalytic polymerization according to claim 7, is characterized in that, polymerization single polymerization monomer is ethene or C
3-8alpha-olefin.
9. a block polymer, it is prepared by the catalytic polymerization described in claim 7 or 8, and preferred described block polymer is ethene or alfon or ethene and C
3-8the multipolymer of alpha-olefin.
10. block polymer according to claim 9, is characterized in that, described polymkeric substance has and is less than 4.0, is more preferably less than the molecular weight distribution mw/mn of 2.8.
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| CN106589181A (en) * | 2016-11-15 | 2017-04-26 | 浙江大学 | Multi-block branched polyethylene and preparation method thereof |
| CN107663252A (en) * | 2016-07-28 | 2018-02-06 | 中国石油化工股份有限公司 | A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization |
| CN108864338A (en) * | 2017-05-12 | 2018-11-23 | 中国石油化工股份有限公司 | A method of carbon monoxide-olefin polymeric and olefinic polymerization for olefinic polymerization |
| CN109694435A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-unsaturated carboxylic acid polymer and preparation method thereof |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
| CN110272526A (en) * | 2018-03-16 | 2019-09-24 | 中国石油化工股份有限公司 | Carbon monoxide-olefin polymeric and its application for vinyl polymerization |
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| CN107663252A (en) * | 2016-07-28 | 2018-02-06 | 中国石油化工股份有限公司 | A kind of method of carbon monoxide-olefin polymeric and its catalysis long-chain alpha-olefin polymerization for long-chain alpha-olefin polymerization |
| CN107663252B (en) * | 2016-07-28 | 2020-09-15 | 中国石油化工股份有限公司 | Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition |
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| CN108864338A (en) * | 2017-05-12 | 2018-11-23 | 中国石油化工股份有限公司 | A method of carbon monoxide-olefin polymeric and olefinic polymerization for olefinic polymerization |
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| CN109694435A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-unsaturated carboxylic acid polymer and preparation method thereof |
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| CN110272526B (en) * | 2018-03-16 | 2021-10-19 | 中国石油化工股份有限公司 | Catalyst composition for ethylene polymerization and application thereof |
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