CN104059173B - A kind of supported late transition metal catalyst for vinyl polymerization - Google Patents
A kind of supported late transition metal catalyst for vinyl polymerization Download PDFInfo
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Abstract
The present invention relates to a kind of loaded late transition metal catalyst for vinyl polymerization, preparation method, this catalyst includes (a) late transition metal compound；(b) chlorination alkyl silica modifier；(c) organo-aluminum compound；The product of (d) silica-gel carrier；Its preparation method includes: the preparation of (1) chlorination alkyl Si modification silica-gel carrier, the preparation of (2) organo-aluminium modified silica gel carrier, the preparation of (3) silica gel load late transition metal catalyst, obtained ethylene Polymerization Catalyzed by Later Transition Metal or combined polymerization have the highest polymerization activity.Used silica gel support preparation method is simple, and the carried catalyst particle shape of gained is good, and size is adjustable.
Description
Technical field
The present invention relates to a kind of loaded late transition metal catalyst for vinyl polymerization, preparation method, and institute
Obtain catalyst application in terms of olefinic polymerization.
Technical background
In the evolution of olefin polymerization catalysis, the nineteen nineties late transition metal of development is urged
Agent has obtained great development and concern.Particularly Ni, Pd and Fe, Co diimine catalysts system
(WO9623010, WO9827124), nickel, palladium catalyst can generate narrow point by ethylene homogeneous polymerization
The branched the most hyperbranched High molecular weight polyethylene of son amount distribution, ferrum, Co catalysts can catalyzed ethylene lifes
Become the Hi-fax of wide molecular weight distribution.But olefinic polymerization is to carry out in homogeneous, the polymer obtained
In amorphous state, it is impossible to use on wide variety of slurry process or gas phase polymerization technique.
At present, in the supported research of late transition metal catalyst, individually use magnesium chloride compound load
Research report less (Macromolecules2004,37 (17), the 6258-6259 of late transition metal catalyst;
CN101817893;CN101531724), usually the magnesium compounds such as magnesium chloride are dissolved in some solvent
Obtain homogeneous solution, the most again by this solution with the carrier impregnation such as silica gel formed complex carrier (Polymer2004,
45 (9), 2877-2882；CN1393479；CN101880342；CN1392165；CN1472229).
But the shortcoming of this method is removing dissolves polar solvent used by magnesium chloride needs higher temperature and/or substantial amounts of has
Machine aluminon, carrier complicated process of preparation, it is unfavorable for industrial mass production.Additionally, also there is employing to have
The silica gel of good particle shape is carrier, as Shih Keng-Yu uses one in WO01/32723
Load the silica gel activating late transition metal catalyst of alkyl aluminum, it is possible to use alkyl aluminum is promoter, tool
There is good catalysis activity.But carrier preparation remains a need for using substantial amounts of alkyl aluminum, and the load of catalyst
Inefficient.Also have by by catalyst ligand structure function, by chamical binding mode by rear transition gold
Metal catalyst is supported on (CN10169111 on silica gel；CN101173012；CN101531724), to improve
The load efficiency of catalyst, but this kind of method catalyst preparation cost is greatly improved, and disadvantage mentioned above limits silicon
The commercial Application of glue loaded late transition metal catalyst.
Summary of the invention
One of the object of the invention is to provide one organo-aluminium/chlorination silicon alkyl/silica gel load late transition metal
The preparation method of catalyst.
The two of the object of the invention are that above-mentioned supported late transition metal catalyst is used for ethylene homo to be closed or be total to
Polymerization, has high polymerization activity.
A kind of supported late transition metal catalyst for vinyl polymerization of the present invention, this catalyst includes following
The product of component:
(1) late transition metal compound；
(2) chlorination silicon alkyl；
(3) organo-aluminum compound；
(4) silica-gel carrier；
Component (1) described late transition metal compound, refers to that the late transition metal shown in formula 1 and 2 is joined
Compound,
Formula 1
In formula 1, R1And R7It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；
R2-R6It is respectively selected from hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing,
The organic group of nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom；And R2-R6In two or more bases
Group's optionally mutual cyclization；
M is the 8th race's metal；
X is identical or different, selected from halogen, alkyl, oxyl, acid group or amido；N is to meet M valence state
Integer；
Formula 2
In formula 2, R8And R11It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；
R9And R10It is respectively selected from hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing,
The organic group of nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom；
And R9And R10Optionally mutual cyclization；M is the 8th race's metal；
X is identical or different, selected from halogen, alkyl, oxyl, acid group or amido；N is to meet M valence state
Integer；
Component (2) described chlorination silicon alkyl is selected from compound: Cl described in below general formulanSi(R1)4-n
Wherein R1Represent C1-20Alkyl, n represents the integer of 1-4；
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or chlorination alkyl aluminum
Compound, alkylaluminoxane formula is:
Or
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
In formula 1, R1And R7Preferably C6-C30Aryl radical, e.g., phenyl, 2-tolyl, 3
-tolyl, 4-tolyl, 2,6-xylyl, mesityl, 2-ethylphenyl,
3-ethylphenyl, 4-ethylphenyl, 2,6-diethyl phenyl, mesityl, 2-are different
Propyl group phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyl, 2,4,6-
Triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,6-bis-uncle
Butyl phenyl, 2,4,6-tri-tert phenyl, 2-Benzylphenyl, 3-Benzylphenyl, 4-benzene
Aminomethyl phenyl, 2,4-benzhydryl phenyl, 2,4,6-tritylphenyl, 1-naphthyl, 2-naphthyl,
2-phenyl, 3-phenyl, 4-phenyl, 2,4-diphenyl phenyl, 2,4,6-tri-
Phenyl, 2-(benzhydryl) phenyl, 3-(benzhydryl) phenyl, 4-(benzhydryl) phenyl, 2,4
-two (benzhydryl) phenyl, 2,4,6-tri-(benzhydryl) phenyl, 2-(trityl) phenyl, 3-(three
Benzyl) phenyl, 4-(trityl) phenyl, 2,4-bis-(trityl) phenyl or 2,4,6-tri-(three
Benzyl) phenyl etc..
R2-R6Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, nitro are substituted
Phenyl, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, benzhydryl, three rings
Decyl, 2-phenyl-isopropyl, wherein preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl,
Normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, uncle oneself
Base, phenyl, adamantyl, 2-phenyl-isopropyl.
The preferred ferrum of M or cobalt；
X preferably is selected from halogen, alkyl and alkoxyl, most preferably chlorine, bromine, iodine, methyl and ethyl.
The synthesis of the metal complex shown in formula 1 is standby according to WO9827124, WO9830612 patent system.
Formula 2
In formula 2, R8And R11Preferably C6-C30Aryl radical, e.g., phenyl, 2-tolyl, 3
-tolyl, 4-tolyl, 2,6-xylyl, mesityl, 2-ethylphenyl,
3-ethylphenyl, 4-ethylphenyl, 2,6-diethyl phenyl, mesityl, 2-are different
Propyl group phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyl, 2,4,6-
Triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,6-bis-uncle
Butyl phenyl, 2,4,6-tri-tert phenyl, 2-Benzylphenyl, 3-Benzylphenyl, 4-benzene
Aminomethyl phenyl, 2,4-benzhydryl phenyl, 2,4,6-tritylphenyl, 1-naphthyl, 2-naphthyl,
2-phenyl, 3-phenyl, 4-phenyl, 2,4-diphenyl phenyl, 2,4,6-tri-
Phenyl, 2-(benzhydryl) phenyl, 3-(benzhydryl) phenyl, 4-(benzhydryl) phenyl, 2,4
-two (benzhydryl) phenyl, 2,4,6-tri-(benzhydryl) phenyl, 2-(trityl) phenyl, 3-(three
Benzyl) phenyl, 4-(trityl) phenyl, 2,4-bis-(trityl) phenyl or 2,4,6-tri-(three
Benzyl) phenyl etc..
R9And R10Preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, uncle
Butyl, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, nitro replace
Phenyl, halogenophenyl, alkyl-substituted phenyl, Cai Ji, xenyl, trityl, benzhydryl, three
Cyclodecane base, 2-phenyl-isopropyl, pyridine radicals, pyrrole radicals, wherein preferably hydrogen atom, methyl, ethyl,
N-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, just oneself
Base, isohesyl, tertiary hexyl, phenyl, adamantyl, 2-phenyl-isopropyl.
The preferred nickel of M or palladium.
X preferably is selected from hydrogen, halogen, alkyl or oxyl, most preferably chlorine, bromine, iodine, methyl, ethyoxyl.
The synthesis of the metal complex shown in formula 2 is according to patent WO9623010.
Component (2) described chlorination silicon alkyl refers to compound described in below general formula: ClnSi(R1)4-n
Wherein R1Represent C1-C12Alkyl, n represents the integer of 1-4, and described chlorination silicon alkyl is selected from trimethyl chlorine
Silane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethylpropyl chlorine silicon
Alkane, dipropyl methylchlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, dichloro
Methyl n-pro-pyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl three
Chlorosilane and Silicon chloride., preferably trim,ethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, dichloro
Diethyl silicon, dichlorophenyl silicon, trichloromethyl silane, trichloroethyl silane and Silicon chloride..
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or chlorination alkyl aluminum
Compound, alkyl aluminum is selected from trialkylaluminium, such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three positive fourths
Base aluminum, tri-n-hexyl aluminum or tri-n-octylaluminium；Chlorination alkyl aluminum is selected from diethylaluminum chloride, dichloride ethyl
Aluminum or ethylaluminum sesquichloride etc..
Alkylaluminoxane formula is:
Or
The wherein preferred methyl of R, a represents the integer of 10-30, selected from MAO (MAO) and improve
MAO (MMAO).
For the ratio between the loaded late transition metal catalyst of ethylene polymerization, each reactant with every gram
Silica-gel carrier meter, chloric ether SiClx addition is 0.01-3mmol, and the addition of organo-aluminium is 0.01-30
Mmol, the addition of late transition metal compound is 1-1000 μm ol.Supported rear mistake for vinyl polymerization
Crossing metallic catalyst, in supported late transition metal catalyst, aluminum weight content is 1-15%, center gold
The weight content belonging to M is 0.05-2%.
The preparation method of a kind of supported late transition metal catalyst for vinyl polymerization of the present invention, including such as
Lower step:
(1) preparation of the silica-gel carrier of chlorination alkyl Si modification: under noble gas such as nitrogen is protected, by silicon
Glue carrier adds in reactor, adds solvent, is dispersed into suspension, adds chlorination silicon alkyl, is warming up to 0-90
DEG C, preferably 30-80 DEG C, stirring reaction 3-24 hour, preferably 3-10 hour, then wash for several times with solvent,
Vacuum drying, obtains the silica-gel carrier containing chlorination alkyl Si modification of good fluidity, and described solvent is
Toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene or saturated alkane.
(2) preparation of organo-aluminium modified silica gel carrier: under noble gas such as nitrogen is protected, by (1st)
The silica-gel carrier obtained in step adds in reactor, adds solvent, is dispersed into suspension, adds organic calorize
Compound, is warming up to 0-90 DEG C, preferably 40-90 DEG C, stirring reaction 3-24 hour, preferably 3-10 hour,
Then wash for several times with solvent, vacuum drying, obtain the silica-gel carrier containing organo-aluminium of good fluidity,
Described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferably toluene.
(3) preparation of modified silica-gel loaded late transition metal catalyst: under noble gas such as nitrogen is protected,
The silica-gel carrier containing alkylaluminoxane that will prepare in (2nd) step, joins and makes serosity in solvent,
The solution of late transition metal catalyst precursor is slowly dropped in this serosity, at 0-90 DEG C, reacts 0.5-24
Hour, preferably 0.5-10 hour, obtain supported late transition metal catalyst, serosity can be directly used in poly-
Close reaction, or gained reactant is removed solvent, washs the solid supported obtaining good fluidity after drying
Late transition metal catalyst, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene,
Preferably toluene, hexane or their mixture.
Supported late transition metal catalyst of the present invention can be used on different polymerizations, such as gas phase
Polymerization and slurry polymerization etc..Can be used for all polymerizations or the copolymerization of alkene, be particularly well-suited to ethylene homo
Close or the copolymerization of ethylene and alpha-olefin, wherein alpha-olefin use propylene, butylene, amylene, hexene,
Octene, 4-methylpentene-1 etc..
In supported late transition metal catalyst method of the present invention, the catalyst of preparation is used directly for
Olefinic polymerization, as in gas-phase polymerization process；Olefinic polymerization can also be used for by additional aluminum alkyl catalyst,
Particularly add in slurry process alkyl aluminum can impurity in removing system, improve poly-to a certain extent
Close activity, and expensive MAO need not be added and make promoter.
The solvent that wherein polymerization is used is selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.Preferably hexane, pentane, heptane,
A kind of in benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, most preferably oneself
A kind of in alkane, toluene, heptane or their mixture.
In supported late transition metal catalyst method, the catalyst of the preparation concentration when polymerization is 1 × 10-8Rub
You/liter～1 × 10-3Mol/L, preferred concentration range is 1 × 10-8Mol/L-1～10-5Mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, preferably 0 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, preferably 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
Modified silica gel carrier preparation method of the present invention is simple, and the catalyst granules form obtained is good, urges
Catalyst particles size is adjustable.
Supported late transition metal catalyst of the present invention has the highest vinyl polymerization catalysis activity.
Supported late transition metal catalyst of the present invention obtains resin powder for olefinic polymerization and has good
Good particle shape, bulk density is high, goes for slurry process and vapor phase method polymerization technique.
Analysis and characterization instrument used in the present invention is as follows:
1, ICP (plasma emission spectrum) characterizes: the percentage by weight of metal in quantitative determination carried catalyst.
The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, polymer molecular weight and the sign of molecular weight distribution: molecular weight and distribution thereof are by gel permeation chromatography (GPC)
Measuring, instrument uses Waters Alliance GPCV2000, and solvent is 1,2,4-trichloro-benzenes, and sample is dense
Degree is lmg/ml, and solvent flow rate is 1.0ml/min;Measuring temperature is 150 DEG C.Secondary measured by each sample.
Embodiment
Embodiment 1
(1) preparation of chlorination alkyl silicon/silica-gel carrier
Under nitrogen protection, take dry silica-gel carrier 10.0 grams and add in glass reactor, add 100 millis
Rise dried hexane, be dispersed into suspension, add 1 milliliter of SiCl2(n-Bu)2, start stirring, heat up
To 30 DEG C, react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(2) preparation of organo-aluminium/chlorination alkyl silicon/silica-gel carrier
Under nitrogen protection, take modified silica gel carrier obtained above 5.0 grams and add in glass reactor, add
60 milliliters of dried toluene, are dispersed into suspension, add the MAO (MAO) of 18 milliliters of 10wt%
Toluene solution, is warming up to 50 DEG C, stirring reaction 4 hours, then washs three times with 50 milliliters × 3 toluene,
Then wash with hexane, vacuum drying, obtain the pressed powder of good fluidity, i.e. contain MAO
Silica-gel carrier.
(3) preparation of supported late transition metal catalyst A
Under nitrogen protection, the silica-gel carrier 2.50 grams containing MAO that will be previously obtained, join
In glass reactor, add 35 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene
0.096 gram of Fe catalyst precarsor [2,6-double [1-(2,4,6 one trimethylbenzene imines) ethyl] pyridines two
Iron chloride, its synthesis is shown in patent WO9827124A1, embodiment 1, and structure sees below] solution be added drop-wise to instead
Answer in device, react 30 minutes at 30 DEG C, then with 35 milliliters of toluene washings, vacuum drying, loaded
Post-transition metal catalyst A.Characterizing through ICP, in catalyst A, Fe weight content is 0.17%, Al
Weight content is 10.20%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/silica-gel carrier
Under nitrogen protection, take 7.01 grams of silica gel (GRACE955, under nitrogen, 150 DEG C of roastings 2.5 hours,
It is warming up to 300 DEG C of roastings 2 hours, then 600 DEG C of roastings 5 hours) add in glass reactor, add
90 milliliters of dried toluene, are dispersed into suspension, add the MAO(methyl alumina of 40 milliliters of 10wt%
Alkane) toluene solution, it is warming up to 50 DEG C, stirring reaction 4 hours, then with 50 milliliters × 3 toluene washings three
Secondary, then wash with hexane, vacuum drying, obtain the pressed powder of good fluidity, i.e. alkylaluminoxane/
Silica-gel carrier.
(3) preparation of supported late transition metal catalyst A*
Under nitrogen protection, the above-mentioned alkylaluminoxane/silica-gel carrier prepared 2.50 grams is joined glass anti-
Answer in device, add 30 milliliters of dried toluene and make serosity, be dissolved in 20 milliliters of toluene 0.048 gram
Fe catalyst precarsor [2,6-double [1-(2,4,6 one trimethylbenzene imines) ethyl] pyridyl iron dichloride]
Solution is added drop-wise in reactor, reacts 30 minutes at 30 DEG C, and then with 30 milliliters of toluene washings, vacuum is done
Dry, obtain supported non-metallocene single site catalysts A*.Characterize through ICP, in catalyst A*, Fe weight
Amount content is 0.18%, and Al weight content is 14.23%.
Embodiment 2
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (1), only by SiCl in embodiment 12(n-Bu)2It is changed to SiCl4。
(2) preparation of organo-aluminium/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2).
(3) preparation of supported late transition metal catalyst B
With embodiment 1 step (3), only by embodiment 1 0.096 gram (2,6-double [1-(2,4,6
One trimethylbenzene imines) ethyl] pyridyl iron dichloride replaces with 0.111 gram of [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridyl iron dichloride] (its structure sees below, and patent WO9827124A1 is shown in its synthesis,
Embodiment 8), obtain loaded late transition metal catalyst B.Characterize through ICP, in catalyst B, Fe weight
Content is 0.20%, and Al weight content is 11.28%.
Embodiment 3
(1) preparation of chlorination silicon alkyl/silica-gel carrier
With (1) preparation method in embodiment 1.
(2) preparation of organo-aluminium/chlorination silicon alkyl/silica-gel carrier
With embodiment 1 step (2), only 18 milliliters of 10%MAO are replaced with 13 milliliters of 2M diethyl bases
Aluminum.
(3) preparation of supported late transition metal catalyst C
With embodiment 1 step (3), only by embodiment 1 0.096 gram [2,6-double [1-(2,4,6
One trimethylbenzene imines) ethyl] pyridyl iron dichloride] replace with 0.098 gram of [(2,6-double [1-(2 one first
Base 6-chloro-benzene imines) ethyl] pyridyl iron dichloride] (its structure sees below, and patent is shown in its synthesis
WO9827124A1, embodiment 2), obtain loaded late transition metal catalyst C.Characterize through ICP, catalysis
In agent C, Fe weight content is 0.19%, and Al weight content is 12.04%.
Embodiment 4
(1), (2) are with (1), (2) preparation method in embodiment 2.
(3) preparation of supported late transition metal catalyst D
With embodiment 2 step (3), only by embodiment 2 0.111 gram [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridyl iron dichloride] replace with 0.145 gram of [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridine ferric bromide] (its structure sees below, and patent WO9827124A1 is shown in its synthesis,
Embodiment 9), obtain loaded late transition metal catalyst D.Characterize through ICP, in catalyst D, Fe weight
Content is 0.20%, and Al weight content is 11.80%.
Embodiment 5
(1), (2) are with (1), (2) preparation method in embodiment 2.
(3) preparation of supported late transition metal catalyst E
With embodiment 2 step (3), only by embodiment 2 0.111 gram [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridyl iron dichloride] replace with 0.114 gram of [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridine cobalt dichloride] (its structure sees below, and patent WO9827124A1 is shown in its synthesis,
Embodiment 7), obtain loaded late transition metal catalyst E.Characterize through ICP, in catalyst E, Co weight
Content is 0.20%, and Al weight content is 11.63%.
Embodiment 6
(1), (2) are with (1), (2) preparation method in embodiment 2.
(3) preparation of supported late transition metal catalyst F
With embodiment 2 step (3), only by embodiment 2 0.111 gram [2,6-double [1-(2,6 one two
Cumene imines) ethyl] pyridyl iron dichloride] replace with 0.325 gram of [2,3-double (2,6-diisopropyl
Base benzene imines) acenaphthene nickelous bromide] (its structure sees below, and J.Am.Chem.Soc.1995 is shown in its synthesis,
117,6414-6415) loaded late transition metal catalyst F, is obtained.Characterize through ICP, in catalyst F,
Ni weight content is 0.60%, and Al weight content is 9.61%.
Comparing embodiment 6
(1) with the preparation method of (1) in comparing embodiment 1.
(3) preparation of supported late transition metal catalyst F*
With embodiment 6 step (3), obtain loaded late transition metal catalyst F*.Characterize through ICP, catalysis
In agent F*, Ni weight content is 0.61%, and Al weight content is 14.06%.
Embodiment 7
(1), (2) are with (1), (2) preparation method in embodiment 6.
(3) preparation of supported late transition metal catalyst G
With embodiment 6 step (3), only by embodiment 6 0.325 gram [2,3-double (2,6-diisopropyls
Base benzene imines) acenaphthene nickelous bromide] replace with 0.281 gram of Ni catalyst precarsor [2,3-double (2,6-
Diisopropyl benzene imines) butane Nickel Bromide] (J.Am.Chem.Soc.1995,117 is shown in synthesis,
6414-6415, structure sees below), obtain loaded late transition metal catalyst G.Characterize through ICP, catalyst G
In, Ni weight content is 0.50%, and Al weight content is 10.11%.
Embodiment 8
(1), (2) are with (1), (2) preparation method in embodiment 6.
(3) preparation of supported late transition metal catalyst H
With embodiment 6 step (3), only by embodiment 6 0.325 gram (2,3-double (2,6-diisopropyls
Base benzene imines) acenaphthene nickelous bromide replaces with 0.231 gram of Ni catalyst precarsor [2,3-double (2,6-bis-
Methylbenzene imines) butane Nickel Bromide] (J.Am.Chem.Soc.1995 is shown in synthesis, 117,6414-6415,
Structure sees below), obtain loaded late transition metal catalyst H.Characterize through ICP, in catalyst H, Ni weight
Content is 0.52%, and Al weight content is 11.23%.
Embodiment 9
(1), (2) are with (1), (2) preparation method in embodiment 6.
(3) preparation of supported late transition metal catalyst I
With embodiment 6 step (3), only by 0.231 gram of Ni catalyst precarsor in embodiment 6 (2,3-double (2,
6-dimethyl benzene imines) butane Nickel Bromide replace with 0.367 gram of Pd catalyst precarsor [2,3-double (2,
6-dimethyl benzene imines) butane methyl diethoxy tetraphenyl boron palladium] (J.Am.Chem.Soc. is shown in synthesis
1995,117,6414-6415, structure sees below), obtain loaded late transition metal catalyst I.Through ICP table
Levying, in catalyst I, Pd weight content is 0.90%, and Al weight content is 11.23%.
High pressure ethylene polymerization is tested
High pressure ethylene polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, respectively replace three times with nitrogen and ethylene, be subsequently adding 1000
Milliliter hexane solvent, along with the addition of hexane, by triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol/L
Add, be subsequently added into the supported late transition metal catalyst 50-200 milligram that above-described embodiment prepares, rise
Pressure, to 80 DEG C, is risen to and maintains 1.0MPa, react 1 hour by temperature.After polyreaction terminates, cooling,
Collect polyethylene particle powder, weigh.
Concrete polymerization result is shown in Table 1.
Table 1, supported late transition metal catalyst polymerization result
Claims (8)
1. the supported late transition metal catalyst for vinyl polymerization, it is characterised in that this catalyst includes
The product of following component:
(1) late transition metal compound；
(2) chlorination silicon alkyl or Silicon chloride. modifying agent；
(3) organo-aluminum compound；
(4) silica-gel carrier；
Component (1) described late transition metal compound, refers to that the late transition metal shown in formula 1 and 2 is joined
Compound,
In formula 1, R1And R7It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；
R2-R6It is respectively selected from hydrogen atom or C1-C20Alkyl；And R2-R6In two or more bases
Group's optionally mutual cyclization；
M is Fe or Co；
X is identical or different, selected from halogen, alkyl or oxyl；N is the integer meeting M valence state；
In formula 2, R8And R11It is respectively selected from C1-C30Alkyl or miscellaneous alkyl；
R9And R10It is respectively selected from hydrogen atom or C1-C20Alkyl, and R9And R10Optionally mutual cyclization；
M is Ni or Pd；
X is identical or different, selected from halogen, alkyl or oxyl；N is the integer meeting M valence state；
Component (2) described chlorination silicon alkyl or Silicon chloride. modifying agent are selected from compound described in below general formula:
ClnSi(R1)4-n
Wherein R1Represent C1-20Alkyl, n represents the integer of 1-4；
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or chlorination alkyl aluminum
Compound, alkylaluminoxane formula is:
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
Supported late transition metal catalyst for vinyl polymerization the most according to claim 1, it is characterised in that
In formula 1, R1And R7It is respectively selected from C6-C30Aryl radical；
In formula 2, R8And R11It is respectively selected from C6-C30Aryl radical.
Supported late transition metal catalyst for vinyl polymerization the most according to claim 1, its feature exists
In, the ratio between each reactant is in terms of every gram of silica-gel carrier, and chlorination silicon alkyl or Silicon chloride. modifying agent add
Entering amount is 0.01-3mmol, and the addition of organo-aluminum compound is 0.01-30mmol, late transition metal chemical combination
The addition of thing is 1-1000 μm ol.
Supported late transition metal catalyst for vinyl polymerization the most according to claim 1, its feature exists
In, aluminum weight content is 1-15%；In formula (1) and formula (2), the weight content of central metal M is
0.05-2%.
Supported late transition metal catalyst for vinyl polymerization the most according to claim 1, its feature exists
In, described chlorination silicon alkyl or Silicon chloride. modifying agent, wherein R1For methyl, ethyl, propyl group or phenyl；
Described alkyl aluminum compound is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, three just
Hexyl aluminum or tri-n-octylaluminium, alkyl aluminum chloride compound is diethylaluminum chloride, ethylaluminium dichloride or again
Half ethylaluminium chloride, described alkylaluminoxane, R is methyl, and a represents the integer of 10-30.
6. the preparation side of the supported late transition metal catalyst for vinyl polymerization that one of claim 1-5 is described
Method, it is characterised in that comprise the following steps:
The first step: under inert gas shielding, silica-gel carrier exists with chlorination silicon alkyl or Silicon chloride. modifying agent
0-90 DEG C is reacted 3-24 hour, obtains chlorination silicon alkyl or Silicon chloride. modifier modification silica gel；
Second step: under inert gas shielding, by first step gained chlorination silicon alkyl or Silicon chloride. modifying agent
Modified silica-gel reacts 3-24 hour at 0-90 DEG C with organo-aluminum compound, obtains organo-aluminum compound modified silicon
Glue；
3rd step: under inert gas shielding, by second step gained organo-aluminum compound modified silica-gel with rear mistake
Cross metallic compound to react 0.5-24 hour at 0-90 DEG C；
The dispersant of above-mentioned reaction is selected from toluene, benzene, dimethylbenzene, hexane, heptane or hexamethylene.
Preparation method the most according to claim 6, it is characterised in that in the first step is reacted, reaction temperature
For 30-80 DEG C；Dispersant used is selected from toluene, hexane, heptane or hexamethylene；In second step reacts, instead
Answering temperature to be 20-90 DEG C, dispersant used is toluene, in three-step reaction, dispersant used be toluene or
Hexane.
8. in claim 1-5, the supported late transition metal catalyst for vinyl polymerization described in any one exists
Application in vinyl polymerization.
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