CN104059175B - A kind of for the supported late transition metal catalyst of vinyl polymerization, method for making and application - Google Patents
A kind of for the supported late transition metal catalyst of vinyl polymerization, method for making and application Download PDFInfo
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Abstract
The present invention relates to a kind of loaded late transition metal catalyst for vinyl polymerization and preparation method, this catalyst includes (a) late transition metal compound；(b) chlorination silicon alkyl；(c) organo-aluminum compound；The product of (d) magnesium chloride support；Its preparation method includes: the preparation of (1) chlorination alkyl Si modification magnesium chloride support, the preparation of the modified chlorinated magnesium carrier of (2) organo-aluminium, (3) magnesium chloride loaded late transition metal catalyst preparation, obtained ethylene Polymerization Catalyzed by Later Transition Metal or combined polymerization have significantly high polymerization activity.Magnesium chloride support preparation method used is simple, and the carried catalyst particle shape of gained is good, and size is adjustable.The copolymerization of the supported catalyst catalyzed ethylene that the method obtains and alpha-olefin, polymerization activity is high and obtains resin powder and has good particle shape, and bulk density is high, it is possible to suitable in slurry process and vapor phase method polymerization technique.
Description
Technical field
The preparation method that the present invention relates to a kind of loaded late transition metal catalyst for vinyl polymerization, and the application that gained catalyst is in olefinic polymerization.
Technical background
In the evolution of olefin polymerization catalysis, the late transition metal catalyst of nineteen nineties development obtains development greatly and pays close attention to.Particularly Ni, Pd and Fe, Co diimine catalysts system (WO9623010, WO9827124), nickel, palladium catalyst can generate the branching of Narrow Molecular Weight Distribution or even hyperbranched High molecular weight polyethylene by ethylene homogeneous polymerization, and ferrum, Co catalysts can generate the Hi-fax that wide molecular weight is distributed by catalyzed ethylene.But olefinic polymerization is to carry out in homogeneous, and the polymer obtained is 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, everybody substantially adopts the silica gel with good particle shape to be carrier, as ShihKeng-Yu uses the silica gel activating late transition metal catalyst of a kind of load alkyl aluminum in WO01/32723, can use alkyl aluminum is promoter, has good catalysis activity.Although also more (PCTInt.Appl.99/21898 is reported in the research for magnesium chloride compound load single site catalysts;US6,455,647;J.Mol.Catal.A2002,188,123;PCTInt.Appl.2004/078804), but the cost of carrier preparation and catalyst load is high, and carrier particle shape is poor, it is impossible to control；Although using spherical magnesium chloride the catalyst of proof load can have good particle shape, but containing components such as alcohol, water, alkoxyls in carrier, carrier preparation complexity, disadvantage mentioned above limiting the commercial Application of magnesium chloride load single site catalysts.
Summary of the invention
One of the object of the invention is in that the preparation method providing a kind of organo-aluminium/chlorination silicon alkyl/magnesium chloride loaded late transition metal catalyst.
The two of the object of the invention are in that above-mentioned supported late transition metal catalyst is used for vinyl polymerization or combined polymerization, have high polymerization activity.
A kind of supported late transition metal catalyst for vinyl polymerization of the present invention, this catalyst includes the product of following component:
(1) late transition metal compound；
(2) chlorination silicon alkyl；
(3) organo-aluminum compound；
(4) magnesium chloride support；
Component (1) described late transition metal compound, refers to the late transition metal complex shown in formula 1 and 2,
Formula 1
In formula 1, R1And R7It is respectively selected from C1-C30Alkyl or assorted alkyl；
R2-R6It is respectively selected from hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom organic group；And R2-R6In two or more groups optionally mutual cyclization；
M is the 8th race's metal；
X is identical or different, the one in halogen, alkyl, oxyl, acid group, amido；N is the integer meeting M valence state；
Formula 2
In formula 2, R8And R11It is respectively selected from C1-C30Alkyl or assorted alkyl；R9And R10It is respectively selected from hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom organic group；And R9And R10Optionally mutual cyclization；M is the 8th race's metal；
X is identical or different, selected from halogen, alkyl oxyl, acid group, amido；N is the integer meeting M valence state；
The described chlorination silicon alkyl of component (2) refers to compound described in below general formula: ClnSi(R1)4-nWherein R1Represent C1-C20Alkyl, n represents the integer of 1-4；
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or alkyl aluminum chloride compound, and wherein alkylaluminoxane formula is::
Or
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
In formula 1, R1And R7It is respectively selected from C1-C30Alkyl, assorted alkyl；Wherein preferred C6-C30Aryl radical and substituted aroma alkyl, e.g., phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,6-xylyls, mesityl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethyl phenyl, mesityl, 2-isopropyl phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,6-di-tert-butyl-phenyls, 2,4,6-tri-tert phenyl, 2-Benzylphenyl, 3-Benzylphenyl, 4-Benzylphenyl, 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-triphenyl phenyl, 2-(benzhydryl) phenyl, 3-(benzhydryl) phenyl, 4-(benzhydryl) phenyl, 2,4-bis-(benzhydryl) phenyl, 2,4,6-tri-(benzhydryl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-bis-(trityl) phenyl or 2,4,6-tri-(trityl) phenyl etc..
R2-R6It is respectively selected from hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom organic group；And R2-R6In two or more groups optionally mutual cyclization.The phenyl of preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, nitro replacement, halogenophenyl, alkyl-substituted phenyl, naphthyl, xenyl, trityl, benzhydryl, adamantyl, 2-phenyl-isopropyl etc.；Wherein preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, adamantyl, 2-phenyl-isopropyl etc..
M is the 8th race's metal, it is preferable that ferrum, cobalt.
X is identical or different, selected from halogen, alkyl and oxyl, it is preferable that halogen, alkyl and alkoxyl.It most preferably is chlorine, bromine, iodine, methyl and ethyl；N is the integer meeting M valence state；
The synthesis of the metal complex shown in formula 1 is standby according to WO9827124, WO9830612 patent system.
Formula 2
In formula 2, R8And R11It is respectively selected from C1-C30Alkyl and assorted alkyl.Wherein preferred C6-C30Aryl radical and substituted aroma alkyl, e.g., phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,6-xylyls, mesityl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,6-diethyl phenyl, mesityl, 2-isopropyl phenyl, 3-isopropyl phenyl, 4-isopropyl phenyl, 2,6-diisopropyl phenyls, 2,4,6-triisopropyl phenyl, 2-tert-butyl-phenyl, 3-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,6-di-tert-butyl-phenyls, 2,4,6-tri-tert phenyl, 2-Benzylphenyl, 3-Benzylphenyl, 4-Benzylphenyl, 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-triphenyl phenyl, 2-(benzhydryl) phenyl, 3-(benzhydryl) phenyl, 4-(benzhydryl) phenyl, 2,4-bis-(benzhydryl) phenyl, 2,4,6-tri-(benzhydryl) phenyl, 2-(trityl) phenyl, 3-(trityl) phenyl, 4-(trityl) phenyl, 2,4-bis-(trityl) phenyl or 2,4,6-tri-(trityl) phenyl etc..
R9And R10Respectively hydrogen atom, chlorine atom, C1-C20Alkyl, heterocyclic compound group, oxygen-containing, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom organic group；And R9And R10Optionally mutual cyclization.Preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, the phenyl that nitro replaces, halogenophenyl, alkyl-substituted phenyl, Cai Ji, xenyl, trityl, benzhydryl, adamantyl, 2-phenyl-isopropyl, pyridine radicals, pyrrole radicals, wherein preferred hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl, n-hexyl, isohesyl, tertiary hexyl, phenyl, adamantyl, 2-phenyl-isopropyl.
M is the 8th race's metal, it is preferable that nickel, palladium.
X is identical or different, selected from halogen, alkyl and oxyl, it is preferable that halogen, alkyl, alkoxyl.It most preferably is chlorine, bromine, iodine, methyl, ethyoxyl.
N is the integer meeting M valence state.
Metal complex shown in formula 2 synthesizes according to patent WO9623010.
The described chlorination silicon alkyl of component (2) refers to compound described in below general formula: ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4, described chlorination silicon alkyl is selected from trim,ethylchlorosilane, chlorotriethyl silane, tri isopropyl chlorosilane, dimethyl ethyl chlorosilane, diethylpropyl chlorosilane, dipropyl methylchlorosilane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, dichloromethyl n-pro-pyl silane, dichloromethyl phenyl silane, trichloromethyl silane, trichloroethyl silane, phenyl trichlorosilane and Silicon chloride. etc., preferred trim,ethylchlorosilane, chlorotriethyl silane, dichloro-dimethyl silicon, Dichlorodiethyl silicon, dichlorophenyl silicon, trichloromethyl silane, trichloroethyl silane and Silicon chloride..
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or alkyl aluminum chloride compound, alkyl aluminum compound is selected from trialkylaluminium, such as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium；Chlorination alkyl aluminum is selected from diethylaluminum chloride, ethylaluminium dichloride or ethylaluminum sesquichloride etc..
Alkylaluminoxane formula is:
Or
Wherein R represents C1-C12Alkyl, a represents the integer of 4-30.
Loaded late transition metal catalyst for ethylene polymerization, ratio between each reactant is in every gram of magnesium chloride support, chloric ether SiClx addition is 0.01-3mmol, and the addition of organo-aluminium is 0.01-30mmol, and the addition of late transition metal compound is 1-1000 μm of ol.
For the supported late transition metal catalyst of vinyl polymerization, in supported late transition metal catalyst, the preferred 1-15% of aluminum weight content, the preferred 0.05-2% of weight content of central metal M.
Described chlorination alkyl silicon, wherein R1For methyl, ethyl, propyl group, n represents the integer of 1-4.
Described has the preferred triethyl aluminum of base aluminum, triisobutyl aluminium, the preferred diethylaluminum chloride of chlorination alkyl aluminum, ethylaluminium dichloride and ethylaluminum sesquichloride, the preferred MAO of alkylaluminoxane (MAO), the MAO (MMAO) improved.
The preparation method of a kind of supported late transition metal catalyst for vinyl polymerization of the present invention, comprises the steps:
(1) preparation of the magnesium chloride support of chlorination alkyl Si modification: under noble gas such as nitrogen protection; magnesium chloride support is added in reactor; add solvent; it is dispersed into suspension; add chlorination alkyl silicon; it is warming up to 0-90 DEG C; preferred 30-80 DEG C; stirring reaction 3-24 hour; preferred 3-10 hour, then with solvent wash for several times, vacuum drying; obtaining the magnesium chloride support containing chlorination alkyl Si modification of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferred toluene or saturated alkane.
(2) preparation of the modified chlorinated magnesium carrier of organo-aluminium: under noble gas such as nitrogen protection; the magnesium chloride support obtained in (1st) step is added in reactor; add solvent; it is dispersed into suspension; it is added with machine aluminium compound; it is warming up to 0-90 DEG C; preferred 40-90 DEG C; stirring reaction 3-24 hour; preferred 3-10 hour, then with solvent wash for several times, vacuum drying; obtaining the magnesium chloride support containing organo-aluminium of good fluidity, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene；Preferred toluene.
(3) preparation of modified chlorinated magnesium-supported late transition metal catalyst: under noble gas such as nitrogen protection, the magnesium chloride support containing alkylaluminoxane that will prepare in (2nd) step, join and solvent is made serosity, the solution of late transition metal catalyst precursor is slowly added dropwise in this serosity, at 0-90 DEG C, react 0.5-24 hour, preferred 0.5-10 hour, obtain supported late transition metal catalyst, serosity can be directly used in polyreaction, or gained reactant is removed solvent, washing obtains the solid supported post-transition metal catalyst of good fluidity after drying, described solvent is toluene, benzene, dimethylbenzene, hexane, heptane, hexamethylene.Preferred toluene, hexane or both mixture.
Supported late transition metal catalyst of the present invention is usable on different polymerizations, such as gas-phase polymerization and slurry polymerization etc..Can be used for all polymerizations of alkene or copolymerization, be particularly well-suited to the copolymerization of ethylene homo conjunction or ethylene and alpha-olefin, wherein alpha-olefin adopts 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；Can also additional aluminum alkyl catalyst for olefinic polymerization, particularly add in slurry process alkyl aluminum can impurity in removing system, improve polymerization activity to a certain extent, make promoter without adding expensive MAO.
Wherein it is polymerized the solvent used selected from alkane, aromatic hydrocarbon or halogenated hydrocarbons.A kind of in preferred hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform, dichloroethanes or their mixture, it is most preferred that for a kind of in hexane, toluene, heptane or their mixture.
In supported late transition metal catalyst method, the catalyst of the preparation concentration when polymerization is 1 × 10-8Mol/L～1 × 10-3Mol/L, it is preferable that concentration range is 1 × 10-8Mol/L-1～10-5Mol/L.
Polymerization temperature is-78 DEG C-100 DEG C, it is preferred to 0 DEG C-90 DEG C.
Polymerization pressure is 0.01-10.0MPa, it is preferable that 0.01-2.0MPa.
The present invention compared with prior art has the following advantages:
Modified chlorinated magnesium carrier preparation method of the present invention is simple, and the catalyst granules form obtained is good, and catalyst particle size is adjustable.
In supported late transition metal catalyst method of the present invention, the catalyst of preparation has significantly high vinyl polymerization catalysis activity.
The catalyst prepared in supported late transition metal catalyst method of the present invention obtains resin powder for olefinic polymerization and has good particle shape, and bulk density is high, it is possible to suitable in slurry process and vapor phase method polymerization technique.
The 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 assay carried catalyst.The P1000 type ICP-AES plasma emission spectrometer that PE company of the instrument selection U.S. produces.
2, the sign of polymer molecular weight and molecular weight distribution: molecular weight and distribution thereof are measured by gel permeation chromatography (GPC), and instrument adopts WatersAllianceGPCV2000, and solvent is 1,2,4-trichloro-benzenes, sample concentration 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 silicon alkyl/magnesium chloride support
Under nitrogen protection, take magnesium chloride support 10.0 grams and add in glass reactor, add 100 milliliters of dried hexanes, be dispersed into suspension, add 1 milliliter of SiCl2(n-Bu)2, start stirring, be warming up to 30 DEG C, react 4 hours, vacuum drying, obtain the pressed powder of good fluidity.
(2) preparation of organo-aluminium/chlorination silicon alkyl/magnesium chloride support
Under nitrogen protection; take modified chlorinated magnesium carrier obtained above 5.0 grams to add in glass reactor, add 60 milliliters of dried toluene, be dispersed into suspension; add MAO (MAO) toluene solution of 18 milliliters of 10wt%; it is warming up to 50 DEG C, stirring reaction 4 hours, then washs three times with 50 milliliters × 3 toluene; then with hexanes wash; vacuum drying, obtains the pressed powder of good fluidity, namely contains the magnesium chloride support of MAO.
(3) preparation of supported late transition metal catalyst A
Under nitrogen protection, the magnesium chloride support 2.50 grams containing MAO that will be previously obtained, join in glass reactor, add 35 milliliters of dried toluene and make serosity, it is dissolved in 20 milliliters of toluene 0.096 gram of Fe catalyst precarsor [2, double, two " the 1-(2 of 6-, 4, 6 one trimethylbenzene imines) ethyl " pyridyl iron dichloride, patent WO9827124A1 is shown in its synthesis, embodiment 1, under structure is shown in] the solution of synthesis be added drop-wise in reactor, react 30 minutes at 30 DEG C, then wash with 35 milliliters of toluene, vacuum drying, obtain supported late transition metal catalyst A.Characterizing through ICP, in catalyst A, Fe weight content is 0.17%, and Al weight content is 10.20%.
Comparing embodiment 1
(1) preparation of alkylaluminoxane/magnesium chloride support
Under nitrogen protection; take 7.01 grams of magnesium chloride supports to add in glass reactor, add 90 milliliters of dried toluene, be dispersed into suspension; add the MAO(MAO of 40 milliliters of 10wt%) toluene solution; it is warming up to 50 DEG C, stirring reaction 4 hours, then washs three times with 50 milliliters × 3 toluene; then with hexanes wash; vacuum drying, obtains the pressed powder of good fluidity, i.e. alkylaluminoxane/magnesium chloride support.
(3) preparation of supported late transition metal catalyst A*
Under nitrogen protection; above-mentioned alkylaluminoxane/the magnesium chloride support prepared 2.50 grams is joined in glass reactor; add 30 milliliters of dried toluene and make serosity; it is dissolved in 20 milliliters of toluene 0.096 gram of Fe catalyst precarsor [2; double; two [the 1-(2 of 6-; 4; 6 one trimethylbenzene imines) ethyl] pyridyl iron dichloride]; (its synthesis is with embodiment 1); solution be added drop-wise in reactor, react 30 minutes at 30 DEG C, then with the washings of 30 milliliters of toluene; vacuum drying, obtains supported non-metallocene single site catalysts A*.Characterizing through ICP, in catalyst A*, Fe weight content is 0.19%, and Al weight content is 14.22%.
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/magnesium chloride support
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, double; two [the 1-(2 of 6-, 4,6 one trimethylbenzene imines) ethyl] pyridyl iron dichloride] replace with 0.111 gram of [(2,6-double; two [1-(2,6 one diisopropyl benzene imines) ethyl] pyridyl iron dichloride] (under its structure is shown in, patent WO9827124A1, embodiment 8 are shown in its synthesis), obtain loaded late transition metal catalyst B.Characterizing through ICP, in catalyst B, Fe weight content is 0.22%, and Al weight content is 11.41%.
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/magnesium chloride support
With embodiment 1 step (2), only 18 milliliters of 10%MAO are replaced with 13 milliliters of 2M diethylaluminum chlorides.
(3) preparation of supported late transition metal catalyst C
With embodiment 1 step (3), only by embodiment 1 0.096 gram [(2, double; two [the 1-(2 of 6-, 4,6 one trimethylbenzene imines) ethyl] pyridyl iron dichloride] (under its structure is shown in, patent WO9827124A1 is shown in its synthesis to replace with 0.098 gram [(2,6-double; two [1-(the 2 chloro-benzene imines of monomethyl 6-) ethyl] pyridyl iron dichloride], embodiment 2), obtain loaded late transition metal catalyst C.Characterizing through ICP, in catalyst C, Fe weight content is 0.20%, and Al weight content is 11.92%.
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, double; two [the 1-(2 of 6-, 6 one diisopropyl benzene imines) ethyl] pyridyl iron dichloride] replace with 0.145 gram [(2, double; two [1-(2,6 one diisopropyl benzene imines) ethyl] the pyridine ferric bromide of 6-] (under its structure is shown in, patent WO9827124A1 is shown in its synthesis, embodiment 9), obtain loaded late transition metal catalyst D.Characterizing through ICP, in catalyst D, Fe weight content is 0.21%, and Al weight content is 11.46%.
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, double; two [the 1-(2 of 6-, 6 one diisopropyl benzene imines) ethyl] pyridyl iron dichloride] replace with 0.114 gram [(2, double; two [1-(2,6 one diisopropyl benzene imines) ethyl] the pyridine cobalt dichloride of 6-] (under its structure is shown in, patent WO9827124A1 is shown in its synthesis, embodiment 7), obtain loaded late transition metal catalyst E.Characterizing through ICP, in catalyst E, Co weight content is 0.21%, and Al weight content is 11.72%.
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, double; two [the 1-(2 of 6-, 6 one diisopropyl benzene imines) ethyl] pyridyl iron dichloride] replace with 0.325 gram [(2,3-double; two (2,6-diisopropyl benzene imines) acenaphthene nickelous bromides] (under its structure is shown in, J.Am.Chem.Soc.1995 is shown in its synthesis, 117,6414-6415) loaded late transition metal catalyst F, is obtained.Characterizing through ICP, in catalyst F, Ni weight content is 0.61%, and Al weight content is 11.21%.
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*.Characterizing through ICP, in catalyst F*, Ni weight content is 0.62%, and Al weight content is 14.97%.
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; two (2,6-diisopropyl benzene imines) acenaphthene nickelous bromide] (J.Am.Chem.Soc.1995 is shown in synthesis to replace with 0.281 gram of Ni catalyst precarsor [(2,3-double; two (2,6-diisopropyl benzene imines) butane Nickel Bromides], 117,6414-6415, under structure is shown in), obtain loaded late transition metal catalyst G.Characterizing through ICP, in catalyst G, Ni weight content is 0.49%, and Al weight content is 9.94%.
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; two (2,6-diisopropyl benzene imines) acenaphthene nickelous bromide] (J.Am.Chem.Soc.1995 is shown in synthesis to replace with 0.231 gram of Ni catalyst precarsor [(2,3-double; two (2,6-dimethyl benzene imines) butane Nickel Bromides], 117,6414-6415, under structure is shown in), obtain loaded late transition metal catalyst H.Characterizing through ICP, in catalyst H, Ni weight content is 0.53%, and Al weight content is 12.41%.
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 [(2 in embodiment 6,3-double; two (2,6-dimethyl benzene imines) butane Nickel Bromide] (J.Am.Chem.Soc.1995 is shown in synthesis to replace with 0.367 gram of Pd catalyst precarsor [(2,3-double; two (2,6-dimethyl benzene imines) butane methyl diethoxy tetraphenyl boron palladiums], 117,6414-6415, under structure is shown in), obtain loaded late transition metal catalyst I.Characterizing through ICP, in catalyst I, Pd weight content is 0.94%, and Al weight content is 12.07%.
High pressure ethylene polymerization is tested
High pressure ethylene polymerization experimentation is as follows:
In the rustless steel polymerization autoclave of 2 liters, three times are respectively replaced with nitrogen and ethylene, it is subsequently adding 1000 milliliters of hexane solvents, addition along with hexane, triethyl aluminum (TEA) hexane solution of 2 milliliter of 1 mol/L is added, is subsequently added into the supported late transition metal catalyst 50-200 milligram that above-described embodiment prepares, is warming up to 80 DEG C, pressure rises to and maintains 1.0MPa, reacts 1 hour.After polyreaction terminates, cooling, collect polyethylene particle powder, weigh.
Concrete polymerization result is listed 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) magnesium chloride support；
Component (1) described late transition metal compound, refers to the late transition metal complex shown in formula 1 and 2,
In formula 1, R1And R7It is respectively selected from C1-C30Alkyl or assorted alkyl；
R2-R6It is respectively selected from hydrogen atom, C1-C20Alkyl；And R2-R6In two or more groups optionally mutual cyclization；
M is the 8th race's metal；
X is identical or different, the one in halogen, alkyl, oxyl；N is the integer meeting M valence state；
In formula 2, R8And R11It is respectively selected from C1-C30Alkyl or assorted alkyl；R9And R10It is respectively selected from hydrogen atom, C1-C20Alkyl；And R9And R10Optionally mutual cyclization；M is the 8th race's metal；
X is identical or different, selected from halogen, alkyl, oxyl；N is the integer meeting M valence state；
The described chlorination silicon alkyl of component (2) or Silicon chloride. modifying agent refer to compound described in below general formula:
ClnSi(R1)4-n
Wherein R1Represent C1-C20Alkyl, n represents the integer of 1-4；
Component (3) described organo-aluminum compound includes alkylaluminoxane, alkyl aluminum compound or alkyl aluminum chloride compound, and wherein alkylaluminoxane formula is:
Wherein R represents the integer that methyl, a represent 4-30.
2. the supported late transition metal catalyst for vinyl polymerization 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.
3. the supported late transition metal catalyst for vinyl polymerization according to claim 1, it is characterized in that, ratio between each reactant is in every gram of magnesium chloride support, chlorination silicon alkyl or Silicon chloride. modifying agent addition are 0.01-3mmol, the addition of organo-aluminum compound is 0.01-30mmol, and the addition of late transition metal compound is 1-1000 μm of ol.
4. the supported late transition metal catalyst for vinyl polymerization according to claim 1, it is characterised in that aluminum weight content is 1-15%；In formula (1), central metal M is ferrum or cobalt；In formula (2), central metal M is nickel or palladium；The weight content of central metal M is 0.05-2%.
5. the supported late transition metal catalyst for vinyl polymerization according to claim 1, it is characterised in that described chlorination silicon alkyl or Silicon chloride. modifying agent, wherein R1Selected from methyl, ethyl or propyl group or phenyl；Described alkyl aluminum compound is selected from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium；Chlorination alkyl aluminum is diethylaluminum chloride, ethylaluminium dichloride or ethylaluminum sesquichloride, and described alkylaluminoxane wherein R is methyl, and a represents the integer of 10-30.
6. the preparation method of the supported late transition metal catalyst for vinyl polymerization described for one of claim 1-5, it is characterised in that comprise the following steps:
The first step: under inert gas shielding, magnesium chloride support reacts 3-24 hour at 0-90 DEG C with chlorination silicon alkyl or Silicon chloride. modifying agent；
Second step: under inert gas shielding, reacts first step gained chlorination silicon alkyl or Silicon chloride. modifier modification magnesium chloride 3-24 hour at 0-90 DEG C with alkylaluminoxane；
3rd step: under inert gas shielding, reacts the second step modified chlorinated magnesium of gained alkylaluminoxane 0.5-24 hour at 0-90 DEG C with late transition metal compound；
The dispersant of above-mentioned reaction is selected from toluene, benzene, dimethylbenzene, hexane, heptane or hexamethylene.
7. the preparation method of catalyst according to claim 6, it is characterised in that in the first step is reacted, magnesium chloride support is 30-80 DEG C with chlorination silicon alkyl or Silicon chloride. modifying agent reaction temperature；Dispersant used is selected from toluene, hexane, heptane or hexamethylene；In second step reacts, reaction temperature is 20-80 DEG C, and dispersant used is toluene；In three-step reaction, dispersant used is selected from toluene or hexane.
8. in claim 1-5 described in any one for the application in vinyl polymerization of the supported late transition metal catalyst of vinyl polymerization.
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