CN105085733B - A kind of catalyst component for olefin polymerization preparation method and corresponding catalyst - Google Patents
A kind of catalyst component for olefin polymerization preparation method and corresponding catalyst Download PDFInfo
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Abstract
The invention provides a kind of preparation method of catalyst component for olefin polymerization and catalyst, methods described includes mixing magnesium compound with organic alcohol compound and atent solvent, add precipitation additive, reaction obtains alcohol adduct and is added in compound titanium solution, solid particle is filtered to isolate to be added in compound titanium solution again, stir and react, be separated by filtration, wash, dry after obtain the catalytic component；Being added in optional step a~d includes the internal electron donor compound of the imine compound shown in formula (I).When the catalyst that the method for the invention is prepared is used for propylene polymerization, the isotactic index of catalyst activity and resulting polymers is high, and catalyst activity decay is slow, and the molecular weight distribution of resulting polymers is wider.
Description
Technical field
The present invention relates to a kind of catalyst component for olefin polymerization preparation method and corresponding catalyst, belong to petrochemical industry neck
Domain.
Background technology
Olefin polymerization catalysis can be divided into three major types：Traditional Ziegler-Natta catalyst, metallocene catalyst and
Non-metallocene catalyst.For traditional propylene polymerization Ziegler-Natta catalyst, with the electron in catalyst
The development of body compound, polyolefin catalyst is also being continuously updated the replacement.The research and development of catalyst are from the first generation
TiCl3AlCl3/AlEt2The TiCl of Cl systems and the second generation3/AlEt2Cl systems, to the third generation magnesium chloride for carrier, monoesters or
The TiCl that aromatic dibasic acid ester is internal electron donor, silane is external electron donor4·ED·MgCl2/AlR3ED systems and new
Two ethers of exploitation, the catalyst system that two esters are internal electron donor, the catalytic polymerization activity and gained of catalyst
Polypropylene isotacticity is all greatly improved.In the prior art, for propylene polymerization titanium catalyst system more than with magnesium,
Titanium, halogen and electron donor are as basis, and wherein electron donor compound is essential component in catalytic component
One of.At present, it has been disclosed that a variety of electron donor compounds, such as monocarboxylic esters or multi-carboxylate, acid anhydrides, ketone, monoether or
Polyether, alcohol, amine etc. and its derivative, wherein what is more commonly used is aromatic dicarboxylic acids' esters, such as positive fourth of phthalic acid two
Ester (DNBP) or diisobutyl phthalate (DIBP) etc., reference can be made to United States Patent (USP) US4784983.United States Patent (USP)
In US4971937 and the component for olefin polymerization catalyst disclosed in European patent EP 0728769, it is special to employ
1, the 3- diether compounds containing two ether groups be electron donor, such as 2- isopropyls -2- isopentyl -1,3- dimethoxys
Propane, 2,2- diisobutyl -1,3- dimethoxy propanes and 9,9- bis- (methoxyl methyl) fluorenes etc..Thereafter a class is disclosed again special
Dibasic aliphatic carboxylic acid ester compound, such as succinate, malonate, glutarate (referring to WO98/56830,
WO98/56834, WO01/57099, WO01/63231 and WO00/55215), the use of this kind of electron donor compound not only may be used
The activity of catalyst is improved, and the molecular weight distribution of gained acrylic polymers is substantially widened.
Most common non-metallocene olefin polymerization catalyst is the transient metal complex containing C=N class multidentate ligands, such as
Brookhart et al. has found diimine late transition metal complex in catalysis in olefine polymerization with higher catalytic activity first
(Johnson L.K.,Killian C.M.,Brookhart M.,J.Am.Chem.Soc.,1995,117,6414；Johnson
L.K.,Ecking S.M.,Brookhart M.,J.Am.Chem.Soc.,1996,118,267).Henceforth, to non-cyclopentadienyl gold
The research of category organic coordination compound causes the great interest of people.McConville et al. reported in 1996 a class chelant β-
Ti, Zr metal complex (A) of diamines are the preceding transition gold of the multidentate ligand of class containing N-N of first case highly active catalytic olefinic polymerization
Metal complex (Scollard J.D., Mcconville D.H., Payne N.C., Vittal J.J, Macromolecules,
1996,29,5241；Scollard J.D.,Mcconville D.H.,J.Am.Chem.Soc.,1996,118,10008).
β-Diamines complex (B) is also the non-metallocene olefin polymerization catalyst of the important part of class containing N-N of a class, by
The characteristics of its structure, the steric hindrance and electronic effect of its part are easy to be easy to by the change of the substituent on arylamine
Regulation and control, the change of different metal and ligand environment, β-diamine based ligand can be matched somebody with somebody in different bonding modes with different metal
5 form corresponding metal complex, and such ligand compound has synthesis simple, it is easy to carry out regulation and control of configuration aspects etc.
Feature, is the complex of ideal research structure and catalyst performance relation, therefore the ligand compound of the class formation draws
Risen people extensive concern (Bourget-Merle L., Lappert M.F., Severn J.R., Chem.Rev., 2002,
102,3031；Kim W.K.,Fevola M.J.,Liable-Sands L.M.,Rheingold A.L.,Theopoid K.H.,
Organometallics, 1998,17,4541；Jin X.,Novak B.M.,Macromolecules,2000,33,6205).
Sinopec Beijing Chemical Research Institute polyethylene room discloses one-class bidentate part in Chinese patent 00107258.7
Metal complex, for ethene and its copolymerization.Then respectively Chinese patent application 02129548.4,
A kind of similar transient metal complex is disclosed in 200410086388.8 and 200710176588.6, for ethene and its altogether
Polymerisation.It is many that the patent 201010554473.8 and 201010108695.7 of Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry application discloses a class
Tooth ligand metallic catalyst, the High molecular weight polyethylene of the ultralow degree of branching is prepared for ethene and its copolymerization.
In above-mentioned related patent report, the catalyst for olefinic polymerization is corresponding ligand metal compound.
Up to now, there is not yet such ligand compound directly applies to olefin polymerization catalysis preparation and its in olefinic polymerization
Relevant report in terms of reaction.
The content of the invention
Urge it is an object of the invention to provide a kind of preparation method of catalytic component for olefinic polymerization and accordingly
Agent component and catalyst, the catalytic component contain imine compound, and the catalyst is used to have during propylene polymerization
There are higher activity and capacity of orientation, the molecular weight distribution of resulting polymers is wider.
To achieve the above object, the invention provides a kind of preparation method of catalyst component for olefin polymerization, including：
A, magnesium compound mixed with organic alcohol compound, add precipitation additive reaction and obtains alcohol adduct；
B, the alcohol adduct is added in compound titanium solution, filters to isolate the first solid particle；
C, first solid particle is added in compound titanium solution again, stirs and react, be then separated by filtration
Go out the second solid particle；
D, the second solid particle obtained with atent solvent washing step c, the catalytic component is obtained after drying；
Wherein, being added in optional step a~d includes the internal electron donor of the imine compound shown in formula (I)
Compound.
Wherein, n is 0~10 integer.
A is carbon or the hetero atom selected from oxygen, sulphur, nitrogen, boron or silicon, preferably carbon.
R and R ' is identical or different, is each independently selected from the substituted or unsubstituted C of hydroxyl, halogen atom1~C20Alkyl,
C2~C20Alkenyl, C6~C20Alkaryl or C10~C20The substituted or unsubstituted C of fused ring aryl, preferably halogen atom1~C8Alkane
Base, C6~C20Alkaryl or C10~C20It is fused ring aryl, more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, the tert-butyl group, amyl group, hexyl, phenyl, halobenzene base, alkyl-substituted phenyl, naphthyl or terphenyl.
R1And R2It is identical or different, it is each independently selected from the substituted or unsubstituted C of halogen atom1~C20Alkyl, C3~C20
Cycloalkyl, C2~C20Alkylene, C2~C20Ester group, C6~C20Aryl or C10~C20Fused ring aryl, preferably halogen atom replace
Or unsubstituted C1~C8Alkyl, C6~C20Aryl or C10~C20Fused ring aryl；RI、RII、R3And R4It is identical or different, each solely
On the spot it is selected from hydrogen, the substituted or unsubstituted C of halogen atom1~C20Alkyl, C3~C20Cycloalkyl, C2~C20Alkylene, C2~C20
Ester group, C6~C20Aryl or C10~C20Fused ring aryl, preferably hydrogen, the substituted or unsubstituted C of halogen atom1~C8Alkyl, C6
~C20Aryl or C10~C20Fused ring aryl；And R1~R4And RIAnd RIIOne or more of group can connect cyclization；R3~
R4And RIAnd RIICan be described arbitrarily comprising substituent of one or several hetero atoms as carbon or hydrogen atom or both on group
Hetero atom is oxygen, sulphur, nitrogen, boron, silicon, phosphorus or halogen atom.
The imine compound can specifically be used：(2,6- diisopropyl benzenes are sub- by the phenyl imido pentanes of 2,4- bis-, 2,4- bis-
Amido) pentane, 2,4- dinaphthyl imido grpups pentane, 2,4- bis- (2,6- imino dimethyl benzenes) pentane, the fourth imido grpups penta of 2,4- bis-
Alkane, 2,4- bis- (4- chlorobenzenes imido grpup) pentane, 2,4- bis- (2,4 dichloro benzene imido grpup) pentane, (the 4- trifluoromethylbenzenes of 2,4- bis-
Imido grpup) pentane, the phenyl imido heptane of 3,5- bis-, 3,5- bis- (2,6- diisopropyls phenyl imido) heptane, (the 2,6- bis- of 3,5- bis-
Methyl phenyl imido) heptane, the fourth imines base heptanes of 3,5- bis-, 2,4- bis- (8- quinoline imido grpup) pentane, (4- quinoline is sub- by 2,4- bis-
Amido) pentane, 2,4- bis- (3- quinoline imido grpup) pentane, 2,4- bis- (the chloro- 6- hydroxyls phenyl imidos of 2-) pentane, 2,4- bis- (2,
4,6- trimethylbenzenes imido grpup) pentane, the fluoro- 2,4- bis- of 1,1,1- tri- (2,6- diisopropyls phenyl imido) pentane, 1,1,1- tri-
Fluoro- 2,4- bis- (2,6- imino dimethyl benzenes) pentane, 1,3- diphenyl -1,3- two (2,6- diisopropyls phenyl imido) third
Alkane, 1,3- diphenyl -1,3- two (2,6- imino dimethyl benzenes) propane, (the 2,6- diisopropyl benzene imines of 1- phenyl -1,3- two
Base) butane, 1- phenyl -1,3- two (2,6- imino dimethyl benzenes) butane, (the 2,6- dimethyl benzene imines of 3- methyl -2,4- two
Base) pentane, 3- ethyls -2,4- two (2,6- imino dimethyl benzenes) pentane, the phenyl imido -4- ethyl heptanes of 3,5- bis-, 3,5-
Two (2,6- diisopropyls phenyl imido) -4- methyl heptanes, 3- ethyls -3,5- two (2,6- diisopropyls phenyl imido) heptane,
3- methyl -3,5- two (2,6- imino dimethyl benzenes) heptane, 3- ethyls -3,5- two (2,6- imino dimethyl benzenes) heptane,
2,4- bis- to chlorobenzene imido grpup pentane, 2- phenyl imidos -4- (2,6- diisopropyls phenyl imido) pentane, 1- (2- furyls) -
1,3- bis- (2,6- diisopropyls phenyl imido) -4,4,4- trifluorobutanes, 1- (2- furyls) (8- quinoline imines of -1,3- two
Base) -4,4,4- trifluorobutanes, 1- (2- furyls) -1,3- two (3- quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furans
Base) -1,3- two (2,6- imino dimethyl benzenes) -4,4,4- trifluorobutanes, 2- phenyl imidos -4- (2,6- dimethyl benzene imines
Base) pentane, 2- phenyl imido -4- are to chlorobenzene imido grpup pentane, (the 2,6- diisopropyls of 2,2,4,4,6,6- hexamethyls -2,4- two
Phenyl imido) pentane, 2- to chlorobenzene imido grpup -4- (2,6- diisopropyls phenyl imido) pentane, 2,2,4,4,6,6- hexamethyls -
2,4- bis- (2,6- imino dimethyl benzenes) pentane, the phenyl imido pentanes of 2,2,4,4,6,6- hexamethyls -2,4- two, 2,2,4,4,
6,6- hexamethyls -2,4- two (to chlorobenzene imido grpup) pentane, 2,2,4,4,6,6- hexamethyls -2,4- two (3- quinoline imido grpup) penta
Alkane, 2,2,4,4,6,6- hexamethyls -2,4- two (8- quinoline imido grpup) pentane, 2- are to chlorobenzene imido grpup -4- (2,6- dimethyl benzenes
Imido grpup) pentane, 1,3- diphenyl -1- phenyl imidos -3- (2,6- imino dimethyl benzenes) propane, 1,3- diphenyl -1- benzene
Imido grpup -3- (2,6- diisopropyls phenyl imido) propane, 2- [1- (2,6- diisopropyls phenyl imido) ethyl] -1- (2,6-
Diisopropyl phenyl imido) hexamethylene, 2- [1- (2,6- imino dimethyl benzenes) ethyl] -1- (2,6- imino dimethyl benzenes)
Hexamethylene, 2- [1- (2,6- dichloros phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylene, 2- [1- (2,6-
Imino dimethyl benzene) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylene, 2- [1- (phenyl imido) ethyl] -1-
(2,6- diisopropyls phenyl imido) hexamethylene and 2- [1- (phenyl imido) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene
At least one of alkane.
The imine compound is prepared as known technology, can by the way that aldehydes or ketones class compound is dissolved in into organic solvent
In, aminated compounds is then added, (acid or alkalescence) back flow reaction, is condensed to yield the chemical combination of corresponding construction under certain condition
Thing.
In the step a of above-mentioned preparation method, preferably by magnesium compound and organic alcohol compound by 2~5 mol ratio and
Atent solvent is mixed, and is warming up to 120~150 DEG C, and precipitation additive is added by magnesium/precipitation additive mol ratio 5~10, and reaction 1~5 is small
When.
In the step b of above-mentioned preparation method, preferably according to titanium/magnesium mol ratio 20~50, by institute at -15~-40 DEG C
State alcohol adduct to be added in compound titanium solution, then heat to 90~110 DEG C, reacted 1~3 hour at 100~130 DEG C, mistake
Solid particle is isolated in filter.
In the step c of above-mentioned preparation method, preferably solid particle is added to again according to titanium/magnesium mol ratio 20~50
In compound titanium solution, stir and reacted 1.5~3 hours at 100~130 DEG C, filter to isolate solid particle.
It is preferred that in step b or step d, bag is added for 1~100 amount according to internal electron donor compound/magnesium mol ratio
Include the internal electron donor compound of the imine compound shown in formula (I)；Add the reaction temperature of internal electron donor compound
For 60~100 DEG C, preferably 80~100 DEG C；Reaction time is 0.5~2 hour, preferably 0.5~1 hour.In urging for finally obtaining
The weight content of imine compound described in agent component is 0.5~20%.
The magnesium compound is selected from magnesium dihalide, the hydrate or alcohol adduct of alkoxy Mei ﹑ Wan Ji Mei ﹑ magnesium dihalides, with
And at least one in the derivative that one of halogen atom is replaced by alkoxy or halogenated alkoxy in magnesium dihalide molecular formula
Plant, preferably magnesium dihalide and its at least one of alcohol adduct and alkoxyl magnesium.
The organic alcohol compound is selected from C2~C8Monohydric alcohol；Described precipitation additive be selected from organic acid anhydride, organic acid,
At least one of ether and ketone；Described atent solvent is selected from C1~C20At least one of alkane, cycloalkane or aromatic hydrocarbons.
The titanium compound formula is TiXn(OR)4-n, R is the alkyl that carbon number is 1~20 in formula, and X is halogen, n=
0~4.Be chosen in particular from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium,
At least one of dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one, preferably titanium tetrachloride.
In above-mentioned catalytic component, described internal electron donor compound removes the chemical combination beyond the region of objective existence described in formula (I), in addition to
Selected from least one of ester, ether, ketone, amine.It is preferred that dihydric alcohol ester type compound, diether compounds or polyhydric aliphatic race/fragrance
Race's carboxylic acid ester compound, including the polybasic carboxylic acid esters compound disclosed in CN85100997, its related content introduce this
In invention.
Present invention also offers a kind of catalyst for olefinic polymerization, the reaction product of following components is included：
A. the catalytic component that method is prepared as previously described；
B. organo-aluminum compound；
C. optional Component organo-silicon compound.
Wherein in terms of every mole of titanium compound, each component amount ratio is A:B:C=1 moles：20~800 moles：0~100
Mole.
Further, the formula of the organo-aluminum compound is AlRnX3-n, wherein R is hydrogen or C1~C20Alkyl, X is
Halogen, n is integer and 0<n≤3.The organo-aluminum compound is chosen in particular from trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, three
Octyl group aluminium, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum, the aluminium ethide of dichloro one and
At least one of ethyl aluminum dichloride, preferably triethyl aluminum and/or triisobutyl aluminium.
In above-mentioned catalyst, in order to obtain the olefin polymer with very high stereoregularity, external electron donor need to be added
Compound, such as formula are RnSi(OR′)4-nOrgano-silicon compound, wherein 0≤n≤3, R and R ' be identical or different alkyl,
Cycloalkyl, aryl, haloalkyl or amido, R can also be halogen atom or hydrogen atom.The organo-silicon compound are specifically selected
Trimethylmethoxysilane, trimethylethoxysilane, trimethyl phenoxysilane, dimethyldimethoxysil,ne, dimethyl
Diethoxy silane, cyclohexyl methyl diethoxy silane, Cyclohexylmethyldimethoxysilane, diphenyl dimethoxy silicon
In alkane, diphenyl diethoxy silane, phenyl triethoxysilane, phenyltrimethoxysila,e and vinyltrimethoxy silane
At least one, preferably Cyclohexyl Methyl Dimethoxysilane and/or diisopropyl dimethoxy silane.
Present invention also offers a kind of pre-polymerized catalyst for olefinic polymerization, the pre-polymerized catalyst includes
The ingredient of solid catalyst stated carries out the prepolymer obtained by prepolymerization with alkene, and pre-polymerization multiple is 0.1~1000g olefinic polymerizations
Thing/g ingredients of solid catalyst.The prepolymerized alkene of progress is preferably ethene or propylene.Prepolymerization can be according to public affairs
The technology known is carried out in gas phase or liquid phase.Prepolymerization step can online be carried out as a part for continuous polymerization process,
Can individually it be carried out in batch process.
Olefinic polyreaction in the present invention is in above-mentioned catalytic component, above-mentioned catalyst or above-mentioned pre-polymerized catalyst
In the presence of carry out.Olefinic polyreaction is carried out according to known polymerization, can be carried out in liquid phase or gas phase, can also be
Carried out under the operation of liquid and gas polymerization stage combination.The polymerization of alkene is carried out using routine techniques, the alkene is preferably
Ethene and propylene.
The present invention has following features：
1. the invention provides a kind of preparation method of the catalytic component for olefinic polymerization, used imines
Compound is used for loaded catalyst and prepares and have no document report for olefinic polyreaction.Conventional non-metallocene olefin polymerization
Contain amine transition metal complex in catalyst, its bond strength is larger, need to use stronger helping in the course of the polymerization process and urge
Agent, such as MAO (MAO), its mechanism of polymerization are single-activity center.It is different from, the Asia that the present invention is used
Aminated compounds remains carbon-to-nitrogen double bon in the molecular structure, and the bond energy that metal is combined during catalyst is formed is relatively low,
Internal electron donor can be played a part of.Simultaneously in MgCl2In the catalyst system of load, not only with metal Ti, it is also possible to
It is coordinated with metal Mg, dynamics model can be formed in polymerization process.Therefore from mechanism of polymerization, the two has essence
Difference.
2. be used for propylene polymerization using catalyst of the present invention, catalyst activity and hydrogen response compared with
Height, decay of activity is slow, and the isotacticity of resulting polymers is adjustable, and the molecular weight distribution of polymer is wider.
Embodiment
Example given below is in order to illustrate the present invention, rather than to limit the invention.
(1) method of testing：
Polyacrylic isotacticity (I.I) is determined with the heptane extraxtion method of boiling；
Melt index (MI) is determined according to ASTMD1238-99；
The molecular weight distribution (Mw/Mn) of polymer is determined using the gel permeation chromatograph of Waters companies manufacture, solvent
With 1,2,4- trichloro-benzenes, styrene is standard specimen；The nmr analysis of compound are poly- with Bruke dmx300MHz nmr determinations
Compound1H-NMR, solvent：Deuterochloroform, TMS is internal standard, temperature 275K.
(2) synthesis of imine compound
The synthesis of embodiment 1 compound 2,4- bis- (2,6- diisopropyls phenyl imido) pentane
In a there-necked flask, nitrogen blows the acetylacetone,2,4-pentanedione of 1.00 grams of addition after row, 40 milliliters of isopropanol and 0.2 milli
Glacial acetic acid is risen, is stirred at room temperature.It is slowly added dropwise at room temperature different into 50 milliliters containing 3.68 grams of 2,6- diisopropyl anilines
Propanol solution, adds rear stirring reaction and 100 DEG C of back flow reactions is warming up to after 1 hour 26 hours.Reaction solution is through being concentrated under reduced pressure, mistake
2.80 grams of weak yellow liquid (yield 67%) is obtained after column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):7.63~7.46
(3H, m, ArH), 3.25~3.38 (6H, m, CH and CH2), 1.21~1.38 (27H, m, CH3), 0.98~1.12 (3H, m,
CH3)；Mass spectrum, FD-mass spectrometry:418.
The synthesis of embodiment 2 compound 2,4- bis- (2,6- imino dimethyl benzenes) pentane
In a there-necked flask, nitrogen blows the acetylacetone,2,4-pentanedione of 1.00 grams of addition after row, 80 milliliters of isopropanol and 0.2 milli
Glacial acetic acid is risen, is stirred at room temperature.It is slowly added dropwise at room temperature into 30 milliliters of isopropyls containing 2.46 grams of 2,6- dimethylanilines
Alcoholic solution, adds rear stirring reaction and 90 DEG C of back flow reactions is warming up to after 0.5 hour 24 hours.Reaction solution is concentrated, crosses post layer
2.72 grams of weak yellow liquid (yield 67%) is obtained after analysis separation.1H-NMR(δ,ppm,TMS,CDCl3):7.72~7.53 (3H,
M, ArH), 3.25~3.31 (2H, m, CH2), 2.31~2.54 (12H, m, CH3), 1.20~1.35 (3H, m, CH3), 0.98~
1.12(3H,m,CH3)；Mass spectrum, FD-mass spectrometry:306.
The synthesis of embodiment 3 compound 2,4- bis- (2,4,6- trimethylbenzenes imido grpup) pentane
In a there-necked flask, nitrogen blows the acetylacetone,2,4-pentanedione of 1.00 grams of addition, 40 milliliters of absolute ethyl alcohol and 0.5 after row
Milliliter glacial acetic acid, stirs at room temperature.It is slowly added dropwise at room temperature into 50 milliliters containing 2.73 grams of 2,4,6- trimethylanilines
Ethanol solution, adds rear stirring reaction and 100 DEG C of back flow reactions is warming up to after 1 hour 36 hours.Reaction solution is through being concentrated under reduced pressure, mistake
2.07 grams of products (yield 62%) are obtained after column chromatography for separation.1H-NMR(δ,ppm,TMS,CDCl3):7.86~7.66 (4H, m,
), ArH 3.16~3.28 (2H, m, CH2), 2.30~2.52 (18H, m, CH3), 1.21~1.34 (3H, m, CH3), 0.98~
1.14(3H,m,CH3)；Mass spectrum, FD-mass spectrometry:334.
The synthesis of embodiment 4 compound 1- phenyl -1,3- two (2,4,6- trimethylbenzenes imido grpup) butane
In one 250 milliliters of there-necked flask, nitrogen blow added after row 0.82 gram benzoylacetone, 80 milliliters different
Propyl alcohol and 0.3 milliliter of glacial acetic acid, stirring and dissolving is uniform at room temperature.It is slowly added dropwise at room temperature molten into 20 milliliters of isopropanols are dissolved in
2.86 grams of 2,4,6- trimethylanilines in liquid, add rear stirring reaction and 90 DEG C of back flow reactions are warming up to after 2 hours 48 hours.
Yellow solid is obtained after reaction solution cooling, with obtaining 1.30 grams of light yellow crystal (yield 66%) after ethyl alcohol recrystallization.1H-
NMR(δ,ppm,TMS,CDCl3):7.96~7.80 (5H, m, ArH), 7.68~7.56 (4H, m, ArH), 3.23~3.36 (2H,
s,CH2), 2.28~2.42 (18H, m, CH3), 1.08~1.28 (3H, m, CH3)；Mass spectrum, FD-mass spectrometry:
396。
The synthesis of embodiment 5 compound 1- phenyl -1,3- two (2,6- diisopropyls phenyl imido) butane
In 250 milliliters of there-necked flasks after row is blown through nitrogen at one, add 0.82 gram benzoylacetone, 60 milliliters
Isopropanol and 0.5 milliliter of formic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 40 milliliters of aqueous isopropanols at room temperature
1.85 grams of 2,6-DIPAs, add rear stirring reaction 2 hours, be warming up to 90 DEG C of back flow reactions 36 hours.Reaction is molten
Liquid obtains faint yellow solid after being concentrated under reduced pressure, with obtaining 1.60 grams of white crystal (yield 61%) after ethyl alcohol recrystallization.1H-
NMR(δ,ppm,TMS,CDCl3):7.96~7.82 (7H, m, ArH), 7.66~7.46 (4H, m, ArH), 3.20~3.43 (6H,
M, CH and CH2), 1.20~1.38 (24H, m, CH3), 0.98~1.12 (3H, m, CH3)；Mass spectrum, FD-mass
spectrometry:480。
The synthesis of embodiment 6 compound 1,3- diphenyl -1,3- two (2,6- diisopropyls phenyl imido) propane
In 250 milliliters of there-necked flasks after row is blown through nitrogen at one, add 1.12 grams benzoyl methane, 80 milliliters
Isopropanol and 0.5 milliliter of acetic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 20 milliliters of aqueous isopropanols at room temperature
1.80 grams of 2,6-DIPAs, add rear stirring reaction 2 hours, be warming up to 90 DEG C of back flow reactions and be cooled to room after 48 hours
Temperature.
Reaction solution obtains yellow solid after being concentrated under reduced pressure, with obtaining 1.65 grams of light yellow crystal after ethyl alcohol recrystallization
(yield 61%).1H-NMR(δ,ppm,TMS,CDCl3):7.96~7.76 (12H, m, ArH), 7.66~7.46 (4H, m, ArH),
3.21~3.36 (6H, m, CH and CH2), 1.13~1.36 (24H, m, CH3)；Mass spectrum, FD-mass spectrometry:542.
The synthesis of embodiment 7 compound 1,3- diphenyl -1,3- two (2,6- imino dimethyl benzenes) propane
In 250 milliliters of there-necked flasks after row is blown through nitrogen at one, add 1.12 grams benzoyl methane, 80 milliliters
Isopropanol and 0.5 milliliter of formic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 20 milliliters of aqueous isopropanols at room temperature
1.30 grams of 2,6- dimethylanilines, add rear stirring reaction 2 hours, be warming up to 90 DEG C of back flow reactions and be cooled to room after 24 hours
Temperature.Reaction solution obtains yellow solid after being concentrated under reduced pressure, with obtaining 1.39 grams of (yields of light yellow crystal after ethyl alcohol recrystallization
65%).1H-NMR(δ,ppm,TMS,CDCl3):7.96~7.67 (12H, m, ArH), 7.66~7.48 (4H, m, ArH), 3.21
~3.25 (2H, s, CH2), 2.11~2.23 (12H, m, CH3)；Mass spectrum, FD-mass spectrometry:430.
The synthesis of embodiment 8 compound 1- phenyl -1,3- two (2,6- imino dimethyl benzenes) butane
In 250 milliliters of there-necked flasks after row is blown through nitrogen at one, add 0.81 gram benzoylacetone, 60 milliliters
Isopropanol and 0.5 milliliter of formic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 30 milliliters of aqueous isopropanols at room temperature
1.30 grams of 2,6- dimethylanilines, add rear stirring reaction 2 hours, be warming up to 90 DEG C of back flow reactions 18 hours.Reaction solution
White solid is obtained after being concentrated under reduced pressure, with obtaining 1.12 grams of white crystal (yield 61%) after ethyl alcohol recrystallization.1H-NMR(δ,
ppm,TMS,CDCl3):7.96~7.76 (5H, m, ArH), 7.66~7.46 (3H, m, ArH), 2.12~2.23 (2H, m,
), CH2 2.12~2.23 (2H, m, CH2), 2.26~2.38 (12H, m, CH3), 2.01~2.02 (2H, s, CH2), 1.01~
1.12(3H,m,CH3)；Mass spectrum, FD-mass spectrometry:368.
The synthesis of embodiment 9 compound 3,5- bis- (2,6- diisopropyls phenyl imido) heptane
In 250 milliliters of there-necked flasks after row is blown through nitrogen at one, add 1.28 grams 3,5- heptadione, 80 milliliters different
Propyl alcohol and 0.5 milliliter of acetic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 20 milliliters of aqueous isopropanols at room temperature
3.68 grams of 2,6-DIPAs, add rear stirring reaction 2 hours, are warming up to 90 DEG C of back flow reactions and are cooled to room after 36 hours
Temperature.Reaction solution obtains yellow liquid after being concentrated under reduced pressure, and 2.36 grams of (yields of weak yellow liquid are obtained after crossing column chromatography for separation
53%).1H-NMR(δ,ppm,TMS,CDCl3):7.46~7.78 (6H, m, ArH), 3.21~3.36 (4H, m, CH), 2.12~
2.23(2H,m,CH2), 1.58~1.86 (4H, m, CH2), 1.26~1.38 (24H, m, CH3), 0.97~1.21 (6H, m,
CH3)；Mass spectrum, FD-mass spectrometry:446.
The synthesis of the compound 2- of embodiment 10 (2- naphthalenes imido grpup) -4- (4- trifluoros phenyl imido) pentane
One blown through nitrogen row after there-necked flask in, add 1.10 grams acetylacetone,2,4-pentanedione, 100 milliliters of toluene and
0.35 gram of p-methyl benzenesulfonic acid, stirs at room temperature.It is slowly added dropwise at room temperature into containing 1.43 grams of 2- naphthylamines, is heated to 130 DEG C
Divide water back flow reaction 20 hours.Room temperature is cooled to, 1.62 grams of 4- 5-trifluoromethylanilines are added, continues reflux water-dividing reaction 24
Hour.Reaction solution obtains saturated solution through removal of solvent under reduced pressure, with sodium acid carbonate and washed, and is extracted respectively with 50 milliliters of absolute ethers
Three times, merge organic phase, anhydrous sodium sulfate drying removes solvent, and head product ethyl alcohol recrystallization obtains the (production of 2.16 grams of products
Rate 58%).1H-NMR(δ,ppm,TMS,CDCl3):8.02~8.16 (3H, m, ArH), 7.86~7.70 (9H, m, ArH), 2.01
~2.16 (2H, s, CH2), 1.21~1.35 (3H, m, CH3), 0.98~1.14 (3H, m, CH3)；Mass spectrum, FD-mass
spectrometry:368。
The synthesis of embodiment 11 compound 2,4- bis- (2,6- diisopropyls phenyl imido) -1,1,1- trifluoropentanes
In there-necked flask after row is blown through nitrogen at one, 1.54 grams of 1,1,1- tri- fluoro- 2,4- pentanediones, 100 millis are added
The toluene and 0.35 gram of p-methyl benzenesulfonic acid risen, stirs at room temperature.It is slowly added dropwise at room temperature into 1.78 grams of 2,6- diisopropyls
Base aniline, is heated to 130 DEG C of reflux water-dividings and reacts 24 hours.Room temperature is cooled to, 1.78 grams of 2,6-DIPAs are added,
Continue reflux water-dividing to react 36 hours.Reaction solution obtains saturated solution through removal of solvent under reduced pressure, with sodium acid carbonate and washed, with 50 millis
Rise absolute ether to extract respectively three times, merge organic phase, anhydrous sodium sulfate drying removes solvent, head product is by column chromatography point
2.83 grams of faint yellow solid products (yield 60%) are obtained from after.1H-NMR(δ,ppm,TMS,CDCl3):8.02~8.16 (3H,
M, ArH), 7.76~7.68 (6H, m, ArH), 3.21~3.36 (4H, m, CH), 2.01~2.16 (2H, s, CH2), 1.22~
1.34(24H,m,CH3), 0.98~1.14 (3H, m, CH3)；Mass spectrum, FD-mass spectrometry:472.
The compound 1- of embodiment 12 (2- furyls) -4,4,4 three fluoro- 1,3- bis- (2,6- diisopropyls phenyl imido) butane
Synthesis
In there-necked flask after row is blown through nitrogen at one, 2.06 grams of 1- (2- furyls) -4,4,4- tri- fluoro- 1,3- is added
Diacetyl, 100 milliliters of toluene and 0.32 gram of p-methyl benzenesulfonic acid, stir at room temperature.It is slowly added dropwise again into 3.68 grams
2,6-DIPA, is heated to 130 DEG C of reflux water-dividings and reacts 72 hours.Reaction solution uses carbonic acid through removal of solvent under reduced pressure
Hydrogen sodium obtains saturated solution washing, is extracted respectively three times with 50 milliliters of absolute ethers, merges organic phase, and anhydrous sodium sulfate drying is removed
Solvent is removed, head product, which is crossed after column chromatography for separation, obtains 2.07 grams of faint yellow solid products (yield 62%).1H-NMR(δ,ppm,
TMS,CDCl3):8.02~8.16 (2H, m, ArH), 7.46~7.58 (4H, m, ArH), 7.06~7.24 (3H, m, ArH),
3.21~3.36 (4H, m, CH), 1.22~1.34 (12H, m, CH3), 1.08~1.14 (12H, m, CH3)；Mass spectrum, FD-mass
spectrometry:524。
The compound 2- of embodiment 13 [1- (2,6- diisopropyls phenyl imido) ethyl] -1- (2,6- diisopropyl benzene imines
Base) hexamethylene synthesis
In there-necked flask after row is blown through nitrogen at one, 2- acetyl cyclohexanones, 100 milliliters of the toluene of 1.40 grams of addition
And 0.32 gram of p-methyl benzenesulfonic acid, stir at room temperature.The 2,6-DIPA into 3.68 grams is slowly added dropwise again, heats
Reacted 62 hours to 130 DEG C of reflux water-dividings.Reaction solution obtains saturated solution through removal of solvent under reduced pressure, with sodium acid carbonate and washed, and uses
50 milliliters of absolute ethers are extracted three times respectively, merge organic phase, and anhydrous sodium sulfate drying removes solvent, and head product crosses column chromatography
2.37 grams of weak yellow liquids (yield 52%) are obtained after separation.1H-NMR(δ,ppm,TMS,CDCl3):7.46~7.58 (2H, m,
), ArH 7.06~7.24 (4H, m, ArH), 3.21~3.36 (4H, m, CH), 1.65~1.70 (1H, m, CH), 1.37~1.40
(6H, m, CH2), 1.22~1.34 (12H, m, CH3), 1.08~1.14 (12H, m, CH3)；Mass spectrum, FD-mass
spectrometry:458。
The compound 2- of embodiment 14 [1- (2,6- imino dimethyl benzenes) ethyl] -1- (2,6- imino dimethyl benzenes) ring
The synthesis of hexane
In there-necked flask after row is blown through nitrogen at one, 2- acetyl cyclohexanones, 100 milliliters of the toluene of 1.40 grams of addition
And 0.32 gram of p-methyl benzenesulfonic acid, stir at room temperature.2, the 6- dimethylanilines into 2.50 grams are slowly added dropwise again, are heated to
130 DEG C of reflux water-dividings react 62 hours.Reaction solution obtains saturated solution through removal of solvent under reduced pressure, with sodium acid carbonate and washed, with 50
Milliliter absolute ether is extracted three times respectively, merges organic phase, and anhydrous sodium sulfate drying removes solvent, and head product crosses column chromatography point
2.37 grams of weak yellow liquids (yield 52%) are obtained from after.1H-NMR(δ,ppm,TMS,CDCl3):7.46~7.58 (2H, m,
), ArH 7.06~7.24 (4H, m, ArH), 4.62~4.66 (0.5H, s, NH), 2.37~2.46 (12H, m, CH3), 1.65~
1.70 (0.5H, m, CH), 1.38~1.43 (4H, m, CH2), 1.22~1.34 (4H, m, CH2), 0.98~1.04 (3H, s,
CH3)；Mass spectrum, FD-massspectrometry:346.
(3) preparation of ingredient of solid catalyst and propylene polymerization
Embodiment 15
(1) preparation of catalyst solid constituent
Under nitrogen protection, 4.8g anhydrous magnesium chlorides, 19.5g isooctanol and 19.5g decane solvents are added to be equipped with and stirred
In the 500ml reactors for mixing device, 130 DEG C are heated to, reaction is completely dissolved for 1.5 hours to magnesium chloride, is added 1.1g phthalic anhydrides, is continued
130 DEG C of reactions are maintained to obtain alcohol adduct in 1 hour；Alcohol adduct is cooled to room temperature.Under nitrogen protection, above-mentioned alcohol adduct is added dropwise
To being cooled in advance in -22 DEG C of 120ml titanium tetrachloride solutions, 100 DEG C are to slowly warm up to, the benzoyloxy pentanes of 2,4- bis- are added
The compound 2 of (0.003 mole) and the structure, 4- bis- (2,6- diisopropyl phenyl imido) pentane (0.003 mole), heating
Maintain 2 hours, filter while hot to 110 DEG C, plus 120 milliliters of titanium tetrachloride, it is raised to 110 degree and reacts 1 hour, filtering.Add toluene
80ml, tributyl phosphate 2.66g, 90 DEG C of maintenance half an hour.With anhydrous hexane solid particle 4 times, solid is obtained after drying
Catalyst.
(2) propylene polymerization
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 0.lmmol, adds above-mentioned ingredient of solid catalyst 8-10mg and 1.2NL hydrogen, is passed through
Liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, and cooling, pressure release obtains PP powders.Aggregated data is shown in Table 1.
Embodiment 16
Be the same as Example 15, only by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is replaced with
2- [1- (2,6- diisopropyls phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylene.
Embodiment 17
Be the same as Example 15, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
1- phenyl -1,3- two (2,6- imino dimethyl benzenes) butane.
Embodiment 18
Be the same as Example 15, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
1- phenyl -1,3- two (2,6- diisopropyls phenyl imido) butane.
Embodiment 19
Be the same as Example 15, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
1,3- diphenyl -1,3- two (2,6- diisopropyls phenyl imido) propane.
Embodiment 20
Be the same as Example 15, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
2,4- bis- (2,4,6- trimethylbenzenes imido grpup) pentane.
Embodiment 21
Be the same as Example 15, simply by the compound 2 in embodiment, the benzoyloxy pentanes of 4- bis- are changed to DNBP.
Embodiment 22
Be the same as Example 14, simply by the compound 2 in embodiment, it is different that the benzoyloxy pentanes of 4- bis- are changed to 2- isopropyls -2-
Amyl group -1,3- dimethoxy propanes.
Embodiment 23
Be the same as Example 15, only by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to 2-
[1- (2,6- diisopropyls phenyl imido)] -1- (2,6- diisopropyls phenyl imido) hexamethylene.
Embodiment 24
(1) preparation of catalyst solid constituent
Under nitrogen protection, 4.8g anhydrous magnesium chlorides, 19.5g isooctanol and 19.5g decane solvents are added to be equipped with and stirred
In the 500ml reactors for mixing device, 130 DEG C are heated to, reaction is completely dissolved for 1.5 hours to magnesium chloride, is added 1.1g phthalic anhydrides, is continued
130 DEG C of reactions are maintained to obtain alcohol adduct in 1 hour；Alcohol adduct is cooled to room temperature.Under nitrogen protection, above-mentioned alcohol adduct is added dropwise
To being cooled in advance in -22 DEG C of 120ml titanium tetrachloride solutions, 100 DEG C are to slowly warm up to, the benzoyloxy pentanes of 2,4- bis- are added
(0.006 mole), is warming up to 110 DEG C and maintains 2 hours, filter while hot, plus 120 milliliters of titanium tetrachloride, is raised to 110 degree of reactions 1 small
When, filtering.Add toluene 80ml and compound 2,4- bis- (2,6- diisopropyls phenyl imido) pentane (0.006 of the structure
Mole), 90 DEG C of maintenance half an hour.With anhydrous hexane solid particle 4 times, solid catalyst is obtained after drying.
(2) propylene polymerization
The step of be the same as Example 15 (2).
Embodiment 25
Identical with embodiment 24, difference is the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido)
Pentane is changed to 2,4- bis- (2,6- imino dimethyl benzenes) pentane.
Embodiment 26
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 15.
Embodiment 27
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 15.
Embodiment 28
Be the same as Example 15, is simply 7.2NL by the hydrogenation quantitative change in embodiment, the results are shown in Table 1.
Embodiment 29
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 18.
Embodiment 30
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 24.
Embodiment 31
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 18.
Embodiment 32
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 24.
Embodiment 33
Be the same as Example 24, is simply 7.2NL by the hydrogenation quantitative change in embodiment, the results are shown in Table 1.
Comparative example 1
(1) preparation of catalyst solid constituent
Under nitrogen protection, 4.8g anhydrous magnesium chlorides, 19.5g isooctanol and 19.5g decane solvents are added to be equipped with and stirred
In the 500ml reactors for mixing device, 130 DEG C are heated to, reaction is completely dissolved for 1.5 hours to magnesium chloride, is added 1.1g phthalic anhydrides, is continued
130 DEG C of reactions are maintained to obtain alcohol adduct in 1 hour；Alcohol adduct is cooled to room temperature.Under nitrogen protection, above-mentioned alcohol adduct is added dropwise
To being cooled in advance in -22 DEG C of 120ml titanium tetrachloride solutions, 100 DEG C are to slowly warm up to, DNBP (0.006 mole) is added, is warming up to
110 DEG C maintain 2 hours, filter while hot, plus 120 milliliters of titanium tetrachloride, are raised to 110 DEG C and react 1 hour, filtering.Add toluene
80ml, tributyl phosphate 2.66g, 90 DEG C of maintenance half an hour.With anhydrous hexane solid particle 4 times, solid is obtained after drying
Catalyst.
(2) propylene polymerization
The step of be the same as Example 15 (2), it the results are shown in Table 1.
Comparative example 2
With comparative example 1, it is simply 7.2NL by the hydrogenation quantitative change in embodiment, the results are shown in Table 1.
Table 1
Note：The "-" of last row represents not survey.
Table 1 illustrates, under the high hydrogen condition of identical, and embodiment 28,33 obtains the melting of polymer compared with comparative example 2
Index is higher, illustrates good using the catalyst hydrogen response of the imine compound.And the polymerization result table under normal condition
Bright, the molecular weight distribution of the polymer of catalyst preparation is relatively wide obtained by use, more suitable for high impact polymer product
Exploitation.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (14)
1. a kind of preparation method of catalyst component for olefin polymerization, including：
A, magnesium compound mixed with organic alcohol compound and atent solvent, add precipitation additive reaction and obtains alcohol adduct；
B, the alcohol adduct is added in compound titanium solution, filters to isolate the first solid particle；
C, first solid particle is added in compound titanium solution again, stirs and react, then filter to isolate
Two solid particles；
The second solid particle that d, washing step c are obtained, the catalytic component is obtained after drying；
Wherein, being added in optional step a~d includes the internal electron donor chemical combination of the imine compound shown in formula (I)
Thing；
Wherein, n is 0~10 integer；
A is carbon or hetero atom silicon；
R and R ' is identical or different, is each independently selected from the substituted or unsubstituted C of hydroxyl, halogen atom1~C20Alkyl, C2~
C20Alkenyl, C6~C20Alkaryl or C10~C20Fused ring aryl；
R1And R2It is identical or different, it is each independently selected from the substituted or unsubstituted C of halogen atom1~C20Alkyl, C3~C20Cycloalkanes
Base, C2~C20Alkylene, C2~C20Ester group, C6~C20Aryl or C10~C20Fused ring aryl；RI、RII、R3And R4It is identical or different,
The substituted or unsubstituted C of hydrogen, halogen atom being each independently selected from1~C20Alkyl, C3~C20Cycloalkyl, C2~C20Alkene
Base, C2~C20Ester group, C6~C20Aryl or C10~C20Fused ring aryl, and R1~R4And RIAnd RIIOne or more of group can
To connect cyclization；R3~R4And RIAnd RIIArbitrarily carbon or hydrogen atom or both can be used as on group comprising one or several hetero atoms
Substituent, described hetero atom is oxygen, sulphur, nitrogen, boron, silicon, phosphorus or halogen atom.
2. according to the method described in claim 1, it is characterised in that R and R ' is each independently selected from halogen atom substitution or not
Substituted C1~C8Alkyl, C6~C20Alkaryl or C10~C20Fused ring aryl.
3. method according to claim 2, it is characterised in that R and R ' is each independently selected from halogen atom substitution or not
Substituted methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, phenyl, halobenzene
Base, alkyl-substituted phenyl, naphthyl or terphenyl.
4. according to the method described in claim 1, it is characterised in that R1And R2Be each independently selected from halogen atom substitution or not
Substituted C1~C8Alkyl, C6~C20Aryl or C10~C20Fused ring aryl；RI、RII、R3And R4It is each independently selected from hydrogen, halogen
The substituted or unsubstituted C of atom1~C8Alkyl, C6~C20Aryl or C10~C20Fused ring aryl.
5. the method according to any one of Claims 1-4, it is characterised in that the imine compound is selected from 2,4- bis-
Phenyl imido pentane, 2,4- bis- (2,6- diisopropyls phenyl imido) pentane, 2,4- dinaphthyl imido grpups the pentane, (2,6- of 2,4- bis-
Imino dimethyl benzene) pentane, the fourth imido grpup pentanes of 2,4- bis-, 2,4- bis- (4- chlorobenzenes imido grpup) pentane, (the 2,4- bis- of 2,4- bis-
Chlorobenzene imido grpup) pentane, 2,4- bis- (4- trifluoromethyls phenyl imido) pentane, the phenyl imido heptane of 3,5- bis-, (the 2,6- of 3,5- bis-
Diisopropyl phenyl imido) heptane, 3,5- bis- (2,6- imino dimethyl benzenes) heptane, the fourth imines base heptanes of 3,5- bis-, 2,4-
Two (8- quinoline imido grpup) pentanes, 2,4- bis- (4- quinoline imido grpup) pentane, 2,4- bis- (3- quinoline imido grpup) pentane, 2,4- bis-
(the chloro- 6- hydroxyls phenyl imidos of 2-) pentane, 2,4- bis- (2,4,6- trimethylbenzenes imido grpup) pentane, the fluoro- 2,4- bis- of 1,1,1- tri-
(2,6- diisopropyls phenyl imido) pentane, 1,1,1- tri- fluoro- 2,4- bis- (2,6- imino dimethyl benzenes) pentane, 1,3- hexichol
Base -1,3- two (2,6- diisopropyls phenyl imido) propane, 1,3- diphenyl -1,3- two (2,6- imino dimethyl benzenes) third
Alkane, 1- phenyl -1,3- two (2,6- diisopropyls phenyl imido) butane, 1- phenyl -1,3- two (2,6- imino dimethyl benzenes)
Butane, 3- methyl -2,4- two (2,6- imino dimethyl benzenes) pentane, 3- ethyls -2,4- two (2,6- imino dimethyl benzenes)
Pentane, the phenyl imido -4- ethyl heptanes of 3,5- bis-, 3,5- bis- (2,6- diisopropyls phenyl imido) -4- methyl heptanes, 3- second
Base -3,5- two (2,6- diisopropyls phenyl imido) heptane, 3- methyl -3,5- two (2,6- imino dimethyl benzenes) heptane, 3-
Ethyl -3,5- two (2,6- imino dimethyl benzenes) heptane, 2,4- bis- are to chlorobenzene imido grpup pentane, 2- phenyl imido -4- (2,6-
Diisopropyl phenyl imido) pentane, 1- (2- furyls) -1,3- two (2,6- diisopropyls phenyl imido) -4,4,4- trifluoro fourths
Alkane, 1- (2- furyls) -1,3- two (8- quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furyls) (3- quinolines of -1,3- two
Quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furyls) -1,3- two (2,6- imino dimethyl benzenes) -4,4,4- trifluoro fourths
Alkane, 2- phenyl imidos -4- (2,6- imino dimethyl benzenes) pentane, 2- phenyl imido -4- to chlorobenzene imido grpup pentane, 2,2,4,
4,6,6- hexamethyls -2,4- two (2,6- diisopropyls phenyl imido) pentane, 2- are to chlorobenzene imido grpup -4- (2,6- diisopropyls
Phenyl imido) pentane, 2,2,4,4,6,6- hexamethyls -2,4- two (2,6- imino dimethyl benzenes) pentane, 2,2,4,4,6,6-
The phenyl imido pentanes of hexamethyl -2,4- two, 2,2,4,4,6,6- hexamethyls -2,4- two (to chlorobenzene imido grpup) pentane, 2,2,4,
4,6,6- hexamethyls -2,4- two (3- quinoline imido grpup) pentane, 2,2,4,4,6,6- hexamethyls -2,4- two (8- quinoline imido grpup)
Pentane, 2- are to chlorobenzene imido grpup -4- (2,6- imino dimethyl benzenes) pentane, 1,3- diphenyl -1- phenyl imido -3- (2,6-
Imino dimethyl benzene) propane, 1,3- diphenyl -1- phenyl imidos -3- (2,6- diisopropyls phenyl imido) propane, 2- [1-
(2,6- diisopropyls phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylene, 2- [1- (2,6- dimethyl benzenes
Imido grpup) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene, 2- [1- (2,6- dichloros phenyl imido) ethyl] -1- (2,
6- diisopropyls phenyl imido) hexamethylene, (2,6- diisopropyl benzenes are sub- by 2- [1- (2,6- imino dimethyl benzenes) ethyl] -1-
Amido) hexamethylene, 2- [1- (phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylenes and 2- [1- (benzene imines
Base) ethyl] one or more in -1- (2,6- imino dimethyl benzenes) hexamethylene.
6. according to the method described in claim 1, it is characterised in that the magnesium compound is selected from magnesium dihalide, alkoxy Mei ﹑ alkane
One of halogen atom is by alkoxy or halogen in the hydrate or alcohol adduct and magnesium dihalide molecular formula of Ji Mei ﹑ magnesium dihalides
At least one of derivative replaced for alkoxy.
7. method according to claim 6, it is characterised in that the magnesium compound is magnesium dihalide and its alcohol adduct and alkane
At least one of epoxide magnesium.
8. according to the method described in claim 1, it is characterised in that the organic alcohol compound is selected from C2~C8Monohydric alcohol；Institute
The precipitation additive stated is selected from least one of organic acid anhydride, organic acid, ether and ketone；Described atent solvent is selected from C1~C20's
At least one of alkane, cycloalkane or aromatic hydrocarbons.
9. according to the method described in claim 1, it is characterised in that the titanium compound formula is TiXn(OR)4-n, R is in formula
Carbon number is 1~20 alkyl, and X is halogen, and n is 0~4.
10. magnesium compound and organic alcohol compound according to the method described in claim 1, it is characterised in that in step a, are pressed 2
~5 mol ratio and atent solvent mixing, is warming up to 120~150 DEG C, is added by magnesium/precipitation additive mol ratio 5~10 and help precipitation
Agent, reacts 1~5 hour；
In step b, according to titanium/magnesium mol ratio 20~50, it is molten at -15~-40 DEG C the alcohol adduct to be added into titanium compound
In liquid, 90~110 DEG C are then heated to, is reacted 1~3 hour at 100~130 DEG C, filters to isolate solid particle；
In step c, solid particle is added in compound titanium solution again according to titanium/magnesium mol ratio 20~50, stir and
100~130 DEG C are reacted 1.5~3 hours, filter to isolate solid particle.
11. method according to claim 10, it is characterised in that in step b or step d, according to internal electron donor
Compound/magnesium mol ratio includes the internal electron donor compound of the imine compound shown in formula (I) for 1~100 amount addition.
12. a kind of catalyst for olefinic polymerization, includes the reaction product of following components：
A. the catalytic component that any one of claim 1 to 11 methods described is prepared；
B. organo-aluminum compound, formula is AlRnX3-n, wherein R is hydrogen or C1~C20Alkyl, X is halogen, and n is integer and 0<n
≤3；
C. a kind of external donor compound being optionally added.
13. a kind of catalyst as claimed in claim 12, it is characterised in that the external donor compound is siliconated
Compound.
14. a kind of application of catalyst as described in claim 12 or 13 in olefin polymerization.
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| CN201410169910.2A CN105085733B (en) | 2014-04-24 | 2014-04-24 | A kind of catalyst component for olefin polymerization preparation method and corresponding catalyst |
| KR1020167032804A KR102293704B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| MYPI2016703904A MY176619A (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| CA2946777A CA2946777C (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| PCT/CN2015/077381 WO2015161827A1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| US15/306,255 US10208145B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| EP15782847.6A EP3135697B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| JP2016564188A JP6804302B2 (en) | 2014-04-24 | 2015-04-24 | Catalyst components for olefin polymerization and catalysts containing them |
| SG11201608921YA SG11201608921YA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst containing the same |
| RU2016145949A RU2688689C2 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerisation and catalyst containing it |
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| CN1405192A (en) * | 2002-11-11 | 2003-03-26 | 中山大学 | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method |
| CN102718897A (en) * | 2011-03-31 | 2012-10-10 | 中国石油化工股份有限公司 | Loaded olefin polymerization solid catalyst ingredient, and preparation method and application thereof |
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| EP2070954A1 (en) * | 2007-12-14 | 2009-06-17 | Total Petrochemicals Research Feluy | Process for the production of a propylene polymer having a broad molecular weight distribution and a low ash content |
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| CN1405192A (en) * | 2002-11-11 | 2003-03-26 | 中山大学 | Titanium-nickel acetylacetonate composite catalyst for preparing branched polyethylene and its preparation method |
| CN102718897A (en) * | 2011-03-31 | 2012-10-10 | 中国石油化工股份有限公司 | Loaded olefin polymerization solid catalyst ingredient, and preparation method and application thereof |
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