CN105085731B - 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 being dissolved in magnesium compound in the solvent of organic epoxy compound thing, organic phosphorus compound and inert diluent composition, mixed after forming homogeneous solution with titanium compound, solids is separated out in the presence of precipitation additive；Then the solids is handled using the internal electron donor for including the imine compound shown in formula (I), internal electron donor is loaded with solids.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：
1) magnesium compound is dissolved in the solvent body of organic epoxy compound thing, organic phosphorus compound and inert diluent composition
In system, mixed after forming homogeneous solution with titanium compound, solids is then separated out in the presence of precipitation additive；
2) solids is handled using internal electron donor, internal electron donor is loaded with the solids, obtain institute
State catalytic component.
The internal electron donor includes the imine compound shown in formula (I)；
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- bis- (2- naphthalenes imido grpup) pentane, 2,4- bis- (1- naphthalenes imido grpup) pentane, (2,6- dimethyl benzenes are sub- by 2,4- bis-
Amido) pentane, the fourth imido grpup pentanes of 2,4- bis-, 2,4- bis- (4- chlorobenzenes imido grpup) pentane, (the 2,4 dichloro benzene imines of 2,4- bis-
Base) pentane, 2,4- bis- (4- trifluoromethyls phenyl imido) pentane, the phenyl imido heptane of 3,5- bis-, (the 2,6- diisopropyls of 3,5- bis-
Phenyl imido) heptane, 3,5- bis- (2,6- imino dimethyl benzenes) heptane, the fourth imines base heptanes of 3,5- bis-, (the 8- quinoline of 2,4- bis-
Imido grpup) pentane, 2,4- bis- (4- quinoline imido grpup) pentane, 2,4- bis- (3- quinoline imido grpup) pentane, (the chloro- 6- of 2- of 2,4- bis-
Hydroxyl phenyl imido) pentane, 2,4- bis- (2,4,6- trimethylbenzenes imido grpup) pentane, (2,6- bis- is different by the fluoro- 2,4- bis- of 1,1,1- tri-
Propyl group 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) propane, 1,3- diphenyl -1,3- two (2,6- imino dimethyl benzenes) propane, 1- phenyl -
1,3- bis- (2,6- diisopropyls phenyl imido) butane, 1- phenyl -1,3- two (2,6- imino dimethyl benzenes) butane, 3- first
Base -2,4- two (2,6- imino dimethyl benzenes) pentane, 3- ethyls -2,4- two (2,6- imino dimethyl benzenes) pentane, 3,5-
Two phenyl imido -4- ethyl heptanes, 3,5- bis- (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- are to chlorobenzene imido grpup pentane, 2- phenyl imidos -4- (2,6- diisopropyls
Phenyl imido) pentane, 1- (2- furyls) -1,3- two (2,6- diisopropyls phenyl imido) -4,4,4- trifluorobutanes, 1- (2-
Furyl) -1,3- two (8- quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furyls) (3- quinoline imines of -1,3- two
Base) -4,4,4- trifluorobutanes, 1- (2- furyls) -1,3- two (2,6- imino dimethyl benzenes) -4,4,4- trifluorobutanes, 2-
Phenyl imido -4- (2,6- imino dimethyl benzenes) pentane, 2- phenyl imido -4- to chlorobenzene imido grpup pentane, 2,2,4,4,6,
(2,6- diisopropyl benzenes are sub- to chlorobenzene imido grpup -4- by 6- hexamethyls -2,4- two (2,6- diisopropyls phenyl imido) pentane, 2-
Amido) pentane, 2,2,4,4,6,6- hexamethyls -2,4- two (2,6- imino dimethyl benzenes) pentane, 2,2,4,4,6,6- pregnancy
The phenyl imido pentanes of base -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) penta
Alkane, 2- are to chlorobenzene imido grpup -4- (2,6- imino dimethyl benzenes) pentane, 1,3- diphenyl -1- phenyl imidos -3- (2,6- bis-
Methyl phenyl imido) 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, [(2,6- dimethyl benzenes are sub- by 1- by 2-
Amido) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene, 2- [1- (2,6- dichloros phenyl imido) ethyl] -1- (2,6-
Diisopropyl phenyl imido) hexamethylene, 2- [1- (2,6- imino dimethyl benzenes) ethyl] -1- (2,6- diisopropyl benzene imines
Base) hexamethylene, 2- [1- (phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylenes and 2- [1- (benzene imines
At least one of base) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene.
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 1 of above-mentioned preparation method) in, the magnesium compound is selected from magnesium dihalide, alkoxy magnesium ﹑ alkane base magnesium ﹑ bis-
The hydrate or alcohol adduct of magnesium halide, and in magnesium dihalide molecular formula one of halogen atom by alkoxy or halogenated alkoxy
At least one of derivative replaced, magnesium compound preferably is in magnesium dihalide and its alcohol adduct and alkoxyl magnesium
It is at least one.
The organic epoxy compound thing is selected from C2~C8Aliphatic olefin, alkadienes or halogenated aliphatic group alkene or diene
At least one of oxide, glycidol ether and inner ether of hydrocarbon.It is chosen in particular from oxirane, expoxy propane, epoxy butane, fourth
In allene oxide thing, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran
At least one.
It is different that the organic phosphorus compound is selected from orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid three
Butyl ester, orthophosphoric acid triphenylmethyl methacrylate, tricresyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, phosphorous acid
At least one of triphenylmethyl methacrylate and triphenylphosphine.
The titanium compound formula is TiXn(OR)4-n, R is C in formula1~C20Alkyl, X is halogen, and n is 0~4.Specifically
Selected from titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl
At least one of epoxide titanium and the ethanolato-titanium of trichlorine one, preferably titanium tetrachloride.
Described precipitation additive is selected from least one of organic acid anhydride, organic acid, ether and ketone；Described inert diluent
Selected from C1~C20At least one of alkane, cycloalkane or aromatic hydrocarbons, be preferably selected from hexane, heptane, octane, decane, benzene, first
At least one of benzene, dimethylbenzene or derivatives thereof.
In the step 2 of above-mentioned preparation method) in, the internal electron donor is also wrapped in addition to the compound shown in formula (I)
Include selected from least one of ester, ether, ketone or amine, preferably diol-lipid compound, polyhydric aliphatic race or aromatic carboxylic acid esters
Class compound, including the polybasic carboxylic acid esters compound disclosed in CN85100997, its related content are introduced into conduct in the present invention
With reference to.
In above-mentioned preparation method, in terms of every mole of magnesium, the consumption of the organic epoxy compound thing is 0.2~10 mole, institute
The consumption for stating organic phosphorus compound is 0.1~3 mole, and the consumption of the titanium compound is 1~15 mole, the internal electron donor
The consumption of compound is 0.005~15 mole, and the consumption of the precipitation additive is 0~5 mole, preferably in the internal electron donor
The consumption of imine compound shown in compound formula of (I) is 0.01~10 mole.
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 the phenyl imido pentanes of 1 compound 2,4- of embodiment bis-
In one 250 milliliters of there-necked flask, nitrogen blows the acetylacetone,2,4-pentanedione of 2.00 grams of addition, 80 milliliters of isopropanol after row
And 0.2 milliliter of glacial acetic acid, stir at room temperature.It is slowly added dropwise and is dissolved in 20 milliliters of aqueous isopropanols at room temperature
3.86 grams of aniline, add rear stirring reaction and 90 DEG C of back flow reactions are warming up to after 1 hour 12 hours.Reaction solution through being concentrated under reduced pressure,
Cross after column chromatography for separation and obtain 3.02 grams of (yield 60%) products.1H-NMR(δ,ppm,TMS,CDCl3):7.96~7.86 (6H,
M, ArH), 7.65~7.46 (4H, m, ArH), 3.02~3.25 (2H, s, CH2), 1.16~1.30 (3H, s, CH3), 0.98~
1.12(3H,s,CH3)；Mass spectrum, FD-mass spectrometry:250.
Synthesis of the compound 2,4- bis- of embodiment 2 to chlorobenzene imido grpup pentane
In one 250 milliliters of there-necked flask, nitrogen blow row after add 1.00 grams acetylacetone,2,4-pentanedione, 50 milliliters of ethanol and
10 milliliters of benzene, stirs at room temperature.2.58 grams be dissolved in 40 milliliters of ethanol solutions are slowly added dropwise at room temperature to chlorine
Aniline, stirring reaction is warming up to 100 DEG C of back flow reactions 24 hours after 2 hours.Reaction solution crosses column chromatography for separation through being concentrated under reduced pressure
After obtain 2.38 grams of (yield 57%) products.1H-NMR(δ,ppm,TMS,CDCl3):7.96~7.86 (4H, m, ArH), 7.38~
7.56 (4H, m, ArH), 3.05~3.28 (2H, s, CH2), 1.16~1.30 (3H, s, CH3), 0.98~1.12 (3H, s, CH3)；
Mass spectrum, FD-mass spectrometry:318.
The synthesis of embodiment 3 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 4 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 5 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 6 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 7 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 8 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 9 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 10 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 11 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 gram 2,6-DIPA, adds rear stirring reaction 2 hours, it is warming up to 90 DEG C of back flow reactions and is 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 12 (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 30 hours.Room temperature is cooled to, 1.62 grams of 4- 5-trifluoromethylanilines are added, continues reflux water-dividing reaction 34
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 13 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 14 (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 15 [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, flows back
Water is divided to react 62 hours.Reaction solution obtains saturated solution through removal of solvent under reduced pressure, with sodium acid carbonate and washed, with 50 milliliters of anhydrous second
Ether is extracted three times respectively, merges organic phase, and anhydrous sodium sulfate drying removes solvent, and head product is crossed after column chromatography for separation and obtained
2.37 grams of weak yellow liquids (yield 52%).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 16 [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：
Embodiment 17
(1) preparation of catalyst solid constituent
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml and tributyl phosphate (TBP) 12.5mL, is warming up to 50 DEG C, and maintain 2.5 hours under stirring.After solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the benzoyloxy pentane 0.003mol of 2,4- bis- and the chemical combination of the structure
Thing 2,4- bis- (2,6- diisopropyl phenyl imido) pentane 0.003mol maintains temperature 1 hour, after heat filtering, adds toluene
150mL, washs secondary, obtains solid, add toluene 100mL, stir 30 minutes, be warming up to 110 DEG C, carries out three washings,
Time is respectively 10 minutes, is eventually adding hexane 60mL and washes twice, solids 7.9g (solid constituent) is obtained, containing Ti：3.7%th,
Mg：20.8%th, Cl：51.5%.
Embodiment 18
Be the same as Example 17, only by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is replaced with
2,4- bis- (2,6- imino dimethyl benzenes) pentane.
Embodiment 19
Be the same as Example 17, 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 20
Be the same as Example 17, 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 21
Be the same as Example 17, 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 22
Be the same as Example 17, 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- imino dimethyl benzenes) propane.
Embodiment 23
Be the same as Example 17, 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 24
Be the same as Example 17, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
1- trifluoromethyls -2,4- two (2,6- diisopropyls phenyl imido) pentane.
Embodiment 25
Be the same as Example 17, simply by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to
1- (2- furyls) -4,4,4- three fluoro- 1,3- bis- (2,6- diisopropyls phenyl imido) butane.
Embodiment 26
Be the same as Example 17, simply by the compound 2 in embodiment, the benzoyloxy pentanes of 4- bis- are changed to DNBP.
Embodiment 27
Be the same as Example 17, 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 28
Be the same as Example 17, 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 29
Be the same as Example 17, only by the compound 2 in embodiment, 4- bis- (2,6- diisopropyl phenyl imido) pentane is changed to 2-
[1- (2,6- imino dimethyl benzenes)] -1- (2,6- imino dimethyl benzenes) hexamethylene.
Embodiment 30
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml and tributyl phosphate (TBP) 12.5mL, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the benzoyloxy pentane 0.006mol of 2,4- bis-, maintain temperature 1 hour, heat
After filtering, toluene 150mL is added, washs secondary, obtains solid, add toluene 100mL, stir 30 minutes, be warming up to 110 DEG C,
Three washings are carried out, the time is respectively 10 minutes, adds the compound 2 of hexane 60mL and the structure, (2, the 6- diisopropyls of 4- bis-
Base phenyl imido) pentane 0.006mol, stirs 30 minutes, adds hexane 60mL and wash twice, obtain solids 7.9g (solid groups
Point), containing Ti：3.5%th, Mg：21.8%th, Cl：50.8%.
(4) polymerization experiment
Embodiment 31
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml, adds solid constituent 10mg and the 1.2NL hydrogen of the preparation of above-described embodiment 17, is passed through
Liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, pressure release, and discharge to obtain PP resins, the results are shown in Table 1.
Embodiment 32
Be the same as Example 31, simply with the solid constituent in the solid constituent alternative embodiment in above-described embodiment 18, as a result
It is shown in Table 1.
Embodiment 33
Be the same as Example 31, simply with the solid constituent in the solid constituent alternative embodiment in above-described embodiment 19, as a result
It is shown in Table 1.
Embodiment 34
Be the same as Example 31, simply with the solid constituent in the solid constituent alternative embodiment in above-described embodiment 20.As a result
It is shown in Table 1.
Embodiment 35
Be the same as Example 31, simply with the solid constituent in the solid constituent alternative embodiment in above-described embodiment 21, as a result
It is shown in Table 1.
Embodiment 36
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 22
Point, it the results are shown in Table 1.
Embodiment 37
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 23
Point, it the results are shown in Table 1.
Embodiment 38
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 24
Point, it the results are shown in Table 1.
Embodiment 39
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 25
Point, it the results are shown in Table 1.
Embodiment 40
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 26
Point, it the results are shown in Table 1.
Embodiment 41
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 27
Point, it the results are shown in Table 1.
Embodiment 42
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 28
Point, it the results are shown in Table 1.
Embodiment 43
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 29
Point, it the results are shown in Table 1.
Embodiment 44
Be the same as Example 31, simply with the solid group in solid constituent alternative embodiment synthesized in above-described embodiment 30
Point, it the results are shown in Table 1.
Embodiment 45
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 31.
Embodiment 46
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 31.
Embodiment 47
Be the same as Example 31, is simply 7.2NL by the hydrogenation quantitative change in embodiment, the results are shown in Table 1.
Embodiment 48
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 32.
Embodiment 49
Polymerization reaction time in embodiment, is simply extended for 2 hours, the results are shown in Table 1 by be the same as Example 36.
Embodiment 50
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 32.
Embodiment 51
Polymerization reaction time in embodiment, is simply extended for 3 hours, the results are shown in Table 1 by be the same as Example 36.
Embodiment 52
Be the same as Example 32, is simply 7.2NL by the hydrogenation quantitative change in embodiment, the results are shown in Table 1.
Comparative example 1
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml and tributyl phosphate (TBP) 12.5mL, is warming up to 50 DEG C under stirring, and maintains 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the benzoyloxy pentane 0.003mol of 2,4- bis-, maintain temperature 1 hour, heat
After filtering, toluene 150mL is added, washs secondary, obtains solid, add toluene 100mL, stir 30 minutes, be warming up to 110 DEG C,
Three washings are carried out, the time is respectively 10 minutes, adds hexane 60mL and washes twice, obtains solids 7.9g (solid constituent),
Containing Ti：2.7%th, Mg：21.5%th, Cl：50.2%.
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, adds the solid constituent 10mg and 1.2NL of above-mentioned preparation
Hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, discharge to obtain PP resins, as a result
It is shown in Table 1.
Comparative example 2
In the reactor being sufficiently displaced from by high pure nitrogen, magnesium chloride 4.8g, toluene 95mL, epoxy chloropropionate are sequentially added
Alkane 4ml, tributyl phosphate (TBP) 12.5mL, are warming up to 50 DEG C under stirring, and maintain 2.5 hours, after solid is completely dissolved,
Phthalic anhydride 1.4g is added, is continued to 1 hour, solution is cooled in less than -25 DEG C, 1 hour TiCl is added dropwise4, delay
Slowly 80 DEG C are warming up to, gradually separate out solids, add the benzoyloxy pentane 0.003mol of 2,4- bis-, maintain temperature 1 hour, heat
After filtering, toluene 150mL is added, washs secondary, obtains solid, add toluene 100mL, be warming up to 110 DEG C, wash for three times
Wash, the time is respectively 10 minutes, add hexane 60mL and stir 30 minutes, add hexane 60mL and wash three times.Obtain solids
7.4g (solid constituent), containing Ti：2.4%th, Mg：22.0%th, Cl：50.6%.
Volume is 5L stainless steel cauldron, after being sufficiently displaced from through gaseous propylene, adds AlEt32.5mL, methylcyclohexyl
Dimethoxysilane (CHMMS) 5ml makes Al/Si (mol)=25, adds the solid constituent 10mg and 7.2NL of above-mentioned preparation
Hydrogen, is passed through liquid propene 2.5L, is warming up to 70 DEG C, maintains this temperature 1 hour, cooling, bleeds off pressure, discharge to obtain PP resins, as a result
It is 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 47,52 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 (17)
1. a kind of preparation method of catalyst component for olefin polymerization, including：
1) magnesium compound is dissolved in the solvent of organic epoxy compound thing, organic phosphorus compound and inert diluent composition, shape
Mixed after into solution with titanium compound, solids is then separated out in the presence of precipitation additive；
2) solids is handled using internal electron donor, internal electron donor is loaded with the solids, obtaining described urge
Agent component；
The internal electron donor includes the imine compound shown in formula (I)；
Wherein, n is 0~10 integer；
A is carbon or silicon；
R and R ' is selected from identical or different hydroxyl, the substituted or unsubstituted C of 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 ' be each independently selected from 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. according to the method described in claim 1, it is characterised in that the imine compound is selected from the phenyl imidos penta of 2,4- bis-
Alkane, 2,4- bis- (2,6- diisopropyls phenyl imido) pentane, 2,4- bis- (2- naphthalenes imido grpup) pentane, 2,4- bis- (1- naphthalenes imido grpup)
Pentane, 2,4- bis- (2,6- imino dimethyl benzenes) pentane, the fourth imido grpup pentanes of 2,4- bis-, 2,4- bis- (4- chlorobenzenes imido grpup) penta
Alkane, 2,4- bis- (2,4 dichloro benzene imido grpup) pentane, 2,4- bis- (4- trifluoromethyls phenyl imido) pentane, the phenyl imidos of 3,5- bis-
Heptane, 3,5- bis- (2,6- diisopropyls phenyl imido) heptane, 3,5- bis- (2,6- imino dimethyl benzenes) heptane, the fourths of 3,5- bis-
(3- quinoline is sub- by imines base heptane, 2,4- bis- (8- quinoline imido grpup) pentane, 2,4- bis- (4- quinoline imido grpup) pentane, 2,4- bis-
Amido) pentane, 2,4- bis- (the chloro- 6- hydroxyls phenyl imidos of 2-) pentane, 2,4- bis- (2,4,6- trimethylbenzenes imido grpup) pentane, 1,
The fluoro- 2,4- bis- of 1,1- tri- (2,6- diisopropyls phenyl imido) pentane, fluoro- 2,4- bis- (the 2,6- dimethyl benzene imines of 1,1,1- tri-
Base) pentane, 1,3- diphenyl -1,3- two (2,6- diisopropyls phenyl imido) propane, (the 2,6- bis- of 1,3- diphenyl -1,3- two
Methyl phenyl imido) propane, 1- phenyl -1,3- two (2,6- diisopropyls phenyl imido) butane, (the 2,6- of 1- phenyl -1,3- two
Imino dimethyl benzene) butane, 3- methyl -2,4- two (2,6- imino dimethyl benzenes) pentane, (the 2,6- of 3- ethyls -2,4- two
Imino dimethyl benzene) pentane, the phenyl imido -4- ethyl heptanes of 3,5- bis-, 3,5- bis- (2,6- diisopropyls phenyl imido) -4-
(2,6- dimethyl benzenes are sub- by methyl heptane, 3- ethyls -3,5- two (2,6- diisopropyls phenyl imido) heptane, 3- methyl -3,5- two
Amido) heptane, 3- ethyls -3,5- two (2,6- imino dimethyl benzenes) heptane, 2,4- bis- be sub- to chlorobenzene imido grpup pentane, 2- benzene
Amido -4- (2,6- diisopropyls phenyl imido) pentane, 1- (2- furyls) -1,3- two (2,6- diisopropyls phenyl imido) -
4,4,4- trifluorobutanes, 1- (2- furyls) -1,3- two (8- quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furyls) -
1,3- bis- (3- quinoline imido grpup) -4,4,4- trifluorobutanes, 1- (2- furyls) -1,3- two (2,6- imino dimethyl benzenes) -
4,4,4- trifluorobutanes, 2- phenyl imidos -4- (2,6- imino dimethyl benzenes) pentane, 2- phenyl imido -4- are to chlorobenzene imines
Base 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,
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) pentane, (8- of 2,2,4,4,6,6- hexamethyls -2,4- two
Quinoline imido grpup) pentane, 2- is to chlorobenzene imido grpup -4- (2,6- imino dimethyl benzenes) pentane, 1,3- diphenyl -1- benzene imines
Base -3- (2,6- imino dimethyl benzenes) 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- imino dimethyl benzenes) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene, 2- [1- (2,6- dichloros phenyl imido) second
Base] -1- (2,6- diisopropyls phenyl imido) hexamethylene, (2,6- bis- is different by -1- by 2- [1- (2,6- imino dimethyl benzenes) ethyl]
Propyl group phenyl imido) hexamethylene, 2- [1- (phenyl imido) ethyl] -1- (2,6- diisopropyls phenyl imido) hexamethylenes and 2-
At least one of [1- (phenyl imido) ethyl] -1- (2,6- imino dimethyl benzenes) hexamethylene.
6. according to the method described in claim 1, it is characterised in that step 1), the magnesium compound is selected from magnesium dihalide, alkane
The hydrate or alcohol adduct of epoxide Mei ﹑ Wan Ji Mei ﹑ magnesium dihalides, and in magnesium dihalide molecular formula one of halogen atom by alkane
At least one of derivative that epoxide or halogenated alkoxy are replaced；
The titanium compound formula is TiXn(OR)4-n, R is C in formula1~C20Alkyl, X is halogen, and n is 0~4.
7. method according to claim 6, it is characterised in that step 1) in, the magnesium compound be selected from magnesium dihalide and
At least one of its alcohol adduct and alkoxyl magnesium.
8. method according to claim 6, it is characterised in that the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, four
In titanium iodide, four titanium butoxides, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl epoxide titanium and the ethanolato-titanium of trichlorine one
At least one.
9. according to the method described in claim 1, it is characterised in that step 1), the organic epoxy compound thing is selected from C2~C8
Aliphatic olefin, alkadienes or halogenated aliphatic alkene or alkadienes at least one of oxide and inner ether；
The organic phosphorus compound be selected from orthophosphoric acid trimethyl, orthophosphoric acid triethyl, orthophosphoric acid tributyl, orthophosphoric acid triphenylmethyl methacrylate,
In tricresyl phosphate, Trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl phosphite and triphenylphosphine
At least one.
10. according to the method described in claim 1, it is characterised in that step 1), the organic epoxy compound thing is sweet to shrink
Oily ether.
11. method according to claim 9, it is characterised in that the organic epoxy compound thing is selected from oxirane, epoxy
Propane, epoxy butane, butadiene oxide, butadiene double oxide, epoxychloropropane, methyl glycidyl ether, two shrink sweet
At least one of oily ether and tetrahydrofuran.
12. according to the method described in claim 1, it is characterised in that step 2), the internal electron donor removes formula (I) institute
Outside the imine compound shown, in addition to selected from least one of ester, ether, ketone, amine.
13. method according to claim 12, it is characterised in that step 2) in, the internal electron donor removes formula (I) institute
Outside the imine compound shown, in addition to dihydric alcohol ester type compound, diether compound or polyhydric aliphatic race/aromatic series carboxylic
Acid esters compound.
14. the method according to any one of claim 1 to 13, it is characterised in that in terms of every mole of magnesium, organic epoxy
The consumption of compound is 0.2~10 mole, and the consumption of the organic phosphorus compound is 0.1~3 mole, the use of the titanium compound
Measure as 1~15 mole, the consumption of the internal electron donor compound is 0.005~15 mole, the consumption of the precipitation additive is 0
~5 moles, rubbed in the consumption of the imine compound shown in the internal electron donor compound formula of (I) for 0.01~10
You.
15. 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 14 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.
16. catalyst according to claim 15, it is characterised in that the external donor compound is organosilicon compound
Thing.
17. a kind of application of catalyst as described in claim 15 or 16 in olefin polymerization.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410169176.XA CN105085731B (en) | 2014-04-24 | 2014-04-24 | A kind of catalyst component for olefin polymerization preparation method and corresponding catalyst |
| 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 |
| CA2946777A CA2946777C (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization, and catalyst containing the same |
| SG11201608921YA SG11201608921YA (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst containing the same |
| MYPI2016703904A MY176619A (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 |
| 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 |
| KR1020167032804A KR102293704B1 (en) | 2014-04-24 | 2015-04-24 | Catalyst component for olefin polymerization and catalyst thereof |
| SA516380135A SA516380135B1 (en) | 2014-04-24 | 2016-10-24 | Catalyst Component for Olefin Polymerization, and Catalyst Containing the Same |
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| EP3339333B1 (en) * | 2016-12-22 | 2020-10-07 | Borealis AG | Ziegler-natta catalyst and preparation thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114276A (en) * | 1997-09-11 | 2000-09-05 | Samsung General Chemicals Co., Ltd. | Catalyst system for olefin polymerization and its use |
| KR20030012095A (en) * | 2001-07-30 | 2003-02-12 | 삼성종합화학주식회사 | Olefin Polymerization Catalyst and Polymerization Process Using the Same |
| CN101205264A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Ethane polymerization solid catalyst and preparation thereof |
| 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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2014
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6114276A (en) * | 1997-09-11 | 2000-09-05 | Samsung General Chemicals Co., Ltd. | Catalyst system for olefin polymerization and its use |
| KR20030012095A (en) * | 2001-07-30 | 2003-02-12 | 삼성종합화학주식회사 | Olefin Polymerization Catalyst and Polymerization Process Using the Same |
| CN101205264A (en) * | 2006-12-22 | 2008-06-25 | 中国石油化工股份有限公司 | Ethane polymerization solid catalyst and preparation thereof |
| 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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