CN102516291A - Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof - Google Patents
Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102516291A CN102516291A CN2011104074674A CN201110407467A CN102516291A CN 102516291 A CN102516291 A CN 102516291A CN 2011104074674 A CN2011104074674 A CN 2011104074674A CN 201110407467 A CN201110407467 A CN 201110407467A CN 102516291 A CN102516291 A CN 102516291A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- schiff
- metal complex
- base transition
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 36
- 125000003545 alkoxy group Chemical group 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002262 Schiff base Substances 0.000 title claims abstract description 15
- -1 Schiff base transition metal Chemical class 0.000 title claims abstract description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 39
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003624 transition metals Chemical class 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 12
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 90
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000010936 titanium Substances 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 230000006837 decompression Effects 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Chemical group 0.000 claims description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 150000002431 hydrogen Chemical group 0.000 claims description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 150000005309 metal halides Chemical class 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 0.000 claims description 3
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 3
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract 2
- 239000012266 salt solution Substances 0.000 abstract 2
- 150000001339 alkali metal compounds Chemical class 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 description 17
- 238000005406 washing Methods 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- 150000002466 imines Chemical class 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000004044 response Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- VOVQCRPOHUWTNH-UHFFFAOYSA-N benzene;phenoxybenzene Chemical compound C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 VOVQCRPOHUWTNH-UHFFFAOYSA-N 0.000 description 3
- 229940052810 complex b Drugs 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OFQBYHLLIJGMNP-UHFFFAOYSA-N 3-ethoxy-2-hydroxybenzaldehyde Chemical compound CCOC1=CC=CC(C=O)=C1O OFQBYHLLIJGMNP-UHFFFAOYSA-N 0.000 description 1
- MKKSTJKBKNCMRV-UHFFFAOYSA-N 5-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Br)C=C1C=O MKKSTJKBKNCMRV-UHFFFAOYSA-N 0.000 description 1
- FSHRURRQIMKUGT-UHFFFAOYSA-N 9-phenyl-1,10-phenanthrolin-2-amine Chemical compound N=C1NC2=C3N=C(C=CC3=CC=C2C=C1)C1=CC=CC=C1 FSHRURRQIMKUGT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a Schiff base transition metal complex containing alkoxy groups, a preparation method thereof and application of a catalyst composition composed of the transition metal complex and aluminum alkyl in catalyzing ethene polymerization, belonging to the technical field of catalysts. The preparation method for the Schiff base transition metal complex containing alkoxy groups comprises the following steps: synthesizing Schiff base ligand through a condensation reaction between substituted salicylaldehyde and an amine compound; reacting the ligand with an alkali metal compound to obtain a ligand salt solution; and reacting the ligand salt solution with MCl4 to prepare the Schiff base transition metal complex. The preparation method is simple; and when used for ethene polymerization, the synthesized Schiff base transition metal complex containing alkoxy groups has the following advantages compared to the prior art: common aluminum alkyl is used as a cocatalyst to substitute expensive MAO during polymerization, and the catalyst composition has high activity under the condition of a small usage amount of the cocatalyst. Hexane is used as a solvent to substitute toluene during polymerization, which is favorable for industrial introduction.
Description
Technical field
The present invention relates to a kind of Schiff's base transition metal complex that contains alkoxy grp and preparation method thereof, and the application of the catalyst composition of forming by this transition metal complex and aluminum alkyls in the catalyzed ethylene polymerization reaction; Belong to catalyst technical field.
Background technology
Schiff alkali received investigator's concern in recent years always.It is synthetic one type of relatively easy part, can come synthetic through amine and aldehyde that has carbonyl and copper reaction.Schiff bases part contains can the coordinate Sauerstoffatom and nitrogen-atoms, and is that metals ion and its coordination provide enough solid spaces through the intermediary carbochain, thus Schiff alkali very easily with post transition metal coordination formation title complex.Chinese patent 101967112A discloses a kind of two (5-bromosalicylaldehyde) quadrol that contracts and has closed the compound method of iron.It is different that Schiff alkali prepares employed raw material mix, and for example pyridylaldehyde and substituted aniline condensation form Schiff alkali, Vanillin and the condensation of 3-EL-970 and form Schiff alkali, 2, and 6-diacylpyridines and substituted aniline condensation form Schiff alkali etc.
But Schiff alkali and rear transition metal synthetic title complex catalysis in olefine polymerization under the effect of promotor, and polymerization activity is higher.Chinese patent 101927187A discloses a kind of Fe that is used for ethylene oligomerization and polymeric catalyzer 2-(6 ' imine pyridyl) benzothiazole
2+, Co
2+, Ni
2+, Cr
3+Muriate.This catalyzer has catalytic performance preferably under promotor modified methylaluminoxane or diethylaluminum chloride effect.Use toluene to be solvent during polymerization, and the mol ratio of metallic aluminium is 200～3000 in Primary Catalysts central metal and the promotor.Patent CN 1934121A discloses two-aryl imine pyridine MXn title complex.To select toluene for use be solvent to polymerization embodiment in this patent, and modified methylaluminoxane is a promotor.Patent CN101348501A discloses 2-imino--9-phenyl-1,10-phenanthroline transient metal complex and preparation method thereof and application.This metal complexes is used for the catalyzed ethylene oligomerisation reaction, shows excellent catalytic activity and high 1-butylene selectivity.Selecting toluene when this catalyzer is used for polymerization for use is solvent, and the mol ratio of metallic aluminium and promotor central metal is 100～2000 in the promotor.
Be used to the synthetic of Schiff aar ligand though o-vanillin has been increasing, the material that contains alkoxy grp comparatively speaking use in Schiff alkali synthetic is still less, especially contains alkoxy grp in the aminated compounds.During the complex-catalyzed olefinic polymerization of Schiff alkali and rear transition metal synthetic in the past with having greater activity; But multiselect uses toluene to be solvent; Modified methylaluminoxane is a promotor; And the mol ratio of metallic aluminium and promotor central metal is higher in the promotor, is unfavorable for suitability for industrialized production.
Summary of the invention
The purpose of this invention is to provide a kind of Schiff's base transition metal complex that contains alkoxy grp and preparation method thereof; This title complex uses common aluminum alkyls to replace expensive MAO as promotor when polymerization; Under promotor consumption situation seldom, catalyzer has very high activity; Replace toluene to make solvent with hexane in the polyreaction, help suitability for industrialized production.
The present invention contains the Schiff's base transition metal complex of alkoxy grp, and its structure is following:
X, Y respectively independently are selected from alkoxyl group, phenoxy, substituent phenoxy in the formula; R
1～R
7Each independently is selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl, phenyl; M is a transition metal; As if Y is amino substituent phenoxy, then structural formula such as figure below, wherein R
8Be the substituting group on the phenyl ring, independently be selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl;
Described alkoxyl group is a methoxy or ethoxy.
The substituting group of substituent phenoxy is C
1～C
6Alkyl, sec.-propyl, the tertiary butyl or amino.
M is titanium or zirconium.
A kind of described preparation method who contains the Schiff's base transition metal complex of alkoxy grp is characterized in that it comprises the steps:
(1) under the anhydrous and oxygen-free condition, in the anhydrous methanol solvent,, under 20～60 ℃, carry out condensation reaction with substituted salicylic aldehydes and aminated compounds, remove by filter the anhydrous methanol solvent, the solid drying that obtains is promptly got schiff base ligand;
(2) under the anhydrous and oxygen-free condition, in dichloromethane solvent, schiff base ligand and the alkali metal cpd that makes above-mentioned preparation earlier-40～60 ℃ of reactions, makes the part salts solution by the mol ratio of about 1:1; Part salts solution and MCl then
4React-40～100 ℃ of mol ratios by 1:1 or 2:1, the decompressing and extracting dichloromethane solvent, resistates dissolves with methylene dichloride, and filtration, filtrate decompression are drained solvent, obtain schiff bases complex with the petroleum ether residual solid afterwards.
The said preparation method who contains the Schiff's base transition metal complex of alkoxy grp, wherein alkali metal cpd is butyllithium or sodium hydride in the step (2); MCl
4Transition metal halide is titanium tetrachloride or zirconium tetrachloride.
Described Schiff's base transition metal complex the quoting in the catalyzed ethylene polymerization reaction that contains alkoxy grp.
Said quoting specifically is under the effect of promotor aluminum alkyl catalyst; This Schiff's base transition metal complex that contains alkoxy grp has catalytic performance in the catalyzed ethylene polymerization reaction; Polyreaction is solvent with the hexane; N (Al): n (Ti) mol ratio is 1～1000:1, and the catalytic activity of this catalyzer can reach 10
6Level, polymkeric substance is a linear polyethylene, its viscosity-average molecular weight is the highest to be 32.34*10
5, melting range is 133～135 ℃.
Described promotor aluminum alkyls is trimethylaluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium.
Ethylene pressure is about 1MPa during described polymerization, and hydrogen pressure is 0～0.5 MPa.
Owing to adopt technique scheme, make the present invention have following advantage and effect:
Preparing method of the present invention is simple; The Schiff's base transition metal complex that synthetic contains alkoxy grp is used for vinyl polymerization and compared with prior art has the following advantages: use common aluminum alkyls to replace expensive MAO as promotor during polymerization; Under promotor consumption situation seldom, catalyzer has very high activity.Replace toluene to make solvent with hexane in the polyreaction, help suitability for industrialized production.
Description of drawings
Fig. 1 is the poly GPC figure of embodiment 9.
Embodiment
Below in conjunction with embodiment the present invention is described further.Following examples are merely several specific embodiment of the present invention, but design concept of the present invention is not limited thereto, and allly utilize this design that the present invention is carried out the change of unsubstantiality, all should belong to the behavior of invading protection domain of the present invention.
Method among the following embodiment if no special instructions, is ordinary method.
Percentage composition among the following embodiment is quality percentage composition (w/w) if no special instructions.Title complex of the present invention can synthesize by following equation:
X, Y respectively independently are selected from alkoxyl group, phenoxy, substituent phenoxy in the formula; R
1～R
7Each independently is selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl, phenyl; M is transition metals Ti or zirconium;
If Y is amino substituent phenoxy, title complex synthetic route of the present invention is following:
R wherein
8Be the substituting group on the phenyl ring, independently be selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl;
Above-mentioned is methoxy or ethoxy in alkoxyl group; The substituting group of substituent phenoxy is C
1～C
6Alkyl, sec.-propyl, the tertiary butyl or amino.
The preparation method of the above-mentioned Schiff's base transition metal complex that contains alkoxy grp, it comprises the steps:
(1) under the anhydrous and oxygen-free condition, in the anhydrous methanol solvent,, under 20～60 ℃, carry out condensation reaction with substituted salicylic aldehydes and aminated compounds, remove by filter the anhydrous methanol solvent, the solid drying that obtains is promptly got schiff base ligand;
(2) under the anhydrous and oxygen-free condition, in dichloromethane solvent, schiff base ligand and the alkali metal cpd that makes above-mentioned preparation earlier-40～60 ℃ of reactions, makes the part salts solution by the mol ratio of about 1:1; Part salts solution and MCl then
4React-40～100 ℃ of mol ratios by 1:1 or 2:1, the decompressing and extracting dichloromethane solvent, resistates dissolves with methylene dichloride, and filtration, filtrate decompression are drained solvent, obtain schiff bases complex with the petroleum ether residual solid afterwards.
Alkali metal cpd in the above-mentioned steps (2) is butyllithium or sodium hydride; MCl
4Transition metal halide is titanium tetrachloride or zirconium tetrachloride.
Further specify the present invention below in conjunction with embodiment, but scope of the present invention is not limited to these embodiment.
Following all synthetic and polyreactions all are under the reaction conditions of anhydrous and oxygen-free, to carry out.
Embodiment 1:
The example that is prepared as with two o-vanillins (phenyl ether) benzene imines titanium complex.
(1) preparation of two o-vanillins (phenyl ether) benzene imine ligand: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diaminodiphenyl oxide is stirred to and is dissolved as colourless transparent solution fully; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.002mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part a, productive rate is 87%.
FT-IR：3430(-OH)，1614(C=N)，1257(C-O)
Ultimate analysis theoretical value (%): C, 71.79; N, 5.98; H, 5.13.Experimental value (%): C, 71.81; N, 6.12; H, 5.20.
(2) preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part a, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 1:1; Behind 30 ℃ of reaction 1h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex A with the petroleum ether residual solid afterwards.Title complex A is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 2:
The example that is prepared as with two 2-hydroxyls-3-ethoxy-benzaldehyde (phenyl ether) benzene imines titanium complex.
(1) method of the two 2-hydroxyls of preparation-3-ethoxy-benzaldehyde (phenyl ether) benzene imine ligand: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diaminodiphenyl oxide is stirred to dissolving fully; In constant pressure funnel, add 10ml anhydrous methanol and 0.002mol2-hydroxyl-3-ethoxy-benzaldehyde; In the there-necked flask 4; 4 '-diaminodiphenyl oxide is stirred to fully after the dissolving the 2-hydroxyl-3-ethoxy-benzaldehyde solution slowly drops in the there-necked flask; Dropwise, reaction solution is behind 30 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part b, productive rate is 80%.
(2) preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part b, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 1:1; Behind 50 ℃ of reaction 1h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex B with the petroleum ether residual solid afterwards.Complex B is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 3:
The example that is prepared as with two 2-hydroxyls-3-methoxyl group-5-tolyl aldehyde (phenyl ether) benzene imines titanium complex.
(1) method of the two 2-hydroxyls of preparation-3-methoxyl group-5-tolyl aldehyde (phenyl ether) benzene imine ligand: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diaminodiphenyl oxide is stirred to and is dissolved as colourless transparent solution fully; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.002mol2-hydroxyl-3-methoxyl group-5-tolyl aldehyde; With 2-hydroxyl-3-methoxyl group-5-tolyl aldehyde solution slowly drops in the there-necked flask; Dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part c, productive rate is 76%.
(2) preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part c, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 60 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 1:1; Behind 50 ℃ of reaction 3h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex C with the petroleum ether residual solid afterwards.Title complex C is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 4:
With the contract example that is prepared as of 4-anisole imines titanium complex of o-vanillin.
(1) prepares the contract method of 4-anisole imine ligand of o-vanillin: in the 250ml there-necked flask, add 80ml anhydrous methanol and 0.001mol4-anisidine, be stirred to fully and dissolve; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.001mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part d, productive rate is 79%.
(2) preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part d, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 60 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 2:1; Behind 50 ℃ of reaction 3h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex D with the petroleum ether residual solid afterwards.Title complex D is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 5:
Contract 4 with two o-vanillins, 4 '-diamino-(2, the 6-di-isopropyl) phenyl ether benzene imines titanium complex be prepared as example
(1) the two o-vanillins of preparation contract 4, the method for 4 '-diamino-(2, the 6-di-isopropyl) phenyl ether part: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diamino-(2, the 6-di-isopropyl) phenyl ether is stirred to dissolving fully; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.002mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part e, productive rate is 82%.
(2) preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part e, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 1:1; Behind 0 ℃ of reaction 3h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex E with the petroleum ether residual solid afterwards.Title complex E is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 6:
Contract 4 with two o-vanillins, 4 '-diamino-(2, the 6-dimethyl-) phenyl ether benzene imines titanium complex be prepared as example.
The two o-vanillins of preparation contract 4, the method for 4 '-diamino-(2, the 6-dimethyl-) phenyl ether benzene imine ligand: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diamino-(2, the 6-dimethyl-) phenyl ether is stirred to dissolving fully; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.002mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part f, productive rate is 70%.
The preparation of titanium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part f, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and titanium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and titanium tetrachloride is 1:1; Behind-20 ℃ of reaction 3h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains titanium complex F with the petroleum ether residual solid afterwards.Title complex F is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 7:
Contract 4 with two o-vanillins, 4 '-diamino-(2, the 6-di-t-butyl) phenyl ether benzene imines zirconium complex be prepared as example
(1) the two o-vanillins of preparation contract 4, the method for 4 '-diamino-(2, the 6-di-t-butyl) phenyl ether benzene imine ligand: in the 250ml there-necked flask, add 40ml anhydrous methanol and 0.001mol4,4 '-diamino-(2, the 6-di-t-butyl) phenyl ether is stirred to dissolving fully; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.002mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 40 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part g, productive rate is 72%.
(2) preparation of zirconium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part g, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and zirconium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and zirconium tetrachloride is 1:1; Behind-20 ℃ of reaction 3h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains zirconium complex G with the petroleum ether residual solid afterwards.Title complex G is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 8:
With the contract example that is prepared as of 4-phenetole imines titanium complex of o-vanillin.
(1) prepares the contract method of 4-phenetole imine ligand of o-vanillin: in the 250ml there-necked flask, add 80ml anhydrous methanol and 0.001mol4-phenetidine, be stirred to fully and dissolve; In constant pressure funnel, add 10ml anhydrous methanol dissolved 0.001mol o-vanillin, o-vanillin solution is slowly dropped in the there-necked flask, dropwise, reaction solution is behind 30 ℃ of reaction 4h, with 20ml anhydrous methanol washing three times; Washing afterreaction liquid moves into the characteristic bottle, filters, dry up and weigh part h, productive rate is 84%.
(2) preparation of zirconium complex: in the 250ml there-necked flask, add 40ml methylene dichloride and part h, the 0.0009mol n-Butyl Lithium is slowly added in the there-necked flask,, make the part salts solution at 30 ℃ of reaction 3h; Insert 10ml methylene dichloride and zirconium tetrachloride in the constant pressure funnel respectively then; The mol ratio of part salts solution and zirconium tetrachloride is 2:1; Behind 50 ℃ of reaction 5h; The decompressing and extracting dichloromethane solvent, resistates with methylene dichloride dissolve repeatedly, filtration, filtrate decompression drain solvent, obtains zirconium complex H with the petroleum ether residual solid afterwards.Title complex H is subsequent use with the fluid-tight of 50ml hexane.
Embodiment 9:
Vinyl polymerization:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 3.44ml concentration that under agitation add the titanium complex A (0.46mmol) that 5ml embodiment 1 makes then successively are the triethyl aluminum of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; The no hydrogen dividing potential drop stops the input of ethylene gas behind the 35min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 79.82g, and catalytic activity is 0.30*10
6GPE/ (molTi
4+H).Use one point method to record poly molecular weight and be 29.12*10
5Use GPC to record Vilaterm PD=11.60, MWD is shown in accompanying drawing 1.Using DSC to record the Vilaterm fusing point is 134.77 ℃.
Embodiment 10:
Vinyl polymerization
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 1.72ml concentration that under agitation add the titanium complex B (0.46mmol) that 5ml embodiment 2 makes then successively are the triethyl aluminum of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; The no hydrogen dividing potential drop stops the input of ethylene gas behind the 40min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 20.30g, and catalytic activity is 0.07*10
6GPE/ (molTi
4+H).Recording poly molecular weight is 32.34*10
5, fusing point is 134.56 ℃.
Embodiment 11:
Vinyl polymerization:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 1.47ml concentration that under agitation add the zirconium complex C (0.20mmol) that 5ml embodiment 3 makes then successively are the triethyl aluminum of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; Hydrogen partial pressure is 0.1MPa, stops the input of ethylene gas behind the 15min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 90.30g, and catalytic activity is 1.86*10
6GPE/ (molZr
4+H).Recording poly molecular weight is 16.32*10
5, fusing point is 133.56 ℃.
Embodiment 12:
Vinyl polymerization:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 5.21ml concentration that under agitation add the titanium complex D (0.35mmol) that 5ml embodiment 4 makes then successively are the triethyl aluminum of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; The no hydrogen dividing potential drop stops the input of ethylene gas behind the 10min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 54.68g, and catalytic activity is 0.95*10
6GPE/ (molTi
4+H).Recording poly molecular weight is 13.43*10
5, fusing point is 134.27 ℃.
Embodiment 13:
Vinyl polymerization:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 3.44ml concentration that under agitation add the titanium complex E (0.35mmol) that 5ml embodiment 5 makes then successively are the trimethylaluminium of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; Hydrogen partial pressure is 0.15MPa, stops the input of ethylene gas behind the 10min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 54.68g, and catalytic activity is 0.72*10
6GPE/ (molTi
4+H).Recording poly molecular weight is 13.43*10
5, fusing point is 133.75 ℃.
Embodiment 14:
Vinyl polymerization:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 5.21ml concentration that under agitation add 5ml embodiment 5 titanium complex E (0.35mmol) then successively are the trimethylaluminium of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; Hydrogen partial pressure is 0.15MPa, stops the input of ethylene gas behind the 10min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 54.68g, and catalytic activity is 0.85*10
6GPE/ (molTi
4+H).Recording poly molecular weight is 13.43*10
5, fusing point is 133.63 ℃.
Embodiment 15:
Reaction kettle is replaced 3 times with nitrogen and hexane; Add the 1L hexane in the still; The hexane solution and the 5.21ml concentration that under agitation add 5ml embodiment 7 zirconium complex G (0.35mmol) then successively are the triisobutyl aluminium of 1.33mol/ml, feed ethene when temperature reaches 50 ℃ in the question response still in the reaction kettle and begin polymerization, and ethylene pressure remains on about 1MPa in the polymerization process; Hydrogen partial pressure is 0.2MPa, stops the input of ethylene gas behind the 10min.Be cooled to and take out polymerisate and air-dry about 30 ℃.Product vacuum-drying 6h after air-dry gets 54.68g, and catalytic activity is 0.81*10
6GPE/ (molTi
4+H).Recording poly molecular weight is 13.43*10
5, fusing point is 133.35 ℃.
Embodiment 16:
Triethyl aluminum described in the foregoing description 9-12 can be substituted by triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or the tri-n-octylaluminium of equivalent, and other method is identical with embodiment 9-15.
Claims (10)
1. Schiff's base transition metal complex that contains alkoxy grp is characterized in that structure is following:
X, Y respectively independently are selected from alkoxyl group, phenoxy, substituent phenoxy in the formula; R
1～R
7Each independently is selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl, phenyl; M is a transition metal.
2. a kind of Schiff's base transition metal complex that contains alkoxy grp according to claim 1 is characterized in that if Y is amino substituent phenoxy, then structural formula such as figure below, wherein R
8Be the substituting group on the phenyl ring, independently be selected from hydrogen, C
1～C
6Alkyl, sec.-propyl, the tertiary butyl;
3. a kind of Schiff's base transition metal complex that contains alkoxy grp according to claim 2, the substituting group that it is characterized in that substituent phenoxy is C
1～C
6Alkyl, sec.-propyl, the tertiary butyl or amino.
4. a kind of Schiff's base transition metal complex that contains alkoxy grp according to claim 1 is characterized in that M is titanium or zirconium; Alkoxyl group is a methoxy or ethoxy.
5. the described preparation method who contains the Schiff's base transition metal complex of alkoxy grp of claim 1 is characterized in that it comprises the steps:
(1) under the anhydrous and oxygen-free condition, in the anhydrous methanol solvent,, under 20～60 ℃, carry out condensation reaction with substituted salicylic aldehydes and aminated compounds, remove by filter the anhydrous methanol solvent, the solid drying that obtains is promptly got schiff base ligand;
(2) under the anhydrous and oxygen-free condition, in dichloromethane solvent, schiff base ligand and the alkali metal cpd that makes above-mentioned preparation earlier-40～60 ℃ of reactions, makes the part salts solution by the mol ratio of about 1:1; Part salts solution and MCl then
4React-40～100 ℃ of mol ratios by 1:1 or 2:1, the decompressing and extracting dichloromethane solvent, resistates dissolves with methylene dichloride, and filtration, filtrate decompression are drained solvent, obtain schiff bases complex with the petroleum ether residual solid afterwards.
6. according to the said a kind of preparation method who contains the Schiff's base transition metal complex of alkoxy grp of claim 5, it is characterized in that alkali metal cpd is butyllithium or sodium hydride in the step (2); MCl
4Transition metal halide is titanium tetrachloride or zirconium tetrachloride.
7. described Schiff's base transition metal complex the quoting in the catalyzed ethylene polymerization reaction that contains alkoxy grp of a claim 1.
8. the application that contains the Schiff's base transition metal complex of alkoxy grp according to claim 7; It is characterized in that it specifically being under the effect of promotor aluminum alkyl catalyst; This Schiff's base transition metal complex that contains alkoxy grp has catalytic performance in the catalyzed ethylene polymerization reaction; Polyreaction is solvent with the hexane, and aluminium titanium mol ratio (n (Al): n (Ti)) is 1～1000:1, and the catalytic activity of this catalyzer can reach 10
6Level, polymkeric substance is a linear polyethylene, its viscosity-average molecular weight is the highest to be 32.34*10
5, melting range is 133～135 ℃.
9. the application that contains the Schiff's base transition metal complex of alkoxy grp according to claim 8 is characterized in that described promotor aluminum alkyls is trimethylaluminium, triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum or tri-n-octylaluminium.
10. the application that contains the Schiff's base transition metal complex of alkoxy grp according to claim 8, ethylene pressure is about 1MPa when it is characterized in that polymerization, hydrogen pressure is 0～0.5 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104074674A CN102516291A (en) | 2011-12-09 | 2011-12-09 | Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011104074674A CN102516291A (en) | 2011-12-09 | 2011-12-09 | Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102516291A true CN102516291A (en) | 2012-06-27 |
Family
ID=46287408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011104074674A Pending CN102516291A (en) | 2011-12-09 | 2011-12-09 | Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516291A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936301A (en) * | 2012-11-07 | 2013-02-20 | 复旦大学 | Tridentate Schiff base titanium-based olefin polymerization catalyst and preparation method and application thereof |
| CN107501444A (en) * | 2017-09-28 | 2017-12-22 | 上海化工研究院有限公司 | Support type benzene oxygen imines polyolefin catalyst and preparation method and application |
| WO2019048842A1 (en) * | 2017-09-05 | 2019-03-14 | Scg Chemicals Co., Ltd. | Catalysts suitable for the ring-opening polymerisation of cyclic esters and cyclic amides |
| WO2019048843A3 (en) * | 2017-09-05 | 2019-04-25 | Scg Chemicals Co., Ltd. | Polymerisation of olefins |
| CN110054211A (en) * | 2018-05-22 | 2019-07-26 | 武汉工程大学 | A method of using chinese cymbidium element alloy metal complex as precursor synthesis porous oxide microballoon |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199052A (en) * | 1997-04-25 | 1998-11-18 | 三井化学株式会社 | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers |
| CN1651472A (en) * | 2004-12-24 | 2005-08-10 | 中国科学院长春应用化学研究所 | IVB family compound of schiff base containing olefine oxo and its use in ethylene polymerization |
| JP2006265541A (en) * | 2005-02-25 | 2006-10-05 | Mitsui Chemicals Inc | Method for polymerizing olefin and polymer obtained thereby |
| CN1995044A (en) * | 2006-12-28 | 2007-07-11 | 沈阳工业大学 | Tetradentate IV B transition metal catalyst, preparation method and uses |
| US20090234073A1 (en) * | 2005-05-11 | 2009-09-17 | Mitsui Chemicals, Inc. | Alpha-Olefin/non-conjugated cyclic polyene copolymers, production processes thereof, and crosslinkable compositions including the copolymer |
-
2011
- 2011-12-09 CN CN2011104074674A patent/CN102516291A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199052A (en) * | 1997-04-25 | 1998-11-18 | 三井化学株式会社 | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and alpha-olefin/conjugated diene copolymers |
| CN1651472A (en) * | 2004-12-24 | 2005-08-10 | 中国科学院长春应用化学研究所 | IVB family compound of schiff base containing olefine oxo and its use in ethylene polymerization |
| JP2006265541A (en) * | 2005-02-25 | 2006-10-05 | Mitsui Chemicals Inc | Method for polymerizing olefin and polymer obtained thereby |
| US20090234073A1 (en) * | 2005-05-11 | 2009-09-17 | Mitsui Chemicals, Inc. | Alpha-Olefin/non-conjugated cyclic polyene copolymers, production processes thereof, and crosslinkable compositions including the copolymer |
| CN1995044A (en) * | 2006-12-28 | 2007-07-11 | 沈阳工业大学 | Tetradentate IV B transition metal catalyst, preparation method and uses |
Non-Patent Citations (2)
| Title |
|---|
| G. W. THEAKER等,: "Zirconium-Catalyzed Polymerization of a Styrene: Catalyst Reactivation Mechanisms Using Alkenes and Dihydrogen", 《MACROMOLECULES》 * |
| 王玉现等,: "双邻香草醛（二苯醚）苯亚胺钛络合物的合成及其乙烯聚合", 《2011中国功能材料科技与产业高层论坛论文集》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936301A (en) * | 2012-11-07 | 2013-02-20 | 复旦大学 | Tridentate Schiff base titanium-based olefin polymerization catalyst and preparation method and application thereof |
| CN102936301B (en) * | 2012-11-07 | 2015-04-22 | 复旦大学 | Tridentate Schiff base titanium-based olefin polymerization catalyst and preparation method and application thereof |
| WO2019048842A1 (en) * | 2017-09-05 | 2019-03-14 | Scg Chemicals Co., Ltd. | Catalysts suitable for the ring-opening polymerisation of cyclic esters and cyclic amides |
| WO2019048843A3 (en) * | 2017-09-05 | 2019-04-25 | Scg Chemicals Co., Ltd. | Polymerisation of olefins |
| CN111278559A (en) * | 2017-09-05 | 2020-06-12 | Scg化学有限公司 | Catalyst suitable for ring-opening polymerization of cyclic esters and cyclic amides |
| CN111655743A (en) * | 2017-09-05 | 2020-09-11 | Scg化学有限公司 | Polymerization of olefins |
| JP2020532583A (en) * | 2017-09-05 | 2020-11-12 | エスシージー ケミカルズ カンパニー，リミテッド | Suitable catalysts for ring-opening polymerization of cyclic esters and cyclic amides |
| CN107501444A (en) * | 2017-09-28 | 2017-12-22 | 上海化工研究院有限公司 | Support type benzene oxygen imines polyolefin catalyst and preparation method and application |
| CN107501444B (en) * | 2017-09-28 | 2020-09-11 | 上海化工研究院有限公司 | Supported phenoxy imine polyolefin catalyst, preparation method and application |
| CN110054211A (en) * | 2018-05-22 | 2019-07-26 | 武汉工程大学 | A method of using chinese cymbidium element alloy metal complex as precursor synthesis porous oxide microballoon |
| CN110054211B (en) * | 2018-05-22 | 2022-05-10 | 武汉工程大学 | Method for synthesizing porous oxide microspheres by taking vanillin alloy complex as precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104394986B (en) | Phosphinyl guanidine compounds, metal salt complexes, catalyst systems, and their use to oligomerize or polymerize olefins | |
| CN100371075C (en) | Catalyst systems for ethylene oligomerisation to linear alpha olefins | |
| CN102786435B (en) | Catalysis systems for preparing highly branched alkane by using olefin | |
| CN102516291A (en) | Schiff base transition metal complex containing alkoxy groups, and preparation method and application thereof | |
| JP6832123B2 (en) | Ligand-based chromium catalysts and applications that catalyze ethylene oligomerization | |
| CA2517362A1 (en) | Hexadentate ligand and catalytic complex therewith | |
| CN100528837C (en) | Double-core nickel series compounds, preparation method and application thereof | |
| EP1904509B1 (en) | Diimine metal complexes, synthesis, and use in oligomerization and polymerization | |
| KR101760821B1 (en) | Catalyst composition for oligomerization of ethylene and processes of oligomerization | |
| CN109134302A (en) | A kind of acenaphthene annulus has the application of the alpha-diimine and its derivative complex of hydroxyl in olefin polymerization | |
| CN109957049B (en) | Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof | |
| CN100546990C (en) | A kind of Tetradentate IV B transition metal catalyst, preparation method and application thereof | |
| CN109180845A (en) | A kind of double-core rhodium metal catalyst, preparation method and application | |
| CN101391979A (en) | Unsymmetrical bis(imino)pyridines iron and cobalt complexes containing halogen, preparation method and use | |
| CN102399119A (en) | Method for catalyzing ethylene oligomerization by using butyryl-substituted 1,10-phenanthroline complex | |
| JP2003527403A (en) | Olefin polymerization | |
| CN106397263A (en) | Ligand compound and preparation thereof, and complex containing ligand compound | |
| CN101041610B (en) | Method for preparing alpha-olefin by ethane oligomerisation | |
| CN105384657A (en) | Catalyst ligand, catalyst and preparation methods and application thereof | |
| Long et al. | Synthesis and characterization of niii and pdii complexes bearing n, n, s tridentate ligands and their catalytic properties for norbornene polymerization | |
| CN105646599A (en) | Pyridinocycloheptane imine nickel complex catalyst, preparation method and application thereof | |
| CN101260122B (en) | 2-(6'-iminopyridyl)quinoxaline metal complex compound and its preparing method and application | |
| CN105218590B (en) | Biphenyl bridging dinuclear iron complex and preparation method thereof and application method | |
| EP2268651B1 (en) | Sterically emcumbered bidentate and tridentate naphthoxy-imine metallic complexes | |
| CN109957050B (en) | Asymmetric (alpha-diimine) nickel olefin catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120627 |