CN104926686A - Alpha-diimine compound, metal complex and load containing compound and application thereof - Google Patents
Alpha-diimine compound, metal complex and load containing compound and application thereof Download PDFInfo
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- CN104926686A CN104926686A CN201510219157.8A CN201510219157A CN104926686A CN 104926686 A CN104926686 A CN 104926686A CN 201510219157 A CN201510219157 A CN 201510219157A CN 104926686 A CN104926686 A CN 104926686A
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- SDOYNYMXQNMQNY-UHFFFAOYSA-N CC(C)c(cc1)ccc1Oc1c(cccc2C3(C4NC(C(C5)C(C6CCCCC6)c6ccccc6)C(C(C6C=CCCC6)C6=CCCC=C6)=CC5F)C(C5C(C(C6C=CCCC6)c6ccccc6)=CC(F)=CC5C(C5C=CCCC5)C5C=CCCC5)=C3)c2c4cc1 Chemical compound CC(C)c(cc1)ccc1Oc1c(cccc2C3(C4NC(C(C5)C(C6CCCCC6)c6ccccc6)C(C(C6C=CCCC6)C6=CCCC=C6)=CC5F)C(C5C(C(C6C=CCCC6)c6ccccc6)=CC(F)=CC5C(C5C=CCCC5)C5C=CCCC5)=C3)c2c4cc1 SDOYNYMXQNMQNY-UHFFFAOYSA-N 0.000 description 1
- IFWFKTUYDFMTBP-UHFFFAOYSA-N CCC(CC1)=CC=C1Oc(cc1)c(cccc2C3O)c2c1C3=O Chemical compound CCC(CC1)=CC=C1Oc(cc1)c(cccc2C3O)c2c1C3=O IFWFKTUYDFMTBP-UHFFFAOYSA-N 0.000 description 1
- GQCDVFWBMZKZJP-UHFFFAOYSA-N CCc1c(C(C2=CC=CCC2)C2=CCCC=C2)cccc1C(C1C(C2)C2CC1)c1ccccc1 Chemical compound CCc1c(C(C2=CC=CCC2)C2=CCCC=C2)cccc1C(C1C(C2)C2CC1)c1ccccc1 GQCDVFWBMZKZJP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an alpha-diimine compound, a metal complex and a load containing the compound and application thereof. The structural formula of the compound is shown as a formula I. The alpha-diimine compound is provided with a hydroxyl radical on a substituent group connected to an acenaphthene ring, the compound can react with active radicals on a carrier after chemical modification to form covalent bonds, so that the alpha-diimine compound is loaded on the carrier in a covalent bonding manner; and the metal complex containing the alpha-diimine compound, the load containing the alpha-diimine compound and a load of the metal complex containing the alpha-diimine compound can be further obtained. The metal complex containing the alpha-diimine compound and the load containing the metal complex can be used in polymerization of olefins as main catalysts. The metal complex of the load-type alpha-diimine compound can overcome the disadvantages of kettle adhesion, difficult control for polymer conformation, large using amount of catalyst promoter, poor heat stability and the like, and the covalent bonding load manner avoids the complex from being separated from the carrier .
Description
Technical field
The present invention relates to olefin catalytic field, be specially a kind of alpha-diimine compound and comprise the metal complexes of this compound, loaded article and their application.
Background technology
The people (J Am Chem Soc, 1995,117:6414) such as nineteen ninety-five Brookhart finds, the late transition metal catalyst of alpha-diimine nickel, palladium at ambient pressure catalyzed ethylene polymerization becomes high-molecular weight polymer.People study discovery further subsequently, alpha-diimine catalyst performance depends primarily on the design of ligand structure, wherein aniline structure is to particularly important (the such as document Macromolecules of the control of catalytic performance, 2000,33:2320, J Am Chem Soc, 2003,125:3068, catalysis journal, 2011,32 (3): 490, Macromoleculares, 2009,42:7789, Macromol Chem Phys, 2011,212:367, Angew Chem IntEd, 2004,43:1821, J Am Chem Soc, 2013,135:16316; And patent of invention WO96/23010, US6103658, CN201010177711.8, CN201210051457.6, CN201210276331.9, CN201010572741.9).
If alpha-diimine title complex is for slurry olefin polymerization or gas-phase olefin polymerization, generally need itself and carrier to carry out load.The carrying method of alpha-diimine title complex can pass through the direct load of physical adsorption.Although direct physical adsorption supporting method is easy, the reactive force of catalyzer and carrier is more weak, and in catalyzed polymerization process, catalyst active center easily comes off.The another kind of method of the load of alpha-diimine title complex is exactly that alpha-diimine title complex is connected with carrier by chemical bond.Coming off of alpha-diimine title complex can be solved like this.Document (Appl Catal A:Gen, 2004,262:13) reports introduces the substituting group of end with double bond in the aniline contraposition of alpha-diimine nickel catalyzator, the vinyl on this catalyzer and vinylbenzene (or SiO
2, vinylbenzene and Vinylstyrene mixture) carry out free-radical polymerized and obtain the alpha-diimine catalyzer of Polymer-supported, but this carrying method can make most alpha-diimine title complex be present in carrier inside, they can not participate in the catalysis of alkene, and little at the alpha-diimine of carrier surface.Document (J Mol Catal A:Chem, 2008,287:57) reports the alpha-diimine part of aniline contraposition with Si-Cl terminal substituent, and Si-Cl substituting group can directly and SiO
2hydroxyl reaction on surface and make catalyzer be grafted on structure on carrier by covalent linkage, but the synthesis step of this kind of loaded article is complicated, is unfavorable for industrialization.The people such as Brookhart (Macromolecules, 2006,39:6341) use AlMe
3, SiCl
4or BCl
3process silicon-dioxide, makes the hydroxyl reaction load of itself and carrier surface, and then has synthesized with-NH
2or the alpha-diimine title complex of-OH functional groups, by-the NH on alpha-diimine
2or Al-Me, Si-Cl or B-Cl key of-OH and carrier surface reacts, alpha-diimine title complex is loaded to (reaction formula as below) on carrier by chemical bond.Although this mode of loading is simple, be connected in imido grpup benzene ring substituents if changed, then the synthesis of this kind of compound will become very difficult, is unfavorable for practical application.
Summary of the invention
The object of the present invention is to provide a kind of new alpha-diimine compound.For this alpha-diimine compound, with hydroxyl on the substituting group being connected to acenaphthene ring, it can with chemical modification after carrier on active group carry out reaction and form covalent linkage, make alpha-diimine compound with the mode of chamical binding by its load on carrier; Meanwhile, the aromatic group in alpha-diimine compound on imido grpup can change as required and arbitrarily.Another object of the present invention is to provide the metal complexes containing this alpha-diimine compound, and the loaded article containing the loaded article of this alpha-diimine compound, the metal complexes containing this alpha-diimine compound.A further object of the present invention there are provided a kind of alpha-diimine compound metal complexes and containing the loaded article of this metal complexes as Primary Catalysts in the polymerization of alkene.And the loaded article of alpha-diimine compound metal title complex is used in the polymerization of alkene as Primary Catalysts, improve the deficiencies such as the sticky still, the polymer morphology that exist in the practical application of homogeneous phase alpha-diimine late transition metal catalyst in current techniques are difficult to control, promotor consumption is many, poor heat stability, and the mode of loading of covalent bonding avoids title complex departs from from carrier.
The technical solution adopted in the present invention is:
A kind of alpha-diimine compound, the structural formula of this compound is as shown in the formula I:
Wherein, R
1for there being substituent or unsubstituted C
6-C
60aryl, C
6-C
60heterocyclic arene base in one; R
2for there being substituent or unsubstituted C
6-C
60aryl, C
6-C
60heterocyclic arene base in one; And R
1and R
2identical or different; Ar has the one in following building stone:
Wherein, n=1,2,3,4,5,6 or 7; R ' is C
1-C
20alkyl;
Described alpha-diimine compound preferably has the one in following structural formula:
Wherein, R
a, R
bfor identical or different hydrogen, C
1-C
20alkyl, aryl or with the one in substituent aryl, the one in preferred hydrogen, methyl, phenyl or halogenophenyl; R
cfor identical or different hydrogen, fluorine, chlorine, bromine, C
1-C
20alkyl, fluorine replace C
1-C
20alkyl, C
1-C
20alkoxyl group or aryl in one, the one in preferred hydrogen, fluorine, methyl, trifluoromethyl or methoxyl group.
A kind of alpha-diimine metal complexes, this metal complexes is obtained by described alpha-diimine compound and rear transition metal reactant salt, wherein said late transition metal salt is the one in nickel salt, palladium salt, platinum salt, molysite or cobalt salt, preferably (DME) NiBr
2, (DME) NiCl
2, (COD) PdClCH
3, (PhCN)
2pdCl
2or the one in (COD) PdMe (NCMe);
The preparation method of described alpha-diimine metal complexes, comprise the following steps: in reactor in a nitrogen atmosphere, late transition metal salt being joined concentration is react in the solution of the alpha-diimine compound of 0.01-0.1mmol/mL, wherein, late transition metal salt and alpha-diimine compound equimolar amount; Stirred at ambient temperature reaction 20-24 hour, concentrating under reduced pressure reaction solution to 1 to five/10th 1/10th of original solution volume, then adds concentrated solution volume ten times to fiftyfold normal hexane precipitation, suction filtration, after solid n-hexane, vacuum-drying obtains alpha-diimine metal complexes; In the solution of described alpha-diimine compound, solvent is methylene dichloride or tetrahydrofuran (THF).
A loaded article for alpha-diimine compound, this loaded article reacts obtained by described alpha-diimine compound and the carrier through modifier treatment; Wherein properties-correcting agent is aluminum alkoxide, aluminum alkyls, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, an alkyl trichlorosilicane, an alkyl tribromo SiClx, TiX
4, SiX
4or BX
3in one, preferable methyl aikyiaiurnirsoxan beta (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO), AlMe
3, AlEt
3, Al (i-Bu)
3, AlEt
2cl, ZnEt
2, TiCl
4, SiCl
4or BCl
3in one;
The preparation method of the described carrier through modifier treatment, comprise the following steps: in reaction flask in a nitrogen atmosphere, under mechanical stirring, carrier is joined in dry toluene and obtains suspension, make the concentration of carrier in suspension be 0.01-0.1g/mL, then add properties-correcting agent by the amount that 1g carrier adds 0.1-50mmol properties-correcting agent, reaction 4-16 hour, temperature of reaction is 0-50 DEG C, and reaction terminates rear filtration, obtains modified support respectively with dry toluene, n-hexane;
The preparation method of the loaded article of described alpha-diimine compound, comprise the following steps: in the carrier of modification, add methylene dichloride obtain modified support suspension, in modified support suspension, the concentration of modified support is 0.01-0.1g/mL, add the anhydrous methylene chloride solution that concentration is the alpha-diimine compound of 0.01-0.1mmol/mL again, wherein, the ratio of alpha-diimine compound and modified support is that every gram of modified support adds 1-5mmol alpha-diimine compound, reaction 1-5 hour, temperature of reaction-20-50 DEG C, filter, and by washed with dichloromethane, vacuum-drying obtains the loaded article of alpha-diimine compound.
A loaded article for alpha-diimine metal complexes, be react obtained by alpha-diimine metal complexes and the carrier through modifier treatment, described properties-correcting agent is aluminum alkoxide, aluminum alkyls, dialkyl group zinc, TiX
4, SiX
4or BX
3; Or be obtained by reacting by the loaded article of alpha-diimine compound and late transition metal salt;
Wherein said late transition metal salt is the one in nickel salt, palladium salt, platinum salt, molysite or cobalt salt, preferably (DME) NiBr
2, (DME) NiCl
2, (COD) PdClCH
3or the one in (COD) PdMe (NCMe);
The loaded article of described alpha-diimine compound, the loaded article of alpha-diimine metal complexes, its carrier is one or more the complex carrier in inorganic oxide, metal-salt, clay, diatomite, polynite, polystyrene resin, carbon black, carbon nanotube and Graphene; Preferred SiO
2, MgCl
2, diatomite, polynite, Al
2o
3, Fe
3o
4, SiO
2/ MgCl
2complex carrier, SiO
2/ composite diatomite carrier, polynite/MgCl
2complex carrier, diatomite/MgCl
2complex carrier or Fe
3o
4/ MgCl
2one in complex carrier;
The preparation method of the loaded article of described alpha-diimine metal complexes is one of following two kinds of methods,
Method one, comprise the following steps: in (1) reaction flask in a nitrogen atmosphere, under mechanical stirring, joined by carrier in toluene, make carrier be 0.01-0.1g/mL in the concentration of suspension, the amount adding 0.1-50mol properties-correcting agent by 1g carrier adds properties-correcting agent, reaction 1-5 hour, temperature of reaction is 0-50 DEG C, and reaction terminates rear filtration, obtains modified support respectively with dry toluene, n-hexane; (2) upwards walk in the modified support obtained and add methylene dichloride, modified support is made to be 0.01-0.1g/mL in the concentration of suspension, add the anhydrous methylene chloride solution that concentration is the alpha-diimine metal complexes of 0.01-0.1mmol/mL, the ratio of alpha-diimine metal complexes and modified support is that every gram of modified support adds 1-5mmol alpha-diimine metal complexes, reaction 4-16 hour, temperature of reaction-20-50 DEG C, filter and use washed with dichloromethane, vacuum-drying obtains the loaded article of alpha-diimine metal complexes;
Or method two, comprises the following steps:
In reaction flask in a nitrogen atmosphere, add methylene dichloride, the compound loaded thing of alpha-diimine containing alpha-diimine compound, the late transition metal salt with alpha-diimine compound equimolar amount, rear transition metal salt concn is 0.01-1mmol/mL methylene dichloride, stirred at ambient temperature reaction 20-24 hour, concentrating under reduced pressure reaction solution is to 1 to five/10th 1/10th of original solution volume, add concentrated solution volume ten times again to fiftyfold normal hexane precipitation, suction filtration, after solid n-hexane, vacuum-drying obtains the loaded article of alpha-diimine metal complexes.
A kind of process for olefin polymerization, the application of described alpha-diimine metal complexes or alpha-diimine metal complexes loaded article, is applied in the vapour phase polymerization of ethene or propylene or the liquid-phase bulk polymerization of slurry polymerization or olefinic monomer or slurry polymerization as Primary Catalysts; Slurry polymerization evaluation experimental step is as follows: through vacuumizing, in the reactor of nitrogen replacement, add the anhydrous solvent that volume is reaction vessel 15 ~ 25%, the olefinic monomer added respectively again, Primary Catalysts and promotor, temperature of reaction is-20-120 DEG C, react after 0.5-4 hour and stop, when products therefrom is the oligopolymer of liquid phase, carry out rectifying separation; Or when products therefrom is solid, then the concentration expressed in percentage by volume adding solvent volume 10-20% is the concentrated hydrochloric acid acidic ethanol of 10%, obtains product afterwards with water and washing with alcohol, filtration, vacuum-drying;
In described polyreaction, solvent is dry toluene or anhydrous n-hexane; When described olefinic monomer is gas, olefin gas pressure is 0.1-10MPa; When olefinic monomer is liquid, in often liter of solvent, olefinic monomer add-on is 0.1-10mol; Primary Catalysts add-on is Primary Catalysts 1 × 10
-5-1 × 10
-3mol/L solvent, the mole number of Primary Catalysts contains the molar basis of metal with it; In promotor and Primary Catalysts, the mol ratio of metal is 20-4000:1;
Described olefinic monomer be preferably in ethene, propylene, 1-butylene, 1-hexene, 1-octene, norbornylene, ethylidene norbornene, vinyl norbornene, Dicyclopentadiene (DCPD), vinylbenzene, alpha-methyl styrene and Vinylstyrene one or more;
Described promotor is aluminum alkyls, alkylaluminoxane or boride, preferred AlEt
2cl, AlEtCl
2, Al
2et
3cl
3, Al
2me
2cl
4, AlEt
3, Al (i-Bu)
3, MAO, EAO, MMAO, B (C
6f
5)
4or B (C
6h
3(CF
3)
2)
4in one.
Beneficial effect of the present invention: the invention provides a kind of alpha-diimine compound, with hydroxyl on the substituting group being connected to acenaphthene ring in its structure, it can with chemical modification after carrier on active group carry out reaction and form covalent linkage, make alpha-diimine compound with the mode load of covalent bond on carrier; Meanwhile, the aromatic group in alpha-diimine compound on imido grpup can change as required and arbitrarily, thus adds the Modulatory character of structure.The loaded article of the metal complexes containing this alpha-diimine compound and the metal complexes containing this alpha-diimine compound can be used in the polymerization of alkene as Primary Catalysts.The loaded article of the metal complexes of this alpha-diimine compound is linked at by the effect of covalent bonding on the carrier of modification by the metal complexes of alpha-diimine compound, such carrying method accurately can control the charge capacity of catalyzer on carrier, and the covalent linkage reactive force between catalyzer and carrier is strong, and catalyzer in polymerization process can be avoided to come off from carrier.With aniline in alpha-diimine structure in the past by active group and carrier reaction load Method compare, this method can not affect substituent change on aniline, and the Modulatory character of catalyst structure to polymer architecture is large; And carrier is away from catalyst metal active centre, decrease the impact of functional group on metal active centres of carrier surface.Compared with the alpha-diimine catalyzer poor heat stability of classical Brookhart, this type of supported catalyst Heat stability is good when olefinic polymerization, temperature of reaction polymerization activity 100 DEG C time still can reach 10
5more than g/molh.The alpha-diimine granules of catalyst form of load is good, glues the situation of still when obviously can improve the polymerization of non-supported catalyst.The present invention is applicable to gas phase polymerization apparatus or the slurry polymerization device of existing catalyst alkene.
Accompanying drawing explanation
Fig. 1 is 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (2 in embodiment 4,4,6-trimethylammonium) benzene imines [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] benzene imines c4 X-ray crystal structure ORTEP figure.
Embodiment
Below in conjunction with embodiment, the present invention is described further.It should be noted that, following embodiment can not as limiting the scope of the invention, and any improvement made on basis of the present invention is all without prejudice to spirit of the present invention.
One, the synthesis of alpha-diimine compound
Described alpha-diimine compound obtains by following steps:
1) 5-halo acenaphthenequinone or 5-nitro acenaphthenequinone with react the aromatic oxide acenaphthenequinone (B) obtained with hydroxyl with polyhydric phenol (A);
2) the aromatic oxide acenaphthenequinone (B) with hydroxyl reacts two (alpha-diimine) (C) of the obtained aromatic oxide acenaphthene with hydroxyl with aromatic amine; Reaction scheme is as follows:
Embodiment 1
Two (2,6-di-isopropyl) the benzene imines c1 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=(2,6-di-isopropyl) phenyl) synthesis:
Its syntheti c route is as follows:
The synthesis of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone b1 (namely as the structure of B compound, wherein Ar=4-ethylphenyl):
The 5-bromo acenaphthenequinone of 13.1g (50mmol) is added, 20.7g (150mmol) K in the reaction flask of 100mL
2cO
3, the DMF of 50mL drying, starts to stir.In whipping process, add 13.8g (100mmol) a1,60 DEG C of reactions, thin layer chromatography following response thing reacts completely, stopped reaction.Pour in frozen water by the dark brown solution of reaction, gained solid is purified through silica gel column chromatography, obtains compound b1 yellow crystals 15g, and productive rate is 94%.
1H NMR(400MHz,CDCl
3):δ8.62(d,J＝8.4Hz,1H),δ8.16(d,J＝7.0Hz,1H),δ8.05(d,J＝7.8Hz,1H),δ7.89(t,J＝7.8Hz,1H),δ7.40(d,J＝8.3Hz,2H),δ7.20(d,J＝8.3Hz,2H),δ7.02(d,J＝7.9Hz,1H),δ3.97(t,J＝6.4Hz,2H),δ2.98(t,J＝6.4Hz,2H).MS(ESI):m/z 319(M+H
+).
The synthesis of two (2,6-di-isopropyl) the benzene imines c1 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone:
The compound b1 of 2.55g (8mmol) is added in the reaction flask of 250mL, 2 of 3.36g (19mmol), 6-diisopropyl aniline, the p-methyl benzenesulfonic acid of 3.27g (19mmol) and the dry toluene of 150mL, this mixture back flow reaction, and the water removing will generated in reaction process.Thin layer chromatography following response, complete to raw material reaction, obtain clarification burgundy solution, precipitation compounds c1 yellow solid 4.15g after solution is concentrated, productive rate is 81%.
1H NMR(400MHz,CDCl
3):δ8.23(d,J＝8.4Hz,1H),δ7.39(t,J＝7.8Hz,1H),δ7.32-7.16(m,8H),δ7.06(d,J＝8.4Hz,2H),δ6.67(d,J＝7.1Hz,1H),δ6.55(d,J＝8.1Hz,1H),δ6.46(d,J＝8.1Hz,1H),δ3.90(t,J＝6.5Hz,2H),δ3.09-3.02(m,4H),δ2.90(t,J＝6.5Hz,2H),δ1.27-1.24(m,12H),δ1.02-0.98(m,12H).MS(ESI):m/z 638(M+H
+).
Embodiment 2
Two (2,6-di-isopropyl) the benzene imines c2 of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-aminomethyl phenyl, R
1=R
2=(2,6-di-isopropyl) phenyl) synthesis:
Its syntheti c route is as follows:
The synthesis of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone b2 (namely as the structure of B compound, wherein Ar=4-aminomethyl phenyl):
The 5-bromo acenaphthenequinone of 13.1g (50mmol) is added, 7.45g (60mmol) p-Hydroxybenzylalcohol, 31.84g (150mmol) K in the reaction flask of 100mL
3pO
4, the DMF of 0.47g (2.5mmol) CuI, 0.62g (5mmol) 2-pyridine carboxylic acid and 50mL drying, heated and stirred 24 hours at 90 DEG C.Then the dark brown solution of reaction is poured in saturated NaCl solution and become brown suspension, with dichloromethane extraction 2-3 time, the anhydrous MgSO of organic phase
4drying, pressure reducing and steaming solvent obtains compound b2 brown crystal 13g, and productive rate is 86%.
1H NMR(400MHz,CDCl
3):δ8.62(d,J＝8.2Hz,1H),δ8.17(d,J＝6.7Hz,1H),δ8.05(d,J＝7.8Hz,1H),δ7.89(t,J＝7.6Hz,1H),δ7.55(d,J＝8.0Hz,2H),7.25(d,J＝8.2Hz,2H),δ7.01(d,J＝7.8Hz,1H),δ4.81(s,2H).MS(ESI):m/z 305(M+H
+).
The preparation process of compound c2 is identical with compound c1 preparation process in embodiment 1, and wherein compound b2 replaces the b1 in embodiment 1.The productive rate of compound c2 is 83%.
1H NMR(400MHz,CDCl
3)δ8.23(d,J＝8.3Hz,1H),δ7.43-7.38(m,3H),δ7.32-7.17(m,6H),δ7.10(d,J＝8.4Hz,2H),δ6.68(d,J＝7.2Hz,1H),δ6.57(d,J＝8.0Hz,1H),δ6.47(d,J＝8.0Hz,1H),δ4.72(s,2H),δ3.09-3.02(m,4H),δ1.27-1.24(m,12H),δ1.02-0.98(m,12H).MS(ESI):m/z 624(M+H
+).
Embodiment 3
Two (2,6-di-isopropyl) the benzene imines c3 of 5-(4-hydroxyphenoxy) acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-phenyl, R
1=R
2=(2,6-di-isopropyl) phenyl) synthesis:
Its syntheti c route is as follows:
The preparation process of compound b3 is identical with compound b1 preparation process in embodiment 1, wherein adopts the 5-bromo acenaphthenequinone in 5-nitro acenaphthenequinone replacement embodiment 1; Compound a 3 replaces the a1 in embodiment 1.The preparation process of compound c3 is identical with compound c1 preparation process in embodiment 1, and wherein compound b3 replaces the b1 in embodiment 1, and the productive rate of compound c3 is 76%.
1H NMR(400MHz,CDCl
3)δ8.24(d,J＝8.3Hz,1H),δ7.37(t,J＝7.5Hz,1H),δ7.29-7.14(m,8H),δ6.96(d,J＝8.9Hz,2H),δ6.86(d,J＝8.9Hz,2H),δ6.65(d,J＝7.1Hz,1H),δ3.09-2.98(m,4H),δ1.24-1.21(m,12H),δ0.99-0.96(m,12H).MS(ESI):m/z 610(M+H
+).
Embodiment 4
5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (2,4,6-trimethylammonium) benzene imines [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] benzene imines c4 is (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=(2,4,6-trimethylammonium) phenyl, R
2=[2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] phenyl) synthesis:
Its syntheti c route is as follows:
2.55g (8mmol) compound b1 is added in the reaction flask of 250mL, 2 of 4.6g (9mmol), 6-bis-[two (4-difluorophenyl) methyl]-4-monomethylaniline, the p-methyl benzenesulfonic acid of 3.27g (19mmol), the methylene dichloride of 30mL ethanol and 50mL, stirring at room temperature 48 hours, filters the orange solids generated in reaction process.After drying, this solid is added containing 100mL toluene, in the reaction flask of the p-methyl benzenesulfonic acid of 3.27g (19mmol) and the 2，4，6-trimethyl aniline of 1.08g (8mmol), heating reflux reaction 48 hours.Purify through silica gel column chromatography after gained solution is concentrated, obtain 2.29g yellow solid c4, productive rate is 31%.From 1,2-ethylene dichloride, crystallization obtains the monocrystalline of X-Ray quality.The monocrystalline of gained is through X-ray crystal Epidemiological Analysis.The ORTEP of monocrystalline is illustrated in Fig. 1.
1H NMR(400MHz,CDCl
3)：δ8.10(d,J＝8.4Hz,1H),δ7.37-7.33(t,3H),δ7.06-6.88(m,16H),δ6.71-6.68(t,3H),δ6.37(t,J＝8.5Hz,4H),δ6.27(d,J＝8.0Hz,1H),δ5.90(d,J＝7.9Hz,1H),δ5.60(s,2H),δ3.95(t,J＝6.4Hz,2H),δ2.94(t,J＝6.4Hz,2H),δ2.42(s,3H),δ2.25(s,3H),δ2.20(s,6H).MS(ESI):m/z 929(M+H
+)。
Embodiment 5
Two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines c5 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=[2,6-bis-(diphenyl-methyl)-4-methyl] phenyl) synthesis:
Its syntheti c route is as follows:
Compound c5 is identical with compound c1 preparation process in embodiment 1, and wherein compound 2,6-bis-(diphenyl-methyl)-4-monomethylaniline replaces the 2,6-DIPA in embodiment 1.The productive rate of compound c5 is 5%.
1H NMR(400MHz,CDCl
3):δ7.73(d,J＝8.4Hz,1H),δ7.30(d,J＝8.9Hz,2H),δ7.14-6.65(m,47H),δ6.20-6.13(m,2H),δ5.97(d,J＝7.9Hz,1H),δ5.71(s,4H),δ3.92(t,J＝6.5Hz,2H),δ2.92(t,J＝6.5Hz,2H),δ2.29(s,3H),δ2.23(s,3H).MS(MALDI-TOF):m/z 1161(M
+).
Embodiment 6
Two [2,6-bis-(diphenyl-methyl)-4-fluorine] the benzene imines c6 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=[2,6-bis-(diphenyl-methyl)-4-fluorine] phenyl) synthesis:
Its syntheti c route is as follows:
Compound c6 is identical with compound c1 preparation process in embodiment 1, and wherein compound 2,6-bis-(diphenyl-methyl)-4-fluoroaniline replaces the 2,6-DIPA in embodiment 1.The productive rate of compound c6 is 6%.
1H NMR(400MHz,CDCl
3):δ7.80(d,J＝8.3Hz,1H),δ7.31(d,J＝8.5Hz,2H),δ7.17-6.68(m,47H),δ6.22-6.17(m,2H),δ5.99(d,J＝8.0Hz,1H),δ5.71-5.70(d,4H),δ3.93(t,J＝6.5Hz,2H),δ2.92(t,J＝6.5Hz,2H).MS(MALDI-TOF):m/z 1168(M
+).
Embodiment 7
Two [2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] the benzene imines c7 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=[2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] phenyl) synthesis:
Its syntheti c route is as follows:
Compound c7 is identical with compound c1 preparation process in embodiment 1, and wherein compound 2,6-bis-(diphenyl-methyl)-4-5-trifluoromethylaniline replaces the 2,6-DIPA in embodiment 1.The productive rate of compound c7 is 4%.
1H NMR(400MHz,CDCl
3):δ7.85(d,J＝8.4Hz,1H),δ7.38-7.31(m,6H),δ7.15-6.66(m,43H),6.20(d,J＝8.0Hz,1H),6.13(d,J＝7.1Hz,1H),δ5.94(d,J＝8.0Hz,1H),δ5.73-5.72(d,4H),δ3.92(t,J＝6.5Hz,2H),δ2.92(t,J＝6.5Hz,2H).MS(MALDI-TOF):m/z 1268(M
+).
Embodiment 8
Two [2,6-bis-(diphenyl-methyl)-4-methoxyl group] the benzene imines c8 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=[2,6-bis-(diphenyl-methyl)-4-methoxyl group] phenyl) synthesis:
Its syntheti c route is as follows:
Compound c8 is identical with compound c1 preparation process in embodiment 1, and wherein compound 2,6-bis-(diphenyl-methyl)-4-anisidine replaces the 2,6-DIPA in embodiment 1.The productive rate of compound c8 is 8%.
1H NMR(400MHz,CDCl
3):δ7.77(d,J＝8.3Hz,1H),δ7.32(d,J＝8.5Hz,2H),δ7.18-6.67(m,47H),δ6.23(t,2H),δ6.04(d,J＝8.0Hz,1H),δ5.75-5.74(d,4H),δ3.95(t,J＝6.5Hz,2H),δ3.69(s,3H),δ3.64(s,3H),δ2.95(t,J＝6.5Hz,2H).MS(MALDI-TOF):m/z 1193(M
+).
Embodiment 9
Two [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] the benzene imines c9 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (namely as the structure of C compound, wherein Ar=4-ethylphenyl, R
1=R
2=[2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl]] phenyl) synthesis:
Its syntheti c route is as follows:
Compound c9 is identical with compound c1 preparation process in embodiment 1, wherein compound 2,6-bis-[two (4-difluorophenyl) methyl] 4-methyl] aniline replaces in embodiment 1 2,6-DIPA.The productive rate of compound c9 is 7%.
1H NMR(400MHz,CDCl
3):δ8.00(d,J＝8.4Hz,1H),δ7.33(d,J＝8.3Hz,2H),δ7.02-6.72(m,31H),6.44(t,J＝8.4Hz,4H),6.32(t,J＝8.4Hz,4H),6.20(d,J＝7.0Hz,1H),6.05(d,J＝8.0Hz,1H),5.81(d,J＝8.0Hz,1H),δ5.63(s,2H),δ5.55(s,2H),δ3.93(t,J＝6.4Hz,2H),δ2.92(t,J＝6.4Hz,2H),δ2.30(s,3H),δ2.23(s,3H).MS(MALDI-TOF):m/z 1304(M
+).
Two, the synthesis of alpha-diimine metal complexes
Embodiment 10
The synthesis of two (2,6-di-isopropyl) the benzene imines nickelous bromide Nic1 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
In a nitrogen atmosphere, in reaction flask, add the compound c1 (1mmol) obtained in embodiment 1, methylene dichloride 50mL, 1,2-glycol dimethyl ether nickelous bromide (DME) NiBr
2(1mmol), stirring at room temperature 24 hours.Then concentrating under reduced pressure reaction solution is to 5mL, adds 50mL normal hexane and is settled out red brown solid.Suction filtration, after solid n-hexane, vacuum-drying obtains title complex Nic10.786g, productive rate: 92%.The ultimate analysis of title complex Nic1: C
44h
48br
2n
2niO
2theoretical value: C 61.78%, H 5.66%, N 3.28%; Experimental value: C 61.77%, H 5.68%, N 3.26%.ICP measures, Ni 6.85% (Wt).
Embodiment 11
The synthesis of two (2,6-di-isopropyl) the benzene imines nickelous bromide Nic2 of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone
Title complex Nic2 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c2 replacement embodiment 10 obtained by embodiment 2.The productive rate of title complex Nic2 is 93%.The ultimate analysis of title complex Nic2: C
43h
46br
2n
2niO
2theoretical value: C 61.39%, H 5.51%, N 3.33%; Experimental value: C 61.37%, H 5.53%, N 3.36%.ICP measures, Ni 6.94%.
Embodiment 12
The synthesis of two (2,6-di-isopropyl) the benzene imines nickelous bromide Nic3 of 5-(4-hydroxyphenoxy) acenaphthenequinone
Title complex Nic3 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c3 replacement embodiment 10 obtained by embodiment 3.The productive rate of title complex Nic3 is 92%.The ultimate analysis of title complex Nic3: C
42h
44br
2n
2niO
2theoretical value: C 60.97%, H 5.36%, N 3.39%; Experimental value: C 60.99%, H 5.33%, N3.37%.ICP measures, Ni7.06%.
Embodiment 13
The synthesis of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (2,4,6-trimethylammonium) benzene imines [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] benzene imines nickelous bromide Nic4
Title complex Nic4 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c4 replacement embodiment 10 obtained by embodiment 4.The productive rate of title complex Nic4 is 90%.The ultimate analysis of title complex Nic4: C
65h
58br
2n
2niO
2theoretical value: C, 64.89%, H, 4.22%, N, 2.44%; Experimental value: C 64.91%, H 4.23%, N 2.42%.ICP measures, Ni 5.09%.
Embodiment 14
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines nickelous bromide Nic5 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
Title complex Nic5 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c5 replacement embodiment 10 obtained by embodiment 5.The productive rate of title complex Nic5 is 90%.The ultimate analysis of title complex Nic5: C
86h
68br
2n
2niO
2theoretical value: C 74.85%, H 4.97%, N 2.03%; Experimental value: C 74.83%, H 4.98%, N 2.07%.ICP measures, Ni 4.23%.
Embodiment 15
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-fluorine] the benzene imines nickelous bromide Nic6 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
Title complex Nic6 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c6 replacement embodiment 10 obtained by embodiment 6.The productive rate of title complex Nic6 is 94%.The ultimate analysis of title complex Nic6: C
84h
62br
2f
2n
2niO
2theoretical value: C 72.69%, H 4.50%, N, 2.02%; Experimental value: C 72.71%, H 4.51%, N 1.98%.ICP measures, Ni 4.22%.
Embodiment 16
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] the benzene imines nickelous bromide Nic7 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone:
Title complex Nic7 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c7 replacement embodiment 10 obtained by embodiment 7.The productive rate of title complex Nic7 is 93%.The ultimate analysis of title complex Nic7: C
86h
62br
2f
6n
2niO
2theoretical value: C 69.42%, H 4.20%, N, 1.88%; Experimental value: C 69.46%, H 4.23%, N 1.86%.ICP measures, Ni 3.91%.
Embodiment 17
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-methoxyl group] the benzene imines nickelous bromide Nic8 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone:
Title complex Nic8 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c8 replacement embodiment 10 obtained by embodiment 8.The productive rate of title complex Nic8 is 90%.The ultimate analysis of title complex Nic8: C
86h
68br
2n
2niO
4theoretical value: C 73.15%, H 4.85%, N, 1.98%; Experimental value: C 73.21%, H 4.83%, N 1.96%.ICP measures, Ni 4.14%.
Embodiment 18
The synthesis of two [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] the benzene imines nickelous bromide Nic9 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone:
Title complex Nic9 is identical with title complex Nic1 preparation process in embodiment 10, wherein adopts the c1 in the compound c9 replacement embodiment 10 obtained by embodiment 9.The productive rate of title complex Nic9 is 92%.The ultimate analysis of title complex Nic9: C
86h
60br
2f
8n
2niO
2theoretical value: C 67.78%, H 3.97%, N, 1.84%; Experimental value: C 67.81%, H 3.95%, N 1.86%.ICP measures, Ni 3.84%.
Embodiment 19
The synthesis of two (2,6-di-isopropyl) the benzene imines Palladous chloride Pdc1 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
In a nitrogen atmosphere, in reaction flask, the alpha-diimine compound c1 (1mmol) that embodiment 1 is obtained is added, (PhCN)
2pdCl
2(1mmol), methylene dichloride 50mL, stirring at room temperature 24 hours.Then concentrating under reduced pressure reaction solution is to 5mL, adds 50mL normal hexane and is settled out red brown solid.Suction filtration, after solid n-hexane, vacuum-drying obtains title complex Pdc10.736g, productive rate: 90%.The ultimate analysis of title complex Pdc1: C
44h
48cl
2n
2o
2pd theoretical value: C 64.91%, H 5.94%, N 3.44%; Experimental value: C 64.89%, H 5.96%, N, 3.46%.ICP measures, Pd 12.95%.
Embodiment 20
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-methyl] the benzene imines Palladous chloride Pdc5 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
Title complex Pdc5 is identical with title complex Pdc1 preparation process in embodiment 19, wherein adopts the c1 in the compound c5 replacement embodiment 19 obtained by embodiment 5.The productive rate of title complex Pdc5 is 93%.The ultimate analysis of title complex Pdc5: C
86h
68cl
2n
2o
2pd theoretical value: C 77.15%, H 5.12%, N 2.09%; Experimental value: C 77.12%, H 5.10%, N 2.11%.ICP measures, Pd 7.92%.
Embodiment 21
The synthesis of two [2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] the benzene imines Palladous chloride Pdc7 of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone:
Title complex Pdc7 is identical with title complex Pdc1 preparation process in embodiment 19, wherein adopts the c1 in the compound c7 replacement embodiment 19 obtained by embodiment 7.The productive rate of title complex Pdc7 is 93%.The ultimate analysis of title complex Pdc7: C
86h
62cl
2f
6n
2o
2pd theoretical value: C 71.40%, H 4.32%, N 1.94%; Experimental value: C 71.46%, H 4.33%, N 1.97%.ICP measures, Pd 7.35%.
Three, the synthesis of alpha-diimine loaded article
Embodiment 22
Trimethyl aluminium key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlMe-c1
In a nitrogen atmosphere, in reaction flask, add 50mL toluene, through 600 DEG C of burnt SiO
2(1g) room temperature is risen to after, then under mechanical stirring, adding trimethyl aluminium (15mmol) under zero degree.Stir after 2 hours, suction filtration is except desolventizing in a nitrogen atmosphere, products obtained therefrom use 20mL toluene wash successively three times, 20mL n-hexane once after, add 20mL methylene dichloride, then slowly instill by the dichloromethane solution of the alpha-diimine compound c1 obtained in embodiment 1 (2mmol alpha-diimine compound c1,20mL methylene dichloride).At room temperature stir after 2 hours, in a nitrogen atmosphere suction filtration removing methylene dichloride, and with drying after washed with dichloromethane 3 times, obtain orange solid product SiO
2-AlMe-c1.Loaded article SiO
2the ultimate analysis of-AlMe-c1: C 16.42%, N 0.87%.
Embodiment 23
Titanium tetrachloride key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2-TiCl
2the synthesis of-c1
Loaded article SiO
2-TiCl
2loaded article SiO in the preparation process of-c1 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the trimethyl aluminium in titanium tetrachloride replacement embodiment 22.Loaded article SiO
2-TiCl
2the ultimate analysis of-c1: C 17.72%, N 0.94%.
Embodiment 24
Zinc ethyl key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone
2the synthesis of-Zn-c2
Loaded article SiO
2loaded article SiO in the preparation process of-Zn-c2 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the trimethyl aluminium in zinc ethyl replacement embodiment 22, adopts the c1 in the compound c2 replacement embodiment 22 obtained by embodiment 2.Loaded article SiO
2the ultimate analysis of-Zn-c2: C 12.74%, N 0.69%.
Embodiment 25
Boron trichloride key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines of 5-(4-hydroxyphenoxy) acenaphthenequinone
2the synthesis of-BCl-c3
Loaded article SiO
2loaded article SiO in the preparation process of-BCl-c3 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the trimethyl aluminium in boron trichloride replacement embodiment 22, adopts the c1 in the compound c3 replacement embodiment 22 obtained by embodiment 3.Loaded article SiO
2the ultimate analysis of-BCl-c3: C 12.92%, N 0.72%.
Embodiment 26
Methylaluminoxane key connects two [2,6-bis-(diphenyl-methyl)-4-methyl] the silicon dioxide carried thing SiO of benzene imines of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlOMe-c5
Loaded article SiO
2loaded article SiO in the preparation process of-AlOMe-c5 and embodiment 22
2the preparation process of-AlOMe-c1 is identical, wherein adopts the trimethyl aluminium in methylaluminoxane replacement embodiment 22, adopts the c1 in the compound c5 replacement embodiment 22 obtained by embodiment 5.Loaded article SiO
2the ultimate analysis of-AlOMe-c5: C 31.41%, N 0.85%.
Embodiment 27
Silicon tetrachloride key connects two [2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] the silicon dioxide carried thing SiO of benzene imines of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2-SiCl
2the synthesis of-c7
Loaded article SiO
2-SiCl
2loaded article SiO in the preparation process of-c7 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the trimethyl aluminium in silicon tetrachloride replacement embodiment 22, adopts the c1 in the compound c7 replacement embodiment 22 obtained by embodiment 7.Loaded article SiO
2-SiCl
2the ultimate analysis of-c7: C 22.04%, N 0.60%.
Embodiment 28
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines magnesium chloride load thing MgCl of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlMe-c1
Under argon shield, the anhydrous MgCl of solvent n-heptane 50mL and 1mol is being added successively with churned mechanically five mouthfuls of bottles
2, and at 35 DEG C, add 4mol propyl carbinol (mol ratio of propyl carbinol and magnesium chloride is 4:1), then temperature programming keeps 3h to 90 DEG C, obtains colourless transparent solution, then solution is cooled to room temperature, add trimethyl aluminium (15mmol).Stir after 2 hours, suction filtration is except desolventizing in a nitrogen atmosphere, products obtained therefrom use 20mL toluene wash successively three times, 20mL n-hexane once after, add 50mL methylene dichloride, then slowly instill by the dichloromethane solution of the alpha-diimine compound c1 obtained in embodiment 1 (2mmol alpha-diimine compound c1,20mL methylene dichloride).At room temperature stir after 4 hours, in a nitrogen atmosphere suction filtration removing methylene dichloride, and with drying after washed with dichloromethane 3 times, obtain solid product MgCl
2-AlMe-c1.Loaded article MgCl
2the ultimate analysis of-AlMe-c1: C 15.12%, N 0.80%.
Embodiment 29
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines aluminium sesquioxide loaded article Al of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone
2o
3the synthesis of-AlMe-c2
Loaded article Al
2o
3loaded article SiO in the preparation process of-AlMe-c2 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the silicon-dioxide in aluminium sesquioxide replacement embodiment 22, adopts the c1 in the compound c2 replacement embodiment 22 obtained by embodiment 2.Loaded article Al
2o
3the ultimate analysis of-AlMe-c2: C 16.81%, N 0.91%.
Embodiment 30
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines Z 250 loaded article Fe of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
3o
4the synthesis of-AlMe-c1
Loaded article Fe
3o
4loaded article SiO in the preparation process of-AlMe-c1 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts the silicon-dioxide in Z 250 replacement embodiment 22.Loaded article Fe
3o
4the ultimate analysis of-AlMe-c1: C14.73%, N 0.78%.
Embodiment 31
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines silicon-dioxide/magnesium chloride load thing SiO of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2/ MgCl
2the synthesis of-AlMe-c1
Under argon shield, the anhydrous MgCl of solvent n-heptane 50mL and 1g is being added successively with churned mechanically five mouthfuls of bottles
2, and at 35 DEG C, add a certain amount of propyl carbinol (mol ratio of propyl carbinol and magnesium chloride is 4:1), then temperature programming keeps 3 hours to 90 DEG C, obtains colourless transparent solution.Then solution is cooled to 60 DEG C, then adds a certain amount of SiO
2(MgCl
2and SiO
2mass ratio equals 1:1), and stop after this temperature stirs 2 hours, obtain SiO through suction filtration drying
2/ MgCl
2complex carrier.
Loaded article SiO
2/ MgCl
2loaded article SiO in the preparation process of-AlMe-c1 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts SiO
2/ MgCl
2complex carrier replaces the SiO in embodiment 22
2.Loaded article SiO
2/ MgCl
2the ultimate analysis of-AlMe-c1: C 14.49%, N 0.75%.
Embodiment 32
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines aluminium sesquioxide/magnesium chloride load thing SiO of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of/diatomite-AlMe-c1
Loaded article SiO
2loaded article SiO in the preparation process of/diatomite-AlMe-c1 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts SiO
2/ composite diatomite carrier replaces the silicon-dioxide in embodiment 22, SiO
2the mass ratio of/composite diatomite carrier is 1:2.Loaded article SiO
2the ultimate analysis of/diatomite-AlMe-c1: C 15.29%, N 0.81%.
Embodiment 33
Trimethyl aluminium key connects two (2,6-di-isopropyl) the benzene imines Z 250/magnesium chloride load thing Fe of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
3o
4/ MgCl
2the synthesis of-AlMe-c1
Fe
3o
4/ MgCl
2siO in the synthesis of complex carrier and embodiment 31
2/ MgCl
2the preparation process of complex carrier is identical, wherein adopts Fe
3o
4replace the SiO in embodiment 31
2.
Loaded article Fe
3o
4/ MgCl
2loaded article SiO in the preparation process of-AlMe-c1 and embodiment 22
2the preparation process of-AlMe-c1 is identical, wherein adopts Fe
3o
4/ MgCl
2complex carrier replaces the silicon-dioxide in embodiment 22.Loaded article Fe
3o
4/ MgCl
2the ultimate analysis of-AlMe-c1: C 14.93%, N 0.79%.
Four, the synthesis of the loaded article of alpha-diimine metal complexes
Method one:
Embodiment 34
Trimethyl aluminium key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines nickelous bromide of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlMe-Nic1
In a nitrogen atmosphere, in reaction flask, add 50mL toluene, through 600 DEG C of burnt SiO
21g, then under mechanical stirring, rises to room temperature after adding trimethyl aluminium (15mmol) under zero degree.Stir after 2 hours, suction filtration is except desolventizing in a nitrogen atmosphere, products obtained therefrom use 20mL toluene wash successively three times, 20mL n-hexane once after, add 50mL methylene dichloride, then slowly instill by the dichloromethane solution of the Nic1 obtained in embodiment 10 (2mmol Nic1,20mL methylene dichloride).At room temperature stir after 5 hours, in a nitrogen atmosphere suction filtration removing methylene dichloride, and with drying after washed with dichloromethane 3 times, obtain solid product SiO
2-AlMe-Nic1.ICP measures loaded article SiO
2the Ni content of-AlMe-Nic1: 2.5% (Wt).
Embodiment 35
Trimethyl aluminium key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines Palladous chloride of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlMe-Pdc1
Loaded article SiO
2loaded article SiO in the preparation process of-AlMe-Pdc1 and embodiment 34
2the preparation process of-AlMe-Nic1 is identical, adopts the Nic1 in the title complex Pdc1 replacement embodiment 34 obtained by embodiment 19.Loaded article SiO
2the content of the Pd of-AlMe-Pdc1: 2.7%.
Embodiment 36
Titanium tetrachloride key connects two (2,6-di-isopropyl) the benzene imines nickelous bromide diatomite/MgCl of 5-(4-hydroxy methyl phenyloxy) acenaphthenequinone
2loaded article diatomite/MgCl
2-TiCl
2the synthesis of-Nic2
Loaded article diatomite/MgCl
2-TiCl
2loaded article SiO in the preparation process of-Nic2 and embodiment 34
2the preparation process of-AlMe-Nic1 is identical, adopts the trimethyl aluminium in titanium tetrachloride replacement embodiment 34, adopts the Nic1 in the title complex Nic2 replacement embodiment 34 obtained by embodiment 11, diatomite/MgCl
2siO in the synthesis of complex carrier and embodiment 31
2/ MgCl
2the preparation process of complex carrier is identical, wherein adopts the SiO in diatomite replacement embodiment 31
2, diatomite and MgCl
2mass ratio be 5.Loaded article diatomite/MgCl
2-TiCl
2the content of the Ni of-Nic2: 1.9%.
Embodiment 37
Methylaluminoxane key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines nickelous bromide of 5-(4-hydroxyphenoxy) acenaphthenequinone
2the synthesis of-AlOMe-Nic3
Loaded article SiO
2loaded article SiO in the preparation process of-AlOMe-Nic3 and embodiment 34
2the preparation process of-AlMe-Nic1 is identical, adopts the trimethyl aluminium in methylaluminoxane replacement embodiment 34, wherein adopts the Nic1 in the title complex Nic3 replacement embodiment 34 obtained by embodiment 12.Loaded article SiO
2the content of the Ni of-AlOMe-Nic3: 1.6%.
Embodiment 38
Trimethyl aluminium key connects 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone (2,4,6-trimethylammonium) benzene imines [2,6-bis-[two (4-difluorophenyl) methyl]-4-methyl] the silicon dioxide carried thing SiO of benzene imines nickelous bromide
2the synthesis of-AlMe-Nic4
Loaded article SiO
2loaded article SiO in the preparation process of-AlMe-Nic4 and embodiment 34
2the preparation process of-AlMe-Nic1 is identical, adopts the Nic1 in the title complex Nic4 replacement embodiment 34 obtained by embodiment 13.Loaded article SiO
2the content of the Ni of-AlMe-Nic4: 1.4%.
Embodiment 39
Zinc ethyl key connects two [2,6-bis-(diphenyl-methyl)-4-methyl] the silicon dioxide carried thing SiO of benzene imines Palladous chloride of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-Zn-Pdc5
Loaded article SiO
2loaded article SiO in the preparation process of-Zn-Pdc5 and embodiment 34
2the preparation process of-AlMe-Nic1 is identical, adopts the trimethyl aluminium in zinc ethyl replacement embodiment 34, wherein adopts the Nic1 in the title complex Pdc5 replacement embodiment 34 obtained by embodiment 20.Loaded article SiO
2the content of the Pd of-Zn-Pdc5: 1.8%.
Method two:
Embodiment 40
Trimethyl aluminium key connects 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone two (2,6-di-isopropyl) benzene imines nickelous bromide silica/silicon algae soil loaded article SiO
2the synthesis of/diatomite-AlMe-Nic1
In a nitrogen atmosphere, in reaction flask, add the alpha-diimine loaded article SiO containing 5mmol alpha-diimine compound obtained in methylene dichloride 50mL, embodiment 32
2/ diatomite-AlMe-c1, then add (DME) NiBr
25mmol, mechanical stirring 24 hours under room temperature.Then concentrating under reduced pressure reaction solution is to 5mL, adds 50mL normal hexane.Suction filtration, after solid n-hexane, vacuum-drying obtains loaded article SiO
2/ diatomite-AlMe-Nic1.Loaded article SiO
2the content of the Ni of/diatomite-AlMe-Nic1: 2.1%.
Embodiment 41
Trimethyl aluminium key connects the two silicon dioxide carried thing SiO of (2,6-di-isopropyl) benzene imines Palladous chloride of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlMe-Pdc1
Loaded article SiO
2loaded article SiO in the preparation process of-AlMe-Pdc1 and embodiment 40
2the preparation process of-AlMe-Nic1 is identical, adopts (DME) NiBr in two cyanobenzene Palladous chlorides replacement embodiments 40
2.Loaded article SiO
2the content of the Pd of-AlMe-Pdc1: 1.6%.
Embodiment 42
Methylaluminoxane key connects two [2,6-bis-(diphenyl-methyl)-4-methyl] the silicon dioxide carried thing SiO of benzene imines nickelous bromide of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2the synthesis of-AlOMe-Nic5
Loaded article SiO
2loaded article SiO in the preparation process of-AlOMe-Nic5 and embodiment 40
2the preparation process of-AlMe-Nic1 is identical, adopts the loaded article SiO obtained by embodiment 26
2-AlOMe-c5 replaces the loaded article SiO in embodiment 40
2-AlMe-c1.Loaded article SiO
2the content of the Ni of-AlOMe-Nic5: 1.5%.
Embodiment 43
Silicon tetrachloride key connects two [2,6-bis-(diphenyl-methyl)-4-trifluoromethyl] the silicon dioxide carried thing SiO of nickelous bromide of 5-[4-(2-hydroxyethyl) phenoxy group] acenaphthenequinone
2-SiCl
2the synthesis of-Nic7
Loaded article SiO
2-SiCl
2loaded article SiO in the preparation process of-Nic7 and embodiment 40
2the preparation process of-AlMe-Nic1 is identical, wherein adopts the loaded article SiO obtained by embodiment 27
2-SiCl
2-c7 replaces the loaded article SiO in embodiment 40
2-AlMe-c1.Loaded article SiO
2-SiCl
2the content of the Ni of-Nic7: 1.9%.
Five, olefinic polyreaction
Embodiment 44
Loaded article SiO
2-AlMe-Nic1 is as Primary Catalysts catalyzed ethylene polymerization
In the 250mL reactor being filled with ethene through nitrogen replacement for three times again, add 50mL dry toluene, heating constant temperature to 30 DEG C, stir and pass into ethene and make to keep pressure 0.5MPa in reactor, add the loaded article SiO of embodiment 34 gained respectively
2(0.02g, in solvent, contained Ni content is 8.52 × 10 to-AlMe-Nic1
-6mol), the promotor MAO (4.4mL of 1.4mol/L, promotor and Primary Catalysts mol ratio are 1000:1), polymerization time is 1 hour, then adding 10mL concentration expressed in percentage by volume is that the acidic ethanol (namely volume ratio is 37% concentrated hydrochloric acid: dehydrated alcohol=1:9) of 10% is to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyethylene 5.11g.SiO
2the catalytic activity of-AlMe-Nic1 is 6.0 × 10
5g/molh (active calculated by the polymerisate quality/amount × per hour of metallics (in the catalyzer)).Polymkeric substance Mw (weight-average molecular weight) is 5.8 × 10
5g/mol, MWD (molecular weight distribution) are 2.8 (GPC records).
13it is 32/1000 carbon atom that C NMR measures polymer branching degree.
Embodiment 45
Loaded article SiO
2-AlMe-Pdc1 is as Primary Catalysts catalyzed ethylene polymerization
Solvent is dry toluene, ethylene pressure 0.5MPa, and temperature of reaction is 100 DEG C, the loaded article SiO that Primary Catalysts is prepared by embodiment 35
2(in solvent, contained Pd content is 5.31 × 10 to-AlMe-Pdc1
-6mol), cocatalyst B (C
6f
5)
4(promotor and Primary Catalysts mol ratio are 1000:1), concrete operations are with embodiment 44, and polymerization time is 0.5 hour.SiO
2the catalytic activity of-AlMe-Pdc1 is 1.3 × 10
7g/molh, polymkeric substance Mw are 4.1 × 10
5g/mol, MWD are 2.2, and polymer branching degree is 83/1000 carbon atom.
Embodiment 46
Loaded article diatomite/MgCl
2-TiCl
2-Nic2 is as Primary Catalysts catalyzed ethylene polymerization
Solvent is anhydrous n-hexane, ethylene pressure 5.0MPa, and temperature of reaction is 80 DEG C, loaded article diatomite/MgCl that Primary Catalysts is prepared by embodiment 36
2-TiCl
2(in solvent, contained Ni content is 5.72 × 10 to-Nic2
-6mol), promotor AlEt
2cl (promotor and Primary Catalysts mol ratio are 500:1), concrete operations are with embodiment 44, and polymerization time is 1 hour.Its activity is 8.9 × 10
6g/molh, polymkeric substance Mw are 5.1 × 10
5g/mol, MWD are 3.3, and polymer branching degree is 49/1000 carbon atom.
Embodiment 47
Loaded article SiO
2-AlOMe-Nic3 is as Primary Catalysts catalyzed ethylene polymerization
Solvent is dry toluene, ethylene pressure 2.0MPa, and temperature of reaction is 20 DEG C, the loaded article SiO that Primary Catalysts is prepared by embodiment 37
2(in solvent, contained Ni content is 4.91 × 10 to-AlOMe-Nic3
-6mol), promotor AlEt
2cl (promotor and Primary Catalysts mol ratio are 500:1), concrete operations are with embodiment 44, and polymerization time is 2 hours.Its activity is 3.2 × 10
5g/molh, polymkeric substance Mw are 4.0 × 10
5g/mol, MWD are 2.6, and polymer branching degree is 45/1000 carbon atom.
Embodiment 48
Loaded article SiO
2-AlMe-Nic4 is polymerized as Primary Catalysts catalyzing propone
Solvent is anhydrous n-hexane, propylene pressure 2.0MPa, and temperature of reaction is 40 DEG C, loaded article SiO prepared by Primary Catalysts embodiment 38
2(in solvent, contained Ni content is 8.65 × 10 to-AlMe-Nic4
-6mol), promotor AlEt
2cl (mol ratio of promotor and Primary Catalysts is 100:1), concrete operations are with embodiment 44, and polymerization time is 2 hours.Its activity is 5.1 × 10
6g/molh, polymkeric substance Mw are 6.3 × 10
5g/mol, MWD are 2.1, and polymer branching degree is 69/1000 carbon atom.
Embodiment 49
Loaded article SiO
2-Zn-Pdc5 is as Primary Catalysts catalysis 1-butylene and ethylene copolymer
Solvent is dry toluene, and 1-butylene is 0.5 with ethylene pressure ratio, makes to keep pressure 0.5MPa in reactor, and temperature of reaction is 80 DEG C, the loaded article SiO that Primary Catalysts is prepared by embodiment 39
2(in solvent, contained Pd content is 7.55 × 10 to-Zn-Pdc5
-6mol), cocatalyst B (C
6f
5)
4(mol ratio of promotor and Primary Catalysts is 800:1), concrete operations are with embodiment 44, and polymerization time is 1.5 hours.Its activity is 1.2 × 10
6g/molh, polymkeric substance Mw are 4.0 × 10
5g/mol, MWD are 2.7, and polymer branching degree is 64/1000 carbon atom.
Embodiment 50
Loaded article SiO
2/ diatomite-AlMe-Nic1 is as Primary Catalysts catalysis 1-hexene oligomerization
In the 250mL reactor through nitrogen replacement three times, add 50mL dry toluene, add the loaded article SiO of the 1-hexene of 5mL, embodiment 40 gained respectively
2(in solvent, contained Ni content is 3.31 × 10 to/diatomite-AlMe-Nic1
-6mol), promotor Al
2et
3cl
3(mol ratio of promotor and Primary Catalysts is 800:1), stirring is warmed up to 40 DEG C, polymerization time is 2 hours, then the acidic ethanol of 10mL 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, in 60 DEG C of vacuum drying ovens dry 8 hours again, obtain product polyethylene.Its activity is 4.6 × 10
6g/molh, polymkeric substance Mw are 4.9 × 10
5g/mol, MWD are 2.7, and polymer branching degree is 53/1000 carbon atom.
Embodiment 51
Loaded article SiO
2-AlMe-Pdc1 is polymerized as Primary Catalysts catalysis 1-decene
In the 250mL reactor through nitrogen replacement three times, add 50mL dry toluene, add the loaded article SiO of 5mL 1-decene, embodiment 41 gained respectively
2(in solvent, the amount of contained Pd is 4.43 × 10 to-AlMe-Pdc1
-6mol), cocatalyst B (C
6h
3(CF
3)
2)
4(mol ratio of promotor and Primary Catalysts is 1200:1), stir and be warmed up to 50 DEG C, polymerization time is 1 hour, then the acidic ethanol of 10mL 10% is added to reaction terminating, with water, washing with alcohol, filtered polymeric, then in 60 DEG C of vacuum drying ovens dry 8 hours, obtain product.Its activity is 6.0 × 10
5g/molh, polymkeric substance Mw are 7.9 × 10
5g/mol, MWD are 2.4.
Embodiment 52
Loaded article SiO
2-AlOMe-Nic5 is polymerized as Primary Catalysts catalysis Dicyclopentadiene (DCPD)
With loaded article SiO prepared by embodiment 42
2(in solvent, contained Ni content is 3.56 × 10 to-AlOMe-Nic5
-5mol) the loaded article SiO in embodiment 51 is replaced
2-AlMe-Pdc1,3g Dicyclopentadiene (DCPD), temperature of reaction 60 DEG C, promotor AlEt
2cl (mol ratio of promotor and Primary Catalysts is 1000:1), operates same embodiment 51.Its activity is 4.0 × 10
5g/molh, polymkeric substance Mw are 3.5 × 10
5g/mol, MWD are 3.0.
Embodiment 53
Loaded article SiO
2-SiCl
2-Nic7 is as Primary Catalysts catalysis norbornene polymerization
With loaded article SiO prepared by embodiment 43
2-SiCl
2(in solvent, contained Ni content is 2.11 × 10 to-Nic7
-5mol) the loaded article SiO in embodiment 51 is replaced
2-AlMe-Pdc1,2.5g norbornylene, promotor MAO (mol ratio of promotor and Primary Catalysts is 600:1), temperature of reaction 90 DEG C, operates same embodiment 51.Its activity is 6.0 × 10
5g/molh, polymkeric substance Mw are 5.4 × 10
5g/mol, MWD are 2.5.
Embodiment 54
Loaded article SiO
2-AlMe-Nic1 is as Primary Catalysts catalysis norbornylene and vinyl norbornene copolymerization
With the loaded article SiO of embodiment 34 gained
2(in solvent, contained Ni content is 2.52 × 10 to-AlMe-Nic1
-5mol) the loaded article SiO in embodiment 51 is replaced
2-AlMe-Pdc1,1.6g norbornylene and 1.1g vinyl norbornene, promotor MAO (mol ratio of promotor and Primary Catalysts is 800:1), temperature of reaction 30 DEG C, operates same embodiment 51.Its activity is 3.9 × 10
5g/molh, polymkeric substance Mw are 4.1 × 10
5g/mol, MWD are 2.6.
Embodiment 55
Loaded article SiO
2-AlOMe-Nic3 is polymerizing styrene catalyzed as Primary Catalysts
With loaded article SiO prepared by embodiment 37
2(in solvent, contained Ni content is 3.53 × 10 to-AlOMe-Nic3
-5mol) the loaded article SiO in embodiment 51 is replaced
2-AlMe-Pdc1,2.5g vinylbenzene, temperature of reaction 60 DEG C, promotor MMAO (mol ratio of promotor and Primary Catalysts is 800:1), operates same embodiment 51.Its activity is 7.8 × 10
5g/molh, polymkeric substance Mw are 5.2 × 10
5g/mol, MWD are 3.0.
Embodiment 56
Title complex Nic8 is as Primary Catalysts catalyzed ethylene polymerization
(in solvent, contained Ni content is 1.51 × 10 to the title complex Nic8 prepared by embodiment 17
-5mol) the loaded article SiO in embodiment 44 is replaced
2-AlMe-Nic1, pass into ethene and make to keep pressure 0.2MPa in reactor, promotor is AlEt
2cl (mol ratio of promotor and Primary Catalysts is 700:1), operates same embodiment 44.Its activity is 9.8 × 10
5g/molh, polymkeric substance Mw are 4.9 × 10
5g/mol, MWD are 3.0, and polymer branching degree is 59/1000 carbon atom.
Embodiment 57
Title complex Pdc5 is as Primary Catalysts catalyzed ethylene polymerization
(in solvent, contained Pd content is 2.56 × 10 to the title complex Pdc5 prepared by embodiment 20
-5mol) the loaded article SiO in embodiment 44 is replaced
2-AlMe-Nic1, pass into ethene and make to keep pressure 0.2M Pa in reactor, promotor is B (C
6f
5)
4(mol ratio of promotor and Primary Catalysts is 1000:1), operates same embodiment 44.Its activity is 5.7 × 10
6g/molh, polymkeric substance Mw are 6.0 × 10
5g/mol, MWD are 2.8, and polymer branching degree is 84/1000 carbon atom.
Embodiment 58
Loaded article SiO
2-AlMe-Nic4 is as Primary Catalysts catalyzed ethylene vapour phase polymerization
The vapour phase polymerization of ethene is carried out in the simulation gas phase reaction kettle of 2L, adds 100g through heat treated sodium-chlor as seed bed, adds ethene, then add promotor MAO 5mmol, be warmed up to 50 DEG C, adds loaded article SiO prepared by embodiment 38
2-AlMe-Nic425mg, polymerization time is 3 hours, and reaction pressure is 1.2MPa, adds ethylene gas by magnetic valve to reactor, and reaction terminates blowing, obtains polyethylene.Its activity is 1.0 × 10
6g/molh.Polymkeric substance Mw is 5.6 × 10
5g/mol, MWD are 2.7.
13it is 38/1000 carbon atom that C NMR measures polymer branching degree.
Unaccomplished matter of the present invention is known technology.
Claims (10)
1. an alpha-diimine compound, is characterized by the structural formula of this compound as shown in the formula I:
Wherein, R
1for there being substituent or unsubstituted C
6-C
60aryl, C
6-C
60heterocyclic arene base in one; R
2for there being substituent or unsubstituted C
6-C
60aryl, C
6-C
60heterocyclic arene base in one; And R
1and R
2identical or different;
Ar has the one in following building stone:
Wherein, n=1,2,3,4,5,6 or 7; R ' is C
1-C
20alkyl.
2. alpha-diimine compound as claimed in claim 1, is characterized by the one preferably had in following structural formula:
Wherein, R
a, R
bfor identical or different hydrogen, C
1-C
20alkyl, aryl or with the one in substituent aryl; R
cfor identical or different hydrogen, fluorine, chlorine, bromine, C
1-C
20alkyl, fluorine replace C
1-C
20alkyl, C
1-C
20alkoxyl group or aryl in one.
3. an alpha-diimine metal complexes, it is characterized by this metal complexes to be obtained by alpha-diimine compound according to claim 1 and rear transition metal reactant salt, wherein said late transition metal salt is the one in nickel salt, palladium salt, platinum salt, molysite or cobalt salt;
The preparation method of described alpha-diimine metal complexes, comprise the following steps: in reactor in a nitrogen atmosphere, late transition metal salt being joined concentration is react in the solution of the alpha-diimine compound of 0.01-0.1mmol/mL, wherein, late transition metal salt and alpha-diimine compound equimolar amount; Stirred at ambient temperature reaction 20-24 hour, concentrating under reduced pressure reaction solution to 1 to five/10th 1/10th of original solution volume, then adds concentrated solution volume ten times to fiftyfold normal hexane precipitation, suction filtration, after solid n-hexane, vacuum-drying obtains alpha-diimine metal complexes;
In the solution of described alpha-diimine compound, solvent is methylene dichloride or tetrahydrofuran (THF).
4. a loaded article for alpha-diimine compound, it is characterized by this loaded article is react obtained by described alpha-diimine compound and the carrier through modifier treatment; Described properties-correcting agent is aluminum alkoxide, aluminum alkyls, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, an alkyl trichlorosilicane, an alkyl tribromo SiClx, TiX
4, SiH
2x
2, SiHX
3, SiX
4or BX
3in one;
The preparation method of the loaded article of described alpha-diimine compound, comprise the following steps: the 1) preparation of modified support: in reaction flask in a nitrogen atmosphere, under mechanical stirring, joined by carrier in dry toluene, make carrier be 0.01-0.5g/mL in the concentration of suspension, the amount adding 0.01-50mol properties-correcting agent by 1g carrier adds properties-correcting agent, reaction 2-12 hour, temperature of reaction is 0-50 DEG C, and reaction terminates rear filtration, obtains modified support respectively with dry toluene, n-hexane, 2) preparation of the loaded article of alpha-diimine compound: add methylene dichloride and obtain modified support suspension in modified support, in modified support suspension, the concentration of modified support is 0.01-0.1g/mL, add the anhydrous methylene chloride solution that concentration is the alpha-diimine compound of 0.01-0.1mmol/mL again, wherein, the ratio of alpha-diimine compound and modified support is the alpha-diimine compound that every gram of modified support adds 1-5mmol, reaction 4-16 hour, temperature of reaction-20-50 DEG C, filter, and by washed with dichloromethane, vacuum-drying obtains the loaded article of alpha-diimine compound.
5. the loaded article of an alpha-diimine metal complexes, it is characterized in that reacting obtained by alpha-diimine metal complexes and the carrier through modifier treatment, described properties-correcting agent is aluminum alkoxide, aluminum alkyls, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, an alkyl trichlorosilicane, an alkyl tribromo SiClx, TiX
4, SiH
2x
2, SiHX
3, SiX
4or BX
3in one; Or be obtained by reacting by the loaded article of alpha-diimine compound and late transition metal salt; Wherein said late transition metal salt is the one in nickel salt, palladium salt, platinum salt, molysite or cobalt salt;
The preparation method of the loaded article of described alpha-diimine metal complexes is one of following two kinds of methods,
Method one, comprise the following steps: in (1) reaction flask in a nitrogen atmosphere, under mechanical stirring, joined by carrier in toluene, make carrier be 0.01-0.1g/mL in the concentration of suspension, the amount adding 0.1-50mol properties-correcting agent by 1g carrier adds properties-correcting agent, reaction 1-5 hour, temperature of reaction is 0-50 DEG C, and reaction terminates rear filtration, obtains modified support respectively with dry toluene, n-hexane; (2) upwards walk in the modified support obtained and add methylene dichloride, modified support is made to be 0.01-0.1g/mL in the concentration of suspension, add the anhydrous methylene chloride solution that concentration is the alpha-diimine metal complexes of 0.01-0.1mmol/mL, the ratio of alpha-diimine metal complexes and modified support is that every gram of modified support adds 1-10mmol alpha-diimine metal complexes, reaction 4-16 hour, temperature of reaction-20-50 DEG C, filter and use washed with dichloromethane, vacuum-drying obtains the loaded article of alpha-diimine metal complexes;
Or method two, comprises the following steps:
In reaction flask in a nitrogen atmosphere, add methylene dichloride, the compound loaded thing of alpha-diimine containing alpha-diimine compound, the late transition metal salt with alpha-diimine compound equimolar amount, rear transition metal salt concn is 0.01-1mmol/mL methylene dichloride, stirred at ambient temperature reaction 20-24 hour, concentrating under reduced pressure reaction solution is to 1 to five/10th 1/10th of original solution volume, add concentrated solution volume ten times again to fiftyfold normal hexane precipitation, suction filtration, after solid n-hexane, vacuum-drying obtains the loaded article of alpha-diimine metal complexes.
6. the loaded article of alpha-diimine metal complexes as claimed in claim 3 or alpha-diimine metal complexes according to claim 5, is characterized by described late transition metal salt preferably (DME) NiBr
2, (DME) NiCl
2, (COD) PdClCH
3, (PhCN)
2pdCl
2or the one in (COD) PdMe (NCMe).
7. the loaded article of alpha-diimine compound as claimed in claim 4 or the loaded article of alpha-diimine metal complexes according to claim 5, it is characterized by wherein properties-correcting agent is aluminum alkoxide, aluminum alkyls, dialkyl group zinc, dialkyl group silicon dichloride, dialkyl group dibromo SiClx, an alkyl trichlorosilicane, an alkyl tribromo SiClx, TiX
4, SiH
2x
2, SiHX
3, SiX
4or BX
3in one, preferable methyl aikyiaiurnirsoxan beta (MAO), ethylaluminoxane (EAO), modified methylaluminoxane (MMAO), AlMe
3, AlEt
3, Al (i-Bu)
3, AlEt
2cl, ZnEt
2, TiCl
4, SiEt
2cl
2, SiEtCl
3, SiCl
4or BCl
3in one.
8. the loaded article of alpha-diimine compound as claimed in claim 4 or the loaded article of alpha-diimine metal complexes according to claim 5, it is characterized by the loaded article of described alpha-diimine compound, the loaded article of alpha-diimine metal complexes, its carrier is one or more the complex carrier in inorganic oxide, metal-salt, clay, diatomite, polynite, polystyrene resin, carbon black, carbon nanotube and Graphene; Preferred SiO
2, MgCl
2, diatomite, polynite, Al
2o
3, Fe
3o
4, SiO
2/ MgCl
2complex carrier, SiO
2/ composite diatomite carrier, polynite/MgCl
2complex carrier, diatomite/MgCl
2complex carrier or Fe
3o
4/ MgCl
2one in complex carrier.
9. an application for alpha-diimine metal complexes as claimed in claim 3 or alpha-diimine metal complexes loaded article according to claim 5, is characterized by them and is applied in the vapour phase polymerization of ethene or propylene or the liquid-phase bulk polymerization of olefinic monomer or slurry polymerization as Primary Catalysts.
10. the application of an alpha-diimine metal complexes as claimed in claim 3 or alpha-diimine metal complexes loaded article according to claim 5, it is characterized by this title complex preferably as Primary Catalysts application in olefin polymerization, comprise following reaction conditions: polymeric reaction temperature is-20-120 DEG C; When olefinic monomer is gas, pressure is 0.1-10MPa; Olefinic monomer be specially in ethene, propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, norbornylene, vinyl norbornene, ethylidene norbornene, Dicyclopentadiene (DCPD), Isosorbide-5-Nitrae-divinyl, vinylbenzene, alpha-methyl styrene and Vinylstyrene one or more.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018119538A1 (en) * | 2016-12-30 | 2018-07-05 | Pontificia Universidad Católica De Chile | Synthesis of polyethylene/carbon nanocomposites using ni(ii) complexes supported on carbon chemically modified with lewis acids |
| CN108383739A (en) * | 2018-03-26 | 2018-08-10 | 河北工业大学 | A kind of aromatic amine and its alpha-diimine complex with hydroxyl and application in olefin polymerization |
| CN108530563A (en) * | 2017-03-03 | 2018-09-14 | 天津工业大学 | A kind of application of the loaded article of alpha-diimine and its metal complex in olefin polymerization |
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| CN109762027A (en) * | 2019-02-14 | 2019-05-17 | 合肥工业大学 | para-aryl-containing substituted α -diimine nickel complex and preparation method and application thereof |
| CN110845360A (en) * | 2018-08-20 | 2020-02-28 | 中国石油天然气股份有限公司 | α -diimine metal complex-loaded load and application thereof in olefin polymerization |
| CN110845359A (en) * | 2018-08-20 | 2020-02-28 | 中国石油天然气股份有限公司 | α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization |
| CN113233994A (en) * | 2021-04-30 | 2021-08-10 | 河北工业大学 | Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof |
| CN114853964A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361184A (en) * | 2000-12-25 | 2002-07-31 | 中国科学院长春应用化学研究所 | Catalyst for binuclear alpha-diimine nickel olefine polymerization |
-
2015
- 2015-04-30 CN CN201510219157.8A patent/CN104926686B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1361184A (en) * | 2000-12-25 | 2002-07-31 | 中国科学院长春应用化学研究所 | Catalyst for binuclear alpha-diimine nickel olefine polymerization |
Non-Patent Citations (2)
| Title |
|---|
| DAO ZHANG ET AL.: "Radical co-polymerization of diiminedibromidenickel(II)-functionalized olefin with styrene: synthesis of polymer-incorporated nickelII -diimine catalysts for ethylene polymerization", 《APPLIED CATALYSIS A: GENERAL》 * |
| YAN-GUO LI ET AL.: "Polymerization of ethylene to branched polyethylene with silica and Merrifield resin supported nickel(II) catalysts with -diimine ligands", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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| CN110845360A (en) * | 2018-08-20 | 2020-02-28 | 中国石油天然气股份有限公司 | α -diimine metal complex-loaded load and application thereof in olefin polymerization |
| CN110845359A (en) * | 2018-08-20 | 2020-02-28 | 中国石油天然气股份有限公司 | α -diimine metal complex hydrogen bond load and application thereof in olefin polymerization |
| CN109762027A (en) * | 2019-02-14 | 2019-05-17 | 合肥工业大学 | para-aryl-containing substituted α -diimine nickel complex and preparation method and application thereof |
| CN109762027B (en) * | 2019-02-14 | 2021-10-22 | 合肥工业大学 | Para-aryl-containing substituted alpha-diimine nickel complex and preparation method and application thereof |
| CN114853964A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and method for producing the same |
| CN114853964B (en) * | 2021-02-04 | 2023-12-22 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and process for producing the same |
| CN113233994A (en) * | 2021-04-30 | 2021-08-10 | 河北工业大学 | Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof |
| CN113233994B (en) * | 2021-04-30 | 2023-01-06 | 河北工业大学 | Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof |
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