CN105061493A - Amine bis(phenolate) tetradentate ligand fourth sub-group metal complex and application thereof - Google Patents
Amine bis(phenolate) tetradentate ligand fourth sub-group metal complex and application thereof Download PDFInfo
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- CN105061493A CN105061493A CN201510501660.2A CN201510501660A CN105061493A CN 105061493 A CN105061493 A CN 105061493A CN 201510501660 A CN201510501660 A CN 201510501660A CN 105061493 A CN105061493 A CN 105061493A
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- 0 CC(C)(C)c(cc1CC(*)(C2)*=C2c2cc(C(C)(C)C)cc(C(C)(c3ccccc3)c3ccccc3)c2O)cc(C(C)(c2ccccc2)c2ccccc2)c1O Chemical compound CC(C)(C)c(cc1CC(*)(C2)*=C2c2cc(C(C)(C)C)cc(C(C)(c3ccccc3)c3ccccc3)c2O)cc(C(C)(c2ccccc2)c2ccccc2)c1O 0.000 description 1
Abstract
The amine bis(phenolate) tetradentate ligand fourth sub-group metal complex and application thereof, and belongs to the technical field of olefin polymerization catalysts. The structural formula of the amine bis(phenolate) tetradentate ligand fourth sub-group metal complex is shown in the description. The amine bis(phenolate) tetradentate ligand fourth sub-group metal complex as a main catalyst, and alkylaluminoxane, halogenated alkyl aluminium, or a mixture of aluminum alkyl and a boron agent as a promoter can be used for catalyzing ethylene homopolymerization, alpha-olefin homopolymerization or copolymerization of ethylene and alpha-olefins. The complex provided by the invention as a catalyst has the advantages of being good in heat resistance and high in polymerization activity during the polymerization process.
Description
Technical field
The invention belongs to olefin polymerization catalysis technical field, be specifically related to one [N, X, O, O] (X=O, N) amine bis-phenol tetradentate ligands the 4th subgroup metal complexes and the application in catalysis in olefine polymerization thereof.
Background technology
Polyolefin products is cheap, abundant raw material, easy machine-shaping, insulativity, good corrosion resistance, high comprehensive performance, is that a class output is maximum, application macromolecular material very widely.As the substitute products of the materials such as glass, metal, paper and concrete, polyolefin products presents wide application prospect, for the manufacture of opticinstrument, chemistry and medical apparatus, electron device and insulating material, gas separation membrane and wrapping material, fiber etc.In the social development in future, poly demand and polyacrylic demand all will obtain huge growth.Olefin polymerization catalysis is through the development of decades, experienced by early stage Ziegle-Natta catalyst system, after metallocene catalysis system that the eighties starts prosperity and development and " non-luxuriant " catalytic systems for polymerization of olefins three was main in the last few years developmental stage, the research range of current olefin polymerization catalysis is more and more wider.Early 1950s, Ziegler TiCl
3/ A1Et
3mixed catalyst system at normal temperatures and pressures catalyzed polymerization ethene obtains linear high-density polyethylene, contemporaneity, Natta TiC1
3/ AlEt
2cl mixed system has successfully prepared isotactic polyprophlene, start the frontier of the Polymer Synthesizing of Ziegler-Natta (Z-N) catalyst system, metallocene compound achieves as Ziegler-Natta homogeneous catalyst of new generation the achievement attracted people's attention in catalysed olefin polymerization, is that recent two decades carrys out one of most active research field in the world.Meanwhile, non-luxuriant catalyzed polymerization system owing to having high reactivity, high tolerance, and can be polymerized various polarity monomer, and the character such as single-component active centre, make it have good application and development prospect.
[the N the most close with the present invention, N, O, O] amine bisphenols tetradentate ligands the 4th subgroup metal complexes appears in the newspapers in DaltonTrans., and 2010,39,4440-4446, its part side arm is pyridyl containing atom N group, and because aryloxy ortho-substituent in part is less or unsubstituted, the title complex obtained is the two ligand structure of monokaryon and dual-core architecture.Such title complex is mainly used in the ring-opening polymerization of catalysis rac-Lactide, and its structure is not suitable for catalysis in olefine polymerization.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the deficiencies in the prior art, the 4th subgroup metal complexes of [N, X, O, O] (X=O, N, S) amine bis-phenol tetradentate ligands providing a class novel and the application in catalysed olefin polymerization thereof.[the N that the present invention is used, X, O, O] (X=N, O, S) in amine bisphenols tetradentate ligands, side arm is dialkyl amido, alkoxyl group, alkylthio containing heteroatom group X, and introduces large space steric hindrance substituting group at aryloxy ortho position, makes it be applicable to monokaryon list part the 4th subgroup metal complexes of synthesis as olefin polymerization catalyst.
Concrete technical scheme is as follows,
A kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes, has following general structure:
Wherein R
1phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group or p-methoxyphenyl; R
2phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl; R
3phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl; R
4hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; X, for containing hetero atom substituents, is dialkyl amido, alkoxyl group, alkylthio, pyridyl, furyl or thienyl; Y is halogen, alkyl, aryl, alkoxyl group or dialkyl amido; M is the 4th B transition metal titanium, zirconium or hafnium.
In a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention, R
1preferred phenyl or p-methylphenyl, R
2preferred phenyl, p-methylphenyl or methyl; R
3preferred phenyl, p-methylphenyl or methyl; R
4preferable methyl or the tertiary butyl; The preferred dimethylamino of X, methoxyl group or methylthio group; The preferred Cl of Y.
In a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention, be preferably as follows 9 kinds of title complex C1 ~ C9 further:
A kind of purposes of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes, it is characterized in that, with described amine bis-phenol tetradentate ligands the 4th subgroup metal complexes for Primary Catalysts, with alkylaluminoxane, or haloalkyl aluminium, or the mixture of aluminum alkyls and boron agent is promotor, for catalyzed ethylene homopolymerization, alpha-olefin homopolymerization or ethene and alpha-olefin copolymer, described alpha-olefin is propylene, 1-butylene, 1-hexene, 1-octene or 1-decene; Wherein in promotor, in aluminium and Primary Catalysts, the mol ratio of metal is 5-20000:1, and in promotor, in boron and Primary Catalysts, the mol ratio of metal is 0-2:1, and in polymerization system, the volumetric molar concentration of alpha-olefin is 0-2mol/L.
In the purposes of a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention, the preferred trimethyl aluminium of described aluminum alkyls, triethyl aluminum or triisobutyl aluminium; Described alkylaluminoxane preferable methyl aikyiaiurnirsoxan beta (MAO) or modified methylaluminoxane (MMAO); The described preferred diethyl aluminum chloride of haloalkyl aluminium or dimethylaluminum chloride; The described preferred Ph of boron agent
3cB (C
6f
5)
3.
In the purposes of a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention, the further preferable methyl aikyiaiurnirsoxan beta of described promotor or modified methylaluminoxane.
The present invention has following beneficial effect:
1, amine bis-phenol tetradentate ligands the 4th subgroup metal complexes Stability Analysis of Structures of the present invention, resistance toheat is good in the course of the polymerization process.
2, the metal complex catalyzed activity of amine bis-phenol tetradentate ligands the 4th subgroup of the present invention is high, can not only catalyzed ethylene homopolymerization and alpha-olefin homopolymerization, can also catalyzed ethylene and alpha-olefin copolymer.
Embodiment
Following examples 1-9 gives 9 kinds of typical structure C1 ~ C9 preparation process in amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention.Embodiment 10 is amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of the present invention as the experimentation of the homopolymerization of Primary Catalysts catalyzed ethylene, propylene homo, ethene and 1-hervene copolymer, ethene and 1-octene copolymer.
The preparation of embodiment 1 title complex C1.
Under-78 DEG C of conditions, be that the toluene solution of the titanium tetrachloride of 0.825mol/L is added drop-wise to the ligand L 1H that 20mL concentration is 0.0165mol/L by 0.4mL concentration
2toluene solution in, be naturally raised to room temperature, stir 3h, drain solvent, can obtain the title complex 223mg of bolarious metal titanium, productive rate 96.2%, is designated as C1.
The preparation of embodiment 2 title complex C2.
Under-78 DEG C of conditions, be that the toluene solution of the titanium tetrachloride of 0.825mol/L is added drop-wise to the ligand L 2H that 20mL concentration is 0.0165mol/L by 0.4mL concentration
2toluene solution in, be naturally raised to room temperature, stir 3h, drain solvent.Get final product the title complex 276.4mg that high yield obtains brick-red compound metal titanium, productive rate 95.6%, is designated as C2.
The preparation of embodiment 3 title complex C3.
Under-78 DEG C of conditions, be that the toluene solution of the titanium tetrachloride of 0.825mol/L is added drop-wise to the ligand L 3H that 20mL concentration is 0.0165mol/L by 0.4mL concentration
2toluene solution in, be naturally raised to room temperature, stir 3h, drain solvent.Can obtain the title complex 287.8mg of bolarious metal titanium, productive rate 87.2%, is designated as C3.
The preparation of embodiment 4 title complex C4.
Under-78 DEG C of conditions, be that the toluene solution of the titanium tetrachloride of 0.825mol/L is added drop-wise to the ligand L 4H that 20mL concentration is 0.0165mol/L by 0.4mL concentration
2diethyl ether solution in, be naturally raised to room temperature, stir 3h, drain solvent.The title complex 300.5mg productive rate 78.4% of bolarious metal titanium can be obtained, be designated as C4.
The preparation of embodiment 5 title complex C5.
Under-78 DEG C of conditions, be that the hexane solution of the butyllithium of 1.6M is added drop-wise to the ligand L 1H that 20mL concentration is 0.0165mol/L by 0.42mL concentration
2toluene solution, under-78 DEG C of conditions, stir the lithium salts that 1h obtains part.Then the lithium salts of part being added drop-wise under-78 DEG C of conditions 20mL concentration is in the toluene solution of the zirconium tetrachloride of 0.0165mol/L, and be naturally raised to room temperature, stirring is spent the night, and drains toluene solution, hexane ultrasound filtration.Obtain the title complex 194.6mg of corresponding zirconium, productive rate 74.2%, is designated as C5.
The preparation of embodiment 6 title complex C6.
Under-78 DEG C of conditions, be that the hexane solution of the butyllithium of 1.6M is added drop-wise to the ligand L 2H that 20mL concentration is 0.0165mol/L by 0.42mL concentration
2toluene solution, under-78 DEG C of condition, stir 1h, obtain the lithium salts of part.Then the lithium salts of part being added drop-wise under-78 DEG C of conditions 20mL concentration is in the toluene solution of the zirconium tetrachloride of 0.0165mol/L, and be naturally raised to room temperature, stirring is spent the night, and drains toluene solution, hexane ultrasound filtration.Obtain the title complex 216mg of corresponding zirconium, productive rate 71.2%, is designated as C6.
The preparation of embodiment 7 title complex C7.
Under-78 DEG C of conditions, be that the hexane solution of the butyllithium of 1.6M is added drop-wise to the ligand L 3H that 20mL concentration is 0.0165mol/L by 0.42mL concentration
2toluene solution, under-78 DEG C of condition, stir 1h, obtain the lithium salts of part.Then the lithium salts of part being added drop-wise under-78 DEG C of conditions 20mL concentration is in the toluene solution of the zirconium tetrachloride of 0.0165mol/L, and be naturally raised to room temperature, stirring is spent the night, and drains toluene solution, hexane ultrasound filtration.Obtain the title complex 235.4mg of corresponding zirconium, productive rate 68.6%, is designated as C7.
The preparation of embodiment 8 title complex C8.
Under-78 DEG C of conditions, be that the hexane solution of the butyllithium of 1.6M is added drop-wise to the ligand L 4H that 20mL concentration is 0.0165mol/L by 0.42mL concentration
2toluene solution, under-78 DEG C of conditions, stir the lithium salts that 1h obtains part.Then the lithium salts of part being added drop-wise under-78 DEG C of conditions 20mL concentration is in the toluene solution of the zirconium tetrachloride of 0.0165mol/L, and be naturally raised to room temperature, stirring is spent the night, and drains toluene solution, hexane ultrasound filtration.Obtain the title complex 222.3mg of corresponding zirconium, productive rate 64.6%, is designated as C8.
The preparation of embodiment 9 title complex C9.
Under-78 DEG C of conditions, be that the hexane solution (0.42mL, 0.66mmol) of the butyllithium of 1.6M is added drop-wise to the ligand L 5H that 20mL concentration is 0.0165mol/L by 0.42mL concentration
2toluene solution, under-78 DEG C of conditions, stir the lithium salts that 1h obtains part.Then the lithium salts of part being added drop-wise under-78 DEG C of conditions 20mL concentration is in the toluene solution of the zirconium tetrachloride of 0.0165mol/L, and be naturally raised to room temperature, stirring is spent the night, and drains toluene solution, hexane ultrasound filtration.Obtain the title complex 238.6mg of corresponding zirconium, productive rate 70.2%.
Embodiment 10 ethylene homo
The polymeric kettle that magnetic stir bar is housed is heated to 120 DEG C, vacuum suction 1h, is filled with the ethylene gas of 0.1MPa, add the 60mL toluene solution with MAO or triisobutyl aluminium or triethyl aluminum activation, then add Primary Catalysts, pass into 0.5MP ethylene gas, stir 20min-120min.Bleed off residual vinyl gas after polyreaction terminates and open reactor, the polyreaction mixed solution obtained is poured in the 3M hydrochloric acid of volume ratio 1:1 and the mixing solutions of ethanol, filter after stirring 5min, dry.Measure its molecular weight.Table 1 is that described Primary Catalysts selects the title complex C1-C9 prepared in above embodiment 1-9 respectively, aggregated data under different polymerization temperatures and Al/M molar ratio, " mol ratio Al/M " in table refers to the mol ratio of the Al in promotor and the metal in Primary Catalysts, in table when promotor uses triisobutyl aluminium or triethyl aluminum, promotor also will use Ph simultaneously
3cB (C
6f
5)
3, consumption is boron in molar ratio: the metal=1.2:1's in Primary Catalysts.
Table 1: vinyl polymerization data
Embodiment 11 ethene hervene copolymer and ethylene octene copolyreaction
The polymeric kettle that magnetic stir bar is housed is heated to 120 DEG C, vacuum suction 1h, be filled with the ethylene gas of 0.1MPa, adding by the 60mL volumetric molar concentration that MAO (methylaluminoxane) activates is the hexene of 0.5-1.5mol/L or the toluene solution of octene, then Primary Catalysts is added, pass into 0.5MP ethylene gas, stir 20min-120min.Bleed off residual vinyl gas after polyreaction terminates and open reactor, the polyreaction mixed solution obtained is poured in the 3M hydrochloric acid of volume ratio 1:1 and the mixing solutions of ethanol, filter after stirring 5min, dry.Measure its molecular weight.Table 2, table 3 are that described Primary Catalysts selects the title complex C5-C7 prepared in above embodiment 5-7 respectively, the aggregated data under different hexenes or octene concentration condition.Table 2 is ethene hervene copolymer data, and table 3 is ethylene octene copolymerization data, and " mol ratio Al/M " in table refers to the mol ratio of the Al in promotor and the metal in Primary Catalysts.
Table 2: ethene hervene copolymer data
Table 3: ethylene octene copolymerization data
Embodiment 12 propylene homo reacts
The polymeric kettle that magnetic stir bar is housed is heated to 120 DEG C, vacuum suction 1h, is filled with the propylene gas of 0.1MPa, add the 60mL toluene solution that MAO (methylaluminoxane) activates, then add Primary Catalysts, pass into 0.5MP propylene gas, stir 20min-120min.Bleed off remaining propylene gas after polyreaction terminates and open reactor, the polyreaction mixed solution obtained is poured in the 3M hydrochloric acid of volume ratio 1:1 and the mixing solutions of ethanol, filter after stirring 5min, dry.Measure its molecular weight.Table 4 is that described Primary Catalysts selects the title complex C5-C7 prepared in above embodiment 5-7, aggregated data under the same conditions respectively, and " mol ratio Al/M " in table refers to the mol ratio of the Al in promotor and the metal in Primary Catalysts.
Table 4: propylene homo data
Claims (6)
1. amine bis-phenol tetradentate ligands a 4th subgroup metal complexes, has following general structure:
Wherein R
1phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group or p-methoxyphenyl; R
2phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl; R
3phenyl, p-methylphenyl, 3,5-bis-(trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl; R
4hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl or phenyl; X, for containing hetero atom substituents, is dialkyl amido, alkoxyl group, alkylthio, pyridyl, furyl or thienyl; Y is halogen, alkyl, aryl, alkoxyl group or dialkyl amido; M is the 4th B transition metal titanium, zirconium or hafnium.
2. a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes according to claim 1, is characterized in that, R
1phenyl or p-methylphenyl, R
2phenyl, p-methylphenyl or methyl; R
3phenyl, p-methylphenyl or methyl; R
4methyl or the tertiary butyl; X is dimethylamino, methoxyl group or methylthio group; Y is Cl.
3. a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes according to claim 1 and 2, is characterized in that having the concrete structure formula of following C1 ~ C9:
4. the purposes of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes of a claim 1, it is characterized in that, with described amine bis-phenol tetradentate ligands the 4th subgroup metal complexes for Primary Catalysts, with alkylaluminoxane, or haloalkyl aluminium, or the mixture of aluminum alkyls and boron agent is promotor, for catalyzed ethylene homopolymerization, alpha-olefin homopolymerization or ethene and alpha-olefin copolymer, described alpha-olefin is propylene, 1-butylene, 1-hexene, 1-octene or 1-decene; Wherein in promotor, in aluminium and Primary Catalysts, the mol ratio of metal is 5-20000:1, and in promotor, in boron and Primary Catalysts, the mol ratio of metal is 0-2:1, and in polymerization system, the volumetric molar concentration of alpha-olefin is 0-2mol/L.
5. the purposes of a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes according to claim 4, it is characterized in that, described aluminum alkyls is trimethyl aluminium, triethyl aluminum or triisobutyl aluminium; Described alkylaluminoxane is methylaluminoxane or modified methylaluminoxane; Described haloalkyl aluminium is diethyl aluminum chloride or dimethylaluminum chloride; Described boron agent is Ph
3cB (C
6f
5)
3.
6. the purposes of a kind of amine bis-phenol tetradentate ligands the 4th subgroup metal complexes according to claim 4 or 5, it is characterized in that, described promotor is methylaluminoxane or modified methylaluminoxane.
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