CN109400642A - A kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands and application - Google Patents

A kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands and application Download PDF

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CN109400642A
CN109400642A CN201811395730.0A CN201811395730A CN109400642A CN 109400642 A CN109400642 A CN 109400642A CN 201811395730 A CN201811395730 A CN 201811395730A CN 109400642 A CN109400642 A CN 109400642A
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母瀛
李彪
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Jilin University
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Abstract

A kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands of the invention and application belong to the technical field of olefin polymerization catalysis.The complex has the following structure general formula:

Description

A kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands and application
Technical field
The invention belongs to olefin polymerization catalysis technical field, in particular to a kind of amine three phenolic compounds of bridging The 4th subgroup metal complex of four tooth of [ONOO] type and its application in catalyzed ethylene polymerization.
Background technique
Many advantages, such as polyolefin product is because of its abundant raw material, cheap, easy to produce and processing, superior performance, And becoming resinous material most welcomed by the people at present, polyolefin industry represents the developing water of a national oil chemical industry It is flat, it is the important component in national economy and defense strategy.Olefin polymerization catalysis determines the inside of polyolefin products Structure and pattern are technologies most crucial in polyolefin industry development process, and three phases are substantially passed through in development: a) .Ziegler-Natta catalyst, this is earliest olefin polymerization catalysis, its appearance has expedited the emergence of polyolefin industry, however this Class catalyst is heterogeneous, it is difficult to be activated completely by co-catalyst, there are dynamics models, and catalytic efficiency is very low, produce simultaneously Ash content in product is very high, increases the difficulty of post-processing；B) metallocene catalyst, this kind of catalyst need in use Using the co-catalyst (MAO or boron additive) of a large amount of valuableness, activated centre is easy poisoning and deactivation, limits it in industrial production On application；C) non-metallocene catalyst, this kind of catalyst have single-activity center, and activity is relatively high, can be catalyzed a variety of The copolymerization of polarity single-point, however few catalyst can combine catalytic activity, thermal stability and service life.The present invention Be intended to design synthesize it is a kind of there is high catalytic activity, high thermal stability, long catalytic life, by catalyst substituent group and poly- Conjunction condition reasonably optimizing can catalyzed ethylene polymerization obtain the catalyst of ultra-high molecular weight polyethylene product.
It is with the most similar background technique of the present invention: the article Chem.Commun. that British scientist Jones is delivered, A kind of catalyst disclosed in 2011,47,12328-12330, but the catalyst of this structure can not catalysis in olefine polymerization, one As be the ring-opening polymerisation for being served only for the catalysis compounds such as lactide.Japanese Scientists Nomura utilizes three benzyls of nitrogen-atoms bridging The compound of phenols has synthesized a series of alkoxide compound of titaniums, zirconium as ligand, and this kind of compound is same as the former, directly When use can not catalysis in olefine polymerization by the modification of alkyl aluminum, and under the re-activation of MAO can be catalyzed second reluctantly Alkene polymerization；However this kind of catalyst is usually using the small group such as methyl as substituent group, maximum substituent group is only tert-butyl, is being urged The useful space protection to metal active centres cannot be formed when changing vinyl polymerization, easily inactivated by alkyl aluminum class attack, be catalyzed the longevity It orders short；On catalyst structure, such catalyst center metallic perimeter is the symmetrical structure of three hexatomic rings, is unfavorable for co-catalysis Agent is to the effective activations of metal active centres, thus polymerization activity is very low, the catalyst series catalyzed ethylene polymerization of synthesis Activity only have 7570kgPE/ (molCatalysth)；In catalyst synthesis, cost of material is high, and step is many and diverse, and modification is tired Difficulty, synthesis condition are harsher；When in use, the co-catalysis dosage needed is very big, and needs alkyl aluminum and a large amount of MAO And with can just show catalytic activity.
Summary of the invention
The problem to be solved in the present invention is to overcome the deficiencies of the prior art and provide three phenolic compounds of a kind of amine bridging The 4th subgroup metal complex of four tooth of [ONOO] type and its application, by reasonably modifying, this kind of catalyst has when in use The characteristics of cocatalyst usage amount is low, and catalytic activity is high, and thermal stability is good, long catalytic life, while when catalyzed ethylene polymerization Ultra-high molecular weight polyethylene product can be obtained.
Specific technical solution is as follows,
A kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands, has the following structure general formula:
Wherein: R1It is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, phenyl, adamantyl, withered Base, Diphenethyl or trityl；
R2It is phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl or methyl；
R3Be phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, Ethyl, propyl, isopropyl, butyl, isobutyl group or tert-butyl；
R4Be phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, Ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl or hydrogen；
R5It is hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；
R6It is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, Diphenethyl or trityl；
R7It is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, Diphenethyl or trityl；
X is halogen, alkyl or aryl；
M is the 4th B transition metal titanium, zirconium or hafnium.
In a kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands of the invention, R1It is preferred that hydrogen, methyl, withered Base, Diphenethyl or trityl；R2It is preferred that phenyl, p-methylphenyl or methyl；R3It is preferred that phenyl, p-methylphenyl or methyl； R4It is preferred that phenyl, p-methylphenyl or methyl；R5It is preferred that hydrogen, methyl or tert-butyl；R6It is preferred that methyl or tert-butyl；R7It is preferred that uncle Butyl；The preferred Ti of M；The preferred Cl of X.
In a kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands of the invention, further preferably following 12 kinds Complex C1~C12,
A kind of purposes of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands, it is characterised in that: with the amine The 4th subgroup metal complex of bridging triphenol tetradentate ligands is major catalyst, with alkylaluminoxane or halogenated alkyl aluminium or alkyl Aluminium and the mixture of boron agent are co-catalyst, are used for catalyzed ethylene polymerization；Wherein aluminium and metal in major catalyst in co-catalyst Molar ratio be 5~40000:1, the molar ratio of metal is 0~2:1 in boron and major catalyst in co-catalyst, ethylene when polymerization The pressure of gas is 0.1~5MPa.
A kind of the 4th subgroup metal complex of amine bridging bis-phenol tetradentate ligands of the invention use on the way, the co-catalysis The further preferred methylaluminoxane of agent or modified methylaluminoxane.
The utility model has the advantages that
1, the more traditional preparation process of the synthesis of ligands and complexes of the present invention is simple, and yield is high.
2, heretofore described catalyst metals center is a five-membered ring, and the dissymmetrical structure of two hexatomic rings replaces Base is big empty resistance substituent group, and catalyst is in use, the resistance to co-catalyst and impurity is high, and stability is good, long catalytic life.
3, heretofore described catalyst thermal stability is fine, and catalytic activity is very high, and most highly active is up to 93264kgPE/ (molTih), relative to the catalyst most highly active 7570kgPE/ (molCatalysth) of Nomura, activity improves 12.3 Times；
4, ultra-high molecular weight polyethylene can be obtained in heretofore described catalyst vinyl polymerization.
Specific embodiment
Example 1-12 below gives in the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands of the present invention 12 kinds of typical structure C1-C12 preparation process.Embodiment 13 is the 4th subgroup of amine bridging triphenol tetradentate ligands gold of the present invention Embodiment of the metal complex as major catalyst catalysis ethylene homo.
Embodiment 1: the preparation of complex C1
By the TiCl of 0.40mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.2726g Ligand L 1H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.2981g of yellow metal titanium, yield 97.4%, note is obtained by filtration For C1.
Embodiment 2: the preparation of complex C2
By the TiCl of 0.40mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.2991g Ligand L 2H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3218g of yellow metal titanium, yield 96.8%, note is obtained by filtration For C2.
Embodiment 3: the preparation of complex C3
By the TiCl of 0.40mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.3486g Ligand L 3H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3795g of yellow metal titanium, yield 99.4%, note is obtained by filtration For C3.
Embodiment 4: the preparation of complex C4
By the TiCl of 0.50mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.3542g Ligand L 4H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3733g of yellow metal titanium, yield 94.1%, note is obtained by filtration For C4.
Embodiment 5: the preparation of complex C5
By the TiCl of 0.48mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.3545g Ligand L 5H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C It takes out 3h again, 3mL hexane ultrasonic vibration is added, be obtained by filtration the complex 0.3536g of rufous Titanium, yield 89.7%, It is denoted as C5.
Embodiment 6: the preparation of complex C6
By the TiCl of 0.37mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.3026g Ligand L 6H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3220g of yellow metal titanium, yield 96.5%, note is obtained by filtration For C6.
Embodiment 7: the preparation of complex C7
By the TiCl of 0.40mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.3511g Ligand L 7H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3737g of yellow metal titanium, yield 97.2%, note is obtained by filtration For C7.
Embodiment 8: the preparation of complex C8
By the TiCl of 0.40mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.2991g Ligand L 8H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.3218g of yellow metal titanium, yield 96.8%, note is obtained by filtration For C8.
Embodiment 9: the preparation of complex C9
By the TiCl of 0.66mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.6883g Ligand L 9H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.6580g of yellow metal titanium, yield 94.8%, note is obtained by filtration For C9.
Embodiment 10: the preparation of complex C10
By the TiCl of 0.54mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.5376g Ligand L 10H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.5436g of yellow metal titanium, yield 93.2%, note is obtained by filtration For C10.
Embodiment 11: the preparation of complex C11
By the TiCl of 0.69mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.7430g Ligand L 11H330mL toluene solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract toluene, at 100 DEG C 3h is taken out again, 3mL hexane ultrasonic vibration is added, and the complex 0.7905g of yellow metal titanium, yield 98.7%, note is obtained by filtration For C11.
Embodiment 12: the preparation of complex C12
By the TiCl of 0.65mL 1.1556mol/L4Solution dilution with toluene to 10mL, is chilled to -78 DEG C, by 0.8303g Ligand L 12H330mL dichloromethane solution be added dropwise in above-mentioned solution, be slowly increased to room temperature, stir 10h, extract solvent, 100 3h is taken out at DEG C again, 3mL hexane ultrasonic vibration is added, the complex 0.8444g of yellow metal titanium is obtained by filtration, yield is 95.4%, it is denoted as C12.
Embodiment 13: vinyl polymerization
Polymeric kettle equipped with magnetic stir bar is heated to 120 DEG C, vacuum suction 1h is filled with the ethylene gas of 0.1MPa, The 60mL toluene solution purified with MAO or triisobutyl aluminium is added, major catalyst is then added, is passed through 0.5MP ethylene gas, stirs Mix 5min-150min.Residual vinyl gas is bled off after polymerization reaction, opens reaction kettle, and obtained polymerization reaction is mixed Object pours into the 3M hydrochloric acid of volume ratio 1:1 and the mixed solution of ethyl alcohol, filters after stirring 5min, dries.Claim its quality, measures it Fusing point surveys its viscosity average molecular weigh.The data obtained is as shown in Table 1 and Table 2.
Table 1 is using C2 as the aggregated data of major catalyst
Serial number MAO(mmol) Temperature DEG C Yield/g Activity Viscosity average molecular weigh × 10-4 Fusing point/DEG C
1 0.4 60 0.6501 39006 66.8 137.2
2 0.6 60 0.7018 42108 64.2 136.5
3 0.8 60 0.7765 46590 62.7 136.2
4 1.0 60 0.8039 48234 59.6 136.5
5 1.2 60 0.8366 50196 56.8 135.7
6 1.4 60 0.7665 45990 53.2 135.9
7 1.2 15 0.3118 18708 78.2 136.2
8 1.2 50 0.8234 49404 57.3 135.8
9 1.2 80 0.8473 50838 32.7 135.4
10 1.2 100 1.1296 67776 19.4 135.1
11 1.2 60 6.5795 —— —— ——
12 —— 60 trace —— —— ——
Polymerizing condition: the dosage of major catalyst C2 is 0.2 μm of ol, polymerization time 5min；Polymerization time is in serial number 11 2.5h；Co-catalyst is Al (iBu) in serial number 123；Active unit is kgPE/ (molTih).
Table 2 is using C1-C12 as the aggregated data of major catalyst；
Serial number Catalyst Yield/g Activity Viscosity average molecular weigh × 10-4 Fusing point/DEG C
1 C1 0.6947 41682 45.6 136.2
2 C2 0.8366 50196 56.8 135.7
3 C3 0.7803 46818 40.9 135.1
4 C4 0.6645 39870 56.7 138.4
5 C5 0.6120 36720 96.4 134.9
6 C6 1.4152 84912 132.0 135.3
7 C7 0.8079 48474 208.3 135.2
8 C8 0.2791 16746 34.1 135.2
9 C9 0.0583 3498 42.1 136.2
10 C10 0.0848 5088 72.0 136.4
11 C11 1.5544 93264 8.4 134.6
12 C12 0.0045 270 12.4 136.5
Note: the dosage of major catalyst is 0.2 μm of ol, and the dosage of co-catalyst is 1.2mmol, polymerization time 5min, Active unit is kgPE/ (molTih).

Claims (5)

1. a kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands, has the following structure general formula:
Wherein: R1It is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, tert-butyl, phenyl, adamantyl, cumyl, two Phenethyl or trityl；
R2It is phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group or p-methoxyphenyl；
R3Be phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, Propyl, isopropyl, butyl, isobutyl group or tert-butyl；
R4Be phenyl, p-methylphenyl, 3,5- bis- (trifluoromethyl) phenyl, pentafluorophenyl group, p-methoxyphenyl, methyl, ethyl, Propyl, isopropyl, butyl, isobutyl group, tert-butyl or hydrogen；
R5It is hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl；
R6It is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, Diphenethyl or trityl；
R7It is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, Diphenethyl or trityl；
X is halogen, alkyl or aryl；
M is the 4th B transition metal titanium, zirconium or hafnium.
2. a kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands according to claim 1, which is characterized in that R1It is hydrogen, methyl, cumyl, Diphenethyl or trityl；R2It is phenyl, p-methylphenyl or methyl；R3It is phenyl, to methyl Phenyl or methyl；R4It is phenyl, p-methylphenyl or methyl；R5It is hydrogen, methyl or tert-butyl；R6It is methyl or tert-butyl；R7It is Tert-butyl；M is Ti；X is Cl.
3. a kind of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands according to claim 1 or 2, feature exist In the complex is specifically following 12 kinds of complex C1~C12:
4. a kind of purposes of the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands described in claim 1, feature exist In: using the 4th subgroup metal complex of amine bridging triphenol tetradentate ligands as major catalyst, with alkylaluminoxane or halogenated Alkyl aluminum or alkyl aluminum and the mixture of boron agent are co-catalyst, are used for catalyzed ethylene polymerization；Wherein aluminium and master in co-catalyst The molar ratio of metal is 5~40000:1 in catalyst, and the molar ratio of boron and metal in major catalyst is 0~2 in co-catalyst: 1, the pressure of ethylene gas is 0.1~5MPa when polymerization.
5. a kind of purposes of the 4th subgroup metal complex of amine bridging bis-phenol tetradentate ligands according to claim 4, special Sign is that the co-catalyst is methylaluminoxane or modified methylaluminoxane.
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CN111943974A (en) * 2020-09-14 2020-11-17 山东京博中聚新材料有限公司 Metal complex, preparation method and application thereof
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