CN109400642B - Amine bridged triphenol tetradentate ligand fourth subgroup metal complex and application thereof - Google Patents

Amine bridged triphenol tetradentate ligand fourth subgroup metal complex and application thereof Download PDF

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CN109400642B
CN109400642B CN201811395730.0A CN201811395730A CN109400642B CN 109400642 B CN109400642 B CN 109400642B CN 201811395730 A CN201811395730 A CN 201811395730A CN 109400642 B CN109400642 B CN 109400642B
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母瀛
李彪
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Jilin University
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Abstract

The invention relates to an amine bridged trisphenol quadridentate ligand fourth subgroup metal complex and application thereof, belonging to the technical field of olefin polymerization catalysts. The complex has the following structural general formula:

Description

Amine bridged triphenol tetradentate ligand fourth subgroup metal complex and application thereof
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to an [ ONOO ] type tetradentate fourth subgroup metal complex with three phenolic compounds bridged by amine and application thereof in catalyzing ethylene polymerization.
Background
Polyolefin products are resin materials which are most popular with people at present due to the advantages of rich raw materials, low price, convenient production and processing, excellent performance and the like, and the polyolefin industry represents the development level of the national petrochemical industry and is an important component part in national economy and national defense strategies. The olefin polymerization catalyst determines the internal structure and appearance of polyolefin products, is the most central technology in the development process of polyolefin industry, and the development mainly comprises three stages: a) Ziegler-Natta catalysts, the earliest olefin polymerization catalysts, have evolved in the polyolefin industry, however, these catalysts are heterogeneous, difficult to activate completely by cocatalysts, have multiple sites of activity, have low catalytic efficiency, and have high ash content in the product, increasing the difficulty of post-treatment; b) metallocene catalysts, which require a large amount of expensive co-catalyst (MAO or boron promoter) during the use process, are easy to poison and deactivate the active center, and limit the application of the catalyst in industrial production; c) non-metallocene catalysts, which have a single active center and relatively high activity, can catalyze multiple polar single-site copolymerization, however, few catalysts can simultaneously consider catalytic activity, thermal stability and service life. The invention aims to design and synthesize a catalyst which has high catalytic activity, high thermal stability and long catalytic life and can catalyze ethylene polymerization to obtain an ultra-high molecular weight polyethylene product by reasonably optimizing a catalyst substituent group and polymerization conditions.
The most similar background art to the present invention is: a catalyst disclosed in chem. Commun, 2011,47,12328-12330, which is published by Jones, England scientist, but the catalyst with the structure can not catalyze olefin polymerization and is generally only used for catalyzing ring-opening polymerization of compounds such as lactide and the like. Nomura, a scientist in Japan, utilizes a compound of three benzyl phenols bridged by nitrogen atoms as a ligand to synthesize a series of alkoxy compounds of titanium and zirconium, the compounds are the same as the former compounds, olefin polymerization cannot be catalyzed when the compounds are directly used, and ethylene polymerization can be catalyzed barely under the secondary activation of MAO through the modification of alkyl aluminum; however, the catalyst generally takes small groups such as methyl groups and the like as substituents, the largest substituent is only tert-butyl, effective space protection on a metal active center cannot be formed when the catalyst is used for catalyzing ethylene polymerization, the catalyst is easy to attack and deactivate by alkyl aluminum, and the catalyst life is short; in the structure of the catalyst, the periphery of the central metal of the catalyst is of a symmetrical structure of three six-membered rings, which is not beneficial to the effective activation of the cocatalyst on the metal active center, so that the polymerization activity is very low, and the activity of the synthesized series of catalysts for catalyzing the ethylene polymerization is only 7570 kgPE/(molCatalyst.h); during the synthesis of the catalyst, the raw material cost is high, the steps are complicated, the modification is difficult, and the synthesis conditions are more rigorous; when used, the amount of cocatalyst required is very large and both the aluminum alkyl and a large amount of MAO are required to exhibit catalytic activity.
Disclosure of Invention
The invention aims to solve the problem of overcoming the defects of the prior art and provides an [ ONOO ] type quadridentate fourth subgroup metal complex of three phenolic compounds bridged by amine and application thereof.
The specific technical scheme is as follows,
an amine bridged trisphenol tetradentate ligand subgroup IV metal complex, which has the following structural general formula:
Figure BDA0001875130780000021
wherein: r1Is hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, phenyl, adamantyl, cumyl, diphenylethyl or trityl;
R2is phenyl, p-methylphenyl, 3, 5-bis (trifluoromethyl) phenyl, pentafluorophenyl, p-methoxyphenyl or methyl;
R3is phenyl, p-methylphenyl, 3, 5-bis (trifluoromethyl) phenyl, pentafluorophenyl, p-methoxyphenyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;
R4is phenyl, p-methylphenyl, 3, 5-bis (trifluoromethyl) phenyl, pentafluorophenyl, p-methoxyphenyl, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or hydrogen;
R5is hydrogen, methyl, ethyl, isopropyl, tert-butyl or phenyl;
R6is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, diphenylethyl or trityl;
R7is hydrogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, cumyl, diphenylethyl or trityl;
x is halogen, alkyl or aryl;
m is a fourth subgroup transition metal titanium, zirconium or hafnium.
In the amine bridged triphenol tetradentate ligand fourth subgroup metal complex of the invention, R1Preferably hydrogen, methyl, cumyl, diphenylethyl or trityl; r2Preferably phenyl, p-methylphenyl or methyl; r3Preferably phenyl, p-methylphenyl or methyl; r4Preferably phenyl, p-methylphenyl or methyl; r5Preferably hydrogen, methyl or tert-butyl; r6Preferably methyl or tert-butyl; r7Tert-butyl is preferredA group; m is preferably Ti; x is preferably Cl.
Among the metal complexes of the fourth subgroup of the amine-bridged trisphenol tetradentate ligands of the present invention, the following 12 complexes C1 to C12 are more preferable,
Figure BDA0001875130780000031
use of an amine bridged trisphenol tetradentate ligand subgroup iv metal complex, characterized in that: the amine bridged trisphenol quadridentate ligand fourth subgroup metal complex is used as a main catalyst, and alkyl aluminoxane, halogenated alkyl aluminum or a mixture of alkyl aluminum and a boron agent is used as a cocatalyst for catalyzing ethylene polymerization; wherein the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 5-40000: 1, the molar ratio of boron in the cocatalyst to metal in the main catalyst is 0-2: 1, the pressure of ethylene gas during polymerization is 0.1-5 MPa.
In the application of the amine bridged bisphenol tetradentate ligand fourth subgroup metal complex, the cocatalyst is further preferably methylaluminoxane or modified methylaluminoxane.
Has the advantages that:
1. compared with the traditional preparation process, the synthesis of the ligand and the complex is simple and high in yield.
2. The catalyst has asymmetric structure of a five-membered ring and two six-membered rings as the metal center, and the substituent is a large steric hindrance substituent, so that the catalyst has high resistance to a cocatalyst and impurities, good stability and long catalytic life when in use.
3. The catalyst has good thermal stability and high catalytic activity, the highest activity can reach 93264 kgPE/(molTi.h), and the activity is improved by 12.3 times compared with 7570 kgPE/(molCatalyst.h) which is the highest activity of Nomura;
4. the catalyst of the invention can catalyze ethylene polymerization to obtain ultra-high molecular weight polyethylene.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Examples 1-12 below show the preparation of 12 typical structures C1-C12 in the metal complex of the fourth subgroup of the amine-bridged trisphenol tetradentate ligand according to the present invention. Example 13 is an example of the amine-bridged trisphenol tetradentate ligand subgroup IV metal complex of the present invention as a procatalyst to catalyze ethylene homopolymerization.
Example 1: preparation of Complex C1
Figure BDA0001875130780000041
0.40mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.2726g of ligand L1H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.2981g of yellow metal titanium complex, wherein the yield is 97.4%, and is recorded as C1.
Example 2: preparation of Complex C2
Figure BDA0001875130780000051
0.40mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.2991g of ligand L2H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3218g of yellow metal titanium complex, wherein the yield is 96.8%, and is recorded as C2.
Example 3: preparation of Complex C3
Figure BDA0001875130780000052
0.40mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.3486g of ligand L3H3Dropping 30mL of toluene solution into the solution, slowly heating to room temperature, stirring for 10h, pumping out toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, ultrasonically oscillating,filtration gave 0.3795g of the yellow metallic titanium complex in 99.4% yield, designated C3.
Example 4: preparation of Complex C4
Figure BDA0001875130780000053
0.50mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and then 0.3542g of ligand L4H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3733g of yellow metal titanium complex, wherein the yield is 94.1%, and is recorded as C4.
Example 5: preparation of Complex C5
Figure BDA0001875130780000061
0.48mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.3545g of ligand L5H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3536g of the reddish brown metal titanium complex, wherein the yield is 89.7%, and the record is C5.
Example 6: preparation of Complex C6
Figure BDA0001875130780000062
0.37mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.3026g of ligand L6H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3220g of yellow metal titanium complex, wherein the yield is 96.5%, and is recorded as C6.
Example 7: preparation of Complex C7
Figure BDA0001875130780000071
0.40mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.3511g of ligand L7H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3737g of yellow metal titanium complex, wherein the yield is 97.2%, and is recorded as C7.
Example 8: preparation of Complex C8
Figure BDA0001875130780000072
0.40mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.2991g of ligand L8H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.3218g of yellow metal titanium complex, wherein the yield is 96.8%, and is recorded as C8.
Example 9 preparation of Complex C9
Figure BDA0001875130780000073
0.66mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.6883g of ligand L9H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.6580g of yellow metal titanium complex, wherein the yield is 94.8%, and is recorded as C9.
Example 10: preparation of Complex C10
Figure BDA0001875130780000081
0.54mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.5376g of ligand L10H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.5436g of yellow metal titanium complex, wherein the yield is 93.2%, and is recorded as C10.
Example 11: preparation of Complex C11
Figure BDA0001875130780000082
0.69mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.7430g of ligand L11H3And (3) dripping 30mL of toluene solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, pumping out the toluene, pumping out at 100 ℃ for 3h, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.7905g of yellow metal titanium complex, wherein the yield is 98.7%, and is recorded as C11.
Example 12: preparation of Complex C12
Figure BDA0001875130780000083
0.65mL of 1.1556mol/L TiCl4The solution was diluted to 10mL with toluene, frozen to-78 deg.C and 0.8303g of ligand L12H3And (3) dropwise adding 30mL of dichloromethane solution into the solution, slowly raising the temperature to room temperature, stirring for 10h, removing the solvent, pumping for 3h at 100 ℃, adding 3mL of hexane, performing ultrasonic oscillation, and filtering to obtain 0.8444g of yellow metal titanium complex, wherein the yield is 95.4%, and is recorded as C12.
Example 13 polymerization of ethylene
Heating a polymerization kettle with a magnetic stirrer to 120 ℃, vacuumizing for 1h, filling ethylene gas with 0.1MPa, adding 60mL of toluene solution purified by MAO or triisobutylaluminum, then adding a main catalyst, introducing 0.5MP ethylene gas, and stirring for 5min-150 min. And (3) after the polymerization reaction is finished, discharging residual ethylene gas, opening the reaction kettle, pouring the obtained polymerization reaction mixture into a mixed solution of 3M hydrochloric acid and ethanol with the volume ratio of 1:1, stirring for 5min, filtering and drying. The mass was weighed, the melting point was measured, and the viscosity average molecular weight was measured. The data obtained are shown in tables 1 and 2.
TABLE 1 polymerization data with C2 as procatalyst
Serial number MAO(mmol) Temperature of Yield/g Activity of Viscosity average molecular weight X10-4 Melting Point/. degree.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 —— —— ——
Polymerization conditions: the dosage of the main catalyst C2 is 0.2 mu mol, and the polymerization time is 5 min; the polymerization time in serial No. 11 was 2.5 h; number 12 cocatalyst was Al (iBu)3(ii) a The activity unit is kgPE/(molTi. h).
Table 2 polymerization data with C1-C12 as procatalyst;
serial number Catalyst and process for preparing same Yield/g Activity of Viscosity average molecular weight X10-4 Melting Point/. degree.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 the main catalyst is 0.2 mu mol, the dosage of the cocatalyst is 1.2mmol, the polymerization time is 5min, and the activity unit is kgPE/(molTi.h).

Claims (2)

1. An amine bridged trisphenol tetradentate ligand subgroup IV metal complex is the following 9 complexes:
Figure FDA0003009012020000011
2. use of the amine-bridged trisphenol tetradentate ligand subgroup IV metal complex of claim 1, wherein: the amine bridged trisphenol quadridentate ligand fourth subgroup metal complex is used as a main catalyst, and alkyl aluminoxane is used as a cocatalyst for catalyzing ethylene polymerization; wherein the molar ratio of aluminum in the cocatalyst to metal in the main catalyst is 5-40000: 1, the pressure of ethylene gas during polymerization is 0.1-5 MPa.
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