CN117659057A - Pyridinamine ligand-scandium complex, preparation method thereof and application thereof in preparing polyisobutene by catalysis - Google Patents
Pyridinamine ligand-scandium complex, preparation method thereof and application thereof in preparing polyisobutene by catalysis Download PDFInfo
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- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052706 scandium Inorganic materials 0.000 title claims abstract description 81
- 229920002367 Polyisobutene Polymers 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 44
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 43
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 230000000536 complexating effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 150000003141 primary amines Chemical class 0.000 claims description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000006482 condensation reaction Methods 0.000 claims description 6
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- -1 pyridine imine Chemical class 0.000 abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 126
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 120
- 239000012300 argon atmosphere Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 16
- 239000007788 liquid Substances 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005882 aldol condensation reaction Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
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Abstract
The invention provides a pyridine amine ligand-scandium complex, a preparation method thereof and application thereof in preparing polyisobutene by catalysis, and belongs to the technical field of catalysts. The pyridine amine ligand-scandium complex provided by the invention has a structure shown in any one of formulas I to III. According to the invention, the pyridine amine ligand (pyridine imine or pyridine amine) is used for complexing with trivalent scandium, and the structure and the reaction rate of the polyisobutene can be better regulated and controlled by changing the framework of the ligand, so that isobutene polymerization can be better realized. The example results show that the polymerization reaction of isobutene can be realized at the normal temperature of 25 ℃ by taking the pyridine amine ligand-scandium complex as a catalyst and assisting with a cocatalyst, so that the polyisobutene with low molecular weight is obtained.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a pyridine amine ligand-scandium complex, a preparation method thereof and application thereof in preparing polyisobutene by catalysis.
Background
Polyisobutenes are colorless, odorless, nontoxic homopolymers of isobutene whose chemical structure is typical of linear saturated polymers. The main part of the molecular skeleton is composed of a repeating unit-CH 2 -C(CH 3 ) 2 -composition, the head is-CH 3 At the end of-CH 2 -C(CH 3 )＝CH 2 Or-ch=c (CH 3 ) 2 . The molecular weight of the polyisobutenes can vary widely, owing to the differences in the preparation process and the production process. Polyisobutenes are classified by molecular weight into high molecular weight polyisobutenes (Mn>100000 Medium molecular weight polyisobutene (Mn of 10000 to 100000), low molecular weight polyisobutene (Mn)<10000)。
The polyisobutene has the excellent characteristics of acid resistance, alkali resistance, water resistance, salt resistance, ozone resistance, aging resistance, good gas barrier property, electrical insulation property and the like, and has good compatibility with asphalt, wax and polyethylene. Currently, the polyisobutylene industry has developed a variety of polymerization methods to obtain polyisobutylene, which can be classified into two types from the catalyst perspective, aluminum-based polyisobutylene and boron-based polyisobutylene, essentially cationic polymerization, i.e., the formation of cations in the reaction system from aluminum or boron reagents, thereby inducing polymerization of monomers. In the polymerization process, side reactions such as intramolecular rearrangement, transfer, isomerization and the like are easy to occur, the structure of the polyisobutene is difficult to control, and the explosion polymerization is easy to occur, so that the reaction process is required to be carried out at an extremely low temperature (-60 ℃).
Disclosure of Invention
In view of the above, the present invention aims to provide a pyridine amine ligand-scandium complex, a preparation method thereof and an application thereof in preparing polyisobutene by catalysis. When the pyridine amine ligand-scandium complex provided by the invention is used as a catalyst for synthesizing polyisobutene, the normal-temperature synthesis of polyisobutene can be realized.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a pyridine amine ligand-scandium complex, which has a structure shown in any one of formulas I-III:
in the formulas I to III, R 1 Is a hydrogen atom or a methyl group;
R 3 is a hydrogen atom;
R 2 is a hydrogen atom or a structure represented by any one of formulas 1 to 11:
x is Cl or acac.
Preferably, the compound has a structure shown in any one of Sc-1 to Sc-15:
the invention provides a preparation method of the pyridine amine ligand-scandium complex, which comprises the following steps:
mixing a soluble trivalent scandium source, a pyridine amine ligand and an organic solvent, and carrying out a complex reaction to obtain a pyridine amine ligand-scandium complex;
the soluble trivalent scandium source is ScCl 3 Or Sc (acac) 3 ；
The pyridine amine ligand has a structure shown in any one of formulas (1) to (3):
preferably, the temperature of the complexing reaction is 0-30 ℃ and the time is 12-72 h.
Preferably, the molar ratio of the soluble trivalent scandium source to the pyridine amine ligand is 1:1-5.
Preferably, the preparation method of the pyridine amine ligand with the structure shown in the formula (2) comprises the following steps:
in the presence of a catalyst, carrying out an amine-aldehyde condensation reaction on primary amine with a structure shown in a formula a and pyridine-2-formaldehyde compounds with a structure shown in a formula b to obtain pyridine amine ligands with a structure shown in a formula (2);
R 2 -NH 2 a formula (a);
the preparation method of the pyridine amine ligand with the structure shown in the formula (1) comprises the following steps:
and (3) carrying out hydrogenation reaction on the pyridine amine ligand with the structure shown in the formula (2) and sodium borohydride to obtain the pyridine amine ligand with the structure shown in the formula (1).
The invention provides application of the pyridine amine ligand-scandium complex in preparing polyisobutene by catalysis.
The invention provides a method for preparing polyisobutene by catalyzing a pyridine amine ligand-scandium complex, which comprises the following steps:
mixing an isobutene monomer, a pyridinamine ligand-scandium complex, a cocatalyst and a solvent, and carrying out polymerization reaction to obtain polyisobutene;
the pyridine amine ligand-scandium complex is the pyridine amine ligand-scandium complex.
Preferably, the cocatalyst comprises a MAO catalyst;
the molar ratio of the pyridine amine ligand-scandium complex to the cocatalyst is 1:50-2000.
Preferably, the molar ratio of the pyridine amine ligand-scandium complex to the isobutene monomer is 1:50-100000;
the temperature of the polymerization reaction is 0-50 ℃ and the time is 2-12 h.
The invention provides a pyridine amine ligand-scandium complex, which has a structure shown in any one of formulas I-III. According to the invention, the pyridine amine ligand (pyridine imine or pyridine amine) is used for complexing with trivalent scandium, and the structure and the reaction rate of the polyisobutene can be better regulated and controlled by changing the framework of the ligand, so that isobutene polymerization can be better realized. Compared with the existing cationic polymerization method for preparing the polyisobutene, the method takes the pyridine amine ligand-scandium complex as the catalyst, and can realize isobutene polymerization under normal temperature in a coordination polymerization mode. The example results show that the polymerization reaction of isobutene can be realized at the normal temperature of 25 ℃ by taking the pyridine amine ligand-scandium complex as a catalyst and assisting with a cocatalyst, so that the polyisobutene with low molecular weight is obtained.
Detailed Description
The invention provides a pyridine amine ligand-scandium complex, which has a structure shown in any one of formulas I-III:
in the formulas I to III, R 1 Is a hydrogen atom or a methyl group;
R 3 is a hydrogen atom;
R 2 is a hydrogen atom or a structure represented by any one of formulas 1 to 11:
x is Cl or acac.
In the present invention, the pyridine amine ligand-scandium complex preferably has a structure shown in any one of Sc-1 to Sc-5:
the invention provides a preparation method of the pyridine amine ligand-scandium complex, which comprises the following steps:
mixing a soluble trivalent scandium source, a pyridine amine ligand and an organic solvent, and carrying out a complex reaction to obtain a pyridine amine ligand-scandium complex;
the soluble trivalent scandium source is ScCl 3 Or Sc (acac) 3 ；
The pyridine amine ligand has a structure shown in any one of formulas (1) to (3):
in the present invention, the source of the pyridinamine ligand is commercially available or self-prepared.
In the present invention, the pyridinamine ligand preferably has a structure represented by any one of formulas 1 to 15:
in the present invention, the preparation method of the pyridine amine ligand having the structure represented by the formula (2) preferably comprises the steps of:
under the condition of a catalyst, carrying out an amine-aldehyde condensation reaction on primary amine with a structure shown in a formula a and pyridine-2-formaldehyde compounds with a structure shown in a formula b to obtain pyridine amine ligands with a structure shown in a formula (2):
R 2 -NH 2 a formula (a);
in the present invention, the catalyst is preferablyMolecular sieves.
In the present invention, the aldol condensation reaction is preferably performed under a protective atmosphere, preferably argon. In the present invention, the molar ratio of the primary amine having the structure represented by formula a to the pyridine-2-carbaldehyde compound having the structure represented by formula b is preferably 1:1.
In the present invention, the amine aldehyde condensation reaction is preferably carried out in an organic solvent, preferably methylene chloride.
In the present invention, the temperature of the amine aldehyde condensation reaction is preferably 10 to 40 ℃, more preferably 20 to 30 ℃; the time is preferably overnight.
In the present invention, after the aldol condensation reaction, the present invention preferably performs a post-treatment of the resulting aldol condensation reaction liquid, the post-treatment preferably comprising the steps of:
after the TLC plate detects that the raw materials are completely reacted, the amine aldehyde condensation reaction liquid is sequentially filtered, subjected to column chromatography, spin-dried and pumped down in vacuum to obtain the pyridine amine ligand with the structure shown in the formula (2).
In the present invention, the preparation method of the pyridine amine ligand having the structure represented by the formula (1) preferably comprises the steps of:
carrying out hydrogenation reaction on the pyridine amine ligand with the structure shown in the formula (2) and sodium borohydride to obtain the pyridine amine ligand with the structure shown in the formula (1);
in the present invention, the molar ratio of the pyridine amine ligand having the structure represented by formula (2) to sodium borohydride is preferably 1:1.
In the present invention, the hydrogenation reaction is preferably carried out in a solvent, preferably methanol.
In the present invention, the temperature of the hydrogenation reaction is preferably 10 to 40 ℃, more preferably 20 to 30 ℃; the time is preferably overnight.
In the present invention, after the hydrogenation reaction, the present invention preferably performs a post-treatment of the resulting hydrogenation reaction liquid, the post-treatment preferably comprising the steps of:
after the TLC plate detects that the raw materials are completely reacted, extracting the hydrogenation reaction liquid, collecting an organic phase, and drying to obtain the pyridine amine ligand with the structure shown in the formula (1).
In the present invention, the extractant used for the extraction is preferably an aqueous sodium carbonate solution; the drying is preferably anhydrous sodium sulfate drying.
In the present invention, the source of the pyridine amine ligand having the structure represented by the formula (3) is preferably commercially available.
After obtaining the pyridine amine ligand, the invention mixes the soluble trivalent scandium source, the pyridine amine ligand and the organic solvent for complex reaction to obtain the pyridine amine ligand-scandium complex. In the present invention, the soluble trivalent scandium source is ScCl 3 Or Sc (acac) 3 . In the present invention, the complexation reaction is preferably performed in a glove box. In the present invention, the organic solvent is preferably methylene chloride.
In the present invention, the molar ratio of the soluble trivalent scandium source to the pyridine amine ligand is preferably 1:1 to 5, more preferably 1:1.05.
In the present invention, the mixing means is preferably: the pyridinamine ligand is dissolved in an organic solvent and the resulting solution is added drop-wise to a test tube containing a soluble trivalent scandium source.
In the present invention, the temperature of the complexation reaction is preferably 0 to 30 ℃, more preferably 10 to 25 ℃, and the time is preferably 12 to 72 hours, more preferably 24 to 48 hours.
After the complexing reaction, the present invention preferably performs a post-treatment on the obtained complexing reaction liquid, and the post-treatment preferably comprises the following steps:
and filtering the complexing reaction liquid under the argon atmosphere, and washing and drying the obtained solid to obtain the pyridine amine ligand-scandium complex.
In the present invention, the washing detergent is preferably n-hexane; the drying mode is preferably vacuum drying.
The invention provides application of the pyridine amine ligand-scandium complex in preparing polyisobutene by catalysis. In the present invention, the polyisobutene is preferably a low molecular weight polyisobutene.
The invention provides a method for preparing polyisobutene by catalyzing a pyridine amine ligand-scandium complex, which comprises the following steps:
mixing an isobutene monomer, a pyridinamine ligand-scandium complex, a cocatalyst and a solvent, and carrying out polymerization reaction to obtain polyisobutene;
the pyridine amine ligand-scandium complex is the pyridine amine ligand-scandium complex.
In the present invention, the molar ratio of the isobutylene monomer to the pyridine amine ligand-scandium complex is preferably 1:400.
In the present invention, the cocatalyst preferably comprises a MAO catalyst. In the present invention, the molar ratio of the pyridine amine ligand-scandium complex to the cocatalyst is preferably 1:200. In the present invention, the promoter acts to abstract a chlorine atom from the complex, so that the activity of the metal center is enhanced, thereby allowing more reaction with the monomer.
In the present invention, the solvent is preferably anhydrous toluene or n-hexane.
In the present invention, the temperature of the polymerization reaction is preferably 0 to 50 ℃, more preferably 25 ℃; the time is preferably 2 to 12 hours, more preferably 5 to 10 hours.
The pyridinamine ligand-scandium complexes provided by the present invention, as well as methods for their preparation and their use in the catalytic preparation of polyisobutene, are described in detail below with reference to the examples, but they are not to be construed as limiting the scope of the present invention.
Example 1
The preparation of the pyridine imine ligands L1 to L8 adopts the following steps:
100mL dry reaction flask, addThe molecular sieve was baked for 30 minutes. Under argon atmosphere, dry dichloromethane, primary amine (1.0 eq.) and pyridine-2-carbaldehyde (1.0 eq.) were added sequentially. The reaction was carried out overnight at room temperature, and the TLC plate detected complete reaction of starting materials. Filtering, column chromatography, spin drying, and vacuum drying to obtain target ligand.
The reaction process is as follows:
the primary amines used for L1 to L8 were as follows:
the specific characterization data are as follows:
white solid, 2.5g, yield: 88%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.58-8.57(d,J＝4.44Hz,1H),8.52(s,1H),8.19-8.17(d,J＝7.92Hz,1H),7.66-7.62(dt,J＝7.68Hz,J＝0.96Hz,1H),7.39-7.38(d,J＝7.40Hz,4H),7.31-7.27(t,J＝7.36Hz,4H),7.22-7.18(t,J＝7.36Hz,3H),5.68(s,1H)； 13 C NMR(100MHz,CDCl 3 ,298K),δ:161.8,154.5,149.1,143.1,136.2,128.3,127.5,126.9,124.6,121.3,77.5.
Colorless liquid, 1.8g, yield: 90%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.65-8.63(m,1H),8.49(s,1H),8.20-8.18(d,J＝7.92Hz,1H),7.78-7.74(dt,J＝1.24Hz,J＝7.6Hz,1H),7.34-7.30(m,5H),7.04-6.99(m,4H),5.65(s,1H)； 13 C NMR(100MHz,CDCl 3 ,298K)δ163.1,162.1,160.7,154.4,149.4,138.9,138.8,136.5,129.2,129.12,125.0,121.5,115.4,115.2,76.0.
Colorless liquid, 0.6g, yield: 68%; 1 H NMR(400MHz,CDCl 3 ,298K)δ8.63-8.62(m,1H),8.47(s,1H),8.21-8.19(d,J＝7.92Hz,1H),7.76-7.71(dt,J＝1.40Hz,J＝7.64Hz,1H),7.32-7.25(m,5H),6.87-6.84(m,4H),5.62(s,1H),3.78(s,6H)； 13 C NMR(100MHz,CDCl 3 ,298K)δ161.4,158.6,154.8,149.3,136.4,135.7,128.7,124.7,121.4,113.8,55.2.
white solid, 2.52g, yield: 83%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.64-8.63(d,J＝4.44Hz,1H),8.10(s,1H),8.08-8.06(d,J＝7.88Hz,1H),7.74-7.70(d,J＝7.32Hz,1H),7.45-7.07(m,11H),4.59-4.55(t,J＝6.80Hz,1H),3.25-3.23(d,J＝6.88Hz,2H)； 13 C NMR(100MHz,CDCl 3 ,298K)δ:161.0,154.4,149.1,143.2,138.4,136.3,129.6,128.3,128.0,127.0,126.1,124.5,121.3,76.8,45.3.
1.40g of pale yellow liquid was found to be 85% yield. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.75-8.69(m,1H),8.61(s,1H),8.21(d,J＝8.0Hz,1H),7.84-7.80(m,1H),7.46-7.35(m,3H),7.31-7.27(m,3H)； 13 C NMR(100MHz,CDCl 3 ,298K)δ160.6,154.5,150.9,149.6,136.7,129.2,126.7,125.1,121.9,121.1.
Yellow liquid, 2.5g, yield: 68%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.64-8.63(m,1H),8.49(s,1H),8.06(d,J＝7.6Hz,1H),7.74-7.69(m,1H),7.74-7.69(m,6H),4.87(s,2H)； 13 C NMR(100MHz,CDCl 3 ,298K)δ:162.88,154.61,149.47,138.76,136.59,128.63,128.23,127.22,124.87,121.40,77.48,77.16,76.84,64.98.
Colorless liquid: 1.8g, yield: 80%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.63-8.60(m,1H),8.34(s,1H),8.12(d,J＝8.0Hz,1H),7.73-7.67(m,1H),7.43(dd,J＝8.4,1.0Hz,2H),7.33(t,J＝7.8Hz,2H),7.28-7.19(m,2H),1.67(s,6H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:158.2,155.3,149.2,147.5,136.4,128.2,126.4,126.0,124.55,121.0,63.0,29.5.
Colorless liquid, 0.78g, yield: 73%. 1 H NMR(400MHz,,CDCl 3 ,298K)δ:8.63(d,J＝4.6Hz,1H),8.33(s,1H),8.04(d,J＝8.0Hz,1H),7.73(td,J＝7.8,1.6Hz,1H),7.29(ddd,J＝7.4,5.0,1.4Hz,1H),1.65(q,J＝7.6Hz,2H),1.26(s,6H),0.85(t,J＝7.6Hz,3H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:156.9,155.7,149.3,136.6,124.4,120.9,60.3,35.8,26.6,8.7.
Example 2
The preparation of the pyridine amine ligands L9 to L14 comprises the following steps:
100mL dry reaction flask, addThe molecular sieve was baked for 30 minutes. Under argon atmosphere, dry dichloromethane, primary amine (1.0 eq.) and pyridine-2-carbaldehyde (1.0 eq.) were added sequentially and the TLC plate detected complete reaction of the starting materials. Filtering, spin-drying, and vacuum-pumping to obtain pyridine imine. Then, methanol, pyridine imine (1.0 eq.) and sodium borohydride (10.0 eq.) were added sequentially to 100mL two-port flask, stirred overnight at room temperature, and the TLC plate detected complete reaction of the starting materials. After quenching the reaction by adding aqueous sodium carbonate, the reaction mixture was extracted with DCM, and the organic phase was collected and concentrated to give the crude target ligand. And purifying by column chromatography to obtain the pyridine amine ligand.
The primary amine used has the following structural formula:
pale yellow liquid, 1.01g, yield: 62%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.61-8.52(m,1H),7.63(td,J＝7.8,1.8Hz,1H),7.39-7.29(m,5H),7.24(d,J＝6.8Hz,1H),7.18-7.13(m,1H),3.93(s,2H),3.84(s,2H),2.19(s,1H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:159.9,149.4,140.2,136.5,128.5,128.4,127.1,122.4,122.0,54.6,53.6.
Pale yellow liquid, 0.64g, yield: 69%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.59-8.53(m,1H),7.65(td,J＝7.6,1.8Hz,1H),7.38(d,J＝7.8Hz,1H),7.19-7.12(m,1H),6.83(s,2H),3.99(s,2H),3.77(s,2H),2.33(s,6H),2.24(s,3H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:160.3,149.3,137.2,136.6,136.5,133.6,129.1,122.5,122.0,55.6,47.3,21.0,19.6.
/>
Pale yellow liquid, 0.93g, yield: 80%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.57(dt,J＝5.0,1.4Hz,1H),7.64(td,J＝7.6,1.8Hz,1H),7.58(d,J＝8.0Hz,2H),7.49(d,J＝8.0Hz,2H),7.29(d,J＝7.8Hz,1H),7.17(m,1H),3.92(s,2H),3.91(s,2H),2.13(s,1H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:159.5,149.5,144.4,136.6,129.4,128.5,125.4,124.4,122.5,122.2,54.6,53.1.
Pale yellow liquid, 0.31g, yield: 91%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.59-8.51(m,1H),7.64(tt,J＝7.6,1.8Hz,1H),7.35-7.19(m,3H),7.15(ddd,J＝7.6,4.8,1.2Hz,1H),6.92-6.81(m,2H),3.91(s,2H),3.79(s,3H),3.78(s,2H),2.14(s,1H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:159.9,158.8,149.4,136.5,132.4,129.6,122.5,122.0,113.9,55.4,54.6,53.0.
Pale yellow liquid, 1.45g, yield: 80%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.59(ddd,J＝4.9,1.7,0.9Hz,1H),7.64(td,J＝7.7,1.8Hz,1H),7.34(d,J＝7.9Hz,1H),7.24-7.14(m,3H),6.77-6.64(m,3H),4.76(s,1H),4.47(s,2H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:158.6,149.3,148.0,136.7,129.3,122.2,121.7,117.7,113.1,49.4.
Pale yellow liquid, 1.51g, yield: 74%. 1 H NMR(400MHz,CDCl 3 ,298K)δ:8.54(ddd,J＝4.8,1.8,1.0Hz,1H),7.61(td,J＝7.6,1.8Hz,1H),7.47-7.40(m,4H),7.33-7.25(m,5H),7.23-7.17(m,2H),7.14(ddd,J＝7.6,4.8,1.2Hz,1H),4.87(s,1H),3.87(s,2H),2.52(s,1H). 13 C NMR(100MHz,CDCl 3 ,298K)δ:159.8,149.4,143.9,136.4,128.6,127.5,127.1,122.6,122.0,67.1,53.5.
The source of the pyridinamine ligand L15 is commercially available.
L15。
Example 3
The preparation process of the pyridine amine ligand-scandium complex comprises the following steps:
in a glove box, dry ScCl was added sequentially to a dry Schlenk tube (50 mL) 3 (1.0 eq.) dichloromethane (8 mL) and the pyridine amine ligands of examples 1-2 (1.05 eq.) were dissolved in dichloromethane (10 mL) and added dropwise to ScCl with stirring 3 In a Schlenk tube, stirred at room temperature for 48 hours. After the reaction is finished, filtering under argon atmosphere, collecting filtrate or solid, pumping, washing the solid with n-hexane for 3 times, and vacuum pumping to obtain target complexes, which are respectively marked as Sc-1-Sc-15.
The structure of the resulting pyridinamine ligand-scandium complex is characterized as follows:
Sc-1
HRMS-ESI(m/z)::Calcd for[C 19 H 16 Cl 2 ScN 2 ]:387.0250；Found 387.0249；
ATR-IR(cm -1 ):1596,1495,1454,1308,1268,1230,1156,1085,1019,1005,991,928,864,822,796,766,741.
Sc-2
HRMS-ESI(m/z):Calcd for[C 19 H 14 Cl 2 F 2 ScN 2 ] + :423.0061；Found:423.0058；
ATR-IR(cm -1 ):1598,1507,1443,1414,1308,1227,1159,1103,1052,1018,967,910,863,839,788,767,745.
Sc-3
HRMS-ESI(m/z):Calcd for[C 21 H 20 Cl 2 ScN 2 O 2 ] + :447.0461；Found:447.0460；
ATR-IR(cm -1 ):1608,1510,1463,1442,1306,1250,1177,1115,1029,907,836,818,784,767,748.
Sc-4
HRMS-ESI(m/z):Calcd for[C 21 H 21 Cl 2 ScN 2 ] + :416.0461；Found:416.0460；
ATR-IR(cm -1 ):1593,1492,1443,1366,1306,1265,1219,1160,1024,979,921,906,773,753,728.
Sc-9
HRMS-ESI(m/z):Calcd for[C 13 H 14 Cl 2 ScN 2 ] + :523.1119；Found:523.1122；
ATR-IR(cm -1 ):3250,3026,2942,1605,1571,1488,1442,1335,1306,1149,1088,1021,995,912,880,765.
Sc-10
HRMS-ESI(m/z):Calcd for[C 16 H 20 Cl 2 ScN 2 ] + :355.0563；Found,355.0562；
ATR-IR(cm -1 ):3290,2979,2948,1608,1573,1486,1441,1363,1312,1151,1080,1051,1022,981,894,869,813,761.
Sc-11
HRMS-ESI(m/z):Calcd for[C 14 H 13 Cl 2 F 3 ScN 2 ] + :380.9967；Found:380.9966；
ATR-IR(cm -1 ):3251,2941,1606,1571,1436,1329,1164,1115,1066,1020,986,900,815,765.
Sc-12
HRMS-ESI(m/z):Calcd for[C 14 H 16 Cl 2 ScN 2 O] + :343.0199；Found:343.0199；
ATR-IR(cm -1 ):3249,2939,2836,2354,1698,1610,1572,1513,1486,1441,1324,1301,1251,1180,1050,1032,994,899,815,765.
application example 1
Scandium complex Sc-5 (10 μmol,1 equiv.) was added sequentially to anhydrous toluene, promoter MAO (2 mmol,200equiv.,1.5M toluene solution, from aledine) and isobutylene (4 mmol,400 equiv.) in a 25mL Schlenk flask under argon atmosphere, the system was allowed to react at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 42%, the molecular weight was 2729g/mol and the PDI was 2.3.
Application example 2
Scandium complex Sc-1 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially under argon atmosphere, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) and the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 50%, the molecular weight was 3257g/mol and the PDI was 2.4.
Application example 3
Scandium complex Sc-2 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 47%, the molecular weight was 2209g/mol and the PDI was 2.3.
Application example 4
Scandium complex Sc-3 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 62%, the molecular weight was 3659g/mol and the PDI was 2.4.
Application example 5
Scandium complex Sc-4 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 69%, the molecular weight was 2003g/mol and the PDI was 2.5.
Application example 6
Scandium complex Sc-6 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 38%, the molecular weight was 2637g/mol and the PDI was 2.5.
Application example 7
Scandium complex Sc-7 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 33%, the molecular weight was 2519g/mol and the PDI was 2.5.
Application example 8
Scandium complex Sc-8 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 33%, the molecular weight was 2519g/mol and the PDI was 2.5.
Application example 9
Scandium complex Sc-9 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 46%, the molecular weight was 2990g/mol and the PDI was 2.5.
Application example 10
Scandium complex Sc-10 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially under argon atmosphere, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) and the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 34%, the molecular weight was 2856g/mol and the PDI was 2.6.
Application example 11
Scandium complex Sc-11 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 39%, the molecular weight was 2900g/mol and the PDI was 2.7.
Application example 12
Scandium complex Sc-12 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 33%, the molecular weight was 3952g/mol and the PDI was 3.0.
Application example 13
Scandium complex Sc-13 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially with anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) under argon atmosphere, the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 29%, the molecular weight was 3620g/mol and the PDI was 2.7.
Application example 14
Scandium complex Sc-14 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially under argon atmosphere, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) and the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 30%, the molecular weight was 3853g/mol and the PDI was 2.4.
Application example 15
Scandium complex Sc-15 (10 μmol,1 equiv.) in a 25mL Schlenk flask was added sequentially under argon atmosphere, anhydrous toluene, cocatalyst MAO (2 mmol,200equiv.,1.5M toluene solution) and isobutylene (4 mmol,400 equiv.) and the system was reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo to give a colorless, viscous polymer, i.e., low molecular weight polyisobutylene.
The yield of the low molecular weight polyisobutene of this example was 60%, the molecular weight was 5853g/mol and the PDI was 2.7.
Comparative example 1
Scandium complex Sc-5 (10. Mu. Mol,1 equiv.) was added sequentially to a 25mL Schlenk flask under argon, anhydrous toluene and isobutylene (4 mmol,400 equiv.) and the system was reacted at 25℃for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo, and no polyisobutylene was produced.
Comparative example 2
Scandium complex Sc-5 (10. Mu. Mol,1 equiv.) was added sequentially in a 25mL Schlenk flask under argon atmosphere, anhydrous toluene, promoter AlMe 3 (2 mmol,200equiv.,1.5M toluene) and isobutylene (4 mmol,400 equiv.) the system was reacted at 25℃for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo, and no polyisobutylene was produced.
Comparative example 3
Scandium complex Sc-5 (10. Mu. Mol,1 equiv.) was added sequentially in a 25mL Schlenk flask under argon, anhydrous toluene, promoter AlEt 3 (2 mmol,200equiv.,1.5M toluene) and isobutylene (4 mmol,400 equiv.) the system was reacted at 25℃for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo, and no polyisobutylene was produced.
Comparative example 4
Scandium complex Sc-5 (10. Mu. Mol,1 equiv.) was added sequentially in a 25mL Schlenk flask under argon atmosphere, anhydrous toluene, promoter Ali-Bu 3 (2 mmol,200equiv.,1.5M toluene) and isobutylene (4 mmol,400 equiv.) the system was reacted at 25℃for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo, and no polyisobutylene was produced.
As can be seen from a combination of comparative examples 2 to 4, the cocatalyst AlMe 3 、AlEt 3 、Ali-Bu 3 Chlorine cannot be pulled from the metal complex to form active metal centers.
Comparative example 5
In a 25mL Schlenk flask under argon atmosphere, anhydrous toluene, co-catalyst MAO (2 mmol,200equiv.,1.5M toluene) and isobutylene (4 mmol,400 equiv.) were reacted at 25 ℃ for 12h, quenched with methanol, washed with methanol, filtered and dried in vacuo, and no polyisobutylene was produced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A pyridine amine ligand-scandium complex having a structure according to any one of formulae I to III:
in the formulas I to III, R 1 Is a hydrogen atom or a methyl group;
R 3 is a hydrogen atom;
R 2 is a hydrogen atom or a structure represented by any one of formulas 1 to 11:
x is Cl or acac.
2. The pyridine amine ligand-scandium complex according to claim 1, having the structure according to any one of Sc-1 to Sc-15:
3. a process for the preparation of a pyridine amine ligand-scandium complex according to claim 1 or 2, comprising the steps of:
mixing a soluble trivalent scandium source, a pyridine amine ligand and an organic solvent, and carrying out a complex reaction to obtain a pyridine amine ligand-scandium complex;
the soluble trivalent scandium source is ScCl 3 Or Sc (acac) 3 ；
The pyridine amine ligand has a structure shown in any one of formulas (1) to (3):
4. the method according to claim 3, wherein the temperature of the complexing reaction is 0 to 30℃and the time is 12 to 72 hours.
5. A method of preparation according to claim 3, wherein the molar ratio of soluble trivalent scandium source to pyridine amine ligand is 1:1-5.
6. A process according to claim 3, wherein,
the preparation method of the pyridine amine ligand with the structure shown in the formula (2) comprises the following steps:
in the presence of a catalyst, carrying out an amine-aldehyde condensation reaction on primary amine with a structure shown in a formula a and pyridine-2-formaldehyde compounds with a structure shown in a formula b to obtain pyridine amine ligands with a structure shown in a formula (2);
R 2 -NH 2 a formula (a);
the preparation method of the pyridine amine ligand with the structure shown in the formula (1) comprises the following steps:
and (3) carrying out hydrogenation reaction on the pyridine amine ligand with the structure shown in the formula (2) and sodium borohydride to obtain the pyridine amine ligand with the structure shown in the formula (1).
7. Use of a pyridine amine ligand-scandium complex according to claim 1 or 2 or prepared by a preparation method according to any one of claims 3 to 6 in the catalytic preparation of polyisobutene.
8. A method for preparing polyisobutene by catalyzing a pyridine amine ligand-scandium complex, comprising the following steps:
mixing an isobutene monomer, a pyridinamine ligand-scandium complex, a cocatalyst and a solvent, and carrying out polymerization reaction to obtain polyisobutene;
the pyridine amine ligand-scandium complex is the pyridine amine ligand-scandium complex according to claim 1 or 2 or the pyridine amine ligand-scandium complex prepared by the preparation method according to any one of claims 3 to 6.
9. The method of claim 8, wherein the cocatalyst comprises a MAO catalyst;
the molar ratio of the pyridine amine ligand-scandium complex to the cocatalyst is 1:50-2000.
10. The method according to claim 8 or 9, characterized in that the molar ratio of the pyridine amine ligand-scandium complex to the isobutene monomer is 1:50-100000;
the temperature of the polymerization reaction is 0-50 ℃ and the time is 2-12 h.
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