CN114478652A - Thiazolimine-cobalt compound and synthesis method and application thereof - Google Patents
Thiazolimine-cobalt compound and synthesis method and application thereof Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 21
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical compound CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 thiazole imine Chemical class 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 150000001448 anilines Chemical class 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 7
- 229940039790 sodium oxalate Drugs 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 claims description 5
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 claims description 3
- BJSVKBGQDHUBHZ-UHFFFAOYSA-N 2,4,6-trifluoroaniline Chemical compound NC1=C(F)C=C(F)C=C1F BJSVKBGQDHUBHZ-UHFFFAOYSA-N 0.000 claims description 3
- MQZSYVVHQUCZHS-UHFFFAOYSA-N 2-benzhydryl-4-methylaniline Chemical compound C(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC(=CC=C1N)C MQZSYVVHQUCZHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- ODUZJBKKYBQIBX-IDEBNGHGSA-N 2,6-difluoroaniline Chemical group N[13C]1=[13C](F)[13CH]=[13CH][13CH]=[13C]1F ODUZJBKKYBQIBX-IDEBNGHGSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 238000002360 preparation method Methods 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000037048 polymerization activity Effects 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000009736 wetting Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/08—Isoprene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a thiazole imine-cobalt compound and a synthesis method and application thereof, wherein the synthesis method comprises the following steps: 2-acetyl thiazole and aniline derivatives are condensed under different conditions to obtain corresponding thiazole imine ligands. And respectively reacting the ligand with anhydrous cobalt chloride in tetrahydrofuran at normal temperature to obtain the thiazolylimine-cobalt compound. The cobalt catalyst synthesized by the method has different electronic effects and steric hindrance effects, and can be used for catalyzing isoprene polymerization.
Description
Technical Field
The invention belongs to the technical field of polyolefin catalysts, and particularly relates to a catalyst for catalyzing isoprene polymerization, and a synthesis method and application thereof.
Background
Rubber is an important polyolefin material, which has an extremely wide range of applications in modern society, such as tire manufacturing, medical equipment, aerospace industry, etc. However, the yield of natural rubber is influenced by climate and other conditions, and the yield of natural rubber is far from meeting the increasing demand of society, so that the development of synthetic rubber is very important. Polyisoprene is favored by researchers because it has the same monomer structure as natural rubber.
The key point of the synthesis of polyisoprene is the development and utilization of the catalyst. At present, the polyisoprene catalyst mainly comprises lithium-based, early transition metal (Sc, Ti, V, Cr, etc.), late transition metal (Fe, Co, Ni, etc.) and rare earth metal (Nd) catalyst. Among them, late transition metal catalysts have become a great research hotspot due to their characteristics of low cost, easy availability, stable properties, etc.
Disclosure of Invention
The invention aims to provide a thiazole imine-cobalt compound and a synthesis method and application thereof.
The invention adopts the following technical scheme to realize the purpose:
a thiazolimine-cobalt compound is characterized in that the structure of the compound is shown as a formula I:
wherein R is1Selected from Me,iPr、F、CHPh2；R2Selected from H, Me and F.
By way of example, the compounds of formula I may be selected from complexes having the following group definitions:
Co1:R1＝iPr,R2＝H；
Co2:R1＝Me,R2＝H；
Co3:R1＝Me,R2＝Me；
Co4:R1＝F,R2＝H；
Co5:R1＝F,R2＝F；
Co6:R1＝CHPh2,R2＝H；
by way of example, the compounds of formula I of the present invention have the structure shown in formula I-1, I-2, I-3, I-4, I-5 or I-6 below:
the present invention also provides a thiazolimine ligand represented by the following formula II:
wherein R is1Selected from Me,iPr、F、CHPh2；R2Selected from H, Me and F.
By way of example, the thiazolimine ligand of the formula II can be selected from complexes having the following group definitions:
L1:R1＝iPr,R2＝H；
L2:R1＝Me,R2＝H；
L3:R1＝Me,R2＝Me；
L4:R1＝F,R2＝H；
L5:R1＝F,R2＝F；
L6:R1＝CHPh2,R2＝H；
as an example, the ligand has a structure represented by the following formula II-1, formula II-2, formula II-3, formula II-4, formula II-5, or formula II-6:
the synthesis method of the thiazole imine-cobalt compound comprises the following steps: reacting 2-acetyl thiazole with an aniline derivative under a certain condition to obtain a corresponding thiazole imine ligand; and reacting the ligand with anhydrous cobalt chloride in tetrahydrofuran to obtain the thiazolylimine-cobalt compound.
The method comprises the following specific steps:
(1) the method comprises the following steps: respectively reacting 2-acetyl thiazole with 2, 6-diisopropylaniline, 2, 6-dimethylaniline and 2,4, 6-trimethylaniline to obtain ligands L1-L3 under the action of formic acid;
the second method comprises the following steps: respectively reacting 2-acetylthiazole with 2, 6-difluoroaniline and 2,4, 6-trifluoroaniline under the action of p-toluenesulfonic acid to obtain ligands L4 and L5;
the third method comprises the following steps: the ligand L6 is obtained by the reaction of 2-acetyl thiazole and 2, 6-benzhydryl-4-methylaniline in sequence under the action of zinc chloride and sodium oxalate.
(2) The prepared ligand reacts with anhydrous cobalt chloride in tetrahydrofuran respectively to prepare a thiazole imine-cobalt compound Co1-Co 6.
Further, the specific synthesis method of the first method in the step (1) is as follows:
carrying out reflux reaction on 2-acetylthiazole and an aniline derivative in methanol for 4-48 h, adding formic acid as a catalyst, concentrating, and purifying to obtain a thiazole imine ligand, wherein the molar ratio of the 2-acetylthiazole to the aniline derivative is 1: 1.
Further, in the first method in the step (1), L1 is recrystallized by methanol at 0-30 ℃; l2, L3 were purified by column chromatography with developing solvent (petroleum ether/dichloromethane) and column wetting with triethylamine.
Further, the specific synthesis method of the second method in the step (1) is as follows:
adding 2-acetylthiazole, an aniline derivative and p-toluenesulfonic acid into anhydrous toluene, refluxing for 12-48 h, removing generated water by using a water separator, concentrating after the reaction is finished, and purifying by column chromatography, wherein the molar ratio of the 2-acetylthiazole to the aniline derivative is 1 (1-3).
Further, in the second method in the step (1), L4 and L5 are purified by column chromatography, a developing agent (petroleum ether/dichloromethane) is used, and triethylamine is used for wetting the column.
Further, the specific synthesis method of the third method in the step (1) is as follows:
adding 2-acetyl thiazole, aniline derivatives and zinc chloride into a flask, refluxing for 1-6 h by using acetic acid as a solvent, filtering, washing and drying; the obtained product is dissolved by dichloromethane, and then reacts with sodium oxalate, liquid separation, drying and concentration are carried out, and then recrystallization is carried out by methanol, so as to obtain ligand L6.
Further, in the third step (1), the washing is sequentially carried out three times by using glacial acetic acid and diethyl ether respectively
Furthermore, in the third method in the step (1), the molar ratio of the 2-acetyl thiazole to the aniline derivative to the zinc chloride to the sodium oxalate is 1:1:1: 2.5.
Further, the specific synthesis method of the compound Co1-Co6 in the step (2) is as follows:
and (2) adding a thiazole imine ligand and anhydrous cobalt chloride into a Schlenk bottle, reacting for 2-24 h in tetrahydrofuran at room temperature, removing part of the solvent, filtering, washing and drying to obtain a compound Co1-Co 6.
Further, the whole process of the step (2) is carried out under argon atmosphere.
Further, the molar ratio of the thiazolimine ligand to the anhydrous cobalt chloride in the step (2) is 1: 1.
Further, the solvent selected in the washing in the step (2) is n-hexane.
The invention has the beneficial effects that: the invention provides a thiazolylimine-cobalt compound and a synthesis method thereof, in the compound, the electronic effect and the space effect of a metal compound can be adjusted by adjusting a substituent on an N-phenyl group, so that the catalytic performance of the compound is adjusted, the prepared thiazolylimine-cobalt compound can be applied to catalyzing the polymerization of isoprene, the catalyst has high activity, and the activity can reach 9.7 multiplied by 10 to the maximum6g·mol-1·h-1。
Drawings
FIG. 1 is an X-ray single crystal diffraction pattern of a thiazoleimine-cobalt compound Co1 obtained in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given the full breadth of the appended claims and any and all insubstantial modifications and variations of those skilled in the art which are intended to be within the scope of the invention as defined by the appended claims.
Example 1
The synthesis method of the thiazolylimine-cobalt compound Co1 in the embodiment is as follows:
(1) adding 2-acetyl thiazole (2.54g,20mmol), 2, 6-diisopropylaniline (3.55g,20mmol) and 50mL of methanol into a round-bottom flask, adding a plurality of drops of formic acid as a catalyst, refluxing for 48h, and continuously stirring; after the reaction was completed, part of the solvent was removed, and then recrystallization was carried out at-30 ℃, filtration was carried out, and the resulting solid was washed with anhydrous methanol cooled in advance and dried to obtain ligand L1. A yellow solid; yield: 51%, 2.91 g;1H NMR(600MHz,CDCl3)δ7.95(d,J＝3.2Hz,1H),7.49(d,J＝3.2Hz,1H),7.18–7.13(m,2H),7.11(dd,J＝8.5,6.7Hz,1H),2.74(hept,J＝6.8Hz,2H),2.23(s,3H),1.15(dd,J＝6.9,3.1Hz,12H)；13C{1H}(151MHz,CDCl3)δ170.25,161.52,144.98,143.82,136.03,124.20,123.19,123.06,28.45,23.09,22.82,17.58。
(2) in a Schlenk bottle, L1(285.6mg,1mmol) and anhydrous cobalt chloride (129.8mg,1mmol) were added followed by 10mL tetrahydrofuran and stirred at room temperature under argon atmosphere for 24 h. After the reaction, the reaction mixture was filtered, and the obtained solid was washed with n-hexane and dried to obtain Co 1. A purple solid; yield: 293.2mg, 70%; elemental analysis: c17H22Cl2CoN2S:C,49.05；H,5.33；N,6.73.Found:C,49.10；H,5.39；N,6.79.
(3) The structure of Co1 was further confirmed by X-ray single crystal diffraction, which is specifically shown in fig. 1.
Example 2
The synthesis method of the thiazolylimine-cobalt compound Co2 in the embodiment is as follows:
(1) the amount of 2-acetylthiazole used in the step (1) of example 1 was replaced with (3.82g,30mmol), 2, 6-diisopropylaniline was replaced with 2, 6-methylaniline (3.64g,30mmol), and the other synthesis methods were the same as in the step (1) of example 1; replacing the purification mode withSilica gel column chromatography, developing solvent (petroleum ether/dichloromethane ═ 100/1), and wetting the column with triethylamine; ligand L2 was obtained. A yellow oily liquid; yield: 4.21g, 61%;1H NMR(600MHz,CDCl3)δ7.94(d,J＝3.2Hz,1H),7.49(d,J＝3.2Hz,1H),7.06(d,J＝7.5Hz,2H),6.95(t,J＝7.5Hz,1H),2.20(s,3H),2.05(s,6H)；13C{1H}(151MHz,CDCl3)δ170.05,161.78,147.26,143.78,127.91,125.71,123.65,123.11,17.91,17.06。
(2) the synthesis of compound Co2 was the same as in step (2) of example 1. A green solid; the yield is 234.3mg and 64 percent; elemental analysis: c13H14Cl2CoN2S:C,43.35；H,3.92；N,7.78.Found:C,43.41；H,3.96；N,7.81.
Example 3
The synthesis method of the thiazolylimine-cobalt compound Co3 in the embodiment is as follows:
(1) the amount of 2-acetylthiazole used in the step (1) of example 1 was replaced with (1.27g,10mmol), 2, 6-diisopropylaniline was replaced with 2,4, 6-trimethylaniline (1.35g,10mmol), and the other synthesis methods were the same as in the step (1) of example 1; replacing the purification mode with silica gel column chromatography, developing with a developing agent (petroleum ether/dichloromethane: 40/1), and wetting the column with triethylamine; ligand L3 was obtained. An orange-yellow solid; yield: 1.56g, 64%;1H NMR(600MHz,CDCl3)δ7.95(d,J＝3.2Hz,1H),7.54(d,J＝3.2Hz,1H),7.11–7.04(m,1H),7.00–6.93(m,2H),2.42(s,3H)；13C{1H}(151MHz,CDCl3)δ170.23,161.94,144.78,143.73,132.89,128.57,125.55,123.00,20.74,17.84,17.00.
(2) the synthesis of compound Co3 was the same as in step (2) of example 1. A dark green solid; yield: 293.1 g; 78 percent; elemental analysis: c14H16Cl2CoN2S:C,44.94；H,4.31；N,7.49.Found:C,44.91；H,4.33；N,7.54.
Example 4
The synthesis method of the thiazolylimine-cobalt compound Co4 in the embodiment is as follows:
(1) in a round bottom flask, 2-acetylthiazole (2.54g,20mmol), 2, 6-difluoroaniline (3.87g,30mmol), and p-toluidine were addedBenzene sulfonic acid (50mg) is refluxed for 48 hours by taking anhydrous toluene as a solvent, and water generated in the reaction process is removed by a water separator; after the reaction was completed, the solvent was removed, and a ligand L4, a developing solvent (petroleum ether/dichloromethane ═ 80/1) was obtained by silica gel column chromatography, and the column was rinsed with triethylamine. A yellow oily liquid; yield: 3.47g, 79%;1H NMR(600MHz,CDCl3)δ7.93(d,J＝3.2Hz,1H),7.47(d,J＝3.2Hz,1H),6.87(s,2H),2.28(s,3H),2.19(s,3H),2.01(s,6H)；19F NMR(565MHz,CDCl3)δ-122.36。
(2) the synthesis of compound Co4 was the same as in step (2) of example 1. A green solid; yield: 280.9mg of the total weight of the powder,
76%; elemental analysis: c11H8Cl2CoF2N2S:C,35.89；H,2.19；N,7.61.Found:C,35.97；H,2.23；N,7.58.
Example 5
The synthesis method of the thiazolylimine-cobalt compound Co5 in the embodiment is as follows:
(1) the amount of 2-acetylthiazole used in the step (1) of example 4 was replaced with (1.27g,10mmol), 2, 6-difluoroaniline was replaced with 2,4, 6-trifluoroaniline (2.20g,15mmol), and the other synthesis methods were the same as in the step (1) of example 1; replacing the purification mode with silica gel column chromatography, developing with a developing agent (petroleum ether/dichloromethane: 100/1), and wetting the column with triethylamine; ligand L5 was obtained. A light yellow solid; yield: 1.56g, 61%;1H NMR(600MHz,CDCl3)δ7.96(d,J＝3.2Hz,1H),7.54(d,J＝3.2Hz,1H),6.77(t,J＝8.2Hz,2H),2.42(s,3H)；19F NMR(565MHz,CDCl3)δ-113.84,-118.98,-118.99.
(2) the synthesis of compound Co5 was the same as in step (2) of example 1. Green solid, yield 303.2mg, 79%; elemental analysis: c11H7Cl2CoF3N2S:C,34.22；H,1.83；N,7.26.Found:C,34.29；H,1.87；N,7.22.
Example 6
The synthesis method of the thiazolylimine-cobalt compound Co6 in the embodiment is as follows:
(1) in a round-bottomed flask, 2-acetylthiazole (1.27g,10mmol), 2, 6-benzhydryl-4-Methylaniline (4.40g,10mmol) and zinc chloride (1.36g,10mmol), then adding 40mL glacial acetic acid, refluxing for 4h while stirring continuously, cooling the reaction to room temperature, filtering, washing the obtained solid with acetic acid and diethyl ether respectively for three times in sequence, and drying; placing the obtained product in a flask, adding dichloromethane to dissolve the product, adding sodium oxalate (3.36g,25mmol) and 50mL of water, stirring vigorously for 2h, separating, drying, concentrating, adding anhydrous methanol, standing and crystallizing to obtain ligand L6. A yellow solid; yield: 4.23g, 77%;1H NMR(600MHz,CDCl3)δ7.22(d,J＝7.6Hz,4H),7.14(ddd,J＝10.8,9.5,5.8Hz,8H),7.03(dd,J＝14.4,7.3Hz,8H),6.69(s,2H),5.27(s,2H),2.17(s,3H),0.90(s,3H)；13C{1H}(151MHz,CDCl3)δ169.65,164.50,144.59,143.72,143.57,142.32,132.60,132.25,129.78,129.53,129.47,128.60,128.46,128.36,128.02,126.29,126.04,122.78,52.12,21.33,16.91。
(2) the synthesis of compound Co6 was the same as in step (2) of example 1. Yellow-green solid, yield 303.2mg, 79%; elemental analysis C38H32Cl2CoN2S:C,67.26；H,4.75；N,4.13.Found:C,67.23；H,4.71；N,4.19.
Example 7
The compound Co1 and diethylaluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) in a glovebox, Co1(3.4mg, 8. mu. mmol), 5mL toluene, 2.4mmol AlEt were added to a Schlenk flask in that order2Cl and 2mL of isoprene, in which case Al/Co ═ 300/1, were reacted at room temperature for 2 h; dripping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing the polymer precipitate for several times by using ethanol, drying the polymer precipitate to constant weight, and weighing the polymer precipitate.
Polymerization Activity: 8.5X 104g·mol-1·h-1The molecular weight of the polymer: m is a group ofn＝3.9×104g·mol-1，PDI＝2.5。
(2) The procedure was as in (1), except that 800. mu. mol of AlEt was added2Cl, when Al/Co is 100, polymerization activity: 8.5X 104g·mol-1·h-1The molecular weight of the polymer: mn＝4.1×104g·mol-1，PDI＝3.2。
(3) The procedure was as in (1), except that 400. mu. mol of AlEt was added2Cl, when Al/Co is 50, polymerization activity: 8.4X 104g·mol-1·h-1The molecular weight of the polymer: mn＝4.6×104g·mol-1，PDI＝2.9。
(4) The procedure was as in (1) except that 80. mu. mol of AlEt was added2Cl, when Al/Co is 10, polymerization activity: 7.8X 104g·mol-1·h-1Molecular weight of the polymer: mn＝9.1×104g·mol-1，PDI＝1.8。
(5) The procedure was as in (1), except that 40. mu. mol of AlEt was added2Cl, when Al/Co ═ 5, polymerization activity: 5.7X 104g·mol-1·h-1Molecular weight of the polymer: mn＝1.0×104g·mol-1，PDI＝3.1。
By reacting with AlEt2The amount of Cl was screened to determine the optimum amount of promoter for Co1, Al/Co 100, which gave the highest activity of 8.5X 104g·mol-1·h-1。
In examples 8-13, Co1 was replaced with a different catalyst and Al/Co was 100, and the polymerization results are shown in the following table.
Example 13
The compound Co1 and diethylaluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) in a glovebox, Co1(3.4mg, 8. mu. mol), 5mL toluene, 2.4mmol AlEt were added to a Schlenk flask in that order2Cl and 2mL of isoprene, with Al/Co being 100/1, at room temperature, reacted for 1 h; dripping hydrochloric acid acidified ethanol solution into the reaction system to quench the reaction to obtain polymer precipitate, washing with ethanol for several times, and oven dryingAnd weighing until the weight is constant.
Polymerization Activity: 1.7X 105g·mol-1·h-1The molecular weight of the polymer: mn＝3.9×104g·mol-1，PDI＝3.1。
(2) The operation steps are the same as (1), and the difference is that: reaction time 30min, polymerization activity: 3.4X 105g·mol-1·h-1The molecular weight of the polymer: mn＝2.3×104g·mol-1，PDI＝3.8。
(3) The operation steps are the same as (1), and the difference is that: reaction time 10min, polymerization activity: 9.7X 105g·mol-1·h-1The molecular weight of the polymer: mn＝3.6×104g·mol-1，PDI＝3.6。
By screening the polymerization time, it was confirmed that when Co1 was used as the catalyst, the optimum reaction time was 10 minutes, at which time the activity was 9.7X 105g·mol-1·h-1The molecular weight of the polymer: mn＝3.6×104g·mol-1And PDI is 3.6. The catalytic activity of the catalyst is equivalent to that of a bidentate cobalt catalyst with a similar structure.
Example 14
The compound Co1 and diethylaluminum chloride are used for catalyzing isoprene polymerization, and the specific steps are as follows:
(1) in a glovebox, Co1(3.4mg, 8. mu. mol), 5mL toluene, 2.4mmol AlEt were added to a Schlenk flask in that order2Cl and 2mL of isoprene, wherein Al/Co is 100/1, the polymerization temperature is room temperature, and the reaction is carried out for 30 min; dripping ethanol solution acidified by hydrochloric acid into the reaction system to quench the reaction to obtain polymer precipitate, washing the polymer precipitate for several times by using ethanol, drying the polymer precipitate to constant weight, and weighing the polymer precipitate.
Polymerization Activity: 3.4X 104g·mol-1·h-1The molecular weight of the polymer: mn＝2.3×104g·mol-1，PDI＝3.8。
(2) The operation steps are the same as (1), and the difference is that: polymerization temperature 50 ℃ polymerization Activity: 3.3X 105g·mol-1·h-1The molecular weight of the polymer: mn＝1.5×104g·mol-1，PDI＝3.9。
(3) The operation steps are the same as (1), and the difference is that: polymerization temperature 70, polymerization activity c: 9.3X 104g·mol-1·h-1The molecular weight of the polymer: mn＝7.2×103g·mol-1，PDI＝5.1。
The optimum reaction temperature was determined to be room temperature by screening the temperature.
In examples 15-19, Co1 was replaced with a different catalyst for 30 minutes at room temperature, and the polymerization results are summarized in the following table.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A thiazolimine-cobalt compound is characterized in that the structure of the compound is shown as a formula I:
wherein R is1Selected from Me, i Pr、F、CHPh2；R2Selected from H, Me and F.
2. A process for the synthesis of a thiazolimine-cobalt compound according to claim 1, comprising the steps of:
(1) reacting 2-acetyl thiazole with an aniline derivative under a certain condition to obtain a thiazole imine ligand;
(2) and reacting the thiazolimine ligand with anhydrous cobalt chloride in tetrahydrofuran in an argon atmosphere to obtain the thiazolimine-cobalt catalyst.
3. The method of synthesizing a thiazolimine-cobalt compound according to claim 2, characterized in that: the preparation method of the thiazolimine ligand in the step (1) comprises the following steps: formic acid is used as a catalyst, 2-acetyl thiazole and aniline derivatives are refluxed in methanol for 48 hours according to the molar ratio of 1:1, a solvent is removed, and the thiazole imine ligand is obtained by column chromatography purification, wherein the aniline derivatives are 2, 6-diisopropyl aniline, 2, 6-dimethyl aniline or 2,4, 6-trimethyl aniline.
4. The method of synthesizing a thiazolimine-cobalt compound according to claim 2, characterized in that: the preparation method of the thiazolimine ligand in the step (1) comprises the following steps: adding 2-acetyl thiazole and an aniline derivative into anhydrous toluene according to the molar ratio of 1 (1-3), taking 1 mol% of p-toluenesulfonic acid as a catalyst, removing water generated in the reaction by using a water separator, refluxing for 12-48 h, removing a solvent, and purifying or recrystallizing by using column chromatography to obtain a thiazolimine ligand; wherein the aniline derivative is 2, 6-difluoroaniline or 2,4, 6-trifluoroaniline.
5. The method of synthesizing a thiazolimine-cobalt compound according to claim 2, characterized in that: the preparation method of the thiazolimine ligand in the step (1) comprises the following steps: adding 2-acetyl thiazole, aniline derivatives and zinc chloride into glacial acetic acid according to a certain proportion, and refluxing for 1-6 h; cooling to room temperature, filtering, washing with acetic acid for 3 times, washing with diethyl ether for 3 times, and drying; dissolving the obtained solid with dichloromethane, adding an aqueous solution of sodium oxalate, adding 1.5-3 times of sodium oxalate, vigorously stirring for 0.5-3 h, separating, drying, removing the solvent, and recrystallizing with methanol to obtain the thiazolimine ligand, wherein the aniline derivative is 2, 6-benzhydryl-4-methylaniline, and the molar ratio of 2-acetylthiazole, the aniline derivative, zinc chloride and sodium oxalate is 1:1:1: 2.5.
6. The method of synthesizing a thiazolimine-cobalt compound according to claim 2, characterized in that: in the step (2), the molar ratio of the thiazolimine ligand to the anhydrous cobalt chloride is 1:1, and the reaction condition is that the mixture is stirred at room temperature for 2-24 hours.
7. A catalytic system characterized by: the catalytic system comprises a main catalyst and a cocatalyst; wherein the main catalyst is the thiazolimine-cobalt compound according to claim 1.
8. The catalytic system according to claim 7, characterized in that: the cocatalyst is diethylaluminum chloride.
9. The catalytic system of claim 7, wherein the molar ratio of the metal Al in the cocatalyst to the central metal Co in the main catalyst is (5-500): 1.
10. A method for catalytically synthesizing polyisoprene, wherein the method is to catalyze isoprene to polymerize by using the catalytic system of any one of claims 7-9.
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