CN111825726A - Benzimidazole catalyst and preparation method thereof - Google Patents
Benzimidazole catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 34
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 23
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- -1 benzimidazole compound Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 150000002815 nickel Chemical group 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 150000001925 cycloalkenes Chemical class 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000005311 nuclear magnetism Effects 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- UGOXYXBNKXBHAB-UHFFFAOYSA-N 1-oxo-3,4-dihydro-2h-naphthalene-2-carbaldehyde Chemical compound C1=CC=C2C(=O)C(C=O)CCC2=C1 UGOXYXBNKXBHAB-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ODGIMMLDVSWADK-UHFFFAOYSA-N 4-trifluoromethylaniline Chemical compound NC1=CC=C(C(F)(F)F)C=C1 ODGIMMLDVSWADK-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
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 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
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/06—Benzimidazoles; Hydrogenated benzimidazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D235/14—Radicals substituted by nitrogen atoms
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/70—Iron group metals, platinum group metals or compounds thereof
- C08F4/7001—Iron group metals, platinum group metals or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/7003—Bidentate ligand
- C08F4/7004—Neutral ligand
- C08F4/7006—NN
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Plural Heterocyclic Compounds (AREA)
Abstract
The structural formula of the benzimidazole catalyst is shown as the formula I:
reacting compound D with [ R ]4NiCl(PPh3)2]Or is [ R4PdCl(PPh3)2]Dissolving in anhydrous tetrahydrofuran, reacting at 30-50 deg.C for 5-10h, and post-treating to obtain benzimidazole catalyst (formula I). The catalyst of the invention isCan still catalyze olefin polymerization at high temperature (120 ℃) and has good activity.
Description
Technical Field
The invention belongs to the field of polymerization of cycloolefins, and particularly relates to a benzimidazole catalyst and a preparation method thereof.
Background
Cycloolefin copolymers (cyclic-olefin copolymers) are high value-added thermoplastic engineering plastics prepared by copolymerizing a cycloolefin monomer and alpha-olefin [ ethylene, E, propylene, P ], and the like. The cycloolefin copolymer is usually prepared by addition polymerization and copolymerization of cycloolefin and alpha-olefin. Compared with the traditional polyolefin, the main chain is introduced with a ring structure, so that the transparency, heat resistance, chemical stability, dielectric property, melt fluidity, thermal insulation and the like of the polyolefin can be effectively improved, and the polyolefin has potential application prospects in the fields of optical devices, automobiles, packaging, electronic appliances and the like.
The most common cyclic olefin coThe copolymer is an ethylene/norbornene copolymer, and the cycloolefin material has many excellent properties but has some defects. For cyclic olefin copolymers, the glass transition temperature (T) of the polymer material increases with the insertion rate of the cyclic olefin monomerg) Exhibit an increasing tendency, and a high comonomer insertion rate often leads to a decrease in the toughness of the material, which has limited the use of ethylene/norbornene copolymers. It was found that when the insertion rate of norbornene is higher than 54 mol%, the glass transition temperature of the ethylene/norbornene copolymer can reach 150 ℃ which is comparable to the T of PCgThe values are similar, however, the norbornene content in the polymer is too high, the brittleness of the polymer material is large, and the toughness is obviously reduced. Therefore, efforts are being made to synthesize novel cycloolefin copolymers, and it is desired that toughness and glass transition temperature of the material can be improved at the same time. The glass transition temperature is an important indicator of the heat resistance of a material and is an important parameter for whether a polymeric material can maintain dimensional stability at high temperatures. The introduction of the bulky steric monomers into the cycloolefin polymer is an important method for improving the glass transition temperature of the cycloolefin polymer, and the introduction of the bulky steric monomers enables the polymer material to have higher glass transition temperature under relatively lower insertion rate of the cycloolefin monomers, and at the moment, the polymer chain also has more ethylene chain segments, the molecular chain is more flexible, the chain entanglement density is larger, so the toughness of the material is also improved. The molecular chain of the vinyl addition polymer taking the norbornene and the derivative thereof as raw materials does not contain C ═ C double bonds, so that the chemical property is more stable, and the application property is better. At present, in the binary and ternary polymerization research of norbornene and alpha-olefin, by introducing monomers with different performances, the method not only effectively improves the high brittleness and the glass transition temperature (T) of polynorborneneg) High solubility and the like, and can synthesize functional COCs with excellent physical and mechanical properties according to the types of comonomers and different structures of polymers. With the demand of people on the application of cycloolefin materials, novel catalysts for catalyzing and synthesizing functional cycloolefin materials are continuously developed, and are well used for catalyzing the copolymerization of norbornene, ethylene and propylene, but in the preparation of norbornene/high-grade norborneneThe alpha-olefin copolymer aspect is still relatively limited. Compared with the former transition metal catalyst, the latter transition metal catalyst has become a research hotspot in the field of olefin polymerization catalysts due to the advantages of simple synthesis, good stability, weak oxophilicity, strong tolerance to heteroatoms and the like, and the nickel catalyst is cheaper and easily available than the palladium catalyst, has good industrial application prospect and has unique performance in the aspect of catalytically synthesizing cycloolefin copolymers. However, since the nickel complex is easy to deactivate or even inactivate at high temperature (above 60 ℃) in the process of catalyzing olefin polymerization, and the high temperature resistance is generally poor, the ligand steric hindrance and the electronic effect need to be further designed to synthesize the nickel catalyst with high catalytic activity and good thermal stability, and effectively catalyze the copolymerization of norbornene and high-grade alpha-olefin.
Disclosure of Invention
In view of the above technical problems, the present invention aims to provide a benzimidazole catalyst with a completely new structure. In order to achieve the purpose, the invention adopts the following technical scheme, wherein the benzimidazole catalyst has the following structural formula:
wherein formula R1，R4Is C1-C6Alkyl, phenyl or substituted phenyl, wherein the substituents on the phenyl ring are C1-C6Alkyl, halo C1-C6Alkyl, CN, NO2、COOH，R2，R3Is selected from H, C1-C6Alkyl, halo C1-C6Alkyl, OH, CN, NO2COOH, M is a nickel atom or a palladium atom.
The invention also provides an intermediate for preparing the compound of the formula I, which has the structure
Wherein R is1-R3Is as defined in claim 1.
The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:
step 1, sequentially adding a compound A, a compound, potassium peroxymonosulfonate and a solvent into a reactor, wherein the molar ratio of the compound A to the compound B to the potassium peroxymonosulfonate is 1 (1-3) to (1-3), and further preferably 1 (1-1.5) to (1-2), the solvent is selected from acetonitrile, DMF, DMSO and toluene, further preferably toluene and DMF, the mass-to-volume ratio of the compound A to the solvent is 40mL/g-80mL/g, further preferably 40mL/g-50mL/g, the reaction temperature is 120-150 ℃, the reaction time is 3-5 hours, and the compound C can be obtained by adopting the conventional aftertreatment in the field;
step 2-in the reactor, adding anhydrous tetrahydrofuran, and reacting the compound C with the compound R1NH2Adding anhydrous magnesium sulfate in titanium tetrachloride as catalyst, reacting at 40-70 deg.C for 2-3 hr, and performing conventional post-treatment in the field to obtain compound D, wherein compound C and R1NH2The molar ratio of the raw materials is 1: (1-5), and more preferably 1: (1-2), wherein titanium tetrachloride accounts for 1-5% of the weight ratio of the compound C, anhydrous magnesium sulfate accounts for 50-80% of the weight ratio of the compound C, and the mass-volume ratio of the compound C to anhydrous tetrahydrofuran is 20-25 mL/g;
step 3-reaction of Compound D with [ R ]4NiCl(PPh3)2]Or is [ R4PdCl(PPh3)2]Dissolving in solvent, reacting at 30-50 deg.C for 5-10h, and performing conventional post-treatment in the art to obtain compound of formula I, wherein the solvent is selected from acetonitrile, anhydrous tetrahydrofuran, dichloromethane, dichloroethane, and further selected from acetonitrile, anhydrous tetrahydrofuran, dichloromethane, compound D and [ R ]4NiCl(PPh3)2]Or is [ R4PdCl(PPh3)2]In a molar ratio of 1: (1-5), and more preferably 1: (1-2), wherein the mass-volume ratio of the compound D to the solvent is 15mL/g-40mL/g, more preferably 15mL/g-20mL/g, and the benzimidazole catalyst (formula I) is obtained by post-treatment, and the structural formula of the compound A-the compound D is shown in the specification, wherein R is1-R4As defined in claim 1:
the invention also relates toProvides an application of norbornene and terminal linear olefin copolymerization, which comprises the following steps: under the protection of inert gas, toluene solution is added in turn, and cocatalyst ethyl aluminum dichloride (EtAlCl) is added in turn at 80-120 DEG C2) The toluene solution and the norbornene/1-hexene mixed solution with different proportions are quickly added into the toluene solution containing the benzimidazole catalyst (the compound shown in the formula I) by an injector under the stirring speed of 300r/min for reaction for 1-3h, the reaction is stopped by acidified ethanol solution (the volume ratio of ethanol to hydrochloric acid is 90:10), the mixture is fully stirred and filtered, and the mixture is washed by ethanol for 3 times and then is dried in a vacuum oven to constant weight.
Wherein the norbornene/1-hexene mixed solution with different proportions is prepared from norbornene and 1-hexene according to the mass ratio of 1 (0.2-0.6), the molar ratio of the benzimidazole catalyst to the norbornene is (0.3% -0.7%): 1, and the cocatalyst EtAlCl is2The mass ratio of the benzimidazole catalyst to the benzimidazole catalyst is (5-15): 1.
the invention has the following beneficial effects:
1. the benzimidazole catalyst (compound shown in the formula I) of the invention obviously improves the stability of the nickel complex by introducing imidazole groups and imine groups.
2. The benzimidazole catalyst has larger steric hindrance effect, can effectively promote the copolymerization of norbornene and 1-hexene, and realizes the toughness increase of the cycloolefin copolymer without changing the glass transition temperature (T) of the cycloolefin copolymergValue).
Drawings
Fig. 1 is a schematic diagram of the crystal structure of example 1.
Detailed Description
The present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
EXAMPLE 1 preparation of Compounds of formula I
Step 1-o-phenylenediamine (0.216g, 2mmol), 1-oxo-3, 4-dihydro-2H-naphthalene-2-carbaldehyde (0.383g, 2.2mmol) and potassium peroxymonosulfonate (2.459g,4mmol) are added into a reactor, 9mL DMF is added to be stirred and dissolved, the reaction is carried out for 5 hours at 120 ℃, 0.01mol/L sodium sulfite solution is added to quench the oxidant after the reaction is finished, the oxidant is diluted by 50mL water and extracted by dichloromethane, and then the compound C with the yield of 85 percent is obtained by column chromatography, and the structure of the compound C is confirmed by nuclear magnetism.1H NMR(400MHz,CDCl3)7.63–7.54(m,3H),7.34(s,1H),7.25(d,J＝9.1Hz,2H),7.21–7.16(m,2H),6.95(s,1H),4.18(s,1H),2.94(d,J＝1.6Hz,2H),2.54(s,1H),2.39(s,1H).13CNMR(100MHz,CDCl3)200.9,150.3,141.6,137.9,135.7,134.6,129.0,127.3,122.8,122.4,118.3,114.8,45.7,28.1,22.9.
Step 2-0.446 g of Compound C and 0.158g of aniline were added to a reactor, and 0.01g of titanium tetrachloride, 0.246g of anhydrous magnesium sulfate and 9mL of anhydrous tetrahydrofuran were added, reacted at 40 ℃ for 3 hours, spin-dried, and subjected to column chromatography to give 0.544g of intermediate Compound D, which was 95% in yield and was confirmed to be Compound D by nuclear magnetism.1H NMR(400MHz,CDCl3)7.68–7.52(m,2H),7.28(m,8H),7.17(s,1H),7.06(d,J＝17.0Hz,2H),4.47(s,1H),2.95(d,J＝1.6Hz,2H),2.63(s,1H),2.30(s,1H).13C NMR(100MHz,CDCl3)166.7,150.1,149.9,138.0,138.0,137.9,132.4,131.6,129.1,129.1,129.0,128.1,128.1,125.6,122.8,122.4,121.8,121.8,118.3,114.8,42.3,28.1,25.2；[M+H]：338.4261.
Step 3-0.544 g of Compound D with 0.211g CH3NiCl(PPh3)2Dissolving in 8.5mL of anhydrous tetrahydrofuran, reacting for 5h at 50 ℃, cooling and crystallizing to obtain 0.435g of benzimidazole catalyst, and determining the structure by XPRD single crystal diffraction.
The use of the compound of formula I as shown in example 1 for the copolymerization of norbornene with terminal linear olefins comprises the following steps:
0.435g of the compound of the formula I shown in example 1 is introduced into a round-bottomed flask and dissolved in 3mL of toluene until use, under an inert gas blanketAdding 50mL of toluene solution, and sequentially adding 1mol/L of cocatalyst EtAlCl at 120 DEG C26.8mL of a toluene solution and 21.4g of a mixed solution of norbornene and 1-hexene in a mass ratio of 1:0.2 were quickly added by syringe to the toluene solution containing the benzimidazole catalyst while stirring at a rate of 300 r/min. After reacting for a period of time, dropwise adding an acidified ethanol solution (ethanol/hydrochloric acid volume ratio is 90:10) to terminate the reaction, fully stirring, filtering, washing with ethanol for 3 times, and drying in a vacuum oven to constant weight.
EXAMPLE 2 preparation of Compound of formula 2
Step 1-3, 4-diaminotoluene (0.244g,2mmol), 1-oxo-3, 4-dihydro-2H-naphthalene-2-carbaldehyde (0.418g, 2.4mmol) and potassium peroxymonosulfonate (2.459g,4mmol) were added to a reactor, 11mL of dmf was added and stirred to dissolve, reaction was carried out at 150 ℃ for 3 hours, 0.01mol/L of sodium sulfite solution was added to quench the oxidant after the reaction was completed, and after dilution with 50mL of water, extraction was carried out with dichloromethane, and then column chromatography was carried out to obtain 0.492g of compound C, the yield was 89%, and the structure of compound C was confirmed by nuclear magnetism.1HNMR(400MHz,CDCl3)7.64-7.47(m,3H),7.34(s,1H),7.22-7.14(m,2H),7.11(s,1H),6.92(s,1H),4.18(s,1H),2.94(d,J＝1.6Hz,2H),2.54(s,1H),2.44-2.31(m,4H).13CNMR(100MHz,CDCl3)200.9,150.3,141.6,137.1,135.8,135.7,134.6,132.7,129.0,129.0,127.3,123.7,117.5,113.8,45.7,28.1,22.9,21.2.
Step 2-0.492 g of Compound C and 0.191g of p-toluidine were charged into a reactor, and 0.01g of titanium tetrachloride, 0.257g of anhydrous magnesium sulfate and 12mL of anhydrous tetrahydrofuran were added, reacted at 40 ℃ for 2 hours, spin-dried, and subjected to column chromatography to obtain 0.625g of intermediate Compound D, which was 96% in yield and was confirmed to be Compound D by nuclear magnetism.1HNMR(400MHz,CDCl3)7.59(d,J＝9.0Hz,2H),7.31(d,J＝0.9Hz,2H),7.26-7.17(m,3H),7.16-7.10(m,3H),7.02(s,1H),6.94(s,1H),4.52(s,1H),3.00(d,J＝1.6Hz,2H),2.61(s,2H),2.46-2.38(m,3H),2.37-2.27(m,3H).13C NMR(100MHz,CDCl3)166.7,150.1,149.5,138.0,137.1,135.8,134.8,132.7,132.4,131.6,130.2,130.2,129.0,128.1,128.1,123.9,123.9,123.7,117.5,113.8,42.3,28.1,25.2,21.2,21.1.
Step 3-0.625 g of Compound D with 0.194g CH3NiCl(PPh3)2Dissolving in 12mL of anhydrous tetrahydrofuran, reacting at 30 ℃ for 10h, cooling and crystallizing to obtain 0.482g of benzimidazole catalyst.
EXAMPLE 3 preparation of the Compound of formula 3
Step 1-3, 4-diaminotoluene (0.244g,2mmol), 1-oxo-3, 4-dihydro-2H-naphthalene-2-carbaldehyde (0.453g,2.6mmol), potassium peroxymonosulfonate (2.459g,4mmol) were added to a reactor, 10mL of dmf was added and stirred to dissolve, reaction was carried out at 130 ℃ for 4 hours, 0.01mol/L of sodium sulfite solution was added to quench the oxidizing agent after the reaction was completed, and after dilution with 50mL of water, extraction was carried out with dichloromethane, after which column chromatography was carried out to obtain 0.492g of compound C, yield was 89%, the structure of compound C was confirmed by nuclear magnetism, 1H NMR (400MHz, CDCl3)7.64-7.47(m,3H),7.34(s,1H),7.22-7.14(m,2H),7.11(s,1H),6.92(s,1H),4.18(s,1H),2.94(d, J ═ 1.6Hz,2H) 2.54(s,1H),2.44-2.31(m,4H).13C NMR (100MHz, CDCl3)200.9,150.3,141.6,137.1,135.8,135.7,134.6,132.7,129.0,129.0,127.3,123.7,117.5,113.8,45.7,28.1,22.9,21.2.
Step 2-0.492 g of Compound C and 0.287g of p-trifluoromethylaniline were charged into a reactor, and 0.01g of titanium tetrachloride, 0.257g of anhydrous magnesium sulfate and 25mL of anhydrous tetrahydrofuran were added, reacted at 40 ℃ for 2 hours, dried by spinning, and subjected to column chromatography to obtain 0.694g of intermediate Compound D, which was 93% in yield and confirmed to be Compound D by nuclear magnetism. 1H NMR (400MHz, CDCl3)7.57-7.50(m,5H),7.37-7.26(m,3H),7.19(s,1H),7.11(d, J ═ 1.7Hz,2H),7.05(s,1H),4.38(s,1H),2.98(d, J ═ 1.6Hz,2H),2.71(s,1H),2.40(s,3H),2.32(s,1H).13C NMR (100MHz, CDCl3)166.7,155.4,150.1,138.0,137.1,135.8,132.7,132.4,131.6,129.0,128.1,128.1,127.3,126.9,126.9,124.5,123.7,122.4,117.5,113.8,42.3,28.1,25.2,21.2.
Step 3-converting 0.694g intoCompound D with 0.155g CH3NiCl(PPh3)2Dissolving in 9mL of anhydrous tetrahydrofuran, reacting at 50 ℃ for 8h, and cooling and crystallizing to obtain 0.461g of benzimidazole catalyst.
EXAMPLE 4 preparation of the Compound of formula 4
Step 1-o-phenylenediamine (0.216g, 2mmol), 1-oxo-3, 4-dihydro-2H-naphthalene-2-carbaldehyde (0.383g, 2.2mmol) and potassium peroxymonosulfonate (2.459g,4mmol) are added into a reactor, 9mL DMF is added to be stirred and dissolved, the reaction is carried out for 5 hours at 120 ℃, 0.01mol/L sodium sulfite solution is added to quench the oxidant after the reaction is finished, the oxidant is diluted by 50mL water and extracted by dichloromethane, and then the compound C with the yield of 85 percent is obtained by column chromatography, and the structure of the compound C is confirmed by nuclear magnetism.1H NMR(400MHz,CDCl3)7.63–7.54(m,3H),7.34(s,1H),7.25(d,J＝9.1Hz,2H),7.21–7.16(m,2H),6.95(s,1H),4.18(s,1H),2.94(d,J＝1.6Hz,2H),2.54(s,1H),2.39(s,1H).13CNMR(100MHz,CDCl3)200.9,150.3,141.6,137.9,135.7,134.6,129.0,127.3,122.8,122.4,118.3,114.8,45.7,28.1,22.9.
Step 2-adding 0.446g of Compound C and 0.158g of aniline to a reactor, and adding 0.01g of titanium tetrachloride, 0.246g of anhydrous magnesium sulfate and 9mL of anhydrous tetrahydrofuran, reacting at 40 ℃ for 3 hours, spin-drying the solvent, and then performing column chromatography to obtain 0.544g of intermediate Compound D, the yield of which is 95%, which was confirmed to be Compound D by nuclear magnetism.1H NMR(400MHz,CDCl3)7.68–7.52(m,2H),7.28(m,8H),7.17(s,1H),7.06(d,J＝17.0Hz,2H),4.47(s,1H),2.95(d,J＝1.6Hz,2H),2.63(s,1H),2.30(s,1H).13C NMR(100MHz,CDCl3)166.7,150.1,149.9,138.0,138.0,137.9,132.4,131.6,129.1,129.1,129.0,128.1,128.1,125.6,122.8,122.4,121.8,121.8,118.3,114.8,42.3,28.1,25.2。
Step 3-0.544 g of Compound D is reacted with 0.211gCH3PdCl(PPh3)2Dissolving in 8.5mL of anhydrous tetrahydrofuran, reacting at 50 deg.C for 5h, cooling, crystallizing0.398g of benzimidazole catalyst was obtained.
Claims (7)
1. A benzimidazole catalyst is characterized in that the structural formula of the catalyst is shown as a formula I:
wherein R is1，R4Is C1-C6Alkyl, phenyl or substituted phenyl, wherein the substituents on the phenyl ring are C1-C6Alkyl, halo C1-C6Alkyl, CN, NO2，COOH，R2，R3Is selected from H, C1-C6Alkyl, halo C1-C6Alkyl, OH, CN, NO2COOH, M is a nickel atom or a palladium atom.
2. A benzimidazole compound has the structure
Wherein R is1-R3Is as defined in claim 1.
3. The process for preparing a benzimidazole catalyst according to claim 1,
step 1, adding a compound A, a compound B and potassium peroxymonosulfonate into a reactor, reacting for 3-5 hours at the temperature of 120-150 ℃ by taking DMF as a solvent, and carrying out post-treatment to obtain a compound C;
step 2-in the reactor, adding anhydrous tetrahydrofuran, and reacting the compound C with the compound R1NH2Adding anhydrous magnesium sulfate in the presence of titanium tetrachloride as a catalyst, reacting at 40-70 ℃ for 2-3 hours, and carrying out post-treatment to obtain a compound D;
step 3-reaction of Compound D with [ R ]4NiCl(PPh3)2]Or is [ R4PdCl(PPh3)2]Dissolving in anhydrous tetrahydrofuran, reacting at 30-50 deg.C for 5-10 hr, and filteringAfter post-treatment, the benzimidazole catalyst (formula I) is obtained
Wherein R is1-R4Is as defined in claim 1.
4. A method for preparing a benzimidazole catalyst according to claim 3, wherein the method comprises the following steps: in the step 1), the molar ratio of the compound A to the compound B to the potassium peroxymonosulfonate is 1 (1-1.5) to 1-2, wherein the mass-volume ratio of the compound A to the DMF is 40mL/g-50 mL/g.
5. A method for preparing a benzimidazole catalyst according to claim 3, wherein the method comprises the following steps: the compounds C and R in the step (2)1NH2The molar ratio of the raw materials is 1: (1-5), the using amount of titanium tetrachloride is 1-5% of the weight ratio of the compound C, the using amount of anhydrous magnesium sulfate is 50-80% of the weight ratio of the compound C, and the mass volume ratio of the compound C to anhydrous tetrahydrofuran is 20-25 mL/g.
6. A method for preparing a benzimidazole catalyst according to claim 3, wherein the method comprises the following steps: the compounds D and [ R ] in the step (3)4NiCl(PPh3)2]Or is [ R4PdCl(PPh3)2]In a molar ratio of 1: (1-5), wherein the mass-to-volume ratio of the compound D to the anhydrous tetrahydrofuran is 15mL/g-20 mL/g.
7. Use of the benzimidazole catalyst of claim 1 in the copolymerization of norbornene with terminal linear olefins.
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