CN114989216B - Nickel phosphine sulfonate compound with strong electron donating property and application thereof - Google Patents
Nickel phosphine sulfonate compound with strong electron donating property and application thereof Download PDFInfo
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- CN114989216B CN114989216B CN202210782667.6A CN202210782667A CN114989216B CN 114989216 B CN114989216 B CN 114989216B CN 202210782667 A CN202210782667 A CN 202210782667A CN 114989216 B CN114989216 B CN 114989216B
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- -1 Nickel phosphine sulfonate compound Chemical class 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 9
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 9
- 238000007334 copolymerization reaction Methods 0.000 claims description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 9
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract description 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 8
- 125000001424 substituent group Chemical group 0.000 abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 4
- 230000037048 polymerization activity Effects 0.000 abstract description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical compound P.[Ni] VOKXPKSMYJLAIW-UHFFFAOYSA-N 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- ZZXDRXVIRVJQBT-UHFFFAOYSA-N 2,3-dimethylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1C ZZXDRXVIRVJQBT-UHFFFAOYSA-N 0.000 description 1
- DRWRVXAXXGJZIO-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl acetate Chemical compound C1C2C(OC(=O)C)CC1C=C2 DRWRVXAXXGJZIO-UHFFFAOYSA-N 0.000 description 1
- LUMNWCHHXDUKFI-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1C2C(CO)CC1C=C2 LUMNWCHHXDUKFI-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical compound P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NMJASRUOIRRDSX-UHFFFAOYSA-N tert-butyl(dichloro)phosphane Chemical compound CC(C)(C)P(Cl)Cl NMJASRUOIRRDSX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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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
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two 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
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
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- Life Sciences & Earth Sciences (AREA)
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- General Health & Medical Sciences (AREA)
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Abstract
The invention discloses a strong electron donating nickel phosphine sulfonate compound and application thereof, wherein the structure of the strong electron donating nickel phosphine sulfonate compound is shown as the following formula (V): Wherein R 1 is selected from one of H, N, N-dialkyl, C1-C6 alkyl and C1-C6 alkoxy; r 2 is independently substituted tert-butyl on the phosphine skeleton; r 3 is selected from one or more of substituted H, isopropyl, C1-C6 alkyl and C1-C6 alkoxy. The co-electron effect of a specific R 1 group in the compound affects the polymerization activity, and simultaneously, the tertiary butyl group substituted by the substituent and the strong electron effect of the R 3 substituent are combined with different substituents on the phosphine skeleton to jointly show different effects on polymerization. Thus, the polyolefin catalyst prepared by the invention has strong electron donating property and high stability.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a strong electron donating nickel phosphine sulfonate compound and application thereof.
Background
In recent years, from the development of imide nickel catalytic systems, phosphine-containing coordinated nickel catalytic systems have also been rapidly developed, which is another important class of branches. Such systems differ greatly from imine systems in the polymerization mechanism. The first example of palladium phosphine sulfonate drop catalyst in 2001 can catalyze the copolymerization of ethylene with carbon monoxide or methyl acrylate, and its discovery opens the door for scientists to enter into the study of phosphine-containing catalytic systems.
With the discovery of the drug catalyst, the task group of Nozaki, scott, mecking, jordan and the like has opened up the study of nickel phosphine sulfonate to catalyze ethylene homopolymerization. Due to the faster chain transfer rate, classical nickel phosphine-sulfonate systems have poor catalytic performance in copolymerization (e.g., low polymerization activity, low molecular weight of the resulting copolymer, and narrow selection of polar monomers). To improve the performance of the phosphine-nickel sulfonate catalysts, researchers have designed phosphine-nickel sulfonate catalysts with different electronic and steric effects. When the axial steric hindrance of the catalyst is increased, the catalyst can be effectively improved, and in addition, the catalyst with electron donating groups is more stable, and the preparation of the polymer is realized in the polymerization and copolymerization of ethylene, so that the application of the phosphine-nickel sulfonate catalytic system in olefin polymerization is greatly expanded.
Disclosure of Invention
In view of the above, the present invention provides a strong electron donating nickel phosphine sulfonate compound and its application. The nickel phosphine sulfonate compound can be used as a polyolefin catalyst, and has rich electrons and high stability.
First, the present invention provides a ligand compound having the structure shown in the following formula (I):
Wherein R 1 is selected from one of H, N, N-dialkyl, C1-C6 alkyl and C1-C6 alkoxy; r 2 is substituted tert-butyl; r 3 is selected from one or more of substituted H, isopropyl, C1-C6 alkyl and C1-C6 alkoxy.
The structure of the ligand compounds of the present invention is preferably:
The preparation method of the ligand compound comprises the steps of reacting a compound with a structure shown in a formula (II) with n BuLi, then reacting with a compound with a structure shown in a formula (III), and reacting the obtained system with a compound with a structure shown in a formula (IV) to obtain the compound with the structure shown in the formula (I).
The method specifically comprises the following steps:
Step 1: slowly adding n BuLi into THF solution dissolved with a compound with a structure shown in a formula (II) at-78 ℃, stirring for 15-20 min, and reacting for 2-3 h at room temperature;
step 2: transferring the system obtained in the step 1 into THF solution in which the structural compound of the formula (III) is dissolved at the temperature of minus 78 ℃ to react for 2 to 3 hours at room temperature;
step 3: slowly adding n BuLi into THF solution dissolved with a compound with a structure shown in a formula (IV) at-78 ℃ and keeping the temperature for reaction for 2-3 h;
Step 4: slowly dropwise adding the system obtained in the step 3 into the reaction system obtained in the step 2 at the temperature of minus 78 ℃, stirring for 15-20 min, slowly heating to room temperature, and reacting for 10-12h; and (3) separating by column chromatography to obtain a target product, namely the compound with the structure shown in the formula (I).
The molar ratio of the compound of formula (II), the compound of formula (III) and the compound of formula (IV) is preferably 1:1:1. Wherein the molar ratio of the compound of formula (II) to n BuLi is 1:2.1.
The present invention is not limited to the column chromatography, and those skilled in the art will be familiar with the present invention.
The reaction scheme is as follows:
Wherein R 1 is selected from H, N, N-dialkyl, C1-C6 alkyl, C1-C6 alkoxy.
R 2 is independently substituted tert-butyl on the phosphine skeleton.
R 3 is selected from one or more of substituted H, isopropyl, C1-C6 alkyl and C1-C6 alkoxy.
In a second aspect, based on the ligand compound, the invention also provides a strong electron donating nickel phosphine sulfonate compound, which has a structure shown in the following formula (V):
Wherein R 1 is selected from one of H, N, N-dialkyl, C1-C6 alkyl and C1-C6 alkoxy; r 2 is independently substituted tert-butyl on the phosphine skeleton; r 3 is selected from one or more of substituted H, isopropyl, C1-C6 alkyl and C1-C6 alkoxy.
The preferable structure of the strong electron donating nickel phosphine sulfonate compound is as follows:
The invention relates to a preparation method of a strong electron donating nickel phosphine sulfonate compound, which is characterized in that a compound with a structure shown in a formula (I) reacts with allyl nickel to obtain the strong electron donating nickel phosphine sulfonate compound with a structure shown in a formula (V).
Specifically, the compound of formula (I) reacts with Na 2CO3 and allyl nickel chloride in DCM, after filtration through celite, the obtained liquid is pumped dry on a vacuum line, the mixed solution of dichloromethane and n-hexane is added, stirring is carried out for 10-15 min, and filtration is carried out to obtain a bright yellow solid, namely the compound of formula (V).
Wherein the molar ratio of the compound of formula (I), na 2CO3 and allyl nickel is 1:2:1.1.
The reaction temperature was room temperature and the reaction time was 12h.
The reaction scheme is as follows:
The invention relates to the application of a strong electron donating nickel phosphine sulfonate compound, which is used as a catalyst in the polymerization reaction of olefin.
The complex can catalyze the homopolymerization reaction of olefin monomers and also can catalyze the copolymerization reaction of olefin monomers and polar monomers. The olefin monomer is selected from polar monomers or nonpolar monomers, and specifically comprises one or more of nonpolar monomers, vinyl polar monomers, allyl polar monomers, long-chain polar monomers and norbornene polar monomers.
Among them, ethylene and norbornene are particularly preferable as the nonpolar monomer;
The polar monomer is particularly preferably a norbornene-type polar monomer such as methyl 5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate or 5-norbornene-2-methanol.
The co-electron effect of a specific R 1 group in the compound with the structure shown in the formula (I) affects the polymerization activity, and meanwhile, the strong electron effect of the tertiary butyl group substituted by the substituent and the R 3 substituent combined with different substituents on the phosphine skeleton jointly shows different effects on polymerization. Thus, the polyolefin catalyst prepared by the invention has strong electron donating property and high stability.
Drawings
FIG. 1 L1- 1 H NMR spectra.
FIG. 2 L1- 31 PNMR spectra.
FIG. 3 L1- 13 C NMR spectra.
FIG. 4 L2- 1 H NMR spectra.
FIG. 5 L2- 31 PNMR spectra.
FIG. 6 L2- 13 C NMR spectrum.
FIG. 7 Ni1- 1 H NMR spectra.
FIG. 8 Ni1- 31 PNMR spectra.
FIG. 9 Ni2- 13 C NMR spectrum.
FIG. 10 is a Ni2- 1 H NMR spectrum.
FIG. 11 Ni2- 31 PNMR spectra.
FIG. 12 Ni2- 13 CNMR spectra.
FIG. 13 nuclear magnetic characterization of Ni1-NBOAc copolymer.
FIG. 14 nuclear magnetic characterization of Ni1-NBCOOMe copolymer.
FIG. 15 nuclear magnetic characterization of Ni1-NBCH 2 OH copolymer.
FIG. 16 Ni1 complex single crystal.
FIG. 17 Ni2 complex single crystal.
Detailed Description
The invention provides a strong electron donating nickel phosphine sulfonate compound, a preparation method and application thereof, and a person skilled in the art can refer to the content of the compound and properly improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The source of the raw material compound is not limited, and the raw material compound may be commercially available or may be prepared according to a method conventional in the art, and the present invention is not limited thereto.
In order to further illustrate the present invention, the compounds, nickel compounds and methods for preparing the same provided by the present invention are described in detail below with reference to examples.
Example 1:
To a solution of anhydrous benzenesulfonic acid (1.58 g,10.00 mmol) in 25ml THF was slowly added 2.1 equivalents n BuLi (2.5M in hexane,8.4mL,2.1eq) and stirred for 15min at-78deg.C, and the reaction system was slowly added dropwise to tert-butylphosphine dichloride (1.59 g,10.00 mmol) dissolved in 10ml THF at-78deg.C and stirred for 10-15min and reacted for 2-4h at room temperature. To a solution of 1, 3-dimethoxybenzene (1.58 g,10.00 mmol) in 25ml THF was slowly added dropwise thereto at-78deg.C in advance, followed by stirring for 15min with 1.1 equivalent n BuLi (2.5M in hexane,4.40mL,1.1eq), and after the completion of the reaction, the mixture was slowly transferred to the system at-78deg.C and reacted at room temperature for 12h. Water (30 ml) and HCl (10 mmol,0.83ml,12 mol/L) were added, extracted by water, DCM, dried over Na 2SO3, concentrated in vacuo and the column chromatographed to give white solid A in yield (2.97 g, 78%).
1H NMR(400MHz,CDCl3)δ8.34(ddd,J＝7.8,4.8,1.0Hz,1H),8.07(dd,J＝12.0,7.5Hz,1H),7.65(t,J＝7.7Hz,1H),7.51(dd,J＝10.5,6.3Hz,2H),6.63(dd,J＝8.5,4.9Hz,2H),3.86(s,6H),1.46(d,J＝18.5Hz,9H).
31PNMR(162MHz,CDCl3)δ1.89(s).
13C NMR(101MHz,CDCl3)δ162.95(s),153.20(d,J＝8.0Hz),137.53(s),134.84(d,J＝9.1Hz),133.81(d,J＝2.9Hz),129.30(d,J＝8.8Hz),128.17(d,J＝11.7Hz),113.98(s),113.15(s),105.26(d,J＝6.2Hz),94.86(s),93.99(s),77.34(d,J＝11.7Hz),77.08(s),76.76(s),56.64(s),34.35(s),33.89(s),27.22(d,J＝3.3Hz).
Example 2:
the procedure was as in example 1, with the sole difference that p-nitrogen dimethylbenzenesulfonic acid (2.01 g,10.0 mmol) was charged. Obtained as a white solid in yield (3.21 g, 75%).
1H NMR(400MHz,CDCl3)δ8.12(dd,J＝8.8,6.3Hz,1H),7.47(t,J＝8.4Hz,1H),7.31(d,J＝14.0Hz,1H),6.86(d,J＝8.4Hz,1H),6.61(dd,J＝8.4,4.8Hz,2H),3.86(s,6H),3.03(s,6H),1.45(d,J＝18.4Hz,9H).
31PNMR(162MHz,CDCl3)δ1.17(s).
13C NMR(101MHz,CDCl3)δ162.86(s),149.42(d,J＝13.3Hz),140.03(d,J＝8.1Hz),137.47(s),130.33(d,J＝10.4Hz),117.39(d,J＝11.0Hz),115.88(s),114.36(s),113.54(s),105.22(d,J＝5.9Hz),94.89(s),94.04(s),78.10–77.83(m),77.53(d,J＝11.9Hz),77.11(d,J＝32.1Hz),56.73(s),40.31(s),34.37(s),33.91(s),27.25(s).
Example 3: preparation of Nickel complexes
Ligand L-1 (0.76 g,1.00 mmol) and Na 2CO3 (0.42 g,2.00 mmol) were taken in a glove box and dissolved in 10mL of DCM and reacted at room temperature for 1-2h, nickel allyl chloride (0.30 g,1.10 mmol) was added thereto and reacted at room temperature for 9-12h. After filtration through celite, the resulting liquid was drained on a vacuum line, a mixed solution of methylene chloride and n-hexane was added, stirred for 10 to 15 minutes, and filtered to give a bright yellow solid Ni-1 in a yield (0.85 g, 91.22%).
1HNMR(400MHz,CDCl3)δ8.18(s,1H),7.55–7.34(m,2H),6.61(s,2H),5.47(s,1H),3.87(s,6H),1.47(d,J＝16.7Hz,9H).
31PNMR(162MHz,CDCl3)δ20.87(s).
13C NMR(101MHz,CDCl3)δ160.60(s),134.55(s),132.99(s),130.38(s),129.02(s),128.30(d,J＝6.5Hz),111.54(s),104.63(s),77.47(s),76.99(d,J＝32.0Hz),76.79–76.46(m),65.88(s),55.53(s),36.14(d,J＝19.6Hz),29.83(d,J＝8.0Hz),15.31(s).
Example 4: preparation of Nickel complexes
In the same manner as above, ligand L2 (0.68 mg,1.00 mmol) was taken out in a glove box to give Ni-2 as a bright yellow solid ((0.61 mg, 90%).
1HNMR(400MHz,CDCl3)δ7.98(dd,J＝8.7,5.6Hz,1H),7.37(t,J＝8.3Hz,1H),6.80–6.44(m,4H),5.45(ddd,J＝20.5,13.6,7.2Hz,1H),3.90(s,6H),2.80(s,6H),1.49(d,J＝16.5Hz,9H).31PNMR(162MHz,CDCl3)δ21.16(s).
13C NMR(101MHz,CDCl3)δ149.69(s),132.87(s),129.45(d,J＝7.6Hz),117.61(s),113.12(s),111.02(s),104.67(s),77.62(s),77.31(s),76.99(s),55.66(s),39.95(s),35.81(d,J＝19.8Hz),30.08(d,J＝8.0Hz).
Example 5: application of catalyzing polymerization of norbornene and polar norbornene
In a glove box, 18mL of toluene was added to a 100mL glass bottle under nitrogen atmosphere. The vessel was heated to 80℃using an oil bath and incubated for 10 minutes. Tris (pentafluorophenyl) borane dissolved in 2ml of methylene chloride and a certain amount of nickel catalyst were injected into the polymerization system by syringe. The reaction was carried out for 60 minutes. Stopping the reaction, adding ethanol to precipitate solid, filtering under reduced pressure, and drying in a vacuum drying oven to obtain white solid. The polymerization results are shown in Table 1. The electron effect of specific electron donating groups in the complex of the invention shows high polymerization activity on ethylene, and also, in the copolymerization of norbornene and polar norbornene, a copolymer with higher insertion ratio is obtained, and the copolymer shows stronger tolerance on monomers containing polar functional groups.
TABLE 1 results of Nickel catalyst catalyzed polymerization of ethylene and copolymerization of norbornene and polar norbornene
a Polymerization conditions Ni catalyst=10 μmol,10eq (C 6F5)3 B, toluene=18 mL, methylene chloride=2 mL, ethylene pressure=8 atm, temperature=80 ℃, time=1 h, activity=10 5g·mol-1·h-1.b polymerization conditions Ni catalyst=10 μmol,10eq (C 6F5)3 B, toluene=18 mL, methylene chloride=2 mL, ethylene pressure=20 atm, temperature=80 ℃, time=1 h, activity=10 5g·mol-1·h-1.c polymerization conditions Ni catalyst=10 μmol,10eq (C 6F5)3 B, nb=0.5 mol/L, toluene=18 mL, methylene chloride=2 mL, temperature=80 ℃, time=1 h, activity=10 5g·mol-1·h-1.d molecular weight measurements were made by GPC using polystyrene as standard trichlorobenzene as solvent 150 degrees).
Claims (3)
1. The application of the strong electron donating nickel phosphine sulfonate compound is characterized in that:
The strong electron donating nickel phosphine sulfonate compound is used as a catalyst in the polymerization reaction of olefin;
the structure of the strong electron donating nickel phosphine sulfonate compound is shown as follows:
2. the use according to claim 1, characterized in that:
The strong electron donating nickel phosphine sulfonate compound is used as a catalyst for catalyzing the homopolymerization reaction of olefin monomers or catalyzing the copolymerization reaction of olefin monomers and polar monomers.
3. The use according to claim 2, characterized in that:
The olefin monomer is selected from polar monomers or nonpolar monomers, and specifically comprises one or more of nonpolar monomers, vinyl polar monomers, allyl polar monomers, long-chain polar monomers and norbornene polar monomers.
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| Modulation of emission properties of phosphine-sulfonate ligand containing copper complexes: playing with solvato-, thermo-, and mechanochromism;Antoine Vacher et al.;Dalton Transactions;第48卷;2128-2134 * |
| Rational Design of High-Performance Phosphine Sulfonate Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers;Min Chen et al.;ACS Catalysis;第7卷;1308-1312 * |
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