CN115073506A - Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof - Google Patents
Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof Download PDFInfo
- Publication number
- CN115073506A CN115073506A CN202210791001.7A CN202210791001A CN115073506A CN 115073506 A CN115073506 A CN 115073506A CN 202210791001 A CN202210791001 A CN 202210791001A CN 115073506 A CN115073506 A CN 115073506A
- Authority
- CN
- China
- Prior art keywords
- alpha
- diimine
- compound
- group
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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 System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
Abstract
The disclosure provides a supported alpha-diimine nickel catalyst and preparation and application of a ligand thereof. The supported alpha-diimine nickel catalyst comprises a carrier and alpha-diimine nickel complex shown as a formula (II)
The substance is loaded on the carrier, A, B is respectively selected from unsubstituted C 1 ～C 20 Alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 Alkoxy of (a) hasWhen the substituent is selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a); r 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (1); r is 6 Any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection; x is selected from any one of halogen and methyl.
Description
Technical Field
The disclosure relates to the technical field of preparation of olefin polymerization catalysts, and particularly relates to a supported alpha-diimine nickel catalyst and preparation and application of a ligand thereof.
Background
The supported heterogeneous catalyst can be prepared by supporting the homogeneous catalyst on an inorganic carrier, and the supported catalyst with uniformly distributed active centers can effectively avoid the problem of kettle adhesion in the polymerization process, so that the polymer particles with controllable morphology are obtained.
In the ethylene polymerization industry, α -diimine catalysts have gained widespread attention in both academic and industrial settings. Compared with other ethylene polymerization catalyst systems, the alpha-diimine catalyst has the following advantages: (1) the alpha-diimine ligand has simple structure and easy synthesis, and can improve the performance of the catalyst by modifying the ligand; (2) the alpha-diimine catalyst has unique chain walking characteristics, and can prepare a branched polyethylene material by using ethylene as a unique polymerization monomer; and the number and type of branching can be adjusted by steric hindrance of the ligand, polymerization reaction conditions (polymerization temperature or ethylene pressure, etc.). (3) The alpha-diimine palladium catalyst can catalyze polar monomers such as ethylene and methyl acrylate to carry out copolymerization, and a polar polyethylene material is prepared by a one-step method. (4) The alpha-diimine nickel catalyst has ultrahigh activity in catalyzing ethylene polymerization, and the activity of the alpha-diimine nickel catalyst can be compared with that of a front transition metal catalyst.
At present, the reports and researches on the application of the supported alpha-diimine catalyst in the ethylene polymerization industry are few, and the supporting effect does not meet the application requirements.
Disclosure of Invention
In view of the above, the main object of the present disclosure is to provide a supported nickel alpha-diimine catalyst and the preparation and use of its ligands, which are intended to at least partially solve at least one of the above mentioned technical problems.
To achieve the above object, as an embodiment of an aspect of the present disclosure, there is provided an α -diimine ligand having a chemical structural formula shown in formula (I): A. b is independently selected from unsubstituted
C 1 ～C 20 Alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent, the above substituent is selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a); r 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a); r is 6 Is selected from any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection.
A, B are each methyl according to embodiments of the present disclosure; r 1 、R 2 、R 3 、R 4 Are each methyl or isopropyl; r 5 Is H; r 6 Is a potassium trifluoroborate group containing crown ether protection.
As an example of another aspect of the present disclosure, there is provided a method for preparing the above α -diimine ligand, comprising the steps of reacting a bromobenzamide compound (C) with an α -diketone compound (D) at 30 to 100 ℃ for 6 to 18 hours under the action of an organic acid catalyst to produce a compound (E);
under the action of a palladium catalyst, reacting the compound (E) with a compound pinacol diboron at 80-100 ℃ for 2-10 h to generate a compound (F);
according to an embodiment of the present disclosure, further comprising: reacting the compound (F) with a compound potassium bifluoride in a mixed solution of an organic solvent and water at the temperature of between 20 and 50 ℃ for 0.5 to 12 hours to generate a compound (G);
according to an embodiment of the present disclosure, further comprising: reacting the compound (G) with the compound 18-crown-6 in an organic solvent at the temperature of between 20 and 50 ℃ for 12 to 96 hours to generate a compound (H);
as an example of yet another aspect of the present disclosure, there is also provided an α -diimine nickel complex having a chemical formula shown in formula (II): A. b is independently selected from unsubstituted C 1 ～C 20 Alkyl group of (A) or (B),
Substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent, the above substituent is selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy of (2); r 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a); r 6 Any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection; x is selected from any one of halogen and methyl.
As an example of still another aspect of the present disclosure, there is also provided a supported α -diimine nickel catalyst, which includes a support, and an α -diimine nickel complex as described above supported on the support; among them, the carrier preferably includes any one of silica, alumina, titania, diatomaceous earth, and zirconia.
As an example of still another aspect of the present disclosure, there is also provided a method for preparing polyolefin using the supported nickel α -diimine catalyst as described above, comprising the steps of: under the action of the supported alpha-nickel diimine catalyst and the cocatalyst, olefin monomers are heated and reacted in an organic solvent.
According to an embodiment of the present disclosure, the above cocatalyst is diethyl aluminum chloride.
According to an embodiment of the present disclosure, the above olefin monomer includes at least one of ethylene, 6-chloro-1-hexene, and methyl 10-undecenoate.
According to the supported alpha-diimine nickel catalyst provided by the embodiment of the disclosure, potassium trifluoroborate group with strong electron supply effect is introduced to the alpha-diimine ligand, so that the adsorption of the carrier to the alpha-diimine nickel complex is enhanced, the stability of the supported alpha-diimine nickel catalyst is increased, and the activity of the supported alpha-diimine nickel catalyst is improved, and the molecular weight of a polymerization product is increased.
Drawings
FIG. 1 is a drawing of an alpha-diimine ligand L1-A obtained from a method of preparing an alpha-diimine ligand according to an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 2 is a drawing of an alpha-diimine ligand L1-A obtained from a method of preparing an alpha-diimine ligand according to an exemplary embodiment of the disclosure 13 C NMR spectrogram;
FIG. 3 is a graph according toPreparation method of alpha-diimine ligand L1-B of an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 4 is a drawing of an alpha-diimine ligand L1-B obtained from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 19 F NMR spectrum;
FIG. 5 is a drawing of an alpha-diimine ligand L1 from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 6 is a drawing of an alpha-diimine ligand L1 from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 13 C NMR spectrum;
FIG. 7 is a drawing of an alpha-diimine ligand L1 from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 19 F NMR spectrum;
FIG. 8 is a drawing of an alpha-diimine ligand L2-A obtained from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 9 is a drawing of an alpha-diimine ligand L2-A obtained from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 13 C NMR spectrum;
FIG. 10 is a drawing of an alpha-diimine ligand L2-B obtained from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 11 is a drawing of an alpha-diimine ligand L2-B from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 13 C NMR spectrum;
FIG. 12 is a drawing of an alpha-diimine ligand L2-B from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 19 F NMR spectrum;
FIG. 13 is a drawing of an alpha-diimine ligand L2 from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 1 H NMR spectrum;
FIG. 14 is an alpha-diimine complex according to an exemplary embodiment of the disclosureProcess for producing alpha-diimine ligand L2 13 C NMR spectrum;
FIG. 15 is a drawing of an alpha-diimine ligand L2 from a method of making an alpha-diimine ligand according to an exemplary embodiment of the disclosure 19 F NMR spectrum; and
fig. 16 is a single crystal diffraction spectrum of an alpha-diimine nickel complex Ni1 according to one exemplary embodiment of the present disclosure.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
So far, the following aspects are mainly reported for the supported diimine catalyst: preparing a nickel diimine catalyst containing hydroxyl and amino functional groups, and loading the catalyst on silica pretreated by trimethylaluminum in a covalent bond manner; loading a nickel diimine catalyst on silicon dioxide pretreated by modified methylaluminoxane; reacting alpha-diimine dimethyl nickel with partially dehydrated zirconium oxide sulfate to prepare a high-activity supported catalyst; the supported catalyst was prepared by supporting alpha-diimine nickel on an aluminum treated inorganic substance. However, the methods reported so far all require the post-treatment of the inorganic support with aluminum alkyl, and the inorganic support without aluminum alkyl treatment has weak adsorption to the catalyst.
According to a general inventive concept of one aspect of the present disclosure, there is provided an α -diimine ligand having a chemical structural formula shown in formula (I):
A. b is independently selected from unsubstituted C 1 ～C 20 Alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent group, it is substitutedRadical selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a); r 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a); r 6 Is selected from any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection.
The alpha-diimine ligands provided by the above embodiments of the present disclosure have enhanced electronegativity of the alpha-diimine ligands by introducing a strong electron withdrawing group, potassium trifluoroborate group, in the para position of the nitrogen atom. Wherein, the crown ether protection in the potassium trifluoroborate group containing crown ether protection increases the steric hindrance of the whole catalyst system on one hand to change the polymerization performance; on the other hand, the solubility of the compound is increased so as to further improve the activity of the catalytic polymerization reaction.
In some embodiments of the disclosure, C 1 ～C 20 The alkyl group of (b) includes methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, etc.; c 1 ～C 20 The alkoxy group of (1) includes methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, hexyloxy, cyclohexyloxy, heptyloxy and the like.
In some embodiments of the present disclosure, A, B are each methyl; r 1 、R 2 、R 3 、R 4 Are each methyl or isopropyl; r 5 Is H; r 6 Is a potassium trifluoroborate group containing crown ether protection.
According to the embodiment of the disclosure, a preparation method of the above alpha-diimine ligand is also provided, under the action of an organic acid catalyst, the bromobenzamide compound (C) and the alpha-diketone compound (D) are heated and reacted for 6h to 18h at 30 ℃ to 100 ℃ to generate a compound (E);
under the action of a palladium catalyst, reacting the compound (E) with a compound pinacol diboron at 80-100 ℃ for 2-10 h to generate a compound (F);
in some embodiments of the disclosure, the organic acid is formic acid and the palladium catalyst is [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium dichloromethane complex.
Some embodiments of the present disclosure further include: reacting the compound (F) with a compound potassium bifluoride in a mixed solution of an organic solvent and water at the temperature of between 20 and 50 ℃ for 0.5 to 12 hours to generate a compound (G);
in some embodiments of the present disclosure, further comprising: reacting the compound (G) with the compound 18-crown-6 in an organic solvent at the temperature of between 20 and 50 ℃ for 12 to 96 hours to generate a compound (H);
there is also provided, in accordance with an embodiment of the present disclosure, an alpha-diimine nickel complex having a chemical structural formula shown in formula (II): A. b is independently selected from unsubstituted C 1 ～C 20 Alkyl, substituted or unsubstituted
Substituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent, the substituent is selected fromC 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a); r 1 、R 2 、R 3 、R 4 、R 5 Each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a); r 6 Any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection; x is selected from any one of halogen and methyl.
According to an embodiment of the present disclosure, there is also provided a supported alpha-nickel diimine catalyst, which includes a carrier, and an alpha-nickel diimine complex as described above, supported on the carrier; among them, the carrier preferably includes any one of silica, alumina, titania, diatomaceous earth, and zirconia.
The supported alpha-diimine nickel catalyst provided by the embodiment of the disclosure enhances the adsorption of the alpha-diimine nickel catalyst to a carrier by introducing potassium trifluoroborate radical ions with strong electron supply effect on a diimine ligand, increases the stability of the supported alpha-diimine nickel catalyst, can obtain the supported catalyst only by stirring the alpha-diimine nickel catalyst and the carrier, and does not need to treat an inorganic carrier by using alkyl aluminum.
There is also provided, in accordance with an embodiment of the present disclosure, a method for preparing a polyolefin using a supported nickel alpha-diimine catalyst as described above, including the steps of: under the action of supported alpha-nickel diimine catalyst and cocatalyst, olefin monomer is heated in organic solvent to react.
According to the method for preparing polyolefin by using the supported alpha-diimine nickel catalyst provided by the embodiment of the disclosure, the stability of the supported alpha-diimine nickel catalyst is improved and the molecular weight of an olefin polymerization product is improved by the strong electron donating effect of potassium trifluoroborate in the alpha-diimine nickel catalyst.
In some embodiments of the present disclosure, the cocatalyst is diethyl aluminum chloride.
In some embodiments of the present disclosure, the olefin monomer comprises at least one of ethylene, 6-chloro-1-hexene, methyl 10-undecenoate. Among them, olefin monomers other than ethylene, such as 6-chloro-1-hexene, methyl 10-undecenoate, can be referred to as polar monomers.
In some embodiments of the present disclosure, the polyethylene prepared by the above method for preparing polyolefin has a melting point of 80 ℃ to 130 ℃ and a molecular weight of 18 to 130 ten thousand.
In some embodiments of the present disclosure, the polar polyethylene prepared by the above method for preparing polyolefin has a polar monomer molar content of 0.1-1.5%, a melting point of 90-150 ℃, and a molecular weight of 5-35 ten thousand.
The disclosure is further illustrated by the following comparative examples and examples. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough explanation of the embodiments of the disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, the details of the following embodiments may be combined arbitrarily into other possible embodiments, without conflict.
Example 1
Preparation of alpha-diimine ligand L1-A
S1: 82mg (0.1mmol) of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex, 0.35g (3.5mmol) of potassium acetate, 0.45g (1mmol) of (2, 6-Me) 2 -4-Br-C 6 H 2 )N＝C(CH 3 )-(CH 3 )C＝N(2,6-Me 2 -4-Br-C 6 H 2 ) 0.76g (3mmol) of pinacol diboron and 50mL of anhydrous dimethylformamide were charged to a 200mL Schlenk flask and the reaction was heated at 90 ℃ for 24 hours.
S2: after the reaction is finished, after the temperature of the mixture is reduced to room temperature, sequentially adding 200mL of ethyl acetate and 100mL of water into the mixture, and carrying out liquid separation extraction; the organic phase obtained by the liquid separation extraction was washed with water 3 times, and the obtained organic phase was dried over anhydrous magnesium sulfate, filtered, and then drained to obtain a dark yellow solid.
S3: dissolving the dark yellow solid obtained in the step S2 in 2mL of dichloromethane, and adding anhydrous methanol for precipitation; and (3) filtering the precipitated yellow solid, washing the yellow solid with absolute methanol for three times, and draining to obtain a pure compound L1-A, wherein the mass of the obtained yellow solid is 0.42g, and the yield is 78%.
S4: and performing nuclear magnetic characterization on the yellow solid L1-A obtained in the step S3.
The mass spectrometry result of compound L1-A was: ESI-MS (M/Z) [ M + H ]] + Calcd for C 32 H 47 B 2 N 2 O 4 :545.3724；Found:.545.3734。
Of the alpha-diimine ligand L1-A shown in FIG. 1 1 Characterization of H NMR results were: 1 H NMR(400MHz,CDCl 3 ):δ7.54(s,4H,aryl-H),2.03(s,12H,PhMe),2.01(s,6H,N＝CMe),1.36(s,24H)。
of the alpha-diimine ligand L1-A shown in FIG. 2 13 Characterization of C NMR results were: 13 C NMR(101MHz,CDCl 3 ):δ167.64(N＝CMe),151.48,134.72,124.15,83.68,25.02,17.66,16.00。
example 2
Preparation of alpha-diimine ligand L1-B
S1: 0.33g (0.5mmol) of L1-A, 50mL of anhydrous methanol, and 1.5mL of an aqueous solution containing 0.24g (3mmol) of potassium hydrogen fluoride were put in a 200mL round-bottomed flask, and the reaction was stirred at room temperature (20 ℃ C. to 25 ℃ C.) for 1 hour.
S2: after the reaction is finished, the solvent in the obtained reaction mixture is pumped to dryness, acetone is added for extraction, and the yellow solid is obtained after filtration;
s3: the yellow solid obtained in the step S2 is washed with 20mL of dichloromethane for three times in sequence to obtain a yellow solid pure product L1-B, the mass of the obtained L1-B is 0.28g, and the yield is 91%.
S4: and performing nuclear magnetic characterization on the yellow solid L1-B obtained in the step S3.
The product L1-B elemental analysis result is: call for C 28 H 38 B 2 F 6 K 2 N 2 :C,54.56；H,6.21；Found:C,54.51；H,6.29。
Of the alpha-diimine ligand L1-B shown in FIG. 3 1 Characterization of H NMR results were: 1 H NMR(400MHz,DMSO):δ7.13(s,4H,aryl-H),2.60(sept,4H,CHMe 2 ),1.95(s,6H,N＝CMe),1.12(d,J＝6.8Hz,12H),1.07(d,J＝6.8Hz,12H)。
of the alpha-diimine ligand L1-B shown in FIG. 4 19 Characterization of F NMR was: 19 F NMR(377MHz,DMSO):δ-138.10。
example 3
Preparation of alpha-diimine ligand L1
S1: 0.28g (0.45mmol) (2,6- i Pr 2 -4-BF 3 K-C 6 H 2 )N＝C(CH 3 )-(CH 3 )C＝N(2,6- i Pr 2 -4-BF 3 K-C 6 H 2 ) 0.24g (0.9mmol) of 18-crown-6 and 40mL of toluene were charged into a 100mL round-bottomed flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 24 hours.
S2: after the reaction was completed, the solvent in the obtained reaction mixture was drained to obtain pure compound L1.
S3: the yellow solid L1 obtained in step S2 was subjected to nuclear magnetic characterization.
The product L1 element analysis result is: call for C 52 H 86 B 2 F 6 K 2 N 2 O 12 :C,54.54；H,7.57；Found:C,54.49；H,7.61。
Of the alpha-diimine ligand L1 shown in FIG. 5 1 Characterization of H NMR results were: 1 H NMR(400MHz,CDCl 3 ):δ7.46(s,4H,aryl-H),3.60(s,48H),2.69(sept,4H,CHMe 2 ),2.00(s,6H,N＝CMe),1.17(d,J＝6.8Hz,12H),1.14(d,J＝6.8Hz,12H)。
of the alpha-diimine ligand L1 shown in FIG. 6 13 Characterization of C NMR results were: 13 C NMR(101MHz,CDCl 3 ):δ168.03(N＝CMe),144.85,132.52,126.53,70.19,28.68,23.54,23.09,16.63。
of the alpha-diimine ligand L1 shown in FIG. 7 19 Characterization of F NMR was: 19 F NMR(377MHz,CDCl 3 ):δ-141.81。
example 4
Preparation of alpha-nickel diimine complex Ni1
S1: 1.14g (1.0mmol) of L1, 0.31g (1.0mmol) of (DME) 2 NiBr 2 And 20mL of methylene chloride were added to a 100mL round-bottom flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 12 hours.
S2: after the reaction is completed, after the solvent in the obtained reaction mixture is drained, the obtained solid is washed by 20mL of n-hexane for three times, and finally the solid pure product Ni1 can be obtained by draining, wherein the mass of the obtained red solid Ni1 is 1.25g, and the yield is 92%.
Elemental analysis (elemental analysis) of the obtained red solid Ni 1: anal.Calcd for C 52 H 86 B 2 Br 2 F 6 K 2 N 2 NiO 12 :C,45.80；H,6.31；Found:C,45.74；H,6.33。
As shown in fig. 16, the single crystal diffraction pattern of the prepared red solid Ni1 further demonstrates that the synthesized alpha-diimine nickel complex structure.
Example 5
Preparation of alpha-nickel diimine complex Ni1-A
S1: 0.66g (1.0mmol) of L1-A, 0.31g (1.0mmol) of (DME) 2 NiBr 2 And 20mL of methylene chloride was added to a 100mL circleThe mixture was stirred at room temperature (20 ℃ C. -25 ℃ C.) in a flask and reacted for 12 hours.
S2: after the reaction is completed, after the solvent in the obtained reaction mixture is drained, the obtained solid is sequentially washed with 20mL of n-hexane for three times, and finally the solid pure product Ni1-A is obtained by draining, wherein the mass of the obtained red solid Ni1-A is 0.82g, and the yield is 93%.
Elemental analysis (for the obtained red solid Ni 1-A): call for C 40 H 62 B 2 Br 2 N 2 NiO 4 :C,54.86；H,7.08；Found:C,54.81；H,7.05。
Example 6
Preparation of alpha-diimine ligand L2-A
S1: 82mg (0.1mmol) of [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride dichloromethane complex, 0.35g (3.5mmol) of potassium acetate, 0.45g (1mmol) of (2, 6-Me) 2 -4-Br-C 6 H 2 )N＝C(CH 3 )-(CH 3 )C＝N(2,6-Me 2 -4-Br-C 6 H 2 ) 0.76g (3mmol) of pinacol diboron and 50mL of anhydrous dimethylformamide were charged in a 200mL Schlenk flask, and the reaction was heated at 90 ℃ for 24 hours.
S2: after the reaction is finished, after the temperature of the mixture is reduced to room temperature, sequentially adding 200mL of ethyl acetate and 100mL of water into the mixture, and carrying out liquid separation extraction; the organic phase obtained by the liquid separation extraction was washed with water 3 times, and the obtained organic phase was dried over anhydrous magnesium sulfate, filtered, and then drained to obtain a dark yellow solid.
S3: dissolving the dark yellow solid obtained in the step S2 in 2mL of dichloromethane, and adding anhydrous methanol for precipitation; the precipitated yellow solid was filtered, washed three times with anhydrous methanol, and dried to obtain pure compound L2-a, the mass of the yellow solid was 0.42g, and the yield was 78%.
S4: and performing nuclear magnetic characterization on the yellow solid L2-A obtained in the step S3.
The mass spectrometry result of the product L2-A is as follows: ESI-MS (M/Z) [ M + H ]] + Calcd for C 32 H 47 B 2 N 2 O 4 :545.3724；Found:.545.3734。
Of the alpha-diimine ligand L2-A shown in FIG. 8 1 Characterization of H NMR results were: 1 H NMR(400MHz,CDCl 3 ):δ7.54(s,4H,aryl-H),2.03(s,12H,PhMe),2.01(s,6H,N＝CMe),1.36(s,24H)。
of the alpha-diimine ligand L2-A shown in FIG. 9 13 Characterization of C NMR results: 13 C NMR(101MHz,CDCl 3 ):δ167.64(N＝CMe),151.48,134.72,124.15,83.68,25.02,17.66,16.00。
example 7
Preparation of alpha-diimine ligand L2-B
S1: 0.27g (0.5mmol) of (2,6-Me 2 -4-PinB-C 6 H 2 )N＝C(CH 3 )-(CH 3 )C＝N(2,6-Me 2 -4-PinB-C 6 H 2 ) 50mL of anhydrous methanol and 1.5mL of an aqueous solution containing 0.24g (3mmol) of potassium hydrogen fluoride were put in a 200mL round-bottomed flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 1 hour.
S2: after the reaction is finished, the solvent in the obtained reaction mixture is pumped to be dry, and then acetone is added for extraction and filtration to obtain solid;
s3: the solid obtained in the step S2 is washed with 20mL of dichloromethane for three times in sequence to obtain a solid pure product L2-B, the mass of the obtained yellow solid L2-B is 0.19g, and the yield is 77%.
S4: and performing nuclear magnetic characterization on the yellow solid L2-B obtained in the step S3.
The product L2-B elemental analysis result is: call for C 20 H 22 B 2 F 6 K 2 N 2 :C,47.64；H,4.40；Found:C,47.60；H,4.45。
FIG. 10 shows an alpha-diimine ligandOf L2-B 1 Characterization of H NMR results were: 1 H NMR(400MHz,DMSO):δ7.01(s,4H,aryl-H),1.92(s,6H,N＝CMe),1.89(s,12H,PhMe).
of the alpha-diimine ligand L2-B shown in FIG. 11 13 Characterization of C NMR results were: 13 C NMR(101MHz,DMSO):δ167.03(N＝CMe),145.60,131.23,121.09,17.57,15.37。
of the alpha-diimine ligand L2-B shown in FIG. 12 19 Characterization of F NMR results: 19 F NMR(377MHz,DMSO):δ-138.40。
example 8
Preparation of alpha-diimine ligand L2
S1: 0.25g (0.45mmol) of (2,6-Me 2 -4-BF 3 K-C 6 H 2 )N＝C(CH 3 )-(CH 3 )C＝N(2,6-Me 2 -4-BF 3 K-C 6 H 2 ) 0.24g (0.9mmol) of 18-crown-6 and 40mL of toluene were charged into a 100mL round-bottomed flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 24 hours.
S2: after the reaction was completed, the solvent in the obtained reaction mixture was drained to obtain pure compound L2.
S3: the yellow solid L2 obtained in step S2 was subjected to nuclear magnetic characterization.
The product L2 elemental analysis results were: call for C 44 H 70 B 2 F 6 K 2 N 2 O 12 :C,51.17；H,6.83；Found:C,51.13；H,6.88。
Of the alpha-diimine ligand L2 shown in FIG. 13 1 Characterization of H NMR results were: 1 H NMR(400MHz,CD 2 Cl 2 ):δ7.19(s,4H,aryl-H),3.58(s,48H),1.99(s,6H,N＝CMe),1.96(s,12H)。
of the alpha-diimine ligand L2 shown in FIG. 14 13 Characterization of C NMR results: 13 C NMR(101MHz,CD 2 Cl 2 ):δ167.90(N＝CMe),146.99,131.60,122.62,70.39,17.88,15.64。
of the alpha-diimine ligand L2 shown in FIG. 15 19 Characterization of F NMR was: 19 F NMR(377MHz,CD 2 Cl 2 ):δ-142.03。
example 9
Preparation of alpha-nickel diimine complex Ni2
S1: 1.03g (1.0mmol) of L2, 0.31g (1.0mmol) of (DME) 2 NiBr 2 And 20mL of methylene chloride were added to a 100mL round-bottom flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 12 hours.
S2: after the reaction is completed, after the solvent in the obtained reaction mixture is drained, the obtained solid is washed by 20mL of n-hexane for three times, and finally the solid pure product Ni2 can be obtained by draining, wherein the mass of the obtained red solid Ni2 is 1.16g, and the yield is 93%.
Elemental analysis of the resulting red solid Ni 2: call for C 44 H 70 B 2 Br 2 F 6 K 2 N 2 NiO 12 :C,42.23；H,5.64；Found:C,42.20；H,5.69。
Example 10
Preparation of alpha-nickel diimine complex Ni2-A
S1: 0.54g (1.0mmol) of L2-A, 0.31g (1.0mmol) of (DME) 2 NiBr 2 And 20mL of methylene chloride were added to a 100mL round-bottom flask, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 12 hours.
S2: after the reaction is completed, after the solvent in the obtained reaction mixture is drained, the obtained solid is washed by 20mL of n-hexane for three times, and finally the solid pure product Ni2-A is obtained by draining, wherein the mass of the obtained red solid Ni2-A is 0.72g, and the yield is 95%.
Elemental analysis (for the obtained red solid Ni 2-A): call for C 32 H 46 B 2 Br 2 N 2 NiO 4 :C,50.34；H,6.03；Found:C,50.30；H,6.05。
Example 11
Supported catalyst Ni1@ SiO 2 Preparation of
S1: the silica carrier is roasted for 6h at 600 ℃ and then stored in a glove box.
S2: mu. mol of Ni1 and 100mg of silica were added to 20mL of methylene chloride, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 8 hours.
S3: after the reaction is finished, filtering the reaction mixture obtained in the step S2, sequentially washing the solid obtained by filtering with 10mL of dichloromethane for three times, and finally pumping to dryness to obtain the supported catalyst Ni1@ SiO 2 。
Example 12
Supported catalyst Ni2@ SiO 2 Preparation of
S1: the silica carrier is roasted for 6h at 600 ℃ and then stored in a glove box.
S2: mu. mol of Ni2 and 100mg of silica were added to 20mL of methylene chloride, and the reaction was stirred at room temperature (20 ℃ C. -25 ℃ C.) for 8 hours.
S3: after the reaction is finished, filtering the reaction mixture obtained in the step S2, sequentially washing the solid obtained by filtering with 10mL of dichloromethane for three times, and finally pumping to dryness to obtain the supported catalyst Ni2@ SiO 2 。
Example 13
Supported catalyst for catalyzing ethylene polymerization
S1: in a glove box, 0.5. mu. mol of the supported catalyst, 50mL of n-hexane was charged into a 350mL pressure resistant polymerization bottle, and the pressure resistant polymerization bottle was attached to a high vacuum ethylene polymerization line and replaced with ethylene three times.
S2: the pressure-resistant polymerization vessel obtained in step S1 was heated, and 0.1mmol of diethylaluminum chloride co-catalyst was added to the pressure-resistant polymerization vessel under a positive pressure of ethylene, and polymerization was carried out for a certain period of time while keeping the pressure of ethylene in the polymerization vessel at a prescribed atmospheric pressure (8 atm).
S3: after the reaction, ethylene in the pressure-resistant polymerization flask was vented, and then hydrochloric acid and methanol were sequentially added to the mixture obtained after the reaction in step S2, followed by filtration.
S4: the filtered polymer obtained in step S3 was washed three times with methanol, dried under vacuum, weighed, and activity calculated, and the data obtained are shown in table 1.
Comparative example 1
Alpha-nickel diimine complex for catalyzing ethylene polymerization
S1: in a glove box, 0.5. mu. mol of an α -nickel diimine complex, 50mL of n-hexane was added to a 350mL pressure resistant polymerization bottle, and the pressure resistant polymerization bottle was attached to a high vacuum ethylene polymerization line and replaced with ethylene three times.
S2: the pressure-resistant polymerization vessel obtained in step S1 was heated, and 0.1mmol of diethylaluminum chloride co-catalyst was added to the pressure-resistant polymerization vessel under a positive pressure of ethylene, and polymerization was carried out for a certain period of time while keeping the pressure of ethylene in the polymerization vessel at a prescribed atmospheric pressure (8 atm).
S3: after the reaction, ethylene in the pressure-resistant polymerization flask was vented, and then hydrochloric acid and methanol were sequentially added to the mixture obtained after the reaction in step S2, followed by filtration.
S4: the filtered polymer obtained in step S3 was washed three times with methanol, dried under vacuum, weighed, and activity calculated, and the data obtained are shown in table 1.
TABLE 1 ethylene polymerization Table a
a Polymerization conditions: catalyst (0.5. mu. mol), diethylaluminum chloride (200equiv), n-hexane (50mL), 8 atmospheres of ethylene, 5 minutes. b The unit of catalyst activity is 10 7 g mol -1 h -1 。 c As determined by gel permeation chromatography. d The number of methyl carbons per 1000 carbon atoms was determined by NMR spectroscopy. e Measured by differential scanning calorimetry.
From the data analysis of table 1, it can be seen that, in the ethylene polymerization reaction, the supported nickel alpha-diimine catalyst improves the activity of the ethylene polymerization reaction and also improves the molecular weight of the polymer of the ethylene polymerization product. The strong electron-donating ability of the potassium trifluoroboride enables the metal center of the catalyst to be more electron-rich, so that the stability of the catalyst can be improved, and the molecular weight of polyethylene catalyzed by the catalyst is higher; meanwhile, the ionic property of the potassium trifluoroborate can also make the potassium trifluoroborate have strong affinity to inorganic solid carriers and have strong adsorption effect on untreated inorganic carriers.
Example 14
Supported catalyst for catalyzing copolymerization of ethylene and polar monomer
S1: in a glove box, 1.0. mu. mol of the supported catalyst, 50mL of anhydrous n-hexane were added to a 350mL pressure-resistant polymerization bottle, and the pressure-resistant polymerization bottle was attached to a high-vacuum ethylene polymerization line and replaced with ethylene three times.
S2: the pressure-resistant polymerization bottle obtained in the step S1 was heated, 0.2mmol of diethylaluminum chloride co-catalyst and 10mmol of 6-chloro-1-hexene were added to the pressure-resistant polymerization bottle under a positive pressure of ethylene, and polymerization was carried out for a certain period of time while keeping the pressure of ethylene in the polymerization bottle at a prescribed atmospheric pressure (4 atm).
S3: after the reaction, ethylene in the pressure-resistant polymerization flask was vented, and then hydrochloric acid and methanol were sequentially added to the mixture obtained after the reaction in step S2, followed by filtration.
S4: the filtered polymer obtained in step S3 was washed three times with methanol, vacuum-dried, weighed, and activity-calculated, and the relevant data obtained are shown in table 2.
TABLE 2 copolymerization of ethylene with polar monomers Table a
a Polymerization conditions catalyst (1.0. mu. mol), diethylaluminum chloride (200equiv), n-hexane (20mL), ethylene at 8atm, 30 ℃ for 60 minutes. b The unit of catalyst activity is 10 5 g mol -1 h -1 。 c Mole of polar monomerMolar insertion ratio, determined by NMR spectroscopy. d Measured by differential scanning calorimetry. e The number of methyl carbons per 1000 carbon atoms was determined by NMR spectroscopy.
From the data analysis of table 2, it can be seen that, in the copolymerization reaction of ethylene and polar monomer, the supported nickel alpha-diimine catalyst improves the reactivity of the copolymerization of ethylene and polar monomer, and also improves the molecular weight of the polymerization product obtained by the copolymerization of ethylene and polar monomer.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. An α -diimine ligand having the formula (I):
A. b is independently selected from unsubstituted C 1 ～C 20 Alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent, the substituent is selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a);
R 1 、R 2 、R 3 、R 4 、R 5 each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a);
R 6 is selected from any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection.
2. An alpha-diimine ligand according to claim 1,
A. b is methyl respectively;
R 1 、R 2 、R 3 、R 4 are each methyl or isopropyl;
R 5 is H;
R 6 is a potassium trifluoroborate group containing crown ether protection.
3. A process for producing an α -diimine ligand of claim 1,
under the action of an organic acid catalyst, heating and reacting a bromobenzamide compound (C) and an alpha-diketone compound (D) at 30-100 ℃ for 6-18 h to generate a compound (E);
under the action of a palladium catalyst, reacting the compound (E) with a compound pinacol diboron at 80-100 ℃ for 2-10 h to generate a compound (F);
4. the method of manufacturing according to claim 3, further comprising:
reacting the compound (F) with a compound potassium bifluoride in a mixed solution of an organic solvent and water at the temperature of between 20 and 50 ℃ for 0.5 to 12 hours to generate a compound (G);
5. the method of claim 4, further comprising:
reacting the compound (G) with the compound 18-crown-6 in an organic solvent at the temperature of between 20 and 50 ℃ for 12 to 96 hours to generate a compound (H);
6. an alpha-diimine nickel complex having the chemical formula shown in formula (II):
A. b is independently selected from unsubstituted C 1 ～C 20 Alkyl, substituted or unsubstituted C 1 ～C 20 Alkoxy, halogen substituted C 1 ～C 20 And A and B are the same, wherein when C is 1 ～C 20 When the alkoxy group of (A) has a substituent, the substituent is selected from C 1 ～C 20 Alkyl of (C) 1 ～C 20 Alkoxy group of (a);
R 1 、R 2 、R 3 、R 4 、R 5 each independently selected from H, C 1 ～C 20 Alkyl of (C) 1 ～C 30 Alkyl-substituted diphenylmethyl, halogen-substituted C 6 ～C 30 Any one of the aryl groups of (a);
R 6 any one of boric acid group, borate group, potassium tetrafluoroborate group and potassium tetrafluoroborate group with crown ether protection;
x is selected from any one of halogen and methyl.
7. A supported alpha-diimine nickel catalyst, which is characterized in that,
the supported nickel alpha-diimine catalyst comprising a support and the nickel alpha-diimine complex of claim 6 supported on the support;
wherein, the carrier preferably comprises any one of silicon dioxide, alumina, titanium dioxide, diatomite and zirconia.
8. A process for preparing polyolefins using the supported nickel alpha-diimine catalyst of claim 7, comprising the steps of:
under the action of the supported alpha-nickel diimine catalyst and the cocatalyst, olefin monomers are heated and reacted in an organic solvent.
9. The method of claim 8,
the cocatalyst is diethyl aluminum chloride.
10. The method of claim 8,
the olefin monomer comprises at least one of ethylene, 6-chloro-1-hexene and 10-methyl undecylenate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791001.7A CN115073506A (en) | 2022-07-05 | 2022-07-05 | Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210791001.7A CN115073506A (en) | 2022-07-05 | 2022-07-05 | Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115073506A true CN115073506A (en) | 2022-09-20 |
Family
ID=83258591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210791001.7A Pending CN115073506A (en) | 2022-07-05 | 2022-07-05 | Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115073506A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115745935A (en) * | 2022-11-24 | 2023-03-07 | 中国科学技术大学 | Coumarin type catalyst ligand, complex catalyst and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608507A (en) * | 2019-01-17 | 2019-04-12 | 中国科学技术大学 | Big steric hindrance diimine nickel catalyst and its ligand, preparation method and purposes |
| CN109956980A (en) * | 2017-12-25 | 2019-07-02 | 杭州星庐科技有限公司 | Ethylidene acenaphthene asymmetry alpha-diimine Raney nickel and its preparation method and application |
-
2022
- 2022-07-05 CN CN202210791001.7A patent/CN115073506A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956980A (en) * | 2017-12-25 | 2019-07-02 | 杭州星庐科技有限公司 | Ethylidene acenaphthene asymmetry alpha-diimine Raney nickel and its preparation method and application |
| CN109608507A (en) * | 2019-01-17 | 2019-04-12 | 中国科学技术大学 | Big steric hindrance diimine nickel catalyst and its ligand, preparation method and purposes |
Non-Patent Citations (3)
| Title |
|---|
| SZABO, MIKLOS J. ET AL: "Copolymerization of Ethylene with Polar Monomers by Anionic Substitution. Theoretical Study Based on Acrylonitrile and the Brookhart Diimine Catalyst", ORGANOMETALLICS, vol. 24, pages 2147 - 2156 * |
| SZABO, MIKLOS J. ET AL: "Copolymerization of ethylene with polar monomers: Chain propagation and side reactions. A DFT theoretical study using zwitterionic Ni(II) and Pd(II) catalysts", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 127, pages 14692 - 14703 * |
| 洪昌文: "后过渡金属催化乙烯聚合及其共聚合研究", 中国博士学位论文全文数据库 工程科技Ⅰ辑, no. 09, pages 3 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115745935A (en) * | 2022-11-24 | 2023-03-07 | 中国科学技术大学 | Coumarin type catalyst ligand, complex catalyst and application thereof |
| CN115745935B (en) * | 2022-11-24 | 2024-02-23 | 中国科学技术大学 | Coumarin type catalyst ligand, complex catalyst and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Durand et al. | The role of nitrogen-donor ligands in the palladium-catalyzed polyketones synthesis | |
| Gong et al. | The enhanced catalytic performance of cobalt catalysts towards butadiene polymerization by introducing a labile donor in a salen ligand | |
| CN108530571B (en) | Iron-based alkylpyridinylimine catalyst and preparation method and application thereof | |
| Sun et al. | Targeting polyethylene waxes: 9-(2-cycloalkylphenylimino)-5, 6, 7, 8-tetrahydrocycloheptapyridylnickel halides and their use as catalysts for ethylene polymerization | |
| CN107428862B (en) | Catalyst composition and method for preparing polyolefin using the same | |
| Zhang et al. | Ni (II) and Fe (II) complexes based on bis (imino) aryl pincer ligands: synthesis, structural characterization and catalytic activities | |
| Konkol et al. | Synthesis, structure and α-olefin polymerization activity of group 4 metal complexes with [OSSO]-type bis (phenolate) ligands | |
| CN108530563B (en) | Application of α -diimine and its metal complex load in olefin polymerization | |
| CN111909196B (en) | IVB-group-containing bimetallic complex catalyst, and preparation method and application thereof | |
| CN115073506A (en) | Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof | |
| CN114315883B (en) | Dibenzofuran phenol IVB metal complex and preparation method thereof, catalyst system and olefin polymerization method | |
| CN111943974A (en) | Metal complex, preparation method and application thereof | |
| CN112358498B (en) | Tetraaryloxy IVB group binuclear metal complex and preparation and application thereof | |
| CN112142775B (en) | Phenolphenanthroline IVB group metal complex and preparation and application thereof | |
| CN107406535B (en) | Composite supported catalyst system and method for preparing polyolefin by using same | |
| CN112876519A (en) | Bridged metallocene compound containing nitrogen or phosphorus heterocyclic ring structure, and preparation method and application thereof | |
| Xu et al. | Novel vanadium (III) complexes with bidentate N, N-chelating iminopyrrolide ligands: Synthesis, characterization and catalytic behaviour of ethylene polymerization and copolymerization with 10-undecen-1-ol | |
| CN105985473B (en) | Catalyst precarsor and preparation method thereof and catalyst and its method of application and ethylene homo | |
| CN108864343B (en) | Binuclear (alpha-diimine) nickel/palladium olefin catalyst, preparation and application | |
| KR100440480B1 (en) | Catalyst for olefin polymerization and method for preparing polyolefins | |
| CN109956978B (en) | Phenanthrenequinone-based asymmetric alpha-diimine nickel catalyst and preparation method and application thereof | |
| CN103288987B (en) | A kind of loaded catalyst for olefinic polymerization and Synthesis and applications thereof | |
| Tsurugi et al. | Preparation and characterization of iminopyrrolyl hafnium complexes as catalyst precursors for α-olefin polymerization | |
| Wang et al. | Synthesis, structure and ethylene polymerization behavior of group 4 metal complexes bearing salicylaldaminato ligands with appended donor functionality | |
| Ogata et al. | Synthesis of palladium (II) pyridyl acylhydrazone complexes and application to homo-and copolymerization of cyclic olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |