WO2018077158A1 - 亚乙烯基苊(α-二亚胺)镍烯烃催化剂、制备方法及应用 - Google Patents

亚乙烯基苊(α-二亚胺)镍烯烃催化剂、制备方法及应用 Download PDF

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WO2018077158A1
WO2018077158A1 PCT/CN2017/107441 CN2017107441W WO2018077158A1 WO 2018077158 A1 WO2018077158 A1 WO 2018077158A1 CN 2017107441 W CN2017107441 W CN 2017107441W WO 2018077158 A1 WO2018077158 A1 WO 2018077158A1
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catalyst
diimine
group
compound
nickel
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傅智盛
何峰
范志强
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浙江大学
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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
    • 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
    • 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
    • C07F15/045—Nickel compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the field of olefin catalytic polymerization, in particular to the preparation and application of a vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst.
  • Polyolefin is a basic material related to the national economy and the people's death, and because of its excellent performance, variety, easy availability and low price, it is widely used in various fields such as industry, agriculture and national defense.
  • the development and application of new catalysts is one of the core driving forces for the advancement and development of the polyolefin industry, and is the key to controlling the structure and performance of polyolefin materials.
  • the Chinese invention patent (CN101812145A) is designed by substituting a para-substituted diphenylethylene skeleton or a fluorenyl skeleton ⁇ -diimine nickel complex. Such complexes can prepare high molecular weight branched polyethylene at higher temperatures by increasing the steric hindrance of the ligand skeleton structure, stabilizing the active center, and improving the thermal stability of the catalyst.
  • the synthesis of such catalyst ligands is complicated, activated by methylaluminoxane, and the ratio of aluminum to nickel in the polymerization process. High (600) is not conducive to industrialization and commercialization.
  • Chinese invention patent CN 201210276331 provides a catalyst (structure shown as formula (IV)):
  • the catalyst effectively improves the heat resistance of the catalyst by introducing an ethylene bridge bond to the skeleton, and is capable of catalyzing ethylene polymerization at ⁇ 60 ° C to obtain a branched polyethylene.
  • this catalyst still has technical defects that it is impossible to prepare a high molecular weight, high degree of branching polyethylene. If a high molecular weight polyethylene is prepared by increasing the polymerization pressure or lowering the polymerization temperature, the degree of branching of the polyethylene is remarkably lowered.
  • the present invention provides a vinylidene fluorene. ( ⁇ -diimine) nickel olefin catalyst, preparation method and application thereof.
  • the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a vinylidene oxime ( ⁇ -diimine) nickel olefin catalyst, a preparation method and application thereof.
  • the solution of the present invention is:
  • O 1 , O 2 , O 3 , O 4 may be the same or different, and may be selected from any one of hydrogen, halogen, alkyl, haloalkyl, aryl or aralkyl;
  • P 1 , P 2 may be the same or different and may be selected from any one of hydrogen, halogen, amino, alkyl, haloalkyl, aryl or aralkyl.
  • the present invention provides a vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst having a chemical structural formula as shown in the formula (I):
  • R 1 is an alkyl group
  • R 2 is hydrogen or an alkyl group
  • X is chlorine or bromine
  • X in the catalyst is preferably bromine, and its chemical structural formula is as shown in formula (II):
  • R 1 is a methyl group, an ethyl group, an isopropyl group or a tert-butyl group
  • R 2 is hydrogen, a methyl group or a tert-butyl group.
  • the invention further provides a preparation method of the vinylidene ruthenium ( ⁇ -diimine) nickel olefin catalyst, the steps of which are as follows:
  • the invention still further provides the use of the vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst for catalyzing the polymerization of ethylene and propylene to prepare polyethylene and polypropylene.
  • the present invention also provides a ligand compound for preparing the vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst of claim 1.
  • R A and R B are as shown in formulas (VI) and (VII), respectively:
  • O 1 , O 2 , O 3 , O 4 may be the same or different, and may be selected from any one of hydrogen, halogen, alkyl, haloalkyl, aryl or aralkyl; P 1 and P 2 may be the same or different and may be selected from any one of hydrogen, halogen, amino, alkyl, haloalkyl, aryl or aralkyl.
  • O 1 , O 2 , O 3 and O 4 are preferably any one of a methyl group, an ethyl group, an isopropyl group or a tert-butyl group; and P 1 and P 2 are preferably hydrogen or a methyl group. Or any of the butyl groups.
  • the compound corresponding to the above structural formula (X) can be complexed with a compound containing a late transition metal such as metal nickel or palladium to form a late transition metal olefin polymerization catalyst. Since the cost of metallic nickel is low, it is a practical choice to synthesize a compound corresponding to structural formula (X) with a metal nickel-containing compound to form a vinylidene ( ⁇ -diimine) nickel olefin catalyst.
  • the biggest innovation of the present invention is that the top of the catalyst skeleton is adjusted to introduce a bridged double bond, i.e., a vinylidene group, and the technique can theoretically optimize all the catalysts of the formula (XI) and (XII) in the prior art, and Various R A and R B in the prior art can be used, and have strong practicability.
  • a vinylidene group on the skeleton naphthalene ring of the catalyst By introducing a vinylidene group on the skeleton naphthalene ring of the catalyst, the skeleton structure of the catalyst is more conjugated, and the skeleton structure is more stable, so that the thermal stability of the catalyst is higher.
  • the skeletal structure of the catalyst is more conjugated, which can restrict the flow of electrons on the skeleton to the metallic nickel, so that the electronegativity of the metallic nickel is stronger, and the chain walking of the catalyst is more favorable, thereby preparing a high molecular weight and a high degree of branching.
  • Polyethylene
  • the present invention has the following beneficial effects:
  • the vinylidene fluorene ( ⁇ -diimine) nickel olefin polymerization catalyst of the present invention has high activity and good thermal stability, and is capable of catalyzing ethylene at a temperature of 60 ° C or higher to obtain a high molecular weight hyperbranched polyethylene.
  • the classic Brookhart catalyst loses its catalytic activity at 60 °C.
  • the vinylidene fluorene ( ⁇ -diimine) nickel olefin polymerization catalyst of the present invention is compared to an ethylene cerium ( ⁇ -diimine) nickel catalyst under the same polymerization conditions (structure is as shown in formula (IV) Shown and the classic Brookhart catalyst (structure shown in formula (III)) can catalyze the polymerization of ethylene to obtain higher molecular weight branched polyethylene to meet more application needs.
  • the vinylidene fluorene ( ⁇ -diimine) nickel olefin polymerization catalyst of the present invention exhibits high activity at an aluminum to nickel ratio of 100, and the thermally stable ⁇ -diimine nickel olefin polymerization reported in the prior art.
  • the aluminum-nickel ratio required for the catalyst to catalyze ethylene polymerization is generally higher than 500, which greatly reduces the production cost.
  • the vinylidene fluorene ( ⁇ -diimine) nickel olefin polymerization catalyst of the invention has low raw material cost and high reaction yield, and can realize industrial production.
  • R 1 is an alkyl group
  • R 2 is hydrogen or an alkyl group
  • X is chlorine or bromine
  • the vinylidene ( ⁇ -diimine) nickel catalyst on the naphthalene ring can form a conjugate with the naphthalene ring, increasing the volume of the conjugated system of the catalyst skeleton, making the catalyst more stable in space structure and reducing The chain transfer reaction of the catalyst in the catalytic process. Therefore, the vinylidene oxime ( ⁇ -diimine) nickel catalyst has higher thermal stability, and the obtained hyperbranched polyethylene has a higher molecular weight.
  • the preparation method of the vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst comprises the following steps:
  • hydrazine is subjected to a double acylation reaction to obtain a compound C1: hydrazine is used as a raw material, and carbon disulfide is a solvent. Anhydrous aluminum bromide was added as a catalyst to obtain a yellow solid anthracenedion C1 under the conditions of oxalyl bromide as an oxidizing agent.
  • compound C2 is subjected to bromination reaction to obtain compound C2: the compound C1 obtained in the step (1) is used as a raw material, carbon tetrachloride is used as a solvent, benzoyl peroxide is used as an initiator, and N-bromosuccinimide (NBS) As a brominating agent, the compound C2 can be obtained by a bromination reaction.
  • NBS N-bromosuccinimide
  • Compound C2 is subjected to elimination reaction to obtain compound C3: the compound C2 obtained in the step (2) is used as a raw material, acetone is used as a solvent, and anhydrous potassium iodide is used as an initiator, and the terpene dione C3 can be obtained by eliminating the reaction.
  • the compound C3 is subjected to a ketoamine condensation reaction with a symmetric aniline to obtain an ⁇ -diimine ligand C4-C8.
  • the terpene diketone (C3) raw material obtained in the step (3), acetonitrile as a solvent and acetic acid as a catalyst are obtained by a ketoamine condensation reaction to obtain an ⁇ -diimine ligand (C4-C8).
  • the four ⁇ -diimine ligands C4-C8 can be complexed with ethylene glycol dimethyl ether [(DME)NiCl 2 ] under anhydrous and anaerobic conditions to obtain a catalyst ( C14-C18).
  • acylation reaction, bromination reaction, elimination reaction, ketoamine condensation reaction and complexation reaction involved in the above catalyst synthesis are all classical reactions in the literature, and the input amount and reaction conditions of each reactant during the synthesis process.
  • the reaction parameters are all common and are well known to those skilled in the art and are not specifically required in the present invention.
  • the use of the vinylidene fluorene ( ⁇ -diimine) nickel olefin catalyst of the present invention in the preparation of polyethylene and polypropylene means that the vinylidene oxime ( ⁇ - in the formula (I) of the present invention is used.
  • a diimine nickel olefin polymerization catalyst in a cocatalyst such as methylaluminoxane, modified methylaluminoxane, diethylaluminum chloride, sesquiethylaluminum chloride or ethylaluminum dichloride
  • ethylene or propylene is catalyzed in the range of 25 to 95 ° C to prepare a higher molecular weight hyperbranched polyethylene or polypropylene.
  • Example 10 The (DME)NiBr 2 in Example 10 was replaced with an equivalent mass of (DME)NiCl 2 , and the remaining conditions were unchanged to obtain a catalyst C14.
  • the mass of the catalyst obtained was 0.254 g and the yield was 57.32%.
  • Example 11 The (DME)NiBr 2 in Example 11 was replaced with an equivalent mass of (DME)NiCl 2 , and the remaining conditions were unchanged to obtain a catalyst C15.
  • the mass of the obtained catalyst was 0.337 g, and the yield was 58.72%.
  • Example 12 The (DME)NiBr 2 in Example 12 was replaced with an equivalent mass of (DME)NiCl 2 , and the remaining conditions were unchanged to obtain a catalyst C16.
  • the mass of the catalyst obtained was 0.282 g and the yield was 55.23%.
  • Example 13 The (DME)NiBr 2 in Example 13 was replaced with an equivalent mass of (DME)NiCl 2 , and the remaining conditions were unchanged to obtain a catalyst C17.
  • the mass of the catalyst obtained was 0.342 g, and the yield was 50.79%.
  • Example 14 The (DME)NiBr 2 in Example 14 was replaced with an equivalent mass of (DME)NiCl 2 , and the remaining conditions were unchanged to obtain a catalyst C18.
  • the mass of the obtained catalyst was 0.291 g, and the yield was 57.48%.
  • the atmospheric pressure polymerization of ethylene is carried out under anhydrous and anaerobic conditions.
  • the ethylene pressure was 0.1 MPa
  • the polymerization temperature was 60 ° C
  • 40 mL of the toluene solution was poured into a 100 mL Schlenk bottle, and then 1.0 mmol of a cocatalyst diethylaluminum chloride was poured thereinto.
  • 5 ⁇ mol of the main catalyst C9 was dissolved in 10 mL of a toluene solution, and it was injected.
  • the polymer solution was poured into an acidified ethanol solution to precipitate, the polymer was filtered, and then washed with ethanol several times, and dried under vacuum at 50 ° C to a constant weight to obtain 0.68 g of a polymer.
  • the catalyst activity was 272 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 25 kg/mol, and the polydispersity coefficient was 1.87.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 106/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C10 to obtain 2.98 g of a polymer.
  • the catalyst activity was 1193 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 243 kg/mol, and the polydispersity coefficient was 1.80.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 116/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the main catalyst used for the polymerization was C11 to obtain 0.79 g of a polymer.
  • the catalyst activity was 316 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 32 kg/mol, and the polydispersity coefficient was 1.82.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 105/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C12 to obtain 2.41 g of a polymer.
  • the catalyst activity was 964 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 213 kg/mol, and the polydispersity coefficient was 1.86.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 112/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C13 to obtain 1.43 g of a polymer.
  • the catalyst activity was 572 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 57 kg/mol, and the polydispersity coefficient was 1.76.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 107/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C14 to obtain 0.59 g of a polymer.
  • the catalyst activity was 236 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 31 kg/mol, and the polydispersity coefficient was 1.82.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 103/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C15 to obtain 2.64 g of a polymer.
  • the catalyst activity was 1056 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 267 kg/mol, and the polydispersity coefficient was 1.89.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 112/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the main catalyst used for the polymerization was C16 to obtain 0.71 g of a polymer.
  • the catalyst activity was 284 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 39 kg/mol, and the polydispersity coefficient was 1.80.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 101/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C17 to obtain 2.30 g of a polymer.
  • the catalyst activity was 921 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 225 kg/mol, and the polydispersity coefficient was 1.87.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 105/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the catalyst used for the polymerization was C18 to obtain 1.34 g of a polymer.
  • the catalyst activity was 536 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 64 kg/mol, and the polydispersity coefficient was 1.85.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 102/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 20, and the polymerization temperature was 25 ° C to obtain 4.16 g of a polymer.
  • the catalyst activity was 1664 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 413 kg/mol, and the polydispersity coefficient was 1.67.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 101/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the polymerization temperature was 80 ° C to obtain 1.39 g of a polymer.
  • the catalyst activity was 556 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 171 kg/mol, and the polydispersity coefficient was 1.88.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 117/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the polymerization temperature was 95 ° C to obtain 0.98 g of a polymer.
  • the catalyst activity was 392 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 142 kg/mol, and the polydispersity coefficient was 1.91.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 120/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the cocatalyst used in the polymerization was diethylaluminum dichloride to obtain 3.31 g of a polymer.
  • the catalyst activity was 1324 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 120 kg/mol, and the polydispersity coefficient was 1.83.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 114/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the cocatalyst used in the polymerization was methylaluminoxane, and 1.41 g of a polymer was obtained.
  • the catalyst activity was 564 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 243 kg/mol, and the polydispersity coefficient was 1.87.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 111/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the cocatalyst used in the polymerization was a modified methyl aluminoxane, and 1.87 g of a polymer was obtained.
  • the catalyst activity was 748 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 223 kg/mol, and the polydispersity coefficient was 1.86.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 112/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the cocatalyst used in the polymerization reaction was sesquiethylaluminum chloride to obtain 3.14 g of a polymer.
  • the catalyst activity was 1256 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 197 kg/mol, and the polydispersity coefficient was 1.86.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 113/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and 0.5 mmol of a cocatalyst of diethylaluminum chloride was added to the polymerization to obtain 2.62 g of a polymer.
  • the catalyst activity was 1049 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 214 kg/mol, and the polydispersity coefficient was 1.84.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 117/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and 2.0 mmol of a cocatalyst of diethylaluminum chloride was added to the polymerization to obtain 3.45 g of a polymer.
  • the catalyst activity was 1380 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 221 kg/mol, and the polydispersity coefficient was 1.87.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 113/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and 3.0 mmol of a cocatalyst of diethylaluminum chloride was added to the polymerization to obtain 3.13 g of a polymer.
  • the catalyst activity was 1252 kg PE [mol(Ni)h] -1
  • the weight average molecular weight of the polymerization product was 231 kg/mol
  • the polydispersity coefficient was 1.88.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 113/1000 carbon atoms.
  • the ethylene pressure polymerization was carried out using a stainless steel high pressure 2 L reactor manufactured by Büchi.
  • the ethylene pressure was 0.4 MPa
  • the polymerization temperature was 60 ° C
  • 1 L of the n-heptane solution was poured into the reaction vessel, and then 2.0 mmol of a cocatalyst diethylaluminum chloride was injected thereto.
  • 10 ⁇ mol of the main catalyst C9 was dissolved in 20 mL of a toluene solution, and it was injected.
  • the polymer solution was poured into an acidified ethanol solution to precipitate, the polymer was filtered, washed with ethanol, and dried under vacuum at 50 ° C to a constant weight to give 25.95 g of a polymer.
  • the catalyst activity was 5190 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 263 kg/mol, and the polydispersity coefficient was 1.80.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 107/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 40, and the ethylene pressure in the polymerization was 1.4 MPa to obtain 38.95 g of a polymer.
  • the catalyst activity was 7790 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 355 kg/mol, and the polydispersity coefficient was 1.81.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 90/1000 carbon atoms.
  • a vinylidene ruthenium ( ⁇ -diimine) nickel catalyst catalyzes the polymerization of propylene
  • the other polymerization conditions and the polymer treatment method were the same as in Example 21, and the reaction gas in the polymerization reaction was 0.1 MPa of propylene to obtain 0.08 g of a polymer.
  • the catalyst activity was 30 kg PP [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 98 kg/mol, the polydispersity coefficient was 1.68, and the degree of branching of the polymer was determined by 1 H-NMR to be 225/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 42 except that the reaction temperature in the polymerization was 25 ° C to obtain 0.35 g of a polymer.
  • the catalyst activity was 132 kg PP [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 159 kg/mol, the polydispersity coefficient was 1.22, and the degree of branching of the polymer was determined by 1 H-NMR to be 241/1000 carbon atoms.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 42 except that the reaction temperature in the polymerization was 0 ° C to obtain 0.29 g of a polymer.
  • the catalyst activity was 109 kg PP [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 142 kg/mol, the polydispersity coefficient was 1.08, and the degree of branching of the polymer was 262/1000 carbon atoms by 1 H-NMR.
  • the other polymerization conditions and the polymer treatment method were the same as in Example 43 except that the cocatalyst used in the polymerization was methylaluminoxane, and 0.27 g of a polymer was obtained.
  • the catalyst activity was 108 kg PP [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 167 kg/mol, and the polydispersity coefficient was 1.20.
  • the catalyst C9 of Example 21 was replaced by the catalyst 3 in the formula (III) (i.e., the classical Brookhart catalyst), and the other operations were the same as in Example 19 to give 2.56 g of a polymer.
  • the catalyst activity was 1024 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 174 kg/mol, and the polydispersity coefficient was 2.0.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 113/1000 carbon atoms.
  • Catalyst 3 in Example (III) (i.e., the classical Brookhart catalyst) was used in place of Catalyst C9 in Example 31, and the other operations were the same as in Example 29 to give 0.76 g of polymer.
  • the catalyst activity was 299 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 85 kg/mol, and the polydispersity coefficient was 2.0.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 111/1000 carbon atoms.
  • the catalyst C9 in Example 21 was replaced with an ethylene sulfonium ( ⁇ -diimine) nickel catalyst represented by the formula (IV), and the other operations were the same as in Example 19 to give 2.75 g of a polymer.
  • the catalyst activity was 1075 kg PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 168 kg/mol, and the polydispersity coefficient was 2.0.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 115/1000 carbon atoms.
  • the catalyst C9 in Example 31 was replaced with an ethylene sulfonium ( ⁇ -diimine) nickel catalyst represented by the formula (IV), and the other operation was the same as that of the operation 29 to give 0.95 g of a polymer.
  • the catalyst activity was 374 kg of PE [mol(Ni)h] -1 , the weight average molecular weight of the polymerization product was 98 kg/mol, and the polydispersity coefficient was 1.8.
  • the degree of branching of the polymer was determined by 1 H-NMR to be 116/1000 carbon atoms.
  • the vinylidene fluorene ( ⁇ -diimine) nickel olefin polymerization catalyst provided by the present invention is better than the existing ( ⁇ -diimine) nickel olefin catalyst. It is thermally stable and can catalyze the polymerization of ethylene under the same polymerization conditions to obtain a higher molecular weight branched polyethylene, which can meet more application requirements.

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Abstract

提供一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂及其制备与应用。合成步骤包括: 苊经过双酰化反应得到化合物C1；对化合物C1与N-溴代琥珀酰亚胺(NBS)进行溴化反应得到C2；对化合物C2进行消除反应得到C3；将化合物C3与对称的苯胺进行酮胺缩合反应，即可得到α-二亚胺配体C4-C8；在无水无氧的条件下，将α-二亚胺配体C4-C8与乙二醇二甲醚二溴化镍络合，即得到最终产品。该催化剂活性更高，热稳定性更好，能够在大于等于60℃下高活性催化乙烯得到高分子量超支化聚乙烯。在同样的聚合条件下可以催化乙烯聚合得到更高分子量的支化聚乙烯，从而满足更多应用需求。制备原料成本低，反应产率高，可以实现工业化生产。

Description

亚乙烯基苊(α-二亚胺)镍烯烃催化剂、制备方法及应用 技术领域
本发明涉及烯烃催化聚合领域，具体提供了一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂的制备及其应用。
背景技术
聚烯烃是关系国计民生的基础材料，并且由于其优异的性能、品种的多样，原料易得和价格低廉，使其广泛应用于工业、农业以及国防等各领域。新催化剂的开发和应用是推动聚烯烃产业进步和发展的核心动力之一，是控制聚烯烃材料的结构与性能的关键。
近几十年来，通过配位聚合获得功能化与差别化聚烯烃材料的研究得到了广泛的关注。1995年由杜邦公司资助的Brookhart研究小组发现含α-二亚胺配体的Ni(Ⅱ)和Pd(Ⅱ)金属络合物可在常压下催化乙烯聚合成高分子量聚合物，由此开发出新一代的后过渡金属催化剂(J.Am.Chem.Soc.,1995,117(23):6414-6415)。这类α-二亚胺镍烯烃催化剂的具体结构如式(Ⅲ)所示：
Figure PCTCN2017107441-appb-000001
到目前为止，大量的研究工作在保持二(芳基)α-二亚胺配体布局不变的情况下，对芳基的邻位基团(图中的R')和二亚胺骨架上的基团(图的R基团)进行了修饰。当R'从异丙基换成甲基时，所得聚合物的支化度和分子量都降低，并且拓扑结构更加线性。然而，这类催化剂的热稳定性差，即使当R'为大位阻的异丙基时，使用这类催化剂制备的聚乙烯分子量和催化剂活性都随温度的上升急剧下降。当聚合温度上升到高于60℃时，催化剂受热迅速分解而失活。中国发明专利(CN101812145A)通过设计一种对位取代二苯亚乙基骨架或莰基骨架α-二亚胺镍配合物。这类配合物通过增加配体骨架结构的位阻，稳定活性中心，提高催化剂的热稳定性，能够在较高温度下制备高分子量支化聚乙烯。然而，合成这类催化剂配体工艺较为复杂，以甲基铝氧烷活化，聚合过程中铝镍比 高(600)，不利于工业化和商业化。中国发明专利CN 201210276331提供了一种催化剂(结构如式(Ⅳ)所示)：
Figure PCTCN2017107441-appb-000002
该催化剂通过在骨架上引入亚乙基桥键，有效地提高了催化剂的耐热性，能够在≥60℃下高活性催化乙烯聚合得到支化聚乙烯。但是，该催化剂仍存在无法制备高分子量、高支化度聚乙烯的技术缺陷。如果通过提高聚合压力或降低聚合温度来制备高分子量的聚乙烯，则聚乙烯的支化度会明显下降。
为了进一步改善(α-二亚胺)镍烯烃催化剂的热稳定性，提升制备的支化聚乙烯的分子量，满足实际生产条件以及更多的实际应用需求，本发明提供了一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂、制备方法及应用。
发明内容
本发明要解决的技术问题是，克服现有技术的不足，提供一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂、制备方法及应用。
为解决技术问题，本发明的解决方案是：
通过调整配体骨架结构，提供一类相对现有技术中的结构式如(Ⅺ)、(Ⅻ)的(α-二亚胺)镍烯烃催化剂更为优化的结构式如(V)的(α-二亚胺)镍烯烃催化剂：
Figure PCTCN2017107441-appb-000003
式(Ⅺ)、(Ⅻ)和(Ⅴ)中，X为氯或溴，RA和RB的结构式分别如式(Ⅵ)和(Ⅶ)所示：
Figure PCTCN2017107441-appb-000004
其中O1、O2、O3、O4可以相同，也可以不同，均可以选自氢、卤素、烷基、含卤烷基、芳基或芳烷基中的任意一种；P1、P2可以相同，也可以不同，均可以选自氢、卤素、氨基、烷基、含卤烷基、芳基或芳烷基中的任意一种。
具体的，本发明提供一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂，其化学结构式如式(I)所示：
Figure PCTCN2017107441-appb-000005
式中R1为烷基，R2为氢或烷基，X为氯或溴。
该催化剂中的X优选为溴，其化学结构式如式(Ⅱ)所示：
Figure PCTCN2017107441-appb-000006
本发明中，所述式(Ⅰ)或(Ⅱ)中，R1为甲基、乙基、异丙基或特丁基，R2为氢、甲基或特丁基。
本发明进一步提供了所述亚乙烯基苊(α-二亚胺)镍烯烃催化剂的制备方法，其步骤如下：
1)苊经过双酰化反应得到化合物C1：
Figure PCTCN2017107441-appb-000007
2)化合物C1与N-溴代琥珀酰亚胺(NBS)进行溴化反应得到化合物C2：
Figure PCTCN2017107441-appb-000008
3)化合物C2进行消除反应得到化合物C3：
Figure PCTCN2017107441-appb-000009
4)化合物C3与对称的苯胺进行酮胺缩合反应，即可得到α-二亚胺配体C4-C8：
Figure PCTCN2017107441-appb-000010
5)在无水无氧的条件下，将α-二亚胺配体C4-C8与乙二醇二甲醚二溴化镍、乙二醇二甲醚二氯化镍、四水合氯化镍或六水合氯化镍中的一种络合，即可得式(Ⅰ)或(Ⅱ)中亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂。
本发明还进一步提供了所述的亚乙烯基苊(α-二亚胺)镍烯烃催化剂在催化乙烯、丙烯聚合，制备聚乙烯、聚丙烯中的应用。
本发明还提供了用于制备权利要求1所述亚乙烯基苊(α-二亚胺)镍烯烃催化剂的配体化合物，
该化合物的结构如式(Ⅹ)所示：
Figure PCTCN2017107441-appb-000011
其中，RA和RB的结构式分别如式(Ⅵ)和(Ⅶ)所示：
Figure PCTCN2017107441-appb-000012
上式中，O1、O2、O3、O4可以相同，也可以不同，均可以选自氢、卤素、烷基、含卤烷基、芳基或芳烷基中的任意一种；P1、P2可以相同，也可以不同，均可以选自氢、卤素、氨基、烷基、含卤烷基、芳基或芳烷基中的任意一种。本发明所述化合物(Ⅹ)中，O1、O2、O3、O4优选甲基、乙基、异丙基或特丁基的任意一种；P1、P2优选氢、甲基或特丁基中的任意一种。
上述结构式(Ⅹ)对应的化合物，可以与含有金属镍或钯等后过渡金属的化合物进行络合，成为后过渡金属烯烃聚合催化剂。由于金属镍的成本较低，因此结构式(Ⅹ)对应的化合物与含有金属镍的化合物进行络合成为亚乙烯基苊(α-二亚胺)镍烯烃催化剂是一种较为实用的选择。
发明原理描述：
本发明的最大的创新点在于调整了催化剂骨架顶部，引入桥联的双键，即亚乙烯基，该技术理论上可以优化现有技术中所有结构式为(Ⅺ)、(Ⅻ)的催化剂，并且现有技术中的各种RA和RB可以沿用，具有很强的实用性。通过在催化剂的骨架萘环上引入亚乙烯基，使得催化剂的骨架结构更加共轭，骨架结构更稳定，从而使得催化剂的热稳定性更高。另外，催化剂的骨架结构更加共轭，可以限制骨架上的电子流动到金属镍上，使得金属镍的电负性更强，更加有利于催化剂的链行走，从而制备高分子量、高支化度的聚乙烯。
与现有技术相比，本发明具有以下有益效果：
1.本发明的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂活性高，热稳定性好，能够在大于等于60℃下高活性催化乙烯得到高分子量超支化聚乙烯。然而，经典的Brookhart催化剂在60℃下就失去催化活性。
2.本发明的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂在同样的聚合条件下相比于亚乙基苊(α-二亚胺)镍催化剂(结构如式(Ⅳ)所示)和经典的Brookhart催化剂(结构如式(Ⅲ)所示)可以催化乙烯聚合得到更高分子量的支化聚乙烯，从而满足更多应用需求。
3.本发明的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂在铝镍比为100时就能显示出高活性，现有技术报道的热稳定性α-二亚胺镍烯烃聚合催化剂催化乙烯聚合时所需铝镍比一般要高于500，极大地降低了生产成本。
4.本发明的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂制备原料成本低，反应产率高，可以实现工业化生产。
具体实施方式
下面以化学结构式如式(I)所示的亚乙烯基苊(α-二亚胺)镍烯烃催化剂为例，对其制备方法及应用方法进行介绍：
Figure PCTCN2017107441-appb-000013
式(Ⅰ)中，其中R1为烷基，R2为氢或烷基，X为氯或溴。
亚乙烯基苊(α-二亚胺)镍催化剂在萘环上的亚乙烯基可以和萘环形成共轭，将催化剂骨架的共轭体系体积增大，使得催化剂在空间结构上更加稳定，减少了催化剂在催化过程中的链转移反应。因此，亚乙烯基苊(α-二亚胺)镍催化剂的热稳定性更高，得到的超支化聚乙烯的分子量更高。
所述的亚乙烯基苊(α-二亚胺)镍烯烃催化剂的制备方法，包括以下步骤：
1)苊经过双酰化反应得到化合物C1：以苊为原料，二硫化碳为溶剂。加入无水溴化铝作催化剂，在草酰溴作氧化剂的条件下得到黄色固体苊二酮C1。
Figure PCTCN2017107441-appb-000014
2)化合物C1进行溴化反应得到化合物C2：以步骤(1)中得到化合物C1为原料，四氯化碳作溶剂，过氧化苯甲酰作引发剂，N-溴代琥珀酰亚胺(NBS)作溴化剂，通过溴化反应可以得到化合物C2。
Figure PCTCN2017107441-appb-000015
3)化合物C2进行消除反应得到化合物C3：以步骤(2)中得到化合物C2为原料，丙酮作溶剂，无水碘化钾作引发剂，通过消除反应可以得到苊烯二酮C3。
Figure PCTCN2017107441-appb-000016
4)化合物C3与对称的苯胺进行酮胺缩合反应，即可得到α-二亚胺配体C4-C8。将步骤(3)中所得苊烯二酮(C3)原料，乙腈为溶剂，乙酸为催化剂，通过酮胺缩合反应得到α-二亚胺配体(C4-C8)。
Figure PCTCN2017107441-appb-000017
5)在无水无氧的条件下，将4种α-二亚胺配体C4-C8与乙二醇二甲醚二溴化镍[(DME)NiBr2]络合，即可得催化剂(C9-C13)；
Figure PCTCN2017107441-appb-000018
或者，在无水无氧的条件下，将4种α-二亚胺配体C4-C8与乙二醇二甲醚二氯化镍[(DME)NiCl2]络合，即可得催化剂(C14-C18)。
Figure PCTCN2017107441-appb-000019
上述催化剂合成过程中所涉及的双酰化反应、溴化反应、消除反应、酮胺缩合反应和络合反应均为文献中的经典反应，在其合成过程中各反应物的投入量和反应条件等反应参数都是通用的，是本技术领域科研工作者所公知的，在本发明中没有特别要求。
本发明所述的亚乙烯基苊(α-二亚胺)镍烯烃催化剂在制备聚乙烯、聚丙烯中的应用是指，将本发明所述式(Ⅰ)中的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂在助催化剂甲基铝氧烷、改性的甲基铝氧烷、一氯二乙基铝、倍半乙基氯化铝或二氯乙基铝中的一种的活化下，在25～95℃范围内催化乙烯或丙烯聚合，制备较高分子量超支化聚乙烯或聚丙烯。
以下通过具体实施例对本发明做进一步的说明。
一、化合物C2的制备
实施例1
将2g(9.6mmol)C1加入装有250mL四氯化碳的500mL三口瓶中，N2保护下在85℃回流30min，向体系中加入5.2g(30mmol)N-溴代琥珀酰亚胺(NBS)和200mg过氧化苯甲酰，将混合物继续在85℃下回流5h。反应结束后，趁热过滤，并用50mL热CCl4洗涤，对于洗涤得到的混合物进行旋转蒸发，除去溶剂四氯化碳，得到黄色固体，为产物C2和NBS的混合物。用二氯甲烷为淋洗液进行柱层析纯化，一共得到产物C2的质量为2.311g，产率为65.57％。
1H-NMR(400MHz，CDCl3，δin ppm)：8.25(dd，2H，Ar-H)，7.91(dd，2H，Ar-H)，6.09(s，2H，CH)。
二、化合物C3的制备
实施例2
将1.25g(34.2mmol)C2在氮气保护下溶于100mL丙酮中，将丙酮溶液加入到250mL的三口瓶中，然后向三口瓶中再加入7.5g(0.46mol)无水碘化钾，在60℃下回流4h。反应结束后，将混合物冷却，倒入硫代硫酸钠的水溶液中，混合物用氯仿萃取三次，再用去离子水洗涤三次，旋转蒸发后得到红色产物C3，产量为0.960g，产率为99.92％。
1H-NMR(400MHz,CDCl3,δin ppm)：8.26(dd,2H,Ar-H)，8.13(dd,2H,Ar-H)，7.69(s，2H，CH)。
实施例3
将80g(0.22mol)C2在氮气保护下溶于6L丙酮中，将丙酮溶液加入到10L的三口瓶中，然后向三口瓶中再加入480g(2.9mol)无水碘化钾，在70℃下回流8h。反应结束后，将混合物冷却，倒入硫代硫酸钠的水溶液中，混合物用氯仿萃取三次，再用去离子水洗涤三次，旋转蒸发后得到红色产物C3，产量为42.1g，产率为93.50％。
1H-NMR(400MHz,CDCl3,δin ppm)：8.25(dd,2H,Ar-H)，8.11(dd,2H,Ar-H)，7.67(s，2H，CH)。
三、配体的制备
实施例4
在氮气保护下向250mL三口瓶中加入0.28g(1.36mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入6mL乙酸，升温至85℃后再继续回流15min，反应瓶中固体完全溶解。之后，趁热向反应瓶中加入0.61mL(2.86mmol)2,6-二甲基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入质量比为0.75％的三乙胺)，一共得到配体C4的质量为0.442g，产率为78.93％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-7.8(s，10H，Ar-H)，7.26(s，2H，CH)，2.35(s，12H，CH3)。
Elem.Anal.Calcd.For C30H24N2：C，87.35％；H，5.86％；N，6.79％。Found：C，87.26％；H，6.02％；N，6.72％。
ESI-MS：m/z 413.20([M+H]+)。
实施例5
在氮气保护下向250mL三口瓶中加入0.30g(1.45mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入6mL乙酸，升温至85℃后再继续回流15min，反应瓶中固体完全溶解，之后，趁热向反应瓶中加入0.65mL(3.09mmol)2,6-二异丙基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入0.75％的三乙胺)，一共得到配体C5的质量为0.583g，产率为76.35％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-8.2(s，10H，Ar-H)，7.26(s，2H，CH)，2.98-3.14(sept，4H，CH(CH3)2)，0.86-1.36(dd，24H，CH(CH3)2)。
Elem.Anal.Calcd.For C38H40N2：C，86.98％；H，7.68％；N，5.34％。Found：C，86.86％；H，7.60％；N，5.54％。
ESI-MS：m/z 525.10([M+H]+)。
实施例6
在氮气保护下向250mL三口瓶中加入0.25g(1.21mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入6mL乙酸，升温至85℃后再继续回流15min，反应瓶中固体完全溶解，之后，趁热向反应瓶中加入0.54mL(2.69mmol)2,4,6-三甲基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷 ＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入0.75％的三乙胺)，一共得到配体C6的质量为0.388g，产率为72.67％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-8.2(s，8H，Ar-H)，7.26(s，2H，CH)，2.42(s，12H，CH3)，2.30(s，6H，CH3)。
Elem.Anal.Calcd.For C32H28N2：C，87.24％；H，6.41％；N，6.36％。Found：C，87.12％；H，6.50％；N，6.38％。
ESI-MS：m/z 441.30([M+H]+)。
实施例7
在氮气保护下向250mL三口瓶中加入0.27g(1.31mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入6mL乙酸，升温至85℃后再继续回流15min，反应瓶中固体完全溶解，之后，趁热向反应瓶中加入0.58mL(2.91mmol)2,4,6-三特丁基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入0.75％的三乙胺)，一共得到配体C7的质量为0.5103g，产率为70.53％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-8.2(s，8H，Ar-H)，7.26(s，2H，CH)，1.45(s，36H，C(CH3)3)，1.32(s，18H，C(CH3)3)。
Elem.Anal.Calcd.For C50H64N2：C，86.65％；H，9.31％；N，4.04％。Found：C，86.42％；H，9.45％；N，4.13％。
ESI-MS：m/z 694.20([M+H]+)。
实施例8
在氮气保护下向250mL三口瓶中加入0.31g(1.50mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入8mL乙酸，升温至90℃后再继续回流20min，反应瓶中固体完全溶解，之后，趁热向反应瓶中加入0.87mL(3.34mmol)2,4,6-三特丁基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入0.75％的三乙胺)，一共得到配体C7的质量为0.822g，产率为78.92％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-8.2(s，8H，Ar-H)，7.26(s，2H，CH)，1.45(s，36H，C(CH3)3)，1.32(s，18H，C(CH3)3)。
Elem.Anal.Calcd.For C50H64N2：C，86.65％；H，9.31％；N，4.04％。Found：C，86.42％；H，9.45％；N，4.13％。
ESI-MS：m/z 694.20([M+H]+)。
实施例9
在氮气保护下向250mL三口瓶中加入0.27g(1.31mmol)化合物C3，加入120mL乙腈，加热至80℃，回流30min，加入6mL乙酸，升温至85℃后再继续回流15min，反应瓶中固体完全溶解，之后，趁热向反应瓶中加入0.7ml(4.26mmol)2,6-二乙基苯胺，85℃回流反应24h。反应结束后，通过旋转蒸发除去乙腈，用石油醚:二氯甲烷＝1:1的淋洗液进行柱层析纯化(淋洗剂中加入0.75％的三乙胺)，一共得到配体C8的质量为0.443g，产率为72.0％。
1H-NMR(400MHz，CD3OD，δin ppm)：6.9-8.2(s，10H，Ar-H)，7.20(s，2H，CH)，2.62(q，8H，CH2)，1.26(t，12H，CH3)。
Elem.Anal.Calcd.For C50H64N2：C，87.14％；H，6.88％；N，5.98％。Found：C，87.02％；H，7.01％；N，5.97％。
ESI-MS：m/z 469.4([M+H]+)。
四、亚乙烯基苊(α-二亚胺)镍络合物的制备
实施例10
将0.263g(0.85mmol)的(DME)NiBr2在氮气保护下加入到50mL的Schlenk瓶中，注入15mL二氯甲烷，搅拌，形成淡黄色悬浮液。将0.338g(0.82mmol)的C4在氮气保护下加入到50mL单颈圆底烧瓶中，注入15mL二氯甲烷，溶液为暗红色。用注射器将该暗红色溶液注入到(DME)NiBr2的悬浮物中，在25℃反应24小时。反应结束后，将二氯甲烷抽干，用25mL乙醚洗涤固体4次，将乙醚抽干得砖红色粉末固体0.459g，即催化剂C9，产率88.67％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，57.10％；H，3.83％；N，4.44％。Found：C，57.02％；H，3.96％；N，4.36％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例11
将0.279g(0.90mmol)的(DME)NiBr2在氮气保护下加入到50mL的Schlenk瓶中，注入15mL二氯甲烷，搅拌，形成淡黄色悬浮液。将0.461g(0.88mmol)的C5在氮气保护下加入到50mL单颈圆底烧瓶中，注入15mL二氯甲烷，溶液为暗红色。用注射器将暗红色溶液注入到(DME)NiBr2的悬浮物中，在25℃反应24小时，将二氯甲烷抽干，用25mL乙醚洗涤固体4次，将乙醚抽干得砖红色粉末固体0.557g，即催化剂C10，产率85.21％。
Elem.Anal.Calcd.For C38H40N2NiBr2：C，61.41％；H，5.42％；N，3.77％。Found：C，61.52％；H，5.54％；N，3.57％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例12
将0.294g(0.95mmol)的(DME)NiBr2在氮气保护下加入到50mL的Schlenk瓶中，注入15mL二氯甲烷，搅拌，形成淡黄色悬浮液。将0.396g(0.90mmol)的C6在氮气保护下加入到50mL单颈圆底烧瓶中，注入15mL二氯甲烷，溶液为暗红色。用注射器将暗红色溶液注入到(DME)NiBr2的悬浮物中，在25℃反应24小时，将二氯甲烷抽干，用25mL乙醚洗涤固体4次，将乙醚抽干得砖红色粉末固体0.497g，即催化剂C11，产率83.79％。
Elem.Anal.Calcd.For C32H28N2NiBr2：C，58.32％；H，4.28％；N，4.25％。Found：C，58.47％；H，4.41％；N，4.27％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例13
将0.264g(0.85mmol)的(DME)NiBr2在氮气保护下加入到50mL的Schlenk瓶中，注入15mL二氯甲烷，搅拌，形成淡黄色悬浮液。将0.453g(0.82mmol)的C7在氮气保护下加入到50mL单颈圆底烧瓶中，注入15mL二氯甲烷，溶液为暗红色。用注射器将暗红色溶液注入到(DME)NiBr2的悬浮物中，在25℃反应24小时，将二氯甲烷抽干，用25mL乙醚洗涤固体4次，将乙醚抽干得砖红色粉末固体0.513g，即催化剂C12，产率81.04％。
Elem.Anal.Calcd.For C50H64N2NiBr2：C，65.88％；H，7.08％；N，3.07％。Found：C，65.62％；H，7.21％；N，3.14％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例14
将0.270g(0.87mmol)的(DME)NiBr2在氮气保护下加入到50mL的Schlenk瓶中，注入15mL二氯甲烷，搅拌，形成淡黄色悬浮液。将0.398g(0.85mmol)的C8在氮气保护下加入到50mL单颈圆底烧瓶中，注入15mL二氯甲烷，溶液为暗红色。用注射器将暗红色溶液注入到(DME)NiBr2的悬浮物中，在25℃反应24小时，将二氯甲烷抽干，用25mL乙醚洗涤固体4次，将乙醚抽干得砖红色粉末固体0.481g，即催化剂C13，产率82.79％。
Elem.Anal.Calcd.For C50H64N2NiBr2：C，59.43％；H，4.69％；N，4.08％。Found：C，58.85％；H，4.78％；N，4.02％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例15
将实施例10中的(DME)NiBr2替换为等物质量的(DME)NiCl2，其余条件不变，得到催化剂C14。得到的催化剂质量为0.254g，产率57.32％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，66.46％；H，4.46％；N，10.83％。Found：C，66.24％；H，4.57％；N，10.74％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例16
将实施例11中的(DME)NiBr2替换为等物质量的(DME)NiCl2，其余条件不变，得到催化剂C15。得到的催化剂质量为0.337g，产率58.72％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，69.75％；H，6.16％；N，8.97％。Found：C，69.54％；H，6.31％；N，8.75％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例17
将实施例12中的(DME)NiBr2替换为等物质量的(DME)NiCl2，其余条件不变，得到催化剂C16。得到的催化剂质量为0.282g，产率55.23％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，67.41％；H，4.95％；N，10.29％。Found：C，67.21％；H，5.12％；N，9.85％。
在红外光谱中，配体中C＝N双键的伸缩振动的特征吸收峰主要在1625～1665cm-1。络合物中的C＝N双键的伸缩振动吸收峰明显向低波数偏移(1615～1650cm-1)，由此可见氮原子与金属镍原子之间发生了有效的配位。
实施例18
将实施例13中的(DME)NiBr2替换为等物质量的(DME)NiCl2，其余条件不变，得到催化剂C17。得到的催化剂质量为0.342g，产率50.79％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，73.00％；H，7.84％；N，7.13％。Found：C，73.42％；H，8.02％；N，7.01％。
实施例19
将实施例14中的(DME)NiBr2替换为等物质量的(DME)NiCl2，其余条件不变，得到催化剂C18。得到的催化剂质量为0.291g，产率57.48％。
Elem.Anal.Calcd.For C30H24N2NiBr2：C，68.26％；H，5.39％；N，9.81％。Found：C，67.82％；H，5.54％；N，9.72％。
五、亚乙烯基苊(α-二亚胺)镍催化剂催化乙烯聚合反应
实施例20
乙烯常压聚合是在无水无氧条件下进行的。乙烯压力为0.1MPa，聚合温度为60℃，将40mL甲苯溶液注入100mL的Schlenk瓶中，随后向其中注入1.0mmol助催化剂氯化 二乙基铝。用10mL甲苯溶液溶解5μmol主催化剂C9，将其注入。聚合半小时后，将聚合物溶液倒入酸化的乙醇溶液中进行沉降，过滤聚合物，然后用乙醇洗涤数次，在50℃下真空干燥至恒重后称量得0.68g聚合物。催化剂活性为272kgPE[mol(Ni)h]-1，聚合产物重均分子量为25kg/mol,多分散系数为1.87。1H-NMR测定聚合物支化度为106/1000个碳原子。
实施例21
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C10，得2.98g聚合物。催化剂活性为1193kgPE[mol(Ni)h]-1，聚合产物重均分子量为243kg/mol,多分散系数为1.80。1H-NMR测定聚合物支化度为116/1000个碳原子。
实施例22
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C11，得0.79g聚合物。催化剂活性为316kgPE[mol(Ni)h]-1，聚合产物重均分子量为32kg/mol,多分散系数为1.82。1H-NMR测定聚合物支化度为105/1000个碳原子。
实施例23
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C12，得2.41g聚合物。催化剂活性为964kgPE[mol(Ni)h]-1，聚合产物重均分子量为213kg/mol,多分散系数为1.86。1H-NMR测定聚合物支化度为112/1000个碳原子。
实施例24
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C13，得1.43g聚合物。催化剂活性为572kgPE[mol(Ni)h]-1，聚合产物重均分子量为57kg/mol,多分散系数为1.76。1H-NMR测定聚合物支化度为107/1000个碳原子。
实施例25
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C14，得0.59g聚合物。催化剂活性为236kgPE[mol(Ni)h]-1，聚合产物重均分子量为31kg/mol,多分散系数为1.82。1H-NMR测定聚合物支化度为103/1000个碳原子。
实施例26
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C15，得2.64g聚合物。催化剂活性为1056kgPE[mol(Ni)h]-1，聚合产物重均分子量为267kg/mol,多分散系数为1.89。1H-NMR测定聚合物支化度为112/1000个碳原子。
实施例27
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C16，得0.71g聚合物。催化剂活性为284kgPE[mol(Ni)h]-1，聚合产物重均分子量为39kg/mol,多分散系数为1.80。1H-NMR测定聚合物支化度为101/1000个碳原子。
实施例28
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C17，得2.30g聚合物。催化剂活性为921kgPE[mol(Ni)h]-1，聚合产物重均分子量为225kg/mol,多分散系数为1.87。1H-NMR测定聚合物支化度为105/1000个碳原子。
实施例29
其它聚合条件及聚合物处理方法与实施例20相同，聚合所用主催化剂为C18，得1.34g聚合物。催化剂活性为536kgPE[mol(Ni)h]-1，聚合产物重均分子量为64kg/mol,多分散系数为1.85。1H-NMR测定聚合物支化度为102/1000个碳原子。
实施例30
其它聚合条件及聚合物处理方法与实施例20相同，聚合反应温度为25℃，得4.16g聚合物。催化剂活性为1664kgPE[mol(Ni)h]-1，聚合产物重均分子量为413kg/mol,多分散系数为1.67。1H-NMR测定聚合物支化度为101/1000个碳原子。
实施例31
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应温度为80℃，得1.39g聚合物。催化剂活性为556kgPE[mol(Ni)h]-1，聚合产物重均分子量为171kg/mol,多分散系数为1.88。1H-NMR测定聚合物支化度为117/1000个碳原子。
实施例32
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应温度为95℃，得0.98g聚合物。催化剂活性为392kgPE[mol(Ni)h]-1，聚合产物重均分子量为142kg/mol,多分散系数为1.91。1H-NMR测定聚合物支化度为120/1000个碳原子。
实施例33
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中使用的助催化剂为二氯乙基铝，得3.31g聚合物。催化剂活性为1324kgPE[mol(Ni)h]-1，聚合产物重均分子量为120kg/mol,多分散系数为1.83。1H-NMR测定聚合物支化度为114/1000个碳原子。
实施例34
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中使用的助催化剂为甲基铝氧烷，得1.41g聚合物。催化剂活性为564kgPE[mol(Ni)h]-1，聚合产物重均分子量为243kg/mol,多分散系数为1.87。1H-NMR测定聚合物支化度为111/1000个碳原子。
实施例35
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中使用的助催化剂为改性的甲基铝氧烷，得1.87g聚合物。催化剂活性为748kgPE[mol(Ni)h]-1，聚合产物重均分子量为223kg/mol,多分散系数为1.86。1H-NMR测定聚合物支化度为112/1000个碳原子。
实施例36
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中使用的助催化剂为倍半乙基氯化铝，得3.14g聚合物。催化剂活性为1256kgPE[mol(Ni)h]-1，聚合产物重均分子量为197kg/mol,多分散系数为1.86。1H-NMR测定聚合物支化度为113/1000个碳原子。
实施例37
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中加入0.5mmol助催化剂氯化二乙基铝，得2.62g聚合物。催化剂活性为1049kgPE[mol(Ni)h]-1，聚合产物重均分子量为214kg/mol,多分散系数为1.84。1H-NMR测定聚合物支化度为117/1000个碳原子。
实施例38
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中加入2.0mmol助催化剂氯化二乙基铝，得3.45g聚合物。催化剂活性为1380kgPE[mol(Ni)h]-1，聚合产物重均分子量为221kg/mol,多分散系数为1.87。1H-NMR测定聚合物支化度为113/1000个碳原子。
实施例39
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中加入3.0mmol助催化剂氯化二乙基铝，得3.13g聚合物。催化剂活性为1252kgPE[mol(Ni)h]-1，聚合产物重均分子量为231kg/mol,多分散系数为1.88。1H-NMR测定聚合物支化度为113/1000个碳原子。
实施例40
乙烯加压聚合采用Büchi公司生产的不锈钢高压2L反应釜。乙烯压力为0.4MPa，聚合温度为60℃，将1L正庚烷溶液注入反应釜中，随后向其中注入2.0mmol助催化剂氯化二乙基铝。用20mL甲苯溶液溶解10μmol主催化剂C9，将其注入。聚合半小时后，将聚合物溶液倒入酸化的乙醇溶液中进行沉降，过滤聚合物，用乙醇洗涤，在50℃下真空干燥至恒重后称量得25.95g聚合物。催化剂活性为5190kgPE[mol(Ni)h]-1，聚合产物重均分子量为263kg/mol,多分散系数为1.80。1H-NMR测定聚合物支化度为107/1000个碳原子。
实施例41
其它聚合条件及聚合物处理方法与实施例40相同，聚合反应中乙烯压力为1.4MPa，得38.95g聚合物。催化剂活性为7790kgPE[mol(Ni)h]-1，聚合产物重均分子量为355kg/mol,多分散系数为1.81。1H-NMR测定聚合物支化度为90/1000个碳原子。
六、亚乙烯基苊(α-二亚胺)镍催化剂催化丙烯聚合反应
实施例42
其它聚合条件及聚合物处理方法与实施例21相同，聚合反应中反应气体为0.1MPa的丙烯，得0.08g聚合物。催化剂活性为30kgPP[mol(Ni)h]-1，聚合产物重均分子量为98kg/mol,多分散系数为1.68，1H-NMR测定聚合物支化度为225/1000个碳原子。
实施例43
其它聚合条件及聚合物处理方法与实施例42相同，聚合反应中反应温度为25℃，得0.35g聚合物。催化剂活性为132kgPP[mol(Ni)h]-1，聚合产物重均分子量为159kg/mol,多分散系数为1.22，1H-NMR测定聚合物支化度为241/1000个碳原子。
实施例44
其它聚合条件及聚合物处理方法与实施例42相同，聚合反应中反应温度为0℃，得0.29g聚合物。催化剂活性为109kgPP[mol(Ni)h]-1，聚合产物重均分子量为142kg/mol,多分散系数为1.08，1H-NMR测定聚合物支化度为262/1000个碳原子。
实施例45
其它聚合条件及聚合物处理方法与实施例43相同，聚合反应中使用的助催化剂为甲基铝氧烷，得0.27g聚合物。催化剂活性为108kgPP[mol(Ni)h]-1，聚合产物重均分子量为167kg/mol,多分散系数为1.20。
七、作为对比实验的比较例
比较例1
用式(Ⅲ)中的催化剂3(即经典的Brookhart催化剂)代替实施例21中的催化剂C9，其它操作与实施例19相同，得2.56g聚合物。催化剂活性为1024kgPE[mol(Ni)h]-1，聚合产物重均分子量为174kg/mol，多分散系数为2.0。1H-NMR测定聚合物支化度为113/1000个碳原子。
比较例2
用式(Ⅲ)中的催化剂3(即经典的Brookhart催化剂)代替实施例31中的催化剂C9，其它操作与实施29相同，得0.76g聚合物。催化剂活性为299kgPE[mol(Ni)h]-1，聚合产物重均分子量为85kg/mol，多分散系数为2.0。1H-NMR测定聚合物支化度为111/1000个碳原子。
比较例3
用式(Ⅳ)所示的亚乙基苊(α-二亚胺)镍催化剂代替实施例21中的催化剂C9，其它操作与实施例19相同，得2.75g聚合物。催化剂活性为1075kgPE[mol(Ni)h]-1，聚合产物重均分子量为168kg/mol，多分散系数为2.0。1H-NMR测定聚合物支化度为115/1000个碳原子。
比较例4
用式(Ⅳ)所示的亚乙基苊(α-二亚胺)镍催化剂代替实施例31中的催化剂C9，其它操作与实施29相同，得0.95g聚合物。催化剂活性为374kgPE[mol(Ni)h]-1，聚合产物重均分子量为98kg/mol，多分散系数为1.8。1H-NMR测定聚合物支化度为116/1000个碳原子。
由以上实施例或比较例的数据可见，本发明提供的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂与现有的(α-二亚胺)镍烯烃催化剂相比，具有更好的热稳定性，并且能够在相同聚合条件下催化乙烯聚合得到更高分子量的支化聚乙烯，可以满足更多的应用需求。
需要特别说明的是，虽然上述具体实施例只是式(Ⅴ)中的可选择项的部分选择及搭配组合方式的示例，对于其它选择及搭配组合方式并未一一提供实施例进行说明。但申请人认为，基于此前本发明具体实施方式部分对亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂的制备和应用方法的介绍，以及可选项在结构式中所起作用具有相同或类似的性质，本领域技术人员能够轻易按同样方式对本发明的其它选择及搭配组合加以实现或验证。

Claims (11)

  1. 一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂，其特征在于，该催化剂的化学结构式如式(Ⅱ)所示：
    Figure PCTCN2017107441-appb-100001
    式中，其中R1为烷基，R2为氢或烷基。
  2. 根据权利要求1所述的催化剂，其特征在于：所述式(Ⅱ)中，R1为甲基、异丙基或特丁基，R2为氢、甲基或特丁基。
  3. 一种制备权利要求1或2中所述亚乙烯基苊(α-二亚胺)镍烯烃催化剂的方法，其特征在于，包括如下步骤：
    1)苊经过双酰化反应得到化合物C1：
    Figure PCTCN2017107441-appb-100002
    2)对化合物C1与N-溴代琥珀酰亚胺进行溴化反应得到C2：
    Figure PCTCN2017107441-appb-100003
    3)对化合物C2进行消除反应得到C3：
    Figure PCTCN2017107441-appb-100004
    4)将化合物C3与对称的苯胺进行酮胺缩合反应，即可得到α-二亚胺配体C4-C7：
    Figure PCTCN2017107441-appb-100005
    5)在无水无氧的条件下，将α-二亚胺配体C4-C7与乙二醇二甲醚二溴化镍络合，即可得式(Ⅱ)所述的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂。
  4. 权利要求1或2所述亚乙烯基苊(α-二亚胺)镍烯烃催化剂在催化乙烯或丙烯聚合，制备聚乙烯或聚丙烯中的应用。
  5. 一种亚乙烯基苊(α-二亚胺)镍烯烃催化剂，其特征在于：该催化剂的化学结构式如式(Ⅴ)所示：
    Figure PCTCN2017107441-appb-100006
    式(Ⅴ)中，X为氯或溴，RA和RB的结构式分别如式(Ⅵ)和(Ⅶ)所示：
    Figure PCTCN2017107441-appb-100007
    其中O1、O2、O3、O4分别选自氢、卤素、烷基、含卤烷基、芳基或芳烷基中的任意一种；P1、P2分别选自氢、卤素、氨基、烷基、含卤烷基、芳基或芳烷基中的任意一种。
  6. 根据权利要求5所述的催化剂，其特征在于：该催化剂的化学结构式如式(Ⅰ)所示：
    Figure PCTCN2017107441-appb-100008
    式(Ⅰ)中，其中R1为烷基，R2为氢或烷基，X为氯或溴。
  7. 根据权利要求6所述的催化剂，其特征在于，所述式(Ⅰ)中，R1为甲基、乙基、异丙基或特丁基，R2为氢、甲基或特丁基。
  8. 权利要求6或7中所述催化剂的制备方法，其特征在于，包括如下步骤：
    1)苊经过双酰化反应得到化合物C1：
    Figure PCTCN2017107441-appb-100009
    2)对化合物C1与N-溴代琥珀酰亚胺进行溴化反应得到C2：
    Figure PCTCN2017107441-appb-100010
    3)对化合物C2进行消除反应得到C3：
    Figure PCTCN2017107441-appb-100011
    4)将化合物C3与对称的苯胺进行酮胺缩合反应，即得到α-二亚胺配体C4-C8：
    Figure PCTCN2017107441-appb-100012
    5)在无水无氧的条件下，将α-二亚胺配体C4-C8与乙二醇二甲醚二溴化镍、乙二醇二甲醚二氯化镍、四水合氯化镍或六水合氯化镍中的任意一种络合，即得到式(Ⅰ)所述的亚乙烯基苊(α-二亚胺)镍烯烃聚合催化剂。
  9. 权利要求5～6所述的亚乙烯基苊(α-二亚胺)镍烯烃催化剂在催化乙烯、丙烯聚合，制备聚乙烯、聚丙烯中的应用。
  10. 用于制备权利要求5所述亚乙烯基苊(α-二亚胺)镍烯烃催化剂的配体化合物，其特征在于，该化合物的结构如式(Ⅹ)所示：
    Figure PCTCN2017107441-appb-100013
    其中，RA和RB的结构式分别如式(Ⅵ)和(Ⅶ)所示：
    Figure PCTCN2017107441-appb-100014
    上式中，O1、O2、O3、O4分别选自氢、卤素、烷基、含卤烷基、芳基或芳烷基中的任意一种；P1、P2分别选自氢、卤素、氨基、烷基、含卤烷基、芳基或芳烷基中的任意一种。
  11. 根据权利要求10所述的配体化合物，其特征在于，所述O1、O2、O3、O4分别选自甲基、乙基、异丙基或特丁基的任意一种；P1、P2分别选自氢、甲基或特丁基中的任意一种。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745358A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 二亚胺金属配合物及其制备方法和应用
CN114316093A (zh) * 2022-01-04 2022-04-12 吉林大学 一种苊醌双亚胺基稀土金属催化剂的制备方法及应用

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109957051B (zh) * 2017-12-25 2022-03-08 杭州星庐科技有限公司 亚乙烯基苊α-二亚胺镍烯烃催化剂及其制备方法和应用
CN110317149B (zh) * 2019-07-31 2022-08-09 安徽大学 大位阻柔性二亚胺配体、基于其的二亚胺镍和钯配合物及其催化应用
CN112745362B (zh) * 2019-10-31 2022-10-21 中国石油化工股份有限公司 二亚胺金属配合物及其制备方法和应用
CN113429502B (zh) * 2021-03-17 2022-09-09 浙江大学 一种改进的（α-二亚胺）镍催化剂及其制备方法和应用
CN116515014A (zh) * 2023-05-10 2023-08-01 浙江大学 一种α-二亚胺镍催化剂及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1226256A (zh) * 1996-07-23 1999-08-18 纳幕尔杜邦公司 烯烃聚合法
CN102827312A (zh) * 2012-08-03 2012-12-19 浙江大学 亚乙基苊（α-二亚胺）镍烯烃催化剂及其制备方法与应用
CN104177528A (zh) * 2014-07-23 2014-12-03 浙江大学 一种乙烯/长链α-烯烃共聚物及其制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7176158B2 (en) * 2002-10-25 2007-02-13 Exxonmobil Chemical Patents Inc. Polymerization catalyst composition
CN1942433A (zh) * 2004-04-27 2007-04-04 北卡罗来纳查佩尔山大学 通过液相色谱法分离不对称二亚胺

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1226256A (zh) * 1996-07-23 1999-08-18 纳幕尔杜邦公司 烯烃聚合法
CN102827312A (zh) * 2012-08-03 2012-12-19 浙江大学 亚乙基苊（α-二亚胺）镍烯烃催化剂及其制备方法与应用
CN104177528A (zh) * 2014-07-23 2014-12-03 浙江大学 一种乙烯/长链α-烯烃共聚物及其制备方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112745358A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 二亚胺金属配合物及其制备方法和应用
CN112745358B (zh) * 2019-10-31 2022-10-21 中国石油化工股份有限公司 二亚胺金属配合物及其制备方法和应用
CN114316093A (zh) * 2022-01-04 2022-04-12 吉林大学 一种苊醌双亚胺基稀土金属催化剂的制备方法及应用
CN114316093B (zh) * 2022-01-04 2023-04-28 吉林大学 一种苊醌双亚胺基稀土金属催化剂的制备方法及应用

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