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Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof

A technology of olefin catalyst and diimine, which is applied in the field of dibinuclear acenaphthene (α-diimine) nickel/palladium olefin catalyst and its preparation, which can solve the problems of restricting industrial application, low molecular weight of polymerization products, and restricting the scope of industrial application, etc. , to achieve the effects of low cost, simple preparation process and high yield

Active Publication Date: 2012-12-19
ZHEJIANG UNIV
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Problems solved by technology

However, the low molecular weight of the polymerized product limits its industrial application
When it catalyzes the polymerization of propylene, the weight average molecular weight of the obtained polymerization product is lower than 100,000, thus restricting its industrial application range

Method used

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  • Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof
  • Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof
  • Binuclear acenaphthene (alpha-diimine) nickel/palladium catalysts for olefins, and preparation method and application thereof

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Experimental program
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preparation example Construction

[0027] The preparation method of described dinuclear acenaphthylene (α-diimine) nickel / palladium olefin catalyst, the steps are as follows:

[0028] 1) Acenaphthene quinone undergoes a double acylation reaction to obtain compound C1, and C1 is then oxidized by benzene selenite anhydride to obtain compound C2:

[0029]

[0030] Using acenaphthylquinone as raw material, carbon disulfide as solvent, adding anhydrous aluminum bromide, under the condition of oxalyl bromide as oxidant, yellow solid C1 is obtained. Compound C2 was obtained through oxidation of benzene selenite anhydride.

[0031] 2) Compound C2 undergoes ketoamine condensation reaction with symmetrical aniline to obtain ligand C3 or C4: the raw material of acenaphthyldione obtained in the above reaction, acetonitrile as solvent, acetic acid as catalyst, α-diimine ligand is obtained through ketoneamine condensation reaction body.

[0032]

[0033] Under the condition of anhydrous and oxygen-free, C3 or C4 and ...

Embodiment 1

[0042] Synthesis of Ligand C3

[0043] Under nitrogen atmosphere and 85°C, after constant temperature for half an hour, add C2 (0.534g, 2.26mmol) into 70mL of acetonitrile, after half an hour, add 15mL of acetic acid, after two hours, add 2.08mL (9.94mmol) 2,6 - Diisopropylaniline, the solution turns reddish brown. After 24 hours, stop the reaction, stand still, and cool naturally. The upper layer is a dark red solution, and the lower layer is a bright red precipitate. The precipitate was washed with 5 × 50 mL of n-heptane, and then dried under vacuum at 70 °C for 48 h. 1.37 g of the product was obtained with a yield of 69.5%.

[0044] 1 H-NMR (400MHz, CDCl 3 , δin ppm): 7.23 (s, 12H, Ar-H), 6.45 (s, 4H, Py-H), 2.91 (sept, 8H, CH (CH 3 ) 2 ),0.86-1.26(dd,48H,CH(CH 3 ) 2 ).

[0045] Elem.Anal.Calcd.For C 62 h 72 N 4 :C,85.27%;H,8.31%;N,6.42%.Found:C,83.40%;H,8.17%;N,6.08%.

[0046] ESI-MS: m / z 873.76 ([M+H] + .

Embodiment 2

[0048] Synthesis of Ligand C4

[0049]Add 0.310g (1.31mmol) of C2 into a 100mL single-neck round bottom flask, add 35mL of acetonitrile and 8mL of acetic acid, and reflux at 90°C for two hours. Then 0.66mL (5.24mmol) of 2,6-dimethylaniline was added and reacted for 24 hours. After the reaction, the solvent was drained, and the crude product was separated by column chromatography (dichloromethane, 1% triethylamine, silica gel) to obtain 0.598 g of the product with a yield of 70.5%.

[0050] 1 H-NMR (400MHz, CDCl 3 , δin ppm):7.11-7.16(d,6H,Ar-Hm),7.04-7.09(t,4H,Ar-Hp),6.66(s,4H,Py-H),2.06-2.12(s,24H, CH 3 ).

[0051] Elem.Anal.Calcd.For C 46 h 40 N 4 :C,85.15%;H,6.21%;N,8.63%.Found:C,85.22%;H,6.22%;N,8.23%.

[0052] ESI-MS: m / z 649.07 ([M+H] + ),671.11([M+Na] + ).

[0053] 2. Preparation of dinuclear acenaphthylene (α-diimine) palladium complex

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Abstract

The invention discloses a preparation method for binuclear acenaphthene (alpha-diimine) nickel / palladium catalysts for olefins and application of the catalysts in catalysis of polymerization of olefins. The binuclear acenaphthene (alpha-diimine) nickel / palladium catalysts for olefins in the invention have structural formulas as represented by formula (I) and formula (II) in the specification. The binuclear acenaphthene (alpha-diimine) palladium catalyst for polymerization of olefins has high activity and good stability and can be used for preparing high-molecular-weight hyperbranched polyethylene with bimodal distribution; the binuclear acenaphthene (alpha-diimine) nickel catalyst for polymerization of olefins has high activity and good stability and can be used for preparing polypropylene with a weight-average molecular weight of more than 100,000 and thermoplastic elastomers with elasticity and a high molecular weight. The preparation method for the synthesized catalysts used for polymerization of olefins has the advantages of a simple process, a short synthetic route, low cost, high yield and easy industrialization.

Description

technical field [0001] The invention relates to the field of catalytic polymerization of olefins, in particular to a dibinuclear acenaphthylene (α-diimine) nickel / palladium olefin catalyst and a preparation method and application thereof. Background technique [0002] Polyolefin is a basic material related to the national economy and people's livelihood, and because of its excellent performance, various varieties, easy availability and low price of raw materials, 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 to promote the progress and development of the polyolefin industry, and is the key to controlling the structure and performance of polyolefin materials. [0003] In recent decades, the study of functionalized and differentiated polyolefin materials obtained by coordination polymerization has received extensive attention. Among them, late transitio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F4/70C07F15/04C07F15/00C08F10/02C08F10/06C08F210/16
CPCY02P20/52
Inventor 傅智盛朱良范志强
Owner ZHEJIANG UNIV
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