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Catalytic system for catalyzing polymerization of conjugated diolefins with bridging amidino-guanidyl dual-core rare-earth metals

A technology of rare earth metals and bridged amidines, which is applied in the field of guanidine dinuclear rare earth metal catalyst systems and bridged amidines, which can solve problems such as different properties, unknowns, and changes in polymerization selectivity.

Inactive Publication Date: 2012-07-04
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At the same time, the complex catalysts in the past are all mononuclear systems. In the binuclear system, whether polyisoprene with different properties from the mononuclear system can be obtained, and whether its polymerization selectivity can be changed through additives is still unknown.

Method used

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  • Catalytic system for catalyzing polymerization of conjugated diolefins with bridging amidino-guanidyl dual-core rare-earth metals
  • Catalytic system for catalyzing polymerization of conjugated diolefins with bridging amidino-guanidyl dual-core rare-earth metals
  • Catalytic system for catalyzing polymerization of conjugated diolefins with bridging amidino-guanidyl dual-core rare-earth metals

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0055] Example 1 The synthesis of alkyl bridged ligands, the preparation process is shown in the figure below:

[0056]

[0057] Weigh 0.416 g (60 mmol) of lithium-sodium alloy, add 10 mL of ether, add 1.18 mL (10 mmol) of 1,4-dibromobutane dropwise at -10 °C, and continue the reaction for 24 hours after the addition is complete. Filter the reaction product with a sand core funnel to obtain a diethyl ether solution of 1,4-butyldilithium. Slowly add the ether solution of 1,4-butyldilithium into the solution of 5.801 g of carbodiimide in tetrahydrofuran under stirring, and then stir for 10 hours after the addition. After the reaction was complete, 1 mL of water was added to quench the reaction, and the product was separated through a column to obtain 3.70 g of the target product, the alkyl bridged amidinyl ligand, with a yield of 47%. 1 H NMR (CDCl 3 , 400 MHz, RT) : δ = 0.98 (d, 12H, CH(C H 3 ) 2 ), 1.15 (d, 12H, CH(C H 3 ) 2 ), 1.18 (d, 12H, CH(C H 3 ) 2 ), 1.28 ...

Embodiment 2

[0058] Example 2 Synthesis of oxygen-containing heteroatom alkyl bridging ligand, the preparation process is shown in the figure below:

[0059]

[0060] Weigh 0.2923 g Li-Na alloy in the glove box, place it in a 50 mL Schlenk bottle, add a stirring bar and 5 mL ether. Pipette 1.65 mL (8.95 mmol) of 4,4'-dichlorobutyl ether into the constant pressure dropping funnel under the condition of flowing N2, slowly drop it into the Schlenk bottle within 15 minutes, and stir at -15 °C React for 24 hours, and filter to obtain the corresponding dilithium salt ether solution. In the glove box, weigh 6.4894 g (17.9 mmol) of carbodiimide and dissolve it with tetrahydrofuran. Use a dropper to slowly add dilithium salt ether solution into the dissolved carbodiimide, and stir for 12 hours. After taking it out, quickly add water to quench and stir for 10 minutes. The product was separated by column, and finally 5.34 g of white powdery solid was obtained, with a yield of 64.5%. 1 H NMR (C...

Embodiment 3

[0061] Example 3 Synthesis of phenyl bridged ligand, the preparation process is shown in the figure below:

[0062]

[0063] At room temperature, slowly drop 2.4 mL of n-butyllithium solution (6 mmol, 2.5 M n-hexane solution) into a stirred 40 mL n-hexane solution containing 0.476 g (2 mmol) of 1,4-dibromobenzene. Keep the temperature at 80°C for 12 hours, and filter through a sand funnel to obtain phenyl dilithium salt (1,4-Li 2 C 6 h 4 ). Dissolve dilithium salt in 20 mL THF at room temperature, stir, slowly drop into 20 mL THF solution containing 1.45 g (4 mmol) carbodiimide, and react for 12 hours to obtain a light brown slurry-like solid. After the reaction is completed, excess distilled water is added to obtain a neutral amidine ligand. The product was extracted with ether and spin-dried to give a yellow solid. The solid was recrystallized from n-hexane at -30°C to obtain 0.48 g of light yellow crystals with a yield of 30%. 1 H NMR (400 MHz, CDCl 3 , RT): δ = 0...

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Abstract

The invention belongs to the technical field of chemical catalysts and particularly relates to a catalytic system for catalyzing the polymerization of conjugated diolefins with bridging amidino-guanidyl dual-core rare-earth metals. The catalytic system consists of bridging amidino-guanidyl rare-earth metal complex, alkyl aluminium and an organic boron salt reagent, and can catalyze conjugated olefins such as isoprene, myrcene, 1, 3-butadiene and 1, 3-pentadiene to carry out solution polymerization. According to the change of the types and the used amount of the aluminium reagents, the polydiolefin with high 3, 4 selectivity or high 1, 4 selectivity can be prepared. The molar ratio of the alkyl aluminium to the rare-earth complex is in a range of 1-100, the molar ratio of the organic boron salt to the rare-earth complex is in a range of 0.5-2.0. The polymerization reaction activity is up to 4.088*103kg / mol h, the conversion ratio of the monomers can reach 100%, and the molecular weight of the obtained polyisoprene can be up to hundreds of thousands, or even higher. The catalytic system has good catalytic polymerization performance for homopolymerization and copolymerization of the conjugated olefins such as the isoprene, myrcene, the 1, 3-butadiene and the 1, 3-pentadiene.

Description

technical field [0001] The invention belongs to the technical field of chemical catalysts, and in particular relates to a bridged amidino-guanidinium dinuclear rare earth metal catalytic system capable of catalyzing the selective active polymerization of conjugated diolefins such as isoprene and myrcene. Background technique [0002] Among various polymer materials, polyconjugated olefin is a kind of polymer with various excellent properties and broad application prospects. Many of them are high-performance rubber or plastic. Among them, polyisoprene rubber (IR) can be divided into cis-1,4-IR, trans-1,4-IR and 3,4-IR. And cis-1,4-IR is the main natural rubber (cis-1,4 content>99%, number average molecular weight is about 2×10 6 g / mol) substitute. Trans 1,4-IR is also called eucommia gum, which has many applications in medical materials, memory materials and other fields. 3,4-IR is a rubber with good application potential. Studies have shown that with the increase of...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F36/04C08F4/52
Inventor 张立新郁夏盈李猛
Owner FUDAN UNIV
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