ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof

A technology of salicylaldimine and olefin catalyst, applied in the field of olefin coordination polymerization, can solve the problems of poor tolerance of polar monomers, single active center, difficult resin processing, etc., and achieve the effect of high catalytic activity

Active Publication Date: 2013-04-10
SHANGHAI RES INST OF CHEM IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Compared with traditional Ziegler-Natta catalysts, metallocene catalysts have high activity and a single active center, but have poor tolerance to polar monomers, are very sensitive to water and oxygen, and the subsequent processing of the synthesized resin is difficult

Method used

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  • ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof
  • ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof
  • ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst and preparation method thereof

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preparation example Construction

[0049] The preparation method of ONS type salicylaldimine binuclear metal olefin catalyst comprises the following steps:

[0050] (1) Preparation of dual-nuclear structure salicylaldehyde or salicylaldehyde derivatives: under an inert atmosphere, mix salicylaldehyde or salicylaldehyde derivatives, glacial acetic acid, and reactants for bridging in a ratio of 0.1-1.0 / mol : 10-100 / ml: 0.05-0.5 / ml, under the action of concentrated sulfuric acid, react at 90-95°C for 24h to obtain binuclear structure salicylaldehyde or salicylaldehyde derivatives;

[0051] The molecular structural formula of the prepared binuclear structure salicylaldehyde or salicylaldehyde derivative is as follows:

[0052]

[0053] (2) Preparation of Schiff's base: under an inert atmosphere, the binuclear structure salicylaldehyde or salicylaldehyde derivatives, amine, and ethanol are prepared in a ratio of 0.1-1 / mol: 0.15-2.0 / ml: 0.01-0.05 / ml: 50-200 / ml, under the catalysis of a small amount of acid, the c...

Embodiment 1

[0069] 3-tert-butylsalicylaldehyde was synthesized from o-tert-butylphenol as the starting material under the catalysis of anhydrous tin tetrachloride. Then under the effect of the concentrated sulfuric acid, obtain 5,5'-methylene-bis-3-tert-butyl salicylaldehyde with trioxane as the bridging reactant. Under the action of p-toluenesulfonic acid, 2-aminodiphenylphenyl sulfide is added to react with the binuclear skeleton to obtain the Schiff base. Schiff base and TiCl 4 Complexation obtains an ONS type binuclear metal olefin polymerization catalyst, and the specific implementation steps are as follows:

[0070] 1) Preparation of 3-tert-butyl salicylaldehyde: under the protection of nitrogen, add 25g of tert-tert-butylphenol, 12.5g of 2,6-lutidine, 200ml of anhydrous toluene to the dry reaction bottle, then drop 2ml After the addition of anhydrous tin tetrachloride was completed, the solution was stirred at room temperature for 0.5 h, and then 10 g of paraformaldehyde was adde...

Embodiment 2

[0075] Use the ONS type binuclear olefin polymerization catalyst prepared in Example 1 to carry out ethylene polymerization: under 1 atm ethylene atmosphere, add successively 13 ml of toluene solution that is dissolved with 3.01 mg of catalyst, 12 mmol of MAO, and 27 ml of anhydrous toluene in a dry polymerization reaction bottle , the catalyst concentration was 0.075 μmol / ml. Stir the reaction at 10°C for 1 h, pour the reactant into 300 ml of 0.5% ethanol hydrochloric acid solution by volume, filter, wash twice with ethanol hydrochloric acid solution of 0.5% by volume, wash three times with ethanol, and vacuum After drying, 0.94 g of polyethylene was obtained. The catalytic activity is 0.16×10 6 gPE·mol -1 Ti·h -1 . The weight average molecular weight of polyethylene M w 3.0×10 5 , The molecular weight distribution index PDI is 2.1.

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Abstract

The invention relates to an ONS (Organometallics) type salicylaldimine binuclear metallic alkene catalyst as well as a preparation method thereof and the application thereof. Under an effect of p-toluenesulfonic acid, bisalicylaldehyde or a bisalicylaldehyde derivative performs condensation reaction with amines containing sulfur atoms in an alcohol solution so as to obtain Schiff base; and the obtained Schiff base has complexing reaction with IVB group transition metal under water-free and oxygen-free conditions so as to obtain the ONS type salicylaldimine binuclear metallic alkene catalyst. Compared with a mononuclear metal alkene catalyst, the ONS type salicylaldimine binuclear metallic alkene catalyst provided by the invention has the advantages of higher catalytic activity and better thermal stability due to binuclear metallic synergistic effect during catalyzing ethylene homopolymerisation or ethylene and 1-hexene copolymerization. Under the pressure of a methylaluminoxane (MAO) or triethylaluminium assisted catalyst and 1 atm ethylene, the ethylene homopolymerisation is catalyzed and the activity can reach 1.6*10<6> gPE/molTi.h; and during catalyzing the ethylene and 1-hexene copolymerization, the activity reaches 3.8*10<5> gPE/molTi.h.

Description

technical field [0001] The invention belongs to the field of olefin coordination polymerization, and relates to the synthesis of ONS-type salicylaldimine binuclear metal catalyst ligands and the preparation method and application of an olefin polymerization catalyst composed of coordination with Group IVB metals. Background technique [0002] Since the discovery in the 1950s that Ziegler-Natta catalysts can effectively catalyze olefin polymerization to obtain high-density polyethylene and isotactic polypropylene, based on the important role of polyolefin materials in the operation of the entire society, a large number of researchers have developed Polyolefin catalysts with higher catalytic activity and the ability to catalyze olefin polymerization to obtain new functional polymers are an extremely important research direction. The traditional catalyst titanium chloride has the characteristics of multiple active centers, which leads to a wide molecular weight distribution of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F110/02C08F4/642C08F210/16
Inventor 康必显杨晴王临才吴向阳吕待清
Owner SHANGHAI RES INST OF CHEM IND
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