Preparation of phenylmethylene bis(tricyclohexylphosphorus)ruthenium dichloride_Industrial additives

Background and overview of emulsifying thickeners^[1]

Phenylmethylenebis(tricyclohexylphosphorus)ruthenium dichloride is a ruthenium catalyst. Ruthenium catalysts have strong tolerance to polar monomers and can polymerize many polar monomers to prepare cyclic olefin copolymers. Cyclic olefin copolymers can be widely used in the manufacture of various optical, information, electrical, and medical materials.

Preparation^[1]

Phenylmethylenebis(tricyclohexylphosphorus)ruthenium dichloride is prepared as follows:

1) Add 4.96 grams of benzaldehyde-p-toluenesulfonylhydrazone, 1.75 grams of sodium methoxide and 40 mL of triethylene glycol into a 100 mL single-neck bottle, and place the single-neck bottle at 60°C The synthesis reaction was carried out in a water bath for 1 hour. After the synthesis reaction is completed, the methanol in the obtained synthesis reaction solution is extracted with a water pump to obtain a synthesis reaction product; the synthesis reaction product is extracted with n-pentane in ice water and then extracted with a saturated NaCl aqueous solution. The obtained extraction product was spin-dried to obtain phenyldiazomethane; the yield of phenyldiazomethane was 50%.

2) Add 4.0 grams of ruthenium tris(triphenylphosphine) dichloride into a 250 mL branch bottle, replace the air in the branch bottle with nitrogen, and inject 40 mL into the branch bottle. Dichloromethane after three times of liquid nitrogen freezing and thawing treatment; place the branch bottle in a cold bath at -78°C, and add phenyldiazo with a mass concentration of 98.5mg/mL at -50°C under stirring conditions Mix 10 mL of a pentane solution of methane. The phenyldiazomethane in the pentane solution of phenyldiazomethane is the phenyldiazomethane prepared above; stir the resulting mixture at -70°C for 10 minutes and then add 40 mL of a dichloromethane solution of tricyclohexylphosphine with a mass concentration of 0.064 g/mL at -50°C was reacted at 25°C for 30 minutes. After the reaction emulsifier is completed, the obtained reaction solution is filtered to remove insoluble matter, the filtered reaction solution is concentrated to 10 mL and then filtered again, and 100 mL of methanol that has been subjected to three liquid nitrogen freezing and thawing treatments is added to the obtained filtered product. Precipitate, wash the obtained precipitate three times with methanol, and then wash it twice with acetone. The washed precipitate is vacuum dried for 3 hours to obtain 2.1 g of product. The yield of the product prepared by the method provided in Example 2 of the present invention is 81%. The product obtained above was subjected to hydrogen nuclear magnetic resonance spectrum and phosphorus spectrum detection, and the detection result showed that the obtained product was phenylmethylene bis(tricyclohexylphosphorus)ruthenium dichloride.