Preparation method of phospholene oxide, substituted phospholene oxide and preparation method of substituted phospholene oxide

Abstract

The invention relates to a preparation method of phospholene oxide, substituted phospholene oxide and a preparation method of the substituted phospholene oxide and belongs to the technical field of organic synthesis. The preparation method of the phospholene oxide comprises the following steps: 1) enabling phosphorus trihalide and chloroethanol to react at -10 to 40 DEG C for 0.5 to 3h so as to obtain a compound shown as a formula I; 2) enabling the compound shown as the formula I, a catalyst, a polymerization inhibitor and 1,3-butadiene to react at room temperature for 4 to 10h; then raisingthe temperature to 40 to 80 DEG C and reacting for 12 to 24h; then raising the temperature to 80 to 100 DEG C and reacting for 8 to 14h to obtain the phospholene oxide. The e preparation method of thephospholene oxide, provided by the invention, takes the phosphorus halide and the chloroethanol as raw materials, and the raw materials are easy to obtain and the price is low; reaction conditions are moderate and the method is simple and feasible and is low-cost.

Description

technical field

[0001] The invention relates to a preparation method of phosphorene oxide, a substituted phosphorene oxide and a preparation method thereof, and belongs to the technical field of organic synthesis. Background technique

[0002] Oligomers of carbodiimide are excellent hydrolytic stabilizers for polymer materials such as polyester, polyether, polyurethane, and synthetic rubber. Polycarbodiimide has good heat resistance, electrical insulation and mechanical properties, and has a wide range of uses in coatings, adhesives, polymer modifiers, and crosslinking agents.

[0003] Since the continuous emergence of organophosphorus catalysts from the 1960s to the 1980s, the use of organophosphorus as a catalyst to synthesize carbodiimides from monoisocyanates has become the mainstream, not only for the synthesis of carbodiimides from monoisocyanates, but also the synthesis of polycarbodiimides from diisocyanates. Diimine is also used to catalyze the synthesis of carbodi...

Examples

Embodiment 1

[0057] The preparation route of the methyl-substituted cyclophosphene oxide of this embodiment is as follows, and the specific preparation method includes the following steps:

[0058]

[0059] 1) Preparation of cyclophosphene oxide

[0060] Under ice-bath conditions, add 250 mL of methylene chloride and 137.0 g of phosphorus trichloride into a reactor equipped with a thermometer, agitator and tail gas absorption device, and add 410.0 g of sodium hydroxide with a mass fraction of 5% in the tail gas absorption device Aqueous solution, then add 41.1g of chloroethanol dropwise to the reactor while stirring, keep the temperature below 0°C during the dropwise addition of chloroethanol, then raise the temperature to 20°C, keep the temperature at 20°C for 1 hour, and remove the solvent by distillation The product was purified to obtain 72.9g of compound 1a;

[0061] Add 72.9g of compound 1a, 0.6g of copper stearate, 1.4g of ferric chloride, and 0.8g of BHT to the autoclave under ...

Embodiment 2

[0065] The preparation method of the methyl-substituted cyclophosphene oxide of the present embodiment comprises the following steps:

[0066]

[0067] 1) Preparation of cyclophosphene oxide

[0068] Under ice-bath conditions, add 250 mL of methylene chloride and 136.9 g of phosphorus trichloride into a reactor equipped with a thermometer, agitator and tail gas absorption device, and add 370.0 g of sodium hydroxide with a mass fraction of 10% in the tail gas absorption device Aqueous solution, then add 80.5g of chloroethanol dropwise to the reactor while stirring, during the process of dropwise adding chloroethanol, keep the temperature below 0°C, then raise the temperature to 30°C, keep the reaction at 30°C for 1.5 hours, remove the solvent by distillation The product was purified to obtain compound 1a144.3g;

[0069] Add 144.3g of compound 1a, 7.5g of copper stearate, 34.9g of ferric chloride, and 35.0g of BHT to the autoclave under an argon atmosphere, cool down to -20°...

Embodiment 3

[0073] The preparation method of the methyl-substituted cyclophosphene oxide of the present embodiment comprises the following steps:

[0074]

[0075] 1) Preparation of cyclophosphene oxide

[0076] Under ice-bath conditions, add 35 mL of methylene chloride, 27.4 g of phosphorus trichloride into the reactor with thermometer, stirrer and tail gas absorption device, and add 46.5 g of sodium hydroxide with a mass fraction of 15% in the tail gas absorption device Aqueous solution, then add 16.4g of chloroethanol dropwise to the reactor while stirring, during the process of dropping chloroethanol, keep the temperature below 0°C, then raise the temperature to 40°C, keep it at 40°C for 0.5 hours, and remove the solvent by distillation The product was purified to obtain 27.5 g of compound 1a;

[0077] Add 27.5g of compound 1a, 2.7g of copper stearate, 5.5g of ferric chloride, and 2.7g of BHT into the autoclave under an argon atmosphere, drop the temperature to -30°C and feed 68.4...

technical field

[0001] The invention relates to a preparation method of phosphorene oxide, a substituted phosphorene oxide and a preparation method thereof, and belongs to the technical field of organic synthesis. Background technique

[0002] Oligomers of carbodiimide are excellent hydrolytic stabilizers for polymer materials such as polyester, polyether, polyurethane, and synthetic rubber. Polycarbodiimide has good heat resistance, electrical insulation and mechanical properties, and has a wide range of uses in coatings, adhesives, polymer modifiers, and crosslinking agents.

[0003] Since the continuous emergence of organophosphorus catalysts from the 1960s to the 1980s, the use of organophosphorus as a catalyst to synthesize carbodiimides from monoisocyanates has become the mainstream, not only for the synthesis of carbodiimides from monoisocyanates, but also the synthesis of polycarbodiimides from diisocyanates. Diimine is also used to catalyze the synthesis of carbodi...

Examples

Embodiment 1

[0057] The preparation route of the methyl-substituted cyclophosphene oxide of this embodiment is as follows, and the specific preparation method includes the following steps:

[0058]

[0059] 1) Preparation of cyclophosphene oxide

[0060] Under ice-bath conditions, add 250 mL of methylene chloride and 137.0 g of phosphorus trichloride into a reactor equipped with a thermometer, agitator and tail gas absorption device, and add 410.0 g of sodium hydroxide with a mass fraction of 5% in the tail gas absorption device Aqueous solution, then add 41.1g of chloroethanol dropwise to the reactor while stirring, keep the temperature below 0°C during the dropwise addition of chloroethanol, then raise the temperature to 20°C, keep the temperature at 20°C for 1 hour, and remove the solvent by distillation The product was purified to obtain 72.9g of compound 1a;

[0061] Add 72.9g of compound 1a, 0.6g of copper stearate, 1.4g of ferric chloride, and 0.8g of BHT to the autoclave under ...

Embodiment 2

[0065] The preparation method of the methyl-substituted cyclophosphene oxide of the present embodiment comprises the following steps:

[0066]

[0067] 1) Preparation of cyclophosphene oxide

[0068] Under ice-bath conditions, add 250 mL of methylene chloride and 136.9 g of phosphorus trichloride into a reactor equipped with a thermometer, agitator and tail gas absorption device, and add 370.0 g of sodium hydroxide with a mass fraction of 10% in the tail gas absorption device Aqueous solution, then add 80.5g of chloroethanol dropwise to the reactor while stirring, during the process of dropwise adding chloroethanol, keep the temperature below 0°C, then raise the temperature to 30°C, keep the reaction at 30°C for 1.5 hours, remove the solvent by distillation The product was purified to obtain compound 1a144.3g;

[0069] Add 144.3g of compound 1a, 7.5g of copper stearate, 34.9g of ferric chloride, and 35.0g of BHT to the autoclave under an argon atmosphere, cool down to -20°...

Embodiment 3

[0073] The preparation method of the methyl-substituted cyclophosphene oxide of the present embodiment comprises the following steps:

[0074]

[0075] 1) Preparation of cyclophosphene oxide

[0076] Under ice-bath conditions, add 35 mL of methylene chloride, 27.4 g of phosphorus trichloride into the reactor with thermometer, stirrer and tail gas absorption device, and add 46.5 g of sodium hydroxide with a mass fraction of 15% in the tail gas absorption device Aqueous solution, then add 16.4g of chloroethanol dropwise to the reactor while stirring, during the process of dropping chloroethanol, keep the temperature below 0°C, then raise the temperature to 40°C, keep it at 40°C for 0.5 hours, and remove the solvent by distillation The product was purified to obtain 27.5 g of compound 1a;

[0077] Add 27.5g of compound 1a, 2.7g of copper stearate, 5.5g of ferric chloride, and 2.7g of BHT into the autoclave under an argon atmosphere, drop the temperature to -30°C and feed 68.4...

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