CN101792463B - Nitrogen-containing aryl hypophosphite metal salt and preparation method thereof - Google Patents

Abstract

The invention relates to a nitrogen-containing aryl hypophosphite metal salt and a preparation method thereof. The nitrogen-containing aryl hypophosphite metal salt has the following structural units: The above-mentioned R is an aryl group or a linear or branched hydrocarbon group containing 0-6 C atoms, and Z is a metal ion. The method is as follows: under the condition of nitrogen protection, carboxyethylphenylphosphinic acid and the compound with active amino groups are reacted and dehydrated under heating conditions, and then the compound containing metal ions is added to the reaction system for reaction; or Carboxyethylphenylphosphinic acid reacts with compounds containing metal ions for purification and then reacts with compounds with active amine groups in a solvent for dehydration under heating conditions. Afterwards, the reaction product is purified and dried to obtain the target product. The product of the invention has stable physical and chemical properties, high flame-retardant performance, safety and environmental protection, and the preparation process is simple and easy, and the cost is low, and is suitable for application in polyesters and polyamides, epoxy resins, glass fiber reinforced plastic resins and the like.

Description

Nitrogen-containing aryl hypophosphite metal salt and preparation method thereof

technical field

The invention relates to a phosphorus-nitrogen synergistic flame retardant compound and a preparation method thereof, in particular to a nitrogen-containing aryl hypophosphite metal salt based on carboxyethylphenylphosphinic acid and a preparation method thereof.

Background technique

As the world's environmental requirements for flame retardants are getting higher and higher, traditional halogenated flame retardants are facing tremendous pressure, and new intumescent phosphorus-nitrogen flame retardants that are environmentally friendly and less polluting are becoming more and more popular. Favored, especially the phosphorus-nitrogen synergistic flame retardant compound is pursued by the industry. The reason is that the phosphorus-nitrogen synergistic flame retardant compound itself has the three elements of the flame retardant mechanism of acid source, carbon source, and gas source, and it contains C-P bonds. After forming a salt with a flame retardant metal compound, it has higher chemical stability. It also has the characteristics of good flame retardancy, low smoke, and low toxicity, so it has become an important direction for the current development and research of flame retardants. However, in terms of the development of organophosphorus flame retardants, my country started late, and has not yet introduced similar organophosphine flame retardants with outstanding performance, which directly limits the industrial development of related flame retardant materials in my country. Therefore, the development of phosphorus-nitrogen synergistic organic The research and development of phosphine flame retardants has urgent practical significance and long-term strategic significance.

Contents of the invention

The object of the present invention is to propose a nitrogen-containing aryl hypophosphite metal salt and a preparation method thereof. The nitrogen-containing aryl hypophosphite metal salt has stable physical and chemical properties, high flame retardancy, safety and environmental protection, and at the same time, its preparation process is simple and easy. The operation is low in cost, and is suitable for various scales of industrial production, thus overcoming the shortcomings in the prior art.

In order to realize the above-mentioned purpose of the invention, the present invention has adopted following technical scheme:

A nitrogen-containing aryl hypophosphite metal salt is characterized in that the nitrogen-containing aryl hypophosphite metal salt has the following structural units:

Wherein, R is an aryl group or a linear or branched hydrocarbon group containing 0 to 6 C atoms, and Z is a metal ion.

Specifically, the metal ion is one or more of Mg ²⁺ , Zn ²⁺ , Al ³⁺ and Ca ²⁺ .

A kind of preparation method of nitrogen-containing aryl hypophosphite metal salt, it is characterized in that, the method is:

Under nitrogen or inert gas protection conditions, react carboxyethylphenylphosphinic acid and compounds with active amino groups in an organic solvent at a temperature of 135-160°C for 4-6 hours, remove the reaction to generate water, and then Add water, soluble metal salt and alkali or metal oxide or metal hydroxide to the mixed reaction system, react for 2 to 50 hours, then filter the mixed reaction system, wash and dry the filtrate to obtain the target product;

Or, mix carboxyethylphenylphosphinic acid with soluble metal salt and alkali or metal oxide or metal hydroxide in water for 2 to 50 hours, then filter the mixed reaction system, wash and dry the filtrate, and Compounds with active amine groups are reacted in an organic solvent at a temperature of 135-160°C for 4-6 hours, and the water generated by the reaction is removed, and then the mixed reaction system is filtered, and the filtrate is washed and dried to obtain the target product;

The molar ratio of the metal ion contained in the above metal ion-containing compound to the carboxyethylphenylphosphinic acid is 1:1 to 1:3, and the carboxyethylphenylphosphinic acid and the active amino group The molar ratio of the compounds is 1:0.5-1:1.

Specifically, the method is as follows:

Under the condition of nitrogen protection, the carboxyethylphenylphosphinic acid and the compound with active amino groups are refluxed in an organic solvent at a temperature of 135-160°C for 4-6 hours, and the water is removed from the reaction, and then mixed with Add water and metal oxide or metal hydroxide to the reaction system, react for 40-50 hours, then filter the mixed reaction system, wash the filtrate with water and small molecule alcohol, and finally dry the filtrate to obtain the target product ;

Or, mix and react carboxyethylphenylphosphinic acid and metal oxide or metal hydroxide in water for 40-50 hours, then filter the mixed reaction system, wash and dry the filtrate, and mix with active amino group The compound is refluxed and reacted in an organic solvent at a temperature of 135-160°C for 4-6 hours, and the water generated by the reaction is removed, then the mixed reaction system is filtered, the filtrate is washed with water and small molecule alcohol, and finally the filtrate is dried. , to obtain the target product.

The method can also be:

Under the condition of nitrogen protection, the carboxyethylphenylphosphinic acid and the compound with active amino groups are refluxed in an organic solvent at a temperature of 135-160°C for 4-6 hours, and the water is removed from the reaction, and then mixed with Add water and alkali to the reaction system until the mixed reaction system becomes clear, then add soluble metal salts, react at a temperature of 90-95°C for 2-3 hours, then filter the mixed reaction system, wash with water and small molecule alcohol Filtrate, and finally the filtrate is dried to obtain the target product;

Or, mix carboxyethylphenylphosphinic acid and alkali in water for reaction, until the mixed reaction system becomes clear, add soluble metal salt, react at 90-95°C for 2-3 hours, and then filter the mixed reaction system , after the filtrate is washed and dried, it reacts with a compound having an active amine group in an organic solvent at a temperature of 135-160°C for 4-6 hours under reflux, removes the water generated by the reaction, and then filters the mixed reaction system to obtain Wash the filtrate with water and small molecule alcohol, and finally dry the filtrate to obtain the target product.

The compound with active amine group is at least one of RNH2 and H2NRNH2, wherein, R aryl group or straight chain or branched hydrocarbon group containing 0-6 C atoms.

Described organic solvent is high boiling point mineral spirits, xylene or dichlorobenzene.

The metal oxide is magnesium oxide, calcium oxide, aluminum oxide or zinc oxide, and the hydroxide is magnesium hydroxide, calcium hydroxide, aluminum hydroxide or zinc hydroxide.

Described alkali is sodium hydroxide or potassium hydroxide.

The small molecule alcohol is methanol or ethanol.

The present invention uses carboxyethylphenylphosphinic acid and compounds with active amino groups (such as monoamines and diamines) as raw materials, and synthesizes carboxyethylphenylphosphinic acid-based compounds through a simple process. The nitrogen aryl hypophosphite metal salt has stable physical and chemical properties, high flame retardancy, safety and environmental protection, and can be used in polyesters and polyamides, epoxy resins, and fiberglass resins.

Compared with prior art, the beneficial effect of the present invention is:

① The nitrogen-containing aryl hypophosphite metal salt of the present invention has better thermal stability and chemical stability, and is used for high-temperature processing;

②The nitrogen-containing aryl hypophosphite metal salt provided by the present invention has a novel structure, can be synthesized by various processes, and is suitable for production by manufacturers of various scales;

③ Since the additive provided by the present invention does not contain halogen, it is non-toxic, safe and beneficial to environmental protection;

④ The preparation method of the present invention is simple, no catalyst, no high-pressure reaction, no complicated equipment, and the process is mature and easy to control.

Detailed ways

The technical solution of the present invention will be further described below in conjunction with specific embodiments.

Embodiment 1 The present embodiment is carboxyethylphenylphosphinoethylenediamine aluminum salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml xylene, stir, and slowly heat up to 140 After reflux reaction at ℃ for 6 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, slowly add 0.1mol sodium hydroxide aqueous solution dropwise, until the reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution , reacted at 90°C for 2 to 3 hours, filtered the mixed reactant with suction, washed with methanol and then washed with water, after drying, it was carboxyethylphenylphosphinoethylenediamine aluminum salt, the yield was 93%, solid There is no change at 300°C, and it turns black and decomposes at around 400°C.

Embodiment 2 The present embodiment is carboxyethylphenylphosphinoethylenediamine calcium salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml of dichlorobenzene, stir, and slowly heat up to After reacting at 160°C for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol potassium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, at 95 React at ℃ for 2 to 3 hours, filter the mixed reactant with suction, wash with ethanol, wash with water, and dry to obtain carboxyethylphenylphosphinoethylenediamine calcium salt. The yield is 94%. No change, it turns black and decomposes at around 400°C.

Embodiment 3 The present embodiment is carboxyethylphenylphosphinoethylenediamine zinc salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml high boiling point solvent oil, stir, and slowly heat up After reacting at 150°C for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol sodium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, in React at 95°C for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry to obtain carboxyethylphenylphosphinoethylenediamine zinc salt. The yield is 92%. There is no change under low temperature, and it turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 1～3 is shown in the following formula:

Embodiment 4 The present embodiment is carboxyethylphenylphosphinoethylenediamine aluminum salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml xylene, stir, and slowly heat up to 140 After reflux reaction at ℃ for 6 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1/6mol alumina, react at 95℃ for 40-50h, filter the mixed reaction product with methanol After washing, it is washed with water and dried to produce carboxyethylphenylphosphinoethylenediamine aluminum salt with a yield of 93%. The solid remains unchanged at 300°C and turns black and decomposes at about 400°C.

Embodiment 5 The present embodiment is carboxyethylphenylphosphinoethylenediamine zinc salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml of dichlorobenzene, stir, and slowly heat up to After reacting at 160°C for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol zinc oxide, react at 90°C for 40-50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphinoethylenediamine zinc salt with a yield of 92%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Embodiment 6 The present embodiment is carboxyethylphenylphosphinoethylenediamine calcium salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol ethylenediamine and 150ml high boiling point solvent oil, stir, and slowly heat up After reacting at 160°C for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol calcium oxide, react at 95°C for 40-50h, filter the mixed reactant with suction, and wash with methanol After washing with water and drying, it is carboxyethylphenylphosphinoethylenediamine calcium salt with a yield of 94%. The solid remains unchanged at 300°C and turns black at about 400°C.

The reaction process of above-mentioned embodiment 4～6 is shown in the following formula:

Embodiment 7 The present embodiment is aluminum salt of carboxyethylphenylphosphorous hydrazide, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml xylene, stir, and slowly raise the temperature to 140°C After reflux reaction for 6 hours, remove the reaction water, cool the reactant, add a certain amount of water in the reaction system, add 0.1mol sodium hydroxide aqueous solution, until the reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry to obtain carboxyethylphenylphosphorous hydrazide aluminum salt. The yield is 94%, and the solid is free at 300°C. Change, blacken and decompose at around 400°C.

Embodiment 8 The present embodiment is carboxyethylphenylphosphorous hydrazide calcium salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml of dichlorobenzene, stir, and slowly heat up to 160 After reacting at ℃ for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol potassium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, at 95℃ After reacting for 2 to 3 hours, the mixed reactant was suction filtered, washed with ethanol, washed with water, and dried to obtain carboxyethylphenylphosphorous hydrazide calcium salt. The yield was 94%, and the solid did not change at 300°C. It turns black and decomposes at around 400°C.

Embodiment 9 The present embodiment is zinc salt of carboxyethylphenylphosphorous hydrazide, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml high boiling point solvent oil, stir, and slowly heat up to After reacting at 150°C for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol sodium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, at 95 React at ℃ for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry to obtain carboxyethylphenylphosphorous hydrazide zinc salt. The yield is 93%, and the solid does not change at 300°C , It turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 7～9 is shown in the following formula:

Embodiment 10 This embodiment is carboxyethylphenylphosphorhydrazide aluminum salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml xylene, stir, and slowly raise the temperature to 140°C After 6 hours of reflux reaction, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1/6mol alumina, react at 95°C for 40-50 hours, filter the mixed reactant with suction, and wash with methanol After washing with water and drying, it is carboxyethylphenylphosphorous hydrazide aluminum salt with a yield of 92%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 11 This example is zinc salt of carboxyethylphenylphosphinohydrazide, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml of dichlorobenzene, stir, and slowly heat up to 160 After reacting at ℃ for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol zinc hydroxide, react at 90℃ for 40~50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphorous hydrazide zinc salt with a yield of 93%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Embodiment 12 This embodiment is carboxyethylphenylphosphorous hydrazide calcium salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.05mol hydrazine hydrate and 150ml high boiling point solvent oil, stir, and slowly heat up to After reacting at 160°C for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol calcium oxide, react at 95°C for 40-50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphorous hydrazide calcium salt with a yield of 94%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 10～12 is shown in the following formula:

Example 13 The present example is carboxyethylphenylphosphinophenyl aluminum salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml xylene, stir, and slowly raise the temperature to 140°C and reflux After reacting for 6 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol sodium hydroxide aqueous solution, until the reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, at 90 ℃ React for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry it to obtain carboxyethylphenylphosphinophenyl aluminum salt. The yield is 92%, and the solid does not change at 300°C. , It turns black and decomposes at about 400°C.

Embodiment 14 The present embodiment is carboxyethylphenyl phosphorous phenyl calcium salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml of dichlorobenzene, stir, and slowly raise the temperature to 160°C After reacting for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol potassium hydroxide aqueous solution until the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, and react at 95°C After 2 to 3 hours, the mixed reactant was filtered with suction, washed with ethanol, washed with water, and dried to obtain carboxyethylphenylphosphine calcium salt. The yield was 91%, and the solid did not change at 300°C. It turns black and decomposes at about ℃.

Example 15 This example is carboxyethylphenylphosphorylphenyl zinc salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml high boiling point solvent oil, stir, and slowly heat up to 150 After reacting at ℃ for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1mol sodium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, at 95℃ After reacting for 2 to 3 hours, the mixed reactant was suction filtered, washed with methanol, washed with water, and dried to obtain carboxyethylphenylphosphinophenyl zinc salt. The yield was 92%, and the solid did not change at 300°C. It turns black and decomposes at around 400°C.

The reaction process of above-mentioned embodiment 13～15 is shown in the following formula:

Example 16 This example is carboxyethylphenylphosphinophenyl aluminum salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml xylene, stir, and slowly raise the temperature to 140°C and reflux After reacting for 6 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.1/6mol alumina, react at 95°C for 40-50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphinophenyl aluminum salt with a yield of 92%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 17 This example is carboxyethylphenylphosphorylphenyl zinc salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml of dichlorobenzene, stir, and slowly raise the temperature to 160°C After reacting for 5 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol zinc hydroxide, react at 90°C for 40-50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphinophenyl zinc salt with a yield of 93%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Embodiment 18 This embodiment is carboxyethylphenylphosphorous phenyl calcium salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, after nitrogen protection, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aniline and 150ml high boiling point solvent oil, stir, and slowly heat up to 160 After reacting at ℃ for 4 hours, remove the reaction water, cool the reactant, add a certain amount of water to the reaction system, add 0.05mol calcium oxide, react at 95℃ for 40-50h, filter the mixed reactant with suction, wash with methanol After washing with water and drying, it is carboxyethylphenylphosphinophenyl calcium salt with a yield of 92%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 16～18 is shown in the following formula:

Example 19 This example is acylphenylphosphine ethylenediamine aluminum salt, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with stirrer and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol sodium hydroxide aqueous solution, after reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, in React at 90°C for 2 to 3 hours, filter with suction, wash with water, dry, and then add 0.05mol ethylenediamine and 150ml xylene for protection with nitrogen, stir, slowly raise the temperature to 140°C and reflux for 6 hours, then remove the reaction water , cool the reactant, filter with suction, wash with methanol and then wash with water, after drying, it is the acylethylphenylphosphinoethylenediamine aluminum salt, the yield is 97%, the solid does not change at 300 ° C, and the solid is unchanged at 400 ° C Turn black and decompose left and right.

Example 20 This example is acylphenylphosphine ethylenediamine zinc salt, and its synthesis process is as follows:

In a 500ml there-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol aqueous sodium hydroxide solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, add 0.05mol ethylenediamine and 150ml of dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 150℃, reflux for 5 hours, and remove the reaction water , cooling the reactant, suction filtration, washing with ethanol and then washing with water, after drying, it is acylphenylphosphinoethylenediamine zinc salt, the yield is 95%, the solid does not change at 300 ° C, and the Turn black and decompose left and right.

Example 21 This example is acylphenylphosphinoethylenediamine calcium salt, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with agitator and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol potassium hydroxide aqueous solution, after the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, and then add 0.05mol ethylenediamine and 150ml of xylene for protection with nitrogen, stir, slowly raise the temperature to 140℃, reflux for 4 hours, and remove the reaction water. Cool the reactant, filter it with suction, wash it with methanol and then wash it with water, and dry it to obtain the calcium salt of acylethylphenylphosphinoethylenediamine. The yield rate is 96%. Blackened and decomposed.

The reaction process of above-mentioned embodiment 19～21 is shown in the following formula

Example 22 This example is acylphenylphosphine ethylenediamine aluminum salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.1/3mol aluminum hydroxide and water, react at 90°C for 45-50h, filter with suction and wash with water , dry, add 0.05mol ethylenediamine and 150ml xylene after nitrogen protection, stir, slowly heat up to 140°C and reflux for 6 hours to remove the reaction water, cool the reactant, suction filter, wash with methanol After washing with water and drying, the acylphenylphosphinoethylenediamine aluminum salt is obtained, with a yield of 95%. The solid remains unchanged at 300°C, but turns black and decomposes at about 400°C.

Example 23 This example is acylphenylphosphine ethylenediamine zinc salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol zinc oxide and water, react at 90°C for 45-50h, filter with suction, wash with water, After drying, add 0.05mol of ethylenediamine and 150ml of dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 160°C for 4 hours, remove the reaction water, cool the reactant, suction filter, wash with ethanol and then After washing with water and drying, it is acylphenylphosphinoethylenediamine zinc salt with a yield of 95%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 24 This example is acylphenylphosphinediamine calcium salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol calcium hydroxide calcium and water, react at 90°C for 40-50h, filter with suction and wash with water , dry, and then add 0.05mol ethylenediamine and 150ml high-boiling solvent oil after nitrogen protection, stir, slowly heat up to 150°C for 4 hours, and then remove the reaction water, cool the reactant, suction filter, and wash with methanol After washing with water and drying, the calcium salt of acylethylphenylphosphinoethylenediamine is obtained, and the yield is 96%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 22～24 is shown in the following formula

Example 25 This example is acylphenylphosphinate aluminum hydrazine hydrate, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with stirrer and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol sodium hydroxide aqueous solution, after reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, in React at 90°C for 2 to 3 hours, filter with suction, wash with water, dry, and then add 0.05mol hydrazine hydrate and 150ml xylene for protection with nitrogen, stir, slowly raise the temperature to 140°C and reflux for 6 hours to remove the reaction water. Cool the reactant, filter it with suction, wash it with methanol and then wash it with water. After drying, it is the aluminum salt of acylethylphenylphosphinate hydrazine hydrate. The yield is 95%. black decomposition.

Example 26 This example is zinc acylphenylphosphinate hydrazine hydrate, and its synthesis process is as follows:

In a 500ml there-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol potassium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, add 0.05mol hydrazine hydrate and 150ml of dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 150℃ and react for 5 hours, remove the reaction water, cool The reactant is suction filtered, washed with ethanol and then washed with water, and after drying, it is the zinc salt of acylethylphenylphosphinate hydrazine hydrate, and the yield is 96%. The solid does not change at 300°C, and turns black at about 400°C break down.

Example 27 This example is calcium salt of acylethylphenylphosphinate hydrazine hydrate, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with agitator and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol potassium hydroxide aqueous solution, after the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, and then add 0.05mol hydrazine hydrate and 150ml xylene for protection with nitrogen, stir, slowly raise the temperature to 140℃, reflux for 4 hours, remove the reaction water, and cool The reactant is suction filtered, washed with methanol and then washed with water, and after drying, it is acylphenylphosphinate hydrazine hydrate calcium salt, and the yield is 94%. The solid does not change at 300°C, and turns black at about 400°C break down.

The reaction process of above-mentioned embodiment 25～27 is shown in the following formula

Example 28 This example is the aluminum salt of acylethylphenylphosphinate hydrazine hydrate, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.1/6mol alumina and water, react at 90°C for 45-50h, filter with suction, wash with water, After drying, add 0.05mol hydrazine hydrate and 150ml xylene after nitrogen protection, stir, slowly raise the temperature to 140°C and reflux for 6 hours to remove the reaction water, cool the reactant, suction filter, wash with methanol and then wash with water , after drying treatment, it is the aluminum salt of acylethylphenylphosphinate hydrazine hydrate, and its yield is 93%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 29 This example is acylphenylphosphinate hydrazine hydrate zinc salt, and its synthesis process is as follows:

In a 500ml three-neck flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol zinc hydroxide and water, react at 90°C for 45-50h, filter with suction, wash with water, After drying, add 0.05mol hydrazine hydrate and 150ml dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 160°C for 4 hours, remove the reaction water, cool the reactant, suction filter, wash with ethanol and then wash with water , after drying treatment, it is acylphenylphosphine hydrazine hydrate zinc salt, the yield rate is 95%, the solid does not change at 300°C, and it turns black and decomposes at about 400°C.

Example 30 This example is calcium salt of acylethylphenylphosphinate hydrazine hydrate, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol calcium hydroxide and water, react at 90°C for 40-50h, filter with suction, wash with water, After drying, add 0.05mol hydrazine hydrate and 150ml high boiling point solvent oil after nitrogen protection, stir, slowly raise the temperature to 150°C for 4 hours, remove the reaction water, cool the reactant, suction filter, wash with methanol and then After washing with water and drying, the calcium salt of acylethylphenylphosphinate hydrazine hydrate is obtained. The yield is 94%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 28～30 is shown in the following formula

Example 31 This example is the aluminum salt of acylethylphenylphosphoraniline, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with stirrer and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol sodium hydroxide aqueous solution, after reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, in React at 90°C for 2 to 3 hours, suction filter, wash with water, dry, and then add 0.1mol aniline and 150ml xylene for protection with nitrogen, stir, slowly raise the temperature to 140°C, reflux for 6 hours, remove the reaction water, and cool The reactant is suction filtered, washed with methanol and then washed with water, and after drying, it is the aluminum salt of acylethylphenylphosphine aniline. The yield is 94%. The solid does not change at 300°C, and it turns black and decomposes at about 400°C. .

Example 32 This example is the zinc salt of acylethylphenylphosphoraniline, and its synthesis process is as follows:

In a 500ml there-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol potassium hydroxide aqueous solution, until the reaction system becomes clear, add 0.05mol zinc sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, add 0.1mol aniline and 150ml of dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 150℃ and react for 5 hours, remove the reaction to form water, and cool the reaction The product was filtered with suction, washed with ethanol and then washed with water. After drying, it was acylethylphenylphosphoranilide zinc salt. The yield was 93%. The solid did not change at 300°C, and it turned black and decomposed at about 400°C.

Example 33 This example is the calcium salt of acylethylphenylphosphanilide, and its synthesis process is as follows:

In the 500ml there-necked flask equipped with agitator and water separator, add 0.1mol carboxyethylphenylphosphinic acid, 0.1mol potassium hydroxide aqueous solution, after the reaction system becomes clear, add 0.05mol calcium sulfate aqueous solution, at 90 React at ℃ for 2 to 3 hours, filter with suction, wash with water, dry, add 0.1mol aniline and 150ml xylene after nitrogen protection, stir, slowly raise the temperature to 140℃, reflux for 4 hours, remove the reaction to form water, and cool the reaction Suction filtration, washing with methanol and then washing with water, after drying treatment, it is acylphenylphosphinohydrazine hydrate calcium salt, the yield is 94%, the solid does not change at 300 °C, and it turns black and decomposes at about 400 °C .

The reaction process of above-mentioned embodiment 31～33 is shown in the following formula

Example 34 This example is acylphenylphosphoraniline aluminum salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.1/6mol alumina and water, react at 90°C for 45-50h, filter with suction, wash with water, After drying, add 0.1mol of aniline and 150ml of xylene after nitrogen protection, stir, slowly raise the temperature to 140°C for reflux reaction for 6 hours, remove the reaction water, cool the reactant, suction filter, wash with methanol, and then wash with water. After drying treatment, it is the aluminum salt of acylethylphenylphosphoranilide, and its yield is 93%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 35 This example is zinc salt of acylethylphenylphosphoraniline, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol zinc hydroxide and water, react at 90°C for 45-50h, filter with suction, wash with water, After drying, add 0.1mol of aniline and 150ml of dichlorobenzene after nitrogen protection, stir, slowly raise the temperature to 160°C for 4 hours, remove the reaction water, cool the reactant, filter with suction, wash with ethanol, and then wash with water. After drying treatment, it is the zinc salt of acylethylphenylphosphine aniline, and its yield is 95%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

Example 36 This example is acylphenylphosphanilide calcium salt, and its synthesis process is as follows:

In a 500ml three-necked flask equipped with a stirrer and a water separator, add 0.1mol carboxyethylphenylphosphinic acid, add 0.05mol calcium hydroxide and water, react at 90°C for 40-50h, filter with suction, wash with water, After drying, add 0.1mol aniline and 150ml high-boiling solvent oil after nitrogen protection, stir, slowly heat up to 150°C for 4 hours, remove the reaction water, cool the reactant, filter with suction, wash with methanol and then wash with water , after drying treatment, it is acylethylphenylphosphoranilide calcium salt, and its yield is 94%. The solid does not change at 300°C, but turns black and decomposes at about 400°C.

The reaction process of above-mentioned embodiment 34～36 is shown in the following formula

Claims (4)

1. The preparation method of carboxyethylphenylphosphinoethylenediamine aluminum salt is characterized in that, the method is: in a 500ml three-necked bottle equipped with a stirrer and a water separator, after feeding nitrogen protection, add 0.1 mol of carboxyethylphenylphosphinic acid, 0.05mol of ethylenediamine and 150ml of xylene, stirred, slowly heated up to 140°C and refluxed for 6 hours to remove the reaction water, cooled the reactant, added water to the reactant, Slowly add 0.1mol sodium hydroxide aqueous solution dropwise until the reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, react at 90°C for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol and then water, and dry it That is, carboxyethylphenylphosphinoethylenediamine aluminum salt, the yield rate is 93%, the solid does not change at 300°C, and turns black and decomposes at 400°C, wherein, the reaction process before adding 0.1/6mol aluminum sulfate aqueous solution As shown in the following formula:

2. The preparation method of carboxyethylphenylphosphinoethylenediamine aluminum salt is characterized in that, the method is: in a 500ml three-necked bottle equipped with a stirrer and a water separator, after feeding nitrogen protection, add 0.1 mol of carboxyethylphenylphosphinic acid, 0.05mol of ethylenediamine and 150ml of xylene, stirred, slowly heated up to 140°C for reflux reaction for 6 hours, then removed the reaction to generate water, cooled the reactant, added water to the reactant, Add 0.1/6 mol of alumina, react at 95°C for 40-50 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry to obtain carboxyethylphenylphosphinoethylenediamine aluminum salt, which produces The rate is 93%, the solid does not change at 300°C, and turns black and decomposes at 400°C, wherein, the reaction process before adding 0.1/6mol alumina is shown in the following formula: 3. The preparation method of carboxyethylphenylphosphinophenyl aluminum salt is characterized in that, the method is: in a 500ml three-necked flask equipped with a stirrer and a water separator, after feeding nitrogen protection, add 0.1mol carboxyl Ethylphenylphosphinic acid, 0.1mol aniline and 150ml xylene, stirred, slowly heated up to 140°C and refluxed for 6 hours to remove the reaction water, cooled the reactant, added water to the reactant, then added 0.1mol hydrogen Sodium oxide aqueous solution, until the reaction system becomes clear, add 0.1/6mol aluminum sulfate aqueous solution, react at 90°C for 2 to 3 hours, filter the mixed reactant with suction, wash with methanol, then wash with water, and dry it to obtain carboxyethylbenzene Phosphinophenyl aluminum salt, its productive rate is 92%, solid does not change at 300 DEG C, and 400 DEG C turns black and decomposes, and wherein, the reaction flow process before adding 0.1/6mol aluminum sulfate aqueous solution is shown in the following formula:

4. The preparation method of carboxyethylphenylphosphinophenyl aluminum salt is characterized in that, the method is: in a 500ml three-necked flask equipped with a stirrer and a water separator, after feeding nitrogen protection, add 0.1mol carboxyl Ethylphenylphosphinic acid, 0.1mol aniline and 150ml xylene, stirred, slowly heated up to 140°C and refluxed for 6 hours to remove the reaction water, cooled the reactant, added water to the reactant, then added 0.1/6mol Alumina, react at 95°C for 40-50 hours, filter the mixed reactant with suction, wash with methanol, wash with water, and dry it to obtain carboxyethylphenylphosphorylphenyl aluminum salt, the yield is 92%, solid There is no change at 300°C, and it turns black and decomposes at 400°C. Among them, the reaction process before adding 0.1/6mol alumina is shown in the following formula: