CN101792463A - Nitrogen-containing aryl hypophosphorous acid metal salt and preparation method thereof - Google Patents
Nitrogen-containing aryl hypophosphorous acid metal salt and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a nitrogen-containing aryl hypophosphorous acid metal salt and a preparation method thereof. The nitrogen-containing aryl hypophosphorous acid metal salt has a structural unit as follows: R is aryl or linear chain or branched chain alkyl containing 0-6 C atoms, and Z is a metal ion. The preparation method comprises the following steps of: reacting propyloic phenyl hypophosphorous acid with a compound containing active amido under the conditions of nitrogen protection and heating for dewatering; then adding a compound containing metal ions to a reaction system to carry out reaction; or reacting the propyloic phenyl hypophosphorous acid with the compound containing the metal ions for purifying, then reacting with the compound containing the active amido in a solvent under the condition of heating for dewatering; and then purifying and drying a reaction product to obtain a target product. The product has stable physical and chemical property, high flame retardant property, safety, environmental protection, simple and easy preparation process and low cost, and is suitable for polyester, polyamide, epoxy resin, glass fibre reinforced plastic resin, and the like.
Description
Technical field
The present invention relates to a kind of phosphorus nitrogen collaborative type flame-retardant compound and preparation method thereof, relate in particular to a kind of with the carboxyethyl phenyl phosphinic acid be the base nitrogenous aryl hypophosphorous acid metal salt and preparation method thereof.
Background technology
Along with the whole world is more and more higher to the environmental requirement of fire retardant, traditional halogenated flame retardant faces huge pressure, environmental protection, the less novel expansion type phosphor nitrogen flame retardant of pollution are then more and more favored by people, and it is high that phosphorus nitrogen cooperative flame retardant compound especially wherein is subjected to chasing after of industry especially.Its reason is, phosphorus nitrogen cooperative flame retardant compound itself promptly has the three elements of acid source, carbon source, source of the gas fire retardant mechanism, and it contains the C-P key, with fire-retardant metallic compound salify after, chemical stability is higher, the characteristic that also has good, the low cigarette of flame retardant properties, low toxicity is so become an important directions of current fire retardant development research.Yet, aspect the organophosphorous fire retardant exploitation, China starts late, so far do not release the outstanding similar organic phosphine fire retardant kind of performance, directly limited the industry development of the relevant fire retardant material of China, therefore, to the exploitation of phosphorus nitrogen synergetic organic phosphine Study of Flame Retardant, have urgent realistic meaning and long-range strategic importance.
Summary of the invention
The objective of the invention is to propose a kind of nitrogenous aryl hypophosphorous acid metal salt and preparation method thereof, this nitrogenous aryl hypophosphorous acid metal salt physical and chemical performance is stable, flame retardant properties is high, safety and environmental protection, simultaneously, its preparation technology is simple to operation, with low cost, be suitable for the demand of various technical scale productions, thereby overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of nitrogenous aryl hypophosphorous acid metal salt is characterized in that, this nitrogenous aryl hypophosphorous acid metal salt has following structural unit:
Wherein, R is aryl or the straight or branched alkyl that contains 0～6 C atom, and Z is a metal ion.
Particularly, described metal ion is Mg
2+, Zn
2+, Al
3+And Ca
2+In one or more.
A kind of preparation method of nitrogenous aryl hypophosphorous acid metal salt is characterized in that, this method is:
Under nitrogen or protection of inert gas condition, carboxyethyl phenyl phosphinic acid and the compound with active amine are reacted 4～6h in organic solvent under 135～160 ℃ temperature condition, slough water generation reaction, in this hybrid reaction system, add entry, soluble metallic salt and alkali or metal oxide or metal hydroxides again, reaction 2～50h, its after-filtration hybrid reaction system leaches thing through washing, drying treatment, is target product;
Or, with carboxyethyl phenyl phosphinic acid and soluble metallic salt and alkali or metal oxide or metal hydroxides hybrid reaction 2～50h in water, and after-filtration hybrid reaction system, leach thing after washing, drying, under 135～160 ℃ temperature condition, in organic solvent, react 4～6h with compound, slough water generation reaction, refilter the hybrid reaction system with active amine, leach thing through washing, drying treatment, be target product;
The mol ratio of institute's metal ion and described carboxyethyl phenyl phosphinic acid is 1: 1～1: 3 in the compound of above-mentioned metal ion, and described carboxyethyl phenyl phosphinic acid is 1: 0.5～1: 1 with the compound mol ratio with active amine.
Say that further this method is specially:
Under the nitrogen protection condition, with carboxyethyl phenyl phosphinic acid and the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, in the hybrid reaction system, add entry and metal oxide or metal hydroxides again, reaction 40～50h, its after-filtration hybrid reaction system leaches thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product;
Or, with carboxyethyl phenyl phosphinic acid and metal oxide or metal hydroxides hybrid reaction 40～50h in water, and after-filtration hybrid reaction system, leach thing through washing, after the drying treatment, with the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, refilter the hybrid reaction system, leach thing with water and small molecular alcohol washing, will leach the thing drying treatment at last, make target product.
This method also can be:
Under the nitrogen protection condition, with carboxyethyl phenyl phosphinic acid and the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, in the hybrid reaction system, add entry and alkali again, to hybrid reaction system change clarification, add soluble metallic salt again, react 2～3h down in 90～95 ℃ temperature condition, its after-filtration hybrid reaction system, leach thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product;
Or, the hybrid reaction in water with carboxyethyl phenyl phosphinic acid and alkali, to hybrid reaction system change clarification, add soluble metallic salt, react 2～3h down in 90～95 ℃ temperature condition, and after-filtration hybrid reaction system, leach thing after washing, drying treatment, with the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, refilter the hybrid reaction system, leach thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product.
Described compound with active amine is at least a among RNH2 and the H2NRNH2, wherein, and R aryl or contain the straight or branched alkyl of 0～6 C atom.
Described organic solvent is high boiling point solvent oil, dimethylbenzene or dichlorobenzene.
Described metal oxide is magnesium oxide, calcium oxide, aluminum oxide or zinc oxide, and described oxyhydroxide is magnesium hydroxide, calcium hydroxide, aluminium hydroxide or zinc hydroxide.
Described alkali is sodium hydroxide or potassium hydroxide.
Described small molecular alcohol is methyl alcohol or ethanol.
The present invention is a raw material with carboxyethyl phenyl phosphinic acid and compound (as an amine, two amine materials) with active amine, synthesizing with the carboxyethyl phenyl phosphinic acid through the simple process process is the nitrogenous aryl hypophosphorous acid metal salt of base, its physical and chemical performance is stable, flame retardant properties is high, and safety and environmental protection, can be used for polyester and polyamide-based, Resins, epoxy is among the fiber glass resin etc.
Compared with prior art, beneficial effect of the present invention is:
1. the thermostability of nitrogenous aryl hypophosphorous acid metal salt of the present invention and chemical stability are better, are used in high temperature process;
2. nitrogenous aryl hypophosphorous acid metal salt novel structure provided by the invention can use kinds of processes synthetic, is suitable for various scale manufacturer production;
3. because not halogen-containing, nontoxic, the safety of additive provided by the invention helps environmental protection;
4. preparation method of the present invention is simple, need not catalyzer, need not reaction under high pressure, need not complex apparatus, and technical maturity, is easy to control.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further.
Embodiment 1 present embodiment is a carboxyethyl phenyl time phosphinylidyne quadrol aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dimethylbenzene of quadrol and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h; the cooling reactant; after in reaction system, adding a certain amount of water, slowly be added dropwise to the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃, the suction filtration mixed reactant is with washing again after the methanol wash; be carboxyethyl phenyl time phosphinylidyne quadrol aluminium salt after the drying treatment; its productive rate is 93%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 2 present embodiments are carboxyethyl phenyl time phosphinylidyne quadrol calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dichlorobenzene of quadrol and 150ml; stir; slough water generation reaction after slowly being warmed up to 160 ℃ of reaction 4h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol potassium hydroxide aqueous solution, after reaction system becomes clarification; add the 0.05mol calcium sulfate aqueous solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the washing with alcohol; be carboxyethyl phenyl time phosphinylidyne quadrol calcium salt after the drying treatment; its productive rate is 94%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 3 present embodiments are carboxyethyl phenyl time phosphinylidyne quadrol zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the high boiling point solvent oil of quadrol and 150ml; stir; slough water generation reaction after slowly being warmed up to 150 ℃ of reaction 5h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.05mol zinc sulfate solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne quadrol zinc salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 1～3 is shown below:
Embodiment 4 present embodiments are carboxyethyl phenyl time phosphinylidyne quadrol aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dimethylbenzene of quadrol and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.1/6mol aluminum oxide; react 40～50h down at 95 ℃, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne quadrol aluminium salt after the drying treatment; its productive rate is 93%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 5 present embodiments are carboxyethyl phenyl time phosphinylidyne quadrol zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dichlorobenzene of quadrol and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 5h, the cooling reactant, in reaction system, add a certain amount of water after; add 0.05mol zinc oxide; 90 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne quadrol zinc salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 6 present embodiments are carboxyethyl phenyl time phosphinylidyne quadrol calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the high boiling point solvent oil of quadrol and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 4h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.05mol calcium oxide; 95 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne quadrol calcium salt after the drying treatment; its productive rate is 94%, and solid is at 300 ℃ of following no changes, 400 ℃ of left and right sides blackening.
The reaction process of the foregoing description 4～6 is shown below:
Embodiment 7 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dimethylbenzene of hydrazine hydrate and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne hydrazine aluminium salt after the drying treatment; its productive rate is 94%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 8 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dichlorobenzene of hydrazine hydrate and 150ml stirs, and sloughs water generation reaction after slowly being warmed up to 160 ℃ of reaction 4h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol potassium hydroxide aqueous solution, after reaction system becomes clarification; add the 0.05mol calcium sulfate aqueous solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the washing with alcohol; be carboxyethyl phenyl time phosphinylidyne hydrazine calcium salt after the drying treatment; its productive rate is 94%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 9 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the high boiling point solvent oil of hydrazine hydrate and 150ml; stir; slough water generation reaction after slowly being warmed up to 150 ℃ of reaction 5h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.05mol zinc sulfate solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne hydrazine zinc salt after the drying treatment; its productive rate is 93%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 7～9 is shown below:
Embodiment 10 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dimethylbenzene of hydrazine hydrate and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.1/6mol aluminum oxide; react 40～50h down at 95 ℃, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne hydrazine aluminium salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 11 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the dichlorobenzene of hydrazine hydrate and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 5h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.05mol zinc hydroxide; 90 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne hydrazine zinc salt after the drying treatment; its productive rate is 93%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 12 present embodiments are carboxyethyl phenyl time phosphinylidyne hydrazine calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.05mol the high boiling point solvent oil of hydrazine hydrate and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 4h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.05mol calcium oxide; 95 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne hydrazine calcium salt after the drying treatment; its productive rate is 94%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 10～12 is shown below:
Embodiment 13 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the dimethylbenzene of aniline and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne benzene aluminium salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 14 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the dichlorobenzene of aniline and 150ml stirs, and sloughs water generation reaction after slowly being warmed up to 160 ℃ of reaction 4h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol potassium hydroxide aqueous solution, after reaction system becomes clarification; add the 0.05mol calcium sulfate aqueous solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the washing with alcohol; be carboxyethyl phenyl time phosphinylidyne benzene calcium salt after the drying treatment; its productive rate is 91%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 15 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the high boiling point solvent oil of aniline and 150ml; stir; slough water generation reaction after slowly being warmed up to 150 ℃ of reaction 5h; the cooling reactant; after in reaction system, adding a certain amount of water, add the 0.1mol aqueous sodium hydroxide solution, after reaction system becomes clarification; add the 0.05mol zinc sulfate solution; at 95 ℃ of reaction 2～3h, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne benzene zinc salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 13～15 is shown below:
Embodiment 16 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the dimethylbenzene of aniline and 150ml; stir; slough water generation reaction after slowly being warmed up to 140 ℃ of back flow reaction 6h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.1/6mol aluminum oxide; react 40～50h down at 95 ℃, the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne benzene aluminium salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 17 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the dichlorobenzene of aniline and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 5h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.05mol zinc hydroxide; 90 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne benzene zinc salt after the drying treatment; its productive rate is 93%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 18 present embodiments are carboxyethyl phenyl time phosphinylidyne benzene calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; after feeding nitrogen protection; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol the high boiling point solvent oil of aniline and 150ml; stir; slowly be warmed up to 160 ℃ of reactions and slough water generation reaction behind the 4h, the cooling reactant, in reaction system, add a certain amount of water after; add the 0.05mol calcium oxide; 95 ℃ are reacted 40～50h down, and the suction filtration mixed reactant is with washing after the methanol wash; be carboxyethyl phenyl time phosphinylidyne benzene calcium salt after the drying treatment; its productive rate is 92%, and solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 16～18 is shown below:
Embodiment 19 present embodiments are acyl ethylphenyl time phosphorus quadrol aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol aqueous sodium hydroxide solution after reaction system becomes clarification, adds the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus quadrol aluminium salt after the drying treatment, its productive rate is 97%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 20 present embodiments are acyl ethylphenyl time phosphorus quadrol zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol aqueous sodium hydroxide solution after reaction system becomes clarification, adds the 0.05mol zinc sulfate solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of back flow reaction 5h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus quadrol zinc salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 21 present embodiments are acyl ethylphenyl time phosphorus quadrol calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol potassium hydroxide aqueous solution after reaction system becomes clarification, adds the 0.05mol calcium sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus quadrol calcium salt after the drying treatment, its productive rate is 96%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 19～21 is shown below
Embodiment 22 present embodiments are acyl ethylphenyl time phosphorus quadrol aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.1/3mol aluminium hydroxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus quadrol aluminium salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 23 present embodiments are acyl ethylphenyl time phosphorus quadrol zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mo l zinc oxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 160 ℃ of reaction 4h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus quadrol zinc salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 24 present embodiments are acyl ethylphenyl time phosphorus quadrol calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mol calcium hydroxide calcium and water; react 40～50h down at 90 ℃; suction filtration, washing, oven dry; the high boiling point solvent oil that adds 0.05mol quadrol and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus quadrol calcium salt after the drying treatment, its productive rate is 96%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 22～24 is shown below
Embodiment 25 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol aqueous sodium hydroxide solution after reaction system becomes clarification, adds the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus hydrazine hydrate aluminium salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 26 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol potassium hydroxide aqueous solution after reaction system becomes clarification, adds the 0.05mol zinc sulfate solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of reaction 5h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus hydrazine hydrate zinc salt after the drying treatment, its productive rate is 96%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 27 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol potassium hydroxide aqueous solution after reaction system becomes clarification, adds the 0.05mol calcium sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus hydrazine hydrate calcium salt after the drying treatment, its productive rate is 94%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 25～27 is shown below
Embodiment 28 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.1/6mol aluminum oxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus hydrazine hydrate aluminium salt after the drying treatment, its productive rate is 93%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 29 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mol zinc hydroxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 160 ℃ of reaction 4h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus hydrazine hydrate zinc salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 30 present embodiments are acyl ethylphenyl time phosphorus hydrazine hydrate calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mol calcium hydroxide and water; react 40～50h down at 90 ℃; suction filtration, washing, oven dry; the high boiling point solvent oil that adds 0.05mol hydrazine hydrate and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus hydrazine hydrate calcium salt after the drying treatment, its productive rate is 94%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 28～30 is shown below
Embodiment 31 present embodiments are acyl ethylphenyl time phosphorus aniline aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol aqueous sodium hydroxide solution after reaction system becomes clarification, adds the 0.1/6mol aluminum sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus aniline aluminium salt after the drying treatment, its productive rate is 94%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 32 present embodiments are acyl ethylphenyl time phosphorus aniline zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol potassium hydroxide aqueous solution after reaction system becomes clarification, adds the 0.05mol zinc sulfate solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of reaction 5h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus aniline zinc salt after the drying treatment, its productive rate is 93%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 33 present embodiments are acyl ethylphenyl time phosphorus aniline calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; 0.1mol potassium hydroxide aqueous solution after reaction system becomes clarification, adds the 0.05mol calcium sulfate aqueous solution; react 2～3h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus hydrazine hydrate calcium salt after the drying treatment, its productive rate is 94%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 31～33 is shown below
Embodiment 34 present embodiments are acyl ethylphenyl time phosphorus aniline aluminium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.1/6mol aluminum oxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dimethylbenzene that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 140 ℃ of back flow reaction 6h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus aniline aluminium salt after the drying treatment, its productive rate is 93%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 35 present embodiments are acyl ethylphenyl time phosphorus aniline zinc salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mol zinc hydroxide and water; react 45～50h down at 90 ℃; suction filtration, washing, oven dry; the dichlorobenzene that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 160 ℃ of reaction 4h; suction filtration; with washing again after the washing with alcohol, be acyl ethylphenyl time phosphorus aniline zinc salt after the drying treatment, its productive rate is 95%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
Embodiment 36 present embodiments are acyl ethylphenyl time phosphorus aniline calcium salt, and its synthesis technique is as follows:
In the 500ml there-necked flask of agitator and water trap is housed; add the 0.1mol carboxyethyl phenyl phosphinic acid; add 0.05mol calcium hydroxide and water; react 40～50h down at 90 ℃; suction filtration, washing, oven dry; the high boiling point solvent oil that adds 0.1mol aniline and 150ml after the feeding nitrogen protection again; stir, slough water generation reaction, the cooling reactant after slowly being warmed up to 150 ℃ of reaction 4h; suction filtration; with washing again after the methanol wash, be acyl ethylphenyl time phosphorus aniline calcium salt after the drying treatment, its productive rate is 94%; solid is at 300 ℃ of following no changes, and 400 ℃ of left and right sides blackening are decomposed.
The reaction process of the foregoing description 34～36 is shown below
Claims (10)
1. a nitrogenous aryl hypophosphorous acid metal salt is characterized in that, this nitrogenous aryl hypophosphorous acid metal salt has following structural unit:
Wherein, R is aryl or the straight or branched alkyl that contains 0～6 C atom, and Z is a metal ion.
2. nitrogenous aryl hypophosphorous acid metal salt as claimed in claim 1 is characterized in that, described metal ion is Mg
2+, Zn
2+, Al
3+And Ca
2+In one or more.
3. the preparation method of a nitrogenous aryl hypophosphorous acid metal salt is characterized in that, this method is:
Under nitrogen or protection of inert gas condition, carboxyethyl phenyl phosphinic acid and the compound with active amine are reacted 4～6h in organic solvent under 135～160 ℃ temperature condition, slough water generation reaction, in this hybrid reaction system, add entry, soluble metallic salt and alkali or metal oxide or metal hydroxides again, reaction 2～50h, its after-filtration hybrid reaction system leaches thing through washing, drying treatment, is target product;
Or, with carboxyethyl phenyl phosphinic acid and soluble metallic salt and alkali or metal oxide or metal hydroxides hybrid reaction 2～50h in water, and after-filtration hybrid reaction system, leach thing after washing, drying, under 135～160 ℃ temperature condition, in organic solvent, react 4～6h with compound, slough water generation reaction, refilter the hybrid reaction system with active amine, leach thing through washing, drying treatment, be target product;
The mol ratio of institute's metal ion and described carboxyethyl phenyl phosphinic acid is 1: 1～1: 3 in the compound of above-mentioned metal ion, and described carboxyethyl phenyl phosphinic acid is 1: 0.5～1: 1 with the compound mol ratio with active amine.
4. the preparation method of nitrogenous aryl hypophosphorous acid metal salt as claimed in claim 3 is characterized in that, this method is specially:
Under the nitrogen protection condition, with carboxyethyl phenyl phosphinic acid and the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, in the hybrid reaction system, add entry and metal oxide or metal hydroxides again, reaction 40～50h, its after-filtration hybrid reaction system leaches thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product;
Or, with carboxyethyl phenyl phosphinic acid and metal oxide or metal hydroxides hybrid reaction 40～50h in water, and after-filtration hybrid reaction system, leach thing through washing, after the drying treatment, with the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, refilter the hybrid reaction system, leach thing with water and small molecular alcohol washing, will leach the thing drying treatment at last, make target product.
5. the preparation method of nitrogenous aryl hypophosphorous acid metal salt as claimed in claim 3 is characterized in that, this method is specially:
Under the nitrogen protection condition, with carboxyethyl phenyl phosphinic acid and the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, in the hybrid reaction system, add entry and alkali again, to hybrid reaction system change clarification, add soluble metallic salt again, react 2～3h down in 90～95 ℃ temperature condition, its after-filtration hybrid reaction system, leach thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product;
Or, the hybrid reaction in water with carboxyethyl phenyl phosphinic acid and alkali, to hybrid reaction system change clarification, add soluble metallic salt, react 2～3h down in 90～95 ℃ temperature condition, and after-filtration hybrid reaction system, leach thing after washing, drying treatment, with the compound with active amine under 135～160 ℃ temperature condition in organic solvent back flow reaction 4～6h, slough water generation reaction, refilter the hybrid reaction system, leach thing with water and small molecular alcohol washing, to leach the thing drying treatment at last, make target product.
6. as the preparation method of each described nitrogenous aryl hypophosphorous acid metal salt in the claim 3～5, it is characterized in that described compound with active amine is RNH
2And H
2NRNH
2In at least a, wherein, R is aryl or the straight or branched alkyl that contains 0～6 C atom.
7. as the preparation method of each described nitrogenous aryl hypophosphorous acid metal salt in the claim 3～5, it is characterized in that described organic solvent is high boiling point solvent oil, dimethylbenzene or dichlorobenzene.
8. as the preparation method of claim 3 or 4 described nitrogenous aryl hypophosphorous acid metal salts, it is characterized in that, described metal oxide is magnesium oxide, calcium oxide, aluminum oxide or zinc oxide, and described oxyhydroxide is magnesium hydroxide, calcium hydroxide, aluminium hydroxide or zinc hydroxide.
9. as the preparation method of claim 3 or 5 described nitrogenous aryl hypophosphorous acid metal salts, it is characterized in that described alkali is sodium hydroxide or potassium hydroxide.
10. as the preparation method of each described nitrogenous aryl hypophosphorous acid metal salt in the claim 4～5, it is characterized in that described small molecular alcohol is methyl alcohol or ethanol.
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| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
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| CN102225999A (en) * | 2011-04-20 | 2011-10-26 | 苏州科技学院 | Nitrogen-containing organic metal phosphinate and preparation method thereof |
| CN107383098A (en) * | 2017-07-12 | 2017-11-24 | 安徽理工大学 | A kind of expandable flame retardant carbon forming agent of nickeliferous synergistic element and preparation method thereof |
| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
| CN114805936A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Flame retardant suitable for ABS resin, preparation method thereof and flame-retardant ABS resin |
| TWI842218B (en) * | 2021-12-17 | 2024-05-11 | 南韓商Ｌｇ化學股份有限公司 | Phosphrous monomoer or oligomer, polyester resin composition and thermoplastic resin composition comprising the same |
| CN115895187A (en) * | 2022-10-19 | 2023-04-04 | 西北师范大学 | Preparation method of flame-retardant epoxy resin material with enhanced mechanical property |
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