JP2007238532A - Fat-soluble metal phosphate and flame retardant or metal extracting agent comprising the same as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phosphorus-based compound useful as a flame retardant or a metal extracting agent. <P>SOLUTION: The fat-soluble organic phosphorus-containing acid salt is prepared by ion exchange of at least one kind of organic phosphorus-containing acids selected from a polyvalent organic phosphoric ester, a polyvalent organic phosphonic acid or a salt thereof with a cationic amphiphilic substance. The fat-soluble organic phosphorus-containing acid salt having a metal ion bonded to a part of the phosphoric ester residue or a part of the phosphonic acid residue is used. The organic phosphoric ester preferably has a plurality of phosphoric ester residues, among them, phytic acid is preferable. The organic phosphonic acid has a plurality of phosphonic acid residues, e.g. nitrilotris(methylenephosphonic acid) or 1-hydroxyethane-1,1-diphosphonic acid is preferable. The cationic amphiphilic substance is preferably a dicationic type having two ammonium groups in the hydrophilic moiety and a long-chain alkyl group or a phenyl-substituted alkyl group in the hydrophobic moiety thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a flame retardant applied to a polymer material product such as a fiber, film, wallpaper, conductor coating material, or a rare earth element, a transition metal element, or an alkaline earth metal element in the chemical industry or the textile industry The present invention relates to a fat-soluble metal phosphate that is useful as an active ingredient of a useful metal extractant that becomes a polyvalent cation in an aqueous solution such as is there.

  Conventionally, flammable polymer materials have been widely used for consumer products such as textiles, packaging films, wallpaper, and wire covering materials, and industrial materials, and it is necessary to make them flame-retardant for safety reasons. A flame retardant is used as an additive. Some flame retardants for polymer materials are chlorinated and brominated. However, there are problems such as the generation of harmful dioxins during combustion and incineration of materials, making them phosphorous flame retardants. Many agents are used.

However, since the phosphorus-based flame retardant is generally volatile, there is a problem of contamination by the volatilized flame retardant, and there is a concern about the generation of toxic phosphine (PH ₃ ) during combustion.
As phosphorus flame retardants, phosphoric acid triesters are well known, but phosphoric acid monoesters, phosphoric acid diesters, and phosphonic acid esters are hardly known.
As a flame retardant containing phytic acid, a simple mixture of phytic acid and guanidinium or a water-soluble amino acid is known (see Patent Document 1). Mixing use is not suitable for hydrophobic substances that occupy a large amount, and they have to be used as a dry film by surface coating.

  On the other hand, phosphorus-based metal scavengers such as phosphoric acid, phosphonic acid and phosphinic acid are well known as metal scavengers. For example, liquid-liquid extraction of rare earth elements using phosphoric acid esters and phosphonic acid esters (Non-patent document 1) or liquid-liquid extraction with phosphinic acid (non-patent document 2), etc., but these phosphorus-based metal extractants have a simple non-cyclic structure. There is a disadvantage that the selectivity to is low.

Moreover, although the metal scavenger having a cyclic skeleton can generally be expected to have high metal selectivity, the synthesis of the skeleton requires a time-consuming method of highly diluted, and the synthesis yield is low. There is a problem.
For these reasons, there is a demand for a metal scavenger / extractant that has a macrocyclic skeleton and can be easily manufactured at low cost.
JP 2002-201475 A T. Sato, “Liquid-liquid extraction of rare-earth elements from aqueousacid solutions by acid organophosphorus compounds,” Hydrometallurgy, 22, 121-140 (1989) S. Nishihama, N, Sakaguchi, T. Hirai, I. Komasawa, “Extraction and separation of rare earth metals using microcapsules containingbis (2-ethylhexyl) phosphinic acid,”, Hydrometallurgy, 64, 35-42 (2002)

  Under such circumstances, the object of the present invention is to provide a flame retardant that is excellent in flame retardancy, hardly volatilizes, and can be mixed and used in a hydrophobic polymer material, or a metal collector having high metal selectivity. It is to provide a phosphorus compound useful as an agent / extractant.

  In order to develop a phosphorus compound having the above-mentioned preferable characteristics, the present inventors have previously made phosphoric acid monoesters having a dissociating group, phosphoric acid diesters, or metal salts thereof generally less volatile, Alternatively, paying attention to being non-volatile, on the other hand, since these are hydrophilic, since many of the polymer materials are hydrophobic, the polymers lack compatibility with such polymer materials. As a result of various researches while paying attention to the problem that it is difficult to use mixed materials, it is possible to form a salt between a specific organic phosphorus-containing acid having a dissociating group and a cationic amphiphile. By adding fat solubility to the salt of the product, the compatibility of the hydrophobic polymer, and hence the problem of miscibility, can be solved, and at the same time the volatility problem, which is a drawback of general phosphorus flame retardants, can be solved. Found that No. 2005-255201).

As a result of further diligent study on the fat-soluble organic phosphorus-containing organic acid prepared by ion exchange between the specific organic phosphorus-containing acid and the cationic amphiphile, the present inventors have found that the organic phosphorus Use of acids having multiple phosphate ester residues or multiple phosphonic acid residues as the contained acids, and using a part of which has a metal ion ionically bonded, can further enhance the effect as a flame retardant. It was found that it can be improved.
In addition, when the cationic amphiphile used here is a dicationic type, and a cationic group such as two quaternary ammonium groups contained in the molecule is linked by a chain structure. In the obtained fat-soluble metal phosphate, a pseudo macrocyclic skeleton is formed, and the inner hole of the macrocyclic skeleton is effective as a site for collecting metal. It has been found that those containing an alkali metal among acid salts can be used as a scavenger for useful metal ions such as rare earth elements because the alkali metal can be exchanged with a polyvalent metal cation. .

The present invention has been completed based on these findings, and is as follows.
(1) Prepared by ion exchange between at least one organic phosphorus-containing acid selected from polyvalent organic phosphates, polyvalent organic phosphonic acids, or salts thereof with a cationic amphiphile A fat-soluble organic phosphorus-containing acid salt, wherein a metal ion is bonded to a part of a phosphate ester residue or a phosphonic acid residue.
(2) The fat-soluble organic phosphorus-containing acid salt according to (1), wherein the polyvalent organic phosphate is phytic acid.
(3) The polyvalent organic phosphonic acid is nitrilotris (methylenephosphonic acid), ethylenediamine-N, N, N ′, N′-tetrakis (methylenephosphonic acid), N- (2-hydroxyethyl) iminobis (methylphosphonic acid) ), [(Hydroxymethyl-phosphonomethyl-amino) -methyl] -phosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, the fat-soluble organic phosphorus-containing acid salt of (1) above.
(4) The above cationic amphiphile having a positive charge in the hydrophilic part and a long-chain aliphatic group or a phenylalkyl group in the hydrophobic part, respectively (1) to (3) Any fat-soluble organic phosphorus-containing acid salt.
(5) The fat-soluble organic phosphorus-containing acid salt according to any one of (1) to (3), wherein the cationic amphiphile is a dicationic type having two cationic groups in the hydrophilic part.
(6) The lipophilicity according to (5) above, wherein the cationic amphiphile has two ammonium groups in the hydrophilic part and a long-chain alkyl group or a phenylalkyl group in the hydrophobic part. Organic phosphorus-containing acid salt.
(7) In the dicationic amphiphile, the chain structure connecting two cationic groups is a hydrocarbon chain having a methylene chain or a phenylene chain or a hydrocarbon chain containing an ether bond (5) A fat-soluble organic phosphorus-containing acid salt.
(8) A metal salt aqueous solution is used for an alkali metal salt aqueous solution of at least one organic phosphorus-containing acid selected from polyvalent organic phosphates, polyvalent organic phosphonic acids, or salts thereof. A solution in which a cationic amphiphile is dispersed is injected, and the alkali metal cation of the organic phosphorus-containing acid is exchanged with a cation of the amphiphile and a metal cation in the metal aqueous solution, and is insoluble in water. The method for producing a fat-soluble organic phosphorus-containing acid salt according to any one of claims 1 to 7, which is recovered as a metal phosphate or a metal phosphonate.
(9) A flame retardant comprising the fat-soluble organic phosphorus-containing acid salt according to any one of (1) to (7) as an active ingredient (10) At least a part of the phosphate ester residue or the phosphonic acid residue The metal extractant which uses the fat-soluble organic phosphorus containing acid salt in any one of said (1) thru | or (7) whose metal ion couple | bonded with is an alkali metal salt as an active ingredient.
(11) The metal extractant according to the above (10), which targets a useful polyvalent metal cation.

Since the fat-soluble organic phosphorus-containing acid salt of the present invention does not contain chlorine or halogen, no toxic gas such as dioxins is generated during combustion. Moreover, since it is a salt, it is not volatile and there is no problem of environmental pollution. Furthermore, since the pyrolyzate is a phosphorus oxide and a metal oxide, the production of phosphine is also suppressed. High solubility in general-purpose organic solvents, excellent compatibility with hydrophobic polymers, and low melting point makes it easy to knead with thermoplastic polymers. It is suitable for use as a flame retardant.
Among the fat-soluble organic phosphorus-containing acid salts of the present invention, a salt containing a monovalent metal such as an alkali metal as a metal is suitable as an extractant for useful metal ions. What it has is suitable as a metal extractant excellent in selective extraction between metal elements.

  The fat-soluble organic phosphorus-containing acid salt of the present invention is cationic with at least one organic phosphorus-containing acid selected from polyvalent organic phosphates, polyvalent organic phosphonic acids, or salts thereof. A fat-soluble organic phosphorus-containing acid salt prepared by ion exchange with an amphiphile, in which metal ions are bonded to part of the phosphate ester residue or part of the phosphonic acid residue. However, these fat-soluble organic phosphorus-containing acid salts are obtained by dispersing a cationic amphiphile in an aqueous metal salt solution in an aqueous solution of an alkali metal salt of a polyvalent phosphate or polyvalent phosphonic acid. The solution is injected, and the alkali metal cation of the alkali metal phosphate or alkali metal phosphonate is ion-exchanged with the cation of the amphiphile, and the alkali metal phosphate or phosphoric acid Some of the alkali metal salt can be prepared by the alkali metal remains or allowed to remain in the salt, or metal ions and the ion exchange in an aqueous metal salt solution.

  The polyvalent organic phosphate ester in the present invention has a plurality of phosphate ester residues, and the phosphate ester component has a phosphate monoester or phosphate diester structure and has a phosphorus content. In many cases, it is desirable to have a plurality of phosphate ester structures in the molecule, and these ester structures usually have an alkoxy group or an aryloxy group moiety, and this alkoxy group can be either primary, secondary or tertiary. Good.

Particularly preferred as such a phosphate ester is natural phytic acid represented by the following chemical formula.

  Further, the phosphonic acid having a plurality of phosphone residues in the present invention has two or more phosphonic acid residues in the molecule, for example, an organic group directly linked to phosphorus has a tertiary amine structure, In addition to these, those having a hydroxyl group or a carboxyl group, and those having a hydroxyl group, and the like can be mentioned. Specific examples thereof include nitrilotris (methylenephosphonic acid), ethylenediamine-N, N, N ′, N'-tetrakis (methylenephosphonic acid), N- (2-hydroxyethyl) iminobis (methylphosphonic acid), [(hydroxymethyl-phosphonomethyl-amino) -methyl] -phosphonic acid, 1-hydroxyethane-1,1-diphosphone Acid, N, N-bis (phosphonomethyl) glycine and the like are easily available and preferable.

These specific compounds are represented by chemical formulas in order as follows, but they are advantageous in that they have a high phosphorus content and are therefore excellent in flame retardancy.

  Any of the above-mentioned phosphate ester salts and phosphonates may be used as long as they are water-soluble. Usually, metal salts, particularly alkali metal salts such as sodium and potassium are preferable. In addition, ammonium, tetramethylammonium, and the like. Lower alkyl ammonium salts such as salts can also be used.

The cationic amphiphile of the present invention preferably has a positive charge in the hydrophilic portion, and the positive charge includes an ammonium, sulfonium, phosphonium structure, preferably an ammonium structure such as primary or secondary. Further, those having a tertiary or quaternary ammonium structure, particularly those having a quaternary ammonium structure are desirable, and those having a tetraalkylammonium structure are particularly preferred because they are easily available.
Furthermore, the cationic amphiphile in the present invention is not limited to a monocation type, and a dication type may be used, but the same hydrophilic substances are used for the hydrophilic portion.

As the cationic amphiphile, those having at least one long-chain aliphatic group per cation in the lipophilic part of both the monocation type and the dication type are used.
Furthermore, the lipophilic part of the cationic amphiphile of the present invention has one or two long-chain alkyl groups or long-chain alkenyl groups in the molecule, and has a micelle or bilayer-like association structure in water. It is desirable to form.

The long chain aliphatic group in the monocation type amphiphile is preferably one having a carbon chain length of usually 4 to 24, preferably 8 to 18, such as a long chain alkyl group, for example, An octadecyl, tetradecyl, hexadecyl group or the like, or a long-chain alkenyl group such as an oleyl or linoleoyl group is desirable.
The long chain aliphatic group in the dicationic amphiphile may be shorter than that in the monocation type, and the carbon chain length is 4 to 24, preferably 6 to 18.

  In addition, the cationic amphiphile of the present invention uses, for its lipophilic part, a phenylalkyl group such as benzyl group, phenylethyl group, 4-phenylbutyl group, for example, instead of the long-chain aliphatic group. You can also.

  Furthermore, as a dicationic amphiphilic substance in the present invention, when a cation moiety such as two quaternary ammonium groups is connected in a chain structure, a polyvalent phosphate ester or a polyvalent phosphonic acid is used. When associated with an ion pair bond, a pseudo macrocyclic skeleton is formed, and the inner pores of the macrocyclic skeleton serve as sites for capturing metal ions. Depending on the degree of ease of incorporation into the inner pores, there is a difference in the ability to collect metal ions. Therefore, selective collection compared to simple phosphate ester or phosphonic acid adsorption, that is, specific metal ions Can be extracted.

As the chain structure, those composed of a hydrocarbon chain having a methylene chain or a phenylene chain and those composed of a hydrocarbon chain containing an ether bond such as an ethylene glycol chain or a propylene glycol chain are used.
In the present invention, when used as a metal extractant, it is preferable to use a hydrocarbon comprising an ether bond having a coordination ability to metal ions. In that case, the ether bond and its structure are important for the selectivity of the metal, and are appropriately selected so as to match the ion radius of the metal ion to be collected.

Specific compounds of these cationic amphiphiles are shown in order by chemical formulas as follows.
In the formula, R represents an alkyl group having 4 to 20 carbon atoms or a phenylalkyl group, and X represents any of Cl, Br, I, CH ₃ SO ₃ , and CH ₃ C ₆ H ₄ SO _3. .

  The dispersion of the cationic amphiphile can be prepared by simply mixing with water and stirring, or by mixing with water and then heating or ultrasonic irradiation.

The fat-soluble metal phosphate of the present invention is prepared by mixing its constituent components in water at a stoichiometric ratio as follows.
(1) General formula P ^{- ·} M ^{+ ·} A ⁺ lipid soluble phosphate alkali metal alkali metal salts of preparing phosphoric acid ester salts represented _{^{(P - · M + 2,}} P - phosphate ester moiety, M ⁺ is an aqueous solution of respectively the metal cation), mono-cationic amphiphile ^{(a + · X -.,} a + mono cationic amphiphile, X ^- is amphiphiles When an aqueous dispersion of each of the onion is shown), an ion pair exchange between the phosphate metal salt and the amphiphile occurs, and the phosphate organic salt (P ⁻ ·· M ⁺ · A ⁺ ) precipitates as a precipitate, and the inorganic salt (M ⁺ .X ⁻ ) remains dissolved in water.
(2) In formula _{^{P - · M ++ (0.5)}} · A +) divalent metal alkali metal salts of preparing phosphoric acid ester salts such as alkaline earth lipophilic phosphate represented (P ^{- -} · M ⁺ _2, P ^- phosphate moiety is, M ⁺ denotes a metal cation) and divalent metal salt _{^{(M ++ · Y -. 2}} ) aqueous solution and, monocationic amphiphiles ^{(a +} X ⁻ and A ⁺ are monocationic amphiphiles, and X ⁻ is an onion of the amphiphile, respectively. When the aqueous dispersion is mixed, the phosphate metal salt and the amphiphile are mixed with each other. The ion pair exchange occurs between the phosphoric acid ester and the organic salt of the phosphate ester (P ⁻⁻ · M ⁺⁺ _(0.5) · A ⁺ ) precipitates as an inorganic salt (M ⁺ · X ⁻ and M ⁺ · Y ⁻ ) remains dissolved in water.
(3) General formula P ^- · M ⁺ · ^A ₊₊ Preparation phosphoric acid ester of an alkali metal salt of a lipophilic phosphate represented by _(0.5) an alkali metal salt _{^{(P - · M + 2,}} P ^- the phosphate moiety, M ⁺ is an aqueous solution of respectively the metal cation), dicationic amphiphiles _{^{(a ++ · X -. 2}} , a ++ is dications type amphiphile, X ^- parents When the aqueous dispersion of the amphiphile is mixed, an ion pair exchange between the phosphate metal salt and the amphiphile occurs, and the phosphate organic salt (P ^{−− _{· M + · a ++ (0.5}} )) was deposited as a precipitate, inorganic salts (M ⁺ · X ^-) is remain dissolved in water.
(4) General formula _{^{P - · M ++ (0.5)}} · alkali metal salts of preparing phosphate esters of the _{A ++} lipophilic alkaline earth such as divalent metal salts of phosphates represented by _{(0.5) ^{(P - · M + 2,}} P - denotes each phosphate moiety, M ⁺ is a metal cation.), and divalent metal salt (M ⁺⁺ · Y ^- ₂₎ and an aqueous solution of dicationic amphiphilic substance _{^{(a ++ · X - 2,}} a ++ is dications type amphiphile, X ^-. is shown respectively pairs onion amphiphile) when mixing the aqueous dispersion of a phosphoric acid ester metal salt An ion pair exchange with the amphiphile occurs, and the organic salt of phosphate ester (P ^-- M ⁺⁺ _(0.5) -A ⁺⁺ _(0.5) ) is precipitated as an inorganic salt. (M ⁺ · X ^- and ^M + · Y ^-) remains in the water as.
(5) Preparation of a fat-soluble metal phosphate containing a trivalent metal or a tetravalent metal Similar to the above (2) or (4), the amphiphilic compound per phosphate of the phosphate ester The mixing is performed at a ratio of one cation, and trivalent or tetravalent metal ions are mixed at a ratio of 1/3 or 1/4 per phosphoric acid of the phosphate ester.
(6) Preparation of fat-soluble metal phosphonate The ratio of the cation of the amphiphile to one phosphonic acid of the polyvalent phosphonic acid, and the divalent, trivalent and tetravalent metal ions are one phosphonic acid. By mixing at a ratio of 1/2, 1/3, and 1/4, it is possible to carry out by essentially the same procedure as the preparation of the fat-soluble metal phosphate.

  As the metal element of the polyvalent metal in the above (5) and (6), an alkaline earth metal such as magnesium or calcium, a metal element such as aluminum, zinc, copper, nickel, iron, manganese, cobalt, or chromium, or a rare earth element is used. be able to. For use as a flame retardant, magnesium, calcium, aluminum and the like are particularly preferable. Further, chloride ions, bromide ions, acetate ions, sulfate ions, nitrate ions, perchlorate ions, phosphate ions, carbonate ions and the like are used as anion components of metal salts.

  In the above (1) to (6), the precipitated phosphate ester salt is separated and recovered from the aqueous phase by filtration, centrifugation, or solvent extraction. When the phosphate metal salt and the cationic amphiphile are mixed stoichiometrically, the resulting precipitate has a nearly stoichiometric composition. If necessary, the fat-soluble phosphate ester can be purified by a reprecipitation method or a recrystallization method. Purification by the reprecipitation method is performed by injecting a fat-soluble phosphate dissolved in a good solvent such as chloroform into a poor solvent such as ethyl acetate or ethanol, and collecting the precipitate by filtration or the like. Purification by recrystallization can be performed with 1,2-dichloroethane, ethyl acetate, toluene or the like.

  The fat-soluble organic phosphorus-containing acid salt in the present invention can be uniformly mixed by kneading with a powder of a thermoplastic hydrophobic polymer such as polyester, polyamide, polyolefin, etc., and suppressing ignition of those polymer materials, Or it can utilize as a flame retardant which shows the self-extinguishing property after ignition.

Moreover, among the fat-soluble organic phosphorus-containing acid salts of the present invention, a salt containing a monovalent metal such as an alkali metal as a metal can be used as an extractant for useful metal ions. That is, among the fat-soluble organic phosphorus-containing acid salts of the present invention, a salt containing a monovalent metal such as an alkali metal as a metal, hydrocarbons such as toluene, xylene, hexane, kerosene, chloroform, dichloromethane, dichloroethane, etc. When dissolved in a halogenated hydrocarbon and the solution is brought into contact with an aqueous solution containing a useful metal salt, the polyvalent metal ion contained in the aqueous solution is contained in the fat-soluble organic phosphorus-containing acid salt of the present invention. A useful polyvalent metal ion is ion-exchanged with a valent metal, taken into the fat-soluble organic phosphorus-containing acid of the present invention, and extracted from the aqueous phase to the organic phase.
Furthermore, as a dicationic amphiphile, when a cation part such as two quaternary ammonium groups is connected in a chain structure, a pseudo macrocyclic skeleton is formed, and metal ions are selectively selected. Collection and extraction are possible.

Next, the best mode for carrying out the present invention will be described in more detail by way of examples, but the present invention is not limited to these.
In addition, the unit L in an Example means a liter.

Using a probe-type ultrasonic device, 4.6 g (6 mmol) of a dicationic amphiphilic substance represented by the above (Chemical Formula 10) (wherein R = C ₁₈ H ₃₇ , X = Br) was heated at 50 ° C. Dispersed in 1 L. Further, 1.85 g (2 mmol) of phytic acid dodeca sodium salt was dissolved in 1 L of warm water at 50 ° C. When an amphiphilic substance dispersion is dropped into an aqueous solution of dodeca sodium phytate over about 5 minutes while stirring vigorously, ion exchange occurs between the amphiphile and phytate, and it is not soluble in water. The phytate formed as a large amount of white precipitate. After cooling, the precipitate was collected by filtration (yield 4.82 g). The resulting precipitate was recrystallized from ethyl acetate and purified.
The analysis results for the purified product obtained are shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.24-1.31 (60H, m, CH ₂ ), 1.73 (4H, bs, CH ₂ ), 3.28 (12H, s, NCH ₃ ), 3.53 (4H, m, NCH ₂ ), 5.4 (4H, s, ArCH ₂ ), 7.62-7.63 (2H, m, ArH), 7.89-7.91 (2H, m, ArH)
Differential scanning thermal analysis: heating rate 5 ° C / min, endotherm 29.9mJ / mg (peak 21.8 ° C).
For reference, the analysis results of the dicationic amphiphile represented by the above (Chemical Formula 10) (wherein R = C ₁₈ H ₃₇ , X = Br) as the raw material are shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.23-1.35 (60H, m, CH ₂ ), 1.71-1.74 (4H, m, CH ₂ ), 3.26 (12H, s , NCH ₃ ), 3.71-3.76 (4H, s, NCH ₂ ), 5.52 (4H, s, ArCH ₂ ), 7.66-7.68 (2H, m, ArH), 8.03-8.05 (2H, m, ArH)
Differential scanning thermal analysis: heating rate 5 ° C / min, endotherm 51.5mJ / mg (peaks 29.5 ° C, 41.0 ° C, 43.2 ° C).

From the above analysis results, in the fat-soluble salt obtained as a result of Example 1, the NMR absorption peak derived from the dicationic amphiphile appears at a position different from the absorption peak of the raw amphiphile, In addition, since the absorption peak of the raw material amphiphile disappears completely, the formation of a stoichiometric ion pair of the amphiphile and phytic acid can be confirmed.
In addition, among the absorption peaks of the amphiphile, the chemical shifts of absorption peaks derived from methylene, methyl groups, and aromatic ring protons adjacent to the ammonium group are particularly large, and the peaks are broadened. This means that the operation of this embodiment does not simply mean mixing of raw materials but supports ion pair exchange. Changes in the chemical shift of the absorption peak derived from the methylene adjacent to the ammonium group and the aromatic ring proton and the extent of the broadening of the peak depend on the type of metal contained in the fat-soluble salt (sodium (this Example 1), calcium ( (See Example 2 below), barium (see Example 3 below), europium (see Example 4 below)). This indicates that the metal contained in the fat-soluble salt is incorporated in the vicinity of the ion pair between the fat-soluble salt ammonium and the phytic acid phosphoric acid, and the outer surface is covered with a hydrophobic functional group such as an alkyl group. This indicates that it exists in the interior, which is the reason for the good solubility of the fat-soluble salt in hydrophobic solvents and hydrophobic polymers.
Furthermore, in the thermal analysis of the fat-soluble salt, an endothermic peak appears at a temperature different from the peak of the raw material amphiphile, indicating that the operation of this example is not simply mixing of raw materials.

In the same manner as in Example 1, 4.62 g (6 mmol) of the amphiphilic substance was dispersed in 1 L of warm water at 50 ° C. containing 1.06 g (6 mmol) of calcium acetate monohydrate. This was added dropwise to an aqueous solution of dodecasodium phytate in the same procedure as in Example 1 to obtain a white precipitate, which was recrystallized with a mixture of dichloroethane and ethyl acetate (50:50) (yield 5.11 g).
The analysis results for the purified product obtained are shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.26-1.39 (60H, m, CH ₂ ), 1.73-1.88 (4H, bs, CH ₂ ), 3.26 (12H, bs , NCH ₃ ), 3.3-3.6 (4H, b, NCH ₂ ), 5.12-5.54 (4H, s, ArCH ₂ ), 7.52-7.66 (2H, b, ArH), 7.74-7.96 (2H, b, ArH)
Differential scanning thermal analysis: heating rate 5 ° C / min, endothermic amount 6.26mJ / mg (peak 29.2 ° C, 39.8 ° C).

In the same manner as in Example 1, 4.62 g (6 mmol) of the amphiphilic substance was dispersed in 1 L of warm water containing 1.53 g (6 mmol) of barium acetate. This was added dropwise to an aqueous solution of dodecasodium phytate in the same procedure as in Example 1 to obtain a white precipitate, which was recrystallized from ethyl acetate (yield 3.81 g).
The analysis results for the purified product obtained are shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.12-1.31 (60H, m, CH ₂ ), 1.71-1.73 (4H, b, CH ₂ ), 3.26 (12H, bs , NCH ₃ ), 4.18-4.2 (4H, b, NCH ₂ ), 5.02-5.32 (4H, bs, ArCH ₂ ), 7.5-7.6 (2H, b, ArH), 7.67-7.79 (2H, b, ArH)
Differential scanning thermal analysis: heating rate 5 ° C / min, endotherm 7.15mJ / mg (peak 13.8 ° C).

In the same manner as in Example 1, 4.62 g (6 mmol) of the amphiphile was dispersed in 1 L of warm water at 50 ° C. containing 4.46 g (4 mmol) of europium nitrate hexahydrate. This was added dropwise to the aqueous phytate dodecasodium salt solution in the same procedure as in Example 1 to obtain a white precipitate (yield 6.42 g).
The analysis results for the purified product obtained are shown below.
¹ H-NMR (TMS): 0.94 (6H, b, CH ₃ ), 1.1-2.0 (64H, b, CH ₂ ), 2.5-3.8 (16H, b, NCH ₃ , NCH ₂ ), 4.7-5.5 (4H , b, ArCH ₂ ), 7.5-8.1 (4H, b, ArH)

Using a probe-type ultrasonic device, 8.49 g (9 mmol) of the dicationic amphiphile represented by the above (Chemical Formula 8) (wherein R = C ₁₈ H ₃₇ , X = Br) is heated at 50 ° C. Dissolved in 1.5 L. Moreover, 2.77 g (3 mmol) of phytic acid dodeca sodium salt was dissolved in 1.5 L of warm water at 50 ° C. When an amphiphilic substance dispersion is dropped into an aqueous solution of dodeca sodium phytate over about 5 minutes while stirring vigorously, ion exchange occurs between the amphiphile and phytate, and it is not soluble in water. The phytate formed as a large amount of white precipitate. After cooling, the precipitate was extracted with chloroform, and the fat-soluble phosphate was recovered by evaporating and removing the solvent from the extract.
The analysis result of the obtained fat-soluble phosphate is shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.23-1.32 (60H, m, CH ₂ ), 1.64-1.72 (4H, m, NCCH ₂ CO), 2.01-2.05 ( 4H, m, NCCH ₂ ), 3.31-3.35 (4H, m, NCH ₂ ), 3.4 (12H, s, NCH ₃ ), 3.6-3.62 (8H, m, OCH ₂ ), 3.67-3.69 (4H, m, OCH ₂ ), 3.74-3.78 (4H, m, NCH ₂ )
For reference, the analysis results of the dicationic amphiphile represented by the above (Chemical Formula 8) (wherein R = C ₁₈ H ₃₇ , X = Br) as the raw material are shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.23-1.34 (60H, m, CH ₂ ), 1.71-1.75 (4H, m, NCCH ₂ CO), 2.09-2.12 ( 4H, m, NCCH ₂ ), 3.41 (12H, s, NCH ₃ ), 3.46-3.49 (4H, m, NCH ₂ ), 3.63-3.68 (12H, m, OCH ₂ ), 3.82-3.86 (4H, m, NCH ₂ )
Differential scanning calorimetry: heating rate 5 ° C / min, endotherm 56.1mJ / mg (peaks 50.2 ° C, 52.4 ° C).

In the same manner as in Example 5, 8.49 g (9 mmol) of the dicationic amphiphile was dispersed in 1.5 L of warm water at 50 ° C. containing 1.59 g (9 mmol) of calcium acetate monohydrate. This was added dropwise to an aqueous solution of dodeca sodium phytate in the same procedure as in Example 5 to obtain a white precipitate. After cooling, the precipitate was extracted with chloroform, and the fat-soluble phosphate was recovered by evaporating and removing the solvent from the extract.
The analysis result about the obtained fat-soluble phosphate is shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.23-1.32 (60H, m, CH ₂ ), 1.64-1.76 (4H, b, NCCH ₂ CO), 1.97-2.11 ( 4H, b, NCCH ₂ ), 3.38 (4H, b, NCH ₂ ), 3.42 (12H, b, NCH ₃ ), 3.57-3.65 (8H, b, OCH ₂ ), 3.64-3.69 (4H, b, OCH ₂ ) 3.75-3.82 (4H, b, NCH ₂ )
Differential scanning calorimetry: Temperature increase rate 5 ° C / min, endotherm 28.8mJ / mg (peak 32.0 ° C)

In the same manner as in Example 5, 8.49 g (9 mmol) of the dicationic amphiphile was dispersed in 1.5 L of warm water at 50 ° C. containing 2.30 g (9 mmol) of barium acetate. This was added dropwise to an aqueous solution of dodeca sodium phytate in the same procedure as in Example 5 to obtain a white precipitate. After cooling, the precipitate was extracted with chloroform, and the fat-soluble phosphate was recovered by evaporating and removing the solvent from the extract.
The analysis result about the obtained fat-soluble phosphate is shown below.
¹ H-NMR (CDCl ₃ , TMS): 0.88 (6H, t, CH ₃ ), 1.23-1.33 (60H, m, CH ₂ ), 1.64-1.73 (4H, m, NCCH ₂ CO), 2.01-2.08 ( 4H, m, NCCH ₂ ), 3.36-3.38 (4H, m, NCH ₂ ), 3.42 (12H, s, NCH ₃ ), 3.62 (8H, s, OCH ₂ ), 3.67 (4H, t, OCH ₂ ), 3.75-3.78 (4H, m, NCH ₂ )
Differential scanning calorimetry: Temperature increase rate 5 ° C / min, endotherm 27.5mJ / mg (peak 32.9 ° C)

  Using a probe-type ultrasonic device, 16.70 g (48 mmol) of octadecyltrimethylammonium chloride was dispersed in 200 ml of warm water at 50 ° C. containing 4.23 g (24 mmol) of calcium acetate monohydrate. 7.38 g (8 mmol) of phytic acid dodeca sodium salt was dissolved in hot water at 50 ° C. Both solutions were poured into 350 ml of 50 ° C. warm water with stirring over about 5 minutes. The mixed solution was further processed with an ultrasonic device for about 5 minutes. After cooling, the fat-soluble salt was recovered by suction filtration (yield 21.14 g).

Ethylenediamine-N, N, N ′, N′-tetrakis (methylenephosphonic acid) (5.00 g, 10 mmol) was neutralized with an aqueous sodium hydroxide solution equivalent to 80 mmol to obtain an octasodium salt. 9.15 g (20 mmol) of a dicationic amphiphile represented by the above (Chemical Formula 7) (wherein R═CH ₂ Ph, X═Cl) is an aqueous solution of 3.52 g (20 mmol) of calcium acetate monohydrate. This solution was dropped into an aqueous solution of ethylenediamine-N, N, N ′, N′-tetrakis (methylenephosphonic acid) to precipitate a fat-soluble salt (yield 10.10 g).

  In the same manner as in Example 2, a fat-soluble salt obtained from 15.83 g (60 mmol) of dodecyltrimethylammonium chloride, 5.29 g (30 mmol) of calcium acetate monohydrate, and 9.23 g (10 mmol) of phytic acid dodecasodium salt Finely powdered, the fat-soluble salt fine powder and the ethylene-vinyl acetate copolymer (vinyl acetate 25 mol%) powder are homogeneously mixed in a proportion of 15% by weight of the fat-soluble salt and 85% by weight of the copolymer. Mixed. The mixed powder is heat-molded to obtain a test piece having a width of 6.5 mm, a length of 150 mm, and a thickness of 3 mm. JIS standard (K7201-2 Plastics-Combustion test method using oxygen index-Part 2 Test at room temperature) When the flame retardancy test was performed according to the results, an oxygen index of 22% was obtained. In addition, the oxygen index in the case of no addition was 20%.

As in Example 10, 13.72 g (30 mmol) of a dicationic amphiphile represented by the above (Chemical Formula 7) (wherein R═CH ₂ Ph, X = Br), calcium acetate monohydrate 5. When a fat-soluble salt obtained from 29 g (30 mmol) and 9.23 g (10 mmol) of phytate dodecasodium salt as a flame retardant was added to the sample so as to be 15% by weight, a test was conducted. An index of 24% was obtained.

In the same manner as in Example 5, fat of 14 mg of a dicationic amphiphile represented by the above (Chemical Formula 8) (wherein R = C ₁₈ H ₃₇ , X = Br) and 4.1 mg of phytate dodecasodium salt A soluble salt (stoichiometric ratio 3: 1) was prepared and the precipitate was extracted with 20 ml of chloroform. 10 ml of an aqueous solution containing yttrim nitrate, cerium nitrate and lanthanum nitrate (2 mmol / L each) and a chloroform solution of a fat-soluble salt were vigorously stirred to extract metal ions. As a result of extracting metal ions from a chloroform solution with 1 mol / L hydrochloric acid and evaluating the ion concentration ratio of the aqueous phase by ICP emission spectroscopic analysis, the analytical value of the extracted metal ions was a lanthanum / yttrium molar ratio of 0.11, cerium. / Yttrium molar ratio of 0.38, indicating that there is good metal ion selectivity between rare earth elements.

As in Example 12, fat solubility of 10 mg of the dicationic amphiphile represented by the above (Chemical Formula 7) (wherein R = C ₁₈ H ₃₇ , X = Cl) and 4.1 mg of phytate dodecasodium salt Extraction with a salt (stoichiometric ratio 3: 1) was carried out and evaluated in the same manner as in Example 12. As a result, the lanthanum / yttrium molar ratio was 0.42 and the cerium / yttrium molar ratio was 0.73.

The fat-soluble organic phosphorus-containing acid salt of the present invention is a flame retardant applied to a polymer material product such as a fiber, a film, a wallpaper, a conductor coating material, or a rare earth element in the chemical industry or the textile industry. It is used as an extractant for useful metals that become polyvalent cations in aqueous solutions of transition metal elements, alkaline earth metal elements, and the like.

Claims (11)

  Fat prepared by ion exchange between at least one organic phosphorus-containing acid selected from polyvalent organic phosphates, polyvalent organic phosphonic acids, or salts thereof and a cationic amphiphile A fat-soluble organic phosphorus-containing acid salt, which is a soluble organic phosphorus-containing acid salt, wherein a metal ion is bonded to a part of a phosphate ester residue or a part of a phosphonic acid residue.   The fat-soluble organic phosphorus-containing acid salt according to claim 1, wherein the polyvalent organic phosphate is phytic acid.   The polyvalent organic phosphonic acid is nitrilotris (methylenephosphonic acid), ethylenediamine-N, N, N ′, N′-tetrakis (methylenephosphonic acid), N- (2-hydroxyethyl) iminobis (methylphosphonic acid), The fat-soluble organic phosphorus-containing acid salt according to claim 1, which is [(hydroxymethyl-phosphonomethyl-amino) -methyl] -phosphonic acid or 1-hydroxyethane-1,1-diphosphonic acid.   The fat according to any one of claims 1 to 3, wherein the cationic amphiphile has a positive charge in the hydrophilic part and a long-chain alkyl group or a phenyl-substituted alkyl group in the hydrophobic part. Soluble organic phosphorus-containing acid salt.   The fat-soluble organic phosphorus-containing acid salt according to any one of claims 1 to 3, wherein the cationic amphiphile is a dicationic type having two cationic groups in the hydrophilic part.   6. The fat-soluble organic substance according to claim 5, wherein the cationic amphiphile has two ammonium groups in the hydrophilic part and a long-chain alkyl group or a phenyl-substituted alkyl group in the hydrophobic part. Phosphorus-containing acid salt.   6. The fat according to claim 5, wherein in the dicationic amphiphile, the chain structure connecting two cationic groups is a hydrocarbon chain having a methylene chain or a phenylene chain, or a hydrocarbon chain containing an ether bond. Soluble organic phosphorus-containing acid salt.   In contrast to an alkali metal salt aqueous solution of at least one organic phosphorus-containing acid selected from a polyvalent organic phosphate ester, a polyvalent organic phosphonic acid, or a salt thereof, Injecting a liquid in which an amphiphile is dispersed, replacing the alkali metal cation of the organic phosphorus-containing acid with the cation of the amphiphile and the metal cation in the aqueous metal solution, and insoluble in water It collect | recovers as salt or metal phosphonate, The manufacturing method of the fat-soluble organic phosphorus containing acid salt in any one of Claim 1 thru | or 7 characterized by the above-mentioned.   The flame retardant which uses the fat-soluble organic phosphorus containing acid salt in any one of Claim 1 thru | or 7 as an active ingredient.   The fat-soluble organic phosphorus-containing acid salt according to any one of claims 1 to 7, wherein the metal ion binding to at least a part of the phosphate ester residue or the phosphonic acid residue is an alkali metal salt. Metal extractant. The metal extractant according to claim 8, which is intended for useful polyvalent metal cations.