JPH0794558B2 - Polymetal organophosphinate copolymer containing different metals and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] Polymetal organophosphinates are so-called heat-resistant inorganic polymers having a ring structure in the main chain. The present invention is
The present invention relates to such an inorganic polymer, and more specifically to a polymetal organophosphinate copolymer containing different metals in the same main chain. The inorganic copolymer obtained in the present invention can be used as a heat resistant resin, a thickener, a coating material, and a lubricant. Furthermore, when the copolymer contains a paramagnetic metal in the main chain, the copolymer exhibits the characteristic property of being ferromagnetic or antiferromagnetic, and in view of many recent studies on such magnetism, The copolymer can also be used as a magnetic polymer.

[Conventional technology]

Conventionally, polymetal organophosphinate (Polymetalo
rganophosphinates) are known to have a structure containing only a single metal atom in the main chain (hereinafter referred to as a homopolymer), and synthesis by various methods has been attempted. For example, suspension polymerization (Block, US 3,255,125), bulk polymerization (Block, US 3,245,953), homogeneous solution polymerization (Saraceno, I)
norg.Chem., Vol.3, No.12,1397 (1964) and Dahl, Inor
g. Chem., Vol. 6, No. 8, 1943 (1967)) and the like, various known synthetic methods are known.

In these synthetic methods, a metal-containing compound and an organic phosphorus compound are generally used and combined with the polymerization. Here, as the metal-containing compound, a divalent to tetravalent metal salt or a metal chelate compound is used, and as the organic phosphorus compound, organic phosphinic acid or a salt thereof is used as a monomer. A report has been made. For example, when a dialkylphosphinic acid is used as the organic phosphinic acid, there is a difference in the structure of the polymer due to the steric hindrance of the alkyl group, and the structure is HSp (spiro ring single chain structure), CSp (linear, spiro ring). There is a report that it has either one of (alternate chain structure) (V. Giancott
i, Makromol, Chem. 154, 271 (1972)).

The HSp type structure means that when the organic phosphinate anion is μ and the metal atom is M, The main skeleton of the following structural formula in which is a structural unit (however, the low-molecular organic ligand that is not involved in main chain formation is omitted) On the other hand, the CSp type structure means that The main skeleton of the following structural formula in which is a structural unit (however, the low-molecular organic ligand that is not involved in main chain formation is omitted) Say what has.

Structural analyzes have been attempted on oligomers of polymetal organophosphinates (eg, V. Giancott
i, Die Makromol.Chem.120, P96, (1968) and P.Colamari
o, Inorg.Chem., Vol, 15, No.4, (1976)), and from these analysis results, polymetal organophosphinate is considered to be mainly a linear polymer having a ring structure in the main chain skeleton. ing.

The oligomer formation reaction will be described below by taking a divalent metal hydroxide as an example. The organic phosphinate anion is μ,
When the organic phosphinic acid is μH, the low molecular weight organic ligand is L, the total number of the ligand is k (k is 2 or more), and the metal is M, the formation reaction is generally represented by the following reaction formula M (OH) ₂ kL + μH → Mμ ₂ kL + H ₂ O nMμ ₂ kL → [Mμ ₂ ] _n (k-2) L + 2nL. In the above reaction formula, first, metal bisphosphinate Mμ ₂ which is a constitutional unit of polymetal organophosphinate is produced. It is believed that this precursor desorbs the ligand and polymerizes.

Further, it is considered that there is no significant correlation between the carbon number of the alkyl group of phosphinic acid and the polymerizability. On the other hand, regarding metal compounds, it is known that the polymerization behavior differs depending on the valence of the metal or the number of coordination sites. As one example, the polymerizability under the same conditions is different between zinc salts or cobalt salts and chromium salts in the case of metal salts, and generally low in the case of metal chelate compounds (Dahl, Inorg. Chem. Vol. 6,8, Aug., 1439,19
67) is known.

Further, it is a well-known fact that polymetal organophosphinates have different heat resistance when the chelate central metals forming the main chain are different (Block, Office of Naval Research, Technical Report).
No.58). For example, in a homopolymer having a symmetrical phenyl group, when the central metal is zinc, the decomposition initiation temperature of the former polymer is about 100 ° C higher than that of chromium, and the heat resistance is excellent. . On the other hand, zinc salts such as zinc acetate generally have low polymerizability, and thus it is extremely difficult to obtain a high molecular weight polymer.

[Problems to be solved by the invention]

In order to solve the above-mentioned drawbacks, the present inventors have introduced a different kind of metal into a polymer main chain by copolymerization of at least two kinds of metal compounds having a valence of 2 or more and thermal stability accompanying the introduction. , Further excellent in heat resistance, but as a result of diligent study on increasing the molecular weight of low-polymerizable metal salts that are difficult to be a high molecular weight by itself, by copolymerization with high-polymerizable metal salts, The present invention was completed by succeeding in obtaining the polymetal organophosphinate copolymer.

[Means for solving problems]

Tetrabutyl titanate is used as the metal compound monomer, and both monomers are soluble in a single organic solvent such as benzene, as in the case of using organic phosphinic acid as the organic phosphorus compound monomer, And, except in the special case where the resulting polymetal phosphinate is soluble in the solvent, in general, both monomers and the resulting polymer are often insoluble in a single organic solvent.

In the prior art, in order to dissolve a metal salt such as a metal halide which is a metal-containing compound, or a metal chelate compound, water or an alcohol solvent is used as a solvent, while an organic phosphinate which is an organic phosphorus compound is used. Similarly, an alcoholic solvent was used for the above because of its solubility. However, the produced coordination polymer of metal bisphosphinate, that is, polymetal organophosphinate, is insoluble in water, alcohol or a mixed solvent thereof. Therefore, since the polymetal organophosphinate is precipitated from the solvent when reaching a certain molecular weight, the polymer having a relatively high molecular weight is essentially not obtained by the reaction in such a solvent system. It has drawbacks.

In consideration of this point, two or more kinds of metal compounds used as monomers and an organic phosphinic acid or a salt thereof are dissolved, and at the same time, a polymetal organophosphinate copolymer produced simultaneously is dissolved. This problem has been solved by using an obtained and compatible mixed solvent system.

That is, the present invention provides the following structural formulas (1) and (2) (Here, M ¹ and M ² represent mutually different metal atoms having valences of 2 or more, a and b respectively represent valences of 2 or more of the metal atoms, Y and Y ′ are halogen or an alkyl group, Representing an organic group such as an alkoxy group, Y and Y'may be different or the same, L ¹ and L ² are neutral ligands or anionic ligands, and n and m are 0 or 2 The above numbers are shown, provided that when n is 0, L ¹ does not exist, and when m is 0, L ² does not exist.

Further, R ¹ and R ² are independently selected from an alkyl group having 1 or more carbon atoms, an aryl group, an alkoxy group, and an aryloxy group, and R ¹ and R ² may be the same or different. →
Represents a coordinate bond to M ¹ or M ² . ) A structural unit represented by the formula (1) is contained in the same main chain, the molar ratio of the structural units (1) and (2) is 95: 5 to 5:95, and the molecular weight is 2,000 to 60,000. A metal-containing polymetal organophosphinate copolymer and a method for producing the same.

The different metal compound used for producing the copolymer of the present invention is represented by the following structural formulas (3) and (4).

M ^{1 (a)} X ₂ Y _a-2 (L ¹ ) n (3) M ^{2 (b)} X ₂ ′ Y ′ _b-2 (L ² ) m (4) (where M ¹ and M ² are atoms A and b are two or more mutually different metal atoms, a and b each represent two or more valences of the metal atom, and X, X ', Y and Y'are halogen atoms or alkyl groups, alkoxy groups and the like. Represents an organic group, X, X ', Y
And Y ′ may be different or the same, L ¹ and L ² represent neutral ligands or anionic ligands, and n and m represent 0 or a number of 2 or more. ) Among these metal compounds, the highly polymerizable metal compounds include chromium compounds such as chromium (III) hydroxide, chromium (II) chloride, chromium (III) chloride, and chromium (III) bromide, or triethylaluminum and diethyl. It is preferable to use an organoaluminum compound such as aluminum hydride. On the other hand, examples of the low-polymerizable metal compound include hydroxides such as zinc hydroxide, beryllium hydroxide, and copper (II) hydroxide, beryllium chloride, manganese chloride, Titanium chloride (I
V), ferric chloride, copper (II) bromide, halides such as cobalt chloride, beryllium sulfate, manganese acetate, iron nitrate,
Acid esters such as copper (II) formate, cyanides such as nickel cyanide and zinc cyanide, organometallic compounds such as diethyl zinc, hydrides such as titanium (IV) hydride and zirconium hydride, and tetraethyl titanate A metal alkoxide is illustrated.

In the present invention, as the metal compound monomer, at least one compound is appropriately selected and used from the above-mentioned high-polymerization metal compound and low-polymerization metal compound. Since the heat resistance of the resulting copolymer needs to exceed the heat resistance of the homopolymer, it is particularly preferable to use a zinc compound or a cobalt compound among the low-polymerizable metal compounds.

The metal compound is preferably as pure as possible in consideration of the influence on the polymerization of other metal compounds contained in the metal compound.

In addition, for those having a reactive group that does not participate in the main chain formation such as tetraethyl titanate and titanium tetrachloride, the reactive group is previously substituted with a low molecular weight reaction-inert organic group, or a chelate is attached to this site. Is preferably used after the reaction is inactive. Chelate formation is generally a chelating agent, taking tetraethyl titanate as an example. It is carried out by reacting dichlorobenzene or salicylic acid with tetraethyl titanate in an organic solvent such as benzene under heating and reflux for several hours.

As the organic phosphorus compound, the following structural formula (5) (Here, R ¹ and R ² are independently selected from an alkyl group having 1 or more carbon atoms, an aryl group, an alkoxy group, and an aryloxy group, and R ¹ and R ² may be the same or different. An organic phosphinic acid or an organic phosphinic acid alkali metal salt represented by Z is preferably hydrogen or an alkali metal can be used. As the alkali metal, sodium, potassium or the like can be used.

Examples of the phosphinic acid include phosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, di-n-butylphosphinic acid, di-t-butylphosphinic acid, di-n-propylphosphinic acid, diisopropylphosphinic acid, di-n-pentyl. Symmetrical dialkylphosphinic acids such as phosphinic acid, dineopentylphosphinic acid, diisopentylphosphinic acid, diphenylphosphinic acid, dibenzylphosphinic acid, di-o-methyltolylphosphinic acid, diphenethylphosphinic acid, dibenzhydrylphosphinic acid , Ditritylphosphinic acid, di-2,4-xylylphosphinic acid, di-p-cumenylphosphinic acid, dimethylphosphinic acid, 2-naphthylphosphinic acid, di-1,1 ': 4',
Symmetrical phosphinic acids having aromatic monocyclic or condensed polycyclic hydrocarbon groups such as 4 ″ -terphenylphosphinic acid, asymmetric phosphinic acids such as methylethylphosphinic acid, butylphenylphosphinic acid, methylphenylphosphinic acid and methyloctylphosphinic acid Phosphates such as ethyl methyl phosphate, ethyl phosphate and diethyl phosphate, and phosphonic acids such as methyl phosphonic acid and ethyl phosphonic acid are exemplified.

Among the above-mentioned organic phosphorus compounds, it is preferable to use a symmetrical phosphinic acid having a symmetrical or asymmetrical dialkyl, diaryl, alkylarylphosphinic acid, aromatic monocyclic or condensed polycyclic hydrocarbon group from the viewpoint of heat resistance.

In the polymerization reaction, the charge ratio of the organic phosphorus compound and the metal compound, which are monomers, is used in the range of 1.4 to 3.3 (molar ratio), and the polymer obtained when it is outside this range has a low degree of polymerization, The yield is also low, which is not preferable.

Further, the charging ratio of the metal compound is preferably such that the ratio of the total amount of the highly polymerizable metal compound to the total amount of the low polymerizable metal compound is 1 or more. This is to avoid homopolymerization of the highly polymerizable metal compound, and when it is less than 1, the obtained polymer is a polymer of a low polymerizable metal compound, that is, a low molecular weight homopolymer or a highly polymerizable metal compound. Becomes a mixture of high molecular weight homopolymer and copolymer, which is a polymer of
Even if a copolymer is obtained, the yield is low, and a high molecular weight product is not obtained, which is not preferable.

When two or more different side chains are introduced into the polymetal organophosphinate copolymer, one side chain structure is asymmetric, and one organic phosphorus compound represented by the structural formula (5), or It is possible to use a mixture of two or more organic phosphorus compounds having a symmetrical side chain structure.

In general, many organic phosphinic acids are sparingly soluble in alcohols and cyclic ethers. Therefore, aromatic hydrocarbons such as benzene, xylene and toluene, chloroform and the like are used as the solvent (A). In this case, since the solvent (A) is a good solvent for the resulting copolymer, the organic phosphinic acid solution is prepared by using the solvent (A) alone. on the other hand,
The alkali metal salt of organic phosphinic acid has water and alcohols as good solvents, but the produced copolymer is not soluble in these solvents. Therefore, it is necessary to add a solvent for dissolving the produced copolymer to the organic phosphinate solution. When water is used as the solvent for the phosphinate, a solvent compatible with water such as tetrahydrofuran must be used as a solvent for dissolving the copolymer. On the other hand, when alcohols are used as the solvent, aromatic hydrocarbons such as benzene, toluene and xylene, tetrahydrofuran, chloroform and the like can be used.

Regarding the solvent (B) for the metal compound, for the metal compound soluble in tetrahydrofuran, tetrahydrofuran alone or a mixed solvent obtained by further adding benzene or the like can be used as the solvent (B). On the other hand, for tetrahydrofuran-insoluble metal compounds soluble in alcohols, a mixed solvent of alcohols and the above-mentioned aromatic hydrocarbons, tetrahydrofuran or chloroform is used as the solvent (B), and water-soluble metal compounds are Water is used as solvent (B).

When the above solvents (A) and (B) are incompatible,
Aromatic hydrocarbon may be used as the solvent (A) and water may be used as the solvent (B). In this case, by adding tetrahydrofuran to the solvent (A) or (B),
It becomes a compatible system. Further, for water-inhibiting metal compounds, it is necessary to sufficiently remove water from the solvent and dehydrate it before use.

The volume ratio of the above solvents (A) and (B) is 1: 0.1.
Used in the range from 0.1: 1.

Although the polymerization time is not particularly limited, it is usually preferably 2 hours to 6 hours because of the problem of gel formation.
However, depending on the combination of two or more metal compounds used, a gel may not be formed even after polymerization for several tens of hours, and in some cases, a gelation tendency may be exhibited. Therefore, the polymerization time must be appropriately selected in consideration of the combination of metal compounds and gelation.

There is no particular restriction on the reaction temperature in the present invention, and generally any temperature from room temperature to the boiling point of the mixed solvent system can be used.

The method for producing the polymetal organophosphinate copolymer provided by the present invention comprises four processes. Each of these processes will be described below.

(1) Preparation of metal compound solution (hereinafter referred to as monomer solution (a)) When a metal halide is used, it is preferable to halogenate a high-purity metal before polymerization and use it. For more information,
An aqueous solution of hydrogen chloride, hydrogen bromide or hydrogen iodide or an alcohol solution is added dropwise to the two different metals and sufficiently halogenated under heating or at room temperature to obtain a metal halide solution. At this time, the time required for halogenation depends on the reactivity of the metal used. Zinc is relatively reactive. While halogenated in a short time, copper is less reactive than zinc and requires heating. On the other hand, chromium has a lower reactivity than zinc at room temperature, but the halogenation time can be considerably shortened by heating. Further, metal sulfates, nitrates and cyanides can be prepared in the same manner as above.

When the organometallic compound is used, it is preferable to dissolve the hexane solution of the organometallic compound in completely dehydrated tetrahydrofuran in an amount equal to or more than the amount used.

(2) Organic phosphorus compound solution (hereinafter referred to as monomer solution (b)
The solvent (A) capable of dissolving 1.4 to 3.3 times the number of moles of the metal used in (1) at room temperature is added and dissolved, and then the nitrogen is completely replaced with the monomer. A solution (b) is obtained. When a mixed solvent containing a poor solvent for the organic phosphorus compound is used as the solvent (A), it is necessary to set the amount of the poor solvent so that the organic phosphorus compound does not precipitate.

(3) Polymerization reaction 1 (precursor synthesis) To the monomer solution (b), the monomer solution (a) was added dropwise under stirring to obtain a mixture of two metal bisphosphinate precursors or a low molecular weight copolymer. obtain. The reaction temperature during the synthesis of this precursor may be room temperature or higher.

Further, when an unstable metal halide is used as the metal compound, the metal halide may be easily oxidized in the air to be unstable. In this case, it is necessary to carry out an oxidation reaction of the obtained copolymer. Further, this oxidation reaction affects not only the stability of the copolymer but also the solubility in the organic solvent used for the polymerization, and when the solubility is low, it is possible to improve the solubility by the oxidation reaction. . As this method, it is preferable to carry out an oxidation reaction in the presence of an oxidizing agent during the polymerization reaction to stabilize the copolymer, and as the oxidizing agent used here, hydrogen peroxide solution, water, etc. are preferably used. To be

(4) Polymerization reaction 2 (precursor polymerization reaction) The precursor solution or the low molecular weight copolymer solution obtained in the polymerization reaction 1 is heated and stirred for 2 hours to 6 hours for polymerization. After completion of the polymerization, the reaction solution is concentrated, poured into a poor solvent for the polymetal organophosphinate copolymer such as methanol to cause precipitation, and the polymer is isolated by filtration and dried by a conventional method.

The polymetal of the present invention obtained by the above-mentioned production method, for example, using an alkali metal salt of di-n-alkylphosphinic acid as the starting organic phosphorus compound and two kinds of metal halides as the metal compound. infrared absorption spectrum of organo phosphinates copolymer, the alkyl group in the vicinity of ^{3000cm -1 C-H, P-} C in the vicinity of 1440cm ^-1, 1000~1200
As absorption of O-P-O and M-OH bonds near cm ^-1, for example, absorption based on Cr-OH bonds near 3600 cm ^-1 is shown.
As a result of elemental analysis, the ratio of the total number of metal atoms and the number of P atoms in the obtained polymer is approximately 1: 2.

Further, as a result of TGA (thermogravimetric analysis) measurement, the polymer of the present invention exhibits a monotonous thermal decomposition behavior, and therefore it is not a blend of homopolymers but a copolymer containing two kinds of metal atoms in the same main chain. It is concluded that it is a polymer.

From the above facts, the constituent elements of the copolymer obtained by the method of the present invention have the following structural formula (however, the low-molecular organic ligand not involved in the main chain formation is omitted): O-PR ₂ -O-M (wherein, R represents an alkyl group, M ¹ and M ² represents the two metals _{^{different) 1 -O-PR 2 -O O}} -PR 2 -O-M 2 -O-PR 2 -O be It is also concluded that the constituents are contained in the same main chain of the copolymer.

Further, since the copolymer is soluble in an organic solvent such as THF and has a film-forming property, the copolymer is essentially a linear polymer having a chain of the above structural units.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

The analysis method and conditions used for the identification and qualification of the copolymer of the present invention are described below.

(1) IR (infrared absorption spectrum) model JASCO IR-810 type infrared spectrophotometer measurement method KBr tablet method (2) TGA (thermogravimetric analysis) model SSC-5000 thermal analyzer TA station manufactured by Seiko Instruments Inc. TG / DTA200 Measurement method Air temperature rise rate 15 ℃ / min Comparative sample Alumina (3) Organic element analysis model Yanagimoto CHN CORDER MT-3 Elemental analysis device, data processing device Measurement method Sample amount 2.0-2.5mg (4) ICP (Inductively Coupled Plasma Emission Spectroscopy) Model Seiko Electronics Plasma Spectrometer SPS 1100 RF Generator HFP 2500F (5) GPC (Gel Permeation Chromatography) Model TOSO HLC-802A CP-8III (Data processing device) Packed column Styrene-divinylbenzene Copolymer gel TSKgel G7000H ₆ / G6000H ₆ / G3000H ₈ system Measurement conditions Column temperature 38 ℃ Flow rate 1.9ml / min Peak detection Differential refractometer (RI) Dissolving liquid Tetrahydrofuran Example 1 A glass filter at the bottom and an extraction tube with a cock 20
In a 0 ml 4-neck round bottom flask (1), add 1.227 ml of hydrochloric acid to 50 ml of
A dropping funnel charged with a solution diluted with THF, a nitrogen blowing pipe, and an exhaust pipe were attached. On the other hand, 0.306 g of metallic chromium and 0.358 g of metallic zinc were charged, and the extraction tube purged with nitrogen was connected to a 1-liter 4-neck round bottom flask (2). After attaching a nitrogen introduction tube and an exhaust tube to the flask (2), charge a THF / methanol mixed solution (500/50 v / v) in which 10 g of sodium didodecylphosphinate was dissolved, and then blow nitrogen into the flask. The reaction system was replaced with nitrogen. Hydrochloric acid was dropped from the dropping funnel of the flask (1) and heated. It showed that hydrogen started to be generated a few minutes after the dropping and metal halide started to be generated. Approximately 2 hours after the completion of dropping, all metal chromium and all metal zinc were halogenated. The solution was concentrated by heating to remove residual hydrogen chloride. After about 30 minutes, this solution was added dropwise to the flask (2) over 40 minutes and polymerized with stirring.
After continuing the reaction at room temperature for 20 hours after the completion of dropping, oxygen was introduced into the system, and after stirring overnight, the product was oxidized and stabilized,
The reaction solution was concentrated and reprecipitated with methanol to obtain 10.0 g (yield 95
%) Of an organic solvent-soluble polymer was obtained.

The polymer was reprecipitated and purified, and IR analysis, elemental analysis, ICP analysis, TGA analysis and GPC measurement were performed. ICP analysis results, Cr-Z
The n content ratio was found to be approximately 1: 1 and the theoretical values calculated assuming the ratio of the structural units 1 and 2 below to be 1: 1 and the elemental analysis values showed good agreement. The infrared absorption spectrum showed peaks consistent with this structure, as shown in FIG. As a result of GPC measurement using a tetrahydrofuran solution of the polymer, the molecular weight of this product was 28000 (polystyrene (PS) conversion). The thermal decomposition behavior of this polymer did not show a two-step decomposition process and showed a monotonous weight loss.

The temperature for 10% weight loss in air was 365 ° C, suggesting that the polymer was a copolymer rather than a blend of zinc phosphinate homopolymer and chromium phosphinate homopolymer.

Polymer composition (organic elemental - elemental analysis, inorganic elements -ICP analysis) structural unit 1 {Cr (OH) (OH 2) (OP (C 12 H 25)
₂ O) ₂ } Structural unit 2 {Zn (OP (C ₁₂ H ₂₅ ) ₂ O) ₂ } Structural unit 1 / Structural unit 2 = 1/1 The calculated logical values are shown in parentheses.

Elemental analysis value Cr 2.2% (theoretical value 2.95%) Zn 3.4 (3.71) P 6.5 (7.0) C 65.4 (65.5) IR characteristic absorption 2925,2850,1465,1123,1052,940,800,720,5
20 Example 2 Using the same reaction apparatus as in Example 1, an ethanol solution obtained by neutralizing 5 g of di-n-decylphosphinic acid with potassium hydroxide was diluted with 500 ml of THF to prepare a solution. Replaced with nitrogen. To this solution, 0.18 g of metallic chromium, 0.24 g of metallic zinc, and 12 ml of hydrochloric acid were added, and a mixed solution of zinc chloride and chromous chloride was added dropwise under nitrogen for 1 hour, and then at room temperature. Polymerization was performed overnight with stirring to obtain a blue polymer solution. Oxygen was introduced into this polymer solution, and an oxidation reaction was carried out with stirring overnight. After passing the obtained green polymer solution to remove the precipitated salt, it was concentrated, reprecipitated, washed with water and dried to give 5.48 g (yield 92%).
A polymer of

As a result of GPC measurement using tetrahydrofuran as an eluent, the molecular weight of this polymer was 32500 (PS conversion), and T
As a result of GA analysis, the temperature is about 10% for weight loss in air.
It was 360 ° C. This polymer was subjected to elemental analysis, ICP analysis and IR analysis. From ICP analysis, Cr-Z in the polymer
The n content ratio was found to be approximately 1: 1 and the following structural unit 1
Comparing the theoretical values calculated assuming the ratio of 1 and 2 to 1: 1 and elemental analysis showed good agreement, and this polymer was not a blend of zinc phosphinate homopolymer and chromium phosphinate homopolymer. It was suggested to be a zinc / chromium copolymer.

Structural unit 1 {Cr (OH) (OH ₂ ) (OP (C ₁₀ H ₂₁ )
₂ O) ₂ } Structural unit 2 {Zn (OP (C ₁₀ H ₂₁ ) ₂ O) ₂ } Structural unit 1 / Structural unit 2 = 1/1 The calculated logical values are shown in parentheses.

Elemental analysis value Cr 3.1% (theoretical value 3.46%) Zn 4.5 (4.35) P 7.9 (8.25) C 64.1 (63.95) H 10.8 (11.47) IR characteristic absorption 2925,2850,1465,1125,1052,940,800,720,5
00 Example 3 Using the same reactor as in Example 1, a solution of 100 ml of ethanol obtained by neutralizing 20 g of diphenylphosphinic acid with potassium hydroxide was diluted with 1000 ml of THF to prepare a nitrogen-substituted solution. Then, to this solution, a mixed solution of zinc chloride and chromium chloride obtained by reacting 1.19 g of metallic chromium and 1.49 g of metallic zinc with 4.77 g of hydrochloric acid was added dropwise under nitrogen over 30 minutes, and then Polymerization was carried out at room temperature for 6 hours with stirring to obtain a blue polymer solution. Oxygen was introduced into this polymer solution, and an oxidation reaction was carried out with stirring overnight. The resulting green polymer solution was passed through to remove precipitated potassium chloride, then concentrated, reprecipitated, washed with water, and dried to obtain 22.2 g (yield 91%) of a polymer.

As a result of GPC measurement using tetrahydrofuran as an eluent, the molecular weight of this polymer was 30,000 (PS conversion).
The temperature for 10% weight loss in air was 450 ° C, which was above 400 ° C for chromium homopolymers. This polymer was subjected to elemental analysis, ICP analysis and IR analysis. From the ICP analysis, it was found that the content ratio of Cr—Zn in the polymer was approximately 1: 1, and the theoretical value and the elemental analysis value calculated assuming that the ratio of the following structural units 1 and 2 was 1: 1. The results were in good agreement, suggesting that the polymer was a zinc / chromium copolymer rather than a blend of zinc phosphinate homopolymer and chromium phosphinate homopolymer.

Structural unit 1 {Cr (OH) (OH ₂ ) (OP (C ₆ H ₅ ) ₂ O) ₂ } Structural unit 2 {Zn (OP (C ₆ H ₅ ) ₂ O) ₂ } Structural unit 1 / Structural unit 2 The logical value calculated assuming = 1/1 is shown in parentheses.

Elemental analysis value Cr 4.8% (theoretical value 4.84%) Zn 5.9 (6.09) P 12.0 (11.545) C 53.8 (53.72) H − (4.04) IR characteristic absorption 3050,3070,1440,1150,1060,1020,1000,75
0,730,690,560,540 Comparative Example 1 Using the same reactor as in Example 1, a chromium (III) chloride solution was added dropwise to an ethanol solution of 10.0 g of potassium di-n-dodecyl phosphinate under nitrogen atmosphere over 1 hour, and at room temperature overnight. The polymerization reaction was carried out with stirring. Chromium chloride solution contains 0.612 grams of metallic chromium and 2.45 ml
It was obtained by reacting a hydrochloric acid solution obtained by adding 50 ml of THF to the hydrochloric acid in Example 1 and diluting it. Oxygen was introduced into the obtained blue polymer solution to oxidize the polymer. The polymer solution was filtered, concentrated, reprecipitated with methanol, filtered, and dried to obtain 9.39 g of a dry polymer (yield 89%).

As a result of GPC measurement using tetrahydrofuran as an eluent, the molecular weight of this polymer was 25000 (PS conversion), and T
As a result of GA analysis, the temperature is 30 for a 10% weight loss in air.
The temperature was 0 ° C., and the decomposition rate was higher than that of the copolymer obtained in Example 1. The results of IR analysis, elemental analysis and ICP analysis of this polymer were in good agreement with the theoretical values of the compound represented by the structural formula below.

Structural unit {Cr (OH) (OH ₂ ) [OP (C ₁₂ H ₂₅ ) ₂ O] ₂ } Elemental analysis and ICP analysis results Cr 5.3% (theoretical value 5.80%) P 6.5 (6.91) C 64.2 (64.32) H 13.0 (12.26) IR characteristic absorption 2900,2850,1465,1100,1058,950,720 Comparative Example 2 Using the same reactor as in Example 1, 5 g of di-n-decylphosphinic acid was neutralized with potassium hydroxide. The obtained ethanol solution was diluted with 600 ml of THF to prepare a solution, and after nitrogen substitution, the solution was mixed with 0.38 g of metallic chromium and 1.50 g of hydrochloric acid to obtain a solution of chromium chloride. The mixture was added dropwise under nitrogen for 40 minutes, and then polymerized with stirring at room temperature for one day to obtain a blue polymer solution. Oxygen was introduced into this polymer solution, and an oxidation reaction was carried out with stirring overnight. The resulting green polymer solution was passed through to remove the precipitated salt, which was then concentrated, reprecipitated, washed with water and dried to obtain 5.88 g (yield 91%) of the polymer.

As a result of GPC measurement using tetrahydrofuran as an eluent, the molecular weight of this polymer was 25000 (PS conversion), and T
As a result of GA analysis, the temperature is about 10% for weight loss in air.
The temperature was 305 ° C, and the decomposition rate was higher than that of the copolymer obtained in Example 2. Elemental analysis of this polymer,
The results of ICP analysis and IR analysis were in good agreement with the theoretical values of the compound represented by the structural formula below.

Structural unit 1 {Cr (OH) (OH ₂ ) (OP (C ₁₀ H ₂₁ ) ₂ O) ₂ Elemental analysis value Cr 5.2% (Theoretical value 5.80%) P 6.8 (6.91) C 53.5 (53.60) H 9.6 (9.78) ) IR characteristic absorption 2900,2850,1465,1100,1058,950,720 Comparative Example 3 Using the same reactor as in Example 1, 5 ml of diphenylphosphinic acid was neutralized with potassium hydroxide to obtain 50 ml.
A solution prepared by diluting the above ethanol solution with 500 ml of THF was prepared, and after substituting with nitrogen, 1.5 g of metallic zinc was reacted with 11.5 ml of hydrochloric acid, and the resulting zinc chloride solution was diluted with 30 ml.
Then, the mixture was added dropwise over a period of 6 minutes and polymerized with stirring at room temperature for 6 hours. After passing through the obtained polymer solution to remove the potassium chloride produced, concentration, reprecipitation, washing with water and drying were carried out to obtain 5.1 g (yield 90%) of the polymer.

As a result of GPC measurement using tetrahydrofuran as an eluent, the molecular weight of this polymer was 4000 (PS conversion), and the degree of polymerization was lower than that of the copolymer with chromium. The results of elemental analysis, ICP analysis and IR analysis of this polymer were in good agreement with the theoretical values of the compound represented by the structural formula below.

Structural units _{{Zn (OP (C 6 H} 5) 2 O) 2} Elemental analysis Zn 12.9% (theory 13.08%) P 12.5 (12.39) C 56.8 (57.68) H 4.2 (4.03) IR characteristic absorption 3050,1435 , 1150,1055,1020,990,750,730,6
90,560,530 [Effect of the invention] As is apparent from the above description, the present invention provides a novel polymetal organophosphinate copolymer containing a different metal.

[Brief description of drawings]

FIG. 1 is a chart showing the infrared absorption spectrum of the compound obtained in Example 1 of the present invention.

Claims (2)

[Claims] 1. The following structural formulas (1) and (2) (Here, M ¹ and M ² represent mutually different metal atoms having valences of 2 or more, a and b respectively represent valences of 2 or more of the metal atoms, and Y and Y ′ are halogen, an alkyl group or Representing an organic group such as an alkoxy group, Y and Y'may be different or the same, L ¹ and L ² are neutral ligands or anionic ligands, and n and m are 0 or 2 The above numbers are shown, provided that L ¹ does not exist when n is 0 and L ² does not exist when m is 0. Further, R ¹ and R ² are an alkyl group having 1 or more carbon atoms or aryl. Group, an alkoxy group, an aryloxy group, and R ¹ and R ² may be the same or different. → represents a coordination bond to M ¹ or M ^2. ) The structural units represented are contained in the same main chain, the molar ratio of the structural units (1) and (2) contained is 95: 5 to 5:95, and the molecular weight is 2,000 to 60,000. There dissimilar metal-containing poly-metal organo phosphinates copolymer. 2. The following general formulas (3) and (4) M ^{1 (a)} X ₂ Y _a-2 (L ¹ ) n (3) M ^{2 (b)} X ₂ ′ Y ′ _b-2 (L ² ) M (4) (wherein M ¹ and M ² represent different metal atoms having valences of 2 or more, a and b respectively represent valences of 2 or more of the metal atoms, and X, X ′, Y and Y'represents a halogen atom or an organic group such as an alkyl group or an alkoxy group, which may be the same as or different from X, X ', Y and Y'. L ¹ and L ² are neutral ligands or anions. Ionic ligand, n or m is 0 or 2
The above numbers are shown. ) And a solution of a mixture of at least two different metal compounds represented by the following structural formula (5) (Here, R ¹ and R ² are independently selected from an alkyl group having 1 or more carbon atoms, an aryl group, an alkoxy group, and an aryloxy group, and R ¹ and R ² may be the same or different. well,
Z represents hydrogen or an alkali metal. ) A mixture of at least one or more organic phosphorus compound represented by the following in an organic solvent solution is polymerized, and at this time, two or more metal compounds used as monomers and an organic phosphinic acid or salts thereof are added. The following structural formulas (1) and (2) are used, which are characterized by using a mixed solvent system which is soluble and, at the same time, is soluble and compatible with the polymetal organophosphinate copolymer produced at the same time. (Here, M ¹ , M ² , a, b, Y, Y ′, L ¹ , L ² , n, m, R ¹ and R ² are the same as above. However, when n is 0, L ¹ is L ² does not exist when m is 0.) A method for producing a dissimilar metal-containing polymetal organophosphinate copolymer containing a structural unit represented by the formula) in the same main chain.