JPH0794560B2 - Method for producing polymetal organophosphinate - 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 a method for producing such an inorganic polymer, that is, a polymetal organophosphinate polymer containing a metal. The inorganic polymer obtained in the present invention can be used as a heat resistant resin, a thickener, a coating material, and a lubricant.

Furthermore, when the polymer contains a paramagnetic metal in the main chain, the polymer exhibits a characteristic property of being ferromagnetic or antiferromagnetic, and in view of many recent studies on such magnetism, It is considered that the polymer is also often used as a polymer magnetic material.

[Problems to be Solved by Prior Art and Invention]

Although various synthetic methods are known for polymetal organophosphinates, the block method (Journal of Polymer Science, A1, Volume 6, p. 1397, 1968) is known as a method for obtaining a polymer having a high molecular weight. Year) is the most effective method. This method involves the reaction of metal salts with an alkali metal salt of an organic phosphinic acid in an alcohol at room temperature to precipitate a low molecular weight polymer (oligomer) which is isolated, purified, dried and then dissolved in an anhydrous organic solvent such as anhydrous chloroform. It is a method of heating and polymerizing for several days in a temperature range near 60 ° C. However, the method is not without any problems, and the isolation, washing, purification, and drying operations of the oligomer are required, and in order to obtain a high-molecular weight polymer, it takes a long time of several days. There are some problems that a polymerization reaction is required and that a dehydration operation of a solvent used for polymerizing the oligomer is required.

Therefore, there is a demand for a method capable of continuously performing an oligomer synthesis reaction and a polymerization reaction of the oligomer, eliminating the need for an oligomer isolation operation, and obtaining a high molecular weight polymer in a short time.

Among the above problems, the reason why the isolation operation of the oligomer is necessary is that the alcohol solvent or water is suitable as the solvent for the alkali metal salt of the organic phosphinic acid and the metal halide, which are the starting materials, whereas the oligomer to be formed is suitable. Is because these solvents are insoluble. On the contrary, as a solvent for dissolving the oligomer, chloroform, benzene, tetrahydrofuran and the like can be mentioned, but the above-mentioned starting materials are insoluble in these solvents.

For this reason, the produced oligomer has a problem that it precipitates in the above reaction system, and the subsequent continuous polymerization reaction of the oligomer is essentially impossible. Next, when the oligomer is polymerized, it is necessary to purify the oligomer. The problem is that the unreacted organic phosphinic acid alkali metal salt having strong coordinating ability inhibits the oligomer growth reaction or grows into an unreacted metal halide. This is due to the inhibition of the oligomer growth reaction due to the coordination of the terminal phosphinato anion.

Therefore, in order to solve the problem of oligomer precipitation, a solvent that dissolves the oligomer and the starting material at the same time is necessary, and such a solvent is related to a system using a metal halide and an alkali metal salt of an organic phosphinic acid as the starting material. Not found.

The present inventors have arrived at the present invention as a result of intensive studies to solve such problems.

[Means for solving problems]

That is, the present invention provides the following general formula (1) M ^(a) X ₂ Y _a-2 (L) _n (1) (where M is a metal atom having a valence of 2 or more, and a is 2 of the metal atom). Representing the above valences, X and Y represent an organic group such as a halogen atom, an alkyl group or an alkoxy group, X and Y may be different or the same, L is a neutral ligand, or The anionic ligand is a low-boiling-point solvent solution of a metal compound represented by the following formula, in which n is 0 or a total coordination number of the ligands of 2 or more. (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. ,
Z represents hydrogen or an alkali metal. ) At least one or more organic phosphorus compounds represented by
A solution of a mixed solvent consisting of a low boiling alcohol solvent and a high boiling substituted aromatic monocyclic hydrocarbon solvent is prepared, and the metal compound solution and the organic phosphorus compound solution are mixed to obtain the following structural formula (3). (Here, M represents a metal atom having a valence of 2 or more, a represents a valence of 2 or more of the metal atom, Y represents an organic group such as a halogen atom, an alkyl group or an alkoxy group, and L is a medium. Or anionic ligand, where n is 0 or 2
When n ₋₂ is 0 or less, the ligand L does not exist. Also, 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. Further, the arrow represents a coordinate bond to the metal M. ) After obtaining a reaction mixture solution containing a low molecular weight polymer consisting of a structural unit represented by the following, the low boiling point solvent is removed from the reaction solution, and then the solution is energized. The present invention relates to a method for producing phosphinate.
The present invention will be described in detail below.

Various monomers can be used as the metal deposit compound monomer represented by the above general formula (1), and the heat resistance of the polymer varies depending on the metal species used, but zinc compounds, cobalt compounds, beryllium compounds, chromium compounds It is preferable to use a metal compound such as On the other hand, in order to avoid the equilibrium reaction, as the metal compound, a halide, a hydroxide, etc., and an organometallic compound whose elimination substance is a gas such as ethane by reaction with an organic phosphinic acid, or a low boiling point substance is eliminated. Preference is given to using metal alkoxides which are separated.

Examples of metal compounds satisfying the above conditions are shown below.

(1) Hydroxide Zn (OH) ₂ , Be (OH) ₂ , Cr (OH) ₃ , Fe (OH) ₃ (2) Halide BeCl ₂ , CrCl ₂ , CrCl ₃ , FeCl ₃ , ZnCl ₂ (3 ) Acid esters Be (OCOCH ₃ ) ₂ , Zn (OCOCH ₃ ) ₂ , Cr (OCOCH ₃ ) ₃ (4) Cyanide Ni (CN) ₂ , Zn (CN) ₂ , Cr (CN) ₃ (5) Organic metal compound _{Al (C 2 H 5) 2} , Al (C 2 H 5) 2 H, Zn (C 2 H 5) 2 (6) hydride TiH _3, TiH ₄ (7) metal alkoxide Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , Zr (OC ₄ H ₉ ) ₄ Here, the term metal compound refers to a wide range of compounds including an organometallic compound such as diethylzinc as shown in the above compound examples. The above compounds do not impose any restrictions on the metal compound monomer.

With respect to the purity of the metal compound monomer, it is preferable to use the metal compound monomer having the highest possible purity in view of the influence on the polymerization of other metal salts contained in the metal salt monomer.

For those having a reactive group that is not involved 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,
Alternatively, it is preferable to form a chelate at this site to inactivate the reaction before use. The metal compounds may be used alone or in combination of two or more.

The organic phosphorus compound represented by the structural formula (2) used in the present invention is an organic phosphinic acid or an organic phosphinic acid alkali metal salt. As the alkali metal, sodium, potassium or the like can be used.

Examples of the phosphinic acid include osphinic 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, dimesitylphosphinic acid, 2-naphthylphosphinic acid, di-1,1 ':
Aromatic monocycles such as 4 ', 1 "-terphenylphosphinic acid,
Symmetrical phosphinic acids having condensed polycyclic hydrocarbon groups, methylethylphosphinic acid, butylphenylphosphinic acid, methylphenylphosphinic acid, methyloctylphosphinic acid and other asymmetric phosphinic acids, and phosphates such as ethylmethylphosphate, ethylphosphate and diethylphosphate Examples thereof include phosphonic acids such as methyl phosphonic acid and ethyl phosphonic acid.

Among the above organophosphorus compounds, from the viewpoint of heat resistance, a symmetrical phosphine having a symmetrical dialkylphosphinic acid, an asymmetrical dialkylphosphinic acid, a diarylphosphinic acid, an alkylarylphosphinic acid, an aromatic monocyclic ring, and a condensed polycyclic hydrocarbon group. It is preferable to use an acid.

In the polymerization reaction of polymetal phosphinate, the charge ratio of the organophosphorus compound to the metal compound which is a monomer is used in the range of 1.4 to 3.3 in terms of molar ratio.
When two or more different side chains are introduced into the polymetal organophosphinate, a kind of organic phosphorus compound represented by the structural formula (2) having an asymmetric side chain structure or a symmetrical side chain structure. It is possible to use a mixture of two or more of the organophosphorus compounds having

Next, the monomer solvent used in the present invention will be described.
When the metal compound is water-soluble or alcohol-soluble such as halide or hydroxide, the solvent is water or various alcohols such as methanol, ethanol and isopropanol, preferably lower alcohols such as methanol or ethanol. It is a kind. For an organic metal compound or a metal compound soluble in an organic solvent such as a metal alkoxide, an aliphatic hydrocarbon such as hexane or tetrahydrofuran is used after dehydration. Therefore, as the solvent of the metal compound, the boiling point at normal pressure is preferably 10
A low boiling point solvent at 0 ° C. or lower is used.

On the other hand, lower alcohols are generally used as the organic solvent capable of dissolving the organic phosphorus compound. However, when the organic phosphorus compound is organic phosphinic acid, these are hardly soluble in alcohols such as methanol, ethanol and isopropanol at room temperature. In this case, it can be solubilized by adding a substituted aromatic monocyclic hydrocarbon solvent such as xylene or toluene.

When the organophosphorus compound is an alkali metal salt of an organic phosphinic acid, on the contrary, alcohols such as methanol, ethanol and isopropanol are suitable as the solvent, but a substituted aromatic monocyclic hydrocarbon solvent may be added. It is possible. On the other hand, examples of the solvent for the polymer include alkyl-substituted benzene such as xylene and toluene, cyano group-substituted benzene such as α-tolunitrile and benzonitrile, substituted benzene such as nitrobenzene, alkoxy-substituted benzene such as anisole, phenetol and veratrol, and monochlorobenzene. , High-boiling substituted aromatic monocyclic hydrocarbon solvents such as halogen-substituted benzene such as ortho-chlorobenzene and metadichlorobenzene. Therefore, as the solvent for the organic phosphorus compound in the present invention, the boiling point at normal pressure is preferable, and the low boiling point alcohol solvent having a boiling point of 100 ° C. or lower and the high boiling point substituted aromatic monocycle having a boiling point at normal pressure of more than 100 ° C. A mixed solvent of hydrocarbon solvents is used. By using such a solvent system, when the low molecular weight polymer is obtained by mixing the metal compound solution and the organic phosphorus compound solution, a solvent system in which the low molecular weight polymer does not precipitate can be obtained. However, when this reaction solvent is heated at a high temperature, the reaction temperature cannot be set to 100 ° C. or higher in the state where water remains, while the reaction system cannot be set in the state where low boiling point solvents such as alcohols remain. However, it is possible to carry out continuous polymerization at a high temperature in a homogeneous system by removing them at the time when the oligomer is formed and leaving only the high boiling polymer solvent.

If the amount of the monomer solvent is larger than the amount of the polymer solvent, the solubility of the low molecular weight polymer in the mixed solvent system is lowered and precipitation occurs. On the other hand, when the amount of the polymerization solvent is larger than that of the monomer solvent, the concentration of the low molecular weight polymer in the polymerization solution after removing the low boiling point solvent becomes small, and thus the growth end reactivity is low. Problems arise. From the above facts, the amount of the polymerization solvent in the mixed solvent system is preferably in the range of 10 to 100 in volume ratio when the amount of the monomer solvent is 1.

The reaction temperature in the present invention can be any temperature from room temperature to the boiling point of the above mixed solvent system when the low molecular weight polymer is synthesized, in general, except when an organometallic compound is used, it may be an extremely low temperature. it can. On the other hand, the polymerizability of the oligomer depends on the polymerization temperature, and at high temperature, preferably
The polymerization reaction at 80 ° C. or higher improves the polymerizability of the low molecular weight oligomer, and a high molecular weight soluble polymer can be obtained in a shorter time than in the conventional method. Therefore, the polymerization reaction is over 80 ℃, especially 90 ℃.
It is preferable to carry out the above temperature.

If the polymerization temperature is too high, there is a problem of insoluble matter formation, so 130 ° C or lower is preferable.

The high boiling point solvent which is a polymerization solvent is preferably a halogen-substituted benzene such as monochlorobenzene, orthochlorobenzene, and metadichlorobenzene from the viewpoint of suppressing the formation of insoluble matter.

Although the polymerization time is not particularly limited, it is usually preferably 2 to 7 hours from the problem of insoluble matter formation, but it is appropriately selected depending on the type of metal compound used as a monomer in relation to insolubilization. There is a need to.

The method for producing the polymetal organophosphinate polymer 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. Specifically, an aqueous solution of hydrogen chloride, hydrogen bromide, hydrogen iodide, or an alcohol solution is added dropwise to the metal compound 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. Iron and zinc are relatively reactive and halogenated in a short time, whereas 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.
Also, metal sulfates and nitrates can be prepared in the same manner as above. When an organometallic compound is used, it is used by dissolving it in a low boiling point solvent such as anhydrous hexane solution or anhydrous tetrahydrofuran.

(2) Organic phosphorus compound solution (hereinafter referred to as monomer solution (b)
That is, 1.4 to 3.3 times the number of moles of the metal used in (1) in the organophosphorus compound is dissolved by adding a minimum amount of a low boiling alcohol solvent capable of dissolving at room temperature. A high boiling point substituted aromatic monocyclic hydrocarbon solvent added for the purpose of dissolving the produced polymer is added to the solution in a volume ratio of 10 to 100 with respect to the low boiling point solvent 1.
After the addition, the monomer solution (b) was completely replaced with nitrogen.
To get

When the high boiling point solvent is a poor solvent with respect to the organic phosphorus compound, the mixing ratio of the low boiling point solvent and the high boiling point solvent is within a range such that the organic phosphorus compound does not precipitate, and the solvent of the low boiling point solvent is It is preferable to set so that the amount of the high boiling point solvent is as large as possible with respect to the amount.

(3) Synthesis of precursor and low molecular weight polymer The monomer solution (a) was added dropwise to the monomer solution (b) with stirring.
Alternatively, the monomer solution (b) is added dropwise to the monomer solution (a) under stirring to obtain a metal bisphosphinate precursor and / or a low molecular weight polymer. There is no problem as long as the reaction temperature at the time of synthesizing the precursor is room temperature or higher, except in a special case where an organometallic compound is used as a monomer.

Further, when an unstable metal halide is used as the metal compound, the metal halide may be easily oxidized in the air and may be unstable. In this case, it is necessary to oxidize the resulting precursor and / or the low molecular weight polymer. Further, this oxidation reaction affects not only the stability of the polymer but also the solubility in the organic solvent used for the polymerization. When the solubility is low or insoluble, the oxidation reaction may improve the solubility. It is possible. As this method, it is preferable to perform an oxidation reaction in the presence of an oxidizing agent during the polymerization reaction to stabilize the polymer and / or the precursor. Examples of the oxidizing agent used here include hydrogen peroxide solution, water, etc. Is preferably used.

(4) Polymerization reaction (polymerization reaction of precursor and / or low molecular weight polymer) The precursor solution and / or the low molecular weight polymer solution obtained in (3) above are heated to the boiling point of the low boiling point solvent or under reduced pressure. After removing the low boiling point solvent with, the temperature is raised to a desired polymerization temperature and the polymerization is performed under heating for 2 to 7 hours. The alcohol and water are removed under reduced pressure or under normal pressure heating, and a reaction device equipped with a distillation lamp is used if necessary. Water is removed azeotropically with a high-boiling solvent, or it is removed by a fractional distillation operation, and when the reaction system reaches the desired polymerization temperature, even if water is present in the reaction system, the removal operation is performed. There is no problem even if you finish. However, the water may be continuously removed by the azeotropic operation even during the polymerization. Since the heating of this reaction solution essentially involves the polymerization of the precursor and / or the low molecular weight polymer, the removal of the low boiling point solvent is carried out under heating and atmospheric pressure rather than under low temperature and reduced pressure. It is advantageous and preferred for polymer formation. After completion of the polymerization, the reaction solution is concentrated, poured into a poor solvent for polymetal organophosphinate such as methanol to cause precipitation, and the polymer is isolated by filtration and dried by a conventional method.

Next, the structure of the polymer obtained by the present invention will be described. For example, by using the sodium salt of diphenylphosphinic acid as the starting organic phosphorus compound and chromium (II) chloride as the metal compound, the infrared of the polymetal organophosphinate of the present invention obtained by the above production method Absorption spectrum is 3050cm ^-1 , 1960cm ^-1 , 1900cm ^-1 , 1820c
m ^-1 , 1,770 cm ^-1 , 1,495 cm ^-1 , 10,20 cm ^-1 , 755 cm ^-1 , 725 cm ^-1 , 695
In the vicinity of cm ^-1 , CH of phenyl group, 1150 cm ^-1 , 1050 cm ^-1
Around, near ^{_{PO 2, 1000cm -1, PO,}} 3600cm -1, 950c
m ^-1 , 725 cm ^-1 , Cr-OH around, 3400 cm ^-1 , H ₂ O → Cr, 45
The absorption due to each bond of CrO is shown in the vicinity of 0 cm ^-1 , and the ratio of the number of Cr and p atoms is shown by inductively coupled plasma emission spectroscopy.
It was 1: 2, and the atomic ratio of P and C was 1: 2 from elemental analysis.

From the above facts, the constituent element of the polymer obtained by the method of the present invention has the following structural formula (however, the low molecular weight organic compound not involved in the main chain constitution is omitted) ← O-PRR'-OMOM -PRR'-O → (where M represents a metal atom, R and R'represent an organic group such as an alkyl group or an aryl group), and the polymer is compatible with an organic solvent such as chloroform or tetrahydrofuran. Since it is soluble, and exhibits film-forming properties and spinnability, it can be concluded that the polymer 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 used for identifying the polymetal phosphinate of the present invention was as follows.

1. Infrared absorption spectrum (IR) was measured by KBr tablet method using JASCO IR-810 type infrared spectrophotometer.

2. The analysis of organic elements (carbon, hydrogen) was carried out under the condition that the sample amount was 2.0-2.5 mg by connecting a data processing computer to a CHN CORDER MT-3 type element analyzer manufactured by Yanagimoto Seisakusho.

3. Inorganic elements (chromium, phosphorus) are analyzed by inductively coupled plasma optical emission spectroscopy (IC
P.) equipment (plasma spectrometer SPS1100 and RF
The generator HFP 2500F) was used.

4. Gel permeation chromatography (GPC) was measured by connecting a data processor PC-8 III to TOSO HLC-802A manufactured by Toyo Soda Kogyo. Packed column is styrene divinylbenzene copolymer gel TSK gel-G7000H6, G6000H6 and G30
Using 00H8 connected in series, column temperature 38 ° C, flow rate 1.9 ml / min, eluent tetrahydrofuran, polymer concentration
The peak was detected using a differential refractometer (RI) under the condition of 1.5 mg / ml.

5. The limit year [η] is the solvent drop time To (sec) and polymer solution drop time measured using an Ubbelohde viscometer.
It was calculated from Ts (seconds) by the following formula. Tetrahydrofuran was used as the solvent, and the measurement was performed at 25 ° C.

(However, c represents the number of grams of the polymer per 100 ml of the solvent.) Example 1 At the time of polymerization, a nitrogen introducing pipe, a 100 ml dropping funnel equipped with an Aldrich sepver cap, a nitrogen introducing pipe, and a fractionating tower were used. In a 1-liter round-bottomed flask having a solvent reflux / distillation column with a reflux column connected to the
A device was used in which a 0 ml ice-cooled trap was connected and the tip of the discharge pipe of this trap was trapped with liquid paraffin.

5 grams diphenylphosphinic acid, 600 ml xylene,
1.5 g of potassium hydroxide and 50 ml of ethanol were charged into a flask and stirred at room temperature under a nitrogen stream to obtain a transparent potassium diphenylphosphinate salt solution. Next, under a nitrogen stream, 1.16 g of metallic chromium was charged into the dropping funnel, and 22.9 ml of 1N hydrochloric acid ethanol solution was injected with a syringe. Generation of hydrogen ceased in about 3 hours, and blue chromium chloride was obtained. This chromium chloride ethanol solution was added dropwise to the flask, and after completion of the addition, stirring was performed for about 1 hour to obtain a pink precursor precipitate.
By oxidizing this solution, a green low molecular weight polymer solution was obtained. The oxidation reaction was completed in about 1 hour. Next, this solution was heated to 70 ° C., ethanol as a monomer solvent was removed and heated to 112 ° C., and thereafter, polymerization was carried out under stirring for 7 hours.

The produced polymer was settled in xylene in a swollen state. After passing this reaction solution and isolating the polymer, the polymer was washed with methanol and pure water and dissolved in 100 ml of tetrahydrofuran. At this time, there was a small amount of insoluble matter in tetrahydrofuran. This solution was poured into 500 ml of ethanol to precipitate a polymer, which was then dried by passing. The obtained polymer was 5.7 g (yield 95%), the viscosity of the soluble part was measured to be [η] = 0.54, and the molecular weight was measured by GPC to be about 200,000 (polystyrene conversion). there were. Also, the concentrated solution of the polymer showed good spinnability. Elemental analysis result and IR analysis result of the polymer (however, the abbreviations w, vw, vs, s and m represent the respective absorption peak intensities, weak, very weak, very strong, strong and middle, and the abbreviations in parentheses b). And s are absorption peak shapes, br
Represents oad and sharp. The same notation was used in the following examples and comparative examples. ) Is shown below.

Elemental analysis value Cr9.7, P11.9, C56.3, H4.5 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Example 2 Using the same reactor as in Example 1, 4.98 g of diphenylphosphinic acid, 1.5 g of potassium hydroxide, 600 ml of nitrobenzene, ethanol 50 ml of was charged to prepare a nitrogen-substituted diphenylphosphinic acid potassium salt solution, and a nitriding-substituted chromium chloride aqueous solution was obtained from 0.59 g of metal chromium and 22.9 ml of a 1N hydrochloric acid aqueous solution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring,
After completion of dropping, the mixture was stirred for about 1.5 hours to obtain a pink precursor precipitate. This solution was oxidized to obtain a green low molecular weight polymer. The oxidation reaction was completed in about 40 minutes. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent. Further, the mixture was heated to 120 ° C. while removing water, and then polymerized with stirring for 4 hours to obtain a viscous solution. The reaction solution was poured into 1 liter of ethanol to cause precipitation, which was then dried. At this time, there was an insoluble precipitate in the reaction solution. The polymer obtained was 5.2 grams (96% yield),
When the viscosity of the soluble part was measured, [η] = 0.45, and when the molecular weight was measured by GPC, the weight average molecular weight was about 175,000.
(Polystyrene equivalent). Also, the concentrated solution of the polymer showed good spinnability.

Elemental analysis value Cr9.8, P11.6, C56.3, H4.3 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Example 3 Using the same reaction apparatus as in Example 1, 4.98 g of diphenylphosphinic acid, 1.5 g of potassium hydroxide, 600 ml of nitrobenzene, ethanol 25 ml was charged to prepare a nitrogen-substituted diphenylphosphinic acid potassium salt solution, and a nitrogen-substituted chromium chloride ethanol solution was obtained from 0.59 g of metal chromium and 22.9 ml of a 1N hydrochloric acid ethanol solution.

This chromium chloride ethanol solution was added dropwise to the potassium diphenylphosphinic acid salt solution with stirring, and after the addition was completed, the solution was stirred for about 1.5 hours to obtain a pink precursor precipitate. This solution was oxidized to obtain a green low molecular weight polymer solution. The oxidation reaction was completed in about 35 minutes.

Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, heated to 115 ° C., and then polymerized with stirring for 5 hours to obtain a viscous solution. The reaction solution was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing. At this time, a product insoluble in the reaction solution was found. The obtained polymer was 5.5 g (yield 92%), the viscosity of the soluble part was measured [η] = 0.47, and the molecular weight was measured by GPC to be about 182,000 (polystyrene conversion). there were. Also, the concentrated solution of the polymer showed good spinnability.

Elemental analysis value Cr9.9, P11.7, C54.7, H4.4 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Comparative Example 1 Using the same reactor as in Example 1, 10 g of diphenylphosphinic acid, 3.0 g of potassium hydroxide, 300 xylene
ml and ethanol 50 ml were charged to prepare a nitrogen-substituted diphenylphosphinic acid potassium salt solution, and a nitrogen-substituted chromium chloride aqueous solution was obtained from 1.19 g of metal chromium and 22.3 ml of a 2N hydrochloric acid ethanol solution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring,
After completion of dropping, the mixture was stirred for about 2.5 hours to obtain a pink precursor precipitate. This solution was oxidized to obtain a green low molecular weight polymer solution. The oxidation reaction was completed in about 1 hour. Next, this solution was polymerized at 60 ° C. for 5 hours with stirring. After pouring the reaction solution into 1 liter of ethanol to precipitate the polymer,
I had The obtained polymer was 11.0 g (yield 92%), the viscosity was measured to be [η] = 0.18, and the molecular weight was measured by GPC to be about 85,000 (in terms of polystyrene).

Elemental analysis value Cr10.2, P12.0, C54.9, H4.0 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755m (s), 725s (s), 695s (s), 450w Comparative Example 2 Using the same reactor as in Example 1, 10 g of diphenylphosphinic acid, 3.0 g of potassium hydroxide, 300 ml of tetrahydrofuran, ethanol A nitrogen-substituted diphenylphosphinic acid potassium salt solution was prepared by charging 50 ml, and a nitrogen-substituted chromium chloride aqueous solution was obtained from 1.19 g of metal chromium and 22.3 ml of a 2N hydrochloric acid ethanol solution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and after completion of the addition, the mixture was stirred for about 2.5 hours to obtain a blue precursor precipitate. This solution was oxidized to obtain a green oligomer solution. The oxidation reaction was completed in about 1 hour. next,
The solution was polymerized at 60 ° C. for 7 hours with stirring. The reaction solution was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing. The obtained polymer was 11.0 g (yield 93.0%), and the viscosity was measured to be [η] = 0.12.
When the molecular weight was measured by GPC, the molecular weight was about 40,00.
It was 0 (polystyrene conversion).

Elemental analysis value Cr9.6, P11.5, C55.0, H3.8 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Comparative Example 3 Using the same reactor as in Example 1, 10 g of diphenylphosphinic acid, 3.0 g of potassium hydroxide, and ethanol 5
A nitrogen-substituted diphenylphosphinic acid potassium salt solution was prepared by charging 0 ml thereof, and a nitrogen-substituted chromium chloride aqueous solution was obtained from 1.19 g of metal chromium and 22.3 ml of a 2N hydrochloric acid ethanol solution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and about 2.
After stirring for 5 hours, a pink precursor precipitate was obtained. Oxygen was blown into this solution using 300 ml of tetrahydrofuran and 50 ml of ion-exchanged water to carry out an oxidation reaction to obtain a green oligomer solution. The oxidation reaction was completed in about 1 hour. next,
The solution was polymerized at 60 ° C. for 5 hours with stirring. The reaction solution was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing. The obtained polymer was 12.0 g (yield 98%), the viscosity was measured to be [η] = 0.09, and the molecular weight was measured by GPC to be about 20,00.
It was 0 (polystyrene conversion).

Elemental analysis value Cr9.5, P11.8, C55.0, H4.0 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755m (s), 725s (s), 695s (s), 450w Example 4 Using the same reactor as in Example 1, 5 g of diphenylphosphinic acid, 300 ml of monochlorobenzene, 1.5 g of water were used. Potassium oxide and 70 ml of ethanol were placed in a flask and stirred at room temperature under a nitrogen stream to obtain a transparent potassium diphenylphosphinate salt solution. Next, under a nitrogen stream, charge the dropping funnel with 1.16 g of metal chromium and
22.9 ml of ethanol solution of hydrochloric acid in ethanol was injected with a syringe. Generation of hydrogen ceased in about 3 hours, and blue chromium chloride was obtained.
This chromium chloride ethanol solution was added dropwise to the flask, and after completion of the addition, the mixture was stirred for about 1 hour to obtain a pink precursor precipitate. By oxidizing this solution, a green low molecular weight polymer solution was obtained. The oxidation reaction was completed in about 1 hour. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, then heated to 117 ° C., and polymerized under stirring for 6 hours to obtain a viscous solution. Scaling was observed on the liquid surface of the inner wall of the flask, but when the deposit was stirred in tetrahydrofuran for a whole day and night, it completely dissolved. The polymer was completely dissolved in monochlorobenzene, and no precipitation of the polymer was observed even when cooled, but some products insoluble in monochlorobenzene were seen. After pouring the reaction solution into 1 liter of ethanol to precipitate the polymer,
Pass dried. The obtained polymer was 5.7 g (yield 95.0
%), And when the solution viscosity was measured, [η] = 0.46
Met. When the molecular weight was measured by GPC, the weight average molecular weight was about 180,000 (in terms of polystyrene). Further, when the dry weight of the insoluble matter was measured, the ratio to the total polymer was about 1%. Moreover, the concentrated solution of the polymer showed good spinnability and film-forming property. The results of elemental analysis and IR analysis of the polymer are shown below.

Elemental analysis value Cr9.9, P10.9, C55.5, H4.6 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1820vw
(B), 1770vw (b), 1475vw (s), 1130vs (s), 1050
s (s), 1020s (s), 1000m (s), 950w (b), 755m
(S), 725s (s), 695s (s), 450w Example 5 Using the same reactor as in Example 1, 5 grams of diphenylphosphinic acid, 300 ml of monochlorobenzene, 1.5 grams of potassium hydroxide, 70 ml of Ethanol was placed in a flask and stirred at room temperature under a nitrogen stream to obtain a transparent potassium diphenylphosphinate salt solution. Next, under a nitrogen stream, charge the dropping funnel with 1.16 g of metal chromium and
22.9 ml of the hydrochloric acid aqueous solution of was injected with a syringe. Generation of hydrogen ceased in about 4 hours, and blue chromium chloride was obtained. This chromium chloride aqueous solution was added dropwise to the flask, and after the completion of the addition, the mixture was stirred for about 2 hours to obtain a pink precursor precipitate. By oxidizing this solution, a green low molecular weight polymer solution was obtained. The oxidation reaction was completed in about 2 hours. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, heated to 115 ° C., and polymerized under stirring for 5 hours to obtain a viscous solution. Scaling was observed on the liquid surface of the inner wall of the flask, but when the deposit was stirred in tetrahydrofuran for a whole day and night, it completely dissolved. The polymer was completely dissolved in monochlorobenzene, and no precipitation of the polymer was observed even when cooled, but some products insoluble in monochlorobenzene were seen. The reaction solution was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing.
The obtained polymer was 5.6 g (yield 95.0%), and the solution viscosity was measured and found to be [η] = 0.45. or,
When the molecular weight was measured by GPC, the weight average molecular weight was about 1
It was 80,000 (polystyrene equivalent). Furthermore, when the dry weight of the insoluble matter was measured, the ratio to the total polymer was
It was about 1%. Moreover, the concentrated solution of the polymer showed good spinnability and film-forming property. Elemental analysis results of the polymer and
The IR analysis results are shown below.

Elemental analysis value Cr9.9, P10.9, C55.5, H4.6 Theoretical value Cr9.8, P11.0, C54.0, H4.8 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Example 6 Using the same reactor as in Example 1, 4.98 g of diphenylphosphinic acid, 1.5 g of potassium hydroxide, 300 ml of orthodichlorobenzene. Then, 50 ml of ethanol was charged and a diphenylphosphinic acid potassium salt solution was prepared under nitrogen substitution, while a chromium chloride ethanol solution was obtained from 0.52.9 g of metal chromium and 22.9 ml of a 1N hydrochloric acid ethanol solution under nitrogen substitution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and after the completion of the dropping, the solution was stirred for about 1.5 hours to obtain a pink precursor precipitate. This solution was oxidized to obtain a green low molecular weight polymer solution. The oxidation reaction was completed in about 40 minutes. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, heated to 120 ° C., and then polymerized with stirring for 4 hours to obtain a viscous solution. The produced polymer was completely dissolved in orthodichlorobenzene, and no precipitate other than potassium chloride could be confirmed. The reaction solution was poured into 1 liter of ethanol to cause precipitation, which was then dried by passing.
The obtained polymer was 5.74 g (yield 96.0%). Further, when the solution viscosity was measured, [η] = 0.47, and when the molecular weight was measured by GPC, the weight average molecular weight was about 180,000 (in terms of polystyrene). A product insoluble in orthodichlorobenzene was isolated, and its dry weight was measured and found to be 0.5% based on the total weight of the polymer. Also, the concentrated solution of the polymer showed good spinnability and film-forming property.

Elemental analysis value Cr9.9, P10.5, C55.9, H4.0 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755m (s), 725s (s), 695s (s), 450w Example 7 Using the same reactor as in Example 1, 4.98 g of diphenylphosphinic acid, 1.5 g of potassium hydroxide, 300 ml of metadichlorobenzene, Then, 25 ml of ethanol was charged and a potassium diphenylphosphinic acid salt solution was prepared under nitrogen substitution, while a chromium chloride ethanol solution was obtained from 22.9 ml of 0.59 g of metal chromium and 1N hydrochloric acid ethanol solution under nitrogen substitution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and the mixture was stirred for about 1.5 hours after completion of the dropping to obtain a pink precursor precipitate. This solution was oxidized to obtain a green low molecular weight polymer solution. The oxidation reaction was completed in about 35 minutes. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, then heated to 115 ° C. and polymerized with stirring for 5 hours to obtain a viscous solution. The produced polymer was completely dissolved in metadichlorobenzene. The reaction solution was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing. The polymer obtained was 5.7 g (yield 96.0%).
When the viscosity was measured, [η] = 0.5,
The weight average molecular weight was about 210,000 (in terms of polystyrene) as measured by GPC. A product insoluble in metadichlorobenzene was isolated, and its dry weight was measured to be 1.8% based on the total weight of the polymer. Also, the concentrated solution of the polymer showed good spinnability and film-forming property.

Elemental analysis value Cr10.0, P11.0, C54.5, H3.8 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755m (s), 725s (s), 695s (s), 450w Comparative Example 4 Using the same reactor as in Example 1, 10 g of diphenylphosphinic acid, 3.0 g of potassium hydroxide, 600 ml of nitrobenzene, ethanol 50 ml was charged and a diphenylphosphinic acid potassium salt solution was prepared under nitrogen substitution. On the other hand, 1.19 g of metal chromium, 2N hydrochloric acid ethanol solution 22.
An aqueous chromium chloride solution was obtained from 3 ml under nitrogen substitution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and after completion of the dropping, the solution was stirred for about 2.5 hours to obtain a precipitate of a blue precursor. This solution was oxidized to obtain a green oligomer solution. The oxidation reaction was completed in about 1 hour. Next, this solution was heated to 70 ° C. to remove ethanol as a monomer solvent, then heated to 118 ° C. while removing water, and then polymerized with stirring for 6 hours to obtain a viscous reaction solution. A large amount of scaling was observed on the liquid surface of the inner wall of the flask, and a large amount of products insoluble in nitrobenzene was found in the solution. Pass this reaction solution,
The excess residue was washed with water to remove potassium chloride. Liquid 1
After pouring into 1 liter of ethanol to precipitate the polymer,
Pass dried. The obtained soluble polymer was 7.3 g (yield 61%), and the viscosity was measured to be [η] = 0.
It was 12. When the molecular weight was measured by GPC, the weight average molecular weight was about 26,000 (in terms of polystyrene). The dry weight of the product insoluble in the organic solvent was as large as 30% based on the total weight of the polymer.

Elemental analysis value Cr10.1, P12.0, C54.5, H4.0 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w Comparative Example 5 Using the same reactor as in Example 1, 10 g of diphenylphosphinic acid, 3.0 g of potassium hydroxide, 600 ml of benzonitrile, Prepare 50 ml of ethanol and prepare a diphenylphosphinic acid potassium salt solution under nitrogen substitution.
Metal chrome 1.19 g, 2N hydrochloric acid ethanol solution 22.3 ml
From the above, an aqueous solution of chromium chloride was obtained under nitrogen substitution. This chromium chloride ethanol solution was added dropwise to the diphenylphosphinic acid potassium salt solution with stirring, and after completion of the dropping, the solution was stirred for about 2.5 hours to obtain a blue precursor precipitate. This solution was oxidized to obtain a green oligomer solution. The oxidation reaction was completed in about 1 hour. Then heat the solution to 70 ° C.,
Remove ethanol as a monomer solvent and remove water while removing 11
The mixture was heated to 6 ° C and then polymerized with stirring for 7 hours. A large amount of scaling was observed on the liquid surface of the inner wall of the flask, and a large amount of products insoluble in benzonitrile was found in the solution.
The reaction solution was passed, the excess residue was washed with water, and potassium chloride was removed. The liquid was poured into 1 liter of ethanol to precipitate a polymer, which was then dried by passing. The obtained soluble polymer weighed 3.46 g (yield 29%), and the viscosity was measured to be [η] = 0.13.
The weight average molecular weight was about 23,000 (converted to polystyrene). The dry weight of the product insoluble in the organic solvent was as large as 60% based on the total weight of the polymer.

Elemental analysis value Cr9.3, P11.1, C55.5, H4.9 Theoretical value Cr9.97, P11.88, C55.29, H4.45 IR characteristic absorption 3600w, 3400w (b), 3050w (s), 1960vw (b), 1900vw
(B), 1820vw (b), 1770vw (b), 1475vw (s), 1130
vs (s), 1050s (s), 1020s (s), 1000m (s), 950w
(B), 755 m (s), 725 s (s), 695 s (s), 450 w [Effect of the invention] The polymerization method of the present invention eliminates the need for oligomer isolation and purification operations which have been a problem in conventional methods. , And it is possible to obtain a high molecular weight polymer in a short time, and further, complicated operations such as dehydration of a solvent, which are required in the conventional method, are unnecessary.
The polymerization operation is significantly simplified.

[Brief description of drawings]

FIG. 1 shows the infrared absorption spectrum of the polymer obtained in Example 1 by the method of the present invention. FIG. 2 shows Example 1 (in the figure) and Comparative Example 1 (in the figure).
The gel permeation chromatography elution curve of the polymer obtained in 1. is shown. FIG. 3 shows Example 7 (in the figure) and Comparative Example 2 (in the figure).
3 shows a molecular weight distribution curve of the polymer obtained in step 1.

Claims (3)

[Claims] 1. A compound represented by the following general formula (1) M ^(a) X ₂ Y _a-2 (L) _n (1) (where M is a metal atom having a valence of 2 or more, and a is 2 of the metal atom). Representing the above valences, X and Y represent an organic group such as a halogen atom, an alkyl group or an alkoxy group, X and Y may be different or the same, L is a neutral ligand, or The anionic ligand is represented by the following structural formula (2), in which n is 0 or a total number of coordinations of the ligands is 2 or more. (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. ,
Z represents hydrogen or an alkali metal. ) At least one or more organic phosphorus compounds represented by
A solution of a mixed solvent consisting of a low boiling alcohol solvent and a high boiling substituted aromatic monocyclic hydrocarbon solvent is prepared, and the metal compound solution and the organic phosphorus compound solution are mixed to obtain the following structural formula (3). (Here, M represents a metal atom having a valence of 2 or more, a represents a valence of 2 or more of the metal atom, Y represents an organic group such as a halogen atom, an alkyl group or an alkoxy group, and L is a medium. Or anionic ligand, where n is 0 or 2
When n ₋₂ is 0 or less, the ligand L does not exist. Also, 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. Further, the arrow represents a coordinate bond to the metal M. ) After obtaining a reaction mixture solution containing a low molecular weight polymer consisting of a structural unit represented by the following, the low boiling point solvent is removed from the reaction solution, and then the solution is heated. Method for producing phosphinate. 2. The process according to claim 1, wherein the low boiling point solvent has a boiling point at atmospheric pressure of 100 ° C. or lower and the high boiling point solvent has a boiling point at atmospheric pressure of more than 100 ° C. Method. 3. A method according to claim 1, wherein heating is performed at 80 ° C. or higher.
Alternatively, the production method according to item 2.