JPH0519489B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an inorganic polymer compound containing early transition metals and a method for producing the same, and more specifically, the present invention relates to an inorganic polymer compound containing early transition metals and a method for producing the same, and more specifically, it is free of impurities such as carbon and hydrogen and exhibits desired electrical conductivity. This invention relates to an inorganic polymer compound containing early transition metals and an efficient method for producing the same. [Prior art and problems to be solved by the invention] Chalcogenide compounds of early transition metals such as niobium and tantalum are inorganic polymer compounds that exhibit interesting physical properties such as unique electromagnetic properties. It is attracting attention in the field. However, to date, the production of the above-mentioned inorganic polymer compounds has been limited to a method in which a mixture of early transition metal powder and chalcogen is subjected to a solid phase reaction at high temperatures of 500 to 1000°C or higher. was. Moreover, the inorganic polymer compounds obtained by this solid-phase reaction do not necessarily exhibit desired physical properties, and it has been difficult to produce ones with practical value. In addition, the present inventors have recently developed a method for synthesizing ethanedithiolate complexes corresponding to monomers and thermally decomposing them into inorganic polymers as a new method for producing the above-mentioned inorganic polymer compounds (patent application 60−
222719 specification). The inorganic polymer compound produced by this method can be given a desired electrical conductivity by selecting the thermal decomposition conditions. However, this inorganic polymer compound has a problem in that about 10 to 20% of carbon and hydrogen derived from thiolate and cation species remain. Therefore, the present inventors conducted further research and aimed to solve the drawbacks of the above-mentioned methods and produce the above-mentioned inorganic polymeric compound, the early transition metal chalcogenide, which has a high heat rate and excellent physical properties using a completely new method. After much consideration. As a result, we succeeded in producing an early transition metal chalcogenide with the desired physical properties by thermally decomposing a specific metal polysulfide complex. An object of the present invention is to provide an early transition metal chalcogenide, which is an inorganic polymer compound having excellent physical properties, and to provide an effective method for producing the same. [Means for Solving the Problems] That is, the present invention has the following compositional formula: MS _a C _b H _c (wherein M represents eobium, zirconium, vanadium, tantalum, or titanium; a is a real number from 2 to 4; b is a real number between 0 and 0.2,
c represents a real number from 0 to 5. _{) ,} and provides an inorganic polymer compound containing an early transition metal represented by the general formula A [M enyl arsonium or tetraalkylammonium, and x and y are positive real numbers. This provides a method to do so. The early transition metal-containing inorganic polymer compound of the present invention has a compositional formula represented by MS _a C _b H _c as described above, and has a particularly high proportion of carbon and hydrogen, i.e., b, c is small. In particular, the proportion of carbon, ie, b, is extremely small. Further, a, b, and c in this composition formula are as described above, and particularly preferably, a is 2 to 4, b is 0 to 0.5, and c is 0 to 5. Further, the early transition metal-containing inorganic polymer compound of the present invention may contain trace amounts of nitrogen (N) and lithium (Li) in the composition formula. According to the manufacturing method of the present invention, the above-mentioned general formula A
By simply thermally decomposing the early transition metal polysulfide complex represented by [M _x S _y ], the composition formula becomes MS _a C _b
The early transition metal-containing inorganic polymer compound of the present invention represented by H _c can be obtained efficiently. As a method for producing the early period transition metal polysulfide complex represented by the general formula A [M _x S _y ] used in the method of the present invention, for example, the general formula MX ¹ _n (wherein
M is the same as above, and X ¹ represents a halogen atom. m indicates the valence of M. ) and the general formula Li ₂ S ₄ (wherein d is 1 to 5
indicates the real number of ) (hereinafter referred to as "Method 1"), or the general formula MX ¹ _n (where M, X ¹ , m
is the same as above. ) metal halide represented by
Lithium polysulfide represented by the general formula Li ₂ S ₄ (wherein d is the same as above) and the general formula (C ₆ H ₅ ) ₄ PX ² (wherein X ² represents a halogen atom).
_{Halogenated tetraphenylphosphonium represented} ^by _{_} ^_ A method (hereinafter referred to as "method 2") in which a halogenated tetraalkylammonium represented by R is an alkyl group may be used (hereinafter referred to as "method 2") can be mentioned. According to method 1 described above, among the early transition metal polysulfide complexes represented by the general formula A [M _x S _y ], a complex represented by the general formula Li [M _x S _y ] where A is lithium is obtained. . In this complex, 3 to 4 molecules of the solvent used may be coordinated with lithium (Li). In order to produce the above-mentioned early transition metal polysulfide complex by this method 1, a halide (metal halide) of an early transition metal may be reacted with lithium polysulfide. Here, the metal halide is represented by the general formula MX ¹ _n , specifically NbCl ₅ , NbBr ₅ , ZrCl ₄ , Zrr ₄ ,
Examples include Vcl ₃ , VBr ₃ , TaCl ₅ , TaBr ₅ , TiCl ₄ , TiBr ₄ and the like. On the other hand, lithium polysulfide has the general formula Li ₂ Sd
Specifically, it is usually expressed as
Examples include Li ₂ S ₄ and Li ₂ S ₅ , but also Li ₂ S, Li ₂ S ₂ ,
There are also Li ₂ S ₃ , etc. Furthermore, in the case of a mixture of the above compounds, d is a non-integer. Note that this lithium polysulfide can be obtained by a method such as stirring metallic lithium and elemental sulfur in liquid ammonium. Method 1 described above proceeds by reacting a metal halide with lithium polysulfide, and in this case, it is preferable to use acetonitrile as a solvent, and the reaction proceeds efficiently when carried out in the presence of acetonitrile. In addition, the reaction temperature at this time is not particularly limited and varies depending on the type of the desired early transition metal polysulfide complex, etc.
Generally -40°C to +50°C, preferably 0°C to 20°C
It may be set within a range of approximately ℃. Furthermore, the quantitative ratio of metal halide and lithium polysulfide added during the reaction may be determined depending on the type of polysulfide complex to be produced, and is not particularly limited. Next, according to method 2, among the early period transition metal polysulfide complexes represented by the general formula A [M _x S _y ], one set [(C ₆ H ₅ ) ₄ P] in which A is tetraphenylphosphonium M _x S _y ], a set in which A is tetraphenylarsonium [(C ₆ H ₅ ) ₄ AS] [M _x
S _y ], or complexes of the general formula [R ₄ N] [M _x S _y ] where A is tetraalkylammonium (wherein R
is an alkyl group). In order to produce an early transition metal polysulfide complex by this method 2, in addition to the aforementioned metal halide and lithium polysulfide, a tetraphenylphosphonium halide, a tetraphenylarsonium halide, or a tetraalkyl halide is used. All you have to do is react with ammonium. Specific examples of the metal halide and lithium polysulfide include those mentioned above. In addition, halogenated tetraphenylphosphonium is represented by the general formula (C ₆ H ₅ ) ₄ PX ² , and specifically (C ₆ H ₅ ) ₄ PBr and (C ₆ H ₅ ) ₄ PCl are mentioned. It will be done. Tetraphenylarsonium halide is represented by the general formula (C ₆ H ₅ ) ₄ AsX ² , and specific examples include (C ₆ H ₅ ) ₄ AsCl, (C ₆ H ₅ ) ₄ AsBr, etc.
Tetraalkylammonium halides are generally
R ₄ NX ² , specifically (C ₂ H ₅ ) ₄ NCl,
Examples include (C ₂ H ₅ ) ₄ NBr, (C ₄ H ₉ ) NCl, and (C ₄ H ₉ ) NBr. In method 2, the reaction can proceed by simultaneously adding a metal halide, lithium polysulfide, and tetraphenyphosphonium halide (or tetraphenylarsonium halide or tetraalkylammonium halide) to the reaction system. It is also possible to prepare the general formula Li (M _x S _y ) using method 1 above, and then react it with halogenated tetraphenylphosphoninium (or halogenated tetraphenylarsonium or halogenated tetraalkylammonium). In either case, the reaction is preferably carried out in the presence of acetonitrile as a solvent, and the reaction temperature and the proportions of each raw material used in this case are based on the method 1 above. _There are _no particular _restrictions on _the complex ( _complex
Ph ₄ P salt) exists slightly more stably in air than the complex (Li salt of complex) represented by the general formula Li (M _x S _y ). According to method 1 or method 2 described above, crystals of the early transition metal polysulfide complex represented by the general formula A [M _x S _y ] as described above can be obtained. A more pure complex can be obtained by dissolving it in a solvent such as DMF and recrystallizing it. In the early transition metal polysulfide complex of the general formula A [M _x S _y ] obtained here, A is lithium (Li), tetraphenylphosphonium ((C ₆ H ₅ ) ₄ P), tetraphenyl arsonium ( (C ₆ H ₅ ) ₄ AS) or tetraalkylammonium (R ₄ N), and M is niobium, zirconium, vanadium, tantalum or titanium. Furthermore, x and y are not necessarily limited to integers,
Although there is no particular limitation as long as it is a positive real number, the ratio y/x of y and x is usually 2 to 4. Specific examples of this polysulfide complex include Li(Nb ₃ S ₁₂ ) when A is lithium, and [(C ₆ H ₅ ) ₄ P] when A is tetraphenylphosphonium.
There is [Nb ₃ S ₁₂ ]. In the method of the present invention, the general formula A obtained as described above is
The early transition metal polysulfide complex of [M _x S _y ] is used as a raw material and is thermally decomposed. The conditions for this thermal decomposition are not particularly limited and may be determined as appropriate depending on various situations, but usually the temperature is set in the range of 200 to 500°C, preferably 400 to 500°C, and the decomposition time is 1 to 12 hours. , preferably 2 to 4 hours. Also,
The atmosphere for thermal decomposition may be a vacuum or an inert gas atmosphere such as argon or nitrogen. The decomposition products produced by this thermal decomposition vary depending on the type of early transition metal polysulfide complex that is the raw material, decomposition temperature, and time, but all of them are inorganic materials containing early transition metals that are low in carbon and hydrogen. It is a polymer compound and has various electrical conductivities. Specifically, as mentioned above, the composition formula
It is represented by MS _a C _b H _c and has some crystallinity. [Effects of the Invention] As described above, according to the present invention, an inorganic polymer compound containing an early transition metal with extremely low content of hydrogen, carbon, etc., specifically, a metal chalcogenide of niobium, zirconium, vanadium, tantalum, or titanium. is obtained. The electrical conductivity of this early transition metal-containing inorganic polymer compound varies greatly depending on the thermal decomposition conditions during production and the type of metal contained, and it is easy to set the electrical conductivity to a desired value. In particular, the early transition metal-containing inorganic polymer compound of the present invention can be easily obtained in either crystalline, non-crystalline, or a mixture of both by selecting the manufacturing conditions. Therefore, it is easy to adjust the electrical conductivity and has excellent moldability. Therefore, the early transition metal-containing inorganic polymer compound of the present invention exhibits good electrical conductivity and can be effectively used in various electrical and electronic materials. [Example] Next, the present invention will be explained in more detail with reference to Examples. Please note that all of the following operations are performed under an argon atmosphere.
Alternatively, the reaction was carried out under vacuum, and the solvent was sufficiently dehydrated and then distilled under an argon atmosphere before use. Reference example 1 (Synthesis of lithium polysulfide (Li ₂ S ₄ ) Metallic lithium 0.66 g (95 mmol) and elemental sulfur (S atom, i.e. 1/8 ₈ ) 6.1 g (190 mmol)
was placed in a 500 ml three-necked flask and equipped with a mechanical stirrer. After bringing the reaction system to -78℃,
When ammonia gas was blown into the mixture while stirring, an orange-brown solution was produced. Blow in ammonia gas until the liquid ammonia becomes about 200ml.
Thereafter, the refrigerant was removed, and ammonia was distilled off at room temperature. After about 3 hours, ammonia will be distilled off.
An orange-brown solid was obtained. This was further dried under reduced pressure overnight to remove ammonia. 7.2 g of lithium polysulfide (Li ₂ S ₄ ) was obtained, sticking to the bottom of the container. Reference Example 2 (Synthesis of lithium polysulfide (Li ₂ S ₅ )) Same as Reference Example 1 except that the elemental sulfur (as S atom, that is, 1/8S ₈ ) was changed to 7.6 g (240 mmol). A similar operation was performed to obtain lithium polysulfide (Li ₂ S ₅ ) in high yield. Reference Example 3 6.3 g (36.2 g) of lithium polysulfide (Li ₂ S ₅ ) obtained in Reference Example 2 60 ml of an acetonitrile solution containing 2.9 g (10.7 mmol) of niobium pentachloride (NbCl ₃ ) was added dropwise in an ice bath to 100 ml of an acetonitrile solution of niobium pentachloride (NbCl 3 ).The color of the solution changed from brown to green in a few minutes.The solution was left overnight. After that, the brown precipitate (decomposed product containing LiCl and Nb) was removed by filtration, and the acetonitrile was distilled off under reduced pressure to obtain a green tar-like solid (5.8 g of polysulfide complex Li[Nb ₃ S ₁₂ ]).
I got it. Reference Example 4 To the solid obtained in Reference Example 3 above, 4.1 g of tetraphenylphosphonium bromide (C ₆ H ₅ ) ₄ PBr (10
A solution (20 ml) of acetonitrile (mmol) was added little by little, stirred, and left in the refrigerator overnight to obtain crude crystals, which were further purified under normal pressure to obtain 3.5 g of crystals.
I got it. The analysis results of this product were as follows. Far-infrared absorption spectrum (Nujol mull, cm
^-1 ) 492m, 369m, 350m, 325m, 290vw, 267w, 187w Ultraviolet-visible absorption spectrum (λmax, nm) _CH3CN solution 560, 612; _CH3OH solution 318, 380sh, 430sh These results and elemental analysis The results revealed that the above crystal was a polysulfide complex represented by the composition formula [(C ₆ H ₅ ) ₄ P] [Nb ₃ S ₁₂ ]. Reference Example 5 6.6 g (44.6 mmol) of lithium polysulfide (Li ₂ S ₄ ) obtained in Reference Example 1 and 3.4 g (14.8 mmol) of zirconium tetrachloride (ZrCl ₄ ) were reacted in acetonitrile at room temperature for 1 hour. As a result, 6.6 g of an orange polysulfide complex Li (Zr _x S _y ) was obtained.
It dissolves in to form a green solution, which is the color of S ₃ ^- . The complex also dissolved in methanol to form a yellow solution. In addition, the analysis results (ultraviolet-
The visible absorption spectrum) was as follows. Ultraviolet-visible absorption spectrum (λmax, nm) CH ₃ OH solution 402 Reference example 6 Vanadium trichloride (VCl ₃ ) 2.4 g (15 mmol)
was added to the acetonitrile suspension of 4.2 g (30.2 mmol) of lithium polysulfide (Li ₂ S ₄ ) obtained in Reference Example 1.
The color of the liquid changed from orange-brown to dark brown. After stirring for 1 hour, insoluble matter was filtered and the solvent was distilled off under reduced pressure to obtain 6.2 g of a black glassy solid (polysulfide complex Li(V _x S _y ). This product was mixed with acetonitrile or Dissolve in DMF to give a green solution,
It also dissolved in methanol to form a yellow solution. The analysis results (ultraviolet-visible absorption spectrum) of this product were as follows. Ultraviolet-visible absorption spectrum (λmax, nm) CH ₃ OH solution 256, 357, 450sh, 490sh, 590sh, 650sh Reference example 7 Lithium polysulfide (Li ₂ S ₄ ) obtained in Reference example 1 6.6 g (44.6 mmol) ) and tantalum pentachloride (TaCl ₅ ) (5.7 g (15.6 mmol)) were reacted in acetonitrile at room temperature for 1 hour to obtain 6.8 g of a reddish brown polysulfide complex Li (Ta _x S _y ). It dissolved in methanol to become a green solution, and dissolved in methanol to become a reddish-brown solution.The analysis results (ultraviolet-visible absorption spectrum) of this substance were as follows: Ultraviolet-visible absorption spectrum (λmax, nm) CH ₃ OH solution 310sh, 370sh, 520sh Example 1 The polysulfide complex Li[Nb ₃ S ₁₂ ] obtained in Reference Example 3 was tar-like and could not be put into the reaction vessel as a solid, so an acetonitrile solution was put into the reaction vessel. The solvent was distilled off under reduced pressure. The obtained green solid weighed 3.5 g. This was placed in a reaction tube, and after reducing the pressure inside the tube, the reaction tube was heated to 400°C in advance. Insert into the furnace,
A thermal decomposition reaction was carried out at 400°C under reduced pressure for 2 hours. Upon heating, the complex changed from green to reddish brown and then to black. As time went on, a yellow liquid adhered to the cooler parts of the reaction vessel. This yellow liquid solidified at room temperature, and melting point measurements revealed it to be elemental sulfur. Elemental analysis of 1.2g of the obtained black solid revealed that it contained 1.12% carbon, 2.15% hydrogen, 0.542% nitrogen, and 28.34% sulfur.
%, and 41.26% niobium, indicating that it is an inorganic polymer compound containing early transition metals. The properties of this product are shown in Table 1, and the X-ray diffraction pattern of the powder of this product is shown in FIG. Example 2 The polysulfide complex Li[Zr _x S _y ] obtained in Reference Example 5 was purified by filtration in the same manner as in Example 1, and 1.3 g of the obtained orange powder was subjected to a thermal decomposition reaction under the same conditions as in Example 1. Ta. As a result, 0.5 g of elemental sulfur and 0.6 g of yellowish brown solid were obtained. As a result of elemental analysis, this yellow-brown solid has 0.51% carbon, 1.18% hydrogen, and 36.82% sulfur.
%, zirconium 45.26%, and was found to be an inorganic polymer compound containing early transition metals.
The properties of this product are shown in Table 1, and the X-ray diffraction pattern of the powder of this product is shown in FIG. Example 3 The polysulfide complex Li (V _x S _y ) obtained in Reference Example 6 was purified by filtration in the same manner as in Example 1, and 2.2 g of the obtained black powder was subjected to a thermal decomposition reaction under the same conditions as in Example 1. As a result, 0.9g of elemental sulfur and 1.0g of black solid were obtained.As a result of elemental analysis, this black solid contained 0.93% carbon, 1.48% hydrogen, 0.54% nitrogen,
The content was 45.73% sulfur and 34.33% vanadium, indicating that it was an inorganic polymer compound containing early transition metals. The properties of this product are shown in Table 1, and the X-ray diffraction pattern of the powder of this product is shown in FIG. Example 4 The polysulfide complex Li [Ta _x S _y ] obtained in Reference Example 7 was purified by filtration in the same manner as in Example 1,
3.2 g of the obtained reddish brown powder was subjected to a thermal decomposition reaction under the same conditions as in Example 1. As a result, 0.5 g of elemental sulfur and 1.4 g of blackish brown solid were obtained. This dark brown solid is
Elemental analysis results: carbon 0.48%, hydrogen 1.18%, nitrogen
0.79%, sulfur 41.38%, tantalum 59.30%,
It was found that this is an inorganic polymer compound containing early period transition metals. The properties of this product are shown in Table 1, and the X-ray diffraction pattern of the powder of this product is shown in FIG. 【table】

[Brief explanation of the drawing]

1 to 4 are X-ray diffraction patterns of the decomposition products (early transition metal-containing inorganic polymer compounds) obtained in Examples 1 to 4, respectively, and θ in the figures is the Bragg angle.

Claims (1)

[Claims] 1. The compositional formula is MS _a C _b H _c (wherein M represents niobium, zirconium, vanadium, tantalum or titanium, a is a real number from 2 to 4, b is a real number from 0 to 0.2,
c represents a real number from 0 to 5. ) is an inorganic polymer compound containing an early transition metal. 2 General formula A [M _x S _y ] (wherein M represents niobium, zirconium, vanadium, tantalum or titanium, and A represents lithium, tetraphenyphosphonium, tetraphenylarsonium or tetraalkylammonium. , x, y are positive real numbers.) MS _a C _b
H _c (where M is the same as above, a is a real number from 2 to 4, b is a real number from 0 to 0.2, and c is a real number from 0 to 5). A method for producing a polymer compound.