JPH047350B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a novel metal phthalocyanine dicarboxylic acid or an alkyl ester thereof. Prior art and its problems Metal phthalocyanine has metal ions in a large π-electron conjugated system, which makes it conductive, photoconductive,
It has attracted attention as a material for energy conversion, electrodes, catalysts, etc., and various studies are being conducted on it. If this metal phthalocyanine is blended with a polymer, it is thought that it will be easier to form films and the like, and a wide range of highly functional polymer materials can be designed. However, metal phthalocyanines are common polymers (e.g. polyacrylic esters, etc.)
It also has low solubility in solvents such as toluene, making it extremely difficult to uniformly disperse it in a polymer, resulting in a drawback of low electrical conductivity. By the way, the present inventors previously synthesized a metal phthalocyanine tetracarboxylic acid in which a -COOH group was introduced into the benzene ring in the phthalocyanine ring for the purpose of increasing solubility and compatibility [H. Shirai
et.al., Makromol.Chem. 180 2073 (1979), etc.]. However, metal phthalocyanine tetracarboxylic acids are still insufficient in terms of solubility and compatibility. It is predicted that the solubility will be improved if this metal phthalocyanine tetracarboxylic acid is converted into an alkyl ester using an alcohol, but this metal phthalocyanine tetracarboxylic acid tetraalkyl ester has an alkyl moiety bonded to a benzene ring. As a result, steric hindrance occurs and the planar phthalocyanine rings are prevented from coming close to each other, resulting in a disadvantage that good electrical conductivity is not achieved. OBJECTS OF THE INVENTION The present invention was made in view of the above circumstances, and its main purpose is to provide a metal phthalocyanine compound that has high electrical conductivity and is easy to manufacture. These objects are achieved by the invention described below. That is, the present invention provides two benzene rings of the four benzene rings condensed in the phthalocyanine ring, respectively.
A metal phthalocyanine dicarboxylic acid and its alkyl ester characterized by having a carboxy group or an alkyloxycarbonyl group bonded thereto. Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The metal phthalocyanine compound in the present invention is
A carboxy group or an alkyloxycarbonyl group is bonded to two of the four benzene rings condensed into the phthalocyanine ring, respectively. In this case, the two benzene rings to which the carboxy group or alkyloxycarbonyl group are bonded may be adjacent to each other in the phthalocyanine ring, or may be adjacent to each other with one benzene ring interposed between them. It is usually obtained as a mixture of these two isomers. Furthermore, the position of the benzene ring to which the alkyl group or alkyloxycarbonyl group is bonded is usually 3-
position or 4-position, 3-position and 3'-position, 3-position and 4'-position, 4-position and 3'-position, 4-position and 4'-position, 3-position and 4'-position,
- position and 3"-position, 3-position and 4"-position, 4-position and 3"-position, and 4-position and 4"-position. It is usually obtained as a mixture of these isomers. In addition, the groups bonded to these positions on the benzene ring are carboxy groups or alkyloxycarbonyl groups, but under normal production conditions, both are carboxy groups or both alkyloxycarbonyl groups, and metal phthalocyanine dicarboxylic acid or its dialkyl ester. The alkyl portion of the alkyloxycarbonyl group may be substituted with other substituents, but is usually unsubstituted and has about 1 to 30 carbon atoms. Furthermore, there are no particular restrictions on the central metal atom,
In addition to Fe, Cu, Co, Ni, etc., V, Pb, Si, Ge,
Sn, Al, Ru, Ti, Zn, Mg, Mn, VO, etc. are possible. In this case, one or two other ligands may be further coordinated above and below the phthalocyanine ring. However, among these, Fe, Ni, Co or
Cu is preferred. Such a metal phthalocyanine compound is synthesized as follows. First, the metal phthalocyanine dicarboxylic acid alkyl ester is synthesized according to the following method. That is, trimellitic anhydride, phthalic anhydride, metal chloride, and urea are mixed and reacted in nitrobenzene using ammonium molybdate as a catalyst. In this case, trimellitic anhydride and phthalic anhydride are preferably used in equimolar amounts. This product is then purified, for example by Soxhlet extraction with methanol, and purified as MtPc(CONH ₂ ).
x (where Mt is a metal atom, Pc is a phthalocyanine ring, and x is an integer of 4 or less). The obtained MtPc(CONH ₂ )x is expressed in KOH,
For example, if hydrolysis is carried out at about 100°C, the precipitate is filtered, washed with water, and further purified with potassium hydroxide, MtPc(COOH)x can be obtained. This was then refluxed with SOCl ₂ , evaporated and washed, and dried to form MtPc.
(COCl) Get x. After this, it is reacted with an alcohol corresponding to the alkyl of the alkyl ester at, for example, 100°C for about 10 hours, and the product is filtered, washed, and dried.
MtPc(COOR)x, where R is an alkyl group, is obtained. Then, this MtPc(COOR)x is dissolved in, for example, benzene, and developed with a silica gel column or the like using benzene/ethanol as a developing solvent.
Evaporation and drying of the first liquid yields MtPc(COOR) ₂ . In this way, MtPc(COOR) ₂ is, as mentioned above, a mixture of each isomer, and regardless of the number of carbon atoms in the alkyl group, its infrared absorption spectrum shows υ(C=O). 1720cm ^-1 , υ(CH ₂ )
2900cm ^-1 exists. On the other hand, in order to synthesize metal phthalocyanine dicarboxylic acid, the above-mentioned MtPc(COOR) ₂ may be refluxed and hydrolyzed in an approximately 1N potassium hydroxide-ethanol solution, followed by separation and purification. Alternatively, preferably equimolar amounts of 2,2-bis(p-trimellitic acid phenyl)propane dianhydride and phthalic anhydride are reacted in the same manner as above, extracted with methanol, etc., purified, and purified in the same manner. If it is hydrolyzed and purified, MtPc(COOH) ₂ can be obtained. In this case, each COOH is bonded to every other benzene ring. MtPc obtained by each of these methods
(COOH) ₂ both indicate υ(C=O) of 1680 cm ^-1 . Note that MtPc(COOH) ₂ in which the above COOH is bonded to adjacent benzene rings may be esterified in the same manner as described above to obtain MtPc(COOR) ₂ . Specific effects of the invention The metal phthalocyanine compound in the present invention is
Since a carboxy group or an alkyloxycarbonyl group is bonded to each of the two benzene rings of the phthalocyanine ring, the solubility is lower than that of a tetracarboxylic acid in which these groups are absent or substituted with four of these groups. improves. That is, it is extremely well soluble in organic solvents such as chloroform, benzene, toluene, dioxane, dimethylformamide, and methyl ethyl ketone. Furthermore, it has extremely high compatibility with resins such as epoxy resins, vinyl chloride-vinyl acetate copolymers, polyurethanes, and the like. Furthermore, unlike tetracarboxylic acid tetraalkyl esters, the approach of the planar phthalocyanine ring is not inhibited by steric hindrance, and the conductivity is not inhibited. Specific Examples of the Invention The present invention will now be described in more detail with reference to Examples. Example 1 8.2 g (0.06 mol) of trimellitic anhydride, 10.6 g (0.06 mol) of phthalic anhydride, nickel chloride (3.7×10 ^-2 mol), and 60 g (1.0 mol) of urea were mixed,
The mixture was placed in a 500 ml three-necked separable flask and reacted in 100 ml of nitrobenzene at 160 to 170°C for 2 hours using ammonium molybdate as a catalyst. After the reaction, the solid product was diluted with methanol.
Unreacted substances and nitrobenzene were removed by time Soxhlet extraction, and the mixture was dried under reduced pressure at 50°C. IR (KBr): 1650cm ^-1 [υ(C=O) of -CONH ₂ ] Put the obtained NiPc (CONH ₂ ) x 20g, potassium hydroxide 500g and pure water 500g into a three-necked flask (No. 2), and add 100 Stirred at ℃ for 24 hours. After the reaction, the product is filtered through a G4 filter,
It was dissolved in about 3 to 4 g of water and passed through a G4 filter to remove insoluble matter. This filtrate was made acidic (PH2) with 6N hydrochloric acid, and the precipitated blue precipitate was filtered off. This precipitate was washed with pure water until the filtrate became neutral. Next, this product was dissolved in 2-5% potassium hydroxide 3-4, purified in the same manner as above, dried at 150 ° C., thoroughly ground in a mortar,
It was further dried under reduced pressure at 70°C to obtain NiPc(COOH)x. Yield: 30-40% IR (KBr): 1720 cm ^-1 [υ(C=O) of -COOH] Next, 5 g of this NiPc(COOH) was refluxed with 20 ml of thionyl chloride for 10 hours. After the reaction, thionyl chloride was removed by evaporation, thoroughly washed with dehydrated benzene, and then dried under reduced pressure at 50°C. 5 g of the obtained NiPc(COCl) and 20 ml of decyl alcohol were mixed and reacted at 100° C. for 10 hours. Methanol was added to the product, filtered, washed thoroughly with methanol, and dried under reduced pressure at 50°C. After dissolving the solid matter in benzene and removing insoluble matter through gravity filtration, the filtrate is evaporated,
The residue was dried under reduced pressure at 50°C to obtain NiPc (COOC ₁₀ H ₂₁ ).
I got x. IR (KBr): 1720cm ^-1 [−COOC ₁₀ H ₂₁ υ (C=
O)] Thereafter, NiPc(COOC ₁₀ H ₂₁ )x was dissolved in benzene and separated by thin layer chromatography using benzene ethanol (V/V) 3/1 as a developing solvent. In addition, NiPc (COOC ₁₀ H ₂₁ ) x was dissolved in benzene and developed in a column packed with silica gel WaKogel C200 using benzene/ethanol (V/V) 3/1 as a developing solvent. was collected and evaporated. The residue was dried under reduced pressure at 50°C. The infrared absorption spectrum of this NiPc(COOC ₁₀ H ₂₁ )x is υ (C=O) 1720 cm ^-1 , υ (CH ₂ ) 2900
It was cm ^-1 . In addition, the electronic spectrum has the following λmax (logε)
It was hot. 664nm (4.32), 606nm (4.47), 470nm (3.35). Furthermore, the elemental analysis values were as follows.

[Table] Note that NiPc(COOC ₁₀ H ₂₁ ) ₂ is a mixture of the above-mentioned isomers. Example 2 In Example 1, NiCl ₂ used as a raw material was
In exactly the same manner except that CuCl ₂ was changed, CuPc
(COOC ₁₀ H ₂₁ ) Got ₂ . IR: υ (C=O) 1720 cm ^-1 υ (CH ₂ ) 2900 cm ^-1 λmax (log ε) 681 nm (4.94) 673 nm (4.95) 611 nm (4.85)

[Table] Example 3 In Example 1, the central metals were Fe, Co, Ni,
When replacing Cu and also changing the number of carbon atoms in the alcohol used for esterification to an arbitrary number below 30, similar υ (C=O) and υ (CH ₂ ) were obtained, and from the results of elemental analysis, MtPc It was confirmed that (COOR) ₂ was obtained. Example 4 NiPc(COOC ₁₀ H ₂₁ ) ₂ of Example 1 was refluxed in a 1N potassium hydroxide-ethanol solution for about 2 hours. The product was separated and purified in the same manner as in Example 1. IR (KBr): 1680 cm ^-1 [-COOH υ (C=O)] This NiPc (COOH) ₂ 2.5 × 10 ^-5 mol was added to 20 ml of
Dissolved in 0.01N potassium hydroxide aqueous solution, 0.05N
While back titrating with hydrochloric acid, check the pH of the system.
Measured with RESARCH model 701A. In addition, the pH for added hydrochloric acid was recorded, a titration curve was determined, and the COOH concentration was calculated. Found14.31% (Calc.13.64%) The results of the electronic spectrum and elemental analysis are as follows. λmax (logε) 679nm (4.02) 603nm (4.11) 472nm (3.17)

[Table] Example 5 In Example 4, CuPc(COOC ₁₀ H ₂₁ ) ₂ was used to obtain CuPc(COOH) ₂ . IR (KBr): υ (C=O) 1680cm ^-1 λmax (logε) 690nm (4.17) 605nm (4.55)

[Table] Similar IR values were obtained for Fe and Co, and elemental analysis confirmed that MtPc(COOH) ₂ was obtained. Example 6 2,2-bis(p-phenyl trimellistate)
30 g (0.06 mol) of propane dianhydride and 10.6 g (0.06 mol) of phthalic anhydride were added in the same manner as in Example 1.
It was reacted with NiCl ₂ and urea, and Soxhlet extracted with methanol. After drying, 5 g of the product was dissolved in as little concentrated sulfuric acid as possible and poured gently into a beaker containing ice to allow precipitation. Pure water was added to this so that the volume was 1. The precipitate was filtered and washed with pure water until neutral. After drying under reduced pressure, with 50% ethanolic KOH
Refluxed for 24 hours. The obtained material was purified in exactly the same manner as in Example 1. IR (KBr): 1680 cm ^-1 [υ (C=O) of −COOH] This elemental analysis and electronic spectrum are
It was the same as Example 4. In addition, COOH of the compound in this case is at the 3-position,
It was attached to the 3″- or 4″-position.

Claims (1)

[Claims] 1. A metal phthalocyanine dicarboxylic acid and its alkyl ester, characterized in that a carboxy group or an alkyloxycarbonyl group is bonded to two of the four benzene rings condensed in the phthalocyanine ring, respectively.