Composite, method for producing bisphenols, and curing agent

Abstract

To provide a complex of a heteropoly acid compound that contains a low proportion of crystal water to affect catalysis or film properties and does not show reversible change in the amount of crystal water.SOLUTION: A complex contains a heteropoly acid compound (A) and a compound (B) having at least one amide group and at least one hydroxy group. The heteropoly acid compound (A) is a compound selected from the group consisting of heteropoly acid containing tungsten and a salt thereof and heteropoly acid containing molybdenum and a salt thereof, and the weight change in the range of 20°C to 200°C is less than 1%.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composite containing a heteropolyacid compound. The present invention also relates to a method for producing bisphenols using the composite as a catalyst, or a curing agent using the composite. [Background technology]

[0002] Heteropolyacid compounds have strong acid strength and oxidizing power and are mainly used as solid acid catalysts. Patent Document 1 discloses a method for producing bisphenols using a heteropolyacid or a salt thereof as a catalyst. However, heteropolyacid compounds are usually hydrates and contain water of crystallization. If the amount of water of crystallization is large, problems such as a decrease in yield can occur when using a heteropolyacid compound as a catalyst.

[0003] Furthermore, Patent Document 2 proposes a method for easily producing a composite of a heteropolyacid compound and a polymer, as a use of heteropolyacid compounds other than as catalysts, and a composite obtained by this method that has high transparency and a desired refractive index. The technology described in Patent Document 2 relates to applications that utilize the solubility and high refractive index of heteropolyacid compounds. However, when heteropolyacid compounds are incorporated into resins, etc., the water of crystallization can sometimes cause a decrease in film properties. Furthermore, while the water of crystallization can be reduced by drying, the hydration structure is reversible, so there is a problem in that the water of crystallization returns to its original state over time. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2-45439 [Patent Document 2] International Publication No. 2013 / 191130 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made in consideration of the above-mentioned problems of the conventional art, and aims to provide a technology using a heteropolyacid compound which has little water of crystallization that affects catalytic activity and membrane properties, and which does not undergo reversible changes in the amount of water of crystallization. [Means for solving the problem]

[0006] As a result of extensive research into heteropolyacid compounds, the inventors have discovered that by combining a heteropolyacid compound with a compound having a specific structure, it is possible to prevent the heteropolyacid from forming a hydrated structure and to obtain a heteropolyacid compound composite that does not undergo reversible changes in water of crystallization.

[0007] To solve the problems, a first aspect of the present invention is a composite comprising a heteropolyacid compound (A) and a compound (B) having at least one amide group and at least one hydroxyl group, wherein the heteropolyacid compound (A) is one or more compounds selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof, and wherein the composite exhibits a weight change of less than 1% at temperatures between 20°C and 200°C. [Effects of the Invention]

[0008] According to the embodiment of the present invention, it is possible to obtain a heteropolyacid compound-containing composite having a small amount of crystallization water and in which the amount of crystallization water does not change reversibly or only slightly. The composite according to this embodiment of the present invention can be used as a catalyst in the synthesis of organic compounds, or can be suitably incorporated into coating films as a functional substance. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment based on the present invention will be described. (First embodiment: composite) The composite of this embodiment is a composite containing a heteropolyacid compound (A) and a compound (B).

[0010] The heteropolyacid compound (A) is a compound selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof. The compound (B) is a compound having at least one amide group and one hydroxyl group.

[0011] The compound (B) preferably has a structure represented by the chemical formula (1), for example. [ka]

[0012] Here, R1 and R2 in formula (1) may be selected appropriately. Examples of R1 and R2 each independently include a hydrogen atom, a hydroxy group, a hydroxyalkyl group, a hydroxyalkenyl group, a hydroxyaralkyl group, a hydroxyaryl group, a carboxy group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, and an aryl group.

[0013] Furthermore, the composite of this embodiment exhibits a weight change of less than 1% at temperatures between 20°C and 200°C.

[0014] In this embodiment, by forming a complex between the heteropolyacid compound (A) and the compound (B), the amide group and the hydroxyl group of the compound (B) act on the binding sites of the crystal water of the heteropolyacid compound, resulting in irreversible bonding. As a result, the composite of this embodiment can suppress the weight change at 20°C to 200°C to less than 1%. In other words, the composite of this embodiment can suppress the hydration of the crystal water and the change in the crystal water due to temperature.

[0015] Here, the weight change of the composite can be determined by thermogravimetric analysis-differential thermal analysis (TG-DTA) in which the composite is heated from 20°C to 200°C in the presence of oxygen.

[0016] (Second embodiment: method for producing bisphenols) The method for producing bisphenols according to this embodiment is characterized in that the composite according to this embodiment is used as a solid acid catalyst.

[0017] That is, in the method for producing bisphenols of this embodiment, the complex of this embodiment is used as a catalyst when a carbonyl compound is reacted with a phenol to produce bisphenols. This makes it possible to produce bisphenols in good yield (see Examples below).

[0018] (Third embodiment: curing agent) The composite of this embodiment may be used as a curing agent. When used as a curing agent, a composite using a compound (B) having a reactive group is used.

[0019] Each compound will be explained in more detail below. (Heteropolyacid compound (A)) The heteropolyacid compound used in this embodiment is selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof.

[0020] Non-limiting examples of tungsten-containing heteropolyacids and molybdenum-containing heteropolyacids include tungstosilicic acid (H4[SiW 12 O 40 ], etc.), phosphotungstic acid (H3[PW 12 O 40 ], etc.), silicomolybdic acid (H4[SiMo 12 O 40 ], etc.), phosphomolybdic acid (H3[PMo 12 O 40 ], etc.), phosphotungstomolybdic acid (H3[PW 12 -xMoxO 40 ], etc.), and phosphorus vanadomolybdic acid (H3[PV 12 -xMoxO 40 ] etc. Specific examples of the salts of these heteropolyacids include alkali metal salts such as sodium and potassium, and ammonium salts.

[0021] Here, the heteropolyacids and salts thereof may be hydrates, anhydrides obtained by heat-treating hydrates, or forms with a low content of water of crystallization. The heteropolyacid compound (A) may be one of the heteropolyacids or salts thereof, or a combination of two or more of the heteropolyacids or salts thereof.

[0022] (Compound (B)) The compound (B) used in this embodiment has at least one amide group and one hydroxyl group.

[0023] The compound (B) preferably has a structure represented by formula (1). With the structure represented by formula (1), the amide group and the hydroxy group are at an appropriate distance from each other, and therefore, it is believed that the complex can be efficiently complexed.

[0024] Examples of the compound (B) having such a structure include N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)acetamide, N-(2-hydroxyethyl)propionamide, N-(2-hydroxyethyl)lactamide, N-(2-hydroxyethyl)hexadecanamide, N,N-bis(2-hydroxyethyl)octanamide, N-(2-hydroxyethyl)acrylamide, N-(hydroxymethyl)acrylamide, and N,N,N',N'-tetrakis(2-hydroxyethyl)hexanediamide.

[0025] When the composite of this embodiment is used as a solid acid catalyst, it is preferable that compound (B) does not have a reactive group. Therefore, N-(2-hydroxyethyl)acetamide or N-(2-hydroxyethyl)propionamide can be preferably used as the composite used as the solid acid catalyst.

[0026] When compound (B) has a reactive group (when at least one of R1 and R2 is a reactive group), the composite of this embodiment can be used as a curing agent. The reactive group can be appropriately selected from, for example, a carbon-carbon double bond, an epoxy group, a silanol group, a peroxide, an azo compound, etc.

[0027] The composite of the present embodiment is mixed with a monomer suitable for each reactive group to carry out a polymerization reaction, during which the composite of the present embodiment acts as a curing agent to obtain a resin composition having a crosslinked structure.

[0028] The ratio of the heteropolyacid compound (A) to the compound (B) constituting the composite can be appropriately selected. It is preferable to composite the compound (B) in approximately the same molar amount as the number of moles of water of hydration of the heteropolyacid compound (A) alone. The method for producing the composite of this embodiment is not particularly limited, and it can be prepared according to a known production method.

[0029] When the compound (B) shown in formula (1) is used as the compound (B), the composite is produced, for example, as follows: That is, the heteropolyacid compound (A) is dissolved in a solvent such as an alcohol or an ether, and the compound (B) is mixed therewith to produce the composite. Alternatively, when the compound (B) is a liquid, the heteropolyacid compound (A) and the compound (B) are directly mixed to produce the composite.

[0030] At this time, the complex precipitated in the mixed solution or the complex directly mixed is washed with a solvent such as water, alcohols, or ethers. The complex is then recovered from the solvent used for washing by centrifugation or filtration, and further dried to obtain a complex of heteropolyacid compound (A) and compound (B). The mixing time is preferably about 30 minutes to 3 days after addition. The drying temperature is preferably 50 to 150°C, and the drying time is preferably about 1 hour to 3 days.

[0031] (others) The present disclosure may also have the following configuration. (1) A method for producing a polymerizable composition comprising a heteropolyacid compound (A) and a compound (B) having at least one amide group and at least one hydroxyl group, the heteropolyacid compound (A) is one or more compounds selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof, A composite that exhibits a weight change of less than 1% at temperatures between 20°C and 200°C. (2) A complex in which the compound (B) is a compound having a structure represented by formula (1). [ka] (3) A method for producing bisphenols, comprising reacting a carbonyl compound with a phenol using the composite of the present disclosure as a solid acid catalyst to produce bisphenols. (4) A curing agent using the composite of the present disclosure, wherein the compound (B) has a reactive group. [Example]

[0032] The present invention will be described in more detail below with reference to examples and comparative examples. Example 1 <Example 1-1> In Example 1-1, an aqueous solution (70 wt %) of tungstosilicic acid tridecahydrate (SiW12, manufactured by Nippon Shinkinzoku Co., Ltd.) was used as the heteropolyacid compound (A).

[0033] Furthermore, N-(2-hydroxyethyl)acrylamide (HEAA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used as compound (B). Then, the heteropolyacid compound (A) and the compound (B) were mixed in a weight ratio of 80:20 to prepare a mixed solution containing a complex.

[0034] The prepared mixture was stirred for 3 hours and then dried overnight in an environment of 100°C to obtain a solid composite of Example 1-1. The weight change of the obtained composite at 20℃-200℃ was 0.54%.

[0035] <Examples 1-2 to 1-5, Comparative Examples 1-1 to 1-3> The composites of Examples 1-2 to 1-5 and Comparative Examples 1-1 to 1-3 were obtained under the same conditions as in Example 1-1, except that the heteropolyacid compound (A) and compound (B) were changed to the substances shown in Table 1. The weight change of each of the obtained composites at 20 to 200°C is also shown in Table 1. The phosphotungstic acid used as the heteropolyacid compound (A) was manufactured by Nippon Shinkinzoku Co., Ltd. All of the substances used for the compound (B) shown in Table 1 were manufactured by Tokyo Chemical Industry Co., Ltd. [Table 1]

[0036] As can be seen from Table 1, in Examples 1-1 to 1-5, in which a compound having one or more amide groups and one or more hydroxyl groups was used as compound (B), the weight change at 20-200°C was less than 1%, indicating that reversible weight change was suppressed.

[0037] Example 2 Example 2 is an example of producing bisphenols by reacting a carbonyl compound with a phenol.

[0038] In the following examples, acetone was used as the carbonyl compound.

[0039] <Example 2-1> A reactor equipped with a reflux condenser and a stirrer was charged with 1.88 g (20 mmol) of phenol and 0.1 g (0.03 mmol) of the solid complex obtained in Example 1-2, and 0.12 g (2.0 mmol) of acetone was added, followed by reaction at 80°C for 6 hours. The yield of bisphenol A was 60%.

[0040] In this example, the yield of bisphenol A was calculated from the results of gas chromatography using the following formula.

[0041] Bisphenol A yield (%) = (bisphenol A produced (mol) ÷ amount of acetone charged (mol)) × 100

[0042] <Comparative Example 2-1> A reactor equipped with a reflux condenser and a stirrer was charged with 1.88 g (20 mmol) of phenol and 0.095 g (0.03 mmol) of tungstosilicic acid 30 hydrate, and 0.12 g (2.0 mmol) of acetone was added, followed by reaction at 80°C for 6 hours. The yield of bisphenol A was 23%.

[0043] As can be seen from a comparison between Example 2-1 and Comparative Example 2-1, when producing bisphenols, the yield of bisphenol A is significantly higher when the composite based on the present invention is used as a catalyst than when a heteropolyacid compound (Comparative Example 2-1) is used alone as a catalyst.

[0044] Example 3 Example 3 is an example that shows the advantages of using the composite of the present invention as a curing agent. <Example 3-1> A composition was prepared by mixing 90 parts by weight of 2-hydroxyethyl methacrylate, 3 parts by weight of azobisisobutyronitrile (AIBN), and 7 parts by weight of the complex obtained in Example 1-1.

[0045] The composition was allowed to stand overnight in a nitrogen atmosphere at an atmospheric temperature of 60°C, yielding a solid resin composition.

[0046] When the obtained resin composition was immersed in water, it did not dissolve and maintained its shape.

[0047] <Comparative Example 3-1> A resin composition was prepared under the same conditions as in Example 3-1, except that the composite obtained in Example 1-1 was not added. When the obtained resin composition was immersed in water, it dissolved.

[0048] <Comparative Example 3-2> A resin composition was prepared under the same conditions as in Example 3-1, except that silicotungstic acid 30-hydrate was used instead of the composite obtained in Example 1-1. When the obtained resin composition was immersed in water, it dissolved.

[0049] As can be seen from a comparison between Example 3-1 and Comparative Examples 3-1 and 3-2, when the composite of the present invention in which compound (B) has a reactive group was mixed, the hardness of the resin composition was significantly increased, indicating that the composite of the present invention can be used as a curing agent.

Claims

1. The composition contains only two types of compounds: a heteropolyacid compound (A) and a compound (B) having at least one amide group and at least one hydroxyl group; the heteropolyacid compound (A) is one or more compounds selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof, the compound (B) is any one of N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)acetamide, N-(2-hydroxyethyl)propionamide, N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)acetamide, and N-(hydroxymethyl)propionamide; A composite characterized by a weight change of less than 1% at temperatures between 20°C and 200°C.

2. A method for producing bisphenols by reacting a carbonyl compound with a phenol using the composite according to claim 1 as a solid acid catalyst. A method for producing bisphenols.

3. A curing agent using the composite according to claim 1, A curing agent characterized in that the compound (B) is either N-(2-hydroxyethyl)acrylamide or N-(hydroxymethyl)acrylamide.

4. The composition contains a heteropolyacid compound (A) and a compound (B) having at least one amide group and at least one hydroxyl group, the heteropolyacid compound (A) is one or more compounds selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof, the compound (B) is any one of N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)acetamide, N-(2-hydroxyethyl)propionamide, N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)acetamide, and N-(hydroxymethyl)propionamide; a method for producing bisphenols by reacting a carbonyl compound with a phenol using, as a solid acid catalyst, a composite characterized by a weight change of less than 1% at 20°C to 200°C; A method for producing bisphenols.

5. The composition contains a heteropolyacid compound (A) and a compound (B) having at least one amide group and at least one hydroxyl group, the heteropolyacid compound (A) is one or more compounds selected from the group consisting of tungsten-containing heteropolyacids and salts thereof, and molybdenum-containing heteropolyacids and salts thereof, the compound (B) is any one of N-(2-hydroxyethyl)acrylamide, N-(2-hydroxyethyl)acetamide, N-(2-hydroxyethyl)propionamide, N-(hydroxymethyl)acrylamide, N-(hydroxymethyl)acetamide, and N-(hydroxymethyl)propionamide; A curing agent using a composite characterized in that the weight change at 20°C to 200°C is less than 1%, A curing agent characterized in that the compound (B) is either N-(2-hydroxyethyl)acrylamide or N-(hydroxymethyl)acrylamide.

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