JPS6328067B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel and useful polyglycidyl compounds,
N,N,N',N'-tetraglycidyl (3-aminomethyl-3,5,5-trimethylcyclohexylamine) (hereinafter abbreviated as N,N,N',N'-tetraglycidylisophoronediamine) and It relates to its manufacturing method. Many N-glycidyl compounds have been known that are produced from the reaction of amines and epichlorohydrin. For example, U.S. Patent No.
In 2951822, N-glycidylamino compounds were prepared from aniline and epichlorohydrin using British Patent No. 2951822.
816923 produced N,N'-diepoxide by the reaction of 4,4'-bis(aminomethyl)diphenylmethane and epichlorohydrin, and in Japanese Patent Publication No. 11312-1973, N,N'-diepoxide was produced by the reaction of aminomethylated diphenyl oxide with epichlorohydrin. Japanese Patent Publication No. 49-14211 describes the preparation of polyglycidyl xylylene diamine from xylylene diamine and epichlorohydrin. The present inventors investigated the physical properties and synthesis of cured products of various polyglycidyl diamine compounds, and found that the N,N , N',N'-tetraglycidyl compound and an epoxy resin curing agent have been found to exhibit a high heat distortion temperature, and the present invention has been achieved based on this finding. That is, the present invention provides N expressed by the following formula,
Relating to N,N',N'-tetraglycidylisophoronediamine. The above polyglycidyl compound according to the present invention generally has the formula () Isophoronediamine represented by the formula () Epichlorohydrin represented by
Alternatively, it can be obtained by conducting an addition reaction in the presence of a quaternary ammonium compound, followed by a ring-closing reaction, and separating and removing the precipitate generated after the reaction and unreacted epichlorohydrin. The present inventors further studied the method for producing the polyglycidyl compound according to the present invention, and the following (a)
It has been found that N,N,N',N'-tetraglycidylisophoronediamine having excellent storage stability can be obtained by employing the steps (e) to (e). That is, (a) water and/or a quaternary ammonium compound is present in epichlorohydrin, and isophoronediamine is added dropwise at a temperature of 60°C or lower to cause an addition reaction; (b) the above reaction product is added at a temperature of 60°C or lower. (3) After removing the precipitate from the reaction product, unreacted epichlorohydrin is collected and removed at a temperature of 100°C or less; (4) The target product is dissolved in the product, but not in water. Wash by adding an insoluble organic solvent, (e) Next, after washing with water, the organic solvent and volatile components in the product are removed at a temperature of 100°C or less. First, the first step is a step in which isophorone diamine and epichlorohydrin in an amount equivalent or more to the primary amine of isophorone diamine are subjected to an addition reaction in the presence of water and/or a quaternary ammonium compound as a catalyst. In this reaction, epichlorohydrin is used in an amount of 6 to 15 mol per mol of isophoronediamine, and water and a quaternary ammonium compound are used as catalysts per mol of isophoronediamine.
They are used in the range of 0.5 to 10 mol and 0.1 to 1.0 mol, respectively. It is desirable that the reaction be carried out at a reaction temperature of 60°C or lower, preferably 20 to 40°C. For this purpose, it is desirable to drop isophorone diamine into a mixture of epichlorohydrin, water and/or a quaternary ammonium compound while removing the reaction heat so that the reaction temperature does not exceed the above-mentioned temperature. After the dropwise addition of isophoronediamine, the reaction rate of the addition reaction, that is, the tertiaryization rate of the amine,
It must be carried out sufficiently until it reaches 95% or more, preferably 98% or more. The tertiary amine can be quantitatively determined by conventional analytical methods. In the above reaction, if the amount of epichlorohydrin is less than 6 moles, the viscosity of the final product, polyglycidyl isophorone diamine, will increase significantly, which is not preferred. Moreover, if the amounts of water and the quaternary ammonium compound are too large, side reactions are likely to occur, which is undesirable and has an adverse effect on the quality of the final product, polyglycidyl isophorone diamine. The second step is a step in which dehydrochlorination is performed by adding an alkali to the chlorohydrin compound, which is the addition reaction product of the first step, and the compound is ring-closed to produce an epoxy ring. For the alkali, use a solid or an aqueous solution with a concentration of 40% by weight or more, and the reaction temperature is 60%.
It is necessary to keep the temperature below ℃. If the temperature is higher than this, reactions between the generated epoxy groups and water and side reactions of epichlorohydrin occur, resulting in loss of epichlorohydrin and unfavorable results in product quality. The third step is a step of removing the precipitate (generally sodium chloride) generated in the dehydrochlorination reaction and recovering unreacted epichlorohydrin. In order to remove the sodium chloride produced in the dehydrochlorination reaction, water is added to dissolve the sodium chloride and separated into an oil phase and an aqueous phase. After discarding the aqueous phase, further water is added to separate the oil phase. Wash with water. Note that in this step, a method may be used in which sodium chloride is removed by filtration before adding water, and then washing is performed with water. The appropriate amount of water used in this water washing step is about 50 to 300 parts by weight per 100 parts by weight of the oil phase.
There is no particular limit to this amount. However, since there is a lot of loss due to wastewater treatment and dissolution of epichlorohydrin in the wastewater, it is desirable to keep the amount as small as possible. The next recovery of unreacted epichlorohydrin is distilled off under reduced pressure. During this recovery operation, it is necessary to maintain the temperature inside the reaction vessel at 100°C or lower, preferably at 80°C or lower. The recovered epichlorohydrin can be used again in the reaction. In this step, it is also possible to adopt a method in which unreacted epichlorohydrin is first recovered and then sodium chloride is removed by filtration or washing with water. The fourth step is a step of treating the product with an organic solvent. That is, an organic solvent that is substantially insoluble in water, chemically inert to polyglycidyl isophorone diamine, and capable of dissolving polyglycidyl isophorone diamine is added to dissolve the polyglycidyl isophorone diamine. By performing this treatment, substances that are inert to organic solvents present in the product are removed,
As a result, the storage stability of the final product is significantly improved. The fifth step is a step in which the oil phase mainly consisting of the target product is washed with water and concentrated by distilling off volatile components and organic solvents to obtain polyglycidyl isophorone diamine, which is the target product. This distillation operation is carried out at a pressure lower than atmospheric pressure, and the maximum temperature within the evaporation vessel must be kept below 100°C. Further, as the evaporation equipment, a thin film evaporator or the like is particularly preferable because it can be used efficiently without exposing the product to high temperatures for a long time. It is necessary to continue the evaporation operation until the polyglycidyl isophorone diamine obtained in this step has a volatile content of 0.5% or less, preferably 0.3% or less. After the evaporation process, the product is processed by filtration as necessary. N,N,N',N'-tetraglycidylisophoronediamine obtained in this way is an epoxy compound having four epoxy groups in one molecule,
It is a viscous liquid with an epoxy equivalent of 100-110 and a viscosity of 150-2000 poise (25℃). This N, N, N′,
N'-tetraglycidyl isophorone diamine is
Since it has a chemical structure that contains a component that acts as a curing agent in its molecule, it can give a cured product even by itself, but it can also be used with known epoxy resin curing agents such as amines, acid anhydrides, and polyamide compounds. , and a curing accelerator as appropriate and blended as necessary, and the mixture is cured at room temperature or under heating to give a cured product having a high heat distortion temperature and high strength. The cured product of N,N,N',N'-tetraglycidyl isophorone diamine of the present invention has high strength, high heat distortion temperature, and excellent heat resistance, so it can be used as a material for electrical parts, structural materials, or resin molds. It is useful and also has excellent adhesive strength with carbon fibers and glass fibers, so it is also effective as a matrix resin for fiber reinforced materials. In addition, the polyglycidyl isophorone diamine of the present invention has excellent compatibility with other epoxy compounds, and can be used with general epoxy resins,
For example, a cured product with excellent performance can be obtained by selecting and mixing polyglycidyl ether type, polyglycidyl ester type, polyglycidyl amine type, or alicyclic type epoxy compounds and curing the mixture. Next, the raw materials used in the present invention will be explained. Isophorone diamine is an aminated version of isophorone obtained by trimerizing acetone, and its main component is 3-aminomethyl-3,5,5-trimethylcyclohexylamine, which can be used alone or after modification to produce epoxy resins. It is used as a hardening agent. There are various quaternary ammonium compounds that can be used as catalysts in the addition reaction in step (a), and examples thereof include tetramethylammonium chloride and trimethylbenzylammonium chloride. The alkali used in the ring-closing reaction in step (b) is particularly preferably sodium hydroxide, but potassium hydroxide can also be used, and some of them may also contain sodium carbonate, potassium carbonate, etc. There is no problem. The solvent used in the solvent treatment step in step (d) is substantially insoluble in water, easily dissolves the target product N,N,N′,N′-tetraglycidylisophoronediamine, and Among inert organic solvents, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene are particularly preferred, and mixtures of two or more of these may also be used. Next, examples of the present invention will be shown. Example: A cooling coil, a stirrer, a nitrogen gas blowing pipe, a thermometer, which allows the inside of the reactor to be constantly cooled.
6475 g of epichlorohydrin and 153 g of trimethylammonium chloride as a catalyst were charged into a reaction vessel equipped with a raw material inlet and pressure reducing piping and heated to 50° C. while stirring. Next, 1225 g of isophorone diamine was added dropwise over a period of 1 hour and 40 minutes. During the dropping of isophoronediamine, care was taken to avoid heat generation, and cold water was passed through a cooling coil so that the temperature inside the reaction vessel was within the range of 40 to 50°C. After the addition was completed, the reaction was continued for another 4 hours at the same temperature to complete the addition reaction. The tertiary amine conversion rate at this time was 100.6%. Next, add 1362g of solid caustic soda while keeping the internal temperature the same.
After the addition took 50 minutes, the reaction was continued for an additional 3 hours. The dehydrochlorination rate at this time was almost 100%. Sodium chloride precipitated by this dehydrochlorination reaction is removed by filtration. Then, after allowing the liquid to stand for 30 minutes, the water produced by the reaction is separated and removed. After washing the obtained oil phase twice with 3000 g of water and separating the oil phase,
Unreacted epichlorohydrin was recovered under a reduced pressure of about 10 mmHg by heating to 80°C, and further 5,600 g of xylene was added to dissolve it, and undissolved matter was removed. The liquid is 3000g of water.
The solution was washed with water, left to stand for 30 minutes, and then separated. The oil phase was transferred to an evaporation container, and the xylene used as a solvent was recovered at 85° C. under a reduced pressure of 5 mmHg, water was removed, and evaporation was performed until the volatile content was reduced to 0.5% or less.
Finally, heating was performed to obtain 2550 g of N,N,N',N'-tetraglycidyl isophorone diamine. Yield 91.4 mol%. The obtained N,N,N',N'-tetraglycidyl isophorone diamine has an epoxy equivalent of 101 and a viscosity of
It has a good storage stability of 1650 poise (25°C). Next, when the N,N,N',N'-tetraglycidyl isophorone diamine was analyzed, the elemental analysis values were: Measured value C: 66.69% H: 9.82% O: 16.44% N: 7.05% Theoretical value C: 67.01% H: 9.64% O: 16.24% N: 7.11% In addition, the infrared absorption spectrum is as shown in FIG. Application example A composition in which 100 parts of N,N,N',N'-tetraglycidyl isophorone diamine obtained in the example was mixed with 104 parts and 26 parts of methylnadic anhydride and Epicure Z (manufactured by Ciel Chemical) as curing agents, respectively. The heat distortion temperature and mechanical strength (flexural strength, flexural modulus) of the cast-cured product were measured. This is shown in Table 1 below. The curing conditions for the cast plate were: room temperature for 14 hours, 90℃ for 2 hours,
120°C for 2 hours, 150°C for 2 hours, and 180°C for 2 hours. 【table】

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of N,N,N',N'-tetraglycidylisophoronediamine.

Claims (1)

[Claims] 1 formula N,N,N',N'-tetraglycidylisophoronediamine represented by 2 Isophoronediamine represented by the formula [formula] and epichlorohydrin represented by the formula [formula] are combined in water and/or
Alternatively, a method for producing N,N,N',N'-tetraglycidyl isophorone diamine, which comprises carrying out an addition reaction in the presence of a quaternary ammonium compound, followed by a ring-closing reaction. 3. The method according to claim 2, wherein the amounts of water and the quaternary ammonium compound are 0.5 to 10 mol and 0.1 to 1.0 mol, respectively, per 1 mol of the compound of formula (). 4 Claim 2 in which 6 to 15 moles of the compound of formula () are used per 1 mole of the compound of formula ()
The method described in section. 5. The method according to claims 2 to 4, wherein the addition reaction and ring-closing reaction between the compound of formula () and the compound of formula () are carried out at a temperature of 60°C or lower. 6. The method according to claim 2, characterized in that the compound of formula () is reacted dropwise into the compound of formula () in the presence of water and/or a quaternary ammonium compound. 7 (a) Presence of water and/or a quaternary ammonium compound in epichlorohydrin, and dropwise addition reaction of isophorone diamine at a temperature of 60°C or lower; (b) Addition reaction to the above reaction product at a temperature of 60°C or lower. Add an alkali to cause a ring-closing reaction, (c) remove the precipitate from the reaction product, and collect and remove unreacted epichlorohydrin at a temperature of 100°C or less; (d) dissolve the desired product in the product, but not in water. (e) Next, after washing with water, the organic solvent and volatile components in the product are removed at a temperature of 100°C or less. The method described in Scope No. 2.