JPH02279684A - Production of isocyanuric acid derivative - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful as an electronic material, optical material, etc., by subjecting a higher melting point stereoisomer of tris(epoxypropyl)isocyanurate and an active hydrogen compound to addition reaction, distilling away the unreacted substance and then separating the compound by crystallization with addition of a poor solvent. CONSTITUTION:A stereoisomer (TEPIC-H), with higher melting point, of tris(2,3- epoxypropyl)isocyanurate (TEPIC) and an active hydrogen compound, reactive with epoxy groups, expressed by the formula HA (H represents hydrogen atom; A represents nucleophilic functional group) are subjected to addition reaction and the unreacted active hydrogen compound is distilled away. Then a poor solvent for TEPIC-H is added to separate the TEPIC-H by crystallization and the poor solvent is removed by distillation to afford an adduct of TEPIC-H with one mol active hydrogen compound expressed by formula I and/or formula II.

Description

[Detailed description of the invention] <Industrial application fields> In the fields of electronic materials, optical materials, crosslinking agents for thermoplastic resins, resists, photographic reagents, pharmaceuticals, thermosetting resin materials, paints, adhesives, etc. Provide new materials.

<Prior art> A functional group in which a useful functional group is added to one or two of the three epoxy groups of tris(2,3-epoxypropyl) isocyanurate (hereinafter abbreviated as TEPIC). Complex compounds can be expected to have a variety of uses.

For example, Japanese Patent Application Laid-Open No. 56-61374 discloses that it is useful in inhibiting cell mitosis, and British Patent No. 1109546 discloses that it is useful in inhibiting cell mitosis.
It is described in the issue as being useful in forming photographic gelatin layers.

On the other hand, in recent years, photocurable resins have been used in electronic component encapsulants, semiconductor resists, solder resists for printed wiring boards, optical materials, etc., but compounds in which epoxy groups and vinyl groups coexist in the same molecule are used in this field. It is attracting a lot of attention because of its excellent curing operation and performance of cured products.

Such compounds include the partial (meth)acrylate of bisphenol A type epoxy resin, the partial (meth)acrylate of bisphenol A type epoxy resin, and the partial (meth)acrylate of phenol novolak or Talezol novolac type epoxy resin.
Examples include meth)acrylate and glycidyl methacrylate.

If (meth)acrylic acid is used as the active hydrogen compound in the 1-molar adduct and 2-molar adduct of TEP I C-H of the present invention, it will become a partial (meth)acrylate of TEPIC, and the same uses as above are expected. can.

Furthermore, TEPIC is a trifunctional poxy compound, and it is generally said that cured products of trifunctional poxy compounds have excellent rigidity but poor flexibility.

Since the 1 molar adduct of the present invention is a difunctional epoxy compound, it has the effect of improving flexibility.

Also, French patent FR-017329 has 1.3-
There is a statement that a resin with excellent heat resistance and weather resistance can be obtained by using a derivative of bis-23-dihydroxypropyl isocyanurate (formula [■]) as a crosslinking agent. By decomposition, derivatives with similar performance to these can be easily obtained.

[■]

However, in the formula, R represents a functional group having a vinyl bond.

<Problem to be solved by the invention> As stated in JP-A No. 56-61374,
Even if you try to add an active hydrogen compound to only one of the three epoxy groups of TEPIC, the three epoxy groups are almost equivalent, so not only 1 mole of active hydrogen compound is added per mole of TEPICI. A 2-mole or 3-mole adduct is produced as a by-product. Even if the amount of active hydrogen compound added is reduced to suppress these by-products, a large amount of unreacted TEPIC remains, making separation not only difficult but also difficult.
The by-product of molar adducts is also unavoidable.

In JP-A No. 56-61374, 1 molar adduct and TEP
TEP by adding the mixture of IC into methanol
Although it is stated that IC precipitates almost quantitatively,
In reality, due to the compatibility between TEPIC and the 1 molar adduct, a considerable amount of TEPIC is dissolved even in the methanol layer in which the 1 molar adduct is dissolved.

Therefore, even if a large amount of methanol is used to reduce the compatibility between the 1 molar adduct and TEPIC, the amount of bone dissolved by TEPIC relative to methanol will increase, so in the end both the 1 molar adduct and TEPIC will dissolve in the methanol layer. I'll come.

Therefore, it is extremely difficult to obtain a highly pure 1 molar adduct using only such fractionation operations, and therefore, JP-A No. 56
-61374 further uses column chromatography for purification, but column chromatography is not an industrially advantageous method because the columns are expensive, a large amount of solvent is required, and the production capacity is small. Therefore, the overall cost will be high.

Means to solve the problem〉 TEPIC has two types: H type with melting point 152-158°C and melting point 9
It is known that two types of stereoisomers exist: the L form (hereinafter referred to as TEP r C-L) with a temperature of 8 to 107 °C, and among these, TEP I C-L is an organic Although relatively soluble in solvents, TEP I C-H is extremely sparingly soluble in organic solvents.

TEPIC obtained by conventional synthesis methods is mostly L-type and contains a small amount of H-type, and commercially available products are also of this type.

H-type TEPIC, which is usually contained in a small amount here, is disadvantageous in terms of use, as it lowers the solubility.

Therefore, there are almost no examples of using TEPIC-H alone in a reaction due to the drawbacks of handling such as high melting point and low solubility.

As a result of extensive research, we added 1 mole of an active hydrogen compound to TEP I C-H as a starting material, and found that
Surprisingly, the solubility of this reaction product in organic solvents is 1.
It was found that the amount increases day by day.

In other words, there is no big difference in solubility in organic solvents between the commonly used TEPIC and its 1 molar adduct, whereas TEP I C-H and its 1 molar adduct have different solubility in organic solvents. found that there was a large difference.

Therefore, if the reaction between TEP I C-H and the active hydrogen compound is stopped at an early stage when not much 2-mole adduct is formed, and after distilling off the unreacted active hydrogen compound, a poor solvent such as methanol is added. Since most of the adducts could be separated, we succeeded in obtaining a highly pure 1 molar adduct by distilling off the solvent.

The active hydrogen compound represented by HA used here is not particularly limited, and may be any compound that reacts with an epoxy group.

1 (An example of A is water as shown in Example 7, but other examples of saturated alcohols include methanol, ethanol, propatool, buta, nol, pentanol, hexanol, etc.) Examples include allyl alcohol, 2-butyn-1-ol, 2
-propyn-1-ol, crotyl alcohol, 3-buten-2-ol, 2-buten-2-ol and the like.

Examples of cyclic alcohols include cyclohexanol, methylcyclohexanol, and the like.

Examples of thiols include methanethiol, ethanethiol, 1-propanethiol, 2-propanethiol, phenylmercaptan, and the like.

Examples of unsaturated fatty acids include acrylic acid, methacrylic acid, crotonic acid, monomethyl maleate, monoethyl maleate, cinnamic acid, and the like.

Examples of saturated fatty acids include acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, etc., and examples of aromatic fatty acids include benzoic acid, salicylic acid, etc.

Furthermore, examples of secondary amines include dimethylamine, diethylamine, dibutylamine, dicyclohexylamine, diarylamine, morpholine, jetanolamine, and the like.

The solvent for these addition reactions may or may not be used, but the reaction proceeds more smoothly when used.

Examples of the solvent to be used include the following, but the solvent is not limited thereto as long as it does not show reactivity under the selected reaction conditions.

Examples of the halogenated hydrocarbon as a solvent include hasychloroethane, 1,1.1-)lichloroethane, 1°L2
,2. -tetrachloroethane, 1,2-dichloroethylene, trichloroethylene, chlorobenzene, orthodichlorobenzene, and the like.

Examples of esters include ethyl acetate, propyl acetate,
Examples include butyl acetate, pentyl acetate, and the like.

Examples of ethers include 1,4-dioxane.

Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, and the like.

Other examples include dimethylformamide and cellosolve.

TEP (as a poor solvent for crystallizing C-H,
Any solvent may be used as long as it is difficult to dissolve TEPIC-H and dissolves well the 1 molar adduct formed, and may be used alone or in a mixed solvent, but methanol, ethanol, and impropanol are preferable. Among them, methanol is advantageous from the viewpoint of cost.

The amount of poor solvent varies depending on the solvent type, but TE
It is preferably 0.5 to 3 times the weight of the PIC adduct, more preferably 0.7 to 1.5 times the weight.

If the amount of the poor solvent is larger than this, the amount of dissolved TEPIC-H increases and the fractionation efficiency decreases, and if it is smaller than this, the viscosity increases and it takes a long time to filter and separate the TEPIC-H.

The crystallization temperature of TEP I C-H is desirably as low as possible within a practical range, and is usually performed around 0°C. T.E.
The crystallization time of P I C-H is desirably as long as possible within a practical range, and is usually about 12 hours.

Examples will be shown below and explained in more detail.

<Example> Example 1 TEPIC-H manufactured by Nissan Chemical Industries (epoxy equivalent: 99
．． 3) 297 g (1,0 mol), acrylic acid 72
(1 mol), 120 g of dichloroethane, and 0.6 g of hydroquinone were reacted for 60 minutes at reflux temperature, and then heated to 100"C under vacuum to distill off volatile components. Next, 220 g of methanol was added. If the mixture is added and slowly cooled to O'C without stirring, unreacted TEP I C-H will precipitate, so this is filtered off and the filtrate is heated to 100°C under high vacuum.
The methanol was distilled off by heating to give 107 g of a colorless viscous liquid product.

The epoxy value of this product was 5.0.

In order to determine the composition, the area ratio of each component was determined using the GPC method according to a conventional method.The results are as follows.TEPIC-H2
X 1 mole adduct 86χ 2 mole adduct 11% 3 mole adduct lχ When this area ratio is replaced with a weight ratio and the calculated value of the epoxy value is calculated, it is 5.1, which is the experimental value. It was confirmed that the area ratio of is almost the same as the weight ratio.

Examples 2 to 10 and Comparative Examples 1 to 4 Table 1 shows the types, amounts, and reaction conditions of each reagent in Example 1.
When the treatment was carried out under the same conditions as in Example 1 except for the following changes, products as viscous liquids with yields and compositions as shown in Tables 1 and 2 were obtained, respectively.

Table-1 Reaction preparation ratio Table-2 Reaction conditions and results 3υ“C 30 minutes TEPIC-H TEPIC-5 TEPIC-G Q ■ ■ ■ The abbreviations in the table are as follows.

High melting point isomer epoxy equivalent weight: 99°, manufactured by Nichiryo Chemical Industry Co., Ltd. High-purity product manufactured by Chemical Industry Co., Ltd., 199.5 account amount, General product manufactured by Chemical Industry Co., Ltd. Epoxy equivalent weight: 104.2 1 mole adduct of hydroquinone active hydrogen compound, active hydrogen 2 molar adduct of compound 3 molar adduct of active hydrogen compound

Claims (3)

[Claims] (1) A stereoisomer with a high melting point (hereinafter abbreviated as TEPIC-H) of tris(2,3-epoxypropyl)isocyanurate (hereinafter abbreviated as TEPIC) and HA (hereinafter abbreviated as TEPIC-H).
H: hydrogen, A: nucleophilic functional group) After conducting an addition reaction with an active hydrogen compound capable of reacting with the epoxy group, the unreacted active hydrogen compound was distilled off, and then TE
After adding a poor solvent for PIC-H to crystallize and separate TEPIC-H, the poor solvent is distilled off to obtain the formula [I]
and/or a method for producing a 1 mol adduct of an active hydrogen compound of TEPIC-H represented by formula [II]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔II〕 (2) The manufacturing method according to claim 1, wherein the purity of the 1 mol adduct of TEPIC-H with an active hydrogen compound is 70% by weight or more. (3) After causing an addition reaction between TEPIC-H and an active hydrogen compound capable of reacting with the epoxy group represented by HA, unreacted active hydrogen compounds are distilled off, and then a poor solvent for TEPIC-H is added. In the method of obtaining a 1 mol adduct of an active hydrogen compound of TEPIC-H and a 2 mol adduct of an active hydrogen compound of TEPIC-H by crystallizing and separating TEPIC-H and then distilling off the poor solvent, the total purity is A method for producing an active hydrogen compound adduct of TEPIC-H having a content of 85% by weight or more.