JPS5855150B2 - Method for producing heterocyclic triglycidyl compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing novel heterocyclic triglycidyl compounds.

Heterocyclic compounds containing glycidyl groups are described in German Patent Publications No. 1932305 and No. 1932306 and French Patent No. 139443.
8 and Swiss Patent No. 345347*.

The methods for producing the compounds are not always satisfactory even in the most costly cases.

Products produced according to the prior art often have problems with storage, and the process is not always easy.

Moreover, the cured products often have insufficient mechanical properties.

The inventors have discovered an excellent storage-stable heterocyclic triglycidyl compound that has high mechanical strength with high dimensional stability even under thermal conditions after curing.

The compound has the general formula (■):. (In the formula, n represents the number 4 or 5.

) represents a divalent group represented by

]. Surprisingly, the novel heterocyclic compound can be easily obtained by reacting a compound represented by the general formula (1) with epino-logenhydrin and then eliminating hydrogen logenide.

The symbol R preferably represents a hydrogen atom or a methyl group.

Particularly preferred are groups where X is: and R represents a hydrogen atom.

The novel triglycidyl compounds are generally clear, colorless to brown liquids that are highly viscous and do not crystallize at room temperature.

The novel triglycidyl compounds can be easily mixed with curing agents such as dicarboxylic anhydrides, ie phthalic anhydride or hexahydrophthalic anhydride, at temperatures of 60 DEG to 120 DEG C.

After curing, a molded product with good mechanical and electrical quality can be produced from the resulting curable mixture.

The mixtures can be used in particular for the production of laminated resins, moldings, casting resins and lacquer resins.

The new bishydantoin compound represented by the formula (1), which is an intermediate of the new l-liglycidyl compound represented by the general formula (I) useful as a component of the curable mixture of the present invention, is A, a cyclo compound represented by the general formula (2): By condensing 2 moles of ureide with 21 moles of 1,3-dichloropropanol containing a group R at the 21-position, or by condensing 1 mole of cycloureide represented by the general formula (■) with 71 moles of shrimp halogen hydride in the presence of an alkali. to obtain the corresponding monoglycidyl compound, and then add another 1 mole of the compound represented by the general formula (■) to this compound, or react 1 mole of cycloureide (C1) represented by the general formula (■) with 71 moles of shrimp halogen hydride. This compound is then reacted with an additional 1 mol of a compound represented by the general formula (■) to form the corresponding monohalogenhydrin compound.
Alternatively, it can be produced by condensing 2 moles of cycloureide represented by the general formula (1) with 1 mole of epihalogenhydrin and eliminating hydrogen halogenide.

The process according to the invention for preparing the compounds of the general formula I is advantageously carried out in the presence of a hydrogen halide acceptor with azeotropic removal of water.

Suitable for this purpose are, for example, an equal amount or a slight excess of alkali hydroxide, most preferably sodium hydroxide.

Preferably the epino-10 genehydrin used is epichlorohydrin.

Optionally, a catalyst such as a quaternary ammonium chloride such as tetramethylammonium hydroxide 1. Tetraethylammonium bromide or benzyltrimethylammonium chloride is further added.

When the starting material of general formula (1) is prepared by the process, the final product of general formula I is obtained in a single step by adding an appropriate amount of epinologenhydrin.

Next, the present invention will be further explained with reference to Examples.

Examples 1 to 10 are examples of the production of the starting material represented by the general formula (2), and Examples 11 to 16 are examples of the production of the novel triglycidyl compounds of the present invention.

Example 1 1,3-bis-(5',5'-dimethylhydantoy=3')-7''ropane-2-olno production 41 glasses equipped with stirrer, thermometer and powerful cooler Glycerin dichlorohydrin (1,3-dichloropropano-
Roux 2) 520 g (3.83 mol), 99.5% 5.5
-dimethyl-hydantoin 981P (7.66 mol),
Potassium carbonate 582f without water in fine powder form? (4,2
1 mol) and commercially available dimethylformamide 96
A mixture consisting of 0rnl is charged.

The pasty mixture is slowly stirred and heated to 120°C; as heating proceeds, the mixture becomes a thin liquid.

Immediately thereafter an exothermic reaction occurs with intense evolution of CO2.

Remove the heating bath and stir the thickening paste vigorously.

After removing the heating bath the temperature rises to 124-126°C.

After 20-30 minutes the exothermic reaction is over and the temperature of the reaction mixture drops to 116°C.

Stirring is continued for a further 5 hours at 126° C. to complete the reaction; the hot reaction mixture is then filtered with a magnetic suction filter to separate the potassium chloride.

The mixture is concentrated to dryness in a rotary evaporator at 70-8°C under water-jet vacuum; the product thus obtained is a clear, slightly yellow melt that crystallizes spontaneously on heating. be.

Drying is continued at 90° C. and 0.2 m door Hg until a constant weight is reached to completely remove volatile components.

Colorless to pale yellow crude crystals 1212.6? (Theoretical value: 119
6, Fl), which melts at 142°C (Mettler Ep 51 ).

This crude product still contains potassium chloride and unreacted starting materials.

The elemental analysis is as follows: 468%C16, 5%H1161
%N and 58% ash (calculated value: 50.0%C16.4%
H, 17.9%N).

The percentage of desired bishydantoin in the crude product is therefore approximately 86%.

For purification, the crude product is recrystallized from water 550S'.

Thus purified product 716.5S' (corresponding to 606% of theory with respect to the dimethylhydantoin used)
get.

The thus purified formula ■: 1,3-bis(5',5'-dimethyl-hydantoinyl-3')-7'' lovanol-2C=3,3
'-(β-hydroxypropylene)-5,5-dimethylhydantoin] melts at 178-181'C.

Elemental analysis: Actual value: 49.5%C16, 4%H117, 6%N, 1
．． 1% ash calculation value: 50.0%C16.4%H, 17.9%N, 0
% Ash Example 2 ■ Preparation of 3-bis-(5'-5'-dimethylhydantoin-3')-propanol-2 3-glycidyl-5 in 128 ml of dimethylformamide
- A solution of 71,171 moles of 5-dimethyl folds (185P) (epoxide content: 5.4 epoxide equivalents/kg) was stirred at 100°C.

Add dimethylhydantoin 1281 in portions over 30 minutes.

The reaction is exothermic, so the heating bath is removed: the temperature rises to 130'C.

After the exothermic reaction has ended, stirring is continued for 5 hours at 130 °C; the clear pale yellow reaction mixture is then solidified to dryness at 70 °C under a water jet vacuum, and 150 °C of water is added.
Recrystallize from m1.

After drying in vacuo at 100°C, clear colorless crystals 152.8
? (49% of theory) is obtained, which melts at 185.6° C. (Mettler Fp 51 ).

Elemental analysis revealed that the obtained product was 1,3-bis(5',5'
-Simethyl-hydantoinyl-3') -70 Indicates that it is panol-2: Actual value: 49.9%C16, 6%H117, 8%N Calculated value: 50.0%C16, 5%H117, 9%N example
3 1,3-bis-(5',5'-dimethyl-hydantoinyl-3')-furopanol-2 production water 600 r/
5,5-dimethyl-hydantoin 640.5 F in Ll
(5 mol) and potassium chloride 3.0'? Stir the solution consisting of at 90°C.

Then add epichlorohydrin 647.5? to this clear colorless solution within 30 minutes. (7.0 mol) was added dropwise.

Stirring is carried out for a further 240 minutes at 97°C.

The hot reaction mixture was then filtered off and the clear pale yellow solution was evaporated under vacuum in a rotary evaporator using a water pump.
Concentrate to dryness at 0'C.

The mass was then heated to a constant mass of 0.15 mmHg.
Dry at 65° C. under reduced pressure.

In this way, a clear, slightly more yellow and highly viscous liquid 110.3P (100% of theory) is obtained, which gradually crystallizes to form a substantial white crystalline product.

Based on the analysis of chlorine, the purity of the product is 90.2% (observed: 14.5% C1, calculated: 16.07% C1)
It is.

The remainder consists of the starting material; a small amount of 3-glycidyl-5,5-dimethyl-hydantoin is also present, which is determined by epoxide titration (found value 20, 2 epoxide equivalents/kg).

Proton-Magnetic Resonance Spectrum C60Mc H-NMR
:3 using tetramethylsilane (TMS) as standard
(measured in deuterochloroform (CDC13) at 5° C.) indicates conformity to the structure of formula (2) by the presence of the following signal.

Furthermore, the mass spectrum is 221 (-M+H)ME
(Molecular ion (theoretical molecular weight 220.7) in mass units and 250ME (M-CH3), 184ME (=M-HC
The presence of fragment ions such as 1) and 177 (-M-HNCO) indicates the presence of a compound represented by the structural formula (2).

Said purity 90.2% 3-(2'-hydroxy-3'chloro-n-propyl)-5,5'-dimethyl-hydantoin 489.5f (2 mol), 5,5-dimethyl-hydantoin 207.5? , water-free powdered potassium carbonate 1
521 and dimethylformamide 1521 is stirred and heated to 120°C.

A vigorous evolution of CO2 occurs and the reaction mixture is reduced to 12
Stir at 1-128°C for a total of 5 hours.

Perform the method as described in detail in A.

Colorless crystalline product 623. Fl (theoretical quantity 9
9.8%) was obtained, which gives the desired compound with a purity of approximately 92%.
Included in % (calculated from elemental analysis).

To complete the purification of the product, it is recrystallized from 310 ml of water.

Clear, colorless crystals are obtained, which melt at 186-187°C.

The elemental analysis is shown below: Observed: 49.6% C, 4% H, 17,6% N Calculated: 499% C, 6,4% H, 17,9% N The product was as described in Example 1 and 1,3-bis-(
5',5'-dimethyl-hydantoinyl a/ )-propanol-2K Match.

Floton-magnetic resonance spectrum (60Mc-HNMR;
(determined in DMSO versus TMS) further indicates the structure of formula (2) by the presence of the following signal at -e.

Example 4 Preparation of 1,3-bis-(5',5'-dimethyl-hydantoin-3')-2-methylpropanol-2 As described in Example 3, β-methylepichlorohydrin 106.6f ( 1 mol) of lithium chloride as a catalyst. using 140rrL of dimethylformamide
5,5-dimethyl-hydantoin 128 in l, IP.

After dropping the epoxide, the mixture is stirred at 128-130°C for an additional 5 hours.

The method as described in Example 1 was carried out and a yellow, clear and highly viscous melt 206f (88% of theory) was obtained as a crude product, the purity of which was determined based on nuclear magnetic spectroscopy and electroanalysis. It is 72%.

This crude 3-(2'-hydroxy-2'-methyl-3'chloro-n-propyl)-5,5-dimethylhydantoin 193.51 (0,592 mol), finely powdered anhydrous potassium carbonate 62.8f1 dimethyl 125 ml of formamide and 75.8 f of 5,5-dimethyl-hydantoin (0,59
A mixture consisting of 2 moles) is stirred at 125°C for 10 hours.

Initially, intense CO2 generation is observed, but it gradually subsides.

The mixture was then cooled to 80°C and 330 Wll of water
is added and the whole is then cooled to 0-5° C. while stirring.

After several hours, the desired substance crystallizes out as a colorless precipitate.

This was filtered and heated at 70°C for 20mm until it reached a constant weight.
Dry with Hg.

A colorless powder 118f (61% of theory) is obtained, which melts at 162-164°C.

The mass spectrum shows a molecular ion (M) expanded to one proton at 327 mass units (min-mass units), which corresponds to a molecular weight of 326.4.

Furthermore, in particular the following fragment peaks (FRAGMETATIO
NS) 311 (-M-CH3), 309 (327-H
2O), 308 (M-H2O), 293 (311-H2
O); 185 (fragment peak between C1 and C2 crosslinks),
etc. are recognized.

Similarly, proton magnetic resonance spectrum (60McHN
MR: determined in CDCl3 versus TMS) shows that the new bishytasotoin corresponds to formula (2).

Example 5 1,3-bis-(5',5'-dimethyl-hydantoinyl-3')-propanol-2 Stirrer, thermometer1. In a 61 tetracone flask equipped with a reflux condenser and a dropping funnel, 5,5-dimethylhydantoin 179:1 (14,0 mol), finely powdered anhydrous potassium carbonate 1015'? (7.35 mol), 10 g of potassium chloride and 1750 ml of dimethylformamide were stirred at 110°C.

Epichlorohydrin 712P (7.7 mol) is added dropwise to this mixture with vigorous stirring within 90 minutes.

The reaction is exothermic and CO2 begins to evolve violently.

When the heating bath is removed, the temperature rises to 135°C.

After the dropwise addition is completed, the exothermic reaction quickly ends. Stirring is continued at 125° C. for 5 hours to complete the reaction.

The reaction mixture is diluted with 300 ml of dimethylformamide; while still hot, the potassium chloride is filtered off from it and
It is then dried to dryness at 120° C. in a rotary evaporator under vacuum with a water jet pump.

Thereafter, it is dried at 120° C. under 0.2 mmHg until it reaches a constant weight.

In this way crude product 2307P was obtained, which was mixed with water 12
Recrystallize from 00rfLl.

Colorless, clear crystals 1351P (12% of theory) are obtained (without work-up of the mother liquor).

The purified product melts at 190-191°C.

Elemental analysis shows that the product is a pure substance and corresponds to formula (■).

This is also seen from the same proton magnetic resonance spectrum.

Elemental analysis Actual value: 49.7%C16, 5%H117, 7%N Calculated value: 49.9%C16, 5%H117, 9%N Example
6 ■・3-Bis-(5′・5′-dimethyl-hydantoinyl-3′)-propanol-2 Repeating the method of Example 5 yields a crude product 2307?, characterized by a brown to yellow color. are separated.

The product melts at 149-152°C and elemental analysis shows that 5.3% inorganic material is still present.

Therefore, the yield of organic material is 218El' (100% of the theoretical amount
%) and, according to elemental analysis, about 95% of the desired product.

The crude product was passed through a cross beater mill to remove inorganic materials and colored by-products.
ml) and then stirred with deionized water at room temperature to obtain a homogeneous mass.

After stirring for 1 hour, the mass is filtered with suction and dried vigorously.

A colorless filter cake is obtained, which is crushed and dried for 24 hours at 100° C. under 30 mmHg.

The purified product is obtained with a yield of 71% (1520'?).

The product is melted at 181-183°C, with an inorganic content of 0.9%.

The purified material thus obtained is used exactly like the material prepared according to Example 5 for the glycidylation reaction.

Example 7 ■・3-bis(5'-methyl-5'-ethyl-hydantoin-3')-propanol-2 In the same manner as in Example 5, 5-bis(5'-methyl-5'-ethyl-hydantoin-3')-propanol containing 4% sodium chloride was prepared.
Methyl-5-ethylhydantoin 148.3P (98,
5%) (1,80 mol) of potassium carbonate 71.2S'
(0,515 mol) of dimethylformamide 5
Epichlorohydrin 46.25P (0,5
mol).

The reaction is carried out and the reaction mixture is purified according to Example 5.

A brittle, clear and light brown glass 172.9S' is obtained (theoretical amount: 170.2f?) which still contains 1.6% of dimethylformamide as an impurity.

This crude product is further worked up in its raw form.

The proton magnetic resonance spectrum (60Mc-HNMR) shows that in addition to a small amount of dimethylformamide (δ-29 and 30), δ-0,8 to 1.05 (multiplet), δ-1,45
(singlet), δ1.55-2.0 (multiplet), δ-36
Signals at 5-37 (multiplet), δ-4,0-42 (multiplet) and δ-5,5-62 (multiplet) indicate the presence of the target substance (Formula ■).

Example 8 ■.3-bis-(5'-isopropylhydantoinyl-3')-propanol-2 As described in Example 5, dimethylformamide 50
5-isopropylhydantoin 142.2P in 0ml (
1 mol), 46.25 f (0.5 mol) of epichlorohydrin, 71.21 (0.515 mol) potassium carbonate and 0.42 potassium chloride.

The method for obtaining the crude product, which does not require purification, is carried out as described in Example 5.

Thus a clear, golden yellow and glassy product 171.
8f is obtained.

It still contains about 1% dimethylformamide as an impurity.

The proton-magnetic resonance spectrum shows agreement with the structure (formula ■) due to the presence of the following signals.

δ-0.8 to 1.2 (triplet), δ-2,0 to 2.3 (multiplet), δ= 6.0-6.3 (multiplet).

Example 9 ■・3-(5・5′~pentamethylene-hydantoin-3′)-propanol-2 Using the method of Example 5, 142.3 f of potassium carbonate and 0.8 f of potassium chloride were added. Dimethylborumamide 9
Epichlorohydrin 92.5 P (1 mol) in 00ml
and 5,5-pentamethylene hydantoy 7336.4? (
2 mol) and condensation.

Purify according to the method of Example 5. In this way, the target bishydantoin 409.91 (W theoretical value: 392.4f)
is obtained.

It still contains about 5% dimethylformamide as a clear yellow crystalline powder.

For purification, recrystallize from dioxane/water in a ratio of 1:3.5 and 2/1.

In this way, colorless clean powder crystal 314.5P (
80.2% of theory) is obtained, which melts at 247.1° C. (Mettler Fp51, 1°/min).

The elemental analysis is shown below.

Observed value Calculated value 57.9% C58, 1% C 7,3% H 7,2% H The mass spectrum matches the expected structure; the molecular ion is measured in mass units 392 (M-theory: 392.4
%); The floton-magnetic resonance spectrum (60McHNMR) shows that it corresponds to the following formula (2).

Example 10 1,3-bis-(5,5'-tetramethylene-hydantoynyl-3')-propanol-2 By the method of Example 5,
React the following mixture: 5,5-tetramethylene hydride 154.2P toin
(1 mol) Epichlorohydrin 4
6.251 (0.5 mol) Potassium carbonate 71.21' (0
, 515 mol) Potassium chloride 0.4z Dimethylformamide 500rrLl Purification and separation of the desired bishydantoin is carried out as described in Example 5.

Without further purification, the crude product was purified using dioxane/water (2:
1) Recrystallize directly from 360rfLl.

98 g of colorless and clean crystals (54% of theory: without purification of the mother liquor) are obtained, melting at 185.2° C. (Mettler Fp 51.2°/min).

The proton-magnetic resonance spectrum is consistent with formula In the apparatus, 1,3-bis-(5',5'-dimethylhydantoynyl-3')-furopanol 2 500P (1,6 mol) obtained by one of the aforementioned methods, 50% tetramethyl chloride Ammonium aqueous solution 17g and epichlorohydrin 5328? (57.6 mol) is stirred at 90° C. for 30 minutes.

The temperature in the reaction mixture is adjusted to 60°C by vigorous circulating distillation at a bath temperature of 150-160°C under reduced pressure of 50-70 mmHg.

Then, while stirring vigorously, add a 50% aqueous solution of sodium hydroxide to 480 ml of sodium hydroxide solution. is added dropwise over a period of 150 minutes; during this process the water present in the reaction mixture is continuously removed by azeotropic distillation from the starting material, separated from the refluxing epichlorohydrin and removed.

After the addition of the aqueous sodium hydroxide solution is complete, distillation is continued under the conditions described above, with epichlorohydrin being recycled, until no further water is separated.

The reaction mixture is then cooled to about 40°C. The sodium chloride formed is removed by suction filtration.

Wash the epichlorohydrin solution with 500 ml of water.

The organic layer is concentrated in a rotary evaporator at a bath temperature of 60-70° C. under water pump vacuum.

In order to remove the volatile fractions in the water vapor, 200 ml of water are added to the mixture and a complete distillation is carried out under the conditions mentioned.

The mixture is then thoroughly concentrated by mixing with 100 ml of toluene, 5 and evaporating to remove water.

Then in a rotary evaporator under 0.2 mmHg 65-70
Dry at °C until constant weight.

A clear and slightly yellow triglycidyl compound (100% of theory) is obtained which is highly viscous at room temperature.

The epoxide content of the triglycidyl compound is 6.20
equivalent/kg (99.2% of the theoretical amount).

The new triepoxide did not crystallize even after 4 months at 5°C and room temperature.

Four months after adding acetate or chloroform at the above temperature, no similar tendency to crystallization could be detected.

Elemental analysis shows a total chlorine content of 1%: further elemental analysis shows 54.6% C; 68% H and 11.0
%N (calculated value: 549%C; 6.7%N and 11,6%
N).

Proton magnetic resonance spectrum (60Mc-HNMR%T
The MS (measured in CDCl3 against K) shows agreement with the following structure, in particular due to the presence of the following signals: -C
- The presence of an absorption band indicates that the desired product has been obtained.

Measurement by vapor osmotic pressure method [“Meklolab 302B (M
The average molecular weight Mn was 470.
(Theoretical value -480).

Furthermore, the Kel permeation chromatogram in tetrahydrofuran is shown to be about 85% molecularly homogeneous.

The new triglycidyl compounds correspond to the general formula M: Example 12 1,3-bis(S/
- 5'-dimethyl-hydantoinyl-3') 2-methyl-propan-2-ol 112.5P (0,3445 mol) was treated in the same manner as in Example 11 by the action of 3.81 mol of a 50% tetramethylammonium chloride aqueous solution. Lower epichlorohydrin 1
435P (15.5 mol).

According to Example 11, 50% aqueous sodium hydroxide solution 10
3.41 (1,294 mol)] *Dehalation and dehydrohalination are carried out.

Work-up and purification of the new glycidyl compound is carried out in the same manner as in Example 11.

Viscous and light brown resin 171f (100% of theoretical amount)
) was obtained, and its epoxide content was 5.67 equivalents/k
g (93.5% of theory).

Total chlorine content is 1.5%.

The new epoxide resin corresponds to the molecular structure shown in the general formula ■: Example 3 Bishydantoin 165 prepared according to Example 7,
．． 111 (0,485 mol) in a 50% aqueous solution of tetramethylammonium chloride as described in Example 11.
Epichlorohydrin 1615f (17,4
5 mol).

The dehydrogenation reaction was carried out in the same manner as in Example 11 using sodium hydroxide 145.11 (1,8], 5 mol).

After work-up and purification by the method according to Example 11, a viscous and clear light brown resin (91.4% of theory) was obtained, with an epoxide content of 5.84 equivalents/kg (99% of theory). %).

The triglycidyl compound produced corresponds to the general formula X■; Example 14 Bishydantoin 1705' obtained according to Example 8
(0,495 mol) was mixed with epichlorohydrin 1663S' (17,89 mol), 50% tetramethylammonium chloride aqueous solution 5.3V and 50% sodium hydroxide aqueous solution 149.1'* (1,869 mol) according to Example 11. Make it react.

After normal work-up, a clear and bright yellow triglycidyl compound 22s, 5P (theoretical value 89,
6%) with an epoxy content of 5.32 epoxide equivalents/kg (90.2% of theory).

Example 15 The following materials are reacted in a similar manner to the method of Example 11.

Bishydantoin 196 prepared according to Example 15.
2f (0.5 mol) Epichlorohydrin 1665f (18 mol) 50% aqueous tetramethylammonium chloride solution 5.31 50% aqueous sodium hydroxide solution 149.7 f (1,8
7 mol) Carrying out the method and work-up according to Example 11, the following is obtained: Light ocher resin 253.5 f (theoretical value 9050
/A) r5.26 poxide equivalent/kg (98.4% of theoretical value
) According to the NMR-spectrum, the new triglycidyl compound corresponds to the formula X: Example 16 The following substances are reacted as described in Example 11:
0,263 mol) Epichlorohydrin 877f (9,4,8 mol) 50
% tetramethylammonium chloride aqueous solution] *2.81 50% sodium hydroxide aqueous solution 788% (0,985 mol) After the work-up described above, a clear and pale yellow resin 139.
51 (99.6% of the theoretical value) was obtained, which is 5,39
and corresponds to formula XVI.

Next, an example of the use of the novel glycidyl compound of the present invention will be shown as a reference example.

Reference Example 1 Manufactured according to Example 11, with 6.2 engineering poxide equivalent/k
A mixture of 54 parts of triepoxide and 64 parts of phthalic anhydride is prepared.

The mixture is allowed to react at 120-130° C. with stirring, resulting in a homogeneous, colorless melt.

Pour it into an aluminum mold preheated to 120°C.

Curing the melt for 2 hours at 120° C. and 11 hours at 150° C. gives a transparent molding, which has the following mechanical properties: Flexural strength VSM 77103): 13-16 Kp/
ma Deflection (VSM 77103): 4.5-5.1 Water absorption (4 days/20°C): 0.7% Reference example 2 Example of clear and colorless melt with 6.2 epoxide equivalents/kg 11 and 146 parts of hexahydrophthalic anhydride.

Benzyldimethylamine 21 is added to this mixture and the homogeneous mixture is poured into an aluminum mold preheated to 100°C.

Cure at 100°G for 2 hours, 120°C for 2 hours and 150°C for 11 hours.

The gelation time of 100 g of the above mixture at 100°C is 20 minutes [Tecam Ge1atio
nTimer)].

The molded product obtained has the following properties: bending strength V
SM 77103): 11-15K p/mt? t Deflection (VSM 77103): 4 to 6 mm Impact bending strength VSM 77105): 12 to 14 Brass” K p /
Mechanical dimensional stability at room temperature according to Cat Martens (Martens 5
0C1P, 5) Er at 23°C: 3.6 Er at 130°C: 3.6 Er at 165°C: 3.6 Dielectric loss factor (50C, P, S) tg at 23°C: o, 008 tg at 130°C: o, o08 tg at 165°C: 0.024 Current resistance at 25°C: 35.1016 crrL Tracking resistance (VDEO303) Stage A3c Arc resistance (vDE 0303) Stage 4 reference example
3 100 parts of the triepoxide produced according to Example 12 was treated in the same manner as in Reference Example 2 to obtain 83 parts of hexahydrophthalic anhydride.
1 part and 1.5 parts of benzyldimethylamine, worked up and cured.

The bright yellow and clear molded product thus obtained has the following properties: VSM 77103): 13-17 Kp/m
4 Deflection (VSM 77103): 4-6mm Impact bending strength VSM 77105): 14-18.5c
rrL-Kp/crtt Heat Distortion (DIN 53461) 2 150°C Water Absorption (4 days/20°C): 0.57% Reference Example 4 Triepoxide 85 prepared according to Example 13 containing 5.84 epoxide equivalents/kg .6P and hexahydrophthalic anhydride 73.3P are mixed, worked up and cured.

By this method, transparent, glass-like, light brown moldings are obtained, which have the following properties: Flexural strength VSM 77103): 10.8-12.0
kg/mm Deflection (VSM 77103): 4-5 mrIL Impact Bending Strength VSM 77105): 10.5-11.75
CTL-Kp/crA Mechanical dimensional stability at high temperatures according to Martens (DIN): 158°C Heat distortion (DIN 53461): 160°C Cold water absorption (4 days/23°C): 0.56% boiling water suction sex(
1 hour/100°C): 0.42% Reference Example 5 188. Of and hexahydrophthalic anhydride 146.5f are mixed, worked up and cured analogously to Reference Example 2.

The resulting clear and bright yellow moldings have the following properties: Arc resistance (ASTM 495): Stage 3 Tracking resistance (DIN 53480): Stage KA 3
c Cold water absorption (4 days at 723°C): 0.58% Flexural strength (VSM 77103): 11.25-12.48
Kp/mm Deflection (VSM 77103): 5.1~53 Dragon impact bending strength VSM 77105): 10.3~10,5
am -Kp /crA Dimensional stability at high temperatures by Martens (DIN) 1
46° C. heat distortion (DIN 53461): 153° C. Reference Example 6 Epoxide resin prepared according to Example 15 containing 5.26 epoxide equivalents/kg 190. IP and hexahydrophthalic anhydride 146.5'f are mixed, worked up and cured analogously to Reference Example 2.

The bright, clear moldings thus obtained have the following properties: Flexural strength VSM 77103): 10.32-1
1.68 kp/mA Impact bending strength VSM 77105): 12.75
Dimensional stability at high temperatures according to k p /cm Martens (DIN):
147°C Heat distortion (DIN 53461): 153-155°C Water absorption (4 days/23°C): 0.38% Water absorption (1 hour/23°C): 0.28% Breakdown voltage (50C, P, 5) (According to IEC Pub, 243) 20 seconds value: 205 to 215 V/crfL tracking resistance (DIN 53480): KA3cA3-tracking resistance (ASTM 495): Stage 3 dielectric loss factor ta
nδ 50°C: 0.0042 150°C: 0.024 Relative permittivity Er, 50C, P, S 50°C: 3.3 100°C: 3.4 130°C: 3.4 140°C: 3.5 150 °C: 3.6 Specific gravity flow resistance SD (DIN 53482) (Ω・cIr
L) *ku 23°C: 5.10" 80°C: 4.1016 Reference Example 7 Triepoxide 92.8S' produced according to Example 16 containing 5.39 epoxide equivalents/kg and hexahydrophthalic anhydride 73.2P is mixed, worked up and cured analogously to Reference Example 2.

The obtained molded product has the following properties.

Bending strength VSM 77103): 10.22-13
, 27 kp/mA Deflection (VSM 77103): 4.1-5.9
mm Impact bending strength VSM 77105) 11.75~
15,75cIfL-kp/crri Dimensional stability at high temperatures according to Martens (DIN): 1
47°C Heat distortion (DIN 53461): 156-158C Water absorption (4 days/23°C): 0.50% Water absorption (1 hour/100°C) 0.37% Reference example 8 Comparative test (a) 9. A mixture consisting of 100 f of commercially available triglycidyl isocyanurate containing tertiary poxide equivalents/kg and 135 g of hexahydrophthalic anhydride is prepared as described in Reference Example 2.

Post-treatment and curing according to Reference Example 2.

(b) 1,3-dipropyl-5,7-sibricidylglycoluril 1001 according to DO81932305
While heating, mix with 41.6 P of hexahydrophthalic anhydride.

The mixture was then heated in the aluminum mold at 140°C.
Time to cure.

The results of the comparative test are shown in the table below.

The following can be seen from the table.

(a) The processability as a casting resin is excellent in the mixture according to Reference Example 2; (b) The mechanical strength of the mixture cured according to Reference Example 2 is somewhat higher than that of the comparative materials, especially the material of section (a).

(c) In particular, the electrical properties of the sample cured according to Reference Example 2 are better than those of the glycoluril derivative at temperatures of 140° C. or higher.

Claims (1)

[Claims] 1 General formula (1): [wherein, X represents a divalent group represented by the following formula: (wherein, n represents a number of 4 or 5). ] In the presence of a hydrogen halide removing agent, 1,3-dichloro-propanol-2 containing a residue R (R represents the meaning below) at the 2-position By reacting with 1 mole of halogenhydrin, a bishydantoin represented by the general formula (1): (wherein, X has the meaning described above, and R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) Compound, then formula■
A heterocyclic compound represented by the general formula (1): (wherein R and )・Production method of liglycidyl compound.