JPS58194874A - Tetrafunctional epoxy compound - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H or CH3). EXAMPLE:1,4-Tetrakis-[beta-methylglycidyloxyphenyl]cyclohexane. USE:A component in epoxy resins, having improved heat resistance, and capable of giving cured articles having improved physical properties. PROCESS:4mol phenol is reacted with 1mol 1,4-cyclohexanedione to give 1,4-tetrakis [hydroxyphenyl]cyclohexane of formula II, which is then reacted with an epihalohydrin or beta-methylepihalohydrin in the presence of a catalyst, e.g. a quaternary ammonium salt, at 50-150 deg.C to form a halohydrin ether. The resultant halohydrin ether is further subjected to the ring closure with an alkaline agent at 35-85 deg.C to afford the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel tetrafunctional epoxy compounds which are useful alone or in combination with other epoxy compounds to provide epoxy resins exhibiting excellent cured physical properties.

Epoxy resins are widely used as thermosetting resins in various fields such as coating, lamination, painting, adhesion, sealing, and molding. As polyfunctional epoxy compounds for epoxy resins, various epoxy compounds such as glycidyl ether type and glycidyl ester type are known. However, the types and physical properties of known polyfunctional epoxy compounds are not necessarily sufficient to satisfy all of the many different resin applications in terms of properties such as curing properties and curing speed.

Example: A bifunctional engineered poxy compound obtained by reacting evabisphenol A and epichlorohydrin in the presence of an aqueous solution of caustic soda has a low heat distortion temperature, and when kept at high temperatures for a long time, the bending strength decreases and the weight decreases significantly. It has its drawbacks.

In addition, Epicoat 103 manufactured by Shell Chemical represented by the following formula
Although it is intended to improve the drawbacks of the above-mentioned difunctional engineered poxy compounds, it is not currently commercially available.

The present inventors focused on the fact that a more polyfunctional epoxy compound or an epoxy compound with more aromatic rings gives a cured epoxy resin product with better heat resistance, and the inventors discovered that [-] By examining various phenol compounds and performing a dehydration condensation reaction between a -valent phenol compound and 1,4-cyclohexanedione, a polyhydric phenol compound having four phenolic hydroxyl groups in the -molecule was obtained. The present invention was completed based on the discovery that a tetrafunctional epoxy compound produced by reacting shrimp halohydrin and then completing the ring-closing reaction with caustic soda can provide a cured product with excellent heat resistance when used with a curing agent.

That is, the present invention provides a tetrafunctional epoxy compound represented by the general formula (1), in which RFiH or CHs is represented.

This tetrafunctional epoxy compound is 1,4-tetrakis[hydroxyphenylcocyclohexane] represented by the following formula (n) obtained by reacting 4 moles of phenol with 1 mole of 1,4-cyclohegysandione f. First, epihalohydrin or β-methylepihalohydrin is reacted at 50 to 150°C in the presence of a catalyst such as a quaternary ammonium salt or a phosphonium salt to form a halohydrin ether, and then an alkali such as caustic soda or caustic potash is reacted to form a halohydrin ether. It can be obtained by carrying out a ring-closing reaction at 35 to 85°C with an agent.

Further, it can be produced by performing addition reaction and dehydrohalogenation reaction at once using an alkaline agent such as caustic soda or caustic potash. The former two-step method can produce an epoxy compound more stably and with higher yield than the latter one-step method.

Examples of the shrimp halohydrin or β-methyl epihalohydrin used as a raw material include epichlorohydrin, shrimp halohydrin, β-methylepichlorohydrin, and β-methyl shrimp bromohydrin.

The amount of shrimp lohydrin or β-methyl epihalohydrin used is 4 to 40 mol, preferably Fi 6 to 20 mol, per 1 mol of the raw material tetravalent phenol compound.

Excessly used epihalohydrin or β-methyl epihalohydrin can be recovered by distillation and reused.

In addition, as a catalyst, for example, tetramethylammonium chloride, tetraethylammonium bromide,
Quaternary ammonium salts such as triethylmethylammonium chloride, tetraethylammonium iodide, cetyltriethylammonium cumbromide, benzyldimethylamine, triethylamine, N, N, N'
, N'-tetramethylny5=tertiary amines such as ethylene diamine, triphenylethylphosphonium diethyl phosphate, and the like.

Particularly preferred are tetramethylammonium chloride or tetraethylammonium bromide.

The amount of catalyst used is usually 1 1 of the raw material tetravalent phenol compound.
The amount is about 0.1 to 3.0 parts by weight per 1 part by weight of 0.00 weight.

Furthermore, examples of alkaline agents include sodium hydroxide,
potassium hydroxide, barium hydroxide, calcium hydroxide,
Examples include potassium carbonate and sodium carbonate, but sodium hydroxide or potassium hydroxide is preferred. The amount of this alkaline agent used is usually 4 to 5 mol per 1 mol of the raw material tetravalent phenol compound. The alkali is usually added to the reaction system in the form of solid particles or as an aqueous solution.

The reaction time is until the reaction is substantially completed, and varies depending on the reaction temperature, etc., but is usually 2 to 10 hours, preferably 2 to 5 hours.

After the reaction is completed, excess epihalohydrin, β-methylepihalohydrin and water are removed under reduced pressure, and the alkali halogenide produced as a by-product is removed from each household to obtain the epoxy compound of the present invention.

In addition, other monohydric phenol compounds such as ortho-cresol, meta-cresol, vala-cresol, ortho-bromophenol, meta-bromophenol, parafuromophenol, propylphenol, butylphenol, octylphenol, nonylphenol, etc. may be used instead of phenol, which is the raw material for polyhydric phenol. can be used, but in this case, the yield of the tetrahydric phenol compound obtained is low, so it is not economical.

Furthermore, it is conceivable to use 1,2-cyclohexanedione and 1,3-cyclohexanedione instead of 1,4-cyclohexanedione as raw materials for providing the polyhydric phenol isomer shown in the structural formula category, but the former is difficult to react with phenol due to steric hindrance. Furthermore, the latter is sold as a reagent and is difficult to obtain industrially in large quantities, making the resulting polyphenol expensive.

As is clear from its structural formula, the tetrafunctional epoxy compound of the present invention produced in this manner is a tetraglycidyl etherified product of the tetravalent phenol compound used as a raw material.

This tetrafunctional epoxy compound includes methyl isobutyl ketone, toluene, xylene, chloroform, trichlene,
Soluble in solvents such as ethyl acetate.

This tetrafunctional epoxy compound can be used alone or in combination with other epoxy compounds for use as an epoxy resin. In other words, if a tetrafunctional epoxy compound is used alone or in combination with one or more other epoxy compounds and is subjected to a curing (crosslinking) reaction with an appropriate curing agent, the thermal properties can be improved. The result is a cured product with outstanding properties. There are no particular restrictions on the other epoxy compounds used in combination, and various epoxy compounds may be used in combination depending on the intended use. Examples of other epoxy compounds used in combination include polyglycidyl ethers such as bisphenol A or bromobisphenol A, polyglycidyl esters such as phthalic acid and cyclohexanedicarboxylic acid, or polyglycidyl amines with aniline or toluidine, etc. etc., monoepoxy compounds such as styrene oxide, cyclohexene oxide, phenyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, persatic acid glycidyl ester, etc., these are 10
It is used in combination with the epoxy compound of the present invention in a proportion of ~90% by weight.

Furthermore, in the epoxy resin using the epoxy compound of the present invention, various curing agents similar to those used in known epoxy resins can be used. For example, aliphatic amines, aromatic amines, heterocyclic amines, Lewis acids such as boron trifluoride and their salts, organic acids, organic acid anhydrides,
Examples include urea or derivatives thereof, and polymercaptans. Specific examples include aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfon, 2,4-diamino-m-xylene; 2-methylimidazole, 2,4.5-triphenylimidazole, 1-dianoe; 1,000 Roux 2 = imidazole such as methyl imidazole, 1,2 < is an imidazole substituted product or a salt of these with an organic acid; organic carboxylic acid such as fumaric acid, trimellitic acid, hexahydrophthalic acid; phthalic anhydride, endo anhydride methylenetetrahydrophthalic acid,
Organic acid anhydrides such as hexahydrofuric anhydride; urea derivatives such as dicyandiamide, melamine, and guanamine; aliphatic polyamines such as nitriethylenetetramine, diethylenetriamine, xylylenediamine, and inphorondiamine; and their ethylene oxide, propylene oxide, etc. Epoxy compounds or adducts with acrylic compounds such as acrylonitrile and acrylic acid can be used.

Furthermore, in addition to a curing agent, the epoxy resin using the epoxy compound of the present invention may optionally contain a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, and a flame retardant. Various additives such as agents, thickeners, and agents for imparting flexibility can be blended.

The epoxy resin cured product using the epoxy compound of the present invention has significantly superior thermal properties such as heat distortion temperature, and has the same or higher mechanical properties than conventional general-purpose bisphenol-based epoxy resins. be. Therefore, this epoxy compound can be advantageously used in various fields such as molding, adhesion, painting, and lamination similar to those for conventional epoxy resins.

A more specific explanation will be given below with reference to Examples, but these Examples are merely illustrative and the present invention is not limited by the Examples.

Example 1 454 parts of 1,4-tetrakis[hydroxyphenyl]cyclohexane, 1.480 parts of epichlorohydrin and 2.72 parts of tetramethylammonium bromide were placed in a 40 flask and reacted at 100°C for about 2 hours.

Next, 330 parts of a 48.5% aqueous solution of caustic soda was gradually added dropwise over a period of 2 hours under conditions of a reaction pressure of about 140 wn Hg% and about 60°C, and the resulting water was removed to carry out a reaction. The reaction was further maintained at the same temperature for 2 hours to complete the reaction.

After the reaction was completed, excess epichlorohydrin was distilled off under reduced pressure, and then dissolved in 1,000 parts of methyl isobutyl ketone, and further washed 2 to 3 times with 1,000 parts of water.

Finally, methyl isobutyl ketone was distilled off to obtain about 630 parts of a brown solid product.

The infrared absorption spectrum of this solid material is shown in FIG.

The melting point of this solid is approximately 71°C, and the epoxy equivalent is 1
90 (theoretical amount 170 Y19 From these results, the solid substance has the general formula [0, where R is H
It is estimated to be an epoxy compound.

Example 2 1,600 parts of β-methylepichlorohydrin was used instead of 1,480 parts of epichlorohydrin.
゛□In the same manner as in Example 1, 1,4-tetrakis-[β-
Methylglycidyloxyphenyl]cyclohexane was obtained in a yield of about 98%.

This product was a brown solid with a melting point of about 76°C and an epoxy equivalent weight of 200.

The tetrafunctional epoxy compound obtained in each example and the diglycidyl ether of bisphenol A "Epicote 828"
” (trade name manufactured by Shell Chemical Co., Ltd.: epoxy equivalent weight 190) was mixed with methyl nadic anhydride as a curing agent and N,N-dimethylbenzylamine as a curing accelerator in the proportions shown in Table 1, and was heated under a reduced pressure of 1. Ota Hg. After degassing for 10 minutes, it was poured into a casting sheet metal mold, precured at 80°C for 3 hours, heated at 150°C for 3 hours, and then heated at 200°C for 3 hours to completely cure. Width 150-1 Thickness 30
A cured product of +s was obtained.

Table 1 shows the physical properties of the obtained cured product.

As understood from the table, the tetrafunctional epoxy compound of the present invention provides a cured product with excellent heat resistance compared to the difunctional epoxy compound.

Note that the measurement was performed according to the following method.

13- Heat deformation temperature: ASTM D-648 Bending strength 1f: JIS K-6911 Tensile strength: Same as above (margin below) 14- Figure 1 shows ■1lptJ11pL obtained in Example 1 of the present invention
! FIG. 1 is an infrared absorption spectrum diagram of one leg of Itton Jun.

Patent applicant: Mitsubishi Yuka Co., Ltd. Agent: Patent Attorney Hidetoshi Furukawa Agent: Patent Attorney Masahisa Nagatani

Claims (1)

[Claims] 1) A novel tetrafunctional epoxy compound represented by the general formula: [wherein R is H or FiCHa].