JPS5946231B2 - 2,4-diglycidyloxyalkylbenzene - Google Patents

Description

[Detailed description of the invention] The present invention relates to novel epoxy compounds.

More specifically, the present invention relates to a novel epoxy compound of low viscosity suitable for mixing with hardeners, as well as for casting and impregnation. Diglycidyl ether obtained by the reaction of resorcinol and epichlorohydrin has been known.

However, although such epoxy compounds react with curing agents to give cured products with excellent physical properties, they have the drawback of being crystallized at room temperature. That is, when mixed with a curing agent and cured at room temperature, the epoxy compound is in a solid or liquid state containing solids, so a uniform mixture with the curing agent cannot be obtained, and therefore curing is difficult. It was hot. Therefore, the usual procedure is to heat and melt the epoxy compound for a short period of time, then mix it with a curing agent while it is in a liquid state either as it is or at a slightly lower temperature, and then harden it at a predetermined temperature. was. Further, examples of liquid epoxy compounds having low viscosity at room temperature include cyclopoxy such as epoxidized vinylcyclohexene, but such epoxy compounds cannot be cured at room temperature.

Therefore, the present inventors conducted extensive research in order to obtain an epoxy compound that can be easily mixed with a curing agent and cured at room temperature without performing operations such as heating and melting as described above. As a result, a novel epoxy compound was obtained which is a liquid with low viscosity at room temperature and gives a cured product having excellent physical properties, thereby completing the present invention. That is,
The gist of the present invention resides in 2,4-diglycidyloxyalkylbenzenes of the formula:

Next, to explain the present invention in detail, the novel epoxy compound of the present invention can be synthesized by various manufacturing methods.

The second and third embodiments of the novel epoxy compound of the present invention are shown below. Usually using resorcinol derivatives as raw materials,
It can be easily manufactured. The resorcinol derivative referred to herein refers to a compound represented by the formula: 2,4-dihydroxytoluene.

As a method for producing the epoxy compound end of the present invention using the above-mentioned resorcinol derivative as a raw material, first, a method for producing it by reacting a reso C-rucinol derivative and an epihalohydrin in the presence of an alkali can be mentioned.

This method will be specifically explained below. The amount of epihalohydrin used is 1 resorcinol derivative
Usually 1 to 20] mol, preferably 6 to 1 mol
It is 5 moles. Further, it is preferable that excess epihalohydrin is recovered by distillation and reused. Examples of the alkali used in the reaction include sodium hydroxide, potassium hydroxide, pentabarium hydroxide, calcium hydroxide, sodium carbonate, and potassium carbonate, but strong alkalis such as sodium hydroxide or potassium hydroxide are preferred. suitable.

In addition, the amount of these alkalis used is usually 2 to 2.5 mol per 1 mol of the resorcinol derivative as a raw material.
It is added to the reaction system as an aqueous solution. The addition time may be at the same time as the start of heating distillation of the raw material, but it is most preferable to add it sequentially as the reaction progresses, since this is efficient. The reaction temperature is appropriately selected from the compounds to be reacted (1), but is usually room temperature to 30'C, preferably 80 to 15'C.

The reaction time can be changed as appropriate depending on the reaction temperature, but it is until the reaction is substantially completed, and is usually 1 to 20 minutes.
time, preferably 2 to 5 hours. After the completion of the reaction, the target epoxy compound is obtained by removing excess epihalohydrin and water under reduced pressure, and then removing the generated alkali halide from door to door.

Usually, after removing epihalohydrin and water, the residue is dissolved in a solvent such as benzene or toluene, and sodium chloride,
After alkali halides such as potassium chloride and atrium bromide are separated from each other, the desired epoxy compound is obtained by distillation under reduced pressure. The epoxy compound of the present invention can also be produced by reacting a resorcinol derivative with a dihalohydrin or a dihalohydrin in the presence of an alkali.

Examples of the dihalohydrin used include dichlorohydrin, dibromohydrin, and the like. This production method uses dihalohydrin instead of epihalohydrin in the first method, and requires twice the amount of alkali used in the reaction as in the first method. It can be produced under almost the same reaction conditions except for the following. Furthermore, the epoxy compound of the present invention can also be produced by reacting a resorcinol derivative with an allyl halide in the presence of an alkali, and then epoxidizing the double bond in the allyloxy group.

Examples of the allyl halide used include allyl chloride, allyl bromide, and the like. As the alkali used in the reaction, sodium hydroxide, potassium hydroxide, sodium carbonate, etc. are usually used, and the amount used is usually 2 to 2.5 mol per 1 mol of the resorcinol derivative as the raw material. Through this reaction, the hydroxyl group of the resorcinol derivative becomes an allyloxy group. Furthermore, the double bond in this substituent can be epoxidized with hydrogen peroxide or a peracid such as peracetic acid or performic acid (this allows the production of the epoxy compound of the present invention. The epoxy compound of the present invention can also be produced by reacting the derivative and allyl alcohol in the presence of a dehydration catalyst, such as an acid, converting the hydroxyl group of the resorcinol derivative to an allyloxy group, and then epoxidizing the double bond in this substituent. can be manufactured.

For epoxidation, hydrogen peroxide or peracetic acid,
Use a peracid such as performic acid. The epoxy compound of the present invention obtained as described above is a diglycidyl ether of the resorcinol derivative used as the raw material.

Such an epoxy compound is cured with a curing agent and put into practical use as an epoxy resin.

When used in combination with a curing agent, the epoxy compound of the present invention can be used not only alone, but also with one or more other epoxy compounds, such as 2,6-dihydroxytoluene, 3,5-dihydroxytoluene, resorcinol. Alternatively, it can be used in combination with a polyglycidyl ether such as bisphenol A. When mixed and used, the characteristics of the epoxy compound of the present invention can be achieved by using the epoxy compound of the present invention in an amount of 50% by weight or more based on the total amount, especially 75% by weight or more when mixed with other non-crystalline epoxy compounds. It's good that it's fully utilized. The curing agents used include those similar to those used in known epoxy resins, such as aliphatic amines, aromatic amines, heterocyclic amines, complex salts of amines and boron trifluoride, and organic acid anhydrides. , urea or its derivatives, and polymercaptan.

Among these, Amis type curing agents are particularly suitable as room temperature curing agents.

Furthermore, since the epoxy compound of the present invention is a liquid with low viscosity at room temperature, it can be easily mixed and hardened at room temperature with hardening agents such as diethylenetriamine, triethylene detramis, dipropylenetriamine, 3 ，
Butyl glycidyl ether adduct of 9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro[5,5]undecane (2:1)N-(2-aminoethyl)piperazine, metaxylylene di Amine, 1,3-bis(aminomethyl)cyclohexane, 3-aminomethyl-
3.5,5-trimethylcyclohexylamine, polyamidoamine, etc. are suitable. During curing, plasticizer,
Organic solvents, reactive diluents, extenders, fillers, reinforcement cutting,
Pigments, dyes, flame retardants, flow inhibitors, flexibility agents, etc. can also be mixed. The method for producing and utilizing the epoxy compound of the present invention has been described in detail above. Since such an epoxy compound is a non-crystalline, low-viscosity liquid at room temperature, it is easy to mix with the Tanitane hardening agent, and especially Desirable for casting and impregnating operations.

Furthermore, the cured product obtained by hardening has better physical properties such as adhesive strength than conventional general-purpose Epibis or diglycidyl ester of phthalic acid.

The epoxy compound of the present invention has the above-mentioned excellent characteristics, and can be used in a wide range of fields similar to those in which conventional epoxy resins have been used, particularly in paints, adhesives, laminated products, sealants, and grouts. It is expected to be applied in fields such as finishing agents. Hereinafter, the method for producing and utilizing the epoxy compound of the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. In the following reference examples, "part" indicates "part by weight" and "%" indicates "% by weight." Production example 2,4-dihydroxytoluene 372.4g (3.00g
mol) and epichlorohydrin 2220.69 (24,0
0 mol) was placed in a 51-3-hole flask equipped with a distillation device, the internal temperature was maintained at 120°C, the mixture was sufficiently stirred, and while distilling, a 50(Fb sodium hydroxide) aqueous solution of 49.69 mol was added to the system.
(6.20 monole as NaOH) was added for 6 hours.

When this addition started, the reaction progressed and a mixture of water and epichlorohydrin distilled out, so this was separated and the epichlorohydrin was returned to the reaction system.
After adding sodium hydroxide, heat for 30 minutes,
As much epichlorohydrin as possible was distilled off at normal pressure. The temperature of the contents of the flask began to rise without any distillation of epichlorohydrin. When the internal temperature reached 1,500 C1, heating distillation was stopped, benzene 11 was added, and the sodium chloride produced by the reaction was removed from door to door. Benzene was distilled off from this benzene-containing solution under reduced pressure of 3 mmHg.

In this way, 521.0 g of distillate and 192.29 g of non-volatile bottom material were obtained.

The epoxy value of this distillate is 0.861 eqm01/10
0f! It was hot. This distillate is further rectified and the first distillate is 105
．． Main distillate of 4g and 180C/3m1LHg 384.5
9 and about 259 residues were obtained. This main fraction was found to be a novel epoxy compound by elemental analysis, epoxy value, IR spectrum, and NMR spectrum.
It was confirmed that the main component is -dihydroxytoluene diglycidyl ether (abbreviated as 2,4-DHTD).

The various analysis results are shown in Table 1, and the 1R spectrum and NM
The R spectra are shown in Figures 1 and 2, respectively. 2,4-DHTDl2,4-DHTD obtained in Reference Example Production Example
and 2,6-DHTD and various other epoxy compounds as control products of the present invention at 10 to 50°C.
The viscosity was measured using an Emira rheometer at a temperature of .

The results are shown in Table 2. Note that the mixture of 2,4-DHTD and 2,6-DHTD is the 2,4-DHTD obtained in the production example.
2,6-dihydroxytoluene synthesized from 75 parts of 4-DHTD and 2,6-dihydroxytoluene according to the same method as in the production example.
It was prepared by heating and mixing 2.5 parts of DHTD.

As is clear from Table 2, the diglycidyl ether of bisphenol A and the diglycidyl ester of phthalic acid already have a very high viscosity at around 20° C., and the diglycidyl ether of resorcinol has crystallized and gradually However, the product of the present invention has a low viscosity even at temperatures below 20°C, and is difficult to operate when mixing with a curing agent.
It can be seen that it is suitable for use at temperatures below room temperature.

Application Example The adhesive strength of various epoxy compounds obtained in the production examples of the present invention and control products of the present invention was measured in accordance with JISS6O4Ol when cured with two types of curing agents.

That is, 1,3-bis(aminomethyl) as a curing agent.
A theoretical amount of cyclohexane is added to the epoxy compound,
Table 3 shows the adhesive strength when cured for 24 hours at 10 C or 24 hours at 20 C.
Table 4 shows the adhesive strength when a predetermined amount of 0 (polyamide amine having an amine value of 350 to 400, manufactured by Daiichi General Co., Ltd.) was blended and cured for 24 hours.

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum diagram of the epoxy compound obtained in the production example, and FIG. 2 is an NMR spectrum diagram of the same compound.

Claims (1)

[Claims] 1. 2,4-dicrycidyloxyalkylbenzene represented by the formula ▲ Numerical formula, chemical formula, table, etc. are available▼.