JPH04255714A - Polyfunctional epoxy resin and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyfunctional epoxy resin and a method for producing the same.

0002

[Background Art] In recent years, with the progress especially in the field of advanced materials,
There is a need to develop base resins with higher performance. For example, epoxy resins used as composite matrix resins used in the aerospace industry are strongly required to have even higher heat resistance and moisture resistance.

However, none of the conventionally known epoxy resins is yet known that satisfies these requirements. For example, the well-known bisphenol-type epoxy resin is liquid at room temperature and is widely used because it has excellent workability and is easy to mix with hardeners, additives, etc., but it has poor heat resistance and moisture resistance. There is a problem with this. Phenol novolak type epoxy resins are known as having improved heat resistance, but they have problems with moisture resistance and impact resistance.

[0004] Therefore, an epoxidized product of phenol aralkyl resin has been proposed for the purpose of improving moisture resistance and impact resistance (Japanese Patent Application Laid-Open No. 63-238,122), but this epoxy compound also has poor heat resistance. is not enough.

[0005] Epoxy compounds of divalent phenol aralkyl resins have also been proposed for the purpose of high heat resistance (
(Special Publication No. 1-79,215). However, this epoxy compound does not have sufficient moisture resistance.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to have excellent performance in heat resistance, moisture resistance, and mechanical properties such as impact resistance, and to be suitable for lamination, molding, casting, etc. An object of the present invention is to provide an epoxy resin useful for applications such as adhesives and a method for producing the same.

[0007]

[Means for Solving the Problems] That is, the present invention provides the following general formula (I)

[C4] It is a polyfunctional epoxy resin represented by

The present invention also provides a polycyclic aromatic dihydroxy compound and 0.1 to 0.9 mol of the following general formula (II) per 1 mol of the polycyclic aromatic dihydroxy compound.

[Chemical Formula 5] By reacting with a condensing agent represented by the following general formula (III
)

This is a method for producing a polyfunctional epoxy resin, which is characterized by producing a polyvalent hydroxy compound represented by the following formula, and then reacting this polyvalent hydroxy compound with epichlorohydrin.

In the polyfunctional epoxy resin represented by the above general formula (I), A is a polycyclic aromatic group, and G is

[C7
] In the glycidyl group represented by R is a hydrogen atom or a methyl group. The polycyclic aromatic group is preferably a fused or non-fused two-ring aromatic group, with particularly preferred examples being a naphthalene group or a biphenyl group. In the polycyclic aromatic group, the glycidyl group may be substituted at any position; for example, in the case of a naphthalene group, it may be at the 1st or 2nd position.

The polyhydric hydroxy compound represented by the general formula (III), which is a raw material for the polyfunctional epoxy resin represented by the general formula (I), contains a polycyclic aromatic diol and the polyfunctional epoxy resin represented by the general formula (II). It can be obtained by reacting the indicated condensing agent.

Examples of polycyclic aromatic diols include dihydroxy compounds such as naphthalene, biphenyl, acenaphthene, fluorene, dibenzofuran, anthracene, and phenanthrene, and bisphenols such as bisphenol F, bisphenol A, bisphenol S, and bisphenol fluorene. . Preferred are dihydroxy compounds of naphthalene and biphenyl. Specifically, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,6-naphthalenediol, 2,
These include 7-naphthalenediol, 4,4-dihydroxybiphenyl, 2,2-dihydroxybiphenyl, and the like.

As the condensing agent represented by the general formula (2),
It may be o-form, m-form, or p-form, but preferably m-form or p-form, and specifically, p-xylylene glycol, α,α'-dimethoxy-p-xylene, α
, α'-diethoxy-p-xylene, α, α'-di-n
-propoxy-p-xylene, α,α'-diisopropoxy-p-xylene, 1,4-di(2-hydroxy-2
-propyl)benzene, 1,4-di(2-methoxy-2
-propyl)benzene, 1,4-di(2-n-propoxy-2-propyl)benzene, 1,4-di(2-isopropoxy-2-propyl)benzene, and the like.

[0013] When the polycyclic aromatic diol and the condensing agent are reacted, the molar ratio of the two should be 1 mole or less of the condensing agent per 1 mole of the polycyclic aromatic diol, preferably 0. It is in the range of 1 to 0.9. If it is less than 0.1 mol, the amount of unreacted polycyclic aromatic diol increases, which reduces the heat resistance of the cured resin product when used as an epoxy resin. Moreover, if it exceeds 0.9 mol, the softening point of the resin becomes high, which may impede the workability of the resin depending on the application. Also,
In general formula (III), n is preferably 15 or less.

The reaction of producing a polyhydric hydroxy compound by reacting the polycyclic aromatic diol with the condensing agent is carried out in the presence of an acid catalyst. This acid catalyst can be appropriately selected from well-known inorganic acids and organic acids, such as hydrochloric acid,
Examples include mineral acids such as phosphoric acid and sulfuric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid, and Lewis acids or solid acids such as zinc chloride, aluminum chloride, and iron chloride.

[0015] This reaction is usually carried out at a temperature of 10 to 250°C and a temperature of 1 to 20°C.
Time is done. In addition, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, diethylene glycol, methyl cellosolve, and ethyl cellosolve, and aromatic hydrocarbons such as benzene, toluene, chlorobenzene, and dichlorobenzene are used as solvents. You can also use

The polyfunctional epoxy resin of the present invention is produced by reacting a polyhydric hydroxy compound represented by the above general formula (III) with epichlorohydrin. This reaction can be carried out in the same manner as a normal epoxidation reaction.

For example, after dissolving the polyvalent hydroxy compound represented by the above general formula (III) in excess epichlorohydrin, the solution is heated at 50 to 150°C in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. , preferably a method of reacting at a temperature of 60 to 120°C for about 1 to 10 hours. The amount of epichlorohydrin used in this case is in the range of 2 to 15 times, preferably 2 to 10 times, the number of moles of hydroxy groups in the polyhydric hydroxy compound. Further, the amount of alkali metal hydroxide used is 0.8 to 1.2 times the mole number of hydroxy groups in the polyhydric hydroxy compound, preferably 0.9 to 1.1 times the mole number of hydroxy groups in the polyvalent hydroxy compound.
It is in the double molar range.

After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off. The desired epoxy resin can be obtained.

In the general formula (I), n is preferably 15 or less, more preferably 10 or less. n is 15
If it is larger, the softening point of the resin will rise, which will impede workability.

[0020]

[Examples] The present invention will be explained in more detail below by showing examples of the present invention. (Synthesis of polyvalent hydroxy compound) Reference example 1,6-dihydroxynaphthalene 16
0 g (1.0 mol), p-xylylene glycol 82.
Add 8g (0.6mol) and add 0.8g of oxalic acid.
was added, and the mixture was reacted at 150° C. for 4 hours with stirring under a nitrogen stream. During this time, the water produced was removed from the system to obtain 214 g of a brown resin. The resulting resin had an OH equivalent of 112 and a softening point of 136° C. as measured in accordance with JIS K 2548. G of the obtained resin
PC chart

It is shown in FIG.

Reference Example 2 A reaction was carried out in the same manner as in Reference Example 1 using 160 g (1.0 mol) of 1,7-dihydroxynaphthalene and 69.0 g (0.5 mol) of p-xylylene glycol. 211 g of resin was obtained. The resulting resin had an OH equivalent of 107 and a softening point of 135°C. GP of the obtained resin
C chart

It is shown in FIG.

Reference Example 3 A reaction was carried out in the same manner as in Reference Example 2 using 160 g (1.0 mol) of 2,7-dihydroxynaphthalene and 69.0 g (0.5 mol) of p-xylylene glycol. 212 g of resin was obtained. The resulting resin had an OH equivalent of 107 and a softening point of 136°C. GP of the obtained resin
C chart

It is shown in FIG.

Reference Example 4 A reaction was carried out in the same manner as in Reference Example 2, except that 186 g (1.0 mol) of 2,2'-dihydroxybiphenyl and 37.0 g of oxalic acid were used to obtain 234 g of a brown resin. The resulting resin had an OH equivalent of 133 and a softening point of 93°C. GPC chart of the obtained resin

It is shown in FIG.

Reference Example 5 80 g (0.5 mol) of 1,5-dihydroxynaphthalene and 34.5 g (0.25 mol) of p-xylylene glycol were placed in a 500 ml four-necked flask, and 200 ml of ethyl cellosolve was added. Dissolved. After dissolution, p
- 3.2 g of toluenesulfonic acid was added, and the mixture was reacted at 130° C. for 8 hours with stirring under a nitrogen stream. After the reaction, the reaction solution was gradually added to a large amount of water with vigorous stirring, and the resulting resin was filtered, washed with water, and dried to obtain 103 g of a powdery brown resin. The resulting resin had an OH equivalent of 106. GPC chart of the obtained resin

It is shown in FIG.

Reference Example 6 The reaction was carried out in the same manner as in Reference Example 5, except that 93 g (0.5 mol) of 4,4'-dihydroxybiphenyl, 260 ml of ethyl cellosolve, and 5.6 g of p-toluenesulfonic acid were added. 112 g of resin was obtained. The resulting resin had an OH equivalent of 124. GPC chart of the obtained resin

It is shown in FIG.

Example 1 100 g of the resin obtained in Reference Example 1 was mixed with 60 g of epichlorohydrin.
0 g, further added 0.3 g of benzyltriethylammonium chloride, and under reduced pressure (150 mmHg),
At 70°C, 73 g of a 40% aqueous sodium hydroxide solution was added dropwise over 3 hours. During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the dropwise addition was completed, the reaction was continued for an additional 30 minutes. Thereafter, the produced salts were removed by filtration, and after further washing with water, epichlorohydrin was distilled off to obtain 141 g of epoxy resin. The epoxy equivalent weight was 176 and the softening point was 96°C. GPC chart of the obtained resin

It is shown in FIG.

[0027] Using this resin,

[Table 1] After preparing an epoxy resin composition with the formulation shown in Table 1, molding (
160° C. for 3 minutes) to obtain a cured test piece. The test piece is 18
After post-curing at 0°C for 12 hours, it was subjected to various physical property tests. results

It is shown in [Table 1].

Example 2 Using 100 g of the resin obtained in Reference Example 2, a reaction was carried out in the same manner as in Example 1 to obtain 148 g of epoxy resin. The epoxy equivalent weight was 173 and the softening point was 79°C. GPC chart of the obtained resin

It is shown in FIG. This resin was subjected to various physical property tests in the same manner as in Example 1. results

It is shown in [Table 1].

Example 3 Using 100 g of the resin obtained in Reference Example 3, a reaction was carried out in the same manner as in Example 1 to obtain 144 g of epoxy resin. The epoxy equivalent weight was 184 and the softening point was 72°C. GPC chart of the obtained resin

It is shown in FIG. This resin was subjected to various physical property tests in the same manner as in Example 1. results

It is shown in [Table 1].

Example 4 Using 100 g of the resin obtained in Reference Example 4, a reaction was carried out in the same manner as in Example 1 to obtain 136 g of epoxy resin. The epoxy equivalent weight was 223 and the softening point was 64°C. GPC chart of the obtained resin

It is shown in FIG. This resin was subjected to various physical property tests in the same manner as in Example 1. results

It is shown in [Table 1].

Example 5 Using 100 g of the resin obtained in Reference Example 5, a reaction was carried out in the same manner as in Example 1 to obtain 139 g of epoxy resin. The epoxy equivalent weight was 226 and the softening point was 69°C. GPC chart of the obtained resin

It is shown in FIG. This resin was subjected to various physical property tests in the same manner as in Example 1. results

It is shown in [Table 1].

Example 6 Using 100 g of the resin obtained in Reference Example 5, a reaction was carried out in the same manner as in Example 1 to obtain 122 g of a crystalline epoxy resin. The epoxy equivalent weight was 193 and the softening point was 113°C. GPC chart of the obtained resin

It is shown in FIG. This resin was subjected to various physical property tests in the same manner as in Example 1. results

It is shown in [Table 1].

Comparative Example o - Using a cresol novolac type epoxy resin, various post-cures were performed in the same manner as in Example 1 to obtain test pieces, which were then subjected to various tests. results

It is shown in [Table 1].

[Table 1]

【Effect of the invention】

The epoxy resin obtained by the present invention can provide a cured product with excellent heat resistance, moisture resistance, and mechanical properties, and can be expected to be used in various applications.

[Brief explanation of the drawing]

FIG. 1 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 1.

FIG. 2 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 2.

FIG. 3 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 3.

FIG. 4 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 4.

FIG. 5 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 5.

FIG. 6 is a GPC chart of the polyhydric hydroxy compound obtained in Reference Example 6.

FIG. 7 is a GPC chart of the epoxy resin obtained in Example 1.

FIG. 8 is a GPC chart of the epoxy resin obtained in Example 2.

FIG. 9 is a GPC chart of the epoxy resin obtained in Example 3.

FIG. 10 shows GPC of the epoxy resin obtained in Example 4.
chart.

FIG. 11 shows GPC of the epoxy resin obtained in Example 5.
chart.

FIG. 12 shows GPC of the epoxy resin obtained in Example 6.
chart.

Claims (3)

[Claims] [Claim 1] The following general formula (I) [Chemical formula 1] A polyfunctional epoxy resin represented by 2. Polycyclic aromatic dihydroxy compound and 0.1 to 1 mole of the polycyclic aromatic dihydroxy compound.
0.9 mol of the following general formula (II) is reacted with a condensing agent represented by the following general formula (III).
) A method for producing a polyfunctional epoxy resin, which comprises producing a polyvalent hydroxy compound represented by the following formula, and then reacting this polyvalent hydroxy compound with epichlorohydrin. 3. The polyfunctional epoxy resin according to claim 1, wherein the polycyclic aromatic group is a fused or non-fused two-ring aromatic group.