JPH0254812B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel polynuclear polyhydric phenols that can provide epoxy resin curable compositions with excellent heat resistance properties by forming polyglycidyl ethers, and a method for producing the same. More specifically, the present invention relates to novel polynuclear polyhydric phenols that can form epoxy resin curable compositions with excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat elastic properties. Conventionally, various compounds have been proposed as polyepoxy compounds used in epoxy resin curable compositions. Recently, in the fields of molding materials, varnishes, printed circuit laminates, optical composite materials (ACM), etc.
There is a demand for an epoxy resin curable composition that has excellent heat resistance properties such as glass transition temperature, heat distortion temperature, and heat elastic properties. Conventionally, as polyepoxy compounds constituting heat-resistant epoxy resin curable compositions, epoxidized phenol novolak resins, epoxidized orthocresol novolak resins, 1,
polyglycidyl ethers of polynuclear polyhydric phenols such as tetraglycidyl ether of 1,2,2-tetrakis(p-hydroxyphenyl)ethane;
Tetraglycidylated xylylenediamine,
Polyglycidylated aromatic polyamines such as hexaglycidylated 1,3,5-triaminomethylbenzyl and triglycidylated isocyanuric acid are widely used. However, epoxy resin curable compositions using these polyepoxy compounds do not have sufficient heat resistance properties as described above, and cannot be used in fields that require heat resistance properties. There is a need for the development of excellent epoxy resin curable compositions. Moreover, many polynuclear polyvalent phenols other than the above-mentioned polynuclear polyvalent phenols have been known so far. For example, ω,ω'-bis(3,4-dihydroxyphenyl)xylene (Japanese Patent Publication No. 13869/1989), 2,4-bis(2,4-dimethylbenzyl)-6-(2-hydroxybenzyl) Phenol [Hiroshi Kakiuchi, Yoshio Tanaka; Polymer Chemistry, 20 , 643
(1963)], 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane and 1,1,5,5-tetrakis(4-hydroxyphenyl)pentane [D.Aelony; J.Applied Polymer Sci ., 4 , 141
(1960)], 1,3-bis(2-p-hydroxyphenyl-2-propyl)benzene [JP-A-58-
13528], 1,4-bis(2-p-hydroxyphenyl-2-propyl)benzene [JP-A-58
Polynuclear polyhydric phenols such as [Publication No. 18331] have been proposed, but even if these polyglycidyl ethers are used as an epoxy resin curable composition, as above, none of them have sufficient heat resistance properties. It could not be used in fields where such characteristics were required. Based on this recognition, the present inventors investigated the development of an epoxy resin curable composition with excellent heat resistance properties, and found that polynuclear polyhydric phenols having a specific structure are novel compounds. It has been discovered that an epoxy resin curable composition using a polyepoxy compound consisting of polyglycidyl ether of polyhydric phenols has excellent heat resistance properties, and the present invention has been achieved. According to the present invention, an epoxy resin curable composition in which a curing agent is blended with a polyepoxy compound consisting of a polyglycidyl ether of a polynuclear polyhydric phenol of the present invention has heat resistance properties such as glass transition temperature, heat distortion temperature, and heat-resistant elastic properties. It has particularly excellent properties and is characterized by excellent mechanical properties such as bending strength, Izot impact strength, and Rockwell hardness. Furthermore, the polynuclear polyhydric phenols of the present invention can be used as stabilizers such as heat-resistant stabilizers, weather-resistant stabilizers, and antioxidants for various polymeric materials, or as curing agents for epoxy resins. To summarize the present invention, the present invention has the general formula [] [Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ] Polynuclear polyhydric phenols represented by the general formula [], [In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and X represents a hydroxyl group or a halogen atom. ] A general formula characterized by reacting with a substituted phenol represented by [] [In the formula, R represents the same group as above, and n represents an integer of 0 to 10. The gist of the manufacturing method invention is a method for manufacturing polynuclear polyhydric phenols represented by the following. The polynuclear polyhydric phenols of the present invention have the general formula [] [Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ] is a polynuclear polyvalent phenol. The dihydroxyphenyl group constituting the polynuclear polyhydric phenol represented by the general formula [] is
3,4-dihydroxyphenyl group, 2,4-dihydroxyphenyl group, or 2,5-dihydroxyphenyl group, and dihydroxyphenylene group is 3,4-dihydroxy-1,6-phenylene group, 2, 4-dihydroxy-1,5-phenylene group or 2,5-dihydroxy-1,3-phenylene group, each of which corresponds to a catechol component unit, a resorcin component unit, or a hydroquinone component unit, and one molecule of polynuclear polyhydric phenol. There is no problem even if two or more types of dihydroxyphenyl groups and two or more types of dihydroxyphenylene groups are included in the group. Further, as R constituting the polynuclear polyhydric phenols represented by the general formula [], hydrogen atoms,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, nonyl group,
Examples include alkyl groups such as decyl group and dodecyl group, aryl groups such as phenyl group, tolyl group, and chlorophenyl group, and halogen atoms such as fluorine, chlorine, and bromine. It does not matter whether it is attached to any position of the para position. In addition, the general formula []
In the polynuclear polyvalent phenols represented by n is an integer from 0 to 10, and these integers are 2
It may also be a mixture of more than one species of polynuclear polyhydric phenols. More specifically, the polynuclear polyhydric phenols represented by the general formula [] of the present invention can be exemplified by the polynuclear polyhydric phenols represented by the following general formulas [] to []. The polynuclear polyvalent phenols of the present invention are produced by combining divalent phenols with the general formula [] in the presence of an acidic catalyst.
It can be produced by reacting with specific substituted phenols represented by: In the method of the present invention, specific examples of dihydric phenols used as raw materials include catechol, resorcinol, and hydroquinone, and mixtures thereof may also be used. The proportion of the dihydric phenol used is usually in the range of 1 to 8, preferably 2 to 4, as a molar ratio to the substituted phenols described below. The substituted phenols used in the method of the present invention have the general formula [] [In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and X represents a hydroxyl group or a halogen atom. ], and more specifically, 2,6-
Bis(hydroxymethyl)phenol, 2,4-
Bis(hydroxymethyl)-6-chlorophenol, 2,6-bis(hydroxymethyl)-p-cresol, 2,4-bis(hydroxymethyl)-
o-cresol, 2,4-bis(hydroxymethyl)-6-ethylphenol, 2,6-bis(hydroxymethyl)-4-propylphenol, 2,
4-bis(hydroxymethyl)-6-bromophenol, 2,6-bis(hydroxymethyl)-4
-hexylphenol, 2,6-bis(hydroxymethyl)-4-octylphenol, 2,4-
Bis(hydroxymethyl)-6-decylphenol, 2,6-bis(hydroxymethyl)-4-dodecylphenol, 2,6-bis(hydroxymethyl)-4-phenylphenol, 2,6-bis(hydroxymethyl) )-4-tolylphenol,
2,6-bis(hydroxymethyl)-4-(p-chlorophenyl)phenol, 2,4-bis(hydroxymethyl)-6-phenylphenol, 2,
6-(chloromethyl)phenol, 2,4-bis(bromomethyl)phenol, 2,6-bis(iodomethyl)-4-chlorophenol, 2,6-
Bis(chloromethyl)-p-cresol, 2,4
-bis(chloromethyl)-o-cresol, 2,
6-bis(chloromethyl)-4-ethylphenol, 2,4-bis(chloromethyl)-6-propylphenol, 2,6-bis(chloromethyl)-
Examples include 4-butylphenol and 2,6-bis(chloromethyl)-4-octylphenol. Specifically, the acidic compounds used in the method of the present invention include sulfuric acid, nitric acid, hydrochloric acid, perchloric acid,
Protonic acids such as phosphoric acid, toluenesulfonic acid and methanesulfonic acid, boron trifluoride, various complexes of boron trifluoride such as boron trifluoride ether complex, aluminum trichloride, tin tetrachloride, zinc chloride, chlorinated chloride Examples include Lewis acids such as iron and titanium tetrachloride. Among these acidic catalysts, it is preferable to use protonic acids, especially nitric acid,
Preference is given to using sulfuric acid, hydrochloric acid, p-toluenesulfonic acid. The proportion of these acidic catalysts used is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of the substituted phenol represented by the above general formula [] as a raw material. In the method of the present invention, the reaction is usually carried out in the presence of a solvent, but it is also possible to carry out the reaction in the absence of a solvent. When the reaction is carried out in the absence of a solvent, it is carried out by heating the raw material mixture above the melting temperature and stirring in the molten state,
The produced water or hydrogen halide is distilled off under normal pressure or reduced pressure. The solvent used when carrying out the reaction in the presence of a solvent includes toluene,
Examples include o-dichlorobenzene, diphenyl ether, decalin, methanol, and ethanol. The proportion of these solvents used is the total of dihydric phenols and substituted phenols in the raw materials.
The amount is usually 80 to 300 parts by weight, preferably 100 to 200 parts by weight per 100 parts by weight. The temperature during the reaction is usually in the range of 40 to 120°C, preferably 50 to 90°C, and the time required for the reaction varies depending on the reaction temperature and other conditions, but is usually 2 to 12 hours. Preferably it is in the range of 4 to 8 hours. The polynuclear polyhydric phenols of the present invention can be obtained by pouring the reaction mixture into a poor solvent such as methanol, acetone, or water to precipitate the mixture, or by distilling off the solvent under heating. In order to use the polynuclear polyhydric phenol of the present invention as a raw material for an epoxy resin curable composition, it is blended in the form of a polyglycidyl ether of the polynuclear polyhydric phenol. Conventionally known methods are employed to produce the polyglycidyl ether of polynuclear polyhydric phenols. For example, by reacting the polynuclear polyhydric phenol represented by the general formula [] with epihalohydrin in the presence of a catalyst to generate a halohydrin ether of the polynuclear polyhydric phenol, It is produced by reacting halohydrin ether of phenols with alkali hydroxide. Examples of epihalohydrin include epichlorohydrin, epibromohydrin, and epiiodohydrin, and epichlorohydrin is preferably used. The usage ratio of the epihalohydrin is 1 phenolic hydroxyl group of the polynuclear polyhydric phenol.
It is usually in the range of 2 to 15 moles.
Examples of the catalyst include alkali hydroxides, amines such as primary amines, secondary amines, and tertiary amines, quaternary ammonium salts, and ammonium compounds such as the above-mentioned amine salts. The amount is usually in the range of 0.005 to 5 moles per mole of phenolic hydroxyl group of the polynuclear polyhydric phenol. This halohydrin etherification reaction is usually
It is carried out at a temperature of 50 to 110°C. In this halohydrin etherification reaction step, a method may be adopted in which the phenolic hydroxyl groups of the polynuclear polyhydric phenols are almost completely converted into halohydrin etherification, or a method may be adopted in which the phenolic hydroxyl groups of the polynuclear polyhydric phenols are partially converted into halohydrin etherification. For example, usually 40 or
By etherifying halohydrin to a range of 80%, a reaction mixture consisting of halohydrin ether of polynuclear polyhydric phenols and raw materials is obtained, and by reacting the reaction mixture with an alkali hydroxide, halohydrin ether is obtained. It is also possible to adopt a method in which the hydrogenation reaction and the dehydrohalogenation reaction proceed simultaneously. The dehydrohalogenation reaction of the halohydrin ether of polynuclear polyhydric phenols is carried out in the presence of an alkali hydroxide such as sodium hydroxide or potassium hydroxide, and the proportion of alkali hydroxide used at that time is determined according to the raw material. The amount is usually in the range of 0.8 to 1.2 moles per mole of phenolic hydroxyl group of the polynuclear polyhydric phenol. The dehydrohalogenation reaction of the halohydrin ether is preferably carried out while removing water produced in the reaction from the reaction system by means such as azeotropic distillation. This dehydrohalogenation reaction is usually carried out in an epihalohydrin solvent, but it can also be carried out in a ketone or aromatic hydrocarbon solvent. The dehydrohalogenation reaction is usually carried out at a temperature of 70 to 110°C. The dehydrohalogenation reaction of the halohydrin ether may be carried out in one step, or may be carried out in two or multiple steps. The polyglycidyl ether of the polynuclear polyhydric phenols is obtained by treating the mixture after the completion of the reaction by a conventional method. Next, the present invention will be specifically explained using Example 1. Example 1 1980 g (18 mol) of resorcin, 504 g (3 mol) of 2,6-dimethylol-p-cresol, 9 g (0.05 mol) of p-toluenesulfonic acid, ethanol
4500g was placed in a reactor and reacted under reflux for 4 hours. Then, the mixture was concentrated to remove ethanol under a reduced pressure of 300 mmHg, and the contents were poured into water 26 to precipitate the product. This is filtered, washed with water, dried and made into resin.
Obtained 740g. The melting point of this resin determined by microscopy is 128~
The temperature was 135°C, and the number average molecular weight n of this resin determined by Kölpermeation chromatography was 360. The IR spectrum of this compound includes phenolic OH at around 3500 cm ^-1 , 1600 cm -1 and
Characteristic absorptions of aromatic nuclei near 1500 cm ^-1 and methyl groups near 1450 cm ^-1 were observed. Table 1 also shows the results of ¹ H nuclear magnetic resonance spectra obtained by dissolving this resin in dimethyl sulfoxide- _d6 .

【table】

[Table] From the above results, it was confirmed that this resin had the following structure. Example 2 In Example 1, 2,6-dimethylol-p-
2750 g of resin was obtained in the same manner as in Example 1 except that 1512 g (9 mol) of cresol was used. The melting point of this resin determined by microscopy is 157 to 172°C, and the number average molecular weight (n) determined by gel permeation chromatography.
is 900, degree of polymerization n is 2, molecular weight distribution (w/n)
was 1.42. In the ¹ H nuclear magnetic resonance spectrum measured by dissolving this resin in dimethyl sulfoxide- _d6 , peaks were observed at the positions listed in Table 1, except that the line width of the peaks became broader. From these results, it was confirmed that this resin had the following structure. Examples 3 to 4 The same procedure as in Reference Example 1 was performed except that hydroquinone and catechol were used instead of resorcinol in Example 1, and the results shown in Table 2 were obtained. Furthermore, structural analysis was performed in the same manner as in Example 1, and it was confirmed that the structure was a structure in which hydroquinone or catechol and p-cresol skeleton were bonded through methylene groups.

[Table] Examples 5 to 8 In Example 2, 2,6-dimethylol-p-
2,6-dimethylol-p- instead of cresol
The results in Table 3 were obtained in the same manner as in Example 2, except that tert-butylphenol, 2,6-dimethylolphenol, and 2,6-dimethylol-p-phenylphenol were used as shown in Table 3. . Further, structural analysis was performed in the same manner as in Example 2, and it was found that resorcinol and p-tert-butylphenol skeleton, p-chlorophenol skeleton, or phenol skeleton were alternately bonded with methylene groups and connected linearly. It was confirmed.

[Table] Reference example 1 615g of resin obtained by the method shown in Example 1
(1.7 mol), 4023 g (43.5 mol) of epichlorohydrin, 57.2 g (0.26 mol) of a 50% aqueous solution of tetramethylammonium chloride, and 64 g of water were placed in a reactor.
The reaction was carried out at 90° C. for 4 hours while stirring. To this was added dropwise 798 g (9.6 mol) of a 48% caustic soda aqueous solution over 1.5 hours. During this time, the condensed distillate was separated, the upper aqueous layer was removed and the lower epichlorohydrin layer was returned to the reactor, maintaining the water concentration in the reaction mixture at about 2%. After the reaction, the reaction mixture was poured into 2250 ml of water, thoroughly stirred, and the organic layer was washed and separated. Furthermore, 2250 ml of water was added and thoroughly stirred to wash the organic layer. After separating the organic layer, 240 ml of 17% aqueous sodium phosphate solution was added to neutralize it. The organic layer was heated to dehydrate, filtered, and the liquid was further concentrated to obtain 960 g of epoxy resin. The number average molecular weight (n) of this resin determined by gel permeation chromatography is
1120, the molecular weight distribution (w/n) was 1.42, the melting point measured by microscopy was 53-58°C, and the epoxy equivalent determined by the hydrochloric acid/dioxane method was 150 g/eq. In the IR spectrum of this resin, in addition to the characteristic absorption of phenyl and methyl groups shown in Example 1, the absorption of phenolic OH around 3500 cm ^-1 disappeared, and newly appeared around 840 cm ^-1 and 900 cm ^-1 . Characteristic absorption of epoxy groups was observed in the sample, confirming that the resin of Example 1 was glycidyl etherified. In addition, this resin was dissolved in CDCl ₃ and measured.
The following structure was confirmed from ¹ H nuclear magnetic resonance spectrum.

[Table] Reference Examples 2 to 6 The procedure was carried out in the same manner as in Reference Example 1, except that the resins obtained by the methods of Example 2, Example 5, Example 6, Example 7, and Example 8 were used as shown in Table 5. Ivy. The characteristic values of the obtained resin were measured in the same manner as in Reference Example 1 and are shown in Table 5. In addition, the IR spectra of these resins and the IR spectra measured when dissolved in dimethyl sulfoxide- _d6
From ^{the 1H} nuclear magnetic resonance spectrum, resorcinol and p-cresol, p-tert-butylphenol, p-chlorophenol, phenol, and p-phenylphenol skeletons are alternately bonded with methylene groups and connected, resulting in epoxidation. It was confirmed that the structure was

[Table] Reference Examples 7-8 The same procedure as in Reference Example 1 was carried out except that the resins obtained by the methods of Examples 3 and 4 were used. Further, the characteristic values of the obtained resin were measured in the same manner as in Reference Example 1, and are shown in Table 6. In addition, the IR spectra of these resins and the IR spectra measured when dissolved in dimethyl sulfoxide- _d6
From the ¹ H nuclear magnetic resonance spectrum, it was confirmed that each of hydroquinone, catechol, and p-cresol were bonded to each other through a methylene group and had an epoxidized structure.

[Table] Reference Example 10, Comparative Example 1 150 g of the resin obtained by the method of Reference Example 1 and 49.5 g of diaminodiphenylmethane were melted and mixed at 80°C, and cast molding was performed. This was heated to 100℃ for 2 hours, and then
It was cured by heating at 150°C for 4 hours. The physical properties of the obtained molded product were measured and the results shown in Table 7 were obtained (Reference example
Ten). In addition, commonly used bisphenol A
Type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd.,
The physical properties of the molded product were measured in the same manner as in Reference Example 8 except that 190 g of EPOMIK R-140) was used. The results are also shown in Table 7 (Comparative Example 1).

[Table] Reference Examples 11 to 17 The same procedure as Reference Example 10 was carried out except that the resins obtained by the methods of Reference Examples 2 to 9 were used as shown in Table 8. The physical properties of the obtained molded product were measured and the results shown in Table 8 were obtained.

[Table] Comparative Examples 2 to 4 The same procedure as in Example 10 was carried out except that a commercially available heat-resistant epoxy resin was used as shown in Table 9. The physical properties of the obtained molded product were measured and the results shown in Table 9 were obtained.

[Table] Reference Example 18, Comparative Example 5 688 g of epoxy resin obtained by the method of Reference Example 2, 37 g of dicyandiamide, benzyldimethylamine
A varnish was prepared by dissolving 2.1 g in 373 g of dimethylformamide. A glass cloth (WE-18K-BZ2) manufactured by Nittobo Co., Ltd. was impregnated with this and dried at 140°C for 4 minutes to prepare a prepreg. Nine sheets of this prepreg were laminated with two sheets of copper foil on both sides and heated at 170℃.
Press molding was performed for 1 hour. The physical properties of the obtained laminate are shown in Table 10 (Reference Example 19). In addition, bisphenol A type epoxy resin (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., EPOMIK R-301) 80
A varnish was prepared by dissolving 20 g of the same (EPOMIK R-140) in 20 g of methyl ethyl ketone, and mixing therewith a solution of 4 g of dicyandiamide and 15 g of dimethylformamide, and a solution of 0.2 g of benzyldimethylamine and 15 g of methyl cellosolve. A glass cloth was impregnated with this varnish, and the prepreg was prepared in the same manner as in Reference Example 10, except that the conditions for preparing the prepreg were 130° C. and 8 minutes. The physical properties of the obtained laminate are shown in Table 10 (Comparative Example 5).

【table】

Claims (1)

[Claims] 1. General formula [] [Wherein, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and n represents an integer of 0 to 10. ] Polynuclear polyvalent phenols. 2 In the presence of an acidic catalyst, dihydric phenol and the general formula [] [In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, or a halogen atom, and X represents a hydroxyl group or a halogen atom. ] A general formula characterized by reacting with a substituted phenol represented by [] [In the formula, R represents the same group as above, and n represents an integer of 0 to 10. ] A method for producing polynuclear polyhydric phenols.