JP3534787B2 - Hydroxybenzyl adduct to trisphenol - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydroxybenzyl group adduct to trisphenol which is useful as an epoxy resin curing agent having excellent uniform curing reactivity. [0002] Conventionally, amines, acid anhydrides, phenol novolak resins and the like have been used as curing agents for epoxy resins. In applications, phenol novolak resins have been reviewed in response to demands for higher performance of products, and are particularly suitably used for electric and electronic materials. [0003] A phenol novolak resin is generally obtained by subjecting a phenol and formaldehyde to an addition condensation reaction in the presence of an acid catalyst. Therefore, the phenol novolak resin is a resin having a broad molecular weight distribution in which a phenol nucleus is mainly bonded by a methylene bond and the phenol nucleus is usually composed of 2 to 20 phenol nuclei. Thus, phenol novolak resin is
Due to the wide molecular weight distribution, it is difficult to obtain a cured product with a high cross-linking density when used as a curing agent for epoxy resins, and slight differences in the preparation of raw materials and production conditions when repeated production is performed. Therefore, there is a problem in reproducibility of molecular weight and molecular weight distribution, and therefore, there is a problem in reliability of cured product quality. With respect to hydroxybenzyl group adducts to phenol compounds, bis-
The case where phenol A and p, p'-bisphenol F are used is described in Japanese Patent Application No. 3-200776, but the case where trisphenols are used as a phenol compound is not known. . [0005] SUMMARY OF THE INVENTION An Problems] The present invention has been made in view of the prior art described above, in particular, hydroxybenzyl to novel tris-phenols Ru excellent uniformity curing reactivity as a curing agent for epoxy resin It is intended to provide an adduct. According to the present invention, there is provided a compound represented by the general formula (I): (Wherein the position of the hydroxyl group in each hydroxybenzyl group is the 2-position or the 4-position), a hydroxybenzyl group adduct to trisphenol represented by the formula: According to the present invention, such a hydroxybenzyl group adduct to trisphenol is prepared according to the present invention.
As a first step, a methylolated trisphenol is produced by reacting trisphenol with formaldehyde in the presence of a basic catalyst, and then, as a second step, the methylolation is carried out in the presence of an acidic catalyst. It can be obtained by reacting phenol with trisphenol . The first step is usually carried out in an aqueous solvent or a mixed solvent of water and an organic solvent in the presence of a basic catalyst.
It is carried out by reacting formaldehyde in excess with the hydroxyl group of trisphenol as a raw material.
As the formaldehyde used in the first step, a commercially available aqueous solution of formalin can be used as it is, and paraformaldehyde or trioxane, which acts in the same manner as formaldehyde in the presence of water, can also be used. Examples of the basic catalyst include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, and divalent salts such as acetates, calcium hydroxide, zinc hydroxide and magnesium hydroxide. Metals, preferably hydroxides and acetates of alkaline earth metals, pyridine,
And tertiary amines such as trimethylamine and tributylamine. Among these, sodium hydroxide or potassium hydroxide is particularly preferably used. The first step is usually carried out in the presence of water. To increase the affinity of trisphenol for water, for example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol , Ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, alcoholic solvents such as carbitol, or tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide,
Water-soluble organic solvents such as N-methylpyrrolidone are also used in some cases. In the first step, the use ratio of formaldehyde to trisphenol is usually in the range of 2.0 to 10 moles, preferably 2.5 to 5 times, the number of hydroxyl groups of trisphenol. The range is 0 moles. The amount of the basic catalyst to be used is generally in the range of 1.0 to 5 times, preferably 1.1 to 1.5 times, the number of hydroxyl groups of trisphenol. The solvent is used in such a range that the total weight of the starting materials, trisphenols and formalin, is usually 10 to 50% by weight, preferably 30 to 45% by weight. The first step is usually carried out at 0-60.
C., preferably at a temperature in the range of 30 to 40.degree. C., usually for about 1 to 72 hours, preferably about 4 to 12 hours, but the method of the present invention is particularly limited to these conditions. It is not done. When such a first step is completed, after neutralizing the basic catalyst in the obtained reaction mixture with an acid, by adjusting the solvent mixture ratio of the organic solvent and water in the reaction mixture, Crystals are precipitated from the solvent, and the crystals are collected by filtration from the reaction mixture, whereby methylolated trisphenol can be obtained. [0015] Then, in a second stage of the process, the reaction of the phenol with respect methylolated trisphenol obtained as described above, usually, the presence of an acidic catalyst, in the presence of no solvent or an organic solvent, methylolated It is carried out by reacting an excess of phenol with respect to the number of hydroxyl groups of trisphenol. In the second step, examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid; and carboxylic acids such as oxalic acid and acetic acid. Acids and the like are used, and among these, hydrochloric acid is particularly preferably used. The second step can be carried out in the absence of a solvent. However, in order to easily adjust the reaction temperature during the reaction, adjust the viscosity of the reaction system, and the like, the second step is preferably performed in the presence of an organic solvent. You can also. Here, examples of the organic solvent include alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, ethers such as tetrahydrofuran and dioxane, and aliphatic amides such as dimethylformamide and dimethylacetamide. However, the present invention is not limited to this. Further, in the second stage of the process, the proportion of the phenol with respect methylolated tris phenol,
It is usually in a range of 1 to 100 moles, preferably 5 moles per mole of the methylol group of the methylolated trisphenol.
It is in the range of ~ 20 times mol. The amount of the acidic catalyst used is usually 0.01 to
It is in the range of 1 mole, preferably in the range of 0.1 to 0.5 mole. When a solvent is used, the total weight of methylolated trisphenol and phenol is usually 20 to 9
It is used in an amount of 5% by weight, preferably 50 to 90%. In the second step, the reaction is carried out usually at a temperature in the range of 10 to 100 ° C., preferably 20 to 50 ° C., usually for 1 to 48 hours, preferably 5 to 2 hours.
Although it is performed for about 0 hours, the present invention is not particularly limited to these conditions. When the second step is completed, the acidic catalyst used is neutralized and removed, and the excess phenol compound and, if a solvent is used, the solvent is distilled off. A hydroxybenzyl group adduct to trisphenol according to the invention can be obtained. [0020] hydroxybenzyl adduct of the present invention to trisphenols is Ru are preferably used in the curing agent application of the epoxy resin, but is not limited thereto. According to the present invention, a novel hydroxybenzyl group adduct to trisphenol is provided, and such an adduct is used as a curing agent excellent in uniform curing reactivity of an epoxy resin . It can be used advantageously. The present invention will be described below with reference to examples.
The present invention is not limited by these examples. In the examples, the analysis of the reaction product between trisferrule and formaldehyde was performed by using a Shimadzu Corporation SPD-10A high-performance liquid chromatograph on a Shimadzu Corporation column (Shimpack CLC-ODS).
(6φ × 150 mm), and a linear gradient from 50% to 100% of methyl alcohol in 60 minutes with methyl alcohol / 0.2% acetic acid water as a solvent and a mobile phase solvent at a flow rate of 1 mL / min. Temperature 5
The measurement was performed at 0 ° C. and a wavelength of 280 nm. The ratio of the constituent components in the composition comprising the mixture of the hydroxybenzyl group adduct to trisphenol was determined by using a Shimadzu Corporation LC-6A gel permeation chromatograph by Showa Denko KK. Column (S
hodex KF-80M, one KF-802, and two KF-801) and tetrahydrofuran as a solvent. It was measured under the condition of mL / min.
The identification of the reaction intermediate and the reaction product was carried out by IR and N
Performed by MR in a conventional manner. The number of parts in the examples indicates the number of parts by weight. EXAMPLE 1 79 parts of a 17% aqueous sodium hydroxide solution contained 1,1-di (4
-Hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane 4
2 parts were added and uniformly dissolved with stirring.
A 73% aqueous formaldehyde solution was added dropwise over 1 hour, and the mixture was further stirred and reacted for 7 hours. During the reaction, the temperature was kept at 40-45 ° C. After completion of the reaction, 68 parts of methyl alcohol was added to the obtained reaction mixture, and the mixture was neutralized with acetic acid.
After stirring for 4 hours, the precipitated crystals were filtered. The obtained crystals were subjected to a reslurry treatment in 68 parts of a 40% aqueous methanol solution at room temperature for 1 hour. Thereafter, the slurry was filtered to obtain crystals, which were dried at 50 ° C. to obtain 41 parts of crystals. As a result of NMR analysis and IR analysis, the crystals were found to be 1,1-di (4-hydroxy-3,5-di (hydroxymethyl) phenyl-1- [4- [2- (4-hydroxy-3 , 5-di (hydroxymethyl) phenyl) -2-propyl] phenyl] ethane (hereinafter 1,1-di (4-hydroxyphenyl) -1- [4- [2- (4-hydroxyphenyl) -2- Propyl] phenyl] ethane, which is referred to as a hexa-adduct of a methylol group.) Next, the above 1,1-di (4-hydroxyphenyl) -1- [4- [2- 30 parts of a hexa-adduct of a methylol group to (4-hydroxyphenyl) -2-propyl] phenyl] ethane was dissolved in 160 parts of methyl alcohol and 376 parts of phenol to prepare a uniform solution. While maintaining the solution at 30 ° C. or lower with stirring, 26 parts of a 35% hydrochloric acid aqueous solution was added dropwise thereto, and after the addition was completed, the mixture was stirred at 30 ° C. for 4 hours to carry out the addition condensation reaction of phenol to the methylol group. After completion of the reaction, 16% was added to the obtained reaction mixture.
63 parts of an aqueous sodium hydroxide solution was added to neutralize the mixture, and the mixture was concentrated and distilled under reduced pressure to remove 537 parts of methyl alcohol, unreacted phenol and water in total from the reaction system.
Next, 80 parts of toluene and 186 parts of water were added to 118 parts of the concentrated distillation residue thus obtained, and the mixture was stirred well to transfer sodium chloride produced by neutralization from the residue to the aqueous layer. The mixture was allowed to stand still and separated to obtain 194 parts of a toluene solution containing a reaction product. This toluene solution was concentrated and distilled under normal pressure and then under reduced pressure to distill 143 parts of toluene, unreacted phenol and water in total, thereby obtaining 1,1-di (4-hydroxyphenyl). ) -1- [4- [2- (4-
There were obtained 51 parts of a reaction product of a hexa-adduct of a methylol group to (hydroxyphenyl) -2-propyl] phenyl] ethane and phenol. As a result of measurement of the reaction product by gel permeation chromatography, the ratio of the peak area of the compound corresponding to the main component was 79%, and the N
As a result of measuring the MR, the compound corresponding to the main component was
1,1-di [4-hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -1- [4- [2- [4
-Hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -2-propyl] phenyl] ethane,
That is, 1,1-di (4-hydroxyphenyl) -1-
[4- [2- [4-hydroxyphenyl] -2-propyl] phenyl] ethane to be a hexa-adduct of a hydroxybenzyl group (addition position of hydroxyl group of hydroxybenzyl group is 4-position or 2-position) Was confirmed. Example 2 1,1 prepared by the same method as described in Example 1
-Di (4-hydroxyphenyl) -1- [4- [2-
30 parts of a hexa-adduct of a methylol group to (4-hydroxyphenyl) -2-propyl] phenyl] ethane was dissolved in 540 parts of phenol without using methyl alcohol. Next, while maintaining the temperature of the solution thus obtained at 30 ° C. or lower under stirring, 35%
26 parts of an aqueous hydrochloric acid solution was added dropwise, and after the addition was completed, the reaction system was stirred at 40 ° C. for 4 hours in a sealed manner to allow an addition condensation reaction of phenol to a methylol group to proceed. Then, after completion of the reaction, post-treatment was performed in the same manner as in Example 1, and 1,
1-di (4-hydroxyphenyl) -1- [4- [2-
52 parts of a reaction product of a hexa-adduct of a methylol group to (4-hydroxyphenyl) -2-propyl] phenyl] ethane and phenol were obtained. As a result of measurement of the reaction product by gel permeation chromatography, the ratio of the peak area corresponding to the main component was 97%, and as a result of NMR measurement, the compound corresponding to the main component was as follows: , 1,1-
Di [4-hydroxy-3,5-di [(hydroxyphenyl) methyl] phenyl] -1- [4- [2- [4-hydroxy-3,5-di [(hydroxyphenyl) methyl]]
Phenyl] -2-propyl] phenyl] ethane, that is,
1,1-di (4-hydroxyphenyl) -1- [4-
It was confirmed that the compound was a hexa-adduct of a hydroxybenzyl group to [2- (4-hydroxyphenyl) -2-propyl] phenyl] ethane (the addition position of the hydroxyl group of the hydroxybenzyl group was the 4- or 2-position).

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07C 39/00 C07C 37/00 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] [Claim 1] The general formula (I) (Wherein, the position of the hydroxyl group in each hydroxybenzyl group is the 2-position or the 4-position.) A hydroxybenzyl group adduct to trisphenol represented by the formula: