JPH07196568A - Bis(hydroxybenzyl)benzene compound, its epoxy resin and their production - Google Patents

Abstract

PURPOSE:To obtain a bis(hydroxybenzyl)benzene compound useful e.g. as a curing agent for polyester, epoxy resin, etc., in high purity and yield by reacting a phenolic compound with an aralkyl compound in the presence of an acid catalyst, removing the acid catalyst from the product and distilling the product in vacuum. CONSTITUTION:This bis(hydroxybenzyl)benzene compound of formula III can be produced by reacting phenol or cresol with an aralkyl compound of formula I (X is a halogen, OH or a 1-4C alkoxy) (e.g. alpha,alpha-dichloroxylene) in the presence of an acid catalyst such as hydrochloric acid or formic acid to obtain a phenolic aralkyl resin composition of formula II (R is H or methyl; (n) is 0-50), removing or inactivating the acid catalyst in the composition and purifying the composition by vacuum distillation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to bis (hydroxybenzyl) benzenes, epoxy resins thereof, and a method for producing them. Bis (hydroxybenzyl) of the present invention
Benzene can be widely used for polyester, polycarbonate, phenol resin, urethane, rubber additive, color developer, antioxidant, epoxy resin, curing agent for epoxy resin, and epoxy resin derived from it can be used for heat resistance. It has excellent properties, mechanical properties, and moldability, and can be used in various fields such as casting, laminating, coating, and semiconductor encapsulation.

[0002]

2. Description of the Related Art Conventionally, examples of producing bis (hydroxybenzyl) benzenes include Chemical Abstracts, 66
Vol. 1858; 19106 y (1967), p-bis (p-hydroxybenzoyl) benzene was reduced to give p-bis (p
-Hydroxybenzyl) benzene is also obtained,
Chemical Abstracts, Vol. 72, p. 34; 32610b (1970
(Year) describes a method for obtaining p-bis (p-hydroxybenzyl) benzene from p-bis (chloromethyl) benzene and phenol. The former method of reduction, which uses anisole and terephthaloyl chloride as starting materials, undergoes condensation, hydrolysis, and reduction reactions and a three-step reaction, which is industrially disadvantageous. The latter method of producing bis (chloromethyl) benzene and phenol as raw materials is advantageous in process. However, the reaction of a phenol or cresol with an aralkyl compound such as bis (chloromethyl) benzene is a Friedel-Crafts condensation reaction with a bifunctional or trifunctional starting compound, so even if it is carried out in excess of phenol, ,
It is known to be a resin (Japanese Patent Publication No. 47-1511).
No. 1). On the other hand, a method of carrying out a large excess of phenol for the purpose of suppressing the polymerization is also disclosed, but an oligomer composition can be obtained even if it is carried out by this method (JP-A-63-238129). ).

Further, the reaction point of phenol is the ortho or para position with respect to the hydroxyl group, and the reactivity is generally higher in the ortho position than in the para position. For this reason, it is extremely difficult to obtain a single compound except for special cases.
Therefore, as a method for obtaining useful bis (hydroxybenzyl) benzenes from phenol or cresols and an aralkyl compound, a method of isolating from a resin or an oligomer composition can be considered. However, the method of isolation from such a composition has considerable complications. That is,
Even if the target product is obtained by the extraction or recrystallization method, the yield is extremely low, which is not practical. Further, in the method by distillation, it is necessary to carry out at a high temperature under a high vacuum, and under such conditions, the bond is cleaved, the yield of the desired product is reduced and the residual polymer is unfavorably produced.

On the other hand, one of the important uses of such bisphenol compounds is as a raw material for epoxy resins. Conventionally, as an epoxidized product of bisphenol, an epoxy resin obtained by condensing a phenol such as bisphenol A or bisphenol F with a ketone or an aldehyde is typical. However, it is the actual situation that the performance of these conventionally used epoxy resins cannot meet the high performance demands of recent years. That is,
When the above epoxy resin is used as the composite material matrix resin, it has excellent heat resistance, adhesiveness, workability, etc.,
The important performance required for composite materials is not sufficient, and improvement is required. For example, in a composite material, it is important that these materials withstand an instantaneous impact such as stress concentration as an external stress. For this reason, ideally, elastic deformation like rubber attracts attention as an element. The elongation at break of the matrix resin is particularly important as a criterion for judging such elastic deformation. The larger the elongation of the matrix resin, the more the defects of the reinforcing agent such as glass fiber, carbon fiber and silica required for the composite material can be compensated. That is, the strength of the composite material as a whole is improved. Further, in the matrix resin of these composite materials, long-term storage stability and heat stability are also important, and such factors include the oxidation resistance stability and water resistance (low moisture absorption) of the matrix resin. is there.

The above-mentioned epoxy resin is often insufficient in performance because of insufficient performance for these required elements. The improvement of such elements is generally derived mainly from the structure, and in recent years, it has been proposed that a phenol resin structure with a xylylene bond is effective for this improvement (JP-A-63-63). 2381
22 and JP-A-5-148333). However, although these epoxy resins contain oily substances, their fluidity at room temperature is still insufficient, and improvement is required. This is because the raw material of the epoxy resin is a resinous substance, so that the molecular weight is further increased and three-dimensionalization is caused during the epoxidation, and as a result, the fluidity is lowered. On the other hand, 1,4-bis (4-hydroxybenzyl)
The epoxidized product of benzene is described in Chemical Abstracts, Vol. 72, p. 34, 32610b (1970). This is a single compound epoxide,
It is described that the method for obtaining such a single compound is not simple as described above, and that the obtained epoxy resin is in the form of a viscous or soft resin.

[0006]

An object of the present invention is to provide a liquid epoxy resin having excellent heat resistance, mechanical properties, moldability, etc., and therefore to provide a bisphenol compound which is a raw material of such an epoxy resin industrially. It is to manufacture at low cost.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems. As a result, the present invention has been completed. That is, the present invention provides a compound represented by the general formula (I) obtained by reacting a phenol or cresol with an aralkyl compound represented by the general formula (I) (Chemical Formula 6) in the presence of an acid catalyst.
I) The bis (represented by the general formula (III) (chemical formula 6) obtained by vacuum distillation after removing or deactivating the acid catalyst component from the phenol aralkyl resin composition represented by the chemical formula (6) TECHNICAL FIELD The present invention relates to hydroxybenzyl) benzenes, a liquid epoxy resin obtained by reacting this with epichlorohydrin, and a method for producing them.

[0008]

[Chemical 6] (In the formula, R represents a hydrogen atom or a methyl group, X represents a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, and n
Is an integer of 0 to 50)

According to the method of the present invention, bis (hydroxybenzyl) benzenes, which have hitherto been difficult to produce, have high purity,
Obtained in high yield. Further, most of the bis (hydroxybenzyl) benzenes obtained by this method are obtained as an isomer mixture, and therefore the epoxy resins derived from them are liquid and have low viscosity. When such an epoxy resin is used as a matrix resin for advanced materials, due to its good impregnability,
Since it is well compatible with inorganic or organic fibers and fillers such as silica, not only the workability is improved, but also a composite material having a high level of performance such as mechanical strength and low variation can be obtained. On the other hand, since the structure of the epoxy resin itself is a structure having high flexibility as described in JP-A-63-238122, the matrix resin is characterized by low water absorption and high elongation. is there. or,
In industrially providing such a useful epoxy resin, it is important that the raw material bis (hydroxybenzyl) benzenes can be stably and inexpensively supplied, but in the method of the present invention, Another feature is that it can be continuously produced using a thin film distiller.

The method of the present invention will be described in detail. The phenol aralkyl resin composition used as a raw material for obtaining the bis (hydroxybenzyl) benzyls of the present invention comprises phenol or cresols such as o-cresol, m-cresol, p-cresol and mixed cresol, and a compound represented by the general formula (I ) The aralkyl compound represented by the formula (1) is produced by a Friedel-Crafts reaction. General formula (I)
In the aralkyl compound represented by, X represents a halogen atom, a hydroxyl group, or a lower alkoxy group having 1 to 4 carbon atoms.
These are, for example, α, α′-dichloro-p-xylene, α, α′-dichloro-m-xylene, α, α′-dichloro-o-xylene, α, α′-dibromo-p-xylene, α. , Α'-dibromo-m-xylene, α, α'-
Difluoro-p-xylene, α, α′-dihydroxy-
p-xylene, α, α′-dihydroxy-m-xylene, α, α′-dihydroxy-o-xylene, α, α ′
-Dimethoxy-p-xylene, α, α'-dimethoxy-
m-xylene, α, α′-dimethoxy-o-xylene,
α, α'-diethoxy-p-xylene, α, α'-diethoxy-m-xylene, α, α'-di-n-propoxy-p-xylene, α, α'-di-n-butoxy-p- Xylene etc. are mentioned. Industrially, α, α′-dichloroxylenes, α, α′-dihydroxyxylenes and α, α′-dimethoxyxylenes are frequently used.

With respect to 1 mol of these aralkyl compounds,
The phenols are usually used in a range of 1.2 to 20 mol, preferably 2 to 10 and more preferably 3 to 8 mol in the resin composition. JP 63
JP-A-238129 discloses that the content of bis (hydroxybenzyl) benzenes in a resin composition is 86 mol% when 20 times mol of phenols is used and 76 mol% when 10 times mol thereof. Therefore, the reaction molar ratio for obtaining the resin composition may be appropriately selected from the above range in consideration of the yield of the desired product and the volumetric efficiency of the reaction.

An acid catalyst is usually used in this Friedel-Crafts condensation reaction. These are inorganic or organic acids, such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, oxalic acid, methanesulfonic acid, p-toluenesulfonic acid, diethylsulfuric acid, zinc chloride, tin chloride, iron chloride, sulfonic acid ion exchange. Examples thereof include resins, trifluoromethanesulfonic acid and teheropolyacid. The amount of these catalysts used is usually 0.001 to 5 wt% with respect to all the raw materials.

As a result of the study by the present inventors, the whole amount to a part of these catalysts remain in the resin composition,
When distilling and collecting unreacted phenols and / or distilling and obtaining bis (hydroxybenzyl) benzenes, which is the object of the present invention, the bond is cleaved or polymerized, and the purity and yield of the obtained target product are obtained. It was found that For example, when a metal-containing catalyst is used, almost the entire amount remains in the resin, so if the distillation is carried out as it is at a high temperature, the desired product can hardly be obtained. Also, a small amount of sulfonic acid residues remains in the use of sulfonic acid type ion exchange resins and organic sulfonic acids, which causes a decrease in yield. Furthermore, even with a volatile catalyst such as hydrochloric acid or a decomposable catalyst such as oxalic acid, if a trace amount remains, a preferable result may not be obtained in some cases. It is known that in the aralkyl compound of the general formula (I), when X is a halogen atom such as a chlorine atom, the condensation reaction proceeds even without a catalyst. In such a case, since a large amount of hydrogen halide gas such as hydrogen chloride is generated, it is often impossible to completely remove it, and it is difficult to obtain good results. The present invention has elucidated the problem caused by such an acid catalyst, and as a result of examining a fundamental solution, as a result, by removing or deactivating the acid residue in the resin, the distillation operation can be carried out without any problem. It is based on the fact that the quality and yield of the obtained bis (hydroxybenzyl) benzenes are not problematic.

Next, the method of the present invention will be specifically described.
As a method of removing or deactivating the catalyst component in the resin composition obtained by the condensation reaction, (1) a method of removing by washing with a liquid separator (2) a method of deactivating by neutralization (3) removing under reduced pressure Method (4) Method of replacing and removing with inert gas or the like (5) Method of removing by thermal decomposition, etc., and the method of the present invention includes at least one or more of these methods. The method of (1) using water separation is frequently used when the condensation reaction catalyst is a heavy metal catalyst such as zinc chloride or tin chloride or a relatively large amount of catalyst.
The water separation is performed once to several times with 0.1 to 10 times by weight of water to hot water with respect to the resin composition to completely remove the acid component. At this time, if the resin has a low softening point, it can be carried out without heating under heating, but it is usually more convenient to use a solvent which is immiscible with water. Examples of such a solvent include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as 1,2-dichloroethane and methylene chloride, methyl ethyl ketone,
Examples thereof include ketones such as methyl isobutyl ketone, and esters such as ethyl acetate and butyl acetate. The amount of these solvents used is about 0.1 to 10 times the volume of the resin composition. After washing and separation with water by such a method, the solvent solution may be charged into a distillation apparatus, and the target product may be distilled following the distillation of the solvent.

In the method of deactivating by neutralizing (2),
Mainly used when a small amount to a small amount of the condensation reaction catalyst remains. This is because, for example, when the condensation reaction can be carried out in a small amount such as trifluoromethane sulfonic acid which is a super strong acid catalyst, when a small amount of sulfonate ion liberated from the sulfonic acid type ion exchange resin remains, a hydrochloric acid or oxalic acid catalyst is used. Is often used even when the methods (3), (4) and (5) remain, and when it is bonded to the phenol nucleus in the resin skeleton like sulfuric acid or diethyl sulfuric acid. In particular, in the phenol aralkyl resin currently industrially produced,
From the relationship that the sulfonic acid residue is somewhat bonded in the skeleton,
This method is suitable when this commercial grade is used as a raw material. As the base used for neutralization, inorganic and organic bases can be used, but preferably inorganic bases, such as ammonium, lithium, potassium,
Carbonates such as sodium, barium, calcium and magnesium, bicarbonates, hydroxides, calcium oxide, magnesium oxide and the like are used. These may be added according to the amount of acid remaining in the resin, but usually a small excess,
For example, it is general to add about 1.1 to 1.5 equivalents.
Further, these may be added directly as they are or as an aqueous solution. In this method, after performing as a pretreatment for distillation, the process can be directly transferred to the distillation step.

The method (3) or (4) is suitable for removing the hydrochloric acid catalyst and the produced hydrogen halides. In this method, for example, the method of (3) performed under reduced pressure is usually performed at the same time as the operation of collecting and distilling off unreacted phenols, but at too high a temperature, the bond is cleaved and the resin composition changes. It is desirable to carry out at least 180 ° C. or lower. The degree of reduced pressure is usually about 300 to 2 mmHg. In the method of substituting and removing with an inert gas or the like of (4), nitrogen, argon, helium, and in some cases air are used, but nitrogen gas is preferably used. This method of substituting with an inert gas is usually carried out in a molten state of the resin, and the substitution can be carried out together with the inert gas discharged from the pipe port introduced into the liquid by the introduction pipe. However, since the method (4) generally requires a long-time treatment and is low in efficiency, it is usually carried out in combination with the method (3). Also,
If the acid residue cannot be completely removed by the method (3) and / or (4), it is unavoidable to use the method (2) together. That is, neutralization of an extremely small amount of acid component with a base affects the distillation result, and therefore must be carefully considered. The method of removing by thermal decomposition of (5) is limited to the case of using a thermally decomposable catalyst such as oxalic acid, which is often carried out in the process of distillation, but leads to complete decomposition. Since the composition change may occur up to this time, it is preferable to use the method (2) together if a more reliable method is required.

In the case of distilling the bis (hydroxybenzyl) benzenes of the present invention, the distillation temperature is preferably low considering the stability of the target product and the residual resin, and is in an industrially feasible range. If you give it a strong name, 200 to 260
The temperature is in the range of ℃, and the vacuum degree at this time is 0.1 to 5 torr.
It is the range of r. This distillation method can be either a batch method or a continuous method using a thin film distillation machine, but industrially, a continuous process using a thin film distillation machine is efficient. In addition, this is also effective in reducing the overall heat history, and is preferable for suppressing coloring of the target product and utilizing the residual resin.

The bis (hydroxybenzyl) benzenes obtained by the method of the present invention can recover 80% or more of the content in the resin composition and have a purity of 95% to 99.8%.
It is possible to obtain a highly pure product. Moreover, what used the phenol species except p-cresol as a raw material is a mixture of three isomers. For example, bis (hydroxybenzyl) benzene made from phenol is a (o-, o'-) form, (o-, p'-) form and (p-, p) represented by the following formula (Formula 7). It is a mixture of three isomers of the'-) form. The ratio of (o-, o'-) isomer, (o-, p'-) isomer and (p-, p'-) isomer is 20-40 / 40-60 / 10 / 10-30 (mol%) , NMR analysis (o-form / p-
Although the (body) ratio varies slightly depending on the type of catalyst and the distillation rate by distillation, the o-body is more common.

[0019]

[Chemical 7] In addition, bis (hydroxy-methyl-benzyl) benzene made from o-cresol is a mixture of three isomers represented by the following formula (Formula 8). The ratio of (o-, o'-) isomer, (o-, p'-) isomer and (p-, p'-) isomer is 5 to 15/35 to 50/35 to 50
(Mol-%), (o-, p'-) and (p-, p'-) isomers are the main components, and (o-, o'-) isomers are relatively small, therefore
The (o-body / p-body) ratio is higher in the p-body.

[0020]

[Chemical 8]

As a method for epoxidizing the bis (hydroxybenzyl) benzenes thus obtained, a known method can be applied. That is, bis (hydroxybenzyl) benzenes and epichlorohydrin usually give 4
It is carried out in the presence of a hydrogen halide acceptor within a temperature range of 0 to 120 ° C. Particularly suitable as the hydrogen halide acceptor of the present invention are alkali metal hydroxides such as potassium hydroxide and sodium hydroxide. The hydrogen halide acceptor was added slowly to the heated mixture of the bis (hydroxybenzyl) benzenes and epihalohydrin to adjust the pH of the reaction mixture.
Is preferably maintained at about 6.5-10. The epihalohydrin used in the reaction is usually 2.0 to 30 times equivalent to the hydroxyl group of the raw material, preferably,
Considering economy, an excess amount of epihalohydrin of 10 times equivalent or less is used. Excess acceptor substances and salts produced as by-products are removed from the reaction product by means such as vacuum distillation and washing with water.

The epoxy resin produced by the method of the present invention can be cured with a conventional curing agent. Typical examples of hardeners are conventional hardeners for epoxy resins, such as bis (4-aminophenyl) methane, aniline / formaldehyde resins, bis (4-aminophenyl) sulfone, propane-1,3-diamine, Hexamethylenediamine, diethylenetriamine, triethylenetetramine, 2,2,4-trimethylhexamine-1,
6-diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane and 3-aminomethyl-
Aliphatic, cycloaliphatic, aromatic and heterocyclic amines such as 3,5,5-trimethylcyclohexylamine (isophoronediamine), polyaminoamides such as those obtained from aliphatic polyamines and dimerized or trimerized fatty acids, phenols , Cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc., obtained by condensation reaction under acidic catalyst, a novolac type phenol resin, naphthol, There are aralkyl resins such as phenylphenol with a xylylene bond, phenol-dicyclopentadiene resins, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexachloro Endomethylene tetrahydrophthalic acid anhydride, pyromellitic acid anhydride, 3,3 ', 4,
Includes 4'-benzophenone tetracarboxylic dianhydride, acids of said anhydrides and polycarboxylic acids such as isophthalic acid and terephthalic acid and their anhydrides. If the curing agent is a polycarboxylic acid or an anhydride thereof, then typically 0.4 to 1.1 equivalents of carboxyl or anhydride groups are used per equivalent of epoxy groups. If the curing agent is a polyphenol, it is convenient to use 0.75-1.25 phenolic hydroxyl groups per equivalent of epoxy groups. Catalytic hardeners are generally used at 1 to 40 parts by weight per 100 parts of epoxy.

[0023]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 A reactor equipped with a stirrer, a thermometer and a condenser was charged with 658 g (7 mol) of phenol and 0.8 of diethylsulfate as a catalyst.
2 g was charged and the temperature was raised to 140 ° C. with stirring.
Then, 166 g of α, α′-dimethoxy-p-xylene
(1 mol) was added dropwise over 2 hours. Methanol produced in the reaction was trapped in a condenser and removed outside the system. After the dropping, the reaction was completed by aging for 2 hours in the temperature range of 140 to 145 ° C. When this reaction solution was analyzed by GPC, the resin composition excluding phenol was 64.4% for n = 0 and 2 for n = 1 in the general formula (II) [R = hydrogen].
2.3%, n = 2 was 8.6%, and n ≧ 3 was 4.7%. The reaction solution was divided into two to obtain 378 g of each solution. Of these, one was added with 20 g of a 5% methanol solution of barium hydroxide octahydrate to carry out neutralization (A),
The other was left as it was without neutralization (B). (Distillation step) The neutralized reaction solution (A) was subjected to twice distillation operation with a Smith type thin film distillation machine [manufactured by ULVAC, Inc., model 2-03 type] to perform unreacted phenol and bis (hydroxybenzyl). Benzene was separated. The first distillation was performed at a set temperature of 190 to 200 ° C. and a set pressure of 4.2 to 4.6 Torr.
Then, the reaction solution of (A) was dropped at 2.4 g / min to distill off unreacted phenol. The recovery amount of phenol is 235
and the residual resin was 131 g. The composition of this resin was exactly the same as that before the distillation. The second distillation is performed at a set temperature of 280 to 290 ° C. and a set pressure of 1.7 to 2
The first residual resin was added dropwise at 1.1 g / min with Torr to obtain bis (hydroxybenzyl) benzene by distillation. The yield of bis (hydroxybenzyl) benzene was 77.2 g. The recovery rate with respect to the content of bis (hydroxybenzyl) benzene contained in the resin of the first residue was 83.8%. The NMR analysis result of the obtained bis (hydroxybenzyl) benzene is shown in the following (Chemical Formula 9).

[0024]

[Chemical 9]

The substitution ratio of methylene group to phenol obtained from the result of NMR analysis is ortho / para = 0.581.
It was /0.419. The melting point was 152 to 156 ° C. Further, the ratio of the three isomers determined by HLC analysis and the purity based on the total thereof were as follows. R. T (min) mol% p-, p'- form 10.7 16.7 o-, p'- form 11.9 51.8 o-, o'- form 13.1 30.1 Total purity 98.6 % The HLC analysis conditions are shown below. -Model: JASCO 880 series (manufactured by JASCO) -Column: ODS column (Yamamura Chemical, YMC-A-3)
12) ・ Mobile phase; acetonitrile / water = 60/40, flow rate = 1
ml / min ・ Wavelength; UV 254nm

Comparative Example 1 In the same manner as in Example 1, the reaction solution (B) divided into two in Example 1 was subjected to a double distillation operation using a Smith type thin film distiller. First
The second distillation yielded 241 g of phenol and 121 g of residual resin. This 1st residual resin is GPC
As a result of analysis, in the general formula (II) [R = hydrogen], n = 0 is 6
0.6%, n = 1 was 21.2%, n = 2 was 10.4%, and n ≧ 3 was 78%. In the second distillation, 53.2 g of a mixture of bis (hydroxybenzyl) benzene and phenol was obtained from the resin in the first residue, which was analyzed to give bis (hydroxybenzyl) benzene of 62. The content was 1%, and the recovery rate with respect to the initial content was 35.8%. Residual resin is GPC
Analysis revealed that n = 1 in the general formula (II) was 11.9%,
= 2 was 7.4% and n ≧ 3 was 80.7%.

Example 2 Commercially available Zyloc resin (trade name; Milex XL-225) containing 34.3% of bis (hydroxybenzyl) benzene and 1.66 mmol / 100 g of sulfonic acid group.
-4L, manufactured by Mitsui Toatsu Kagaku Co., Ltd.) (350 g) is melted by heating, and then 0.7 g of calcium hydroxide is added thereto to obtain 140 to 150
The mixture was stirred and neutralized at 0 ° C. for 2 hours. Then, the molten resin was transferred to a Claisen type distillation flask, and the degree of vacuum was 2 to 2.5T.
Distilled at orr. The distillation temperature was 238 ° C., and 96.2 g of the target bis (hydroxybenzyl) benzene was obtained. The recovery rate with respect to the content was 80.2%, and the purity was 99.2%. The o / p ratio is 0.51 / 0.
It was 49.

Comparative Example 2 Distillation was performed under the same conditions as in Example 2 without neutralizing the Zyloc resin of Example 2. As a result, the desired product was not obtained, and phenol was distilled out to give phenol 44
The procedure was completed when g was recovered. The residual resin had a higher molecular weight than the original resin, and the content of bis (hydroxybenzyl) benzene was 11.2%.

Example 3 A reactor was charged with 324 g (3 mol) of o-cresol,
Α, α'-dichloro-p while maintaining at 100 to 110 ° C
-124 g (0.7086 mol) of xylene was added over 2 hours. On the way, hydrogen chloride gas generated was absorbed in water and removed. Immediately after the completion of the addition, the temperature was started to be raised, and the reaction was completed by aging at 145 to 150 ° C. for 1 hour. The reaction solution was divided into two to obtain 195 g of a stock solution for distillation. GPC analysis of this product revealed that the composition excluding unreacted o-cresol was represented by the general formula (II) [R = C
H ₃ ], n = 0 is 47.8%, n = 1 is 23.7%, n
= 2 was 12.0%, and n ≧ 3 was 16.5%. (Distillation step) Charge one reaction solution into a Claisen type distillation flask equipped with a capillary connected to nitrogen gas,
Unreacted o-cresol was recovered while performing dehydrochlorination gas treatment under reduced pressure of an aspirator at 140 to 150 ° C. The vacuum temperature was up to 26 Torr, and the recovery amount was 95.5 g. The residual resin had exactly the same composition as the raw material when o-cresol was removed. next,
As it is, the vacuum system is replaced with a vacuum pump to raise the temperature, and bis (hydroxy-methyl-benzyl) benzene is added to 239-
Distillation at 240 ° C / 2 Torr gave 42.5 g of the desired product. The recovery rate for the content is 88.0%, and HL
As a result of C analysis, o-, o'-body / o-, p'-body / p-, p'-body = 1
It was a mixture of three isomers of 0.6 / 45.3 / 43.0 (mol%).

Comparative Example 3 The other split solution of Example 3 was heated as it was, and unreacted o-cresol was recovered by distillation under normal pressure, and the internal temperature 201 to
92 g of o-cresol was obtained at 230 ° C. The remaining resin contained 3.5% of o-cresol and had a composition in which n = 0 was reduced. Subsequently, in order to distill the target bis (hydroxy-methyl-benzyl) benzene, the distillation was performed in the same manner as in Example 3 under a vacuum of a vacuum pump. The obtained distillate was 36.9 g, and as a result of HLC analysis, it was the target product containing 9.9% of o-cresol. The recovery rate based on the content of the distillate stock solution was 69.6%.

Example 4 72.5 g (0.25 mol) of bis (hydroxybenzyl) benzene obtained in Example 1 and 370 g of epichlorohydrin were placed in a reaction vessel equipped with a stirrer, a thermometer and a Dean Stark azeotropic distillation trap. (4 mol) was charged. The temperature of this mixture was raised to 110 to 115 ° C. with stirring, and then 52 g of a 40% sodium hydroxide aqueous solution was added dropwise over 4 hours within the same temperature range. Water distilled by azeotropic distillation was continuously separated and collected, and epichlorohydrin was refluxed in the reactor. Distilled water was not observed completely after 1 hour from the completion of the dropping, and the reaction was completed. Then, excess epichlorohydrin was distilled off under reduced pressure of an aspirator, and 250 ml of methyl isobutyl ketone was added to the residue and dissolved.
Insoluble inorganic salts were removed by filtration, and water was added to this filtrate for washing and liquid separation. Then, the solvent was distilled and recovered by vacuum distillation to obtain 83.5 g of a light yellow transparent liquid epoxy resin. Epoxy equivalent is 213 g / eq and viscosity (by Tokyo Keiki, E-type viscometer) is 72 g / cm · sec (35
℃).

Example 5 Using 185 g (2 mol) of epichlorohydrin for 31.8 g (0.1 mol) of bis (hydroxymethyl-benzyl) benzene obtained in Example 3, the same procedure as in Example 4 was conducted. A yellow transparent liquid epoxy resin was obtained. Yield 4
At 2.5 g, the epoxy equivalent was 220.6 g / eq, and the viscosity was 56 g / cm · sec (35 ° C.).

Use Examples 1-2 and Comparative Use Example 1 For each of the epoxy resins of Examples 4 and 5 and, for comparison, each epoxy resin of Epicoat 828 (manufactured by Yuka Shell Chemical Co.) derived from bisphenol A, a curing agent. An acid anhydride (Epicure YH-306: manufactured by Yuka Shell Chemical Co., Ltd.) and 2,4,6-tris (dimethylaminomethyl) phenol (TAP) as an accelerator were blended under the conditions shown in Table 1 (Table 1). The physical properties of the cured resin were measured. The results are shown in Table-1.

[0034]

[Table 1] ・ Curing conditions 80 ° C / 3hr + 120 ° C / 6hr ・ Compounding ………… Weight ratio. -Gelization time ... According to JIS K-6910. -Heat deformation temperature ... According to JIS K-7207.・ Water absorption rate during boiling: Boiling 100 ° C / 2 hours.・ Tensile strength: According to JIS K-7113.

[0035]

As described above in detail, when the bis (hydroxybenzyl) benzenes of the present invention are obtained from a resin composition by distillation, the bis (hydroxybenzyl) benzene is cleaved by a slight amount of a catalyst component or a by-produced acid component to give the desired product. Yield and purity are reduced. or,
Since the residual resin also becomes a polymer by rearrangement, its use is limited. In order to solve such a problem, in the method of the present invention, by deactivating or removing the trace amount of the catalyst component and the acid component, the cleavage at the time of distillation is prevented, and high-purity bis (hydroxybenzyl) benzenes are obtained. It can be obtained in high yield. In addition, even by the method of thin film distillation, which is advantageous for industrial implementation, bis (hydroxybenzyl) benzenes can be obtained with high purity and high yield without the inclusion of phenols, and useful bisphenol compounds can be provided at low cost. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // C07B 61/00 300 (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Higashi Mitsui Pressure Chemical Co., Ltd.

Claims (10)

[Claims] 1. A compound represented by the general formula (II) (formula 3) obtained by reacting a phenol or cresol with an aralkyl compound represented by the general formula (I) (formula 1) in the presence of an acid catalyst. A bis (hydroxybenzyl) benzene represented by the general formula (III) (Chemical Formula 2), characterized in that the acid catalyst component is removed or deactivated from the phenol aralkyl resin composition Method. [Chemical 1] (In the formula, X represents a halogen atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms). (In the formula, R represents a hydrogen atom or a methyl group, and n is 0 to
It is an integer up to 50) (In the formula, R represents a hydrogen atom or a methyl group) 2. The bis (hydroxybenzyl) according to claim 1, wherein the acid catalyst component is neutralized with an inorganic base and then vacuum distilled.
A method for producing benzenes. 3. The method for producing bis (hydroxybenzyl) benzenes according to claim 1 or 2, wherein vacuum distillation is performed using a thin film distillation apparatus. 4. Bis (hydroxybenzyl) benzenes obtained by the method according to claim 1. 5. An isomer mixture obtained from phenol by the method according to any one of claims 1 to 3,
The ratio of (O-, O'-) form / (O-, P'-) form / (P-, P'-) form is 20-40
/ 40 to 60/10 to 30 (mol%), a bis (hydroxybenzyl) benzene isomer mixture represented by the general formula (IV) [Chemical 4] 6. An isomer mixture obtained from o-cresol according to any one of claims 1 to 3, wherein (O-, O'-) form / (O-, P'-) form / The ratio of (P-, P'-) body is 5
~ 15 / 35-50 / 35-50 (mol%) general formula (V)
A bis (hydroxy-methyl-benzyl) benzene isomer mixture represented by the chemical formula (5). [Chemical 5] 7. A method for producing a liquid epoxy resin, which comprises reacting the bis (hydroxybenzyl) benzenes according to claim 4 with epihalohydrin. 8. A liquid epoxy resin obtained by the method according to claim 7. 9. A liquid epoxy resin obtained by reacting the bis (hydroxybenzyl) benzene isomer mixture according to claim 5 with epihalohydrin. 10. A liquid epoxy resin obtained by reacting the bis (hydroxy-methyl-benzyl) benzene isomer mixture according to claim 6 with epihalohydrin.