JPH0751611B2 - Method for producing phenolic resin and bisphenol - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing a phenol resin and bisphenol, and more specifically, to a high-purity phenol resin which has a low molecular weight distribution control and does not contain impurities such as a catalyst. And a method for selectively producing a high-purity bisphenol rich in para-bound isomer (hereinafter simply referred to as para-bound) and free from impurities such as catalysts in a high yield.

[Problems to be Solved by Prior Art and Invention]

Originally, phenols (P) having two or more functional sites (ortho position and para position) react with aldehydes (A) to form polynuclear compounds of various molecular weights to form polymolecular phenol resins. It has been known for a long time that it has properties such as oxalic acid, hydrochloric acid, sulfuric acid,
Phenolic resins typified by novolak resins using strong acidic catalysts such as paratoluene sulfonic acid and resole resins using strong alkaline catalysts such as caustic soda, caustic potash, and amines are widely used as industrial resins.

However, since phenol resin production by these conventional methods is carried out in a homogeneous reaction in which a catalyst is dissolved in the reaction system, various technical considerations are generally given to the molecular weight distribution of the resin in the condensation step and the concentration step. However, it is difficult to control the reaction in a strongly acidic reaction system, which is said to be particularly effective for obtaining a resin having a high para-orientation property, and it is easy to cause bumping, explosion, etc. When the compounding ratio (A / P) exceeds 0.8,
In particular, since the polymer ratio of the resin is likely to progress in the concentration step, there is a problem that a fairly advanced manufacturing technique is required for implementation on an industrial scale.

On the other hand, with the recent diversification of phenol resin applications, there is an ever-increasing demand for high-purity phenol resins that do not include catalysts and the like that are particularly suitable for electrical and electronic materials. However, as a method for removing the catalyst in the above homogeneous reaction method, although complicated steps such as washing with water or neutralization have been conventionally adopted, such a method is not only complicated, but the catalyst is completely removed from the phenol resin. It was difficult to remove.

Further, as a method for producing bisphenol rich in bisphenols, particularly para-conjugates, in order to promote the addition condensation reaction at the para-functional site of phenols, while suppressing the production of condensates of trinuclear or higher, to a minimum, For example, using a strong acid catalyst such as hydrochloric acid, sulfuric acid, paratoluene sulfonic acid,
Mixing molar ratio of aldehydes to phenols is 0.5
The method adjusted as follows, that is, the method of reacting in the presence of a large excess of phenols, has been considered to be more effective than before. However, there are problems in the following points when the method is carried out on an industrial scale. That is, in this type of strongly acidic reaction system, it is difficult to control the reaction due to the large heat generation, and it is easy to cause bumping, explosion, etc. Therefore, a fairly advanced manufacturing technology is required for implementation on an industrial scale. . Therefore, in general, production under relatively mild reaction conditions by adjusting the amount of catalyst and the like is adopted, and therefore it is difficult to obtain bisphenol rich in para-conjugate.

Due to the low blending molar ratio of the starting materials, the yield of bisphenol is very low.

Since the above catalyst is hydrophilic, it is generally difficult to completely remove it from the reaction system.When the above catalyst, particularly a catalyst residue, remains in the product, it is used in the secondary processing in which it is used as a raw material. Can cause serious problems.

Another object of the present invention is to exceed 7 nuclides which are obtained by efficiently reacting phenols and aldehydes and then separating and removing the catalyst without sudden heat generation or abnormal polymerization. It is an object of the present invention to provide a method for producing a high-purity phenol resin which does not substantially contain a polynuclear component, has a low controlled molecular weight distribution, and does not contain impurities such as a catalyst.

Another object of the present invention is to obtain a high-purity phenol resin having a low controlled molecular weight distribution by removing unreacted monomers while minimizing the polymerization of the condensation product after the catalyst separation. It is to provide a manufacturing method.

Another object of the present invention is to provide a method for producing a high-purity phenol resin which is rich in para orientation and has a low controlled molecular weight distribution.

Another object of the present invention is to provide a high-purity bisphenol which is mainly composed of a para-conjugate and does not contain impurities such as a catalyst in a selective and high yield, and is safe and easy without requiring a high-level production technique. Another object of the present invention is to provide a method for producing bisphenol that can be produced on an industrial scale.

[Means and Actions for Solving the Problems]

As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that they are substantially insoluble in water and / or organic solvents as reaction catalysts and can release hydrogen ions or hydroxide ions. By using a solid catalyst, the degree of freedom in controlling the molecular weight is higher than in the conventional method, and it is possible to produce a high-purity phenol resin that does not contain impurities such as catalysts. In particular, a solid catalyst that can release hydrogen ions is used. In this case, it was found that it is possible to produce a phenol resin and bisphenol having a high degree of para orientation even under a reaction condition far milder than that of the conventional method, and based on this finding, further studies were conducted to complete the present invention. It is a thing.

That is, according to the present invention, phenols and aldehydes in the presence of a solid catalyst phase that is substantially insoluble in water and / or organic solvent and capable of releasing hydrogen ions or hydroxide ions, and A method for producing a phenol resin is provided, which comprises reacting at a temperature and then separating and removing a solid catalyst phase.

Similarly, phenols and aldehydes are reacted at a temperature of 80 ° C. or lower in the presence of a solid catalyst phase that is substantially insoluble in water and / or an organic solvent and can release hydrogen ions or hydroxide ions. After that, the solid catalyst phase is separated and removed to obtain a phenol resin, and then the phenol resin is reacted and / or concentrated to provide a method for producing a phenol resin.

One of the features of the present invention is that, in order to solve the above-mentioned problems in the conventional homogeneous reaction method, it is substantially insoluble in water and / or an organic solvent and has a hydrogen ion (H ⁺ ) or a hydroxide ion ( OH ^-) to use a releasable solid catalyst, moreover is the adoption of heterogeneous reaction method far heavily used than catalytic amount levels in the prior art.

That is, in the present invention, contained in the solid catalyst (H ⁺⁾ or (OH ^-) phenols and aldehydes for the ionic catalyst is the reaction system is released into the liquid phase is shifted to acidic or alkaline, etc. It is presumed that it reacts with other compounds to form a phenol resin. Further, what is interesting in the reaction of the present invention is that it does not involve the exothermic reaction as seen in the conventional homogeneous reaction method. This is the present invention is a heterogeneous reaction moves between the phases between the solid and liquid phases (H ⁺⁾ or (OH ^-) because is working sustained manner, sudden heat generation or abnormal polymerization It is thought that this is suppressed.

Examples of the solid catalyst include H-type cation exchange resins, for example, a copolymer of styrene and divinylbenzene or a styrene-based strongly acidic ion-exchange resin having a sulfonic acid group bonded to a styrene polymer, and a phenol-based compound. Sulfonic acid type strong acid type such as phenol type strong acid type ion exchange resin in which sulfonic acid group is bound to condensate of aldehydes, or methacrylic acid type weak acid type ion exchange resin or carboxylic acid type weak acid having carboxylic acid group Carboxylic acid type weakly acidic type such as acidic type ion exchange resin or OH type anion exchange resin, for example, a strongly basic anion obtained by binding a quaternary ammonium group as an exchange group to the above polycondensation type polymer substrate. Exchange resins, weakly basic anion exchange resins with primary to tertiary amines, and other inorganic silicon phosphate compounds And the like. Among these, strong acidic cation exchange resins and strong basic anion exchange resins are particularly preferably used from the viewpoint of catalytic activity. In particular, the H-type strongly acidic cation exchange resin is advantageous in obtaining a phenol resin having a high para orientation because it has an action of preferentially promoting the addition condensation reaction at the para position with respect to the hydroxyl group of phenols. Further, the structure may be either porous type or gel type.

In the case of a salt type cation exchange resin such as -SO ₃ Na,
Before use, it is treated with hydrochloric acid solution or sulfuric acid solution to convert it to H type, and in the case of salt type anion exchange resin such as -NH ₄ Cl, it is treated with caustic soda solution etc. to OH type. It can be used by converting.

The form of use of the ion-exchange resin is not particularly limited, and it can be used in any shape such as powder, condyle powder, beads, fibers, and film, and for adjusting the catalyst activity as necessary. The water content of the ion exchange resin may be adjusted as desired before use.

Examples of such solid catalysts include SPC-108, SPC-112, SPC-118, SC-10 as H-type acidic cation exchange resin.
4, SC-108, CNP-80 (above is Mitsui Toatsu Fine Co., Ltd.), C
C-260H, CC-276H, CC-290H (The above are Sumitomo Chemical Co., Ltd.), RCP-145H, RCP-150H, SK113A, PK228LH (The above are Mitsubishi Kasei Co., Ltd.), Anb-200CH (Organo) ,Also
As an OH type strongly basic anion exchange resin, DIAION SA10 OH manufactured by Mitsubishi Kasei Co., Ltd. Further, as an inorganic silicon phosphate compound, MIZUKANEX-300 (Mizawa Chemical Co., Ltd.) and the like can be mentioned.

The amount of solid catalyst used in the heterogeneous reaction method according to the present invention is not particularly limited, but is much larger than that in the conventional homogeneous reaction method.

For example, the amount of catalyst used in the conventional batch system is generally several% by weight or less than 1% by weight with respect to phenols because of difficulty in controlling the reaction as described above. However, the amount of solid catalyst in the present invention is
It is usually in the range of 5 to 500% by weight, preferably 10 to 200% by weight, based on the weight of the phenols. When the amount of the catalyst is less than 5% by weight, it has a catalytic action (H ⁺ ) or (O
H ^-) is low yield of the phenol resin due to the lack, also undesirably degrades the straight yields due to the increased amount of resin adhering to the solid catalyst exceeds 500% by weight. Thus, the method of the present invention is characterized by the use of a large amount of catalyst which is surprisingly different from the catalytic reaction in the prior art.

Further, in the reaction for producing the phenol resin in the present invention, the reaction temperature is important from the viewpoints of efficiently reacting the phenols and the aldehydes while suppressing the polymerization and preventing the deterioration of the ion exchange resin. The reaction temperature is appropriately selected according to the types of phenols and aldehydes used as starting materials and their blending molar ratios, the amount and type of solid catalyst used, and generally a temperature of 80 ° C. or lower is suitable. Yes, it is preferably 50 ° C. or lower, more preferably 40 ° C. or lower. When the reaction temperature is higher than 80 ° C., a high molecular weight phenol resin is produced or the ion exchange resin is deteriorated, which is not preferable.

The reaction time is not particularly limited and may be appropriately determined according to the reaction conditions such as the type of starting material, the blending molar ratio, the amount and type of the solid catalyst used, the reaction temperature and the like.

The blending molar ratio of the aldehydes to the phenols in the present invention can be used in a wide range of 0.3 to 6.0, but from the viewpoint of economic efficiency, it is usually 0.3 to 3.0, preferably 0.
7 to 2.0. If the compounding molar ratio is less than 0.3, the production rate of the phenol resin is low, while if it is more than 6.0, a large amount of unreacted aldehydes remain, which is not economical.

However, the molecular weight of the desired phenol resin is not necessarily controlled only by the blending molar ratio, but the solid catalyst amount,
It includes infinite adjustment within a limited range by the combination of reaction temperature and time.

The method for adjusting the blending molar ratio is not particularly limited, and any measures can be taken.For example, the mixing molar ratio can be adjusted at once at the start of the reaction, or the aldehydes can be added in several times in the step of producing the phenol resin. Alternatively, it may be intermittently added dropwise to adjust in a multi-step manner, and further, a method in which a phenol resin is generated and a solid catalyst is separated, and then phenols or aldehydes are additionally added, and the like are exemplified.

The phenols used as a starting material in the present invention include:
There is no particular limitation, for example, phenol, resorcin,
Glycinol, hydroquinone, catechol, orthocresol, metacresol, paracresol, orthoethylphenol, metaethylphenol, orthoisopropylphenol, metaisopropylphenol, 2,5
-Xylenol, 2,6-xylenol, 3,5-xylenol, 3-methyl-6-t-butylphenol, orthophenylphenol, orsononylphenol, metachlorophenol, parachlorophenol, orthobromophenol, 4-methylresocil, paraisopropenyl Phenol, para-tert-butylphenol, bisphenol A, bisphenol F, bisphenol S, etc. are used alone or as a mixture of two or more kinds.

Further, examples of the aldehydes include formaldehyde-providing substances such as formalin, paraformaldehyde, paraoxymethylene, dioxane, trioxane, acetals, glyoxal, acetaldehyde, butyraldehyde, propylaldehyde, crotonaldehyde, furfural, benzaldehyde, paraoxybenzaldehyde, glyoxyl. Examples thereof include acids and mixtures thereof, but are not limited thereto. The form of using these starting materials may be liquid, solution or gas.

In the present invention, the reaction mode of the phenols and aldehydes in the presence of the solid catalyst is not particularly limited, for example, a method of reacting the mixture of the three in a stationary state, stirring by mechanical shearing force or ultrasonic waves. Or a method of reacting while giving vibration, or a method of reacting a starting material in a state in which a resin catalyst is surrounded and separated in advance by gold steel or the like in order to facilitate an operation of separating a reaction product and a resin in a subsequent step, etc. And a continuous method such as a method of allowing a mixture of starting materials to pass through a fixed bed of a solid catalyst for reaction.

One of the characteristics of the method of the present invention is that the produced phenol resin and the solid catalyst can be easily and clearly separated, and a high-purity phenol resin containing no solid catalyst can be obtained. Although some hydrogen ions or hydroxide ions remain in the phenol resin after separating the solid catalyst according to the method of the present invention, it causes a problem in secondary processing using the phenol resin as in the conventional method. Catalytic residues such as acid radicals and base radicals that may possibly remain do not remain at all, and the residual amount of hydrogen ions or hydroxide ions is generally smaller than in the conventional method.

The method for separating the produced phenol resin and the solid catalyst is not particularly limited, and may be carried out according to separation operations such as conventionally known filtration separation, centrifugation, specific gravity separation, solvent extraction, etc. depending on the state of the phenol resin. . Generally, when the phenol resin is in a liquid state, it is generally used as it is, and when it is in a solid state such as crystallinity, a method in which an appropriate organic solvent is added to the reaction system to dissolve the reaction product and then the mixture is filtered is generally used. is there.
On the other hand, the separated and recovered solid catalyst was first washed with an organic solvent or the like to recover the phenolic resin, and if no decrease in catalytic activity was observed, it could be continuously used as it was, but the activity decreased. In this case, it may be reused after performing a regeneration process by a known method.

A preferred embodiment of the method of the present invention is to continuously react and / or concentrate the phenol resin obtained by separating from the solid catalyst by the above operation.

Here, the reaction and / or concentration means to reduce unreacted phenols contained in the phenol resin, unreacted aldehydes, water content and, if necessary, catalysts by a chemical or physical method. And, it means an operation for obtaining only necessary components.

In this step, if necessary, a general catalyst that has been conventionally used is not separately added and the reaction concentration is not hindered, but when it is reacted in the reaction concentration step, it is dissolved in the phenol resin (H ⁺ ) Or (OH ⁻ ) is sufficiently possible, which is preferable from the viewpoint of the object and effect of the present invention.

Further, for example, since a hemiformal bond or a polyoxymethylene bond may be present in a phenol resin produced under a reaction condition in which the mixing molar ratio of aldehydes to phenol is high, in such a case, the reaction by cleavage recombination may occur. Progress can also occur.

Further, when the phenol resin is further reacted and concentrated, even if high temperature concentration is carried out, an abnormal polymerization reaction is suppressed. This is probably because the solid catalyst was separated.

In the present invention, examples of the step of reacting and / or concentrating include vacuum distillation concentration, specific gravity separation concentration, flushing concentration, granulation separation concentration, fluidized dry concentration, reduced pressure dry concentration, azeotropic dehydration concentration, heat concentration, organic solvent. Extraction concentration, decantation concentration, extraction concentration, etc. may be performed either continuously or batchwise or in combination.

According to such a method of the present invention, impurities such as a solid catalyst and a catalyst residue have a so-called low controlled molecular weight distribution, which is substantially free of polynuclear components exceeding 7 nuclides in the molecular weight distribution. A high-purity phenolic resin containing no hydrogen, and further such a phenolic resin having a very low content of unreacted monomers and the like are provided.

Such phenol resin is a low-viscosity epoxy resin base resin, epoxy curing agent, polycarbonate resin, polyester resin, polyurethane resin, phenoxy resin, and other raw materials, IC sealing materials, IC substrates, glass phenol substrates for molding materials, paper phenol. For electrical and electronic materials such as laminated boards,
In addition to FRP, SMC, foamed phenol, adhesives, photoresists, toners, inks, paints, rubber compounds, brake linings, clutch facings, plywood, felt binders, refractories , Casting, shell mold, organic self-curing binder, impregnation, carbon, urethane bonding, etc. In particular, in recent years, there is a possibility that the applications of phenolic resins will be greatly expanded in the fields of electric and electronic materials, which are required to have higher reliability and higher performance.

The present invention provides, in another aspect, a production method capable of obtaining a bisphenol enriched in para-conjugate under reaction conditions far milder than those of conventional methods.

That is, according to the present invention, in the presence of an H-type acidic cation exchange resin, phenol, resorcin, catechol, and
These derivatives, in which one or more phenols selected from the group consisting of substituted phenols having a hydrogen atom reactive in the para position to the hydroxyl group are reacted with aldehydes at a temperature of 80 ° C or lower A method for producing bisphenol is provided.

As described above, in the method of the present invention, bisphenol is obtained as one aspect of the above-mentioned method for producing a phenol resin, and if reaction conditions are appropriately selected, a phenol mainly containing bisphenol is substantially used. The resin can be produced, and the bisphenol thus obtained is obtained as it is, or if necessary, the unreacted monomers and other resin components are separated and further purified to obtain high-purity bisphenol.

An H-type acidic cation exchange resin is used as a solid catalyst for the production of bisphenol. The H-type acidic cation exchange resin is as described above. Among them, strongly acidic type such as styrene cation exchange resin is preferable from the viewpoint of catalytic activity, and either porous type or gel type can be used structurally, but porous type having a large surface area is particularly preferable. .

Further, the amount of the H-type acidic cation exchange resin (hereinafter, simply referred to as a resin catalyst) used is not particularly limited, but it is important for preferentially performing the addition condensation reaction at the para position with respect to the hydroxyl group of the phenols. Is.

For example, the amount of catalyst used in the conventional batch system is generally several% by weight or less than 1% by weight with respect to phenols because of difficulty in controlling the reaction as described above. However, the quantitative level of the resin catalyst in the present invention is usually 10 based on the weight of phenols.
It is characterized by using a large amount of catalyst, which is surprisingly different from the catalytic reaction in the prior art, such as ˜500 wt%, preferably 10-200 wt%, more preferably 20-150 wt%.

In addition, from the viewpoint of preferentially promoting the addition condensation reaction at the para position of the phenolic compound molecule, suppressing the generation of condensate of trinuclear or higher, and preventing the functional deterioration of the resin catalyst. The reaction temperature is mentioned as an important requirement.

The reaction temperature is appropriately selected depending on the types of phenols and aldehydes used as starting materials and their blending molar ratios, and the amount and type of resin catalyst used, but generally 80
Temperatures below ℃, preferably below 50 ℃ are adopted. When the reaction temperature is higher than 80 ° C, the resin catalyst is deteriorated and unnecessary high-molecular-weight polynuclear bodies are formed, which is not preferable.

The reaction time is not particularly limited and may be appropriately determined depending on the reaction conditions such as the type of starting material, the blending molar ratio, the amount and type of the resin catalyst used, the reaction temperature and the like.

Further, the mixing molar ratio of phenols and aldehydes is an important technical requirement for obtaining bisphenol efficiently.

The compounding molar ratio according to the present invention can be used in a wide range of 0.3 to 6.0, but in terms of economy, it is usually 0.3 to 3.0, preferably
It is selected from the range of 0.5 to 2.0, more preferably 0.5 to 1.5. When the blending molar ratio is less than 0.3, the yield of bisphenol is low, while when it is more than 6.0, a large amount of unreacted aldehydes remain and it is not economical.

The method for adjusting the blending molar ratio is not particularly limited, and any measures can be taken.For example, even if it is adjusted at once at the start of the reaction, or the aldehydes are added to the phenols in several times or intermittently. It may be added dropwise to adjust in multiple steps.

The phenols used as a starting material here are phenol, resorcin, catechol, or derivatives thereof, which are substituted phenols having a reactive hydrogen atom in the para position to the hydroxyl group. The substituent of the substituted phenols is not particularly limited, but specific examples of representative substituted phenols include, for example, orthocresol, metacresol, orthoethylphenol, metaethylphenol, orthoisopropylphenol, metaisopropylphenol, 2, 5-dimethylphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, 3-methyl-
6-t-butylphenol, orthophenylphenol, orthononylphenol, metachlorophenol,
Examples include ortho bromophenol, 4-methylresorcin, and mixtures thereof.

On the other hand, typical examples of aldehydes are not particularly limited, and include, for example, formalin, paraformaldehyde,
Formaldehyde-supplying substances such as paraoxymethylene, dioxane, trioxane, acetals, acetaldehyde, butyraldehyde, propylaldehyde, crotonaldehyde, furfural, benzaldehyde, paraoxybenzaldehyde, glyoxylic acid, etc. can be used alone or in combination. You can The form of using these starting materials may be liquid, solution or gas.

Next, the reaction mode of the phenols and the aldehydes in the presence of the resin catalyst can be the same as that described above in the case of producing the phenol resin.

The method for separating the resin catalyst and the reaction product can also be the same as described above in the case of producing the phenol resin.

Finally, bisphenol can be separated from the obtained separated mother liquor by a method such as distillation or crystallization to obtain a high-purity bisphenol rich in para-conjugate and free of impurities such as catalysts. . Here, one of the features of the method of the present invention is that when separating bisphenol, a large amount of unreacted phenol remaining from the separated mother liquor after separating the solid catalyst remains as in the case of producing bisphenol by the conventional method. The bisphenol is crystallized by a known crystallization method such as simply separating the separated mother liquor as it is or concentrating it to an appropriate concentration and then leaving it at room temperature or under cooling, and filtering it out. Is to obtain high-purity bisphenol. This is because in the case of the conventional method, a large amount of unreacted phenol remains because a large excess of phenol is used, and this residual phenol acts as a good solvent for bisphenol and does not allow bisphenol to crystallize. On the other hand, in the method of the present invention, the blending molar ratio of aldehydes / phenols is high,
In addition, since the reaction is efficient, there is little residual phenol that acts as a good solvent for bisphenol, and it is possible to minimize the formation of trinuclear or higher oligomers that have some solvent action. Since only a small amount of the substance that acts as a solvent is present in the separated mother liquor, it is rich in para-conjugate simply by crystallizing.
Alternatively, high-purity bisphenol close to a pure product can be obtained in high yield.

Further, if necessary, by further purifying by a recrystallization method, a distillation method, or the like, a bisphenol consisting only of the para-conjugate can be obtained.

The bisphenol obtained by the method of the present invention is usually used as a crystal, a solution or the like, but it is expected that the heat resistance is improved as compared with the conventional bisphenol due to the high content of para-conjugate. Viscous epoxy compound, polycarbonate resin, polyester resin,
It is expected to be used for raw materials such as polyurethane resin, reactive flame retardants due to halogenation, and antioxidants.

〔The invention's effect〕

As described above, in the method of the present invention, since the addition condensation reaction proceeds mildly, it is possible to react the phenols far more efficiently by the conventional homogeneous reaction method and control the polymerization. .

In particular, when a strongly acidic solid catalyst is used, the addition-condensation reaction at the para-functional site of phenols is preferentially promoted, so that a phenol resin having a high para-orientation can be produced. However, the phenol resin is expected to have higher heat resistance than conventional phenol resins.

Further, in the production process of the phenol resin, since it does not generate heat unlike the conventional method, it is possible to produce it on a large-scale scale (for example, 50 to 100 ^t batch) which has never been used.

Further, since the solid catalyst used in the present invention is substantially insoluble in water and / or organic solvent, it is possible to easily and clearly separate the produced phenol resin and the solid catalyst, and the phenol resin containing no solid catalyst is used. Is obtained.
For this reason, the polymerization of the phenol resin in the reaction concentration step after the catalyst separation is suppressed to a minimum, the further adjustment of the molecular weight accompanying the removal of unreacted monomers becomes easy, and a phenol resin with a concentrated molecular weight distribution is obtained. Obtainable.

According to the method of the present invention having such characteristics, a high-purity phenol resin having a so-called low-controlled molecular weight distribution substantially free of polynuclear components exceeding 7 nuclides and containing no impurities such as catalysts. And a phenol resin having a very low content of unreacted monomers and the like.

Further, according to the method of the present invention, high-purity bisphenol containing no impurities such as a catalyst mainly containing a para-conjugate in a high yield can be produced safely and easily on an industrial scale without requiring advanced production technology. Can be manufactured in.

〔Example〕

Hereinafter, the method of the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, all "parts" and "%" in these Examples and Comparative Examples are based on weight unless otherwise specified.

Examples 1 to 10 Solid catalysts shown in Table 1 in Erlenmeyer flasks equipped with a sealed stopper
No.1 to No.10 (Examples 1 to 10 respectively) 4.7g each
After weighing, phenol 9.4 and 47% formalin 5.1g
A mixed solution (mixing molar ratio 0.8) was charged. The flask was placed in a shaker with a constant temperature bath, the temperature was set to 40 ° C., and the condensation reaction was performed for 24 hours with shaking.

After completion of the reaction, 36 cc of tetrahydrofuran was injected to make a uniform solution of the phenol resin in order to measure the molecular weight distribution of the produced phenol resin and to prevent further time-dependent change of the condensation reaction. High-performance liquid chromatography of the solution (manufactured by Toyo Soda, HLC-802U column, TSKG1000H8, TSK
G2000H8 (1 each) was used to measure the molecular weight distribution of the produced phenolic resin.

FIG. 1 shows an example of a liquid chromatography chart of Example 1. From the chart, the amount of unreacted phenol was determined from the calibration curve previously measured and plotted, and the reaction rate was calculated. The average number of phenol nuclei was determined by calculating the molecular weight of each peak of the phenol resin from an inspection line prepared from a novolak resin using bisphenol A as a starting material to determine the number of nuclei.

To measure the ratio of the para bond (P) indicating the bonding position of the artaldehydes to the hydroxyl group of phenols and the total of ortho bonds (O), that is, P / P + 0, the reaction product was dissolved in acetone. Then, after filtering the solid catalyst, the solvent was removed in a desiccator at room temperature under reduced pressure, and the solid catalyst was dissolved in pyridine d ₅ , and TMS (tetramethylsilane) was added as an internal standard, and a nuclear magnetic resonance analyzer ( 1H-NM
R). The area of 4,4 ′ methylene bond of 3.5 to 3.9 PPM is I ₄₄ ′, the area of 2,4 ′ methylene bond of 3.9 to 4.3 PPM is I ₂₄ ′, and the area of 2,2 ′ methylene bond of 4.3 to 4.6 PPM is Area as I ₂₂ The results are summarized in Table 2.

From the results of FIG. 1 and Table 2, the phenol resin according to the present invention has an overwhelmingly high reaction rate obtained from unreacted phenol.
Further, it is recognized that the phenol resin is mainly a para-bonded phenol resin having a molecular weight distribution in a low molecular weight region of at most hexanuclear.

Comparative Example 1 Phenol 940 g and 37% formalin 535 g (blending molar ratio 0.6
6) and 4.7 g (0.5% / phenol) of solid catalyst No. 12 were charged in a flask and reacted at 80 ° C. for 6 hours, then dissolved in tetrahydrofuran and analyzed as an analysis sample in the same manner as in Examples 1-10. The results of the same are shown in FIG. 1 and Table 2.

From FIG. 1 and Table-2, it is clear that the product of Comparative Example 1 (conventional method) contains a large amount of unreacted phenol and a large amount of polymer polynuclear bodies.

Comparative Example 2 When No. 12 was used as a catalyst under the same compounding conditions and reaction conditions as in Examples 1 to 10, the contents were discharged by skipping the stopper of the flask.

Comparative Example 3 Under the same conditions as in Comparative Example 2, 1% of catalyst No. 12 / phenol was charged and reacted. The unreacted phenol in the produced phenol resin is 20%, the reaction rate is 69.3%, and the molecular weight distribution is 7.
There was a peak exceeding the nuclei, which was significantly different from the examples.

Examples 11 to 18 Phenols (P), aldehydes (A) and their molar ratios were reacted under the conditions shown in Table 3 in the same manner as in Examples 1 to 10 to determine the reaction rate.

Example 19 According to the compounding conditions of Example 3, the reaction temperature was 50 ° C., 80 ° C., 10
The reaction time was determined in the same manner as in Examples 1 to 10 by changing the temperature to 0 ° C. It was 8, 2, 48 hours respectively.

As a result, at high temperature, the distribution of the molecular weight moved to the polymer side at the same time, and at 100 ° C, a peak representing a polynuclear body of 8 or more nuclei appeared, and at 100 ° C, the catalyst seems to be inferior. The phenol monomer rapidly decreased within 1 hour after the initial reaction, and thereafter the reaction proceeded very slowly.

Example 20 Under the conditions of Examples 1 to 10, using solid catalyst No. 11,
The same reaction was performed and the reaction time was extended and continued for 48 hours. Unreacted phenol was 30% and about 54% was resinified.

Example 21 940 g of phenol and 510 g of 47% formalin (F / P = 0.8) are weighed in a three-necked flask, and further 470 g of a strongly acidic ion exchange resin (SPE112 manufactured by Mitsui Toatsu Fine Co., Ltd.) is charged at a temperature of 40 ° C. The mixture was stirred for 24 hours and the phenol resin reaction was carried out. The reaction system gradually changed from the state in which the solid catalyst was suspended to the state in which the crystalline phenol resin was dispersed.

After injecting methanol into the flask to make the phenol resin component into a solution, it was filtered under reduced pressure to separate the ion exchange resin and the phenol resin. The liquid chromatography chart of the phenol resin A at this time is as shown in FIG. 2, and a phenol resin having a small amount of phenol monomer and a small amount of high molecular weight region was prepared. Phenolic resin does not contain so-called residual catalyst, but P
-H was 2-3.

Then, the phenol resin A was continuously concentrated in a flask equipped with a pressure reducing device, and when the temperature reached 165 ° C., the phenol resin A was stopped, transferred to a metal vat of the contents and cooled to obtain a resin A ′.

A liquid chromatography chart of Resin A'is shown in FIG. It was possible to obtain a phenol resin containing almost no free phenol and having a high molecular weight of 8 nuclides or more. The resin yield at this time was 677 g.

Example 22 Phenol 940 g and 47% formalin 1277 g (F / P = 2) were blended, and a similar reaction was performed according to Example 21. The reaction system was in a liquid state even after the completion of the reaction, and the solid catalyst was in a suspended state, and the ion exchange resin and the phenol resin could be separated by filtration.

1000 g of water was poured into the filtrate phenol resin and allowed to stand, the phenol resin was precipitated and separated, and the supernatant was removed. The phenol resin B at this time showed a liquid chromatography chart as shown in FIG. 4, and was a phenol resin with a small amount of free phenol.

Then, the phenol resin B was concentrated under reduced pressure and concentrated at 150 ° C. to obtain a solid resin-B ′, and the chart is similarly shown in FIG. 885 g of a phenol resin containing almost no unreacted phenol was obtained.

Example 23 940 g of phenol and 47% formalin 1277 (F / P = 2) were mixed and weighed in a three-necked flask, and as a strongly basic ion exchange resin, DIAION SA / 10AOH (dry type) manufactured by Mitsubishi Kasei. , Water content 3%) was added and reacted at 40 ° C. for 96 hours to form a phenol resin. After the reaction was completed, it was in a liquid state in which a phenol resin having a very low viscosity and an ion exchange resin were mixed, and filtration separation was very easy. Liquid chromatography of the filtered phenol resin C was as shown in FIG. 6, and it was a phenol resin in which various methylol compounds distributed in the low molecular region were mixed. At this time, the phenol resin had a faint amine odor, and there was a possibility that a part of the quaternary ammonium salt was released from the anionic exchange resin and an addition reaction occurred.

The phenol resin was concentrated under reduced pressure at 50 ° C. to obtain a resole resin C ′. As shown in FIG. 7, the resin contained a small amount of unreacted phenol and contained a large amount of methylon compound.

Example 24 Orthocresol 1080 g, 47% formalin 1277 g (F / O.
C = 2.0) was weighed in the same manner as in Example 21, 540 g of SPC-112 manufactured by Mitsui Toatsu Fine Co., Ltd. was added, and the mixture was reacted at 40 ° C. for 24 hours. After the phenol resin D and the catalyst are separated by filtration, the phenol resin adhering to the catalyst is washed with methanol and combined with the phenol resin. Got ‘

As shown in FIG. 8, the resin D ′ contained almost no unreacted orthocresol and had a summarized molecular weight distribution.

The obtained resin D'was 1188 g, which was a yield of 110% based on the charged orthocresol.

Comparative Example 4 Phenol 940 g and 47% formalin 511 g (F / P = 0.8) were weighed into a three-necked flask, and paratoluenesulfonic acid 4.7 g was added.
(0.5% / P) was added, the temperature was raised to 100 ° C., and the reaction was carried out for 3 hours. The liquid chromatography chart of the phenol resin E at the end of the condensation is shown in FIG.

Next, the supernatant waste liquid was decanted and removed, and then dehydrated and concentrated under reduced pressure, and when it reached 160 ° C., it was discharged to obtain a resin E ′. A liquid chromatography chart of Resin E'is shown in FIG. The resin yield at this time was 900 g,
It was a resin having a distribution up to the polymer region containing free phenol.

Comparative Example 5 Phenol resin was prepared by reacting under the same conditions as in Comparative Example 4 except that 940 g of phenol and 1277 g of 47% formalin (F / P = 2) were used. However, at 100 ° C. or lower where water could not be drained, stirring became impossible, and a curing reaction occurred in the flask.

Example 25 Orthocresol 10 in flask with temperature system and stirrer
00 parts, 47% formalin 473 parts (blending ratio 0.8) and H-type strong acid ion exchange resin (Mitsui Toatsu Fine SPE-112)
After adding 500 parts of water content 40-45%, macroporous type), the reaction was carried out at a temperature of 30-40 ° C for 24 hours while stirring and mixing.

Next, hot water was injected to wash and remove unreacted monomers, and then the reaction product was dissolved with hot toluene and the ion exchange resin was filtered off. The filtrate was cooled to about 20 ° C to crystallize bisphenol, the crystals were filtered and dried under reduced pressure at about 50 ° C to obtain 850 parts of bisphenol (yield 85% / orthogresol). The bisphenol was about 100% para-para conjugate.

In the following Examples and Comparative Examples, the composition of bisphenol was measured by gas chromatography, and the ratio of peak heights of ortho-ortho, ortho-para and para-para conjugates eluted in this order was determined. The composition ratio was used. The measurement conditions are as follows.

Model: Shimadzu Gas Chromatography GC6AM Detector: FID (hydrogen flame ionization detector) Column: Silicone OV-17 (3φ x 3m) Injection temperature: 280 ° C Column temperature: 150-300 ° C (heating rate 20 ° C / min) Sample volume: 2μ (sample 500mg / 20cc acetone) Example 26 Phenol 520 parts in a flask equipped with a thermometer and a stirrer, 4
282 parts of 7% formalin (blending molar ratio 0.8) and H type strongly acidic ion exchange resin (Mitsui Toatsu Fine SPC-118 water content
After adding 260 parts (55-60%, macroporous type), the reaction was carried out at a temperature of about 30 ° C. for 24 hours while mixing with stirring. Next, hot water was injected to wash and remove unreacted monomers, and then the reaction product was dissolved with hot toluene and the ion exchange resin was filtered off. The filtrate was cooled to about 20 ° C. to crystallize bisphenol, the crystals were filtered and dried under reduced pressure at about 50 ° C. to obtain 338 parts of bisphenol (yield 65% / phenol). The bisphenol was a mixture of about 95% para-para conjugate and about 5% para-ortho conjugate.

Example 27 A bisphenol was obtained by the same reaction operation as in Example 2 except that the compounding molar ratio of formaldehyde to phenol in the example was changed to 2.0. (Yield 60% / phenol). The obtained bisphenol was a mixture of 94% para-para isomer and 6% orthopara isomer.

Example 28 Phenol 500 parts in a flask equipped with a thermometer and a stirrer,
451 parts of benzaldehyde (mixing molar ratio 0.8) and H type strongly acidic ion exchange resin (SPC-112 manufactured by Mitsui Toatsu Fine Co., Ltd., dried, 2-3% water content, macroporous type)
After adding 125 parts, mix with stirring at a temperature of about 30 ° C.
Weekly reactions were performed. Then, hot toluene was injected to dissolve the reaction product, and the ion exchange resin was filtered off in a warm state. The filtrate was cooled to about 10 ° C. to crystallize bisphenol, the crystals were filtered and dried under reduced pressure at about 50 ° C. to obtain 300 parts of bisphenol (yield 60% / phenol). The bisphenol was almost 100% para-para conjugate bis (para-hydroxyphenyl) phenylmethane.

Example 29 A reaction operation was performed in the same manner as in Example 4 except that 306 parts of n-butyraldehyde (mixing molar ratio of 0.8) was used instead of benzaldehyde in Example 4 (however, crystallization was performed at -10 ° C).
Thus, 255 parts of bisphenol (yield 51% / phenol) was obtained.

The bisphenol was approximately 100% para-para conjugate 1,1 bis (para-hydroxyphenyl) butane.

Example 30 500 parts of catechol in a flask equipped with a thermometer and a stirrer 37%
Formalin 184 parts (blending molar ratio 0.5) and H-type strongly acidic ion exchange resin (Mitsui Toatsu Fine SPC-118 water content 50-
After adding 250 parts of 60% macroporous type), the mixture was reacted with stirring at 0 ° C. for 3 days. Acetone was injected to dissolve the reaction product, and the ion exchange resin was filtered off. The filtrate was concentrated under reduced pressure to obtain a composition and then recrystallized from hot toluene to obtain 200 parts of bisphenol. (Yield 40% / phenol). The bisphenol obtained was a mixture of 95% bis (3,4 dihydroxyphenyl) methane and 5% (3,4 dihydrooxyphenyl)-(2,3 dihydrooxyphenyl) methane.

Comparative Example 6 Phenol 520 parts in a flask equipped with a thermometer and a stirrer, 4
After adding 53 parts of 7% formalin (mixing molar ratio 0.15) and 2.6 parts of para-toluenesulfonic acid as a catalyst, the reaction was carried out at reflux temperature for 4 hours while stirring and mixing. Then, unreacted phenol is removed by vacuum distillation to remove bisphenol.
156 parts (yield 30% / phenol) were obtained. This bisphenol contains a small amount of trinuclear or higher polymer, and 2
The composition of the monomers was a mixture of about 28% para-para conjugate, about 55% para-ortho conjugate, about 17% ortho-ortho conjugate.

[Brief description of drawings]

1 to 10 are all charts of liquid chromatography of phenolic resins obtained in Examples and Comparative Examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location // C07B 61/00 300 (72) Inventor Isao Kai Kaifu, Niwa-gun, Aichi Minamiyama Nii 26 ― 4 Inside Asahi Organic Materials Co., Ltd. (72) Inventor Kazuo Tamemoto Niizu, Fuso-cho, Niwa-gun, Aichi 26- 4 Asahi Organic Materials Co., Ltd.

Claims (3)

[Claims] 1. Phenols and aldehydes in the presence of a solid catalyst phase that is substantially insoluble in water and / or organic solvents and can release hydrogen ions (H ⁺ ) or hydroxide ions (OH ⁻ ). Is reacted at a temperature of 80 ° C. or lower, and then the solid catalyst phase is separated and removed. 2. Phenols and aldehydes are treated at 80 ° C. in the presence of a solid catalyst phase which is substantially insoluble in water and / or an organic solvent and can release hydrogen ions or hydroxyl ions.
A method for producing a phenol resin, which comprises reacting at the following temperature, separating and removing a solid catalyst phase to obtain a phenol resin, and then reacting and / or concentrating the phenol resin. 3. A phenol, resorcin, catechol, or a derivative thereof in the presence of an H-type acidic cation exchange resin, which is selected from the group consisting of substituted phenols having a hydrogen atom reactive at the para position to the hydroxyl group. A method for producing bisphenol, which comprises reacting one or more phenols and aldehydes at a temperature of 80 ° C. or lower.