KR970007339B1 - Method for simultaneous preparation of bisphenol f and novolak phenol resins - Google Patents

Abstract

None.

Description

Combined method of bisphenol F and noblock type phenol resin

1 is a schematic diagram showing a representative example of an aspect of the present invention.

2 is a schematic diagram showing a representative example of another aspect of the present invention.

3 is an analytical diagram showing the distribution of each nucleus in the phenolic resin obtained in Example 5. FIG.

4 is an analytical diagram showing the distribution of each nucleolus present in the phenol resin obtained in Example 6. FIG.

5 is an analytical diagram showing the distribution of each nucleus present in the phenol resin obtained in Example 8. FIG.

6 is an analytical diagram showing the distribution of each nucleus present in the phenol resin obtained in Comparative Example 6. FIG.

7 is an analytical diagram showing the distribution of each nucleus present in the phenol resin obtained in Example 15. FIG.

8 is an analytical diagram showing the distribution of each nucleolus present in the phenolic resin obtained in Example 17. FIG.

9 is an analytical diagram showing the distribution of each nucleus present in the phenol resin obtained in Comparative Example 7. FIG.

In Figs. 3 to 9, ②, ③, ④, ⑤, and ⑥ denote binuclear bodies, trinuclear bodies, tetranuclear bodies, 5-nuclear bodies and hexanuclear bodies, respectively.

The present invention relates to a method for co-solving bisphenol F and a novolak-type phenol resin. Specifically, the present invention is a high-purity bisphenol F and / or general purpose bisphenol F and a dinuclear content with a large amount of nucleophiles, and preferably a novolak-type phenolic resin with a high content of trinuclears and tetranuclears, especially a trinucleus. Furthermore, the present invention relates to a method for co-solving a high molecular weight novolak-type phenolic resin having a low content of dinuclear bodies and a high content of trinuclear bodies.

In recent years, high purity bisphenol F and general purpose bisphenol F having a large nucleus content are demanded as raw materials for epoxy resins or polycarbonate resins. On the other hand, various novolac-type phenol resins are widely used in the field of electric and electronic materials in recent years, as resist resins, binders for casting production, curing agents for epoxy resins or basic resins for epoxy resins.

Both bisphenol F and novolak type phenolic resins are prepared stoichiometrically from excess phenol and formaldehyde in the presence of an acid catalyst. The difference between the two is the molar ratio of the reaction between phenol and formaldehyde (hereinafter referred to as "P / F"). Usually bisphenol F is prepared in the range of P / F = 20-50, and 4,4′-dihydroxydiphenolmethane (hereinafter referred to as 4,4′-form), 2,4′- in the reaction product Three kinds of 2, such as dihydroxydiphenolmethane (hereinafter referred to as 2,4'-form) and 2,2'-dihydroxydiphenylmethane (hereinafter referred to as 2,2'-form) In addition to the nucleus, 7 to 12 wt% of the trinuclear nucleus (hereinafter referred to as multinuclear) obtained by polycondensation of phenol and formaldehyde is included.

It is known that this polynuclear body has a great influence on the physical properties of the epoxy resin obtained by epoxidizing bisphenol F. That is, when there are few polynuclear bodies, an epoxy resin will become easy to crystallize. On the contrary, when there are many polynuclear bodies, a viscosity of an epoxy resin will become high and workability will worsen.

First, general purpose bisphenol F is described. General purpose bisphenol F is bisphenol F which contains about 88-93 weight% of binary nucleus, preferably about 90-93 weight%, and is useful as a raw material of low viscosity epoxy resin.

Japanese Unexamined Patent Publication No. 55-124730 discloses a method for producing general purpose bisphenol F. In this method, bisphenol F useful as a raw material of epoxy resin is obtained by setting the reaction molar ratio (P / F) of phenol to formaldehyde to 25-50.

Japanese Unexamined Patent Application Publication No. 63-238032 shows that by using activated clay as a catalyst, bisphenol F suitable as a raw material for epoxy resin can be produced even if the reaction molar ratio is reduced to about 20.

However, in this method, even if the reaction molar ratio (P / F) is about 20, the ratio of the produced bisphenol F to the reaction mass is about 0.1 low. Therefore, when the production efficiency is low, a large amount of energy is used to separate excess phenol. in need.

Next, high purity bisphenol F is described. High-purity bisphenol F is a bisphenol F containing more nucleophiles than general-purpose bisphenol F, and is usefully used as a raw material for epoxy resin for paint.

Japanese Unexamined Patent Publication No. 90-166114 discloses bisphenol F containing at least 95% by weight of binuclear bodies, preferably at least 98% by weight of bisphenol F. Thus, paints comprising epoxy resin as components are composed of bisphenol F containing 92% by weight of binuclear bodies. It is described that it is excellent in the point of corrosion resistance of a coating film, chemical-resistance, etc. than the coating material which consists of the obtained epoxy resin as a component.

However, in the prior art, obtaining a high-purity bisphenol F having a binuclear content of 98% by weight or more by reaction of phenol and formaldehyde cannot be achieved even if the reaction molar ratio P / F is 100 or more. impossible.

For example, when the unreacted phenol is removed from the reaction product of phenol and formaldehyde followed by continuous parallel flash distillation, the dinuclear content of the still-bottom product in the gas-liquid equilibrium state The dinucleate content of the distillate will not be more than 98% by weight unless it is made to be at least 30% by weight. However, this method of leaving a large number of useful nuclei in the effluent is not economical.

Japanese Unexamined Patent Publication No. 39-8399 discloses a method for producing high purity bisphenol F. The purpose of this published invention is to obtain a reaction product having a content of 40-80% by weight of 4,4'-form in an isomeric mixture. This method is a method of obtaining a high purity bisphenol F by obtaining a mixture mainly containing two nuclei by two batches of single distillation, and then recrystallizing with toluene. However, the composition of the effluent after distillation by two batches of single distillation, the contents of useful dinuclear bodies and polynuclear bodies contained in the filtrate after recrystallization, and its recovery method are not disclosed. In addition, a large amount of solvent must be evaporated in order to recover useful components from the filtrate after recrystallization, which requires a lot of energy.

Next, a novolak type phenol resin is described. Novolak-type phenol resins are usually produced by reacting phenol and formaldehyde in the range of P / F = 1-2, and have an average nucleus number of 4-5 and a dinuclear content of 10-30% by weight.

The nucleus distribution of the novolak-type phenolic resin is known to be determined by the molar ratio P / F of phenol and formaldehyde. For example, when P / F = 2, a novolak-type phenolic resin having a composition of dinuclear content of about 25 area%, trinuclear content of about 20 area% and tetranuclear content of about 15 area% is obtained. . The larger the P / F, the higher the dinuclear content of the resin is, and the softening point of the resin is lowered.

The term "area%" as used herein to express the content of each nucleus in a novolak-type phenolic resin and a high molecular weight novolak-type phenolic resin refers to the resin by gel permeation chromatography (using two columns: Brand name: G4000HXL + G2500HXL + G2000HXL, Eluent: tetrahydrofuran).

When the novolak-type phenolic resin is used as a raw material or curing agent of epoxy resin, if the content of the nucleolus in the novolak-type phenolic resin increases, defects such as wrinkling of the molded product and a decrease in strength due to a decrease in the crosslinking density occur. In addition, there is a need for a novolak-type phenolic resin having a low content of dinuclear bodies.

Moreover, when using it as a hardening | curing agent of an epoxy resin or a base resin of an epoxy resin, in order to improve the intensity | strength of hardened | cured material, reduction of the content of the unreacted raw material which does not contribute to a crosslinking reaction, or a component below a binary nucleus is calculated | required.

On the other hand, there is a branch diagram as one of the performances required for the phenol resin. If the viscosity can be lowered while maintaining other properties such as heat resistance and strength of the phenolic resin, workability, reactivity, flowability and impregnation will be greatly improved. Moreover, there exists an advantage that fillers, such as an inorganic filler, can be mixed according to a use. When used as a binder for producing a mold, it is required to reduce the content of components below the nucleus in the resin, i.e., the nucleus and the unreacted raw material, in order to reduce the soot generated during the mold operation in addition to the low viscosity.

In addition, phenolic curing agents for epoxy resins for electric and electronic applications, which are in increasing demand in recent years, are also required to have a low viscosity and a low nucleus content.

Generally, phenol and formaldehyde are reacted in the range of P / F = 2-3 to produce a low molecular weight resin, that is, a resin of low viscosity. However, when using a low molecular weight thing as a hardening | curing agent, since it contains many components below the nucleus which does not contribute to a crosslinking reaction, there exists a fault that the intensity | strength of hardened | cured material becomes inadequate.

For example, when the reaction is carried out at a molar ratio P / F = 5/2 in order to lower the viscosity, a low molecular weight product is obtained as a reaction product and has a low melt viscosity. However, since it contains a large amount of unreacted raw materials or binary bodies which do not contribute to the crosslinking reaction, a problem of strength lack occurs during the curing reaction. However, if the nucleus is further removed again, a resin having a composition of about 35 area% and a tetranuclear content of about 23 area% in the portion except for the nucleus is obtained, and a sufficient amount of the cured product is obtained. However, since the nucleus is removed, a sufficiently low viscosity cannot be achieved.

For example, if the reaction is made with P / F = 5/4 so that the content of dinuclear in the resin is reduced, the dinuclear content is about 9 area%, the trinuclear content is about 8 area%, and the tetranuclear content is about 6 area%. The novolak type phenol resin which has a composition is obtained. In this case, the content of the nucleophile of the resin decreases, but since the reaction product of a high molecular flavor is generated and the viscosity increases, problems such as deterioration in workability, reactivity, fluidity, and impregnation occur.

In order to reduce the binary content of the novolak-type phenolic resin as described above, P / F must be reduced inevitably by the conventional method, and the softening point and viscosity of the resulting novolak-type phenolic resin increase, resulting in fluidity during molding. This gets worse.

In such a situation, an attempt has recently been made to dehydrate the initial condensate formed through the reaction, to dephenol, and then to remove the nucleus again by an operation such as extraction or steam distillation and reduced pressure distillation. At this time, when the nucleus is removed, the strength is higher than in the case where the nucleus is contained in a large amount, but the viscosity is also increased.

As described in Japanese Patent Application Laid-Open No. 62-501780 for a method for producing a novolak-type panol resin having a small nucleus content, a method of extracting the nucleus using hot water after the reaction or Japanese Patent Application Laid-Open No. 90-60915 As described in the publication, there is a method in which a slightly soluble solvent is added to water, followed by adding a water-soluble alcohol and water to remove the nucleus.

However, these methods do not indicate the effective use of the dinuclear bodies thus removed, so that the nucleus in an amount of about 20% by weight relative to the novolak-type phenolic resin is eventually discarded. In addition, these methods require a large amount of energy since the large amount of water and solvent used must be evaporated in order to recover useful dinuclear bodies.

For example, as a mold-making binder, Japanese Unexamined Patent Publication No. 60-133017 discloses that the content of a binary nucleus and a content of six or more nuclei are lowered, but the viscosity of the resin is still too high.

Japanese Unexamined Patent Publication Nos. 62-267314, 62-275121, and 62-277419 disclose a resin having a lower nucleus content, but still have a too high viscosity.

Therefore, using the conventional reaction molar ratio, even if the content of the nucleus is reduced, novolak-type phenolic resins having low melt viscosity while maintaining reliability on various properties such as mechanical strength and heat resistance cannot be produced.

SUMMARY OF THE INVENTION The object of the present invention is to solve the above problems and to achieve high purity bisphenol F and / or general purpose bisphenol F having a nucleus content of 95% by weight or more, and a novolac phenol resin and / or a high molecular weight furnace having a binuclear content of 15 area% or less. It is to provide a method for co-balancing a phenol resin.

The present invention has been studied to achieve the above object, and the inventors have found that the above object can be achieved by effectively utilizing the distillate when distilling crude bisphenol F, thereby finally completing the present invention. .

That is, the first aspect of the present invention

(1) a preparation step of reacting phenol with formaldehyde in the presence of an acid catalyst and removing the acid catalyst, water and unreacted phenol from the obtained product to obtain the crude bisphenol F;

(2) The distillation of this bisphenol F yields a high purity bisphenol F having a dinuclear content of at least 95% by weight, preferably at least 98% by weight as a distillate, and a binuclear content of 15 area% or less as a effluent, preferably It is a combined process of the high purity bisphenol F and novolak-type phenol resin characterized by including the distillation step of obtaining a novolak-type phenol resin of 10 area% or less.

The second aspect of the present invention is the production step of (1) reacting phenol and formaldehyde in the presence of an acid catalyst, and removing the acid catalyst, water and unreacted phenol from the reaction product obtained to obtain the crude bisphenol F; (2) By distilling a part of said bisphenol F, high purity bisphenol F having a dinuclear content of at least 95% by weight, preferably at least 98% by weight as a distillate, and having a dinuclear content of 15 area% or less as a effluent, preferably Distillation step of obtaining a novolak-type phenolic resin of 10 area% or less; And (3) mixing the high-purity bisphenol F and the rest of the bisphenol F to obtain a general-purpose bisphenol F, wherein the general purpose bisphenol F and the novolac-type phenol resin are combined.

A third aspect of the present invention is the production step of (1) reacting phenol and formaldehyde in the presence of an acid catalyst, and removing the acid catalyst, water and unreacted phenol from the reaction product obtained to obtain the crude bisphenol F; (2) distillation of a portion of the said bisphenol F yields a high purity bisphenol F having a dinucleus content of at least 95% by weight, preferably at least 98% by weight as a distillate, and a binuclear content of 15 area% or less as a effluent. Distillation step of obtaining a novolak-type phenol resin, preferably 10 area% or less; And (3) a mixing step of mixing a part of the high purity bisphenol F and the rest of the bisphenol F to obtain a general purpose bisphenol F, wherein the high purity bisphenol F, the general purpose bisphenol F, and the novolak-type phenol resin are combined. to be.

The fourth aspect of the present invention is a polymerization step of obtaining a high molecular weight novolak type phenolic resin by reacting the novolak type phenolic resin obtained in the first, second or third embodiment in the presence of formaldehyde and an acid catalyst. A high purity phenolic resin F and / or general-purpose bisphenol F and a high molecular weight novolak-type phenolic resin are included. In this case, only a part of the novolak-type phenol resin may be polymerized to co-exist novolak-type phenol resin and high molecular weight novolak-type phenol resin.

In the distillation step of the combined acid method of the present invention, a pressure distillation apparatus equipped with a distillation unit, a partial condensor, and a complete condensor is used. Continuous feeding of bisphenol F to an evaporator maintained at 5 mmHg, temperature 220-250 ° C .; A portion of the gas produced in the evaporator is partially condensed in the condenser and returned to the evaporator, and distillation of the bisphenol F is continuously distilled off while continuously extracting the effluent from the evaporator, or a plurality of evaporators installed in series Using a distillation apparatus having an ideal condenser and a pre-shrinkage device, the bisphenol F is continuously supplied to the evaporator of the first stage of the plurality of evaporators maintained at a pressure of 1-5 mmHg and a temperature of 200 to 250 ° C .; Each of the evaporator effluents is continuously fed to the next stage evaporator, and a portion of the evaporation gas from the final stage evaporator maintained at a pressure of at least 1-5 mmHg and a temperature of 220-250 ° C. is condensed into a condenser to obtain It is preferable to return distillate to the evaporator and to continuously distill the bisphenol F while continuously extracting the effluent from the evaporator, and in this case, a multi-tubular cylindrical heat exchanger or a coil heat exchanger is used as the dividing machine, and ) Is preferably in the range of 0.05-0.5.

The present invention is explained in more detail.

In this specification, the bisphenol F is a reaction between phenol and formaldehyde in the presence of an acid catalyst to remove the acid catalyst, water and unreacted substance from the reaction mixture.

In the present invention, the high-purity bisphenol F is bisphenol F containing 95 wt% or more of the nucleus, preferably bisphenol F containing 98 wt% or more of the nucleus, and the general purpose bisphenol F is 88-93 wt% of 2 Bisphenol F containing the nucleus.

In the present invention, the novolak-type phenolic resin is a novolak-type phenolic resin having a content of binuclear body of 15 area% or less, and a high molecular weight novolak-type phenolic resin is a leachate obtained in the distillation step in the present invention. It is obtained by reacting a volak type phenol resin with formaldehyde in the presence of an acid catalyst, and is preferably a high molecular weight novolac type phenol resin having a weight average molecular weight of more than 340 and a dinuclear content of 10 area% or less.

Particularly preferred novolak-type phenolic resins of the present invention are those having a small nucleolus content in the resin, and having a nucleolus distribution with a high amount of trinuclear bodies and tetranuclear bodies, especially trinuclear bodies. Novolak-type phenolic resins capable of producing cured products having low melt viscosity and high crosslinking degrees, which have not been obtained so far, can be obtained by resins having such a characteristic nucleus distribution.

The dinuclear content of the novolak-type phenolic resin is preferably 15 area% or less, particularly 10 area% or less. Since the nucleus does not contribute to the crosslinking reaction, the content is preferably smaller. However, increasing the content of the nucleolus lowers the viscosity, so that the nucleolus can be contained within the required degree of crosslinking.

The content of the trinuclear body in the total resin except for the nucleolus of the novolak type phenol resin is preferably 50 area% or more. If the content of the trinuclear is 50 area% or more, a novolak-type phenol resin having a low melt viscosity can be obtained.

In the content of the ternary and tetranuclear bodies in the portions excluding the dinuclear bodies, the sum is preferably 80 area% or more. Since the components below the dinuclear body, that is, unreacted phenol and the nucleus do not contribute to the crosslinking reaction, the higher the content rate of the components of the trinuclear body or more is preferable. In addition, the more the low molecular weight component, the lower the melt viscosity of the resin. Therefore, when the sum of the content of the trinuclear body and the tetranuclear body in the novolak-type phenol resin is 80 area% or more, a resin having low melt viscosity can be produced.

The dinuclear content of the high molecular weight novolak-type phenol resin is determined by the dinuclear content in the novolak-type phenol resin and the amount of formaldehyde added. Since the components below the nucleus, that is, unreacted phenol and the nucleus component, do not contribute to the crosslinking reaction, the content of the nucleolus is preferably less to improve the strength of the cured product. However, since the viscosity decreases so that a binary nucleus content rate is high, you may contain a binary nucleus as long as it is in an allowable range in hardened | cured material strength. Preferably the dinuclear content in this resin is 10 area% or less.

The high molecular weight novolak-type phenolic resin contained the percentage of the nucleus content in the remaining portion of the resin except the nucleus in the number average molecular weight x.

y 7900 / (x-210) (but x = 300-800)

It is represented by and it is preferable that a trinucleide content rate is high. In this case, a high molecular weight novolak-type phenolic resin having a low melt viscosity that cannot be obtained with a novolak-type phenolic resin having the same glass transition point (hereinafter, referred to as Tg) when cured can be obtained.

Hereinafter, the present invention will be described in detail with reference to FIGS. 1 and 2.

First, according to the 1st aspect of this invention, the method of co-operating high purity bisphenol F (6) and the novolak-type phenol resin 10 with little dinuclear content is demonstrated in detail.

The stoichiometric excess of phenol and formaldehyde is charged to the preparation step (reaction step to dephenol step) (1). Specifically, phenol, formaldehyde, and a new catalyst are charged to a reactor equipped with, for example, a stirrer, a temperature controller, a reflux condenser, a preheater, a decompression device, and reacted for a predetermined time at a predetermined temperature under stirring. The acid catalyst, the product water, and the ground phenol are removed from the reaction product to obtain the bisphenol F (2).

Examples of the phenol used in the present invention include, for example, cresol, o-, p- or m- substituted alkylphenols besides phenol.

Formaldehyde may exemplify formalin, formaldehyde, hexamethylene tetramine, trioxane and cyclic formal.

The reaction molar ratio P / F is usually 6 or more, preferably 6-30, and more preferably 6-20. The larger the reaction molar ratio P / F, the greater the content of the trinuclear body in the portion excluding the nucleolus in this resin.

The acid catalyst used in step (1) may be a solid acid catalyst fixed bed such as a cation exchange resin, or may be hydrochloric acid, sulfuric acid, salicylic acid, p-toluene sulfonic acid, and oxalic organic acid and inorganic acid.

The reaction temperature and reaction time vary depending on the type, amount of catalyst used or the reaction volume ratio P / F, etc., but are usually 50-110 ° C and 0.5-10 hours.

When a fixed bed catalyst such as a cation exchange resin is used, it is not necessary to remove the catalyst after the reaction, and unreacted formaldehyde, generated water, and the like are removed by a distillation under reduced pressure. In the case of using inorganic acids such as hydrochloric acid and oxalic acid, the acid catalyst is removed together with unreacted formaldehyde, charged water, and generated water at the same time by distillation under reduced pressure.

Subsequently, unreacted phenol is removed by distillation under reduced pressure or the like. These separations and removals may be performed separately, or a condenser and a condenser may be used together to partially condense and remove phenol by providing a condenser and then condense water and the like by the condenser. Of course, the recovered phenol can be used again as a raw material.

Thus, the nucleophile content in the zobisphenol F (2) obtained in step (1) is, for example, using oxalic acid as a catalyst, 68 wt% when P / F = 6, and 78 when P / F = 10. It is 87 weight% when it carries out by weight% and P / F = 20.

Zobisphenol F (2) is then sent to distillation step (4). The distillation apparatus used in the distillation step of the present invention is preferably provided with a condenser capable of condensing a part of the evaporated gas from the distillation and returning the condensate to the distillation. In the present invention, a falling thin film type or centrifugal thin film type evaporator is used. Etc. are preferably used. In the case of using a plurality of stills, each still may be provided with a divider or may not have a divider, but at least the evaporator used in the final stage is preferably provided with a divider. Also in this case, the type of evaporator which is preferably used is as described above.

In the present invention, when the distillation temperature exceeds 250 ° C, decomposition and / or coloring of bisphenol F may occur. Moreover, when it is less than 200 degreeC, the pressure is required to be less than 1 mmHg.

For example, in the distillation step according to the present invention, the bisphenol F is continuously supplied to a distillation apparatus equipped with an evaporator, a condenser, and a condenser, and the evaporation gas generated from this distiller is produced at a pressure of 1-5 mmHg and a temperature of 220-250 ° C. A part is condensed using a condenser, the condensate is distilled while returning to this still, and the remainder of the evaporated gas is condensed using a condenser to continuously produce high-purity bisphenol F as an effluent, and the effluent. Pull out continuously.

Or the following method using, for example, three stills as the distillation step.

In this method, the crude bisphenol F is continuously supplied to the first stage distillation to evaporate at a pressure of 1-5 mmHg and a temperature of 200-250 ° C. and introduce all the amount of the boil-off gas generated from the evaporator into the pre-shaft; Alternatively, a portion of the boil-off gas is condensed by using a condenser, and the condensate is distilled while returning to the first-stage distiller to introduce another portion of the boil-off gas into the pre-shaft while removing the effluent from the first-stage distiller The bisphenol F is distilled off as it is continuously supplied to a two-stage still. Also in the distillator of the second stage, the distillation is carried out in the same manner as in the first stage, and the effluent of the distillator is continuously supplied to the third stage. The evaporator of the third stage is also at the same pressure as the first stage, preferably at a temperature of 220-250 ° C. to condense a portion of the evaporated gas generated in this still by using a condenser and return the condensate to the third stage. Distillation and distillation introduce another portion of this boil-off gas into the preheater. At the same time, the effluent is withdrawn continuously from this third stage still. The uncondensed gas of each stage can be collected and condensed in the preheater to produce high purity bisphenol F as an effluent.

The fractionation ratio of the said condenser, ie, the weight ratio of the condensate to the uncondensed gas in this condenser, is usually in the range of 0.05-0.5. If the fractionation ratio is less than 0.05, the content of the dinuclear body contained in the percolating mole is 15 area%. If it tries to suppress below, the dinuclear content contained in an outflow will be less than 98 weight%, and when a fractionation ratio exceeds 0.5, extra energy will be needed.

By returning the condensate to the distiller using these condensers, the dinucleide content contained in the effluent can easily be 98% by weight or more even when the dinuclear content contained in the effluent reaches 15 area% or less.

In the case of using a plurality of distillers, it is preferable to adjust the content of the binuclear body in the feed liquid fed to the final stage still to 30 area% or more. If the area is less than 30%, the sum of the dinuclear contents of the effluents of all the evaporators may be less than 98% by weight, no matter how much the nucleus content is contained in the distillate of the final stage.

Preferred examples of the preshaft used in the present invention include a multi-tubular cylindrical heat exchanger and a co-heat exchanger. As a partial condenser, a tubular cylindrical heat exchanger, a coil type heat exchanger, etc. are mentioned. In addition, the evaporation line from the evaporator to the electric storage machine may be of a type that cools externally.

The dinuclear content contained in the effluent from the distillation step of the present invention is 1-15 area%, preferably 1-10 area%. If it exceeds 15 area%, the yield of useful nuclei decreases, and below 1 area%, the distillation temperature becomes high, which leads to problems of decomposition and coloring of effluents or effluents.

Another advantage of the present invention is that by controlling the content of the nucleolus contained in the effluent to 15 area% or less, preferably 10 area% or less, it is possible to form a effluent that can be used as a useful novolak-type phenolic resin having less nucleus. Can be. It is also possible to polymerize the effluent and formaldehyde by condensing it into a high molecular weight novolak-type phenolic resin with a low content of dinuclear body.

By distilling the crude bisphenol F (2) under the distillation conditions, it is possible to obtain a high-purity bisphenol F (6) as the distillate 5 and a novolak-type panol resin 10 having a small nucleus content as the distillate. By appropriately selecting the pressure and temperature conditions in the above ranges, the dinuclear content in the effluent is 15 area% or less, and the dinuclear content in the effluent 5 is 95% by weight or more. If the content of the nucleus in the effluent exceeds 15 area%, the effluent becomes paste-shaped and difficult to handle, and when used as a raw material or curing agent for epoxy resins, the resulting molded product may be crushed or molded. The strength of is lowered. Moreover, when the binary nucleus content contained in the effluent 5 is less than 95 weight%, when this is used as a raw material of an epoxy resin, the corrosion resistance and chemical resistance of the epoxy resin obtained fall.

The novolak-type phenolic resin 10 containing a small amount of binary nucleus as a effluent is extracted from the distillation tube, cooled to about 40 ° C. or lower by cooling in air, or forcedly cooled, and preferably pulverized. It is set as the novolak-type phenol resin 10 with little content. There is no restriction | limiting in particular in the grinding | pulverization method, The mill, such as a bowl mill and a jet mill, is used preferably.

According to the second aspect of the present invention, when combining the general purpose bisphenol F and the novolak-type phenolic resin having a low content of dinuclear bodies, the molar ratio P / F of phenol to formyl is usually in the range of 6-20. F (2) is split in two at appropriate ratios to the bisphenol F (3) and the bisphenol F (9). Divided zobisphenol F (3) is sent to distillation stage 4 and distilled.

The obtained effluent 5 is sent to the mixing step 7. On the other hand, the divided bisphenol F (9) is sent directly to the mixing step (7) and mixed with the effluent (5) to give a general-purpose bisphenol F (8) containing 88-93% by weight of the nucleus. There is no restriction | limiting in particular in the kind of apparatus to mix, What is necessary is just to use for mixing of normal liquid, For example, the tank or fixed mixer provided with a stirrer, etc. are used.

For example, when the reaction between phenol and formaldehyde is carried out at P / F = 10 to produce a general-purpose bisphenol F having 91% by weight of a nucleophile, the above split ratio (divided zobisphenol F (3) / divided zobisphenol F The weight ratio of (9)) may be about 68 to 32. At the same time, the novolak-type phenolic resin 10 having a low nucleus content is about 18% by weight relative to the general-purpose bisphenol F as a distillation step (4). The dinuclear content in this effluent is preferably 15 area% or less, particularly 10 area% or less.

Even if the split ratio is increased, high purity bisphenol F (6) and general purpose bisphenol F (8) can be produced simultaneously. The high-purity bisphenol F (6) and general purpose bisphenol F (8) may be formed into a liquid sieve by keeping warm, or may be granulated by being sent to a granulation step separately installed to form a granular product.

According to the third aspect of the present invention, when high-purity bisphenol F (6), general purpose bisphenol F (8), and novolak-type phenolic resin 10 having a low nucleophile content are used together, the same procedure as in the second embodiment provides high purity. Bisphenol F is obtained, and the same procedure as in the second embodiment is carried out except that a part of the high-purity bisphenol F and the rest of the bisphenol F are mixed to obtain a general purpose bisphenol F.

According to the fourth aspect of the present invention, the high-purity bisphenol F (6) and / or the general-purpose bisphenol F (8) and the novolak-type phenol resin (10) having a low dinuclear content and / or the high molecular weight furnace having a low dinuclear content The method of co-balancing the volacic phenol resin 12 will be described.

Also in the fourth embodiment, the high-purity bisphenol F (6), general purpose bisphenol F (8) and the novolak-type phenolic resin 10 having a low nucleophile content are the same as in the first, second or third embodiment. Are manufactured.

At least a part of the obtained novolac-type phenol resin 10 having a low nucleolus content is sent to the polymerization step 11. The manufacturing method of high molecular weight novolak-type phenol resin in this step (11) is performed by the following method.

That is, the novolak-type phenol resin 10, formaldehyde and the catalyst having a small nucleus content in the reactor in step 11 are charged, and reacted for 0.5-10 hours at a temperature range of 50-110 ° C under stirring.

Formaldehyde may be exemplified by formalin, p-formaldehyde, hexamethylenetetramine trioxane and cycloformal.

As a catalyst of a novolak-type phenol resin and a formaldehyde reaction, inorganic acids, such as hydrochloric acid and a sulfuric acid, and organic acids, such as salicylic acid, paratoluene sulfonic acid, and oxalic acid, are mentioned.

The obtained reaction product is heated to remove residual catalyst, unreacted formaldehyde and produced water, thereby obtaining a high molecular weight novolak-type phenolic resin 12 having a low nucleophile content. The novolak-type phenolic resin 12 is removed from the reactor and cooled to about 40 ° C. or lower by cooling in air or by forced cooling, preferably pulverized. There is no restriction | limiting in particular in the grinding | pulverization method, A mill, such as a bowl mill and a jet mill, is used preferably.

The novolak-type phenol resin of the present invention is a resin having a low nucleophilic content and preferably a high trinuclear content. When the content of the trinuclear body in the portion excluding the components less than the dinuclear body is 50 area% or more, or the sum of the content of the trinucleus content and the tetranuclear body is 80 area% or more, a resin having a sufficiently low viscosity can be obtained at the time of high molecular weight.

The weight ratio (hereinafter referred to as N / F) of formaldehyde and a novolak-type phenol resin 10 having a small nucleus content is preferably 15 or more. The softening point of the high molecular weight novolak-type phenolic resin obtained at less than 15 N / F is over 120 DEG C, and when used as a molding material or the like, for example, it is difficult to handle because of poor fluidity.

The content of dinuclear body contained in the high molecular weight novolak-type phenolic resin prepared in this manner is about 3-6 area%. It is 18-23 area% when the nucleus content of the novolak-type phenol resin conventionally used as a curing agent for epoxy resins is, for example, a softening point of 80 ° C., and 6-9 when the softening point is 120 ° C. Considering area%, it becomes small enough. Moreover, the weight average molecular weight (Mw) is about 340-1600, the number average molecular weight (Mn) is about 300-800, and Mw / Mn which is a parameter which shows molecular weight distribution becomes about 1.2-2.5, and a narrow molecular weight distribution is obtained.

One of the advantageous features of the present invention is the high-purity bisphenol F (6) and / or general purpose bisphenol F (8) and novolac-type phenolic resins having a low nucleophile content by changing the reaction molar ratio P / F in step (1). 10) and / or since the production cost of the high molecular weight novolak-type phenolic resin 12 with a low content of two-liquid can be controlled, the present invention can meet various demands.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, evaluation or measurement of the various characteristic values in an Example and a comparative example were performed by the method of following (1)-(5).

(1) Measurement of 4,4'-form, 2,4'-form, and 2,2'-form in high-purity bisphenol F and general-purpose bisphenol F: liquid chromatography (column: manufactured by Wortz, trade name: Radial Pack C18) , Eluent: acetonitrile / water, with gradient). The results are expressed in weight percent using an internal standard method and expressed as the total amount of the binary amounts of the three components.

(2) Measurement of each nucleus content and number average molecular weight in novolak-type phenolic resin and high molecular weight novolak-type phenolic resin: The content of each nucleus was gel permeation chromatography (two columns: manufactured by Ortho Co., Ltd. , Eluent: tetrahydrofuran). The average molecular weight was computed by making the molecular weight according to the number of phenol nuclei correspond to each peak measured similarly.

(3) Viscosity: The distillate was measured at 130 ° C and high molecular weight novolak type phenolic resin at 150 ° C using an ICI cone & plate viscometer (Research Equipment Co., Ltd .: London).

(4) Glass transition temperature (Tg): It measured by TMA (thermomechanical measurement) method.

(5) Softening point: Measured according to the method specified in JIS K-2207.

Preparation of the epoxy hardener:

Each of the effluents obtained in Examples 5-8, 14-16 and Comparative Example 6-7 was used as a curing agent, and the base resin and the catalyst were dissolved in a small amount of acetone as much as possible, and a mold plate having a thickness of about 3 mm was prepared for evaluation. The compounding ratio of the base resin and the catalyst is 49 parts by weight of the curing agent and 1 part by weight of the catalyst based on 100 parts by weight of the main resin. Epoxy resin (ECON-102S manufactured by Nippon Kayaku Co., Ltd .: epoxy equivalent, 214, softening point 75.0 ° C., viscosity 6.3 P (150 ° C.) was used as a base resin. Triphenylphosphine (TPP) was used as a catalyst.

Example 1

A phenol solution containing 47% formalin and a molar ratio of phenol / formaldehyde dissolved in 0.046% by weight of a oxalic acid dihydrate in a stainless steel stirred tank reactor equipped with a stirrer, a thermostat, a reflux condenser, a recorder, and a decompression device. (P / F) was 20, and it adjusted continuously so that the total supply amount of a good solution might be 3560 kg / hr.

The reaction mixture was allowed to react for 70 hours at a reaction temperature of 4 ° C. and a residence time, and the obtained reaction mixture was continuously extracted and fed to the packed distillation column continuously. It heated to 170 degreeC under reduced pressure of 20 mmHg, remove | eliminated water and unreacted material, and obtained the bisphenol F.

The composition of the obtained bisphenol F was 4,4'-body: 28.9% by weight, 2,4'-body: 38.2% by weight, 2,2'-body: 10.9% by weight, and the total amount of these two nuclei was 78.0% by weight. It was.

This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a pressure of 3 mmHg, and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator used a jacketed one, and fruit flowed through the jacket. In the centrifugal thin film evaporator, a coil type heat exchanger was installed as a condenser, and the fractionation ratio (weight ratio) was adjusted by flowing cooling water through the coil of the condenser so that a part of the evaporated gas was condensed into the condenser and returned to the evaporator.

When the fruit quantity was adjusted so that the temperature of the effluent was 245 ° C, and the amount of cooling water was adjusted so that the fractional ratio (weight ratio) was 0.2, the dinuclear body weight of the effluent was 6% by weight, and the binuclear body weight of the effluent was 98% by weight. To obtain a high purity bisphenol F containing 98% by weight of a binary nucleus. No coloration was observed in the obtained high purity bisphenol F.

Example 2

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained bisphenol F was the same as in Example 1. This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a pressure of 3 mmHg and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator uses a jacketed one and flows the fruit through the jacket. In the centrifugal thin film evaporator, a coil type heat exchanger was installed as a partial condenser, and the evaporated gas was partially condensed in the partial condenser and returned to the evaporator.

The fractionation ratio (weight ratio) was adjusted by making a cooling water flow through the coil of a divider. When the amount of fruit is controlled so that the temperature of the effluent is 240 ° C., and the amount of cooling water is adjusted so that the fractional ratio (weight ratio) is 0.2, the dinuclear body weight of the effluent is 10% by weight, and the binuclear body weight of the effluent is 99%. It became% and the high purity bisphenol F containing 99 weight% of nucleophiles was obtained. Coloring was not observed in the obtained high purity bisphenol F.

Example 3

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained zobisphenol F was the same as in Example 1. This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a vacuum degree of 3 mmHg, and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator used a jacketed one and allowed the fruit to flow through the jacket. In the centrifugal thin film evaporator, a coil type heat exchanger was installed as a partial condenser so that the evaporated gas was partially condensed in the partial condenser and returned to the evaporator.

The fractionation ratio (weight ratio) was adjusted by making a cooling water flow through the coil of a divider. When the amount of fruit is adjusted so that the silver content of the effluent is 240 ° C., and the amount of cooling water is adjusted so that the fractionation ratio (weight ratio) is 0.1, the dinuclear body weight of the effluent is 10% by weight and the binuclear body weight of the effluent is 98.4 weight. It became% and obtained the high purity bisphenol F containing 98.4 weight% of nucleophiles. Coloring was not observed in the obtained high purity bisphenol F.

Example 4

Bisphenol F was prepared in the same manner as in Example 1. The composition of the obtained bisphenol F was the same as in Example 1.

This zobisphenol F was continuously fed at 30 kg / hr to the centrifugal thin film evaporator of the first stage weighted at a pressure of 3 mmHg, and the effluent and the effluent were taken out continuously. The dinuclear body weight in the effluent was 50% by weight. This effluent was fed to a second stage centrifugal thin film evaporator operated at 3 mmHg pressure and the effluent and effluent were drawn off continuously. The evaporator effluents of the first and second stages were mixed and drawn off.

Two centrifugal thin film evaporators were used, each with a jacket attached and the jacket flowed with fruit. In the second centrifugal thin film evaporator, a coil type heat exchanger was installed as a condenser, and the gas generated in the evaporator was partially fractionated in the condenser to return to the evaporator.

The fractionation ratio (weight ratio) was adjusted by making cooling water apply | coil to the coil of this partitioning machine. Adjust the amount of fruit of each evaporator so that the temperature of the effluent of the first and second evaporators becomes 227 ° C and 240 ° C respectively, and adjust the amount of water so that the fractional ratio (weight ratio) in the second evaporator is 0.2. As a result of the adjustment, the dinuclear mass of the effluent of the second stage evaporator is 10% by weight, and the dinuclear mass of the sum of the effluents of the first and second stage evaporators is 99.3 wt%, and the 9 nuclei are 99.3 wt%. High purity bisphenol F containing% was obtained. Coloring was not observed in the obtained high purity bisphenol F.

Comparative Example 1

Bisphenol F was prepared in the same manner as in Example 1. The composition of the obtained zobisphenol F was the same as in Example 1. This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a pressure of 3 mmHg, and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator used a jacketed one and allowed the fruit to flow through the jacket. As a result of adjusting the amount of fruit so that the temperature of the effluent was 245 ° C, the binuclear body weight of the effluent was 6% by weight, the binuclear body weight of the effluent was 84% by weight, and bisphenol F containing 84% by weight of the nucleus was obtained. .

Comparative Example 2

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained bisphenol F is the same as in Example 1. This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a pressure of 3 mmHg and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator used a jacketed one and allowed the fruit to flow through the jacket. As a result of adjusting the amount of the fruit so that the temperature of the effluent was 240 ° C., the dinuclear body weight of the effluent was 10% by weight and the binuclear body weight of the effluent was 89.5% by weight, thereby obtaining bisphenol F containing 89.5% by weight of the nucleus. .

Comparative Example 3

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained zobisphenol F was the same as in Example 1.

This bisphenol F was fed continuously to the centrifugal thin film evaporator operated at a pressure of 3 mmHg at 30 kg / hr and continuously, and the effluent and the effluent were taken out continuously. The centrifugal thin film evaporator used a jacketed one and allowed the fruit to flow through the jacket. As a result of adjusting the amount of fruit so that the temperature of the effluent was 230 ° C, the dinuclear body weight of the effluent was 30% by weight and the binuclear body weight of the effluent was 98% by weight. Got it.

Although the purity of the obtained bisphenol F was high, since a useful dinuclear body was contained in a large quantity, the method of obtaining high purity bisphenol F was unsatisfactory in terms of efficiency.

Comparative Example 4

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained zobisphenol F was the same as in Example 1.

This zobisphenol F was continuously fed at 30 kg / hr to a centrifugal thin film evaporator operated at a pressure of 3 mmHg and the effluent and the effluent were continuously drawn off. The centrifugal thin film evaporator used a jacketed one and allowed the fruit to flow through the jacket. As a result of adjusting the temperature of the fruit so that the temperature of the effluent was 227 ° C, the dinuclear body weight of the effluent was 50% by weight and the binuclear body weight of the effluent was 99.4% by weight. Got it.

Although the purity of the obtained bisphenol F was high, since a useful dinuclear body was contained in a large quantity, the method of obtaining high purity bisphenol F was bad in terms of efficiency.

Comparative Example 5

Zobisphenol F was prepared in the same manner as in Example 1. The composition of the obtained zobisphenol F was the same as in Example 1.

This zobisphenol F was supplied to a rectification tower equipped with 10 perforated plates operated at a tower static pressure of 3 mmHg at 110 kg / kr, and the effluent and the effluent were continuously drawn out.

The tower top was equipped with a recorder, and the reflux ratio was set to 0.2 by opening and closing the solenoid valve by a timer. Top bottom temperature was controlled by fruit.

Attempt to set the column bottom temperature so that the amount of dinuclear body in the effluent was 10% by weight, but the column top pressure was increased due to the formation of phenol by the decomposition of bisphenol F above 260 ° C, so that safe operation was not possible.

Example 5

2000 g of phenol, 287.5 g of 37% formalin (P / F = 6), and 5.6 g of oxalic acid dihydrate were charged into a 3000 ml reactor made of stainless steel equipped with a stirrer, a temperature controller, a reflux condenser, a preheater, a decompression device, and the like. It heated to 70 degreeC, stirring, and operated the reflux condenser, and reacted for 4 hours at atmospheric pressure.

Next, the obtained reaction product was heated to 160 ° C. under atmospheric pressure to remove water and a small amount of phenol, and again heated to a pressure of 20 mmHg and a temperature of 170 ° C. to separate unreacted phenol. Moreover, it heated to pressure 6mmHg and the temperature of 210 degreeC, removed unreacted phenol, and obtained the bisphenol F.

The amount of the obtained bisphenol F was 640 g, the composition was 26.5 weight% of 4,4'-forms, 32.6 weight% of 2,4'-forms, 8.9 weight% of 2,2'-forms, and 68.0 weight% of total dinuclear bodies.

Next, as a Demister (trade name), the bisphenol F was distilled using the apparatus which attached the McMahon packing of diameter 15mm and height 20mm. The distillation was carried out at a pressure of 3 mmHg until the final temperature reached 250 ° C. to obtain 440 g of high-purity bisphenol F as a distillate and 198 g of a novolak-type phenol resin containing less nucleus as a effluent. The effluent was cooled to room temperature by air cooling to obtain a pulverizable solid.

The composition of high-purity bisphenol F is shown in Table 1, and the nucleolus weight, molecular weight, softening point, and viscosity of the novolak-type phenol resin with less nucleus are shown in Table 2. Table 3 shows the amount of dinuclear bodies of the sorbents, the content of trinuclear bodies in the remaining portions excluding the dinuclear bodies, the sum of the trinuclear bodies and the tetranuclear-containing incense, the viscosity, and the Tg of the epoxy cured product. 3 shows an analysis diagram showing the distribution of each nucleus of the produced novolac phenolic resin.

Example 6

2000 g of phenol and 172.5 g of 37% aqueous formalin solution were mixed (P / F = 10), 5.6 g of oxalic acid dihydrate was added, and the reaction was carried out at 70 ° C. for 4 hours. The mixture of reaction products was then heated to 160 ° C. under atmospheric pressure to remove water and small amounts of phenol and again to final 20 mmHg, 170 ° C. to separate unreacted phenol. Then, it heated to 6 mmHg and 210 degreeC, and removed phenol.

The obtained bisphenol F was 350 g, the composition was 28.9 weight% of 4,4'-form, 38.2 weight% of 2,4'-form, 10.9 weight% of 2,2'-form, and the sum total of these dinuclear bodies was 78.0 weight%. .

Next, distillation was performed to 3 mmHg and the final temperature of 245 degreeC using the apparatus with a 15 mm diameter and 20 mm height MICMA packing, and the high-purity bisphenol F 270g and 79 g of the precipitate were obtained. The effluent was cooled to room temperature, yielding a pulverizable solid.

Table 1 shows the composition of the high-purity bisphenol F in Table 1, the dinuclear weight, molecular weight, softening point, and viscosity of the effluent. Table 3 shows the amount of the dinuclear body of the effluent, the sum of the trinuclear content of the remaining portions except the dinuclear body, the sum of the trinuclear body and the tetranuclear content, the viscosity, and the Tg of the epoxy cured product. 4 is an analysis diagram showing the distribution of each nucleus of the novolak-type phenolic resin.

Example 7

Zobisphenol F was obtained under the same conditions as in Example 5 except that 2000 g of phenol and 86.3 g of 37% formalin (P / F = 20) were mixed and used.

Since the obtained bisphenol F was 200 g, the composition was 28.7 weight% of 44'-forms, 43.5 weight% of 2,4'-forms, and 14.8 weight% of 2,2'-forms, these dinuclear bodies were 87.0 weight%.

Next, distillation was performed to 3 mmHg and the final temperature of 245 degreeC using the apparatus similar to Example 5, and 171 g of high-purity bisphenol F and 27 g of distillates were obtained. The precipitate was cooled to room temperature to obtain a pulverized solid.

The composition of high-purity bisphenol F is shown in Table 1, and the amount of dimer nucleus, molecular weight, softening point, and viscosity are shown in Table 2. Table 3 shows the amount of the dinuclear body of the effluent, the sum of the trinuclear content of the remaining portions excluding the dinuclear body, the sum of the trinuclear body and the tetranuclear content, the viscosity, and the Tg of the epoxy cured product.

Example 8

The reaction was carried out under the same conditions as in Example 5 except that 2000 g of phenol and 57.5 g of 37% formalin aqueous solution were mixed (P / F = 30).

Next, distillation was performed to 3 mmHg and the final temperature of 240 degreeC using the apparatus similar to Example 5, and 13g of precipitates were obtained. The effluent was cooled to room temperature, yielding a comminuteable solid.

The composition of high-purity bisphenol F is shown in Table 1, and the amount of the dinucleated dimer, the triatomic weight, the softening point, and the viscosity are shown in Table 2. Table 3 shows the amount of the dinuclear body of the effluent, the content of the trinuclear body in the remaining portions excluding the dinuclear body, the sum of the dinuclear body and the tetranuclear content, the viscosity, and the Tg of the epoxy cured product. 5 shows an analysis diagram showing the distribution of each nucleus of the novolac phenolic resin.

Comparative Example 6

The reaction was carried out under the same conditions as in Example 5 except that 2000 g of phenol and 172.5 g of 37% formalin aqueous solution were mixed (P / F = 10/1).

Next, distillation was performed to 3 mmHg and the final temperature of 220 degreeC using the apparatus similar to Example 5, and 97 g of precipitates were obtained. The effluent was cooled to room temperature, yielding a pulverizable paste-like solid.

Table 3 shows the amount of the dinuclear body of the effluent, the trinucle containing content of the remaining portion except the dinuclear body, the sum of the trinuclear and tetranuclear content, the viscosity, and the Tg of the epoxy cured product. 6 shows an analysis chart showing the distribution of each nucleus of the novolac phenolic resin.

Example 9

Except having made the final temperature of distillation 237 degreeC, 260 g of high purity bisphenol F and 89 g of obtained matters were obtained on the conditions similar to Example 6. Even when the effluent was cooled to room temperature, it was paste-like, and thus no grinding was possible.

The composition of high-purity bisphenol F is shown in Table 1, and the amount of dimer nucleus, molecular weight, softening point, and viscosity are shown in Table 2.

Example 10

200g of bisphenol F was obtained on the conditions similar to Example 5. 170 g of this bisphenol F was distilled under the same conditions as in Example 5 to obtain 117 g of high purity bisphenol F and 52 g of a effluent. The effluent was cooled to room temperature, yielding a comminuteable solid.

30 g of remaining bisphenol F and 117 g of high-purity bisphenol F were mixed to obtain 147 g of general-purpose bisphenol F containing 91% by weight of a binary nucleus.

The composition of the general-purpose bisphenol F is shown in Table 1, and the binuclear weight, molecular weight, softening point, and viscosity of the effluent are shown in Table 2.

Example 11

Next, 200 g of bisphenol F was obtained under the same conditions as in Example 6. This dibisphenol F135.6g was distilled under the same conditions as in Example 6 to obtain high purity bisphenol F04g and 30 g of a effluent. The effluent was cooled to room temperature, yielding a comminuteable solid.

64.4 g of the remaining bisphenol F and 04 g of high-purity bisphenol F were mixed to obtain 168.4 g of general-purpose bisphenol F having a binuclear weight of 91% by weight.

The composition of the general-purpose bisphenol F is shown in Table 1, and the binuclear weight, molecular weight, softening point, and viscosity of the effluent are shown in Table 2.

Example 12

200 g of bisphenol F was obtained on the same conditions as in Example 7. 70.8 g of this bisphenol F was distilled under the same conditions as in Example 7 to obtain 60 g of high-purity bisphenol F and 9 g of the effluent. The effluent was cooled to room temperature, yielding a comminuteable solid.

The remaining bisphenol F 129.2 g and the high purity bisphenol F 60 g were mixed to obtain a general purpose bisphenol F 189.2 g containing 91 wt% of the nucleoside mass.

The composition of the general-purpose bisphenol F is shown in Table 1 in the dinuclear weight, molecular weight, and softening point viscosity of the effluent in Table 2.

Table 1

TABLE 2

Note) Unit of 2 nucleus weight is% by weight

Mw is weight average molecular weight, Mn is number average molecular weight, dispersion is Mw / Mn, softening point is unit of ℃ viscosity and poise P (measurement temperature: 130 ° C)

TABLE 3

Note) The unit of content is area%.

Trinucle-containing fragrance and 3 + 4 nucleolus content are the sum of trinuclear bodies and trinuclear bodies and tetranuclide contents of the remainder except the binuclear body in resin.

The unit of viscosity is P (measured at 130 ° C). The unit of Tg is ° C.

Example 13

The reaction and distillation were carried out in the same manner as in Example 5, to obtain 440 g of high-purity bisphenol F as an effluent and 198 g of a novolak-type phenol resin containing less nucleates as a effluent. 0.28% by weight of 9.6% by weight of oxalic acid dihydrate was added to 37% formalin and 37% formalin was reacted at 100 ° C for 4 hours. The reaction mixture was then heated at a pressure of 200 mmHg to a final temperature of 160 ° C. to remove water and unreacted formalin.

Table 4 shows the nucleophile weight, molecular weight, softening point, and viscosity of the novolak-type phenol cutlery having a low nucleophile content.

Example 14

The reaction and distillation were carried out in the same manner as in Example 6 to obtain a high-purity bisphenol F as a distillate and a novolak-type phenol resin containing less nucleates as a precipitate. A novolak-type phenolic resin containing less nucleates was obtained under the same conditions as in Example 13 except that 5.0% by weight of 37% formalin was added to the obtained leachate. Table 4 shows the nucleolus weight, molecular weight, softening point, and viscosity of the obtained novolak-type phenolic resin with less nucleolus.

Table 5 shows the binucle content of the obtained resin, the trinucleus content of the remaining portions excluding the binucle, the number average molecular weight, the viscosity, and the Tg of the cured product.

Example 15

Reaction and distillation were carried out in the same manner as in Example 6 to obtain a high-purity bisphenol F as a distillate, and a novolak-type phenol resin containing less nucleus as a precipitate. A novolak-type phenolic resin containing few nucleates was obtained under the same conditions as in Example 13 except that 8.0% by weight of 37% formalin was added to the obtained leachate.

Table 4 shows the amount of dinuclear body, molecular weight, softening point, and viscosity of the obtained novolak-type phenol resin having a small nucleolus content. Table 5 shows the nucleophile content rate of the obtained resin, the trinucleate content rate, the number average molecular weight, the viscosity, and the cured product of the remaining portions excluding the nucleus. Fig. 7 shows an analysis diagram showing the distribution of each nucleus of the novolac phenolic resin.

Example 16

The reaction and distillation were carried out in the same manner as in Example 6 to obtain a high-purity bisphenol F as a distillate and a novolak-type phenol resin containing less nucleates as a precipitate. A novolak-type phenolic resin containing few nucleates was obtained under the same conditions as in Example 13 except that 10.0% by weight of 37% formalin was added to the obtained leachate. Table 4 shows the nucleolus weight, molecular weight, softening point, and viscosity of the novolak-type phenolic resin having less dinuclear bodies.

Table 5 shows the binucle content of the obtained resin, the trinucleus content of the remaining portions excluding the binucle, the number average molecular weight, the viscosity, and the Tg of the cured product.

Example 17

The reaction and distillation were carried out in the same manner as in Example 6 to obtain a high-purity bisphenol F as a distillate and a novolak-type phenol cutler with few dinuclear bodies as a precipitate. A novolak-type phenolic resin containing few nucleates was obtained under the same conditions as in Example 13 except that 15.0 wt% of 37% formalin was added to the obtained effluent.

Table 4 shows the nucleolus weight, molecular weight, softening point, and viscosity of the obtained novolak-type phenolic resin having a low nucleophile content. FIG. 8 shows an analysis chart showing the distribution of each nucleus of the novolac phenolic resin.

Example 18

Reaction and distillation were carried out under the same conditions as in Example 7 to obtain a high-purity bisphenol F as a distillate and a novolak-type phenol resin containing less nucleus as a precipitate. A novolak-type phenolic resin containing less nucleophile was obtained under the same conditions as in Example 13 except that 10.4% by weight of 37% formalin was added to the obtained leachate. Table 4 shows the nucleolus weight, molecular weight, softening point, and viscosity of the obtained novolak-type phenolic resin having a low nucleophile content.

Table 4

Note) Unit of 2 nucleus weight is% by weight

Mw is weight average molecular weight Mn is number average molecular weight, dispersion is Mw / Mn softening point unit is t viscosity unit is poise (measurement temperature: 150 ° C)

Comparative Example 7

The reaction was carried out under the same conditions as in Example 6 except that 2000 g of phenol and 1035 g of 37% aqueous formalin solution were mixed (P / F = 5/3). Next, distillation was performed to 3 mmHg and final temperature of 220 degreeC using the apparatus similar to Example 6, and 13g of precipitates were obtained. The resultant was cooled to room temperature, whereby a paste-like crosslinkable product that could not be pulverized was obtained.

Table 2 shows the two-liquid content of the effluent, the trinucleus content of the remaining portions except the dinuclear body, the number average molecular weight, the viscosity, and the Tg of the cured product. FIG. 9 shows an analysis diagram showing the distribution of each nucleus of the novolac phenolic resin.

Table 5

Note) The unit of content rate is area%.

The trinuclear content and the number average molecular weight are the trinuclear content and the number average molecular weight of the remaining portion except the dinuclear in the resin. The unit of viscosity is P (measured at 150 ° C).

The unit of Tg is ° C.

In the present invention, the bisphenol F and / or the general-purpose bisphenol F and the novolac-type phenol having little nucleus are used because the effluent and the distillate when distilling the crude bisphenol F obtained by the reaction are effectively used in various embodiments described above. A high molecular weight novolak-type phenolic resin having a small amount of resin and / or a dinuclear body can be used in combination, and industrial waste is hardly generated. By appropriately changing the P / F of phenol and formaldehyde, high-purity bisphenol F, general purpose phenol resin F, novolak-type phenol resin with less nucleus, and high molecular weight novolak-type phenol resin with less nucleus can be combined at a ratio that meets demand. (倂 産) can be.

Claims (24)

(1) a production step of reacting phenol with formaldehyde in the presence of an acid catalyst, removing the acid catalyst, water, and unreacted phenol from the reaction product obtained to obtain the crude bisphenol F; (2) By continuously distilling a portion of the said bisphenol F while continuously extracting the effluent from the distillator maintained at a pressure of 1-5 mmHg, a high purity bisphenol F having a dinuclear content of 95% by weight or more was obtained as an effluent. Distillation step of obtaining a novolak-type phenol resin having a binuclear content of 15 area% or less; (3) a high-purity bisphenol F and a high molecular weight novolac-type phenolic resin, comprising a step of polymerizing the novolaking phenol resin and formaldehyde in the presence of an acid catalyst to obtain a high molecular weight novolak-type phenolic resin. Method of translation. (1) a preparation step of reacting phenol with formaldehyde in the presence of an acid catalyst and removing the acid catalyst, water and unreacted phenol from the obtained reaction product to obtain the crude bisphenol F; (2) By continuously distilling a portion of the said bisphenol F while distilling the effluent continuously in a distillator maintained at a pressure of 1-5 mmHg, a high purity bisphenol F having a dinuclear content of 95% by weight or more as an effluent was obtained. Distillation step of obtaining a novolak-type phenol resin having a binuclear content of 15 area% or less; (3) mixing the high purity bisphenol F with the remaining jobisphenol F to obtain a general purpose bisphenol F; (4) a general-purpose bisphenol F and a high molecular weight novolak-type phenolic resin, comprising the step of reacting the novolak-type phenolic resin with formaldehyde in the presence of an acid catalyst to obtain a high molecular weight novolak-type phenolic resin. Method of translation. The method according to claim 4, wherein the phenol and formaldehyde are reacted in a molar ratio (P / F) of 6-30. The method of claim 1, wherein in the distillation step, the bisphenol F is continuously supplied to an evaporator maintained at a pressure of 1-5 mmHg and a temperature of 220-250 ° C., and a portion of the gas generated in the evaporator is fractionated by a condenser. And returning the evaporator to the evaporator and distilling the bisphenol F continuously while continuously extracting the effluent from the evaporator. The method of claim 1, wherein in the distillation step, the bisphenol F is continuously fed to the first stage evaporator of the plurality of evaporators maintained at a pressure of 1-5 mmHg and a temperature of 200-250 ° C., and the effluent of each evaporator is continuously fed. After supplying to the evaporator of the next stage, at least a portion of the evaporated gas from the evaporator of the last stage maintained at a pressure of 1-5mmHg, the temperature 220-250 ° C is divided into a condenser and returned to the evaporator of the final stage, A process for condensation, characterized in that distillation of the bisphenol F is carried out continuously while continuously extracting the effluent from the final stage evaporator. 5. A translation method according to claim 4, wherein the condenser is a multi-tube cylindrical heat exchanger or a coil heat exchanger. The translation method according to claim 4, wherein the fractionation ratio (weight ratio) is in the range of 0.05-0.5. The method according to claim 4, wherein the dinuclear content in the effluent is 98% by weight or more. The method according to claim 4, wherein the dinuclear content in the effluent is 10 area% or less. 6. A translation method according to claim 5, wherein the condenser is a multi-tube cylindrical heat exchanger or a coil heat exchanger. The method according to claim 5, wherein the fractionation ratio (weight ratio) is in the range of 0.05-0.5. 6. The method of claim 5, wherein the dinuclear content in the effluent is at least 98% by weight. The method according to claim 5, wherein the dinuclear content in the effluent is 10 area% or less. The method according to claim 5, wherein the phenol and formaldehyde are reacted in a molar ratio (P / F) of 6-30. The method of claim 2, wherein in the distillation step, the bisphenol F is continuously supplied to an evaporator maintained at a pressure of 1-5 mmHg and a temperature of 220-250 ° C, and a portion of the gas generated in the evaporator is fractionated by a condenser. And returning the evaporator to the evaporator and distilling the bisphenol F continuously while continuously extracting the effluent from the evaporator. The method of claim 2, wherein in the distillation step, the bisphenol F is continuously fed to a first stage evaporator of a plurality of evaporators maintained at a pressure of 1-5 mmHg and a temperature of 200-250 ° C., and the effluent of each evaporator is continuously fed. After supplying to the evaporator of the next stage, at least a portion of the evaporated gas from the evaporator of the last stage maintained at a pressure of 1-5mmHg, the temperature 220-250 ° C into a powder mill to return to the evaporator of the final stage, and also A process for condensation, characterized in that distillation of the bisphenol F is carried out continuously while continuously extracting the effluent from the final stage evaporator. 16. The method according to claim 15, wherein the condenser is a shell and tube heat exchanger. 17. A method according to claim 15, wherein the fractionation ratio (weight ratio) is in the range of 0.05-0.5. 18. The method of claim 15, wherein the dinuclear content in the effluent is at least 98% by weight. The method according to claim 15, wherein the dinuclear content in the effluent is 10 area% or less. 17. The method according to claim 16, wherein the splitter is a multi-tube cylindrical heat exchanger or a coil heat exchanger. 17. The method of claim 16, wherein the fractionation ratio (weight ratio) is in the range of 0.05-0.5. 17. The method of claim 16, wherein the binucle content in the effluent is at least 98% by weight. 17. The process according to claim 16, wherein the dinuclear content in the effluent is 10 area% or less.