JP6907883B2 - 1,1-bis (4-hydroxyphenyl) dodecane and its production method - Google Patents

Description

The present invention relates to 1,1-bis (4-hydroxyphenyl) dodecane and a method for producing the same. More specifically, the present invention relates to 1,1-bis (4-hydroxyphenyl) dodecane having excellent storage stability and a method for producing the same.
The present invention also relates to a method for producing a resin such as a polycarbonate resin using the 1,1-bis (4-hydroxyphenyl) dodecane.

The bisphenol compound is a useful compound widely used as a raw material for a thermoplastic resin such as a polycarbonate resin and a thermosetting resin such as an epoxy resin. Among them, 1,1-bis (4-hydroxyphenyl) dodecane having an undecyl group, which is a flexible long-chain alkyl group, has a soft segment derived from a long-chain alkyl group in the molecular skeleton, so that it is a polycarbonate resin or an epoxy resin. When used as a raw material for the above-mentioned resins, flexibility can be imparted to the resin, and the long-chain alkyl group also increases lipophilicity, thus imparting low water absorption and chemical resistance specific to the above-mentioned resins. You can also expect to do it. For this reason, raw materials for polycarbonate resins in automobile materials, electrical and electronic equipment materials, housing and building materials, and materials for manufacturing parts in other industrial fields, adhesives, paints, civil engineering and construction materials, and insulating materials for electrical and electronic equipment parts. , Can be suitably used as a raw material for an epoxy resin in a sealing material or the like.

Particularly in recent years, in the field of electrical and electronic equipment parts, in accordance with the demand for miniaturization and high performance of equipment, the resin materials used for them are required to have improved flexibility, heat resistance, and water absorption characteristics. The above-mentioned bisphenol compound capable of providing a resin satisfying such performance is very useful.

Such a bisphenol compound is produced by a known method, for example, by condensing an aldehyde, acetal, thioacetal, trioxane or the like corresponding to an alkane linking a 4-hydroxyphenyl group with the phenol compound in the presence of an acid catalyst. However, the process for producing a bisphenol compound usually includes a purification step of dissolving the reaction product in a solvent to precipitate or suspend the solid to make it powdery and separating by-products. For example, Patent Document 1 describes 1,1-bis (4-hydroxyphenyl) octadecane or 1,1-bis (4-hydroxyphenyl) octadecane, which is a bisphenol compound having a long-chain alkyl group similar to 1,1-bis (4-hydroxyphenyl) dodecane. As a method for producing bis (4-hydroxyphenyl) docosane, a method of dissolving a reaction product in methylene chloride, which is a chlorine-containing solvent, to precipitate a solid is disclosed. Further, in Patent Document 2, as a method for producing 1,1-bis (4-hydroxyphenyl) heptane, which is a bisphenol compound having a similar long-chain alkyl group, it is produced by reacting with toluene, which is an aromatic hydrocarbon solvent. A method of dissolving a substance to precipitate a solid is disclosed.

Japanese Unexamined Patent Publication No. 59-131623 Chinese Patent Application Publication No. 15577797

As a result of diligent studies by the present inventor, it has been clarified that 1,1-bis (4-hydroxyphenyl) dodecane produced according to the methods of Patent Documents 1 and 2 easily absorbs moisture and has a problem in storage stability. Further, when a polycarbonate resin is produced using the compound as a raw material, a fatal drawback that a polycarbonate resin having stable quality cannot be obtained has been clarified.

In view of the above problems, the present invention provides 1,1-bis (4-hydroxyphenyl) dodecane having excellent storage stability, a method for producing the same, and a method for producing a resin such as a polycarbonate resin using the same. With the goal.

As a result of diligent studies, the present inventor obtained 1,1-bis (4-hydroxyphenyl) dodecane as a specific crystalline state, resulting in excellent storage stability of 1,1-bis (4-hydroxyphenyl). ) We have found that dodecane can be easily produced, and have completed the present invention.
That is, the gist of the present invention lies in the following [1] to [7].

[1] A 1,1-bis (4-hydroxyphenyl) dodecane characterized by having at least one X-ray diffraction peak at a diffraction angle (2θ) of 4.40 ° or less in powder X-ray diffraction analysis using CuKα rays. Crystal.

[2] In powder X-ray diffraction analysis using CuKα rays, the diffraction angles (2θ) are 4.05 ° ± 0.20 °, 12.10 ° ± 0.20 °, 18.55 ° ± 0.20 °, 19. 1 according to [1], which has an X-ray diffraction peak at 40 ° ± 0.20 ° and 19.95 ° ± 0.20 °, and has a melting point of 80 ° C. or higher and 90 ° C. or lower. , 1-bis (4-hydroxyphenyl) dodecane crystals.

[3] The moisture content measured after drying under reduced pressure at 40 ° C. for 1 hour and then exposing for 4 hours under constant temperature and humidity conditions of 20 ° C. and 80% RH shall be 0.01% by mass or more and 2% by mass or less. The crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to [1] or [2].

[4] A heating step of heating the powder of 1,1-bis (4-hydroxyphenyl) dodecane at 50 ° C. or higher is included, and the powder of 1,1-bis (4-hydroxyphenyl) dodecane is added after the heating step. The method for producing a crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of [1] to [3], which comprises melting or not dissolving in a solvent.

[5] A method for producing a resin, which comprises using the crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of [1] to [3] as a raw material.

[6] A method for producing a polycarbonate resin, which comprises using the crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of [1] to [3] as a raw material.

[7] The method for producing a polycarbonate resin according to [6], wherein the polycarbonate resin is produced by a melt transesterification method.

According to the present invention, 1,1- (4-hydroxyphenyl) dodecane which is excellent in storage stability and can stably obtain a polycarbonate resin of desired quality when used as a resin raw material such as a polycarbonate resin can be obtained. Can be easily provided.

It is an X-ray diffraction pattern of the crystal obtained in Example 1. FIG. It is an X-ray diffraction pattern of the crystal obtained in Comparative Example 1. It is an X-ray diffraction pattern of the crystal obtained in Comparative Example 2.

The embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example of the embodiments of the present invention, and the following description contents do not exceed the gist of the present invention. It is not limited to.
In addition, when the expression "~" is used in this specification, it shall be used as an expression including numerical values or physical property values before and after the expression.

[Bisphenol compound]
<X-ray diffraction peak>
Crystalline of 1,1-bis (4-hydroxyphenyl) dodecane of the present invention (hereinafter, may be referred to as "bisphenol compound of the present invention") (hereinafter, referred to as "crystal of the present invention") In powder X-ray diffraction analysis with CuKα rays, the diffraction angle is 2θ = 4.40 ° or less, preferably 4.30 ° or less, particularly preferably 4.20 ° or less, and particularly preferably 4.15 °. The following is a crystal having at least one X-ray diffraction peak. Further, it preferably has at least one X-ray diffraction peak at a diffraction angle of 2θ = 3.70 ° or more, more preferably 3.80 ° or more, particularly preferably 3.85 ° or more, and particularly preferably 3.95 ° or more. It is a crystal. A crystal having an X-ray diffraction peak within this range tends to improve the storage stability of the bisphenol compound of the present invention, which is preferable.

The crystal of the present invention has a diffraction angle (2θ) of 4.05 ° ± 0.20 ° (3.85 ° to 4.25 °) and 12.10 ° ± 0. 20 ° (11.90 ° to 12.30 °), 18.55 ° ± 0.20 ° (18.35 ° to 18.75 °), 19.40 ° ± 0.20 ° (19.20 ° ~ 19.60 °) and 19.95 ° ± 0.20 ° (19.75 ° to 20.15 °), respectively, with X-ray diffraction peaks and a melting point of 80 ° C or higher and 90 ° C or lower. preferable. Here, "± 0.20 °" represents the existence range of the peak including the measurement error. When the crystal of the present invention is a crystal having the above-mentioned X-ray diffraction peak and melting point, the storage stability of the bisphenol compound of the present invention tends to be further improved, which is preferable.

In particular, from the viewpoint of storage stability, the crystal of the present invention has a diffraction angle of 2θ = 3.70 ° or more and 4.40 ° or less, preferably 3.80 ° or more and 4.30 in powder X-ray diffraction analysis using CuKα rays. It has at least one X-ray diffraction peak at ° or less, particularly preferably 3.85 ° or more and 4.20 ° or less, particularly preferably 3.95 ° or more and 4.15 ° or less, and has a diffraction angle (2θ). 4.05 ° ± 0.20 ° (this peak corresponds to the peak with a diffraction angle of 2θ = 4.40 ° or less), 12.10 ° ± 0.20 °, 18.55 ° ± 0.20 It is preferable to have an X-ray diffraction peak at °, 19.40 ° ± 0.20 °, and 19.95 ° ± 0.20 °, and further, it has such an X-ray diffraction peak and has a melting point of 80 ° C. It is particularly preferable that the temperature is 90 ° C. or lower.

The crystal body of the present invention may consist of only one crystal form, or may be a mixture of a plurality of crystal forms, for example, 2 to 3 crystal forms (polymorphic crystals). Any crystal exhibiting the above-mentioned X-ray diffraction peak behavior can sufficiently exert the effect of the present invention. In the case of a mixture of a plurality of crystal forms, 4.41 is compared with the largest X-ray diffraction peak existing at 2θ = 3.70 ° to 4.40 ° in the X-ray diffraction diagram. The X-ray diffraction peak does not exist at ° to 5.50 °, or if it does exist, the intensity ratio of the largest X-ray diffraction peak is preferably 1 time or less, preferably 0.5 times or less. It is more preferably 0.2 times or less, and particularly preferably 0.2 times or less. Having such an X-ray diffraction peak intensity ratio tends to further improve the storage stability of the bisphenol compound of the present invention, which is preferable. Such crystals can be easily obtained, for example, by subjecting a powder of 1,1-bis (4-hydroxyphenyl) dodecane to a heating step of heating to 50 ° C. or higher.

Details of the powder X-ray diffraction analysis of the crystal are as described in the section of Examples described later.

<Melting point>
The melting point of the crystal of the present invention is usually 70 ° C. or higher, preferably 75 ° C. or higher, and particularly preferably 80 ° C. or higher. Further, it is usually 100 ° C. or lower, preferably 95 ° C. or lower, and particularly preferably 90 ° C. or lower. When the melting point is within the above range, the storage stability of the bisphenol compound of the present invention tends to be improved, which is preferable.
Here, the melting point refers to the temperature at which the solid begins to melt when the temperature is raised at 2 ° C./min using an SMP3 melting point measuring device manufactured by STUART Scientific.

<Moisture content>
The crystal of the present invention may contain water. The water content is a water content measured after drying the crystal of the present invention at 40 ° C. for 1 hour under reduced pressure and then exposing it at 20 ° C. and 80% RH under constant temperature and humidity conditions for 4 hours, and is usually 0.01 mass by mass. % Or more, preferably 0.1% by mass or more, usually 2% by mass or less, preferably 1.5% by mass or less. When the water content is within the above range, the safety when producing a polycarbonate resin by using the bisphenol compound of the present invention as a polycarbonate resin raw material is improved.
As described in the section of Examples described later, the moisture content was determined by drying the sample under reduced pressure at 40 ° C. for 1 hour, exposing the sample at 20 ° C. and 80% RH for 4 hours under constant temperature and humidity conditions, and then Karl Fischer. Measured by the method. When measuring the moisture content, drying under reduced pressure at 40 ° C. for 1 hour and then exposing for 4 hours under constant temperature and humidity conditions of 20 ° C. and 80% RH removes the moisture adhering to the powder surface and between the molecules. This is to accurately measure the amount of water entering the gap, and by measuring the water content after performing such a treatment, it is possible to measure the amount of water that cannot be removed in a normal storage state.

[Manufacturing of bisphenol compounds]
The bisphenol compound of the present invention is prepared by a known method, for example, by condensing an aldehyde, acetal, thioacetal, trioxane or the like corresponding to a dodecane linking two 4-hydroxyphenyl groups with the phenol compound in the presence of an acid catalyst. It can be easily manufactured. As an example, a method for reacting dodecanal with phenol, for example, is shown below.

<Phenol / dodecanal ratio>
The ratio of dodecanal to phenol when producing the bisphenol compound of the present invention is not particularly specified as long as the conditions for producing the bisphenol compound of the present invention are not specified. It is preferably mol times or more, and particularly preferably 3 mol times or more. When the amount of phenol is at least the above lower limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable. On the other hand, the ratio of phenol to dodecanal is usually 20 mol times or less, preferably 15 mol times or less, and particularly preferably 10 mol times or less. When the amount of phenol is not more than the above upper limit value, the load of the step of separating unreacted phenol tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.

When producing the bisphenol compound of the present invention, dodecanal and phenol may be produced in a mixed state in all amounts, or may be produced by continuously or intermittently adding either one or both. It is preferable to add dodecanal continuously or intermittently from the viewpoint that the bisphenol compound of the present invention can be easily produced more efficiently.

<Acid catalyst>
Examples of the acid catalyst used in producing the bisphenol compound of the present invention include inorganic acid catalysts such as phosphoric acid, oxalic acid, hydrochloric acid, and sulfuric acid; acetic acid, trifluoroacetic acid, methanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonic acid. Organic acid catalysts such as; acidic ion exchange resins such as Diaion (registered trademark) SK104H (manufactured by Mitsubishi Chemical Corporation) and the like. Of these acid catalysts, using a strongly acidic acid catalyst such as hydrochloric acid, methanesulfonic acid, toluenesulfonic acid, or Diaion (registered trademark) SK104H tends to efficiently produce the bisphenol compound of the present invention. Yes, it is preferable to use hydrochloric acid, methanesulfonic acid or toluenesulfonic acid.

The amount of the acid catalyst used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention can be efficiently produced, but the amount of acid of the acid catalyst with respect to dodecanal is usually 0.001 mol times or more. The amount is preferably 0.005 mol times or more, and particularly preferably 0.01 mol times or more. When the amount of acid is at least the above lower limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable. The amount of acid in the acid catalyst with respect to dodecanal is usually 10 mol times or less, preferably 5 mol times or less, and particularly preferably 1 mol times or less. When the amount of acid is not more than the above upper limit value, the load of the step of separating the acid catalyst after use tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.

<Third component>
When producing the bisphenol compound of the present invention, the reaction system may contain a third component for the purpose of activating the condensation reaction. Specific examples of the third component include quaternary ammonium salts such as tetraethylammonium bromide, tetrabutylammonium hydrosulfate, and tetrabutylammonium chloride; methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, 2-propanethiol, and n. -Butyl mercaptan, sec-butyl mercaptan, t-butyl mercaptan, n-pentyl mercaptan, 3-methyl-2-butane thiol, isoamyl mercaptan, n-hexyl mercaptan, cyclohexanethiol, n-heptyl mercaptan, n-octyl mercaptan, 2 -Ethyl-1-hexanethiol, n-nonyl mercaptan, n-decyl mercaptan, n-undecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecanethiol, n-hexadecyl mercaptan, n-octadecyl mercaptan , N-docosyl mercaptan, 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,10-decandithiol, thio Methyl glycolate, ethyl thioglycolate, butyl thioglycolate, octyl thioglycolate, 2-ethylhexyl thioglycolate, methyl 2-mercaptopropionate, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 3-mercapto Examples thereof include sulfur-containing compounds such as octadecyl propionate. Of these, it is preferable to use a sulfur-containing compound as the third component because the bisphenol compound of the present invention can be easily produced. On the other hand, it is preferable not to use these third components because the step of separating the third component after use becomes unnecessary in the production of the bisphenol compound of the present invention. In addition, these third components may be used in a state of being supported on a resin or the like.

The amount of the third component used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention can be efficiently produced, but the amount of the third component is usually 0.001 mol times as large as that of dodecanal. The above is preferably 0.005 mol times or more, and particularly preferably 0.01 mol times or more. When the amount of the third component is at least the above lower limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable. The amount of the third component with respect to dodecanal is usually 1 mol times or less, preferably 0.5 mol times or less, and particularly preferably 0.2 mol times or less. When the amount of the third component is not more than the above upper limit value, the load of the step of separating the third component after use tends to be reduced in the production of the bisphenol compound of the present invention, which is preferable.

<Solvent>
When producing the bisphenol compound of the present invention, the reaction may be carried out using a solvent. Specific examples of the solvent include a linear hydrocarbon solvent having 5 to 18 carbon atoms such as n-pentane, n-hexane, n-heptane, n-octane and petroleum ether; and a branch having 5 to 18 carbon atoms such as isooctane. Chain hydrocarbon solvent; cyclic hydrocarbon solvent having 5 to 18 carbon atoms such as cyclohexane, cyclooctane and methylcyclohexane; water; alcohol solvent such as methanol, ethanol, isopropanol and butanol; nitrile solvent such as acetonitrile; dibutyl ether and the like Ether solvent; Ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; Ester solvent such as ethyl acetate and butyl acetate; Nitrogen-containing solvent such as dimethylformamide and dimethylacetamide; Sulfur-containing solvent such as dimethyl sulfoxide and sulfolane; Methylene chloride, chloroform, dichloroethane Chlorine-containing solvent such as; aromatic hydrocarbon solvent such as benzene, toluene, xylene and the like. It is preferable to use these solvents because the operability of the reaction can be improved, such as suppressing the solidification of the raw material during the reaction and suppressing an unexpected side reaction due to internal heat generation. On the other hand, it is preferable not to use these solvents because the separation between the polyhydric phenol compound of the present invention and the solvent becomes unnecessary and the purification step of the polyhydric phenol compound of the present invention can be simplified.

The amount of the solvent used in producing the bisphenol compound of the present invention is not particularly specified as long as the bisphenol compound of the present invention can be efficiently produced, but the amount of the solvent is usually 0.1% by mass or more with respect to dodecanal. It is preferably 0.2 mass times or more, and particularly preferably 0.5 mass times or more. When the amount of the solvent is at least the above lower limit value, the effect of the solvent tends to be exhibited more efficiently during the production of the bisphenol compound of the present invention, which is preferable. The amount of the solvent is usually 20 times by mass or less, preferably 10 times by mass or less, and particularly preferably 5 times by mass or less with respect to dodecanal. When the amount of the solvent is not more than the above upper limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable.

<Reaction temperature>
The reaction temperature at the time of producing the bisphenol compound of the present invention is usually 0 ° C. or higher, preferably 15 ° C. or higher, and particularly preferably 30 ° C. or higher. When the reaction temperature is at least the above lower limit value, it tends to be easy to prevent the reaction mixture from solidifying, which is preferable. On the other hand, the reaction temperature is usually 150 ° C. or lower, preferably 120 ° C. or lower, and particularly preferably 90 ° C. or lower. When the reaction temperature is not more than the upper limit value, the bisphenol compound of the present invention tends to be efficiently produced, which is preferable.

<Purification>
The step of producing the bisphenol compound of the present invention preferably includes a step of removing the acid catalyst used after the reaction. Specific examples of the acid catalyst removal step include a base neutralization step, a removal step by dissolving in a solvent, a removal step by filtration, and the like. Of these, when an inorganic acid catalyst or an organic acid catalyst is used as the acid catalyst, a neutralization step with a base is included, and when a heterogeneous catalyst is used, a removal step by filtration is included. Tends to be able to be removed, which is preferable. The acid catalyst removing steps may be used alone or in combination of two or more.
Further, when these removal steps are carried out, it is preferable to carry out the steps in a state where the mixture containing the bisphenol compound of the present invention is dissolved or suspended in a solvent. Specific examples thereof include a solvent that can be used in producing the phenol compound of the present invention. Of these solvents, it is preferable to use a solvent selected from at least one of the hydrocarbon solvents because the purification treatment of the bisphenol compound of the present invention can be facilitated and the cost at the time of production can be reduced. It is particularly preferable to use a solvent containing a hydrocarbon solvent. These solvents may be used alone or in combination of two or more. When a solvent is used in the reaction step of the bisphenol compound of the present invention, the solvent may be used as it is as the solvent in the removal step.

Specific examples of the base used in the base neutralization step include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, and phosphorus. Inorganic bases having alkali metal atoms or alkaline earth metal atoms such as sodium monohydrogen acid, potassium monohydrogen phosphate, sodium phosphate, potassium phosphate, magnesium hydroxide, calcium hydroxide, sodium hydride, sodium amide; Organic bases having alkali metal atoms or alkaline earth metal atoms such as sodium acid, potassium citrate, sodium succinate, potassium succinate, calcium succinate, sodium methoxyde, potassium methoxyde, potassium-tert-butoxide; pyridine, Examples thereof include nitrogen-containing compounds such as aniline, triethylamine, N, N-dimethylaniline, morpholine, 1,4-diazabicyclo [2,2,2] octane, and diazabicycloundecene. Of these, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium acetate, potassium acetate, cesium acetate, sodium hydroxide, potassium hydroxide, sodium monohydrogen phosphate, potassium monohydrogen phosphate, Bases having alkali metal atoms or alkaline earth metal atoms such as sodium phosphate, potassium phosphate, magnesium hydroxide, calcium hydroxide, sodium hydride, sodium citrate, potassium citrate, sodium succinate, potassium succinate, etc. It is preferable to use it because it facilitates removal of the neutralizing salt. In addition, these bases may be used alone or in combination of two or more.

In the neutralization step, a second component may be added for the purpose of adjusting the acidity of the reaction mixture. Specific examples thereof include organic acids such as acetic acid, citric acid, succinic acid, and malic acid; heteroatoms other than oxygen such as phosphoric acid, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium chloride, and monosodium citrate. Examples include acids containing. The type and amount of the second component are variously selected depending on the type and amount of the acid catalyst used in the reaction step and the base used in the neutralization step, and the target value of the acidity of the reaction mixture after neutralization.

It is preferable that the reaction mixture after the neutralization step is weakly acidic or weakly basic because the stability of the bisphenol compound of the present invention tends to be improved. When the reaction mixture is weakly acidic or weakly basic, the pH of the aqueous layer is usually 2 or more when water is added to the mixture to adjust the mass ratio of water and other components to 1: 3. It means that it is preferably 3 or more, particularly preferably 4 or more, usually 11 or less, preferably 10 or less, and particularly preferably 9 or less. When the pH of the aqueous layer is within the above range, the stability of the bisphenol compound of the present invention tends to be improved, which is preferable.

Specific examples of the solvent used in the acid catalyst removal step by dissolving in a solvent include water; organic solvents such as methanol, ethanol, propanol, dimethyl sulfoxide, diethyl ether, and N-methylpyrrolidone. Of these, it is preferable to use water because the purification process can be simplified.
In the above step, a second component may be added in order to increase the removal efficiency. Specific examples thereof include organic salts such as sodium methanesulfonate; and inorganic salts such as sodium chloride and sodium sulfate. The type and amount of the second component are variously selected depending on the removal efficiency of the acid catalyst.

Filter agents used in the acid catalyst removal step by filtration include powdery, crushed or spherical filters such as activated carbon, silica gel, activated white clay, and diatomaceous earth; fibrous or cloth-like filters such as filter paper, filter cloth, and thread-wound filter. Examples thereof include a filter agent molded into the above. Various filters are selected based on the properties of the acid catalyst used, the possibility of reusing the acid catalyst, and the like.
In addition, these removal steps are a part of components other than the bisphenol compound of the present invention such as unreacted raw materials, by-products, reaction or the second and third components used in the removal step of the acid catalyst and the acid catalyst, or It may also serve as a step of removing all of them.

The method for producing a bisphenol compound of the present invention comprises a step of removing low boiling point components such as a solvent and unreacted raw materials from a mixture containing the bisphenol compound of the present invention by concentration (hereinafter, may be referred to as a concentration step). It is preferable to include it. By carrying out this step, the efficiency of taking out the bisphenol compound of the present invention in the precipitation step described later tends to be improved. The concentration step is usually carried out under heating and depressurizing conditions. The heating temperature is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and particularly preferably 80 ° C. or higher. Further, it is usually 200 ° C. or lower, preferably 180 ° C. or lower, and particularly preferably 160 ° C. or lower. When the heating temperature is within the above temperature range, the concentration step can be efficiently carried out, and the decomposition of the bisphenol compound of the present invention tends to be suppressed. The heating temperature in this concentration step refers to the temperature of the heat medium used for heating. The degree of decompression is usually less than 760 Torr, preferably 200 Torr or less, more preferably 100 Torr or less, and particularly preferably 50 Torr or less. When the degree of decompression is not more than the above upper limit value, the concentration step tends to be carried out efficiently. On the other hand, although the lower limit is not particularly specified, it is usually 0.1 Torr or more, preferably 1 Torr or more, more preferably 10 Torr or more, and particularly preferably 10 Torr or more from the viewpoint that a widely and generally used decompression device can be used. Is 20 Torr or more.

The method for producing a bisphenol compound of the present invention is a step of precipitating the bisphenol compound of the present invention from a reaction mixture containing the bisphenol compound of the present invention obtained by the reaction from a solvent containing at least one aliphatic hydrocarbon solvent (hereinafter,). , May be referred to as a "precipitation step"). Specific examples of the aliphatic hydrocarbon solvent used include linear hydrocarbon solvents having 5 to 18 carbon atoms such as n-pentane, n-hexane, n-heptane, n-octane and petroleum ether; isooctane and the like. Branched chain hydrocarbon solvents having 5 to 18 carbon atoms; cyclic hydrocarbon solvents having 5 to 18 carbon atoms such as cyclohexane, cyclooctane, and methylcyclohexane can be mentioned. Of these, it is preferable to use an aliphatic hydrocarbon solvent having 6 to 10 carbon atoms, and an aliphatic hydrocarbon solvent having 6 to 8 carbon atoms is preferable because the solvent can be easily removed from the bisphenol compound of the present invention. Is more preferable. Further, these aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

Further, the solvent used in the precipitation step may contain a solvent other than the aliphatic hydrocarbon solvent as the second solvent. Specific examples thereof include water; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitrile solvents such as acetonitrile; ether solvents such as dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate, butyl acetate and the like. Ester solvent; Nitrogen-containing solvent such as dimethylformamide and dimethylacetamide; Sulfur-containing solvent such as dimethylsulfoxide and sulfolane; Chlorine-containing solvent such as methylene chloride, chloroform and dichloroethane; Can be mentioned. Of these, it is preferable to include either an alcohol solvent or an aromatic hydrocarbon solvent as the second solvent because the bisphenol compound of the present invention tends to be efficiently purified. These second solvents may be used alone or in admixture of two or more.

The mixing ratio of the second solvent and the aliphatic hydrocarbon solvent is not particularly limited as long as the characteristics of the bisphenol compound of the present invention are not impaired, and may be appropriately set and used. The ratio is usually 10 to 99% by mass. It is preferable that the composition ratio of the aliphatic hydrocarbon solvent in all the solvents is not more than the above upper limit value so that by-products can be easily removed efficiently. Further, when it is at least the above lower limit value, it is possible to prevent the bisphenol compound of the present invention from being selectively dissolved and removed in the second solvent, that is, to prevent a decrease in yield, which is preferable. From such a viewpoint, the composition ratio of the aliphatic hydrocarbon solvent in the total solvent is more preferably 20 to 98% by mass, further preferably 25 to 97% by mass, and 30 to 96% by mass. It is particularly preferable to have.

The mixing ratio of the reaction mixture containing the bisphenol compound of the present invention and the solvent containing at least one of the above-mentioned aliphatic hydrocarbon solvents is not particularly specified as long as the bisphenol compound of the present invention can be efficiently precipitated, but it is usually not specified. The mass ratio of the total solvent to the reaction mixture containing the bisphenol compound of the present invention is preferably 0.2 times or more, more preferably 0.5 times or more, and particularly preferably 1 time or more. On the other hand, this mass ratio is preferably 100 times or less, more preferably 50 times or less, and particularly preferably 10 times or less. When the mass ratio of all solvents is at least the above lower limit value, the bisphenol compound of the present invention tends to be preferentially precipitated, while when it is at least the above upper limit value, the production efficiency of the bisphenol compound of the present invention is improved. It tends to improve and is preferable.

When mixing the reaction mixture containing the bisphenol compound of the present invention with the above-mentioned solvent containing at least one aliphatic hydrocarbon solvent and the second solvent, the aliphatic hydrocarbon solvent and the second solvent may be added separately. , The reaction mixture may be mixed in a premixed state. From the viewpoint of improving the production efficiency of the bisphenol compound of the present invention, it is preferable to mix the solvent in advance.

The temperature at which the reaction mixture containing the bisphenol compound of the present invention is mixed with the solvent containing at least one of the above aliphatic hydrocarbon solvents is usually 0 ° C. or higher, preferably 20 ° C. or higher, particularly preferably 40 ° C. or higher. , Usually below the boiling point of the solvent, preferably below the boiling point of the solvent (-5) ° C., particularly preferably below the boiling point of the solvent (-10) ° C. When the temperature is not less than the above lower limit value and not more than the upper limit value, the bisphenol compound of the present invention can be efficiently dissolved, which is preferable. Here, when two or more kinds of solvents are mixed and used, the boiling point of the above-mentioned solvent represents the boiling point of the mixed solvent.

The temperature of the precipitation step for precipitating the bisphenol compound of the present invention after mixing is not particularly limited as long as the characteristics of the bisphenol compound of the present invention are not impaired, and can be appropriately set, but is usually −20 ° C. or higher. It is preferably −10 ° C. or higher, and particularly preferably 0 ° C. or higher. On the other hand, this temperature is usually 70 ° C. or lower, preferably 65 ° C. or lower, and particularly preferably 60 ° C. or lower. When the temperature of the precipitation step is within the above range, the bisphenol compound of the present invention tends to be efficiently purified, which is preferable.

In the precipitation step, a seed crystal of the bisphenol compound of the present invention may be added in order to improve the precipitation efficiency of the bisphenol compound of the present invention. The amount of seed crystals is usually 0.0001 to 10% by mass with respect to the reaction mixture containing the bisphenol compound of the present invention from the viewpoint of improving the production efficiency of the bisphenol compound of the present invention, and is 0.0005 to 5 It is preferably 0.001 to 1%, and particularly preferably 0.001 to 1%.

After the bisphenol compound of the present invention is precipitated in the above-mentioned precipitation step, the powder of the bisphenol compound of the present invention is recovered from the solvent used by solid-liquid separation by filtration, centrifugation, decantation or the like.

The number of times of the precipitation step is variously selected according to the degree of purification of the bisphenol compound of the present invention, but from the viewpoint of simplifying the purification process, it is usually preferably 3 times or less, and more preferably 2 times or less. It is preferable, and it is particularly preferable that it is once.

The powder of the bisphenol compound of the present invention after the precipitation step may be further washed with a solvent for the purpose of cleaning the surface or the inside of the crystal. Specific examples of the solvent used in this washing step include the above-mentioned aliphatic hydrocarbon solvent and the solvent mentioned as the second component. The temperature of the main cleaning treatment is usually −20 ° C. or higher, preferably −10 ° C. or higher, particularly preferably 0 ° C. or higher, and usually 70 ° C. or lower, preferably 60 ° C. or lower, particularly preferably 50 ° C. or lower. When the cleaning temperature is within the above range, it tends to be possible to suppress excessive dissolution of the bisphenol compound of the present invention in the cleaning solvent, which is preferable.

Even if the powder of the bisphenol compound of the present invention obtained through the above precipitation step and washing is further subjected to solvent removal treatment by heating, depressurization, air drying, etc. to obtain a bisphenol compound of the present invention substantially containing no solvent. good. Here, the temperature at the time of the desolvation treatment is usually 20 ° C. or higher, preferably 40 ° C. or higher in order to allow the desolvation treatment to proceed smoothly. The upper limit of the temperature is usually equal to or lower than the melting point of the bisphenol compound of the present invention, preferably 75 ° C. or lower, and particularly preferably 72 ° C. or lower.

<Heating process>
As described above, the bisphenol compound of the present invention is the above-mentioned acid catalyst removing step, concentration step, and precipitation from the reaction mixture containing the bisphenol compound of the present invention obtained by the reaction, preferably after the reaction. By subjecting the powder of the bisphenol compound of the present invention purified through any of the steps, the washing step and the desolvation treatment, preferably all of these steps, to the heating step of heating at 50 ° C. or higher, the above-mentioned X It can be easily obtained as a crystal of the present invention satisfying the linear diffraction peak, the melting point and the water content. Here, the temperature in the present heating step refers to the temperature of the bisphenol compound powder of the present invention.

The heating temperature in this heating step is 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 65 ° C. or higher. On the other hand, the upper limit of the heating temperature is below the melting point of the bisphenol compound of the present invention, preferably below the melting point, more preferably 75 ° C. or lower, and particularly preferably 72 ° C. or lower. When the heating temperature is 50 ° C. or higher, the crystal of the present invention satisfying the above-mentioned X-ray diffraction peak, melting point and water content can be easily obtained. On the other hand, if the heating temperature exceeds the melting point of the bisphenol compound of the present invention, the bisphenol compound of the present invention melts and the powder properties deteriorate, which is not preferable.

The heating time in the heating step may be any time as long as the crystal of the present invention can be obtained, and is not particularly limited and depends on the heating temperature, but is usually 2 hours or more, preferably 6 hours or more, and usually 96 hours. Hereinafter, it is preferably 48 hours or less. When the heating time is at least the above lower limit, the crystal of the present invention can be easily obtained. On the other hand, when the heating time is not more than the above upper limit, the production time for producing the bisphenol compound of the present invention is shortened and the production efficiency is improved, which is preferable.

In particular, when the heating temperature is high, the heating time is preferably set short, and when the heating temperature is low, the heating time is preferably set long. As described above, it is preferable to carry out the test for 12 hours or more at 60 ° C., 6 hours or more at 65 ° C., 3 hours or more at 70 ° C., and 2 hours or more at 75 ° C.

The atmosphere of the heating step is not particularly limited, but it is preferable to carry out the process in an atmosphere that does not substantially contain water from the viewpoint of avoiding a long heating time derived from water. Specific examples thereof include a dehydrated solvent atmosphere, a dry gas atmosphere, and a reduced pressure atmosphere. However, the reduced pressure atmosphere makes it easy to substantially eliminate the moisture in the atmosphere. ,preferable.
The heating step can be carried out in any step as long as the bisphenol compound of the present invention is carried out in a powder state and the obtained powder is not melted again or dissolved in a solvent in the subsequent steps. That is, this heating step may be carried out at the same time as any one of the acid catalyst removing step, the precipitation step, the washing step, the solvent removal treatment and the like.

[Reason why the bisphenol compound of the present invention is excellent in storage stability]
The bisphenol compound of the present invention has an undecyl group in the side chain, which is a long-chain and easily mobile alkyl group. In powder X-ray diffraction analysis using CuKα rays, a crystal having no X-ray crystal diffraction peak at a diffraction angle (2θ) of 4.40 ° or less has a small intermolecular orientation in the crystal lattice and water molecules between the molecules. It is considered that the storage stability is low because it has a gap that allows it to easily enter. The bisphenol compound of the present invention, which is such a crystal, has a risk of mass fluctuation due to moisture absorption during storage. In particular, when used as a resin raw material to be described later, it is a well-known fact that if a mass shift occurs, non-uniformity occurs in the molecular weight and molecular weight distribution of the obtained resin, which greatly affects the stability of resin production, which is not preferable. ..
On the other hand, a crystal having an X-ray crystal diffraction peak at a diffraction angle (2θ) of 4.40 ° or less has a large intermolecular orientation in the crystal lattice, a small intermolecular gap, and is difficult for water molecules to enter and is preserved. It is considered to be highly stable. In particular, the diffraction angles (2θ) are 4.05 ° ± 0.20 °, 12.10 ° ± 0.20 °, 18.55 ° ± 0.20 °, 19.40 ° ± 0.20 °, 19.95 °. A crystal having a characteristic X-ray diffraction peak at ± 0.20 ° is a crystal having excellent thermal stability, and tends to be particularly excellent in storage stability.
Such crystals of the bisphenol compound of the present invention can be preferentially obtained by undergoing a heating step of heating the powder of the bisphenol compound obtained by the reaction to 50 ° C. or higher.

[Use]
The bisphenol compound of the present invention includes polyether resins, polyester resins, polycarbonate resins, polyurethane resins, acrylic resins and the like used for various purposes such as optical materials, recording materials, insulating materials, transparent materials, electronic materials, adhesive materials and heat resistant materials. It can be used as a constituent, an additive, or a precursor thereof, such as various thermoplastic resins, various thermosetting resins such as epoxy resin, unsaturated polyester resin, phenol resin, polybenzoxazine resin, and cyanate resin. .. The bisphenol compound of the present invention can also be used as a pH adjuster, a surfactant and the like.

Of these, the bisphenol compound of the present invention can be used as a raw material for a polycarbonate resin, and due to its excellent storage stability, a polycarbonate resin of a desired quality can be stably obtained, and the manufacturing process is stable and safe. This is preferable because the effect of the present invention can be effectively obtained.

[Polycarbonate resin]
Hereinafter, a polycarbonate resin produced by using the bisphenol compound of the present invention (hereinafter, may be referred to as “polycarbonate resin of the present invention”) will be described.
As will be described later, the polycarbonate resin of the present invention means a polycarbonate resin in a broad sense including polyester carbonate.

<Structural unit of polycarbonate resin>
The polycarbonate resin of the present invention is produced by using the bisphenol compound of the present invention, and is derived from this bisphenol compound and is a carbonate structural unit represented by the following formula (1) (hereinafter, "structural unit (1)". ) ”Is sometimes referred to.) Includes at least.

The polycarbonate resin of the present invention may consist of only the structural unit (1), and the structural unit (1) and a carbonate structural unit derived from a dihydroxy compound other than the bisphenol compound of the present invention (hereinafter, hereinafter, It may be referred to as "another structural unit"). Further, the other structural units may be of only one type or of a plurality of types.

Specific examples of other constituent units include carbonate constituent units derived from aliphatic dihydroxy compounds such as 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and isosorbide; bisphenol A, 2, Examples thereof include carbonate constituent units derived from aromatic dihydroxy compounds such as 2-bis (3-methyl-4-hydroxyphenyl) propane, bisphenol S, and resorcinol. In addition, for example, the carbonate constituent unit described on pages 21 to 31 of the "Polycarbonate Resin Handbook" (Nikkan Kogyo Shimbun, first edition) can also be preferably used. Of these, it is preferable to contain a carbonate constituent unit derived from bisphenol A or 2,2-bis (3-methyl-4-hydroxyphenyl) propane because the characteristics of the polycarbonate resin are excellent. Further, each structural unit in the polycarbonate resin may be in a random shape or a block shape.

The ratio of the structural unit (1) contained in the polycarbonate resin of the present invention to the other structural units is not particularly specified, but usually, the structural unit (1) is 1 mol% or more 99 with respect to the total carbonate structural units in the polycarbonate resin. It is mol% or less, preferably 3 mol% or more and 70 mol% or less, and particularly preferably 10 mol% or more and 50 mol% or less. When the structural unit (1) is within the above range, various characteristics derived from the structural unit (1) can be exhibited, and the characteristics of other structural units can be imparted, which is preferable.

<Tg of polycarbonate resin>
The glass transition temperature (Tg) of the polycarbonate resin of the present invention is not particularly limited, but is usually 60 ° C. or higher, preferably 70 ° C. or higher, and particularly preferably 80 ° C. or higher. On the other hand, the glass transition temperature (Tg) of the polycarbonate resin of the present invention is usually 170 ° C. or lower, preferably 160 ° C. or lower, and more preferably 150 ° C. or lower. When Tg is within the above range, the handleability of the polycarbonate resin of the present invention tends to be improved, which is preferable.

The glass transition temperature (Tg) of the polycarbonate resin of the present invention is measured by heating about 10 mg of the polycarbonate resin sample at a heating rate of 20 ° C./min using a differential operating calorimeter (DSC6220 manufactured by SII). Then, in accordance with JIS-K7121, the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepwise change part of the glass transition is maximized. It is the temperature at which the outer glass transition starts.

The glass transition temperature (Tg) of the polycarbonate resin is affected by various physical properties such as the structural unit (1), the type and ratio of other structural units, and the molecular weight of the polycarbonate resin. However, it is easy to obtain a polycarbonate resin having an arbitrary glass transition temperature (Tg).

<Molecular weight of polycarbonate resin>
The molecular weight of the polycarbonate resin of the present invention is not particularly limited, but the viscosity average molecular weight (Mv) converted from the solution viscosity is usually 9,000 to 100,000. When the molecular weight of the polycarbonate resin is within the above range, the effect of the structural unit (1) on the polycarbonate resin tends to be more exhibited, which is preferable. From this point of view, the viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention is preferably 10,000 or more, more preferably 11,000 or more, still more preferably 11,500 or more, and preferably 30 or more. It is 000 or less, more preferably 24,000 or less, still more preferably 20,000 or less.

When controlling the viscosity average molecular weight of the polycarbonate resin of the present invention within the above range, two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, the viscosity average molecular weight is The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention may be controlled by mixing with a polycarbonate resin outside the above suitable range.

Here, for the viscosity average molecular weight (Mv) of the polycarbonate resin, the intrinsic viscosity (extreme viscosity) [η] (unit: dL / g) at a temperature of 20 ° C. is determined by using methylene chloride as a solvent and using an Ubbelohde viscous meter. , Schnell's viscosity formula, that is, a value calculated from ^{η = 1.23 × 10 -4} Mv ^0.83. The intrinsic viscosity (extreme viscosity) [η] is a value calculated by the following formula by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dL).

The intrinsic viscosity (dL / g) of the aromatic polycarbonate resin of the present invention correlates with the above-mentioned viscosity average molecular weight, but is usually 0.23 to 1.74, preferably 0.25 or more, and more preferably 0. It is .28 or more, more preferably 0.29 or more. Further, it is preferably 0.65 or less, more preferably 0.54 or less, and further preferably 0.46 or less.

<Amount of terminal hydroxyl groups in polycarbonate resin>
The amount of terminal hydroxyl groups of the polycarbonate resin of the present invention is not particularly limited as long as it does not impair the excellent physical properties of the polycarbonate resin of the present invention, but is usually 10 to 2000 ppm, preferably 20 ppm or more, and more preferably 50 ppm. Above, it is more preferably 100 ppm or more, while it is preferably 1700 ppm or less, more preferably 1500 ppm or less, still more preferably 1200 ppm or less. When the amount of terminal hydroxyl groups is not less than the lower limit of the above range, the hue and productivity of the polycarbonate resin of the present invention and the polycarbonate resin composition using the same can be further improved, and not more than the upper limit of the above range. If this is the case, the thermal stability and wet-heat stability of the polycarbonate resin of the present invention and the polycarbonate resin composition using the same can be further improved.

The amount of terminal hydroxyl groups of the polycarbonate resin of the present invention can be adjusted within the above range by any known method. For example, when the polycarbonate resin of the present invention is polycondensed by a transesterification reaction, the amount of terminal hydroxyl groups can be adjusted by adjusting the mixing ratio of the carbonate ester and the dihydroxy compound; the degree of reduced pressure during the transesterification reaction, etc. Can be adjusted to a range.

Further, as a more aggressive adjustment method, a method of separately mixing a terminal terminator at the time of reaction can be mentioned. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters. In addition, as the terminal terminator, 1 type may be used, and 2 or more types may be used in arbitrary combination and ratio.

Further, when the aromatic polycarbonate resin of the present invention is produced by an interfacial polymerization method, the amount of terminal hydroxyl groups can be arbitrarily adjusted by adjusting the amount of the molecular weight modifier (terminal terminator).

The unit of the terminal hydroxyl group concentration is the mass of the terminal hydroxyl group expressed in ppm with respect to the mass of the polycarbonate resin. The measuring method is colorimetric quantification by the titanium tetrachloride / acetic acid method (the method described in Macromol. Chem. 88 215 (1965)). For a polycarbonate resin composed of carbonate constituent units derived from a plurality of dihydroxy compounds, a sample in which the corresponding dihydroxy compounds are mixed according to the copolymerization ratio is prepared at a concentration of at least 3 levels, and a calibration curve is obtained from the data of 3 points or more. After subtracting, measure the amount of terminal hydroxyl groups in the copolymerized polycarbonate resin. The detection wavelength is 546 nm.

[Manufacturing method of polycarbonate resin]
The polycarbonate resin of the present invention is obtained by polycondensing the bisphenol compound of the present invention and other dihydroxy compounds used as needed with a carbonate-forming compound. Here, as a specific example of the other dihydroxy compound, the dihydroxy compound for forming the above-mentioned other structural unit can be mentioned.

Examples of carbonate-forming compounds include carbonyl halides, carbonate esters and the like. As the carbonate-forming compound, one type may be used, or two or more types may be used in any combination and ratio.

Specific examples of the carbonyl halide include phosgene; a bischloroformate of a dihydroxy compound, a haloformate of a monochloroformate of a dihydroxy compound, and the like.

Specifically, the carbonate ester may be a compound represented by the following formula (2), such as aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, cyclic carbonates and the like. Examples thereof include carbonates of dihydroxy compounds.

In the formula (2), R ¹ and R ² independently represent an alkyl group having 1 to 30 carbon atoms, an aryl group, or an arylalkyl group, respectively. Hereinafter, when R ¹ and R ² are an alkyl group or an arylalkyl group, they may be referred to as a dialkyl carbonate, and when they are an aryl group, they may be referred to as a diaryl carbonate. Among them, from the viewpoint of reactivity with the dihydroxy compound ^{, both R 1} and R ² are preferably aryl groups, and the carbonate ester is more preferably a diaryl carbonate represented by the following formula (3).

In formula (3), R ³ and R ⁴ independently represent a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, and 4 to 20 carbon atoms, respectively. Or an aryl group having 6 to 20 carbon atoms, and p and q each independently represent an integer of 0 to 5.

Specific examples of the carbonate ester include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate, bis (4-methylphenyl) carbonate, bis (4-chlorophenyl) carbonate, and bis (4-chlorophenyl) carbonate. Fluorophenyl) carbonate, bis (2-chlorophenyl) carbonate, bis (2,4-difluorophenyl) carbonate, bis (4-nitrophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (methylsalitylphenyl) carbonate, Examples thereof include (substitute) diaryl carbonate such as ditril carbonate, and diphenyl carbonate is particularly preferable.

In addition, these carbonate esters can be used alone or in mixture of 2 or more types.

Further, the carbonate ester may be replaced with a dicarboxylic acid or a dicarboxylic acid ester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less. Representative dicarboxylic acids or dicarboxylic acid esters that can be substituted include terephthalic acid, isophthalic acid, diphenyl terephthalate, diphenyl isophthalate and the like. When substituted with such a dicarboxylic acid or dicarboxylic acid ester, a polyester carbonate is obtained.

The polycarbonate resin of the present invention can be produced by a conventionally known polymerization method, and the polymerization method is not particularly limited. Examples of the polymerization method include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.
Hereinafter, particularly suitable of these methods will be specifically described.

<Interfacial polymerization method>
A case where the polycarbonate resin of the present invention is produced by an interfacial polymerization method will be described.
In the interfacial polymerization method, the pH is usually maintained at 9 or higher in the presence of an organic solvent and an alkaline aqueous solution inert to the reaction, and the raw material dihydroxy compound is reacted with a carbonate-forming compound (preferably phosgene). A polycarbonate resin is obtained by performing interfacial polymerization in the presence of a polymerization catalyst. If necessary, a molecular weight modifier (terminal terminator) may be present in the reaction system, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The raw material dihydroxy compounds and carbonate-forming compounds are as described above. Among the carbonate-forming compounds, it is preferable to use phosgene, and the method when phosgene is used is particularly called a phosgene method.

The organic solvent inert to the reaction is not particularly limited, and is, for example, chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, dichlorobenzene and the like; aromatic hydrocarbons such as benzene, toluene and xylene. Hydrogen; etc. As the organic solvent, one type may be used, or two or more types may be used in any combination and ratio.

The alkaline compound contained in the alkaline aqueous solution is not particularly limited, and examples thereof include alkali metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, and alkaline earth metal compounds. Of these, sodium hydroxide and potassium hydroxide are preferable. As the alkaline compound, one type may be used, or two or more types may be used in any combination and ratio.

The concentration of the alkaline compound in the alkaline aqueous solution is not limited, but is usually used in an amount of 5 to 10% by mass in order to control the pH of the reaction in the alkaline aqueous solution to 10 to 12. Further, for example, when phosgene is blown, the molar ratio of the raw material dihydroxy compound to the alkaline compound is usually 1: 1 in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. It is preferably 9 or more, particularly 1: 2.0 or more, and usually 1: 3.2 or less, especially 1: 2.5 or less.

The polymerization catalyst is not particularly limited, but is, for example, an aliphatic tertiary amine such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine; N, N'-dimethylcyclohexylamine, N, N'-diethylcyclohexyl. Alicyclic tertiary amines such as amines; aromatic tertiary amines such as N, N'-dimethylaniline, N, N'-diethylaniline; trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride and the like. Tertiary ammonium salts and the like; pyridines; guanines; guanidine salts; etc. As the polymerization catalyst, one type may be used, or two or more types may be used in any combination and ratio.

The molecular weight modifier is not particularly limited, and examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group; fatty alcohols such as methanol and butanol; mercaptans; phthalates, and the like, among which aromatic phenols are used. preferable. Specific examples of such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, and p-isobutylphenol. ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn- Hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on- Nonylphenol, m-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di -T-butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, a monoalkylphenol having a linear or branched alkyl group with an average carbon number of 12 to 35 at the ortho-position, meta-position or para-position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-Hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl) fluorene; 4- (1-adamantyl) phenol and the like can be mentioned. Among these, pt-butylphenol, p-phenylphenol and p-cumylphenol are preferably used. As the molecular weight adjusting agent, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the molecular weight modifier used is not particularly limited, but is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol, based on 100 mol of the raw material dihydroxy compound. It is less than a mole. By setting the amount of the molecular weight adjusting agent used in this range, the thermal stability and hydrolysis resistance of the obtained polycarbonate resin can be improved.

At the time of the reaction, the order of mixing the reaction substrate (reaction raw material), reaction medium (organic solvent), catalyst, additives, etc. is arbitrary as long as the desired polycarbonate resin can be obtained, and an appropriate order can be set arbitrarily. Just do it. For example, when phosgene is used as the carbonate-forming compound, the molecular weight modifier is mixed at any time between the reaction (phosgenation) between the raw material dihydroxy compound and phosgene and the start of the polymerization reaction. can.

The reaction temperature is not particularly limited, but is usually 0 to 40 ° C., and the reaction time is not particularly limited, but is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

<Fused transesterification method>
Next, a case where the polycarbonate resin of the present invention is produced by the melt transesterification method will be described.
In the melt ester exchange method, for example, a transesterification reaction between a carbonate ester and a raw material dihydroxy compound is performed. The raw material dihydroxy compound and carbonate ester are as described above.

The ratio of the raw material dihydroxy compound to the carbonate ester (including when a part of the carbonate ester is replaced with the above-mentioned dicarboxylic acid or dicarboxylic acid ester; the same applies hereinafter) is arbitrary as long as the desired polycarbonate resin can be obtained. However, it is preferable to use these carbonate esters in excess with respect to the raw material dihydroxy compound when polymerizing with the dihydroxy compound. That is, the amount of the carbonate ester used is preferably 1.01 to 1.30 times (molar ratio), and more preferably 1.02 to 1.20 times (molar ratio) with respect to the dihydroxy compound. More preferred. If this molar ratio is too small, the number of terminal hydroxyl groups of the obtained polycarbonate resin will increase, and the thermal stability of the resin will tend to deteriorate. On the other hand, if the molar ratio is too large, the reaction rate of transesterification decreases, it becomes difficult to produce a polycarbonate resin having a desired molecular weight, and the residual amount of carbonate ester in the resin increases, so that during molding or molding. It may cause an odor when it is made into a product.

When producing a polycarbonate resin by the transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known ones can be used. As the transesterification catalyst, for example, an alkali metal compound and / or an alkaline earth metal compound is preferably used. Alternatively, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination. As the transesterification catalyst, one type may be used, or two or more types may be used in any combination and ratio.

In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 320 ° C. The pressure during the reaction is not particularly limited, but is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, the melt polycondensation reaction may be carried out under the above conditions while removing by-products.

The reaction form can be either a batch method or a continuous method. In the case of batch method, the order of mixing the reaction substrate, reaction medium, catalyst, additives and the like is arbitrary as long as a desired polycarbonate resin can be obtained, and an appropriate order may be set arbitrarily. However, above all, considering the stability of the polycarbonate resin and the like, it is preferable to carry out the molten transesterification reaction in a continuous manner.

In the molten transesterification method, a catalyst deactivator may be used if necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof, phosphorus-containing acidic compounds and derivatives thereof, and the like. As the catalyst deactivator, one type may be used, or two or more types may be used in combination in any combination and ratio.

The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, and more than 1 equivalent, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. It is usually 10 equivalents or less, preferably 8 equivalents or less. Furthermore, it is usually 1 ppm or more, and usually 100 ppm or less, preferably 50 ppm or less, with respect to the obtained polycarbonate resin.

Since the bisphenol compound of the present invention is excellent in storage stability, it can be suitably used because a polycarbonate resin can be stably produced by either the above-mentioned interfacial polymerization method or melt transesterification method. Among the methods for producing these polycarbonate resins, using the melt transesterification method reduces the risk of problems that may occur in production such as the foaming phenomenon derived from the long-chain undecyl group of the bisphenol compound of the present invention, and increases productivity. It is preferable because it is expensive.

Examples of the present invention are shown below, but the present invention is not limited thereto. The various analysis methods in the synthetic example are as follows.

[Measurement of melting point]
An SMP3 melting point measuring device manufactured by STUART Scientific Co., Ltd. was used. The temperature of the sample was raised at 2 ° C./min, and the temperature at which the solid began to melt was observed. The number of tests was 3, and the average temperature was defined as the melting point.

[Liquid Chromatography (LC) Analysis]
After dissolving 20 mg of the sample in 100 ml of acetonitrile, a mixed solution of acetonitrile / 0.1% by mass ammonium acetate aqueous solution was used as an eluent for 5 μl of the sample, and measurement and analysis were performed under the following conditions. LC purity was obtained as an area ratio at 254 nm.
(Measurement condition)
Controller: SCL-10AVP manufactured by Shimadzu Corporation
Column: GL Sciences inertsil ODS3V (4.6 x 150 mm, 5 μm)
Column oven: CTO-10AVP manufactured by Shimadzu Corporation, 40 ° C.
Pump: LC-10ADVP manufactured by Shimadzu Corporation, flow rate 1.0 ml / min Elution conditions: K1-acetonitrile, K2-0.1 mass% ammonium acetate aqueous solution K1 / K2 = 60/40 (0-5 minutes)
K1 / K2 = 60/40 → 95/5 (linear concentration change, 5-30 minutes)
K1 / K2 = 95/5 (30-80 minutes)
(Ratio is volume ratio)
Detector: Shimadzu SPD-10AVP UV 254nm
(Analysis conditions)
Software: LC-solution ver. Made by Shimadzu Corporation. 1.22SP1
Settings: Slope = 5, Slope = 200, Drift = 0, T.I. DBL = 1000, Min. Area = 500

[Measurement of water content]
The crystalline powder obtained in each example was taken in a 200 mg chalet, dried under reduced pressure at 40 ° C. for 1 hour, exposed at 20 ° C. and 80% RH for 4 hours, and then exposed to a Karl Fischer titer (Curl Fischer Moisture Analyzer). The water content of each powder was measured by KF-200) manufactured by Mitsubishi Chemical Analytech Co., Ltd., and obtained as% by mass with respect to the powder.

[Powder X-ray diffraction (XRD) analysis]
Using an XRD diffractometer (X'Pert Pro MPD manufactured by PANalytical), measurement was performed under the following conditions, and diffraction peaks in the range of 2θ = 3.00 to 25.00 ° were analyzed.
X-ray output (CuKα): 40kV, 30mA
Scanning range (2θ): 3.00 to 70.00 °
Measurement mode: Continuus

[Differential Scanning Calorimetry (DSC)]
The measurement was performed under the following conditions using a DSC measuring device (DSC6220 manufactured by Hitachi High-Tech Science Corporation).
Sample amount: Approximately 5 mg
Temperature range: 5 to 115 ° C, temperature rise at 10 ° C / min Atmosphere: N ₂ 50 ml / min Sample container: Al

[Synthesis of 1,1-bis (4-hydroxyphenyl) dodecane]
<Synthesis example 1>
Phenol (237 g) was heated to 40 ° C. to melt it, and then concentrated hydrochloric acid (3.15 g) was added. A mixed solution of dodecanal (92.0 g) and toluene (55.2 g) was added dropwise thereto over 4 hours. After the dropping, the mixture was aged at 40 ° C. for 1 hour, the reaction was stopped with a 5 mass% sodium hydrogen carbonate aqueous solution (55.9 g), and then a 7.7 mass% sodium dihydrogen phosphate aqueous solution (51.9 g) was added. rice field. Toluene, phenol and water were distilled off from the reaction mixture under reduced pressure, the mixture was extracted with toluene (405 g), and washed with water (230 g) four times. After distilling off the solvent, toluene (330 g) and heptane (330 g) were added to the obtained residue (193 g), and the mixture was heated to an internal temperature of 70 ° C. to dissolve it. Then, the temperature was lowered to an internal temperature of 5 ° C. at a rate of 10 ° C./hour to complete powder precipitation. The obtained powder was filtered and then dried at 70 ° C. for 1 hour under reduced pressure (20 Torr) to obtain crude crystals. A mixture of toluene (368 g) and heptane (184 g) was added to the obtained crude crystals (55.8 g), and the mixture was stirred at an internal temperature of 15 ° C. for 1 hour. The obtained mixed solution was filtered and dried under reduced pressure (20 Torr) at 70 ° C. for 1 hour to obtain crude crystals. A mixture of toluene (368 g) and heptane (184 g) was added to the obtained crude crystals (49.2 g), and the mixture was stirred at an internal temperature of 15 ° C. for 1 hour. The obtained mixed solution was filtered, sprinkled and washed with heptane (27.6 g) at 15 ° C. three times, and then dried under reduced pressure (20 Torr) at 40 ° C. for 48 hours to 1,1-bis (4-hydroxyphenyl). ) A white solid of dodecane (44.7 g) was obtained. The LC purity of this product was 100%.

[Heat treatment of 1,1-bis (4-hydroxyphenyl) dodecane]
<Example 1>
A mixed solution of toluene (18 g) and heptane (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1 and dissolved by raising the temperature to 60 ° C. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals were heated under vacuum conditions (20 Torr) and heated for 48 hours after the powder temperature reached 55 ° C., whereby 4.3 g of crystals of 1,1-bis (4-hydroxyphenyl) dodecane was obtained. Got The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.02 °, 12.08 °, 18.58 °, 19.40 °, 19.95 °
Melting point: 84 ° C

<Example 2>
A mixed solution of toluene (18 g) and heptane (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1 and dissolved by raising the temperature to 60 ° C. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 6 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 3g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.04 °, 12.13 °, 18.56 °, 19.44 °, 19.93 °
Melting point: 86 ° C

<Example 3>
Toluene (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, and the temperature was raised to 60 ° C. to dissolve it. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 6 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 9g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.02 °, 12.08 °, 18.53 °, 19.48 °, 19.93 °
Melting point: 86 ° C

<Example 4>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, a mixed solution of methyl isobutyl ketone (MIBK, 2.5 g) and heptane (27 g) was added, and the temperature was raised to 60 ° C. And dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 60 ° C., they are heated for 6 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 2g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.04 °, 12.13 °, 18.56 °, 19.44 °, 20.02 °
Melting point: 85 ° C

<Example 5>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, a mixed solution of ethanol (EtOH, 3.0 g) and heptane (33 g) was added, and the temperature was raised to 60 ° C. It was dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals were heated under vacuum conditions (20 Torr) to obtain 2.8 g of 1,1-bis (4-hydroxyphenyl) dodecane crystals for 6 hours after the powder temperature reached 60 ° C. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.02 °, 12.11 °, 18.56 °, 19.42 °, 20.00 °
Melting point: 87 ° C

<Example 6>
Isopropanol (IPA, 4.8 g) and heptane (24 g) were added to the residue (16.0 g) obtained after distilling off the solvent in the same manner as in Synthesis Example 1, and the mixture was heated to an internal temperature of 70 ° C. and dissolved. Then, the temperature was lowered to an internal temperature of 5 ° C. at a rate of 10 ° C./hour to complete powder precipitation. After filtering the obtained powder, sprinkle and wash with a mixed solution of IPA (0.80 g) and heptane (4.0 g) at 15 ° C. three times to wash 1,1-bis (4-hydroxyphenyl) dodecane. Wet crystals were obtained. The LC purity of the wet crystal was 99.6%. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 24 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 1g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.04 °, 12.14 °, 18.58 °, 19.42 °, 19.95 °
Melting point: 88 ° C

<Example 7>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, a mixed solution of n-butanol (BuOH, 3.0 g) and heptane (33 g) was added, and the temperature was raised to 60 ° C. And dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 60 ° C., they are heated for 6 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 5g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.02 °, 12.12 °, 18.58 °, 19.40 °, 19.95 °
Melting point: 88 ° C

<Example 8>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, a mixed solution of isobutanol (iBuOH, 4.5 g) and heptane (25 g) was added, and the temperature was raised to 60 ° C. Was dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 6 hours to obtain 1,1-bis (4-hydroxyphenyl) dodecane. 4.4 g of a crystal of the above was obtained. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.03 °, 12.11 °, 18.58 °, 19.42 °, 19.94 °
Melting point: 87 ° C

<Example 9>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1, a mixed solution of 2-butanol (2-BuOH, 4.5 g) and heptane (25 g) was added, and the temperature was adjusted to 60 ° C. The temperature was raised to dissolve it. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 2 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 4g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.02 °, 12.07 °, 18.53 °, 19.40 °, 19.95 °
Melting point: 88 ° C

<Example 10>
Methylene chloride (30 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1 and the temperature was raised to 40 ° C. to dissolve it. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 60 ° C., they are heated for 12 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 4g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.00 °, 12.09 °, 18.56 °, 19.39 °, 19.95 °
Melting point: 83 ° C

<Comparative example 1>
Methylene chloride (30 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1 and the temperature was raised to 40 ° C. to dissolve it. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 40 ° C., they are heated for 12 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 6g. The X-ray diffraction peak and melting point of the obtained crystal were as follows. From the comparison with the melting point described in Patent Document 1, it was determined that this crystal body is the same crystal body as that described in Patent Document 1.
X-ray diffraction peak (2θ): 4.43 °, 4.71 °, 4.93 °, 14.87 °, 15.89 °, 19.41 °, 19.96 °, 23.33 °
Melting point: 77 ° C

<Comparative example 2>
A mixed solution of toluene (18 g) and heptane (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Synthesis Example 1 and dissolved by raising the temperature to 60 ° C. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) dodecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 40 ° C., they are heated for 12 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) dodecane. I got 5g. The X-ray diffraction peak and melting point of the obtained crystal were as follows.
X-ray diffraction peak (2θ): 4.94 °, 14.88 °, 15.91 °, 19.35 °, 19.97 °, 20.87 °, 23.32 °
Melting point: 78 ° C

The endothermic behavior of this crystal by DSC was as follows.
DSC (endothermic temperature range): 33-52 ° C, 52-77 ° C (phase transition), 77-105 ° C (melting)

[Synthesis of 1,1-bis (4-hydroxyphenyl) nonane]
<Synthesis example 2>
Toluene (330 g) and heptane (330 g) were added to the solvent-distilled residue (160 g) obtained in the same manner as in Synthesis Example 1 except that dodecanal was changed to nonanal (71.0 g), and the internal temperature was raised to 70 ° C. It was heated and dissolved. Then, the temperature was lowered to an internal temperature of 15 ° C. at a rate of 10 ° C./hour to complete powder precipitation. The obtained powder was filtered and dried under reduced pressure (20 Torr) at 70 ° C. to obtain crude crystals. Toluene (330 g) and heptane (330 g) were added to the obtained crude crystals, and the mixture was heated to an internal temperature of 70 ° C. and dissolved. Then, after lowering the temperature to 38 ° C., a seed crystal (50.0 mg) of 1,1-bis (4-hydroxyphenyl) nonane was added. After aging for 30 minutes, the temperature was lowered to an internal temperature of 15 ° C. at a rate of 10 ° C./hour to complete powder precipitation. The obtained powder is filtered, sprinkled and washed with heptane (27.6 g) at 15 ° C. three times, and then dried under reduced pressure (20 Torr) at 40 ° C. for 48 hours to obtain the desired 1,1-bis (4-hydroxy). A white solid (56.0 g) of phenyl) nonane was obtained. The LC purity of this product was 98.9%.

[Heat treatment of 1,1-bis (4-hydroxyphenyl) nonane]
<Reference example 1>
A mixed solution of toluene (18 g) and heptane (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) nonane obtained in Synthesis Example 2 and dissolved by raising the temperature to 60 ° C. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) nonane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 40 ° C., they are heated for 12 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) nonane. I got 6g. The LC purity of the obtained crystal was 100%, and the X-ray diffraction peak and melting point were as follows.
X-ray diffraction peak (2θ): 4.86 °, 9.73 °, 14.61 °, 16.78 °, 17.14 °, 18.94 °, 19.70 °, 21.02 °, 23. 76 °
Melting point: 96 ° C

<Reference example 2>
A mixed solution of toluene (18 g) and heptane (18 g) was added to 5.0 g of 1,1-bis (4-hydroxyphenyl) nonane obtained in Synthesis Example 3 and dissolved by raising the temperature to 60 ° C. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) nonacan. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 60 ° C., they are heated for 6 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) nonane. I got 6g. The LC purity of the obtained crystal was 100%, and the X-ray diffraction peak and melting point were as follows.
X-ray diffraction peak (2θ): 4.86 °, 9.72 °, 14.63 °, 16.76 °, 17.14 °, 18.95 °, 19.69 °, 21.02 °, 23. 75 °
Melting point: 96 ° C

[Synthesis of 1,1-bis (4-hydroxyphenyl) nonadecane]
<Synthesis example 3>
IPA (84 g) and heptane (420 g) were added to the solvent-distilled residue (230 g) obtained in the same manner as in Synthesis Example 1 except that dodecanal was changed to nonadecanal (141 g), and the mixture was heated to an internal temperature of 70 ° C. And dissolved. Then, the temperature was lowered to an internal temperature of 15 ° C. at a rate of 10 ° C./hour to complete powder precipitation. The obtained powder is filtered, sprinkled with heptane (47 g) three times, washed, and then dried under reduced pressure (20 Torr) at 40 ° C. for 48 hours to obtain the desired white solid of 1,1-bis (4-hydroxyphenyl) nonadecane (4). 67.6 g) was obtained. The LC purity of this product was 98.3%.

[Heat treatment of 1,1-bis (4-hydroxyphenyl) nonadecane]
<Reference example 3>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) nonadecane obtained in Synthesis Example 3, a mixed solution of IPA (3.0 g) and heptane (25.0 g) was added, and the temperature was raised to 60 ° C. Dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) nonadecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 40 ° C., they are heated for 24 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) nonadecane. I got 7g. The LC purity of the obtained crystal was 100%, and the X-ray diffraction peak and melting point were as follows.
X-ray diffraction peak (2θ): 3.67 °, 7.31 °, 14.77 °, 16.37 °, 18.40 °, 20.31 °, 21.45 °, 21.86 °, 22. 75 °
Melting point: 93 ° C

<Reference example 4>
To 5.0 g of 1,1-bis (4-hydroxyphenyl) nonadecane obtained in Synthesis Example 3, a mixed solution of IPA (3.0 g) and heptane (25.0 g) was added, and the temperature was raised to 60 ° C. Dissolved. The obtained solution was cooled to an internal temperature of 15 ° C. at 10 ° C./hour and then aged for 1 hour. The obtained suspension was filtered to obtain wet crystals of 1,1-bis (4-hydroxyphenyl) nonadecane. The obtained wet crystals are heated under vacuum conditions (20 Torr), and after the powder temperature reaches 70 ° C., they are heated for 24 hours to obtain crystals of 1,1-bis (4-hydroxyphenyl) nonadecane. I got 7g. The LC purity of the obtained crystal was 100%, and the X-ray diffraction peak and melting point were as follows.
X-ray diffraction peak (2θ): 3.68 °, 7.29 °, 14.75 °, 16.39 °, 18.40 °, 20.28 °, 21.48 °, 21.88 °, 22. 77 °
Melting point: 93 ° C

The water content of each of the powders obtained in Examples 1 to 10, Comparative Examples 1 and 2 and Reference Examples 1 to 4 was measured by the method described above. Regarding the powder of Comparative Example 2, after measuring the water content, the powder was further heated under vacuum conditions (20 Torr), and the water content of the powder obtained immediately after heating for 1 hour after the powder temperature reached 40 ° C. was measured. When measured again, it was 1.3% by mass.

The results are summarized in Table 1.
In addition, X-ray diffraction patterns of the crystals obtained in Example 1, Comparative Example 1, and Comparative Example 2 are shown in FIGS. 1 to 3, respectively.

Comparing Examples 1 to 10 and Comparative Examples 1 and 2, it is clear that the crystals obtained in Examples 1 to 10 have low water content. This is a crystal obtained in Examples 1 to 10 having an X-ray diffraction peak within a range of 2θ = 4.40 ° or less in powder X-ray diffraction analysis, and such a crystal is low. Indicates that it exhibits water-containing behavior.
Further, the powders obtained in Examples 1 to 10 show almost the same X-ray diffraction pattern regardless of the crystallization solvent. Since the difference in treatment between Example 2 and Comparative Example 2 and Example 10 and Comparative Example 1 is the heating temperature of the powder, this result shows that a specific crystal exhibiting low water content behavior when heated at 50 ° C. or higher. It shows that the phase has changed to. This is because in the DSC analysis of the powder obtained in Comparative Example 2, an endothermic peak at 52 to 77 ° C. showing phase transition behavior was observed before the endothermic peak at 77 to 105 ° C. indicating melting. Is also supported.
It is clear that the crystals obtained in Comparative Examples 1 and 2 have a higher water content after the test than in Examples 1 to 10 and exhibit high water content behavior. Further, in Comparative Example 2, when the sample after the test was further dried under reduced pressure at 40 ° C. for 1 hour, the water content decreased to 1.3% by mass. From this, the crystals obtained in Comparative Examples 1 and 2 are crystals that easily absorb and desorb water, and may cause vertical fluctuations in mass depending on the surrounding environment, and therefore have low storage stability. I understand.

Further, in order to obtain the crystals of the present invention, it is not always necessary to take out the pure bisphenol compound of the present invention once as in Examples 1 to 5 and Examples 7 to 10 and then go through the precipitation step again. It can also be obtained by taking out the bisphenol compound of the present invention from the mixture containing the bisphenol of the present invention by a precipitation step as in Example 6, and then carrying out the solvent removal and heating steps as it is. This means that it is important that there is a step of heating the powder, and that the steps up to that point are not important for the crystalline material.

In addition, in Reference Examples 1 and 2, 1,1-bis (4-hydroxyphenyl) nonadecane relating to 1,1-bis (4-hydroxyphenyl) nonane instead of 1,1-bis (4-hydroxyphenyl) dodecane. In Reference Examples 3 and 4, the structure of the crystal did not change regardless of the heat treatment conditions, and none of them showed water-containing behavior. Since the difference between Reference Examples 1 and 2 and Reference Examples 3 and 4 and Examples 1 to 10 and Comparative Examples 1 and 2 is the length of the alkane chain of the bisphenol compound, this result is obtained when a resin is used. Only when the bisphenol compound of the present invention, which is expected to impart useful flexibility, is used, a water-containing behavior that affects storage stability is exhibited, and the same applies to alkane chains longer or shorter. It can be said that this supports the excellent finding of the present invention that it shows a novel finding that the behavior is not expressed, and that the crystal property can be controlled by a simple method of heat treatment and the water-containing behavior can be suppressed.

[Manufacturing of polycarbonate resin]
<Example 11>
Reaction of 77.65 g of 1,1-bis (4-hydroxyphenyl) dodecane obtained in Example 1, 50.00 g of bisphenol A (manufactured by Mitsubishi Chemical Co., Ltd.), and 98.74 g of diphenyl carbonate (manufactured by Mitsubishi Chemical Co., Ltd.) It was put into a glass reactor having an internal capacity of 150 mL equipped with a vessel heating device and a reactor pressure regulator, and 0.07 mg of cesium carbonate (manufactured by Kishida Chemical Co., Ltd.) was further added as a catalyst to obtain a raw material mixture. Next, the inside of the glass reactor was depressurized to about 100 Pa (0.75 Torr), and then the operation of restoring the pressure to atmospheric pressure with nitrogen was repeated three times to replace the inside of the reactor with nitrogen. After the nitrogen substitution, the outside temperature of the reactor was set to 220 ° C., the internal temperature of the reactor was gradually raised, and the mixture was dissolved. Then, the stirrer was rotated at 100 rpm. Then, while distilling off the phenol produced by the oligomerization reaction of the dihydroxy compound and diphenyl carbonate performed inside the reactor, the pressure inside the reactor was increased from 101.3 kPa (760 Torr) to 13 in absolute pressure over 40 minutes. The pressure was reduced to .3 kPa (100 Torr). Subsequently, the transesterification reaction was carried out for 80 minutes while maintaining the pressure in the reactor at 13.3 kPa and further distilling off phenol. After that, the outside temperature of the reactor is raised to 240 ° C., and the pressure inside the reactor is reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 40 minutes, and the distilled phenol is removed from the system. Removed. After that, the outside temperature of the reactor is further raised to the final polymerization temperature of 250 ° C., the absolute pressure inside the reactor is reduced to 30 Pa (about 0.2 Torr), the rotation speed of the stirrer is reduced to 30 rpm, and the polycondensation reaction is carried out. Was done. Next, when the stirrer of the reactor reaches a predetermined stirring power, the polycondensation reaction is terminated, the inside of the reactor is restored to an absolute pressure of 101.3 kPa with nitrogen, and the polycarbonate resin is released from the reactor. Was extracted. The time required for the polymerization reaction was 300 minutes.
The obtained polycarbonate resin was dissolved in methylene chloride (6.0 g / L), and the ultimate viscosity was measured at a temperature of 20 ° C. using an Ubbelohde viscous tube (manufactured by Moriyu Rika Kogyo Co., Ltd.). It was .37 (unit: dL / g). Further, the amount of terminal hydroxyl groups of the polycarbonate resin was measured by colorimetric quantification by the titanium tetrachloride / acetic acid method (the detection wavelength is 546 nm by the method described in Macromol. Chem. 88 215 (1965)), and the amount was 720 mass ppm. there were.

<Example 12>
The polycarbonate resin was produced in the same manner as in Example 11 except that the 1,1-bis (4-hydroxyphenyl) dodecane obtained in Example 9 was used as the 1,1-bis (4-hydroxyphenyl) dodecane. went. The time required for the polymerization was 300 minutes, and the obtained polycarbonate resin had an ultimate viscosity [η] = 0.37 (unit: dL / g). Moreover, when the amount of the terminal hydroxyl group was measured, it was 730 mass ppm.

<Comparative example 3>
The polycarbonate resin was produced in the same manner as in Example 11 except that the 1,1-bis (4-hydroxyphenyl) dodecane obtained in Comparative Example 2 was used as the 1,1-bis (4-hydroxyphenyl) dodecane. The time required for polymerization was 450 minutes, and the obtained polycarbonate resin had an ultimate viscosity [η] = 0.30 (unit: dL / g). Moreover, when the amount of the terminal hydroxyl group was measured, it was 350 mass ppm.
In Comparative Example 3, although the polymerization was carried out under the same conditions as in Examples 11 to 12, the polymerization activity was poor and the ultimate viscosity did not increase sufficiently, that is, the molecular weight did not increase. Further, it can be seen that the amounts of the terminal hydroxyl groups in Examples 11 and 12 are at the same level, whereas those in Comparative Example 3 are significantly different.
From these results, it is possible to proceed with a sufficient polymerization reaction by producing a polycarbonate resin using crystals of 1,1-bis (4-hydroxyphenyl) dodecane having a low water content, and the polycarbonate resin. It is clear that the amount of terminal hydroxyl groups, which is important in the quality of the above, is stable, and a polycarbonate resin of good quality can be stably produced.

Claims (7)

Crystals of 1,1-bis (4-hydroxyphenyl) dodecane characterized by having at least one X-ray diffraction peak at a diffraction angle (2θ) of 4.40 ° or less in powder X-ray diffraction analysis using CuKα rays. .. In powder X-ray diffraction analysis using CuKα rays, the diffraction angles (2θ) are 4.05 ° ± 0.20 °, 12.10 ° ± 0.20 °, 18.55 ° ± 0.20 °, 19.40 ° ±. The 1,1- according to claim 1, which has an X-ray diffraction peak at 0.20 ° and 19.95 ° ± 0.20 °, and has a melting point of 80 ° C. or higher and 90 ° C. or lower. Crystal of bis (4-hydroxyphenyl) dodecane. It is characterized in that the moisture content measured after drying under reduced pressure at 40 ° C. for 1 hour and then exposing at 20 ° C. and 80% RH for 4 hours under constant temperature and humidity conditions is 0.01% by mass or more and 2% by mass or less. The crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to claim 1 or 2. A heating step of heating the powder of 1,1-bis (4-hydroxyphenyl) dodecane at 50 ° C. or higher is included, and the powder of 1,1-bis (4-hydroxyphenyl) dodecane is melted or melted after the heating step. The method for producing a crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of claims 1 to 3, which is not soluble in a solvent. A method for producing a resin, which comprises using the crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of claims 1 to 3 as a raw material. A method for producing a polycarbonate resin, which comprises using the crystal of 1,1-bis (4-hydroxyphenyl) dodecane according to any one of claims 1 to 3 as a raw material. The method for producing a polycarbonate resin according to claim 6, wherein the polycarbonate resin is produced by a melt transesterification method.

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