JP5183579B2 - High purity 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane and process for producing the same - Google Patents

Description

The present invention relates to high-purity 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane useful as a raw material for heat-resistant polyesters, polyurethanes, polycarbonates, epoxy resins, modified acrylic resins, and the like, and a method for producing the same.

As a method for producing 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane, a method in which cyclododecanone and 2-methylphenol are subjected to dehydration condensation using hydrogen chloride gas and thiol as a catalyst is disclosed. (Patent Document 1).
However, since hydrogen chloride gas is highly corrosive and difficult to handle, special equipment is required for industrial use. For this reason, development of a process for producing 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane in an industrially advantageous manner with high purity and high yield without using hydrogen chloride gas is required. It was.
The present applicant previously proposed a method for producing a cyclic hydrocarbon derivative from a specific cyclic ketone and a specific compound in the presence of a heteropolyacid catalyst as a method not using hydrogen chloride gas (Patent Document 2). However, when 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane is produced using this method, the compounds represented by the formulas (1) to (3) are contained in the compound. It was found that 1% by weight or more was contained. Further, in this method, the reaction may be delayed.
In order to produce a more uniform polymer using the compound as an optical resin raw material, a high-purity raw material in which the compounds represented by the formulas (1) to (3) are reduced is more preferable. Development of a highly pure 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane reduced in the compound represented by (3) and an industrially advantageous production method thereof has been demanded.

JP 59-166528 A Japanese Patent Application No. 2009-73027

  The present invention is a high-purity 1,1-bis- in which the compounds represented by the formulas (1) to (3) useful as raw materials for heat-resistant polyesters, polyurethanes, polycarbonates, epoxy resins, modified acrylic resins and the like are reduced. The present invention provides (4-hydroxy-3-methylphenyl) cyclododecane and a method for producing the same.

In the conventional method, the present inventors paid attention to the fact that an organic solvent and 2-methylphenol are distilled together with water during the reaction, and as a result of intensive studies, cyclododecanone and 2-methylphenol are present in the presence of a heteropolyacid. In the method for producing 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane by reacting phenol, the reaction is carried out at a temperature range of 30 to 90 ° C. under reduced pressure reflux of 4.0 × 10 ³ Pa or less. Under the conditions, without allowing the organic solvent or 2-methylphenol to be distilled off, the reaction can be prevented by delaying the reaction by extracting only water from the reaction system and reacting with the formula ( It has been found for the first time that highly pure 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane having a reduced content of the compounds represented by 1) to (3) can be obtained. Of the present invention has been completed.

High purity 1,1-bis- in which the compounds represented by the formulas (1) to (3) useful as raw materials for heat-resistant polyester, polyurethane, polycarbonate, epoxy resin, modified acrylic resin, etc. are reduced by the present invention. An industrially advantageous production method capable of preventing (4-hydroxy-3-methylphenyl) cyclododecane and its reaction delay can be provided.

  Hereinafter, the present invention will be described together with embodiments thereof.

The heteropolyacid used in the present invention is generally a complex oxide acid composed of two or more different oxide complexes, and a part or all of these protons replaced with other cations. Heteropolyacids include, for example, oxyacid ions of elements such as phosphorus, arsenic, tin, silicon, titanium and zirconium (for example, phosphoric acid and silicic acid) and oxyacid ions of elements such as molybdenum, tungsten, vanadium, niobium and tantalum. (Vanadic acid, molybdic acid, tungstic acid), and various heteropolyacids are possible by combinations thereof.
.

The element of oxygen acid constituting the heteropolyacid is not particularly limited, but for example, copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, arsenic , Antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, iridium, platinum and the like. Among these, those containing at least one selected from (A) phosphorus or silicon and (B) vanadium, molybdenum or tungsten as a constituent element are preferable.

As the heteropolyacid anion constituting the heteropolyacid skeleton, those having various compositions can be used. For _example, such _{XM 12 O 40, XM 12 O} 42, XM 18 O 62, XM 6 O 24 and the like. A preferred heteropolyacid anion composition is XM ₁₂ O ₄₀ . In each formula, X is an element such as silicon or phosphorus, and M is an element such as vanadium, molybdenum, or tungsten. Specific examples of heteropolyacids having these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, phosphovanadomolybdic acid, phosphotungstomolybdic acid, phosphovanadomolybdic acid, and cytungstomolybdic acid, Examples include phosphovanadotungstic acid.

The heteropolyacid may be a free heteropolyacid, and may be used as a salt of a heteropolyacid by replacing some or all of the protons with other cations. Accordingly, the heteropolyacid referred to in the present invention includes salts of these heteropolyacids. Examples of cations that can be substituted with protons include ammonium, alkali metals, alkaline earth metals, and the like.

The heteropolyacid may be an anhydride or a crystal water-containing product, but the anhydride is preferred because the reaction is faster and the formation of by-products is suppressed. In the case of a crystal water-containing material, effects similar to those of the anhydride can be obtained by performing dehydration treatment such as drying under reduced pressure or azeotropic dehydration with a solvent in advance. The heteropolyacid may be used in a form supported on a support such as activated carbon, alumina, silica-alumina, or diatomaceous earth. These heteropolyacids may be used alone or in combination of two or more. Moreover, you may use together other catalysts other than heteropoly acid in the range which does not impair the objective of this invention as needed.

The amount of heteropolyacid used is not particularly limited, but in order to obtain a sufficient reaction rate, it is 0.0001 times by weight or more, preferably 0.001 to 30 times by weight with respect to the cyclic ketones as a raw material. More preferably, it is 0.01 to 5 times by weight. If it is more than 30 times by weight, it is economically undesirable.

  Although the usage-amount of 2-methylphenol in this invention is not specifically limited, From the point of reactivity, workability | operativity, and economical efficiency, it is 3-25 mol normally with respect to 1 mol of cyclododecanone. , Preferably 5 to 15 mol. When the amount of 2-methylphenol used is less than 5 mol, crystals (products) may be precipitated during the reaction, and the reactivity and workability may deteriorate. On the other hand, if the amount of 2-methylphenol used is more than 25 mol times, it is economically disadvantageous.

The reaction of cyclododecanone and 2-methylphenol is performed, for example, by adding cyclododecanone, 2-methylphenol and heteropolyacid to a reactor, and at a temperature of 30 to 90 ° C. under reduced pressure reflux of 4.0 × 10 ³ Pa or less. This can be done by returning the organic solvent or 2-methylphenol to the reaction system using an oil / water separator or the like, and withdrawing only water out of the reaction system.

  Although the reaction temperature in this invention changes with the presence or absence of a solvent, its kind and quantity, and a pressure reduction degree, it is 30-90 degreeC, Preferably it is 50-80 degreeC. When the reaction temperature is higher than 90 ° C., the purity and yield are lowered due to the increase of by-products. Further, the product is unfavorably colored. When the reaction temperature is lower than 30 ° C., the reaction does not proceed or it takes a long time to complete the reaction, which is not preferable.

Vacuum degree in the present invention is 4.0 × ¹⁰ 3 Pa or less, preferably 3.0 × ¹⁰ 3 Pa or less, more preferably ^{0.1 × 10 3 Pa~2.0 × 10 3} Pa. When the reaction temperature is 30 to 90 ° C. and the degree of vacuum exceeds 4.0 × 10 ³ Pa, the reaction does not proceed or it takes a long time to complete, which is not preferable.

In the present invention, if necessary, the reaction can be carried out under reduced pressure using an azeotropic dehydration solvent as long as the object of the present invention is not impaired. The azeotropic dehydration solvent used in the reaction is not particularly limited, but is an aromatic hydrocarbon solvent such as toluene or xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene or dichlorobenzene, pentane, hexane or heptane. Aliphatic hydrocarbon solvents such as dichloromethane, halogenated aliphatic hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane, aliphatic ethers such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran and dioxane And cyclic ether solvents, ester solvents such as ethyl acetate and butyl acetate, nitrile solvents such as acetonitrile, propionitrile, butyronitrile, and benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl Amide solvents such as 2-pyrrolidinone, and the like. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, and more preferred are toluene, xylene, chlorobenzene and dichlorobenzene. The amount used is not particularly limited, but is usually 5 parts by weight or less, preferably 2 parts by weight or less based on cyclododecanone. An appropriate amount of solvent accelerates the reaction, but if the amount used is large, the reaction may be slow.

After the reaction, the 1,1-bis- (4-hydroxy-3-methyl-phenyl) cyclododecane in the reaction solution contains about 1% by weight of the compounds represented by the formulas (1) to (3). .

A method for obtaining high-purity 1,1-bis- (3-methyl-4-hydroxyphenyl) cyclododecane, in which the content of impurities represented by the formulas (1) to (3) of the present invention is 0.5% by weight or less, For example, there is a method in which a solvent is added to a reaction solution containing about 1% by weight of the compounds represented by the above formulas (1) to (3), cooling crystallization is performed, and precipitated crystals are separated by filtration. . When the content of the impurities represented by the formulas (1) to (3) in the obtained crystal exceeds 0.5% by weight, the same operation is repeated until it becomes 0.5% by weight or less. Can be obtained.

(Example)
Examples of the present invention are shown below, but the present invention is not limited thereto.
In the examples, unless otherwise specified,% is an area percentage value in HPLC, and parts are based on weight.
The purity and the content of the compounds represented by formulas (1) to (3) were measured by HPLC. The compounds represented by (1) to (3) can be accurately measured at a detection wavelength UV of 280 nm by HPLC.

The HPLC measurement conditions are as follows.
HPLC measurement conditions:
Equipment: Shimadzu LC-2010A
Column: L-Column ODS (5 μm, 4.6 mmφ × 150 mm)
Mobile phase: Liquid A: water / methanol = 70/30 (v / v), liquid B: methanol liquid B concentration: 30% → 100% (25 minutes) → 100% (35 minutes)
Flow rate: 1.0 ml / min, column temperature: 40 ° C., detection wavelength: UV 280 nm

In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and Dean-Stark type oil-water separator, 23.7 g (0.130 mol) of cyclododecanone, 183 g (1.69 mol) of 2-methylphenol and catalyst Phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] 0.60 g and dodecanethiol 1.32 g were added, and 2-methylphenol was refluxed at a temperature of 70 ° C. and 1.3 × 10 ³ Pa under reduced pressure. The reaction was carried out for 4 hours while removing only the produced water out of the system without distilling off. To the resulting reaction mixture, 132 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. After adding 164 g of toluene to the obtained concentrate and dissolving 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane at 115 ° C., the resulting solution was cooled to 100 ° C. and 1 The mixture was kept warm for 5 hours and then cooled to 5 ° C. The precipitated crystals were taken out by filtration and dried to obtain 38.5 g of white crystals of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (yield 77.9%, purity 99.0%). , (Contents of compounds represented by (1) to (3) 0.7%). The obtained crystals were recrystallized from toluene, and reduced high-purity 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane white crystals of the compounds represented by formulas (1) to (3) 35.8 g (yield 72.4%, purity 99.6%, content of compounds represented by (1) to (3), detection limit less than 0.01%) was obtained.

In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and Dean-Stark type oil-water separator, 23.7 g (0.130 mol) of cyclododecanone, 183 g (1.69 mol) of 2-methylphenol and catalyst Phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] 0.60 g and dodecanethiol 1.32 g were added, and 2-methylphenol was obtained at a temperature of 50 ° C. under reduced pressure reflux of 0.65 × 10 ³ Pa. The reaction was carried out for 6 hours while removing only the produced water out of the system without distilling off. To the resulting reaction mixture, 132 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. After adding 164 g of toluene to the obtained concentrate and dissolving 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane at 115 ° C., the resulting solution was cooled to 100 ° C. and 1 The mixture was kept warm for 5 hours and then cooled to 5 ° C. The precipitated crystals were taken out by filtration and dried to give 43.0 g of white crystals of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (yield 86.9%, purity 99.5%). , (Content 0.3% of compounds represented by (1) to (3)).

In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and Dean-Stark type oil-water separator, 23.7 g (0.130 mol) of cyclododecanone, 183 g (1.69 mol) of 2-methylphenol and catalyst Phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] 0.60 g and dodecanethiol 1.32 g were added, and 2-methylphenol was heated under reduced pressure at a temperature of 80 ° C. and 2.0 × 10 ³ Pa. The reaction was carried out for 4 hours while removing only the produced water out of the system without distilling off. To the resulting reaction mixture, 132 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. After adding 164 g of toluene to the obtained concentrate and dissolving 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane at 115 ° C., the resulting solution was cooled to 100 ° C. and 1 The mixture was kept warm for 5 hours and then cooled to 5 ° C. The precipitated crystals were collected by filtration and dried to give 32.8 g of white crystals of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (yield 66.2%, purity 98.4%). And (1) to (3), the content of the compound represented by 1.0%) was obtained. To the obtained crystals, 231 g of toluene was added and recrystallized to reduce the high purity 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane of the compounds represented by formulas (1) to (3). 30.5 g (yield 61.5%, purity 98.8%, content of compounds represented by (1) to (3), detection limit less than 0.01%) was obtained.

In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and Dean-Stark type oil-water separator, 23.7 g (0.130 mol) of cyclododecanone, 98.4 g (0.910 mol) of 2-methylphenol As a catalyst, phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] 0.60 g and dodecanethiol 1.32 g were added, and the temperature was 70 ° C. under reduced pressure reflux of 1.3 × 10 ³ Pa. The reaction was carried out for 4 hours while removing only the produced water out of the system without distilling off methylphenol. To the resulting reaction mixture, 154 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 86 ° C. and washed with water. The organic layer obtained by separating the organic layer was refluxed and dehydrated, and 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane was dissolved at 115 ° C. The solution was cooled to 5 ° C. after being kept warm for 1 hour. The precipitated crystals were removed by filtration and dried to give 36.8 g of white crystals of 1,1-bis- (3-methyl-4-hydroxyphenyl) cyclododecane (yield 74.4%, purity 99.0%, The content of the compound represented by (1) to (3) was 0.8%. The obtained crystals were recrystallized from toluene, and reduced high-purity 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane white crystals of the compounds represented by formulas (1) to (3) 34.2 g (yield 69.2%, purity 98.8%, content of compounds represented by (1) to (3), detection limit less than 0.01%) was obtained.

(Comparative Example 1)
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and T-shaped tube, 23.7 g (0.13 mol) of cyclododecanone, 183 g (1.69 mol) of 2-methylphenol and phosphotungsten as a catalyst 0.6 g of acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] and 2.63 g (0.013 mol) of n-dodecyl mercaptan were added, and water produced by the reaction was maintained while maintaining the temperature at 70 ° C. The mixture was stirred for 8 hours while being removed from the system under a reduced pressure of 3 × 10 ³ Pa. (While removing water outside the system under reduced pressure, it was confirmed that 2-methylphenol was distilled off together with water.) Toluene was added to the resulting reaction mixture, and the resulting toluene mixture was adjusted to 70 ° C. After adding water, the mixture was neutralized with sodium hydroxide and washed with water. The resulting organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. Toluene was added to the resulting mixture and heated to dissolve it, and then the obtained solution was cooled to 5 ° C. as it was. The precipitated crystals were taken out by filtration and dried to give 41 g of white crystals of 1,1-bis (4-hydroxy-3-methylphenyl) cyclododecane (yield 82.8%, purity 98.3%, (1 ) To (3) content of compound represented by 1.5%)).

(Comparative Example 2)
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and T-tube, cyclododecanone 93.2 g (0.51 mol), 2-methylphenol 737 g (6.82 mol) and phosphotungsten as a catalyst 2.32 g of acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] and 5.03 g of dodecanethiol were added, and water generated by the reaction was maintained at 70 ° C. under reduced pressure at 1.3 × 10 ³ Pa. The mixture was stirred for 20 hours while being removed from the system. (While removing water outside the system under reduced pressure, it was confirmed that 2-methylphenol was distilled off together with water.) To the resulting reaction mixture was added 520 g of toluene and an aqueous sodium hydroxide solution, and the mixture was heated at 70 ° C. Washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. To the obtained concentrate, 644 g of toluene was added and 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane was dissolved at 115 ° C., and then the resulting solution was cooled to 100 ° C. The mixture was kept warm for 5 hours and then cooled to 5 ° C. The precipitated crystals were taken out by filtration and dried to give 116 g of white crystals of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (yield 59.4%, purity 93.9% (1 ) To (3) content 4.0%).

(Comparative Example 3)
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and Dean-Stark type oil-water separator, 23.7 g (0.130 mol) of cyclododecanone, 183 g (1.69 mol) of 2-methylphenol and catalyst Phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] 0.60 g and dodecanethiol 1.32 g were added, and 2-methylphenol was added at a temperature of 100 ° C. under a reduced pressure of 5.0 × 10 ³ Pa under reduced pressure. The reaction was carried out for 8 hours while removing only the produced water out of the system without distilling off. To the resulting reaction mixture, 132 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess 2-methylphenol. After adding 164 g of toluene to the obtained concentrate and dissolving 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane at 115 ° C., the resulting solution was cooled to 100 ° C. and 1 The mixture was kept warm for 5 hours and then cooled to 5 ° C. The precipitated crystals were removed by filtration and dried to give 16.1-g white crystals of 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane (yield 32.5%, purity 92.6%). The content of the compound represented by (1) to (3) was 5.2%.

Claims (1)

In the method for producing 1,1-bis- (4-hydroxy-3-methylphenyl) cyclododecane by reacting cyclododecanone and 2-methylphenol in the presence of a heteropolyacid, 4.0 × 10 ³ The total content of the compounds represented by the following formulas (1) to (3), wherein only water is withdrawn out of the reaction system in the temperature range of 30 to 90 ° C. under reduced pressure reflux of Pa or less. Of 0.5% by weight or less, a method for producing high-purity 1,1-bis- (3-methyl-4-hydroxyphenyl) cyclododecane.