JP2556862B2 - Process for producing bis (3-phenyl-4-hydroxyphenyl) sulfone - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel method for producing bis (3-phenyl-4-hydroxyphenyl) sulfone. More specifically, the present invention relates to a method for producing bis (3-phenyl-4-hydroxyphenyl) sulfone, which is used as a raw material of polycarbonate suitable as a material for an optical device element, in a simple process in a high yield. Is.

[Prior Art] Conventionally, polycarbonate has been widely used in many fields as engineering plastics because of its excellent transparency, heat resistance, mechanical strength, and the like, and in recent years, these properties have been utilized. For example, it has come to be used as a material for optical device elements such as lenses, prisms, audio disks, optical memory disks, and optical fibers.

By the way, an optical device element is required to have excellent optical characteristics. Therefore, conventionally, an acrylic resin, which has an extremely high light transmittance and also has excellent moldability, is particularly preferable as a resin glass. Methyl methacrylate has been mainly used. However, this acrylic resin does not always have sufficient heat resistance, and
It is inferior in moisture resistance.Therefore, the optical device element made of this material suffers from performance deterioration due to moisture absorption during storage, and it is difficult to use in applications requiring heat resistance. Was.

Therefore, it has been attempted to use polycarbonate, which is excellent in heat resistance and moisture resistance and has good transparency, as an element for optical devices. However, the conventional polycarbonate resin mainly uses 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) as a starting material, and has a molecular chain of a molecular chain at the time of molding such as injection molding or compression molding. Optical anisotropy is likely to occur due to orientation and residual stress, and birefringence is likely to occur due to this. Therefore, it is not suitable as a material for an optical device element that requires high precision, and it is inevitable that the application will be restricted. For example, an optical disc used for reading and writing information by light using a laser beam cannot be used as a memory of a computer or the like, and is used as a so-called compact disc for audio.

On the other hand, a polycarbonate obtained from 4,4'-dihydroxydiphenyl sulfone (bisphenol S) is known, but this one is excellent in heat resistance and mechanical strength, but is optically non-uniform. Since the molded product exhibits large birefringence, it has a drawback that it is difficult to use as a material for an optical device element.

Under these circumstances, the inventors of the present invention have conducted repeated research on polycarbonate that is excellent in heat resistance, mechanical strength, etc., and is optically uniform and has a small birefringence. As a result, bis (3-phenyl-4) It has been found that a polycarbonate obtained from -hydroxyphenyl) sulfone has the above-mentioned properties and is useful as a material for an optical device element.

This bis (3-phenyl-4-hydroxyphenyl)
Sulfones have traditionally been polyarylene ether sulfones,
It is known to be useful as a raw material for polysulfone, polyester, etc., or as a color developing agent for pressure-sensitive paper. As a method for producing the same, for example, from o-phenylphenol and thionyl chloride, bis (3-phenyl- After obtaining 4-hydroxyphenyl) sulfoxide,
A bis (3-phenyl-4-hydroxyphenyl) sulfide is obtained by reacting an oxidizing agent such as hydrogen peroxide on the compound to oxidize the sulfoxide group of the compound into a sulfone group, or from o-phenylphenol and sulfurdichloride. Then, a method of reacting with an oxidizing agent such as hydrogen peroxide to oxidize the sulfide group of the compound into a sulfone group is used.

However, in both of these methods, 2
In addition to the complicated process such as the need for steps, the yield is not good.

[Problems to be Solved by the Invention] The present invention provides a bis (3- Phenyl-4
The purpose of the present invention is to provide a method for producing -hydroxyphenyl) sulfone in a high yield by a simple one-step reaction process.

[Means for Solving Problems] The present inventors have earnestly studied to develop a method for producing bis (3-phenyl-4-hydroxyphenyl) sulfone by a simple process with high yield, and as a result, It was found that the above object can be achieved by reacting o-phenylphenol and a sulfonating agent at a predetermined temperature in the presence of a specific catalyst, and the present invention has been completed based on this finding. It was

That is, in the present invention, in the presence of an aromatic sulfonic acid catalyst, o-phenylphenol and a sulfonating agent are mixed with 100
The present invention provides a method for producing bis (3-phenyl-4-hydroxyphenyl) sulfone, which comprises reacting at a temperature of ~ 200 ° C.

 Hereinafter, the present invention will be described in detail.

The sulfonating agent used in the method of the present invention is not particularly limited, and any one conventionally selected as a sulfonating agent, such as concentrated sulfuric acid, anhydrous sulfuric acid, fuming sulfuric acid, or chlorosulfonic acid, may be selected. Can be used.

The amount of these sulfonating agents used is usually selected in the range of 0.1 to 0.5 mol per mol of o-phenylphenol. If this amount is less than 0.1 mol, the amount of unreacted o-phenylphenol is too large, which is not practical. On the other hand, if it exceeds 0.5 mol, the production amount of sulfonic acid increases, which is not preferable.

As the aromatic sulfonic acid used as a catalyst, for example, benzenesulfonic acid, chlorobenzenesulfonic acid, bromobenzenesulfonic acid, fluorobenzenesulfonic acid, benzene-1,3-disulfonic acid, chlorobenzene-2,4-disulfonic acid, Examples thereof include toluene sulfonic acid and xylene sulfonic acid. These catalysts may be used alone or in combination of two or more, and the amount used is usually selected in the range of 0.5 to 10 mol% based on the sulfonating agent.

The reaction temperature in the method of the present invention is selected in the range of 100 to 200 ° C, preferably 120 to 180 ° C. If this temperature is less than 100 ° C, the reaction rate is too slow to be practical, while if it exceeds 200 ° C, the amount of by-products produced increases, and tar formation tends to occur.

Although a reaction solvent may not be used, for example, when concentrated sulfuric acid or the like is used as a sulfonating agent, it is advantageous to use an azeotropic solvent in order to distill off water generated in the reaction out of the system. . As the azeotropic solvent, a solvent which is inert to the reaction and is azeotropic with water, such as chlorobenzene, is preferably used.

This reaction is carried out by the reaction formula when sulfuric acid is used as the sulfonating agent. Can be expressed as It seems that the reaction indicated by is occurring.

When chlorosulfonic acid is used as the sulfonating agent, the reaction formula is Can be expressed as It seems that the reaction indicated by is occurring.

The method for producing a polycarbonate using the bis (3-phenyl-4-hydroxyphenyl) sulfone thus obtained is not particularly limited, and a conventionally known method such as interfacial polycondensation between the sulfone and phosgene can be used. Legitimate, a method by transesterification reaction of the sulfone with a diaryl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, the sulfone, A method by a transesterification reaction with a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate, a method by a transesterification reaction between a resin group ester of the sulfone and the dialkyl carbonate, a sulfone of a noble metal catalyst such as palladium. Standing down and reacted with carbon monoxide and chlorine, such as direct method for producing a polycarbonate, it can be used any method.

Further, the bis (3-phenyl-4-hydroxyphenyl) sulfone and other bisphenols such as 2,2-
It is also possible to produce a polycarbonate copolymer according to the above-mentioned method in combination with bis (4-hydroxyphenyl) propane (bisphenol A) or the like.

The polycarbonate or polycarbonate copolymer thus obtained is excellent in heat resistance, mechanical strength, etc., and is optically uniform and has little birefringence, and is useful as a material for an element for optical devices. Examples of the optical device element include so-called lenses for steel cameras, video cameras, telescopes, eyeglasses, contact lenses, sunlight concentrators, prisms such as pentaprisms,
Concave mirrors, mirrors such as polygons, optical elements such as optical fiber optical waveguides, video discs, audio discs, discs such as optical memory discs, and other elements that can exert their functions by transmitting or reflecting light. be able to.

The bis (3-phenyl-4-hydroxyphenyl) sulfone obtained by the method of the present invention is, in addition to the polycarbonate raw material used as the material for the optical device element,
For example, it is also useful as a raw material for polyarylene ether sulfone, polysulfone, polyester, etc., or as a developer for pressure-sensitive paper.

[Effects of the Invention] According to the method of the present invention, bis (3-phenyl-4-hydroxyphenyl) sulfone can be produced in a high yield by a simple one-step reaction process. It is preferably used for various purposes including a raw material of polycarbonate which is useful as a material for an element.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

Example o-Phenylphenol 391 g (2.3 mol), 98% sulfuric acid 1
00 g (1.00 mol), 100 g of chlorobenzene and 9.5 g (0.05 mol) of benzenesulfonic acid were charged into the reactor and heated with stirring. At around 135 ° C, the produced water azeotropically distilled with chlorobenzene. Distillate is condensed to 2
The phases were separated, and the organic phase was continuously returned to the reactor to continue the reaction.

Ten hours after the start of distillation, the internal temperature reached 165 ° C and the amount of distilled water reached 36 ml. To this, 500 ml of xylene was added, and the mixture was cooled to precipitate crystals, which crystals were separated by filtration and recrystallized from xylene to obtain 340 g of crystals having a melting point of 251-252 ° C. The yield was 85% (vs. H ₂ SO ₄ ).

Its molecular weight (m ⁺ ) is 402, and ¹ H-NMR
(Acetone d6) δppm is 7.16 (2H, d), 7.31 to 7.47
(6H, m), 7.58 (4H, d), 7.83 (2H, dd), 7.91
(2H, d).

From the above, the crystal is It was confirmed to be bis (3-phenyl-4-hydroxyphenyl) sulfone having a structure shown by.

Reference example 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) 90.0 g, 6 wt% NaOH aqueous solution 650 ml
Was dissolved in, and 300 ml of methylene chloride was added, and phosgenecus was blown at a rate of 1000 ml / min until the pH reached 10 with vigorous stirring. Then, the mixture was allowed to stand and separate to obtain a polycarbonate precursor having a chloroformate terminal and a polymerization degree of 2 to 3.

Next, 300 ml of this precursor was diluted to 450 ml with methylene chloride, 1.0 g of pt-butylphenol was added thereto, and 35 g of bis (3-phenyl-4-hydroxyphenyl) sulfone obtained in Example was added to 2N. After adding a solution dissolved in 150 ml of an aqueous NaOH solution, 1.0 ml of a 0.5 M aqueous solution of triethylamine as a catalyst was added with vigorous stirring and the reaction was carried out for 1 hour.

After completion of the reaction, dilute with methylene chloride 1 and water, 0.01N
After washing with an aqueous solution of NaOH, water, an aqueous solution of 0.01N HCl, and water in this order, this methylene chloride solution was poured into methanol 5 to obtain a white polycarbonate copolymer.

The reduced viscosity of this polycarbonate is 0.69 dl / g,
The glass transition temperature measured with a differential scanning calorimeter is 158 ° C.
Met. Further, the refractive index was 1.6030 20 ° C.), and the birefringence of the bar flow molded product was 130 nm in terms of optical path difference. The birefringence of polycarbonate made from bisphenol A is as large as 400 nm.

The composition of the polycarbonate copolymer is as follows from the NMR measurement.

Claims (1)

(57) [Claims] 1. Bis (3-phenyl-4-hydroxyphenyl), characterized in that o-phenylphenol and a sulfonating agent are reacted at a temperature of 100 to 200 ° C. in the presence of an aromatic sulfonic acid catalyst. Method for producing sulfone.