JP2574797B2 - New polycarbonate polymer and method for producing the same - Google Patents

Description

The present invention relates to a novel polycarbonate polymer and a method for producing the same. More specifically, the present invention relates to a novel polycarbonate-based polymer having excellent optical properties, for example, useful as a material for optical equipment, particularly having a high refractive index, and a method for producing the same.

[Conventional technology]

Conventionally, typical polycarbonate resins are 2,2
A compound obtained by reacting phosgene or diphenyl carbonate with -bis- (4-hydroxyphenyl) propane (bisphenol A) is known.
Because of its excellent properties such as excellent transparency, heat resistance and mechanical properties, and good molding accuracy, it is widely used as an engineering plastic in many fields.

By the way, plastic optical elements are lighter than glass ones, have excellent impact resistance, and do not require polishing.
In recent years, its demand has been increasing because of its advantages such as easy mass production and mass production of aspherical lenses. As a material of the plastic optical element, a polycarbonate polymer is known to be useful because it has excellent transparency and excellent optical properties such as a high refractive index (Japanese Patent Laid-Open No. 58-126119). JP-A-58-179224), and with the expanded use of the optical element, development of a new material having more excellent optical properties has been desired.

[Problems to be solved by the invention]

An object of the present invention is to provide a novel polycarbonate-based polymer having excellent optical properties, which is useful as a material for an optical device or the like under such circumstances.

[Means for solving the problem]

The present inventors have conducted extensive research on a novel polycarbonate polymer, and as a result, a novel polycarbonate polymer obtained by reacting a dihydric phenol having a specific structure with a carbonate-forming compound, It has been found that it has excellent optical properties such as having a high refractive index,
Based on this finding, the present invention has been completed.

That is, the present invention relates to the general formula [X in the formula is an ether bond, or (However, R ¹ and R ² each represent a hydrogen atom,
5) alkyl group or phenyl group), CH _{2 n}
(Where n is an integer of 2 to 10) or (Wherein n 'is an integer of 4 to 8). A reduced viscosity [η _{SP of} a 0.5 g / dl concentration solution using methylene chloride as a solvent at a temperature of 20 ° C. / c] is 0.2 dl / g or more. The polycarbonate polymer has a general formula (Wherein X in the formula has the same meaning as described above), and a carbonate-forming compound.

In the polymer of the present invention, the dihydric phenol used as a raw material is a compound having a structure represented by the general formula (II), and specifically, bis (3-phenyl-4-hydroxyphenyl) methane, 1,1 -Bis (3-phenyl-4-
Hydroxyphenyl) ethane, 1,2-bis (3-phenyl-4-hydroxyphenyl) ethane, 2,2-bis (3
-Phenyl-4-hydroxyphenyl) propane, 1,3
-Bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) butane, 1,4-bis (3-phenyl-4-hydroxyphenyl) butane, 2, 2-bis (3-phenyl-4
-Hydroxyphenyl) octane, 1,8-bis (3-phenyl-4-hydroxyphenyl) octane, 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, diphenyl-bis (3- Phenyl-4-
Hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclopentane, 1,1-
Bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 3,3'-diphenyl-4,4'-dihydroxydiphenyl ether and the like can be mentioned.

On the other hand, examples of the carbonate-forming compound include phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-carbonate.
Examples include bisaryl carbonates such as p-chlorophenyl carbonate and dinaphthyl carbonate.

As a method for producing the polymer of the present invention, known methods used in producing polycarbonate from bisphenol A, for example, a direct reaction of dihydric phenol with phosgene,
Alternatively, a method such as transesterification with a dihydric phenol bisaryl carbonate can be employed.

In the former direct reaction method between a dihydric phenol and phosgene, the dihydric phenol represented by the general formula (II) is reacted with phosgene usually in the presence of an acid binder and a solvent. As the acid binder, for example, pyridine or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used. As the solvent, for example, methylene chloride, chlorobenzene, xylene or the like is used. Further, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used to promote the polycondensation reaction, and pt is used to adjust the degree of polymerization.
It is desirable to carry out the reaction by adding a molecular weight regulator such as -butylphenol or phenylphenol. Further, if desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added. Reaction is usually 0-15
It is carried out at a temperature of 0 ° C, preferably in the range of 5 to 40 ° C. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 1 minute.
0 hours, preferably 1 minute to 2 hours. During the reaction, it is desirable to maintain the pH of the reaction system at 10 or more.

On the other hand, in the latter transesterification method, a dihydric phenol represented by the general formula (II) and a bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure.
The reaction is usually performed at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of reduced pressure is finally preferably 1 m
At a pressure of not more than mHg, phenols derived from the bisaryl carbonate generated by the transesterification are distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction, but is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. If desired, the reaction may be carried out by adding the above-mentioned molecular weight regulator or antioxidant.

The polymer of the present invention thus obtained has the general formula (Wherein X has the same meaning as described above) is a novel polycarbonate-based polymer comprising a repeating unit represented by the following formula: 0.5 g / dl using methylene chloride as a solvent
The reduced viscosity [η _SP / c] of the concentrated solution at a temperature of 20 ° C. is 0.
It is more than 2dl / g. If the reduced viscosity is less than 0.2 dl / g, the degree of polymerization is too low to sufficiently achieve the object of the present invention.

The polymer of the present invention has a particularly high refractive index and, for example, 2,2-bis (3-phenyl-4) as a dihydric phenol.
-Hydroxyphenyl) propane has a refractive index of 1.6662 at a temperature of 20 ° C. and 1-phenyl-1,1-bis (3-phenyl-
The refractive index of the polycarbonate obtained from 4-hydroxyphenyl) ethane was 1.6750. In contrast, the refractive index of polycarbonate obtained from bisphenol A is
It was 1.5850.

Examples of the method for molding the polymer of the present invention include methods usually used for molding a polycarbonate resin, such as injection molding, compression molding, low-links method which is a compromise between injection molding and compression molding, and micromolding. Any method can be used.

In the molding method, the polymer of the present invention may be molded as it is, but if desired, various components may be added to the polymer, for example, phosphites for preventing coloring and deterioration of transparency, and melt. A plasticizer or the like for increasing the index value may be blended and molded, or another resin may be blended and molded as long as the properties of the polymer of the present invention are not impaired.

Examples of the phosphites used in this case include tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trisstearyl phosphite, triphenyl phosphite, tricresyl phosphite, and tris ( Nonylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, decyldiphenylphosphite, phenyl-di-2
-Ethylhexyl phosphite, phenyldidecyl phosphite, tricyclohexyl phosphite, distearyl pentaerythrityl diphosphite, diphenylpentaerthrityl diphosphite and the like.

Further, as the plasticizer, for example, 2-ethylhexyl phthalate, n-butyl phthalate, isodecanyl phthalate, tridecanyl phthalate, heptyl phthalate,
Alkyl phthalates such as nonyl phthalate, alkyl esters of dibasic acids such as 2-ethylhexyl adipate and 2-ethylhexyl sebacate, and alkyl phosphates such as tributyl phosphate, trioctyl phosphate, tricresyl phosphate, and triphenyl phosphate And epoxidized fatty acid esters such as epoxidized octyl oleate and epoxidized butyl oleate, polyester plasticizers, and chlorinated fatty acid esters.

〔Example〕

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.

Production Example 1 Production of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane 510 g (3 mol) of o-phenylphenol and acetone 58
g (1 mol) were mixed, heated to 60 ° C. and dissolved, 10 g of mercaptoacetic acid was added as a catalyst, and hydrochloric acid gas was blown in for 36 hours with stirring. After washing the obtained reaction product three times with warm water, the organic phase was heated to 190 ° C. under reduced pressure. Then, the residue was dissolved in 400 ml of methylene chloride,
After adding 500 ml of a prescribed sodium hydroxide aqueous solution and stirring,
Crystals were precipitated by cooling on ice, and the crystals were methylene chloride 400m
After washing twice with 1 l, washing with 500 ml of a 2N aqueous sodium solution, and then adding to 1 N hydrochloric acid 2 and stirring, the crystals were filtered, washed several times with water, and dried under reduced pressure.

Thus, 154 g of crystals (yield 40%) were obtained. This compound had a melting point of 58-60 ° C. and a purity of 99.3%. Analysis of this compound by proton NMR confirmed that it was 2,2-bis (3-phenyl-4-hydroxyphenyl) propane having the following structure.

Production Example 2 1-phenyl-1,1-bis (3-phenyl-
Production of 4-hydroxyphenyl) ethane 1-phenyl-1 having the following structure was prepared in the same manner as in Production Example 1, except that 120 g (1 mol) of acetophenone was used instead of acetone. , 1−
Bis (3-phenyl-4-hydroxyphenyl) ethane
110 g (25% yield) were obtained. The melting point of this compound is 67-68 ° C
And the purity was 99.1%.

Production Example 3 Production of 1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane 510 g (3 mol) of o-phenylphenol and 98 g (1 mol) of cyclohexanone were mixed, heated to 60 ° C. and dissolved. After that, add 150 g of 90% by weight sulfuric acid and stir
The reaction was performed at 70 ° C. for 24 hours. The reaction product obtained is diluted with monochlorobenzene 1 and washed three times with warm water.
The organic phase was heated to 190 ° C. under reduced pressure, and the solvent and unreacted raw materials were distilled off. Then, the residue was dissolved in 400 ml of methylene chloride, 500 ml of a 5N aqueous sodium hydroxide solution was added, and the mixture was stirred. After cooling with ice, the crystals were washed twice with 500 ml of methylene chloride. After washing with 300 ml of a normal aqueous sodium solution, 2N hydrochloric acid 2
After the addition and stirring, the crystals were filtered, washed several times with water, and then recrystallized with an acetone-cyclohexane mixed solution.

Thus, 189 g of crystals (yield 45%) was obtained. The melting point of this compound is ¹ H-NMR (acetone d ₆ ) δ at 143 to 145 ° C.
(Ppm) is 1.6 to 1.8 (10H, m), 6.89 (2H, d), 7.10
(2H, dd), 7.2-7.4 (8H, m), 7.56 (4H, dd)
The molecular weight (m +) was 420.

From this, it was confirmed that this compound had the following structure.

Example 1 A flask with a baffle plate having an internal volume of 1 was obtained in Production Example 1.
2,2-bis (3-phenyl-4-hydroxyphenyl)
60 g of propane, 1 g of pt-butylphenol as a molecular weight regulator and 500 ml of methylene chloride were added and dissolved, and then 300 ml of water and 1 ml of triethylamine as a catalyst were added, and phosgene gas at a temperature of 20 to 30 ° C. and 300 to 400 ml / min with stirring. Injected at the rate of. During the phosgene gas injection, the pH of the reaction system becomes 10
A 12 N aqueous solution of sodium hydroxide was added dropwise so as not to cause the following. After blowing phosgene gas for 25 minutes, the mixture was reacted at 20 to 25 ° C. for 1 hour with stirring. After completion of the reaction, the product was diluted with 700 ml of methylene chloride, washed with water, 0.01N sodium hydroxide, water, 0.01N hydrochloric acid and water in that order, and poured into methanol of 5 to precipitate a polymer. And collected. 64 g of polymer terminated (97% yield)
Met.

The polymer obtained here uses methylene chloride as a solvent.
Reduced viscosity [ηsp / c] of 0.5g / dl concentration solution (the same applies hereinafter)
Was 0.42 dl / g, and the glass transition temperature was 138 ° C. In addition, this polymer, by infrared absorption spectrum analysis,
Located in absorption by the carbonyl group of 1650 cm ^-1, absorption due to an ether bond was observed at the position of 1240 cm ^-1, it is recognized to have a carbonate bond was polycarbonate having the following repeating units. Further, the refractive index of this polycarbonate at 20 ° C. was a large value of 1.6662.

Example 2 A polymer was produced in the same manner as in Example 1 except that 65 g of 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) ethane obtained in Production Example 2 was used.

The reduced viscosity of the obtained polymer [ηsp / c] is 0.45 dl / g,
The glass transition temperature was 174 ° C and the refractive index was 1.6750. Infrared absorption spectrum analysis revealed that the polymer had a carbonate bond, and this polymer had the following repeating units.

Example 3 Except for using 1-phenyl-1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane obtained in Production Example 3 as the dihydric phenol, the reduced viscosity [ ηsp / c] 0.59 dl / g, glass transition temperature 16
A 1 ° C. polymer was obtained.

The infrared absorption spectrum of this polymer showed the same absorption as in Example 1 and was confirmed to be a polycarbonate having the following repeating unit. Its refractive index at 20 ° C is 1.
657.

Example 4 85 g (0.224 mol) of 2,2-bis (3-phenyl-4-hydroxyphenyl) propane obtained in Production Example 1 was dissolved in 650 ml of a 1.5 N aqueous potassium hydroxide solution, and 250 ml of methylene chloride was added. Phosgene gas was blown in at a rate of 1000 ml / min until the pH reached 10 with vigorous stirring.
After the reaction, the mixture was allowed to stand and separated to obtain a methylene chloride solution of the ogolimer having a chloroformate group terminal.

300 ml of this solution was diluted to 450 ml with methylene chloride, and 0.5 g of pt-butylphenol, 2,2-
24.0 g (0.063 mol) of bis (3-phenyl-4-hydroxyphenyl) propane was added to and dissolved in 140 ml of a 2N aqueous solution of potassium hydroxide, and 1.0 ml of a 5% by weight aqueous solution of triethylamine was used as a catalyst with vigorous stirring. In addition, the reaction was carried out for one hour. After the reaction, the reaction was diluted with 1.5 of methylene chloride, washed with water, 0.01N hydrochloric acid and water in that order, and the methylene chloride phase was poured into methanol to precipitate a polymer, which was recovered at 80 ° C. For 24 hours. The yield of the polymer was 112 g.

The polymer obtained here has a reduced viscosity (ηsp / c) of 0.52
dl / g. Further, this polymer by infrared absorption spectrum analysis, absorption by carbonyl group at the position of 1650 cm ^-1, absorption due to an ether bond was observed at the position of 1240 cm ^-1, it is recognized to have a carbonate bond, It was a polycarbonate comprising the following repeating units. Furthermore, the refractive index of this polycarbonate at 20 ° C. is 1.
6662.

Comparative Example A polycarbonate having the following repeating units was obtained in the same manner as in Example 1, except that 2,2-bis (4-hydroxyphenyl) propane was used as the dihydric phenol. This polycarbonate has a reduced viscosity (ηsp / c) of 0.51
dl / g, and the refractive index at 20 ° C. was 1.5850.

[Effect of the Invention] The polycarbonate polymer of the present invention is a novel one, particularly having a high refractive index, and is excellent in optical properties, and as a material for various optical devices, for example, a steel camera, a video camera, It can be used for telescopes, glasses, contact lenses, prisms, optical fibers, video discs, audio discs, optical memory discs, etc.

Also, it is useful as a material for various molded products as an engineering plastic.

Claims (2)

(57) [Claims] (1) General formula [X in the formula is an ether bond, or (However, R ¹ and R ² each represent a hydrogen atom,
5, CH _{2 n} (where n is an integer of 2 to 10) or (Wherein n 'is an integer of 4 to 8). The reduced viscosity at 20 ° C. of a 0.5 g / dl concentration solution using methylene chloride as a solvent and the reduced viscosity [η _SP / c] is 0.2 dl / g or more. 2. The general formula [X in the formula is an ether bond, or (However, R ¹ and R ² each represent a hydrogen atom,
5, CH _{2 n} (where n is an integer of 2 to 10) or (Wherein, n 'is an integer of 4 to 8). A general formula characterized by reacting a dihydric phenol represented by the following formula with a carbonate-forming compound. (Wherein X has the same meaning as described above), and the reduced viscosity [η _SP / c] at 20 ° C. of a 0.5 g / dl concentration solution using methylene chloride as a solvent has a value of 0.2. A method for producing a polycarbonate polymer having a dl / g or more.