JP2538566B2 - Novel polymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a material for optical equipment, a material for electric / electronic equipment,
Optical properties used as other general molding materials,
The present invention relates to a novel polycarbonate-based polymer having excellent heat resistance and a method for producing the same.

[Conventional technology]

Polycarbonate resin is generally bisphenol A
A material obtained by reacting [2,2-bis (4-hydroxyphenyl) propane] as a raw material with a carbonic acid ester-forming compound such as phosgene or diphenyl carbonate is used. However, the polycarbonate resin thus obtained is used in a wide range of applications because it is excellent in transparency, heat resistance, and mechanical strength. Due to its large refraction, it was not satisfactory as a material for optical equipment.

[Problems to be solved by the invention]

An object of the present invention is to provide a novel polycarbonate polymer having excellent heat resistance and excellent optical properties, particularly a small photoelastic coefficient and a small birefringence, and a method for producing the same.

[Means for Solving Problems] As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that the specific object is achieved by polymerizing a specific bisphenol, and this finding The present invention has been completed based on the above.

That is, the polymer of the present invention, And expression (In the formula, R ¹ , R ² , and R ³ are each hydrogen or a C _{1 to} C ₅ alkyl group, and X ¹ , X ² , X ³ , and X ⁴ are each hydrogen or C ₁
To a C ₅ alkyl group, Y is a C _{1 to} C ₅ alkoxy group or a C _{6 to} C ₁₀ phenoxy group), and a repeating unit represented by [I] A solution having a m / m + n value of 0.05 to 1 when the number is m and the number of repeating units represented by [II] is n and the concentration is 0.5 g / dl in methylene chloride as a solvent. The reduced viscosity [ηsp / c] at 20 ° C. is 0.3 dl / g or more. In the polymer of the present invention, when the value of m / m + n is less than 0.05, the decrease in photoelastic coefficient becomes insufficient. Preferably 0.2
It is desirable to set it to ~ 0.8. If the reduced viscosity is less than 0.3 dl / g, the mechanical strength will be insufficient.

The polymers of the present invention have the formula And expression (In the formula, R ¹ , R ² , R ³ , X ¹ , X ² , X ³ , X ⁴ and Y have the same meanings as described above) [III] /
It can be produced by using a compound having a molar ratio of [III] + [IV] of 0.05 to 1 and reacting it with a carbonate ester-forming compound.

Examples of the [III] dihydric phenols used in the present invention include, for example, 2,2-bis (4-hydroxyphenyl)
-2- (4-methoxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) -2- (4-phenoxyphenyl) ethane, 2,2-bis (3-methyl-4-hydroxyphenyl) -2 -(4-methoxyphenyl) ethane and the like.

Examples of the divalent denols of [IV] include bis (4-
Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) pentane, 4,4-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl)
Examples include heptane and 2,2-bis (4-hydroxyphenyl) octane.

Examples of the carbonic acid ester-forming compounds include diaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate, and carbonic acid such as phosgene and bromophosgene. Examples thereof include halides. Of these, diphenyl carbonate and phosgene are preferable.

The method for producing the polymer of the present invention includes bisphenol A
A known method used for producing a polycarbonate from the above can be adopted, for example, a method such as a direct reaction between a dihydric phenol and phosgene or a transesterification reaction between a dihydric phenol and a bisaryl carbonate.

In the former direct reaction method of dihydric phenol and phosgene, usually in the presence of an acid binder and a solvent, the dihydric phenol represented by the general formula [III] and [IV] [III] alone or [III] III] and [IV] are used together in a predetermined ratio to react with phosgene. 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 may be used to accelerate the polycondensation reaction, and phenol, phenylphenol, cumylphenol, p may be used to adjust the degree of polymerization. It is desirable to carry out the reaction by adding a molecular weight regulator such as -t-butylphenol. If desired, a small amount of an antioxidant such as sodium sulfite or sodium hydrosulfite may be added.

The blending ratio of [III] and [IV] of dihydric phenol is [II
The molar ratio of [I] / [III] + [IV] is 0.05-1. To obtain a polymer with a small photoelastic coefficient,
It suffices to increase the proportion of the compound [III] used.

The reaction is usually carried out at a temperature in the range of 0 to 150 ° C, preferably 5 to 40 ° C. The reaction time depends on the reaction temperature, but is usually 1 minute to 5 hours, preferably 5 minutes to 3 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, the dihydric phenol represented by the general formulas [III] and [IV] and bisaryl carbonate are mixed and reacted at a high temperature under reduced pressure. The reaction is usually 100 to 350 ° C, preferably 200
It is carried out at a temperature in the range of up to 300 ° C., and the degree of vacuum is finally set to preferably 1 mmHg or less, and the phenols derived from the bisaryl carbonate produced by the transesterification reaction are distilled out of the system. Although the reaction time depends on the reaction temperature and the degree of reduced pressure, it 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.

Further, in advance, polycondensation of bisphenol and phosgene represented by the formula [III] or polycondensation of bisphenol and diphenyl carbonate to obtain an oligomer, and the oligomer is reacted with a dihydric phenol represented by the formula [IV] Alternatively, conversely, the dihydric phenol represented by the formula [IV] and phosgene or diphenyl carbonate may be polycondensed in advance, and then the bisphenol [III] may be reacted.

The thus obtained polymer of the present invention is a novel polycarbonate polymer composed of repeating units represented by the above general formula [I] or [I] and [II],
Temperature of 0.5g / dl solution with methylene chloride as solvent 20
The reduced viscosity [ηsp / c] at 0 ° is 0.3 dl / g or more.

Examples of the method for molding the polymer of the present invention include methods commonly used for molding polycarbonate resins, such as injection molding method, compression molding method, low-link method and micromolding, which are eclectic methods of injection molding and compression molding. Any method can be used from the inside.

In the molding method, the polymer of the present invention may be molded as it is, but if desired, various components of the polymer,
For example, phosphite esters for preventing coloration and deterioration of transparency, may be molded by blending with a plasticizer for increasing the melt index value, and the characteristics of the polymer of the present invention You may mix and mold other resin in the range which does not impair.

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,
Nonyl phthalates and other alkyl phthalates, 2-ethylhexyl adipate, 2-ethylhexyl sebacate and other dibasic acid alkyl esters, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate and other alkyl phosphates Examples thereof include epoxidized fatty acid esters such as epoxidized octyl oleate and epoxidized butyl oleate, polyester plasticizers, and chlorinated fatty acid esters.

In addition to the polymer obtained in the present invention, for example, an ultraviolet absorber, a colorant, a fluorescent whitening agent, a flame retardant, an antistatic agent,
Fillers, reinforcing agents and the like may be added and blended as necessary.

〔Example〕

Hereinafter, the present invention will be described in detail based on Examples,
The present invention is not limited to this.

Example 1 2,2-bis (4-hydroxyphenyl) -2-as dihydric phenol of the formula [III] was placed in a flask having an internal volume of 2 liters.
A solution prepared by dissolving 90 g of (4-methoxyphenyl) ethane in 600 ml of an aqueous solution of 8% by weight sodium hydroxide, 300 ml of methylene chloride, 2.0 g of pt-butylphenol as a molecular weight regulator, and 10% by weight of triethylamine as a catalyst. 1 ml was added, and phosgene gas was blown thereinto for 30 minutes with stirring to carry out the reaction. A solution of the reaction product in methylene chloride was further diluted with methylene chloride to make 1 as a whole, and 1 part of water was added.
, 0.01N sodium hydroxide aqueous solution 500ml, water 500m
l, washed with 500 ml of 0.01 N hydrochloric acid and 500 ml of water in this order, and poured into methanol to obtain 93 g of a white polymer.

This polymer has a reduced viscosity [ηsp / c] of 0.5 dl / g measured at 20 ° C. in a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent (measured under the same conditions in the following examples), The glass transition temperature (Tg) was 158 °. Further, the by polymer infrared absorption spectrum analysis, absorption by carbonyl group at the position of 1650 cm ^-1, absorption by an ether group was observed at the position of 1240 cm ^-1, to have a carbonate bond was observed. From this, this polymer is recognized as a polycarbonate composed of the following repeating units.

Next, the photoelastic coefficient of this polymer was measured to be 39 ×
It was 10 ^-13 dyne / cm ² . The above results are summarized in the table.

Example 2 2,2-bis (4-hydroxyphenyl) -2- (4-
1,1-bis (4-hydroxyphenyl) -1- (4-phenoxyphenyl) instead of methoxyphenyl) ethane
In the same manner as in Example 1 except that 90 g of ethane was used, 92 g of a polycarbonate having the following repeating unit was obtained.

The properties of this polycarbonate are shown in the table.

Example 3 2,2-bis (4-hydroxyphenyl) -2- (4-
The same procedure as in Example 1 was repeated except that 90 g of 2,2-bis (3-methyl-4-hydroxyphenyl) -2- (4-methoxyphenyl) ethane was used instead of methoxyphenyl) ethane. Polycarbonate composed of units
Got 95g.

The properties of this polycarbonate are shown in the table.

Comparative Example 1 The same operation as in Example 1 was carried out except that 90 g of 2,2-bis (4-hydroxyphenyl) propane was used as the dihydric phenol to obtain 95 g of a general polycarbonate composed of the following repeating units. It was The properties of this product are shown in the table.

[Effects of the Invention] The polycarbonate polymer of the present invention is a novel one, is an engineering plastic having a small photoelastic coefficient and excellent optical properties, and is an optical device such as a digital audio disk or an optical memory disk. Its industrial value is extremely high as a material for automobiles and a material for electric and electronic devices.

Claims (2)

(57) [Claims] 1. A formula And expression (In the formula, R ¹ , R ² , and R ³ are each hydrogen or a C _{1 to} C ₅ alkyl group, and X ¹ , X ² , X ³ , and X ⁴ are each hydrogen or C ₁
To a C ₅ alkyl group, Y is a C _{1 to} C ₅ alkoxy group or a C _{6 to} C ₁₀ phenoxy group), and a repeating unit represented by [I] A solution having a m / m + n value of 0.05 to 1 when the number is m and the number of repeating units represented by [II] is n and the concentration is 0.5 g / dl in methylene chloride as a solvent. Polymer having a reduced viscosity [ηsp / c] of 0.3 dl / g or more at 20 ° C. 2. A formula And expression (In the formula, R ¹ , R ² , and R ³ are each hydrogen or a C _{1 to} C ₅ alkyl group, and X ¹ , X ² , X ³ , and X ⁴ are each hydrogen or C ₁
To C ₅ alkyl group and Y is a C _{1 to} C ₅ alkoxy group or a C _{6 to} C ₁₀ phenoxy group) [III] / [III] + [IV] Molar ratio of 0.05 ~
A compound of formula (1) which is used to react with a carbonic acid ester forming compound. And expression (Wherein R ¹ , R ² , R ³ , X ¹ , X ² , X ³ , X ⁴ and Y have the same meanings as described above),
When the number of repeating units represented by [I] is m and the number of repeating units represented by [II] is n, the value of m / m + n satisfies 0.05 to 1, and methylene chloride is Use as solvent
Reduced viscosity of a 0.5g / dl concentration solution at 20 ℃ [ηsp / c]
Of 0.3 dl / g or more.