JPH0692480B2 - Polycarbonate copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polycarbonate-based copolymer and a method for producing the same, and more specifically, it has two kinds of specific repeating units at a constant ratio and has good transparency. TECHNICAL FIELD The present invention relates to a polycarbonate-based copolymer having excellent heat resistance and an efficient production method thereof.

[Prior Art and Problems to be Solved by the Invention] Conventionally, a polycarbonate resin produced from 2,2-bis (4'-hydroxyphenyl) propane (commonly called bisphenol A) has excellent mechanical properties. Because
It is used for a wide range of purposes. However, as various applications have expanded, the performance requirements for polycarbonate resins have become stricter, and there is a demand for polycarbonate polymers having superior performance.

Therefore, the present inventors have made various studies in view of such a situation.

[Means for Solving Problems] As a result, by introducing a specific copolymer component into a conventional polycarbonate at a specific ratio, a heat-resistant factory can be used without impairing the excellent transparency of the polycarbonate. I found that I can measure. The present invention has been completed based on such findings.

That is, the present invention is The repeating unit [I] represented by [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R ³ and R ⁴ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group. Show. ] The repeating unit [II] represented by the formula [1], the molar ratio of the repeating unit [I] is 5% or more and less than 40%, and a solution of methylene chloride as a solvent at a concentration of 0.5 g / dl at 20 ° C. To provide a polycarbonate-based copolymer having a reduced viscosity [η _sp / c] of 0.3 dl / g or more.
The present invention also provides 4,4'-dihydroxydiphenyl represented by [In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as described above. ] The method of manufacturing the said polycarbonate type copolymer is also provided by making the bisphenol compound and the carbonic acid ester forming derivative represented by these react.

The polycarbonate-based copolymer of the present invention is a copolymer composed of repeating units [I] and [II] as described above,
These proportions are such that the repeating unit [I] has a molar fraction of 5% or more.
It is adjusted to be less than 40%. Here, when the mole fraction of the repeating unit [I] is less than 5%, the heat resistance improving effect of the obtained polycarbonate copolymer becomes small, while when the mole fraction of the repeating unit [I] becomes 40% or more, it is obtained. The transparency of the obtained polycarbonate-based copolymer decreases.

The degree of polymerization of the polycarbonate-based copolymer of the present invention may be appropriately determined depending on the application etc., but the reduced viscosity at 20 ° C. of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent [η _sp / c] is 0.3 dl / g or more, preferably 0.3-1.0 dl / g
Should be polymerized to give a copolymer of Here, when the reduced viscosity is less than 0.3 dl / g, the copolymer obtained has low mechanical strength.

As the repeating unit represented by the above general formula [II], R ¹
~ There are various types depending on the type and position of R ⁴ , but if the structure of the specific repeating unit is shown, And so on.

The polycarbonate-based copolymer in the present invention has the repeating units [I] and [II] described above, and there are various types such as random copolymers, block copolymers and alternating copolymers thereof.

The polycarbonate-based copolymer of the present invention can be produced by various methods, and the above-mentioned method of the present invention efficiently produces a high-quality polycarbonate-based copolymer.

In the method of the present invention, 4,4′-represented by the above formula [III]
The dihydroxydiphenyl, the bisphenol compound represented by the general formula [IV] and the carbonic acid ester-forming derivative are introduced into the reaction system and reacted. Where 4,4 ′
-The supply ratio of dihydroxydiphenyl and the bisphenol compound represented by the general formula [IV] is not particularly limited, but this 4,4'-dihydroxydiphenyl forms a repeating unit [I] and is represented by the general formula [IV]. Taking into consideration that the bisphenol compound formed forms a repeating unit [II], 4,4′-dihydroxydiphenyl / bisphenol compound = 5/95 to 40/60 (molar ratio), preferably 10/90 to
It should be 35/65 (molar ratio). The amount of the carbonic acid ester-forming derivative introduced is preferably the total number of moles of the above 4,4'-dihydroxydiphenyl and the bisphenol compound represented by the general formula [IV] or more. The types of carbonic acid ester forming derivatives are
It may be appropriately selected depending on the use of the polycarbonate-based copolymer to be produced, but generally diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate or dinaphthyl carbonate. And the like, and further carbonic acid halides such as phosgene and bromophosgene are used, among which diphenyl carbonate and phosgene are preferable.

These 4,4'-dihydroxydiphenyl, general formula [IV]
The reaction of the bisphenol compound and the carbonate-forming derivative represented by is preferably carried out in the molten state in the presence of a known catalyst, and the reaction temperature is usually 180 ° C or higher, preferably 200 ° C or higher, more preferably 250 ° C. ~ 350
It is about ℃. The pressure of the reaction is arbitrary, but it is desirable to reduce the pressure as the reaction proceeds.

[Effect of the Invention] The thus obtained polycarbonate-based copolymer of the present invention has good transparency and excellent heat resistance. Furthermore, it has good chemical resistance and mechanical strength.
Therefore, the polycarbonate copolymer of the present invention can be widely and effectively utilized as a material for various industrial devices, and is particularly useful as a material for optical devices.

[Examples] Next, the present invention will be described in detail with reference to Examples.

Example 1 In a reactor with an internal volume of 1 equipped with a baffle, 12.2 g (0.075 mol) of 4,4'-dihydroxydiphenyl and 39.9 g (0.175 mol) of 2,2-bis (4'-hydroxyphenyl) propane were added. Of phosgene gas at a rate of 900 ml / min while adding 250 ml of methylene chloride and stirring vigorously.
Blown for a minute. Then, the obtained reaction product was separated by standing to obtain a methylene chloride solution of a polycarbonate precursor having a degree of polymerization of 2 to 3 in the organic layer and having a chloroformate group in the molecule.

Next, a methylene chloride solution of this polycarbonate precursor
300 ml was further diluted with methylene chloride to a total of 450 ml. After adding 2.0 g of p-tert-butylphenol as a molecular weight regulator to this, 4.6 g of 4,4'-dihydroxydiphenyl and 2,2-bis (4'-hydroxyphenyl) propane 15.3 were added to a 2N aqueous sodium hydroxide solution. A solution in which g was dissolved was added and mixed. 1 ml of a 5% by weight aqueous solution of triethylamine as a polymerization catalyst while stirring this mixed solution.
Was added and the polycondensation reaction was carried out at 28 ° C. for 1 hour. After completion of the reaction, the product was diluted with methylene chloride 1 and washed successively with 1.5 l of switching, 0.5 l of water and 0.5 l of 0.01N hydrochloric acid. The organic layer thus obtained was poured into 2 l of methanol to obtain a white copolymer.

The copolymer obtained here uses methylene chloride as a solvent.
Reduced viscosity of 0.5g / dl concentration solution at 20 ℃ [η _sp / c]
Was 0.58 dl / g. The position is based on the benzene ring absorption results 1580 cm ^-1 and 1490cm ^-1 in the infrared absorption spectrum analysis of this copolymer, the absorption based on the carbonyl group at the position of 1650 cm ^-1, the ether bond at the position of 1240 cm ^-1 Based on absorption. As a result of nuclear magnetic resonance spectrum analysis, the mole fraction of the repeating unit [I] was 30%.

The thermal properties of this copolymer have a glass transition temperature of 16
It was 0 ° C. The transparency was 90% when the total light transmittance was measured according to JIS-K-6719. The results are summarized in Table 1.

Example 2 The amount of 4,4'-dihydroxydiphenyl used in the synthesis of the polycarbonate precursor was 9.3 g (0.05 mol), and the amount of 2,2-bis (4'-hydroxyphenyl) propane was 45.6 g.
A copolymer was obtained in the same manner as in Example 1 except that (0.2 mol) was used. The properties of this copolymer are shown in Table 1.

Example 3 The amount of 4,4'-dihydroxydiphenyl used in the synthesis of the polycarbonate precursor was 6.98 g (0.0375 mol), and the amount of 2,2-bis (4'-hydroxyphenyl) propane was 48.5 g.
A copolymer was obtained in the same manner as in Example 1 except that the amount was (0.2125 mol). The properties of this copolymer are shown in Table 1.

Example 4 The amount of 4,4'-dihydroxydiphenyl used in the synthesis of the polycarbonate precursor was 4.65 g (0.025 mol), and the amount of 2,2-bis (4'-hydroxyphenyl) propane was 51.3 g.
A copolymer was obtained in the same manner as in Example 1 except that the amount was (0.225 mol). The properties of this copolymer are shown in Table 1.

Comparative Example 1 A polycarbonate was obtained in the same manner as in Example 1 except that 4,4'-dihydroxydiphenyl was not used at all. The properties of this product are shown in Table 1.

Comparative Example 2 The amount of 4,4'-dihydroxydiphenyl used in the synthesis of the polycarbonate precursor was 23.25 g (0.125 mol), and the amount of 2,2-bis (4'-hydroxyphenyl) propane was 28.5 g.
A copolymer was obtained in the same manner as in Example 1 except that the amount was (0.125 mol). The properties of this copolymer are shown in Table 1.

Claims (4)

[Claims] 1. A formula The repeating unit [I] represented by [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R ³ and R ⁴ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group. Show. ] The repeating unit [II] represented by the formula [1], the molar ratio of the repeating unit [I] is 5% or more and less than 40%, and a solution of methylene chloride as a solvent at a concentration of 0.5 g / dl at 20 ° C. A polycarbonate-based copolymer having a reduced viscosity [η _sp / c] of 0.3 dl / g or more. 2. A formula 4,4'-dihydroxydiphenyl represented by [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and R ³ and R ⁴ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an aryl group. Show. ] The bisphenol compound and the carbonic acid ester forming derivative represented by The repeating unit [I] represented by [In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as described above. ] The repeating unit [II] represented by the formula [1], the molar ratio of the repeating unit [I] is 5% or more and less than 40%, and a solution of methylene chloride as a solvent at a concentration of 0.5 g / dl at 20 ° C. The method for producing a polycarbonate-based copolymer having a reduced viscosity [η _sp / c] of 0.3 dl / g or more. 3. A 4,4'-dihydroxydiphenyl and a bisphenol compound are added in a ratio of the former / the latter = 5/95 to 40/60 (molar ratio), and the carbonic acid ester-forming derivative is added to the 4,4'-dihydroxy compound. The production method according to claim 2, wherein the reaction is carried out by adding the diphenyl and the bisphenol compound in a total molar number or more. 4. The carbonic acid ester-forming derivative is diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate, phosgene or bromophosgene. The manufacturing method according to item 2.