JP2520098B2 - 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 a specific repeating unit, heat resistance,
The present invention relates to a polycarbonate-based copolymer having excellent mechanical strength and optical properties, and a method for efficiently producing the same.

[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. Therefore, 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 new polycarbonate-based copolymers with even better performance have been demanded.

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

[Means for Solving Problems] As a result, it was found that a polycarbonate-based copolymer having a specific repeating unit and a reduced viscosity of a certain value or more has various desired physical properties. The present invention has been completed.

That is, the present invention relates to the general formula [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, respectively. . ] The repeating unit [I] represented by [Wherein R ⁴ and R ⁵ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, respectively, and r, s
Each represents an integer of 1 or 2. Z is a direct bond, alkylidene having 1 to 11 carbon atoms, phenylalkylidene having 7 to 12 carbon atoms, diphenylmethylidene, and 5 carbon atoms.
9 cycloalkylidene, alkylene having 2 to 10 carbon atoms,
Indicates SO ₂ , SO, O, S or CO. ] And a reduced viscosity [η _sp / c] at 20 ° C of a solution of 0.5 g / dl in methylene chloride as a solvent is 0.2 dl / g or more. The present invention provides a polycarbonate copolymer. Further, the present invention has the general formula [Wherein R ¹ , R ² and R ³ are the same as above. ] Biphenylyl group-containing dihydric phenol represented by the general formula [In the formula, R ⁴ , R ⁵ , Z and r, s are the same as above. ] A method for producing the above-mentioned polycarbonate-based copolymer is provided by reacting a dihydric phenol represented by the following formula with a carbonic acid ester-forming derivative.

The polycarbonate-based copolymer of the present invention has the repeating unit [I] represented by the general formula [A] and the repeating unit [II] represented by the general formula [B]. The mole fraction of the repeating units [I] and [II] is not particularly limited, and varies depending on the type and purpose of use of the copolymer and cannot be uniquely determined. When the mole fraction is m and the mole fraction of the repeating unit [II] is n, The value of is 0.01 to 0.99, preferably 0.05 to 0.95.

Further, regarding the polymerization degree of the polycarbonate-based copolymer of the present invention, the reduced viscosity [η _sp / c] at 20 ° C of a solution having a concentration of 0.5 g / dl using methylene chloride as a solvent is 0.2 dl / g or more, preferably The range is 0.3 to 0.8 dl / g. Here, when the reduced viscosity [η _sp / c] is less than 0.2 dl / g, the resulting copolymer has low mechanical strength.

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

The repeating unit [I] in the polycarbonate-based copolymer of the present invention is various depending on the type and position of R ^{1 to} R ^{3 in} the general formula [A]. If you show the structure of a specific repeating unit, And so on.

On the other hand, the repeating unit [II] in the polycarbonate-based copolymer of the present invention is represented by the general formula [B] as described above, and the types and positions of R ⁴ , R ^{5 and} the types of Z in the formula are Alternatively, there are various types depending on the numbers of r and s. If you show the structure of a typical repeating unit [II], , Etc., but the repeating unit [I] corresponding to the specific example of the dihydric phenol represented by the general formula [B '] described later
I] can also be given.

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

In the method of the present invention, a biphenylyl group-containing dihydric phenol represented by the general formula [A '], a dihydric phenol represented by the general formula [B'] and a carbonic acid ester-forming derivative are introduced into a reaction system and reacted. Let Here, the introduction amount of the carbonic acid ester forming derivative may be equal to or more than the total amount of the biphenylyl group-containing dihydric phenol of the general formula [A ′] and the dihydric phenol of the general formula [B ′]. desirable. The introduction ratio of the biphenylyl group-containing dihydric phenol of the general formula [A '] and the dihydric phenol of the general formula [B'] is not particularly limited, but usually the former: the latter = 1:99 to 99: 1. (Molar ratio) is preferable.

In order to obtain a polycarbonate-based copolymer having a high refractive index, it is preferable to increase the proportion of the biphenylyl group-containing dihydric phenol. For example, the biphenylyl group-containing dihydric phenol of the general formula [A ']: the general formula [B '] Dihydric phenol = 50:50 to 95: 5 (molar ratio).

The type of biphenylyl group-containing dihydric phenol represented by the general formula [A ′] used in the method of the present invention is as follows.
Although it varies depending on R ¹ , R ² and R ³ , it may correspond to the repeating unit [I] represented by the general formula [A] in the polycarbonate copolymer to be produced. The biphenylyl group-containing dihydric phenol can be produced by various methods. [Wherein R ¹ is the same as above. ] An acylbiphenyl represented by the formula (eg, acetylbiphenyl, benzoylbiphenyl (4-phenylbenzophenone), formylbiphenyl, propionylbiphenyl, etc.) and a general formula [In the formula, R ² and R ³ are the same as above. ] The phenol or substituted phenol represented by the above formula is obtained by reacting in the presence of a condensing agent such as hydrochloric acid, phosphorus pentachloride, sulfuric acid and polyphosphoric acid.

On the other hand, regarding the type of the dihydric phenol represented by the general formula [B ′] used in the method of the present invention, R ⁴ , R ⁵ ,
It varies depending on Z, r, and s, and may correspond to the repeating unit [II] represented by the general formula [B] in the polycarbonate-based copolymer to be produced. Specific compounds include:
Bis (4-hydroxyphenyl) alkanes such as 2,2-bis (4'-hydroxyphenyl) propane (bisphenol A) and 2,2-bis (4'-hydroxyphenyl) butane, 1,1-bis (4 ') -Hydroxyphenyl) -1-
Bis (4-hydroxyphenyl) such as phenylethane
Bis (4-hydroxyphenyl) cycloalkanes such as phenylalkane, 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4'-hydroxyphenyl) cyclohexane and further bis ( 4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-vidoxyphenyl) ether, bis (4-hydroxyphenyl) thioether, bis (4-hydroxyphenyl) ketone , 4,4′−
Dihydroxydiphenyl, other bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-
Examples thereof include halogenated bisphenols such as dichloro-4-hydroxyphenyl) propane.

There are various carbonic acid ester-forming derivatives used in the method of the present invention, but in general, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate or dinaphthyl. Diaryl carbonates such as carbonates, and carbonic acid halides such as phosgene and bromophosgene are used. Of these, diphenyl carbonate or phosgene is preferable.

The conditions for the reaction (polycondensation reaction) of the biphenylyl group-containing dihydric phenol of the general formula [A '], the dihydric phenol of the general formula [B'] and the carbonic acid ester-forming derivative are selected according to the kind of the compound used and the desired compound. Although it depends on the degree of polymerization of the polymer and cannot be uniquely determined, it is usually a suitable catalyst in a solvent such as a halogenated hydrocarbon such as methylene chloride or chlorobenzene or pyridine, preferably in a methylene chloride solvent. , An alkali, a molecular weight modifier, etc. may be used. Here, various monohydric phenols can be used as the molecular weight modifier, and preferred examples include phenol, tert-butylphenol, phenylphenol, cumylphenol and the like.

In the method of the present invention, the biphenylyl group-containing dihydric phenol represented by the general formula [A ′] and the divalent phenol represented by the general formula [B ′] may be reacted with the carbonate-forming derivative as monomers. In addition, one of the above dihydric phenols may first be reacted with a carbonic acid ester-forming derivative to form an oligomer, and this oligomer may be reacted with the remaining dihydric phenol monomer. The oligomer may be reacted with the forming derivative to form an oligomer, and the oligomers may be reacted with each other.

[Effects of the Invention] The polycarbonate-based copolymer of the present invention thus obtained is characterized by excellent transparency and various optical properties, and particularly a high refractive index.

Therefore, the polycarbonate-based copolymer of the present invention can be widely and effectively utilized as various industrial device elements, is particularly useful as a material for optical devices, and has a particularly high refractive index, which plays an important role in downsizing of optical devices. Expected to perform.

[Examples] Next, examples of the present invention will be described in more detail.

Example 1 (1) Synthesis of biphenylyl group-containing dihydric phenol 50 g (0.26 mol) of acetylbiphenyl and 75 g (0.8 mol) of phenol were mixed, heated to 60 ° C. and dissolved, and then 5 g of mercaptoacetic acid was added. Hydrochloric acid gas was blown into the mixture for 24 hours with stirring, and the mixture was reacted for 72 hours. Next, the reaction solution was washed several times with hot water at 70 ° C., and the organic phase was heated to 180 ° C. under reduced pressure (14 mmHg) to evaporate the evaporated material. The residue was dissolved in 250 ml of xylene, cooled to precipitate crystals, and then recrystallized using a methanol-xylene mixed solution to give 65
g of dihydric phenol was obtained. This product has a melting point of 184-185.
C., and the purity was 99.1%. In addition, from the analysis by proton nuclear magnetic resonance (H-NMR), 1- having the following structural formula
It was confirmed to be (4-biphenyl) -1,1-bis (4-hydroxyphenyl) ethane.

(2) Production of copolymer In a flask having an internal volume of 1, a solution prepared by dissolving 70 g (0.307 mol) of 2,2-bis (4'-hydroxyphenyl) propane in 480 ml of a 6% sodium hydroxide aqueous solution, Add 250 ml of methylene chloride and 900 ml of phosgene gas under stirring.
Blow for 14 minutes at a supply rate of / min. Then, the product was separated by standing to obtain a methylene chloride solution of a polycarbonate oligomer having a chloroformate group terminal and a polymerization degree of 2 to 3 in the organic layer.

Then 150 ml of the resulting solution was diluted with methylene chloride to 2 ml.
It was diluted to 25 ml and 1.0 g of p-tert-butylphenol was dissolved as a molecular weight regulator. Next, (1) above
1- (4-biphenyl) -1,1-bis (4-
A solution prepared by dissolving 14.0 g of hydroxyphenyl) ethane in 70 ml of a 2N aqueous sodium hydroxide solution was added, and 0.5 ml of a 5% aqueous solution of triethylamine was added as a catalyst, and then 2.7 ml of a 12N aqueous sodium hydroxide solution was added. Then, the reaction was carried out for 1 hour with stirring. After completion of the reaction, the obtained product was diluted with 500 ml of methylene chloride, washed with water, 0.01N aqueous sodium hydroxide solution, water, 0.01N hydrochloric acid, and water in this order, poured into 3 L of methanol, and mixed with The polymer was collected by precipitation.

This copolymer is 0.5 g / dl in methylene chloride as solvent.
The reduced viscosity [η _sp / c] of the concentrated solution at 20 ℃ is 0.48dl
It was / g. Also, 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, to have a carbonate bond was observed. Furthermore, 1 H-NMR spectrum analysis revealed that the repeating unit [I] of the formula [A] had a mole fraction of 21%. From these, it was confirmed that this copolymer had the following structural formula.

The refractive index of this polycarbonate copolymer at 20 ° C. was 1.5931.

Example 2 The same procedure was performed as in (2) of Example 1 except that the amount of 1- (4-biphenyl) -1,1-bis (4-hydroxyphenyl) ethane used was 7.0 g. The reduced viscosity [η _sp / c] of the obtained copolymer was 0.42 dl / g, and the molar fraction of the repeating unit [I] of the above formula [A] was 12% from the 1 H-NMR spectrum analysis.
Met. The refractive index of this product at 20 ° C is 1.59.
It was 15.

Example 3 (1) Synthesis of biphenylyl group-containing dihydric phenol 4-phenylbenzophenone and phenol are condensed using phosphorus pentachloride as a condensing agent to give 1- (4-biphenyl) -1-phenyl-1,1. -Bis (4-hydroxyphenyl) methane was synthesized. It had the following structural formula and had a melting point of 118 to 120 ° C. and a purity of 96.3%.

(2) Production of copolymer 1- (4) obtained in (1) above in place of 1- (4-biphenyl) -1,1-bis (4-hydroxyphenyl) ethane
-Biphenyl) -1-phenyl-1,1-bis (4-hydroxyphenyl) methane was used in the same manner as in (2) of Example 1 except that a copolymer consisting of the following repeating units was obtained. It was

The reduced viscosity [η _sp / c] of this copolymer is 0.45 dl / g,
The refractive index at 20 ° C. was 1.6015.

Reference Example 1 2,2-bis (4'-hydroxyphenyl) as a raw material
The refractive index at 20 ° C. of the polycarbonate (reduced viscosity 0.51 dl / g) obtained by the usual phosgene method using propane was 1.5850.

Claims (3)

(57) [Claims] 1. A general formula [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, respectively. . ] The repeating unit [I] represented by [In the formula, R ⁴ and R ⁵ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and r, s
Each represents an integer of 1 or 2. Z is a direct bond, alkylidene having 1 to 11 carbon atoms, phenylalkylidene having 7 to 12 carbon atoms, diphenylmethylidene, and 5 carbon atoms.
9 cycloalkylidene, alkylene having 2 to 10 carbon atoms, SO ₂ ,
Indicates SO, O, S or CO. ] And a reduced viscosity (η _sp / c) of a solution of 0.5 g / dl concentration in methylene chloride as a solvent at 20 ° C is 0.2 dl / g or more. And a polycarbonate-based copolymer. 2. General formula [In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and R ² and R ³ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, respectively. . ] A biphenylyl group-containing dihydric phenol represented by the general formula [In the formula, R ⁴ and R ⁵ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a phenyl group, and r, s
Each represents an integer of 1 or 2. Z is a direct bond, alkylidene having 1 to 11 carbon atoms, phenylalkylidene having 7 to 12 carbon atoms, diphenylmethylidene, and 5 carbon atoms.
9 cycloalkylidene, alkylene having 2 to 10 carbon atoms,
Indicates SO ₂ , SO, O, S or CO. ] A general formula characterized by reacting a dihydric phenol represented by [In the formula, R ¹ , R ² and R ³ are the same as above. ] The repeating unit [I] represented by [Wherein R ⁴ , R ⁵ , r, s and Z are the same as defined above. ] A polycarbonate-based polymer having a repeating unit [II] represented by and having a reduced viscosity [η _sp / c] of 0.2 dl / g or more at 20 ° C. in a solution of 0.5 g / dl in methylene chloride as a solvent. How to make a coalesce. 3. 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 method according to item 2.