JPH06234838A - New polycarbonate and its production - Google Patents

Abstract

PURPOSE:To obtain a new polycarbonate useful as a molding material, etc., having excellent compatibility, solvent selectivity, heat resistance, mechanical strength, etc., by reacting a specific dihydric phenol, etc., with a carbonic acid ester-forming compound. CONSTITUTION:A dihydric phenol of formula I [R1 to R8 are H, halogen, alkoxy, (substituted) alkyl, alkenyl or aryl; one of R9 and R10 is a benzidine of formula II (R11 and R13 are alkyl, alkenyl, etc.; R12 and R14 are alkyl, aryl, etc.) and the other is H, alkyl, aryl, etc.; R9 and R10 are benzidine of formula II] or the dihydric phenol and a dihydric phenol of formula III [R15 to R22 are H, halogen, (substituted) alkyl, etc.; X is S, SO2, 0, etc.] are reacted with a carbonic acid ester-forming compound such as phosgene to give the objective polymer comprising a repeating unit of formula IV or repeating units of formula IV and formula V, having the composition of the repeating unit of formula IV of 0<formula IV/(formula IV+formula IV, <=1 by molar ratio.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polycarbonate polymer and a method for producing the same. INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a novel polycarbonate polymer having a benzidine structure in a side chain in a repeating unit, and is useful as a plastic molding material or a polymer alloy material.

[0002]

2. Description of the Prior Art Most of polycarbonate resins currently produced are 2,2-bis (4-hydroxyphenyl).
It is a bisphenol A type polycarbonate made from propane (bisphenol A). Bisphenol A-type polycarbonate is a polycarbonate resin with well-balanced cost, heat resistance, mechanical strength, etc., but with the expansion of applications of polycarbonate in recent years, polycarbonates with more excellent physical properties are desired, and various structures are required. Polycarbonates that have been developed (for example, JP-A-63-108023, JP-A-64-66236, JP-A-4-11627, etc.). However, there is a strong demand from the market for polycarbonates having physical properties superior to those or having specific physical properties, and development of new polycarbonates is required.

[0003]

Accordingly, the present invention provides a polycarbonate polymer having more excellent physical properties or specific physical properties as compared with conventional polycarbonate polymers.

[0004]

As a result of intensive studies to solve the conventional problems, the inventors of the present invention have found that a polycarbonate polymer having a benzidine structure as a side chain in a repeating unit is a novel one not described in the literature. It was found that polycarbonate is useful as various molding materials and raw materials for polymer alloys, and the present invention has been completed based on this finding. (Below margin)

That is, the present invention is represented by the following general formula (A)

[0006]

[Chemical 7]

(In the formula, R _{1 to} R _{8 each} represent hydrogen, halogen, an alkoxy group, or an alkyl group, an alkenyl group, or an aryl group which may have a substituent. At least one of R ₉ and R ₁₀ is A group containing a benzidine represented by the following general formula (B), one of the remaining is hydrogen, and an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent,
Alternatively, both R ₉ and R ₁₀ represent a group containing benzidine represented by the following general formula (B). ) General formula (B)

[0008]

[Chemical 8]

(Where R is₁₁And R₁₃Are the substituents
May have an alkyl group, alkenyl group, or ar
R represents a Coxy group₁₂And R₁₄Each has a substituent
Optionally an alkyl group, an alkenyl group, an alkoxy group, or
Or an aryl group. In this, R₁₁~ R₁₄Out
The gap becomes a divalent group, and-(CH₂) A-in combination with R
₉Or R_TenForm a group. a represents the integer of 0-5. )
A repeating unit (A) having a benzidine structure represented by
And the following general formula (C)

[0010]

[Chemical 9]

(In the formula, R _{15 to} R ₂₂ each represent hydrogen, halogen, or an alkyl group or aryl group which may have a substituent. X represents

[0012]

[Chemical 10]

Wherein R ₂₃ and R ₂₄ each represent hydrogen, halogen, an alkyl group or an aryl group which may have a substituent, or R ₂₃ and R ₂₄ are bonded together,
Represents a group forming a carbocycle or a heterocycle, b is 0 to 20,
c represents an integer of 0 to 2000. ), The composition of the repeating unit represented by the formula (A) is 0 <(A) /
The present invention provides a polycarbonate polymer having ((A) + (C)) ≦ 1 and a method for producing the same.

The polycarbonate polymer having a benzidine structure represented by the above-mentioned general formula (A) or the copolymer of the general formula (A) and the general formula (C) of the present invention has the following general formula (D).

[0015]

[Chemical 11]

(Wherein R _{1 to} R ₁₀ have the same meanings as in formula (A) above) or the divalent phenol (D) and the following general formula (E).

[0017]

[Chemical 12]

(Wherein each of R _{15 to} R ₂₂ and X has the same meaning as in the above formula (A)), a dihydric phenol (E) is reacted with a carbonic acid ester forming compound. It can be manufactured.

The dihydric phenol represented by the general formula (D) is one in which at least one of R ₉ and R ₁₀ has a benzidine structure represented by the general formula (B). in compounds as exemplified below, has a benzidine _{structure, - (CH 2) a -} , a (a is an integer from 0 to 5) bonded to the alkylene group represented by, R ₉ or R ₁₀ Form. However, it is not limited to these compounds.

[0020]

[Chemical 13]

Specific examples of the dihydric phenol represented by the general formula (E) include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (44hydroxyphenyl) propane (bisphenol A; BPA), 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α,
ω-bis [3- (O-hydroxyphenyl) propyl]
Examples include polydimethylsiloxane and bisphenol.

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

The dihydric phenol represented by the general formula (D) can be prepared by a known method using phenols and ketones or aldehydes having a benzidine structure, for example, 3 to 30 per 1 mol of ketones or aldehydes. It can be easily produced by adding a molar excess of phenols and reacting under an acid catalyst such as hydrogen chloride.

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

In the former phosgene method, the dihydric phenol represented by the general formula (D) or the general formula (D) is usually reacted with phosgene in the presence of an acid binder and a solvent. Let Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used, and in order to control the degree of polymerization, a molecular weight control such as phenol or pt-butylphenol is performed. It is desirable to add the agent to carry out the reaction. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually 0 to 150 ° C., preferably 5 to 4
The range of 0 ° C is suitable. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction, the reaction system
It is desirable to keep the pH above 10.

On the other hand, in the latter transesterification method, the dihydric phenol represented by the general formula (D) or the general formula (D) and the bisaryl carbonate are mixed, and the mixture is heated under reduced pressure at a high temperature. React at. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of reduced pressure is finally set to preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction. Is removed from 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. Further, if desired, the molecular weight regulator,
The reaction may be carried out by adding an antioxidant or a branching agent.

[0027]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

[0028]

【Example】

Example 1 In 580 ml of 8.8% (w / v) sodium hydroxide aqueous solution, Table-1
197.6 g of a dihydric phenol having a benzidine structure represented by the structural formula (1) and 0.1 g of hydrosulfite were added and dissolved. To this, 360 ml of methylene chloride was added, and pt-butylphenol (PTBP) was added while stirring at 15 ° C.
2.0 g was added and then 51 g phosgene was introduced over 60 minutes. After completion of the introduction, vigorously stir to emulsify the reaction solution,
After the emulsification, 0.2 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing solution was repeatedly washed with water until the pH became neutral. Then, 470 ml of isopropanol was added to precipitate the polymer. Let The precipitate was filtered and dried to obtain a powdery polymer. This polymer has a concentration of 0.5 g in methylene chloride.
/ Dl solution has a limiting viscosity [η] of 0.47dl at 20 ℃
It was / g.

The above-obtained polymer was analyzed by infrared absorption spectrum. As a result, absorption by a carbonyl group at a position of 1650 cm-1 and absorption by an ether bond at a position of 1240 cm-1 were confirmed, and it was confirmed that the polymer had a carbonate bond. Was done. In addition, almost no absorption derived from hydroxyl groups was observed at the position of 3650 to 3200 cm-1. Therefore, this polymer was recognized as a polycarbonate polymer composed of the repeating units shown in Table 1.

Example 2 In place of the dihydric phenol represented by the structural formula (1), 236 g of the dihydric phenol represented by the structural formula (2) shown in Table 1 was used.
The same procedure as in Example 1 was performed. The intrinsic viscosity [η] of the obtained polymer was 0.47 dl / g, and it was confirmed by infrared absorption spectrum analysis that this polymer was a polycarbonate polymer having the repeating unit shown in Table 1.

Example 3 Instead of the dihydric phenol of structural formula (1), 98.8 g of dihydric phenol of structural formula (1) and bisphenol A45.6
Example 1 was repeated except that g was used. The intrinsic viscosity [η] of the obtained polymer was 0.46 dl / g, and it was confirmed by infrared absorption spectrum analysis that this polymer was a polycarbonate polymer having the repeating unit shown in Table 1.

[0033]

[Table 1]

[0034]

INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a polymer having a benzidine structure in a side chain in a repeating unit, and can provide a novel polycarbonate used for various molding materials and polymer alloy raw materials. The polycarbonate polymer of the present invention is expected to be improved in compatibility with other polymers and solvent selectivity due to, for example, a change in solubility parameter.

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[Procedure amendment]

[Submission date] February 4, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction content]

[Document name] Statement

Title: Novel polycarbonate polymer and method for producing the same

[Claims]

[Chemical 1] (In the formula, R _{1 to} R ₈ represent hydrogen, a halogen, an alkoxy group, and an alkyl group, an alkenyl group or an aryl group which may each have a substituent. At least one of R ₉ and R ₁₀ has the following general formula ( B) a group containing benzidine, one of which is hydrogen, an alkyl group, an alkenyl group or an aryl group which may have a substituent, or R ₉ or R ₁₀
Both of these represent a group containing benzidine represented by the following general formula (B). ) General formula (B)

[Chemical 2](In the formula, R₁₁And R₁₃May each have a substituent.
Represents an alkyl group, an alkenyl group, or an alkoxy group.
And R₁₂And R₁₄Are each optionally substituted
Kill group, alkenyl group, alkoxy group, or aryl
Indicates a group. In this, R₁₁~ R₁₄One of them is bivalent
Base,-(CH₂) A-in combination with R ₉Or R_Ten
Form a group. a represents the integer of 0-5. )

[Chemical 3] (In the formula, R _{15 to} R ₂₂ each represent hydrogen, halogen, or an alkyl group or aryl group which may have a substituent.
X represents the following.

[Chemical 4] Here, R ₂₃ and R ₂₄ each represent hydrogen, halogen, an alkyl group or an aryl group which may have a substituent, or
R ₂₃ and R ₂₄ represent a group which is bonded together to form a carbocycle or a heterocycle, b represents 0 to 20 and c represents an integer of 0 to 2000. )

[Chemical 5] (In the formula, each of R _{1 to} R ₁₀ has the same meaning as in the formula (A).)

[Chemical 6] (In the formula, each of R _{15 to} R ₂₂ and X has the same meaning as in the formula (A).)

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polycarbonate polymer and a method for producing the same. INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a novel polycarbonate polymer having a benzidine structure in a side chain in a repeating unit, and is useful as a plastic molding material or a polymer alloy material.

[0002]

2. Description of the Prior Art Most of polycarbonate resins currently produced are 2,2-bis (4-hydroxyphenyl).
It is a bisphenol A type polycarbonate made from propane (bisphenol A). Bisphenol A-type polycarbonate is a polycarbonate resin with well-balanced cost, heat resistance, mechanical strength, etc., but with the expansion of applications of polycarbonate in recent years, polycarbonates with more excellent physical properties are desired, and various structures are required. Polycarbonates that have been developed (for example, JP-A-63-108023, JP-A-64-66236, JP-A-4-11627, etc.). However, there is a strong demand from the market for polycarbonates having physical properties superior to those or having specific physical properties, and development of new polycarbonates is required.

[0003]

Accordingly, the present invention provides a polycarbonate polymer having more excellent physical properties or specific physical properties as compared with conventional polycarbonate polymers.

[0004]

As a result of intensive studies to solve the conventional problems, the inventors of the present invention have found that a polycarbonate polymer having a benzidine structure as a side chain in a repeating unit is a novel one not described in the literature. It was found that polycarbonate is useful as various molding materials and raw materials for polymer alloys, and the present invention has been completed based on this finding.

That is, the present invention is a repeating unit (A) having a benzidine structure represented by the following general formula (A) or a polymer comprising (A) and a repeating unit represented by the following general formula (C). And the composition of the repeating unit represented by the formula (A) is 0 <(A) / ((A) + (C)) ≦ in molar ratio.
And a method for producing the same.

[0006]

[Chemical 7]

(In the formula, R _{1 to} R _{8 each} represent hydrogen, halogen, an alkoxy group, or an alkyl group, an alkenyl group, or an aryl group which may have a substituent. At least one of R ₉ and R ₁₀ is A group containing a benzidine represented by the following general formula (B), one of the remaining is hydrogen, and an alkyl group, an alkenyl group, or an aryl group, each of which may have a substituent,
Alternatively, both R ₉ and R ₁₀ represent a group containing benzidine represented by the following general formula (B). ) General formula (B)

[0008]

[Chemical 8]

(Where R is₁₁And R₁₃Are the substituents
May have an alkyl group, alkenyl group, or ar
R represents a Coxy group₁₂And R₁₄Each has a substituent
Optionally an alkyl group, an alkenyl group, an alkoxy group, or
Or an aryl group. In this, R₁₁~ R₁₄Out
The gap becomes a divalent group, and-(CH₂) A-in combination with R
₉Or R_TenForm a group. a represents the integer of 0-5. )

[0010]

[Chemical 9]

(In the formula, R _{15 to} R ₂₂ each represent hydrogen, halogen, or an alkyl group or aryl group which may have a substituent. X represents the following.

[0012]

[Chemical 10]

Here, R ₂₃ and R ₂₄ each represent hydrogen, halogen, an alkyl group or an aryl group which may have a substituent, or R ₂₃ and R ₂₄ are bonded together to form a carbocycle or a heterocycle. Represents a group forming a ring, b is 0 to 20, c is 0 to 2
Represents an integer of 000. )

The polycarbonate polymer having a benzidine structure represented by the general formula (A) or the copolymer of the general formula (A) and the general formula (C) of the present invention is represented by the following general formula (D). A dihydric phenol with a carbonic acid ester-forming compound, or the dihydric phenol (D)
And a dihydric phenol represented by the following general formula (E) can be reacted with a carbonic acid ester forming compound.

[0015]

[Chemical 11]

(In the formula, each of R _{1 to} R ₁₀ has the same meaning as in the formula (A).)

[0017]

[Chemical 12]

(In the formula, R _{15 to} R ₂₂ and X respectively have the same meanings as in the formula (A)).

The dihydric phenol represented by the general formula (D) is one in which at least one of R ₉ and R ₁₀ has a benzidine structure represented by the general formula (B). in compounds as exemplified below, has a benzidine _{structure, - (CH 2) a -} , a (a is an integer from 0 to 5) bonded to the alkylene group represented by, R ₉ or R ₁₀ Form. However, it is not limited to these compounds.

[0020]

[Chemical 13]

Specific examples of the dihydric phenol represented by the general formula (E) include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfoxide, bis (4-
Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (44hydroxyphenyl) propane (bisphenol A; BPA), 2,2 -Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ
), 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3) -
Bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-
Hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α,
ω-bis [3- (O-hydroxyphenyl) propyl]
Examples include polydimethylsiloxane and biphenol.

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

The dihydric phenol represented by the general formula (D) can be prepared by a known method using phenols and ketones or aldehydes having a benzidine structure, for example, 3 to 30 per 1 mol of ketones or aldehydes. It can be easily produced by adding a molar excess of phenols and reacting under an acid catalyst such as hydrogen chloride.

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

In the former phosgene method, the dihydric phenol represented by the general formula (D) or the general formula (D) is usually reacted with phosgene in the presence of an acid binder and a solvent. Let Examples of the acid binder include pyridine and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used, and in order to control the degree of polymerization, a molecular weight control such as phenol or pt-butylphenol is performed. It is desirable to add the agent to carry out the reaction. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfite or a branching agent such as phloroglucin or isatin bisphenol may be added. The reaction is usually 0 to 150 ° C., preferably 5 to 4
The range of 0 ° C is suitable. The reaction time depends on the reaction temperature, but is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours. During the reaction, the reaction system
It is desirable to keep the pH above 10.

On the other hand, in the latter transesterification method, the dihydric phenol represented by the general formula (D) or the general formula (D) and the bisaryl carbonate are mixed, and the mixture is heated under reduced pressure at a high temperature. React at. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of reduced pressure is finally set to preferably 1 mmHg or less, and phenols derived from the bisaryl carbonate produced by the transesterification reaction. Is removed from 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. Further, if desired, the molecular weight regulator,
The reaction may be carried out by adding an antioxidant or a branching agent.

[0027]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

[0028]

Example 1 In 580 ml of 8.8% (w / v) aqueous sodium hydroxide solution, Table 1
197.6 g of a dihydric phenol having a benzidine structure represented by the structural formula (1) and 0.1 g of hydrosulfite were added and dissolved. To this, 360 ml of methylene chloride was added, and pt-butylphenol (PTBP) was added while stirring at 15 ° C.
2.0 g was added and then 51 g phosgene was introduced over 60 minutes. After completion of the introduction, vigorously stir to emulsify the reaction solution,
After the emulsification, 0.2 ml of triethylamine was added, and the mixture was stirred for about 1 hour for polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the washing solution was repeatedly washed with water until the pH became neutral. Then, 470 ml of isopropanol was added to precipitate the polymer. Let The precipitate was filtered and dried to obtain a powdery polymer. This polymer has a concentration of 0.5 g in methylene chloride.
/ Dl solution has a limiting viscosity [η] of 0.47dl at 20 ℃
It was / g.

The results of the obtained above polymer was analyzed from the infrared absorption spectrum, absorption by carbonyl group at the position of 1650 cm ^-1, observed absorption by an ether bond at the position of 1240 cm ^-1, confirmed to have a carbonate bond Was done. In addition, almost no absorption derived from hydroxyl groups was observed at the position of 3650 to 3200 cm ^-1 . Therefore, this polymer was recognized as a polycarbonate polymer composed of the repeating units shown in Table 1.

Example 2 In place of the dihydric phenol represented by the structural formula (1), 236 g of the dihydric phenol represented by the structural formula (2) shown in Table 1 was used.
The same procedure as in Example 1 was performed. The intrinsic viscosity [η] of the obtained polymer was 0.47 dl / g, and it was confirmed by infrared absorption spectrum analysis that this polymer was a polycarbonate polymer having the repeating unit shown in Table 1.

Example 3 Instead of the dihydric phenol of structural formula (1), 98.8 g of dihydric phenol of structural formula (1) and bisphenol A45.6
Example 1 was repeated except that g was used. The intrinsic viscosity [η] of the obtained polymer was 0.46 dl / g, and it was confirmed by infrared absorption spectrum analysis that this polymer was a polycarbonate polymer having the repeating unit shown in Table 1. (Below margin)

[0033]

[Table 1]

Example 4 Example 4 was repeated except that 241.6 g of the dihydric phenol represented by the following structural formula (3) was used in place of the dihydric phenol represented by the structural formula (1).

[0035]

[Chemical 14]

The polymer obtained has an intrinsic viscosity [η] of 0.4.
At 7 dl / g, this polymer was confirmed to be a polycarbonate polymer having the following repeating unit by infrared absorption spectrum analysis.

[0037]

[Chemical 15]

[0038]

INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a polymer having a benzidine structure in a side chain in a repeating unit, and can provide a novel polycarbonate used for various molding materials and polymer alloy raw materials. The polycarbonate polymer of the present invention is expected to be improved in compatibility with other polymers and solvent selectivity due to, for example, a change in solubility parameter.

Claims (2)

[Claims] 1. The following general formula (A):(In the formula, R₁~ R₈Is hydrogen, halogen, alkoxy group, it
An alkyl group and an alkenyl group, each of which may have a substituent,
Or an aryl group. R₉, R_TenAt least one is down
A group containing benzidine represented by the general formula (B), the rest being
One of which is hydrogen, and an alkyl each optionally having a substituent
Group, alkenyl group, or aryl group, or R₉, R_Ten
Both of which are both represented by the following general formula (B): benzidine
A group containing is shown. ) General formula (B):(In the formula, R₁₁And R₁₃May each have a substituent.
Represents an alkyl group, an alkenyl group, or an alkoxy group.
And R₁₂And R₁₄Are each optionally substituted
Kill group, alkenyl group, alkoxy group, or aryl
Indicates a group. In this, R₁₁~ R₁₄One of them is bivalent
Base,-(CH₂) A-in combination with R ₉Or R_Ten
Form a group. a represents the integer of 0-5. )
A repeating unit (A) having a benzidine structure and one of the following
General formula (C)(In the formula, R₁₅~ R_{twenty two}Is hydrogen, halogen, respectively substituted
An alkyl group or an aryl group which may have a group is shown.
X isAnd here R_{twenty three}, R_{twenty four}Is hydrogen, halogen, each
An alkyl group or aryl group which may have a substituent
Represents or R_{twenty three}And R_{twenty four}Are bound together to form a carbocycle or
Represents a group forming a heterocycle, b is 0 to 20, c is 0 to 2000
Represents the integer. ) Selected from repeating units (C)
A repeating unit composed of repeating units represented by formula (A)
The composition of the return unit is 0 <(A) / ((A) +
(C)) ≦ 1 polycarbonate polymer. (Below margin) 2. The following general formula (D): (In the formula, R _{1 to} R ₁₀ each have the same meaning as in the above formula (A).) Or a divalent phenol (D) and the following general formula (E): ] (In the formula, R _{15 to} R ₂₂ and X each have the same meaning as in the formula (A).) The dihydric phenol (E) is reacted with a carbonic acid ester forming compound. A method for producing a polycarbonate polymer, characterized in that the polycarbonate polymer described above is obtained.