JPH06293827A - New polycarbonate polymer and its production - Google Patents

Abstract

PURPOSE:To provide a new polycarbonate polymer containing triphenylamine structure in the recurring unit in the form of a side chain, having excellent compatibility to other polymers and solventselectivity and useful as a raw material for polymer alloy, etc. CONSTITUTION:This polymer is composed of (A) the recurring unit having triphenylamine structure and expressed by formula I [R1 to R8 are H, halogen, alkoxy, etc.; R9 and R10 are group containing triphenylamine and expressed by formula II (R11 to R16 are H, halogen, etc.) or the unit A and (B) the recurring unit of formula III (R17 to R24 are H, halogen, etc.; X is S, O, etc.). The molar ratio of the component A is selected to satisfy the formula 0<A/(A+B)<=1.

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. The polycarbonate polymer of the present invention is a novel polycarbonate polymer having a triphenylamine structure in a side chain in the 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 produced from propane (= bisphenol A). Bisphenol A
The type polycarbonate is a polycarbonate resin that is well balanced in terms of cost, heat resistance, mechanical strength, etc., but with the expanding applications of polycarbonate in recent years, polycarbonates with superior physical properties are desired, and polycarbonates with various structures Have been developed (for example, JP-A-63-108023, JP-A-64-66236, JP-A-4-11627). 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 present inventors have found that a polycarbonate polymer having a triphenylamine structure in a side chain in a repeating unit is a novel polycarbonate. However, they have found that they are useful as various molding materials and raw materials for polymer alloys, and have completed the present invention based on this finding.

That is, the present invention represents a repeating unit (A) having a triphenylamine structure represented by the following general formula (A), or a repeating unit represented by the formula (A) and the following general formula (C). A polycarbonate polymer having a repeating unit represented by formula (A) in a molar ratio of 0 <(A) / ((A) + (C)) ≦ 1 The manufacturing method is provided.

[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 as follows. A group containing a triphenylamine represented by the general formula (B), the other one is hydrogen, an alkyl group, an alkenyl group or an aryl group which may have a substituent, respectively, or both R ₉ and R ₁₀ are Both represent a group containing triphenylamine represented by the following general formula (B).) General formula (B)

[0008]

[Chemical 8]

(In the formula, R _{11 to} R ₁₆ are hydrogen, halogen, an alkyl group which may have a substituent, an alkoxy group, an alkenyl group or an aryl group, an arylamino group, an aryl-substituted alkenyl group, an aryl ether group. ,
An aminoaryl ether group, or a group in which R ₁₁ and R ₁₂ or R ₁₃ and R ₁₄ or R ₁₅ and R ₁₆ are combined to form a carbocycle or a heterocycle, and one of R _{11 to} R ₁₆ There will divalent radical, - (CH ₂₎ a - combines with to form a R ₉ or R ₁₀ groups. a represents the integer of 0-5. )

[0010]

[Chemical 9]

(In the formula, each of R _{17 to} R ₂₄ represents hydrogen, halogen or an alkyl group or aryl group which may have a substituent. X represents the following.

[0012]

[Chemical 10]

Here, R ₂₅ and R ₂₆ each represent hydrogen, halogen, an alkyl group which may have a substituent or an aryl group, or R ₂₅ and R ₂₆ 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
Represents an integer of 2000. )

The polycarbonate polymer having a triphenylamine 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). Or reacting the dihydric phenol represented by the formula with a carbonic acid ester forming compound, or reacting the dihydric phenol (D) and the dihydric phenol represented by the following general formula (E) with the carbonic acid ester forming compound. Can be manufactured by.

[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 _{17 to} R ₂₄ and X each have the same meaning 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 triphenylamine structure represented by the general formula (B). is a compound as illustrated below, has a triphenylamine _{structure, - (CH 2) a -} (a is an integer of up to 0-5) combined with an alkylene group represented by,
Form R ₉ or R ₁₀ . However, it is not limited to these compounds.

[0020]

[Chemical 13]

[0021]

[Chemical 14]

[0022]

[Chemical 15]

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 (4-hydroxyphenyl) propane (= bisphenol A; BPA), 2 , 2-bis (4-
Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (= bisphenol Z; BP
Z), 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 triphenylamine structure, for example,
It can be easily produced by adding an excess of 3 to 30 mol of phenols to 1 mol of ketones or aldehydes and reacting them under an acid catalyst such as hydrogen chloride.

The method for producing the polymer of the present invention is 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) and phosgene are usually reacted with each other in the presence of an acid binder and a solvent. Let As the acid binder, for example, pyridine or hydroxide of alkali metal such as sodium hydroxide or potassium hydroxide is used, and as the solvent, for example, methylene chloride, chloroform, chlorobenzene or xylene is used. Further, 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 heated at a high temperature under reduced pressure. 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 preferably 1 mmHg or less at the final stage of the reaction, and is derived from the bisaryl carbonate produced by the transesterification reaction. Phenols 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. Further, if desired, the reaction may be carried out by adding the above-mentioned molecular weight regulator, antioxidant or branching agent.

[0029]

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

Example 1 580 ml of 8.8% (w / v) sodium hydroxide aqueous solution was added to Table 1
188.4 g of a dihydric phenol having a triphenylamine 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, 2.0 g of pt-butylphenol (PTBP) was added with stirring at 15 ° C, and then 51 g of phosgene was introduced over 60 minutes. After completion of the introduction, the reaction solution was emulsified by vigorous stirring, 0.2 ml of triethylamine was added after emulsification, 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] at a temperature of 20 ℃ of 0.46dl
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 The procedure of Example 1 was repeated, except that 199.6 g of the dihydric phenol having the structural formula (2) shown in Table 1 was used instead of the dihydric phenol having the structural formula (1). 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.

Example 3 In place of the dihydric phenol represented by the structural formula (1), 194 g of the divalent phenol represented by the structural formula (3) shown in Table 1 was used.
The same procedure as in Example 1 was performed. The intrinsic viscosity [η] of the obtained polymer was 0.46 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.

Example 4 The procedure of Example 1 was repeated, except that 205.2 g of the dihydric phenol having the structural formula (4) shown in Table 1 was used instead of the dihydric phenol having the structural formula (1). The intrinsic viscosity [η] of the obtained polymer was 0.46 dl / g, and it was confirmed by infrared absorption spectrum analysis that the polymer was a polycarbonate polymer having the repeating unit shown in Table 1.

Example 5 Except that 308 g of the dihydric phenol of the structural formula (5) shown in Table 2 was used instead of the dihydric phenol of the structural formula (1).
The same procedure as in Example 1 was performed. The intrinsic viscosity [η] of the obtained polymer was 0.48 dl / g, and it was confirmed from the infrared absorption spectrum analysis that this polymer was a polycarbonate polymer having repeating units shown in Table 2.

Example 6 Instead of the dihydric phenol of structural formula (1), 99.8 g of dihydric phenol of structural formula (2) 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 2.

[0038]

[Table 1]

[0039]

[Table 2]

Example 7 The same as Example 1 except that 229.2 g of a dihydric phenol represented by the following structural formula (6) was used instead of the structural formula (1) in Example 1 as the dihydric phenol. It was carried out.

[Chemical 16]

The intrinsic viscosity [η] of the obtained polymer was 0.4.
At 6 dl / g, this polymer was confirmed to be a polycarbonate polymer having the following repeating units by infrared absorption spectrum analysis.

[Chemical 17]

Example 8 The same as Example 1 except that 229.2 g of a dihydric phenol represented by the following structural formula (7) was used instead of the structural formula (1) in Example 1 as the dihydric phenol. It was carried out.

[Chemical 18]

The intrinsic viscosity [η] of the obtained polymer was 0.4.
At 7 dl / g, this polymer was recognized as a polycarbonate polymer having the following repeating units by infrared absorption spectrum analysis.

[Chemical 19]

Example 9 The same as Example 1 except that 243.6 g of a dihydric phenol represented by the following structural formula (8) was used instead of the structural formula (1) in Example 1 as the dihydric phenol. It was carried out.

[Chemical 20]

The intrinsic viscosity [η] of the obtained polymer was 0.4.
At 7 dl / g, this polymer was recognized as a polycarbonate polymer having the following repeating units by infrared absorption spectrum analysis.

[Chemical 21]

[0046]

INDUSTRIAL APPLICABILITY The polycarbonate polymer of the present invention is a polymer having a triphenylamine 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. Triphenyl represented by the following general formula (A):
Repeating unit (A) having amine structure, or formula
Represented by the repeating unit represented by (A) and the following general formula (C)
A polymer of the formula (A)
The composition of the repeating unit represented by is 0 <(A) /
Polycarbonate polymerization with ((A) + (C)) ≦ 1
body. [Chemical 1](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
Group containing triphenylamine represented by general formula (B)
And the other one may have hydrogen and each may have a substituent.
An alkyl group, an alkenyl group or an aryl group, or
R₉, R_TenBoth are represented by the following general formula (B).
A group containing a phenylamine is shown. ) General formula (B):(In the formula, R₁₁~ R₁₆Are hydrogen, halogen, and substituents
May have an alkyl group, an alkoxy group, an alkenyl
Group, aryl group, arylamino group, aryl ether
A group or an aminoaryl ether group, or R₁₁When
R₁₂Or R₁₃And R₁₄Or R₁₅And R₁₆Combined with carbon
Represents a group forming a ring or a heterocycle, R₁₁~ R ₁₆Uchizu
That becomes a divalent group,-(CH₂) A-in combination with R₉
Or R_TenForm a group. a represents the integer of 0-5. ) [Chemical 3](In the formula, R₁₇~ R_{twenty four}Are hydrogen, halogen or
The alkyl group or aryl group which may have a substituent is shown.
X represents the following. [Chemical 4]R here_{twenty five}, R₂₆Are hydrogen, halogen and substituent
Represents an alkyl group or an aryl group which may have
R_{twenty five}And R₂₆Bind together to form a carbocycle or heterocycle
Represents a group to be formed, b is an integer of 0 to 20, c is an integer of 0 to 2000
Represent ) 2. A divalent phenol represented by the following general formula (D) is reacted with a carbonic acid ester forming compound, or the divalent phenol (D) and a divalent represented by the following general formula (E) are used. The method for producing a polycarbonate polymer according to claim 1, wherein phenol is reacted with a carbonic acid ester forming compound. [Chemical 5] (In the formula, each of R _{1 to} R ₁₀ has the same meaning as in the above formula (A).) (In the formula, each of R _{17 to} R ₂₄ and X has the same meaning as in the formula (A).)