JPH06172508A - Aromatic copolycarbonate - Google Patents

Abstract

PURPOSE:To obtain a copolymer excellent in heat resistance and heat stability and having good transparency and moldability by copolymerizing 9,9-bis(4- hydroxyphenyl)fluorene, an isomer thereof and other dihydric phenol. CONSTITUTION:An aromatic copolycarbonate which consists of structural units of formulas I, II and III and in which the units of formula II account for 0.02-20% and those of formulas I and III each account for 2-65% based on all the units. In the formulas, R1 to R4 are each H, halogen, etc.; R5 to R8 are each H, halogen, etc.; W is a single bond, alkylidene, phenyl, etc.; R9 and R10 are each H, halogen, etc.; and m and n are each 1 to 4. It is obtained by copolymerizing 9,9-bis(4-hydroxyphenyl)fluorene with other dihydric phenol and copolymerizing the copolymer with an isomer of 9,9-bis(4-hydroloxyphenyl) fluorene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to aromatic polycarbonate copolymers. More specifically, it relates to an aromatic polycarbonate copolymer having excellent heat resistance and thermal stability, good transparency and moldability.

[0002]

2. Description of the Related Art 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as bisphenol A), which is conventionally known as a typical aromatic polycarbonate resin, is supplemented with a carbonate precursor such as phosgene or diphenyl carbonate. The polycarbonate resin derived from bisphenol A obtained by the reaction is widely used as an engineering plastic because it has many excellent properties such as excellent transparency, heat resistance and mechanical properties and good dimensional accuracy. However, in recent years, in consideration of lightness, thinness, shortness, and increased use under more severe conditions, higher heat resistance is required in addition to optical characteristics such as light transmittance.

In order to improve the heat resistance of aromatic polycarbonate resins, various aromatic polycarbonate resins using various monomers that are more rigid than bisphenol A have been proposed, and 9,9-bis (4-hydroxyphenyl) has been proposed. It is known that an aromatic polycarbonate resin having excellent heat resistance can be obtained by reacting fluorene with a carbonate precursor (US Pat. No. 3,546,165). However, when synthesizing the aromatic polycarbonate resin, a large amount of a gel-like substance insoluble in the solvent is produced, and the yield of the solvent-soluble component is 60 to 70% at most, which is not practical, and the aromatic polycarbonate resin is Even if the resin is melt-molded, there is a problem that the melt viscosity is too high to be molded. In order to solve this problem, a copolymerization with other dihydric phenol was tried, but coloration is likely to occur at the time of heating and melting, and it is desired to improve moldability and thermal stability.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic polycarbonate resin which is particularly excellent in heat resistance and heat stability and has good transparency and moldability.
The present inventor has conducted extensive studies to achieve the above object, and as a result, a copolymer of 9,9-bis (4-hydroxyphenyl) fluorene and another dihydric phenol was further
It was found that when a specific amount of 9-bis (4-hydroxyphenyl) fluorene isomer is copolymerized, an aromatic polycarbonate resin having excellent heat resistance and thermal stability, good transparency and moldability can be obtained. It was The present invention has been completed based on this finding.

[0005]

The present invention provides the following general formula [1]:

[0006]

[Chemical 4]

[Wherein R _{1 to} R ₄ are hydrogen atoms, halogen atoms, phenyl groups, and alkyl groups having 1 to 3 carbon atoms, and R _{1 to} R ₄ may be the same or different] Structural unit, the following general formula [2]

[0008]

[Chemical 5]

[In the formula, R _{5 to} R ₈ are a hydrogen atom, a halogen atom, a phenyl group or an alkyl group having 1 to 3 carbon atoms, and R _{5 to} R ₈ may be the same or different] Structural unit and the following general formula [3]

[0010]

[Chemical 6]

[Wherein W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group,
A sulfone group, a sulfoxide group, a sulfide group or an oxide group, R ₉ and R ₁₀ are hydrogen atoms, halogen atoms,
A phenyl group, an alkyl group having 1 to 3 carbon atoms, R ₉
And R ₁₀ may be the same or different, and m and n are each an integer of 1 to 4].
The structural unit represented by the general formula [2] is 100% of all structural units.
The present invention relates to an aromatic polycarbonate copolymer having 0.02 to 20 units per unit and a total of 2 to 65 units of the structural units represented by the general formulas [1] and [2].

The constitutional unit represented by the general formula [1] is
It is obtained by the reaction of 9,9-bis (4-hydroxyphenyl) fluorenes with a carbonate precursor material. 9,9-bis (4-hydroxyphenyl) used here
Examples of fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, and 9,9-bis (3-ethyl-4-hydroxyphenyl). ) Fluorene and the like, which may be used either individually or in combination of two or more, with 9,9-bis (4-hydroxyphenyl) fluorene being particularly preferred.

The dihydric phenol forming the constitutional unit represented by the above general formula [2] is an isomer of the above 9,9-bis (4-hydroxyphenyl) fluorene, for example, 9- (2- Hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene, 9- (3-methyl-2-hydroxyphenyl) -9- (3-methyl-4-hydroxyphenyl) fluorene, 9- (3-ethyl-2- Hydroxyphenyl) -9- (3-ethyl-4-hydroxyphenyl) fluorene and the like can be mentioned, and these may be used alone or in combination of two or more, and particularly 9- (2-hydroxyphenyl) -9- (4- Hydroxyphenyl) fluorene is preferred.

The dihydric phenol forming the constitutional unit represented by the general formula [3] is a dihydric phenol other than the above 9,9-bis (4-hydroxyphenyl) fluorenes and isomers thereof, for example, 4 , 4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane,
Bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-
Phenyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-isopropyl-4-hydroxyphenyl)
Propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) ) Propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-
Examples thereof include dihydroxydiphenyl sulfide and 4,4′-dihydroxydiphenyl oxide, which may be used alone or in combination of two or more. Bisphenol A, 1,
1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) ethane, 1,
1-Bis (4-hydroxyphenyl) -1-phenylethane is preferable, and bisphenol A is particularly preferable.

The proportion of the above dihydric phenol used, that is, the proportion of the constitutional units [1], [2] and [3] of the aromatic polycarbonate copolymer of the present invention, is 100.
This is the ratio of the structural unit [2] to 0.02 to 20 units and the total of the structural units [1] and [2] to 2 to 65 units per unit. When the ratio of the structural unit [2] is less than 0.02 unit, it is difficult to obtain good moldability and thermal stability, and when it exceeds 20 units, the thermal stability is rather deteriorated. A ratio of 0.05 to 10 units is particularly preferable. When the total of the structural units [1] and [2] is less than 2 units, it is difficult to obtain sufficient heat resistance, and when it exceeds 65 units, the moldability becomes poor.

The aromatic polycarbonate copolymer of the present invention is produced by reacting a predetermined ratio of the above dihydric phenol with a carbonate precursor substance. It is usually produced by an interfacial polycondensation method using phosgene or a transesterification reaction using a carbonic acid diester.

In the interfacial polycondensation reaction using phosgene,
Usually, the above-mentioned dihydric phenol is dissolved in an aqueous solution of an acid binder, and phosgene is reacted in the presence of an organic solvent.
As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used, and as the organic solvent, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. The reaction is usually 0 to 40 ° C,
Preferably, the process is completed at 20 to 30 ° C. for several minutes to 5 hours. It is preferable to keep the pH of the reaction system at 10 or higher as the reaction progresses. Further, it is desirable to use an end terminating agent such as phenol or p-tert-butylphenol as a molecular weight modifier, and a catalyst may be used to accelerate the reaction. Examples of the catalyst include triethylamine, tetra-n-butylammonium bromide, tetra-n
A tertiary amine such as butylphosphonium bromide,
Examples thereof include quaternary ammonium compounds and quaternary phosphonium compounds. Further, if necessary, an antioxidant such as hydrosulfite can be added.

The transesterification reaction using a carbonic acid diester is carried out by distilling an alcohol or a phenol produced by stirring the dihydric phenol at a predetermined ratio with the carbonic acid diester in an inert gas atmosphere while heating. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is depressurized to facilitate the distillation of the alcohol or phenol produced and complete the reaction.
Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, among which diphenyl carbonate is preferable.

A polymerization catalyst can also be used to accelerate the polymerization rate. As the polymerization catalyst, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and hydroxides of boron and aluminum can be used. Alkaline metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts,
Zinc compounds, boron compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds,
It is possible to use a catalyst such as a zirconium compound which is usually used in an esterification reaction or a transesterification reaction.
The catalyst may be used alone or in combination of two or more kinds. The amount of these catalysts used is 0.0001 to 1% by weight, preferably 0.000, relative to the dihydric phenol as a raw material.
It is selected in the range of 5 to 0.5% by weight. The aromatic polycarbonate copolymer thus obtained has a molecular weight of 0.19 to 0.63, which is suitable as a specific viscosity measured at 20 ° C. in a methylene chloride solution having a concentration of 0.7 g / dl.
0.26-0.45 is preferable.

The aromatic polycarbonate copolymer of the present invention is used for films and other molded articles. As the molding method, a method used for molding a usual polycarbonate resin, for example, an injection molding method, a compression molding method, an extrusion molding method,
Any method such as a solution casting method can be used. At the time of molding, the aromatic polycarbonate copolymer of the present invention may be molded as it is, but if necessary, for example, a heat stabilizer, an antioxidant, a light stabilizer, a colorant, an antistatic agent, a lubricant, a mold release agent. You may shape | mold by adding additives, such as an agent. Also, the aromatic polycarbonate copolymer of the present invention can be used as a mixture with another polycarbonate resin or another thermoplastic resin.

[0021]

EXAMPLES The present invention will be further described with reference to the following examples. In the examples, parts and% are parts by weight and% by weight. In addition, each item was measured by the following methods. (a) Specific viscosity: 0.7 g of polymer in 100 ml of methylene chloride
It was dissolved in and measured at 20 ° C. (b) Thermal stability: 3 g of the polymer was sealed in a test tube, degassed under vacuum, heat-treated at 330 ° C. for 4 hours, dissolved in 200 ml of methylene chloride, and 600 nm and 400 nm using a 10 cm cell.
The light transmittance of nm can be measured by Hitachi Ltd. spectrophotometer U-33.
00 was measured. (c) Glass transition temperature: Measured with a DSC-910 manufactured by DuPont at a temperature rising rate of 10 ° C./min. (d) Fluidity (MFR): 28 using Toyo Seiki Seisakusho SEMI AUTO MELT INDEXER
It was measured at 0 ° C. and 2.16 kgf / cm ² .

[0022]

Example 1 A reactor equipped with a thermometer and a stirrer was charged with 569 parts of ion-exchanged water and 48.5% aqueous sodium hydroxide solution 3.
7.4 parts were charged, to which was added 3.85 parts of 9,9-bis (4-hydroxyphenyl) fluorene, 0.10 parts of 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene and bisphenol. After dissolving 23.26 parts of A, 337 parts of methylene chloride was added, and 15.7 parts of phosgene was blown into the reaction mixture at 15 ° C. for about 40 minutes while vigorously stirring. Next, raise the internal temperature to 28 ° C and p-
After 0.68 parts of tert-butylphenol was added to emulsify, 0.06 parts of triethylamine was added and stirring was continued for 2 hours to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. 1 part (yield 96.3%) was obtained. The specific viscosity of this polymer is 0.3
60, glass transition temperature is 161 ℃, MFR is 7.1 g / 1
After 0 minutes, the light transmittance after heat treatment is 95% at 600 nm, 4
It was 54% at 00 nm.

[0023]

Example 2 9,9-bis (4-hydroxyphenyl)
Polymer 29 in the same manner as in Example 1 except that the amount of fluorene used was 3.76 parts and the amount of 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene was 0.19 parts. 0.4 part (yield 97.3%) was obtained. This polymer had a specific viscosity of 0.357, a glass transition temperature of 160 ° C., an MFR of 8.1 g / 10 minutes, and a light transmittance after heat treatment of 96% at 600 nm and 61% at 400 nm.

[0024]

Example 3 9,9-bis (4-hydroxyphenyl)
7.52 parts of fluorene, 0.38 parts of 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene, 20.68 parts of bisphenol A and p- Polymer 30.6 parts (yield 97.1%) was obtained in the same manner as in Example 1 except that the amount of tert-butylphenol used was 1.02 parts. The specific viscosity of this polymer is 0.264, the glass transition temperature is 171 ° C, and the MF
R is 15.0 g / 10 minutes, light transmittance after heat treatment is 60
It was 96% at 0 nm and 63% at 400 nm.

[0025]

Comparative Example 1 9,9-bis (4-hydroxyphenyl)
Same as Example 1 except that the amount of fluorene used was 3.73 parts, the amount of bisphenol A used was 21.8 parts, and 9- (2-hydroxyphenyl) -9- (4-hydroxyphenyl) fluorene was not used. Polymer 28.1
Part (yield 99.2%) was obtained. This polymer has a specific viscosity of 0.361, a glass transition temperature of 162 ° C. and an MFR of 6.0.
g / 10 minutes, the light transmittance after heat treatment is 86 at 600 nm
% And 26% at 400 nm.

[0026]

The aromatic polycarbonate copolymer of the present invention has a high glass transition temperature, excellent transparency, and good moldability. Therefore, high heat resistance and optical properties are required. It is useful in fields such as headlamp lenses and optical fibers.

Claims (1)

[Claims] 1. The following general formula [1]: [Wherein R _{1 to} R ₄ are a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms, and R _{1 to} R _{4 are}
May be the same or different]
The following general formula [2] [In the formula, R _{5 to} R ₈ are a hydrogen atom, a halogen atom, a phenyl group, and an alkyl group having 1 to 3 carbon atoms, and R _{5 to} R _{8 are}
May be the same or different] and a structural unit represented by the following general formula [3] [In the formula, W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group, a sulfone group,
A sulfoxide group, a sulfide group or an oxide group,
R ₉ and R ₁₀ are hydrogen atom, halogen atom, phenyl group,
An alkyl group having 1 to 3 carbon atoms, R ₉ and R ₁₀ may be the same or different, and m and n are each an integer of 1 to 4]. [2]
The structural unit represented by the formula is 0.
An aromatic polycarbonate copolymer having 02 to 20 units and a total of 2 to 65 units of the structural units represented by the general formulas [1] and [2].