JPH04370114A - Halogenated polycarbonate copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer useful as a material for optical devices such as head lamp lens, having high refractive index, excellent heat resistance, flame retardance and optical properties, comprising given amounts of specific constituent units, respectively. CONSTITUTION:The objective copolymer comprising (A) a constituent unit shown by formula I [Z is single bond, (phenyl-substituted) alkylidene, cycloalkylidene, sulfone or sulfido or oxido; X is halogen] and (B) a constituent unit shown by formula II [W is single bond, (phenyl-substituted) alkylidene, cycloalkylidene, sulfone, sulfido or oxido; R<1> and R<2> are H, halogen, phenyl or 1-3C alkyl; m and n are 1-4] in a ratio of 95-5 units component A based on 100 units of the constituent units. The copolymer, for example, is obtained by condensing given amounts of dibromodiphenylbiphenyldiol and dihydroxybiphenyl with a bisaryl carbonate.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a novel halogenated polycarbonate copolymer, and more specifically, a novel halogenated polycarbonate copolymer that has excellent heat resistance and flame retardancy, has a particularly high refractive index, and has excellent optical properties. This invention relates to halogenated polycarbonate copolymers.

0002

[Prior Art] Conventionally, polycarbonate obtained by reacting 2,2-bis(4-hydroxyphenyl)propane [commonly known as bisphenol A] with phosgene or diphenyl carbonate has good transparency, heat resistance, mechanical properties, and dimensional stability. Because of its excellent properties, it has been widely used in many fields as an engineering plastic. however,
In recent years, as molded products have become lighter, thinner, shorter, and smaller, there has been a desire to develop new materials that have excellent heat resistance, flame retardancy, and a high refractive index, such as lenses that are used closer to a heat source.

0003

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate having excellent heat resistance, flame retardancy, particularly high refractive index, and excellent optical properties.

[0004] As a result of intensive research aimed at achieving the above object, the present inventors have discovered that a new halogenated polycarbonate copolymer obtained by using a halogenated dihydric phenol having a specific structure as a copolymerization component has been developed. It has high heat resistance, excellent flame retardancy, and a high refractive index.
It was also discovered that it is optically superior. The present invention was completed based on this knowledge.

[0005]

[Means for Solving the Problems] The present invention is based on the following general formula (
1)

[0006]

A structural unit represented by [Formula Z is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl-substituted alkylidene group, a sulfone group, a sulfide group, or an oxide group, and X is a halogen atom] and General formula (2) below

00
07]

[Formula W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl-substituted alkylidene group, a sulfone group, a sulfide group, or an oxide group, and R1 and R2 are a hydrogen atom, a halogen atom, a phenyl group, or a carbon [1 to 3 alkyl groups, R1 and R2 may be the same or different, and m and n are each integers of 1 to 4]
It concerns a halogenated polycarbonate copolymer consisting of the structural units represented by the formula (1) and having 95 to 5 structural units represented by the general formula (1) per 100 structural units.

Specifically, the dihydric phenol constituting the structural unit represented by the general formula (1) is 3,3'-
Dibromo-5,5'-diphenyl-1,1'-biphenyl-4,4'-diol, bis(3-bromo-5-phenyl-4-hydroxyphenyl)methane, 1,1-bis(3-bromo- 5-phenyl-4-hydroxyphenyl)ethane, 2,2-bis(3-bromo-5-phenyl-
4-hydroxyphenyl)propane, 2,2-bis(3
-bromo-5-phenyl-4-hydroxyphenyl)butane, 1,1-bis(3-bromo-5-phenyl-4-
hydroxyphenyl)cyclohexane, bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfone, bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfide, bis(3-bromo-5-phenyl-4) -hydroxyphenyl) oxide, etc. Among them, bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfone and bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfide are preferred.

Further, the dihydric phenol constituting the structural unit represented by general formula (2) is specifically 4,4'-
Dihydroxybiphenyl, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 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(3,5-dibromo-4-hydroxyphenyl)
Propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,
Examples include 4'-dihydroxydiphenyl oxide. Among them, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)
-1-phenylethane is preferred.

[0010] Examples of the carbonate precursor used for producing the above-mentioned structural unit from the above-mentioned dihydric phenol include phosgene, diphenyl carbonate, and the like.

The method for producing the halogenated polycarbonate copolymer of the present invention includes a method used in producing polycarbonate from bisphenol A, such as a reaction between dihydric phenol and phosgene, or a reaction between dihydric phenol and bisaryl carbonate. A transesterification reaction can be used.

In the reaction between dihydric phenol and phosgene,
The reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, pyridine, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, etc. are used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used to promote the reaction, and it is desirable to use a terminal capping agent such as phenol or p-tert-butylphenol as a molecular weight regulator.

The proportion of dihydric phenols providing the structural unit (1) can be arbitrarily combined within the range of 95 to 5 mol%, but is preferably in the range of 85 to 20 mol%. If the proportion of dihydric phenol providing the structural unit (1) is less than 5 mol %, a desired high refractive index cannot be obtained, and if it exceeds 95 mol %, the molded piece becomes brittle and is not practical.

When a phenol substituted with a bulky substituent at the ortho position, such as the dihydric phenol providing the structural unit (1), is copolymerized with a phenol unsubstituted at the ortho position, the reaction rate is quite different. difficult to copolymerize. Therefore, during the reaction, it is preferable to devise a reaction mode that takes into account the reaction rate, such as synthesizing the oligomer of the structural unit (1) in advance and then copolymerizing it with other dihydric phenols. The reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.
It is usually preferable to keep the pH during the reaction at 10 or higher.

On the other hand, in the transesterification reaction, dihydric phenol and bisaryl carbonate are mixed in the presence of an inert gas and reacted under reduced pressure, usually at 120 to 350°C. The degree of reduced pressure is changed stepwise, and finally, the generated phenols are distilled out of the system at a pressure of 1 mmHg or less. The reaction time is usually about 1 to 4 hours. Further, a molecular weight regulator and an antioxidant may be added as necessary.

The thus obtained halogenated polycarbonate copolymer of the present invention has the above general formulas (1) and (2).
This is a novel polycarbonate copolymer having the structural unit represented by If the degree of polymerization is too small, the resulting molded product will become brittle, so
．． The specific viscosity of the solution having a concentration of 7 g/100 ml is preferably 0.15 or more, particularly preferably 0.2 to 2.5.

The halogenated polycarbonate copolymer of the present invention is used as a film or a molded article. Casting, extrusion, injection, compression molding, etc. can be used as the molding method, and if necessary, ordinary polycarbonate stabilizers such as phosphite ester, phosphate ester, hindered phenol, etc. can be used. You can also add Furthermore, additives such as light stabilizers, colorants, antistatic agents, lubricants, mold release agents, and small amounts of alkali metal salts can also be added.

The halogenated polycarbonate copolymer of the present invention can also be used by adding it to other thermoplastic resins.

[0019]

[Examples] The present invention will be further explained with reference to Examples below. In addition, parts in the examples are parts by weight, and % is weight %.

[0020]

[Synthesis Example 1] Synthesis of bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfone To 791 parts of methanol, add bis(3-phenyl-4-hydroxyphenyl)sulfone [manufactured by Sanko Kagaku Co., Ltd.] 402
328 parts of Br2 are added dropwise to the solution while stirring and cooling to 10-15° C. in an ice bath. 6 after completion of dripping
Raise the temperature to 0-70℃, continue stirring for about 30 minutes, and add Br2.
After the yellow color disappeared, the contents were cooled, filtered, washed with methanol, and dried to obtain 532 parts of white powder (yield 95%). This powder had a Br2 content of 28.3%, and was confirmed to be bis(3-bromo-5-phenyl-4-hydroxyphenyl) sulfone by proton NMR analysis.

[0021]

[Example 1] 48.4 parts of a 48% caustic soda aqueous solution was placed in a reactor equipped with a thermometer and a stirrer, and bisphenol A3
After dissolving 2.5 parts of bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfone obtained in Synthesis Example 1 and 0.1 part of hydrosulfite, 529 parts of methylene chloride, p -Add 1 part of tert-butylphenol and 0.25 part of triethylamine, and stir for 15~
At 25°C, 21.6 parts of phosgene was bubbled in over 50 minutes. Next, 7 parts of 48% caustic soda aqueous solution was added, and 2
The reaction was completed by stirring at 8-33°C for about 1 hour. After the reaction, the product was diluted with methylene chloride and washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, methylene chloride was evaporated to give 48.2 parts of polymer. was obtained (yield 95%).

This polymer had a specific viscosity of 0.374 at 20°C and a glass transition temperature of 153°C in a solution having a concentration of 0.7 g/100ml using methylene chloride as a solvent. The infrared absorption spectrum of this polymer is 1780c.
Absorption by carbonyl group of carbonate at m-1, 12
Absorption due to ether bond is seen near 00 cm-1,
Recognized to have carbonate bonds, 1340c
Absorption derived from sulfone was observed at m-1 and 1100 cm-1, and NMR spectrum analysis revealed that sulfone bis(
The molar fraction of the (3-bromo-5-phenyl-4-oxyphenylene) structural unit was 15.5 mol%. The UL-94 combustion test result of a 1.6 mm thick test piece of this polymer was V-1, and the refractive index measured with an Abbe refractometer was 1.598.

[0023]

[Example 2] The same procedure as in Example 1 was carried out except that the amount of bisphenol A used was 19.0 parts and the amount of bis(3-bromo-5-phenyl-4-hydroxyphenyl)sulfone was 46.8 parts. 67.3 parts of polymer was obtained (yield: 9
6%).

This polymer had a specific viscosity of 0.281 and a glass transition temperature of 185°C. In addition, in the infrared absorption spectrum of this polymer, absorption due to the carbonyl group of carbonate is observed at 1780 cm-1, absorption due to ether bond is observed near 1200 cm-1, and it is recognized that the polymer has a carbonate bond.
Absorption derived from sulfone was observed in 1, and NMR spectrum analysis revealed that the molar fraction of the sulfone bis(3-bromo-5-phenyl-4-oxyphenylene) structural unit was 54 mol%. The UL-94 combustion test result of a 1.6 mm thick test piece of this polymer was V-0, and the refractive index measured with an Abbe refractometer was 1.620.

[0025]

[Example 3] 71 parts of polymer was prepared in the same manner as in Example 2 except that 24.2 parts of 1,1-bis(4-hydroxyphenyl)-1-phenylethane was used in place of bisphenol A used in Example 2. was obtained (yield 94.2%).

This polymer had a specific viscosity of 0.351 and a glass transition temperature of 203°C. In addition, in the infrared absorption spectrum of this polymer, absorption due to the carbonyl group of carbonate is observed at 1780 cm-1, absorption due to ether bond is observed near 1200 cm-1, and it is recognized that the polymer has a carbonate bond.
Absorption derived from sulfone was observed in 1, and NMR spectrum analysis revealed that the molar fraction of the sulfone bis(3-bromo-5-phenyl-4-oxyphenylene) structural unit was 52 mol%. The UL-94 combustion test result of a 1.6 mm thick test piece of this polymer was V-0, and the refractive index measured with an Abbe refractometer was 1.631.

[0027]

[Comparative Example 1] The glass transition temperature of polycarbonate (viscosity average molecular weight 22,500) consisting of bisphenol A is 1
UL-9 for a test piece with a thickness of 1.6 mm at 48°C.
4 combustion test result was V-2, and the refractive index measured with an Abbe refractometer was 1.584.

[0028]

Effects of the Invention The halogenated polycarbonate copolymer of the present invention is novel and has a higher glass transition temperature, excellent flame retardancy, and particularly high refractive index compared to polycarbonate made only of bisphenol A. It has excellent optical properties, so it is suitable for fields that require high heat resistance, flame retardance, and optical properties, such as headlamp lenses,
It is useful as a material for various optical devices such as camera lenses, safety glasses lenses, prisms, optical fibers, and optical discs. It is also useful as a material for various electrical and electronic parts that require flame retardancy.

Claims (1)

[Claims] [Claim 1] The following general formula (1) [Formula Z is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group, a sulfone group, a sulfide group, or an oxide group, and X is a halogen is an atom] and the following general formula (2) [Chemical formula 2
[In the formula, W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl-substituted alkylidene group, a sulfone group, a sulfide group, or an oxide group, and R1 and R2 are a hydrogen atom, a halogen atom, a phenyl group, and a carbon number of 1 to 3 alkyl group, R1 and R2 may be the same or different, m and n are each an integer of 1 to 4]
A halogenated polycarbonate copolymer consisting of structural units represented by the formula (1), wherein the number of structural units represented by general formula (1) is 95 to 5 units per 100 structural units.