JPS61268726A - Polycarbonate copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer with improved heat resistance and strength, by reaction, in a basic state, between 2,2-bis(4'-hydroxyphenyl)propane, 1,1-bis(4'-hydroxyphenyl)-1,1-diphenylmethane and phosgene. CONSTITUTION:An alkaline aqueous solution of mixture of (A) 2,2-bis(4'- hydroxyphenyl)propane of formula I and (B) 1,1-bis(4'-hydroxyphenyl)-1,1- diphenylmethane of formula II is mixed with an organic solvent followed by introducing phosgene into the system to carry out reaction, thus obtaining the objective copolymer having recurring units of formulae III and IV, respectively, with a molar fraction of the recurring unit of formula III being 10-90% and a reduced viscosity [etaSP/C] at 20 deg.C being 0.3-3.0dl/g determined in the form of a methylene chloride solution of concentration 0.5g/dl.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polycarbonate copolymer and a method for producing the same, and more specifically, a novel polycarbonate copolymer that is composed of specific repeating units and has excellent heat resistance and mechanical strength. This invention relates to polymers and efficient methods of producing them.

[Prior art and problems to be solved by the invention] Polycarbonate that has been commonly used is 2,2-
It is obtained by reacting bis(4'-hydroxyphenyl)propane (commonly known as bisphenol A) with phosgene or diphenyl carbonate, and is a resin with excellent heat resistance and mechanical strength.

By the way, as the uses of polycarbonate have expanded in recent years, even better heat resistance and mechanical strength have been required for its performance, and conventional polycarbonate as described above is unable to fully meet these demands. Can not.

Therefore, the present inventors have conducted extensive research to develop a new polycarbonate that can fully satisfy the above-mentioned required characteristics, and have finally completed the present invention.

[Means for solving problems]

That is, the present invention has a repeating unit (1) represented by the formula and a repeating unit (II) represented by □, and the molar fraction of the repeating units (1) and (II) is from 0.1 to
0.9 and a concentration of 0.5 g/d at 20°C
The reduced viscosity [η, , / C) of the methylene chloride solution of 1 is 0
．． 3 to 1.0 dl/g, and 2,2-bis(4°-hydroxyphenyl)propane and 1,1-bis(4”) The present invention provides a method for producing the polycarbonate copolymer described above, characterized in that an alkaline aqueous solution of a mixture of -hydroxyphenyl)-1,1-diphenylmethane is mixed with an organic solvent, and then phosgene is introduced and reacted.

The polycarbonate copolymer of the present invention is composed of the above-mentioned repeating units CI) and (II), and the molar fraction of each of these repeating units CI) and (It) is that of the repeating unit (1). If m+n, where m is the mole fraction and n is the mole fraction of the repeating unit CI, is less than 0.1, the resulting copolymer will have poor moldability, and if it exceeds 0.9, the heat resistance will be improved. is not sufficient.

Although the degree of polymerization of the polycarbonate copolymer of the present invention varies, it is usually at a concentration of 0.5 g/d at 20°C.
The reduced viscosity [η, , / C) of the methylene chloride solution of f is 0
．． 3-1.0dl/g, preferably 0.35-0.7d
The range is 1/g. Here, the reduced viscosity [η-P/
C) is 0.3dj! If the amount is less than 1.0d/g, the mechanical strength of the copolymer will be low, while if it exceeds 1.0d17g, the fluidity will decrease and the moldability will deteriorate.

The polycarbonate copolymer of the present invention has the above-mentioned repeating units (1) and (II), and there are various types thereof such as random copolymers, block copolymers, and alternating copolymers.

Although the polycarbonate copolymer of the present invention can be produced by various methods, the above-mentioned production method of the present invention is particularly preferred. That is, 2,2-bis(4°-hydroxyphenyl)propane (bisphenol A) represented by the formula and 1,1-bis(4°-hydroxyphenyl)-1,1-diphenylmethane represented by the formula are used as raw materials. This is dissolved in an alkaline aqueous solution such as sodium hydroxide, mixed with a halogenated hydrocarbon such as methylene chloride or chlorobenzene, or an organic solvent such as lysine, and then phosgene is introduced into this and reacted. The polycarbonate copolymer of the present invention is produced by this method. At this time, the mixing ratio of bisphenol A and 1,1-bis(4'-hydroxyphenyl)-1,1-diphenylmethane is not particularly limited, but the reaction of bisphenol A and phosgene produces repeating units [! ] is formed, Mata 1.1-
The repeating unit (If) is formed by the reaction of his(4'-hydroxyphenyl)-1,1-diphenylmethane and phosgene.
1,1-bis(4'-hydroxyphenyl)-1,1-diphenylmethane.
It should be between 0 and 90 mol%, preferably between 15 and 85 mol%. The amount of phosgene introduced is usually bisphenol A and 1.1-bis(4'-hydroxyphenyl)-1.
The amount may be equal to or more than the total amount of l-diphenylmethane.

Furthermore, an appropriate catalyst or molecular weight regulator may be added during this reaction. Here, suitable catalysts include tertiary amines and quaternary ammonium salts.

Furthermore, as molecular weight regulators, there are various m-phenols, such as H3.Other conditions for the above reaction are not particularly limited,
In short, the polymerization degree may be adjusted as appropriate so that the degree of polymerization has a predetermined reduced viscosity [ηsr/C].

The polycarbonate copolymer of the present invention thus obtained has repeating units [I] as described above.

It has the same degree of polymerization as (II), and its terminal group varies depending on the molecular weight regulator used, but for example, etc. are bonded thereto.

The polycarbonate copolymer of the present invention can also be produced by various methods other than the method of the present invention described above.

For example, (i) bisphenol A is reacted with a carbonate-forming compound such as phosgene or diphenyl carbonate to obtain an oligomer, and this oligomer is reacted with 1,1-bis(4''-hydroxyphenyl)-1,1-diphenylmethane. (ii) a method of reacting 1,1-bis(4°-hydroxyphenyl)-1,1-diphenylmethane with a carbonate-forming compound to obtain an oligomer, and reacting this oligomer with bisphenol A;
iii) A method of reacting bisphenol A and 1,1-bis(4''-hydroxyphenyl)-1,1-diphenylmethane with a carbonate ester-forming compound to obtain each oligomer, and then reacting the oligomers with each other. can give.

〔Effect of the invention〕

As described above, the polycarbonate copolymer of the present invention has significantly improved heat resistance and mechanical strength compared to conventional polycarbonate 1-, and can be used as a material for electrical and electronic devices and materials for various mechanical parts. It is widely and effectively used.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 2.2-bis(4′-hydroxyphenyl)propane 1
8.24 g (0.08 mol) and 1.1-bis(4”-
Hydroxyphenyl)-1,1-diphenylmethane7.
04 g (0.0'2 mol) in 200 mf of a 2N sodium hydroxide aqueous solution, and 200 mj of methylene chloride as a solvent. and 0.45 g of paratertiary-butylphenol as a molecular weight regulator.
(0,003 mol) was added and mixed, and further triethylamine 1. Q ml was added thereto, and phosgene gas was blown therein at a rate of 200 ml/llln for 15 minutes at 20°C. Then, the supply of phosgene was stopped, and the reaction was carried out at 28° C. for 1 hour. Add 500ml of methylene chloride to the reaction product! was added and washed with 1.51 parts of water. Further, the organic layer was washed with 11 parts of 0.01N hydrochloric acid and 1 part of water, and then dropped into 21 parts of methanol to be reprecipitated to recover the copolymer. Then, it was dried under reduced pressure at 120°C for 5 hours. The copolymer thus obtained was 0.5 g/dI! using methylene chloride as a solvent! The reduced viscosity [η,,/C) of a solution with a concentration of 0.65 dI! /g. In addition, as a result of infrared absorption spectrum analysis of this copolymer, absorption due to the C-C bond of the benzene ring at 1590 cm-', absorption due to the C-H bond of the benzene ring at 3030 cm-' and 830ca+-', and absorption at 2850 Cffi -
'Absorption by isopropyl group and 1650 cm
-' absorption due to carbonyl group was observed. Regarding thermal properties, the glass transition temperature was 211°C. Furthermore, the fluidity of this copolymer was determined at 280°C and under a load of 21
The melt index at 60 g was 1.8 g/10 minutes, and the tensile strength measured using a test piece molded at 350° C. was 700 kg/cut.

Examples 2-4 2.2-bis(4′-hydroxyphenyl)propane and 1.1-bis(4′-hydroxyphenyl)-1,1-
The same procedure as in Example 1 was conducted except that the mixing ratio of diphenylmethane was 4:6.3 molar ratio and i:9 molar ratio. The properties of the obtained copolymer are shown in Table 1.

Comparative Example 1 The same procedure as in Example 1 was carried out except that only 22.8 g (0.L mol) of 2,2-bis(4'-hydroxyphenyl)propane was used as the raw dihydric phenol.

The properties of the obtained polymer are shown in Table 1.

Comparative Example 2 As the raw dihydric phenol, 1,1-bis(4'-hydroxyphenyl)-1,1-diphenylmethane 35.
The same procedure as in Example 1 was carried out except that only 2 g (0.1 mol) was used. The obtained polymers are shown in Table 1.

From the above results, the copolymer of the present invention has sufficiently improved heat resistance and tensile strength compared to the commonly used polycarbonate made from 2,2-bis(4-hydroxyphenyl)propane [Comparative Example 1]. It is permitted to do so. Also, 1,1-bis(4'-hydroxyphenyl)-1,1
- Polycarbonate from diphenylmethane [Comparative Example 2
] is recognized to have poor moldability and lack practicality.

(proceeding officer) (self-motivated) May 19, 1985

Claims (2)

[Claims] (1) It has a repeating unit [I] represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and a repeating unit [II] represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ , and the above repeating unit A methylene chloride solution with a value of m/m+n of 0.1 to 0.9, where the molar fractions of [I] and [II] are m and n, respectively, and a concentration of 0.5 g/dl at 20 ° C. The reduced viscosity [η_s_p/c] of 0.3 to 1
．． Polycarbonate copolymer with 0 dl/g. (2) 2,2-bis(4'-hydroxyphenyl)propane represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and 1,1-bis represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The method is characterized in that an alkaline aqueous solution of a mixture of (4'-hydroxyphenyl)-1,1-diphenylmethane is mixed with an organic solvent, and then phosgene is introduced and reacted. It has a repeating unit [I] represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and a repeating unit [II] represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the repeating unit [I] The value of m/m+n is 0.1 to 0.9 when the molar fraction of [II] is m and n, respectively, and the reduced viscosity of a methylene chloride solution with a concentration of 0.5 g/dl at 20°C [η_s_p/c] is 0.3 to 1
．． 0 dl/g.