JPH0689127B2 - Polycarbonate random copolymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polycarbonate random copolymer and a method for producing the same, and more specifically, it is a novel polycarbonate composed of specific repeating units and having excellent heat resistance and mechanical strength. TECHNICAL FIELD The present invention relates to a random copolymer and an efficient production method thereof.

[Problems to be Solved by Prior Art and Invention]

Conventionally used polycarbonate is 2,
It is obtained by reacting 2-bis (4'-hydroxyphenyl) propane (commonly called bisphenol A) with phosgene or diphenyl carbonate, and is a resin excellent in heat resistance and mechanical strength.

By the way, in recent years, along with the expansion of applications of polycarbonate, further excellent heat resistance and mechanical strength are required for its performance, and the conventional polycarbonate as described above can sufficiently satisfy these requirements. Can not.

Therefore, the present inventors have conducted intensive studies to develop a new polycarbonate that can sufficiently satisfy the above-mentioned required properties, and have completed the present invention.

[Means for solving problems]

That is, the present invention is The repeating unit [I] represented by When the repeating unit [II] is represented by the following formula and the mole fractions of the repeating units [I] and [II] are m and n, respectively. Is 0.1-0.9 and the concentration at 20 ℃ is 0.5g / d
l methylene chloride solution has a reduced viscosity [η _SP / c] of 0.3 to 1.0 d
A polycarbonate random copolymer that is l / g is provided with the formula 2,2-bis (4'-hydroxyphenyl) represented by
Propane and formula 1,1-bis (4'-hydroxyphenyl) represented by
The present invention provides a method for producing a polycarbonate random copolymer, which comprises mixing an alkaline aqueous solution of a mixture of -1,1-diphenylmethane with an organic solvent, and then introducing phosgene to cause a reaction.

The polycarbonate random copolymer of the present invention is composed of the above repeating units [I] and [II]. Regarding the mole fraction of each of these repeating units [I] and [II], the repeating units are When the mole fraction of [I] is m and the mole fraction of the repeating unit [II] is n, The value of is 0.1 to 0.9, preferably 0.15 to 0.85. here If the value is less than 0.1, the copolymer obtained has poor moldability, and if it exceeds 0.9, the heat resistance is not sufficiently improved.

The degree of polymerization of the polycarbonate random copolymer of the present invention is various, but usually the concentration at 20 ° C. is 0.5 g / dl.
The reduced viscosity [η _SP / c] of the methylene chloride solution of
/ g, preferably 0.35 to 0.7 dl / g. Here, if the reduced viscosity [η _SP / c] is less than 0.3 dl / g, the mechanical strength of the copolymer will be low, while if it exceeds 1.0 dl / g, the fluidity will decrease and the moldability will deteriorate. .

The polycarbonate random copolymer of the present invention is a random copolymer having the repeating units [I] and [II].

The polycarbonate random copolymer of the present invention can be produced by various methods, but the above-mentioned production method of the present invention is most preferable. That is, the expression 2,2-bis (4'-hydroxyphenyl) represented by
Propane (bisphenol A) and formula 1,1-bis (4'-hydroxyphenyl) represented by
-1,1-Diphenylmethane as a raw material, which is dissolved in an alkaline aqueous solution such as sodium hydroxide, is mixed with a halogenated hydrocarbon such as methylene chloride or chlorobenzene, or an organic solvent such as pyridine, and then mixed with this. The polycarbonate random copolymer of the present invention is produced by introducing phosgene and reacting it.
At this time, the mixing ratio of bisphenol A and 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane is not particularly limited, but the repeating unit [I] is formed by the reaction of bisphenol A and phosgene. In consideration of the fact that the repeating unit [II] is formed by the reaction of 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane with phosgene, bisphenol A and 1,1 -Bis (4'-hydroxyphenyl) -1,1
-10-90 mol% relative to the total amount with diphenylmethane,
It should preferably be 15-85 mol%. The amount of phosgene introduced is usually equimolar or more than the total amount of bisphenol A and 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane.

Further, in this reaction, an appropriate catalyst or molecular weight modifier may be added. Here, as the catalyst, tertiary amines and quaternary ammonium salts are suitable.
Further, as the molecular weight regulator, there are various monohydric phenols, for example, and so on.

Other conditions for the above reaction are not particularly limited,
In short, it may be appropriately adjusted so that the polymerization degree has a predetermined reduced viscosity [η _SP / c].

The polycarbonate random copolymer of the present invention thus obtained has the repeating units [I], [I
I] has a degree of polymerization and its terminal group varies depending on the molecular weight modifier used. And so on.

The polycarbonate random 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 the oligomer is reacted with 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane. Or (ii) 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane is reacted with a carbonic acid ester forming compound to obtain an oligomer, and this oligomer is reacted with bisphenol A, or ( iii) A method in which bisphenol A and 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane are separately reacted with a carbonic acid ester forming compound to obtain respective oligomers, and the oligomers are reacted with each other is known. can give.

〔The invention's effect〕

As described above, the polycarbonate random copolymer of the present invention has remarkably improved heat resistance and mechanical strength as compared with conventional polycarbonates, and is widely used as a material for electric / electronic devices and various mechanical parts. It is effectively used.

Further, the polycarbonate random copolymer of the present invention is excellent in transparency and has a small photoelastic coefficient, so that it is useful as a material for optical devices.

〔Example〕

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

Example 1 2,2-bis (4'-hydroxyphenyl) propane 18.24
g (0.08 mol) and 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane 7.04 g (0.02 mol),
To a solution prepared by dissolving 200 ml of 2N aqueous sodium hydroxide solution, 200 ml 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, 1.0 ml of triethylamine was further added as a catalyst, and phosgene gas was blown into this at 20 ° C. at a rate of 200 ml / min for 15 minutes. Then, the supply of phosgene was stopped and the reaction was carried out at 28 ° C. for 1 hour. Methylene chloride (500 ml) was added to the reaction product, and the mixture was washed with 1.5 l of water. Further, the organic layer was washed with 0.01N hydrochloric acid 1 and water 1 in this order, then dropped into 2 l of methanol and reprecipitated to recover a copolymer. Then, it was dried under reduced pressure at 120 ° C. for 5 hours. The copolymer thus obtained,
The reduced viscosity [η _sp / c] of a 0.5 g / dl concentration solution using methylene chloride as a solvent was 0.65 dl / g. In addition, as a result of infrared absorption spectrum analysis of this copolymer, absorption at 1590 cm ⁻¹ by C—C bond of benzene ring, 3030 cm ⁻¹ and 830 cm ⁻¹
Absorption by C-H bond of a benzene ring, the absorption by the isopropyl group in 2850 cm ^-1, and absorption by carbonyl group at 1650 cm ^-1 was observed. Regarding the thermal properties, the glass transition temperature was 211 ° C. Furthermore, regarding the fluidity of this copolymer, the melt index at 280 ° C. and a load of 2160 g was 1.8 g / 10 minutes, and the tensile strength measured using a test piece molded at 350 ° C. was 700 kg / cm ² . .

Examples 2-4 2,2-bis (4'-hydroxyphenyl) propane and 1,1
Same as Example 1 except that the mixing ratio of -bis (4'-hydroxyphenyl) -1,1-diphenylmethane was 4: 6,3: 7,1: 9. The properties of the obtained copolymer are shown in Table 1.

Comparative Example 1 Only 22.8 g (0.1 mol) of 2,2-bis (4'-hydroxyphenyl) propane was used as the starting dihydric phenol,
Others were the same as in Example 1. The properties of the polymer obtained are shown in Table 1.

Comparative Example 2 As a dihydric phenol as a raw material, 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane 35.2 g (0.1
Mol) was used, and otherwise the same as in Example 1. The polymers obtained are shown in Table 1.

From the above results, the copolymer of the present invention has sufficient heat resistance and tensile strength as compared with the commonly used polycarbonate [Comparative Example 1] from 2,2-bis (4′-hydroxyphenyl) propane. It is recognized that it will improve. Further, it is recognized that the polycarbonate obtained from 1,1-bis (4'-hydroxyphenyl) -1,1-diphenylmethane [Comparative Example 2] is inferior in moldability and poor in practicality.

Claims (2)

[Claims] 1. A formula The repeating unit [I] represented by When the repeating unit [II] is represented by the following formula and the mole fractions of the repeating units [I] and [II] are m and n, respectively. Is 0.1-0.9 and the concentration at 20 ℃ is 0.5g / d
l methylene chloride solution has a reduced viscosity [η _sp / c] of 0.3 to 1.0 d
Polycarbonate random copolymer with l / g. 2. A formula 2,2-bis (4'-hydroxyphenyl) represented by
Propane and formula 1,1-bis (4'-hydroxyphenyl) represented by
1, an alkaline aqueous solution of a mixture of -1,1-diphenylmethane is mixed with an organic solvent, and then phosgene is introduced and reacted, The repeating unit [I] represented by When the repeating unit [II] is represented by the following formula and the mole fractions of the repeating units [I] and [II] are m and n, respectively. Is 0.1-0.9 and the concentration at 20 ℃ is 0.5g / d
l methylene chloride solution has a reduced viscosity [η _sp / c] of 0.3 to 1.0 d
A method for producing a polycarbonate random copolymer having an l / g.