JPH0774303B2 - Polycarbonate composition and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polycarbonate composition, a method for producing the same, and a polycarbonate modified composition containing the polycarbonate composition. More specifically, the present invention relates to a balance between fluidity and impact resistance. Of the polycarbonate composition, an efficient production method thereof, and a polycarbonate modified composition containing the polycarbonate composition and having excellent physical properties.

[Problems to be Solved by Prior Art and Invention]

Conventionally, some commercially available polycarbonates are high flow grades with simply reduced molecular weight to allow molding of complex and thinned products. However, such high flow grade polycarbonate is
There is a problem that mechanical strength, especially low temperature Izod impact strength, is poor due to the low molecular weight.

Therefore, the present inventor has conducted earnest studies to develop a polycarbonate or a polycarbonate composition which does not deteriorate in mechanical strength even when the molecular weight is reduced.

[Means for Solving the Problems]

As a result, tert-octylphenol (ie 1,1,3,3-tetramethylbutylphenol) as a molecular weight regulator
In addition, it was found that a polycarbonate composition in which p-tert-butylphenol or phenol was used at a fixed ratio and these were bonded at the molecular terminal position had performance suitable for the above purpose. The present invention has been completed based on such findings.

That is, the present invention is The main unit is a repeating unit represented by the formula (a) at the terminal position. A tert-octylphenoxy group represented by and (b)
formula A p-tert-butylphenoxy group and / or a formula The phenoxy group represented by the formula (a) is bound at a ratio of 10 to 99 mol% of tert-octylphenoxy group and (b) 90 to 1 mol% of p-tert-butylphenoxy group and / or phenoxy group. The present invention provides a polycarbonate composition, a method for producing the same, and a polycarbonate modified composition containing the polycarbonate composition. The polycarbonate composition of the present invention has a repeating unit represented by the above formula [I] as a main chain, and has a tert-octylphenoxy group (terminal group represented by the formula [II] at the terminal position. (A)) (Specifically, p-
There are tert-octylphenoxy group, o-tert-octylphenoxy group and m-tert-octylphenoxy group, and especially p
A -tert-octylphenoxy group is preferred. ) Together with a p-tert-butylphenoxy group represented by the formula [III] and / or a phenoxy group represented by the formula [IV] (terminal group (b)), 10 to 99 mol% of the terminal group (a), 90% to 1 mol% of the group (b), preferably 20 to 99% by mol of the terminal group (a) and 80 to 1% by mol of the terminal group (b). Here, if the terminal group (a) is less than 10 mol%, the mechanical strength will be insufficient.

The polycarbonate composition of the present invention has a main chain composed of repeating units of the formula [I] having an end group (a) bonded to one end and a terminal group (b) bonded to the other end, ] A mixture of a terminal group (a) bonded to both ends of a main chain composed of repeating units of [] and a mixture of terminal groups (b) bonded to both ends of a main chain composed of repeating units of the formula [I] (for example, , A mixture of, a mixture with, a mixture with, or a mixture with), and the average value of the terminal groups thereof is the above-mentioned ratio (mol%).

Further, various polycarbonates constituting the polycarbonate composition of the present invention, although not particularly limited as to the molecular weight, usually viscosity average molecular weight of 10,000 or more, preferably
It is 10,000 to 50,000, particularly preferably 15,000 to 30,000.

The polycarbonate composition of the present invention is a mixture of various polycarbonates having the repeating unit represented by the formula [I] as the main chain as described above and having the terminal group (a) and the terminal group (b) bonded at the terminal position. However, a small amount of repeating units other than the repeating unit of the formula [I] may be mixed in the molecular chain.

To produce the polycarbonate composition of the present invention,
There are various methods that can be considered, but there are roughly two methods. First, as the method I, in producing a polycarbonate composition, (a) tert-octylphenol (specifically, p-tert-octylphenol, o-tert-octylphenol or m-tert-octylphenol) 10 to 99 mol% And (b) p-tert
-Butylphenol and / or phenol 90-1
The method is characterized by using a mol% molecular weight regulator. Method II includes (a) a polycarbonate having 10-99 tert-octylphenoxy group bonded at the terminal position.
The method is characterized by kneading mol% and (b) 90 to 1 mol% of a polycarbonate having a p-tert-butylphenoxy group and / or a phenoxy group bonded at the terminal position.

In the above method I, when reacting bisphenol A dissolved in an alkaline aqueous solution with phosgene in the presence of an inert organic solvent, the molecular weight modifier ((a) tert-octylphenol 10 to 99 is used before or after the reaction. Mol%
And (b) p-tert-butylphenol and / or 90 to 1 mol% of phenol) are added and the interfacial polycondensation reaction is carried out to obtain the desired polycarbonate composition. Alternatively, a pyridine method may be used in which bisphenol A and the above-mentioned molecular weight modifier are dissolved in pyridine or a mixed solvent of pyridine and an inert organic solvent, and phosgene is blown into the solution to react.

It should be noted that other dihydric phenols may be used in place of or in addition to bisphenol A used as a raw material, in which case a polycarbonate composition containing a polycarbonate having a main chain of repeating units corresponding to the dihydric phenol used. It becomes a thing.

According to the above method I, the obtained polycarbonate composition is mainly composed of the above-mentioned mixture (1) to (3).

On the other hand, in method II, bisphenol A and phosgene are reacted using tert-octylphenol as a molecular weight regulator to produce a polycarbonate (A ₁ ) having a tert-octylphenoxy group at the molecular end, and separately from this. Polycarbonate (A ₂ ) having a p-tert-butylphenoxy group at the molecular end by reacting bisphenol A with phosgene using p-tert-butylphenol and / or phenol as a molecular weight modifier and / or a molecular end A desired polycarbonate composition can be obtained by producing a polycarbonate (A ₃ ) having a phenoxy group and kneading A ₁ 10 to 99 mol% with A ₂ and / or A ₃ 90 to ₁ mol%. . Also, the above A ₂ , A
Instead of or together with ₃ , a polycarbonate having a p-tert-butylphenoxy group at one molecular end and a phenoxy group at the other molecular end can also be used.

According to the above method II, the obtained polycarbonate composition is mainly composed of the mixture described above.

The polycarbonate constituting the polycarbonate composition of the present invention has sufficient mechanical properties and molding processability as it is because the specific substituents are bonded to the terminal positions at a constant ratio, and the polycarbonate is further Phosphorus antioxidant 0.01 to 0.1 to 100 parts by weight of the composition
The polycarbonate modified composition to which 3 parts by weight is added has a further excellent performance. This composition
It is obtained by mixing the above-mentioned polycarbonate composition and a phosphorus-based antioxidant by a known method.

Examples of the phosphorus-based antioxidant used here include tris (nonylphenyl) phosphite, 2-ethylhexidiphenylphosphite, trimethylphosphite, triethylphosphite, tributylphosphite, trioctylphosphite, and trinonylphosphite. Fight, tridecyl phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphosphite, tris (2-
Trialkylphosphites such as chloroethyl) phosphite and tris (2,3-dichloropropyl) phosphite; Tricycloalkylphosphites such as tricyclohexylphosphite; Triphenylphosphite, tricresylphosphite, tris (ethylphenyl) ) Phosphite, tris (butylphenyl) phosphite,
Triaryl phosphites such as tris (hydroxyphenyl) phosphite; trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate, distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate , Trialkyl phosphates such as tris (2,3-dichloropropyl) phosphate; tricycloalkyl phosphates such as tricyclohexyl phosphate; triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyl diphenyl phosphate, etc. , Triaryl phosphate, etc., which may be used alone or in a mixture of two or more kinds. It may be.

The amount of the phosphorus-based antioxidant is 0.01 to 0.13 with respect to 100 parts by weight of the polycarbonate composition of the present invention as described above.
It is necessary to select within the range of parts by weight. Here, if the blending amount of the phosphorus-based antioxidant is less than 0.01 parts by weight, the improvement of the mechanical strength of the resulting modified composition is small, and there is a risk of coloration. The strength tends to decrease.

In the polycarbonate composition of the present invention, other additives such as lubricants may be added if desired. Examples of this lubricant include stearyl alcohol, stearic acid monoglyceride, stearic acid ester such as pentaerythritol stearic acid ester, and beeswax. When this lubricant is added, it is preferable to add it in the range of 2000 to 4000 ppm with respect to the polycarbonate composition in order to improve the releasability at the time of molding.

In addition, in the polycarbonate composition of the present invention, an inorganic filler, a flame retardant, a stabilizer, a colorant and the like may be appropriately blended.

〔Example〕

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

Preparation Example (Preparation of Polycarbonate Oligomer) Bisphenol A was added to 400% 5% sodium hydroxide aqueous solution.
60 kg was dissolved to prepare an aqueous sodium hydroxide solution of bisphenol A.

Then, the sodium hydroxide aqueous solution of bisphenol A kept at room temperature was supplied at a flow rate of 138 / hour and methylene chloride was supplied at a flow rate of 69 / hour at an inner diameter of 10 mm and a tube length of 1 mm.
It was introduced into a 0 m tubular reactor through an orifice plate, and phosgene was co-currently injected into the reactor at a flow rate of 10.7 kg / hour, and 3
The reaction was continued for a period of time. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid is
Adjusted to show 10-11. The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and a methylene chloride phase (220) was collected. To this, methylene chloride 170 was further added, and the mixture was thoroughly stirred. Polycarbonate oligomer (concentration: 317 g /) was used. The degree of polymerization of the polycarbonate oligomer obtained here was 3 to 4.

Synthesis Example 1 (Production of Polycarbonate Resin A ₁ ) 9.0 Polycarbonate Oligomer Obtained in Preparation Example above
0.51 mol of p-tert-octylphenol [4- (1,1,3,3-tetramethylbutyl) phenol] as a molecular weight modifier was dissolved therein. Meanwhile, sodium hydroxide 2
Dissolve 3.5 g (0.59 mol) in 600 cc of water and add triethylamine
Add 5.2 cc, add this to the polycarbonate oligomer in which the molecular weight regulator is dissolved, and add 1 at room temperature at 500 rpm.
Stir for hours.

Then, an aqueous sodium hydroxide solution of methylene chloride 9.6 and bisphenol A (bisphenol A 611 g,
(Containing 357 g of NaOH) was added, and the mixture was stirred at 500 rpm for 2 hours at room temperature.

After that, methylene chloride 3 was added, followed by washing with water 5, washing with 0.01N aqueous sodium hydroxide solution 5 with alkali, washing with 0.1N hydrochloric acid 5 with acid, and washing with water 5, and finally removing methylene chloride. Chip-shaped polycarbonate (polycarbonate resin A ₁ )
Got The viscosity average molecular weight of the obtained polycarbonate resin A ₁ was 1.9 × 10 ⁴ .

Synthesis Example 2 (Production of Polycarbonate Resin A ₂ ) The same procedure as in Synthesis Example 1 was performed except that the molecular weight modifier was changed from p-tert-octylphenol to p-tert-butylphenol in Synthesis Example 1, and a chip shape was obtained. Polycarbonate (polycarbonate resin A ₂ ) was obtained. The viscosity average molecular weight of the obtained polycarbonate resin A ₂ is 1.9.
It was × 10 ⁴ .

Synthesis Example 3 (Production of Polycarbonate Resin A ₃ ) In Synthesis Example 1, the same operation as in Synthesis Example 1 was performed except that the molecular weight modifier was changed from p-tert-octylphenol to phenol. Resin A ₃ ) was obtained. The viscosity average molecular weight of the obtained polycarbonate resin A ₃ was 1.9 × 10 ⁴ .

Synthetic Example 4 (Production of Polycarbonate Resin A ₄ ) In Synthetic Example 1, the molecular weight regulator was replaced by 0.51 mol of p-tert-octylphenol, and instead of 0.51 mol of p-tert-octylphenol, 0.255 mol of p-tert-octylphenol and p-tert-butylphenol.
A chip-like polycarbonate composition (polycarbonate resin A ₄ ) was obtained by performing the same operations as in Synthesis Example 1 except that the amount was 0.255 mol. Obtained polycarbonate resin
The viscosity average molecular weight of A ₄ was 1.9 × 10 ⁴ .

Synthetic Example 5 (Production of Polycarbonate Resin A ₅ ) Synthetic Example 1 except that in Synthesis Example 1, p-tert-octylphenol was 0.459 mol and phenol was 0.051 mol instead of p-tert-octylphenol of 0.51 mol. The same operation as in 1 was carried out to obtain a chip-shaped polycarbonate composition (polycarbonate resin A ₅ ). The viscosity average molecular weight of the obtained polycarbonate resin A ₅ was 1.9 × 10 ⁴ .

Examples 1 to 9, Comparative Example 1 and Reference Examples 1 to 3 The polycarbonate resins (A _{1 to} A ₅ ) obtained in the above Synthetic Examples 1 to 4 were mixed at the weight ratios shown in Table 1 below, and 220 to 270 ℃
Then, it was extruded and granulated. The obtained pellets were injection-molded and the Izod impact strength was measured. The results are shown in Table 2.

Examples 10 to 15, Comparative Example 2 and Reference Examples 4 and 5 Polycarbonate resins (A _{1 to} A ₅ ) obtained in the above Synthesis Examples 1 to 4 and phosphorous antioxidants in the quantitative ratios shown in Table 3 below. (B _1: tris (nonylphenyl) phosphite, B _2: 2-
Ethylhexyl diphenyl phosphite),
The polycarbonate resin was modified by an extruder at 0 to 270 ° C. and granulated. The obtained pellets were injection-molded and the Izod impact strength was measured.

The results are shown in Table 4.

Next, the molar ratio of the p-tert-octylphenoxy group, the p-tert-butylphenoxy group and the phenoxy group in the polycarbonate resin (polycarbonate or polycarbonate composition) or a modified product thereof in the above Examples and Comparative Examples is determined by the proton nuclear magnetic field. It was calculated from the measured values of the resonance spectrum (deuterated chloroform solvent). The results are shown in Table 5.

Furthermore, the Izod impact strength of the sample obtained from the polycarbonate resin (polycarbonate or polycarbonate composition) or its modified product in the above-mentioned Examples, Comparative Examples and Reference Examples at −5 ° C., and p-tert-octyl in the sample. The relationship between the phenoxy group and the molar ratio of the p-tert-butylphenoxy group is shown in FIG.

〔The invention's effect〕

According to the present invention, it is possible to obtain a so-called high-flow high-impact polycarbonate composition having high flowability and excellent impact resistance, particularly low temperature impact resistance, and a modified composition thereof.

Therefore, the polycarbonate composition and the modified composition thereof of the present invention can be molded into thin-walled and complicated shapes which have been difficult in the past, and have a sufficient mechanical strength even when the molecular weight is lowered to obtain a high flow grade. Can be held.

Therefore, the polycarbonate composition and its modified composition of the present invention can be used for various industrial materials such as household appliances, O
Widely and effectively used in equipment and building materials.

[Brief description of drawings]

FIG. 1 shows the Izod impact strength of a sample obtained from the polycarbonate resin (polycarbonate or polycarbonate composition) or its modified product in Examples, Comparative Examples and Reference Examples, and the p-tert-octylphenoxy group and p in the sample. It is a graph which shows the relationship with the molar ratio of -tert- butylphenoxy group.

Claims (5)

[Claims] 1. A formula The main unit is a repeating unit represented by the formula (a) at the terminal position. A tert-octylphenoxy group represented by and (b)
formula A p-tert-butylphenoxy group and / or a formula The phenoxy group represented by the formula (a) is bound at a ratio of 10 to 99 mol% of tert-octylphenoxy group and (b) 90 to 1 mol% of p-tert-butylphenoxy group and / or phenoxy group. A polycarbonate composition. 2. A polycarbonate having (a) a tert-octylphenoxy group bonded at the terminal position and (b) p-te at the terminal position.
A mixture with a polycarbonate having rt-butylphenoxy groups and / or phenoxy groups bound thereto.
The polycarbonate composition described. 3. Use of a molecular weight modifier comprising (a) 10-99 mol% of tert-octylphenol and (b) 90-1 mol% of p-tert-butylphenol in producing a polycarbonate composition. The method for producing the polycarbonate composition according to claim 1, wherein 4. A polycarbonate having 10 to 99 mol% of a polycarbonate having (a) a tert-octylphenoxy group bonded at the terminal position and a polycarbonate (90) having a (b) p-tert-butylphenoxy group and / or a phenoxy group bonded at the terminal position. 1 mol%
The method for producing a polycarbonate composition according to claim 2, characterized in that and are kneaded. 5. A phosphorus-based antioxidant of 0.01 to 0.13 per 100 parts by weight of the polycarbonate composition according to claim 1 or 2.
A polycarbonate modified composition, characterized in that parts by weight are added.