Copolycarbonate and composition comprising the same

Abstract

The present invention relates to copolycarbonates and a composition comprising the same. The copolycarbonate according to the present invention has a structure in which specific siloxane compounds are introduced in the main chain of polycarbonate and thus exhibits the effects of improving impact strength at room temperature, impact strength at low-temperature, and melt index.

Claims

1. A polycarbonate composition comprising: a copolycarbonate; and a polycarbonate, wherein the copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g/mol, which comprises: a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2, and a repeating unit represented by the following Formula 3: ##STR00015## in the above Formula 1, each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is independently hydrogen, C.sub.1-10 alkyl, or halogen, and Z is C.sub.1-10 alkylene unsubstituted or substituted by phenyl, C.sub.3-10 cycloalkylene, O, S, SO, SO.sub.2, or CO, ##STR00016## in the above Formula 2, each of Ra is independently C.sub.1-10 alkylene, each of R.sub.5 is independently hydrogen, or C.sub.1-13 alkyl, and n is an integer of 1 to 40, ##STR00017## in the above Formula 3, each of Rb is independently C.sub.1-10 alkylene, each of R.sub.6 is independently hydrogen, or C.sub.1-13 alkyl, and m is an integer of 41 to 85, wherein a ratio of the weight of the repeating unit represented by Formula 1 to the total weight of the repeating units represented by Formula 2 and Formula 3 is 1:0.04 to 1:0.07, and wherein a weight ratio of the copolycarbonate and the polycarbonate is from 80:20 to 50:50.

2. The polycarbonate composition of claim 1 wherein the repeating unit represented by the Formula 1 is derived from one or more aromatic diol compounds selected from the group consisting of bis(4-hydroxyphenyl) methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and a,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

3. The polycarbonate composition of claim 1 wherein the repeating unit represented by the Formula 1 is represented by the following Formula 1-1: ##STR00018##

4. The polycarbonate composition of claim 1 wherein each of R.sub.5 is independently C.sub.1-6 alkyl.

5. The polycarbonate composition of claim 1 wherein each of R.sub.6 is independently C.sub.1-6 alkyl.

6. The polycarbonate composition of claim 1 wherein R.sub.5 and R.sub.6 are the same as each other.

7. The polycarbonate composition of claim 1 wherein n is an integer of 10 to 35.

8. The polycarbonate composition of claim 1 wherein m is an integer of 45 to 85.

9. The polycarbonate composition of claim 1 wherein the repeating unit represented by the Formula 2 is represented by the following Formula 2-1: ##STR00019##

10. The polycarbonate composition of claim 1 wherein the repeating unit represented by the Formula 3 is represented by the following Formula 3-1: ##STR00020##

11. The polycarbonate composition of claim 1 wherein the copolycarbonate has a weight average molecular weight of 15,000 to 35,000 g/mol.

12. The polycarbonate composition of claim 1, wherein the polycarbonate comprises the repeating unit represented by the following Formula 4: ##STR00021## in the above Formula 1, each of R′.sub.1, R′.sub.2, R′.sub.3 and R′.sub.4 are independently hydrogen, C.sub.1-10 alkyl, or halogen, and Z′ is C.sub.1-10 alkylene unsubstituted or substituted by phenyl, C.sub.3-10 cycloalkylene, O, S, SO, SO.sub.2, or CO.

13. The polycarbonate composition of claim 1, wherein the weight ratio of the copolycarbonate and the polycarbonate is from 80:20 to 60:40.

Description

MODE FOR THE INVENTION

(1) Below, the preferred embodiments are presented to aid in the understanding of the invention. However, these examples are provided only for illustration of the present invention, and should not be construed as limiting the present invention by the examples.

Preparation Example 1: Production of Polyorganosiloxane (AP-30)

(2) ##STR00013##

(3) 42.5 g (142.8 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed. The mixture was then placed in 3 L flask together with 1 part by weight of an acid clay (DC-A3) compared to 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60° C. for 4 hours. After completion of the reaction, the reaction product was diluted with ethyl acetate and quickly filtered using a celite. The repeating unit (n) of the unmodified polyorganosiloxane thus prepared was confirmed through .sup.1H NMR and the result was 30.

(4) In the resulting terminal-unmodified polyorganosiloxane, 9.57 g (71.3 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karstedt's platinum catalyst were introduced and reacted at 90° C. for 3 hours. After completion of the reaction, the unreacted polyorganosiloxane was removed by conducting the evaporation under the conditions of 120° C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was a pale yellow oil and the repeating unit (n) was 30. Further purification was not required. The preparation of the polyorganosiloxane represented by the Formula 1 was confirmed through .sup.1H NMR and this was designated as AP-30.

Preparation Example 2: Preparation of Polyorganosiloxane (AP-60)

(5) ##STR00014##

(6) 57.5 g (193.2 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed. The mixture was then introduced in 3 L flask together with 1 part by weight of an acid clay (DC-A3) compared to 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60° C. for 4 hours. After completion of the reaction, the reaction product was diluted with ethyl acetate and quickly filtered using a celite. The repeating unit (n) of the unmodified polyorganosiloxane thus prepared was confirmed through .sup.1H NMR and the result was 60.

(7) In the resulting terminal-unmodified polyorganosiloxane, 7.07 g (60.6 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karstedt's platinum catalyst were introduced and reacted at 90° C. for 3 hours. After completion of the reaction, the unreacted polyorganosiloxane was removed by conducting the evaporation under the conditions of 120° C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was a pale yellow oil and the repeating unit (n) was 60. Further purification was not required. The preparation of the polyorganosiloxane represented by the Formula 1 was confirmed through .sup.1H NMR and this was designated as AP-60.

Preparation Example 3: Preparation of Polycarbonate

(8) 978.4 g of Bisphenol A (BPA), 1,620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were introduced in 20 L glass reactor. After confirming that BPA was completely dissolved in a nitrogen atmosphere, 3,670 g of methylene chloride and 18.3 g of p-tert-butylphenol were introduced and mixed. To this mixture, 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added dropwise for one hour. At this time, a NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and introduced. After 10 minutes, pH was adjusted to 3 with a 1N aqueous hydrochloric acid solution and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to give a polycarbonate resin in the form of a powder. The molecular weight was measured with GPC using PC Standard and the result confirmed that the weight average molecular weight was 27,500 g/mol.

Example 1

(9) Step 1: Preparation of Copolycarbonate

(10) 978.4 g of Bisphenol A (BPA), 1.620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were introduced in 20 L glass reactor. After confirming that BPA was completely dissolved in a nitrogen atmosphere, 3,670 g of methylene chloride, 18.3 g of p-tert-butylphenol, and 55.2 g of polyorganosiloxane previously prepared (mixture of 80% by weight of polyorganosiloxane (AP-30) of Preparation Example 1 and 20% by weight of polyorganosiloxane (AP-60) of Preparation Example 2) were introduced and mixed. To this mixture, 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added dropwise for one hour. At this time, a NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and introduced. After 10 minutes, pH was adjusted to 3 with 1N aqueous hydrochloric acid solution and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to give a copolycarbonate resin in the form of a powder. The molecular weight of the resulting copolycarbonate was measured with GPC using PC Standard and the result confirmed that the weight average molecular weight was 29,500 g/mol.

(11) Step 2: Preparation of Injection Specimen

(12) To the copolycarbonate prepared in the step 1, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite, 0.010 parts by weight of octadecyl-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate, and 0.030 parts by weight of pentaerythritoltetrastearate were added, and the resulting mixture was pelletized using a vented φ30 mm twin screw extruder. Thereafter, a specimen was injection-molded using a cylinder temperature of 300° C. and a mold temperature of 90° C. using the N-20C injection molding machine of JSW Co., Ltd.

Example 2

(13) The copolycarbonate and its specimen were prepared in the same method as in Example 1, except that 55.2 g of polyorganosiloxane (mixture of 20% by weight of polyorganosiloxane (AP-30) of Preparation Example 1 and 80% by weight of polyorganosiloxane (AP-60) of Preparation Example 2) was used.

Example 3

(14) The polycarbonate composition and its specimen were prepared using 80% by weight of copolycarbonate prepared in step 1 of Example 1 and 20% by weight of polycarbonate of Preparation Example 3, instead of the copolycarbonate prepared in step 2 of Example 1.

Comparative Example 1

(15) The copolycarbonate and its specimen were prepared by the same method as in Example 1, except that 55.2 g of polyorganosiloxane (100% by weight of polyorganosiloxane (AP-30) of Preparation Example 1) was used.

Comparative Example 2

(16) The copolycarbonate and its specimen were prepared by the same method as in Example 1 except that 55.2 g of polyorganosiloxane (100% by weight of polyorganosiloxane (AP-60) of Preparation Example 1) was used.

Comparative Example 3

(17) The molded specimen of the copolycarbonate was prepared using the polycarbonate of Preparation Example 3, instead of the copolycarbonate prepared in step 2 of Example 1.

Experimental Example: Evaluation of Physical Properties

(18) The physical properties of the copolycarbonate specimens prepared in the Examples and the polycarbonate specimens prepared in the Comparative Examples were measured in the following manner and the results were shown in Table 1 below.

(19) Weight average molecular weight (g/mol): measured by Agilent 1200 series using PC Standard.

(20) Melt index (MI): measured in accordance with ASTM D 1238 (300° C., 1.2 kg conditions).

(21) Impact strength at room temperature, and impact strength at low-temperature (J/m): measured at 23° C. and −30° C. in accordance with ASTM D256 (⅛ inch, Notched Izod).

(22) Repeating unit: measured by .sup.1H-NMR using a Varian 500 MHz.

(23) Transparency (Haze): measured by specimens with a thickness of 3 mm in accordance with ASTM D1003.

(24) TABLE-US-00001 TABLE 1 Impact Impact Weight strength strength average at room at low Melt molecular temperature temperature index weight Trans- Classi- (23° C., (−30° C., (MI, (Mw, parency fication J/m) J/m) g/10 min) g/mol) (Haze, %) Ex. 1 640 519 15 27,300 0.5 Ex. 2 680 591 10 29,100 0.9 Ex. 3 611 484 18 27,400 0.3 Com. 561 115 18 26,800 0.3 Ex. 1 Com. 713 630 7 30,900 2.9 Ex. 2 Com. 660 116 14 27,500 0.1 Ex. 3