Copolycarbonate and composition comprising the same

Abstract

The present invention relates to a copolycarbonate and a molded article comprising the same. The copolycarbonates according to the present invention has a structure in which a specific siloxane compound is introduced in a main chain of the polycarbonate, and has effects of improving impact strength at room temperature, impact strength at low temperature, and melt index properties.

Claims

1. A copolycarbonate comprising: 1) a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, and 2) a repeating unit represented by the following Chemical Formula 4, wherein the copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g/mol: ##STR00023## in Chemical Formula 2, each of X.sub.2 is independently C.sub.1-10 alkylene, each of Y.sub.1 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, alkoxy or C.sub.6-20 aryl, each of R.sub.2 is independently hydrogen; or C.sub.1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl-substituted C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and m is an integer of 10 to 200, ##STR00024## in Chemical Formula 3, each of X.sub.3 is independently C.sub.1-10 alkylene, each of Y.sub.2 is independently C.sub.1-10 alkoxy, each of R.sub.3 is independently hydrogen; or C.sub.1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl-substituted alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and l is an integer of 10 to 200, ##STR00025## in Chemical Formula 4, X is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO, and R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen.

2. The copolycarbonate of claim 1, wherein R.sub.1, R.sub.2 and R.sub.3 are each independently C.sub.1-6 alkyl.

3. The copolycarbonate of claim 1, in n, m and 1 are each independently an integer of 30 to 60.

4. The copolycarbonate of claim 1, wherein a weight ratio between the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 is 1:99 to 99:1.

5. The copolycarbonate of claim 1, wherein Chemical Formula 2 is represented by the following Chemical Formula 2-1: ##STR00026##

6. The copolycarbonate of claim 1, wherein Chemical Formula 3 is represented by the following Chemical Formula 3-1: ##STR00027##

7. The copolycarbonate of claim 1, wherein the repeating unit represented by Chemical Formula 4 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-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)diphenylmethane.

8. The copolycarbonate of claim 1, wherein Chemical Formula 4 is represented by the following Chemical Formula 4-1: ##STR00028##

9. The copolycarbonate of claim 1, wherein the copolycarbonate has a weight average molecular weight of 15,000 to 40,000 g/mol.

10. A polycarbonate composition comprising: a polycarbonate; and the copolycarbonate of claim 1.

11. The polycarbonate composition of claim 10, therein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

12. The polycarbonate composition of claim 10, wherein the polycarbonate comprises a repeating unit represented b e following Chemical Formula 5: ##STR00029## in Chemical Formula 5, R.sub.4, R.sub.5, R.sub.6 and R.sub.7 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, X is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2 or CO.

13. The polycarbonate composition of claim 10, wherein a weight ratio of the copolycarbonate and the polycarbonate is from 99:1 to 1:99.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

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

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

(2) ##STR00017##

(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) relative 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 30 when confirmed through .sup.1H NMR.

(4) To 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 added and reacted at 90 C. for 3 hours. After completion of the reaction, the unreacted polyorganosiloxane was removed by conducting evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was pale yellow oil and the repeating unit (n) was 30, and further purification was not required. The preparation thereof was confirmed through .sup.1H NMR and this was designated as AP-30.

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

(5) ##STR00018##

(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) relative 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 60 when confirmed through .sup.1H NMR.

(7) To 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 added and reacted at 90 C. for 3 hours. After completion of the reaction, the unreacted polyorganosiloxane was removed by conducting evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was pale yellow oil, the repeating unit (n) was 60, and further purification was not required. The preparation thereof was confirmed through .sup.1H NMR and this was designated as AP-60.

Preparation Example 3: Preparation of Polyorganosiloxane (MB-30)

(8) ##STR00019##

(9) The polyorganosiloxane was prepared in the same manner as in Preparation Example 1, except that 3-methylbut-3-enyl 4-hydroxybenzoate (14.7 g) was used instead of 2-allyphenol, and the repeating unit (m) was 30, which was confirmed through .sup.1H NMR and designated as MB-30.

Preparation Example 4: Preparation of Polyorganosiloxane (MB-60)

(10) ##STR00020##

(11) The polyorganosiloxane was prepared in the same manner as in Preparation Example 2, except that 3-methylbut-3-enyl 4-hydroxybenzoate (10.8 g) was used instead of 2-allyphenol, and the repeating unit (m) was 60, which was confirmed through .sup.1H NMR and designated as MB-60.

Preparation Example 5: Preparation of Polyorganosiloxane (Eu-30)

(12) ##STR00021##

(13) The polyorganosiloxane was prepared in the same manner as in Preparation Example 1, except that Eugenol (11.7 g) was used instead of 2-allyphenol, and the repeating unit (l) was 30, which was confirmed through .sup.1H NMR and designated as Eu-30.

Preparation Example 6: Preparation of Polyorganosiloxane (Eu-60)

(14) ##STR00022##

(15) The polyorganosiloxane was prepared in the same manner as in Preparation Example 2, except that Eugenol (8.7 g) was used instead of 2-allyphenol, and the repeating unit (l) was 60, which was confirmed through .sup.1H NMR and designated as Eu-60.

Example 1-1

(16) 1) Preparation of Copolycarbonate Resin

(17) 978.4 g of Bisphenol A (BPA), 1,620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were added to 20 L glass reactor. After confirming that BPA was completely dissolved under 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 wt. % of polyorganosiloxane (AP-30) of Preparation Example 1 and 20 wt. % of polyorganosiloxane (MB-30) of Preparation Example 3) were added 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 added. 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 resin was measured by GPC using PC Standard and the result confirmed that the weight average molecular weight was 28,100 g/mol.

(18) 2) Preparation of Injection Specimen

(19) To the copolycarbonate resin prepared above, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite, 0.010 parts by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 0.030 parts by weight of pentaerythritoltetrastearate were added, and the resulting mixture was pelletized using a 30 mm twin screw extruder provided with a vent. Thereafter, a specimen was injection-molded at a cylinder temperature of 300 C. and a mold temperature of 80 C. using an injection molding machine N-20C (manufactured by JSW, Ltd.)

Examples 1-2 to 6-4 and Comparative Examples 1 to 6

(20) The copolycarbonate resin and its injection-molded specimen were prepared in the same method as in Example 1-1, except that the kind and content of polyorganosiloxane was used as shown in Table 1 below. In Table 1, Comparative Examples 1 to 6 show that one kind of polyorganosiloxane was used.

(21) TABLE-US-00001 TABLE 1 Preparation Preparation Preparation Preparation Preparation Preparation Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 (AP-30) (AP-60) (MB-30) (MB-60) (Eu-30) (Eu-60) 20 wt % 20 wt % 20 wt % % 20 wt % 20 wt % 20 wt % Preparation Comparative Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1 Example 1 (AP-30) 80 wt % Preparation Comparative Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2 Example 2 (AP-60) 80 wt % Preparation Example 3-1 Example 3-2 Comparative Example 3-3 Example 3-4 Example 3 Example 3 (MB-30) 80 wt % Preparation Example 4-1 Example 4-2 Comparative Example 4-3 Example 4-4 Example 4 Example 4 (MB-60) 30 wt % Preparation Example 5-1 Example 5-2 Example 5-3 Example 5-4 Comparative Example 5 Example 5 (Eu-30) 80 wt % Preparation Example 6-1 Example 6-2 Example 6-3 Example 6-4 Comparative Example 6 Example 6 (Eu-60) 80 wt %

Comparative Example 7

(22) The polycarbonate resin and its injection-molded specimen were prepared in the same method as in Example 1, except that the polyorganosiloxane was not used.

Experimental Example: Evaluation of Physical Properties

(23) The physical properties of the copolycarbonate specimens prepared in the examples and of the polycarbonate specimens prepared in the comparative examples were determined in the following manner and the results were shown in Tables 2 to 4 below. Weight average molecular weight (g/mol): measured by PC Standard using Agilent 1200 series. Melt Index (MI): measured in accordance with ASTM D 1238 (conditions of 300 C. and 1.2 kg). 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 ( inch, Notched Izod). Repeating unit: determined by .sup.1H-NMR using Varian 500 MHz.

(24) TABLE-US-00002 TABLE 2 Impact strength at Weight strength at Impact Melt average room low index molecular Example temperature temperature (MI) weight Number (23 C., J/m) (30 C., J/m) (g/10 min) (Mw, g/mol) Example 1-1 663 210 15 28,100 Example 1-2 823 711 11 29,500 Example 1-3 480 120 16 27,800 Example 1-4 531 180 17 27,500 Comparative 561 115 18 26,800 Example 1 Example 2-1 632 480 13 29,300 Example 2-2 780 695 9 30,900 Example 2-3 610 435 12 28,800 Example 2-4 635 448 14 28,300 Comparative 713 630 7 30,900 Example 2

(25) TABLE-US-00003 TABLE 3 Impact Impact Weight strength at strength at Melt average room room index molecular Example temperature temperature (MI) weight Number (23 C., J/m) (23 C., J/m) (g/10 min) (Mw, g/mol) Example 3-1 266 266 25 25,900 Example 3-2 528 528 16 27,100 Example 3-3 218 218 26 25,800 Example 3-4 323 323 20 26,300 Comparative 443 443 18 26,800 Example 3 Example 4-1 618 618 15 27,800 Example 4-2 590 590 14 28,500 Example 4-3 448 448 20 26,500 Example 4-4 438 438 16 26,900 Comparative 486 486 14 27,500 Example 4

(26) TABLE-US-00004 TABLE 4 Impact Impact Weight strength at strength at Melt average room low index molecular Example temperature temperature (MI) weight Number (23 C., J/m) (30 C., J/m) (g/10 min) (Mw, g/mol) Example 5-1 480 261 17 27,100 Example 5-2 528 463 13 28,100 Example 5-3 231 136 22 25,300 Example 5-4 665 593 14 30,100 Comparative 124 117 33 25,100 Example 5 Example 6-1 650 499 17 27,900 Example 6-2 703 580 12 28,500 Example 6-3 689 615 14 30,000 Example 6-4 765 638 9 31,800 Comparative 659 636 7 31,300 Example 6 Comparative 660 116 14 27,500 Example 7