Copolycarbonate and composition containing the same

Abstract

Disclosed is a copolycarbonate including aromatic polycarbonate-based repeating units represented by Chemical Formula 1 and Chemical Formula 2; and aromatic polycarbonate-based repeating units having siloxane bonds represented by Chemical Formula 3 and Chemical Formula 4: ##STR00001##
copolycarbonate provides improved impact strength at low-temperature, improved YI (yellow index), and improved melt index simultaneously.

Claims

1. A copolycarbonate comprising: i) a repeating unit represented by the following Chemical Formula 1, ii) a repeating unit represented by the following Chemical Formula 2, iii) a repeating unit represented by the following Chemical Formula 3, and iv) 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: ##STR00019## in the Chemical Formula 1, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z.sub.1 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, ##STR00020## in the Chemical Formula 2, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11, and R.sub.12 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z.sub.2 and Z.sub.3 are each independently 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 A is C.sub.1-15 alkylene, ##STR00021## in the Chemical Formula 3, each of X.sub.1 is independently C.sub.1-10 alkylene, each of R.sub.13 is independently hydrogen; 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 n is an integer of 10 to 200, ##STR00022## in the Chemical Formula 4, 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, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, each of R.sub.14 is independently hydrogen; 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.

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

3. The copolycarbonate of claim 1, wherein the repeating unit represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1: ##STR00023##

4. The copolycarbonate of claim 1, wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, R.sub.10, R.sub.11 and R.sub.12 are each independently hydrogen, methyl, chloro, or bromo.

5. The copolycarbonate of claim 1, wherein Z.sub.2 and Z.sub.3 are each independently a linear or brached C.sub.1-10 alkylene unsubstituted or substituted with phenyl, cyclohexane-1,1-diyl, O, S, SO, SO.sub.2, or CO.

6. The copolycarbonate of claim 1, wherein A is a linear C.sub.1-10 alkylene.

7. The copolycarbonate of claim 1, wherein the repeating unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-1: ##STR00024##

8. The copolycarbonate of claim 1, wherein the weight ratio of the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 2 is 1:0.001 to 1:0.3.

9. The copolycarbonate of claim 1, wherein the weight ratio between the weight of the repeating unit represented by Chemical Formula 1 and the total weight of one or more of the repeating unit represented by Chemical Formula 3 and the repeating unit represented by Chemical Formula 4 is 1:0.001 to 1:0.1.

10. The copolycarbonate of claim 1, wherein the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2: ##STR00025##

11. The copolycarbonate of claim 10, wherein R.sub.13 is methyl.

12. The copolycarbonate of claim 1, wherein the repeating unit represented by Chemical Formula 4 is represented by the following Chemical Formula 4-2: ##STR00026##

13. The copolycarbonate of claim 12, wherein R.sub.14 is methyl.

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

15. A polycarbonate composition comprising the copolycarbobnate of claim 1, and a polycarbonate.

16. The polycarbonate composition of claim 15, wherein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

17. The polycarbonate composition of claim 15, wherein the above polycarbonate comprises a repeating unit represented by the following Chemical Formula 5: ##STR00027## in the Chemical Formula 5, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z 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.

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 designated as AP-30. AP-30 was pale yellow oil and the repeating unit (n) was 30 when confirmed through .sup.1H NMR using a Varian 500 MHz and further purification was not required.

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

(5) ##STR00018##

(6) 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 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 (m) of the terminal-unmodified polyorganosiloxane thus prepared was 60 when confirmed through .sup.1H NMR.

(7) To the resulting terminal-unmodified polyorganosiloxane, 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate 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 siloxane was removed by conducting evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was designated as MB-60. MB-60 was pale yellow oil, the repeating unit (m) was 60 when confirmed through .sup.1H NMR using a Varian 500 MHz and further purification was not required.

Example 1

(8) 978.4 g of Bisphenol A (BPA), 3.927 g of BPDA (bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate), 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, 17.9 g of p-tert-butylphenol (PTBP), and 44.028 g of polyorganosiloxane previously prepared and 4.892 g of polyorganosiloxane (MB-60) of Preparation Example 2 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. Alter 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.

Examples 2 to 6 and Comparative Examples 1 to 4

(9) The copolycarbonate were prepared by the same method as in Example 1, except that the reaction materials were used in the content as shown in Table 1 below.

(10) TABLE-US-00001 TABLE 1 BPA(g) BPDA(g) AP-30(g) MB-60(g) Example 1 978.4 3.927 44.028 4.892 Example 2 974.4 14.66 43.848 4.872 Example 3 961.8 48.17 43.281 4.809 Example 4 974.4 14.66 46.284 2.436 Example 5.sup.1) 974.4 14.66 43.281 4.809 Example 6 974.4 14.66 43.848 4.872 Comparative 979.9 Example 1 Comparative 961.8 41.031 4.559 Example 2 Comparative 969.0 29.06 Example 3 Comparative 979.9 48.995 Example 4 .sup.1)31.92 g of PTBP was used

Experimental Example: Confirmation of Characteristics of Copolycarbonate

(11) The weight average molecular weight of the copolycarobates prepared in the examples and comparative examples were measured by GPC using PC Standard with Agilent 1200 series.

(12) In addition, with respect to 1 part by weight of the respective copolycarbonates prepared in the examples and comparative examples, 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 pentaerythritol tetrastearate were added thereto, and the resulting mixture was pelletized using a 30 mm twin-screw extruder provided with a vent, and 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.) to prepare a desired specimen.

(13) The characteristics of the above specimens were determined by the following method and the results were shown in Table 2 below.

(14) 1) Impact strength at room temperature: measured at 23 C. in accordance with ASTM 0256 ( inch, Notched Izod).

(15) 2) Impact strength at low temperature: measured at 30 C. in accordance with ASTM D256 ( inch, Notched Izod).

(16) 3) YI (Yellow Index): A specimen (width/length/thickness=60 mm/40 mm/3 mm) was prepared by injection molding and YI (Yellow Index) was measured using Color-Eye 7000A (manufactured by X-Rite Ltd.) in accordance with ASTM 01925. The measurement condition was as follows. Measurement temperature: room temperature (23 C.) Aperture size: Large area of view Measurement method: transmittance was measured in a spectral range (360 nm to 750 nm).

(17) 4) Melt index (MI): measured in accordance with ASTM 01238 (conditions of 300 C. and 1.2 kg).

(18) TABLE-US-00002 TABLE 2 Impact strength Impact strength at room at low MI Mw temperature temperature (g/10 (g/mol) (J/m) (J/m) YI min) Example 1 34000 1000 980 1.79 6.1 Example 2 34000 960 924 1.78 7.5 Example 3 34000 890 830 1.75 13.2 Example 4 34000 840 635 1.76 7.2 Example 5 27000 780 600 1.69 19.3 Example 6 34000 834 685 1.79 8.3 Comparative 34000 950 190 1.75 5.7 Example 1 Comparative 34000 1090 980 5.9 4.1 Example 2 Comparative 34000 820 230 0.93 14.4 Example 3 Comparative 34000 890 484 5.3 4.2 Example 4