Copolycarbonate and composition containing the same

Abstract

Disclosed is a polycarbonate composition including a polycarbonate; and a copolycarbonate, where the copolycarbonate includes an aromatic polycarbonate-based first repeating unit; and aromatic polycarbonate-based second repeating units having siloxane bonds, which include a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, where the copolycarbonate has a melt index (MI) of 3 to 9 g/10min as measured in accordance with ASTM D1238 (300 C., 1.2 kg conditions), and a transparency of 87 to 91% as measured in accordance with ASTM D1003 (layer thickness of 3 mm): ##STR00001## The copolycarbonate in the composition exhibits an excellent transparency and a high spiral flow while having a high impact strength at room temperature and a low melt index.

Claims

1. A polycarbonate composition comprising: a polycarbonate; and a copolycarbonate, wherein the copolycarbonate comprises: an aromatic polycarbonate-based first repeating unit; and aromatic polycarbonate-based second repeating units having siloxane bonds, wherein the copolycarbonate has a melt index (MI) of 3 to 9 g/10 min as measured accordance with ASTM D1238 (300 C., 1.2 kg conditions), and a transparency of 87 to 91% as measured in accordance with ASTM D1003 (layer thickness of 3 mm), and wherein the second repeating units comprise a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3: ##STR00017## in Chemical Formula 2, each of X.sub.1 is independently C.sub.1-10 alkylene, each of R.sub.5 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.1-10haloalkyl; or C.sub.6-20 aryl, and n is an integer of 10 to 50, ##STR00018## in Chemical Formula 3, 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.6 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.1-10haloalkyl; or C.sub.6-20 aryl, and m is an integer of 55 to 80.

2. The polvcarhonate composition of claim 1, wherein the copolycarbonate has a spiral flow of 16 to 25 cm as measured in accordance with ASTM D3123 (300 C., mold temperature of 80 C., capillary thickness of 1.5 mm, holding pressure of 2000 bar).

3. The polycarbonate composition of claim 1, wherein the copolycarbonate has a ratio of the spiral flow and the melt index (MI) (cm/g/10 min) of 1.7 to 5.0.

4. The polycarbonate composition of claim 1, wherein the copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g/mol.

5. The polycarbonate composition of claim 1, wherein the first repeating unit is represented by Chemical Formula 1: ##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 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.

6. The polvcarbonate composition of claim 5, 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, bis(4-hydroxyphenyl)diphenylmethane, and ,-bis[3-(o-hydroxyphenyl)propyl]polydimethylsilaxane.

7. The polycarbonate composition of claim 5, wherein When Chemical Formula 1 is represented by the following Chemical Formula 1-1: ##STR00020##

8. The polycarbonate composition of claim 1, wherein the weight ratio of the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 is from 80:20 to 95:5.

9. The polycarbonate composition of claim 1, wherein the repeating unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-2: ##STR00021##

10. The polycarbonate composition of claim 1, wherein the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2: ##STR00022##

11. The polycarbonate composition of claim 1, wherein the copolycarbonate has an impact strength at low-temperature of 700 to 950 J/m as measured at 30 C. in accordance with ASTM D256 (inch, Notched Izod).

12. The polycarbonate composition of claim 1, wherein the copolycarbonate has an impact strength at room temperature of 700 to 1000 J/m as measured at 23 C. in accordance with ASTM D256 (inch , Notched Izod).

13. The polycarbonate composition of claim 1, wherein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

14. The polycarbonate composition of claim l, wherein the polycarbonate comprises a repeating unit represented by Chemical Formula 4: ##STR00023## in Chemical Formula 4, 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 to assist 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

Preparation of Polyorganosiloxane (AP-30)

(2) ##STR00014##

(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 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 a 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) ##STR00015##

(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) 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 (m) of the 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 a pale yellow oil and the repeating unit (m) was 60 when confirmed through .sup.1H NMR using a Varian 500 MHz, and further purification was not required.

Preparation Example 3

Preparation of Polyorganosiloxane (Eu-50)

(8) ##STR00016##

(9) 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.7 g (13 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 terminal-unmodified polyorganosiloxane thus prepared was 50 when confirmed through .sup.1H NMR.

(10) To the resulting terminal-unmodified polyorganosiloxane, 6.13 g (29.7 mmol) of Eugenol 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 the evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was designated as Eu-50. Eu-50 was a pale yellow oil and the repeating unit (n) was 50 when confirmed through .sup.1H NMR using a Varian 500 MHz, and further purification was not required.

Example 1

(11) Step 1: Preparation of Copolycarbonate Resin

(12) 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, 17.5 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 (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. After 10 minutes, pH was adjusted to 3 with 1 N 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 30,231 g/mol.

(13) 2) Preparation of Injection-Molded Specimen

(14) With respect to 1 part by weight of 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 using a cylinder temperature of 300 C. and a mold temperature of 80 C. using the N-20C injection molding machine manufactured by JSW Co., Ltd.

Example 2

(15) The copolycarbonate resin and its injection-molded specimen were prepared in the same method as in Example 1, except that the total weight of polyorganosiloxane was 36.8 g (mixture of 80% by weight of polyorganosiloxane (AP-30) of Preparation Example 1 and 20% by weight of polyorganosiloxane (MB-60)).

Comparative Example 1

(16) The copolycarbonate resin and its injection-molded specimen were prepared by the same method as in Example 1, except that only 36.8 g of polyorganosiloxane (AP-30) of Preparation Example 1 was used as polyorganosiloxane.

Comparative Example 2

(17) The copolycarbonate resin and its injection-molded specimen were prepared by the same method as in Example 1, except that only 36.8 g of polyorganosiloxane (Eu-50) of Preparation Example 3 was used as polyorganosiloxane.

Comparative Example 3

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

Experimental Example

Evaluation of Physical Properties

(19) The weight average molecular weight of the resin prepared in the Examples and Comparative Examples were measured by GPC using PC Standard with Agilent 1200 series.

(20) The physical properties of the specimens prepared with the resins of the Examples and the Comparative Examples were measured in the following manner and the results were shown in Table 1 below. Weight average molecular weight (g/mol): measured by GPC using PC Standard with Agilent 1200 series. Melt Index (MI): measured in accordance with ASTM D1238 (300 C., 1.2kg conditions). Impact strength at room temperature: measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod). Impact strength at low-temperature: measured at 30 C. in accordance with ASTM D256 ( inch. Notched Izod). Transparency (Tt, %): measured in accordance with ASTM D1003 (layer thickness of 3 mm). The equipment used in the measurement and the range of measurement are as follows. Equipment name: Ultra scan pro (Focus, Inc.) Measurement range: 350-1050 nm Repeating units: determined by 1 H-NMR using Varian 500 MHz. Spiral flow: measured in accordance with ASTM D3123 (300 C., mold temperature of 80 C., capillary thickness of 1.5 mm, holding pressure of 2000 bar). In addition, the value of spiral flow was divided into the value of the melt index (MI).

(21) TABLE-US-00001 TABLE 1 Impact Impact Weight strength strength Melt (Spiral average at room at low- index Spiral flow)/ molecular temperature temperature (g/10 flow (Melt weight Transparency (J/m) (J/m) min) (cm) index) (g/mol) (%) Com. 686 225 15 20 1.33 23,329 90.3 Ex. 1 Com. 802 678 10 15 1.50 26,166 85.2 Ex. 2 Com. 870 194 10 16 1.60 31,312 91.3 Ex. 3 Ex. 1 925 813 6 18 3.00 30,231 90.6 Ex. 2 826 785 8 20 2.50 29,842 89.9

(22) As shown in Table 1 above, the copolycarbonate according to the present invention (Examples 1 and 2) exhibited an excellent transparency while maintaining an excellent impact strength at room temperature. Further, it could be confirmed that the copolycarbonate according to the present invention exhibited a high spiral flow while having a low melt index(MI) compared to the Comparative Examples.