COPOLYCARBONATE AND COMPOSITION COMPRISING THE SAME

Abstract

The present disclosure relates to a copolycarbonate having improved flowability while maintaining excellent impact strength at room temperature and low temperature, and a composition including the same.

Claims

1. A copolycarbonate, comprising: a repeating unit represented by Chemical Formula 1, a repeating unit represented by Chemical Formula 2, a repeating unit represented by Chemical Formula 3, and a repeating unit represented by Chemical Formula 4: ##STR00016## in Chemical Formula 1, R.sub.1 to 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, ##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.1-10 haloalkyl; or C.sub.6-20 aryl, and n is an integer of 10 to 200, ##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; 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, ##STR00019## in Chemical Formula 4, Z.sub.2 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 l is an integer of 1 to 10.

2. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1: ##STR00020##

3. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-2: ##STR00021##

4. The copolycarbonate according to claim 3, wherein R.sub.5 is methyl.

5. The copolycarbonate according to claim 1, wherein n is an integer of 10 to 50.

6. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2: ##STR00022##

7. The copolycarbonate according to claim 6, wherein R.sub.6 is methyl.

8. The copolycarbonate according to claim 1, wherein m is an integer of 30 to 70.

9. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 4 is represented by the following Chemical Formula 4-2: ##STR00023##

10. The copolycarbonate according to claim 1, wherein a weight average molecular weight is 1,000 to 100,000 g/mol.

11. A polycarbonate composition comprising the copolycarbonate according to claim 1, and a polycarbonate.

12. The polycarbonate composition according to claim 11, wherein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0097] The present invention will be described in more detail with reference to the following Examples. However, the following examples are for illustrative purposes only, and the invention is not intended to be limited by the following examples.

Preparation Example 1: AP-PDMS(n=34)

[0098] ##STR00014##

[0099] 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 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 34 when confirmed through .sup.1H NMR.

[0100] To the resulting terminal-unmodified polyorganosiloxane, 4.81 g (35.9 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 siloxane was removed by conducting evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was designated as AP-PDMS (n=34). AP-PDMS was pale yellow oil and the repeating unit (n) was 34 when confirmed through .sup.1H NMR using Varian 500 MHz, and further purification was not required.

Preparation Example 2: MBHB-PDMS(m=58)

[0101] ##STR00015##

[0102] 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 58 when confirmed through .sup.1H NMR.

[0103] 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 MBHB-PDMS (m=58). MBHB-PDMS was pale yellow oil, the repeating unit (m) was 58 when confirmed through .sup.1H NMR using Varian 500 MHz and further purification was not required.

Example 1 (Copolymerization of 3.5% PDMS(95:5)+0.5% SBC)

[0104] To a 2 L main reactor equipped with a nitrogen purge device and a condenser and enabling maintenance at room temperature using a circulator, 620 g of H.sub.2O, 116.47 g of bisphenol A (BPA), 5.5 g of AP PDMS prepared in Preparation Example 1, 0.29 g of MBHB PDMS prepared in Preparation Example 2, 0.93 g of Sebacoyl chloride, 102.5 g of NaOH, and 200 ml of MeCl.sub.2 were injected, followed by stirring for a few minutes.

[0105] After stopping the nitrogen purge, 62 g of triphosgene and 120 g of MeCl.sub.2 were added to a 1 L round-bottom flask to dissolve triphosgene. Then, the dissolved triphosgene solution was slowly injected to the main reactor where the BPA solution was dissolved. After completion of injection, 2.12 g of PTBP was added, followed by stirring for about 10 minutes. After completion of stirring, 97 g of 40 wt % NaOH aqueous solution was added and 1.16 g of TEA as a coupling agent was added thereto. At this time, a reaction pH was maintained at 1113. After the reaction solution was allowed to stand for a time for sufficient reaction, pH was decreased to 34 by addition of HCl to terminate the reaction. After stopping the stirring, a polymer layer and an aqueous layer were separated and then the aqueous layer was removed, and the residue was repeatedly washed with pure H.sub.2O again, and this washing process was repeated 3 to 5 times.

[0106] After completion of washing, only the polymer layer was extracted, and the polymer crystals were obtained by reprecipitation using a non-solvent such as methanol, H.sub.2O or the like.

[0107] In this regard, a weight average molecular weight of the prepared copolycarbonate was 55,000 g/mol.

Example 2 (Copolymerization of 3.5% PDMS(95:5)+1.5% SBC)

[0108] A copolycarbonate was prepared in the same manner as in Example 1, except that the sebacoyl chloride was used in an amount of 2.92 g.

Example 3 (Copolymerization of 3.5 PDMS(90:10)+0.5% SBC)

[0109] A copolycarbonate was prepared in the same manner as in Example 1, except that the AP PDMS was used in an amount of 5.24 g, and the MBHB PDMS was used in an amount of 0.58 g.

Comparative Example 1 (Mixing of 7% PDMS(95:5)+NPC)

[0110] The copolycarbonate, which was prepared in the same manner as in Example 1, except that the AP PDMS was used in an amount of 5.24 g, the MBHB PDMS was used in an amount of 0.58 g, and the sebacoyl chloride was not used, and the polycarbonate (Neat PC; weight average molecular weight of 55,000 g/mol), which was prepared in the same manner as in Example 1, except that AP PDMS, MBHB PDMS, and sebacoyl chloride were not used, were mixed at a weight ratio of 1:1 and extruded.

Comparative Example 2 (3.5% PDMS(95:5))

[0111] A copolycarbonate was prepared in the same manner as in Example 1, except that the sebacoyl chloride was not used.

Experimental Example

[0112] Each property was measured by the following method. The results are given in the following Table 1.

[0113] 1) weight average molecular weight (Mw): measured by GPC with PS standard using Agilent 1200 series.

[0114] 2) impact strength at room temperature and low temperature: measured in accordance with ASTM D256 ( inch, Notched Izod) at room temperature and 30 C. (low temperature).

[0115] 3) flowability (Melt Index; MI): measured in accordance with ASTM D1238 (300 C., 1.2 kg condition).

[0116] 4) chemical resistance (Jig Test): 13 mm*64 mm* inch specimen was adhered closely to Mini Jig (58.5R), 5 mm*13 mm cotton was placed in the center, and then 0.5 ml of Nivea Sun spray was put thereon. The time at which the gap occurred in the adhered specimen was measured.

TABLE-US-00001 TABLE 1 Compar- Compar- Exam- Exam- Exam- ative ative ple 1 ple 2 ple 3 Example 1 Example 2 Mw (g/mol) 55,000 55,000 55,000 54,800 55,200 impact 860 850 850 840 850 strength at room temperature (J/mol) impact 600 580 630 680 620 strength at low temperature (J/mol) MI 10.4 11.2 9.8 6.3 6.8 (g/10 min) chemical 23 20 25 20 18 resistance (min)

[0117] Referring to Table 1, it was confirmed that the copolycarbonates prepared in Examples 1 to 3 in which a specific polysiloxane structure and a sebacoyl structure were introduced into the main chain of the polycarbonate, exhibited not only the same level of impact strength at room temperature and low temperature but also excellent flowability and fluidity, compared with the copolycarbonate of Comparative Example 1 in which only a polysiloxane structure was introduced into the main chain of the polycarbonate, and the copolycarbonate of Comparative Example 2 in which the copolycarbonate of Comparative Example 1 was mixed with a general polycarbonate.