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 polycatbonate-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 ratio of an impact strength at room temperature and an impact strength at low-temperature (impact strength at room temperature/impact strength at low-temperature) as measured at 23 C. and 30 C., respectively, in accordance with ASTM D256 ( inch, Notched Izod) is 1.01 to 1.30, and the impact strength at room temperature is 840 to 1000 J/m: ##STR00001##

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 ratio of an impact strength at room temperature and an impact strength at low-temperature (impact strength at room temperature/impact strength at low-temperature) as measured at 23 C. and 30 C., respectively, in accordance with ASTM D256 ( inch, Notched Izod) is 1.01 to 1.30, and the impact strength at room temperature is 840 to 1000 J/m, 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.1-10 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; 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.

2. The polycarbonate composition of claim 1, wherein the impact strength at low-temperature is 650 to 950 J/m.

3. The polycarbonate composition of claim 1, wherein the melt index as measured in accordance with ASTM D1238 (300 C., 1.2 kg conditions) is 3 to 20 g/10 min.

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 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 polycarbonate 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-phenyl ethane, bis(4-hydroxyphenyl)diphenylmethane, and ,-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

7. The polycarbonate composition of claim 5, wherein the 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 99:1 to 1:99.

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 a polysiloxane structure is not introduced in a main chain of the polycarbonate.

12. The polycarbonate composition of claim 1, wherein the polycarbonate comprises a repeating unit represented by Chemical Formula 4: ##STR00023## in the above 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 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 by the examples.

Preparation Example 1

Preparation of AP-PDMS (n=34)

(2) ##STR00014##

(3) 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) 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 34 when confirmed through .sup.1H NMR.

(4) 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 a pale yellow oil and the repeating unit (n) was 34 when confirmed through .sup.1H NMR using a Varian 500 MHz, and further purification was not required.

Preparation Example 2

Preparation of MBHB-PDMS (m=58)

(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 terminal-unmodified polyorganosiloxane thus prepared was 58 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 MBHB-PDMS (m=58). MBHB-PDMS was a pale yellow oil and the repeating unit (m) was 58 when confirmed through .sup.1H NMR using a Varian 500 MHz, and further purification was not required.

Preparation Example 3

Eugenol-PDMS

(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 evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was designated as Eugenol-PDMS. Eugenol-PDMS 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) 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and dissolved with mixing under a N.sub.2 atmosphere. 4.3 g of PTBP (para-tert butylphenol) and the mixed solution (weight ratio of 90:10) of 5.91 g of AP-PDMS (n=34) prepared in Preparation Example 1 and 0.66 g of MBHB-PDMS (m=58) prepared in Preparation Example 2 were dissolved in MC (methylene chloride) and added thereto. Subsequently, 128 g of TPG (triphosgene) was dissolved in MC and a dissolved TPG solution added thereto and reacted for 1 hour while maintaining pH of the TPG solution at 11 or more. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to conduct a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4 to remove TEA, and pH of a produced polymer was adjusted to neutral pH of 6 to 7 by washing three times with distilled water. The polymer thus obtained was re-precipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to give a final copolycarbonate.

Example 2

(12) The copolycarbonate was prepared in the same method as in Example 1, except that the weight ratio of AP-PDMS (n=34) and MBHB-PDMS (m=58) was 95:5.

Example 3

(13) The copolycarbonate was prepared in the same method as in Example 1, except that the weight ratio of AP-PDMS (n=34) and MBHB-PDMS (m=58) was 97:3.

Example 4

(14) The copolycarbonate was prepared in the same method as in Example 1, except that the weight ratio of AP-PDMS (n=34) and MBHB-PDMS (m=58) was 99:1.

Example 5

(15) The copolycarbonate was prepared in the same method as in Example 1, except that the weight ratio of AP-PDMS (n=34) and MBHB-PDMS (m=58) was 95:5 and the addition amount of the molecular weight modifier PTBP (para-tort butylphenol) was adjusted.

Comparative Example 1

(16) 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to a polymerization reacotor, and dissolved with mixing under a N.sub.2 atmosphere. 4.3 g of PTBP (para-tert butylphenol) and 6.57 g of Eugenol-PDMS prepared in Preparation Example 3 were dissolved in MC (methylene chloride) and added thereto. Subsequently, 128 g of TPG (triphosgene) was dissolved in MC and a dissolved TPG solution added thereto and reacted for 1 hour while maintaining pH of the TPG solution at 11 or more. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to conduct a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4 to remove TEA, and pH of a produced polymer was adjusted to neutral pH of 6 to 7 by washing three times with distilled water. The polymer thus obtained was re-precipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to give a final copolycarbonate.

Comparative Example 2

(17) The copolycarbonate was prepared by the same method as in Comparative Example 1, except that AP-PDMS was used instead of Eugenol-PDMS.

Experimental Example

Confirmation of Characteristics of Copolycarbonate

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

(19) In addition, with respect to 1 part by weight of the respective copolycarbonate 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 the N-20C injection molding machine of JSW Co., Ltd to prepare a desired specimen.

(20) The characteristics of the above specimens were measured in the following manner and the results were shown in Table 1 below.

(21) 1) Impact strength at room temperature: measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod).

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

(23) 3) YI (yellow index): Specimen (width/length/thickness=60 mm/40 mm/3 mm) was injection-molded at 300 C., and then YI (yellow index) was measured under the following conditions by using Color-Eye 7000A (X-rite Inc.) in accordance with ASTM 01925. Measurement temperature: room temperature (23 C.) Aperture size: Large area of view Measurement method: transmittance was measured in a spiral range (360 nm to 750 nm)

(24) TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Com. Ex. 1 Com. Ex. 2 Weight average molecular 31,000 31,000 31,000 31,000 28,100 26,100 25,000 weight (g/mol) Impact strength at room 963 940 880 850 845 802 650 temperature(J/m) Impact strength at low- 902 840 750 700 678 678 533 temperature (J/m) Impact strength at room 1.06 1.12 1.17 1.21 1.25 1.18 1.22 temperature/Impact strength at low-temperature YI (Yellow Index) 6.27 5.55 5.21 4.21 2.43 6.74 3.71

(25) As shown in Table 1 above, the copolycarbonate according to the present invention had superior impact strength at low-temperature and impact strength at room temperature as compared with Comparative Examples 1 and 2. In particular, the copolycarbonate according to the present invention had small difference between an impact strength at room temperature and an impact strength at low-temperature and thereby exhibited excellent impact resistance.