Copolycarbonate and composition comprising 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 an impact strength at room temperature of 840 to 1000 J/m as measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod), and the copolycarbonate satisfies Equation 1: ##STR00001##
TS/TS.sub.00.80.[Equation 1] The copolycarbonate in the composition provides an improved chemical resistance and impact strength simultaneously.

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 second repeating units comprise a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3, wherein the copolycarbonate has an impact strength at room temperature of 840 to 1000 J/m as measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod), and wherein the copolycarbonate satisfies Equation 1: ##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 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.1-5 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 55 to 80,
TS/TS.sub.00.80[Equation 11] in Equation 1, TS.sub.0 is tensile stress measured in accordance with ASTM D638, and TS represents tensile stress measured in accordance with ASTM D638, after contacted with ethyl acetate for 168 hours in accordance with ASTM D543 (PRACTICE B).

2. The polycarbonate composition of claim 1, wherein the copolycarbonate satisfies Equation 2:
TS/TS.sub.00.50[Equation 2] in Equation 2, TS.sub.0 is tensile stress measured in accordance with ASTM D638, and TS represents tensile stress measured in accordance with ASTM D638, after contacted with toluene for 168 hours in accordance with ASTM D543 (PRACTICE B).

3. The polycarbonate composition of claim 1, wherein the copolycarbonate has an impact strength at low temperature of 600 to 1000 J/m as measured at 30 C. in accordance with ASTM D256 ( inch, Notched Izod).

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-phenylethane, 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 a weight ratio of the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3 is 1:99 to 99:1.

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 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.

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

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

AP-PQMS (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 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

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 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 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

Eucienol-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 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 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 introduced in 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 was 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 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 mixed solution (weight ratio of 95:5) of 6.24 g of AP-PDMS (n=34) prepared in Preparation Example 1 and 0.33 g of MBHB-PDMS (m=58) prepared in Preparation Example 2 was used.

Comparative Example 1

(13) 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 6.57 g of AP-PDMS prepared in Preparative Example 1 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 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

(14) The copolycarbonate was prepared by the same method as in Comparative Example 1, except that Eugenol-PDMS prepared in Preparation Example 3 instead of AP-PDMS (n=34) prepared in Preparation Example 1 was used.

Comparative Example 3

(15) The copolycarbonate was prepared by the same method as in Comparative Example 1, except that AP-PDMS (n=34) prepared in Preparation Example 1 was not used.

Experimental Example

Confirmation of Characteristics of Copolycarbonate

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

(17) 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 (JSW, Ltd.) to prepare a desired specimen.

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

(19) 1) Chemical resistance: the tensile stress (kg/cm.sup.2) was measured (TS.sub.0) in accordance with ASTM D638 (specimen thickness: 3.2 mm). Then, after selecting a solvent as shown in Table 1 below, experiments were conducted based on JIG Strain R1.0 in accordance with ASTM D543 (PRACTICE B). A cotton cloth (2 cm2 cm) was placed on the center of each specimen at room temperature (23 C.). The solvent was dropped on the cloth enough to be volatilized every day and the specimen was in contact with the solvent for 168 hours. After the experiment was completed, the solvent on the specimen was completely removed with a clean cloth, and the tensile stress was again measured (TS) in accordance with ASTM D638 to calculate TS/TS.sub.0.

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

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

(22) 4) Melt index (MI): measured in accordance with ASTM D1238 (conditions of 300 C. and 1.2 kg).

(23) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Example 1 Example 2 Example 1 Example 2 Example 3 Chemical Standard 1 1 1 1 1 resistance HCl 0.99 0.99 0.99 0.98 0.89 (sovent) NaOH 0.98 0.97 0.97 0.94 0.90 (TS/TS.sub.0) Ethyl Acetate 0.93 0.89 0.74 0.76 0.63 MeOH 1 1 0.99 0.95 0.91 Toluene 0.56 0.53 0.41 0.50 0.37 Impact strength at room 889 839 651 802 870 temperature (J/m) Impact strength at low 731 718 533 679 194 temperature (J/m) Weight average molecular 30,200 29,800 24,900 28,900 31,300 weight Melt index (g/10 min) 8 9 12 10 11

(24) As shown in Table 1 above, the copolycarbonate according to the present invention (Examples 1 and 2) exhibited superior chemical resistance as compared with Comparative Examples 1 to 3, and particularly, the difference was significant when ethyl acetate and toluene were used as the solvent. Also, examples exhibited superior impact strength at low temperature and impact strength at room temperature as compared with comparative examples.

(25) Accordingly, it could be confirmed that the copolycarbonate according to the present invention exhibited improved chemical resistance and impact strength simultaneously.