Copolycarbonate resin composition

Abstract

Disclosed is a copolycarbonate composition including: a copolycarbonate having an aromatic polycarbonate-based first repeating unit and one or more aromatic polycarbonate-based second repeating units having siloxane bonds; and a polycarbonate, where the copolycarbonate composition has an impact strength at room temperature of 830 to 1000 J/m as measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod), where the one or more aromatic polycarbonate-based second repeating units having siloxane bonds include a repeating unit represented by Chemical Formula 2 and a repeating unit represented by Chemical Formula 3: ##STR00001##
and where the copolycarbonate composition satisfies the following Equation 1:
1.0682X+0.51<Y<1.0682X+1.2.[Equation 1] The copolycarbonate composition provides an improved mobility.

Claims

1. A copolycarbonate composition comprising: a copolycarbonate comprising an aromatic polycarbonate-based first repeating unit and one or more aromatic polycarbonate-based second repeating units haying siloxane bonds, and a polycarbonate, wherein the copolycarbonate composition has an impact strength at room temperature of 830 to 1000 J/m as measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod), wherein the one or more aromatic polycarbonate-based second repeating units having siloxane bonds 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 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; 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, and wherein the copolycarbonate composition satisfies the following Equation 1:
1.0682X+0.51<Y<1.0682X+1.2[Equation 1] in the Equation 1, X means a silicon content (wt. %) relative to the total weight of the copolycarbonate and polycarbonate, and Y means a value in which the FID intensity obtained through TD (Time-domain) FID experiment is normalized at 0.1 msec.

2. The copolycarbonate composition of claim 1, wherein X is 0.1 to 20.

3. The copolycarbonate composition of claim 1, wherein the copolycarbonate composition satisfies the following Equation 1-1:
1.0682X+0.60<Y<1.0682X+1.0[Equation 1-1] in the Equation 1-1, X and Y are the same as defined in claim 1.

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

5. The copolycarbonate composition of claim 1, wherein the aromatic polycarbonate-based first repeating unit is represented by the following 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 copolycarbonate composition of claim 1, wherein the aromatic polycarbonate-based first repeating unit 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)sulthne, bis(4-hydroxyphenyi)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.

7. The copolycarbonate composition of claim 1, wherein the aromatic polycarbonate-based first repeating unit is represented by the following Chemical Formula 1-1: ##STR00020##

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

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

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

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 illustrates graphically the T2 relaxation measured according to the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) Preferred embodiments will be provided below 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-34

(3) ##STR00014##

(4) 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 terminal-unmodified polyorganosiloxane thus prepared was 34 when confirmed through .sup.1H NMR.

(5) 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-34. AP-34 was 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

MB-58

(6) ##STR00015##

(7) 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.

(8) 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-58. MB-58 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

EU-50

(9) ##STR00016##

(10) 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), 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 terminal-unmodified polyorganosiloxane thus prepared was 50 when confirmed through .sup.1H NMR.

(11) 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 EU-50. EU-50 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.

PREPARATION EXAMPLE 4

PC

(12) 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. 4.7 g of PTBP (para-tert butylphenol) was dissolved in MC (methylene chloride) and was added thereto. 128 g of TPG (triphosgene) was dissolved in MC and 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 then 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 polycarbonate, which was designated as PC.

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 polydimethylsiloxane (the mixed solution (weight ratio: 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 then 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 then 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

(14) 20 parts by weight of the copolycarbonate prepared in Example 1 and 80 parts by weight of the polycarbonate (PC) prepared in Preparation Example 4 were mixed to prepare the desired copolycarbonate composition.

EXAMPLE 3

(15) 40 parts by weight of the copolycarbonate prepared in Example 1 and 60 parts by weight of the polycarbonate (PC) prepared in Preparation Example 4 were mixed to prepare the desired copolycarbonate composition.

EXAMPLE 4

(16) 60 parts by weight of the copolycarbonate prepared in Example 1 and parts by weight of the polycarbonate (PC) prepared in Preparation Example 4 were mixed to prepare the desired copolycarbonate composition.

EXAMPLE 5

(17) 80 parts by weight of the copolycarbonate prepared in Example 1 and parts by weight of the polycarbonate (PC) prepared in Preparation Example 4 were mixed to prepare the desired copolycarbonate composition.

COMPARATIVE EXAMPLE

(18) The copolycarbonate was prepared in the same manner in Example 1, except that 6.57 g of EU-50 prepared in Preparation Example 3 was used as the polydimethylsiloxane.

EXPERIMENTAL EXAMPLE

(19) With respect to 1 part by weight of the copolycarbonate or copolycarbonate composition prepared in the examples and comparative example, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosposphite, 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 molded specimen.

(20) The physical properties of the above specimens were determined by the following method:

(21) 1) Weight average molecular weight (Mw): measured by GPC using PC standard with Agilent 1200 series.

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

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

(24) 4) Silicon content (wt. %): The silicon content was measured through NMR analysis.

(25) 5) TD (Time-domain)-NMR HD experiment: Experimental setup was made using the minispec mq20 Polymer Research System in accordance with Minispec standard operating procedure manual of SOP-0274-0k Bruker Optics Inc. to obtain FID data.

(26) The results thus obtained were shown in Table 1 below and the results of TD (Time-domain)-NMR FID experiments were shown in FIG. 1.

(27) In FIG. 1, X-axis means a silicon content (wt. %) in the copolycarbonate composition, and Y-axis means a normalized FID intensity measured in TD (Time-domain)-NMR FID experiments.

(28) TABLE-US-00001 TABLE 1 Impact strength Impact strength at room at low Mw temperature temperature TD-NMR Fid (g/mol) (J/m) (J/m) X Y Example 1 30000 889 732 6.23 7.364 Example 2 24100 807 190 1.26 2.008 Example 3 25400 822 243 2.45 3.374 Example 4 27200 830 641 3.75 4.780 Example 5 28400 849 707 4.77 5.752 Comparative 26100 802 679 4.92 6.466 Example

(29) As shown in Table 1 and FIG. 1, it could be confirmed that in the case of Examples according to the present invention, X and Y satisfied the Equation 1, whereas in the case of Comparative Example, X and Y did not satisfy the Equation 1. Thus, particularly, it could also be confirmed that there was a difference in the impact strength at room temperature.