Copolycarbonate and composition comprising the same

Abstract

The present disclosure relates to a copolycarbonate having improved impact strength at low temperature and yellow index simultaneously, a composition including the same, and the copolycarbonate comprising: an aromatic polycarbonate-based first repeating unit, an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and an aromatic polycarbonate-based third repeating unit having at least one siloxane bond containing fluoro-substituted C.sub.1-15 alkyl.

Claims

1. A copolycarbonate, comprising: an aromatic polycarbonate-based first repeating unit, an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and an aromatic polycarbonate-based third repeating unit having at least one siloxane bond containing fluoro-substituted C.sub.1-15 alkyl, wherein the first repeating unit is represented by the following Chemical Formula 1: ##STR00013## 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 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, wherein the second repeating unit is represented by the following Chemical Formula 2: ##STR00014## 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; or C.sub.6-20 aryl, and n is an integer of 10 to 200, wherein the third repeating unit is represented by the following Chemical Formula 3: ##STR00015## in Chemical Formula 3, each of X.sub.2 is independently C.sub.1-10 alkylene, each of Y is independently a single bond, 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, R.sub.7 is C.sub.1-15 alkyl substituted with one to three fluoro, each of R.sub.8 is independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, C.sub.6-20 aryl, hydroxy, or halogen, and m and l are each independently an integer of 1 to 200, wherein the copolycarbonate has YI (Yellow Index) of 1 to 3.9 in accordance with ASTM D1925, and the copolycarbonate has impact strength at low temperature of 700 to 1000 J/m, measured at 30 C. in accordance with ASTM D256 ( inch, Notched Izod).

2. The copolycarbonate according to claim 1, wherein the copolycarbonate has impact strength at room temperature of 800 to 1100 J/m, measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod).

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

4. The copolycarbonate according to claim 1, wherein a weight ratio of the second repeating unit and the third repeating unit is 1:99 to 99:1.

5. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-2: ##STR00016##

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

7. The copolycarbonate according to claim 1, wherein R.sub.7 is (CH.sub.2).sub.pCH.sub.qF.sub.r, in the chemical formula, p is an integer of 0 to 10, q is an integer from 0 to 2 and r is an integer from 1 to 3, and q+r is 3.

8. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2: ##STR00017##

9. The copolycarbonate according to claim 1, wherein the sum of m and 1 is an integer of 30 to 70.

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

11. The polycarbonate composition according to claim 10, wherein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a .sup.1H NMR graph of the compound prepared in Preparation Example 2.

(2) FIG. 2 is a .sup.1H NMR graph (top) of the compound prepared in Preparation Example 1, and a .sup.1H NMR graph (bottom) of the copolycarbonate prepared in Example 1 using the same.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) 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)

(4) ##STR00011##

(5) 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.

(6) 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: SiF-PDMS(m+1=50)

(7) ##STR00012##

(8) 35.70 g of the sum of octamethylcyclotetrasiloxane and poly (methyl-trifluoropropyl) dimethylsiloxane and 2.40 g (17.8 mmol) of tetramethyldisiloxane were mixed, and the mixture was 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 poly (methyl-trifluoropropyl) dimethylsiloxane, 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 (the sum of m and l) of the terminal-unmodified polyorganosiloxane thus prepared was 50 when confirmed through .sup.1H NMR.

(9) To the resulting terminal-unmodified polyorganosiloxane, 0.01 g (50 ppm) of Karstedt's platinum catalyst was added and reacted at 90 C. for 1 hour. And then, 4.81 g (35.9 mmol) of 2-allylphenol was further added thereto and reacted 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. In this manner, a liquid type of pale yellow transparent terminal-modified polyorganosiloxane was obtained.

(10) Thereafter, 1,000 mL (based on liquid phase) of chloroform (CHCl.sub.3) was added to a refluxable 2,000 mL three-necked flask, and 7.1 g of terephthaloyl chloride was dissolved slowly at room temperature (20 to 26 C.) for 1 hour while maintaining nitrogen atmosphere. Then, 25 g of triethylamine was added thereto and reacted for 1 hour. 175 g of the terminal-modified polyorganosiloxane was added thereto, and sufficiently reacted to prepare the compound represented by the above formula, and it was confirmed by .sup.1H NMR.

Example 1

(11) 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and mixed and dissolved in N.sub.2 atmosphere. 4.3 g of PTBP (para-tert butylphenol), 16.7 g of AP-PDMS (n=34) prepared in Preparation Example 1 and 0.17 g of SiF-PDMS (m+1=50) (a weight ratio of 99:1) were dissolved in MC (methylene chloride), and added thereto. Thereafter, 128 g of TPG (triphosgene) was dissolved in MC, and this was added thereto to carry out the reaction for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to perform coupling reaction. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4 to remove TEA and washed three times with distilled water to adjust the pH of the resulting polymer to 6-7, neutral. The polymer obtained above was reprecipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to obtain a final copolycarbonate.

Example 2

(12) A copolycarbonate was prepared in the same manner as in Example 1, except that the AP-PDMS was used in an amount of 16 g, and the SiF-PDMS was used in an amount of 0.85 g (a weight ratio of 95:5).

Example 3

(13) A copolycarbonate was prepared in the same manner as in Example 1, except that the AP-PDMS was used in an amount of 15.2 g, and the SiF-PDMS was used in an amount of 1.69 g (a weight ratio of 90:10).

Example 4

(14) A copolycarbonate was prepared in the same manner as in Example 1, except that the AP-PDMS was used in an amount of 14.3 g, and the SiF-PDMS was used in an amount of 2.54 g (a weight ratio of 85:15).

Example 5

(15) A copolycarbonate was prepared in the same manner as in Example 1, except that the AP-PDMS was used in an amount of 15.2 g, and the SiF-PDMS was used in an amount of 1.69 g (a weight ratio of 90:10). And then, the above copolycarbonate and a general PC having a molecular weight of about 29,000 (Comparative Example 1) were mixed at a weight ratio of 8:2.

Comparative Example 1

(16) 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and mixed and dissolved in N.sub.2 atmosphere. 4.86 g of PTBP (para-tert butylphenol) was dissolved in MC (methylene chloride), and added thereto. Thereafter, 128 g of TPG (triphosgene) was dissolved in MC, and this was added thereto to carry out the reaction for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to perform coupling reaction. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4 to remove TEA and washed three times with distilled water to adjust the pH of the resulting polymer to 6-7, neutral. The polymer obtained above was reprecipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to obtain a final copolycarbonate.

Comparative Example 2

(17) 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and mixed and dissolved in N.sub.2 atmosphere. 4.3 g of PTBP (para-tert butylphenol), and 16.9 g of AP-PDMS(n=34) prepared in Preparation Example 1 were dissolved in MC (methylene chloride), and added thereto. Thereafter, 128 g of TPG (triphosgene) was dissolved in MC, and this was added thereto to carry out the reaction for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to perform coupling reaction. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4 to remove TEA and washed three times with distilled water to adjust the pH of the resulting polymer to 6-7, neutral. The polymer obtained above was reprecipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to obtain a final copolycarbonate.

Experimental Example

(18) Each property was measured by the following method. The results are given in the following Table 1.

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

(20) 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).

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

(22) 4) YI (Yellow Index): measured in accordance with ASTM D1925.

(23) TABLE-US-00001 TABLE 1 Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Mw (g/mol) 30,000 30,000 30,000 30,000 28,000 30,000 30,000 impact 900 950 980 990 850 870 750 strength at room temperature (J/mol) impact 850 910 940 950 750 200 600 strength at low temperature (J/mol) YI 3.2 3.3 3.5 3.7 2.5 1.2 4

(24) Referring to Table 1, it was confirmed that the copolycarbonates prepared in Examples 1 to 5 in which two kinds of specific polysiloxane structures were introduced into the main chain of the polycarbonate exhibited the same level of impact strength at room temperature and low temperature, compared with the general polycarbonate of Comparative Example 1 and the copolycarbonate of Comparative Example 2 in which one kind of polysiloxane structure was introduced into the main chain of the polycarbonate.

(25) Further, it was confirmed that the copolycarbonates prepared in Examples 1 to 5 exhibited improved YI (Yellow Index) compared with the copolycarbonate of Comparative Example 2 in which one kind of polysiloxane structure was introduced into the main chain of the polycarbonate.