POLYCARBONATE COPOLYMER

Abstract

Provided is a polycarbonate copolymer including a repeating unit of the following Chemical Formula 1, where the polycarbonate copolymer can have improved heat resistance:

##STR00001##

wherein in Chemical Formula 1, R.sub.1, R.sub.2, n1 and n2 are as defined in the specification.

Claims

1. A polycarbonate copolymer, comprising a repeating unit of Chemical Formula 1: ##STR00012## wherein in Chemical Formula 1: R.sub.1 and R.sub.2 are each independently hydrogen, a C.sub.1-10 alkyl, a C.sub.1-10 alkoxy, or halogen; and n1 and n2 are each independently an integer of 0 to 4.

2. The polycarbonate copolymer according to claim 1, wherein R.sub.1 is hydrogen.

3. The polycarbonate copolymer according to claim 1, wherein each R.sub.2 is independently hydrogen, a C.sub.1-4 alkyl, a C.sub.1-4 alkoxy, or halogen.

4. The polycarbonate copolymer according to claim 1, wherein each R.sub.2 is independently hydrogen, methyl, or chloro.

5. The polycarbonate copolymer according to claim 1, wherein the repeating unit of Chemical Formula 1 is any one selected from the group consisting of: ##STR00013##

6. The polycarbonate copolymer according to claim 1, wherein the polycarbonate copolymer further comprises a repeating unit of Chemical Formula 2: ##STR00014## wherein in Chemical Formula 2: X is a C.sub.1-10 alkylene that is unsubstituted or substituted with phenyl, a C.sub.3-15 cycloalkylene that is unsubstituted or substituted with a C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO; and R.sub.1 to R.sub.4 are each independently hydrogen, a C.sub.1-10 alkyl, a C.sub.1-10 alkoxy, or halogen.

7. The polycarbonate copolymer according to claim 6, wherein Chemical Formula 2 is the following: ##STR00015##

8. The polycarbonate copolymer according to claim 6, wherein a weight ratio between the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 is 10:90 to 90:10.

9. The polycarbonate copolymer according to claim 1, wherein a weight average molecular weight of the polycarbonate copolymer is 10,000 to 100,000.

10. The polycarbonate copolymer according to claim 1, wherein a glass transition temperature of the polycarbonate copolymer is 150 to 220 C.

11. An article comprising the polycarbonate copolymer according to claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0053] FIG. 1 is shows .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 1 of the present disclosure.

[0054] FIG. 2 is shows .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 2 of the present disclosure.

[0055] FIG. 3 is shows .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 3 of the present disclosure.

EXAMPLES

[0056] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to examples. However, the following examples are merely illustrative of embodiments of the present invention, and the scope of the present disclosure is not limited thereby.

[0057] The following physical properties were measured in the Examples and Experimental Examples below. [0058] 1) Weight average molecular weight (g/mol): It was calibrated and measured by PC standard using Agilent 1200 series, [0059] 2) Glass transition temperature ( C.): It was measured by DSC Q100 (TA Instruments).

Preparation Example 1: Preparation of Monomer 1

[0060] ##STR00008##

[0061] o-Phenylenediamine (13 g; 120 mmol) and 35% HCl (3.3 mL) were added to a round bottom flask, purged with nitrogen gas for 30 minutes, and then stirred for 1 hour. A PP compound (10 g, 31.4 mmol) was added thereto, and the temperature was slowly raised to 154 C., followed by reaction for 22 hours. After cooling to 120 C., distilled water (30 mL) and 35% HCl (15.4 mL) were added, and stirred for 1 hour. The reaction mixture was cooled to room temperature, filtered, washed with distilled water, and dried. This was dissolved in NaOH solution, absorption-filtered with charcoal and precipitated in HCl. The precipitate was recovered to prepare Monomer 1. The NMR data of the prepared Monomer 1 is shown in FIG. 1, and the MS data is as follows.

[0062] MS: [M+H].sup.+=391

Preparation Example 2: Preparation of Monomer 2

[0063] ##STR00009##

[0064] Monomer 2 was prepared in the same manner as in Preparation Example 1, except that 3,4-diaminotoluene (15.4 g, 125.6 mmol) was used instead of o-phenylenediamine. The NMR data of the prepared Monomer 2 is shown in FIG. 2, and the MS data is as follows.

[0065] MS: [M+H].sup.+=405

Preparation Example 3: Preparation of Monomer 3

[0066] ##STR00010##

[0067] Monomer 3 was prepared in the same manner as in Preparation Example 1, except that 4,5-dimethylbenzene-1,2-diamine (17 g, 125.6 mmol) was used instead of o-phenylenediamine. The NMR data of the prepared Monomer 3 is shown in FIG. 3, and the MS data is as follows.

[0068] MS: [M+H].sup.+=419

Preparation Example 4: Preparation of Monomer 4

[0069] ##STR00011##

[0070] Monomer 4 was prepared in the same manner as in Preparation Example 1, except that 4-chlorobenzene-1,2-diamine (17 g, 125.6 mmol) was used instead of o-phenylenediamine. The NMR data of the prepared Monomer 4 is as follows.

[0071] MS: [M+H].sup.+=425

Example 1: Preparation of Polycarbonate Copolymer

[0072] In a 2 L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining a room temperature with a circulator, water (620 g), bisphenol A (BPA; 98.34 g), Monomer 1 (28.05 g), 40 wt % aqueous NaOH solution (102.5 g), and MeCl.sub.2 (200 mL) were added, and stirred for about 10 minutes. Nitrogen purging was stopped, and triphosgene (62 g) and MeCl.sub.2 (120 g) were added to a 1 L round bottom flask. After dissolving triphosgene, the dissolved triphosgene solution was slowly added to the main reactor. When the addition was completed, PTBP (p-tert-butylphenol; 2.66 g) was added, and stirred for about 10 minutes. Then, 40 wt % NaOH aqueous solution (97 g) was added and then TEA (triethylamine; 1.16 g) was added as a coupling agent. At this time, the reaction pH was maintained at 11 to 13. In order to complete the reaction after 30 minutes, HCl was added and the pH was dropped to 3-4.

[0073] Then, the process of stopping the stirring, separating the organic layer and the aqueous layer, then removing the aqueous layer, and adding pure water again for washing was repeated 3 to 5 times. When the washing was completed, only the organic layer was extracted, and polycarbonate copolymer crystals were obtained by a reprecipitation method using a non-solvent using methanol. At this time, the prepared polycarbonate copolymer had a weight average molecular weight of 47,000 g/mol.

Examples 2 to 12: Preparation of Polycarbonate Copolymer

[0074] A polycarbonate copolymer was prepared in the same manner as in Example 1, except for adjusting the monomers and the use amount shown in Table 1 below instead of Monomer 1. At this time, the reaction time was adjusted so that the weight average molecular weight of the prepared polycarbonate copolymer was 47,000.

Comparative Example: Preparation of Polycarbonate

[0075] A polycarbonate copolymer was prepared in the same manner as in Example 1, except that Monomer 1 was not used. At this time, the reaction time was adjusted so that the weight average molecular weight of the prepared polycarbonate was 47,000.

[0076] The glass transition temperatures of the polycarbonate copolymers prepared in Examples and Comparative Examples were measured, and the results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Content of Monomer Tg (glass relative to the total transition weight of polycarbonate temperature: Monomer copolymer C.) Example 1 Monomer 1 20 wt % 155 Example 2 Monomer 1 60 wt % 172 Example 3 Monomer 1 80 wt % 190 Example 4 Monomer 2 20 wt % 157 Example 5 Monomer 2 60 wt % 173 Example 6 Monomer 2 80 wt % 192 Example 7 Monomer 3 20 wt % 160 Example 8 Monomer 3 60 wt % 179 Example 9 Monomer 3 80 wt % 203 Example 10 Monomer 4 20 wt % 152 Example 11 Monomer 4 60 wt % 168 Example 12 Monomer 4 80 wt % 181 Comparative (Not used) 147 Example

[0077] As shown in Table 1, it can be confirmed that the polycarbonate copolymer including the repeating unit of Chemical Formula 1 according to Examples of the present disclosure has an increased in glass transition temperature as compared to the polycarbonate of Comparative Examples. Therefore, it can be confirmed that as the structure of Chemical Formula 1 according to the present disclosure is included in the structure of the polycarbonate, the heat resistance is improved.