POLYCARBONATE COPOLYMER

Abstract

The present disclosure relates to a polycarbonate copolymer, and can provide a polycarbonate copolymer that includes a repeating unit having a specific structure, thereby being improved particularly in heat resistance.

Claims

1. A polycarbonate copolymer, comprising: a repeating unit represented by Chemical Formula 1; and a repeating unit represented by Chemical Formula 2 or Chemical Formula 3: ##STR00014## 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 a halogen, and n1 and n2 are each independently an integer of 0 to 4, ##STR00015##

2. The polycarbonate copolymer of claim 1, wherein: R.sub.1 is hydrogen.

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

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

5. The polycarbonate copolymer of claim 1, wherein: the repeating unit represented by Chemical Formula 1 is any one selected from the group consisting of the following: ##STR00016##

6. The polycarbonate copolymer of claim 1, wherein: the polycarbonate copolymer contains 0.01 to 80% by weight of the repeating unit represented by Chemical Formula 1, and 0.01 to 80% by weight of the repeating unit represented by Chemical Formula 2 or Chemical Formula 3.

7. The polycarbonate copolymer of claim 1, wherein: the polycarbonate copolymer further comprises a repeating unit represented by Chemical Formula 4: ##STR00017## wherein in Chemical Formula 4, X is a C.sub.1-10 alkylene unsubstituted or substituted with phenyl, a C.sub.3-15 cycloalkylene 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 a halogen.

8. The polycarbonate copolymer of claim 7, wherein: the repeating unit represented by Chemical Formula 4 is: ##STR00018##

9. The polycarbonate copolymer of claim 7, wherein: the polycarbonate copolymer contains 20 to 80% by weight of the repeating unit represented by Chemical Formula 4.

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

11. The polycarbonate copolymer of claim 1, wherein: a glass transition temperature of the polycarbonate copolymer is 155 to 245 C.

12. The polycarbonate copolymer of claim 1, wherein: a tensile strength of the polycarbonate copolymer is 67 to 95 MPa.

13. An article comprising the polycarbonate copolymer of claim 1.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0058] FIG. 1 shows .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 1 of the present disclosure.

[0059] FIG. 2 shows the .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 2 of the present disclosure.

[0060] FIG. 3 shows the .sup.1H NMR (DMSO-d.sub.6) data of the compound prepared in Preparation Example 3 of the present disclosure.

DETAILED DESCRIPTION

[0061] Hereinafter, embodiments of the present disclosure will be described in more detail with reference to the following Examples. However, the following Examples are for illustrative purpose only and not intended to limit the scope of the present disclosure.

[0062] Respective physical properties were measured as follows. [0063] 1) Weight average molecular weight (g/mol): calibrated and measured with PC standard using Agilent 1200 series. [0064] 2) Glass transition temperature ( C.): measured with DSC Q100 (TA Instrument).

PREPARATION EXAMPLE

Preparation Example 1-1: Preparation of Monomer 1-1

[0065] ##STR00009##

[0066] In a round bottom flask, O-phenylenediamine (13 g; 120 mmol) and 35% HCl (3.3 mL) were added, and the mixture was purged with nitrogen gas for 30 minutes and then stirred for 1 hour. 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. The reaction mixture was cooled to 120 C., distilled water (30 mL) and 35% HCl (15.4 mL) were added, and stirred for 1 hour. After cooling to room temperature, the reaction mixture was filtered, washed with distilled water, and then dried. This was dissolved in a NaOH solution, adsorbed and filtered with charcoal, precipitated in HCl, and the precipitate was recovered to prepare Monomer 1-1. The NMR data of the prepared Monomer 1-1 is shown in FIG. 1, and the MS data are as follows.

[0067] MS: [M+H].sup.+=391

Preparation Example 1-2: Preparation of Monomer 1-2

[0068] ##STR00010##

[0069] Monomer 1-2 was prepared in the same manner as in Preparation Example 1-1, except that 3,4-diaminotoluene (15.4 g, 125.6 mmol) was instead of o-phenylenediamine. The NMR data of the prepared Monomer 1-2 is shown in FIG. 2, and the MS data are as follows.

[0070] MS: [M+H].sup.+=405

Preparation Example 1-3: Preparation of Monomer 1-3

[0071] ##STR00011##

[0072] Monomer 1-3 was prepared in the same manner as in Preparation Example 1-1, 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 1-3 are shown in FIG. 3, and the MS data are as follows.

[0073] MS: [M+H].sup.+=419

Preparation Example 1-4: Preparation of Monomer 1-4

[0074] ##STR00012##

[0075] Monomer 1-4 was prepared in the same manner as in Preparation Example 1-1, except that 4-chlorobenzene-1,2-diamine (17 g, 125.6 mmol) was used instead of o-phenylenediamine. The MS data of the prepared Monomer 1-4 are as follows.

[0076] MS: [M+H].sup.+=425

Preparation Examples 2-1 and 2-2

[0077] The following Monomers were purchased and used from Deepak Novochem Technologies Limited, respectively.

##STR00013##

Example 1: Preparation of Polycarbonate Copolymer

[0078] In a 2 L main reactor equipped with a nitrogen purge and a condenser and capable of maintaining room temperature with a circulator, water (620 g), bisphenol A (BPA; 98.18 g), Monomer 1-3 (4.19 g), 40 wt. % NaOH aqueous solution (102.5 g), and MeCl.sub.2 (200 mL) were added, and Monomer 2-1 (36.41 g) was further added. Then, the mixture was stirred for about 10 minutes. The nitrogen purge was stopped, and triphosgene (62 g) and MeCl.sub.2 (120 g) were added to a 1 L round bottom flask to dissolve triphosgene, and then the dissolved triphosgene solution was slowly added to the main reactor. When the addition was completed, PTBP (p-tert-butylphenol; 2.84 g) was added, and stirred for about 10 minutes. Then, 40 wt. % of 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 terminate the reaction after 30 minutes, HCl was added to drop the pH to 3-4.

[0079] Then, the process of stopping stirring, separating the organic layer and the aqueous layer, then removing the aqueous layer, adding pure water again and washing the mixture was repeated 3 to 5 times. After washing was completed, only the organic layer was extracted, and a polycarbonate copolymer crystal was obtained by reprecipitation methods using methanol as a non-solvent. At this time, the prepared polycarbonate copolymer had a weight average molecular weight of 47,000 g/mol. As a result of analyzing the prepared polycarbonate copolymer by NMR, it was confirmed that the repeating units derived from the Compounds 2-1 and 1-3 were contained at 18 wt. % and 2 wt. %, respectively, based on the weight of the total repeating units, and the remaining Examples and Comparative Examples below were also analyzed in the same manner.

Examples 2 to 12: Preparation of Polycarbonate Copolymers

[0080] Polycarbonate copolymers were prepared in the same manner as in Example 1, except that the used amount of Monomer 1-3, Monomer 2-1 and BPA was adjusted (Examples 2 to 6), or Monomer 2-2 was used instead of monomer 2-1, and the used amount of Monomer 1-3, Monomer 2-2 and BPA (Examples 7 to 12) was adjusted. At this time, the amount of PTBP (p-tert-butylphenol) as an end-capping agent was adjusted so that the weight average molecular weight of the prepared polycarbonate copolymer was 47,000.

Comparative Examples 1 to 3: Preparation of Polycarbonate

[0081] Polycarbonate was prepared in the same manner as in Example 1, except that Monomer 1-3 was not used, and the used amounts of Monomer 2-1 and BPA were adjusted. At this time, the amount of PTBP (p-tert-butylphenol) as an end-capping agent was adjusted so that the weight average molecular weight of the prepared polycarbonate copolymer was 47,000.

Comparative Examples 4 to 6: Preparation of Polycarbonate

[0082] Polycarbonate was prepared in the same manner as in Example 1, except that Monomer 1-3 was not used, Monomer 2-2 was used instead of Monomer 2-1, and the used amounts of Monomer 2-2 and BPA were adjusted. At this time, the amount of PTBP (p-tert-butylphenol) as an end-capping agent was adjusted so that the weight average molecular weight of the polycarbonate copolymer was 47,000.

Comparative Example 7: Preparation of Polycarbonate

[0083] Polycarbonate was prepared in the same manner as in Example 1, except that Monomers 1-3 and 2-1 were not used. The amount of PTBP (p-tert-butylphenol) as an end-capping agent was adjusted so that the weight average molecular weight of the polycarbonate copolymer was 47,000.

Experimental Example

[0084] With respect to the polycarbonate copolymers prepared in Examples and Comparative Examples, the glass transition temperature and the tensile strength were measured, and the tensile strength was measured according to ISO 527. The results are shown in Table 1 below. In Table 1 below, the content of each monomer means the content of the monomer relative to the total weight of the polycarbonate copolymer.

TABLE-US-00001 TABLE 1 Content Content Content of of of Mono- Mono- Mono- Content mer mer mer of Tensile 1-3 2-1 2-2 BPA Tg strength Unit wt % wt % wt % wt % C. MPa Example 1 2.0 18.0 0 80.0 160 68 Example 2 0.2 19.8 0 80.0 159 67 Example 3 6.0 54.0 0 40.0 193 77 Example 4 0.6 59.4 0 40.0 191 74 Example 5 8.0 72.0 0 20.0 214 81 Example 6 0.8 79.2 0 20.0 212 78 Example 7 2.0 0 18.0 80.0 163 69 Example 8 0.2 0 19.8 80.0 162 68 Example 9 6.0 0 54.0 40.0 203 79 Example 10 6.0 0 59.4 40.0 201 76 Example 11 8.0 0 72.0 20.0 233 86 Example 12 0.8 0 79.2 20.0 231 82 Comparative 0 20.0 0 80.0 159 66 Example 1 Comparative 0 60.0 0 40.0 190 73 Example 2 Comparative 0 80.0 0 20.0 211 76 Example 3 Comparative 0 0 20.0 80.0 161 67 Example 4 Comparative 0 0 60.0 40.0 200 75 Example 5 Comparative 0 0 80.0 20.0 230 80 Example 6 Comparative 0 0 0 100.0 147 63 Example 7

[0085] As shown in Table 1, it was confirmed that the polycarbonate copolymer containing the repeating unit according to the present disclosure had a higher glass transition temperature than the polycarbonates of Comparative Examples. Therefore, it can be confirmed that as the repeating unit according to the present disclosure is included in the structure of the polycarbonate, thereby being improved in heat resistance.