Copolycarbonate and method for preparing the same

Abstract

Provided is a copolycarbonate comprising a first repeating unit of Chemical Formula 1, a second repeating unit of Chemical Formula 2, and a terminal capping group of Chemical Formula 3: ##STR00001##
Also provided are a method of preparing the copolycarbonate and a molded article including the copolycarbonate.

Claims

1. A copolycarbonate comprising a first repeating unit of the following Chemical Formula 1, a second repeating unit of the following Chemical Formula 2, and a terminal capping group of the following Chemical Formula 3: ##STR00013## wherein in Chemical Formula 1: R.sub.1 to R.sub.3 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; and a, b, and c are each independently an integer from 1 to ##STR00014## wherein in Chemical Formula 2: Z 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; R.sub.4 and R.sub.5 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; and d and e are each independently an integer from 1 to 4; ##STR00015## wherein in Chemical Formula 3: R.sub.6 and R.sub.7 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; m and n are each independently an integer from 1 to 4; and the asterisk (*) indicates a bonding point.

2. The copolycarbonate of claim 1, wherein in Chemical Formula 1, R.sub.1 to R.sub.3 are each hydrogen.

3. The copolycarbonate of claim 1, wherein the second repeating unit of Chemical Formula 2 is a repeating unit of the following Chemical Formula 2-1: ##STR00016##

4. The copolycarbonate of claim 1, wherein in Chemical Formula 2, R.sub.4 and R.sub.5 are each hydrogen.

5. The copolycarbonate of claim 1, wherein in Chemical Formula 3, R.sub.6 and R.sub.7 are each hydrogen.

6. The copolycarbonate of claim 1, wherein a molar ratio of the first repeating unit of Chemical Formula 1 and the second repeating unit of Chemical Formula 2 is 1:99 to 50:50.

7. The copolycarbonate of claim 1, wherein the terminal capping group of Chemical Formula 3 is included in an amount from 0.0001% by weight to 0.1% by weight with respect to the total amount of the copolycarbonate.

8. The copolycarbonate of claim 1, wherein a weight average molecular weight of the copolycarbonate is 10,000 g/mol to 100,000 g/mol.

9. A method of preparing a copolycarbonate, the method comprising the step of polymerizing a composition including a monomer of the following Chemical Formula 4, a monomer of the following Chemical Formula 5, a terminal capping agent containing an aromatic diol of the following Chemical Formula 6, and a carbonate precursor: ##STR00017## wherein in Chemical Formula 4: R.sub.1 to R.sub.3 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; and a, b, and c are each independently an integer from 1 to 4; ##STR00018## wherein in Chemical Formula 5: Z 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; R.sub.4 and R.sub.5 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; and d and e are each independently an integer from 1 to 4; ##STR00019## wherein in Chemical Formula 6: R.sub.6 and R.sub.7 are each independently hydrogen or a substituted or unsubstituted C.sub.1-60 alkyl; and m and n are each independently an integer from 1 to 4.

10. The method of claim 9, wherein the monomer of Chemical Formula 5 is 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-methylphenyl)propane, 2,2-bis(-1-hydroxy-3,5-dimethylphenyl)propane, 1-bis(4-hydroxyphenyl)-1-phenylethane, and bis(4-hydroxyphenyl)diphenylmethane.

11. The method of claim 9, wherein the terminal capping agent further includes one or more selected from the group consisting of p-Cert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontyl phenol.

12. The method of claim 9, wherein the carbonate precursor is selected from the group consisting of phosgene, triphosgene, diphosgene, bromophosgene, di methyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, di tolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthylcarbonate, bis(diphenyl) carbonate, and bishaloformate.

13. A molded article comprising the copolycarbonate of claim 1.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Hereinafter, preferred examples will be provided for better understanding of the present invention. However, the following examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.

EXAMPLES AND COMPARATIVE EXAMPLES: PREPARATION OF COPOLYCARBONATE

Example 1

(2) To a 20 L glass reactor, 1,014.57 g (4.44 mol) of bisphenol A (BPA), 1785 g of a 40% NaOH aqueous solution, 156.64 g (0.45 mol) of hydroquinone bis(4-hydroxybenzoate), and 7500 g of distilled water were introduced. After confirming that BPA was completely dissolved under a nitrogen atmosphere, 4700 g of methylene chloride was added and mixed. To this mixture, 3850 g of methylene chloride in which 565,3 g (1.q mol) of triphosgene was dissolved was added dropwise for one hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, 60 g (0.28 mol) of 2,4-dihydroxybenzophenone dissolved in 400 g of methylene chloride was added dropwise. After completion of the dropwise addition, the mixture was left for 15 minutes, and then 10 g of triethylamine was introduced. After 10 minutes, the mixture was adjusted to pH 3 using a 1 N aqueous hydrochloric acid solution, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to obtain a copolycarbonate resin in the form of a powder.

(3) The finally obtained copolycarbonate resin included the following repeating units, wherein a molar ratio % of a first-A repeating unit and a second-A repeating unit was about 9:91:

(4) ##STR00011##

Example 2

(5) A copolycarbonate resin was obtained in the form of a powder in the same manner as in Example 1, except that 316 g (0.9 mol) of hydroquinone bis(4-hydroxybenzoate) was introduced.

(6) The finally obtained copolycarbonate resin included the same repeating units as in Example 1, wherein a molar ratio (%) of the first repeating unit and the second repeating unit was about 17:83.

Example 3

(7) A copolycarbonate resin was obtained in the form of a powder in the same manner as in Example 1, except that 30 g, instead of 60 g, of 2,4-dihydroxybenzophenone was introduced as a terminal capping agent, and 22 g of p-tert-butylphenol (PTBP) was further introduced.

(8) The finally obtained copolycarbonate resin included the same repeating units as in Example 1, wherein a molar ratio (%) of the first repeating unit and the second repeating unit was about 9:91.

Example 4

(9) A copolycarbonate resin was obtained in the form of a powder in the same manner as in Example 1, except that 22 g of p-tert-butylphenol (PTBP) was further introduced in addition to 60 g of 2,4-dihydroxybenzophenone as a terminal capping agent.

(10) The finally obtained copolycarbonate resin included the same repeating units as in Example 1, wherein a molar ratio (%) of the first repeating unit and the second repeating unit was about 9:91.

Comparative Example 1

(11) To a 20 L glass reactor, 978.4 g (4.29 mol) of bisphenol A (BPA), 3.927 g (0.006 mol) of BPDA (bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate), 1620 g of a 40% NaOH aqueous solution, and 7500 g of distilled water were introduced. After confirming that BPA was completely dissolved under a nitrogen atmosphere, 3670 g of methylene chloride and 17.9 g (0.11 mol) of p-tert-butylphenol (PTBP) were added and mixed. To this mixture, 3850 g of methylene chloride in which 542.5 g (1.8 mol) of triphosgene was dissolved was added dropwise for one hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the mixture was left for 15 minutes, and then 195.7 g of triethylamine dissolved in methylene chloride was introduced. After 10 minutes, the mixture was adjusted to pH 3 using a 1 N aqueous hydrochloric acid solution, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to obtain a copolycarbonate resin in the form of a powder.

Comparative Example 2

(12) To a 20 L glass reactor, 232 g (1.02 mol) of bisphenol A (BPA), 385 g of a 32% NaOH aqueous solution, and 1784 g of distilled water were introduced. After confirming that BPA was completely dissolved under a nitrogen atmosphere, 14.3 g (0.1 mol) of p-tert-butylphenol (PTBP) and a mixture (a weight ratio of 95:5) of 12.54 g (0.004 mol) of AP-PDMS (2-allylphenol-substituted polydimethylsiloxane) and 0.66 g (0.0001 mol) of MBHB-PDMS (2-methyl-1-butene hydroxybenzoate-substituted polydimethylsiloxane) were added and mixed. To this mixture, 3850 g of methylene chloride in which 128 g (0.43 mol) of triphosgene was dissolved was added dropwise for one hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the reaction product was left for 15 minutes, and 46 g of triethylamine dissolved in methylene chloride was added thereto. After 10 minutes, the mixture was adjusted to pH 3 using a 1 N aqueous hydrochloric acid solution, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to obtain a copolycarbonate resin in the form of a powder.

(13) AP-PDMS is a compound of the following Chemical Formula A, and MBHB-PDMS is a compound of the following Chemical Formula B:

(14) ##STR00012##

Comparative Example 3

(15) 70% by weight of the copolycarbonate of Comparative Example 1 and 30% by weight of the copolycarbonate of Comparative Example 2 were mixed.

Comparative Example 4

(16) 50% by weight of the copolycarbonate of Comparative Example 1 and 50% by weight of the copolycarbonate of Comparative Example 2 were mixed.

Comparative Example 5

(17) To a 20 L glass reactor, 1014.57 g (4.44 mol) of bisphenol A (BPA), 1785 g of a 40% NaOH aqueous solution, 130 g (0.61 mol) of (2-hydroxyphenyl)(4-hydroxyphenyl)methanone, 130 g (037 mol) of bis(3-hydroxyphenyl) isophthalate, and 7500 g of distilled water were introduced. After confirming that BPA was completely dissolved under a nitrogen atmosphere, 4700 g of methylene chloride and 64 g (0.18 mol) of bis(3-hydroxyphenyl) terephthalate were added and mixed. To this mixture, 3850 g of methylene chloride in which 565.3 g (1.90 mol) of triphosgene was dissolved was added dropwise for one hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, 44 g (0.29 mol) of p-tert-butylphenol (PTBP) dissolved in 400 g of methylene chloride was added dropwise. After completion of the dropwise addition, the reaction product was left for 15 minutes, and 10 g of triethylamine was added thereto. After 10 minutes, the mixture was adjusted to pH 3 using a 1 N aqueous hydrochloric acid solution, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated, and then precipitated in methanol to obtain a copolycarbonate resin in the form of a powder.

Comparative Example 6

(18) A copolycarbonate was prepared in the same manner as in Comparative Example 5, except that 60 g (0.28 mol) of 2,4′-dihydroxybenzophenone was used instead of p-tert-butylphenol (PTBP).

Experimental Example: Evaluation of Physical Properties of Copolycarbonate

(19) With respect to 1 part by weight of each of the copolycarbonate resins prepared in the examples and comparative examples, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite was added, and the resulting mixture was pelletized using a Bau Tech small-sized twin-screw extruder, and then injection-molded using a HAKKE small-sized injection molding machine at a cylinder temperature of 300° C. and a mold temperature of 80° C. to prepare each specimen.

(20) Weight average molecular weights of the resins prepared in the examples and comparative examples were determined by GPC with a PC standard using Agilent 1200 series, and the results are shown in Table 1 below.

1) Weather Resistance Evaluation Test

(21) The copolycarbonate specimens prepared in the examples and comparative examples were irradiated with UV in accordance with ASTM G151 and G155 according to UL746C UV & Water Exposure Test using a weatherometer (ATLAS, CI5000).

(22) First, the yellow index (Y.I.) was measured in accordance with ASTM D630 for the specimens that were not irradiated with UV, the specimens that were irradiated with UV for 500 hours, and the specimens that were irradiated with UV for 1000 hours, and the results are shown in Table 1 below.

2) Impact Strength (kJ/m.SUP.2.)

(23) Impact strength (kJ/m.sup.2) was measured using an impact tester of Toyoseiki in accordance with ASTM D256 for the copolycarbonate specimens prepared in the examples and comparative examples, and the results are shown in Table 1 below.

(24) TABLE-US-00001 TABLE 1 Weather resistance Impact resistance Section 0 h 500 h 1000 h (kJ/m.sup.2) Example 1 1.34 2.43 9.8 530 Example 2 1.38 3.04 5.32 533 Example 3 1.44 3.01 6.66 524 Example 4 1.30 2.88 6.98 511 Comparative 1.05 12.31 19.85 522 Example 1 Comparative 3.53 15.61 23.22 538 Example 2 Comparative 2.23 13.33 20.38 512 Example 3 Comparative 2.88 14.02 26.55 527 Example 4 Comparative 1.13 7.45 13.22 547 Example 5 Comparative 1.59 6.25 11.4 569 Example 6

(25) As shown in Table 1, it was confirmed that specific structures of the repeating units and the terminal capping group can be introduced into the copolycarbonates according to the present invention, thereby improving weather resistance and impact strength at the same time.

(26) In contrast, although those of the comparative examples exhibited impact strength equivalent to those of the examples, the yellow index was remarkably increased over time upon light irradiation.