Copolycarbonate and composition comprising the same

Abstract

The present invention relates to a copolycarbonate and a composition comprising the same, and more specifically to a technique for improving flame retardance and chemical resistance while maintaining inherent impact strength and melt index of the copolycarbonate, by comprising a branched repeating unit in the copolycarbonate structure.

Claims

1. A copolycarbonate comprising repeating units represented by Chemical Formulae 1 to 3, and a branched repeating unit represented by Chemical Formula 4, wherein one or more of the repeating units represented by Chemical Formulae 1 to 3 are linked to each other via the branched repeating unit represented by Chemical Formula 4, and wherein the copolycarbonate has a weight average weight molecular weight of 1,000 to 100,000 g/mol: ##STR00022## 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, ##STR00023## in the 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 1 to 200, ##STR00024## in the 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.1-10 haloalkyl; or C.sub.6-20 aryl, and m is an integer of 1 to 200, ##STR00025## in the Chemical Formula 4, R.sub.7 is hydrogen, C.sub.1-10 alkyl, or ##STR00026## R.sub.8, R.sub.9, R.sub.10 and R.sub.11 are each independently hydrogen, C.sub.1-10 alkyl, halogen, C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and n1, n2, n3 and n4 are each independently an integer of 1 to 4.

2. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 1 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)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-3,5-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, bis(4-hydroxyphenyl)diphenylmethane, and ,-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

3. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1: ##STR00027##

4. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 2 is represented by the following Chemical Formula 2-2: ##STR00028##

5. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2: ##STR00029##

6. The copolycarbonate according to claim 1, wherein n is an integer of 10 to 35.

7. The copolycarbonate according to claim 1, wherein m is an integer of 45 to 100.

8. The copolycarbonate according to claim 1, wherein the repeating unit represented by Chemical Formula 4 is represented by the following Chemical Formula 4-2 or Chemical Formula 4-3: ##STR00030##

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

10. The polycarbonate composition according to claim 9, wherein a polysiloxane structure is not introduced in a main chain of the polycarbonate.

11. The polycarbonate composition of claim 9, wherein the polycarbonate comprises a repeating unit represented by the following Chemical Formula 5: ##STR00031## in the Chemical Formula 5, 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, 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.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) 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: Preparation of Polyorganosiloxane (AP-30)

(2) ##STR00020##

(3) 42.5 g (142.8 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 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 30 when confirmed through .sup.1H NMR.

(4) To the resulting terminal-unmodified polyorganosiloxane, 9.57 g (71.3 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 polyorganosiloxane was removed by conducting evaporation under the conditions of 120 C. and 1 torr. The terminal-modified polyorganosiloxane thus prepared was designated as AP-30. AP-30 was pale yellow oil and the repeating unit (n) was 30 when confirmed through .sup.1H NMR using Varian 500 MHz, and further purification was not required.

Preparation Example 2: Preparation of Polyorganosiloxane (MB-60)

(5) ##STR00021##

(6) 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 60 when confirmed through .sup.1H NMR.

(7) 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-60. MB-60 was pale yellow oil, the repeating unit (m) was 60 when confirmed through .sup.1H NMR using Varian 500 MHz and further purification was not required.

Preparation Example 3

(8) 978.4 g of Bisphenol A (BPA), 620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were added to 20 L glass reactor. After confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride and 18.3 g of p-tert-butylphenol (PTBP) were added and mixed. To this mixture, 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added dropwise for one hour. At this time, a NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added. After 10 minutes, pH was adjusted to 3 with 1N 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 give a polycarbonate resin in the form of a powder.

Example 1

(9) 978.4 g of Bisphenol A (BPA), 3.2 g of THPE (1,1,1-tris(4-hydroxyphenyl)ethane), 1,620 g of NaOH 32% aqueous solution, and 7,500 g of distilled water were added to 20 L glass reactor. After confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 21.0 g of p-tert-butylphenol (PTBP), 44.16 g of polyorganosiloxane (AP-30) and 11.04 g of polyorganosiloxane (MB-60) of Preparation Example 2 were added and mixed. To this mixture, 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added dropwise for one hour. At this time, a NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added. After 10 minutes, pH was adjusted to 3 with 1N 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 give a copolycarbonate resin in the form of a powder.

Example 2

(10) The copolycarbonate resin was prepared in the same manner as in Example 1, except that 0.98 g of THPE was used.

Example 3

(11) 80 parts by weight of the copolycarbonate prepared in Example 1 and 20 parts by weight of the polycarbonate prepared in Preparation Example 3 were mixed to prepare a copolycarbonate resin composition.

Comparative Example 1

(12) The copolycarbonate resin was prepared in the same manner as in Example 1, except that THPE was not used, and PTBP was used in an amount of 18.3 g instead of 21.0 g.

Comparative Example 2

(13) The copolycarbonate resin was prepared in the same manner as in Example 1, except that 55.2 g of the polyorganosiloxane (AP-30) of Preparation Example 1 was used and the polyorganosiloxane (MB-60) of Preparation Example 2 was not used.

Comparative Example 3

(14) The copolycarbonate resin was prepared in the same manner as in Example 1, except that the polyorganosiloxane (AP-30) of Preparation Example 1 and the polyorganosiloxane (MB-60) of Preparation Example 2 were not used.

Comparative Example 4

(15) The polycarbonate resin prepared in Preparation Example 3 was used as Comparative Example 4.

(16) The used amount of the main reactants in the examples and comparative examples are shown in Table 1 below.

(17) TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Example 4 AP-30 44.16 g 44.16 g Example 44.16 g 55.2 g MB-60 11.04 g 11.04 g 1 and 11.04 g BPA 978.4 g 978.4 g Preparative 978.4 g 978.4 g 978.4 g 978.4 g TPG 542.5 g 542.5 g Example 542.5 g 542.5 g 542.5 g 542.5 g PTBP 21.0 g 18.3 g 3.sup.1) 18.3 g 21.0 g 21.0 g 18.3 g THPE 3.2 g 0.98 g 3.2 g 3.2 g .sup.1)80 parts by weight of copolycarbonate of Example 1 and 20 parts by weight of polcarbonate of Preparation Example 3

Experimental Example

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

(19) The characteristics of the above specimens were determined by the following method:

(20) 1) Weight average molecular weight (g/mol): measured by GPC using PC standard with Agilent 1200 series.

(21) 2) Impact strength at room temperature: measured at 23 C. in accordance with ASTM 0256 ( inch, Notched Izod).

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

(23) 4) Melt Index (MI): measured in accordance with ASTM D1238 (conditions of 300 C. and 1.2 kg).

(24) 5) Flame retardance: The flame retardance was evaluated according to UL 94V. Specifically, five retardant specimens with a thickness of 3.0 mm required for the application of retardant test were prepared and the evaluation was conducted according to the following procedure.

(25) First, a 20 mm high flame was applied to the specimen for 10 seconds and then the combustion time (t1) of the specimen was measured, and the combustion process was recorded. Then, if burning ceases after the first flame application, the flame is reapplied for an additional 10 seconds. The combustion time (t1) and the glowing time (t3) were measured and the combustion process was recorded. These were similarly applied to the five specimens and the evaluation was conducted according to the criteria shown in Table 2 below.

(26) TABLE-US-00002 TABLE 2 Flame retardance grade V-0 V-1 V-2 Individual combustion time Below 10 Below 30 Below 30 (t1 or t2 of secons seconds seconds individual specimens) Total combustion time of five Below 50 Below 250 Below 250 specimens(total sum seconds seconds seconds of t1 and t2 of five specimens) Combustion and glowing Below 30 Below 60 Below 60 time after second flame seconds seocnds seocnds application(sum of t2 and t3 of individual specimens) Whether the specimens drip Not drip Not drip Drip flaming particles

(27) 6) Chemical resistance: The specimen (thickness: 3.2 mm) for measuring the tensile stress in accordance with ASTM D638 was prepared, and the chemical resistance was measured based on JIG Strain R1.0 in accordance with ASTM D543 (PRACTICE B).

(28) Specifically, a cotton cloth (2 cm2 cm) was placed on the center of each specimen at room temperature (23 C.). The time required until the destruction of each specimen occurs from a moment that 2 ml of solvent (Nivea Aqua protect sun spray-SPF30, manufactured by Beiersdorf AG) drops on the cloth, was measured and the evaluation was conducted according to the following criteria.

(29) : 24 hours or more

(30) : 1 to 24 hours

(31) : 1 minute to 1 hour

(32) x: within 1 minute

(33) The results thus obtained are shown in Table 3 below.

(34) TABLE-US-00003 TABLE 3 Unit Ex. 1 Ex. 2 Ex. 3 C. Ex. 1 C. Ex. 2 C. Ex. 3 C. Ex. 4 Mw g/mol 30,100 29,300 29,800 29,500 28,900 28,100 27,500 Impact strength at J/m 878 840 811 823 613 690 660 room temperature Impact strength at J/m 760 728 699 711 165 138 116 low temperature Melt Index g/10 min 10 12 11 11 11 12 14 Flame retardance V-0 V-0 V-1 V-1 V-1 V-2 V-2 Chemical X X resistance