Polyorganosiloxane and copolycarbonate prepared by using the same

Abstract

The present invention relates to a novel polyorganosiloxane capable of producing a copolycarbonate having improved chemical resistance and flame retardancy while maintaining the intrinsic physical properties of a polycarbonate resin and to a copolycarbonate prepared by using the same.

Claims

1. A polyorganosiloxane represented by Chemical Formula 2:
B-A-B[Chemical Formula 2] wherein, in Chemical Formula 2, A is a divalent functional group containing C.sub.6-20 arylene, B is ##STR00012## each of R.sub.1 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.2 is C.sub.1-15 alkyl substituted with one to three fluoro, each of R.sub.3 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, X is CO, or CO(C.sub.6-10 arylene)-CO, Y is C.sub.1-10 alkylene, Z is a bond, or COO, n is an integer of 1 to 2000, and m is an integer of 1 to 2,000.

2. The polyorganosiloxane according to claim 1, wherein R.sub.2 in Chemical Formula 2 is (CH.sub.2).sub.pCH.sub.qF.sub.r, wherein p is an integer of 1 to 10, q and r is an integer of 0 to 3, and q+r is 3.

3. The polyorganosiloxane according to claim 1, wherein A in Chemical Formula 2 is ##STR00013## wherein R.sub.4 is hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl.

4. The polyorganosiloxane according to claim 1, wherein each of R.sub.1 in Chemical Formula 2 is independently C.sub.1-10 alkyl.

5. The polyorganosiloxane according to claim 1, wherein Y in Chemical Formula 2 is C.sub.1-5 alkylene.

6. The polyorganosiloxane according to claim 1, wherein the polyorganosiloxane is a compound of the following structure: ##STR00014## wherein n and m are as defined in claim 1.

7. A copolycarbonate comprising (i) a repeating unit represented by Chemical Formula 4, and (ii) a repeating unit represented by Chemical Formula 5, wherein the copolycarbonate has a weight average molecular weight of 1,000 to 1,000,000 g/mol: ##STR00015## wherein, in Chemical Formula 4, A is a divalent functional group containing C.sub.6-20 arylene, each of R.sub.1 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.2 is C.sub.1-15 alkyl substituted with one to three fluoro, each of R.sub.3 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, X is CO, or CO(C.sub.6-10 arylene)-CO, Y is C.sub.1-10 alkylene, Z is a bond, or COO, n is an integer of 1 to 2000, and m is an integer of 1 to 2,000, ##STR00016## wherein, in Chemical Formula 5, R.sub.5 to R.sub.8 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z.sub.1 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.

8. The copolycarbonate according to claim 7, wherein the repeating unit represented by Chemical Formula 5 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)sulphide, 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-dichlororophenyl)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, and bis(4-hydroxyphenyl)diphenylmethane.

9. A molded article comprising the copolycarbonate of claim 8.

10. A molded article comprising the copolycarbonate of claim 7.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a .sup.1H-NMR graph of the compound prepared in Example

(2) FIG. 2 shows a .sup.1H-NMR graph of the copolycarbonate prepared in Example 1.

(3) FIG. 3 shows a .sup.1H-NMR graph of the compound prepared in Example 2.

(4) FIG. 4 shows a .sup.1H-NMR graph of the copolycarbonate prepared in Example 2.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(5) Hereinafter, preferred examples are presented to assist in understanding of the present invention. However, these examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Example 1

(6) (1) Preparation of Modified Polyorganosiloxane

(7) ##STR00010##

(8) 35.70 g of the sum of octamethylcyclotetrasiloxane and poly(methyl-trifluoropropyl)dimethylsiloxane was mixed with 2.40 g (17.8 mmol) of tetramethyldisiloxane. The mixture was then placed in 3 L flask together with 1 part by weight of an acid day (DC-A3) compared to 100 parts by weight of the sum 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 (sum of n and m) of the unmodified polyorganosiloxane thus obtained was 50 when confirmed through .sup.1H NMR (FIG. 1).

(9) To the resulting terminal-unmodified polyorganosiloxane, 0.01 g (50 ppm) of Karstedt's platinum catalyst were added and reacted at 90 C. for 3 hours. 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. Thereby, the terminal-modified polyorganosiloxane having a liquid, pale yellow transparent property was obtained.

(10) (2) Preparation of Copolycarbonate

(11) 232 g of bisphenol A, 1,784 g of distilled water and 385 g of sodium hydroxide were added to a polymerization reactor and mixed under a nitrogen atmosphere to completely dissolve bisphenol A. Then, 875 g of methylene chloride, 4.3 g of PTBP (para-tert butylphenol) and 13.4 g of the compound prepared in Step 1 above was added and mixed. To this mixture, 920 g of methylene chloride in which 130 g of TPG (triphosgene) was dissolved was added dropwise for one hour. At this time, a sodium hydroxide aqueous solution was maintained at pH 11. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 46 g of triethylamine was dissolved in methylene chloride and added. After a total reaction time of 1 hour and 30 minutes, pH was lowered to 4, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated. The polymer thus obtained was precipitated in methanol and dried at 120 C. to obtain a final powdery copolycarbonate resin. The preparation thereof was confirmed through .sup.1H NMR (FIG. 2).

Example 2

(12) (1) Preparation of Modified Polyorganosiloxane

(13) ##STR00011##

(14) The terminal-modified polyorganosiloxane was obtained in the same manner as in Step 1 of Example 1. Subsequently, 1,000 mL (based on liquid) 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 for 1 hour while maintaining nitrogen atmosphere at room temperature (20 to 26 C.). Then, 25 g of triethylamine was added thereto and allowed to react for 1 hour, and then 175 g of the above modified polyorganosiloxane was added and sufficiently reacted to prepare a compound represented by the above chemical formula. The preparation thereof was confirmed through .sup.1H NMR (FIG. 3).

(15) (2) Preparation of Copolycarbonate Resin

(16) 232 g of bisphenol A, 1,784 g of distilled water and 385 g of sodium hydroxide were added to a polymerization reactor and mixed under a nitrogen atmosphere to completely dissolve bisphenol A. Then, 875 g of methylene chloride, 4.3 g of PTBP (para-tert butylphenol) and 7.0 g of the compound prepared in Step 1 above (5.2 wt. % of polycarbonate resin based on the solid content) was added and mixed. To this mixture, 920 g of methylene chloride in which 130 g of TPG (triphosgene) was dissolved was added dropwise for one hour. At this time, a sodium hydroxide aqueous solution was maintained at pH 11. After completion of the dropwise addition, the reaction product was aged for 15 minutes, and 46 g of triethylamine was dissolved in methylene chloride and added. After a total reaction time of 1 hour and 30 minutes, pH was lowered to 4, and then washed three times with distilled water. Subsequently, the methylene chloride phase was separated. The polymer thus obtained was precipitated in methanol and dried at 120 C. to obtain a final powdery copolycarbonate resin. The preparation thereof was confirmed through .sup.1H NMR (FIG. 4).

Example 3

(17) The powdery copolycarbonate was prepared in the same manner as in Example 2, except that 3.5 g (2.6 wt. % of polycarbonate resin based on the solid content) was used instead of 7.0 g of the compound prepared in Step 1, in Step 2 of Example 2.

Comparative Example 1

(18) The powdery copolycarbonate was prepared in the same manner as in Example 2, except that the compound prepared in Step 2 was not used, in Step 2 of Example 2.

Experimental Example: Evaluation of Physical Properties of Copolycarbonate Resin

(19) The physical properties of the injection-molded specimens of the copolycarbonates prepared in Examples and Comparative Examples were determined in the following manner and the results were shown in Table 1 below. Weight average molecular weight (g/mol): measured by PC Standard using Agilent 1200 series. Repeating unit: determined by .sup.1H-NMR using Varian 500 MHz. Chemical resistance: The amount of weight reduction was measured by contacting the solvent for 168 hours according to ASTM D 543 method (evaluation criteria: Excellent (reduced by 1 to 3 wt. %), Good (reduced by 3 to 10. wt %), Poor (reduced by 10 wt. % or more). Impact strength at room temperature and impact strength at low temperature (J/m): measured at 23 C. and 30 C. according to ASTM D256 ( inch, Notched Izod). Melt Index (MI): measured according to ASTM D 1238 (conditions of 300 C. and 1.2 kg). Flame retardancy: measured according to L 94 method.

(20) TABLE-US-00001 TABLE 1 Comparative Example 1 Example 2 Example 3 Example Weight average 32,300 30,400 29,800 29,500 molecular weight (g/mol) Chemical HCl resistance NaOH (solvent) MeOH Toluene Impact 23 C. 72 78 72 78 strength 30 C. 68 67 48 11 (kg .Math. cm/cm) Melt Index 13 9 10 8 g/10 min) Flame retardancy V-0 V-0 V-0 V-2