NOVEL POLYORGANOSILOXANE AND COPOLYCARBONATE PREPARED BY USING THE SAME

Abstract

The present invention relates to a novel polyorganosiloxane capable of producing a copolycarbonate having improved hardness and to a copolycarbonate prepared by using the same. The novel polyorganosiloxane according to the present invention can be used as a monomer of a copolycarbonate, and it can exhibit improved hardness and chemical resistance simultaneously while maintaining the intrinsic properties of copolycarbonate due to the alkylene or isosorbide-derived structure included in the formula thereof.

Claims

1. A polyorganosiloxane represented by the following Chemical Formula 1: ##STR00013## in the Chemical Formula 1, R.sub.1 to R.sub.4 are each 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, each of R.sub.5 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, each of X is independently —CO—, or —CO—(C.sub.6-10 arylene)-CO—, each of Y is independently C.sub.1-10 alkylene, each of Z is independently a bond, or —COO—, L is C.sub.1-10, or ##STR00014## and each of n is independently an integer of 1 to 99.

2. The polyorganosiloxane according to claim 1, wherein R.sub.1 to R.sub.4 are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3-(oxiranylmethoxy)propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl,

3. The polyorganosiloxane according to claim 1, wherein R.sub.5 is hydrogen, or C.sub.1-4 alkoxy.

4. The polyorganosiloxane according to claim 1, wherein X is —CO—, or —CO-(phenylene)-CO—.

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

6. The polyorganosiloxane according to claim 1, wherein L is a linear C.sub.5-9 alkylene, or ##STR00015##

7. The polyorganosiloxane according to claim 1, wherein the polyorganosiloxane represented by the Chemical Formula 1 is a compound represented by Chemical Formula 1-1 or 1-2: ##STR00016## in Chemical Formula 1-1, n is as defined in claim 1, ##STR00017## in Chemical Formula 1-2, n is as defined in claim 1.

8. The polyorganosiloxane according to claim 1, wherein the polyorganosiloxane has a weight average molecular weight of 700 to 8000.

9. A copolycarbonate having a weight average molecular weight of 1,000 to 100,000 g/mol, comprising a repeating unit represented by the following Chemical Formula 2 and a repeating unit represented by the following Chemical Formula 3: ##STR00018## in the Chemical Formula 2, R.sub.1 to R.sub.4 are each 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, each of R.sub.5 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, each of X is independently —CO—, or —CO—(C.sub.6-10 arylene)-CO—, each of Y is independently C.sub.1-10 alkylene, each of Z is independently a bond, or —COO—, L is C.sub.1-10 alkylene, or ##STR00019## and each of n is independently an integer of 1 to 99, ##STR00020## in the Chemical Formula 3, R.sub.6 to R.sub.9 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and X.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.

10. The copolycarbonate according to claim 9, wherein X.sub.1 is a linear or branched C.sub.1-10 alkylene unsubstituted or substituted with phenyl, cyclohexane-1,1-diyl, O, S, SO, SO.sub.2, or CO.

11. The copolycarbonate according to claim 9, wherein R.sub.6 to R.sub.9 are each independently hydrogen, methyl, chloro, or bromo.

12. A molded article produced using the copolycarbonate of claim 9.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0059] FIG. 1 shows a NMR data of the polyorganosiloxane according to one example of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0060] 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.

Preparation Example 1: Preparation of AP-PDMS

[0061] ##STR00010##

[0062] 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 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 terminal-unmodified polyorganosiloxane thus obtained was 34 when confirmed through .sup.1H NMR.

[0063] To the resulting terminal-unmodified polyorganosiloxane, 4.81 g (35.9 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 siloxane was removed by conducting evaporation under the conditions of 120° C. and 1 torr. The terminal-modified polyorganosiloxane thus obtained was designated as AP-PDMS (n=34). AP-PDMS is a pale yellow oil, and the repeating unit (n) was 34 when confirmed through .sup.1H NMR using Varian 500 MHz, and further purification was not required.

Preparation Example 2: Preparation of Compound Represented by Chemical Formula 1-1

[0064] ##STR00011##

[0065] 50 g of isosorbide (hereinafter referred to as ISB) was added to a refluxable 1000 mL round flask reactor to which 400 mL of methylene chloride was added, and the mixture was stirred under a nitrogen atmosphere. Then, 80 g of triethylamine was added thereto. Subsequently, 65 g of triphenylphosphine was added, and the mixture was reacted at room temperature for 10 minutes to 3 hours. Triethylamine salt was removed by using a filter to which 100 g of AP-PDMS prepared in Preparation Example 1 was added and reacted. The reaction product was worked up with sodium bicarbonate, washed with distilled water, and the pH was adjusted to neutral and allowed to stand overnight under reduced pressure to prepare a compound represented by the Chemical Formula 1-1.

Preparation Example 3: Preparation of Compound Represented by Chemical Formula 1-2

[0066] ##STR00012##

[0067] 200 mL of chloroform was added to a 500 mL round flask reactor to which 10 g of AP-PDMS prepared in Preparation Example 1 was added. Then, 0.4 g of sebacoyl chloride was added dropwise and reacted under reflux for 2 hours. After completion of the reaction, the reaction mixture was washed and neutralized to prepare a compound represented by the Chemical Formula 1-2. The NMR data of the compound prepared above is shown in FIG. 1.

Example 1

[0068] 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and mixed and dissolved under a N.sub.2 atmosphere. To this mixture, 4.3 g of PTBP (para-tert butylphenol) and 6.57 g of the compound represented by the Chemical Formula 1-2 prepared in Preparation Example 3 were added by dissolving in MC (methylene chloride). Next, 128 g of TPG (triphosgene) was dissolved in MC and the mixture was added and reacted for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of triethylamine (TEA) was added to perform a coupling reaction. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4, TEA was removed, and the reaction mixture was washed three times with distilled water and the pH of the resulting polymer was adjusted to neutral, 6-7. The polymer thus obtained was re-precipitated with a mixed solution of methanol and hexane and was then dried at 120° C. to obtain a final copolycarbonate.

Example 2

[0069] The copolycarbonate was prepared in the same manner as in Example 1, except that 13.14 g of the compound represented by the Chemical Formula 1-2 prepared in Preparation Example 3 was used.

Example 3

[0070] The copolycarbonate was prepared in the same manner as in Example 1, except that 3.94 g of the compound represented by the Chemical Formula 1-2 prepared in Preparation Example 3 was used.

Example 4

[0071] The copolycarbonate was prepared in the same manner as in Example 1, except that 1.31 g of the compound represented by the Chemical Formula 1-2 prepared in Preparation Example 3 was used.

Example 5

[0072] The copolycarbonate was prepared in the same manner as in Example 1, except that 6.57 g of the compound represented by the Chemical Formula 1-1 prepared in Preparation Example 2 was used.

Comparative Example

[0073] 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and mixed and dissolved under a N.sub.2 atmosphere. To this mixture, 4.3 g of PTBP (para-tert butylphenol) was added by dissolving in MC (methylene chloride). Next, 128 g of TPG (triphosgene) was dissolved in MC and the mixture was added and reacted for 1 hour while maintaining the pH at 11 or higher. After 10 minutes, 46 g of TEA (triethylamine) was added to perform a coupling reaction. After a total reaction time of 1 hour and 20 minutes, the pH was lowered to 4 to remove TEA, and the reaction product was washed three times with distilled water and the pH of the resulting polymer was adjusted to neutral, 6-7. The polymer thus obtained was re-precipitated with a mixed solution of methanol and hexane and was then dried at 120° C. to obtain a final copolycarbonate.

Experimental Example

[0074] The weight average molecular weight of the copolycarbonates prepared in the Examples and Comparative Example were measured by GPC using PC Standard with Agilent 1200 series.

[0075] In addition, with respect to 1 part by weight of the respective copolycarbonates prepared in the Examples and Comparative Example, 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 030 mm twin-screw extruder provided with a vent, and was injection-molded at a cylinder temperature of 300° C. and a mold temperature of 90° C. using an injection molding machine N-20C (JSW, Ltd.) to prepare a desired specimen. The physical properties of the above specimens were determined in the following manner.

[0076] 1) Pencil hardness: The pellets were extruded using a heating press to produce 10×10 specimens and the specimen was drawn with a pencil hardness tester (500 g) and confirmed with the naked eye.

[0077] 2) Glass transition temperature (Tg): The temperature was raised from 20° C. to 200° C. at a temperature raising rate of 10° C./min using a differential scanning calorimeter, quenched up to 20° C., and then heated again to 200° C., thereby measuring the glass transition temperature.

[0078] 3) Chemical resistance: Izod impact specimens were fixed to a small jig (strain 48.5R). A cloth (length×width=1 cm×0.5 cm) was placed on the specimen, and 0.5 mL of Nivea sunspay as the solvent for testing chemical resistance was dropped on the cloth. Thereafter, the time until the Izod specimens were cracked and broken was measured to evaluate the chemical resistance.

[0079] The results are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Comparative Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Example Weight average 31,500 31,500 31,500 31,500 31,500 31,500 molecular weight(g/mol) Pencil hardness 148.6 HB 2B 2B B 2B Glass transition 148.6 147.8 151.2 151.8 150.2 152.1 temperature(Tg, ° C.) Chemical 1500 2500 1200 980 1400 600 resistance(sec)