Fluorine-containing polysiloxane, polysiloxane-polycarbonate copolymer comprising the same as repeated unit with improved chemical resistance, flame retardancy and weatherability, and method for preparing the copolymer

Abstract

The present invention relates to a fluorine-containing polysiloxane, a polysiloxane-polycarbonate copolymer comprising the same as a repeating unit, and a method for manufacturing the copolymer. More specifically, the invention relates to a polysiloxane of a specific structure having a siloxane unit having a terminal containing an optionally substituted hydroxyphenyl group and a fluorine-containing side chain, and a polysiloxane-polycarbonate copolymer comprising the polysiloxane and a polycarbonate block as repeating units, which has excellent chemical resistance, excellent flame retardancy, and excellent weather resistance, and a method for manufacturing the same.

Description

Technology Field

[0001] The present invention relates to a fluorine-containing polysiloxane, a polysiloxane-polycarbonate copolymer comprising the same as a repeating unit, and a method for manufacturing the copolymer. More specifically, the invention relates to a polysiloxane of a specific structure having a siloxane unit having a terminal containing an optionally substituted hydroxyphenyl group and a fluorine-containing side chain, and a polysiloxane-polycarbonate copolymer comprising the polysiloxane and a polycarbonate block as repeating units, which has excellent chemical resistance, excellent flame retardancy, and excellent weather resistance, and a method for manufacturing the same. Background Technology

[0002] Polycarbonate resin is widely used as an electrical component, mechanical part, and industrial resin due to its excellent heat resistance, mechanical properties (particularly impact strength), and transparency. In particular, when polycarbonate resin is used in the electrical and electronic fields where significant heat is dissipated—such as for TV housings, computer monitor housings, photocopiers, printers, laptop batteries, and lithium battery cases—excellent flame retardancy and chemical resistance are required in addition to heat resistance and mechanical properties. Furthermore, excellent weather resistance (i.e., stability against weather and light) is necessary for use in automotive exteriors and construction materials.

[0003] First, the most common method used to impart flame retardancy to polycarbonate resin is to mix bromine- or chlorine-based compounds, which are halogen flame retardants, into the resin. However, while the use of halogen flame retardants provides sufficient flame-retardant functionality in the event of a fire, the generation of hydrogen halide gas during resin processing not only causes mold corrosion and environmental pollution but also produces dioxins, which are toxic gases harmful to the human body, leading to increasing calls for regulations on their use. To address this, a flame-retardant polycarbonate resin composition has been developed that simultaneously uses alkali metal salts as non-halogen flame retardants and fluorinated polyolefin resins as anti-dripping agents. However, in this case, the fluorinated ethylene-based resins and metal salt-based flame retardants used to ensure the flame retardancy of the polycarbonate resin lead to a decrease in transparency, which is one of the advantages of polycarbonate resin.

[0004] To overcome this phenomenon of reduced transparency, silicone-based additives and alloys with silicone-based copolymers have been proposed (e.g., U.S. Patent Publication No. 2003-0105226). However, while the technology using silicone-based additives has the advantage of being environmentally friendly as a non-halogen flame retardant, it has disadvantages such as still low transparency, relatively high cost, and limited ability to achieve various colors when used as exterior materials. Furthermore, there is a problem in that its application to large products is limited due to insufficient fluidity for injection molding into large parts.

[0005] Accordingly, there is a need to develop polycarbonate resins or compositions thereof that can achieve harmonious physical properties by sufficiently exhibiting flame retardancy while possessing excellent transparency, fluidity, and low-temperature impact strength, in addition to excellent chemical resistance and weather resistance. The problem to be solved

[0006] The objective of the present invention is to provide a polysiloxane-polycarbonate copolymer and a method for manufacturing the same, which simultaneously possesses superior chemical resistance, flame retardancy, and weather resistance compared to conventional polysiloxane-polycarbonate copolymers while maintaining the excellent transparency and mechanical properties inherent to polycarbonate. means of solving the problem

[0007] To solve the above-mentioned technical problem, the present invention provides a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by the following chemical formula 1:

[0008] [Chemical Formula 1]

[0009]

[0010] In the above chemical formula 1,

[0011] R1 independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, and

[0012] R2 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group, and

[0013] R3 independently represents an alkylene group having 2 to 8 carbon atoms, and

[0014] R4 independently represents a hydrocarbon group having 1 to 13 carbon atoms, and

[0015] m each independently represents an integer from 0 to 4, and

[0016] n represents an integer from 1 to 3, and

[0017] a represents an integer from 2 to 1,000, and

[0018] b represents an integer from 1 to 500, and

[0019] However, the ratio of a to b is 1.92 or greater.

[0020] Another aspect of the present invention provides a polysiloxane-polycarbonate copolymer comprising, as a repeating unit, a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1; and a polycarbonate block.

[0021] Another aspect of the present invention provides a method for producing a polysiloxane-polycarbonate copolymer, comprising: (1) reacting a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 with an oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and (2) polymerizing the intermediate using a first polymerization catalyst.

[0022] Another aspect of the present invention provides a molded article comprising the polysiloxane-polycarbonate copolymer. Effects of the invention

[0023] The polysiloxane-polycarbonate copolymer according to the present invention maintains the excellent inherent properties of polycarbonate, such as impact resistance and transparency, while possessing significantly superior chemical resistance compared to conventional polysiloxane-polycarbonate copolymers and ensuring excellent flame retardancy without the addition of flame retardants. Additionally, since it possesses excellent weather resistance, it can be applied to various uses such as construction materials, automotive parts, electrical / electronic parts, and housing parts. Brief explanation of the drawing

[0024] Figure 1 shows the state in which a tensile specimen wrapped in cotton cloth is mounted on a test device during a chemical resistance test performed in an embodiment of the present invention. Figure 2 shows a UV irradiation device used in a weathering test performed in an embodiment of the present invention. Specific details for implementing the invention

[0025] The present invention will be described in more detail below.

[0026] As used herein, the term "reaction product" refers to a substance formed by the reaction of two or more reactants.

[0027] Additionally, although terms such as "first," "second," etc. are used in this specification to describe polymerization catalysts, said polymerization catalysts are not limited by such terms. These terms are used merely to distinguish the polymerization catalysts from one another. For example, the first polymerization catalyst and the second polymerization catalyst may be of the same type of catalyst or may be of different types of catalysts.

[0028] In addition, the letter "R" used to represent hydrogen, halogen atoms and / or hydrocarbon groups, etc. in the chemical formulas described herein has a numerical subscript, but the "R" is not limited by such subscript. The "R" independently represents hydrogen, halogen atoms and / or hydrocarbon groups, etc. For example, regardless of whether two or more "R"s have the same or different numerical subscripts, these "R"s may represent the same hydrocarbon group or different hydrocarbon groups.

[0029] Fluorine-containing hydroxyphenyl-terminated polysiloxane

[0030] The fluorine-containing hydroxyphenyl-terminated polysiloxane according to the present invention is a compound comprising a terminal containing an optionally substituted hydroxyphenyl group, a fluorine-free siloxane unit, and a siloxane unit containing fluorine in a side chain, represented by the following chemical formula 1.

[0031] [Chemical Formula 1]

[0032]

[0033] In the above chemical formula 1,

[0034] R1 independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group, and

[0035] R2 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group, and

[0036] R3 independently represents an alkylene group having 2 to 8 carbon atoms, and

[0037] R4 independently represents a hydrocarbon group having 1 to 13 carbon atoms, and

[0038] m each independently represents an integer from 0 to 4, and

[0039] n represents an integer from 1 to 3, and

[0040] a represents an integer from 2 to 1,000, and

[0041] b represents an integer from 1 to 500, and

[0042] However, the ratio of a to b is 1.92 or greater.

[0043] In the above chemical formula 1, if the ratio of a to b is less than 1.92, the flame retardancy becomes significantly poor.

[0044] In one embodiment, in the above formula 1, a may be an integer of 2 or more, 5 or more, 10 or more, 15 or more, or 20 or more, and may also be an integer of 1,000 or less, 750 or less, 500 or less, 250 or less, 100 or less, 50 or less, or 30 or less, but is not limited thereto.

[0045] In one embodiment, in the above formula 1, b may be an integer of 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, and may also be an integer of 500 or less, 375 or less, 250 or less, 125 or less, 50 or less, 25 or less, or 15 or less, but is not limited thereto.

[0046] In one embodiment, the ratio of a to b in the above formula 1 may be 1.92 or more, 1.95 or more, 2 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, 2.5 or more, 2.6 or more, 2.7 or more, 2.8 or more, 2.9 or more, 3 or more, 4 or more, 5 or more, or 6 or more, and may also be less than 29, 28 or less, 27 or less, 26 or less, 25 or less, 24 or less, 23 or less, 22 or less, 21 or less, 20 or less, 15 or less, 12 or less, 11.5 or less, 11 or less, 10.5 or less, 10 or less, 9.5 or less, or 9 or less, but is not limited thereto. More specifically, the ratio of a to b may be 2 to 10, and more specifically, 2.2 to 9, but is not limited thereto.

[0047] More specifically, the hydrocarbon group having 1 to 13 carbon atoms may be an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group or aralkoxy group having 7 to 13 carbon atoms, or an alkalyl group or alkalyloxy group having 7 to 13 carbon atoms.

[0048] For example, the alkyl group may be methyl, ethyl, or propyl; the alkylene group may be ethylene or propylene; the halogen atom may be Cl or Br; the alkoxy group may be methoxy, ethoxy, or propoxy; and the aryl group may be phenyl, chlorophenyl, or tolyl (preferably phenyl).

[0049] In one embodiment, the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 1 may be a reaction product of a polysiloxane of Formula 2-1 and a compound of Formula 2-2.

[0050] [Chemical Formula 2-1]

[0051]

[0052] [Chemical Formula 2-2]

[0053]

[0054] In the above Chemical Formula 2-1, R2, R4, n, a, and b are as defined in the above Chemical Formula 1, and

[0055] In the above chemical formula 2-2, R1 is as defined in the above chemical formula 1, and h represents an integer from 1 to 7.

[0056] In one embodiment, the molar ratio of the compound of Formula 2-1 to the compound of Formula 2-2 used to produce the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 1 may be 1:4 to 1:1, and more specifically, 1:3 to 1:2. If the molar ratio of the compound of Formula 2-1 to the compound of Formula 2-2 falls outside the above range, it may affect the degree of polymerization between the polysiloxane and the polycarbonate, which may be a factor in the degradation of physical properties such as flame retardant effect and transparency.

[0057] Polysiloxane-polycarbonate copolymer

[0058] The polysiloxane-polycarbonate copolymer according to the present invention comprises, as repeating units, a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by the above chemical formula 1; and a polycarbonate block.

[0059] In one embodiment, the polycarbonate block may comprise a structure represented by the following chemical formula 3:

[0060] [Chemical Formula 3]

[0061]

[0062] In the above formula 3, R5 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of an alkyl group (e.g., an alkyl group having 1 to 20 carbon atoms or 1 to 13 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (e.g., an alkenyl group having 2 to 20 carbon atoms or 2 to 13 carbon atoms), an alkoxy group (e.g., an alkoxy group having 1 to 20 carbon atoms or 1 to 13 carbon atoms), a halogen atom (e.g., Cl or Br), and a nitro group.

[0063] In one embodiment, the aromatic hydrocarbon group may be derived, for example, from a compound of Formula 4 below:

[0064] [Chemical Formula 4]

[0065]

[0066] In the above chemical formula 4,

[0067] X represents a linear, branched, or cyclic alkylene group that does not have a functional group (e.g., a linear alkylene group having 1 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms); or a linear, branched, or cyclic alkylene group comprising one or more functional groups selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a naphthyl group, a phenyl group, or an isobutylphenyl group, and

[0068] R6 and R7 each independently represent a halogen atom (e.g., Cl or Br), or a linear, branched, or cyclic alkyl group (e.g., a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms), and

[0069] p and q independently represent integers from 0 to 4.

[0070] The compound of Formula 4 above is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis(4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-Bis(4-hydroxyphenyl)butane, 2,2-Bis(4-hydroxyphenyl)pentane, 2,2-Bis(4-hydroxyphenyl)hexane, 2,2-Bis(4-hydroxyphenyl)nonane, 2,2-Bis(3-methyl-4-hydroxyphenyl)propane, 2,2-Bis(3-fluoro-4-hydroxyphenyl)propane, 4-methyl-2,2-Bis(4-hydroxyphenyl)pentane, 4,4-Bis(4-hydroxyphenyl)heptane, diphenyl-Bis(4-hydroxyphenyl)methane, Resorcinol, Hydroquinone, 4,4'-Dihydroxyphenyl Ether [Bis(4-hydroxyphenyl)Ether], 4,4'-Dihydroxy-2,5-Dihydroxydiphenyl ether, 4,4'-Dihydroxy-3,3'-Dichlorodiphenyl ether, Bis(3,5-Dimethyl-4-hydroxyphenyl)ether, Bis(3,5-Dichloro-4-hydroxyphenyl)ether, 1,4-Dihydroxy-2,5-Dichlorobenzene, 1,4-Dihydroxy-3-methylbenzene, 4,4'-Dihydroxydiphenol[p,p'-Dihydroxyphenyl], 3,3'-Dichloro-4,4'-Dihydroxyphenyl, 1,1-Bis(4-hydroxyphenyl)cyclohexane, 1,1-Bis(3,5-Dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-Bis(3,5-dichloro-4-hydroxyphenyl)cyclohexane, 1,1-Bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-Bis(4-hydroxyphenyl)cyclododecane, 1,1-Bis(4-hydroxyphenyl)butane, 1,1-Bis(4-hydroxyphenyl)decane, 1,4-Bis(4-hydroxyphenyl)propane, 1,4-Bis(4-hydroxyphenyl)butane, 1,4-Bis(4-hydroxyphenyl)isobutane, 2,2-Bis(4-hydroxyphenyl)butane, 2,2-Bis(3-chloro-4-hydroxyphenyl)propane, Bis(3,5-dimethyl-4-hydroxyphenyl)methane, Bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-Bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-Bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-Bis(4-hydroxyphenyl)-2-methyl-butane, 4,4'-thiodiphenol[Bis(4-hydroxyphenyl)sulfone], It may be selected from bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl)sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, or 2,6-dihydroxynaphthalene, but is not necessarily limited thereto. A representative example is 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A). For other functional dihydric phenols, refer to U.S. Patents US 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, etc., and the above dihydric phenols may be used alone or in combination of two or more.

[0071] In one embodiment, the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 in the polysiloxane-polycarbonate copolymer of the present invention may be 2.1 to 24.9 weight% with respect to the total weight of the copolymer. If the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 1 in the copolymer is less than 2.1 weight%, chemical resistance may be reduced, and if it exceeds 24.9 weight%, tensile strength and flame retardancy may be reduced.

[0072] More specifically, the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 in the polysiloxane-polycarbonate copolymer of the present invention may be, for example, 2.1 wt% or more, 2.2 wt% or more, 2.3 wt% or more, 2.4 wt% or more, 2.5 wt% or more, 2.6 wt% or more, 2.7 wt% or more, 2.8 wt% or more, 2.9 wt% or more, or 3 wt% or more, and may also be 24.9 wt% or less, 24.5 wt% or less, 24 wt% or less, 23.5 wt% or less, 23 wt% or less, 22.5 wt% or less, 22 wt% or less, 21.5 wt% or less, 21 wt% or less, 20.5 wt% or less, or 20 wt% or less, but is not limited thereto.

[0073] In one embodiment, the viscosity average molecular weight (M) of the polysiloxane-polycarbonate copolymer according to the present invention V, The viscosity average molecular weight (g / mol) can be 15,000 to 50,000, more specifically 17,000 to 40,000, and more preferably 19,000 to 30,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is excessively lower than the above level, mechanical properties may deteriorate, and conversely, if it is excessively higher than the above level, problems may arise in processing the resin due to an increase in melt viscosity.

[0074] According to another aspect of the present invention, a method for producing a polysiloxane-polycarbonate copolymer is provided, comprising: (1) reacting a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 with an oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and (2) polymerizing the intermediate using a first polymerization catalyst.

[0075] In one embodiment, the step of forming the (1) polysiloxane-polycarbonate intermediate may include mixing a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and an oligomeric polycarbonate in a weight ratio of 2.1:97.9 to 24.9:75.1.

[0076] In addition, in one embodiment, the step of forming the (1) polysiloxane-polycarbonate intermediate comprises forming a mixture comprising a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and an oligomeric polycarbonate, wherein the mixture may also comprise a phase transition catalyst, a molecular weight regulator, and a second polymerization catalyst.

[0077] In addition, in one embodiment, the step of (1) forming a polysiloxane-polycarbonate intermediate comprises: forming a mixture comprising a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and an oligomeric polycarbonate; and extracting an organic phase from the resulting mixture after the reaction between the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and the oligomeric polycarbonate is completed; and the step of (2) polymerizing the polysiloxane-polycarbonate intermediate may comprise providing a first polymerization catalyst to the extracted organic phase.

[0078] In one embodiment, the oligomeric polycarbonate used in the manufacture of the polysiloxane-polycarbonate copolymer may be an oligomeric polycarbonate having a viscosity-average molecular weight of 800 to 20,000 (more preferably 1,000 to 15,000). If the viscosity-average molecular weight of the polycarbonate is excessively lower than the above level, the molecular weight distribution may widen and physical properties may deteriorate, while conversely, if it is excessively higher than the above level, reactivity may deteriorate.

[0079] In one specific example, The above-described oligomeric polycarbonate can be prepared by adding a divalent phenolic compound of the aforementioned chemical formula 4 (e.g., bisphenol) to an alkaline aqueous solution to form a phenolic salt, and then reacting the salted phenolic compound with dichloromethane injected with phosgene gas. For the preparation of the oligomer, it is desirable to maintain the molar ratio of phosgene to the divalent phenolic compound in the range of about 1:1 to 1.5:1, more preferably about 1:1 to 1.2:1. If the molar ratio of phosgene to the divalent phenolic compound is less than 1, reactivity may decrease, and if the molar ratio of phosgene to the divalent phenolic compound exceeds 1.5, problems with processability may arise due to an excessive increase in molecular weight.

[0080] The above oligomer formation reaction can generally be carried out at a temperature in the range of about 15 to 60°C, and an alkali metal hydroxide (e.g., sodium hydroxide) can be used to control the pH of the reaction mixture.

[0081] In one embodiment, the polysiloxane-polycarbonate copolymer can be prepared by adding a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 to an organic phase-aqueous phase mixture containing polycarbonate, and then adding a molecular weight regulator and a catalyst in stages.

[0082] As a molecular weight regulator, a monofunctional compound similar to the monomer used in the manufacture of polycarbonate may be used. The monofunctional compound may be, for example, a phenol-based derivative such as p-isopropylphenol, p-tert-butylphenol (p-tert-butylphenol, PTBP), p-cumylphenol, p-isooctylphenol, and p-isononylphenol; or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) may be used.

[0083] Polymerization catalysts and / or phase transition catalysts may be used as catalysts. For example, triethylamine (TEA) may be used as a polymerization catalyst, and for example, a compound of the following chemical formula A may be used as a phase transition catalyst.

[0084] [Chemical Formula A]

[0085] (R8)4Q + X -

[0086] In the above chemical formula A, R8 represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or -OR9. Here, R9 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

[0087] Specifically, the phase transition catalyst may be, for example, [CH3(CH2)3]4NX, [CH3(CH2)3]4PX, [CH3(CH2)5]4NX, [CH3(CH2)6]4NX, [CH3(CH2)4]4NX, CH3[CH3(CH2)3]3NX, or CH3[CH3(CH2)2]3NX. In the above chemical formulas, X represents Cl, Br, or -OR9, where R9 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

[0088] The content of the phase transition catalyst is preferably about 0.01 to 10 weight percent based on the total weight of the mixture of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 1 and the oligomeric polycarbonate. If the content is less than 0.01 weight percent, reactivity may decrease, and if the content exceeds 10 weight percent, it may precipitate or transparency may decrease.

[0089] In one embodiment, a polysiloxane-polycarbonate copolymer is prepared, and then the organic phase dispersed in methylene chloride is separated after alkaline washing. Subsequently, the organic phase is washed using a 0.1N hydrochloric acid solution and then washed repeatedly with distilled water 2 to 3 times. Once washing is complete, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, and granulation is performed using a certain amount of pure water in the range of 70 to 80°C. If the temperature of the pure water is below 70°C, the granulation speed slows down, which may result in a very long granulation time; if the temperature of the pure water exceeds 80°C, it may become difficult to obtain a polycarbonate shape of a constant size. Once granulation is complete, it is preferable to dry it first at 100 to 110°C for 5 to 10 hours, and then dry it secondly at 110 to 120°C for 5 to 10 hours.

[0090] The polysiloxane-polycarbonate copolymer according to the present invention maintains the excellent inherent properties of polycarbonate, such as impact resistance and transparency, while possessing significantly superior chemical resistance compared to conventional polysiloxane-polycarbonate copolymers and ensuring excellent flame retardancy without the addition of flame retardants, so it can be applied to various uses such as construction materials, automotive parts, electrical / electronic parts, and housing parts.

[0091] Accordingly, according to another aspect of the present invention, a molded article comprising a polysiloxane-polycarbonate copolymer of the present invention is provided.

[0092] The method of manufacturing a molded article using the polysiloxane-polycarbonate copolymer of the present invention is not particularly limited, and methods generally used for manufacturing resin molded articles (e.g., extrusion or injection, etc.) may be used as is or appropriately modified.

[0093] The present invention will be explained in more detail below through examples, but this is for the purpose of explaining the invention only, and the scope of the invention is not limited in any way by the examples.

[0094] [Example]

[0095] <Preparation of Fluorine-Containing Hydroxyphenyl-Terminated Polysiloxanes>

[0096] Example A1

[0097] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 204.19 g (0.09 mol) of a fluorine-containing polysiloxane corresponding to Chemical Formula 5 (AFSP600, a colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.3 g (100 ppm) of a platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 27.60 g (0.21 mol) of 2-allylphenol was slowly added over 1 hour, and the mixture was refluxed for 5 hours. After the reaction was complete, the solvent toluene was removed from the reaction solution, and the solution was dried in a vacuum oven for 24 hours to prepare the fluorine-containing hydroxyphenyl-terminated polysiloxane of Chemical Formula 6 below.

[0098] [Chemical Formula 5]

[0099]

[0100] [Chemical Formula 6]

[0101]

[0102] Example A2

[0103] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 226.36 g (0.09 mol) of a fluorine-containing polysiloxane corresponding to Chemical Formula 7 (AFSP601, colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.4 g (100 ppm) of a platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 29.61 g (0.22 mol) of 2-allylphenol was slowly added over 1 hour, and the mixture was refluxed for 5 hours. After the reaction was complete, the solvent toluene was removed from the reaction solution, and the solution was dried in a vacuum oven for 24 hours to prepare the fluorine-containing hydroxyphenyl-terminated polysiloxane of Chemical Formula 8 below.

[0104] [Chemical Formula 7]

[0105]

[0106] [Chemical Formula 8]

[0107]

[0108] Example A3

[0109] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 200.13 g (0.08 mol) of polysiloxane corresponding to Chemical Formula 9 (AFSP602, colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.2 g (100 ppm) of platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 24.05 g (0.18 mol) of 2-allylphenol was slowly added over 1 hour, and the mixture was refluxed for 5 hours. After the reaction was completed, the solvent toluene was removed from the reaction solution, and the polysiloxane of Chemical Formula 10 was prepared by drying in a vacuum oven for 24 hours.

[0110] [Chemical Formula 9]

[0111]

[0112] [Chemical Formula 10]

[0113]

[0114] Example A4

[0115] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 206.7 g (0.07 mol) of polysiloxane corresponding to Chemical Formula 11 (AFSP603, colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.2 g (100 ppm) of platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 21.78 g (0.16 mol) of 2-allylphenol was slowly added over 1 hour, and the mixture was refluxed for 5 hours. After the reaction was completed, the solvent toluene was removed from the reaction solution, and the polysiloxane of Chemical Formula 12 was prepared by drying in a vacuum oven for 24 hours.

[0116] [Chemical Formula 11]

[0117]

[0118] [Chemical Formula 12]

[0119]

[0120] Comparative Example A1

[0121] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 199.39 g (0.09 mol) of the polysiloxane corresponding to Chemical Formula 13 (APSP200, a colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.2 g (100 ppm) of platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 24.21 g (0.18 mol) of 2-allylphenol was slowly added over 1 hour and refluxed for 5 hours. After the reaction was completed, the solvent toluene was removed from the reaction solution, and the hydroxyphenyl-terminated polysiloxane of Chemical Formula 14 was prepared by drying in a vacuum oven for 24 hours.

[0122] [Chemical Formula 13]

[0123]

[0124] [Chemical Formula 14]

[0125]

[0126] Comparative Example A2

[0127] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 255.36 g (0.09 mol) of the polysiloxane corresponding to Formula 15 (AFSP6029, a colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.4 g (100 ppm) of platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 33.75 g (0.22 mol) of 2-allylphenol was slowly added over 1 hour and refluxed for 5 hours. After the reaction was completed, the solvent toluene was removed from the reaction solution, and the solution was dried in a vacuum oven for 24 hours to prepare the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 16.

[0128] [Chemical Formula 15]

[0129]

[0130] [Chemical Formula 16]

[0131]

[0132] Comparative Example A3

[0133] A condenser was fitted into a 500 mL three-necked flask, and under a nitrogen atmosphere, 202.29 g (0.07 mol) of polysiloxane corresponding to Chemical Formula 17 (AFSP604, colorless transparent liquid from Miwon Corporation) was dissolved in 100 ml of toluene, and then 1.2 g (100 ppm) of platinum (Pt) catalyst (Pt-CS-1.8CS from UMICORE) was added. While the solution was heated, 19.49 g (0.15 mol) of 2-allylphenol was slowly added over 1 hour, and the mixture was refluxed for 5 hours. After the reaction was completed, the solvent toluene was removed from the reaction solution, and the polysiloxane of Chemical Formula 18 was prepared by drying in a vacuum oven for 24 hours.

[0134] [Chemical Formula 17]

[0135]

[0136] [Chemical Formula 18]

[0137]

[0138] <Preparation of Polysiloxane-Polycarbonate Copolymers>

[0139] Example B1: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A1 (3 wt% based on total copolymer weight)

[0140] An oligomeric polycarbonate mixture having a viscosity-average molecular weight of about 1,000 was prepared by interfacially reacting bisphenol A in an aqueous solution with phosgene gas in the presence of methylene chloride. The organic phase of the obtained oligomeric polycarbonate mixture was collected, and an aqueous sodium hydroxide solution, the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1 (in an amount of 3 wt% based on the total weight of the copolymer), tetrabutyl ammonium chloride (TBACl, in an amount of 0.1 wt% based on the total weight of the copolymer), methylene chloride, and p-tert-butylphenol (PTBP, in an amount of 0.4 wt% based on the total weight of the copolymer) were mixed therein and reacted for 2 hours. After phase separation occurred, only the organic phase was collected, and an aqueous sodium hydroxide solution, methylene chloride, and triethylamine (TEA, in an amount of 0.015 wt% based on the total weight of the copolymer) were added and reacted for 3 hours. Triethylamine (TEA, in an amount of 0.02 wt% based on the total weight of the copolymer) was added again to the reacted organic phase and reacted for an additional 2 hours. After phase separation occurred, the organic phase with increased viscosity was collected, distilled water and methylene chloride were added to it, and after alkaline washing, it was separated again. Subsequently, the organic phase was washed with a 0.1N aqueous hydrochloric acid solution and then washed 2 to 3 times repeatedly with distilled water. After washing was completed, the organic phase was granulated at 76°C using a certain amount of pure water. After granulation was completed, the fluorine-containing polysiloxane-polycarbonate copolymer was prepared by drying it first at 110°C for 8 hours and secondly at 120°C for 10 hours. The physical properties of the polysiloxane-polycarbonate copolymer prepared above were measured and listed in Table 1 below.

[0141] Example B2: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A1 (6 wt% based on total copolymer weight)

[0142] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1 was changed from 3% by weight to 6% by weight based on the total weight of the copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0143] Example B3: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A1 (6 wt% based on total copolymer weight)

[0144] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1 was changed from 3% by weight based on the total weight of the copolymer to 9% by weight based on the total weight of the copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0145] Example B4: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A1 (15 wt% based on total copolymer weight)

[0146] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the content of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1 was changed from 3% by weight to 15% by weight based on the total weight of the copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and listed in Table 1 below.

[0147] Example B5: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A2 (3 wt% based on total copolymer weight)

[0148] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 8 obtained in Example A2 (in an amount of 3% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0149] Example B6: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A2 (6 wt% based on total copolymer weight)

[0150] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 8 obtained in Example A2 (in an amount of 6% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0151] Example B7: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A2 (9 wt% based on total copolymer weight)

[0152] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 8 obtained in Example A2 (in an amount of 9% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0153] Example B8: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A2 (20 wt% based on total copolymer weight)

[0154] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 8 obtained in Example A2 (in an amount of 20 wt% based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0155] Example B9: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A3 (9 wt% based on total copolymer weight)

[0156] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 10 obtained in Example A3 (in an amount of 9% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0157] Example B10: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Example A4 (9 wt% based on total copolymer weight)

[0158] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 12 obtained in Example A4 (in an amount of 9 wt% based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0159] Comparative Example B1: Linear polycarbonate resin with a viscosity-average molecular weight of 21,200 g / mol

[0160] The physical properties of a linear polycarbonate resin (Samyang Corporation, TRIREX 3022IR) with a viscosity average molecular weight of 21,200 g / mol were measured and listed in Table 1 below.

[0161] Comparative Example B2: Linear polycarbonate resin with a viscosity-average molecular weight of 70,900 g / mol

[0162] A linear polycarbonate resin with a viscosity-average molecular weight of 70,900 g / mol was prepared in the same manner as in Example B1, except that the fluorine-containing polysiloxane of Formula 6 obtained in Example A1 was not used. The physical properties of the prepared polycarbonate resin were measured and listed in Table 1 below.

[0163] Comparative Example B3: Preparation of a polysiloxane-polycarbonate copolymer using the hydroxy-terminated polysiloxane of Comparative Example A1 (9 wt% based on total copolymer weight)

[0164] A polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the hydroxyphenyl-terminated polysiloxane of Formula 10 obtained in Comparative Example A1 (in an amount of 9% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0165] Comparative Example B4: Preparation of a polysiloxane-polycarbonate copolymer using the polysiloxane of Comparative Example A2 (9 wt% based on the total weight of the copolymer).

[0166] The same method as in Example B1 was performed except that the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 16 obtained in Comparative Example A2 (in an amount of 9% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1, but the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 16 was not well dissolved, so it was impossible to manufacture a polysiloxane-polycarbonate copolymer.

[0167] Comparative Example B5: Preparation of a polysiloxane-polycarbonate copolymer using the fluorine-containing hydroxyphenyl-terminated polysiloxane of Comparative Example A3 (9 wt% based on total copolymer weight).

[0168] A fluorine-containing polysiloxane-polycarbonate copolymer was prepared by performing the same method as in Example B1, except that the hydroxyphenyl-terminated polysiloxane of Formula 18 obtained in Comparative Example A3 (in an amount of 9% by weight based on the total weight of the copolymer) was used instead of the fluorine-containing hydroxyphenyl-terminated polysiloxane of Formula 6 obtained in Example A1. The physical properties of the prepared fluorine-containing polysiloxane-polycarbonate copolymer were measured and are listed in Table 1 below.

[0169] Methods for Measuring Physical Properties

[0170] (1) H-NMR (Nuclear Magnetic Resonance Spectrometer)

[0171] Measurements were performed using Bruker’s Avance DRX 300. The copolymer was identified by H-NMR using the peak of the methyl group of dimethylsiloxane observed at 0.2 ppm, the peak of the methylene group of the polysiloxane-polycarbonate bond observed at 2.6 ppm, and the peak of the methoxy group of the polysiloxane-polycarbonate bond observed at 3.9 ppm.

[0172] (2) Viscosity average molecular weight (M V : g / mol)

[0173] The viscosity of the methylene chloride solution was measured at 20°C using a Ubbelohde viscometer, and the intrinsic viscosity [η] was calculated from this using the following equation.

[0174] [η]=1.23x10 -5 MV 0.83

[0175] (3) Chemical resistance

[0176] A) After injecting tensile specimens according to ASTM D638 using the polysiloxane-polycarbonate copolymer obtained in the examples and comparative examples, a cotton cloth was wrapped around each tensile specimen as shown in Fig. 1, and after placing the tensile specimen wrapped in the cotton cloth on a 1.5% Strain ESCR Zig and applying force, 5 ml of acetone was dropped onto the cotton cloth, and immediately after, whether each tensile specimen was destroyed was visually checked.

[0177] B) In addition, the tensile strength was measured according to ASTM D638 without dropping acetone onto each of the above tensile specimens.

[0178] C) In addition, each tensile specimen with 5 ml of acetone added was left for one week under conditions of 50% humidity and a temperature of 23°C, and then the tensile strength was measured according to ASTM D638 and compared with the tensile strength of each tensile specimen before the addition of acetone.

[0179] (4) Flame retardancy

[0180] The flame retardancy was measured using the UL-94 flame retardancy test method prescribed by Underwriter's Laboratories (UL) of the United States. This method evaluates flame retardancy based on the burning time or dripping ability after applying a burner flame to a vertically fixed specimen of a certain size for 10 seconds. The burning time is the length of time the specimen continues to burn with a flame after the flame is removed, and the ignition of the cotton due to dripping is determined by the ignition of the cotton used for marking located approximately 300 mm below the bottom of the specimen due to dripping from the specimen. The flame retardancy grades are classified according to the table below.

[0181]

[0182] (5) Weather resistance (light resistance / UV stability)

[0183] A specimen (Color specimen, 1.5 mm) was placed in the UV irradiation device shown in Fig. 2 and irradiated with UV light (220 V, 50 / 60 Hz) for 72 hours, and then the weather resistance performance was compared by measuring the values ​​of △YI and △E before and after UV irradiation using a colorimeter.

[0184]

[0185]

[0187] As shown in Table 1 above, it can be confirmed that the polysiloxane-polycarbonate copolymers prepared in Examples B1 to B10 according to the present invention exhibit superior chemical resistance, flame retardancy, and weather resistance (light resistance, UV stability) compared to the linear polycarbonate resins prepared in Comparative Examples B1 and B2 and the polysiloxane-polycarbonate copolymers prepared in Comparative Examples B3 and B5. In particular, in the case of Comparative Example B5, the ratio of fluorine-non-containing repeating units to fluorine (F)-containing repeating units in the polysiloxane (i.e., the ratio of a to b in Formula 1) was low at 1.91, and it was confirmed that the flame retardancy was poor due to rapid dripping caused by the clumping of fluorine-containing parts during combustion, which induces drip burn. In the case of Comparative Example B4, the ratio of fluorine-non-containing repeating units to fluorine (F)-containing repeating units in the polysiloxane (i.e., the ratio of a to b in Formula 1) was excessively high at 29, so the fluorine-containing hydroxyphenyl-terminated polysiloxane did not dissolve well, making it impossible to manufacture a polysiloxane-polycarbonate copolymer.

Claims

Claim 1 A polysiloxane-polycarbonate copolymer comprising: a repeating unit derived from a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by the following formula 1; and a polycarbonate block; wherein the content of the repeating unit derived from the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by formula 1 is 9 to 20 weight% based on the total weight of the copolymer: [Formula 1] In the above chemical formula 1, R1 independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group; R2 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group; R3 independently represents an alkylene group having 2 to 8 carbon atoms; R4 independently represents a hydrocarbon group having 1 to 13 carbon atoms; m independently represents an integer from 0 to 4; n represents an integer from 1 to 3; a represents an integer from 2 to 1,000; and b represents an integer from 1 to 500, provided that the ratio of a to b is 2.3 to 2.

625. Claim 2 The polysiloxane-polycarbonate copolymer according to claim 1, wherein the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Chemical Formula 1 is the reaction product of the polysiloxane of Chemical Formula 2-1 and the compound of Chemical Formula 2-2: [Chemical Formula 2-1] [Chemical Formula 2-2] In the above chemical formula 2-1, R2, R4, n, a, and b are as defined in chemical formula 1 of claim 1, and in the above chemical formula 2-2, R1 is as defined in chemical formula 1 of claim 1, and h represents an integer from 1 to 7. Claim 3 The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polycarbonate block comprises a structure represented by the following chemical formula 3: [Chemical Formula 3] In the above chemical formula 3, R5 represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is substituted or unsubstituted with one or more substituents selected from the group consisting of alkyl groups, cycloalkyl groups, alkenyl groups, alkoxy groups, halogen atoms, and nitro groups. Claim 4 In claim 3, a polysiloxane-polycarbonate copolymer in which the aromatic hydrocarbon group is derived from a compound of the following formula 4: [Formula 4] In the above formula 4, X represents a linear, branched, or cyclic alkylene group that does not have a functional group; or a linear, branched, or cyclic alkylene group comprising one or more functional groups selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a naphthyl group, a phenyl group, or an isobutylphenyl group; R6 and R7 each independently represent a halogen atom; or a linear, branched, or cyclic alkyl group; and p and q each independently represent an integer from 0 to 4. Claim 5 delete Claim 6 The polysiloxane-polycarbonate copolymer according to claim 1, having a viscosity-average molecular weight of 15,000 to 50,000 g / mol. Claim 7 A method for preparing a polysiloxane-polycarbonate copolymer comprising: (1) a step of reacting a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by the following Chemical Formula 1 with an oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and (2) a step of polymerizing the intermediate using a first polymerization catalyst; wherein the step (1) of forming the polysiloxane-polycarbonate intermediate comprises a step of mixing the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Chemical Formula 1 and the oligomeric polycarbonate in a weight ratio of 9:91 to 20:80: [Chemical Formula 1] In the above chemical formula 1, R1 independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, or an aryl group; R2 independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group; R3 independently represents an alkylene group having 2 to 8 carbon atoms; R4 independently represents a hydrocarbon group having 1 to 13 carbon atoms; m independently represents an integer from 0 to 4; a represents an integer from 2 to 1,000; and b represents an integer from 1 to 500, provided that the ratio of a to b is 2.3 to 2.

625. Claim 8 delete Claim 9 A method for producing a polysiloxane-polycarbonate copolymer according to claim 7, wherein (1) the step of forming a polysiloxane-polycarbonate intermediate comprises the step of forming a mixture comprising a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and an oligomeric polycarbonate in a weight ratio of 9:91 to 20:80, and said mixture also comprises a phase transition catalyst, a molecular weight regulator and a second polymerization catalyst. Claim 10 A method for producing a polysiloxane-polycarbonate copolymer according to claim 7, wherein (1) the step of forming a polysiloxane-polycarbonate intermediate comprises forming a mixture comprising a fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and an oligomeric polycarbonate in a weight ratio of 9:91 to 20:80; and the step of extracting an organic phase from the resulting mixture after the reaction between the fluorine-containing hydroxyphenyl-terminated polysiloxane represented by Formula 1 and the oligomeric polycarbonate is completed; and (2) the step of polymerizing the polysiloxane-polycarbonate intermediate comprises providing a first polymerization catalyst to the extracted organic phase. Claim 11 A method for producing a polysiloxane-polycarbonate copolymer according to claim 7, wherein the viscosity average molecular weight of the oligomeric polycarbonate is 800 to 20,000 g / mol. Claim 12 A molded article comprising a polysiloxane-polycarbonate copolymer according to any one of claims 1 to 4 and 6. Claim 13 delete Claim 14 delete Claim 15 delete Claim 16 delete Claim 17 delete

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