KR102258391B1 - Polysiloxane-polycarbonate copolymer having excellent impact resistance, flame retardancy and transparency and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate copolymer having improved impact resistance, flame retardancy and transparency, and a method for preparing the same, and more particularly, to a branched polysiloxane, linear polysiloxane and polycarbonate block comprising a repeating unit as a repeating unit, excellent impact resistance At the same time, it relates to a polysiloxane-polycarbonate copolymer exhibiting excellent flame retardancy and transparency, and a method for preparing the same.

Description

Polysiloxane-polycarbonate copolymer with excellent impact resistance, flame retardancy and transparency, and manufacturing method thereof

The present invention relates to a polysiloxane-polycarbonate copolymer having improved impact resistance, flame retardancy and transparency, and a method for preparing the same, and more particularly, to a branched polysiloxane having a specific structure, a linear polysiloxane having a specific structure, and a polycarbonate block as a repeating unit It relates to a polysiloxane-polycarbonate copolymer having excellent flame retardancy and transparency, and at the same time having improved mechanical strength such as impact resistance, and a method for manufacturing the same.

Polycarbonate resin has excellent heat resistance, mechanical properties (especially impact strength) and transparency, and thus is widely used as an electrical component, mechanical component, and industrial resin. In particular, when polycarbonate resin is used as a case material for TV housings, computer monitor housings, copiers, printers, notebook batteries, and lithium batteries that emit a lot of heat in the electrical and electronic fields, excellent flame retardancy is required as well as heat resistance and mechanical properties. .

The most common method used to impart flame retardancy to a polycarbonate resin is to mix a bromine-based or chlorine-based compound, which is a halogen flame retardant, into the polycarbonate resin. However, when a halogen flame retardant is used, the flame retardant function is sufficiently exhibited in case of fire, but hydrogen halide gas is generated during resin processing, which not only causes mold corrosion and environmental pollution problems, but also generates dioxin, a toxic gas harmful to the human body during combustion. The movement to regulate its use is expanding. To cope with this, a flame-retardant polycarbonate resin composition using an alkali metal salt as a non-halogen flame retardant and a fluorinated polyolefin-based resin as an anti-dripping agent has been developed. However, in this case, there is a problem in that transparency, one of the advantages of the polycarbonate resin, is deteriorated due to the fluorinated ethylene-based resin and the metal salt-based flame retardant used to ensure the flame retardancy of the polycarbonate resin.

In order to overcome such a decrease in transparency, an alloy with a silicone-based additive and a silicone-based copolymer has been proposed. However, the technology using the silicone-based additive has the advantage of being environmentally friendly as a non-halogen flame retardant, but has a disadvantage in that transparency is still low, relatively expensive, and various colors are limited when used as an exterior material. In addition, there is a problem in that the fluidity is insufficient for injection into large-sized products, so that the application to large-sized products is limited.

Accordingly, there is a demand for the development of a polycarbonate resin composition that can achieve harmonious physical properties such as excellent transparency, fluidity and impact strength (especially low-temperature impact strength) while sufficiently exhibiting flame retardancy.

US Patent Publication No. 2003/0105226

The present invention is intended to solve the problems of the prior art as described above, and it is a technical task to provide a polysiloxane-polycarbonate copolymer having excellent flame retardancy, as well as excellent impact resistance and transparency, and a method for manufacturing the same.

In order to solve the above technical problem, the present invention provides a polysiloxane represented by the following Chemical Formula 1; polysiloxanes other than the polysiloxanes of formula (1); And it provides a polysiloxane-polycarbonate copolymer comprising a polycarbonate block as a repeating unit:

[Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group,

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,

R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

k independently represents an integer of 1 to 4,

l, m and n each independently represent an integer of 0 to 4, with the proviso that at least one of l, m and n is not 0,

x and y each independently represent an integer of 0-100.

The present invention also provides a step of reacting a polysiloxane of Formula 1 below, a polysiloxane other than the polysiloxane of Formula 1 and an oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; And it provides a method for preparing a polysiloxane-polycarbonate copolymer comprising the step of polymerizing the intermediate using a first polymerization catalyst:

[Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group,

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,

R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

k independently represents an integer of 1 to 4,

l, m and n each independently represent an integer of 0 to 4, with the proviso that at least one of l, m and n is not 0,

x and y each independently represent an integer of 0-100.

The present invention also provides a molded article manufactured using the polysiloxane-polycarbonate copolymer according to the present invention in order to solve the above technical problem.

The polysiloxane-polycarbonate copolymer according to the present invention can dramatically improve flame retardancy without adding a flame retardant, and at the same time, can maintain excellent properties inherent to polycarbonate such as impact resistance and transparency. For example, it can be variously applied to construction materials, automobile parts, office equipment, housings of electric/electronic products, and the like.

Hereinafter, the present invention will be described in more detail.

As used herein, the term “reaction product” refers to a substance formed by the reaction of two or more reactants.

In addition, although terms such as “first” and “second” are used herein to describe a polymerization catalyst, the polymerization catalyst is not limited by these terms. These terms are only used to distinguish polymerization catalysts from one another. For example, the first polymerization catalyst and the second polymerization catalyst may be the same type of catalyst or different types of catalyst.

In addition, the English letter "R" used to represent hydrogen, a halogen atom and/or a hydrocarbon group in the chemical formulas described herein has a subscript represented by a number, but the "R" is in this subscript is not limited by The "R" represents, independently of each other, hydrogen, a halogen atom and/or a hydrocarbon group. For example, two or more "R"s may represent the same hydrocarbon group or different hydrocarbon groups, regardless of whether two or more "R"s have the same or different number of subscripts.

The present invention relates to a polysiloxane of Formula 1; Polysiloxane of Formula 2; And it relates to a polysiloxane-polycarbonate copolymer comprising a polycarbonate block as a repeating unit.

branched polysiloxane

The polysiloxane-polycarbonate copolymer according to the present invention includes polysiloxane represented by the following formula (1) as a repeating unit. The polysiloxane of Formula 1 below is a compound in which siloxanes including siloxane having a hydroxyphenyl group are linked in a side chain.

[Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group,

R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,

R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,

k independently represents an integer of 1 to 4,

l, m and n each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, provided that at least one of l, m and n is not 0,

x and y each independently represent an integer from 0 to 100, preferably an integer from 0 to 50, more preferably an integer from 0 to 10, Or an integer of 2 to 100, preferably an integer of 2 to 50, more preferably an integer of 2 to 10.

More specifically, the hydrocarbon group having 1 to 13 carbon atoms is 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, or a cycloalkoxy group having 6 to 10 carbon atoms. of an aryloxy group, an aralkyl group or aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms.

More specifically, 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; The aryl group may be phenyl, chlorophenyl or tolyl (preferably, phenyl).

In a preferred embodiment, the polysiloxane of Formula 1 may be a reaction product of a polysiloxane of Formula 4 and a compound of Formula 5 below.

[Formula 4]

In Formula 4, R ₁ , R ₂ , l, m, n, x and y are the same as defined in Formula 1 above.

[Formula 5]

In Formula 5, R ₄ and k are as defined in Formula 1 above, and h represents an integer of 1 to 7.

The molar ratio of the compound of Formula 4 to the compound of Formula 5 used for preparing the polysiloxane of Formula 1 is preferably maintained in the range of 1:4 to 1:1, and maintaining it in the range of 1:3 to 1:2 more preferably. When the molar ratio of the compound of Formula 4 to the compound of Formula 5 is out of the above range, it may affect the degree of polymerization between the polysiloxane and the polycarbonate, thereby reducing flame retardancy and transparency.

linear polysiloxane

The polysiloxane-polycarbonate copolymer according to the present invention includes a polysiloxane other than the polysiloxane of Formula 1 as a repeating unit, and specifically includes the polysiloxane of Formula 2 below. The polysiloxane represented by the following formula (2) is a hydroxyl-terminated siloxane compound having a hydroxyl group at the terminal.

[Formula 2]

In Chemical Formula 2,

R ₅ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R ₆ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,

R ₇ independently represents an alkylene group having 2 to 8 carbon atoms,

A is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,

m independently represents an integer of 0 to 4,

n independently represents an integer of 2 to 1,000, preferably an integer of 2 to 500, more preferably an integer of 5 to 100.

Specifically, in R ₅ of Formula 2, the halogen atom may be Cl or Br; The alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as methyl, ethyl or propyl; The alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as methoxy, ethoxy or propoxy; The aryl group may be an aryl group having 6 to 10 carbon atoms, such as phenyl, chlorophenyl or tolyl;

In R ₆ of Formula 2, the hydrocarbon group having 1 to 13 carbon atoms is an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, an alkenyl group having 2 to 13 carbon atoms, an alkenyloxy group having 2 to 13 carbon atoms, 3 to carbon atoms. 6 cycloalkyl group, C3-6 cycloalkoxy group, C6-C10 aryloxy group, C7-13 aralkyl group, C7-13 aralkoxy group, C7-13 alkaryl group or carbon number 7 to 13 alkaryloxy groups;

In A of Formula 2, X is, for example, an aliphatic group having 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, an aliphatic group having 1 to 20 carbon atoms including oxygen, nitrogen or sulfur atoms in the main chain, 3 to carbon atoms It may be a cycloalkylene group of 6, or an arylene group that may be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol, and may be represented by, for example, the following formulas Aa to Ah.

[Formula Aa]

[Formula Ab]

[Formula Ac]

[Formula Ad]

[Formula Ae]

[Formula Af]

[Formula Ag]

[Formula Ah]

In one embodiment, the hydroxy-terminated siloxane of Formula 2 may be a reaction product of a hydroxy-terminated siloxane of Formula 2a with an acyl compound (ie, a hydroxyl-terminated siloxane having an ester bond).

[Formula 2a]

In Formula 2a, R ₅ , R ₆ , R ₇ , m and n are the same as defined in Formula 2 above.

The hydroxy-terminated siloxane of Formula 2a may be prepared by synthesizing, for example, a compound of Formula 2b having a hydroxyl group and a double bond and a compound of Formula 2c containing silicone in a molar ratio of 2:1 using a platinum catalyst. can be manufactured.

[Formula 2b]

In Formula 2b, R ₅ and m are as defined in Formula 2 above, and k represents an integer of 1 to 7.

[Formula 2c]

In Formula 2c, R ₆ and n are as defined in Formula 2 above.

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다. 또한 상기 화학식 2a의 히드록시 말단 실록산의 제조와 관련하여 미국특허 US 6,072,011호를 참조할 수 있다.Specifically, as the hydroxy-terminated siloxane of Formula 2a, a siloxane monomer from Dow Corning (

) can be used, but is not necessarily limited thereto. Also, reference may be made to US Pat. No. 6,072,011 regarding the preparation of the hydroxy-terminated siloxane of Formula 2a.

The acyl compound used for preparing the hydroxy-terminated siloxane of Formula 2 may have, for example, an aromatic, aliphatic, or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and when aliphatic, it may have 1 to 20 carbon atoms. In addition, the acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy-terminated siloxane of Formula 2 may be a reaction product of the hydroxy-terminated siloxane of Formula 2a with a diisocyanate compound (ie, hydroxy-terminated siloxane having a urethane bond).

Here, the diisocyanate compound is, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate, or 4,4'-methylenediphenyl di It may be isocyanate (4,4'-methylenediphenyl diisocyanate).

polysiloxane -Polycarbonate copolymer

The polysiloxane-polycarbonate copolymer according to the present invention is a polysiloxane of Formula 1 (ie, a polysiloxane block having a hydroxyphenyl group in a side chain) and a polysiloxane other than the polysiloxane of Formula 1 (ie, as a polysiloxane of Formula 2, a hydroxyl group at the terminal) and a polycarbonate block of Formula 3 to be described later together with a polysiloxane block having a repeating unit.

[Formula 3]

In Chemical Formula 3,

R ₈ is an alkyl group (eg, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 20 carbon atoms, preferably 3 to 6 carbon atoms), an alkenyl group (eg, An alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 13 carbon atoms), an alkoxy group (eg, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 13 carbon atoms), a halogen atom (eg Cl or Br) or nitro represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, substituted or unsubstituted with . Here, the aromatic hydrocarbon group may be derived from, for example, a compound of Formula 6 below.

[Formula 6]

In Formula 6,

X is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl (e.g., a straight 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);

R ₉ and R ₁₀ are each independently a halogen atom (eg, Cl or Br), or a straight, branched or cyclic alkyl group (eg, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a carbon number represents a cyclic alkyl group of 3 to 10),

p and q each independently represent the integer of 0-4.

Specifically, the compound of Formula 6 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-hydroxy Phenyl) pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, resorcinol, hydroquinone, 4,4'-di Hydroxyphenyl 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-dichloro Benzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-di Hydroxyphenyl, 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-hydroxyl) oxyphenyl) 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], 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'-tetra methyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene, It is not necessarily limited to this. A typical example is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, and the dihydric phenols are singly or in combination of two or more. can be used

As another monomer of the polycarbonate block, a carbonate precursor, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate, or dimethyl carbonate may be used.

In a preferred embodiment, the content of the polysiloxane of Formula 1 in the polysiloxane-polycarbonate copolymer of the present invention is 0.5 to 20% by weight, preferably 1 to 20% by weight, more preferably 3 based on the total weight of the copolymer. to 15% by weight. When the content of the polysiloxane of Formula 1 is less than 0.5% by weight, flame retardancy may be poor, and when the content of the polysiloxane of Formula 1 exceeds 20% by weight, transparency and processability may be reduced.

In a preferred embodiment, the content of the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) in the polysiloxane-polycarbonate copolymer of the present invention is 0.5 to 20% by weight based on the total weight of the copolymer, preferably may be 1 to 20% by weight, more preferably 2 to 15% by weight. When the content of the polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 0.5% by weight, impact resistance may be poor, and polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) ), when the content exceeds 20% by weight, transparency may be reduced.

In a preferred embodiment, in the polysiloxane-polycarbonate copolymer of the present invention, the total content of the polysiloxane of Formula 1 and polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) is 1 based on the total weight of the copolymer to 25% by weight, preferably 3 to 20% by weight, more preferably 5 to 20% by weight, even more preferably 5 to 15% by weight. When the total content of the polysiloxane of Formula 1 and a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) is less than 1% by weight, flame retardancy and/or impact resistance may be poor, and the polysiloxane of Formula 1 When the total content of the polysiloxane other than the polysiloxane of Chemical Formula 1 (specifically, the polysiloxane of Chemical Formula 2) exceeds 25% by weight, processability and transparency may be deteriorated.

In a preferred embodiment, the polysiloxane of the present invention-polycarbonate copolymer of the present invention contains the polysiloxane of Formula 1 as a repeating unit and a polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) in a weight ratio of 1:9 to 9:1, preferably 1:8 to 8:1, more preferably 2:7 to 7:2, even more preferably 2:7 to 6:3, most preferably 4:5 to 5 : can be 4. By adjusting the weight ratio of the polysiloxane of Formula 1 and the polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) within the above range, flame retardancy, impact resistance and transparency can all be excellently exhibited.

In a preferred embodiment, the content of the polycarbonate block in the polysiloxane-polycarbonate copolymer of the present invention is 75 to 99% by weight, preferably 80 to 97% by weight, more preferably 80 to 95% by weight based on the total weight of the copolymer. % by weight, even more preferably 85 to 95% by weight. If the content of the polycarbonate block is less than 75% by weight, transparency and processability may be reduced, and if the content of the polycarbonate block exceeds 99% by weight, flame retardancy and impact resistance may be reduced.

In a preferred embodiment, the polysiloxane-polycarbonate copolymer according to the present invention may have a viscosity average molecular weight (M _V ) of 15,000 to 200,000, more preferably 15,000 to 100,000. If the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is less than 15,000, mechanical properties may be significantly reduced, and if it exceeds 200,000, there may be problems in processing the resin due to an increase in melt viscosity.

The present invention also relates to a process for preparing the aforementioned polysiloxane-polycarbonate copolymer.

The polysiloxane-polycarbonate copolymer production method according to the present invention is a polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) and an oligomeric polycarbonate in an aqueous alkali solution and reacting under interfacial reaction conditions consisting of an organic phase to form a polysiloxane-polycarbonate intermediate; and polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst.

In a preferred embodiment, the step of forming the polysiloxane-polycarbonate intermediate comprises a polysiloxane mixture content of the polysiloxane of Formula 1 and a polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) and the oligomeric polycarbonate content. mixing in a weight ratio of 1:99 to 25:75, preferably 3:97 to 20:80, more preferably 5:95 to 20:80, even more preferably 5:95 to 15:85 may include. When the polysiloxane mixture content of the polysiloxane of Formula 1 and a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) is less than 1% by weight, flame retardancy and/or impact resistance may be poor, and the polysiloxane of Formula 1 and Formula 1 When the polysiloxane (specifically, the polysiloxane of Formula 2) mixture content other than the polysiloxane of 1 is more than 25 wt%, processability and transparency may be deteriorated.

The polysiloxane-polycarbonate used in the preparation of the polycarbonate copolymer according to the present invention may be an oligomeric polycarbonate having a viscosity average molecular weight of 800 to 20,000, preferably 1,000 to 15,000. If the viscosity average molecular weight of the polycarbonate is less than 800, molecular weight distribution may be widened and physical properties may be deteriorated, and if it exceeds 20,000, reactivity may be reduced.

In one preferred embodiment, The oligomeric polycarbonate may be prepared by adding the above-described dihydric phenols to an aqueous alkali solution to form a phenol salt, and then reacting the phenols in the salt state into dichloromethane injected with phosgene gas. For the preparation of polycarbonate oligomers, it is desirable to maintain the molar ratio of phosgene to dihydric phenols (eg, bisphenol A) in the range of about 1:1 to 1.5:1, more preferably about 1:1 to 1.2:1. desirable. If the molar ratio of phosgene to the dihydric phenol compound is less than 1, the reactivity may decrease, and if the molar ratio of phosgene to the dihydric phenol compound exceeds 1.5, there may be a problem in processability due to an excessive increase in molecular weight.

The polycarbonate oligomer formation reaction may be generally performed at a temperature in the range of about 15 to 60° C., and an alkali metal hydroxide (eg, sodium hydroxide) may be used to adjust the pH of the reaction mixture.

In a preferred embodiment, the step of forming the polysiloxane-polycarbonate intermediate comprises the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) and an oligomeric polycarbonate. and forming a mixture, wherein the mixture may include a phase transfer catalyst, a molecular weight modifier, and a second polymerization catalyst.

In a preferred embodiment, the step of forming the polysiloxane-polycarbonate intermediate comprises the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) and an oligomeric polycarbonate. forming a mixture to and extracting the organic phase from the resulting mixture after the reaction of the polysiloxane of Formula 1 above, a polysiloxane other than the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) and the oligomeric polycarbonate is completed, wherein the polysiloxane - The step of polymerizing the polycarbonate intermediate may include providing a first polymerization catalyst to the extracted organic phase.

Specifically, the polysiloxane-polycarbonate copolymer according to the present invention is a polysiloxane other than the polysiloxane of Formula 1 and the polysiloxane of Formula 1 (specifically, polysiloxane of Formula 2) in an organic phase-aqueous mixture containing polycarbonate. It can be prepared by adding a molecular weight modifier and a catalyst step by step.

As the molecular weight modifier, a monofunctional compound similar to a monomer used for preparing polycarbonate may be used. Monofunctional substances include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, and p-isononyl. phenol-based derivatives such as phenol and the like; or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) may be used.

A polymerization catalyst and/or a phase transfer catalyst may be used as the catalyst. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound of Formula 7 below may be used.

[Formula 7]

(R ₁₁ ) ₄ Q ⁺ X ^-

In Formula 7, R ₁₁ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or —OR ₁₂ . Here, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase transfer catalyst is, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ ( CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX . In the above formulas, X represents Cl, Br or -OR ₁₂ , where R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight based on the total weight of the mixture of the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2), and the oligomeric polycarbonate. Do. If the content is less than 0.01% by weight, the reactivity may be reduced, and if the content exceeds 10% by weight, it may precipitate as a precipitate or the transparency may be deteriorated.

In a preferred embodiment, after preparing the polysiloxane-polycarbonate copolymer, the organic phase dispersed in methylene chloride may be separated after alkali washing. Subsequently, the organic phase may be washed with a 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. When washing is complete, the concentration of the organic phase dispersed in methylene chloride is adjusted to be constant, and granulation can be performed using a certain amount of pure water in the range of 70 to 80°C. If the temperature of the pure water is less than 70 ℃, the assembly speed is slowed, the assembly time may be very long, and if the temperature of the pure water exceeds 80 ℃, it may be difficult to obtain the shape of the polycarbonate in a certain size. When the granulation is completed, it is preferably dried at 100 to 110° C. for 5 to 10 hours, and secondly at 110 to 120° C. for 5 to 10 hours.

The present invention also relates to a molded article produced using the polysiloxane-polycarbonate copolymer of the present invention.

The method for producing a molded article using the polysiloxane-polycarbonate copolymer of the present invention is not particularly limited, and the method generally used for manufacturing a resin molded article (for example, an extrusion process or an injection process, etc.) Can be used.

The molded article according to the present invention can be variously applied to fields requiring flame retardancy, and for example, it can be variously applied to construction materials, automobile parts, office equipment, and parts (housing) of electric/electronic products, but limited thereto. it doesn't happen

Hereinafter, the present invention will be described in more detail through Examples, but these are only for explaining the present invention, and the scope of the present invention is not limited in any way by the Examples.

[ Example ]

< of polysiloxane Manufacturing>

Manufacturing example 1: branched polysiloxane Produce

A 500 mL three-neck flask was equipped with a condenser, and 50.44 g (0.1 mole) of the polysiloxane corresponding to Chemical Formula 4 (Damipolychem F5032, colorless transparent liquid, viscosity: 5 cP) was dissolved in 50 ml of toluene under a nitrogen atmosphere, followed by platinum ( 0.008 g (100 ppm) of Pt) catalyst (CP101 manufactured by Dami Polychem) was added. While the solution was heated, 26.8 g (0.2 mole) of 2-allylphenol was slowly added for 1 hour and refluxed for 5 hours. After removing the solvent toluene from the reaction solution, the polysiloxane of the following formula (8) was prepared by drying in a vacuum oven for 24 hours.

[Formula 8]

Manufacturing example 2: branched polysiloxane Produce

A condenser was installed in a 500 mL three-neck flask, and 49.04 g (0.1 mole) of the polysiloxane corresponding to Chemical Formula 4 (Damipolychem F5032, colorless and transparent liquid, viscosity: 5 cP) was dissolved in 50 ml of toluene under a nitrogen atmosphere, followed by platinum ( 0.008 g (100 ppm) of Pt) catalyst (CP101 manufactured by Dami Polychem) was added. While the solution was heated, 40.2 g (0.3 mole) of 2-allylphenol was slowly added for 1 hour and refluxed for 5 hours. After removing the solvent toluene from the reaction solution, it was dried in a vacuum oven for 24 hours to prepare a polysiloxane represented by the following formula (9).

[Formula 9]

Manufacturing example 3: Linear polysiloxane Produce

A 500 mL three-neck flask was equipped with a condenser, and 0.4 mol of Dow Corning's monomer BY16-799 was dissolved in 300 mL of chloroform under a nitrogen atmosphere, and then 67 mL of a triethylamine (TEA) catalyst was added. While the solution was refluxed, 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform, added slowly for 1 hour, and refluxed for 12 hours. After removing the solvent of the reaction solution, it was dissolved in acetone and washed with hot distilled water. By drying in a vacuum oven for 24 hours, a hydroxy-terminated siloxane having an ester bond of the following Chemical Formula 10 was prepared.

[Formula 10]

< polysiloxane -Preparation of polycarbonate copolymer>

Example 1

An oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000 was prepared by interfacially reacting bisphenol A and phosgene gas in an aqueous solution in the presence of methylene chloride. The organic phase of the obtained oligomeric polycarbonate mixture was collected, and therein, an aqueous sodium hydroxide solution, the branched polysiloxane of Formula 8 prepared in Preparation Example 1 (in an amount of 8% by weight based on the total weight of the copolymer), the Preparation Example Linear polysiloxane of formula 10 prepared in 3 (in an amount of 1% by weight based on the total weight of the copolymer), tetrabutyl ammonium chloride (TBACl, in an amount of 0.1% by weight based on the total weight of the copolymer), methylene chloride and After mixing p-tert-butylphenol (PTBP, in an amount of 0.4% by weight based on the total weight of the copolymer), the mixture was reacted for 2 hours. After the layer separation occurred, only the organic phase was collected, sodium hydroxide aqueous solution, methylene chloride, and triethylamine (TEA, 0.015% by weight based on the total weight of the copolymer) were added and reacted for 3 hours. Triethylamine (TEA, in an amount of 0.02% by weight based on the total weight of the copolymer) was added to the reacted organic phase, followed by further reaction for 2 hours. After the layer separation occurred, the organic phase with increased viscosity was collected, distilled water and methylene chloride were added thereto, washed with alkali, and then separated again. Subsequently, the organic phase was washed with a 0.1N hydrochloric acid solution, followed by repeated washing with distilled water 2-3 times. After washing was completed, the organic phase was granulated at 76° C. using a certain amount of pure water. After the assembly was completed, the first was dried at 110° C. for 8 hours, and secondly at 120° C. for 10 hours. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 2

Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 7 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 2 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 3

The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 6 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 3 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 4

The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 5 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 4 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 5

Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 4 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 5 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 6

The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 3 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 6 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 7

Same as Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 2 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 7 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 8

The same as in Example 1, except that the content of the branched polysiloxane of Formula 8 was changed from 8 wt% to 1 wt%, and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 8 wt% A polysiloxane-polycarbonate copolymer was prepared by the method. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 9

Instead of the branched polysiloxane of Formula 8 prepared in Preparation Example 1 (8% by weight based on the total weight of the copolymer), the branched polysiloxane of Formula 9 prepared in Preparation Example 2 (5% by weight based on the total weight of the copolymer) A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the content of the linear polysiloxane of Chemical Formula 10 was changed from 1 wt% to 4 wt%. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example 10

Instead of the branched polysiloxane of Formula 8 prepared in Preparation Example 1 (8% by weight based on the total weight of the copolymer), the branched polysiloxane of Formula 9 prepared in Preparation Example 2 (4% by weight based on the total weight of the copolymer) A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the content of the linear polysiloxane of Chemical Formula 10 was changed from 1 wt% to 5 wt%. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Comparative Example 1

The physical properties of a linear polycarbonate (Samyang Corporation, TRIREX 3030IR) having a viscosity average molecular weight of 30,000 were measured and described in Table 2 below.

Comparative Example 2

A linear polycarbonate having a viscosity average molecular weight of 70,000 was prepared in the same manner as in Example 1, except that polysiloxane was not used. The physical properties of the prepared polycarbonate resin were measured and described in Table 2 below.

Comparative Example 3

Polysiloxane in the same manner as in Example 1, except that the branched polysiloxane of Formula 8 prepared in Preparation Example 1 was not used and the content of the linear polysiloxane of Formula 10 was changed from 1 wt% to 9 wt% - A polycarbonate copolymer was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 2 below.

Comparative Example 4

Polysiloxane in the same manner as in Example 1, except that the linear polysiloxane of Chemical Formula 10 prepared in Preparation Example 3 was not used and the content of the branched polysiloxane of Chemical Formula 8 was changed from 8 wt% to 9 wt% - A polycarbonate copolymer was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

Comparative Example 5

Formula prepared in Preparation Example 2 instead of using the linear polysiloxane of Formula 10 prepared in Preparation Example 3, and instead of the branched polysiloxane of Formula 8 (8% by weight based on the total weight of the copolymer) prepared in Preparation Example 1 A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the branched polysiloxane of No. 9 (9% by weight based on the total weight of the copolymer) was used. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and shown in Table 2 below.

[Table 1]

[Table 2]

As shown in Table 1, the polysiloxane-polycarbonate copolymers prepared in Examples 1 to 10 according to the present invention were excellent in low-temperature impact strength with an impact strength of 30 (kg cm/cm) or more, and transmittance of 85% or more As a result, transparency was excellent, and flame retardancy was also very excellent.

However, as shown in Table 2, in the case of the linear polycarbonate resin (Comparative Examples 1 and 2), the transparency was excellent, but the low-temperature impact strength and flame retardancy were very poor, and the polysiloxane that did not contain the branched polysiloxane of a specific structure- In the case of the polycarbonate copolymer (Comparative Example 3), transparency and low-temperature impact strength were excellent, but the flame retardancy was poor, and in the case of a polysiloxane-polycarbonate copolymer that did not contain a linear polysiloxane of a specific structure (Comparative Examples 4 and 5) , transparency and flame retardancy were excellent, but low-temperature impact strength was relatively poor.

The measurement and evaluation methods for the physical properties described in Tables 1 and 2 are as follows.

(a) H-NMR (nuclear magnetic resonance spectroscopy): Measured using an Avance DRX 300 manufactured by Bruker. By H-NMR, the peak of the methyl group of dimethylsiloxane observed at 0.2 ppm, the peak of the methylene group of the polysiloxane-polycarbonate bonding portion observed at 2.6 ppm, and the peak of the methoxy group of the polysiloxane-polycarbonate bonding portion observed at 3.9 ppm are copolymers was confirmed.

(b) Viscosity average molecular weight (M _V ): The viscosity of the methylene chloride solution was measured at 20° C. using an Ubbelohde Viscometer, and the intrinsic viscosity [η] was calculated from this using the following formula.

[η]=1.23x10 ^-5 Mv ^{0 .83}

(c) Transmittance: The transmittance was measured using a haze meter (HAZE-GARD PLUS manufactured by BYK GARDNER).

(d) Flame retardancy: It was measured by the UL-94 flame retardancy test method, which is a method prescribed by Underwriter's Laboratories (UL) of the United States. This method is a method to evaluate the flame retardancy from the burning time or drip property after attaching the flame of a burner to a specimen of a certain size fixed vertically for 10 seconds. Combustion time is the length of time that the specimen continues flame-burning after the flame is moved away, and the ignition of the cotton by drip means that the cotton for labeling, which is about 300mm below the lower end of the specimen, is ignited by the dripping material from the specimen. It is determined by, and the grade of flame retardancy is divided according to Table 3 below.

[Table 3]

(e) Impact strength: In accordance with ASTM D256, a notch was made on the test piece and evaluated under a low temperature condition of -30°C. The final test result was calculated as the average of the test results of 10 specimens.

Claims (17)

Polysiloxane of Formula 1;
polysiloxanes other than the polysiloxanes of formula (1); and
including a polycarbonate block as a repeating unit,
The weight ratio of the polysiloxane of formula (1) and polysiloxane other than the polysiloxane of formula (1) is 1:8 to 8:1,
Polysiloxane-polycarbonate copolymer:
[Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
k independently represents an integer of 1 to 4,
l, m and n each independently represent an integer of 0 to 4, with the proviso that at least one of l, m and n is not 0,
x and y each independently represent an integer of 0-100. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polysiloxane other than the polysiloxane of the formula (1) is a polysiloxane of the following formula (2):
[Formula 2]

In Chemical Formula 2,
R ₅ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₆ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₇ independently represents an alkylene group having 2 to 8 carbon atoms,
A is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,
m independently represents an integer of 0 to 4,
n independently represents an integer of 2 to 1,000. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polysiloxane of formula (1) is a reaction product of a polysiloxane of formula (4) and a compound of formula (5):
[Formula 4]

In Formula 4,
R ₁ , R ₂ , l, m, n, x and y are as defined in Formula 1,
[Formula 5]

In Formula 5,
R ₄ and k are as defined in Formula 1, and h represents an integer of 1 to 7. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the polycarbonate block is represented by the following formula (3):
[Formula 3]

In Chemical Formula 3,
R ₈ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom or an aromatic hydrocarbon group having 6 to 30 carbon atoms substituted or unsubstituted with nitro. The polysiloxane-polycarbonate copolymer according to claim 4, wherein _{the aromatic hydrocarbon group of R 8} of Formula 3 is derived from a compound of Formula 6 below:
[Formula 6]

In formula (6),
X is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, naphthyl or isobutylphenyl;
R ₉ and R ₁₀ are each independently a halogen atom; or a straight, branched or cyclic alkyl group,
p and q each independently represent the integer of 0-4. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the content of the polysiloxane of Formula 1 is 0.5 to 20 wt% based on the total weight of the copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the content of polysiloxane other than the polysiloxane of Formula 1 is 0.5 to 20 wt% based on the total weight of the copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the total content of the polysiloxane of the formula (1) and the polysiloxane other than the polysiloxane of the formula (1) is 1 to 25% by weight based on the total weight of the copolymer. delete The polysiloxane-polycarbonate copolymer according to claim 1, wherein the viscosity average molecular weight is 15,000 to 200,000. The polysiloxane of Formula 1, polysiloxane other than the polysiloxane of Formula 1, and oligomeric polycarbonate are reacted so that the weight ratio of the polysiloxane of Formula 1 and polysiloxane other than the polysiloxane of Formula 1 is 1:8 to 8:1 under interfacial reaction conditions forming a polysiloxane-polycarbonate intermediate; and
A method for preparing a polysiloxane-polycarbonate copolymer comprising the step of polymerizing the polysiloxane-polycarbonate intermediate using a first polymerization catalyst:
[Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxy group,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 10 carbon atoms,
k independently represents an integer of 1 to 4,
l, m and n each independently represent an integer of 0 to 4, with the proviso that at least one of l, m and n is not 0,
x and y each independently represent an integer of 0-100. The method of claim 11, wherein the polysiloxane other than the polysiloxane of Formula 1 is a polysiloxane of Formula 2 below:
[Formula 2]

In Chemical Formula 2,
R ₅ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₆ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₇ independently represents an alkylene group having 2 to 8 carbon atoms,
A is X or NH-X-NH, wherein X is a linear or branched aliphatic group having 1 to 20 carbon atoms; a cycloalkylene group having 3 to 20 carbon atoms; or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, which is substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a carboxyl group,
m independently represents an integer of 0 to 4,
n independently represents an integer of 2 to 1,000. 12. The method of claim 11, wherein the polysiloxane-forming step of the polycarbonate intermediate comprises a mixture content of the polysiloxane of Formula 1 and a polysiloxane other than the polysiloxane of Formula 1 and the oligomeric polycarbonate content in a weight ratio of 1:99 to 25:75. A method for preparing a polysiloxane-polycarbonate copolymer, comprising the step of mixing. 12. The method of claim 11, wherein the step of forming the polysiloxane-polycarbonate intermediate comprises forming a mixture comprising the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1, and an oligomeric polycarbonate, wherein the mixture undergoes a phase change A method for preparing a polysiloxane-polycarbonate copolymer, also comprising a catalyst, a molecular weight modifier and a second polymerization catalyst. 12. The method of claim 11, wherein the step of forming the polysiloxane-polycarbonate intermediate comprises: forming a mixture comprising the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1, and an oligomeric polycarbonate; and extracting the organic phase from the resulting mixture after the reaction of the polysiloxane of Formula 1, a polysiloxane other than the polysiloxane of Formula 1, and the oligomeric polycarbonate is completed; Polysiloxane- polycarbonate intermediate, wherein the step of polymerizing the polysiloxane- polycarbonate copolymer production method comprising the step of providing a first polymerization catalyst to the extracted organic phase. The method of claim 11, wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000. A molded article manufactured using the polysiloxane-polycarbonate copolymer according to any one of claims 1 to 8 and 10.