TWI738059B - 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 excellent impact resistance, flame retardancy and transparency, and method for preparing the same, and more specifically, to a polysiloxane-polycarbonate copolymer comprising a branched polysiloxane having a specific structure, a linear polysiloxane having a specific structure, and a polycarbonate block as a repeat unit, which has excellent flame retardancy and transparency, and improved mechanical strength such as impact resistance, and method for preparing the same.

Description

Polysiloxane-polycarbonate copolymer with excellent impact resistance, flame retardancy and light transmittance and method for preparing the copolymer

The present invention relates to a polysiloxane-polycarbonate copolymer having excellent impact resistance, flame retardancy and light transmittance and a method for preparing the copolymer, and more specifically, to a polysiloxane-polycarbonate copolymer having a specific structure as a repeating unit Branched polysiloxanes, linear polysiloxanes with specific structures, and polysiloxane-polycarbonate copolymers of polycarbonate blocks, which have excellent flame retardancy and light transmittance, and have improved The mechanical strength such as impact resistance, and the method of preparing the copolymer.

Polycarbonate resins are widely used as electrical parts, mechanical parts, and industrial resins due to their excellent heat resistance, mechanical properties (especially impact strength), and light transmittance. In particular, when polycarbonate resins are used as housing materials for TV housings, computer monitor housings, copiers, printers, laptop batteries, lithium batteries, etc., they generate a lot of heat in the electrical and electronic fields and require not only heat resistance And mechanical properties, excellent flame retardancy is also required.

The most common method for imparting flame retardancy to polycarbonate resins is to mix a bromine or chlorine-based compound (which is a halogen flame retardant) with the polycarbonate resin. When halogen flame retardants are used, they are fully Flame retardant function. However, hydrogen halide gas is generated during the resin processing process, which can cause mold corrosion and environmental pollution, as well as dioxin, which is a toxic gas harmful to the human body during the combustion process. Therefore, there are more and more actions to regulate its use. In order to solve this problem, a flame-retardant polycarbonate resin composition using both an alkali metal salt as a non-halogen flame retardant and a fluorinated polyolefin resin as an anti-drip agent has been developed. However, in this case, due to the use of fluorinated vinyl resins and metal salt flame retardants to ensure the flame retardancy of the polycarbonate resin, there is a decrease in light transmittance (which is one of the advantages of polycarbonate resin) problem.

In order to overcome this decrease in light transmittance, alloys with polysiloxane-based additives and polysiloxane-based copolymers have been proposed. Although the technology using silicone-based additives has the advantage of being environmentally friendly as a non-halogen flame retardant, it also has the following disadvantages: the light transmittance is still low, the price is relatively expensive, and when it is used as an external material, The realization of various colors is limited. In addition, due to the lack of fluidity to be injected into large injection molded products, there is a problem that limits the application to large products.

Therefore, there is a need to develop a polycarbonate resin composition that can achieve excellent light transmittance, fluidity, impact strength (especially low-temperature impact strength) and other coordinated characteristics while fully exerting flame retardancy.

Prior art: (Patent Publication 1) US Patent Publication No. 2003/0105226.

The purpose of the present invention is to provide a polysiloxane-polycarbonate copolymer with excellent impact resistance, flame retardancy and light transmittance and a preparation method thereof.

In order to achieve the technical purpose, the present invention provides a polysiloxane-polycarbonate copolymer, which contains the following as repeating units: polysiloxane of the following formula 1 and polysiloxanes other than the polysiloxane of formula 1 Oxane, and polycarbonate block:

In Formula 1, R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, and R ₃ independently represents a An alkylene having 2 to 8 carbon atoms, R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 6 to An aryl group of 10 carbon atoms, k independently represents an integer from 1 to 4, and each of l, m and n independently represents an integer from 0 to 4, provided that at least one of l, m and n is not 0, And x and y represent an integer from 0 to 100, respectively.

In order to achieve the technical purpose, the present invention further provides a method for preparing polysiloxane-polycarbonate copolymer, which comprises: making the polysiloxane of the following formula 1 and polysiloxanes other than the polysiloxane of formula 1 The step of reacting oxane and oligomeric polycarbonate under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and using the first polymerization catalyst to polymerize the polysiloxane-polycarbonate intermediate Body steps:

In Formula 1, R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, and R ₃ independently represents having An alkylene having 2 to 8 carbon atoms, R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 6 to An aryl group of 10 carbon atoms, k independently represents an integer from 1 to 4, and each of l, m and n independently represents an integer from 0 to 4, provided that at least one of l, m and n is not 0, And x and y represent an integer from 0 to 100, respectively.

In order to achieve the technical purpose, the present invention also provides molded articles prepared using the polysiloxane-polycarbonate copolymer according to the present invention.

Beneficial effect

The polysiloxane-polycarbonate copolymer according to the present invention can significantly improve the flame retardancy without adding a flame retardant, and at the same time can maintain the excellent inherent properties of polycarbonate, such as impact resistance and light transmittance . Therefore, the present invention can be used in various fields where flame retardancy is required, for example, building materials, automobile parts, office equipment, housings for electrical/electronic products, and the like.

The present invention will be described in detail below.

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

In addition, in this specification, "first", "second", etc. are used to describe the polymerization catalyst, but the polymerization catalyst is not limited by these terms and is only used to distinguish the polymerization catalyst. For example, the first polymerization catalyst and the second polymerization catalyst may be the same kind of catalyst, or may be different kinds of catalysts.

In addition, in the chemical formula described herein, the English letter "R" used to represent hydrogen, a halogen atom, and/or a hydrocarbon group, etc., has a subscript represented by a number, but the "R" is not limited to a subscript. Each "R" independently represents hydrogen, halogen atom and/or hydrocarbon group, etc. For example, regardless of whether two or more "Rs" have the same or different subscripts, these "Rs" can represent the same or different hydrocarbon groups.

The present invention relates to a polysiloxane-polycarbonate copolymer comprising the following as repeating units: polysiloxane of the following formula 1; polysiloxanes other than the polysiloxane of formula 1; and polysiloxane Carbonate block.

Branched polysiloxane

The polysiloxane-polycarbonate copolymer of the present invention contains polysiloxane of the following formula 1 as a repeating unit. The polysiloxane of the following formula 1 is a compound in which a siloxane is connected, and the siloxane includes a siloxane having a hydroxyphenyl group on a side chain.

In Formula 1, R ₁ may independently represent a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, R ₂ may independently represent a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, and R ₃ may independently Ground represents an alkylene group having 2 to 8 carbon atoms, R ₄ can independently represent a hydrogen atom, a halogen atom, a hydroxyl 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 can independently represent an integer from 1 to 4, and each of l, m and n can independently represent an integer from 0 to 4, preferably 0 to 2, provided that l At least one of, m and n is not 0, and each of x and y may independently represent an integer from 0 to 100, preferably from 0 to 50, and more preferably from 0 to 10, or an integer from 2 to 100, Preferably from 2 to 50, and more preferably from 2 to 10.

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 an alkenyloxy group having 2 to 13 carbon atoms, having 3 to 6 carbon atoms Cycloalkyl or cycloalkoxy of carbon atoms, aryloxy having 6 to 10 carbon atoms, aralkyl or aralkoxy having 7 to 13 carbon atoms, or having 7 to 13 carbon atoms Alkaryl or alkaryloxy.

More specifically, the alkyl group may be a methyl group, an ethyl group, or a propyl group; the alkylene group may be an ethylene group or a propylene group. 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 the reaction product of the polysiloxane of Formula 4 below and the compound of Formula 5 below.

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

In Formula 5, R ₄ and k are the same as those defined in Formula 1, and h represents an integer from 1 to 7.

It is preferable to keep the molar ratio of the compound of formula 4 to the compound of formula 5 between 1:4 and 1:1, more preferably in the range of 1:3 to 1:2. When the molar ratio of the compound of Formula 4 to the compound of Formula 5 is outside the above range, the degree of polymerization of polysiloxane and polycarbonate may be affected, which may be a factor that reduces flame retardancy and light transmittance.

Linear polysiloxane

The polysiloxane-polycarbonate copolymer according to the present invention contains polysiloxane other than the polysiloxane of Formula 1 as a repeating unit, and specifically contains the polysiloxane of Formula 2 below. The polysiloxane of the following formula 2 is a hydroxyl-terminated siloxane compound with the following characteristics:

In Equation 2,

R ₅ may independently represent a hydrogen atom, a halogen atom, a hydroxyl 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 may independently represent a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group,

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

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

m can independently represent an integer from 0 to 10, preferably from 0 to 4, and

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

Specifically, in R ₅ of Formula 2, the halogen atom may be Cl or Br; and the alkyl group may be an alkyl group having 1 to 13 carbon atoms, such as a methyl group, an ethyl group, or a propyl group. The alkoxy group may be an alkoxy group having 1 to 13 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group. 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 hydrocarbyl group having 1 to 13 carbon atoms may be an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, and an alkyl group having 2 to 13 carbon atoms. Alkenyl, alkenyloxy having 2 to 13 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, cycloalkoxy having 3 to 6 carbon atoms, aryloxy having 6 to 10 carbon atoms Group, an aralkyl group having 7 to 13 carbon atoms, an aralkoxy group having 7 to 13 carbon atoms, an alkaryl group having 7 to 13 carbon atoms, or an alkaryloxy group having 7 to 13 carbon atoms base;

In A of Formula 2, X may be, for example, an aliphatic group having 1 to 20 carbon atoms that is unsubstituted or substituted by a halogen atom, or an aliphatic group having 1 to 20 carbon atoms that contains oxygen, nitrogen or sulfur atoms in the main chain. An aliphatic group of carbon atoms, a cycloalkylene or arylalkylene group having 3 to 6 carbon atoms that can be derived from bisphenol A, resorcinol, hydroquinone, or diphenol, which can be, for example, as follows The formulas Aa to Ah are represented.

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

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

The hydroxyl-terminated silicone of formula 2a can be synthesized, for example, by using a platinum catalyst to synthesize a compound of the following formula 2b having a hydroxyl group and a double bond with a molar ratio of 2:1 and a compound of the following formula 2c containing silicone. preparation.

In Formula 2b, R ₅ and m are the same as those defined in Formula 2, and k represents an integer from 1 to 7.

In Formula 2b, R ₆ and n are the same as those defined in Formula 2.

)用作式2a的羥基封端的矽氧烷，但不必限於此。亦參見關於式2a的羥基封端的矽氧烷的製備的美國專利公開第6,072,011號。 Specifically, Dow Corning's silicone monomer (

) Used as the hydroxyl-terminated siloxane of formula 2a, but it is not necessarily limited to this. See also U.S. Patent Publication No. 6,072,011 on the preparation of hydroxy-terminated siloxanes of formula 2a.

The acyl compound used to prepare the hydroxy-terminated silicone of Formula 2 may have, for example, an aromatic, aliphatic, or mixed structure including aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and if it is aliphatic, it may have 1 to 20 carbon atoms. In addition, the acyl compound may also contain halogen, oxygen, nitrogen or sulfur atoms.

In another embodiment, the hydroxy-terminated siloxane of the above formula 2 may be the reaction product of the hydroxy-terminated siloxane of the above formula 2a and a diisocyanate compound (ie, a hydroxy-terminated silicone having a urethane bond) Oxane).

In this case, the diisocyanate compound may be, for example, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 4,4'-methylene diphenyl diisocyanate.

Polysiloxane-polycarbonate copolymer

The polysiloxane-polycarbonate copolymer according to the present invention contains the polycarbonate block of the following formula 3 as a repeating unit, and the polysiloxane of the above formula 1 (that is, the one having a hydroxyphenyl group on the side chain) Polysiloxane block) and polysiloxanes other than the polysiloxane of Formula 1 (that is, a polysiloxane block having a hydroxyl group at the terminal as the polysiloxane of Formula 2).

In Equation 3,

R ₈ may represent an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted by an alkyl group (for example, an alkyl group having 1 to 20, preferably 1 to 13 carbon atoms), a cycloalkyl group (for example, , Cycloalkyl having 3 to 20, preferably 3 to 6 carbon atoms), alkenyl (e.g., alkenyl having 2 to 20, preferably 2 to 13 carbon atoms), alkoxy (e.g. , Having 1 to 20, preferably 1 to 13 carbon atoms (alkoxy), halogen atoms (such as Cl or Br) or nitro substituted. The aromatic hydrocarbon group can be derived from, for example, the compound of Formula 6 below.

In Equation 6,

X is a linear, branched or cyclic alkylene group without a functional group; or a linear, branched or cyclic alkylene group with a functional group (for example, a linear alkylene group having 1 to 10 carbon atoms) Group, branched alkylene having 3 to 10 carbon atoms, or cyclic alkylene having 3 to 10 carbon atoms) containing at least one selected from the group consisting of sulfides, ethers, sulfites, ketones, naphthalenes Linear, branched or cyclic alkylene group or functional group of isobutyl phenyl group,

R ₉ and R ₁₀ are each independently a halogen atom (e.g. Cl or Br); or a linear, branched or cyclic alkyl group (e.g., a linear alkylene group having 1 to 10 carbon atoms, having 3 to A branched alkylene group of 10 carbon atoms or a cyclic alkylene group of 3 to 10 carbon atoms) and

p and q each independently represent an integer from 0 to 4.

Specifically, the compound of the above formula 6 may be selected from, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxyphenyl)methane, Phenyl)-(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-naphthalene-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, m-benzene Diphenol, hydroquinone (hydroquinone, also known as hydroquinone), 4,4'-dihydroxydiphenyl 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-hydroxybenzene) Yl)-2-methylbutane, 4,4'-thiodiol [bis(4-hydroxyphenyl) sulfide], bis(3,5-dimethyl-4-hydroxyphenyl) sulfide, double (3-chloro-4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfide, bis(3-methyl-4-hydroxyphenyl) sulfide , Double(3,5-two Methyl-4-hydroxyphenyl) sulfide, bis(3,5-dibromo-4-hydroxyphenyl) sulfene, 44,-dihydroxybenzophenone, 3,3',5,5'- Tetramethyl-4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene, But it is not limited to this. Generally, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) can be used. Other functional dihydric phenols can refer to U.S. Patent No. 2,999,835, U.S. Patent No. 3,028,365, U.S. Patent No. 3,153,008, U.S. Patent No. 3,334,154, and so on. The dihydric phenol can be used alone or in combination of two or more.

As other monomers of the polycarbonate block, carbonate precursors such as carbamoyl chloride (phosgene), carbamoyl bromide, bissulfonate, diphenyl carbonate, or dimethyl carbonate can be used.

In a preferred embodiment, based on the polysiloxane-polycarbonate copolymer of the present invention, the content of the polysiloxane of formula 1 based on the total weight of the copolymer may be 0.5 to 20% by weight, preferably 1 to 20% by weight, more preferably 3 to 15% by weight. If the content of the polysiloxane of Formula 1 is less than 0.5% by weight, flame retardancy may be poor. If the content of the polysiloxane of Formula 1 is greater than 20% by weight, light transmittance and workability may be reduced.

In a preferred embodiment, in the polysiloxane-polycarbonate copolymer of the present invention, polysiloxanes other than the polysiloxane of formula 1 (specifically, the polysiloxane of formula 2 The content of) can be 0.5 to 20% by weight, preferably 1 to 20% by weight. Based on the total weight of the copolymer, it is preferably 2 to 15% by weight, more preferably 2 to 15% by weight. If the content of polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 0.5% by weight, impact resistance may deteriorate. If the content of polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) exceeds 20% by weight, the light transmittance may decrease.

In a preferred embodiment, in the polysiloxane-polycarbonate copolymer of the present invention, the polysiloxane of formula 1 and polysiloxanes other than the polysiloxane of formula 1 (specifically The total content of the polysiloxane of formula 2 can be 1 to 25%. Relative to the total weight of the copolymer, it is preferably 3 to 20% by weight, more preferably 5 to 20% by weight, and even more preferably 5 to 15% by weight. If the total content of the polysiloxane of Formula 1 and polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 1% by weight, Then the flame retardancy and/or impact resistance may deteriorate. If the total content of the polysiloxane of Formula 1 and polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is greater than 25% by weight, processability and light transmittance Degree may decrease.

In a preferred embodiment, the polysiloxane of formula 1 contained as a repeating unit in the polysiloxane-polycarbonate copolymer of the present invention and polysiloxanes other than the polysiloxane of formula 1 The weight ratio of the alkane (specifically, the polysiloxane of formula 2) may be 1:9 to 9:1, preferably 1:8 to 8:1, more preferably 2:7 to 7:2, even more Best 2:7 to 6:3, best 4:5 to 5:4. By adjusting the weight ratio of the polysiloxane of Formula 1 to polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) within the above range, the resistance can be excellently displayed. Flammability, impact resistance and light transmittance.

In a preferred embodiment, the content of the polycarbonate block in the polysiloxane-polycarbonate copolymer of the present invention may be 75 to 99% by weight, preferably 80 to 97% by weight, and more It is preferably from 80 to 95% by weight, and more preferably from 85 to 95% by weight of the total weight of the copolymer. If the content of the polycarbonate block is less than 75% by weight, light transmittance and processability may decrease. If the content of the polycarbonate block is more than 99% by weight, flame retardancy and impact resistance may decrease.

In a preferred embodiment, the viscosity average molecular weight (Mv) of the polysiloxane-polycarbonate copolymer according to the present invention may be 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, the mechanical properties may be significantly reduced. If the viscosity average molecular weight exceeds 200,000, the resin may have problems in processing due to the increase in melt viscosity.

The invention also relates to a method for preparing the above-mentioned polysiloxane-polycarbonate copolymer.

The method for preparing a polysiloxane-polycarbonate copolymer according to the present invention includes a step of forming a polysiloxane-polycarbonate intermediate by making the polysiloxane of the above formula 1 except for the polysiloxane of the formula 1 Polysiloxanes other than oxanes (specifically, polysiloxanes of formula 2) and oligomeric polycarbonates are combined with alkali aqueous solution and A step of reacting under interface reaction conditions composed of an organic phase; and using the first polymerization catalyst to polymerize the above-mentioned polysiloxane-polycarbonate intermediate.

In a preferred embodiment, the step of forming a polysiloxane-polycarbonate intermediate may include combining the polysiloxane of formula 1 with polysiloxanes other than the polysiloxane of formula 1 (specifically , The step of mixing the mixture of polysiloxane of formula 2 and oligomeric polycarbonate. The weight ratio of polycarbonate is 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 . If the content of the mixture of the polysiloxane of Formula 1 and polysiloxanes other than the polysiloxane of Formula 1 (specifically, the polysiloxane of Formula 2) is less than 1% by weight, the flame retardancy and/ Or impact resistance may deteriorate. If the content of the polysiloxane mixture of the polysiloxane of formula 1 and polysiloxanes other than the polysiloxane of formula 1 (specifically, the polysiloxane of formula 2) is greater than 25% by weight, then Workability and light transmittance may be reduced.

The oligomeric polycarbonate used in the preparation of the polysiloxane-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, the molecular weight distribution may become broad and physical properties may decrease. If the viscosity average molecular weight is greater than 20,000, the reactivity may decrease.

In a preferred embodiment, the oligomeric polycarbonate can be prepared by adding the above-mentioned dihydric phenol compound to an aqueous alkali solution to prepare phenol in the salt state, and then make the phenol in the salt state in methylene chloride injected with phosgene Prepare by reaction. In order to prepare polycarbonate oligomers, it is desirable to maintain the molar ratio of phosgene to dihydric phenolic compounds (such as bisphenol A) at about 1:1 to 1.5:1, more preferably about 1:1 to 1.2: Within the range of 1. If the molar ratio of phosgene to the dihydric phenol compound is less than 1, the reactivity may decrease. If the molar ratio of phosgene to the dihydric phenol compound exceeds 1.5, there is a problem in processability due to excessive increase in molecular weight.

The formation reaction of the polycarbonate oligomer can generally be carried out at a temperature of about 15 to 60°C, and an alkali metal hydroxide (such as sodium hydroxide) can be used to adjust the pH of the reaction mixture.

In a preferred embodiment, the step of forming a polysiloxane-polycarbonate intermediate includes forming a polysiloxane containing the above formula 1, and polysiloxanes other than the polysiloxane of formula 1 (specifically Specifically, the step of a mixture of polysiloxane of Formula 2) and oligomeric polycarbonate, wherein the mixture may further include a phase transfer catalyst, a molecular weight regulator, and a second polymerization catalyst.

In a preferred embodiment, the step of forming a polysiloxane-polycarbonate intermediate may include forming a polysiloxane containing the above formula 1 polysiloxane except for the polysiloxane of formula 1 ( Specifically, the step of a mixture of polysiloxane of formula 2) and oligopolycarbonate; and the polysiloxane of formula 1 above, polysiloxanes other than polysiloxane of formula 1 (specifically After the reaction between the polysiloxane of formula 2 and the oligomeric polycarbonate is completed, the step of extracting the organic phase from the resulting mixture; and the step of forming the polysiloxane-polycarbonate intermediate may include the step of extracting the organic The phase provides the first polymerization catalyst step.

Specifically, the polysiloxane-polycarbonate copolymer according to the present invention can be obtained by combining the above-mentioned polysiloxane of formula 1 and the above-mentioned polysiloxane other than the polysiloxane of formula 1 (specifically, formula 2 The polysiloxane) is prepared by adding polycarbonate-containing organic substances, and the molecular weight regulator and catalyst are gradually added.

As the molecular weight regulator, a monofunctional compound similar to the monomer used to prepare the polycarbonate can be used. Monofunctional compounds include, for example, phenol-based derivatives such as p-propofol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol, p-isononylphenol, etc. ; Or aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) can be used.

As the catalyst, a polymerization catalyst and/or a phase transfer catalyst can be used. As the polymerization catalyst, for example, triethylamine (TEA) can be used, and as the phase transfer catalyst, for example, a compound represented by the following formula 7 can 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 -OR12. 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 may be, 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 formula, 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.

With respect to the polysiloxane of the above formula 1, the total weight of the mixture of the polysiloxane (specifically, the polysiloxane of the formula 2) and the oligomeric polycarbonate other than the polysiloxane of the formula 1, The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight. If the content of the phase transfer catalyst is less than 0.01% by weight, the reactivity may decrease. If the content exceeds 10% by weight, precipitation or decrease in light transmittance may occur.

In a preferred embodiment, after preparing the polysiloxane-polycarbonate copolymer, the organic phase dispersed in dichloromethane can be alkali washed and then separated. Subsequently, the organic phase can be washed with a 0.1N hydrochloric acid solution, and then washed with distilled water twice or three times. When the washing is completed, the concentration of the organic phase dispersed in dichloromethane is constantly adjusted, and granulation is performed by using a certain amount of pure water at 70 to 80°C. If the temperature of the pure water is lower than 70°C, the granulation speed will slow down and the granulation time may be very long. If the temperature of pure water exceeds 80°C, it may be difficult to obtain polycarbonate of uniform size. After the granulation is completed, it is preferable to dry at 100 to 110°C for 5 to 10 hours for the first time and at 110 to 120°C for 5 to 10 hours for the second time.

The present invention also relates to molded articles prepared using the polysiloxane-polycarbonate copolymer of the present invention.

The method for preparing molded articles using the polysiloxane-polycarbonate copolymer of the present invention is not particularly limited, and the methods generally used for preparing resin molded articles (for example, extrusion method or injection method, etc.) can be used as they are or appropriately modified .

The molded article according to the present invention can be variously applied to fields requiring flame retardancy, such as building materials, automobile parts, parts (housings) of office equipment, and electrical/electronic products, but is not limited thereto.

The present invention will be explained in more detail by the following examples. However, the scope of the present invention is not limited in any way by this embodiment.

Example

<Preparation of Polysiloxane>

Preparation Example 1: Preparation of branched chain polysiloxane

Install the condenser in a 500mL three-necked flask and dissolve 50.44g (0.1 mol) of polysiloxane (F5032, Damipolychem Co. Ltd., colorless and transparent liquid, viscosity: 5cP) corresponding to Formula 4 in a nitrogen atmosphere In 50 ml of toluene, 0.008 g (100 ppm) of platinum (Pt) catalyst (CP101 of Damipolychem Co. Ltd) was added thereto. While heating the solution, slowly add 26.8 g (0.2 mol) of 2-allylphenol for 1 hour and reflux for 5 hours. After the completion of the reaction, the solvent toluene was removed from the solution, and the product was dried in a vacuum oven for 24 hours to prepare a polysiloxane of the following formula 8.

Preparation Example 2: Preparation of branched polysiloxane

Install the condenser in a 500mL three-necked flask and dissolve 50.44g (0.1 mol) of polysiloxane (F5032, Damipolychem Co. Ltd., colorless and transparent liquid, viscosity: 5cP) corresponding to Formula 4 in 50ml of toluene Under a nitrogen atmosphere, 0.008 g (100 ppm) of platinum (Pt) catalyst (CP101 of Damipolychem Co. Ltd) was added thereto. While heating the solution, 40.2 g (0.3 mol) of 2-allylphenol was slowly added for 1 hour and refluxed for 5 hours. After the completion of the reaction, the solvent toluene was removed from the solution, and the product was dried in a vacuum oven for 24 hours to prepare a polysiloxane of the following formula 9.

Preparation Example 3: Preparation of linear polysiloxane

After installing the condenser in a 500 mL three-necked flask and dissolving 0.4 mol of monomer BY16-799 (Dow Corning) in 300 mL of chloroform under a nitrogen atmosphere, 67 mL of triethylamine (TEA) catalyst was added to it . Under the reflux of the solution, 0.2 mol of terephthaloyl chloride (TCL) was dissolved in 1,000 mL of chloroform, and then slowly added to the solution for 1 hour, and the resulting solution was refluxed for 12 hours. After the reaction was completed, the solvent was removed from the solution, and the product was dissolved in acetone and washed with hot distilled water. By drying in a vacuum oven for 24 hours, a hydroxyl-terminated polysiloxane having an ester bond having the following formula 10 was prepared.

<Preparation of polysiloxane-polycarbonate copolymer>

Example 1

The bisphenol A in the aqueous solution and phosgene were interface-reacted in the presence of dichloromethane to prepare an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. The organic phase was collected from the obtained oligomeric polycarbonate mixture, and the sodium hydroxide aqueous solution, the branched polysiloxane of formula 8 prepared in Example 1 (based on the total weight of the copolymer was 8% by weight) ), the linear polysiloxane of formula 10 prepared in Example 3 (based on the total weight of the copolymer, 1% by weight), tetrabutylammonium chloride (TBACl, based on the total weight of the copolymer, by weight 0.1%), dichloromethane and p-tert-butylphenol (PTBP, 0.4% by weight based on the total weight of the copolymer) were added to the organic phase and reacted for 2 hours. After separating the layers, only the organic phase was collected, and sodium hydroxide aqueous solution, dichloromethane and triethylamine (TEA, 0.015% by weight based on the total weight of the copolymer) were added to the organic phase and reacted for 3 hours. Triethylamine (TEA, 0.02% by weight based on the total weight of the copolymer) was added again to the reacted organic phase for further reaction for 2 hours. After the layers were separated, the organic phase with increased viscosity was collected, and distilled water and dichloromethane were added to it, washed with alkali, and then separated again. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2 to 3 times. The washing is completed, and a certain amount of pure water is used to granulate the organic phase at 76°C. After the granulation was completed, the product was dried at 110°C for 8 hours for the first time, and then dried at 120°C for 10 hours for the second time. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 2

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 7% by weight and changing the content of the linear polysiloxane of Formula 10 from 1% by weight to 2% by weight, the implementation In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 3

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 6% by weight and changing the content of the linear polysiloxane of Formula 10 from 1% by weight to 3% by weight, in order to implement In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 4

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 5% by weight and changing the content of the linear polysiloxane of Formula 10 from 1% by weight to 4% by weight, the implementation of In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 5

In addition to changing the content of the branched polysiloxane of formula 8 from 8% by weight to 4% by weight, and changing the content of the linear polysiloxane of formula 10 from 1% by weight to 5% by weight, the In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 6

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 3% by weight, and changing the content of the linear polysiloxane of Formula 10 from 1% by weight to 6% by weight, the In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 7

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 2% by weight, and changing the content of the linear polysiloxane of Formula 10 from 1% by weight to 7% by weight, to In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 8

In addition to changing the content of the branched polysiloxane of Formula 8 from 8% by weight to 1% by weight and the content of the linear polysiloxane of Formula 10 from 1% by weight to 8% by weight, in order to implement In the same manner as in Example 1, a polysiloxane-polycarbonate copolymer was prepared. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 9

Except for using the branched polysiloxane of formula 9 prepared in Preparation Example 2 (5% by weight based on the total weight of the copolymer) instead of the branched polysiloxane of formula 8 prepared in Preparation Example 1. Except that the content of linear polysiloxane of formula 10 was changed from 1% by weight to 4% by weight, polysiloxane-polycarbonate was prepared in the same manner as in Example 1, except that the content of linear polysiloxane of formula 10 was changed from 1% by weight to 4% by weight based on the total weight Copolymer. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Example 10

Except for using the branched polysiloxane of formula 9 prepared in Preparation Example 2 (4% by weight based on the total weight of the copolymer) instead of the branched polysiloxane of formula 8 prepared in Preparation Example 1. Except that the content of the linear polysiloxane of formula 10 was changed from 1% by weight to 5% by weight, a polysiloxane-polycarbonate was prepared in the same manner as in Example 1 (8% by weight based on the total weight). Copolymer. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 1 below.

Comparative example 1

The properties of linear polycarbonate (Samyang Corp., TRIREX 3030IR) with a viscosity average molecular weight of 30,000 were measured, and the results are shown in Table 2 below.

Comparative example 2

Except not using polysiloxane, a linear polycarbonate having a viscosity average molecular weight of 70,000 was prepared in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative example 3

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% by weight to 9% by weight, the same as Example 1 The polysiloxane-polycarbonate copolymer was prepared in the same way. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 2 below.

Comparative example 4

Except that the linear polysiloxane of Formula 10 prepared in Preparation Example 3 was not used and the content of the branched polysiloxane of Formula 8 was changed from 8% by weight to 9% by weight, the same as in Example 1 The polysiloxane-polycarbonate copolymer was prepared in the same way. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 2 below.

Comparative example 5

Except not using the linear polysiloxane of formula 10 prepared in Preparation Example 3 and the branched polysiloxane of formula 9 prepared in Preparation Example 2 (based on 9 wt% of the total weight of the copolymer) ) In place 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-polysiloxane was prepared in the same manner as in Example 1. Carbonate copolymer. The properties of the prepared polysiloxane-polycarbonate copolymer were measured, and the results are shown in Table 2 below.

[Table 1]

[Table 2]

As shown in Table 1, the polysiloxane-polycarbonate copolymers prepared in Examples 1 to 10 of the present invention have excellent impact strength of 30 (kgcm/cm) or higher at low temperature impact strength, excellent The transmittance is more than 85% and excellent flame retardancy.

However, as shown in Table 2, in the case of the linear polycarbonate resin (Comparative Examples 1 and 2), the light transmittance is excellent, but the impact strength and flame retardancy at low temperature are very poor. In the case where the polycarbonate copolymer does not have a branched polysiloxane with a specific structure (Comparative Example 3), the light transmittance and impact strength at low temperatures are excellent, But the flame retardancy is poor. Moreover, in the case where the polycarbonate copolymer does not have a linear polysiloxane having a specific structure (Comparative Examples 4 and 5), the light transmittance and flame retardancy are excellent, but the impact strength at low temperature is relatively poor.

The measurement and evaluation methods of the properties shown in Table 1 and Table 2 are as follows.

(a) 1 H-NMR (Nuclear Magnetic Resonance Spectroscopy): This analysis was performed by using Avance DRX 300 (Bruker). Using 1 H-NMR, the methyl peak of dimethylsiloxane observed at 0.2 ppm, the methylene peak of polysiloxane-polycarbonate bonding part observed at 2.6 ppm, and The methoxy peak of the polysiloxane-polycarbonate bonding portion observed at 3.9 ppm confirms the copolymer.

(b) Viscosity average molecular weight (Mv): Measure the viscosity of the methylene chloride solution at 20°C using an Ubbelohde viscometer, and calculate the limiting viscosity [η] according to the following formula.

[η]=1.23x10 ^-5 Mv ^0.83

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

(d) Flame retardancy: Flame retardancy is measured by the UL-94 flame retardancy test defined by Underwriter's Laboratories (UL) in the United States. This method aims to evaluate the flame retardancy based on the burning time or dripping properties after applying the flame of the burner to a fixed sample of a certain size for 10 seconds. The burning time refers to the time that the sample continues to burn after the flame falls. The cotton fire caused by dripping was determined by the cotton used for marking, which was located about 300mm below the bottom of the sample, and the bottom of the sample was dripped and burned by burning particles from the sample. The flame retardant grades are divided according to Table 3 below.

[table 3]

(e) Impact strength: The impact strength is evaluated by notching the sample at a low temperature of -30°C according to ASTM D256. The final test result is calculated as the average of the test results of 10 samples.

Claims (16)

A polysiloxane-polycarbonate copolymer comprising the following as repeating units: polysiloxane of formula 1; polysiloxanes other than polysiloxane of formula 1; and polycarbonate blocks:

In Formula 1, R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, and R ₃ independently represents having An alkylene having 2 to 8 carbon atoms, R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 6 to An aryl group of 10 carbon atoms, k independently represents an integer from 1 to 4, and each of l, m and n independently represents an integer from 0 to 4, provided that at least one of l, m and n is not 0, And x and y respectively represent an integer from 0 to 100, wherein the weight ratio of the polysiloxane of the formula 1 to the polysiloxanes other than the polysiloxane of the formula 1 is 1:8 to 8:1. The polysiloxane-polycarbonate copolymer according to the first item of the scope of patent application, wherein the polysiloxane other than the polysiloxane of formula 1 is a polysiloxane of the following formula 2:

In Formula 2, R ₅ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms. R ₆ independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxyl group, R ₇ independently represents an alkylene group having 2 to 8 carbon atoms, A is X or NH-X-NH, where X is A straight or branched chain aliphatic group with 1 to 20 carbon atoms; a cycloalkylene group with 3 to 20 carbon atoms; or unsubstituted or substituted by halogen atoms, alkyl groups, alkoxy groups, aryl groups Or a carboxy-substituted mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, m independently represents an integer of 0 to 10, and n independently represents an integer of 2 to 1,000. The polysiloxane-polycarbonate copolymer as described in item 1 of the scope of patent application, wherein the polysiloxane of formula 1 is a reaction product of the polysiloxane of formula 4 below and the compound of formula 5 below :

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

In Formula 5, R ₄ and k are the same as those defined in Formula 1, and h represents an integer from 1 to 7. The polysiloxane-polycarbonate copolymer described in item 1 of the scope of patent application, wherein the polycarbonate block is represented by the following formula 3:

In Formula 3, R ₈ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that is unsubstituted or substituted with an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or a nitro group. The polysiloxane-polycarbonate copolymer as described in item 4 of the scope of patent application, wherein _{the aromatic hydrocarbon group of R 8} in formula 3 is derived from the compound of formula 6 below:

X is a linear, branched or cyclic alkylene group without a functional group; or contains at least one functional group selected from the group consisting of sulfide, ether, sulfene, sulfide, ketone, naphthyl or isobutylphenyl Linear, branched or cyclic alkylene group, R ₉ and R ₁₀ are each independently a halogen atom; or linear, branched or cyclic alkyl group, and p and q each independently represent 0 to An integer of 4. The polysiloxane-polycarbonate copolymer as described in item 1 of the scope of patent application, wherein the content of the polysiloxane of formula 1 is 0.5 to 20% by weight of the total weight of the copolymer. The polysiloxane-polycarbonate copolymer as described in item 1 of the scope of the patent application, wherein, relative to the total weight of the copolymer, the content of the polysiloxane other than the polysiloxane of formula 1 is 0.5 to 20% by weight. The polysiloxane-polycarbonate copolymer as described in item 1 of the patent application, wherein based on the total weight of the copolymer, the polysiloxane of formula 1 and the polysiloxane of formula 1 other than the polysiloxane of formula 1 The total content of polysiloxane is 1 to 25% by weight. The polysiloxane-polycarbonate copolymer as described in item 1 of the scope of the patent application has a viscosity average molecular weight of 15,000 to 200,000. A method for preparing a polysiloxane-polycarbonate copolymer, comprising: preparing polysiloxane of the following formula 1, polysiloxanes other than the polysiloxane of formula 1, and oligomeric polycarbonate in The step of reacting under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; and the step of using the first polymerization catalyst to polymerize the polysiloxane-polycarbonate intermediate:

In Formula 1, R ₁ independently represents a hydrogen atom, a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms, or a hydroxyl group, and R ₃ independently represents having An alkylene having 2 to 8 carbon atoms, R ₄ independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 6 to An aryl group of 10 carbon atoms, k independently represents an integer from 1 to 4, and each of l, m and n independently represents an integer from 0 to 4, provided that at least one of l, m and n is not 0, And x and y respectively represent an integer from 0 to 100, wherein the weight ratio of the polysiloxane of formula 1 to the polysiloxanes other than the polysiloxane of formula 1 is 1:8 to 8:1. The method for preparing a polysiloxane-polycarbonate copolymer as described in item 10 of the scope of patent application, wherein the polysiloxane other than the polysiloxane of formula 1 is the polysiloxane of formula 2 below :

In Formula 2, R ₅ independently represents a hydrogen atom, a halogen atom, a hydroxyl 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 having 1 to 13 carbon atoms, or a hydroxyl group, R ₇ independently represents an alkylene group having 2 to 8 carbon atoms, A is X or NH-X-NH, where X is Straight or branched chain aliphatic groups of 1 to 20 carbon atoms; cycloalkylene groups of 3 to 20 carbon atoms; or unsubstituted or substituted by halogen atoms, alkyl groups, alkoxy groups, aryl groups or A carboxy-substituted mononuclear or polynuclear arylene group having 6 to 30 carbon atoms, m independently represents an integer of 0 to 10, and n independently represents an integer of 2 to 1,000. The method for preparing polysiloxane-polycarbonate copolymer as described in item 10 of the scope of patent application, wherein the step of forming the polysiloxane-polycarbonate intermediate includes a weight of 1:99 to 25:75 The step of mixing the mixture of the polysiloxane of Formula 1 and the polysiloxane other than the polysiloxane of Formula 1 with the oligomeric polycarbonate. The method for preparing a polysiloxane-polycarbonate copolymer according to the tenth item of the scope of patent application, wherein the step of forming a polysiloxane-polycarbonate intermediate includes forming a polysiloxane containing the formula 1 A step of the mixture of the polysiloxane other than the polysiloxane of Formula 1 and the oligomeric polycarbonate, wherein the mixture further includes a phase transfer catalyst, a molecular weight regulator and a second polymerization catalyst. The method for preparing a polysiloxane-polycarbonate copolymer according to the tenth item of the scope of patent application, wherein the step of forming a polysiloxane-polycarbonate intermediate includes forming a polysiloxane containing the formula 1 , The step of the mixture of the polysiloxane other than the polysiloxane of formula 1 and the oligomeric polycarbonate; and the step of the polysiloxane of formula 1 and the polysiloxane of formula 1 other than After the reaction of the polysiloxane and the oligomeric polycarbonate is completed, the step of extracting the organic phase from the resulting mixture; and the step of forming the polysiloxane-polycarbonate intermediate includes providing the extracted organic phase with a step A polymerization catalyst step. According to the method for preparing polysiloxane-polycarbonate copolymer as described in item 10 of the scope of patent application, the viscosity average molecular weight of the oligomeric polycarbonate is 800 to 20,000. A molded product is prepared by using any one of the first to ninth items of the patent scope of the polysiloxane-polycarbonate copolymer.