KR101530322B1 - Polysiloxane-polycarbonate copolymer having improved transparency and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and a process for producing the polysiloxane-polycarbonate copolymer. More specifically, the present invention relates to a polysiloxane-polycarbonate copolymer having three or more polysiloxane-alkylene groups in a siloxane monomer structure of an ester type or urethane type constituting a copolymer Polycarbonate copolymers having excellent low-temperature impact resistance and excellent transparency by having at least three alkylene linking groups, and a process for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and a method for producing the same. BACKGROUND ART POLYSILOXANE-POLYCARBONATE COPOLYMER HAVING IMPROVED TRANSPARENCY AND METHOD FOR PREPARING THE SAME

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and a process for producing the polysiloxane-polycarbonate copolymer. More specifically, the present invention relates to a polysiloxane-polycarbonate copolymer having three or more polysiloxane-alkylene groups in a siloxane monomer structure of an ester type or urethane type constituting a copolymer Polycarbonate copolymers having excellent low-temperature impact resistance and excellent transparency by having at least three alkylene linking groups, and a process for producing the same.

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and is excellent in dimensional stability, heat resistance and optical transparency, and is widely used in industrial applications. However, polycarbonate has excellent impact resistance at room temperature, but has a weak point that the impact resistance sharply drops at low temperatures.

Studies have been conducted on various copolymers to improve these vulnerabilities, and as a result, polysiloxane-polycarbonate copolymers have been proposed (US Patent Publication No. 2003/0105226).

Polysiloxane-polycarbonate copolymers are known to have relatively good impact resistance at low temperatures. However, the conventional polysiloxane-polycarbonate copolymer essentially requires a high content of siloxane for the low-temperature impact resistance development, and the increase of the content of the siloxane limits the transparency of the polysiloxane-polycarbonate copolymer, .

Thus, development of a copolymer showing excellent low-temperature impact resistance and exhibiting excellent transparency has been demanded.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a novel polysiloxane-polycarbonate copolymer exhibiting excellent low-temperature impact resistance and excellent transparency and a process for producing the same.

In order to accomplish the above object, the present invention provides a polysiloxane-polycarbonate copolymer comprising a hydroxyl-terminated polysiloxane and a polycarbonate block as repeating units, wherein the hydroxy-terminated polysiloxane is represented by the following formula (1) A polysiloxane-polycarbonate copolymer is provided:

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₉ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,

R ₂ , R ₃ and R ₄ Each independently represent an unsubstituted or substituted hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group,

R ₅ , R ₆ , R ₇ and R ₈ , which may be the same or different, each independently represent an unsubstituted or substituted alkylene group having 2 to 20 carbon atoms,

m and r independently represent an integer of 0 to 4,

n1 to n6 each independently represents an integer of 0 to 200,

Provided that at least two of n1 to n3 are not 0, at least one of n4 to n6 is not 0,

a1 to a6 are each independently 0 or 1,

Provided that a1 is 0 if n1 is 0 and a1 is 1 if n1 is not 0; a2 is 0 if n2 is 0, and a2 is 1 if n2 is not 0; a3 is 0 if n3 is 0, and a3 is 1 if n3 is not 0; a4 is 0 if n4 is 0, and a4 is 1 if n4 is not 0; a5 is 0 if n5 is 0, and a5 is 1 if n5 is not 0; a6 is 0 if n6 is 0 and a6 is 1 if n6 is not 0,

A represents a structure represented by the following formula (2).

(2)

In Formula 2,

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

According to another aspect of the present invention, there is provided a process for preparing a polysiloxane-polycarbonate intermediate, which comprises mixing a hydroxy-terminated polysiloxane of Formula 1 with an oligomeric polycarbonate and then reacting under an interfacial reaction condition to form a polysiloxane-polycarbonate intermediate; And polymerizing the intermediate. The present invention also provides a process for producing a polysiloxane-polycarbonate copolymer.

According to another aspect of the present invention, there is provided a molded article comprising the polysiloxane-polycarbonate copolymer.

The polysiloxane-polycarbonate copolymer according to the present invention exhibits excellent low-temperature impact resistance and exhibits excellent transparency that is not exhibited in a conventional resin having a high siloxane content. Therefore, a molded article having both transparency and low-temperature impact resistance , Office equipment and housings of electric / electronic products, film and sheet products, etc.).

As used herein, the term "reaction product" means a material in which two or more reactants are formed by reaction.

In addition, although the terms "first", "second" and the like are used herein to describe a polymerization catalyst, the polymerization catalyst is not limited by these terms. These terms are merely used to distinguish polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be the same kind of catalyst or different kinds of catalysts.

The letter "R" used to represent hydrogen, a halogen atom and / or a hydrocarbon group in the formulas described in the present specification has a subscript indicated by a numeral, but the letter "R" But is not limited thereto. The "R" represents, independently of each other, hydrogen, a halogen atom and / or a hydrocarbon group. For example, the "R" s may represent the same hydrocarbon group or may represent other hydrocarbon groups, irrespective of whether two or more "R" have the same or different numbers of subscripts.

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

(A) a hydroxy terminal Polysiloxane

The hydroxyl-terminated polysiloxane contained as a repeating unit in the polysiloxane-polycarbonate copolymer of the present invention has a structure represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

R ₁ and R ₉ may be the same or different and each independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group. For example, 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 methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms such as methoxy, Ethoxy or propoxy, and the aryl group may be an aryl group of 6 to 10 such as phenyl, chlorophenyl or tolyl.

R ₂ , R ₃ and R ₄ May be the same or different from each other and each independently represent a hydrocarbon group having 1 to 13 carbon atoms which is unsubstituted or substituted (for example, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group) . For example, R ₂ , R ₃ and R ₄ Each independently represent an unsubstituted or substituted alkyl 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, aryl having 6 to 10 carbon atoms An aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.

R ₅ , R ₆ , R ₇ and R ₈ , which may be the same or different, each independently represent a C 2-20, more preferably C 2-10, still more preferably C 2-5 (E.g., a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or an aryl group).

m and r independently represent an integer of 0 to 4;

n1 to n6 each independently represents an integer of 0 to 200; Provided that at least two of n 1 to n 3 are not 0 and at least one of n 4 to n 6 is not 0.

For example, the lower limit of each of n1 to n6 may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and the upper limit may be 200, 150, 100, 90, 80, 60, 50, 40, 30, or 20, but is not limited thereto. In addition, the sum of all n1 to n6 present in the formula (1) is preferably in the range of 3 to 202, more preferably in the range of 10 to 100, and still more preferably in the range of 20 to 80, It is not.

a1 to a6 each independently represent 0 or 1; Provided that a1 is 0 if n1 is 0 and a1 is 1 if n1 is not 0; a2 is 0 if n2 is 0, and a2 is 1 if n2 is not 0; a3 is 0 if n3 is 0, and a3 is 1 if n3 is not 0; a4 is 0 if n4 is 0, and a4 is 1 if n4 is not 0; a5 is 0 if n5 is 0, and a5 is 1 if n5 is not 0; a6 is 0 if n6 is 0 and a6 is 1 if n6 is not 0.

A represents a structure represented by the following formula (2).

(2)

In Formula 2,

X is Y or NH-Y-NH, wherein Y is a linear or branched aliphatic group of 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; A cycloalkylene group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group (e.g., a cycloalkylene group having 3 to 6 carbon atoms); Or a mononuclear or polycyclic arylene group having 6 to 30 carbon atoms which is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. For example, Y is an aliphatic group substituted with a halogen atom or an unsubstituted aliphatic group, an aliphatic group containing an oxygen, nitrogen or sulfur atom in the main chain, or an aryl group derived from bisphenol A, resorcinol, hydroquinone or diphenyl phenol And may be represented, for example, by the following formulas (2a) to (2h).

(2a)

(2b)

[Chemical Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

In one embodiment, the hydroxy-terminated polysiloxane of formula (1) may be the reaction product of a linear hydroxy-terminated siloxane having a hydroxyphenyl end group with an acyl compound. Here, the acyl compound may have a mixed structure including, for example, aromatic, aliphatic, or both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms. When the acyl compound is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further contain a halogen, an oxygen, a nitrogen or a sulfur atom.

In another embodiment, the hydroxy-terminated polysiloxane of Formula 1 may be the reaction product of a dihydroxy-terminated siloxane having a hydroxyphenyl end group with a diisocyanate compound. Here, the diisocyanate compound may be, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate or 4,4'-methylenediphenyl diisocyanate. (4,4'-methylenediphenyl diisocyanate).

The hydroxy-terminated polysiloxane of formula (1) may have a symmetrical structure centering on the linking group A, or may have an asymmetric structure. Specific examples of the hydroxy-terminated polysiloxane of the formula (1) include, but are not limited to, the following.

The hydroxy-terminated polysiloxane of formula (1) may have a molecular weight (number average molecular weight, Mn) of preferably 900 to 16,000, more preferably a molecular weight of 1,100 to 12,000, even more preferably 1,200 to 7,000. If the molecular weight of the hydroxy-terminated polysiloxane is less than 900, the resulting copolymer may have insufficient low-temperature impact resistance. If the molecular weight exceeds 16,000, the reactivity becomes poor and the polysiloxane-polycarbonate copolymer may be synthesized at a desired molecular weight .

The preferred content of the hydroxy-terminated polysiloxane of the formula (1) in the polysiloxane-polycarbonate copolymer of the present invention is 1 to 40% by weight, more preferably 2 to 30% by weight, based on the total weight of the copolymer. If the content of the hydroxy-terminated polysiloxane in the copolymer is less than 1% by weight, the low-temperature impact resistance of the resultant copolymer may be insufficient. If the content is more than 40% by weight, physical properties such as fluidity, The manufacturing cost is increased, which is not desirable from the economical point of view. In the present invention, excellent low-temperature impact resistance and transparency can be exerted at the same time, while using relatively high molecular weight siloxane monomers.

(B) Polycarbonate block

The polycarbonate block contained as a repeating unit in the polysiloxane-polycarbonate copolymer according to the present invention may have a repeating unit represented by the following general formula (3).

(3)

In Formula 3,

R ₁₀ represents an alkyl group having 1 to 20 carbon atoms (e.g., an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (e.g., an alkenyl group having 2 to 13 carbon atoms) (For example, an alkoxy group having 1 to 13 carbon atoms), a halogen atom or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted with nitro.

Here, the aromatic hydrocarbon group may be derived from a compound having a structure represented by the following formula (3a).

[Chemical Formula 3]

In the above formula (3a)

L represents an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, L may be a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.

R ₁₁ independently represents a hydrogen atom, a halogen atom, or an alkyl group, for example, a straight, branched or cyclic alkyl group having from 1 to 20 carbon atoms and having from 3 to 20 carbon atoms (preferably from 3 to 6).

a and b independently represent an integer of 0 to 4;

The compound of formula (3a) is, for example, selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis ) - (4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1- Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, Bis (4-hydroxyphenyl) propane, bis (3-methyl-4-hydroxyphenyl) propane, 2,2- , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5- (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) decane, 1,1- Bis (4-hydroxyphenyl) propane, 1,4-bis (4- (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) Bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis -Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, ', 5,5'-tetramethyl-4,4'-dihydroxybenzophe , 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

In the case of the carbonate precursor, as other monomers of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bishaloformate, diphenyl carbonate or dimethyl carbonate can be used.

(C) Polysiloxane - Polycarbonate Copolymer

The polysiloxane-polycarbonate copolymer of the present invention can be obtained by mixing a hydroxy-terminated polysiloxane of the above-mentioned formula (1) with an oligomeric polycarbonate (for example, a hydroxy-terminated polysiloxane: oligomeric polycarbonate in a weight ratio of 1:99 to 10:90 Followed by reaction under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; And polymerizing the intermediate, preferably in the presence of a first polymerization catalyst.

The oligomeric polycarbonate used in the preparation of the polysiloxane-polycarbonate copolymer preferably has a viscosity average molecular weight of 800 to 20,000, more preferably 800 to 15,000, and most preferably 1,000 to 12,000. If the viscosity average molecular weight of the oligomeric polycarbonate is less than 800, the molecular weight distribution may be widened and the physical properties may be deteriorated. If it exceeds 20,000, the reactivity may be lowered.

In one embodiment, the oligomeric polycarbonate may be prepared by adding the above-mentioned dihydric phenol compound to an alkaline aqueous solution to form a phenol salt state, and then adding a phenol salt in a salt form into dichloromethane injected with a phosgene gas . For oligomer preparation, it is desirable to maintain the molar ratio of phosgene to bisphenol in the range of about 1: 1 to 1.5: 1, more preferably about 1: 1 to 1.2: 1. If the molar ratio of phosgene to bisphenol is less than 1, the reactivity may be deteriorated. If the molar ratio of bisphenol to phosgene exceeds 1.5, the workability may be deteriorated due to an excessive molecular weight increase.

The oligomerization reaction may be generally carried out at a temperature in the range of about 15 to 60 DEG C, and an alkali metal hydroxide (e.g., sodium hydroxide) may be used to adjust the pH of the reaction mixture.

In one embodiment, the step of forming the intermediate comprises forming a mixture comprising a hydroxy-terminated polysiloxane and an oligomeric polycarbonate, wherein the mixture comprises a phase transfer catalyst, a molecular weight modifier and a second polymerization catalyst Lt; / RTI > Also, the step of forming the intermediate may comprise the steps of: forming a mixture comprising a hydroxy-terminated polysiloxane and an oligomeric polycarbonate; And extracting the organic phase from the resulting mixture after the reaction of the hydroxy endopolysiloxane with the oligomeric polycarbonate is completed, wherein the step of polymerizing the intermediate comprises the step of providing a first polymerization catalyst to the extracted organic phase May include.

Specifically, the polysiloxane-polycarbonate copolymer of the present invention can be prepared by adding the hydroxy-terminated polysiloxane of the above formula (1) to an organic phase-water mixture containing a polycarbonate, and gradually introducing a molecular weight regulator and a catalyst.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the polycarbonate may be used. The monofunctional material may be, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. As the polymerization catalyst, for example, triethylamine (TEA) can be used. As the phase transfer catalyst, for example, a compound of the following formula (4) can be used.

[Chemical Formula 4]

(R ₁₂ ) ₄ Q ⁺ X ^-

In the general formula (4), R ₁₂ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or -OR ₁₃ . Here, R ₁₃ 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, 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, CH 3 [CH 3 (CH 2) 2] can be a ₃ NX have. In the above formulas, X represents Cl, Br or -OR ₁₃ , wherein R ₁₃ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. When the phase transfer catalyst is used, its content is preferably 0.01 wt% or more in terms of transparency of the resultant copolymer, but is not limited thereto.

In one embodiment, the polysiloxane-polycarbonate copolymer is prepared and then the organic phase dispersed in methylene chloride is alkaline cleaned and then separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, and granulation is performed using a predetermined amount of pure water in the range of 30 to 100 ° C, preferably 60 to 80 ° C. If the pure water temperature is less than 30 ° C, the assembling speed is decreased and the assembling time may become very long. When the pure water temperature exceeds 100 ° C, it may become difficult to obtain the polycarbonate shape to a certain size. When the assembly is completed, drying is preferably performed at 100 to 120 ° C for 5 to 10 hours, more preferably at 100 to 110 ° C for 5 to 10 hours, and further at 110 to 120 ° C for 5 to 10 hours .

The polysiloxane-polycarbonate copolymer according to the present invention preferably has a viscosity average molecular weight (Mv) of 15,000 to 30,000, more preferably 17,000 to 22,000. If the viscosity average molecular weight of the copolymer is less than 15,000, the mechanical properties may be significantly deteriorated. If the viscosity average molecular weight exceeds 30,000, the melt viscosity may increase, which may cause problems in processing the resin.

The polysiloxane-polycarbonate copolymer according to the present invention is excellent in both transparency and low-temperature impact resistance and can be usefully used for production of film and sheet products such as office equipment and housings for electric / electronic products.

Thus, in accordance with another aspect of the present invention, there is provided a molded article comprising the polysiloxane-polycarbonate copolymer of the present invention.

The method of molding the polysiloxane-polycarbonate copolymer of the present invention into a molded article is not particularly limited, and a molded article can be manufactured by a method generally used in the plastic molding field.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Manufacturing example  1: Asymmetric hydroxy terminal Polysiloxane  Produce

A condenser was attached to a 100 mL three-necked flask, and 0.03 mol of 2-allylphenol and 0.03 mol of hydride terminated polydimethylsiloxane (hydride terminated) were completely dissolved in 50 mL of chlorobenzene , And 0.00364 mmol of a platinum catalyst (platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) were added and refluxed for 24 hours. The solvent in the reaction solution was removed, washed with distilled water, and dried in a vacuum oven for 24 hours to prepare an asymmetric hydroxy-terminated polysiloxane compound having a structure of the following formula (5a).

[Chemical Formula 5a]

Manufacturing example  2: hydroxy terminal Polysiloxane  Produce

Except that 0.03 mol of the compound of the formula (5a) and 0.015 mol of vinyl terminated polydimethylsiloxane (vinyl terminated) were used instead of the 2-allylphenol and the hydride terminated polydimethylsiloxane, Was prepared. The hydroxy-terminated polysiloxane compound had a structure of < RTI ID = 0.0 >

 [Chemical Formula 5]

Manufacturing example  3: ester type hydroxy terminal Polysiloxane  Produce

A condenser was attached to a 500 mL three-necked flask, 0.4 mol of the compound of the formula (5) was dissolved in 300 mL of chloroform under nitrogen atmosphere, and 67 mL of triethylamine (TEA) catalyst was added. A solution obtained by dissolving 0.2 mol of terephthaloylchloride (TCL) in 1,000 mL of chloroform was slowly added over 1 hour while refluxing the solution, and refluxed for 12 hours. After the solvent of the reaction solution was removed, the solution was dissolved in acetone and washed with hot distilled water. And dried in a vacuum oven for 24 hours to prepare a hydroxyl-terminated polysiloxane having an ester bond (number average molecular weight: 5,024) represented by the following formula (6). The peak of the ethylene group between the polysiloxane observed at 0.4 to 0.5 ppm by H-NMR, the hydrogen peak of the first carbon of the adjacent aliphatic chain adjacent to the terminal phenyl group observed at 2.6 ppm, and the benzene ring of TCL observed at 8.35 ppm ) And the hydrogen peak of the benzene ring of the polysiloxane observed at 6.75 to 7.35 ppm.

 [Chemical Formula 6]

Manufacturing example  4: urethane type hydroxy terminal Polysiloxane  Produce

Under nitrogen, 0.0666 mol of the compound of the formula (5) was dissolved in 100 mL of benzene, and 1,4-diazabicyclo [2,2,2] -octane ). A solution obtained by dissolving 0.0333 mol of 4,4-methylene bis (phenyl isocyanate) in 200 mL of benzene was slowly added over 1 hour while refluxing the above solution. The above solution was refluxed for 12 hours. After the solvent of the reaction solution was removed, it was dissolved in acetone and washed with hot distilled water. And dried in a vacuum oven for 24 hours. Thus, a hydroxyl-terminated polysiloxane having a urethane bond represented by the following formula (7) (molecular weight: 5,144) was prepared. The peak of the ethylene group between the polysiloxane observed at 0.4 to 0.5 ppm by H-NMR, the hydrogen peak of the first carbon of the aliphatic chain adjacent to the terminal phenyl group observed at 2.6 ppm and the hydrogen peak of the 4,4- The hydrogen peak of the benzene ring of the bis (phenyl isocyanate), the peak of the methylene group of 4,4-methylene bis (phenyl isocyanate) observed at 3.8 to 3.9 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.75 to 7.35 ppm As shown in Fig.

 (7)

Example  One: Polysiloxane - Preparation of Polycarbonate Copolymer

Bisphenol A in an aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 4.5 wt% of an ester type hydroxyl-terminated polysiloxane represented by the formula (6) dissolved in methylene chloride, 1.8 mL of tetrabutyl ammonium chloride (TBACl), p-tert-butylphenol ) And 275 μL of triethylamine (TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. As a result of the reaction, the mixture was allowed to stand for separation. After the layer separation, only the organic phase was sampled, and 170 g of aqueous sodium hydroxide solution, 360 g of methylene chloride and 300 μL of 15 wt% aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase with increased viscosity was washed with alkali and separated. Subsequently, the organic phase was washed with 0.1 N hydrochloric acid solution and then washed repeatedly with distilled water two to three times. After the washing was completed, the organic phase was assembled at 76 DEG C using a certain amount of pure water. After the assembly was completed, it was dried at 110 ° C for 8 hours and then at 120 ° C for 10 hours. The hydrogen peak of the first carbon of the aliphatic chain adjacent to the terminal phenyl group observed at 2.6 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.95 to 7.5 ppm To identify the copolymer. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and reported in Table 1 below.

Example  2: Polysiloxane - Preparation of Polycarbonate Copolymer

Polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the urethane type hydroxy-terminated polysiloxane of the formula (7) was used in an amount of 4.5 wt% instead of the ester type hydroxy-terminated polysiloxane of the formula (6). The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and reported in Table 1 below.

Comparative Example  One

≪ Preparation of hydroxy-terminated polysiloxane >

A condenser was attached to a 100 mL three-necked flask, and 0.03 mol of 2-allylphenol and 0.015 mol of hydride-terminated polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere. Then, a platinum (0) -1,3-divinyl -1,1,3,3-tetramethyldisiloxane complex) was added thereto and refluxed for 24 hours. After removing the solvent of the reacted solution, it was washed with distilled water. Thus, a hydroxy-terminated polysiloxane (molecular weight: 4,703) represented by the following formula (8) was prepared.

[Chemical Formula 8]

≪ Preparation of polysiloxane-polycarbonate copolymer >

Polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the compound of the formula (8) was used in an amount of 4.5% by weight in place of the ester-type hydroxy-terminated polysiloxane of the formula (6). The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and reported in Table 1 below.

Comparative Example  2

<Preparation of ester type hydroxy-terminated polysiloxane>

A condenser was attached to a 100 mL three-necked flask, and 0.03 mol of 2-allylphenol and 0.015 mol of hydride-terminated polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere. Then, a platinum (0) -1,3-divinyl -1,1,3,3-tetramethyldisiloxane complex) was added thereto and refluxed for 24 hours. After removing the solvent of the reacted solution, it was washed with distilled water. Thus, a hydroxy-terminated polysiloxane (molecular weight: 2,479) represented by the following general formula (9) was prepared.

[Chemical Formula 9]

Next, a condenser was attached to a 500 mL three-necked flask, and 0.4 mol of the compound of formula (9) was dissolved in 300 mL of chloroform under nitrogen atmosphere, and 67 mL of triethylamine (TEA) catalyst was added. A solution obtained by dissolving 0.2 mol terephthaloyl chloride in 1,000 mL of chloroform was added slowly for 1 hour while refluxing the solution, and refluxed for 12 hours. After the solvent of the reaction solution was removed, it was dissolved in acetone and washed with hot distilled water. And dried in a vacuum oven for 24 hours to prepare a hydroxyl-terminated polysiloxane having an ester bond (number average molecular weight: 5,090) represented by the following formula (10). The hydrogen peak of the first carbon of the aliphatic chain adjacent to the terminal phenyl group observed at 2.6 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of benzene ring of the polysiloxane observed at 6.75 to 7.35 ppm It was confirmed that the hydrogen was synthesized by the hydrogen peak of the ring.

[Chemical formula 10]

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

Polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the compound of the formula (10) was used in an amount of 4.5 wt% instead of the ester type hydroxy-terminated polysiloxane of the formula (6). The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and reported in Table 1 below.

Comparative Example  3

&Lt; Preparation of urethane type hydroxy-terminated polysiloxane >

Under nitrogen, 0.0666 mol of the compound of the formula (9) was dissolved in 100 mL of benzene, and then 6.66 mmol of 1,4-diazabicyclo [2.2.2] -octane was added. Under refluxing the above solution, 0.0333 mol of 4,4-methylenebis (phenylisocyanate) dissolved in 200 mL of benzene was added slowly for 1 hour. The above solution was refluxed for 12 hours. The solvent of the reaction solution was removed, dissolved in acetone, and washed with hot distilled water. And dried in a vacuum oven for 24 hours. Thus, a hydroxy-terminated polysiloxane having a urethane bond (molecular weight: 5,210) represented by the following formula (11) was prepared. Hydrogen bonded to the first carbon of the aliphatic chain adjacent to the terminal phenyl group in the following formula (11) was confirmed at 2.75 ppm.

(11)

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

Polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1, except that the compound of Formula 11 was used in an amount of 4.5 wt% instead of the ester-type hydroxy-terminated polysiloxane of Formula 6. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and reported in Table 1 below.

The physical properties of the polysiloxane-polycarbonate copolymer prepared in the above Examples and Comparative Examples are as follows.

(a) H-NMR (nuclear magnetic resonance spectroscope): Measured using Avance DRX 300 from Bruker.

(b) Viscosity average molecular weight (Mv): The viscosity of the methylene chloride solution was measured at 20 占 폚 using a Ubbelohde Viscometer, and the intrinsic viscosity [?] was calculated from the following formula.

^{[η] = 1.23x10 -5 Mv 0} .83

(c) Impact strength: The impact strength was measured at room temperature and -50 캜 using an impact tester (RESIL IMPACTOR from CEAST).

(d) Transmittance: The transmittance was measured using a haze meter (Haze-Gard Plus manufactured by BYK GARDNER).

As shown in Table 1, the polysiloxane-polycarbonate copolymers prepared according to the present invention had excellent low-temperature impact resistance and superior transparency (transmittance 90 %).

Claims (11)

A polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated polysiloxane and a polycarbonate block as repeating units, wherein the hydroxy-terminated polysiloxane is represented by the following formula (1):
[Chemical Formula 1]

In Formula 1,
R ₁ and R ₉ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ , R ₃ and R ₄ each independently represent an unsubstituted or substituted 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 having 3 to 6 carbon atoms, An alkoxy group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms; Or a hydroxy group,
R ₅ , R ₆ , R ₇ and R ₈ each independently represent an unsubstituted or substituted alkylene group having 2 to 20 carbon atoms,
m and r independently represent an integer of 0 to 4,
n1 to n6 each independently represents an integer of 0 to 200,
Provided that at least two of n1 to n3 are not 0, at least one of n4 to n6 is not 0,
a1 to a6 are each independently 0 or 1,
Provided that a1 is 0 if n1 is 0 and a1 is 1 if n1 is not 0; a2 is 0 if n2 is 0, and a2 is 1 if n2 is not 0; a3 is 0 if n3 is 0, and a3 is 1 if n3 is not 0; a4 is 0 if n4 is 0, and a4 is 1 if n4 is not 0; a5 is 0 if n5 is 0, and a5 is 1 if n5 is not 0; a6 is 0 if n6 is 0 and a6 is 1 if n6 is not 0,
A represents a structure represented by the following formula (2).

(2)

In Formula 2,
X is Y or NH-Y-NH, wherein Y is a linear or branched aliphatic group of 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; A cycloalkylene group substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; Or a mononuclear or polycyclic arylene group having 6 to 30 carbon atoms which is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. The polysiloxane-polycarbonate copolymer of claim 1, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of from 900 to 16,000. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the content of the hydroxy-terminated polysiloxane is 1 to 40% by weight based on the total weight of the copolymer. The polysiloxane-polycarbonate copolymer of claim 1, having a viscosity average molecular weight of from 15,000 to 30,000. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the hydroxy-terminated polysiloxane has a symmetrical structure about the linking group A. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the hydroxy-terminated polysiloxane has an asymmetric structure centered on the linking group A. Preparing a polysiloxane-polycarbonate intermediate by mixing a hydroxy-terminated polysiloxane of Formula 1 with an oligomeric polycarbonate and then reacting under an interfacial reaction condition; And polymerizing said intermediate. &Lt; RTI ID = 0.0 &gt; 8. &lt; / RTI &gt; A process for preparing a polysiloxane-polycarbonate copolymer,

[Chemical Formula 1]

In Formula 1,
R ₁ and R ₉ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ , R ₃ and R ₄ each independently represent an unsubstituted or substituted 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 having 3 to 6 carbon atoms, An alkoxy group, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or alkaryloxy group having 7 to 13 carbon atoms; Or a hydroxy group,
R ₅ , R ₆ , R ₇ and R ₈ each independently represent an unsubstituted or substituted alkylene group having 2 to 20 carbon atoms,
m and r independently represent an integer of 0 to 4,
n1 to n6 each independently represents an integer of 0 to 200,
Provided that at least two of n1 to n3 are not 0, at least one of n4 to n6 is not 0,
a1 to a6 are each independently 0 or 1,
Provided that a1 is 0 if n1 is 0 and a1 is 1 if n1 is not 0; a2 is 0 if n2 is 0, and a2 is 1 if n2 is not 0; a3 is 0 if n3 is 0, and a3 is 1 if n3 is not 0; a4 is 0 if n4 is 0, and a4 is 1 if n4 is not 0; a5 is 0 if n5 is 0, and a5 is 1 if n5 is not 0; a6 is 0 if n6 is 0 and a6 is 1 if n6 is not 0,
A represents a structure represented by the following formula (2).

(2)

In Formula 2,
X is Y or NH-Y-NH, wherein Y is a linear or branched aliphatic group of 1 to 20 carbon atoms substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; A cycloalkylene group substituted or unsubstituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group; Or a mononuclear or polycyclic arylene group having 6 to 30 carbon atoms which is unsubstituted or substituted by a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group. The process for preparing a polysiloxane-polycarbonate copolymer according to claim 7, wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000. 8. The process of claim 7, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of from 900 to 16,000. 8. The process of claim 7, wherein the polysiloxane-polycarbonate copolymer produced has a viscosity average molecular weight of from 15,000 to 30,000. A molded article comprising the polysiloxane-polycarbonate copolymer of any one of claims 1 to 6.