KR20180042178A - Polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance, and to a method for preparing the same. More specifically, the present invention relates to a polysiloxane-polycarbonate copolymer which includes polysiloxane having a specific structure with hydroxyphenyl groups at both terminals and polycarbonate blocks as repeating units, and has excellent impact resistance at low temperatures as well as excellent transparency.

Description

TECHNICAL FIELD [0001] The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and low-temperature impact resistance, and a process for producing the polysiloxane-polycarbonate copolymer. The polysiloxane-

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and low-temperature impact resistance and a process for producing the polysiloxane-polycarbonate copolymer. More specifically, the present invention relates to a polysiloxane-polycarbonate copolymer having a hydroxyphenyl group at both terminals, Polycarbonate copolymer having excellent low-temperature impact resistance and excellent transparency, and a method 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-mentioned problems of the prior art, and it is a technical object of the present invention to provide a novel polysiloxane-polycarbonate copolymer having excellent low-temperature impact resistance and excellent transparency.

In order to accomplish the above object, the present invention provides a polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated polysiloxane and a polycarbonate block as recurring units,

[Chemical Formula 1]

In Formula 1,

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

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

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

R ₄ independently represents a divalent hydrocarbon group having 2 to 30 carbon atoms,

L independently represents a divalent linking group selected from a ketone bond, an ester bond, a peptide bond, and combinations thereof,

A represents a divalent polycyclic group,

m is independently an integer of 0 to 4,

n independently represents an integer of 1 to 200;

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.

Since the polysiloxane-polycarbonate copolymer according to the present invention has excellent low-temperature impact resistance and excellent transparency, it is required to provide a molded article which requires both transparency and low-temperature impact resistance (for example, a housing for office equipment and electrical and electronic products, And the like).

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.

In addition, the alphabet "R" used to represent hydrogen, or a non-hydrogen substituent such as a halogen atom and / or a hydrocarbon group in the formulas described in this specification has a subscripted number, but the "R" But are not limited to these subscripts. R "represents, independently of each other, hydrogen, or a non-hydrogen substituent such as 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. Further, when the number of "R" in the formula described in this specification is 0, it means that hydrogen is present at the substitution position.

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

(A) a hydroxy-terminated polysiloxane

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

[Chemical Formula 1]

In Formula 1,

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. More specifically, the halogen atom may be Cl or Br, and the alkyl group may be an alkyl group having 1 to 13 carbon atoms (e.g., methyl, ethyl or propyl), and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms Methoxy, ethoxy or propoxy), and the aryl group may be an aryl group having 6 to 10 carbon atoms (e.g., phenyl, chlorophenyl or tolyl).

R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group. More specifically, R ₂ is an alkyl group or alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, 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 an alkaryloxy group having 7 to 13 carbon atoms.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms. More specifically, R ₃ may be a linear or branched alkylene group having 2 to 8 carbon atoms, and more specifically may be a linear or branched alkylene group having 2 to 6 carbon atoms.

R ₄ independently represents a divalent hydrocarbon group having 2 to 30 carbon atoms. More specifically, R ₄ is a linear or branched alkylene group of 2 to 13 carbon atoms, a linear or branched alkenylene group of 2 to 13 carbon atoms, a cycloalkylene group of 3 to 6 carbon atoms, an arylene group of 6 to 10 carbon atoms, (For example, a divalent hydrocarbon group having an alkylene group having 2 to 13 carbon atoms and an arylene group having 6 to 10 carbon atoms).

L is independently selected from a ketone bond [-C (= O) -], an ester linkage [-C (= O) -O-], a peptide linkage [-C (= O) -NH-] ≪ / RTI > is a divalent linking group. More specifically, L may be an ester linkage, a peptide linkage, or a combination thereof.

A represents a divalent polycyclic group. More specifically, A is a monocyclic group having 2 or more (e.g., 2 to 6, more specifically 2 to 4) monocyclic groups (e.g., an aliphatic monocyclic group having 5 to 8 carbon atoms, an aromatic mono A cyclic group, an aliphatic monoheterocyclic group having 5 to 8 ring atoms, or an aromatic monoheterocyclic group having 5 to 6 ring atoms) may be directly connected or a separate linking group (e.g., alkyl having 1 to 8 carbon atoms Polynuclear polycyclic group (e.g., biphenyl group, bisphenyl group, benzophenone group, phenylbenzoate, phenoxybenzene, etc.) connected through a nitrogen atom, a nitrogen atom, a sulfur atom, Or a fused polycyclic group (e.g., a naphthalene group, anthracene group, benzotriazole group, indine, pentalene, fluorene, etc.) in which two or more of the above monocyclic groups are fused. Here, the monoheterocyclic group may contain 1 to 3 atoms selected from N, O and S (for example, indolin, benzothiophene, benzofuran, etc.). The number of total ring atoms forming the polycyclic structure of A (excluding the number of carbon atoms of the linking group connecting the monocyclic structures) may be, for example, 7 to 36, more specifically 10 to 24 However, the present invention is not limited thereto.

When R ₁ , R ₂ , R ₃ , R ₄ or A can have a substituent, they may be each independently unsubstituted or substituted. (More specifically, an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl, or propyl), an alkoxy group (more specifically, a substituted or unsubstituted alkyl group having 1 to 13 carbon atoms An alkoxy group such as methoxy, ethoxy or propoxy), an aryl group (more specifically, an aryl group having 6 to 10 carbon atoms such as phenyl, chlorophenyl or tolyl), and the like.

In the general formula (1), n is an integer of 1 to 200. More specifically, the lower limit of n may be 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20 and the upper limit of n may be 200, 190, 180, 170, 160, 150, , 120, 110, or 100, but is not limited thereto.

The hydroxy-terminated polysiloxane may have a molecular weight (number average molecular weight, Mn) of preferably 500 to 15,000, more preferably 800 to 12,000, even more preferably 1,200 to 7,000. If the molecular weight of the hydroxyl-terminated polysiloxane is less than 500, the low-temperature impact resistance of the resultant copolymer may be insufficient. If the molecular weight exceeds 15,000, the reactivity becomes poor and the polysiloxane-polycarbonate copolymer may be synthesized at a desired molecular weight .

The content of the hydroxy-terminated polysiloxane in the polysiloxane-polycarbonate copolymer of the present invention is preferably 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.

(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 formula (2).

(2)

In Formula 2,

R ₅ is (alkenyl group, for example, a carbon number of 2 to 13) carbon atoms of 1 to 20 alkyl group (for example, a carbon number of alkyl group of from 1 to 13), a cycloalkyl group (e.g., a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group, an alkoxy group (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 (2a).

(2a)

In the above formula (2a)

X is 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, X is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms and 3 to 6 carbon atoms.

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

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

The compound of formula (2a) 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 by stepwise 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 (3) can be used.

(3)

(R ₇ ) ₄ Q ⁺ Y ^-

In Formula 3, R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Y represents a halogen atom or -OR ₈ . Here, R ₈ 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 NY, [CH 3 (CH 2) 3] 4 PY, [CH 3 (CH 2) 5] 4 NY, [CH 3 _{(CH 2) 6] 4 NY} , [CH 3 (CH 2) 4] 4 NY, CH 3 [CH 3 (CH 2) 3] 3 NY, CH 3 [CH 3 (CH 2) 2] 3 can be NY have. In the above formulas, Y represents Cl, Br or -OR ₈ , wherein R ₈ 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 viscosity average molecular weight (Mv) of the polysiloxane-polycarbonate copolymer according to the present invention may be, for example, from 10,000 to 100,000, and more specifically from 15,000 to 80,000.

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 electrical and 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]

≪ Preparation of hydroxy-terminated polysiloxane >

Example 1

15 g of octamethylcyclotetrasiloxane, 2.5 g of 1,1,3,3-tetramethyldisiloxane, 0.5 g of p-toluenesulfonic acid, Placed in a reactor under nitrogen atmosphere and stirred at 90 < 0 > C for 5 hours. Subsequently, the unreacted material was removed by purifying at 60 캜 under vacuum to obtain a hydrogen-terminated polysiloxane of the following formula (E1-1) (number average molecular weight: about 1,200).

[E1-1]

¹ H-NMR (CDCl ₃ , ppm): 0-0.3 (48, m), 4.71 (1, s).

On the other hand, 3.6 g of acrylic acid (acrylic aicd), 5.7 g of bisphenol A and 0.5 g of H ₂ SO ₄ were added to the reactor and stirred at 130 ° C for 2 hours. Thereafter, the reaction mixture was purified under vacuum at 100 캜 to remove unreacted materials and water to obtain a compound having a double bond of the following formula (E1-2).

[E1-2]

_{^{1 H-NMR (CDCl 3,}} ppm): 1.48 ppm (6H, s), 6.06 ppm (2H, q), 6.36 ppm (2H, q), 6.90ppm (2H, q), 7.15 ppm (4H, q) , 7.38 ppm (4H, q)

Next, 100 g of the hydrogen-terminated polysiloxane of the formula (E1), 9.3 g of the compound of the formula (E2) and 4.0 g of 2-allylphenol were mixed at room temperature for 10 minutes, IPA), 0.5 g of H ₂ PtCl ₆ dissolved therein was added dropwise. After reaction for 3 hours, the reaction product was purified under vacuum at 100 DEG C to obtain a hydroxy-terminated polysiloxane of the following formula (E1). The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E1]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.68 ppm (4H, t), 1.05 ppm (4H, t), 1.48 ppm (6H, 4H, m), 2.67 ppm (2H, m), 6.70 ppm (2H, m), 6.85 ppm m), 7.37 ppm (4H, m)

Example 2

A mixture of 5.0 g of methyl methacrylate, 5.7 g of bisphenol A and 0.5 g of H ₂ SO ₄ was obtained in the same manner as in the preparation of the compound of the formula E1-2 in Example 1, Lt; / RTI >

[E2-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 1.63 ppm (6H, s), 3.02 ppm (4H, , 7.38 ppm (4H, q)

Next, by using 100 g of the hydrogen-terminated polysiloxane of the formula E1-1, 10.7 g of the compound of the formula E2-1 and 4 g of 2-allylphenol, the hydroxy terminal of the following formula E2 was obtained in the same manner as in the preparation of the compound of the formula E1 in Example 1, To obtain a polysiloxane. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E2]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324 H, m), 0.65 ppm (6 H, m), 0.75 ppm (6 H, m), 2.02 ppm (2H, m), 2.33 ppm (4H, d), 2.64 ppm (2H, s), 2.69 ppm , 7.03 ppm (2H, m), 7.11 ppm (4H, m), 7.25 ppm (2H, m), 7.34 ppm (4H,

Example 3

(E3-1) was obtained in the same manner as in the preparation of the compound of the formula (E1-2) in Example 1, except that 8.1 g of 4-allyl-benzoic acid, 5.7 g of bisphenol A and 0.5 g of H ₂ SO ₄ were used. Of a double bond.

[E3-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 3.13 ppm (4H, d), 4.85 ppm (4H, m), 5.68 ppm , 7.38 ppm (8H, q), 7.91 ppm (4H, m)

Next, the same procedure as in the preparation of the compound of the formula (E1) in Example 1 was carried out with 100 g of the hydrogen-terminated polysiloxane of the formula E1-1, 13.8 g of the compound of the formula E3-1 and 4 g of 2-allylphenol, To obtain a polysiloxane. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E3]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324 H, m), 0.67 ppm (8 H, m), 1.48 ppm (6 H, s), 1.68-1.82 ppm (1H, m), 6.70 ppm (1H, m), 6.81 ppm (1H, m), 7.25 ppm (1H, m), 7.34 ppm (1H, d), 7.38 ppm (4H, m), 7.83 ppm (4H,

Example 4

Acrylic acid, 5.65 g of 2,2-bis (4-aminophenyl) propane, and 0.5 g of H ₂ SO ₄ , A compound having a double bond of the following formula (E4-1) was prepared in the same manner as in the preparation of the compound.

[E4-1]

_{^{1 H-NMR (CDCl 3,}} ppm): 1.49 ppm (6H, s), 5.90 ppm (2H, q), 6.25 ppm (2H, q), 6.57 ppm (2H, q), 7.07 ppm (4H, q) , 7.37 ppm (4H, q)

Next, by using 100 g of the hydrogen-terminated polysiloxane of the formula E1-1, 9.2 g of the compound of the formula E4-1, and 4 g of 2-allylphenol, the hydroxy terminal of the following formula E4 was obtained in the same manner as the compound of the formula E1 of Example 1, To obtain a polysiloxane. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E4]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.67 ppm (4H, t), 1.00 ppm (4H, t), 1.48 ppm (6H, m), 7.06 ppm (2H, m), 2.55 ppm (4H, t), 2.69 ppm (4H, t), 6.70 , 7.25 ppm (2H, m), 7.36 ppm (2H, m)

Example 5

Methyl methacrylate 5.0g, 2,2- bis (4-aminophenyl) propane 5.65g, H ₂ SO ₄ using 0.5g, to the same method as the formula E1-2 compound prepared in Example 1 Formula E5- 1 < / RTI >

[E5-1]

_{^{1 H-NMR (CDCl 3,}} ppm): 1.49 ppm (6H, s), 1.65 ppm (6H, s), 3.00 ppm (4H, s), 5.01 ppm (4H, q), 7.07 ppm (4H, q) , 7.36 ppm (4H, q)

Next, by using 100 g of the hydrogen-terminated polysiloxane of the formula E1-1, 10.6 g of the compound of the formula E5-1 and 4 g of 2-allylphenol, the hydroxy terminal of the following formula E5 was obtained in the same manner as the compound of the formula E1 of Example 1, To obtain a polysiloxane. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E5]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.67 ppm (4H, t), 1.08 ppm (6H, d), 1.48 ppm (8H, m), 7.08 ppm (2H, m), 2.45 ppm (4H, d), 2.69 ppm , 7.25 ppm (2H, m), 7.36 ppm (4H, m)

Example 6

4-allyl-benzoic acid 8.1g, 2,2- bis (4-aminophenyl) to the same manner as the formula E1-2 compound prepared in Example 1 using a propane 5.65g, H ₂ SO ₄ 0.5g, formula E6 -1. ≪ / RTI >

[E6-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 3.13 ppm (4H, d), 4.85 ppm (4H, m), 5.67 ppm , 7.35 ppm (4H, m), 7.38 ppm (4H, q), 7.87 ppm (4H, m)

Next, by using 100 g of the hydrogen-terminated polysiloxane of the formula E1-1, 13.7 g of the compound of the formula E6-1 and 4 g of 2-allylphenol, the hydroxy terminal of the following formula E6 was obtained in the same manner as the compound of the formula E1 of Example 1, To obtain a polysiloxane. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[E6]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324 H, m), 0.66 ppm (8 H, m), 1.48 ppm (6 H, m), 6.70 ppm (1H, m), 6.81 ppm (1H, s), 6.86 ppm (1H, , 7.25 ppm (1H, m), 7.34 ppm (1H, d), 7.38 ppm (4H, m), 7.83 ppm (4H,

≪ Preparation of polysiloxane-polycarbonate copolymer >

Example 7

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 were added 4.5 wt% of the hydroxy-terminated polysiloxane of the formula (E1) in Example 1, 1.8 mL of tetrabutyl ammonium chloride (TBACl) dissolved in methylene chloride, 1.8 mL of p-tert-butylphenol (PTBP) and 275 μL of triethylamine (TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. After the reacted oligomeric polycarbonate mixture was layered, only the organic phase was sampled, and 170 g of an aqueous solution of sodium hydroxide, 360 g of methylene chloride and 300 μL of a 15% by weight 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 cleaning 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. H-NMR showed peaks of the methylene group of the polysiloxane observed at 2.6 ppm and 2.65 ppm and hydrogen peaks of the benzene ring of TCL observed at 8.35 ppm and hydrogen peaks of the benzene ring of the polysiloxane observed at 6.95 to 7.5 ppm Respectively. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Examples 8 to 12

Polysiloxane-polycarbonate copolymers were prepared in the same manner as in Example 7 except that 4.5% by weight of the compounds of the formulas E2 to E6 were used as the hydroxy-terminated polysiloxanes in Examples 8 to 12, respectively. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Example 13

Except that a hydrogen-terminated polydimethylsiloxane having a number-average molecular weight of 2,000 of the same skeleton structure was used instead of the compound of the formula E1-1 having a number average molecular weight of 1,200, the hydroxy-terminated polysiloxane prepared in the same manner as in Example 1 was used , And a polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 7. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Example 14

In the same manner as in Example 7, except that 2.78 g of p-tert-butylphenol (PTBP) was changed to 0.78 g and the reaction time was doubled after the first layer separation to react for 4 hours, A polysiloxane-polycarbonate copolymer having a molecular weight of about 70,000 was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Comparative Example 1: Production of direct-bond type hydroxy-terminated polysiloxane

0.03 mol of 2-allylphenol and 0.015 mol of hydrogen-terminated polydimethylsiloxane of the following formula (CE1-1) were completely dissolved in 50 mL of chlorobenzene in a nitrogen atmosphere, and then a platinum (0) - 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added thereto and refluxed for 24 hours. The solvent in the reacted solution was removed and washed with distilled water to prepare a hydroxy-terminated polysiloxane of the following formula (CE1). The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[Formula (CE1-1)

≪ RTI ID = 0.0 &

Comparative Example 2: Preparation of a hydroxy-terminated polysiloxane having a phenyl diester linkage group

0.03 mol of 2-allylphenol and 0.015 mol of hydrogen-terminated polydimethylsiloxane of formula (E1-1) were completely dissolved in 50 mL of chlorobenzene under a nitrogen atmosphere, and a platinum (0) -1 , 3-divinyl-1,1,3,3-tetramethyldisiloxane complex) were added and refluxed for 24 hours. The solvent in the reacted solution was removed and washed with distilled water to prepare a hydroxy-terminated polysiloxane of the following formula (CE2-1).

[Chemical formula (CE2-1)

Next, a condenser was attached to a 500 mL three-necked flask, and 0.4 mol of the compound of the formula (CE2-1) was dissolved in 300 mL of chloroform under nitrogen atmosphere, and then 67 mL of triethylamine (TEA) was added. After 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform while the solution was being refluxed, it was added slowly for 1 hour 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. The hydroxy-terminated polysiloxane of formula CE2 was prepared by drying in a vacuum oven for 24 hours. The hydrogen peak of the methylene group of the polysiloxane 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 6.75 to 7.35 ppm . The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[Formula CE2]

Comparative Example 3: Preparation of a hydroxy-terminated polysiloxane having a bisphenyl diurethane linkage group

Under nitrogen, 0.0666 mol of the compound of formula CE2-1 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. 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 hydroxy-terminated polysiloxane of the following formula (CE3). Hydrogen bonded to the first carbon of the aliphatic chain adjacent to the terminal phenyl group in the following formula (CE3) was confirmed at 2.75 ppm. The physical properties of the hydroxy-terminated polysiloxane were measured and reported in Table 1 below.

[Formula CE3]

Comparative Examples 4 to 6

Polysiloxane-polycarbonate copolymers were prepared in the same manner as in Example 7 except that 4.5% by weight of the compounds of the formulas CE1 to CE3 were used as the hydroxy-terminated polysiloxanes in Comparative Examples 4 to 6. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

As can be seen from the above Table 1, the hydroxy-terminated siloxanes prepared according to the examples of the present invention showed an overall excellent yield as compared with those prepared according to the comparative examples. Also, as can be seen from Table 2, the polysiloxane-polycarbonate copolymers prepared according to the examples of the present invention exhibited excellent low-temperature impact resistance and transparency as compared with those prepared according to the comparative examples.

The physical properties evaluation methods shown in Tables 1 and 2 are as follows.

(a) 1H-NMR (Nuclear Magnetic Resonance Spectrometer): Measured using Avance DRX 300 from Bruker.

(b) Yield: [actually synthesized compound weight (g) / theoretical composite weight (g)] * 100%

(c) 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.

[?] = 1.23 x 10 ^-5 Mv ^0.83

(d) Impact strength: The impact strength was measured at room temperature and low temperature (-60 ° C) using an impact tester (RESIL IMPACTOR manufactured by CEAST). The low temperature impact resistance was evaluated as follows.

[Ductile: Excellent impact resistance at low temperatures. Brittle: poor impact resistance at low temperature]

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

Claims (14)

Polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated polysiloxane of the following formula (1) and a polycarbonate block as repeating units:
[Chemical Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a divalent hydrocarbon group of 2 to 30 carbon atoms,
L independently represents a divalent linking group selected from a ketone bond, an ester bond, a peptide bond and a combination thereof,
A represents a divalent polycyclic group,
m is independently an integer of 0 to 4,
n independently represents an integer of 1 to 200; The polysiloxane-polycarbonate copolymer according to claim 1, wherein R ₃ is independently a linear or branched alkylene group having 2 to 6 carbon atoms. The compound according to claim 1, wherein R ₄ is independently a linear or branched alkylene group having 2 to 13 carbon atoms, a linear or branched alkenylene group having 2 to 13 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, An arylene group having 1 to 10 carbon atoms, or a combination thereof. The polysiloxane-polycarbonate copolymer of claim 1, wherein L is independently an ester bond, a peptide bond or a combination thereof. The compound according to claim 1, wherein A is a polynuclear polycyclic group in which two or more monocyclic groups are directly connected to each other or connected via a separate linkage; Or a fused polycyclic group in which two or more monocyclic groups are fused. 6. The compound according to claim 5, wherein the monocyclic group is independently selected from the group consisting of an aliphatic monocyclic group having 5 to 8 carbon atoms, an aromatic monocyclic group having 6 carbon atoms, an aliphatic monoheterocyclic group having 5 to 8 ring atoms, Is an aromatic monoheterocyclic group having 5 to 6 carbon atoms. The polysiloxane-polycarbonate copolymer of claim 1, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of from 500 to 15,000. 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 10,000 to 100,000. 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. ≪ RTI ID = 0.0 > 8. < / RTI > A process for preparing a polysiloxane-polycarbonate copolymer,
[Chemical Formula 1]

In Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₂ independently represents a hydrocarbon group having 1 to 13 carbon atoms or a hydroxy group,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a divalent hydrocarbon group of 2 to 30 carbon atoms,
L independently represents a divalent linking group selected from a ketone bond, an ester bond, a peptide bond and a combination thereof,
A represents a divalent polycyclic group,
m is independently an integer of 0 to 4,
n independently represents an integer of 1 to 200; The process for preparing a polysiloxane-polycarbonate copolymer according to claim 10, wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000. The process for preparing a polysiloxane-polycarbonate copolymer according to claim 10, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of 500 to 15,000. 11. The process of claim 10, wherein the polysiloxane-polycarbonate copolymer produced has a viscosity average molecular weight of 10,000 to 100,000. A molded article comprising the polysiloxane-polycarbonate copolymer of any one of claims 1 to 9.