WO2013176349A1 - Novel polysiloxane, method for preparing same and polycarbonate-polysiloxane copolymer comprising same - Google Patents

Abstract

The present invention relates to novel polysiloxane, to a method for preparing same and to a polycarbonate-polysiloxane copolymer comprising same. The polysiloxane is represented by the chemical formula 1 of Claim 1. The polysiloxane has an end group with reduced electron density, thus improving low temperature shock resistance and yellowness index.

Description

Novel polysiloxanes, preparation methods thereof and polycarbonate-polysiloxane copolymers comprising the same

The present invention relates to novel polysiloxanes, methods for their preparation and polycarbonate-polysiloxane copolymers comprising the same. More specifically, the present invention relates to a novel polysiloxane having improved low temperature impact resistance and yellowness index by applying an end group having a reduced electron density, a preparation method thereof, and a polycarbonate-polysiloxane copolymer including the same.

Polycarbonate is a thermoplastic resin having an aromatic polycarbonate ester bond, and is excellent in mechanical properties, self-extinguishing, dimensional stability, heat resistance, and the like, and is a representative engineering plastic that has an increasing range of applications such as electrical and electronic product exterior materials and automotive parts. In recent years, the use of such polycarbonate has been further expanded, many researches for improving the properties of the polycarbonate for various applications. In particular, many examples of the study on the copolymerization method using two or more different structures of diol and a method of controlling various properties by including a polymer having a different structure in the polycarbonate backbone have been reported.

Japanese Patent No. 3350617 discloses a silicone-polycarbonate block copolymer having a polydiorganosiloxane in which 10 to 100 diorganosiloxy units are chemically bonded. Japanese Patent No. 3337040 discloses a polycarbonate-polyorganosiloxane copolymer (AB type block copolymer) having excellent release properties, impact resistance, and the like obtained by copolymerizing polycarbonate and polyorganosiloxane having an alkyl group or an aryl group at one end thereof. have. Korean Unexamined Patent Publication No. 10-2007-0071446 discloses a polycarbonate resin composition which includes a polyether sulfone resin and a core-shell type impact reinforcing material in a polycarbonate resin and improves chemical resistance and heat resistance while maintaining impact resistance. , Korean Patent Laid-Open Publication No. 10-2009-0035031, which includes chemical resistances including polycarbonate terpolymers comprising structures derived from at least three different dihydroxy groups, strength enhancers and grafted hard copolymers. And thermoplastic compositions having improved scratch resistance.

Particularly, polycarbonate-polysiloxane copolymers in which eugenol polysiloxane disclosed in US Pat. There is a disadvantage that it is easy to increase the yellowness index of the copolymer by increasing oxidation of the aromatic ring.

It is an object of the present invention to provide a novel polysiloxane, a method for producing the same, and a polycarbonate-polysiloxane copolymer including the same, which is excellent in low temperature impact resistance and can improve yellowness index.

Another object of the present invention is to provide a novel polysiloxane having excellent physical properties such as heat resistance, impact resistance, transparency, moldability, appearance and the like, a method for preparing the same, and a polycarbonate-polysiloxane copolymer comprising the same.

Still another object of the present invention is to provide a method for preparing the polycarbonate-polysiloxane copolymer.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the invention relates to polysiloxanes. The polysiloxane is represented by the following formula (1):

[Formula 1]

(In Formula 1, R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen or alkoxy group, A and B is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, and Z is a substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon group including an ester group, an ester bond, a urethane bond, or a combination thereof, and each Y independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group, Or an ester group, m and n each independently represent an integer of 4 to 100).

In an embodiment, the polysiloxane may be represented by Formula 2:

[Formula 2]

(In Formula 2, R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in Formula 1).

Another aspect of the present invention relates to a method for producing the polysiloxane. The preparation method includes preparing a polysiloxane represented by Chemical Formula 1 by reacting a monohydroxysiloxane represented by Chemical Formula 6 with a diene:

[Formula 6]

(In Formula 6, R ₁ , R ₂ , A, Y and m are as defined in Formula 1).

In an embodiment, the monohydroxysiloxane represented by Formula 6 may be prepared by reacting a siloxane terminated with a hydride represented by Formula 4 with a phenol derivative represented by Formula 5:

[Formula 4]

(In Formula 4, R ₁ , R ₂ and m are as defined in Formula 1);

[Formula 5]

(In Formula 5, Y is as defined in Formula 1, D is a substituted or unsubstituted C2-C20 hydrocarbon group having a double bond, or a terminal having a -O- or -S- is a double bond Substituted or unsubstituted C2-C20 hydrocarbon group.

Another aspect of the invention relates to a polycarbonate-polysiloxane copolymer comprising the polysiloxane. The polycarbonate-polysiloxane copolymer includes a polysiloxane unit represented by Formula 7:

[Formula 7]

(In Chemical Formula 7, R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in Chemical Formula 1, and * is a polycarbonate unit linking group).

In an embodiment, the polysiloxane units may be included in an amount of 0.1 to 20% by weight in the main chain of the polycarbonate-polysiloxane copolymer.

Another aspect of the present invention relates to a method for producing the polycarbonate-polysiloxane copolymer. The preparation method includes polymerizing a polysiloxane, an aromatic dihydroxy compound, and a phosgene-based compound represented by Chemical Formula 1.

In an embodiment, the aromatic dihydroxy compound may be an aromatic dihydroxy compound represented by Formula 8 below:

[Formula 8]

(In Formula 8, A ₁ is a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted C1-C5 alkylidene group, a substituted or unsubstituted C3-C6 cycloalkylene group, A substituted or unsubstituted C5-C6 cycloalkylidene group, -CO-, -S-, or -SO _2- , R ₃ and R ₄ are each independently a substituted or unsubstituted C1-C30 alkyl group, or A substituted or unsubstituted C6-C30 aryl group, a and b each independently represent an integer of 0 to 4).

The present invention is excellent in low-temperature impact resistance, yellowness index can be improved by introducing a polysiloxane having a new terminal functional group which can have an effect on improving the yellowness in the polycarbonate-polysiloxane copolymer, The present invention has the effect of providing a novel polysiloxane having excellent physical properties such as impact resistance, transparency, moldability, appearance, a preparation method thereof, and a polycarbonate-polysiloxane copolymer including the same.

1 is an NMR spectrum of polysiloxane prepared according to Example 1 of the present invention.

2 is an NMR spectrum of polysiloxane prepared according to Example 2 of the present invention.

3 is an NMR spectrum of a polycarbonate-polysiloxane copolymer prepared according to Example 3 of the present invention.

Hereinafter, the present invention will be described in detail.

Polysiloxane according to the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently C1-C10 (C1-10) alkyl group, C6-C18 aryl group, or C1-C10 alkyl group having a halogen or alkoxy group or C6-C18 aryl Group, preferably an alkyl group of C1-C6, more preferably an alkyl group of C1-C3, for example a methyl group.

In the context of the present invention, an "alkyl group" includes a linear or branched alkyl group.

A and B are each independently a substituted or unsubstituted C2-C20 (divalent) hydrocarbon group, or a substituted or unsubstituted C2-C20 (divalent) hydrocarbon group having -O- or -S-. For example, a substituted or unsubstituted C2-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, or a substituted or unsubstituted C2-C20 alkylene group having -O- or -S- or A substituted or unsubstituted C6-C20 arylene group, preferably a C2-C10 alkylene group, more preferably a C2-C6 alkylene group, most preferably a propylene group.

In the context of the present invention, "hydrocarbon group" means a linear, branched or cyclic saturated or unsaturated hydrocarbon group. In addition, in the specification of the present invention, "substituted" means that the hydrogen atom is substituted by substituents such as an alkyl group of C1-C10, an aryl group of C6-C18, halogen, a combination thereof and the like. The substituent may be preferably an alkyl group of C1-C6, more preferably an alkyl group of C1-C3.

Z is a substituted or unsubstituted C1-C24 (divalent) hydrocarbon group, or a substituted or unsubstituted C1-C24 (divalent) hydrocarbon group including an ester bond, a urethane bond, or a combination thereof. For example, substituted or unsubstituted C4-C24 alkylene group, substituted or unsubstituted C10-C24 cycloalkylene group, or substituted or unsubstituted, with or without ester bonds, urethane bonds, or combinations thereof. A substituted or unsubstituted C4-C14 alkylene group, a substituted or unsubstituted C10-C14 cycloalkyl, with or without a C10-C24 arylene group, preferably an ester bond, a urethane bond, or a combination thereof Or a substituted or unsubstituted C10-C14 arylene group.

In the Si—Z—Si bond of the formula of the present invention, Si may be bonded to the Z group itself or to a substituent of Z.

Each independently represents a hydrogen atom, a halogen, a C1-C18 halogenated alkyl group, a cyano group (-CN), or an ester group, preferably a hydrogen atom, a cyano group (-CN), or an ester group, more preferably It is a hydrogen atom.

In the present invention, Y may be present in 1 to 4, preferably 1 to 2, in each benzene moiety.

m and n are each independently an integer of 4 to 100, preferably an integer of 10 to 50, more preferably an integer of 20 to 40. For example, m + n can be an integer from 10 to 100.

The polysiloxane according to the present invention has a structure in which a functional group including an alkyl group, an aryl group, a cycloalkyl group, or the like, with or without an ester bond, a urethane bond, or the like is added between the siloxane blocks. In addition, the siloxane block includes a hydroxyl group terminal capable of polymerizing with a polymer such as polycarbonate, polyester, polyphosphonate, and the like. Therefore, it can be used as a siloxane monomer for the production of siloxane-polymer polymers, functional groups such as alkyl groups, aryl groups, cycloalkyl groups or the like in condensed polymers such as polycarbonate resins, polyester resins, polyphosphonates or the like It may be possible to tune the properties of the siloxane-polymer copolymer derived from the addition structure or to add new physical properties. That is, the polysiloxane according to the present invention can contribute to the expression of new physical properties or improvement of existing physical properties as a monomer of the siloxane-polymer polymer. The physical properties may include, but are not limited to, heat resistance, hydrolysis resistance, chemical resistance, (low temperature) impact resistance, flame retardancy, and the like.

In particular, when using eugenol-type end groups in polysiloxanes, methoxy groups (MeO-) of eugenol increase electron density to promote oxidation of aromatic rings and to promote yellowing. On the other hand, the end groups of the polysiloxane according to the present invention can reduce the electron density and inhibit oxidation of the aromatic ring, thereby improving yellowness.

In one embodiment, the polysiloxane represented by Chemical Formula 1 may be represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in Formula 1.

Specific examples of the polysiloxane represented by Chemical Formula 2 may include polysiloxanes represented by the following Chemical Formula 3, but are not limited thereto.

[Formula 3]

In Formula 3, m and n are as defined in Formula 1.

In the method for preparing polysiloxane according to an embodiment of the present invention, for example, preparing a polysiloxane represented by Chemical Formula 1 by reacting a monohydroxysiloxane represented by Chemical Formula 6 with a diene (second step) ) May be included. Here, the monohydroxysiloxane represented by Formula 6 may be prepared by reacting a siloxane terminated with a hydride represented by Formula 4 with a phenol derivative represented by Formula 5 below (first step).

[Formula 4]

In Formula 4, R ₁ , R ₂ and m are as defined in Formula 1.

[Formula 5]

In Chemical Formula 5, Y is as defined in Chemical Formula 1, D is a substituted or unsubstituted C2-C20 hydrocarbon group having a double bond, or a substituent having a double bond having a terminal having -O- or -S-. Or an unsubstituted C2-C20 hydrocarbon group. For example, a substituted or unsubstituted C2-C20 alkyl group whose terminal is a double bond, a substituted or unsubstituted C6-C20 aryl group whose terminal is a double bond, or a terminal having -O- or -S- is double A substituted or unsubstituted C2-C20 alkyl group which is a bond or a substituted or unsubstituted C6-C20 aryl group whose terminal is a double bond, preferably a C2-C10 alkyl group whose terminal is a double bond, more preferably An alkyl group of C2-C6 which is a double bond, most preferably an allyl group. Here, D of the phenol derivative may react with siloxane terminated with hydride to form A of monohydroxysiloxane represented by the formula (6).

[Formula 6]

In Formula 6, R ₁ , R ₂ , A, Y and m are as defined in Formula 1.

Here, as the compounds represented by Formulas 4 to 6, two or more compounds having different R ₁ , R ₂ , A, D, Y, and m may be used, respectively, and A, m, etc. may be different from the above Formula 6 The compound represented may represent A, B, m, n, etc. of the compound represented by Chemical Formula 1 by reacting with a diene.

In one embodiment, the hydroxyl group (-OH) groups of Formula 5 and 6 may be bonded to the position 2 of the benzene moiety.

First step

The first step is a step of synthesizing the monohydroxysiloxane represented by Chemical Formula 6 by reacting the siloxane terminated with the hydride represented by Chemical Formula 4 and the phenol derivative represented by Chemical Formula 5 in the presence of a catalyst.

As the catalyst, a catalyst containing platinum may be used. For example, the catalyst may be a platinum element itself or a compound containing platinum, preferably, H ₂ PtCl ₆ , Pt ₂ [(CH ₂ = CH) Me ₂ Si] ₂ O ₃ , Rh [(cod ) ₂ ] BF ₄ , Rh (PPh ₃ ) ₄ Cl, Pt / C and the like can be used alone or in combination, but is not limited thereto. More preferably, Pt / C, for example 10% Pt / C can be used. The amount of the catalyst used may be, for example, 10 to 500 ppm, preferably 50 to 150 ppm with respect to the whole reactant.

The reaction may be performed in an organic solvent, and examples of the organic solvent may include, but are not limited to, 1,2-dichloroethane, toluene, xylene, dichlorobenzene, mixed solvents thereof, and the like. Preferably in toluene.

The reaction may control the reaction temperature and reaction time according to the reactivity of the reactants (Formula 4 and Formula 5). For example, the reaction may be carried out at a reaction temperature of 60 to 140 ℃, preferably 110 to 120 ℃, 2 to 12 hours, preferably 3 to 5 hours.

The compound of formula 4 prepared in the first step may be purified and used in the next step or in situ in the next step without further purification.

2nd step

The second step is to prepare a polysiloxane represented by Chemical Formula 1 by reacting the monohydroxysiloxane represented by Chemical Formula 6 with a diene.

The diene may react with the compound represented by Chemical Formula 6 to represent Z in Chemical Formula 1, and a non-limiting example of the diene may be substituted or unsubstituted C1-C24 having a double bond at both ends. And a hydrocarbon group or both terminals are double bonds, and examples of a substituted or unsubstituted C1-C24 hydrocarbon group including an ester bond, a urethane bond, or a combination thereof can be exemplified. Substituted or unsubstituted C4-C24 linear or branched saturated or unsaturated hydrocarbon groups, substituted or unsubstituted C10-C24 cyclic saturation, with or without ester bonds, urethane bonds, or combinations thereof A substituted or unsubstituted unsaturated hydrocarbon group, preferably at both ends with a double bond and with or without ester bonds, urethane bonds or combinations thereof C4-C14 may be a linear or a date saturated or unsaturated hydrocarbon group, a substituted or unsubstituted, saturated or unsaturated hydrocarbon ring of the C10-C14 ring topography.

For example, after completing the first step, the polysiloxane represented by Chemical Formula 1 may be prepared by reacting in situ by adding the diene without purifying the monohydroxysiloxane represented by Chemical Formula 6. .

In the reaction of monohydroxyarylsiloxane and diene, the reaction temperature and reaction time can be appropriately controlled. For example, the reaction temperature and reaction time used in the first step may be used as it is, but is not limited thereto.

The polysiloxane prepared can be purified and obtained through conventional methods. For example, after the completion of the second step, the reaction product is filtered to remove the catalyst, and the obtained filtrate is concentrated to remove the reaction solvent and the by-product of low molecular weight, thereby obtaining the polysiloxane represented by Chemical Formula 1. Depending on the purity of the polysiloxane, further purification may be carried out.

The polycarbonate-polysiloxane copolymer according to the present invention includes a polysiloxane unit represented by the following formula (7).

[Formula 7]

In Formula 7, R ₁ , R ₂ , A, B, Z, Y, m, and n are as defined in Formula 1, and * is a polycarbonate unit linking group.

The polysiloxane unit is included in the main chain of the polycarbonate-polysiloxane copolymer, for example, 0.1 to 20% by weight, preferably 5 to 15% by weight. The low temperature impact resistance is excellent in the above range, the yellowness index (YI) can be improved.

The polycarbonate-polysiloxane copolymer, for example, based on the silicon content of 1 to 4% by weight, has a haze of 11 mm or less, preferably 0.1 to 10.5%, more preferably 1 to 3% of a 2.5 mm thick specimen. Can be.

The weight average molecular weight of the polycarbonate-polysiloxane copolymer may be, for example, 8,000 to 100,000 g / mol, but is not limited thereto.

The polycarbonate-polysiloxane copolymer may be prepared by, for example, polymerizing a polysiloxane represented by Chemical Formula 1, an aromatic dihydroxy compound, for example, an aromatic dihydroxy compound and a phosgene-based compound represented by Chemical Formula 8 below. Can be.

[Formula 8]

In Formula 8, A ₁ is a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted C1-C5 alkylidene group, a substituted or unsubstituted C3-C6 cycloalkylene group, substituted Or an unsubstituted C5-C6 cycloalkylidene group, -CO-, -S-, or -SO _2- , each of R ₃ and R ₄ is independently a substituted or unsubstituted C1-C30 alkyl group, or a substitution Or an unsubstituted C6-C30 aryl group, a and b are each independently an integer of 0 to 4.

Here, the substitution is a hydrogen atom of a halogen group, C1-C30 alkyl group, C1-C30 haloalkyl group, C6-C30 aryl group, C2-C30 heteroaryl group, C1-C20 alkoxy group, a combination thereof Mean substituted by a substituent.

Specific examples of the aromatic dihydroxy compound include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl ) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane etc. can be illustrated. Preferably, as the aromatic dihydroxy compound, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, or 1,1-bis- (4-hydroxyphenyl) -cyclohexane can be used, and more preferably 2,2-bis- (4-hydroxyphenyl) -propane also called bisphenol-A can be used.

With respect to 100 parts by weight of the polysiloxane and aromatic dihydroxy compound represented by the formula (1), the content of the polysiloxane represented by the formula (1) is, for example, 0.1 to 20 parts by weight, preferably 5 to 15 parts by weight, The content of the aromatic dihydroxy compound is, for example, 80 to 99.9 parts by weight, preferably 85 to 95 parts by weight. The low temperature impact resistance is excellent in the above range, the yellowness index (YI) can be improved.

As the phosgene-based compound used in the present invention, for example, phosgene, triphosgene, diphosgene, and the like can be exemplified, and the amount of the phosgene-based compound is the same as that of the conventional polycarbonate-polysiloxane copolymer. Can be used, but is not limited thereto.

In a specific embodiment, in the method for preparing the polycarbonate-polysiloxane copolymer, an aromatic dihydroxy compound is added to an aqueous basic solution, an organic solvent, polysiloxane represented by Formula 1 is added and mixed, and a phosgene-based compound is added. It can be prepared by interfacial polymerization. By applying the interfacial polymerization in this way, it is possible to secure remarkably excellent transparency compared to the melt polymerization.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Example 1: Preparation of Polysiloxanes

344.5 g (1.16 mol) of octamethylcyclotetrasilane, 52.0 g (0.375 mol) of tetramethyldisilane and 500.0 ml of trifluoromethanesulfonic acid were added to the reaction vessel and stirred at 25 ° C for 24 hours. 14 g of MgO was added and stirred for 1 hour. The stirred reaction product was filtered, and then unreacted material was removed under high temperature vacuum to obtain 300 g of oligodimethylsiloxane. 300 g of the oligodimethylsiloxane and 0.5 g of Pt / C were added to 270 ml of toluene, followed by stirring and heating to 110 ° C. Next, a mixture solution of 28.2 g (0.21 mol) of 2-allylphenol and 30 ml of toluene was slowly added dropwise. After 2-allylphenol was added dropwise, 9 g (0.11 mol) of 1,5-hexadiene was added dropwise, stirred at 110 ° C for 1 hour, and then cooled to 25 ° C. After the reaction was filtered, the unreacted material was removed under a high temperature vacuum to obtain 320 g of polysiloxane A represented by the following Chemical Formula 3a in an oil state. The NMR (Briker AVANCE III & Ultrashield Magnet, 300 MHz) spectrum of the prepared polysiloxane is shown in FIG. 1.

[Formula 3a]

(In Formula 3a, m + n is 40)

Example 2: Preparation of Polysiloxanes

Instead of 52.0 g (0.375 mol) of tetramethyldisilane, except that 26.0 g (0.129 mol) of tetramethyldisilane was used in the same manner as in Preparation Example 1, polysiloxane B represented by the following Chemical Formula 3b in an oil state 290 g were obtained. The NMR (Briker AVANCE III & Ultrashield Magnet, 300 MHz) spectrum of the prepared polysiloxane is shown in FIG. 2.

[Formula 3b]

(In Formula 3b, m + n is 60)

Example 3: Preparation of Polycarbonate-Polysiloxane Copolymer

To a glass stirred reactor was added 7,000 ml of H ₂ O, 2,000 ml of 50% NaOH aqueous solution, and 1,500 g (6570.6 mmol) of 2,2-bis (4-hydroxyphenyl) propane (BPA), followed by vigorous stirring and solution temperature Stir for 1 hour while maintaining at 20-25 ° C. To this was added 41.5 g (275.9 mmol) of t-butyl phenol, 3000 ml of methylene chloride, and 112.4 g (34.2 mmol) of the above polysiloxane A (Example 1), followed by dissolving 974.91 g (9855.9 mmol) of triphosgene. 3,000 ml of methylene chloride solution was slowly added to the reactor for 1 hour and stirred for 1 hour while maintaining the solution temperature at 20-25 ° C. 7.8 g (77.1 mmol) of triethylethylamine were added thereto, and the mixture was stirred for 2 hours while maintaining the solution temperature at 30 to 35 ° C. After stirring was complete, the organic layer was separated, neutralized by addition of 7,000 ml of 10% HCl solution, and then washed several times with water until the pH reached neutral. After washing, the solvent of the organic layer was lowered and dried using a trimixer (manufacturer: Inoue Co., Ltd., TX-15) to obtain a polycarbonate-polysiloxane copolymer in a powder state. As a result of DOSY (Diffusion Ordered Spectroscopy) analysis of the obtained copolymer, it was confirmed that polysiloxane was present in the main chain of polycarbonate. Si content was 2.1% by weight by 1 H NMR. The weight average molecular weight (Mw) of the GPC analysis was 20,846 g / mol. The NMR (Briker AVANCE III & Ultrashield Magnet, 300 MHz) spectrum of the prepared polycarbonate-polysiloxane copolymer is shown in FIG. 3.

Example 4: Preparation of Polycarbonate-Polysiloxane Copolymer

A polycarbonate-polysiloxane copolymer in a powdered state was obtained in the same manner as in Example 3, except that 109.9 g (26.3 mmol) of Polysiloxane B (Example 2) was used instead of the Polysiloxane A. DOSY analysis of the obtained copolymer confirmed that the siloxane polymer was present in the main chain of the polycarbonate, and the Si content was 2.1% by weight based on 1H NMR analysis. The weight average molecular weight (Mw) of the GPC analysis was 20,235 g / mol.

Comparative Example 1: Preparation of Polycarbonate-Polysiloxane Copolymer

A polycarbonate-polysiloxane copolymer in a powdered state was obtained in the same manner as in Example 3, except that 114.5 g (34.2 mmol) of the polysiloxane C represented by the following Formula 9a was used instead of the polysiloxane A. DOSY analysis of the obtained copolymer confirmed that the siloxane polymer was present in the main chain of polycarbonate, and the Si content was 2.1% by weight based on 1H NMR analysis. GPC analysis showed a weight average molecular weight (Mw) of 20,750 g / mol.

[Formula 9a]

(In Formula 9a, m + n is 40.)

Comparative Example 2: Preparation of Polycarbonate-Polysiloxane Copolymer

A polycarbonate-polysiloxane copolymer in a powdered state was obtained in the same manner as in Example 3, except that 110.1 g (22.8 mmol) of the polysiloxane D represented by the following Formula 9b was used instead of the polysiloxane A. DOSY analysis of the obtained copolymer confirmed that the siloxane polymer was present in the main chain of polycarbonate, and the Si content was 2.0% by weight based on 1H NMR analysis. GPC analysis showed a weight average molecular weight (Mw) of 20,142 g / mol.

[Formula 9b]

(In Formula 9b, m + n is 60.)

Property measurement method

The copolymers prepared in Examples 3 and 4 and Comparative Examples 1 and 2 were dried at 120 ° C. for 4 hours, and then 10 Oz. The injection molding machine was injected under molding conditions of 270 to 290 ° C. and a mold temperature of 70 ° C. to prepare specimens having a thickness of 2.5 mm.

(1) Yellowness Index (YI) Evaluation: YI was measured on a 2.5 mm thick specimen using a spectrophotometer (CM-3600d) manufactured by KONIKA MINOLTA.

(2) Haze (%) and Permeability (%) Evaluation: Haze and permeability were measured on a 2.5 mm thick specimen using a Haze Meter (NDH-5000) manufactured by NIPPON DENSHOKU.

Table 1

	Si No.	Si content (wt%)	Molecular Weight (Mw)	YI	Haze (%)	Permeability (%)
Example 3	40	2.1	20,846	20.8	1.8	85.8
Example 4	60	2.1	20,235	16.7	2.5	83.8
Comparative Example 1	40	2.1	20,750	31.7	1.8	82.8
Comparative Example 2	60	2.0	20,142	32.1	4.2	81.3

From the results in Table 1, polycarbonate-polysiloxane copolymers (Examples 3 and 4) prepared from polysiloxanes (Examples 1 and 2) containing terminal groups according to the present invention are eugenol type Compared to the polycarbonate-polysiloxane copolymers (Comparative Examples 1 and 2) prepared from polysiloxanes containing short-term, it can be seen that the yellowness (YI) is significantly improved and the permeability is excellent. In addition, in the case of Example 4 having a high silicon number (m + n), it can be seen that the haze was remarkably reduced as compared with Comparative Example 2.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

1. Polysiloxane represented by the following formula (1):

   [Formula 1]

   

   (In Formula 1, R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen or alkoxy group, A and B is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, and Z is a substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon group including an ester group, an ester bond, a urethane bond, or a combination thereof, and each Y independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group, Or an ester group, m and n each independently represent an integer of 4 to 100).
2. The polysiloxane according to claim 1, wherein the polysiloxane is represented by the following Chemical Formula 2:

   [Formula 2]

   

   (In Formula 2, R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in Formula 1).
3. A method for producing polysiloxane, comprising the step of reacting a monohydroxysiloxane represented by Formula 6 with a diene to produce a polysiloxane represented by Formula 1 below:

   [Formula 1]

   

   (In Formula 1, R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen or alkoxy group, A and B is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, and Z is a substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon group including an ester group, an ester bond, a urethane bond, or a combination thereof, and each Y independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group, Or an ester group, m and n are each independently an integer of 4 to 100;

   [Formula 6]

   

   (In Formula 6, R ₁ , R ₂ , A, Y and m are as defined in Formula 1).
4. The polycarbonate of claim 3, wherein the monohydroxysiloxane represented by Chemical Formula 6 is prepared by reacting a siloxane terminated with a hydride represented by Chemical Formula 4 with a phenol derivative represented by Chemical Formula 5. Polysiloxane copolymer:

   [Formula 4]

   

   (In Formula 4, R ₁ , R ₂ and m are as defined in Formula 1);

   [Formula 5]

   

   (In Formula 5, Y is as defined in Formula 1, D is a substituted or unsubstituted C2-C20 hydrocarbon group having a double bond, or a terminal having a -O- or -S- is a double bond Substituted or unsubstituted C2-C20 hydrocarbon group.
5. A polycarbonate-polysiloxane copolymer comprising a polysiloxane unit represented by the following general formula (7):

   [Formula 7]

   

   (In Formula 7, R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen or alkoxy group, A and B is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, and Z is a substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon group including an ester group, an ester bond, a urethane bond, or a combination thereof, and each Y independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group, Or an ester group, m and n each independently represent an integer of 4 to 100, and * is a polycarbonate unit linking group.
6. The polycarbonate-polysiloxane copolymer according to claim 5, wherein the polysiloxane unit is included in the main chain of the polycarbonate-polysiloxane copolymer in an amount of 0.1 to 20 wt%.
7. Method for producing a polycarbonate-polysiloxane copolymer comprising the step of polymerizing a polysiloxane, an aromatic dihydroxy compound, and a phosgene-based compound represented by the formula (1):

   [Formula 1]

   

   (In Formula 1, R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group, or a C1-C10 alkyl group or a C6-C18 aryl group having a halogen or alkoxy group, A and B is each independently a substituted or unsubstituted C2-C20 hydrocarbon group, or a substituted or unsubstituted C2-C20 hydrocarbon group having -O- or -S-, and Z is a substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon group including an ester group, an ester bond, a urethane bond, or a combination thereof, and each Y independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group, Or an ester group, m and n each independently represent an integer of 4 to 100).
8. 8. The method of claim 7, wherein the aromatic dihydroxy compound is represented by the following Chemical Formula 8.

   [Formula 8]

   

   (In Formula 8, A ₁ is a single bond, a substituted or unsubstituted C1-C5 alkylene group, a substituted or unsubstituted C1-C5 alkylidene group, a substituted or unsubstituted C3-C6 cycloalkylene group, A substituted or unsubstituted C5-C6 cycloalkylidene group, -CO-, -S-, or -SO _2- , R ₃ and R ₄ are each independently a substituted or unsubstituted C1-C30 alkyl group, or A substituted or unsubstituted C6-C30 aryl group, a and b each independently represent an integer of 0 to 4).

Images