KR20140086772A - Polycarbonate-polysiloxane copolymer and method for preparing the same - Google Patents

Abstract

A polycarbonate-polysiloxane copolymer of the present invention is characterized by being obtained from an aromatic dihydroxy compound including dimethyl bisphenol A (DMBPA), a carbonate precursor and polysiloxane represented by chemical formula 1 of claim 1. The polycarbonate-polysiloxane copolymer improves scratch resistance and yellowness index by introducing the polysiloxane of a specific structure and aromatic dihydroxy compounds.

Description

POLYCARBONATE-POLYSILYLCANE COPOLYMER AND POLYCARBONATE-POLYSILOXANE COPOLYMER AND METHOD FOR PREPARING THE SAME

The present invention relates to polycarbonate-polysiloxane copolymers and processes for their preparation. More specifically, the present invention relates to a polycarbonate-polysiloxane copolymer improved in scratch resistance and yellowness index by introducing polysiloxane and aromatic dihydroxy compound having a specific structure, and a method for producing the same

Polycarbonate is a thermoplastic resin having an aromatic polycarbonate ester bond and excellent in mechanical properties, self-extinguishing properties, dimensional stability, heat resistance, etc., and is a typical engineering plastic whose applications range of electric and electronic exterior materials and automobile parts are increasing day by day. Recently, the use of such polycarbonate has been further expanded, and studies for improving properties of polycarbonate have been conducted for various applications. Particularly, many examples of studies on controlling various properties by incorporating polymers having different structures into the polycarbonate backbone than the copolymerization method using two or more kinds of diols having different structures have been reported.

For example, polysiloxane-polycarbonate copolymers having an eugenol polysiloxane introduced into the main chain of polycarbonate disclosed in U.S. Patent No. 6,657,018 and the like are excellent in transparency and moldability, and are widely used. However, Has the disadvantage that it increases the yellowness index of the copolymer by promoting the oxidation of the aromatic ring by increasing the density.

Although the polycarbonate resin has excellent moldability and the like, it has a defect that the surface hardness is low and the surface of the molded article is prone to be scratched. Also, the conventional polysiloxane-polycarbonate copolymer copolymerized using the polycarbonate resin has low surface hardness, It has drawbacks that it is liable to cause sucking on the surface.

Therefore, it is necessary to develop a polycarbonate-polysiloxane copolymer improved in scratch resistance, yellowness index and the like.

An object of the present invention is to provide a polycarbonate-polysiloxane copolymer excellent in scratch resistance and capable of improving a yellowness index and a method for producing the same.

Another object of the present invention is to provide a polycarbonate-polysiloxane copolymer excellent in physical properties such as heat resistance, transparency, moldability and appearance, and a process for producing the same.

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 polycarbonate-polysiloxane copolymers. The polycarbonate-polysiloxane copolymer is characterized in that it is obtained from an aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA), a carbonate precursor and a polysiloxane represented by the following formula 1:

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group or a C1-C10 alkyl group having a halogen or alkoxy group or a C6-C18 aryl group, and A and B is 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 containing an ester bond, a urethane bond or a combination thereof, each Y is independently a hydrogen atom, a halogen, a C1-C18 halogenated alkyl group, a cyano group ( -CN), or an ester group, and m and n are each independently an integer of 4 to 100).

In an embodiment, the polysiloxane may be represented by the following formula:

(2)

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

In an embodiment, the content of the dimethyl bisphenol A in the aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA) may be 5 to 100% by weight.

In an embodiment, the aromatic dihydroxy compound comprising dimethyl bisphenol A may comprise 20 to 90% by weight of dimethyl bisphenol A and 10 to 80% by weight of aromatic dihydroxy compound except dimethyl bisphenol A.

In an embodiment, the content of the polysiloxane represented by the formula (1) in the polysiloxane represented by the formula (1) and the aromatic dihydroxy compound containing the dimethyl bisphenol A (DMBPA) is 0.1 to 20% by weight, the dimethyl bisphenol The content of the aromatic dihydroxy compound containing A (DMBPA) may be 80 to 99.9% by weight.

In an embodiment, the polycarbonate-polysiloxane copolymer may have a width of 300 탆 or less and a pencil hardness of F or higher by a ball type scratch profile test.

Another aspect of the invention relates to a process for making the polycarbonate-polysiloxane copolymer. The method comprises polymerizing an aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA), a carbonate precursor and a polysiloxane represented by the above formula (1).

The present invention relates to a polycarbonate-polysiloxane copolymer excellent in scratch resistance, capable of improving a yellowness index and excellent in physical properties such as heat resistance, transparency, moldability and appearance, and a process for producing the polycarbonate- Effect.

1 is an NMR spectrum of a polysiloxane prepared according to Production Example 1 of the present invention.
2 is an NMR spectrum of the polysiloxane prepared according to Production Example 2 of the present invention.

Hereinafter, the present invention will be described in detail.

The polycarbonate-polysiloxane copolymer according to the present invention is characterized in that it is obtained from an aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA), a carbonate precursor and a polysiloxane represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, a C6 to C18 aryl group, a C1 to C10 alkyl group having a halogen or an alkoxy group, or a C6 to C18 aryl Group, preferably a C1-C6 alkyl group, more preferably a C1-C3 alkyl group such as a methyl group.

In the present specification, "alkyl group" includes a linear or branched alkyl group.

A and B are each independently a substituted or unsubstituted C2-C20 (bivalent) hydrocarbon group or a substituted or unsubstituted C2-C20 (bivalent) 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, and most preferably a propylene group.

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

Z is a substituted or unsubstituted C1-C24 (bivalent) hydrocarbon group containing a substituted or unsubstituted C1-C24 (bivalent) hydrocarbon group or an ester bond, a urethane bond or a combination thereof. For example, a substituted or unsubstituted C4-C24 alkylene group, a substituted or unsubstituted C10-C24 cycloalkylene group, a substituted or unsubstituted C1-C24 alkylene group, A substituted or unsubstituted C4-C14 alkylene group, with or without an arylene group, preferably an ester bond, a urethane bond or a combination thereof, of a substituted C10-C24, a substituted or unsubstituted C10-C14 cycloalkyl 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 a substituent of Z. [

Y each independently represents a hydrogen atom, a halogen, a halogenated alkyl group of C1-C18, a cyano group (-CN), or an ester group, preferably a hydrogen atom, a cyano group (-CN) Is a hydrogen atom.

In the present invention, Y may be present in each benzene moiety from one to four, preferably from one to two.

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 may be an integer of 10 to 100.

The polysiloxane used in the present invention has a structure in which a functional group including an alkyl group, an aryl group, or a cycloalkyl group, etc., is added between siloxane blocks with or without ester bond, urethane bond, or the like. In addition, the siloxane block contains a hydroxyl group terminal capable of polymerizing with a polymer such as polycarbonate, polyester, or polyphosphonate. Therefore, it can be used as a siloxane monomer for the production of a polymer of a siloxane-polymer, and it is also possible to use a condensation polymer such as a polycarbonate resin, a polyester resin and a polyphosphonate with a functional group such as an alkyl group, an aryl group or a cycloalkyl group, It is possible to control the physical properties of the siloxane-polymer copolymer derived from the addition structure or to make it possible to add new physical properties. That is, the polysiloxane according to the present invention can contribute to the development of new physical properties or the improvement of the existing properties as monomers of the siloxane-polymer. The physical properties include, but are not limited to, heat resistance, hydrolysis resistance, chemical resistance, impact resistance, flame retardancy and the like.

In an embodiment, the polysiloxane represented by Formula 1 may be represented by Formula 2 below.

(2)

Wherein R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in the above formula (1).

The polysiloxane represented by the formula (1) can be prepared, for example, by reacting a diene with a monohydroxy siloxane represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, R ₁ , R ₂ , A, Y and m are as defined in Formula 1.

The monohydroxy siloxane represented by Formula 5 may be prepared by reacting a hydride terminated siloxane represented by Formula 3 with a phenol derivative represented by Formula 4 below.

(3)

[Chemical Formula 4]

Wherein R ₁ , R ₂ , Y, and m are as defined in Formula 1, D is a substituted or unsubstituted C2-C20 hydrocarbon group having a double bond at the terminal thereof, or -O- or -O- And a substituted or unsubstituted C2-C20 hydrocarbon group having a double bond at the terminal having S-. 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 double terminal having -O- or -S- A substituted or unsubstituted C2-C20 alkyl group whose terminal is a double bond or a substituted or unsubstituted C6-C20 aryl group, preferably a C2-C10 alkyl group whose terminal is a double bond, more preferably a terminal A C2-C6 alkyl group which is a double bond, and most preferably an allyl group. Here, D of the phenol derivative is capable of reacting with hydride-terminated siloxane to form A of the monohydroxy siloxane.

Herein, as the compounds represented by the above-mentioned formulas (3) and (4), at least two compounds having different R ₁ , R ₂ , A, D, Y and m may be used. The compound to be displayed may react with diene to represent A, B, m, n, etc. of the compound represented by the formula (1).

In an embodiment, the hydroxyl group (-OH) group of Formula 4 may be bonded to the benzene moiety at position 2.

The hydride-terminated siloxane represented by the formula (3) and the phenol derivative represented by the formula (4) may be reacted in the presence of a catalyst to prepare the monohydroxy siloxane represented by the formula (5).

As the catalyst, a catalyst containing platinum may be used. For example, the catalyst may be a platinum element itself or a compound comprising 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, or the like, alone or in combination. More preferably, Pt / C, for example, 10% Pt / C can be used.

The amount of the catalyst to be used may be, for example, 10 to 500 ppm, preferably 50 to 150 ppm, relative to the whole reactant.

The reaction may be carried out in an organic solvent, and examples of the organic solvent include 1,2-dichloroethane, toluene, xylene, dichlorobenzene, a mixed solvent thereof, and the like, but the present invention is not limited thereto. Preferably in toluene.

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

The compound of formula 5 prepared by the above reaction can be used in the next step by purification or in situ in the next step without further purification.

Next, the monohydroxy siloxane represented by the formula (5) may be reacted with diene to prepare the polysiloxane represented by the formula (1).

The diene may be reacted with the compound represented by the formula (5) to represent Z of the formula (1). Non-limiting examples of the diene include substituted or unsubstituted C1-C24 Or a substituted or unsubstituted C1-C24 hydrocarbon compound having both terminals at the terminals thereof and containing an ester bond, a urethane bond or a combination thereof, and examples thereof include a hydrocarbon compound having a double bond at both terminals Substituted or unsubstituted C4-C24 linear or branched saturated or unsaturated hydrocarbon compounds, with or without ester bonds, urethane bonds or combinations thereof, substituted or unsubstituted C10-C24 cyclic saturated Or an unsaturated hydrocarbon compound, preferably both ends of which are double bonds, with or including ester bonds, urethane bonds or combinations thereof It may be a substituted or a linear or branched, saturated or unsaturated hydrocarbon compounds, substituted or saturated or unsaturated cyclic hydrocarbon compounds in an unsubstituted C10-C14 of branched unsubstituted C4-C14.

For example, the monohydroxy siloxane represented by the formula (5) is prepared by reacting the hydride-terminated siloxane represented by the formula (3) with the phenol derivative represented by the formula (4), and then the produced monohydroxy siloxane is purified The diene may be added and reacted in situ to prepare the polysiloxane represented by the above formula (1).

In the reaction of the monohydroxyarylsiloxane and the diene, the reaction temperature and the reaction time can be appropriately controlled. For example, the reaction may be carried out at a reaction temperature of 60 to 140 캜, preferably 110 to 120 캜 for 2 to 12 hours, preferably 3 to 5 hours, but is not limited thereto.

The polysiloxane produced can be purified and obtained through conventional methods. For example, after reacting the monohydroxysiloxane with diene, the reaction product is filtered to remove the catalyst, and the resulting filtrate is concentrated to remove the reaction solvent and low molecular weight byproducts to obtain the polysiloxane represented by Formula 1 . Depending on the purity of the polysiloxane, additional purification steps can be performed.

The aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA) used in the present invention has a content of dimethyl bisphenol A in the total aromatic dihydroxy compound of 5 to 100% by weight, And preferably 20 to 90% by weight. Polycarbonate-polysiloxane copolymer having excellent scratch resistance in the above range can be obtained.

Examples of the aromatic dihydroxy compounds other than the dimethyl bisphenol A include aromatic dihydroxy compounds represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, A ₁ represents 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 CO, S, and SO ₂ , R ₃ and R ₄ are each independently selected from the group consisting of a substituted or unsubstituted C 1 -C 30 alkyl group and a substituted or unsubstituted C 5 -C 6 cycloalkylidene group, An unsubstituted C6-C30 aryl group, and a and b are each independently an integer of 0 to 4. Herein, the substitution is such that the hydrogen atom is replaced by a halogen atom, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a C1-C20 alkoxy group, Substituted by a substituent.

Specific examples of the aromatic dihydroxy compound represented by Formula 6 include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis 2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) , 2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, and the like. Preferably, the aromatic dihydroxy compound is 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) 1,1-bis- (4-hydroxyphenyl) -cyclohexane may be used, and 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, may be more preferably used.

In an embodiment, the aromatic dihydroxy compound may include 20 to 90% by weight of dimethyl bisphenol A (DMBPA) and 10 to 80% by weight of an aromatic dihydroxy compound excluding dimethyl bisphenol A (DMBPA) Of the polycarbonate-polysiloxane copolymer may be a terpolymer made therefrom.

As the carbonate precursor used in the present invention, a carbonate precursor used in a conventional polycarbonate-polysiloxane copolymer can be used. For example, phosgene, triphosgene, diphosgene, diaryl carbonate and the like can be used. It does not. The aromatic dihydroxy compound comprising dimethyl bisphenol A (DMBPA) and the carbonate precursor form a polycarbonate unit upon polymerization.

The polycarbonate-polysiloxane copolymer according to the present invention contains units derived from the above polysiloxane (represented by the following formula (7)) in the main chain, for example, 0.1 to 20% by weight, preferably 5 to 15% Can be added and polymerized. The yellowness index (YI) can be improved in the above range.

(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 polycarbonate-polysiloxane copolymer may have a 2.5 mm thickness haze of 11% or less, preferably 0.1 to 10.5%, more preferably 1 to 3%, based on 1 to 4% by weight of silicon content have.

In an embodiment, the polycarbonate-polysiloxane copolymer has a scratch width of 300 탆 or less, for example, 200 to 300 탆 by a ball type scratch profile test, and 500 g Under the load conditions, the pencil hardness may be in the range of F or more, for example, F to 3H.

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

Another aspect of the invention relates to a process for making the polycarbonate-polysiloxane copolymer. The polycarbonate-polysiloxane copolymer may be prepared by a conventional copolymer production method. For example, an aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA), a carbonate precursor, and a carbonate precursor represented by Formula 1 And then polymerizing the polysiloxane.

In the specific examples, the content of the polysiloxane represented by the formula (1) in the polysiloxane represented by the formula (1) and the aromatic dihydroxy compound containing the dimethyl bisphenol A (DMBPA) is, for example, 0.1 to 20% Preferably 5 to 15% by weight, and the content of the aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA) is, for example, 80 to 99.9% by weight, preferably 85 to 95% by weight. The yellowness index (YI) can be improved in the above range.

The amount of the carbonate precursor used may be the same as the amount used in the preparation of a conventional polycarbonate-polysiloxane copolymer, but is not limited thereto.

In an embodiment, the polycarbonate-polysiloxane copolymer is prepared by introducing an aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA) into a basic aqueous solution, adding an organic solvent, a polysiloxane represented by Formula 1 And mixing them, and introducing a carbonate precursor to prepare by interfacial polymerization. By applying the interfacial polymerization as described above, it is possible to secure significantly superior transparency compared to the melt polymerization.

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

Example

Manufacturing example  One: Polysiloxane  Produce

To the reaction vessel were added 344.5 g (1.16 mol) of octamethylcyclotetrasilane, 52.0 g (0.375 mol) of tetramethyldisilane and 500.0 ml of trifluoromethanesulfonic acid, and the mixture was stirred at 25 DEG C for 24 hours. 14 g of MgO was added and stirred for 1 hour. The stirred reaction product was filtered, and the unreacted material was removed under high-temperature vacuum to obtain 300 g of oligodimethylsiloxane. 0.5 g of Pt / C was added to 300 g of the above oligodimethylsiloxane and 270 ml of toluene, and the mixture was stirred and heated to 110 ° C. Next, a mixed 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, and the mixture was stirred at 110 DEG C for 1 hour and then cooled to 25 DEG C. [ The reaction product was filtered, and the unreacted material was removed under high-temperature vacuum to obtain 320 g of an oil-form polysiloxane A represented by the following formula (2a). NMR (Bruker AVANCE III & Ultrashield Magnet, 300 MHz) spectrum of the prepared polysiloxane is shown in FIG.

(2a)

(In the above formula (2a), m + n is 40.)

Manufacturing example  2: Polysiloxane  Produce

Except that 26.0 g (0.129 mol) of tetramethyldisilane was used in place of 52.0 g (0.375 mol) of tetramethyldisilane, thereby obtaining the polysiloxane B 290 g. NMR (Bruker AVANCE III & Ultrashield Magnet, 300 MHz) spectrum of the prepared polysiloxane is shown in FIG.

(2b)

(In the above formula (2b), m + n is 60.)

Example  One

7000 ml of H ₂ O, 2000 ml of 50% NaOH aqueous solution and 750 g (3285.3 mmol) of 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2- 3-methylphenyl) propane (DMBPA) (750 g, 2925.7 mmol) was added, followed by vigorous stirring and stirring for 1 hour while maintaining the solution temperature at 20 to 25 ° C. After adding 41.3 g (274.8 mmol) of t-butylphenol, 3000 ml of methylene chloride and 106.3 g (32.3 mmol) of the polysiloxane A (Preparation Example 1), 921.6 g (24843.9 mmol) of triphosgene 3000 ml of a methylene chloride solution was slowly added to the reactor for 1 hour and stirred for 1 hour while the solution temperature was maintained at 20 to 25 占 폚. 9.7 g (96.3 mmol) of triethylamine was added thereto, and the mixture was stirred for 2 hours while maintaining the temperature of the solution at 30 to 35 占 폚. After the stirring was completed, the organic layer was separated, neutralized by adding 7000 ml of 10% HCl solution, and then washed several times with water until the pH reached neutral. After the washing, the solvent of the organic layer was lowered and dried using a tri-mixer (manufacturer: Inoue Co., Ltd., equipment name: TX-15) to obtain a powdered polycarbonate-polysiloxane copolymer. As a result of DOSY (Diffusion Ordered Spectroscopy) analysis of the obtained copolymer, it was confirmed that the polysiloxane was bonded to the main chain of the polycarbonate, and analysis by 1 H NMR revealed that the Si content was 2.1 wt%. As a result of GPC analysis, the weight average molecular weight (Mw) was 19,329 g / mol.

Example  2

Polycarbonate-polysiloxane copolymer in powder form was obtained in the same manner as in Example 1 except that 103.9 g (24.9 mmol) of polysiloxane B (Production Example 2) was used in place of the polysiloxane A. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate and analyzed by 1 H NMR to find that the Si content was 2.1 wt%. As a result of GPC analysis, the weight average molecular weight (Mw) was 21,382 g / mol.

Example  3

Except that only 1684.4 g (6570.6 mmol) of 2,2-bis (4-hydroxy-3-methylphenyl) propane (DMBPA) was used without using the 2,2-bis (4-hydroxyphenyl) , A polycarbonate-polysiloxane copolymer in the form of powder was obtained in the same manner as in Example 1. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate and analyzed by 1 H NMR to find that the Si content was 2.1 wt%. As a result of GPC analysis, the weight average molecular weight (Mw) was 20,421 g / mol.

Comparative Example  One

Except that the above polysiloxane C was replaced with 111.2 g (34.2 mmol) of polysiloxane C represented by the following formula (2c) instead of the above polysiloxane A and the above 2, 2-bis (4-hydroxy-3-methylphenyl) propane Except that 1,500 g (6570.6 mmol) of 2-bis (4-hydroxyphenyl) propane (BPA) was used in place of the 1,2-bis (4-hydroxyphenyl) propane. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, the weight average molecular weight (Mw) was 20,129 g / mol.

[Chemical Formula 2c]

(In the above formula (2c), n is 40.)

Comparative Example  2

Polycarbonate-polysiloxane copolymer in powder form was obtained in the same manner as in Example 1, except that 111.2 g (34.2 mmol) of the polysiloxane C was used instead of the polysiloxane A. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate, and the weight average molecular weight (Mw) was 20,484 g / mol by GPC analysis.

Comparative Example  3

Bis (4-hydroxyphenyl) propane (BPA) was used instead of the above polysiloxane A and 111.2 g (34.2 mmol) of the above polysiloxane C were used instead of the above- -3-methylphenyl) propane (DMBPA) (1684.4 g, 6570.6 mmol) was used in place of the polycarbonate-polysiloxane copolymer in Example 1, to obtain a powdery polycarbonate-polysiloxane copolymer. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, the weight average molecular weight (Mw) was 21,285 g / mol.

Comparative Example  4

Except that 1500 g (6570.6 mmol) of 2,2-bis (4-hydroxyphenyl) propane (BPA) was used without using the 2,2-bis (4-hydroxy-3-methylphenyl) propane , A polycarbonate-polysiloxane copolymer in the form of powder was obtained in the same manner as in Example 1. As a result of DOSY analysis of the obtained copolymer, it was confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate, and the weight average molecular weight (Mw) was 20,292 by GPC analysis.

How to measure property

The copolymers prepared in Examples 1 to 3 and Comparative Examples 1 to 4 were dried at 120 DEG C for 4 hours, Molded at a molding temperature of 270 to 290 ° C and a mold temperature of 70 ° C to prepare specimens having a thickness of 2.5 mm. Physical properties of the specimens were measured in the following manner.

(1) Evaluation of Yellowness Index (YI)

YI was measured on a 2.5 mm thick specimen using a KONIKA MINOLTA Spectrophotometer (CM-3600d).

(2) Evaluation of haze (%) and permeability (%)

The haze and permeability were measured on a 2.5 mm-thick specimen using a haze meter (NDH-5000) from NIPPON DENSHOKU.

(3) Pencil hardness: The sample was allowed to stand at 23 캜 and 50% RH for 48 hours, and the pencil hardness was measured according to JIS K 5401 standard. The scratch resistance is evaluated by 3B, 2B, B, HB, F, H, 2H and 3H according to the pencil hardness results. The higher the H value, the better the scratch resistance. The higher the B value, Is lowered.

(4) Scratch resistance: Measured by Ball-type Scratch Profile (BSP) test. L90mm x W50mm x t2.5mm A scratch with a length of 10 to 20 mm was applied to the specimen surface with a load of 1000 g and a scratch speed of 75 mm / min using a spherical metal tip of 0.7 mm in diameter. The profile of the applied scratch was surface-scanned with a metal stylus tip having a diameter of 2 탆 using a contact type surface profile analyzer (XP-1) manufactured by Ambios Co., Ltd. to evaluate a scratch width (탆) as a measure of scratch resistance. At this time, the scratch resistance increases as the measured scratch width decreases.

Si content
(wt%) Molecular Weight
(Mw) YI Haze
(%) Permeability
(%) pencil
Hardness Scratch resistance
(탆) Example 1 2.1 19,329 21.8 2.0 85.3 F 265 Example 2 2.1 21,382 22.5 2.9 82.9 F 261 Example 3 2.1 20,421 23.2 2.1 85.0 H 233 Comparative Example 1 2.0 20,129 31.7 1.8 82.8 2B 364 Comparative Example 2 2.1 20,484 33.0 2.1 82.1 F 271 Comparative Example 3 2.1 21,285 33.8 2.2 81.8 H 236 Comparative Example 4 2.0 20,292 20.8 1.8 85.8 2B 360

From the results shown in the above Table 1, it can be seen that the polycarbonate-containing polysiloxane prepared from 2,2-bis (4-hydroxy-3-methylphenyl) propane (DMBPA) Polysiloxane copolymers (Examples 1 and 2 and 3) are superior in scratch resistance to polycarbonate-polysiloxane copolymer (Comparative Example 1) prepared from polysiloxane containing end groups of eugenol type And the yellowness index (YI) is improved.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

A polycarbonate-polysiloxane copolymer obtained from an aromatic dihydroxy compound containing dimethyl bisphenol A, a carbonate precursor and a polysiloxane represented by the following formula 1:
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group or a C1-C10 alkyl group having a halogen or alkoxy group or a C6-C18 aryl group, and A and B is 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 containing an ester bond, a urethane bond or a combination thereof, each Y is independently a hydrogen atom, a halogen, a C1-C18 halogenated alkyl group, a cyano group ( -CN), or an ester group, and m and n are each independently an integer of 4 to 100).
The polycarbonate-polysiloxane copolymer according to claim 1, wherein the polysiloxane is represented by the following formula (2):
(2)

(Wherein R ₁ , R ₂ , A, B, Z, Y, m and n are as defined in Formula 1).
The polycarbonate-polysiloxane copolymer according to claim 1, wherein the content of the dimethyl bisphenol A in the aromatic dihydroxy compound containing dimethyl bisphenol A is 5 to 100% by weight.
The aromatic dihydroxy compound according to claim 1, wherein the aromatic dihydroxy compound containing dimethyl bisphenol A comprises 20 to 90% by weight of dimethyl bisphenol A and 10 to 80% by weight of aromatic dihydroxy compound except dimethyl bisphenol A Polycarbonate-polysiloxane copolymer.
[2] The method of claim 1, wherein the polysiloxane represented by Formula 1 and the aromatic dihydroxy compound comprising dimethyl bisphenol A (DMBPA) comprise 0.1 to 20% by weight of the polysiloxane represented by Formula 1, Wherein the content of the aromatic dihydroxy compound containing dimethyl bisphenol A (DMBPA) is 80 to 99.9% by weight.
The polycarbonate-polysiloxane copolymer according to claim 1, wherein the polycarbonate-polysiloxane copolymer is a polycarbonate-polysiloxane copolymer having a width of 300 mu m or less and a pencil hardness of F or more by a Ball type Scratch Profile Test Copolymer.
A process for producing a polycarbonate-polysiloxane copolymer, which comprises polymerizing an aromatic dihydroxy compound containing dimethyl bisphenol A, a carbonate precursor and a polysiloxane represented by the following formula 1:
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a C1-C10 alkyl group, a C6-C18 aryl group or a C1-C10 alkyl group having a halogen or alkoxy group or a C6-C18 aryl group, and A and B is 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 containing an ester bond, a urethane bond or a combination thereof, each Y is independently a hydrogen atom, a halogen, a C1-C18 halogenated alkyl group, a cyano group ( -CN), or an ester group, and m and n are each independently an integer of 4 to 100).

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