KR20140118274A - Novel polysiloxane, method for preparing the same and polycarbonate-polysiloxane copolymer containing the same - Google Patents

Abstract

The present invention relates to a novel polysiloxane with improved mobility and workability by applying an aliphatic hydrocarbon group to a terminal end, to a manufacturing method thereof. and to a polycarbonate-polysiloxane copolymer including the same. The polysiloxane is indicated as chemical formula 1. In chemical formula 1, R_1 and R_2 are a substituted or non-substituted alkyl group of C1-C18 or a substituted or non-substituted aryl group of C6-C18, respectively. X is a substituted or non-substituted hydrocarbon group of C2-C20 or a substituted or non-substituted hydrocarbon group of C2-C20 including -O- or -S- (A hydrocarbon group connected to Y is an aliphatic family or an alicyclic family), respectively. Y is a hydroxyl group, an amine group or an epoxy group, respectively. Z is a substituted or non-substituted hydrocarbon group of C1-C20, an ester bond, an urethane bond, -O-, -S-, -SO_2-, -CO-, -NR- (Here, R is a hydrogen atom, an alkyl group of C1-C18 or an aryl group of C6-C18) or a substituted or non-substituted hydrocarbon group including the combination thereof of C1-C20. And m and n are an integer of 4-100, respectively.

Description

TECHNICAL FIELD The present invention relates to a novel polysiloxane, a process for producing the same, and a polycarbonate-polysiloxane copolymer containing the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polysiloxane,

The present invention relates to novel polysiloxanes, processes for their preparation and polycarbonate-polysiloxane copolymers containing them. More specifically, the present invention relates to a novel polysiloxane with improved flowability and processability, a process for its preparation and polycarbonate-polysiloxane copolymers containing 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.

Further, in order to improve the mechanical properties of the polycarbonate, a method of blending with other materials has been proposed. However, in the case of blending with other materials, the phase separation due to the difference in solubility between the materials is often observed, which is a disadvantage that inherent transparency of the polycarbonate is deteriorated. For example, studies have been conducted to physically mix a siloxane monomer with a polycarbonate in order to impact, melt flow, improve moldability, and the like of the polycarbonate. However, in this case, even a small amount of siloxane added results in a significant drop in transparency, which hinders the various color representations of the resins required recently.

On the other hand, in the case of the chemical blending, the copolymerization method is a method of polymerizing two or more kinds of monomers together to improve physical properties, and can be used to synthesize a high-performance polycarbonate. Of these copolymers, copolymers of polycarbonate-polysiloxane are disclosed in Korean Patent Laid-Open No. 10-0077519 in which high transparency is maintained while improving ductility, workability, weather resistance, impact resistance after coating, and the like. In particular, improved low-temperature impact resistance and chemical resistance to dilute solvents in paints during coating have made it possible to expand into portable applications requiring a variety of applications, especially color diversity, which were difficult to use in conventional polycarbonate.

However, in order to use the above-mentioned polycarbonate-polysiloxane copolymer for commercial use such as a portable device exterior material, the product production rate has to be further improved, and further excellent fluidity and processability have been demanded.

It is an object of the present invention to provide a novel polysiloxane having improved flowability and processability, a process for producing the same, and a polycarbonate-polysiloxane copolymer containing the same.

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

It is a further object of the present invention to provide a process 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:

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, each X is independently a substituted or unsubstituted C2- C20 hydrocarbon group or a substituted or unsubstituted C2-C20 hydrocarbon group containing -O- or -S- (wherein the hydrocarbon group connected to Y is aliphatic or alicyclic), each Y is independently a hydroxyl group, an amine a group or an epoxy group, Z is a substituted or unsubstituted group of the unsubstituted C1-C20 hydrocarbon, or an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R Is a substituted or unsubstituted C1-C20 hydrocarbon group containing a hydrogen atom, a C1-C18 alkyl group or a C6-C18 aryl group, or a combination thereof, and m and n are each independently an integer of 4 to 100 .

In an embodiment, each X may be independently substituted with an alkyl group or an aryl group.

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

[Formula 1a]

Wherein R ₁ , R ₂ , Y, Z, m and n are as defined in Formula 1, R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and, X ¹ are each independently C1-C18 2 to 4 is an aliphatic or alicyclic hydrocarbon group, X ² is a single bond, each independently, or a substituted or a beach group of the unsubstituted C1-C18 hydrocarbon group, X ³ and X ⁴ are each independently a group is C1-C16 2 or 3 of a hydrocarbon, X ⁵ is a substituted or unsubstituted alkylene group of C1-C5, _{-O-, -S-, -SO 2 -,} -NR- , and (wherein, R is an aryl group of C6-C18 alkyl group or a hydrogen atom, C1-C18) or a combination thereof, a, b, c, d , e and f are each independently 0 or 1 (provided that any of d or e is 0 if any of a + b + c + d + e = 3, a, b or c is zero).

Another aspect of the invention relates to a process for preparing the polysiloxane. The preparation method comprises reacting a monohydroxy siloxane represented by the following formula 2 with diene to prepare a polysiloxane represented by the formula 1:

(2)

Wherein R ₁ , R ₂ , X, Y and m are as defined in the above formula (1).

In an embodiment, the monohydroxysiloxane represented by Formula 2 may be prepared by reacting a hydride-terminated siloxane represented by Formula 3 with a compound represented by Formula 4:

(3)

In Formula 3, R ₁ , R _2, and m are as defined in Formula 1;

[Chemical Formula 4]

In Formula 4, Y is as defined in Formula 1, and X "is a substituted or unsubstituted C2-C20 hydrocarbon group whose terminal is a double bond or a substituted or unsubstituted alkylene group containing -O- or -S- C20 hydrocarbon group (provided that the hydrocarbon group connected to Y is aliphatic or alicyclic).

Another aspect of the present invention relates to a polycarbonate-polysiloxane copolymer comprising the polysiloxane. The polycarbonate-polysiloxane copolymer comprises a polysiloxane unit represented by the following formula (5): < EMI ID =

[Chemical Formula 5]

In Formula 5, R ₁ , R ₂ , X, Z, m and n are as defined in Formula 1, and * is a polycarbonate unit linking group.

In an embodiment, each X may be independently substituted with an alkyl group or an aryl group, the carbon being located second from the polycarbonate unit linking group (*).

In an embodiment, the polysiloxane unit may be represented by the following 5a.

[Chemical Formula 5a]

In Formula _{5a, R 1, R 2,} Z, m and n are as defined in Formula _{1, R 3, R 4,} R 5, R 6, X 1, X 2, X 3, X 4, X ⁵ , a, b, c, d, e and f are as defined in the above formula (1a).

In embodiments, the polycarbonate-polysiloxane copolymer may have a weight average molecular weight of 15,000 to 50,000 g / mol.

In embodiments, the polycarbonate-polysiloxane copolymer may have a melt index (MI) of 1 to 100 g / 10 min at 250 ° C and 10 kgf.

Another aspect of the present invention relates to a process for making the polycarbonate-polysiloxane copolymer. The production method includes a step of polymerizing the polysiloxane represented by Formula 1, the aromatic dihydroxy compound, and the phosgene-based compound:

In an embodiment, the aromatic dihydroxy compound may be an aromatic dihydroxy compound represented by the following Formula 6:

[Chemical Formula 6]

In Formula 6, A 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 or unsubstituted C1- unsubstituted cycloalkyl of C5-C6 alkylidene group, -CO-, -S-, or -SO ₂ -, and, R ₇ and R ₈ are each independently a substituted or unsubstituted C1-C30 alkyl group, or a substituted or An unsubstituted C6-C30 aryl group, p and q are each independently an integer of 0 to 4;

The present invention provides a novel polysiloxane having improved fluidity and processability and excellent physical properties such as heat resistance, impact resistance, transparency, moldability and appearance, a process for producing the same, a polycarbonate-polysiloxane copolymer containing the same, and a process for producing the same And has the effect of the invention.

Hereinafter, the present invention will be described in detail.

The polysiloxane according to the present invention is represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, preferably a C1-C6 alkyl group, more preferably a Is an alkyl group of C1-C3, for example, a methyl group.

In the specification of the present invention, "alkyl group" means a linear, branched or cyclic alkyl group unless otherwise specified.

X each independently represents a substituted or unsubstituted C2-C20 substituted or unsubstituted C2-C20, for example, a (C2-C20) hydrocarbon group or -O- or -S-, For example, a (divalent) hydrocarbon group of C3-C18. Provided that the hydrocarbon group connected to Y is aliphatic or alicyclic. For example, X may be a substituted or unsubstituted C2-C20, for example a C3-C18 linear, branched or cyclic alkylene group or a C7-C20, for example a C8-C18 alkylarylene group, For example a linear, branched, or cyclic alkylene group of C 3 -C 18, or a C 7 -C 20, for example, a C 8 -C 18 alkylarylene group, . Here, the moiety connected to Y is an alkylene group.

In the specification of the present invention, "hydrocarbon group" means a linear, branched, or cyclic saturated or unsaturated hydrocarbon group unless otherwise specified, and in the case of "branched type" 4 or more. 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.

In one embodiment, each X may be independently substituted with an alkyl group or an aryl group. In this case, it is possible to inhibit the elimination reaction, which is an alkene formation reaction, which may occur in the reactor (Y) connected to the carbon (α carbon positioned at the first position from Y).

Each Y is independently a hydroxyl group, an amine group or an epoxy group, preferably a hydroxyl group.

Z is a substituted or unsubstituted C1-C20 (2 a) a hydrocarbon group, or an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R is A substituted or unsubstituted C1-C20 (bivalent) hydrocarbon group containing a hydrogen atom, a C1-C18 alkyl group or a C6-C18 aryl group, or a combination thereof. For example, an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- , or do not contain, or a combination thereof, a substituted or unsubstituted C1-C20, For example, C4-C18 linear, branched or cyclic alkylene groups or C6-C20, for example C8-C18, arylene groups.

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. [

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

The polysiloxane according to the invention is an ester bond between the siloxane block, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR-, and the like, or a combination thereof that does not include, an alkylene group , An arylene group, and the like. The siloxane block has a reactor (Y) having a hydroxyl group, an amine group or an epoxy group capable of polymerizing with a polymer such as polycarbonate, polyester or polyphosphonate at the terminal, and a substituted or unsubstituted And an alkylene group having 1 to 18 carbon atoms. Therefore, it can be used as a siloxane monomer for the production of a polymer of a siloxane-polymer, and a condensation polymer such as a polycarbonate resin, a polyester resin and a polyphosphonate can be obtained from a functional group such as an alkyl group or an aryl group, It is possible to control the physical properties of the resulting siloxane-polymer copolymer or make it possible to add new properties, and the alkylene group is connected to the reactor (Y) to improve the flowability and processability. That is, the polysiloxane according to the present invention is a monomer of a siloxane-polymer polymer having improved flowability and processability, and can contribute to the development of new physical properties and the improvement of existing properties. The physical properties include, but are not limited to, heat resistance, hydrolysis resistance, chemical resistance, (low temperature) impact resistance, flame retardancy and the like.

In a specific example, the polysiloxane represented by the formula (1) may be represented by the following formula (1a).

[Formula 1a]

Wherein R ₁ , R ₂ , Y, Z, m and n are as defined in Formula 1, R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a substituted or unsubstituted and C1-C18 alkyl group, or a substituted or unsubstituted aryl groups, unsubstituted C6-C18 of, for example, R ₅ and R ₆ is an unsubstituted or substituted, except for a hydrogen atom C1-C18 alkyl group, or a substituted or unsubstituted Or a C6-C18 aryl group, which may be bonded to each other to form a cyclic hydrocarbon group. X ¹ is independently a C1 to C18, for example, a C2 to C16 di- to tetravalent aliphatic or alicyclic hydrocarbon group, and each X ² independently represents a single bond or a substituted or unsubstituted C1 to C18 hydrocarbon group, for example, a single bond, substituted or unsubstituted C1-C10 alkylene group or a substituted or non-substituted cycloalkyl group of the unsubstituted C5-C18, X ³ and X ⁴ are each independently a C1-C16 of the second or 3 is a hydrocarbon group, X ⁵ is C1-C5 substituted or unsubstituted alkylene _{group, -O-, -S-, -SO 2 -} , -NR- ( wherein, R is an alkyl group or a C1-C18 C6- A, b, c, d, e, and f are each independently 0 or 1, or a combination thereof. Provided that any one of d or e is 0 if any of a, b, c, d, and e is 3, a, b, Means that the corresponding group (X ³ , X ² , X ⁴ , R ₅ , R ₆ or X ⁵ ) does not exist when a, b, c, d, e or f is 0, It means that the group exists. For example, when b is 0, the carbon at the position β and X ¹ may form an alicyclic ring. In one embodiment, b may be 0, d may be 0, and f may be 1. In another embodiment, b may be 0, d may be 0, and f may be 0. Also, when b is 1, when a is 1, c is 0, d is 1, and e is 0, X ¹ may form an alicyclic ring with the carbon at the position β. Also, when a and c are 0 and b is 1, the carbon at the position β and X ¹ can be connected to X ² . In this case, d and e are one.

Specific examples of the polysiloxane represented by the above formula (1a) include, but are not limited to, polysiloxanes having the following chemical structure.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

(상기 화학식에서, R₁, R₂, Y, Z, m 및 n은 상기 화학식 1에서 정의한 바와 같고, i는 0 내지 3의 정수이다).

Wherein R ₁ , R ₂ , Y, Z, m and n are as defined in the above formula (1), and i is an integer of 0 to 3.

The method for producing a polysiloxane according to the present invention includes, for example, a step of reacting a monohydroxy siloxane represented by the following general formula (2) with diene to prepare a polysiloxane represented by the general formula (1) (second step) . Here, the monohydroxy siloxane represented by the following formula (2) can be prepared by reacting a hydride terminated siloxane represented by the following formula (3) with a compound represented by the following formula (4) (step 1).

(2)

(3)

[Chemical Formula 4]

In the above formulas 2 to 4, R ₁ , R ₂ , X, Y and m are as defined in Formula 1, and X "is a double bond and a substituted or unsubstituted C 2 -C 20, for example, C 3 Or a substituted or unsubstituted C2-C20, for example, a (C2-C18) (2-membered) hydrocarbon group containing -O- or -S-, X "is a linear, branched, or cyclic alkyl group of a substituted or unsubstituted C2-C20, for example, a C3-C18, or a substituted or unsubstituted C7-C20 , For example a C8-C18 alkylaryl group, or a substituted or unsubstituted C2-C20, for example C3-C18, linear, branched or cyclic, having a double bond at the end and -O- or -S- Or cyclic alkyl groups or C7-C20, for example C8-C18 alkylaryl groups. Here, the moiety connected to Y is an alkylene group.

Herein, X "of the compound represented by the general formula (4) is capable of reacting with hydride-terminated siloxane to form X of monohydroxysiloxane.

Here, as the compounds represented by the above-mentioned formulas (2) to (4), two or more compounds having different R ₁ , R ₂ , X, X ", Y and m may be used, and X" 4 may react with diene to represent X, m, n, etc. of the compound represented by the formula (1).

In an embodiment, the compound represented by the formula (4) may be represented by the following formula (4a).

[Chemical Formula 4a]

In Formula _{4a, R 3, R 4,} R 5, R 6, X 2, X 3, X 4, X 5, Y, a, b, c, d, e and f are as defined in the formula (1a) And X " ¹ is a C1 to C18, for example, a C2 to C16, di- to tetravalent aliphatic or alicyclic hydrocarbon group containing a double bond at the terminal for the hydrosilylation reaction.

Step 1

The first step is a step of synthesizing the monohydroxy siloxane represented by Formula 2 by reacting the hydride terminated siloxane represented by Formula 3 with a compound represented by Formula 4 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 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 can be carried out at a reaction temperature of 60 to 140 캜, preferably 110 to 120 캜, for 2 to 12 hours, preferably for 3 to 5 hours.

In an embodiment, the equivalent ratio of the hydride-terminated siloxane represented by Formula 3 to the compound represented by Formula 4 may be 1: 1 to 1: 1.5, but is not limited thereto.

The compound of formula 4 prepared in the first step can be used in the next step by purification or in situ in the next step without further purification.

Step 2

The second step is to react the monohydroxy siloxane represented by the formula (2) with diene to prepare the polysiloxane represented by the formula (1).

The diene may react with the monohydroxysiloxane represented by the formula (2) to represent Z in the formula (1). Non-limiting examples of the diene include substituted or unsubstituted a C1-C20 (2) a hydrocarbon group, or both ends a double bond, ester bond, urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R is A substituted or unsubstituted C1-C20 (bivalent) hydrocarbon group including a hydrogen atom, a C1-C18 alkyl group or a C6-C18 aryl group, or a combination thereof, double bond, an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- , or do not contain, or a combination thereof, a substituted or unsubstituted C1-C20, for example, For example, it may be a C4-C18 linear, branched or cyclic alkylene group or C6-C20, for example a C8-C18 arylene group. Non-limiting examples of the dienes include, but are not limited to, 1,3-butadiene, 1,4-pentadiene, 1,6-hexadiene, 1,7-heptadiene and the like.

For example, after completion of the first step, the monohydroxysiloxane represented by the formula (2) is not purified, and the diene is added thereto to carry out an in situ reaction to prepare the polysiloxane represented by the 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 temperature and the reaction time used in the first step may be used as they are, but the present invention is not limited thereto.

The polysiloxane produced 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 resulting filtrate is concentrated to remove the reaction solvent and low molecular weight byproducts to obtain the polysiloxane represented by the above formula (1). Depending on the purity of the polysiloxane, additional purification steps can be performed.

The polycarbonate-polysiloxane copolymer according to the present invention comprises a polysiloxane unit represented by the following formula (5).

[Chemical Formula 5]

In Formula 5, R ₁ , R ₂ , X, Z, m and n are as defined in Formula 1, and * is a polycarbonate unit linking group.

In one embodiment, each X may be independently substituted with an alkyl group or an aryl group, wherein the carbon located at the second position from the polycarbonate unit linking group (*) (the [beta] -positioning carbon) is all substituted.

In an embodiment, the polysiloxane unit may be represented by the following 5a.

[Chemical Formula 5a]

In Formula _{5a, R 1, R 2,} Z, m and n are as defined in Formula _{1, R 3, R 4,} R 5, R 6, X 1, X 2, X 3, X 4, X ⁵ , a, b, c, d, e and f are as defined in the above formula (1a).

The polysiloxane unit is included in the main chain of the polycarbonate-polysiloxane copolymer, and may be contained, for example, in an amount of 0.1 to 20% by weight, preferably 5 to 15% by weight. The fluidity and processability are excellent in the above range.

The polycarbonate-polysiloxane copolymer has a melt index (MI) of 1 to 100 g / 10 min, preferably 2 to 60 g / 10 min, measured at 250 캜 and 10 kgf, according to the ASTM D1238 evaluation method. It can be 10 minutes.

The polycarbonate-polysiloxane copolymer may have a weight average molecular weight of 15,000 to 50,000 g / mol, preferably 19,000 to 40,000 g / mol.

The polycarbonate-polysiloxane copolymer of the present invention can be produced by polymerizing a polysiloxane represented by the above-mentioned formula (1), an aromatic dihydroxy compound, for example, an aromatic dihydroxy compound represented by the following formula 6 and a phosgene-based compound .

[Chemical Formula 6]

In Formula 6, A 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 or unsubstituted C1- unsubstituted cycloalkyl of C5-C6 alkylidene group, -CO-, -S-, or -SO ₂ -, and, R ₇ and R ₈ are each independently a substituted or unsubstituted C1-C30 alkyl group, or a substituted or An unsubstituted C6-C30 aryl group, p and q 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 include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- ) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2- (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 can be used, and 2,2-bis- (4-hydroxyphenyl) -propane, more preferably called "bisphenol-A" have.

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, based on 100 parts by weight of the polysiloxane and the aromatic dihydroxy compound represented by the formula (1) 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 phosgene compound used in the present invention may be any conventional phosgene compound used in the production of polycarbonate. For example, phosgene, triphosgene, and diphosgene may be added to a conventional polycarbonate-polysiloxane copolymer But the present invention is not limited thereto.

In a specific example, the polycarbonate-polysiloxane copolymer is prepared by introducing an aromatic dihydroxy compound into a basic aqueous solution, adding and mixing an organic solvent, a polysiloxane represented by the above formula (1), and a phosgene compound Can be prepared by interfacial polymerization. By applying the interfacial polymerization as described above, excellent transparency can be secured compared with 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

Example  One: Polysiloxane  Produce

344.5 g (1.16 mol) of octamethylcyclotetrasilane, 69.3 g (0.50 mol) of tetramethyldisilane and 375 ml of trifluoromethanesulfonic acid were added to the reaction vessel and 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 350 g of oligodimethylsiloxane. To 350 g of the above oligodimethylsiloxane and 250 ml of toluene, 0.5 g of Pt / C was added and the mixture was stirred and heated to 110 ° C. Next, a mixed solution of 24.0 g (0.21 mol) of 6-heptene-1-ol and 30 ml of toluene was slowly added dropwise. After dropwise addition of 6-hepten-1-ol, 9 g (0.11 mol) of 1,5-hexadiene was added dropwise and the mixture was stirred at 110 ° C for 1 hour and then cooled to 25 ° C. The reaction product was filtered, and the unreacted material was removed under a high-temperature vacuum to obtain 370 g of an oil-form polysiloxane A represented by the following formula (1b).

[Chemical Formula 1b]

In the above formula (1b), m + n is 30.

Example  2: Polysiloxane  Produce

Except that 29.7 g (0.21 mol) of tetramethyldisilane was used in place of 69.3 g (0.50 mol) of the above tetramethyldisilane, the same procedure as in Example 1 was repeated to obtain the polysiloxane B 280 g was obtained.

[Chemical Formula 1c]

In the above formula (1c), m + n is 70.

Example  3: Polysiloxane  Produce

27.4 g (0.24 mol) of 2,2-dimethyl-4-penten-1-ol was added in place of 24.0 g (0.21 mol) of the hepten- 320 g of polysiloxane C in an oil state represented by the following formula (1d) was obtained in the same manner as in Example 1, except that the catalyst was used.

≪ RTI ID = 0.0 &

In the above formula (1d), m + n is 30.

Example  4: Polysiloxane - Preparation of Polycarbonate Copolymer

7 L of distilled water and 2 L of a 50% NaOH aqueous solution were added to a 20 L glass reactor and mixed and stirred. After 1.5 kg of 2,2-bis (4-hydroxyphenyl) propane (BPA) was added and stirred, when the solution temperature became 22 DEG C or lower, 41.5 g of t-butylphenol, 3 L of methylene chloride, (Example 1) (122 g) was added, followed by vigorous stirring. A solution of 974 g of triphosgene in 3 L of methylene chloride was slowly added to the reactor at a rate of 60 ml per minute and stirred. When the temperature of the solution reached 23 占 폚 or less, 7.8 g of triethylamine was added and the mixture was stirred for 2 hours while maintaining the reactor temperature at 30 占 폚 or higher. After the stirring was completed, the organic layer was separated, washed once with a mixture of 6 L of water and 10 mL of 50 wt% NaOH, once with 6 L of water and 60 mL of 35% HCl mixed aqueous solution, and twice with 12 L of distilled water. After washing, the organic layer was slowly stirred in an agitator and a methanol solution of the same volume ratio was added over 1 hour to obtain a white precipitate. The precipitate was separated by filtration and dried at 80 DEG C for 12 hours to obtain a final 1.5 kg 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 21,500 g / mol.

Example  5: Polysiloxane - Preparation of Polycarbonate Copolymer

1.5 kg of a polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 3, except that 112 g of polysiloxane B (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 21,900 g / mol.

Example  6: Polysiloxane - Preparation of Polycarbonate Copolymer

1.5 kg of a polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 3, except that 125 g of polysiloxane C (Example 3) 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 21,700 g / mol.

Comparative Example  One: Polysiloxane - Preparation of Polycarbonate Copolymer

1.5 kg of a polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 3, except that 118 g of the polysiloxane D represented by the following formula (7a) 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 analysis by 1 H NMR revealed that the Si content was 2.2 wt%. As a result of GPC analysis, the weight average molecular weight (Mw) was 21,300 g / mol.

[Formula 7a]

Comparative Example  2: Polysiloxane - Preparation of Polycarbonate Copolymer

1.5 kg of polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 3, except that 110.1 g of polysiloxane E represented by the following formula (7b) 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 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 22,300 g / mol.

[Formula 7b]

Comparative Example  3: Polysiloxane - Preparation of Polycarbonate Copolymer

1.5 kg of a polycarbonate-polysiloxane copolymer was obtained in the same manner as in Example 3, except that 121 g of the polysiloxane F represented by the following formula (7c) 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 analyzed by 1 H NMR to find that the Si content was 2.0 wt%. As a result of GPC analysis, the weight average molecular weight (Mw) was 21,600 g / mol.

[Formula 7c]

How to measure property

The copolymers prepared in Examples 3 and 4 and Comparative Examples 1 and 2 were dried at 120 DEG C for 4 hours, Molded at an extruder at a molding temperature of 270 to 290 ° C and a mold temperature of 70 ° C to prepare specimens. Physical properties of the specimens are shown in Table 1 below.

(1) Evaluation of liquidity

Based on ASTM D1238 evaluation method, the meltability was evaluated by measuring melt index (MI: unit: g / 10 min) at a temperature of 250 캜 and 10 kgf.

(2) Processability evaluation

According to the ASTM D3123 evaluation method, the spiral flow (unit: mm) was measured at a temperature of 320 DEG C and a thickness of 1 mm to evaluate the workability.

Si No. Si content
(wt%) Molecular Weight
(Mw, g / mol) Melt Index
(g / 10 min) Spiral Flow
(mm) Example 4 30 2.1 21,500 35 143 Example 5 70 2.1 21,900 34 141 Example 6 30 2.1 21,700 33 139 Comparative Example 1 30 2.2 21,300 30 132 Comparative Example 2 70 2.1 22,300 28 130 Comparative Example 3 30 2.0 21,600 28 129

From the results in the above Table 1, it can be seen that the polycarbonate-polysiloxane copolymers (Examples 4 to 6) prepared from the polysiloxanes according to the present invention (Examples 1 to 3) are superior to the polycarbonate-polysiloxane copolymers of Comparative Examples 1 to 3 , Workability and fluidity are 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 (12)

A polysiloxane represented by the following formula (1):
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, each X is independently a substituted or unsubstituted C2- C20 hydrocarbon group or a substituted or unsubstituted C2-C20 hydrocarbon group containing -O- or -S- (wherein the hydrocarbon group connected to Y is aliphatic or alicyclic), each Y is independently a hydroxyl group, an amine a group or an epoxy group, Z is a substituted or unsubstituted group of the unsubstituted C1-C20 hydrocarbon, or an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R Is a substituted or unsubstituted C1-C20 hydrocarbon group containing a hydrogen atom, a C1-C18 alkyl group or a C6-C18 aryl group, or a combination thereof, and m and n are each independently an integer of 4 to 100 .
2. The polysiloxane according to claim 1, wherein X is each independently an alkyl group or an aryl group, wherein the carbon located at the second position from Y is all substituted.
The polysiloxane according to claim 1, wherein the polysiloxane is represented by the following formula (1a):
[Formula 1a]

Wherein R ₁ , R ₂ , Y, Z, m and n are as defined in Formula 1, R ₃ , R ₄ , R ₅ and R ₆ are each independently a hydrogen atom, a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and, X ¹ are each independently C1-C18 2 to 4 is an aliphatic or alicyclic hydrocarbon group, X ² is a single bond, each independently, or a substituted or a beach group of the unsubstituted C1-C18 hydrocarbon group, X ³ and X ⁴ are each independently a group is C1-C16 2 or 3 of a hydrocarbon, X ⁵ is a substituted or unsubstituted alkylene group of C1-C5, _{-O-, -S-, -SO 2 -,} -NR- , and (wherein, R is an aryl group of C6-C18 alkyl group or a hydrogen atom, C1-C18) or a combination thereof, a, b, c, d , e and f are each independently 0 or 1 (provided that any of d or e is 0 if any of a + b + c + d + e = 3, a, b or c is zero).
Reacting a monohydroxy siloxane represented by the following formula (2) with diene to prepare a polysiloxane represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, each X is independently a substituted or unsubstituted C2- C20 hydrocarbon group or a substituted or unsubstituted C2-C20 hydrocarbon group containing -O- or -S- (wherein the hydrocarbon group connected to Y is aliphatic or alicyclic), each Y is independently a hydroxyl group, an amine a group or an epoxy group, Z is a substituted or unsubstituted group of the unsubstituted C1-C20 hydrocarbon, or an ester bond, a urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R Is a substituted or unsubstituted C1-C20 hydrocarbon group containing a hydrogen atom, a C1-C18 alkyl group or a C6-C18 aryl group, or a combination thereof, and m and n are each independently an integer of 4 to 100 ;
(2)

Wherein R ₁ , R ₂ , X, Y and m are as defined in the above formula (1).
The process for producing a polysiloxane according to claim 4, wherein the monohydroxy siloxane represented by the formula (2) is prepared by reacting a hydride terminated siloxane represented by the following formula (3) with a compound represented by the following formula :
(3)

In Formula 3, R ₁ , R _2, and m are as defined in Formula 1;
[Chemical Formula 4]

In Formula 4, Y is as defined in Formula 1, and X "is a substituted or unsubstituted C2-C20 hydrocarbon group whose terminal is a double bond or a substituted or unsubstituted alkylene group containing -O- or -S- C20 hydrocarbon group (provided that the hydrocarbon group connected to Y is aliphatic or alicyclic).
A polycarbonate-polysiloxane copolymer comprising a polysiloxane unit represented by the following formula (5):
[Chemical Formula 5]

In Formula 5, R ₁ and R ₂ are each independently a substituted or unsubstituted C1-C18 alkyl group or a substituted or unsubstituted C6-C18 aryl group, and each X is independently a substituted or unsubstituted C2- C20 hydrocarbon group or a substituted or unsubstituted C2-C20 hydrocarbon group containing -O- or -S- (wherein the hydrocarbon group connected to Y is aliphatic or alicyclic), Z is a substituted or unsubstituted C1 hydrocarbon group, or an ester bond -C20, urethane _{bond, -O-, -S-, -SO 2 -} , -CO-, -NR- ( wherein, R is an alkyl group or a C6-C18 a hydrogen atom, C1-C18 And m and n are each independently an integer of 4 to 100, and * is a polycarbonate unit linking group.
7. The polycarbonate-polysiloxane copolymer according to claim 6, wherein X is each independently substituted with an alkyl group or an aryl group, the carbon being located second from the polycarbonate unit linkage (*).
7. Polycarbonate-polysiloxane copolymer according to claim 6, wherein the polysiloxane unit is represented by the following formula
[Chemical Formula 5a]

In Formula 5a, R _1, R _2, Z, m and n are as defined in Formula _{5, R 3, R 4,} R 5 and R ₆ are each independently C1- ring hydrogen atom, a substituted or unsubstituted an alkyl group or substituted or unsubstituted C6-C18 aryl groups, C18, X ¹ are each independently C1-C18 2 to 4 is an aliphatic or alicyclic hydrocarbon group, X ² is a single bond, each independently, or substituted or an unsubstituted C1-C18 hydrocarbon group, X ³ and X ⁴ are each independently selected from a group of 2 or 3 C1-C16 hydrocarbon group, X ⁵ is C1-C5 substituted or unsubstituted alkylene group, -O _{-, -S-, -SO 2 -,} -NR- , and (wherein, R is an aryl group of C6-C18 alkyl group or a hydrogen atom, C1-C18) or a combination thereof, a, b, c, d , e And f are each independently 0 or 1, provided that any one of d or e is 0 when any one of a, b, c is 0, or a + b + c + d + e = 3.
7. The polycarbonate-polysiloxane copolymer of claim 6, wherein the polycarbonate-polysiloxane copolymer has a weight average molecular weight of from 15,000 to 50,000 g / mol.
The polycarbonate-polysiloxane copolymer according to claim 6, wherein the polycarbonate-polysiloxane copolymer has a melt index (MI) of 1 to 100 g / 10 min at 250 캜 and 10 kgf.
A process for producing a polycarbonate-polysiloxane copolymer, which comprises polymerizing the polysiloxane, the aromatic dihydroxy compound, and the phosgene-based compound according to any one of claims 1 to 3.
The process for producing a polycarbonate-polysiloxane copolymer according to claim 11, wherein the aromatic dihydroxy compound is an aromatic dihydroxy compound represented by the following Formula 6:
[Chemical Formula 6]

In Formula 6, A 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 or unsubstituted C1- unsubstituted cycloalkyl of C5-C6 alkylidene group, -CO-, -S-, or -SO ₂ -, and, R ₇ and R ₈ are each independently a substituted or unsubstituted C1-C30 alkyl group, or a substituted or An unsubstituted C6-C30 aryl group, p and q are each independently an integer of 0 to 4;