KR102115799B1 - Polysiloxane-polycarbonate copolymer having improved transparency and low temperature impact resistance and method for preparing the same - Google Patents

Abstract

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and low-temperature impact resistance, and a method of manufacturing the same, and more specifically, a polysiloxane block having a specific structure having hydroxyphenyl groups at both ends and a polycarbonate block as repeating units. The present invention relates to a polysiloxane-polycarbonate copolymer having excellent low-temperature impact resistance and excellent transparency and a method for manufacturing the same.

Description

POLYSILOXANE-POLYCARBONATE COPOLYMER HAVING IMPROVED TRANSPARENCY AND LOW TEMPERATURE IMPACT RESISTANCE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a polysiloxane-polycarbonate copolymer having improved transparency and low-temperature impact resistance, and a method of manufacturing the same, and more specifically, a polysiloxane block having a specific structure having hydroxyphenyl groups at both ends and a polycarbonate block as repeating units. The present invention relates to a polysiloxane-polycarbonate copolymer having excellent low-temperature impact resistance and excellent transparency and a method for manufacturing the same.

Polycarbonate is widely used for industrial purposes because it has excellent mechanical properties such as tensile strength and impact resistance, and excellent dimensional safety, heat resistance, and optical transparency. However, polycarbonate has excellent impact resistance at room temperature, but at low temperatures, there is a vulnerability that impact resistance is rapidly reduced.

In order to improve these vulnerabilities, research into various copolymers has been continued, and as a result, a polysiloxane-polycarbonate copolymer has been proposed (US Patent Publication No. 2003/0105226).

Polysiloxane-polycarbonate copolymers are known to have relatively good impact resistance at low temperatures. However, the existing polysiloxane-polycarbonate copolymer essentially requires a high content of siloxane to express low-temperature impact resistance, and an increase in the content of siloxane is problematic in inhibiting the transparency of the polysiloxane-polycarbonate copolymer, which is limited to commercial use. Is working.

Accordingly, development of a copolymer exhibiting excellent low temperature impact resistance and excellent transparency is required.

The present invention is to solve the problems of the prior art as described above, and has a technical problem to provide a novel polysiloxane-polycarbonate copolymer having excellent low-temperature impact resistance and excellent transparency and a method for manufacturing the same.

In order to achieve the above technical problem, the present invention provides a polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated polysiloxane of Formula 1 and a polycarbonate block as a repeating unit:

[Formula 1]

In Chemical Formula 1,

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

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

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

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

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

A represents a divalent polycyclic group,

m independently represents an integer from 0 to 4,

n independently represents an integer of 1 to 200.

According to another aspect of the present invention, mixing the hydroxy-terminated polysiloxane of Formula 1 and an oligomeric polycarbonate, and then reacting under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; And it provides a method for producing a polysiloxane-polycarbonate copolymer comprising the step of polymerizing the intermediate.

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

Since the polysiloxane-polycarbonate copolymer according to the present invention has excellent low-temperature impact resistance and also excellent transparency, molded articles requiring transparency and low-temperature impact resistance at the same time (eg, housings, film and sheet products for office equipment and electrical and electronic products) Etc.).

As used herein, the term "reaction product" refers to a substance formed by the reaction of two or more reactants.

Further, in this specification, the terms "first", "second", and the like are used to describe a polymerization catalyst, but the polymerization catalyst is not limited by these terms. These terms are only used to distinguish the polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be the same type of catalyst, or different types of catalyst.

In addition, the English letter "R" used to represent hydrogen, or a non-hydrogen substituent such as a halogen atom and / or a hydrocarbon group in the chemical formula described herein has a subscript represented by a number, but the "R" is It is not limited by this subscript. The "R" represents, independently of each other, hydrogen or a non-hydrogen substituent such as a halogen atom and / or a hydrocarbon group. For example, regardless of whether two or more "R" s have the same or different numbers of subscripts, these "Rs" may represent the same hydrocarbon group or different hydrocarbon groups. In addition, when the number of “R” s in the formulas described herein is 0, it means that hydrogen is present at the corresponding substitution position.

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

(A) hydroxy terminal polysiloxane

The hydroxy-terminated polysiloxane included as a repeating unit in the polysiloxane-polycarbonate copolymer of the present invention is characterized by having a structure represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

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

R ₂ independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms. More specifically, R ₂ is an alkyl group or an alkoxy group having 1 to 13 carbon atoms, an alkenyl group or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or cycloalkoxy group having 3 to 6 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, It may be an aralkyl group or an aralkoxy group having 7 to 13 carbon atoms, or an alkaryl group or an alkaryloxy group having 7 to 13 carbon atoms.

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

R ₄ independently represents a divalent hydrocarbon group having 2 to 30 carbon atoms. More specifically, R ₄ is a linear or branched alkylene group having 2 to 13 carbon atoms, a linear or branched alkenylene group having 2 to 13 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, an arylene group having 6 to 10 carbon atoms, or It may be a combination of these (eg, a divalent hydrocarbon group having 2 to 13 alkylene groups and 6 to 10 arylene groups).

L is independently selected from ketone bond [-C (= O)-], ester bond [-C (= O) -O-], peptide bond [-C (= O) -NH-], and combinations thereof Indicates a divalent linking group. More specifically, L can be an ester bond, a peptide bond or a combination thereof.

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

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

In Chemical Formula 1, n is an integer of 1 to 200. More specifically, the lower limit of n can be 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20, and the upper limit of n is 200, 190, 180, 170, 160, 150, 140, 130 , 120, 110 or 100, but is not limited thereto.

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

The preferred content of the hydroxy-terminated polysiloxane in the polysiloxane-polycarbonate copolymer of the present invention is 1 to 40% by weight, more preferably 2 to 30% by weight, based on the total weight of the copolymer. When the content of the hydroxy-terminated polysiloxane in the copolymer is less than 1% by weight, the low-temperature impact resistance of the resulting copolymer may be insufficient, and when the content exceeds 40% by weight, physical properties such as fluidity and heat resistance and transparency may be deteriorated. The manufacturing cost is increased, which is undesirable from an economic point of view.

(B) Polycarbonate block

The polycarbonate block included as a repeating unit in the polysiloxane-polycarbonate copolymer according to the present invention may have a repeating unit represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R ₅ is an alkyl group having 1 to 20 carbon atoms (eg, an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (eg, an alkenyl group having 2 to 13 carbon atoms), an alkoxy group (For example, an alkoxy group having 1 to 13 carbon atoms), or an aromatic hydrocarbon group having 6 to 30 carbon atoms, which is unsubstituted or substituted with a halogen atom or nitro.

Here, the aromatic hydrocarbon group may be derived from a compound having the structure of Formula 2a.

[Formula 2a]

In Formula 2a,

X is an alkylene group, a straight, branched or cyclic alkylene group having no functional group, or a straight, branched or cyclic alkylene including functional groups such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, and isobutylphenyl. Group. Preferably, X may be a linear, branched or cyclic alkylene group having 3 to 6 carbon atoms.

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

a and b independently represent the integer of 0-4.

The compound of Formula 2a is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) )-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1 -Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis ( 4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy Phenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2- Bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) methane, Resorcinol, Hydroquine, 4,4'-dihydroxyphenyl ether [Bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether , Bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1, 4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4- Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,4-bis (4-hydroxyphenyl) butane , 1,4-bis (4-hydr Oxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxy) Phenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5- Dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methyl-butane , 4,4'-thiodiphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone , Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) Sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'- Dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Representative of these is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to U.S. Patents US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the divalent phenols alone or in combination of two or more. Can be used.

In the case of a carbonate precursor, as another monomer of the polycarbonate resin, for example, carbonyl chloride (phosgene), carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate can be used.

(C) polysiloxane-polycarbonate copolymer

In the polysiloxane-polycarbonate copolymer of the present invention, the above-mentioned hydroxy-terminated polysiloxane of Formula 1 and oligomeric polycarbonate are mixed (for example, hydroxy-terminated polysiloxane: oligomeric polycarbonate in a weight ratio of 1:99 to 10:90). And then reacted under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; And polymerizing the intermediate, preferably in the presence of a first polymerization catalyst.

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

In one embodiment, the oligomeric polycarbonate may be prepared by adding the above-described divalent phenol compounds to an aqueous alkali solution to make a phenol salt state, and then reacting the salt phenols with dichloromethane injected with phosgene gas. . For oligomer production, it is desirable to maintain the molar ratio of phosgene to bisphenol in the range of about 1: 1 to 1.5: 1, more preferably about 1: 1 to 1.2: 1. If the molar ratio of phosgene to bisphenol is less than 1, reactivity may be lowered, and when the molar ratio of phosgene to bisphenol exceeds 1.5, processability may be reduced due to excessive increase in molecular weight.

The oligomer forming reaction may be generally performed at a temperature in the range of about 15 to 60 ° C, and alkali metal hydroxide (eg, sodium hydroxide) may be used to adjust the pH of the reaction mixture.

In one embodiment, forming the intermediate comprises forming a mixture comprising a hydroxy-terminated polysiloxane and an oligomeric polycarbonate, the mixture comprising a phase change catalyst, a molecular weight modifier, and a second polymerization catalyst May be In addition, the step of forming the intermediate, forming a mixture comprising a hydroxy-terminated polysiloxane and an oligomeric polycarbonate; And extracting the organic phase from the resulting mixture after the reaction of the hydroxy-terminated polysiloxane and the oligomeric polycarbonate is completed, wherein polymerizing the intermediate comprises providing a first polymerization catalyst to the extracted organic phase. It may be included.

Specifically, the polysiloxane-polycarbonate copolymer of the present invention can be prepared by adding the hydroxy-terminated polysiloxane of Formula 1a to the organic-aqueous mixture containing polycarbonate, and gradually introducing a molecular weight modifier and a catalyst.

As the molecular weight modifier, a monofunctional compound similar to a monomer used in polycarbonate production may be used. The monofunctional substance is, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p-isooctylphenol and p-isononyl It may be a phenol-based derivative such as phenol, or an aliphatic alcohol. Preferably, p-tert-butylphenol (PTBP) can be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst can be used. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, the compound of Formula 3 may be used.

[Formula 3]

^{_{(R 7) 4 Q + Y}} -

In Chemical Formula 3, R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Y represents a halogen atom or -OR ₈ . Here, R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase transition catalyst is, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NY, [CH ₃ (CH ₂ ) ₃ ] ₄ PY, [CH ₃ (CH ₂ ) ₅ ] ₄ NY, [CH ₃ (CH ₂ ) ₆ ] ₄ NY, [CH ₃ (CH ₂ ) ₄ ] ₄ NY, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NY, CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NY have. In the above formulas, Y represents Cl, Br or -OR ₈ , where R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms. When the phase transition catalyst is used, its content is preferably 0.01% by weight or more in terms of transparency of the resultant copolymer, but is not limited thereto.

In one embodiment, the polysiloxane-polycarbonate copolymer is prepared, and then the organic phase dispersed in methylene chloride is alkali washed and separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2-3 times. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of pure water in the range of 30 to 100 ° C, preferably in the range of 60 to 80 ° C. If the temperature of the pure water is less than 30 ° C, the assembly speed may be slowed and the assembly time may be very long, and when the temperature of the pure water exceeds 100 ° C, it may be difficult to obtain a polycarbonate shape with a constant size. When the assembly is completed, it is preferable to dry at 100 to 120 ° C for 5 to 10 hours, more preferably 5 to 10 hours at 100 to 110 ° C first, and 5 to 10 hours at 110 to 120 ° C second. .

The viscosity average molecular weight (Mv) of the polysiloxane-polycarbonate copolymer according to the present invention may be, for example, 10,000 to 100,000, and more specifically 15,000 to 80,000.

The polysiloxane-polycarbonate copolymer according to the present invention has excellent transparency and low-temperature impact resistance at the same time, and thus can be usefully used to produce products of films and sheets, such as housings for office equipment and electrical and electronic products.

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

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

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[Example]

<Preparation of hydroxy-terminated polysiloxane>

Example 1

Octamethylcyclotetrasiloxane 15g, 1,1,3,3-tetramethyldisiloxane (1,1,3,3, -tetramethyldisiloxane) 2.5g, p-toluenesulfonic acid (p-toluenesulfonic acid) 0.5g It was placed in a reactor under a nitrogen atmosphere and stirred at 90 ° C. for 5 hours. Subsequently, the unreacted substance was removed by purification at 60 ° C. under vacuum to obtain a hydrogen-terminated polysiloxane represented by the following Chemical Formula E1-1 (number average molecular weight: about 1,200).

[Formula E1-1]

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

On the other hand, acrylic acid (acrylic aicd) 3.6g, bisphenol A (bisphenol A) 5.7g, H ₂ SO ₄ 0.5g was added to the reactor and stirred at 130 ℃ for 2 hours. Thereafter, the mixture was purified at 100 ° C. under vacuum to remove unreacted substances and moisture, thereby obtaining a compound having a double bond represented by the following Chemical Formula E1-2.

[Formula E1-2]

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

Next, 100 g of hydrogen-terminated polysiloxane of formula E1, 9.3 g of compound of formula E2, and 4.0 g of 2-allylphenol were mixed at room temperature for 10 minutes, and then isopropyl alcohol was maintained while maintaining the reaction temperature at 90 ° C ( IPA) 0.5 g of H ₂ PtCl ₆ dissolved in 10 g was added dropwise. After the reaction for 3 hours, it was purified at 100 ° C. under vacuum to obtain a hydroxy-terminated polysiloxane of the formula (E1). The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E1]

¹ H-NMR (CDCl ₃ , ppm): 0 ~ 0.5 ppm (324H, m), 0.68 ppm (4H, t), 1.05 ppm (4H, t), 1,48 ppm (6H, s), 1.71 ppm ( 4H, m), 2.67 ppm (8H, m), 6.70 ppm (2H, m), 6.85 ppm (2H, m), 7.03 ppm (2H, m), 7.12 ppm (4H, m), 7.25 ppm (2H, m), 7.37 ppm (4H, m)

Example 2

Using the methyl methacrylate (methyl methacrylate) 5.0g, bisphenol A 5.7g, H ₂ SO ₄ 0.5g, in the same manner as in the preparation of the compound of formula E1-2 of Example 1 having a double bond of the formula E2-1 The compound was prepared.

[Formula E2-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 1.63 ppm (6H, s), 3.02 ppm (4H, s), 5.01 ppm (4H, q), 7.14 ppm (4H, q) , 7.38 ppm (4H, q)

Next, using 100 g of the hydrogen-terminated polysiloxane of Formula E1-1, 10.7 g of the compound of Formula E2-1, and 4 g of 2-allylphenol, the same method as in the preparation of the Formula E1 compound of Example 1 was used to prepare the hydroxy terminal of Formula E2. Polysiloxane was obtained. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E2]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.65 ppm (6H, m), 0.75 ppm (6H, d), 1.48 ppm (6H, s), 1.70 ppm (4H, m), 2.02 ppm (2H, m), 2.33 ppm (4H, d), 2.64 ppm (2H, s), 2.69 ppm (2H, t), 6.70 ppm (2H, m), 6.86 ppm (2H, m) , 7.03 ppm (2H, m), 7.11 ppm (4H, m), 7.25 ppm (2H, m), 7.34 ppm (4H, m)

Example 3

4-allyl-benzoic acid (4-allyl-Benzoic acid) 8.1g, bisphenol A 5.7g, H ₂ SO ₄ 0.5g in the same manner as in the preparation of the compound of formula E1-2 of Example 1 using the following formula E3-1 A compound having a double bond was prepared.

[Formula E3-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 3.13 ppm (4H, d), 4.85 ppm (4H, m), 5.68 ppm (2H, m), 7.15 ppm (4H, m) , 7.38 ppm (8H, q), 7.91 ppm (4H, m)

Next, using 100 g of the hydrogen-terminal polysiloxane of Formula E1-1, 13.8 g of the compound of Formula E3-1, and 4 g of 2-allylphenol, the same method as in the preparation of the compound of Formula E1 of Example 1 was followed by the hydroxy end of Formula E3. Polysiloxane was obtained. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E3]

¹ H-NMR (CDCl ₃ , ppm): 0 to 0.5 ppm (324H, m), 0.67 ppm (8H, m), 1.48 ppm (6H, s), 1.68 to 1.82 ppm (8H, m), 2.63 ppm ( 8H, m), 6.70 ppm (1H, m), 6.81 ppm (1H, s), 6.86 ppm (1H, m), 7.03 ppm (1H, m), 7.10 ppm (9H, m), 7.20 ppm (1H, m), 7.25 ppm (1H, m), 7.34 ppm (1H, d), 7.38 ppm (4H, m), 7.83 ppm (4H, m)

Example 4

3.6 g of acrylic acid, 2,2-bis (4-aminophenyl) propane (2,2-bis (4-aminophenyl) propane) 5.65 g, H ₂ SO ₄ 0.5 g of Example 1, formula E1-2 A compound having a double bond of Formula E4-1 below was prepared in the same manner as in preparing the compound.

[Formula E4-1]

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

Next, using 100 g of the hydrogen-terminated polysiloxane of Formula E1-1, 9.2 g of the compound of Formula E4-1, and 4 g of 2-allylphenol, the same method as in the preparation of the Formula E1 compound of Example 1 was followed by the hydroxy end of Formula E4. Polysiloxane was obtained. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E4]

¹ H-NMR (CDCl ₃ , ppm): 0 to 0.5 ppm (324H, m), 0.67 ppm (4H, t), 1.00 ppm (4H, t), 1.48 ppm (6H, s), 1.71 ppm (4H, m), 2.55 ppm (4H, t), 2.69 ppm (4H, t), 6.70 ppm (2H, m), 6.86 ppm (2H, m), 7.03 ppm (2H, m), 7.06 ppm (4H, m) , 7.25 ppm (2H, m), 7.36 ppm (2H, m)

Example 5

Using the methyl methacrylate 5.0g, 2,2-bis (4-aminophenyl) propane 5.65g, H ₂ SO ₄ 0.5g, in the same manner as in the formula E1-2 compound preparation of Example 1, the following formula E5- A compound having a double bond of 1 was prepared.

[Formula E5-1]

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

Next, using 100 g of the hydrogen-terminated polysiloxane of Formula E1-1, 10.6 g of the compound of Formula E5-1, and 4 g of 2-allylphenol, the same method as in the preparation of the Formula E1 compound of Example 1 was followed by the hydroxy end of Formula E5. Polysiloxane was obtained. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E5]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.67 ppm (4H, t), 1.08 ppm (6H, d), 1.48 ppm (8H, m), 1.71 ppm (4H, m), 2.45 ppm (4H, d), 2.69 ppm (4H, t), 6.70 ppm (2H, m), 6.86 ppm (2H, m), 7.03 ppm (2H, m), 7.07 ppm (4H, m) , 7.25 ppm (2H, m), 7.36 ppm (4H, m)

Example 6

4-allyl-benzoic acid 8.1g, 2,2-bis (4-aminophenyl) propane 5.65g, H ₂ SO ₄ 0.5g, in the same manner as in the preparation of the compound of formula E1-2 of Example 1, the following formula E6 A compound having a double bond of -1 was prepared.

[Formula E6-1]

¹ H-NMR (CDCl ₃ , ppm): 1.48 ppm (6H, s), 3.13 ppm (4H, d), 4.85 ppm (4H, m), 5.67 ppm (2H, m), 7.07 ppm (4H, m) , 7.35 ppm (4H, m), 7.38 ppm (4H, q), 7.87 ppm (4H, m)

Next, using the same method as in the preparation of the compound of formula E1 in Example 1, using 100 g of the hydrogen-end polysiloxane of formula E1-1, 13.7 g of the compound of formula E6-1, and 4 g of 2-allylphenol, the hydroxy end of formula E6 Polysiloxane was obtained. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Formula E6]

¹ H-NMR (CDCl ₃ , ppm): 0-0.5 ppm (324H, m), 0.66 ppm (8H, m), 1.48 ppm (6H, s), 1.75 ppm (8H, m), 2.65 ppm (8H, m), 6.70 ppm (1H, m), 6.81 ppm (1H, s), 6.86 ppm (1H, m), 7.03 ppm (1H, m), 7.10 ppm (9H, m), 7.20 ppm (1H, m) , 7.25 ppm (1H, m), 7.34 ppm (1H, d), 7.38 ppm (4H, m), 7.83 ppm (4H, m)

<Preparation of polysiloxane-polycarbonate copolymer>

Example 7

400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000 was prepared by interfacial reaction of bisphenol A and phosgene gas in an aqueous solution in the presence of methylene chloride. Dissolved in methylene chloride in the obtained oligomeric polycarbonate mixture, 4.5% by weight of hydroxy-terminated polysiloxane of Formula E1 of Example 1 and tetrabutyl ammonium chloride (TBACl) 1.8 mL, p-tert-butylphenol (PTBP) 2.68 g, triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes. After separating the reacted oligomeric polycarbonate mixture layer, only the organic phase was collected. Here, 170 g of sodium hydroxide aqueous solution, 360 g of methylene chloride, and 300 μL of 15% by weight aqueous solution of triethylamine were mixed and reacted for 2 hours. After separating the layers, the organic phase having increased viscosity was washed after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2-3 times. After the washing was completed, the organic phase was assembled using a certain amount of pure water at 76 ° C. After the assembly was completed, it was first dried at 110 ° C for 8 hours, and secondly dried at 120 ° C for 10 hours. The copolymer of the peak of the methylene group of the polysiloxane observed at 2.6 ppm and 2.65 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of the polysiloxane observed at 6.95 to 7.5 ppm Confirmed. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Examples 8 to 12

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

Example 13

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

Example 14

In Example 7, p-tert-butylphenol (PTBP) 2.68 g was changed to 0.78 g, and the reaction was performed for 4 hours by increasing the reaction time 2 times after the first layer separation, and the viscosity was averaged. A polysiloxane-polycarbonate copolymer having a molecular weight of about 70,000 was prepared. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

Comparative Example 1: Preparation of a direct bond type hydroxy terminated polysiloxane

A 100 mL three-necked flask was equipped with a condenser, and under nitrogen atmosphere, 0.03 mol of 2-allylphenol and 0.015 mol of a hydrogen-terminated polydimethylsiloxane of formula CE1-1 below were completely dissolved in 50 mL of chlorobenzene, followed by a platinum catalyst (platinum (0)- 0.00364 mmol of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added and refluxed for 24 hours. After removing the solvent of the reacted solution, it was washed with distilled water to prepare a hydroxy-terminated polysiloxane of Chemical Formula CE1. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Chemical Formula CE1-1]

[Chemical Formula CE1]

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

A 100 mL 3-neck flask was equipped with a condenser, and under nitrogen atmosphere, 0.03 mol of 2-allylphenol and 0.015 mol of hydrogen-terminated polydimethylsiloxane of formula E1-1 were completely dissolved in 50 mL of chlorobenzene, and then a platinum catalyst (platinum (0) -1 , 3-divinyl-1,1,3,3-tetramethyldisiloxane complex) 0.00364 mmol was added and refluxed for 24 hours. After removing the solvent of the reacted solution, it was washed with distilled water to prepare a hydroxy-terminated polysiloxane of the following formula CE2-1.

[Chemical Formula CE2-1]

Next, a condenser was attached to a 500 mL 3-neck flask, and 0.4 mol of the compound of formula CE2-1 was dissolved in 300 mL of chloroform under a nitrogen atmosphere, and then 67 mL of triethylamine (TEA) was added. After refluxing the solution, 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform, and then slowly added for 1 hour and refluxed for 12 hours. After the reaction solution was removed, the solvent was dissolved in acetone and washed with hot distilled water. The hydroxy-terminated polysiloxane of formula CE2 was prepared by drying in a vacuum oven for 24 hours. The synthesis of the peak of the methylene group of the polysiloxane observed at 2.6 ppm by H-NMR and the hydrogen peak of the Benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of polysiloxane observed at 6.75 to 7.35 ppm Was confirmed. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Chemical Formula CE2]

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

After dissolving 0.0666 mol of the compound of formula CE2-1 in 100 mL of benzene under nitrogen conditions, 6.66 mmol of 1,4-diazabicyclo [2,2,2] -octane was added. In the state of refluxing the above solution, a solution in which 0.0333 mol of 4,4-methylene bis (phenyl isocyanate) was dissolved in 200 mL of benzene was slowly added for 1 hour. The above solution was refluxed for 12 hours. After the reaction solution was removed, the solvent was dissolved in acetone and washed with hot distilled water. By drying in a vacuum oven for 24 hours, a hydroxy-terminated polysiloxane of formula CE3 below was prepared. In the following formula CE3, hydrogen bound to the first carbon of the aliphatic chain adjacent to the terminal phenyl group was confirmed at 2.75 ppm. The physical properties of the prepared hydroxy-terminated polysiloxane were measured and are shown in Table 1 below.

[Chemical Formula CE3]

Comparative Examples 4 to 6

In Comparative Examples 4 to 6, a polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 7, except that 4.5 wt% of the compounds of Formulas CE1 to CE3 were used as hydroxy-terminated polysiloxanes, respectively. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and are shown in Table 2 below.

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

The methods for evaluating the physical properties shown in Tables 1 and 2 are as follows.

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

(b) Yield: [Actually synthesized compound weight (g) / Theoretical compound weight (g)] * 100%

(c) Viscosity average molecular weight (Mv): The viscosity of the methylene chloride solution was measured at 20 ° C using a Ubbelohde Viscometer, from which the intrinsic viscosity [η] was calculated by the following equation.

[η] = 1.23x10 ^-5 Mv ^0.83

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

[Ductile: Excellent impact resistance at low temperature vs. Brittle: Low temperature impact resistance]

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

Claims (14)

Polysiloxane-polycarbonate copolymer comprising a hydroxy-terminated polysiloxane of Formula 1 and a polycarbonate block as a repeating unit:
[Formula 1]

In Chemical Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a divalent hydrocarbon group having 2 to 30 carbon atoms,
L independently represents a divalent linking group selected from ester bonds or peptide bonds,
A is

ego,
m independently represents an integer from 0 to 4,
n independently represents an integer of 1 to 200. The polysiloxane-polycarbonate copolymer according to claim 1, wherein R ₃ is independently a C 2-6 linear or branched alkylene group. The method according to claim 1, R ₄ is independently a linear or branched alkylene group having 2 to 13 carbon atoms, a linear or branched alkenylene group having 2 to 13 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, or 6 to 10 carbon atoms. Arylene group, or a combination of these, characterized in that the polysiloxane-polycarbonate copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of 500 to 15,000. The polysiloxane-polycarbonate copolymer according to claim 1, wherein the content of the hydroxy-terminated polysiloxane is 1 to 40% by weight based on the total weight of the copolymer. The polysiloxane-polycarbonate copolymer according to claim 1, which has a viscosity average molecular weight of 10,000 to 100,000. Mixing the hydroxy-terminated polysiloxane of Formula 1 and an oligomeric polycarbonate, and then reacting under interfacial reaction conditions to form a polysiloxane-polycarbonate intermediate; And comprising the step of polymerizing the intermediate, a method for producing a polysiloxane-polycarbonate copolymer:
[Formula 1]

In Chemical Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
R ₂ independently represents a hydrocarbon group or a hydroxy group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
R ₄ independently represents a divalent hydrocarbon group having 2 to 30 carbon atoms,
L independently represents a divalent linking group selected from ester bonds or peptide bonds,
A is

ego,
m independently represents an integer from 0 to 4,
n independently represents an integer of 1 to 200. 8. The method of claim 7, wherein the oligomeric polycarbonate has a viscosity average molecular weight of 800 to 20,000. The method of claim 7, wherein the hydroxy-terminated polysiloxane has a number average molecular weight of 500 to 15,000. The method of claim 7, wherein the prepared polysiloxane-polycarbonate copolymer has a viscosity average molecular weight of 10,000 to 100,000. A molded article comprising the polysiloxane-polycarbonate copolymer of any one of claims 1 to 6. delete delete delete