WO2016036203A1

WO2016036203A1 - Copolycarbonate and composition containing same

Info

Publication number: WO2016036203A1
Application number: PCT/KR2015/009370
Authority: WO
Inventors: 황영영; 반형민; 박정준; 홍무호; 이기재; 전병규; 고운; 손영욱
Original assignee: 주식회사 엘지화학
Priority date: 2014-09-05
Filing date: 2015-09-04
Publication date: 2016-03-10

Abstract

The present invention relates to a copolycarbonate and a composition containing the same. The copolycarbonate, according to the present invention, has a structure in which a specific siloxane compound is introduced into a polycarbonate main chain, and thus room temperature impact strength, low temperature impact strength, and fluidity properties can be improved.

Description

【Specification】

[Name of invention]

Copolycarbonate and Compositions Comprising the Same

[Cross Citation with Related Application (s)]

This application is filed with Korean Patent Application No. 10-2014-0118991, filed Sep. 5, 2014.

Claims the benefit of priority based on Korean Patent Application No. 10-2015-0109123 filed on July 31, 2015 and Korean Patent Application No. 10-2015-0125112 filed on September 3, 2015, and is disclosed in the literature of the Korean patent applications. All content is included as part of this specification.

Technical Field

The present invention relates to a copolycarbonate and a composition comprising the same, and more particularly to a copolycarbonate and a composition comprising the same, which is economically manufactured, improved room temperature layer strength, low temperature impact strength and fluidity. Background Art

Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have excellent lamella strength, numerical stability, heat resistance and transparency, and exterior materials for automobiles, automobile parts, building materials, and optical parts. It is applicable to a wide range of fields. These polycarbonate resins have recently been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic diol compounds having different structures to introduce a different structure into the main chain of the polycarbonate. . In particular, research into introducing a polysiloxane structure into the main chain of polycarbonate has been conducted, but most of the technologies have a disadvantage in that the production cost is high, and the chemical resistance, the laminar strength, especially the low temperature laminar strength increases, on the contrary, the fluidity decreases. The inventors have overcome the above disadvantages, the room temperature impact strength, As a result of intensive studies of copolycarbonates having improved low-temperature impact strength and fluidity properties, the present invention was completed by confirming that the copolycarbonates incorporating a specific siloxane compound into the polycarbonate backbone satisfy the above.

[Content of invention]

[Problem to solve]

The present invention is to provide a copolycarbonate with improved impact strength at room temperature, low silver impact strength and fluidity properties.

In addition, the present invention is to provide a polycarbonate composition comprising the copolycarbonate and polycarbonate.

The present invention also provides an article comprising the copolycarbonate or polycarbonate composition.

[Measures of problem]

In order to solve the above problems, the present invention

A repeating unit represented by the following formula 1,

A repeating unit represented by Formula 2 and

Including a repeating unit represented by the formula (3),

Copolycarbonates having a weight average molecular weight of 1,000 to 100, 000 g / n l are provided:

In Chemical Formula 1,

i to are each independently hydrogen, C- ₁₀ alkyl or halogen, Z is du) alkylene, C cycloalkylene, 0 S, SO, S0 ₂ or CO, unsubstituted or substituted with phenyl,

[Formula 2]

In Chemical Formula 2,

Ra is each independently d- ₁₀ alkylene,

Each Y is independently d-H) alkoxy,

¾ are each independently hydrogen or C _W3 alkyl,

n is an integer from 1 to 40,

[Formula 3]

In Chemical Formula 3,

Each R b is independently CHO alkylene,

Each Y 'is independently d- ₁₀ alkoxy,

¾ is each independently hydrogen or Cw ₃ alkyl

m is an integer of 41-150. Copolycarbonate according to the present invention, includes a polycarbonate structure formed of a repeating unit represented by the formula (1). In general, the polycarbonate is excellent in overall mechanical properties, but the room temperature strength, low temperature impact strength and fluidity properties are inferior, it is necessary to introduce a structure other than the polycarbonate structure to improve this. In the present invention, in addition to the repeating unit represented by the formula (1), the polysiloxane formed by the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) has a structure copolymerized in polycarbonate, through which Compared to the polycarbonate of the room temperature impact strength, low temperature laminar strength and fluid properties are significantly improved. In particular, the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are different from each other in the number of repeating units (n and m) of the silicon oxide in each formula. According to Comparative Examples and Examples to be described later, compared to the case in which only one of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3), the phase silver impact strength, low-temperature layer strength and It was confirmed that the degree of improvement of the fluidity properties was significantly increased, which is due to the result of the complementary action of the degree of improvement of properties by each repeating unit. Hereinafter, the present invention will be described in more detail. Repeat unit represented by Formula 1

The repeating unit represented by Formula 1 is formed by reacting an aromatic diol compound and a carbonate precursor. In Formula 1, preferably, to R ₄ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, Z is straight or branched chain d- ₁₀ alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethanol 1, 1-diyl, propane-2, 2-diyl, butane -2, 2-diyl, 1-phenylethane -1, 1-diyl, or diphenylmethylene. Also preferably, Z is cyclonucleic acid-1,1-diyl, 0, S, SO, S0 ₂ , or CO. Preferably, the repeating unit represented by Formula 1 is bis (4 ᅳ) Hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4 -Hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenolol A, 2, 2-bis (4-hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl ) Cyclonucleic acid, 2, 2-bis (4-hydroxy-3, 5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2, 2- Bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5 ᅳ dimethylphenyl) propane, 1, 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, And 3, 0 _bis [3- (0 -hydroxyphenyl) propyl] polydimethylsiloxane It can be derived from any one or more of an aromatic diol compound is selected from eu

The meaning of " ¹ derived from the aromatic diol compound" means that the hydroxy group and the carbonate precursor of the aromatic diol compound react to form a repeating unit represented by the formula (1). For example, when bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, are polymerized, the repeating unit represented by Formula 1 is represented by the following Formula 1-1:

Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate and bis (Diphenyl) carbonate, phosgene, triphosgene, One or more selected from the group consisting of diphosgene, bromophosgene and bishaloformates can be used. Preferably, triphosgene or phosgene can be used. Repeating unit represented by the formula (2) and repeating unit represented by the formula (3) The repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) are formed by reacting a siloxane compound and a carbonate precursor, respectively. In the formula 2, Ra is preferably each independently C ₂ - ₄ alkylene and is, most preferably, _{propane-1,3-diyl-10} alkylene, more preferably C _2. In addition, Y is preferably d- ₄ alkoxy, more preferably methoxy. R ₅ is preferably each independently d- ₆ alkyl, more preferably each independently ₃ alkyl, and most preferably methyl. In Formula 3, Rb are preferably each independently C ₂ - ₄ alkylene and is, most preferably, _{propane-1,3-diyl-10} alkylene, more preferably C _2. In addition, Y 'is preferably d- ₄ alkoxy, more preferably methoxy. Further, ¾ is preferably each independently d- ₆ alkyl, more preferably each independently d- ₃ alkyl, most preferably methyl. Also preferably, Ra and Rb are the same as each other. Also preferably, Y and Y 'are the same. Also preferably, ¾ and ¾ are identical to each other. Also preferably, Chemical Formula 2 is represented by the following Chemical Formula 2-1: [Formula 2-1]

Also preferably, Chemical Formula 3 is represented by the following Chemical Formula 3-1: [Formula 3-1]

Also preferably, in Chemical Formula 1, n is 10 or more, 15 or more, 20 or more, or 25 or more, and an integer of 35 or less. Also preferably, m in Formula 2 is an integer of 45 or more, 50 or more, or 55 or more and 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, or 65 or less. Preferably, the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are each derived from a siloxane compound represented by Formula 2-2 and a siloxane compound represented by Formula 3-2.

[Formula 2-2]

In Chemical Formula 2-2,

The definitions of Ra, Y, R ₅ and n are as defined above.

[Formula 3-2]

In Chemical Formula 3-2,

The definitions of Rb, Υ ', and m are as defined above. The term “derived from the siloxane compound” means that the hydroxyl group and the carbonate precursor of each siloxane compound react to form a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 . In addition, the carbonate precursor that can be used to form the repeating units represented by Formulas 2 and 3, the formula

It is as described in the carbonate precursor which can be used for formation of the repeating unit of 1. The method for producing the siloxane compound represented by Formula 2-2 and the siloxane compound represented by Formula 3-2 is as follows.

Scheme 1

7

In the reaction form 1,

Y, R ₅ and the definition of n is as previously defined, Ra 'is a C ₂ - ₁₀ alkenyl, and Al, [banung formula 2]

Banung in the formula 2, ^"

Υ ', the definition of Re and m are as defined above, Rb' is a C ₂ - ₁₀ alkenyl is. It is preferable that the reactions of the reaction systems 1 and 2 are carried out under a metal catalyst. It is preferable to use a Pt catalyst as the metal catalyst, and as a Pt catalyst, an Ashby catalyst, a Karlstedt catalyst, a Lamoreaux catalyst, a Speyer catalyst, a PtCl ₂ (C0D),

One or more selected from the group consisting of PtCl ₂ (benzonitrile) ₂ , and ¾PtBr ₆ can be used. The metal catalyst is 0.001 parts by weight, 0.005 parts by weight, or 0.01 parts by weight or more, 1 part by weight, 0.1 parts by weight or less, or 0.05 parts by weight based on 100 parts by weight of the compound represented by Formula 7 or 8. It can be used in parts or less. In addition, the reaction temperature is preferably -80 to 100 ^° C. In addition, the reaction time is preferably 1 hour to 5 hours. In addition, the compound represented by Formula 7 or 8 may be prepared by reacting organodisiloxane and organocyclosiloxane under an acid catalyst, and n and m may be controlled by adjusting the content of the reaction compound. The reaction temperature is preferably 50 to 70 ^° C. In addition, the reaction time is preferably 1 hour to 6 hours. As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisiloxane, and nuxaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. The organodisiloxane is 0.01 parts by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxane. As the acid catalyst, at least one selected from the group consisting of ¾SO ₄ , HC10 ₄ , AICI3, SbCl ₅ , S11CI4 and acidic clay may be used. In addition, the acid catalyst is 0.1 part by weight or more, 0.5 parts by weight or more, or 1 part by weight or more, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. Can be used. In particular, by controlling the content of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3), it is possible to improve the low-temperature laminar strength and fluidity of the copolycarbonate at the same time, preferably represented by the formula (2) The weight ratio of the repeating unit and the repeating unit represented by Formula 3 is 99: 1 to 1:99, more preferably 80:20 to 20:80. The weight ratio of the repeating unit is a weight ratio of the siloxane compound, for example, the siloxane compound represented by Formula 2-2 and the siloxane compound represented by Formula 3-2. Daewoong. Copolycarbonate

The copolycarbonate according to the present invention includes a repeating unit represented by Chemical Formulas 1 to 3, preferably a random copolymer. Also preferably, the copolycarbonate according to the present invention has a weight average molecular weight (g / mol) of 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, 2 000 or more, or 28,000 or more. The weight average molecular weight is 34,000 or less, 33,000 or less, 32,000 or less, 31,000 or less, or 30,000 or less. In addition, the weight ratio of the total weight of the repeating unit represented by the formula (1) and the total increase of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) (Formula 1: (Formula 2 + Formula 3)) is 1 : 0.04-0.07 is preferable. Copolycarbonate according to the present invention is prepared by a manufacturing method comprising the step of adding a composition comprising the aromatic diol compound, the compound represented by the formula (2-2), the compound represented by the formula (3-3) and the carbonate precursor described above can do. In the polymerization, the total amount of the compound represented by Formula 2-2 and the compound represented by Formula 3-2 in the composition is based on 100% by weight of the composition.

At least 0.1% by weight, at least 0.5% by weight, at least 1% by weight, or at least 1.5% by weight,

Preference is given to 20% by weight or less, 10% by weight or less, 7% by weight or less, 5% by weight or less, or 4% by weight aha. In addition, the ^"aromatic dieul compound based on 100% by weight of the composition 40 It may be used in an amount of at least 50% by weight, at least 50% by weight, or at least 55% by weight, and may be used at 80% by weight, at 70% by weight, or at most 65% by weight. The carbonate precursor may be used in an amount of 10% by weight, 20% by weight, or 30% by weight, 60% by weight, 50% by weight, or 40% by weight with respect to 100% by weight of the composition. In addition, as the polymerization method, for example, an interfacial polymerization method can be used. In this case, the reaction can be carried out at normal pressure and low temperature, and the molecular weight can be easily adjusted. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, after the prepolymerization (pre-polymer i zat ion), the coupling agent, and then polymerizing again. In this case, a high molecular weight copolycarbonate may be obtained. The materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary. As the acid binder, for example, an amine compound such as sodium hydroxide, alkali metal hydroxide of potassium hydroxide or pyridine can be used. The organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of polycarbonate. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used. In addition, the interfacial polymerization is a reaction such as triethylamine, tetra-n-butylammonium bromide, tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. Accelerators may additionally be used. The reaction silver of the interfacial polymerization is preferably 0 to 40 ^° C, the reaction time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH in 9 or more or 11 or more in interfacial polymerization reaction. In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of polymerization, during the start of the polymerization, or after the start of the polymerization. Mono-alkyl phenol may be used as the molecular weight regulator, and the mono-alkyl phenol is, for example, p-tert butyl phenol, P-cumylphenol, decyl phenol, dodecyl phenol, tetradecyl phenol, nuxadecyl phenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is large. The molecular weight modifier is, for example, 0.01 parts by weight or more, 0, 1 parts by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound. The desired molecular weight can be obtained within this range. Polycarbonate Composition

The present invention also provides a polycarbonate composition, comprising the copolycarbonate and polycarbonate. Although the copolycarbonate may be used alone, the physical properties of the copolycarbonate can be controlled by using a polycarbonate together if necessary. Preferably, the polycarbonate includes a repeating unit represented by Formula 4 below:

[Formula 4]

In Chemical Formula 4,

R'i to R'4 are each independently hydrogen, d- ₁₀ alkyl or halogen,

Z 'is unsubstituted or dM alkylene, C ₃ substituted by _phenyl-10 is a cycloalkylene, 0, S, SO, S0 2 or CO. The repeating unit represented by Chemical Formula 4 is formed by reacting an aromatic diol compound and a carbonate precursor. The aromatic diol compound and carbonate precursor which can be used are the same as described above in the repeating unit represented by the formula (1). Preferably, in Formula 4 to R'4 and Z ', are the same as ¾ to ¾ and Z of the formula (1) described above, respectively. Also preferably ^: the repeating unit represented by Chemical Formula 4 is represented by the following Chemical Formula 4-1.

In the polycarbonate composition, the weight ratio of copolycarbonate and polycarbonate is preferably 99: 1 to 1:99 ^', more preferably 90:10 to 50:50, and most preferably 80:20 to 60: 40. The present invention also provides an article comprising the copolycarbonate, or the polycarbonate composition. Preferably, the article is an injection molded article. In addition, the article is at least one selected from the group consisting of antioxidants, thermal stabilizers, photostabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. It can be included as. In the method for producing the article, the copolycarbonate and the additive according to the present invention, such as antioxidants are mixed using a mixer, the mixture is extruded by an extruder to produce a pellet, the pellet is dried and then injected It may include the step of injection into the molding machine.

【Effects of the Invention】

As described above, the copolycarbonate incorporating a specific siloxane compound into the polycarbonate main chain according to the present invention has an effect of improving room temperature impact strength, low temperature impact strength, and fluidity properties.

[Specific contents to carry out invention]

Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. Preparation Example 1 Preparation of Polyorganosiloxane (Eu-30)

42.5 g (142.8 隱 ol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed, and the mixture was then mixed with acidic clay (DC-A3) to 100 parts by weight of octamethylcyclotetrasiloxane. It was placed in a 3L flask with parts by weight and reacted at 60 ° C. for 4 hours. After completion of reaction, it was diluted with ethyl acetate and filtered quickly using celite. The repeating unit (n) of the unmodified polyorganosiloxane thus obtained was 30 as confirmed by ¾ NMR. 11.7 g (71.3 7 ol) of eugenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the obtained terminal unmodified polyorganosiloxane at 90 ^° C. for 3 hours. Reacted for a while. After completion of reaction, unreacted polyorganosiloxane was removed by evaporation at 120 ^° C and 1 torr. The terminally modified polyorganosiloxane thus obtained was a light yellow oil, (n) was 30, and no further purification was necessary, its preparation was confirmed by ¾ NMR, named Eu-30. Preparation Example 2 Preparation of Polyorganosiloxane (Eu-60)

After mixing 57.5 g (193.2 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane, the mixture was mixed with acidic clay (DC-A3) to 1 part of 100 parts by weight of octamethylcyclotetrasiloxane. The solution was poured into a 3L flask and reacted at 60 ^° C for 4 hours. After completion of reaction, it was diluted with ethyl acetate and filtered quickly using celite. The repeating unit (m) of the unmodified polyorganosiloxane thus obtained was found to be 60 by ¾ NMR. 8.7 g of eugenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the terminal unmodified polyorganosiloxane obtained above. It was added and reacted for 3 hours at 90 ^° C. After the completion of reaction, Mibanung polyorganosiloxane was removed by evaporation at 120 ^° C and 1 torr. The terminally modified polyorganosiloxane thus obtained was a light yellow oil, the repeating unit (m) was 60, no further purification was required, and its preparation was confirmed by ¾ NMR, named Eu-60. Preparation Example 3 Preparation of Polycarbonate

978.4 g of bisphenol A (BPA), 1,620 g of NaOH 32% aqueous solution, 7, 500 g of distilled water were added to a 20 L glass reactor, and after confirming that BPA was completely dissolved in a nitrogen atmosphere, methylene chloride 3, 670 g and 18.3 g of p-tert-butylphenol was added and mixed. To this was added 3850 g of methylene chloride dissolved in 542.5 g of triphosgene dropwise for 1 hour. At this time, the NaOH aqueous solution was maintained at pH 12. After completion of the dropwise addition, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was added to methylene chloride. After 10 minutes, the pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, washed three times with distilled water, the methylene chloride phase was separated, and then precipitated in methanol to obtain a powdery polycarbonate resin. Molecular weight was measured by GPC using PC standard (Standard) to confirm that the weight average molecular weight is 27, 500 g / irol. Example 1

Step 1) Preparation of Copolycarbonate

978.4 g of bisphenol A (BPA), 1,620 g of NaOH 32% solution, 7,500 g of distilled water were added to a 20 L glass reactor (Gl ass), and after confirming that BPA was completely dissolved in a nitrogen atmosphere, methylene chloride 3,670 g, 18.3 g of p-tert-butylphenol, 55.2 g of polyorganosiloxane prepared above (80 wt% of polyorganosiloxane (Eu-30) of Preparation Example 1 and polyorganosilic acid (Eu-60) 20 of Preparation Example 20) wt% of the mixture) was added and mixed. To this was added dropwise 3, 850 g of methylene chloride, 542.5 g of triphosphene, was added dropwise for 1 hour. At this time, the aqueous NaOH solution was maintained at ί) Η 12. After completion of the dropwise addition, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was added to methylene chloride. 10 minutes later, 1N The pH was adjusted to 3 with aqueous hydrochloric acid, washed three times with distilled water, the methylene chloride phase was separated, and the methane was precipitated in to obtain a powdery copolycarbonate. Obtained copolycarbonate was measured by GPC using PC standard (Standard) to determine the weight average molecular weight of 29, 600 g / mc l. Step 2) Preparation of Injection Specimen

0.05 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) in the copolycarbonate prepared in step 1 After adding 0.010 parts by weight of propionate and 0.030 parts by weight of pentaerythrite tetrastearate, pelletizing it with a 30 mm twin screw extruder with a vent, and then using a cylinder using JSW N-20C injection molding machine Molded specimens were injection molded at a temperature of 300 ^° C and a mold temperature of 80 ^° C. Example 2

Prepared in the same manner as in Example 1, except that 55.2 g of polyorganosiloxane (20 wt% of polyorganosiloxane (Eu 30) of Preparation Example 1 and polyorganosiloxane (Eu-60) 80 ¾ of Preparation Example 2) Copolycarbonates and molded specimens thereof were prepared, respectively. Example 3

80 wt% of the copolycarbonate prepared in Step 1 of Example 1 and 20 wt% of the polycarbonate of Preparation Example 3 were used instead of the copolycarbonate of Step 2 of Example 1 to prepare a composition and a specimen thereof. It was. Comparative Example 1

Prepared in the same manner as in Example 1, using 55.2 g of polyorganosiloxane (100 ^% of polyorganosiloxane (Eu-30) of Preparation Example 1), copolycarbonate and its molded specimens were prepared, respectively. . Comparative Example 2

Prepared in the same manner as in Example 1, using 55.2 g of polyorganosiloxane (100% of polyorganosiloxane (Eu-60) of Preparation Example 2), copolycarbonates and molded specimens thereof were prepared, respectively. Comparative Example 3

Using the polycarbonate of Preparation Example 3, instead of the copolycarbonate of Step 2 of Example 1, a molded specimen thereof was prepared. Experimental Example: Evaluation of Properties

The properties of the copolycarbonate prepared in Example and the polycarbonate specimen prepared in Comparative Example were measured by the following method, and the results are shown in Table 1 below.

* Weight average molecular weight (g / mol): measured by PC standard using Agi lent 1200 series.

* Flowability (MI): measured according to ASTM D1238 (300 ^° C, 1.2 kg conditions).

* Room temperature layer strength and low temperature impact strength (J / m): ASTM D256 (l / 8 inch, Notched

Izod) was measured at 23 ^° C and -30 ^° C respectively.

* Repeating unit: measured by _NMR using Varian 500MHz.

Table 2

Comparative Example 2 659 636 10 30,300 Comparative Example 3 660 116 14 27,500

Claims

[Patent Claims]

[Claim 1]

A repeating unit represented by the following formula 1,

A repeating unit represented by Formula 2, and

Including a repeating unit represented by the formula (3),

Copolycarbonates having a weight average molecular weight of 1,000 to 100, 000 g / mol:

In Chemical Formula 1,

Ri to are each independently hydrogen, Cwo alkyl or halogen,

Z is unsubstituted or substituted with phenyl;

And ₁₀ cycloalkylene, 0, S, SO, S0 2 or CO, - Killen, C ₃

2]

In Chemical Formula 2,

Ra ^ is each independently alkylene,

Each Y is independently alkoxy,

¾ are each independently hydrogen or d- ₁₃ alkyl,

n is an integer from 1 to 40,

[Formula 3]

In Chemical Formula 3,

Each R b is independently d-κ) alkylene,

Each Y 'is independently d- ₁₀ alkoxy,

Each R ₆ is independently hydrogen or d- ₁₃ alkyl,

m is an integer of 41-150.

[Claim 2]

According to claim 1,

The repeating unit represented by the formula (1) is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide , Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4—hydroxyphenyl) Butane, 1,1-bis (4-hydroxyphenyl) cyclonucleic acid, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy ᅳ 3, 5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4—hydroxy-3-chlorophenyl) propane, 2, 2— Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5 ᅳ dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, and a, omega bis [3— (0 -hydroxyphenyl ) Propyl] polydimethylsiloxane, characterized in that derived from at least one aromatic diol compound selected from the group consisting of

Copolycarbonate.

[Claim. Clause 3] In u,

The repeating unit represented by Formula 1 is characterized in that represented by the formula 1-1,

Copolycarbonate:

[Claim 4]

The method of claim 1,

¾ is each independently d- ₆ alkyl,

Copolycarbonate.

[Claim 5]

The method of claim 1,

R ₆ is each independently d- ₆ alkyl,

Copolycarbonate.

[Claim 6]

The method of claim 1,

¾ and are the same as each other,

Copolycarbonate.

[Claim 7]

The method of claim 1,

n is an integer of 10 to 35,

Copolycarbonate.

[Claim 8]

According to claim 1,

m is an integer of 45 to 100, characterized in that

Copolycarbonate.

[Claim 9]

In that U term,

The repeating unit represented by Formula 2 is characterized in that represented by the formula 2-1,

Copolycarbonate:

[Formula 2-1]

[Claim 10]

In U,

The repeating unit represented by the formula (3) is characterized in that represented by the formula (3-1),

Copolycarbonate:

[Formula 3-1]

[Claim 11]

The method of claim 1, The copolycarbonate has a weight average molecular weight of 15,000 to 35,000 g / i) l,

Copolycarbonate.

[Claim 12]

A polycarbonate composition comprising the copolycarbonate of any one of claims 1 to 11 and a polycarbonate.

[Claim 13]

The method of claim 12,

The polycarbonate is characterized in that it comprises a repeating unit represented by the following formula (4),

Polycarbonate composition

In Chemical Formula 4,

R'i to R'4 are each independently hydrogen, alkyl or halogen, Z 'is substituted by unsubstituted or phenyl Beach alkylene, C ₃ - ₁₀ Saha claw alkylene, 0, S, SO, S0 ₂ or CO.

[Claim 14]

The method of claim 12,

The weight ratio of the copolycarbonate and polycarbonate is characterized in that 99: 1 to 1:99,

Polycarbonate composition.