WO2016089027A1 - Copolycarbonate and composition containing same - Google Patents

Abstract

The present invention relates to copolycarbonate and a molded product containing same, the copolycarbonate, according to the present invention, having a structure introducing a certain siloxane compound in a polycarbonate main chain, thereby enabling the improvement of room temperature impact strength, low temperature impact strength, and fluidity properties.

Description

 【Specification】

 [Name of invention]

 Copolycarbonate and Compositions Comprising the Same

 [Cross Citation with Related Application (s)]

 This application is the Korean Patent Application No. 10-2014-0173005 dated December 4, 2014,

Claiming the benefit of priority based on Korean Patent Application No. 10—2015-0109123 filed on July 31, 2015, and Korean Patent Application No. 10-2015-0159656 filed on November 13, 2015. All contents disclosed in the literature of the corresponding Korean patent applications are 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, and improved at room temperature impact strength, low temperature impact strength and fluidity. Background Art

Polycarbonate resins are prepared by condensation polymerization of aromatic di- like bisphenol A and carbonate precursors such as phosgene, and have excellent impact strength, numerical stability, heat resistance and transparency, and are used in exterior materials for automobiles, automobile parts, building materials, and optical parts. It is applied 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. However, most of the technologies have a high production cost, and if the chemical resistance, the laminar strength, especially the low temperature laminar strength is increased, the fluidity is deteriorated. The inventors have overcome the above disadvantages, room temperature layer strength, As a result of intensive studies on the copolycarbonates having improved low silver 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 room temperature impact strength. It is to provide a copolycarbonate with improved low impact strength and flow properties.

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

 In addition, the present invention is to provide an article comprising the copolycarbonate, or a polycarbonate composition.

 [Measures of problem]

 In order to solve the above problems, the present invention

 1) at least two repeating units selected from the group consisting of repeating units represented by the following Formulas 1 to 3, and

 2) comprising a repeating unit represented by the following formula (4),

 Copolycarbonates having an increased average molecular weight of from 1,000 to 100, 000 g / mo l are provided:

 [Formula 1]

 In Chemical Formula 1,

 ¾ are each independently d-) alkylene,

1 is each independently hydrogen; Unsubstituted or oxiranyl. Oxiranyl-substituted C _1-10 alkoxy, or C ₆ to-the d- _{15 20} substituted with arylalkyl; halogen; Alkoxy; Allyl: haloalkyl; ₂₀ is an aryl, - or C ₆

n is an integer from 10 to 200,

In Chemical Formula 2,

¾ are each independently d- ₁₀ alkylene.

₂₀ is an aryl, - \ ^ is hydrogen, _(6-alkyl, halogen, hydroxy, Ci-6 alkoxy, or C ₆ each independently

Each ¾ is independently hydrogen; Unsubstituted or oxiranyl group, an alkoxy substituted by oxiranyl group, or a C ₆ - ₂₀ aryl substituted with a d- ₁₅ alkyl; halogen; Cwo alkoxy: allyl: d-Q haloalkyl; ₂₀ is an aryl, - or C ₆

 m is an integer from 10 to 200,

 In Chemical Formula 3 above.

Each X ₃ is independently Cwo alkylene,

 ^ Is each independently Cwo alkoxy.

¾ is each independently hydrogen; Unsubstituted or oxiranyl group, a d- K) is substituted by oxiranyl alkoxy, or C ₆ - ₂₀ aryl substituted with C ₅ alkyl; halogen; Alkoxy; Allyl; d- ₁₀ haloalkyl; ₂₀ is an aryl, - or C ₆

 1 is an integer from 10 to 200.

[Formula 4]

In Chemical Formula 4,

X is unsubstituted or substituted phenyl or Cwo alkylene, unsubstituted or substituted with a C ₃ to _10, alkyl-cycloalkyl and X _15, 0, S, SO, S0 _2, or CO,

R ₄ to R ₇ are each independently hydrogen, ( ₁₀ alkyl. Du) alkoxy. Or halogen. Copolycarbonate according to the present invention includes a polycarbonate structure formed of a repeating unit represented by the formula (4). In general, polycarbonate is excellent in overall mechanical properties, but the room temperature impact strength, low temperature impact strength and fluidity properties are inferior, in order to improve this structure other than the polycarbonate structure needs to be introduced. In the present invention, in addition to the repeating unit represented by the formula (4), polysiloxane formed by two or more repeating units selected from the group consisting of repeating units represented by the formula (1) to 3 has a structure copolymerized in polycarbonate . This significantly improves the room temperature impact strength, low temperature laminar strength and fluidity properties compared to the conventional polycarbonate. Especially. In the present invention, it may include a repeating unit selected from the group consisting of repeating units represented by Formulas 1 to 3. It is characterized by including two or more kinds. According to the comparative examples and examples to be described later, it was confirmed that the room temperature impact strength, low silver layer strength and the degree of improvement of flow properties significantly increased when including two or more types, compared to the case of including a single species, This is due to the result of the complementary action of the degree of improvement of physical properties by the repeating unit. Below. The present invention is explained in more detail. Two or more repeating units selected from the group consisting of repeating units represented by Formulas 1 to 3

Copolycarbonate according to the present invention includes two or more repeating units selected from the group consisting of repeating units represented by the formula (1) to (3). Specifically, the term "two or more kinds of repeating units" as used herein means 1) one repeating unit represented by the formula (1) and one repeating unit represented by the formula (2). 2) one repeating unit represented by Formula 1 and one repeating unit represented by Formula 3, or 3) one repeating unit represented by Formula 2 and one repeating unit represented by Formula 3. . Specific examples of the above may be exemplified in the embodiments to be described later. The increase ratio between the two or more repeating units may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15, More preferably, it is 20: 80-80: 20. In the general formula (1), preferably ¾ are each independently C ₂ - ₄ alkylene and is, most preferably, _{propane-1,3-diyl-10} alkylene, more preferably C _2. Also preferably, are each independently hydrogen, methyl, ethyl, propyl,

3-phenylpropyl, 2-phenylpropyl, 3 '(oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoro Roethyl, 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. More preferably, ^ is each independently dK ₎ alkyl, more preferably d- ₆ alkyl, more preferably d- ₃ alkyl, most Preferably methyl. Also preferably, n is i) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or an integer of 35 or less, or iii) 50 or more, or 55 or more, It is an integer of 70 or less, 65 or less, or 60 or less. Also preferably, Chemical Formula 1 is represented by Chemical Formula 1-1.

In the formula 2, preferably ¾ are each independently C ₂ - to ₆ alkylene, more preferably isobutylene. Also preferably, ^ is hydrogen. Also preferably _, ^ is each independently hydrogen _, methyl _, ethyl _, propyl. 3-phenylpropyl, 2-phenylpropyl. 3- (oxyranylmethoxy) propyl, fluoro, chloro. Bromo. Io. Methoxy, epoxy, propoxy. Allyl, 2,2,2-trifluoroethyl, 3,3,3—trifluoropropyl, phenyl, or naphthyl. More preferably, ¾ is each independently Cw ₀ alkyl, more preferably alkyl, more preferably d- ₃ alkyl, most preferably methyl. Also preferably, ni is i) an integer from 30 to 60, or ii) 20 or more.

25 or more, or 30 or more. An integer of 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, and an integer of 70 or less, 65 or less, or 60 or less. Formula 2 is represented by the following Formula 2-1:

In Formula 3, preferably X ₃ are each independently C ₂ - ₁₀ alkylene. More preferably, the C ₂ - ₄ alkylene, most preferably propane -1.3- diyl. Also preferably. Y ₂ is d- ₆ alkoxy, more preferably d- ₄ alkoxy, most preferably methoxy. Also preferably, ¾ is each independently hydrogen, methyl. Ethyl, propyl.

3'phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chlorobrom bromo, iodo, mesopic, ecoxy, propoxy, allyl, 2,2,2-trifluoro Roethyl, 3, 3, 3'trifluorouropropyl, phenyl, or naphthyl. More preferably, _¾ is each independently alkyl, more preferably d- ₆ alkyl, more preferably C-3 alkyl and most preferably methyl. Also preferably, 1 is i) an integer of 30 to 60, or Π) 20 or more and 25 or more. Or 30 or more and 40 or less. Or an integer of 35 or less, or iii) an integer of 50 or more, or 55 or more, and 70 or less, 65 or less, or 60 or less. Also preferably, Formula 3 is represented by the following Formula 3-1:

 -One]

Preferably. The repeating unit represented by the above formulas (1) to (3) is derived from the real special compound represented by the siloxane compound represented by the following formulas 1-2, 2-2 and 3'2, respectively.

 In Chemical Formula 1-2,

 Xi, i and n are as defined above in Formula 1,

 [Formula 2-2]

 In Chemical Formula 2 ′ 2,

X ₂ , Yi, R ₂ and ni are as defined above in formula (2).

 [Formula 3-2]

In Chemical Formula 3-2,

X ₃ . Y2. ¾ and 1 are as defined in the formula (3). The meaning of “derived from the real special compound” means that the hydroxyl group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by each of Chemical Formulas 1 to 3 above. Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclonuclear carbonate. Diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-in-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene. One or more selected from the group consisting of bromophosgene and bishaloformates can be used. Preferably, triphosgene or phosgene can be used. In addition, the compounds represented by Chemical Formulas 1-2, 2-2, and 3-2 may be prepared by the methods of the following reactions 1 to 3, respectively.

[Class 1]

 0

 1 -2 in the reaction formula 1,

'It is C ₂ - ₁₀ alkenyl group, and, X, Rj and _n are as defined above in formula (I).

In the reaction form 2,

'Is O alkenyl, and X_o. YL R. and _m are as defined in Formula 2 above,

 In the reaction form 3,

'It is C ₂ - ₁₀ alkenyl, and Al, X _3, Y _2. R ₃ and 1 are the same as defined in the formula (3). The reaction of the reaction formulas 1 to 3 is preferably performed under a metal catalyst. Pt catalyst is preferably used as the metal catalyst, Pt Ashby catalyst, Karlstedt catalyst, Lamoreaux catalyst, Spire er catalyst, PtC l ₂ (C0D),

One or more selected from the group consisting of PtCl ₂ (benzonitrile) ₂ , and H ₂ PtBr ₆ can be used. The metal catalyst is 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight or more, 1 part by weight, 0.1 part by weight or less, based on 100 parts by weight of the compound represented by Formula 11, 13, or 15, or It can be used at 0.05 parts by weight or less. In addition, the reaction temperature is preferably so to ioo ^° c. In addition, the reaction time is preferably 1 hour to 5 hours. In addition, the compound represented by Formula 11, 13 or 15 may be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, it is possible to control the content of the reaction material to control n, m and 1 . 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 based on 100 parts by weight of the organocyclosiloxane of 0.01 weight part or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less. As the acid catalyst, at least one selected from the group consisting of H ₂ S0 ₄ , HC10 ₄ , AICI3, SbCl ₅ , SnCU, and acidic clay may be used. In addition, the acid The catalyst may be 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 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. Especially. By adjusting the content of the repeating unit represented by Formulas 1 to 3, it is possible to improve the physical properties of the copolycarbonate, the weight ratio of the repeating unit is a siloxane compound used for copolycarbonate polymerization, for example, the formula 1-2, It corresponds to the weight ratio of the siloxane compound represented by 2-2 and 3-2. Repeating unit represented by the formula (4)

Copolycarbonate according to the present invention includes a repeating unit represented by the formula (4). The repeating unit represented by Chemical Formula 4 is formed by reacting an aromatic diol compound and a carbonate precursor. In Formula 4 above. Preferably, to R ₇ are each independently hydrogen, methyl, chloro, or bromo. Further preferably, X is a straight chain or branched chain substituted with a phenyl ring, or beach ₍₁₀ alkyl alkylene, more preferably methylene, ethane-1,1-diyl, propane -2.2- diyl, butane-2, 2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylten, and preferably, X is cyclonucleic acid-ι, ι-diyl, 0, S, SO, S0 ₂ , or CO. Preferably, the repeating unit represented by Formula 4 is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl) 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, 2,2bisbis (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 ᅳ hydroxy-3-methylphenyl) propane, 2.2-bis ( 4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ᅳ 1-phenylethane, bis (4-hydroxyspecificphenyl) diphenylmethane, and α, ω— Any one or more aromatic di selected from the group consisting of bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane can be derived from the compound. The term “derived from an aromatic diol compound” means that a hydroxyl group of a aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (4). for example. When bisphenol A, which is an aromatic diol compound, and triphosgene, which is a carbonate precursor, are polymerized, the repeating unit represented by Formula 4 is represented by the following Formula 4-1.

 -One]

As the carbonate precursor, it is the same as described in the carbonate precursor that can be used to form the repeating units of Formulas 1 to 3 described above. Copolycarbonate

The copolycarbonate according to the present invention includes 1) at least two repeating units selected from the group consisting of repeating units represented by the above formulas (1) to (3), and 2) repeating units represented by the above formula (4). Preferably, the copolycarbonate is a random copolymer. Preferably. Copolycarbonate according to the present invention is increased average Molecular weight (g / mol) is 15,000 or more, 16,000 or more, 17,000 or more, 18,000 or more, 19,000 or more, 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24.000 or more, or 25,000 or more, 40,000 or less, 39,000 or less, 38,000 or less , 37,000 or less, 36,000 or less, 35,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less. The copolycarbonate according to the present invention is selected from the group consisting of i) an aromatic dialkyl compound, ii) a compound represented by the formula (1-1), a compound represented by the formula (2-1), and a compound represented by the formula (3-1). It can be prepared by a manufacturing method comprising the step of polymerizing a composition comprising two or more selected, and iii) a carbonate precursor. In the polymerization, at least two kinds selected from the group consisting of a compound represented by Formula 1-1, a compound represented by Formula 2-1, and a compound represented by Formula 3-1 are based on 100% by weight of the composition. 0.1 weight% or more, 0.5 weight ^< ¾ or more, 1 weight ¾ or more. Or 1.5% by weight or more, 20% by weight or less, 10% by weight or less, 7% by weight or less, 5% by weight or less, or 4% by weight or less may be used. The aromatic diol compound may be used in an amount of 40 wt% or more, 50 wt% or more, or 55 wt% or more, 80 wt% or less, 70 wt% or less, or 65 wt% or less with respect to 100 wt% of the composition. have. 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 or less, based on 100% by weight of the composition. In addition, as the polymerization method, for example, an interfacial polymerization method may be used. In this case, the polymerization reaction is possible at atmospheric pressure and low temperature, and the molecular weight is easily controlled. The interfacial polymerization is the presence of an acid binder and an organic solvent It is preferable to carry out under. In addition, the interfacial polymerization may include, for example, pre-polynier i zat i on, followed by adding a coupling agent and then doubling 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 the materials 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 alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine can be used. The organic solvent is not particularly limited as long as it is a solvent usually used for the polymerization of polycarbonate. For example, halogenated hydrocarbons such as methylene chloride chlorobenzene can be used. In addition, the interfacial polymerization is a reaction such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-11-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds to promote reaction. Accelerators may additionally be used. The reaction temperature of the interfacial polymerization is preferably 0 to 40 ^° C, the reaction time is preferably 10 minutes to 5 hours. In addition, during interfacial polymerization reaction. The pH is preferably maintained at 9 or higher. Also. 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 polymerization, or after the start of polymerization. Mono-alkylphenol can be used as the molecular weight regulator. remind Mono-alkylphenols include, for example, pt ert-butylphenol, p ᅳ cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. At least one member selected from the group consisting of: Preferably it is p-tert- butylphenol, and in this case, a 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 more, or 1 part by weight or more based on 100 parts by weight of an aromatic diol compound, and 10 parts by weight or less. It is contained in 6 weight part or less or 5 weight part or less, and can obtain desired molecular weight within this range. Polycarbonate composition

 The present invention also provides a polycarbonate composition comprising the copolycarbonate and polycarbonate. The copolycarbonate may be used alone, but the physical properties of the copolycarbonate may be controlled by using a polycarbonate together as necessary. The polycarbonate is distinguished from the copolycarbonate according to the present invention in that a polysiloxane structure is not introduced into the main chain of the polycarbonate. Preferably. The polycarbonate includes a repeating unit represented by Formula 5 below:

 [Formula 5]

In Formula 5 above.

R '4 to R' 7 are each independently hydrogen, Ci-K) alkyl, d-H) alkoxy, or halogen, X 'is substituted with an alkylene, unsubstituted or substituted alkyl, unsubstituted or substituted with phenyl or C ₃ - ₁₅ cycloalkylene, 0, S. SO. SO ₂ , or CO. Also preferably, the polycarbonate has a weight average molecular weight of 15,000 to 35,000 g / mol. More preferably, the extended average molecular weight (g / mol) is at least 20,000. 21,000 or more, 22,000 or more. More than 23,000, More than 24,000, More than 25,000. At least 26,000, at least 27,000, or at least 28,000. In addition, the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. The repeating unit represented by Formula 5 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 (4). Preferably, R'4 to R in the general formula 5 _'7 and X' are the same as in the general formula 4 R ₄ to R ₇ and X described above, respectively. Also preferably, the repeating unit represented by Formula 5 is. It is represented by following Chemical formula 5-1.

 -One]

In the polycarbonate composition. The increase ratio of copolycarbonate and polycarbonate is preferably 99: 1 to 1:99. More preferably 90:10 to 50:50. Most preferably 80:20 to 60:40. Also . The present invention provides an article comprising the copolycarbonate, or the polycarbonate composition. Preferably. The article is an injection molded article. In addition, the article is an antioxidant, heat stabilizer, light stabilizer. Plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, fluorescent whitening agents, UV absorbers. It may further comprise one or more selected from the group consisting of pigments and dyes. Method for producing the article. After the additives such as copolycarbonate and antioxidant according to the present invention are mixed using a mixer, the mixture is extruded by an extruder to prepare pellets. The pellet may be dried and then injected into an injection 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 that the phase silver impact strength and the low temperature laminar strength and fluidity properties are improved. . [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.

42.5 g (142.8 mniol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 6.8ol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with acidic clay (DC-A3) to 100 parts by weight of octamethylcyclotetrasiloxane. Into the 3L flask (flask) with the increase portion and reacted for 4 hours at 60 ° C. After completion of the reaction, it was diluted with ethyl acetate and filtered quickly using Sealite (celite). The repeating unit (n) of the unmodified polyorganosiloxane thus obtained was found to be 30 by NMR. 9.57 g (71.3 nimol) of 2-allylphenol and 0.01 g (50 ppin) of Karlstedt's latinum catalyst were added to the terminal unmodified polyorganosiloxane, which was reacted at 90 ^° C. for 3 hours. I was. Mibanung polyorganosiloxane after completion of the reaction was removed by evaporation at 120 ^° C, 1 torr conditions. The terminally modified polyorganosiloxane thus obtained was light yellow oil, and the repeating unit (n) was 30. No further purification was necessary and its preparation was confirmed by ^ NMR, which was named AP-30. Preparation Example 2 Preparation of Polyorganosiloxane (AP-60)

5 g (193.2 nimol) of octamethylcyclotetrasiloxane. After mixing tetramethyldisiloxane 2.26 g (16.8 mmol), it is common to the compounds acid clay (DC-A3) octamethylcyclotetrasiloxane 100 increased portion than 1 into a 3L flask (flask) with increased portion 60 ^° Reaction with C was carried out 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 found to be 60 by NMR. To the terminal unmodified polyorganosiloxane, 7.07 g (60.6 nimol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added and reacted at 90 ^° C. for 3 hours. I was. After the reaction Mibanung polyorganosiloxane was removed by evaporation at 120 ^° C, 1 ton 'conditions. The terminally modified polyorganosilic acid thus obtained is a light yellow oil. The repeating unit (n) was 60 and no further purification was necessary, its preparation was confirmed by ^ NMR, which was named AP-60. -30)

Except for using 3-methylbut-3-enyl 4-hydroxybenzoate (14.7 g) instead of 2-allylphenol. Polyorganosilic acid was prepared in the same manner as in Preparation Example 1. The repeating unit (m) was 30, which was confirmed by ^ NMR, which was named MB-30. -60)

 A polyorganosiloxane was prepared in the same manner as in Preparation Example 2, except that 3-methylbut-3-enyl 4-hydroxybenzoate (10.8 g) was used instead of 2-allylphenol. The repeating unit (m) was 60, which was confirmed by ^ NMR, which was named MB-60.

Polyorganosiloxane was prepared in the same manner as in Preparation Example 1, except that eugenol (11.7 g) was used instead of 2-allylphenol, and the repeating unit (1) was 30, which was confirmed by NMR. It was named Eu-30. Preparation Example 6 Preparation of Polyorganosiloxane (Eu-60)

 Except for using eugenol (8.7 g) instead of 2-allylphenol. Polyorganosiloxane was prepared in the same manner as in Preparation Example 2. Repeat unit (1) was 60, confirmed by ^ NMR. It was named Eu-60. Example 1-1

 1) Preparation of Copolycarbonate Resin

Into a 20L glass reaction machine, add 978.4 g of bisphenol A (BPA), 1.620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water. 18.3 g, 55.2 g of previously prepared polyorganosiloxane (80 wt% of polyorganosilic acid (AP-30) of Preparation Example 1 and 20 \% of polyorganosiloxane (MB-30) of Preparation Example 3) Was added and mixed. To this was added dropwise 3,850 g of methylene chloride dissolved in 542.5 g of triphosgene for 1 hour. At this time, the aqueous NaOH 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 copolycarbonate resin. The obtained copolycarbonate resin was measured for molecular weight by GPC using PC standard (Standard) and the weight average molecular weight 28, 100 g / niol was confirmed. 2) Preparation of Injection Specimen

0.050 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite and octadecyl-3 '(3,5-di-tert-butyl-4-hydroxyphenyl) prop in the prepared copolycarbonate resin 0.010 parts by weight of cypionate and 0.030 parts by weight of pentaerythrite tetrastearate are pelletized using a vented Φ 30ωιιι twin screw extruder, and then the cylinder temperature 300 using JSW Co., Ltd. N— 20C injection molding machine. ^The specimen was injection molded at a mold temperature of 80 ^° C. Examples 1-2 to 6-4 and Comparative Examples 1 to 6

 Prepared in the same manner as in Example 1-1, but the type and content of polyorganosiloxane as shown in Table 1 below. Copolycarbonate resins and injection specimens thereof were prepared, respectively. In Table 1, Comparative Examples 1 to 6 mean that a single polyorganosiloxane species was used.

 Table 1

Comparative Example 7

 Except not using a polyorganosiloxane in Example 1, polycarbonate resins and injection specimens thereof were prepared in the same manner.

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 Tables 2 to 4 below.

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

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

* Impact strength at room temperature and impact strength at low temperature (J / m): measured at 23 ^° C and -30 ^° C according to ASTM D256 (l / 8 inch, Notched Izod), respectively.

 * Repeating unit: measured by -NMR using a Varian 500MHz.

 [Table 2]

 Cold Impact Strength Cold Impact Strength Fluidity (MI) Weight Average Molecular Weight Example No.

 (23t.J / m) (-3C C, J / m) (g / 10 min) (Mw.g / mol) Example 1-1 663 210 15 28.100 Example 1 one 2 823 711 11 29,500

 480 120 16 27,800 Examples 1-4 531 180 17 27,500 Comparative Example 1 561 115 18 26,800 Examples 2-1 632 480 13 29.300 Examples 2-2 .780 695 9 30,900 Examples 2-3 610 435 12 28,800 Examples 2-4 635 448 14 28,300 Comparative example 2 713 630 7 30,900

Table 3

Example No. San Ochon O 'ᄋ 工 Fluidity (MI) Weight average molecular weight (23 ^° C. J / m) (23 ° C. J / m) (g / 10 min) (Mw, g / mol) Example 3-1 266 266 25 25,900 Example 3-2 528 528 16 27.100 Example 3-3 218 218 26 25.800 Example 3-4 323 323 20 26,300 Comparative Example 3 443 443 18 26, 800 Example 4-1 618 618 15 27.800 Example 4-2 590 590 14 28,500 Example 4-3 448 448 20 26.500 Examples 4-4 438 438 16 26.900 Comparative example 4 486 4S6 14 27, 500

4]

Claims

[Patent Claims]

 [Claim 11

 1) at least two repeating units selected from the group consisting of repeating units represented by the following Formulas 1 to 3, and

 2) comprising a repeating unit represented by the following formula (4),

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

 In Chemical Formula 1,

 ¾ are each independently C-K) alkylene,

Ri are each independently hydrogen, unsubstituted or substituted by oxiranyl group, a d-) substituted with oxiranyl alkoxy, or C ₆ - ₁₅ alkyl substituted with a d- ₂₀ aryl; halogen; d-) alkoxy; Allyl; d-haloalkyl; ₂₀ is an aryl, - or C ₆

 n is an integer from 10 to 200.

 [Formula 2]

 In Chemical Formula 2,

Each X ₂ is independently ( ₁₀ alkylene,

Each \ 'is independently hydrogen. d- ₆ alkyl. Halogen. Hydroxyl入Ci- alkoxy or C ₆ - ₂₀ aryl.

¾ is each independently hydrogen; D- ₁₅ alkyl unsubstituted or substituted with oxiranyl, d- ₁₀ alkoxy substituted with oxiranyl, or C _e - ₂₀ aryl; Halogen: du) alkoxy; Allyl; Haloalkyl; Or C ₆ — ₂₀ aryl,

m is an integer from 10 to 200. [Formula 3]

 In Chemical Formula 3,

 ¾ are each independently d-w alkylene,

Each Y ₂ is independently d-) alkoxy.

¾ is each independently hydrogen; Unsubstituted or oxiranyl, the CHO-alkoxy substituted by oxiranyl group, or C ₆ - ₂₀ aryl substituted with a d- ₁₅ alkyl; halogen; Alkoxy: allyl: d-) haloalkyl; Or C ₆ - ₂₀ aryl.

 1 is an integer from 10 to 200,

 [Formula 4]

In Chemical Formula 4,

X is unsubstituted or substituted phenyl or a d- ₁₀ alkylene, unsubstituted or substituted with Cwo alkyl substituted by C ₃ - ₁₅ cycloalkylene is, 0, S, SO, S0 _2, or CO,

1¾ to R? Are each independently hydrogen, Cw ₀ alkyl, or halogen.

[Claim 2]

 The method of claim 1.

 The two or more repeat units. One repeating unit represented by the formula (1) and one repeating unit represented by the formula (2), one repeating unit represented by the formula (1) and one repeating unit represented by the formula (3), or repeating unit represented by the formula (2)

Characterized in that it comprises one species and one repeating unit represented by the formula (3) Cordleycarbonate.

[Claim 3]

 The method of claim 1,

Ri. Copolycarbonate, R ₂ and R ₃ are each independently d- ₆ alkyl.

【Claim 4】.

 In that U term.

 n, m and 1 are each independently an integer of 30 to 60,

 Copolycarbonate.

[Claim 5]

 The method of claim 1,

 An increase ratio between two or more repeating units selected from the group consisting of repeating units represented by Chemical Formulas 1 to 3 may be 1:99 to 99: 1.

 Copolycarbonate.

[Claim 6]

 In U,

 Formula 1 is characterized in that represented by the formula 1-1, Copolycarbonate:

 [Formula 1-1]

[Claim 7]

 The method of claim 1,

 Formula 2 is a copolycarbonate characterized in that represented by the formula

[Claim 8]

 The method of claim 1,

 Formula 3 is represented by the following formula 3-1, copolycarbonate:

[Claim 9]

 The method of claim 1.

The repeating unit represented by the formula (4) is bis (4-hydroxyphenyl) methane. Bis (4'hydroxyphenyl) ether, bis (4-hydroxyspecificphenyl) sulfone, bis (4'hydroxyphenyl) sulfoxide. Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyspecialphenyl) 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 ᅳ 3, 5-dibromophenyl) propane, 2, 2-bis (4-hydroxy ᅳ 3,5-dichlorophenyl) propane, 2,2bisbis (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-hydroxya-3, 5-dimethylphenyl) Propane, 1,1-bis (4-hydroxyphenyl) —1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and α, ω ᅳ bis [3- (0 -hydroxyphenyl) propyl] Characterized in that derived from any one or more aromatic diol compound selected from the group consisting of polydimethylsiloxane,

 Copolycarbonate.

[Claim 10]

 The method of claim 1.

 Formula 4 is represented by the following formula (4). Copolycarbonate:

 -One]

[Claim 11]

 The method of claim 1.

 The copolycarbonate is characterized in that the weight average molecular weight of 15,000 to 40,000 g / mol.

 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 (5),

 Polycarbonate Composition:

 5]

In Formula 5 above.

R ^* ₄ to R '7 are each independently hydrogen, Cwo alkyl, Cwo alkoxy, or halogen,

Alkylene unsubstituted or substituted with phenyl. Substituted by unsubstituted or C _wo alkyl C ₃ - ₁₅ cycloalkylene, 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.

[Claim 15]

 The method of claim 12.

 The polycarbonate is characterized in that no polysiloxane structure is introduced into the main chain of the polycarbonate.

 Polycarbonate composition.