WO2016089134A2 - Copolycarbonate and composition containing same - Google Patents

Abstract

The present invention relates to a copolycarbonate and a composition containing the same and, specifically, to a technique of improving flame retardancy and chemical resistance while maintaining intrinsic impact strength and flowability of the copolycarbonate by comprising a branched repeat unit in a structure of the copolycarbonate.

Description

 [Name of invention]

 Copolycarbonate and Compositions Comprising the Same

 [Cross Citation with Related Application (s)]

 This application claims the benefit of priority based on Korean Patent Application No. 10-2014—0173005 dated December 4, 2014 and Korean Patent Application No. 10-2015-0170792 dated December 2, 2015. All content disclosed in the literature is included as part of this specification.

 Technical Field

 The present invention relates to a copolycarbonate and a composition comprising the same, to include a branched repeat unit in the copolycarbonate structure, to a technique for improving the flame resistance and chemical resistance while maintaining the impact strength and fluidity of the copolycarbonate will be.

 Background Art

Polycarbonate resin is prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, numerical stability, heat resistance and transparency, and are used for exterior materials, automotive parts, building materials, and optical parts of electric and electronic products. It is applied to a wide range of fields. In order to apply such polycarbonate resins in recent years, many studies have been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic dialkyl compounds to introduce units having different structures into the main chain of polycarbonate. . In particular, research into introducing a polysiloxane structure into the backbone of polycarbonate is underway, but most of the technologies are expensive to produce. It is disadvantageous in that flame resistance and chemical resistance are poor. The inventors hereby include branched repeat units as described below. The present invention was completed by confirming that the intrinsic laminar strength and fluidity of copolycarbonate can be improved while maintaining flame resistance and chemical resistance. [Content of invention]

 [Problem to solve]

 The present invention is to provide a copolycarbonate with improved flame retardancy and chemical resistance while maintaining the inherent impact strength and fluidity of the copolycarbonate.

 Also. The present invention is to provide a composition comprising the copolycarbonate.

 [Measures of problem]

 In order to solve the above problems, the present invention provides the following copolycarbonate:

 To include a repeating unit of the formula 1 to 3,

 It includes a branched repeat unit of the formula (4).

 At least one repeating unit of formula 1 to 3 is connected to each other by a branched repeating unit of formula 4,

 Have an extended average molecular weight of 1,000 to 100,000 g / mol.

 Copolycarbonate:

 [Formula 1]

In Chemical Formula 1 _,

Ri to R ₄ are each independently hydrogen. Ci-! O alkyl, alkoxy. Or halogen,

Z is C- ₁₀ alkylene unsubstituted or substituted with phenyl. An unsubstituted or substituted alkyl or CHO C ₃ - ₁₅ cycloalkylene, 0, S, SO, S0 2. Or CO,

[Formula 2]

 In Chemical Formula 2,

 : Are each independently d-) alkylene.

Each R ₅ is independently hydrogen; Unsubstituted or oxiranyl. D- ₁₀ alkoxy substituted with oxiranyl. Or C ₆ - ₂₀ alkyl substituted with aryl; Halogen: alkoxy; Allyl; d-w haloalkyl; ₂₀ is an aryl, - or C ₆

 n is an integer from 1 to 200.

 In Chemical Formula 3 above.

 ¾ are each independently d-K) alkylene,

Yl is each independently hydrogen. Ci-6 alkyl. Halogen, heat special. ( ₆ alkoxy. Or C _6-20 aryl,

Each ¾ is independently hydrogen: unsubstituted or oxiranyl. The d- substituted with oxiranyl ₁₀ alkoxy, or C ₆ - ₂₀ aryl substituted with a d- ₁₅ alkyl; Halogen: d- ₁₀ alkoxy; Allyl: C _wo haloalkyl; Or C ₆ - ₂₀ aryl.

 m is an integer from 1 to 200.

[Formula 4]

R _S to 1 are each independently hydrogen, d-K) alkyl. Halogen, CHO alkoxy: allyl; CHO haloalkyl: or C _6-20 aryl,

nl to n4 are each independently an integer of 1 to 4; . Polycarbonate is prepared by condensation polymerization of an aromatic diol compound such as bisphenol A and a carbonate precursor such as phosgene. It has excellent impact strength, numerical stability, heat resistance and transparency, and is applied to a wide range of fields such as exterior materials for automobiles, automobile parts, building materials, and optical parts. In order to further improve the physical properties of the polycarbonate, it is possible to introduce a polysiloxane structure in the main chain of the polycarbonate, thereby improving the various physical properties. However, in spite of the above, in order to be suitable for various applications, the polycarbonate having a polysiloxane structure should be excellent in flame retardancy and chemical resistance. To this end, it can be used with various additives, but such additives are one factor that degrades the inherent properties of polycarbonate. Accordingly, in the present invention, a polysiloxane structure is introduced into the main chain of the polycarbonate, and a branched repeating unit is introduced as described below, thereby maintaining the physical properties of the copolycarbonate to the maximum and at the same time flame retardant and chemical resistance. It can be improved. Hereinafter, the present invention will be described in more detail. Recurring Unit of Formula 1

The repeating unit represented by the formula (1) is formed by reacting an aromatic di compound with a carbonate precursor. In Chemical Formula 1 _, preferably. Are each independently hydrogen, methyl, chloro, or bromo. Also preferably, Z is a straight or branched chain c _wo alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-ι, ι-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-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-hydroxy Phenyl) butane, 1.1-bis (4-hydroxyphenyl) cyclonucleic acid. 2, 2-bis (4—hydroxy-3,5-dibromophenyl) propane, 2, 2-bis (4 ᅳ hydroxy-3, 5-dichlorophenyl) propane, 2,2-bis (4 ᅳ hydroxythoxy—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-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1 ᅳ phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and 01, 0) -bis [3- (0 -hydroxyphenyl) propyl] polydimethylsiloxane can be derived from any one or more aromatic diol compounds selected from the group consisting of. Said "derived from the aromatic diol compound" means. It means that the hydroxyl group of the aromatic di compound and the carbonate precursor react to form a repeating unit represented by the formula (1). For example, when bisphenol A which is an aromatic diol compound and triphosphene which is a carbonate precursor are integrated. The repeating unit represented by Formula 1 is represented by the following Formula 1-1:

 -One ]

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, and ditoryl carbonate. 1 selected from the group consisting of bis (chlorophenyl) carbonate, di-111-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate More than one species can be used. Preferably, triphosgene or phosgene can be used. Recurring Unit of Formula 2 and Recurring Unit of Formula 3

In Formula 2, 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 ᅳ _¾ is each independently hydrogen _, methyl _, ethyl _, propyl, 3-phenylpropyl, 2-phenylpropyl, 3— (oxyranylmethoxy) propyl. Fluoro, chloro, bromo. Iodo, Meeshi. Ethoxy. Propoxy, allyl, 2, 2, 2- Trifluoroethyl ᅳ 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably, ᅳ _¾ is each independently d-ω alkyl, more preferably C alkyl, more preferably alkyl, and most preferably methyl. Also preferably, n is 10 or more, 15 or more, 20 or more, 25 or more, 30 or more, 31 or more, or 32 or more, 50 or less, 45 or less, 40 or less, 39 or less, 38 or less, or 37 or less Is an integer. In Formula 3, preferably. ¾ are each independently a C ₂ - to ₁₀ alkylene, more preferably C ₂ - ₆ alkylene and most preferably isobutylene. Also preferably, ^ is hydrogen. Also preferably, ¾ is each independently hydrogen _, methyl _, ethyl _, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, medo Ci, ethoxy, propoxy, allyl, 2, 2, 2-trifluoroethyl, 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each R ₆ is independently d- ₁₀ alkyl, more preferably d- ₆ alkyl, still more preferably d- ₃ alkyl, most preferably methyl. Also preferably, the in is 40 or more, 45 or more, 50 or more, 5 or more. 56 or more, 57 or more, or 58 or more. It is an integer of 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or 62 or less. 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 2-1 and a siloxane compound represented by Formula 3-1.

In Formula 2-1, the definitions of XL R ₅ and n are as defined above. [Formula 3-1]

In Chemical Formula 3-1. X ₂ . The definitions of WR ₆ and m are as defined above. The term 'derived from the siloxane compound' means that the hydroxy group and the carbonate precursor of each of the siloxane compounds 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 of Formulas 2 and 3 is the same as described above for the carbonate precursor that can be used to form the repeating units of Formula 1. The method for producing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 is as follows.

Scheme 1

 6

In the reaction 1 above.

.V is a C ₂ - ₁₀ alkenyl, and Al,

Xi. R ₅ and n are as defined above,

 [Banungsik 2]

 8 9

 In the reaction form 2, ᅳ

¾ 'is C2- ₁₀ alkenyl,

The definitions of X ₂ , Yi, ¾ and m are as defined above. 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 Pt catalyst as the metal catalyst, Ashby catalyst, Karlstedt catalyst as Pt catalyst. Lamoreaux catalyst, Spe i er catalyst. PtCl 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 0.05 part by weight based on 100 parts by weight of the compound represented by Formula 7 or 9. 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 9 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 reactant. 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, nuxamethyldisil, siloxane 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 part by weight or more, or 2 parts by weight or more, based on 100 parts by weight of the organocyclosiloxane, and 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 SO ₄ , HC10 ₄ , AICI 3, SbC 1 ₅ , SnCl _4, and acidic clay may be used. In addition, the acid catalyst is 0.01 parts by weight based on 100 parts by weight of the organocyclosiloxane It is more than 0.5 weight part or more, or 1 weight part or more. 10 parts by weight or less. 5 parts by weight or less, or 3 parts by weight or less can be used. Especially . 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 simultaneously improve the low-temperature impact strength and YKYellow Index of the copolycarbonate. The weight ratio between the repeating units may be 1:99 to 99: 1. Preferably from 3:97 to 97: 3, from 5:95 to 95: 5, from 10:90 to 90:10. Or 15:85 to 85:15. More preferably, it is 20: 80-80: 20. The weight ratio of the repeating units are siloxane compounds, such as siloxane compounds, and repetition _(unit represented by Advantageously, the formula (2) to increase the ratio of the siloxane compound represented by Formula 3-1 represented by the above formula (2) eu 1, It is represented by the following formula 2-2:

 [Formula 2-2]

In Formula 2-2, R ₅ and n are as defined above. Preferably, R ₅ is methyl. Also preferably, the repeating unit represented by the formula _{3 is} represented by Formula 3-2:

一 2]

In formula 3-2. R ₆ and m are as defined above. Preferably, R ₆ is methyl. Preferably, the repeating unit represented by the formula (1). The weight ratio of the total weight of the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 (Formula 1: (Formula 2 + Formula 3)) is 1: 0.001 to 1: 0.2, more preferably 1 : 0.01 to 1: 0.1. The increase ratio of the repeating unit is based on the weight ratio of the aromatic dialkyl compound used to form the repeating unit of Formula 1 and the siloxane compound used to form the repeating unit of Formulas 2 and 3. Recurring Unit of Formula 4

 Copolycarbonate according to the present invention, in addition to the above-described repeating units of the formula 1 to 3 includes a branched repeating unit, such as the formula (4). Accordingly, one or more of the above-described repeating units of Formulas 1 to 3 are connected to each other by branched repeating units of the following Formula 4 so that the main chain is branched, thereby maintaining the impact strength and fluidity of the copolycarbonate, while maintaining flame resistance and flame resistance. It can improve chemistry.

Preferably, R ₇ is C _H3 alkyl, or

More preferably. Ci-4 alkyl. Is methyl and most preferably ^■ In addition, preferably, ¾ to R _U are each independently, hydrogen, C alkyl. Or halogen, more preferably hydrogen. The repeating unit represented by Chemical Formula 4 is derived from an aromatic polyhydric alcohol compound represented by Chemical Formula 4-1.

[Formula 4-1]

In Chemical Formula 4-1.

R ₇ is hydrogen, du) alkyl, or

Rs to Rii and nl to n4 are as defined above. The meaning of “derived from an aromatic polyhydric alcohol compound” means that the hydroxy group and the carbonate precursor of the aromatic polyhydric alcohol compound react to form a repeating unit represented by the formula (4). for example. When the aromatic polyhydric alcohol compound is THPE (ll, l-tris (4-hyc-oxyphenyl) ethane), polymerized with the tricarbonate, a carbonate precursor. The repeating unit represented by Formula 4 is represented by the following Formula 4-2:

 [Formula 4-2]

As another example, the aromatic polyhydric alcohol compound is 4.4 ', 4'',4' ¹ '- Methanetetrayltetraphenol (4.4 '.4''.4''' -methanetetrayltetraphenol). When polymerized with the tricarbonate, a carbonate precursor. The repeating unit represented by Formula 4 is represented by the following Formula 4-3:

 -3]

The carbonate precursor which can be used for formation of the repeating unit of Formula 4 above. As described above for the carbonate precursor that can be used to form the repeating unit of Formula 1 described above. Preferably. The weight ratio of the repeating unit represented by Formula 1 and the repeating unit represented by Formula 4 is 1: 0.001 to 1: 0.1. It is excellent in the physical-property improvement effect of a copolycarbonate in the said range. The weight ratio as defined above is based on the weight ratio of the aromatic dialkyl compound and the aromatic polyhydric alcohol compound used to form the repeating units of Formulas 1 and 4. Copolycarbonate

Copolycarbonate according to the present invention. It can be prepared by polymerizing the aforementioned aromatic diol compound, aromatic polyhydric alcohol compound, carbonate precursor and one or more siloxane compounds. The aromatic dihydric compound, aromatic polyhydric alcohol compound, carbonate precursor and one or more siloxane compounds are as described above. In addition, the weight ratio of each compound is as above-mentioned. As the polymerization method, for example, an interfacial polymerization method can be used. In this case, the reaction can be combined 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. Also. The interfacial polymerization may include, for example, prepolymerization (1 ⁾ 1-6-[) 01-| 1 ^ 23 ^ 011), followed by introducing a coupling agent and then polymerizing again, in which case a high molecular weight nose Polycarbonate can 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 polymerization of polycarbonate, and halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used as an example. In addition, the interfacial polymerization is a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. 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, in interfacial polymerization reaction, pH is It is preferable to keep it at 9 or more or 11 or more. 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 the polymerization, during the start of the polymerization or after the start of the polymerization. Mono-alkylphenol can be used as the molecular weight regulator. The mono-alkylphenols are, for example, p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontyl. It is 1 or more types chosen from the group which consists of phenols, Preferably it is p-tert- butylphenol, In this case, a molecular weight control effect is large. The molecular weight modifier is, for example, 0.01 part by weight, 0,1 part by weight, or 1 part by weight or more based on 100 parts by weight of the aromatic diol compound. 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less and the desired molecular weight can be obtained within this range. Also preferably, the copolycarbonate may have a weight average molecular weight

15,000 to 35,000 g / inol. More preferably, the extended average molecular weight (g / mol) is at least 20.000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 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. Polycarbonate composition

In addition, the present invention comprises the aforementioned copolycarbonate and polycarbonate. It provides a polycarbonate composition. 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 delicarbonate includes a repeating unit represented by Formula 5 below:

 [Formula 5]

In Formula 5 above.

R'i to R'4 are each independently hydrogen. du) alkyl, d- ₁₀ alkoxy. Or halogen,

Z 'is d- ₁₀ alkylene unsubstituted or substituted with phenyl. ₁₅ cycloalkylene, 0, S, SO, S0 2, CO, or - unsubstituted or Cwo alkyl substituted with C _3. Also preferably, the polycarbonate may have a weight average molecular weight

15.000 to 35,000 g / mol. More preferably, the weight average molecular weight (g / mol) is at least 20.000, at least 21,000, at least 22,000, at least 23,000. 24.000 or more, 25.000 or more, 26,000 or more, 27.000 or more. Or 28.000 or more. 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 (1). Preferably. To R ' ₄ and Z' of the formula (5), respectively, The same as in Formula 1 to R ₄ and Z. Also preferably, the repeating unit represented by Formula 5 is represented by the following Formula 5-1:

 -One ]

In the polycarbonate composition, the increase ratio of the copolycarbonate and the polycarbonate is preferably 99: 1 to 1:99, more preferably 90:10 to 50:50, most preferably 80:10 to 60: 40. ᅳ Also. The present invention is the above-mentioned copolycarbonate or ^:

An article comprising a polycarbonate composition is provided. Preferably, the article is an injection molded article. Also. The article is for example an antioxidant. Heat stabilizer. Light stabilizer. Plasticizers, antistatic agents. Nuclear floor may further comprise one or more selected from the group consisting of flame retardants, lubricants, impact modifiers, optical brighteners, ultraviolet absorbers, pigments and dyes. In the method for producing the article, the additives such as copolycarbonate and antioxidant according to the present invention are mixed using a mixer, and then the mixture is extruded into an extruder to produce pellets, and the pellets are dried, followed by an injection molding machine. It may include the step of injection into.

 【Effects of the Invention】

As described above, the copolycarbonate according to the present invention and the composition comprising the same, by introducing a polysiloxane structure in the main chain of the polycarbonate, and also by introducing a branched repeat unit, Maintaining maximum physical properties and improving flame retardancy and chemical resistance.

 [Specific contents to carry out invention]

 Below. Preferred embodiments are presented to aid the understanding of the invention. However, the following examples are only for illustrating the present invention. This invention is not limited only to these.

42.5 g (142.8 mmol) 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 octamethylcyclotetrasilic acid. Into 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 Sealite (celite). The repeating unit (n) of the unmodified polyorganosiloxane thus obtained was found to be 30 by NMR. 9.57 g (71.3 mmol) of 2-allylphenol and 0.01 g (50 ppni) of Karlstedt's platinum catalyst were added to the terminal unmodified polyorganosiloxane, which was reacted at 90 ^° C. for 3 hours. I was. After the reaction was completed, unreacted polyorganosiloxane was removed by evaporation at 120 ^° C. 1 ton ᅳ. The terminal modified polyorganosiloxane thus obtained was named AP-30. AP-30 is a pale yellow oil, and the repeat unit (n) was found to be 30 by ^ NMR using a Varian 500 MHz, and no further purification was necessary. Preparation Example 2 Preparation of Polyorganosiloxane (MB-60)

47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (ll mmol) of tetramethyldisiloxane were mixed. The mixture was placed in a 3L flask with 1 part by weight of acidic clay (DC—A3) relative to 100 parts by weight of octamethylcyclotetrasiloxane and reacted at 60 ^° C. for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (m) of the terminal unmodified polyorganosiloxane thus obtained was found to be 60 by NMR. 3-methylbut-3-enyl to the terminal unmodified polyorganosiloxane obtained above.

6.13 g (29.7 隱 ol) of 4-methylbut-3-enyl 4-hydroxybenzoate and 0.01 g (50 ppm) of Karlsteck's platinum catalyst were added for 3 hours at 90 ^° C. Reacted for a while. After the reaction. Mibanung real specialty was removed by evaporation at 120 ^° C, 1 ton-. The terminal modified polyorganosiloxane thus obtained was named MB-60. MB-60 is a soft snack oil, and it is confirmed that the repeat unit (m) is 60 by ¾ NMR using a Varian 500MHz. No further purification was necessary. Preparation Example 3

978.4 g of bisphenol A (BPA), 1.620 g of a 32% aqueous NaOH solution, in a 20 L glass reaction vessel. After 7,500 g of distilled water was added and it was confirmed that BPA was completely dissolved in a nitrogen atmosphere, 3,670 g of methylene chloride and 18.3 g of p-tert-butylphenol (PTBP) were 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. 10 minutes later. After adjusting the pH to 3 with 1N aqueous hydrochloric acid solution. After washing three times with distilled water, the methylene chloride phase was separated. Precipitated in methanol to give a powdered polycarbonate resin Obtained. Example 1

 In a 20L glass reaction machine, add 978.4 g of bisphenol A (BPA), 3.2 g of THPE (1, 1, 1-tris (4-hydroxypheny 1) et hane), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water. After confirming that BPA is completely dissolved in the atmosphere. 3.670 g of methylene chloride, 21.0 g of p-tert-butylphenol (PTBP), 44.16 g of previously prepared polyorganosiloxane (AP-30) and 11.04 g of polyorganosiloxane (MB-60) of Preparation Example 2 were added thereto. 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. 10 minutes later. 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 the methane was precipitated in to obtain a powdery copolycarbonate resin. Example 2

 A copolycarbonate resin was obtained in the same manner as in Example 1, except that 0.98 g of THPE was used. Example 3

 A copolycarbonate resin composition was prepared by mixing 80 parts by weight of the copolycarbonate prepared in Example 1 and 20 parts by weight of the polycarbonate prepared in Preparation Example 3. Comparative Example 1

A copolycarbonate resin was obtained in the same manner as in Example 1, except that 18.3 g of PTBP was used instead of 21.0 g without THPE. Comparative Example 2

 55.2 g of the polyorganosiloxane (AP-30) of Preparation Example 1 was used, and the polyorganosiloxane (MB- 60) of Preparation Example 2 was not used. Polycarbonate resin was obtained. Comparative Example 3

 A copolycarbonate resin was obtained in the same manner as in Example 1, except that the polyorganosiloxane of Preparation Example 1 (AP-30) and the polyorganosiloxane (MB-60) of Preparation Example 2 were not used. . Comparative Example 4

 Polycarbonate resin prepared in Preparation Example 3 was used as Comparative Example 4. The amount of the main reactants used in Examples and Comparative Examples was as shown in Table 1 below.

 Table 1

Experimental Example

 Copolycarbonates or compositions prepared in Examples and Comparative Examples

0.050 part by weight of tris (2,4-di-tert-butylphenyl) phosphite, octadecyl-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate per 1 part by weight Was added 0.010 parts by weight, and pentaerythrite tetrastearate was added, and pelletized using a φ30 kV twin-screw extruder with a vent, followed by JSW N-20C. A specimen was prepared by injection molding at a cylinder temperature 3 (xrc, mold temperature 8 (rc) using an injection molding machine. The characteristics of the specimen were measured by the following method.

 1) Weight average molecular weight (g / mol): Agilent 1200 series was measured by GPC using PC standard (Standard).

2) Phase Silver Hot Lapium Strength: Measured at 23 ^° C based on ASTM D256 (1/8 inch, Notched IzodHl).

3) Low temperature impact strength: measured at-30 ^° C based on ASTM D256 (1/8 inch, Notched IzodHl.

4) Melt Index (MI): Measured according to ASTM D 1238 (300 ^° C., 1.2 kg conditions).

 5) Flame retardancy: Flame retardancy was evaluated based on UL 94V. Specifically, five flame retardant specimens having a thickness of 3.0 kPa required for application of the flame retardant test were prepared and evaluated as follows.

 First, a flame of 20 mu m height was contacted with the specimen for 10 seconds, and then the combustion time (tl) of the specimen was measured, and the combustion pattern was recorded. Subsequently, when combustion was terminated after the first contact, the burning time (t2) and the burning time (glowing time. T3) of the specimen after contacting for 10 seconds were again measured, and the burning pattern was recorded. The same applies to the five specimens, and then evaluated based on the criteria in Table 2.

 Table 2

6) Chemical resistance: According to ASTM D638, a specimen (thickness: 3.2 ■) for measuring the tensile strength is prepared, ASTM To D543 (PRACTICE B). Based on the JIG Strain R1.0 was measured for chemical resistance. Specifically, a cotton cloth (2 cm 2 cm) was placed at the center of the specimen at room temperature (23 ^° C), and 2 mL of solvent (NIVEA © Aqua Protect Sunspray -SPF30, manufactured by Beiersdorf) was dropped on the cloth. The time taken from the moment to the breakage of each specimen was measured and evaluated based on the following criteria.

 © ： More than 24 hours

 O ： 1 hour to 24 hours

 Δ: 1 minute to 1 hour

 X: The result is shown in following Table 3 within 1 minute.

 [Table 3]

Claims

Claims 11 Claims 11 The repeating unit of the following formula (1) to 3, including the branched repeating unit of the formula (4), wherein at least one repeating unit of the formula 1 to 3 is branched repeating unit of 4 Connected to each other and having a weight average molecular weight of 1,000 to 100,000 g / m. Copolycarbonate:

 [Formula 1]

 In Formula 1 above.

R to R ₄ are each independently hydrogen. d- ₁₀ alkyl. ₁₀ alkoxy. Or halogen,

A substituted C ₃ to ₁₀ alkylene, unsubstituted or Cwo _alkyl-15 cycloalkylene and Z is an unsubstituted or C-substituted by phenyl or beach. 0, S. SO. S0 ₂ . Or CO

 [Formula 2]

 In Chemical Formula 2,

 > ^ Are each independently alkylene.

R ₅ are each independently hydrogen, unsubstituted or substituted oxiranyl, the κ-d) alkoxy optionally substituted with oxiranyl, or C ₆ - ₂₀ aryl substituted with a d- _15: halogen; Alkoxy; Allyl; d-κ) haloalkyl; Or C ₆ - ₂₀ aryl.

 n is an integer from 1 to 200.

[Formula 3]

In Chemical Formula 3,

Each X ₂ is independently d-) alkylene,

^ Are each independently hydrogen, d- ₆ alkyl, halogen, hydroxy, d- _e alkoxy. ₂₀ is an aryl, - or C ₆

¾ is each independently hydrogen; D- ₁₅ alkyl unsubstituted or substituted with oxiranyl, oxiranyl, or d- ₁₅ alkoxy substituted with C ₆ — ₂₀ aryl: halogen; d-) alkoxy; Allyl; Haloalkyl: or C ₆ - ₂₀ aryl.

 ill is an integer from 1 to 200,

 [Formula 4]

In Chemical Formula 4

0

R ₇ is hydrogen, d- ₁₀ alkyl, or

Rs to Rii are each independently hydrogen, Ci-io alkyl, halogen, alkoxy allyl; CHO haloalkyl; ₂₀ is an aryl, - or C ₆

 nl to n4 are each independently an integer of 1 to 4

[Claim 2]

In that U term The repeating unit represented by the formula (1) is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy phenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide Said, 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 — 3,5'dichlorophenyl) propane, 2, 2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxyaluminum-3-chlorophenyl) propane, 2, 2-bis (4-hydroxy-3-methylphenyl) propane, 2, 2-bis (4-hydroxy- 3.5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane , Bis (4-hydroxyphenyl) diphenylmethane, and α. ω—bis [3- (0 -hydroxyphenyl) propyl] polydimethylsiloxane, characterized in that any one or more aromatic di selected from the group consisting of

 Copolycarbonate.

[Claim 3]

 The method of claim 1.

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

 Copolycarbonate:

 -One]

[Claim 4]

 The method of claim 1.

The repeating unit represented by Formula 2 is represented by the following formula. Copolycarbonate:

 [Formula 2-2]

[Claim 5]

 The method of claim 1,

 Unit represented by the formula (3), characterized in that represented by the following formula,

 Copolycarbonate:

[Formula 3-2]

[Claim 6]

 The method of claim 1,

 n is an integer of 10 to 35,

 Copolycarbonate.

[Claim 71

 The method of claim 1,

 m is an integer of 45 to 100,

 Copolycarbonate.

[Claim 8]

In paragraph 1 The repeating unit represented by Chemical Formula 4 is represented by the following Chemical Formula 4-2 or Chemical Formula 4-3.

 Copolycarbonate:

 [Formula 4-2]

[Claim 9]

 A copolycarbonate according to any one of claims 1 to 8, and a licarbonate. Polycarbonate composition.

[Claim 10]

The method of claim 9. The polycarbonate is characterized in that the polysiloxane structure is not introduced into the main chain of the polycarbonate,

 Polycarbonate composition.

[Claim 11]

 According to claim 9,

 The polycarbonate is characterized in that it comprises a repeating unit represented by the following formula (5),

 Polycarbonate Composition:

 [Formula 5]

In Formula 5 above.

 R'1 to R'4 are each independently hydrogen. d-) alkyl. Alkoxy, or halogen,

VII 'is d-O alkylene unsubstituted or substituted with phenyl. _{15 cycloalkylene, 0. S, SO, S0 2} , CO, or - unsubstituted or Cwo alkyl substituted with C _3.