WO2016089134A2 - Copolycarbonate and composition containing same - Google Patents

Copolycarbonate and composition containing same Download PDF

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Publication number
WO2016089134A2
WO2016089134A2 PCT/KR2015/013156 KR2015013156W WO2016089134A2 WO 2016089134 A2 WO2016089134 A2 WO 2016089134A2 KR 2015013156 W KR2015013156 W KR 2015013156W WO 2016089134 A2 WO2016089134 A2 WO 2016089134A2
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WO
WIPO (PCT)
Prior art keywords
formula
bis
copolycarbonate
repeating unit
hydroxyphenyl
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PCT/KR2015/013156
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French (fr)
Korean (ko)
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WO2016089134A3 (en
Inventor
황영영
박정준
홍무호
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020150170792A external-priority patent/KR101786568B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP15866220.5A priority Critical patent/EP3228648B1/en
Priority to US15/316,727 priority patent/US9902853B2/en
Priority to CN201580040675.1A priority patent/CN106574044B/en
Priority to PL15866220T priority patent/PL3228648T3/en
Priority to JP2017500068A priority patent/JP6454774B2/en
Publication of WO2016089134A2 publication Critical patent/WO2016089134A2/en
Publication of WO2016089134A3 publication Critical patent/WO2016089134A3/en

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  • 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.
  • 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]
  • 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.
  • the present invention is to provide a composition comprising the copolycarbonate.
  • the present invention provides the following copolycarbonate:
  • At least one repeating unit of formula 1 to 3 is connected to each other by a branched repeating unit of formula 4,
  • Ri to R 4 are each independently hydrogen. Ci-! O alkyl, alkoxy. Or halogen,
  • Z is C- 10 alkylene unsubstituted or substituted with phenyl.
  • CO
  • 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.
  • 3 ⁇ 4 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 3 ⁇ 4 is independently hydrogen: unsubstituted or oxiranyl.
  • n is an integer from 1 to 200.
  • 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.
  • 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.
  • Recurring Unit of Formula 1 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.
  • Chemical Formula 1 preferably. Are each independently hydrogen, methyl, chloro, or bromo.
  • Z is a straight or branched chain c wo alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane- ⁇ , ⁇ -diyl, propane-2, 2-diyl, butane- 2, 2-diyl, 1-phenylethane, 1,1 "diyl, or diphenylmethylene.
  • Z is cyclonucleic acid-1,1-diyl, 0, S, SO, S0 2 , or CO.
  • 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 ⁇ hydroxy-3, 5-dichlorophenyl) propane, 2,2-bis (4 ⁇ 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 ⁇ 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).
  • the repeating unit represented by Formula 1 is represented by the following Formula 1-1:
  • 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.
  • 3 ⁇ 4 are each independently C 2 - 4 alkylene and is, most preferably, propane-1,3-diyl-10 alkylene, more preferably C 2.
  • ⁇ 3 ⁇ 4 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 ⁇ 3, 3, 3-trifluoropropyl, phenyl, or naphthyl.
  • ⁇ 3 ⁇ 4 is each independently d- ⁇ alkyl, more preferably C alkyl, more preferably alkyl, and most preferably methyl.
  • 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.
  • 3 ⁇ 4 are each independently a C 2 - to 10 alkylene, more preferably C 2 - 6 alkylene and most preferably isobutylene.
  • ⁇ is hydrogen.
  • 3 ⁇ 4 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.
  • each R 6 is independently d- 10 alkyl, more preferably d- 6 alkyl, still more preferably d- 3 alkyl, most preferably methyl.
  • 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.
  • .V is a C 2 - 10 alkenyl, and Al,
  • Xi. R 5 and n are as defined above,
  • X 2 , Yi, 3 ⁇ 4 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),
  • 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.
  • the reaction temperature is preferably 80 to 100 ° C.
  • the reaction time is preferably 1 hour to 5 hours.
  • 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.
  • the reaction time is preferably 1 hour to 6 hours.
  • the organodisiloxane one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, nuxamethyldisil, siloxane and nuxaphenyldisiloxane can be used.
  • 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.
  • 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.
  • 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 .
  • 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.
  • 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:
  • R 5 and n are as defined above.
  • R 5 is methyl.
  • the repeating unit represented by the formula 3 is represented by Formula 3-2:
  • R 6 and m are as defined above.
  • R 6 is methyl.
  • 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.
  • 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.
  • R 7 is C H3 alkyl, or More preferably. Ci-4 alkyl. Is methyl and most preferably ⁇
  • 3 ⁇ 4 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.
  • 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.
  • 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:
  • the aromatic polyhydric alcohol compound is 4.4 ', 4'',4' 1 '- Methanetetrayltetraphenol (4.4 '.4''.4''' -methanetetrayltetraphenol).
  • a carbonate precursor When polymerized with the tricarbonate, a carbonate precursor.
  • the repeating unit represented by Formula 4 is represented by the following Formula 4-3:
  • 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.
  • 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 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.
  • the weight ratio of each compound is as above-mentioned.
  • 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-
  • 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.
  • 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.
  • 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.
  • interfacial polymerization reaction pH is It is preferable to keep it at 9 or more or 11 or more.
  • 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.
  • the copolycarbonate may have a weight average molecular weight
  • 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.
  • the said weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less.
  • 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.
  • the delicarbonate includes a repeating unit represented by Formula 5 below:
  • 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.
  • the polycarbonate may have a weight average molecular weight
  • 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).
  • R ' 4 and Z' of the formula (5) respectively, The same as in Formula 1 to R 4 and Z.
  • the repeating unit represented by Formula 5 is represented by the following Formula 5-1:
  • 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.
  • the present invention is the above-mentioned copolycarbonate or :
  • An article comprising a polycarbonate composition is provided.
  • the article is an injection molded article.
  • the article is for example an antioxidant.
  • 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.
  • 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.
  • 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.
  • BPA bisphenol A
  • THPE 1, 1-tris (4-hydroxypheny 1) et hane
  • AP-30 previously prepared polyorganosiloxane
  • MB-60 polyorganosiloxane
  • 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 was obtained in the same manner as in Example 1, except that 0.98 g of THPE was used.
  • 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
  • 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.
  • Phase Silver Hot Lapium Strength Measured at 23 ° C based on ASTM D256 (1/8 inch, Notched IzodHl).
  • MI Melt Index
  • 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.

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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

【발명의 명칭】  [Name of invention]
코폴리카보네이트 및 이를 포함하는 조성물  Copolycarbonate and Compositions Comprising the Same
【관련 출원 (들)과의 상호 인용】  [Cross Citation with Related Application (s)]
본 출원은 2014년 12월 4일자 한국 특허 출원 제 10-2014— 0173005호 및 2015년 12월 2일자 한국 특허 출원 제 10-2015-0170792호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.  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.
【기술분야】  Technical Field
본 발명은 코폴리카보네이트 및 이를 포함하는 조성물에 관한 것으로， 코폴리카보네이트 구조에 분지형 반복 단위를 포함함으로써， 코폴리카보네이트 본연의 충격강도 및 유동성은 유지하면서 난연성 및 내화학성을 향상시키는 기술에 관한 것이다.  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.
【배경기술】  Background Art
폴리카보네이트 수지는 비스페놀 A와 같은 방향족 디올과 포스겐과 같은 카보네이트 전구체가 축중합하여 제조되고, 우수한 충격강도 , 수치안정성, 내열성 및 투명성 등을 가지며, 전기전자 제품의 외장재, 자동차 부품, 건축 소재, 광학 부품 등 광범위한 분야에 적용된다. 이러한 폴리카보네이트 수지는 최근 보다 다양한 분야에 적용하기 위해 2종 이상의 서로 다른 구조의 방향족 디을 화합물을 공중합하여 구조가 다른 단위체를 폴리카보네이트의 주쇄에 도입하여 원하는 물성을 얻고자 하는 연구가 많이 시도되고 있다. 특별히 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입시키는 연구도 진행되고는 있으나, 대부분의 기술들이 생산 단가가 높고. 난연성 및 내화학성이 떨어진다는 단점이 있다. 이에 본 발명자들은, 후술할 바와 같이 분지형 반복 단위를 포함함으로써. 코폴리카보네이트 본연의 층격강도 및 유동성은 유지하면서 난연성 및 내화학성을 향상시킬 수 있음을 확인하여 본 발명을 완성하였다. 【발명의 내용】 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]
【해결하려는 과제】  [Problem to solve]
본 발명은 코폴리카보네이트 본연의 충격강도 및 유동성은 유지하면서 난연성 및 내화학성을 향상된 코폴리카보네이트를 제공하기 위한 것이다.  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.
또한. 본 발명은 상기 코폴리카보네이트를 포함하는 조성물을 제공하기 위한 것이다.  Also. The present invention is to provide a composition comprising the copolycarbonate.
【과제의 해결 수단】  [Measures of problem]
상기 과제를 해결하기 위하여 , 본 발명은 하기의 코폴리카보네이트를 제공한다:  In order to solve the above problems, the present invention provides the following copolycarbonate:
하기 화학식 1 내지 3의 반복 단위를 포함하고,  To include a repeating unit of the formula 1 to 3,
하기 화학식 4의 분지형 반복 단위를 포함하며 .  It includes a branched repeat unit of the formula (4).
하기 화학식 1 내지 3의 반복 단위 증 하나 이상이 하기 화학식 4의 분지형 반복 단위에 의해 서로 연결되어 있고,  At least one repeating unit of formula 1 to 3 is connected to each other by a branched repeating unit of formula 4,
증량 평균 분자량이 1,000 내지 100,000 g/mol인 .  Have an extended average molecular weight of 1,000 to 100,000 g / mol.
코폴리카보네이트:  Copolycarbonate:
[화학식 1]  [Formula 1]
Figure imgf000003_0001
상기 화학식 1에서,
Figure imgf000003_0001
In Chemical Formula 1 ,
Ri 내지 R4는 각각 독립적으로 수소. Ci-!o 알킬 , 알콕시. 또는 할로겐이고, Ri to R 4 are each independently hydrogen. Ci-! O alkyl, alkoxy. Or halogen,
Z는 비치환되거나 또는 페닐로 치환된 C -10 알킬렌. 비치환되거나 또는 CHO 알킬로 치환된 C3-15 사이클로알킬렌, 0, S, SO, S02. 또는 CO이고, 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,
[화학식 2]
Figure imgf000004_0001
[Formula 2]
Figure imgf000004_0001
상기 화학식 2에서,  In Chemical Formula 2,
：^은 각각 독립적으로 d- ) 알킬렌이고.  : Are each independently d-) alkylene.
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐. 옥시라닐로 치환된 d-10 알콕시. 또는 C6-20 아릴로 치환된 알킬; 할로겐: 알콕시; 알릴; d- w 할로알킬; 또는 C6-20 아릴이고, 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
n은 1 내지 200의 정수이고.  n is an integer from 1 to 200.
Figure imgf000004_0002
Figure imgf000004_0002
상기 화학식 3에서.  In Chemical Formula 3 above.
¾은 각각 독립적으로 d-K) 알킬렌이고,  ¾ are each independently d-K) alkylene,
Yl는 각각 독립적으로 수소. Ci-6 알킬 . 할로겐 , 히드특시 . ( 6 알콕시 . 또는 C6-20 아릴이고, Yl is each independently hydrogen. Ci-6 alkyl. Halogen, heat special. ( 6 alkoxy. Or C 6-20 aryl,
¾는 각각 독립적으로 수소 : 비치환되거나 또는 옥시라닐 . 옥시라닐로 치환된 d-10 알콕시, 또는 C6-20 아릴로 치환된 d-15 알킬; 할로겐: d-10 알콕시; 알릴: Cwo 할로알킬; 또는 C6-20 아릴이고. 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.
m은 1 내지 200의 정수이고.  m is an integer from 1 to 200.
[화학식 4 ]
Figure imgf000005_0001
[Formula 4]
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0002
RS 내지 1은 각각 독립적으로 수소, d- K) 알킬. 할로겐, CHO 알콕시: 알릴； CHO 할로알킬: 또는 C6-20 아릴이고, R S to 1 are each independently hydrogen, d-K) alkyl. Halogen, CHO alkoxy: allyl; CHO haloalkyl: or C 6-20 aryl,
nl 내지 n4는 각각 독립적으로 1 내지 4의 정수이다. . 폴리카보네이트는 비스페놀 A와 같은 방향족 디올 화합물과 포스겐과 같은 카보네이트 전구체가 축중합하여 제조되는 것으로. 우수한 충격강도, 수치안정성, 내열성 및 투명성 등을 가지며, 전기전자 제품의 외장재, 자동차 부품, 건축 소재, 광학 부품 등 광범위한 분야에 적용된다. 이러한 폴리카보네이트의 물성을 보다 개선하기 위하여, 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입시킬 수 있으며, 이에 따라 여러 물성을 개선할 수 있다. 그러나, 상기에도 불구하고 다양한 응용 분야에 적합하도록, 폴리실록산 구조가 도입된 폴리카보네이트는 난연성과 내화학성이 우수하여야 한다. 이를 위하여 각종 첨가제와 함께 사용될 수 있으나, 이러한 첨가제는 폴리카보네이트 본연의 물성을 떨어뜨리는 한 요인이 된다. 이에 본 발명에서는 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입하고, 또한 후술할 바와 같이 분지형 반복단위를 도입함으로써, 코폴리카보네이트의 물성을 최대한 유지함과 동시에 난연성과 내화학성을 개선할 수 있다. 이하ᅳ 본 발명을 보다 상세히 설명한다. 화학식 1의 반복단위 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
상기 화학식 1로 표시되는 반복 단위는, 방향족 디을 화합물 및 카보네이트 전구체가 반응하여 형성된다. 상기 화학식 1에서, 바람직하게는. 내지 ^는 각각 독립적으로 수소, 메틸, 클로로, 또는 브로모이다. 또한 바람직하게는, Z는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 cwo 알킬렌이며, 보다 바람직하게는 메틸렌, 에탄 -ι,ι-디일， 프로판 -2, 2-디일, 부탄 -2, 2-디일, 1-페닐에탄ᅳ 1,1ᅳ디일, 또는 디페닐메틸렌이다. 또한 바람직하게는, Z는 사이클로핵산 -1,1-디일, 0, S, SO, S02, 또는 CO이다. 바람직하게는, 상기 화학식 1로 표시되는 반복 단위는 비스 (4- 히드록시페닐)메탄 비스 (4-히드록시페닐)에테르, 비스 (4- 히드록시페닐)설폰, 비스 (4-히드록시페닐)설폭사이드, 비스 (4- 히드록시페닐)설파이드, 비스 (4-히드록시페닐)케톤, 1,1-비스(4- 히드록시페닐)에탄, 비스페놀 A, 2，2—비스 (4-히드록시페닐)부탄， 1.1- 비스 (4-히드록시페닐)시클로핵산. 2, 2-비스 (4—히드록시 -3,5- 디브로모페닐)프로관, 2, 2-비스 (4ᅳ히드록시 -3, 5-디클로로페닐)프로판， 2,2- 비스 (4ᅳ히드톡시— 3-브로모페닐)프로판, 2, 2-비스 (4—히드록시 -3- 클로로페닐)프로판, 2, 2-비스 (4-히드록시 -3-메틸페닐)프로판, 2, 2-비스 (4- 히드록시 -3, 5—디메틸페닐)프로판， 1,1—비스 (4-히드록시페닐 )-1ᅳ페닐에탄, 비스 (4-히드록시페닐)디페닐메탄, 및 01 , 0)-비스[3-( 0 - 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래할 수 있다. 상기 '방향족 디올 화합물로부터 유래한다'의 의미는. 방향족 디을 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 화학식 1로 표시되는 반복 단위를 형성하는 것을 의미한다. 예컨대, 방향족 디올 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 증합된 경우. 상기 화학식 1로 표시되는 반복 단위는 하기 화학식 1—1로 표시된다 :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:
-1 ]  -One ]
Figure imgf000007_0001
Figure imgf000007_0001
상기 카보네이트 전구체로는, 디메틸 카보네이트, 디에틸 카보네이트, 디부틸 카보네이트, 디시클로핵실 카보네이트, 디페닐 카보네이트, 디토릴 카보네이트. 비스 (클로로페닐) 카보네이트, 디 -111- 크레실 카보네이트 , 디나프틸 카보네이트 , 비스 (디페닐 ) 카보네이트 , 포스겐, 트리포스겐, 디포스겐, 브로모포스겐 및 비스할로포르메이트로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 바람직하게는, 트리포스겐 또는 포스겐을 사용할 수 있다. 화학식 2의 반복단위 및 화학식 3의 반복단위 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
상기 화학식 2에서, 바람직하게는. ¾는 각각 독립적으로 C2-10 알킬렌이고, 보다 바람직하게는 C2-4 알킬렌이고, 가장 바람직하게는 프로판—1 , 3—디일이다. 또한 바람직하게는ᅳ ¾는 각각 독립적으로 수소, 메틸, 에틸, 프로필, 3-페닐프로필, 2—페닐프로필, 3— (옥시라닐메톡시)프로필. 플루오로, 클로로, 브로모. 아이오도, 메특시. 에톡시. 프로폭시, 알릴, 2 , 2 , 2- 트리플루오로에틸ᅳ 3 , 3 , 3-트리플루오로프로필, 페닐, 또는 나프틸이다. 또한 바람직하게는ᅳ ¾는 각각 독립적으로 d-ω 알킬이고, 보다 바람직하게는 C 알킬이고, 보다 바람직하게는 알킬이고, 가장 바람직하게는 메틸이다. 또한 바람직하게는, 상기 n은 10 이상, 15 이상, 20 이상, 25 이상, 30 이상, 31 이상, 또는 32 이상이고, 50 이하, 45 이하, 40 이하, 39 이하, 38 이하, 또는 37 이하의 정수이다. 상기 화학식 3에서, 바람직하게는. ¾는 각각 독립적으로 C2-10 알킬렌이고, 보다 바람직하게는 C2-6 알킬렌이고, 가장 바람직하게는 이소부틸렌이다. 또한 바람직하게는， ^는 수소이다. 또한 바람직하게는， ¾는 각각 독립적으로 수소, 메틸, 에틸, 프로필, 3-페닐프로필, 2—페닐프로필， 3- (옥시라닐메톡시)프로필, 플루오로, 클로로, 브로모, 아이오도, 메특시, 에록시, 프로폭시, 알릴, 2 , 2 , 2- 트리플루오로에틸, 3 , 3 , 3-트리플루오로프로필， 페닐, 또는 나프틸이다. 또한 바람직하게는, R6는 각각 독립적으로 d-10 알킬이고, 보다 바람직하게는 d-6 알킬이고， 보다 바람직하게는 d-3 알킬이고, 가장 바람직하게는 메틸이다. 또한 바람직하게는, 상기 in은 40 이상, 45 이상, 50 이상, 5 & 이상. 56 이상， 57 이상, 또는 58 이상이고. 80 이하, 75 이하, 70 이하, 65 이하, 64 이하, 63 이하, 또는 62 이하의 정수이다. 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위는 각각 하기 화학식 2-1로 표시되는 실록산 화합물 및 하기 화학식 3-1로 표시되는 실록산 화합물로부터 유래한다.
Figure imgf000009_0001
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.
Figure imgf000009_0001
상기 화학식 2-1에서, XL R5 및 n의 정의는 앞서 정의한 바와 같다. [화학식 3-1] In Formula 2-1, the definitions of XL R 5 and n are as defined above. [Formula 3-1]
Figure imgf000009_0002
상기 화학식 3-1에서. X2. W R6 및 m의 정의는 앞서 정의한 바와 같다. 상기 '실록산 화합물로부터 유래한다'의 의미는, 상기 각각의 실록산 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 각각의 화학식 2로 표시되는 반복 단위 및 화학식 3으로 표시되는 반복 단위를 형성하는 것을 의미한다. 또한, 상기 화학식 2 및 3의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체는, 앞서 설명한 화학식 1의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체에서 설명한 바와 같다. 상기 화학식 2-1로 표시되는 실록산 화합물 및 상기 화학식 3-1로 표시되는 실록산 화합물의 제조 방법은 각각 하기 반웅식 1 및 2와 같다.
Figure imgf000009_0002
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.
[반응식 1]
Figure imgf000010_0001
Scheme 1
Figure imgf000010_0001
6  6
Figure imgf000010_0002
Figure imgf000010_0002
상기 반웅식 1에서. In the reaction 1 above.
.V는 C2-10 알케닐이고, .V is a C 2 - 10 alkenyl, and Al,
Xi. R5 및 n의 정의는 앞서 정의한 바와 같고, Xi. R 5 and n are as defined above,
[반웅식 2]  [Banungsik 2]
Figure imgf000010_0003
Figure imgf000010_0003
8 9  8 9
Figure imgf000010_0004
Figure imgf000010_0004
상기 반웅식 2에서, ᅳ  In the reaction form 2, ᅳ
¾'는 C2-10 알케닐이고, ¾ 'is C2- 10 alkenyl,
X2, Yi, ¾ 및 m의 정의는 앞서 정의한 바와 같다. 상기 반웅식 1 및 반웅식 2의 반웅은, 금속 촉매 하에 수행하는 것이 바람직하다. 상기 금속 촉매로는 Pt 촉매를 사용하는 것이 바람직하며 , Pt 촉매로 애쉬바이 (Ashby)촉매, 칼스테드 (Karstedt)촉매. 라모레오 (Lamoreaux)촉매 , 스파이어 (Spe i er )촉매 . PtCl2(C0D) ,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),
PtCl2 (벤조니트릴 )2 , 및 H2PtBr6로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 상기 금속 촉매는 상기 화학식 7 또는 9로 표시되는 화합물 100 중량부를 기준으로 0.001 중량부 이상, 0.005 중량부 이상, 또는 0.01 중량부 이상이고, 1 중량부 이하, 0. 1 중량부 이하, 또는 0.05 중량부 이하로 사용할 수 있다. 또한, 상기 반응 온도는 80 내지 100 °C가 바람직하다. 또한, 상기 반응 시간은 1시간 내지 5시간이 바람직하다. 또한, 상기 화학식 7 또는 9로 표시되는 화합물은 오르가노디실록산과 오르가노시클로실록산을 산 촉매 하에서 반웅시켜 제조할 수 있으며, 상기 반응 물질의 함량을 조절하여 n 및 m을 조절할 수 있다. 상기 반웅 온도는 50 내지 70°C가 바람직하다. 또한, 상기 반웅 시간은 1시간 내지 6시간이 바람직하다. 상기 오르가노디실록산으로 , 테트라메틸디실록산 , 테트라페닐디실록산， 핵사메틸디실,록산 및 핵사페닐디실록산으로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한, 상기 오르가노시클로실록산은 일례로 오르가노시클로테트라실록산을 사용할 수 있으며, 이의 일례로 옥타메틸시클로테트라실록산 및 옥타페닐시클로테트라실록산 등을 들 수 있다. 상기 오르가노디실록산은， 상기 오르가노시클로실록산 100 중량부를 기준으로 0. 1 중량부 이상, 또는 2 중량부 이상이고， 10 중량부 이하. 또는 8 증량부 이하로 사용할 수 있다. 상기 산 촉매로는 H2S04 , HC104 , AICI3 , SbC l 5 , SnCl4 및 산성 백토로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한, 상기 산 촉매는 오르가노시클로실록산 100 증량부를 기준으로 0. 1 중량부 이상, 0.5 증량부 이상, 또는 1 증량부 이상이고. 10 증량부 이하. 5 증량부 이하, 또는 3 증량부 이하로 사용할 수 있다. 특히 . 상기 화학식 2로 표시되는 반복 단위와 상기 화학식 3으로 표시되는 반복 단위의 함량을 조절하여, 코폴리카보네이트의 저온충격강도와 YKYellow Index)를 동시에 개선할 수 있다. 상기 반복단위 간의 중량비는 1:99 내지 99:1가 될 수 있다. 바람직하게는 3:97 내지 97:3, 5：95 내지 95:5, 10:90 내지 90:10. 또는 15:85 내지 85:15이고. 보다 바람직하게는 20:80 내지 80:20이다. 상기 반복 단위의 중량비는 실록산 화합물, 예컨대 상기 화학식 2ᅳ1로 표시되는 실록산 화합물 및 상기 화학식 3-1로 표시되는 실록산 화합물의 증량비에 바람직하게는, 상기 화학식 2로 표시되는 반복 (단위는, 하기 화학식 2-2로 표시된다 : 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:
[화학식 2-2]  [Formula 2-2]
Figure imgf000012_0001
상기 화학식 2-2에서, R5 및 n은 앞서 정의한 바와 같다. 바람직하게는, R5는 메틸이다. 또한 바람직하게는, 상기 화학식 3로 표시되는 반복 단위는, 화학식 3-2로 표시된다:
Figure imgf000012_0001
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]
Figure imgf000012_0002
一 2]
Figure imgf000012_0002
화학식 3-2에서. R6 및 m은 앞서 정의한 바와 같다. 바람직하게는, R6는 메틸이다. 바람직하게는, 상기 화학식 1로 표시되는 반복 단위와. 상기 화학식 2로 표시되는 반복 단위 및 상기 화학식 3으로 표시되는 반복 단위의 총 중량의 중량비 (화학식 1: (화학식 2 + 화학식 3))는, 1:0.001 내지 1:0.2이고, 보다 바람직하게는 1:0.01 내지 1:0.1이다. 상기 반복 단위의 증량비는 상기 화학식 1의 반복 단위를 형성하는데 사용되는 방향족 디을 화합물 및 상기 화학식 2 및 3의 반복 단위를 형성하는데 사용되는 실록산 화합물의 중량비에 대웅된다. 화학식 4의 반복단위 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
본 발명에 따른 코폴리카보네이트는, 상술한 화학식 1 내지 3의 반복단위 외에 상기 화학식 4와 같은 분지형 반복단위를 포함한다. 이에 따라 상술한 화학식 1 내지 3의 반복 단위 중 하나 이상이 하기 화학식 4의 분지형 반복 단위에 의해 서로 연결되어 주쇄가 분지형이 되어, 코폴리카보네이트 본연의 충격강도 및 유동성은 유지하면서 난연성 및 내화학성을 향상시킬 수 있다.  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.
바람직하게는, R7은 CH3 알킬 , 또는
Figure imgf000013_0001
이고, 보다 바람직하게는. Ci-4 알킬이고. 가장 바람직하게■ 메틸이다 또한 바람직하게는, ¾ 내지 RU은 각각 독립적으로, 수소, C 알킬. 또는 할로게이고, 보다 바람직하게는 수소이다. 상기 화학식 4로 표시되는 반복 단위는 하기 화학식 4-1로 표시되는 방향족 다가 알코을 화합물로부터 유래한다. Preferably, R 7 is C H3 alkyl, or
Figure imgf000013_0001
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.
[화학식 4-1] [Formula 4-1]
Figure imgf000014_0001
상기 화학식 4-1에서.
Figure imgf000014_0001
In Chemical Formula 4-1.
R7은 수소, d-u) 알킬, 또는
Figure imgf000014_0002
이고, Rs 내지 Rii 및 nl 내지 n4는 앞서 정의한 바와 같다. 상기 '방향족 다가 알코올 화합물로부터 유래한다'의 의미는, 방향족 다가 알코올 화합물의 하이드록시기와 카보네이트 전구체가 반웅하여 상기 화학식 4로 표시되는 반복 단위를 형성하는 것을 의미한다 . 예컨대. 방향족 다가 알코올 화합물이 THPE(l.l,l-tris(4- hyc -oxyphenyl)ethane)인 경우, 카보네이트 전구체인 트리포스겐과 중합된 경우. 상기 화학식 4로 표시되는 반복 단위는 하기 화학식 4— 2로 표시된다: R 7 is hydrogen, du) alkyl, or
Figure imgf000014_0002
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:
[화학식 4-2]  [Formula 4-2]
Figure imgf000014_0003
Figure imgf000014_0003
또 다른 예로, 방향족 다가 알코을 화합물이 4.4' ,4' ' ,4' 1 '- 메탄테트라일테트라페놀 (4.4' .4' ' .4' ' '-methanetetrayltetraphenol)인 경우. 카보네이트 전구체인 트리포스겐과 중합된 경우. 상기 화학식 4로 표시되는 반복 단위는 하기 화학식 4-3으로 표시된다: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]  -3]
Figure imgf000015_0001
상기 화학식 4의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체는. 앞서 설명한 화학식 1의 반복 단위의 형성에 사용할 수 있는 카보네이트 전구체에서 설명한 바와 같다. 바람직하게는. 상기 화학식 1로 표시되는 반복 단위와 상기 화학식 4로 표시되는 반복 단위의 중량비는 1:0.001 내지 1:0.1이다. 상기의 범위에서 코폴리카보네이트의 물성 향상 효과가 우수하다. 상기에서 의미하는 중량비는 상기 화학식 1 및 4의 반복 단위를 형성하는데 사용되는 방향족 디을 화합물 및 방향족 다가 알코올 화합물의 중량비에 대웅된다. 코폴리카보네이트
Figure imgf000015_0001
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
본 발명에 따른 코폴리카보네이트는. 상술한 방향족 디올 화합물, 방향족 다가 알코을 화합물, 카보네이트 전구체 및 하나 이상의 실록산 화합물을 중합하여 제조할 수 있다. 상기 방향족 디을 화합물, 방향족 다가 알코을 화합물, 카보네이트 전구체 및 하나 이상의 실록산 화합물은 앞서 설명한 바와 같다. 또한, 각 화합물의 중량비는 앞서 설명한 바와 같다. 또한, 상기 중합 방법으로는, 일례로 계면증합 방법을 사용할 수 있으며. 이 경우 상압과 낮은 온도에서 증합 반웅이 가능하며 분자량 조절이 용이한 효과가 있다. 상기 계면중합은 산결합제 및 유기용매의 존재 하에 수행하는 것이 바람직하다. 또한. 상기 계면중합은 일례로 선중합( 1)1-6-[)01 -|1 ^ 23^ 011 ) 후 커플링제를 투입한 다음, 다시 중합시키는 단계를 포함할 수 있고， 이 경우 고분자량의 코폴리카보네이트를 얻을 수 있다. 상기 계면중합에 사용되는 물질들은 폴리카보네이트의 중합에 사용될 수 있는 물질이면 특별히 제한되지 않으며, 그 사용량도 필요에 따라 조절할 수 있다. 상기 산결합제로는 일례로 수산화나트륨, 수산화칼륨 등의 알칼리금속 수산화물 또는 피리딘 등의 아민 화합물을 사용할 수 있다. 상기 유기 용매로는 통상 폴리카보네이트의 중합에 사용되는 용매이면 특별히 제한되지 않으며, 일례로 메틸렌클로라이드, 클로로벤젠 등의 할로겐화 탄화수소를 사용할 수 있다. 또한， 상기 계면중합은 반응 촉진을 위해 트리에틸아민, 테트라 -n- 부틸암모늄브로마이드, 테트라—n-부틸포스포늄브로마이드 등의 3차 아민 화합물, 4차 암모늄 화합물, 4차 포스포늄 화합물 등과 같은 반응 촉진제를 추가로 사용할 수 있다. 상기 계면중합의 반웅 온도는 0 내지 40 °C인 것이 바람직하며, 반웅 시간은 10분 내지 5시간이 바람직하다. 또한, 계면중합 반웅 중, pH는 9이상 또는 11이상으로 유지하는 것이 바람직하다. 또한, 상기 계면중합은 분자량 조절제를 더 포함하여 수행할 수 있다. 상기 분자량 조절제는 중합개시 전, 중합개시 중 또는 중합개시 후에 투입할 수 있다. 상기 분자량 조절제로 모노 -알킬페놀을 사용할 수 있으며. 상기 모노—알킬페놀은 일례로 p-tert-부틸페놀, P-쿠밀페놀, 데실페놀, 도데실페놀， 테트라데실페놀, 핵사데실페놀, 옥타데실페놀, 에이코실페놀, 도코실페놀 및 트리아콘틸페놀로 이루어진 군으로부터 선택된 1종 이상이고, 바람직하게는 p-tert-부틸페놀이며， 이 경우 분자량 조절 효과가 크다. 상기 분자량 조절제는 일례로 방향족 디올 화합물 100 중량부를 기준으로 0.01 중량부 이상, 0,1 중량부 이상, 또는 1 중량부 이상이고. 10 증량부 이하, 6 중량부 이하, 또는 5 중량부 이하로 포함되고ᅳ 이 범위 내에서 원하는 분자량을 얻을 수 있다. 또한 바람직하게는, 상기 코폴리카보네이트는 중량 평균 분자량이Copolycarbonate 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 내지 35,000 g/inol이다. 보다 바람직하게는, 상기 증량 평균 분자량 (g/mol)은 20.000 이상, 21,000 이상, 22,000 이상, 23,000 이상, 24,000 이상， 25.000 이상, 26,000 이상， 27,000 이상, 또는 28,000 이상이다. 또한, 상기 중량 평균 분자량은 34,000 이하, 33,000 이하, 또는 32,000 이하이다. 폴리카보네이트 조성물 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
또한， 본 발명은 상술한 코폴리카보네이트 및 폴리카보네이트를 포함하는. 폴리카보네이트 조성물을 제공한다. 상기 코폴리카보네이트를 단독으로도 사용할 수 있으나, 필요에 따라 폴리카보네이트를 함께 사용함으로서 코폴리카보네이트의 물성을 조절할 수 있다. 상기 폴리카보네이트는, 폴리카보네이트의 주쇄에 폴리실록산 구조가 도입되어 있지 않다는 점에서, 본 발명에 따른 코폴리카보네이트와 구분된다. 바람직하게는, 상기 들리카보네이트는 하기 화학식 5로 표시되는 반복 단위를 포함한다: 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:
[화학식 5]  [Formula 5]
Figure imgf000018_0001
상기 화학식 5에서.
Figure imgf000018_0001
In Formula 5 above.
R'i 내지 R'4는 각각 독립적으로 수소. d-u) 알킬, d-10 알콕시. 또는 할로겐이고, R'i to R'4 are each independently hydrogen. du) alkyl, d- 10 alkoxy. Or halogen,
Z'는 비치환되거나 또는 페닐로 치환된 d-10 알킬렌. 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌, 0, S, SO, S02, 또는 CO이다. 또한 바람직하게는, 상기 폴리카보네이트는 중량 평균 분자량이Z '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 내지 35,000 g/mol이다. 보다 바람직하게는, 상기 중량 평균 분자량 (g/mol)은 20.000 이상, 21,000 이상, 22,000 이상, 23,000 이상. 24.000 이상, 25.000 이상, 26,000 이상, 27.000 이상. 또는 28.000 이상이다. 또한, 상기 중량 평균 분자량은 34,000 이하. 33,000 이하, 또는 32,000 이하이다. 상기 화학식 5로 표시되는 반복 단위는, 방향족 디올 화합물 및 카보네이트 전구체가 반응하여 형성된다. 상기 사용할 수 있는 방향족 디올 화합물 및 카보네이트 전구체는. 앞서 화학식 1로 표시되는 반복 단위에서 설명한 바와 동일하다. 바람직하게는. 상기 화학식 5의 내지 R'4 및 Z'는, 각각 앞서 설명한 화학식 1의 내지 R4 및 Z와 동일하다. 또한 바람직하게는, 상기 화학식 5로 표시되는 반복 단위는, 하기 화학식 5—1로 표시된다: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:
-1 ]  -One ]
Figure imgf000019_0001
Figure imgf000019_0001
상기 폴리카보네이트 조성물에서, 코폴리카보네이트 및 폴리카보네이트의 증량비는 99 : 1 내지 1 : 99인 것이 바람직하며, 보다 바람직하게는 90 : 10 내지 50 : 50 , 가장 바람직하게는 80：20 내지 60 : 40이다. ᅳ 또한. 본 발명은 상술한 코폴리카보네이트 또 :
Figure imgf000019_0002
폴리카보네이트 조성물을 포함하는 물품을 제공한다. 바람직하게는, 상기 물품은 사출 성형품이다. 또한. 상기 물품은 일례로 산화방지제. 열안정제. 광안정화제. 가소제, 대전방지제. 핵저ᄂ 난연제, 활제, 충격보강제, 형광증백제, 자외선흡수제, 안료 및 염료로 이루어진 군으로부터 선택된 1종 이상을 추가로 포함할 수 있다. 상기 물품의 제조 방법은, 본 발명에 따른 코폴리카보네이트와 산화방지제 등과 같은 첨가제를 믹서를 이용하여 혼합한 후, 상기 혼합물을 압출기로 압출성형하여 펠릿으로 제조하고, 상기 펠릿을 건조시킨 다음 사출성형기로 사출하는 단계를 포함할 수 있다. 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 :
Figure imgf000019_0002
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.
【발명의 효과】  【Effects of the Invention】
상기에서 살펴본 바와 같이 , 본 발명에 따른 코폴리카보네이트 및 이를 포함하는 조성물은, 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입하고, 또한 분지형 반복단위를 도입함으로써, 코폴리카보네이트의 물성을 최대한 유지함과 동시에 난연성과 내화학성을 개선할 수 있다는 특징이 있다. 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.
【발명을 실시하기 위한 구체적인 내용】  [Specific contents to carry out invention]
이하. 발명의 이해를 돕기 위하여 바람직한 실시예들이 제시된다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐. 본 발명을 이들만으로 한정하는 것은 아니다.  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.
Figure imgf000020_0001
Figure imgf000020_0001
옥타메틸시클로테트라실록산 42.5 g(142.8 mmol), 테트라메틸디실록산 2.26 g(16.8 mmol)을 혼합한 후, 이 혼합물을 산성백토 (DC— A3)를 옥타메틸시클로테트라실특산 100. 중량부 대비 1 중량부와 함께 3L 플라스크 (flask)에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후 이를 에틸아세테이트로 희석하고 씰라이트 (celite)를 사용하여 빠르게 필터링하였다. 이렇게 수득된 미변성 폴리오르가노실록산의 반복 단위 (n)는 NMR로 확인한 결과 30이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 2-알릴페놀 9.57 g(71.3 mmol) 및 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppni)을 투입하여 90°C에서 3시간 동안 반응시켰다. 반응 종료 후 미반응 폴리오르가노실록산은 120°C. 1 tonᅳ의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 AP-30으로 명명하였다. AP-30은 연황색 오일이며, Varian 500MHz을 이용하여 ^ NMR을 통해 반복 단위 (n)는 30임을 확인하였으며, 더 이상의 정제는 필요하지 않았다. 제조예 2: 폴리오르가노실록산 (MB-60)의 제조
Figure imgf000021_0001
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)
Figure imgf000021_0001
옥타메틸시클로테트라실록산 47.60 g(160 mmol), 테트라메틸디실록산 1.5 g(ll mmol)을 혼합한 후. 상기 혼합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC— A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반응시켰다. 반웅 종료 후 , 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복 단위 (m)는 NMR로 확인한 결과 60이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 3-메틸부트 -3-에닐47.60 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.
4-하이드록시벤조에이트 (3-methylbut-3-enyl 4-hydroxybenzoate) 6.13 g(29.7 隱 ol)과 칼스테드 백금 촉매 (Karsteck's platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반응시켰다. 반웅 종료 후. 미반웅 실특산은 120°C, 1 ton-의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 MB-60으로 명명하였다. MB- 60는 연황낵 오일이며, Varian 500MHz을 이용하여 ¾ NMR을 통해 반복 단위 (m)는 60임을 확인하였으며. 더 이상의 정제는 필요하지 않았다. 제조예 3 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
20L 글라스 (Glass) 반웅기에 비스페놀 A(BPA) 978.4 g, NaOH 32% 수용액 1.620 g. 증류수 7,500 g을 넣고 질소 분위기에서 BPA가 완전히 녹은 것을 확인한 후, 메틸렌클로라이드 3,670 g, p-tert-부틸페놀 (PTBP) 18.3 g을 투입하여 혼합하였다. 여기에 트리포스겐 542.5 g을 녹인 메틸렌클로라이드 3,850 g을 1시간 동안 적가하였다. 이때, NaOH 수용액을 pH 12로 유지하였다. 적가 완료 후 15분간 숙성하였고, 트리에틸아민 195.7 g을 메틸렌클로라이드에 녹여 투입하였다. 10분 후. 1N 염산 수용액으로 pH를 3으로 맞춘 후. 증류수로 3회 수세하고 나서, 메틸렌클로라이드 상을 분리한 다음. 메탄올에 침전시켜 분말상의 폴리카보네이트 수지를 수득하였다. 실시예 1 978.4 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
20L 글라스 (Glass) 반웅기에 비스페놀 A(BPA) 978.4 g, THPE( 1 , 1 , 1-t r i s ( 4-hydroxypheny 1 )et hane ) 3.2 g, NaOH 32% 수용액 1,620 g, 증류수 7,500 g을 넣고 질소 분위기에서 BPA가 완전히 녹은 것을 확인한 후. 메틸렌클로라이드 3.670 g, p-tert-부틸페놀 (PTBP) 21.0 g, 앞서 제조한 폴리오르가노실록산 (AP-30) 44.16 g 및 제조예 2의 폴리오르가노실록산 (MB- 60) 11.04 g을 투입하여 흔합하였다. 여기에 트리포스겐 542.5 g을 녹인 메틸렌클로라이드 3,850 g을 1시간 동안 적가하였다. 이때, NaOH 수용액을 pH 12로 유지하였다. 적가 완료 후 15분간 숙성하였고, 트리에틸아민 195.7 g을 메틸렌클로라이드에 녹여 투입하였다. 10분 후. 1N 염산 수용액으로 pH를 3으로 맞춘 후， 증류수로 3회 수세하고 나서, 메틸렌클로라이드 상을 분리한 다음, 메탄을에 침전시켜 분말상의 코폴리카보네이트 수지를 수득하였다. 실시예 2  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
THPE를 0.98 g을 사용하는 것을 제외하고, 상기 실시예 1과 동일한 방법으로 코폴리카보네이트 수지를 수득하였다. 실시예 3  A copolycarbonate resin was obtained in the same manner as in Example 1, except that 0.98 g of THPE was used. Example 3
실시예 1에서 제조한 코폴리카보네이트 80 중량부 및 제조예 3에서 제조한 폴리카보네이트 20 중량부를 흔합하여, 코폴리카보네이트 수지 조성물을 제조하였다. 비교예 1  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
THPE를 사용하지 않고, 또한 PTBP를 21.0 g 대신 18.3 g을 사용하는 것을 제외하고， 상기 실시예 1과 동일한 방법으로 코폴리카보네이트 수지를 수득하였다. 비교예 2 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
제조예 1의 폴리오르가노실록산 (AP-30)을 55.2 g을 사용하고, 제조예 2의 폴리오르가노실록산 (MB— 60)은 사용하지 않는 것을 제외하고, 상기 실시예 1과 동일한 방법으로 코폴리카보네이트 수지를 수득하였다. 비교예 3  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
제조예 1의 폴리오르가노실록산 (AP-30) 및 제조예 2의 폴리오르가노실록산 (MB-60)을 사용하지 않는 것을 제외하고, 상기 실시예 1과 동일한 방법으로 코폴리카보네이트 수지를 수득하였다. 비교예 4  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
제조예 3에서 제조한 폴리카보네이트 수지를 비교예 4로 사용하였다. 상기 실시예 및 비교예의 주요 반응 물질의 사용량은 하기 표 1과 같았다.  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.
【표 1】  Table 1
Figure imgf000023_0001
실험예
Figure imgf000023_0001
Experimental Example
상기 실시예 및 비교예에서 제조한 코폴리카보네이트 또는 조성물 Copolycarbonates or compositions prepared in Examples and Comparative Examples
1 중량부에 대하여ᅳ 트리스 (2,4-디 -tert—부틸페닐)포스파이트 0.050 중량부, 옥타데실 -3-(3,5-디 -tert-부틸— 4-히드록시페닐)프로피오네이트를 0.010 중량부, 펜타에리스리를테트라스테아레이트를 0.030 중량부 첨가하여, .벤트 부착 Φ30關 이축압출기를 사용하여, 펠릿화한 후, JSW (주) N-20C 사출성형기를 사용하여 실린더 온도 3(xrc, 금형 온도 8(rc로 사출성형하여 시편을 제조하였다. 상기 시편의 특성을 하기의 방법으로 측정하였다. 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) 중량평균분자량 (g/mol): Agilent 1200 series를 이용하여 PC 스텐다드 (Standard)를 이용한 GPC로 측정하였다.  1) Weight average molecular weight (g / mol): Agilent 1200 series was measured by GPC using PC standard (Standard).
2) 상은온층격강도: ASTM D256( 1/8 inch, Notched IzodHl 의거하여 23°C에서 측정하였다. 2) Phase Silver Hot Lapium Strength: Measured at 23 ° C based on ASTM D256 (1/8 inch, Notched IzodHl).
3) 저온충격강도: ASTM D256( 1/8 inch, Notched IzodHl 의거하여 - 30°C에서 측정하였다. 3) Low temperature impact strength: measured at-30 ° C based on ASTM D256 (1/8 inch, Notched IzodHl.
4) 유동성 (Melt Index; MI): ASTM D 1238 ( 300 °C , 1.2kg 조건)에 의거하여 측정하였다. 4) Melt Index (MI): Measured according to ASTM D 1238 (300 ° C., 1.2 kg conditions).
5) 난연성 : UL 94V에 의거하여 난연성을 평가하였다. 구체적으로， 난연 test 적용에 필요한 3.0 隱 두께의 난연 시편을 5개 준비하고, 하기에 따라 평가하였다.  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.
먼저, 20 隱 높이의 불꽃을 10초간 시편에 접염 후, 시편의 연소 시간 (tl)을 측정하고, 연소 양상을 기록하였다. 이어, 1차 접염 후 연소가 종료되면, 다시 10초간 접염 후 시편의 연소 시간 (t2) 및 불똥이 맺힌 시간 (glowing time. t3)을 측정하고, 연소 양상을 기록하였다. 5개 시편에 대해 동일하게 적용한 다음， 하기 표 2의 기준으로 평가하였다.  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.
【표 2】  Table 2
Figure imgf000024_0001
Figure imgf000024_0001
6) 내화학성: ASTM D638에 의거하여, 인장응력 (Tensile strength)을 측정하기 위한 시편 (두께: 3.2 ■)을 제조하여, ASTM D543( PRACTICE B)에 . 의거하여 JIG Strain R1.0을 기준으로 내화학성을 측정하였다. 구체적으로， 상온 (23°C)에서 면재질의 헝겊 (2 cm 2 cm)을 시편 중앙에 얹어놓고, 용매 (니베아© 아쿠아 프로텍트 선스프레이 -SPF30, 바이어스도르프사 제조) 2 mL을 헝겊에 떨어뜨린 순간으로부터 각 시편의 파괴가 발생할 때까지 걸리는 시간을 측정하고, 하기 기준으로 평가하였다. 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.
© ： 24시간 이상  © ： More than 24 hours
O ： 1시간 내지 24시간  O ： 1 hour to 24 hours
Δ ： 1분 내지 1시간  Δ: 1 minute to 1 hour
X ： 1분 이내 상기 결과를 하기의 표 3에 나타내었다.  X: The result is shown in following Table 3 within 1 minute.
【표 3]  [Table 3]
Figure imgf000025_0001
Figure imgf000025_0001

Claims

【특허청구범위】 【청구항 11 하기 화학식 1 내지 3의 반복 단위를 포함하고, 하기 화학식 4의 분지형 반복 단위를 포함하며 , 하기 화학식 1 내지 3의 반복 단위 증 하나 이상이 4의 분지형 반복 단위에 의해 서로 연결되어 있고, 중량 평균 분자량이 1,000 내지 100,000 g/m 인. 코폴리카보네이트: 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:
[화학식 1]  [Formula 1]
Figure imgf000026_0001
Figure imgf000026_0001
상기 화학식 1에서.  In Formula 1 above.
R 내지 R4는 각각 독립적으로 수소. d-10 알킬. 10 알콕시. 또는 할로겐이고, R to R 4 are each independently hydrogen. d- 10 alkyl. 10 alkoxy. Or halogen,
Z는 비치환되거나 또는 페닐로 치환된 C -10 알킬렌, 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌. 0, S. SO. S02. 또는 CO이고 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
[화학식 2]  [Formula 2]
Figure imgf000026_0002
Figure imgf000026_0002
상기 화학식 2에서,  In Chemical Formula 2,
>^은 각각 독립적으로 알킬렌이고.  > ^ Are each independently alkylene.
R5는 각각 독립적으로 수소: 비치환되거나 또는 옥시라닐 , 옥시라닐로 치환된 d-κ) 알콕시, 또는 C6-20 아릴로 치환된 d-15 알킬: 할로겐; 알콕시; 알릴; d-κ) 할로알킬; 또는 C6-20 아릴이고. 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.
n은 1 내지 200의 정수이고.  n is an integer from 1 to 200.
[화학식 3]
Figure imgf000027_0001
상기 화학식 3에서, [Formula 3]
Figure imgf000027_0001
In Chemical Formula 3,
X2은 각각 독립적으로 d- ) 알킬렌이고, Each X 2 is independently d-) alkylene,
^는 각각 독립적으로 수소, d-6 알킬 , 할로겐 , 히드록시 , d-e 알콕시 . 또는 C6-20 아릴이고, ^ Are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- e alkoxy. 20 is an aryl, - or C 6
¾는 각각 독립적으로 수소 ; 비치환되거나 또는 옥시라닐 , 옥시라닐로 치환된 d- ) 알콕시, 또는 C6— 20 아릴로 치환된 d-15 알킬: 할로겐; d- ) 알콕시; 알릴; 할로알킬: 또는 C6-20 아릴이고. 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.
ill은 1 내지 200의 정수이고,  ill is an integer from 1 to 200,
[화학식 4 ]  [Formula 4]
Figure imgf000027_0002
상기 화학식 4에서
Figure imgf000027_0002
In Chemical Formula 4
0
Figure imgf000027_0003
0
Figure imgf000027_0003
R7은 수소, d-10 알킬, 또는 이고, R 7 is hydrogen, d- 10 alkyl, or
Rs 내지 Rii은 각각 독립적으로 수소, Ci-io 알킬, 할로겐, 알콕 알릴; CHO 할로알킬 ; 또는 C6-20 아릴이고, Rs to Rii are each independently hydrogen, Ci-io alkyl, halogen, alkoxy allyl; CHO haloalkyl; 20 is an aryl, - or C 6
nl 내지 n4는 각각 독립적으로 1 내지 4의 정수  nl to n4 are each independently an integer of 1 to 4
【청구항 2 ] [Claim 2]
저 U항에 있어서 상기 화학식 1로 표시되는 반복 단위는, 비스 (4—히드록시페닐)메탄, 비스 (4—히드록시페닐)에테르 , 비스 (4-히드특시페닐)설폰 , 비스 (4- 히드록시페닐)설폭사이드, 비스 (4ᅳ히드록시페닐)설파이드, 비스 (4- 히드록시페닐)케톤, 1,1-비스 (4—히드록시페닐)에탄, 비스페놀 A, 2,2- 비스 (4ᅳ히드록시페닐)부탄, 1,1-비스 (4-히드록시페닐)시클로핵산, 2,2- 비스 (4-히드록시 -3, 5—디브로모페닐)프로판, 2, 2-비스 (4—히드록시— 3, 5ᅳ 디클로로페닐)프로판, 2, 2-비스 (4-히드록시 -3-브로모페닐)프로판, 2,2- 비스 (4-히드특시 -3—클로로페닐)프로판, 2, 2-비스 (4-히드록시 -3- 메틸페닐)프로판, 2, 2-비스 (4-히드록시— 3.5-디메틸페닐)프로판, 1,1- 비스 (4-히드록시페닐 )-1-페닐에탄, 비스 (4-히드록시페닐)디페닐메탄, 및 α . ω—비스 [3-( 0 -히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디을 화합물로부터 유래한 것을 특징으로 하는, 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
코폴리카보네이트.  Copolycarbonate.
【청구항 3】 [Claim 3]
제 1항에 있어서 .  The method of claim 1.
상기 화학식 1로 표시되는 반복단위는 하기 화학식 1-1로 표시되는 것을 특징으로 하는.  The repeating unit represented by the formula (1) is characterized in that represented by the formula (1-1).
코폴리카보네이트: Copolycarbonate:
-1]  -One]
Figure imgf000028_0001
Figure imgf000028_0001
【청구항 4] [Claim 4]
제 1항에 있어서 .  The method of claim 1.
상기 화학식 2로 표시되는 반복 단위는, 하기 화학식 표시되는 것을 특징으로 하는. 코폴리카보네이트: The repeating unit represented by Formula 2 is represented by the following formula. Copolycarbonate:
[화학식 2-2]  [Formula 2-2]
Figure imgf000029_0001
Figure imgf000029_0001
【청구항 5】 [Claim 5]
제 1항에 있어서 ,  The method of claim 1,
상기 화학식 3으로 표시되는 단위는, 하기 화학식 표시되는 것을 특징으로 하는,  Unit represented by the formula (3), characterized in that represented by the following formula,
코폴리카보네이트:  Copolycarbonate:
[화학식 3-2]
Figure imgf000029_0002
[Formula 3-2]
Figure imgf000029_0002
【청구항 6】 [Claim 6]
제 1항에 있어서 ,  The method of claim 1,
n은 10 내지 35의 정수인 것을 특징으로 하는,  n is an integer of 10 to 35,
코폴리카보네이트.  Copolycarbonate.
【청구항 71 [Claim 71
제 1항에 있어서 ,  The method of claim 1,
m은 45 내지 100의 정수인 것을 특징으로 하는,  m is an integer of 45 to 100,
코폴리카보네이트.  Copolycarbonate.
【청구항 8] [Claim 8]
제 1항에 있 상기 화학식 4로 표시되는 반복 단위는, 하기 화학식 4-2 또는 화학식 4-3으로 표시되는 것을 특징으로 하는. 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.
코폴리카보네이트:  Copolycarbonate:
[화학식 4-2 ] [Formula 4-2]
Figure imgf000030_0001
Figure imgf000030_0001
【청구항 9] [Claim 9]
제 1항 내지 제 8항 증 어느 한 항의 코폴리카보네이트, 및 리카보네이트를 포함하는. 폴리카보네이트 조성물.  A copolycarbonate according to any one of claims 1 to 8, and a licarbonate. Polycarbonate composition.
【청구항 10】 [Claim 10]
제 9항에 있어서. 상기 폴리카보네이트는, 폴리카보네이트의 주쇄에 폴리실록산 구조가 도입되어 있지 않은 것을 특징으로 하는, The method of claim 9. The polycarbonate is characterized in that the polysiloxane structure is not introduced into the main chain of the polycarbonate,
폴리카보네이트 조성물.  Polycarbonate composition.
【청구항 11】 [Claim 11]
저】 9항에 있어서,  According to claim 9,
상기 폴리카보네이트는 하기 화학식 5로 표시되는 반복 단위를 포함하는 것을 특징으로 하는,  The polycarbonate is characterized in that it comprises a repeating unit represented by the following formula (5),
폴리카보네이트 조성물:  Polycarbonate Composition:
[화학식 5]  [Formula 5]
Figure imgf000031_0001
상기 화학식 5에서.
Figure imgf000031_0001
In Formula 5 above.
R' l 내지 R'4는 각각 독립적으로 수소. d- ) 알킬. 알콕시, 또는 할로겐이고,  R'1 to R'4 are each independently hydrogen. d-) alkyl. Alkoxy, or halogen,
Ζ'는 비치환되거나 또는 페닐로 치환된 d- O 알킬렌. 비치환되거나 또는 Cwo 알킬로 치환된 C3-15 사이클로알킬렌, 0. S, SO, S02, 또는 CO이다. 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.
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