WO2016089136A1 - Copolycarbonate resin composition - Google Patents

Copolycarbonate resin composition Download PDF

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Publication number
WO2016089136A1
WO2016089136A1 PCT/KR2015/013158 KR2015013158W WO2016089136A1 WO 2016089136 A1 WO2016089136 A1 WO 2016089136A1 KR 2015013158 W KR2015013158 W KR 2015013158W WO 2016089136 A1 WO2016089136 A1 WO 2016089136A1
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Prior art keywords
copolycarbonate
bis
repeating unit
formula
hydroxyphenyl
Prior art date
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PCT/KR2015/013158
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French (fr)
Korean (ko)
Inventor
박정준
황영영
홍무호
반형민
박희용
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020150170811A external-priority patent/KR101666670B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201580002905.5A priority Critical patent/CN105899611A/en
Priority to EP15845501.4A priority patent/EP3162853B1/en
Priority to JP2016535724A priority patent/JP6227784B2/en
Priority to US15/028,833 priority patent/US9777112B2/en
Priority to PL15845501T priority patent/PL3162853T3/en
Publication of WO2016089136A1 publication Critical patent/WO2016089136A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/38—General preparatory processes using other monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a copolycarbonate composition excellent in physical properties.
  • Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have 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. These polycarbonate resins have recently been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic diol compounds having different structures to introduce a different structure into the main chain of the polycarbonate. .
  • This' invention is to provide a copolycarbonate composition comprising the copolycarbonate to a polycarbonate and optionally.
  • the present invention is i) an aromatic polycarbonate-based first repeating unit; And a copolycarbonate comprising an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, or ii) a copolycarbonate composition comprising the copolycarbonate and a polycarbonate, wherein the copolycarbonate composition Provides a copolycarbonate art composition, which satisfies Equation 1 below:
  • X silicone content (% by weight) relative to the total weight of the copolycarbonate and polycarbonate
  • Copolycarbonate (A) which concerns on this invention means the polymer in which the polysiloxane structure was introduce
  • the aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic dialkyl compound and a carbonate precursor : preferably provides a copolycarbonate represented by the following Chemical Formula 1:
  • Ri are each independently hydrogen, alkyl, d- 10 alkoxy, or halogen
  • Z is unsubstituted or substituted with a d- 10 alkylene, unsubstituted or alkyl substituted in the phenyl by C 3 - 15 cycloalkylene eu 0, S, SO, S0 2. Or CO.
  • 3 ⁇ 4 to are each independently hydrogen, methyl, chloro or bromo.
  • Z is straight or branched alkylene unsubstituted or substituted with phenyl. More preferably, they are methylene, ethane -1,1-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 Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4—hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy 3-chlorophenyl) propane, 2,
  • the carbonate precursor dimethyl. Carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-111- One or more selected from the group consisting of cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate can be used. Preferably, triphosgene or phosgene can be used.
  • the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds. At least one siloxane compound and a carbonate precursor are formed by reaction, and preferably, a copolycarbonate comprising a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 3 is provided:
  • Each R 5 is independently hydrogen; 20 aryl substituted with - the Cwo alkyl, or C 6 unsubstituted or substituted, or oxiranyl, oxiranyl 15 alkyl; halogen; Alkoxy; Allyl; C wo haloalkyl; 20 is an aryl, - or C 6
  • n is an integer from 10 to 200
  • 3 ⁇ 4 are each independently d- 10 alkylene
  • ⁇ are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- koksi 6, or C 6 - 20 aryl, and, 3 ⁇ 4 is each independently hydrogen;
  • a d-) is substituted by unsubstituted or substituted oxiranyl, oxiranyl alkoxy, or C 6 - 20 aryl group substituted with an alkyl CH5; halogen; d- 10 alkoxy; Allyl; d- 10 haloalkyl; 20 is an aryl, - or C 6
  • m is an integer of 10-200.
  • 3 ⁇ 4 are each independently C 2 - will be 10 alkylene, more preferably C 2 - 4 alkylene. Most preferably propane-1, 3-diyl.
  • each R 5 is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodome Oxy, ethoxy, propoxy, allyl, 2, 2.2- , trifluoroethyl. 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably.
  • Each 3 ⁇ 4 is independently alkyl, more preferably d- 6 alkyl, more preferred is d- 3 alkyl and most preferably methyl.
  • n is an integer of 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 to be.
  • 3 ⁇ 4 it will be each independently C 2 _ 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, methoxy, ethoxy, propoxy, allyl. 2, 2, 2- Trifluoroethyl, 3, 3, 3-trifluoropropyl, phenyl, or naphthyl.
  • each R 6 is independently d- ⁇ ) alkyl, more preferably d-6 alkyl, more preferably d- 3 alkyl, and most preferably methyl.
  • m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or 62 or less Is an integer.
  • 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.
  • 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 the formula (2) and a repeating unit represented by the formula (3).
  • the carbonate precursor that can be used to form the repeating units of Formulas 2 and 3, the repeat of Formula 1 It is as described in the carbonate precursor which can be used for formation of a unit.
  • the method for producing the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1 is as follows.
  • 'It is C 2 - 10 alkenyl, and Al,
  • Alkenyl and 10 know, - 3 ⁇ 4 'is C 2
  • the definitions of X 2 , Yi, R 6 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.
  • Pt catalyst is preferably used as the metal catalyst.
  • the metal catalyst is 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight or more, 1 part by weight, 0.1 part by weight or less, 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 compound represented by Formula 7 or 9 can be prepared by reacting organodisiloxane and organocyclosiloxy acid under an acid catalyst.
  • N and m may be adjusted by adjusting the content of the reaction material.
  • the reaction temperature is 50 to 70 ° C 'is preferred. Further, the reaction time, 1 hour to 6 hours is preferred.
  • As said organodisiloxane tetramethyl disiloxane and tetraphenyl disiloxane.
  • One or more types selected from the group consisting of nucleated methyldisiloxane and nucleated phenyldisiloxane 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 parts 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 8 parts by weight or less.
  • the acid catalyst at least one selected from the group consisting of H 2 S0 4 , HC10 4) A1C1 3 , SbCl 5 , SnCl 4, and acidic clay may be used.
  • the acid catalyst is 0.1 parts by weight, 0.5 parts by weight or more, or 1 part by weight, based on 100 parts by weight of the organocyclosiloxane, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less can be used. have.
  • the content of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) the physical properties can be adjusted.
  • the weight ratio between the repeating units may be 1:99 to 99: 1.
  • it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15 : More preferably, it is 20: 80-80: 20.
  • the weight ratio of the repeating unit corresponds to the weight ratio of the siloxane compound, for example, the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1.
  • the repeating unit represented by Formula 2 is represented by Formula 2-2:
  • 3 ⁇ 4 and n are as defined above.
  • 3 ⁇ 4 is methyl.
  • the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2:
  • R 6 and m are as defined above.
  • 3 ⁇ 4 is methyl.
  • the copolycarbonate includes both a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2-2, and a repeating unit represented by Formula 3-2.
  • the present invention provides a method for producing a copolycarbonate, comprising the step of polymerizing an aromatic diol compound, a carbonate precursor and at least one siloxane compound.
  • the aromatic diol compound, carbonate precursor and one or more siloxane compounds are as described above.
  • the at least one siloxane compound is an aromatic diol.
  • 0.1 wt% or more 0.5 wt% or more, 1 wt% or more, or 1.5 wt% or more, 20 wt% or less, 10 wt% or less, relative to 100 wt% of the total of the compound, carbonate precursor, and one or more siloxane compounds
  • the aromatic diol compound is 40% by weight or more, 50% by weight or more, or 55% by weight or more, 80% by weight or less, 70% by weight to 100% by weight of the total of the aromatic diol compound, the carbonate precursor and the one or more siloxane compounds.
  • the carbonate precursor is 10% by weight, 20% by weight, or 30% by weight, 60% by weight, 50% by weight or less, based on 100% by weight of the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds in total. Or up to 40% by weight.
  • the polymerization method for example, an interfacial polymerization method can be used. In this case, the polymerization reaction can be performed at normal pressure and low silver 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.
  • the interfacial polymerization may include a step of introducing a coupling agent after prepolymerization (pre-polymer i zat ion), and then polymerizing again, in which case a high molecular weight copolycarbonate may be obtained.
  • the materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.
  • the acid binder for example, alkali metal hydroxides such as sodium hydroxide, cal hydroxide f & quot ; or amine compounds such as pyridine can be used.
  • the organic solvent is not particularly limited as long as it is a solvent usually used for the polymerization of polycarbonate.
  • halogenated hydrocarbons such as methylene chloride, chlorobenzene, etc. may be used, and the interfacial polymerization may be carried out by tertiary reaction such as triethylamine, tetra- 1-butylammonium bromide, tetra-n-butylphosphonium bromide, etc. to promote reaction.
  • Amine compound, further reaction may be used such as quaternary ammonium compound, quaternary phosphonium compound, etc.
  • the reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C., the reaction time is 10 minutes to 5 hours Moreover, it is preferable to maintain pH in 9 or more or 11 in an interfacial polymerization reaction.
  • the interfacial polymerization may be performed by further including a molecular weight modifier The molecular weight modifier may be carried out before, during or after the start of the polymerization. It can be put in.
  • Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, 'p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octa It is at least one selected from the group consisting of decylphenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is large.
  • the molecular weight modifier is, for example, based on 100 parts by weight of the aromatic diol compound, 0.01 part by weight or more, 0,1 part by weight subphase, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less.
  • the desired molecular weight can be obtained within this range.
  • the copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g / mol, more preferably 15,000 to 35,000 g / mol.
  • the weight average molecular weight is at least 20,000 g / mol, at least 21,000 g / mol, at least 22,000 g / mol, at least 23,000 g / mol, at least 24,000 g / mol, at least 25,000 g / mol, at 26,000 g / mol 27,000 g / mol or more, or 28.000 g / mol or more. Also.
  • the weight average molecular weight is 34,000 g / mol or less, 33,000 g / mol or less, or 32,000 g / mol or less.
  • the polycarbonate (B) according to the present invention is distinguished from the copolycarbonate (A) in that a polysiloxane structure is not introduced into the main chain of the polycarbonate.
  • the polycarbonate includes a repeating unit represented by Formula 4 below:
  • R'i to R'4 are each independently hydrogen, Cwo alkyl, Cwo alkoxy, or halogen
  • the polycarbonate (B) has a weight average molecular weight of 1,000 to 100,0000 g / mol, more preferably 10,000 to 35,000 g / mol ⁇ more preferably, the weight average molecular weight (g / mol ) Is over 11,000. More than 12,000, More than 13,000, More than 14,000, More than 15,000, More than 16.000 ' , More than 17,000, or More than 18,000.
  • the weight average molecular weight (g / mol) is 34,000 or less, 33,000 or less, 32,000 or less, 31,000 or less, 30,000 or less, or 29,000 or less.
  • the repeating unit represented by Chemical Formula 4 is formed by reacting an aromatic diol compound and a carbonate precursor.
  • the aromatic diol compound and carbonate precursor which can be used are the same as described above in the repeating unit represented by the formula (1).
  • R 4 and Z 'of Formula 4 are the same as Ri to R 4 and Z of Formula 1, respectively.
  • the repeating unit represented by Formula 4 is represented by the following Formula 4-1:
  • the manufacturing method of the said polycarbonate (B) is the same as the manufacturing method of the said copolycarbonate (A) except that one or more siloxane compounds are not used.
  • Copolycarbonate Resin Composition is the same as the manufacturing method of the said copolycarbonate (A) except that one or more siloxane compounds are not used.
  • the copolycarbonate resin composition according to the present invention comprises the above-mentioned copolycarbonate (A) and optionally polycarbonate (B).
  • X in Equation 1 denotes a silicon content (wtD) in the copolycarbonate resin composition, and may be measured by NMR analysis.
  • the polycarbonate (B) is a copoly because no polysiloxane structure is introduced.
  • X can be adjusted by adjusting the content of polycarbonate (B) in the carbonate resin composition, preferably X is 0.1 to 20, more preferably, 1 to 10, and most preferably 1.2 to 7.0
  • the Y value of Equation 1 may be measured by a TD (Time-domain) -NMR Fid experiment as described in the following Experimental Example
  • a copoly according to the present invention While the carbonate composition is included in the range of Equation 1, the comparative example is not included in the range thereof, and thus it can be confirmed that the fluidity (mobi li ty) of the polymer structure is decreased. The difference in mobi li ty) can be seen to affect various properties. More preferably, the copolycarbonate composition according to the present invention satisfies Equation 1-1 below:
  • Copolycarbonate composition according to the present invention preferably has a weight average molecular weight (g / mol) of 1,000 to 100, 000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, or 27,000 or more. Or 28,000 or more. The weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less.
  • the copolycarbonate composition according to the present invention preferably has a weight average molecular weight (g / mol) of 1,000 to 100, 000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, or 27,000 or more. Or 28,000 or more. The weight average molecular weight is 34,000 or less, 33,000 or less, or
  • Phase measured at 23 ° C according to ASTM D256 (l / 8 inch, Notched Izod) has an impact strength of 750 to 1000 J / m. More preferably, the room temperature impact strength (J / m) is 760 or more, 770 or more, 780 or more. 790 or more, 800 or more , 810 or more, 820 or more , 830 or more. 840 or more, 850 or more. 860 or more or 870 or more. In addition, the room temperature impact strength (J / ni) is the higher the value is excellent, there is no upper limit, for example, may be 990 or less, 980 or less, or 970 or less.
  • the copolycarbonate composition according to the present invention preferably low temperature impact strength measured at -30 ° C based on ASTM D256 (l / 8 ' inch, Notched Izod) is 150 to 1000 J / m. More preferably, the low silver impact strength (J / m) is 160 or more, 170 or more, 180 or more, 190 or more, or 200 or more. In addition, the low temperature impact strength (J / m) is the higher the value is better, there is no upper limit, for example, may be 990 or less, 980 or less, or 970 or less.
  • the copolycarbonate resin composition an antioxidant if necessary, heat stabilizers, light stabilizers, plasticizers, antistatic shop, nucleating agent, a flame retardant, a lubricant, an impact modifier, fluorescent consisting of brighteners, ultraviolet absorbers, pigments and dyes It may further comprise any one or more selected from the group.
  • the present invention also provides an article comprising the copolycarbonate resin composition.
  • the article is an injection molded article.
  • the copolycarbonate resin composition according to the present invention and the above-mentioned additives are mixed as necessary using a mixer, and then the mixture is extruded by an extruder to produce pellets, and the pellets are dried. It may include the step of injection into the injection molding machine.
  • a copolycarbonate having a polysiloxane structure introduced into the main chain of the polycarbonate according to the present invention, and optionally a copolycarbonate composition comprising a polycarbonate is characterized by TD (Time-domain) -NMR Fid analysis. The condition is satisfied.
  • 1 is a graph showing the T2 re laxat ion measured according to the present invention.
  • Preparation Example 1 AP-34 47.60 g of octamethylcyclotetrasiloxane (160 ⁇ 01) and 2.40 g (17.8 mmol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane to 1 part of acidic clay (DC-A3). The mixture was poured into a 3L flask and reacted at 60 ° C for 4 hours.
  • DC-A3 acidic clay
  • terminal unmodified polyor repeating unit (n) was found to be 34 NMR. 4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the obtained terminal unmodified polyorganosiloxane, and the reaction was carried out at 90 ° C. for 3 hours. I was. After the reaction was completed, unreacted siloxane was removed by evaporation under conditions of 12 (C, 1 torr. The end modified polyorganosiloxane thus obtained was named 'AP-34'. AP-34 is light yellow oil. It was confirmed that the repeating unit (n) was 34 by NMR using a Varian 500 MHz, and no further purification was necessary.
  • Example 3 20 parts by weight of copolycarbonate of Example 1 and Preparation Example 4 80 parts by weight of polycarbonate (PC) were mixed to prepare a copolycarbonate composition.
  • PC polycarbonate
  • Example 4 40 parts by weight of copolycarbonate of Example 1 and 60 parts by weight of polycarbonate (PC) of Preparation Example 4 were mixed to prepare a copolycarbonate ointment composition.
  • PC polycarbonate
  • Example 5 60 parts by weight of copolycarbonate of Example 1 and 40 parts by weight of polycarbonate (PC) of Preparation Example 4 were mixed to prepare a copolycarbonate composition.
  • PC polycarbonate
  • Weight average molecular weight (Mw) Agi lent 1200 ser ies were measured by GPC using a standard PC (Standard).
  • Silicon content (wt%) The silicon content was measured by NMR analysis.
  • TD (Ti me-doma in) -NMR Fid experiment The setup using the mini spec mq20 Polymer Research System and following the standard operating procedure "SOP-0274-0k Bruker Opt i cs Mini spec standard operating procedure" And f id data was obtained. The results are shown in Table 1 below, and the results of TD (Ti me-doma in) -NMR Fid experiments are also shown in FIG. 1.
  • the X axis means silicon content (% by weight) in the copolycarbonate composition
  • the Y axis means TD (Time in domain) —Normal Fid intensity measured in an NMR Fi d experiment.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Provided is a copolycarbonate composition which comprises: a copolycarbonate comprising an aromatic polycarbonate first repeating unit and an aromatic polycarbonate second repeating unit that has at least one siloxane bond; or ii) the copolycarbonate and a polycarbonate, the copolycarbonate satisfying mathematical formula (1). [Mathematical formula (1)] 1.0682*X+0.51<Y<1<1.0682*X+1.2 (In mathematical formula (1), X represents the silicone content (weight%) relative to the total weight of copolycarbonate and polycarbonate, and Y represents the Fid intensity value, obtained via a Time-domain (TD) Fid test, normalized at 0.1 msec.) A copolycarbonate resin composition according to the present invention has excellent mobility, and has various excellent physical properties.

Description

【명세서】  【Specification】
【발명의 명칭】  [Name of invention]
코폴리카보네이트 수지 조성물  Copolycarbonate Resin Composition
【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 10-2015-0170811호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원의 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. 10-2015-0170811 dated December 2, 2015. All content disclosed in the literature is included as part of this specification.
【기술분야】  Technical Field
본 발명은 물성이 우수한 코폴리카보네이트 조성물에 관한 것이다. The present invention relates to a copolycarbonate composition excellent in physical properties.
【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 디올 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， 내화학성이나 충격강도， 특히 저온충격강도가 증가하면 반대로 유동성 등이 저하되는 단점이 있다. 따라서， 여러 물성을 동시에 개선하기 위해서는 폴리카보네이트의 화학 구조， 폴리카보네이트 사슬의 유동성 (mobi l i ty) 등이 다각적으로 검토되어야 한다. 이에 본 발명에서는 TD(Time-doniain)ᅳ 匪 R Fi d 실험을 통하여 분자의 mobi l i ty를 분석하였다. ^  Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have 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. These polycarbonate resins have recently been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic diol compounds having different structures to introduce a different structure into the main chain of the polycarbonate. . In particular, research into introducing a polysiloxane structure into the main chain of polycarbonate has been conducted, but most of the technologies have a disadvantage in that the production cost is high, and chemical resistance or impact strength, particularly low temperature impact strength, increases, and consequently, fluidity decreases. Therefore, in order to simultaneously improve various physical properties, the chemical structure of polycarbonate, the fluidity of the polycarbonate chain (mobi l i ty), and the like must be examined in various ways. Therefore, in the present invention, Mobi l i ty of molecules was analyzed by TD (Time-doniain) ᅳ R Fi d experiment. ^
Fi d s ignal pat tern에 나타나는 중요한 NMR 정보는 T2 rel axat ion time으로서, 분자 구조의 flexibility에 따라 차이를 보이며, 이에 따라 Fid signal에서 decay rate가 달라진다. 즉， 분자가 rigid 할수록 Fid decay rate가 빨라지고, flexible 할수록 Fid decay rate가 느려진다. 이에 본 발명에서는, 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입한 코폴리카보네이트 및 선택적으로 폴리카보네이트를 포함하는 코폴리카보네이트 조성물에 대한 TD(Time-domain)-NMR Fid 분석을 통하여， 각종 물성이 우수한 코폴리카보네이트 조성물을 제조하였다. Important NMR information on fis ignal pat tern is T2 rel axat ion As time, the difference depends on the flexibility of the molecular structure, and thus the decay rate in the Fid signal varies. In other words, the rigider the molecule, the faster the Fid decay rate, and the flexible, the slower the Fid decay rate. Therefore, in the present invention, through the TD (Time-domain) -NMR Fid analysis of the copolycarbonate having a polysiloxane structure in the polycarbonate main chain and optionally the polycarbonate composition comprising a polycarbonate, Polycarbonate compositions were prepared.
【발명의 내용】  [Content of invention]
【해결하려는 과제】  [Problem to solve]
본 ' 발명은 코폴리카보네이트 및 선택적으로 폴리카보네이트를 포함하는 코폴리카보네이트 조성물을 제공하기 위한 것이다. This' invention is to provide a copolycarbonate composition comprising the copolycarbonate to a polycarbonate and optionally.
또한, 본 발명은 상기 코폴리카보네이트 조성물을 포함하는 물품을 제공하기 위한 것이다.  It is also an object of the present invention to provide an article comprising the copolycarbonate composition.
【과제의 해결 수단】  [Measures of problem]
상기 과제를 해결하기 위하여, 본 발명은 i) 방향족 폴리카보네이트계 제 1 반복 단위; 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트를 포함하거나, 또는 ii) 상기 코폴리카보네이트 및 폴리카보네이트를 포함하는， 코폴리카보네이트 조성물이고, 상기 코폴리카보네이트 조성물은 하기 수학식 1을 만족하는, 코폴리카보네아트 조성물을 제공한다:  In order to solve the above problems, the present invention is i) an aromatic polycarbonate-based first repeating unit; And a copolycarbonate comprising an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, or ii) a copolycarbonate composition comprising the copolycarbonate and a polycarbonate, wherein the copolycarbonate composition Provides a copolycarbonate art composition, which satisfies Equation 1 below:
[수학식 1]  [Equation 1]
1.0682XX + 0.51 < Y < 1.0682XX + 1.2  1.0682XX + 0.51 <Y <1.0682XX + 1.2
상기 수학식 1에서.  In Equation 1 above.
X는 상기 코폴리카보네이트 및 폴리카보네이트의 총 중량 대비 실리콘 함량 (중량 %)을 의미하고，  X means silicone content (% by weight) relative to the total weight of the copolycarbonate and polycarbonate,
Y는 TDCTimeᅳ domain) Fid 실험을 통하여 얻어진 Fid Intensity 값을 0.1 msec에서 normalized 한 값을 의미한다. 이하, 본 발명을 상세히 설명하며， 각 성분의 구분 및 설명의 편의를 위하여 코폴리카보네이트는 'A'로, 폴리카보네이트는 'B'로 표시한다. 코폴리카보네이트 (A) Y means the normalized Fid Intensity value obtained from the TDCTime domain domain Fid experiment at 0.1 msec. Hereinafter, the present invention will be described in detail, and the classification and description of each component For convenience, the copolycarbonate is labeled 'A' and the polycarbonate is labeled 'B'. Copolycarbonate (A)
본 발명에 따른 코폴리카보네이트 (A)는, 폴리카보네이트의 주쇄에 폴리실록산구조가도입된 고분자를 의미한다. 구체적으로， 상기 방향족 폴리카보네이트계 제 1 반복 단위는 방향족 디을 화합물 및 카보네이트 전구체가 반응하여 형성되는 것으로 : 바람직하게는 하기 화학식 1로 표시되는 코폴리카보네이트를 제공한다 : Copolycarbonate (A) which concerns on this invention means the polymer in which the polysiloxane structure was introduce | transduced into the main chain of polycarbonate. Specifically, the aromatic polycarbonate-based first repeating unit is formed by reacting an aromatic dialkyl compound and a carbonate precursor : preferably provides a copolycarbonate represented by the following Chemical Formula 1:
[화학식 1]  [Formula 1]
R :\싀R: \ 싀
Figure imgf000005_0001
상기 화학식 1에서，
Figure imgf000005_0001
In Chemical Formula 1,
Ri 내지 는 각각 독립적으로 수소， 알킬 , d-10 알콕시， 또는 할로겐이고， Ri to are each independently hydrogen, alkyl, d- 10 alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 d-10 알킬렌， 비치환되거나 또는 에 알킬로 치환된 C3-15사이클로알킬렌ᅳ 0, S, SO, S02. 또는 CO이다. 바람직하게는. ¾ 내지 는 각각 독립적으로 수소， 메틸, 클로로 또는 브로모이다. 또한 바람직하게는， Z는 비치환되거나 또는 페닐로 치환된 직쇄 또는 분지쇄의 알킬렌이며. 보다 바람직하게는 메틸렌， 에탄 -1，1-디일， 프로판 -2 ,2-디일， 부탄— 2, 2-디일， 1—페닐에탄 -1,1—디일, 또는 디페닐메틸렌아다. 또한 바람직하게는, Z는 사이클로핵산 -1,1-디일， 0, S, SO, S02, 또는 CO이다. 바람직하게는 상기 화학식 1로 표시되는 반복단위는 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)프로판， 2, 2-비스 (4-히드록시 -3,5-디클로로페닐)프로판, 2,2- 비스 (4—히드록시—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 )-1-페닐에탄, 비스 (4-히드록시페닐)디페닐메탄, 및 (1， 0 -비스[3-( 0 - 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디올 화합물로부터 유래할 수 있다ᅳ 상기 '방향족 디올 화합물로부터 유래한다'의 의미는， 방향족 디올 화합물의 하이드록시기와 카보네이트 전구체가 반응하여 상기 화학식 1로' 표시되는 반복단위를 형성하는 것을 의미한다 . 예컨대, 방향족 디을 화합물인 비스페놀 A와 카보네이트 전구체인 트리포스겐이 중합된 경우, 상기 화학식 1로 표시되는 반복단위는 하기 화학식 1-1로 표시된다:Z is unsubstituted or substituted with a d- 10 alkylene, unsubstituted or alkyl substituted in the phenyl by C 3 - 15 cycloalkylene eu 0, S, SO, S0 2. Or CO. Preferably. ¾ to are each independently hydrogen, methyl, chloro or bromo. Also preferably, Z is straight or branched alkylene unsubstituted or substituted with phenyl. More preferably, they are methylene, ethane -1,1-diyl, propane-2,2-diyl, butane- 2, 2-diyl, 1-phenylethane -1,1- diyl, or diphenylmethylene. Also preferably, Z is cyclonucleic acid-1,1-diyl, 0, S, SO, S0 2 , or CO. Preferably, the repeating unit represented by Formula 1 is bis (4-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 Hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4—hydroxy-3-bromophenyl) propane, 2, 2-bis (4-hydroxy 3-chlorophenyl) propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenyl Ethane, bis (4-hydroxyphenyl) diphenylmethane, and (1, 0-bis [3- (0-hydroxy) Phenyl) propyl] polydimethylsiloxane may be derived from any one or more aromatic diol compounds selected from the group consisting of ᅳ derived from an aromatic diol compound means that the hydroxy group and the carbonate precursor of the aromatic diol compound react means for forming a "repeating unit represented by the formula (I). for example, when the aromatic compound is a bisphenol a and the carbonate precursor dieul of triphosgene the polymerization, to the repeating unit represented by the formula (I) by the following formula 1-1 Is displayed:
-1]  -One]
Figure imgf000006_0001
Figure imgf000006_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. 또한, 상기 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위는. 하나 이상의 실록산 화합물 및 카보네이트 전구체가 반응하여 형성되는 것으로, 바람직하게는 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위를 포함하는 코폴리카보네이트를 제공한다: As the carbonate precursor, dimethyl. Carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-111- One or more selected from the group consisting of cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate can be used. Preferably, triphosgene or phosgene can be used. In addition, the aromatic polycarbonate-based second repeating unit having one or more siloxane bonds. At least one siloxane compound and a carbonate precursor are formed by reaction, and preferably, a copolycarbonate comprising a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 3 is provided:
Figure imgf000007_0001
Figure imgf000007_0001
상기 화학식 2에서,  In Chemical Formula 2,
^은 각각 독립적으로 CHO 알킬렌이고ᅳ  Are each independently CHO alkylene
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 Cwo 알콕시, 또는 C6-20 아릴로 치환된 -15 알킬; 할로겐; 알콕시; 알릴; Cwo 할로알킬; 또는 C6-20 아릴이고， Each R 5 is independently hydrogen; 20 aryl substituted with - the Cwo alkyl, or C 6 unsubstituted or substituted, or oxiranyl, oxiranyl 15 alkyl; halogen; Alkoxy; Allyl; C wo haloalkyl; 20 is an aryl, - or C 6
n은 10 내지 200의 정수이고,  n is an integer from 10 to 200,
Figure imgf000007_0002
Figure imgf000007_0002
상기 화학식 3에서,  In Chemical Formula 3,
¾은 각각 독립적으로 d-10 알킬렌이고， ¾ are each independently d- 10 alkylene,
^은 각각 독립적으로 수소， d-6 알킬, 할로겐, 히드록시， d-6 콕시 , 또는 C6-20 아릴이고， ¾는 각각 독립적으로 수소 ; 비치환되거나 또는 옥시라닐 , 옥시라닐로 치환된 d- ) 알콕시, 또는 C6-20 아릴로 치환된 CH5 알킬; 할로겐; d-10 알콕시 ; 알릴; d-10 할로알킬; 또는 C6-20 아릴이고， ^ Are each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- koksi 6, or C 6 - 20 aryl, and, ¾ is each independently hydrogen; A d-) is substituted by unsubstituted or substituted oxiranyl, oxiranyl alkoxy, or C 6 - 20 aryl group substituted with an alkyl CH5; halogen; d- 10 alkoxy; Allyl; d- 10 haloalkyl; 20 is an aryl, - or C 6
m은 10 내지 200의 정수이다. 상기 화학식 2에서, 바람직하게는， ¾는 각각 독립적으로 C2-10 알킬렌이고, 보다 바람직하게는 C2-4 알킬렌이고, . 가장 바람직하게는 프로판 -1 , 3-디일이다. 또한 바람직하게는， R5는 각각 독립적으로 수소, 메틸, 에틸, 프로필 , 3-페닐프로필 , 2-페닐프로필， 3- (옥시라닐메록시 )프로필， 플루오로, 클로로, 브로모, 아이오도 메톡시, 에톡시, 프로폭시， 알릴, 2 , 2.2-, 트리폴루오로에틸. 3 , 3 , 3-트리플루오로프로필, 페닐, 또는 나프틸이다. 또한 바람직하게는. ¾는 각각 독립적으로 알킬이고， 보다 바람직하게는 d-6 알킬이고， 보다' 바람직하게는 d-3 알킬이고 가장 바람직하게는 메틸이다. 또한 바람직하게는, 상기 n은 10 이상, 15 이상， 20 이상 25 이상, 30 이상, 31 이상, 또는 32 이상아고， 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- (옥시라닐메특시)프로필, 플루오로. 클로로, 브로모， 아이오도, 메록시， 에톡시, 프로폭시， 알릴. 2 , 2 , 2- 트리플루오로에틸， 3 , 3 , 3-트리플루오로프로필， 페닐, 또는 나프틸이다. 또한 바람직하게는， R6는 각각 독립적으로 d-κ) 알킬이고， 보다 바람직하게는 d-6 알킬이고， 보다 바람직하게는 d-3 알킬이고， 가장 바람직하게는 메틸이다. 또한 바람직하게는， 상기 m은 40 이상, 45 이상, 50 이상， 55 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. m is an integer of 10-200. In the above formula (2), preferably, ¾ are each independently C 2 - will be 10 alkylene, more preferably C 2 - 4 alkylene. Most preferably propane-1, 3-diyl. Also preferably, each R 5 is independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodome Oxy, ethoxy, propoxy, allyl, 2, 2.2- , trifluoroethyl. 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably. Each ¾ is independently alkyl, more preferably d- 6 alkyl, more preferred is d- 3 alkyl and most preferably methyl. Also preferably, n is an integer of 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 to be. In Formula 3, preferably, ¾ it will be each independently C 2 _ 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, methoxy, ethoxy, propoxy, allyl. 2, 2, 2- Trifluoroethyl, 3, 3, 3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each R 6 is independently d-κ) alkyl, more preferably d-6 alkyl, more preferably d- 3 alkyl, and most preferably methyl. Also preferably, m is 40 or more, 45 or more, 50 or more, 55 or more, 56 or more, 57 or more, or 58 or more, 80 or less, 75 or less, 70 or less, 65 or less, 64 or less, 63 or less, or 62 or less Is an integer. 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
Figure imgf000009_0001
상기 화학식 2-1에서， ， R5 및 n의 정의 정의한 바와 [화학식 3—1] In Formula 2-1, ， R 5 And n As defined in the definition [Formula 3-1]
Figure imgf000009_0002
상기 화학식 3-1에서， ¾， Υ1 ; R6 및 ni의 정의는 앞서 정의한 바와
Figure imgf000009_0002
In Chemical Formula 3-1, ¾, Υ 1; The definitions of R 6 and ni are as defined above.
상기 '실록산 화합물로부터 유래한다'의 의미는， 상기 각각의 실록산 화합물의 하이드록시기와 카보네이트 전구체가 반응하여 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. 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 the formula (2) and a repeating unit represented by the formula (3). . In addition, the carbonate precursor that can be used to form the repeating units of Formulas 2 and 3, the repeat of Formula 1 It is as described in the carbonate precursor which can be used for formation of a unit. 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
Figure imgf000010_0002
상기 반웅식 1에서， 6
Figure imgf000010_0002
In the reaction form 1,
'는 C2-10 알케닐이고， 'It is C 2 - 10 alkenyl, and Al,
Xi , R5 및 n의 정의는 앞서 정의한 바와 같고， The definitions of Xi, R 5 and n are as defined above,
[반응식 2]  Scheme 2
Figure imgf000010_0003
Figure imgf000010_0003
8 9
Figure imgf000010_0004
8 9
Figure imgf000010_0004
3-1  3-1
상기 반웅식 2에서，  In the reaction form 2,
¾ '는 C2-10 알케닐이고, X2 , Yi , R6 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 (Speier )촉매 , PtCl^COD) ,Alkenyl and 10 know, - ¾ 'is C 2 The definitions of X 2 , Yi, R 6 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. Pt catalyst is preferably used as the metal catalyst. As the Pt catalyst, Ashby catalyst, Karlstedt catalyst, Lamoreaux catalyst, Spire catalyst, PtCl ^ COD,
PtCl2(벤조니트릴)^ 및 ¾PtBr6로 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, 상가 반응 시간은 1시간 내지 5시간이 바람직하다. 또한， 상기 화학식 7 또는 9로 표시되는 화합물은 오르가노디실록산과 오르가노시클로실톡산을 산 촉매 하에서 반웅시켜 제조할 수 있으며 . 상기 반웅 물질의 함량을 조절하여 n 및 m을 조절할 수 있다. 상기 반웅 온도는 50 내지 70°C가' 바람직하다. 또한 , · 상기 반응 시간은 1시간 내지 6시간이 바람직하다. 상기 오르가노디실록산으로, 테트라메틸디실록산， 테트라페닐디실록산. 핵사메틸디실록산 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 중량부 이하로 사용할 수 있다. 상기 산 촉매로는 H2S04, HC104) A1C13, SbCl5, SnCl4 및 산성 백토로 이루어진 군으로부터 선택된 1종 이상을 사용할 수 있다. 또한， 상기 산 촉매는 오르가노시클로실록산 100 중량부를 기준으로 0.1 중량부 이상, 0.5 중량부 이상, 또는 1 중량부 이상이고, 10 중량부 이하, 5 중량부 이하， 또는 3 중량부 이하로 사용할 수 있다. 특히， 상기 화학식 2로 표시되는 반복 단위와 상기 화학식 3으로 표시되는 반복 단위의 함량을 조절하여， 물성을 조절할 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 2-1로 표시되는 실록산 화합물 및 상기 화학식 3-1로 표시되는 실록산 화합물의 중량비에 대응된다. 바람직하게는， 상기 화학식 2로 표시되는 반복 단위는-， 하기 화학식 2-2로 표시된다: One or more selected from the group consisting of PtCl 2 (benzonitrile) ^ and ¾PtBr 6 can be used. The metal catalyst is 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight or more, 1 part by weight, 0.1 part by weight or less, 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. Moreover, as for addition reaction time, 1 hour-5 hours are preferable. In addition, the compound represented by Formula 7 or 9 can be prepared by reacting organodisiloxane and organocyclosiloxy acid under an acid catalyst. N and m may be adjusted by adjusting the content of the reaction material. The reaction temperature is 50 to 70 ° C 'is preferred. Further, the reaction time, 1 hour to 6 hours is preferred. As said organodisiloxane, tetramethyl disiloxane and tetraphenyl disiloxane. One or more types selected from the group consisting of nucleated methyldisiloxane and nucleated phenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. The organodisiloxane is 0.01 parts by weight or more, or 2 parts by weight or more, based on 100 parts by weight of the organocyclosiloxane, and 10 parts by weight Or 8 parts by weight or less. As the acid catalyst, at least one selected from the group consisting of H 2 S0 4 , HC10 4) A1C1 3 , SbCl 5 , SnCl 4, and acidic clay may be used. In addition, the acid catalyst is 0.1 parts by weight, 0.5 parts by weight or more, or 1 part by weight, based on 100 parts by weight of the organocyclosiloxane, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less can be used. have. In particular, by adjusting the content of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3), the physical properties can be adjusted. The weight ratio between the repeating units may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3, 5: 95-95: 5, 10: 90-90: 10, or 15: 85-85: 15 : More preferably, it is 20: 80-80: 20. The weight ratio of the repeating unit corresponds to the weight ratio of the siloxane compound, for example, the siloxane compound represented by Formula 2-1 and the siloxane compound represented by Formula 3-1. Preferably, the repeating unit represented by Formula 2 is represented by Formula 2-2:
[화학식 2-2]  [Formula 2-2]
Figure imgf000012_0001
Figure imgf000012_0001
상기 화학식 2-2에서， ¾ 및 n은 앞서 정의한 바와 같다. 바람직하게는， ¾는 메틸이다. 또한 바람직하게는， 상기 화학식 3으로 표시되는 반복 단위는， 하기 화학식 3-2로 표시된다:  In Formula 2-2, ¾ and n are as defined above. Preferably, ¾ is methyl. Also preferably, the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2:
[화학식 3-2]
Figure imgf000013_0001
[Formula 3-2]
Figure imgf000013_0001
상기 화학식 3-2에서， R6 및 m은 앞서 정의한 바와 같다. 바람직하게는， ¾는 메틸이다. 또한 바람작하게는, 상기 코폴리카보네이트는， 상기 화학식 1-1로 표시되는 반복 단위， 상기 화학식 2-2로 표시되는 반복 단위 및 상기 화학식 3-2로 표시되는 반복 단위를 모두 포함한다. 또한， 본 발명은 상술한 코폴리카보네이트의 제조 방법으로서, 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물을 중합하는 단계를 포함하는 코폴리카보네이트의 제조 방법을 제공한다. 상기 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실톡산 화합물은 앞서 설명한 바와 같다. 상기 중합시， 상기 하나 이상의 실록산 화합물은， 방향족 디올. 화합물, 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량 %에 대해 0. 1 증량 % 이상, 0.5 증량 % 이상， 1 중량 % 이상， 또는 1.5 중량 % 이상이고， 20 중량 % 이하, 10 증량 % 이하, 7 중량 % 이하, 5 중량 % 이하， 4 중량 % 이하， 3 중량 % 이하， 또는 2 중량 % 이하를 사용할 수 있다. 또한， 상기 방향족 디올 화합물은, 방향족 디올 화합물, 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량 %에 대해 40 증량 % 이상， 50 중량 % 이상, 또는 55 중량 % 이상이고， 80 중량 % 이하， 70 증량 % 이하， 또는 65 중량 % 이하로 사용할 수 있다. 또한， 상기 카보네이트 전구체는， 방향족 디올 화합물， 카보네이트 전구체 및 하나 이상의 실록산 화합물 총합 100 중량 %에 대해 10 중량 % 이상, 20 중량 % 이상, 또는 30 중량 %이고， 60 중량 % 이하， 50 중량 % 이하， 또는 40 중량 % 이하로 사용할 수 있다. 또한， 상기 중합 방법으로는， 일례로 계면중합 방법을 사용할 수 있으며, 이 경우 상압과 낮은 은도에서 중합 반웅이 가능하며 분자량 조절이 용이한 효과가 있다. 상기 계면중합은 산결합제 및 유기용매의 존재 하에 수행하는 것이 바람직하다. 또한， 상기 계면중합은 일례로 선중합 (pre-polymer i zat ion) 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, 수산화칼 f" 등의 알칼리금속 수산화물 또는 피리딘 등의 아민 화합물을 사용할 수 있다. 상기 유기 용매로는 통상 폴리카보네이트의 증합에 사용되는 용매이면 특별히 제한되지 않으며， 일례로 메틸렌클로라이드. 클로로벤젠 등의 할로겐화 탄화수소를 사용할 수 있다. 또한， 상기 계면중합은 반웅 촉진을 위해 트리에틸아민， 테트라一 n- 부틸암모늄브로마이드， 테트라 -n—부틸포스포늄브로마이드 등의 3차 아민 화합물. 4차 암모늄 화합물， 4차 포스포늄 화합물 등과 같은 반웅 촉진제를 추가로 사용할 수 있다. 상기 계면중합의 반응 온도는 0 내지 40°C인 것이 바람직하며， 반응 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 선택돤 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 아상， 또는 1 중량부 이상이고， 10 중량부 이하， 6 증량부 이하， 또는 5 중량부 이하로 포함되고， 이 범위 내에서 원하는 분자량을 얻을 수 있다. 상기 코폴리카보네이트는， 중량 평균 분자량이 1,000 내지 100,000 g/mol , 보다 바람직하게는 15,000 내지 35,000 g/mol이다. 보다 바람직하게는， 상기 중량 평균 분자량은 20,000 g/mol 이상， 21,000 g/mol 이상， 22,000 g/mol 이상, 23,000 g/mol 이상, 24,000 g/mol 이상， 25,000 g/mol 이상， 26,000 g/mol 이상， 27.000 g/mol 이상， 또는 28.000 g/mol 이상이다. 또한. 상기 중량 평균 분자량은 34,000 g/mol 이하， 33,000 g/mol 이하, 또는 32,000 g/mol 이하이다. 폴리카보네이트 (B) In Formula 3-2, R 6 and m are as defined above. Preferably, ¾ is methyl. Also preferably, the copolycarbonate includes both a repeating unit represented by Formula 1-1, a repeating unit represented by Formula 2-2, and a repeating unit represented by Formula 3-2. In addition, the present invention provides a method for producing a copolycarbonate, comprising the step of polymerizing an aromatic diol compound, a carbonate precursor and at least one siloxane compound. The aromatic diol compound, carbonate precursor and one or more siloxane compounds are as described above. In the polymerization, the at least one siloxane compound is an aromatic diol. 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, or 1.5 wt% or more, 20 wt% or less, 10 wt% or less, relative to 100 wt% of the total of the compound, carbonate precursor, and one or more siloxane compounds Up to 5 wt%, up to 5 wt%, up to 4 wt%, up to 3 wt%, or up to 2 wt% may be used. In addition, the aromatic diol compound is 40% by weight or more, 50% by weight or more, or 55% by weight or more, 80% by weight or less, 70% by weight to 100% by weight of the total of the aromatic diol compound, the carbonate precursor and the one or more siloxane compounds. Or less than or equal to 65% by weight. In addition, the carbonate precursor is 10% by weight, 20% by weight, or 30% by weight, 60% by weight, 50% by weight or less, based on 100% by weight of the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds in total. Or up to 40% by weight. In addition, as the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction can be performed at normal pressure and low silver and the molecular weight can be easily adjusted. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include a step of introducing a coupling agent after prepolymerization (pre-polymer i zat ion), and then polymerizing again, in which case a high molecular weight copolycarbonate may be obtained. The materials used for the interfacial polymerization are not particularly limited as long as they are materials that can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide, cal hydroxide f &quot; or amine compounds such as pyridine can be used. The organic solvent is not particularly limited as long as it is a solvent usually used for the polymerization of polycarbonate. For example, halogenated hydrocarbons such as methylene chloride, chlorobenzene, etc. may be used, and the interfacial polymerization may be carried out by tertiary reaction such as triethylamine, tetra- 1-butylammonium bromide, tetra-n-butylphosphonium bromide, etc. to promote reaction. Amine compound, further reaction may be used such as quaternary ammonium compound, quaternary phosphonium compound, etc. The reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C., the reaction time is 10 minutes to 5 hours Moreover, it is preferable to maintain pH in 9 or more or 11 in an interfacial polymerization reaction. In addition, the interfacial polymerization may be performed by further including a molecular weight modifier The molecular weight modifier may be carried out before, during or after the start of the polymerization. It can be put in. Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, 'p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octa It is at least one selected from the group consisting of decylphenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is large. The molecular weight modifier is, for example, based on 100 parts by weight of the aromatic diol compound, 0.01 part by weight or more, 0,1 part by weight subphase, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less. The desired molecular weight can be obtained within this range. The copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g / mol, more preferably 15,000 to 35,000 g / mol. More preferably, the weight average molecular weight is at least 20,000 g / mol, at least 21,000 g / mol, at least 22,000 g / mol, at least 23,000 g / mol, at least 24,000 g / mol, at least 25,000 g / mol, at 26,000 g / mol 27,000 g / mol or more, or 28.000 g / mol or more. Also. The weight average molecular weight is 34,000 g / mol or less, 33,000 g / mol or less, or 32,000 g / mol or less. Polycarbonate (B)
본 발명에 따른 폴리카보네이트 (B)는， 폴리카보네이트의 주쇄에 폴리실록산 구조가 도입되어 있지 않다는 점에서, 상기 코폴리카보네이트 (A)와 구분된다. 바람직하게는， 상기 폴리카보네이트는 하기 화학식 4로 표시되는 반복단위를 포함한다:  The polycarbonate (B) according to the present invention is distinguished from the copolycarbonate (A) in that a polysiloxane structure is not introduced into the main chain of the polycarbonate. Preferably, the polycarbonate includes a repeating unit represented by Formula 4 below:
[화학식 4]
Figure imgf000016_0001
상기 화학식 4에서， [Formula 4]
Figure imgf000016_0001
In Chemical Formula 4,
R'i 내지 R'4는 각각 독립적으로 수소, Cwo 알킬， Cwo 알콕시, 또는 할로겐이고,  R'i to R'4 are each independently hydrogen, Cwo alkyl, Cwo alkoxy, or halogen,
Z'는 비치환되거나 또는 페닐로 치환된 d-10 알킬렌， 비치환되거나 또는 알킬로 치환된 C3-15 사이클로알킬렌, 0， S, SO, S02, 또는 CO이다. 또한 바람직하게는, 상기 폴리카보네이트 (B)는 중량 평균 분자량이 1,000 내지 100,0000 g/mol, 보다 바람직하게는 10,000 내지 35,000 g/mol이다ᅳ 보다 바람직하게는, 상기 중량 평균 분자량 (g/mol)은 11,000 이상. 12,000 이상， 13,000 이상， 14,000 이상， 15,000 이상， 16.000 이상'， 17,000 이상， 또는 18,000 이상이다. 또한， 상기 중량 평균 분자량 (g/mol)은 34,000 이하， 33,000 이하， 32,000 이하, 31,000 이하， 30,000 이하， 또는 29,000 이하이다. 상기 화학식 4로 표시되는 반복단위는， 방향족 디올 화합물 및 카보네이트 전구체가 반응하여 형성된다 . 상기 사용할 수 있는 방향족 디올 화합물 및 카보네이트 전구체는， 앞서 화학식 1로 표시되는 반복단위에서 설명한 바와 동일하다. 바람직하게는, 상기 화학식 4의 내지 R'4 및 Z'는， 각각 앞서 설명한 화학식 1의 Ri 내지 R4 및 Z와 동일하다. 또한 바람직하게는 상기 화학식 4로 표시되는 반복단위는， 하기 화학식 4ᅳ 1로 표시된다: Z 'is unsubstituted or substituted with d- 10 alkylene, unsubstituted or alkyl-substituted phenyl C 3 - 15 cycloalkylene, 0, S, SO, S0 2, or CO. Also preferably, the polycarbonate (B) has a weight average molecular weight of 1,000 to 100,0000 g / mol, more preferably 10,000 to 35,000 g / mol ᅳ more preferably, the weight average molecular weight (g / mol ) Is over 11,000. More than 12,000, More than 13,000, More than 14,000, More than 15,000, More than 16.000 ' , More than 17,000, or More than 18,000. The weight average molecular weight (g / mol) is 34,000 or less, 33,000 or less, 32,000 or less, 31,000 or less, 30,000 or less, or 29,000 or less. The repeating unit represented by Chemical Formula 4 is formed by reacting an aromatic diol compound and a carbonate precursor. The aromatic diol compound and carbonate precursor which can be used are the same as described above in the repeating unit represented by the formula (1). Preferably, R 4 and Z 'of Formula 4 are the same as Ri to R 4 and Z of Formula 1, respectively. Also preferably, the repeating unit represented by Formula 4 is represented by the following Formula 4-1:
[화학식 4-1] [Formula 4-1]
Figure imgf000017_0001
Figure imgf000017_0001
또한, 상기 폴리카보네이트 (B)의 제조 방법은， 하나 이상의 실록산 화합물을 사용하지 않는다는 점을 제외하고는 상기 코폴리카보네이트 (A)의 제조 방법과 동일하다. 코폴리카보네이트수지 조성물 In addition, the manufacturing method of the said polycarbonate (B) is the same as the manufacturing method of the said copolycarbonate (A) except that one or more siloxane compounds are not used. Copolycarbonate Resin Composition
본 발명에 따른 코폴리카보네이트 수지 조성물은， 상술한 코폴리카보네이트 (A) 및 선택적으로 폴리카보네이트 (B)를 포함한다. 상기 수학식 1의 X는 코폴리카보네이트 수지 조성물 내 실리콘 함량 (wtD을 의미하며， NMR 분석을 통하여 측정할 수 있다. 또한, 상기 폴리카보네이트 (B)는 폴리실록산 구조가 도입되어 있지 않기 때문에, 코폴리카보네이트 수지 조성물 내 폴리카보네이트 (B)의 함량을 조절하여 , X를 조절할 수 있다. 바람직하게는 X는 0. 1 내지 20이고， 보다 바람직하게는， 1 내지 10이고， 가장 바람직하게는 1.2 내지 7.0이다. 또한， 상기 수학식 1의 Y 값은， 후술할 실험예와 같이 TD(Time-domain)-NMR Fid 실험으로 측정할 수 있다. 본 발명의 일실시예에 따르면， 본 발명에 따른 코폴리카보네이트 조성물은， 수학식 1의 범위에 포함되는 반면, 비교예는 이의 범위에 포함되지 않으며 따라서 고분자 구조의 유동성 (mobi l i ty)가 떨어짐을 확인할 수 있다. 또한， 이러한 유동성 (mobi l i ty)의 차이는 각종 물성에 영향을 미침을 확인할 수 있다. 보다 바람직하게는, 본 발명에 따른 코폴리카보네이트 조성물은 , 하기 수학식 1-1을 만족한다: The copolycarbonate resin composition according to the present invention comprises the above-mentioned copolycarbonate (A) and optionally polycarbonate (B). X in Equation 1 denotes a silicon content (wtD) in the copolycarbonate resin composition, and may be measured by NMR analysis. In addition, the polycarbonate (B) is a copoly because no polysiloxane structure is introduced. X can be adjusted by adjusting the content of polycarbonate (B) in the carbonate resin composition, preferably X is 0.1 to 20, more preferably, 1 to 10, and most preferably 1.2 to 7.0 In addition, the Y value of Equation 1 may be measured by a TD (Time-domain) -NMR Fid experiment as described in the following Experimental Example According to an embodiment of the present invention, a copoly according to the present invention While the carbonate composition is included in the range of Equation 1, the comparative example is not included in the range thereof, and thus it can be confirmed that the fluidity (mobi li ty) of the polymer structure is decreased. The difference in mobi li ty) can be seen to affect various properties. More preferably, the copolycarbonate composition according to the present invention satisfies Equation 1-1 below:
[수학식 1-1]  [Equation 1-1]
1.0682 XX + 0.60 < Y < 1.0682XX + 1.0  1.0682 XX + 0.60 <Y <1.0682XX + 1.0
상기 수학식 1-1에서，  In Equation 1-1,
X 및 Y는 앞서 정의한 바와 같다. 본 발명에 따른 코폴리카보네이트 조성물은， 바람직하게는 중량 평균 분자량 (g/mol)이 1,000 내지 100, 000이고， 보다 바람직하게는 15,000 내지 35,000 이다. 보다 바람직하게는, 상기 중량 평균 분자량은 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 이하ᅳ 또는 32,000 이하이다. 또한， 본 발명에 따른 코폴리카보네이트 조성물은, 바람직하게는 X and Y are as defined above. Copolycarbonate composition according to the present invention, preferably has a weight average molecular weight (g / mol) of 1,000 to 100, 000, more preferably 15,000 to 35,000. More preferably, the weight average molecular weight is 20,000 or more, 21,000 or more, 22,000 or more, 23,000 or more, 24,000 or more, 25,000 or more, 26,000 or more, or 27,000 or more. Or 28,000 or more. The weight average molecular weight is 34,000 or less, 33,000 or less, or 32,000 or less. In addition, the copolycarbonate composition according to the present invention, preferably
ASTM D256(l/8 inch, Notched Izod)에 의거하여 23°C에서 측정한 상은충격강도가 750 내지 1000 J/m이다. 보다 바람직하게는, 상기 상온충격강도 (J/m)는 760 이상， 770 이상, 780 이상. 790 이상, 800 이상， 810 이상, 820 이상， 830 이상. 840 이상, 850 이상. 860 이상ᅳ 또는 870 이상이다. 또한， 상기 상온충격강도 (J/ni)는 그 값이 높을수록 우수한 것이어서 상한의 제한은 없으나， 일례로 990 이하， 980 이하， 또는 970 이하일 수 있다. 또한, 본 발명에 따른 코폴리카보네이트 조성물은， 바람직하게는 ASTM D256(l/8 ' inch, Notched Izod)에 의거하여 -30°C에서 측정한 저온충격강도가 150 내지 1000 J/m이다. 보다 바람직하게는， 상기 저은충격강도 (J/m)는 160 이상， 170 이상, 180 이상 190 이상 또는 200 이상이다. 또한， 상기 저온충격강도 (J/m)는 그 값이 높을수록 우수한 것이어서 상한의 제한은 없으나, 일례로 990 이하, 980 이하, 또는 970 이하일 수 있다. 또한， 상기 코폴리카보네이트 수지 조성물은， 필요에 따라 산화방지제， 열안정제， 광안정화제， 가소제， 대전방지게, 핵제,, 난연제， 활제， 충격보강제, 형광증백제, 자외선흡수제， 안료 및 염료로 이루어진 군으로부터 선택된 어느 하나 이상을 추가로 포함할 수 있다. 또한， 본 발명은 상기 코폴리카보네이트 수지 조성물을 포함하는 물품을 제공한다. 바람직하게는， 상기 물품은 사출 성형품이다. 상기 물품의 제조 방법은, 본 발명에 따른 코폴리카보네이트 수지 조성물과 필요에 따라 상술한 첨가제를 믹서를 이용하여 흔합한 후， 상기 혼합물을 압출기로 압출성형하여 펠릿으로 제조하고， 상기 펠릿을 건조시킨 다음사출성형기로 사출하는 단계를 포함할 수 있다. Phase measured at 23 ° C according to ASTM D256 (l / 8 inch, Notched Izod) has an impact strength of 750 to 1000 J / m. More preferably, the room temperature impact strength (J / m) is 760 or more, 770 or more, 780 or more. 790 or more, 800 or more ， 810 or more, 820 or more ， 830 or more. 840 or more, 850 or more. 860 or more or 870 or more. In addition, the room temperature impact strength (J / ni) is the higher the value is excellent, there is no upper limit, for example, may be 990 or less, 980 or less, or 970 or less. In addition, the copolycarbonate composition according to the present invention, preferably low temperature impact strength measured at -30 ° C based on ASTM D256 (l / 8 ' inch, Notched Izod) is 150 to 1000 J / m. More preferably, the low silver impact strength (J / m) is 160 or more, 170 or more, 180 or more, 190 or more, or 200 or more. In addition, the low temperature impact strength (J / m) is the higher the value is better, there is no upper limit, for example, may be 990 or less, 980 or less, or 970 or less. Moreover, the copolycarbonate resin composition, an antioxidant if necessary, heat stabilizers, light stabilizers, plasticizers, antistatic shop, nucleating agent, a flame retardant, a lubricant, an impact modifier, fluorescent consisting of brighteners, ultraviolet absorbers, pigments and dyes It may further comprise any one or more selected from the group. The present invention also provides an article comprising the copolycarbonate resin composition. Preferably, the article is an injection molded article. In the method for producing the article, the copolycarbonate resin composition according to the present invention and the above-mentioned additives are mixed as necessary using a mixer, and then the mixture is extruded by an extruder to produce pellets, and the pellets are dried. It may include the step of injection into the injection molding machine.
【발명의 효과】  【Effects of the Invention】
상기에서 살펴본 바와 같이, 본 발명에 따른 폴리카보네이트의 주쇄에 폴리실록산 구조를 도입한 코폴리카보네이트 및 선택적으로 폴리카보네이트를 포함하는 코폴리카보네이트 조성물은， TD(Time-domain) - NMR Fid 분석에 따른 특정 조건을 만족한다는 특징이 있다.  As described above, a copolycarbonate having a polysiloxane structure introduced into the main chain of the polycarbonate according to the present invention, and optionally a copolycarbonate composition comprising a polycarbonate, is characterized by TD (Time-domain) -NMR Fid analysis. The condition is satisfied.
【도면의 간단한 설명】  [Brief Description of Drawings]
도 1은， 본 발명에 따라 측정한 T2 re laxat ion을 그래프로 나타낸 것이다.  1 is a graph showing the T2 re laxat ion measured according to the present invention.
【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. 제조예 1: AP-34 옥타메틸시클로테트라실록산 47.60 g(160 隱 01)， 테트라메틸디실록산 2.40 g(17.8 mmol)을 흔합한 후， 상기 흔합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후， 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가 반복단위 (n)는 ¾ NMR로 확인한 결과 34이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 2-알릴페놀 4.81 g(35.9 mmol)과 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반응시켰다. 반웅 종료 후， 미반응 실록산은 12( C, 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 'AP-34'로 명명하였다. AP- 34는 연황색 오일이며, Varian 500MHz을 이용하여 NMR을 통해 반복단위 (n)는 34임을 확인하였으며， 더 이상의 정제는 필요하지 않았다. -58 Hereinafter, preferred embodiments are presented to help understand the invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. Preparation Example 1 AP-34 47.60 g of octamethylcyclotetrasiloxane (160 隱 01) and 2.40 g (17.8 mmol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane to 1 part of acidic clay (DC-A3). The mixture was poured into a 3L flask and reacted at 60 ° C for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. Thus obtained terminal unmodified polyor repeating unit (n) was found to be 34 NMR. 4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the obtained terminal unmodified polyorganosiloxane, and the reaction was carried out at 90 ° C. for 3 hours. I was. After the reaction was completed, unreacted siloxane was removed by evaporation under conditions of 12 (C, 1 torr. The end modified polyorganosiloxane thus obtained was named 'AP-34'. AP-34 is light yellow oil. It was confirmed that the repeating unit (n) was 34 by NMR using a Varian 500 MHz, and no further purification was necessary.
Figure imgf000020_0001
Figure imgf000020_0001
옥타메틸시클로테트라실록산 4그 60. g(160 隱 ol), 테트라메틸디실록산 1.5 g(ll mmol)을 혼합한 후, 상기 흔합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DC-A3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반웅시켰다. 반웅 종료 후, 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (m)는 ¾ NMR로 확인한 결과 58이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 3ᅳ메틸부트— 3ᅳ에닐 4-하이드록시벤조에이트 (3-methylbut-3-enyl 4-hydroxybenzoate) 6.13 g(29.7 mmol)과 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반응시켰다. 반응 종료 후， 미반응 실록산은 120°C. 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 'MB-58'로 명명하였다. MB— 58는 연황색 오일이며， 500MHz을 이용하여 ¾ NMR을 통해 반복단위 (m)는 58임을 확인하였으며， 더 이상의 정제는 필요하지 않았다. 제조예 3: EU-5060 g of octamethylcyclotetrasiloxane 4 g (160 隱 ol) and 1.5 g (ll mmol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (DC-A3). ) Into a 3L flask with 1 part by weight 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 ¾ NMR. As a result, it was 58. 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and a Carlsted platinum catalyst were added to the terminal unmodified polyorganosiloxane obtained above. 0.01 g (50 ppm) of Karstedt's platinum catalyst was added thereto and reacted at 90 ° C. for 3 hours. After the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. 1 torr. The terminal modified polyorganosiloxane thus obtained was named 'MB-58'. MB—58 is a pale yellow oil, and the repeat unit (m) was 58 by ¾ NMR using 500 MHz, and no further purification was necessary. Preparation Example 3 EU-50
Figure imgf000021_0001
Figure imgf000021_0001
옥타메틸시클로테트라실록산 47.60 g(160 mmol), 테트라메틸디실록산 1.7 g(13 mmol)을 혼합한 후. 상기 흔합물을 옥타메틸시클로테트라실록산 100 중량부 대비 산성백토 (DOA3) 1 중량부와 함께 3L 플라스크에 넣고 60°C로 4시간 동안 반응시켰다. 반응 종료 후, 에틸아세테이트로 희석하고 셀라이트를 사용하여 빠르게 필터링하였다. 이렇게 수득된 말단 미변성 폴리오르가노실록산의 반복단위 (n)는 ¾ NMR로 확인한 결과 50이었다. 상기 수득된 말단 미변성 폴리오르가노실록산에 유게놀 (Eugenol) 6.13 g(29.7 mmol)과 칼스테드 백금 촉매 (Karstedt ' s platinum catalyst) 0.01 g(50 ppm)을 투입하여 90°C에서 3시간 동안 반응시켰다. 반응 종료 후, 미반웅 실록산은 12( C, 1 torr의 조건으로 이베이퍼레이션하여 제거하였다. 이렇게 수득한 말단 변성 폴리오르가노실록산을 'EU— 50'으로 명명하였다. EU-50는 연황색 오일이며, Varian 500MHz을 이용하여 NMR을 통해 반복단위 (n)는 50임을 확인하였으며, 더 이상의 정제는 필요하지 않았다. 제조예 4: PC 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.7 g (13 mmol) of tetramethyldisiloxane were mixed. The mixture was added to 100 parts by weight of octamethylcyclotetrasiloxane with 1 part by weight of acidic clay (DOA3) in a 3L flask and reacted at 60 ° C. for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (n) of the terminal unmodified polyorganosiloxane thus obtained was found to be 50 by ¾ NMR. 6.13 g (29.7 mmol) of Eugenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the obtained terminal unmodified polyorganosiloxane at 90 ° C. for 3 hours. Reacted. After the completion of the reaction, Mibanung siloxane was removed by evaporation under conditions of 12 (C, 1 torr. The terminally modified polyorganosiloxane thus obtained was named 'EU-50'. EU-50 is light yellow oil. NMR using a Varian 500 MHz The repeating unit (n) was found to be 50, and no further purification was necessary. Preparation Example 4 PC
중합 반웅기에 물 Γ784 g, NaOH 385 g 및 BPA(bisphenol A) 232 g을 넣고, N2 분위기 하에 혼합하여 녹였다. 여기에 PTBP(para-tert butyl phenol) 4.7 g을 MCXmethylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(tri phosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반응시킨 다음 10분 뒤에 TEA(triethylamine) 46 g을 넣어 커플링 (coupling) 반웅을 시켰다. 총 반웅시간 1시간 20분이 지난 다음 pH를 4로 낮추어 TEA를 제거하였고， 증류수로 3회 세척하여 생성된 중합체의 PH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄을과 핵산 흔합용액에서 재침전시켜 수득한 다음， 이를 120°C에서 건조하여 최종 폴리카보네이트를 얻었으며， 이를 'PC'라 명명하였다. 실시예 1 Water Γ 784 g, NaOH 385 g and BPA (bisphenol A) 232 g was added to the polymerization reactor, mixed under N 2 atmosphere, and dissolved. To this, 4.7 g of PT- (para-tert butyl phenol) was dissolved in MCXmethylene chloride). Then, 128 g of TPG (tri phosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 minutes, and then 46 g of TEA (triethylamine) was added for coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation of methane in a nucleic acid mixture solution and then dried at 120 ° C. to obtain a final polycarbonate, which was termed 'PC'. Example 1
중합 반웅기에 물 1784 g, NaOH 385 g 및 BPA bisphenol A) 232 g을 넣고， N2 분위기 하에 흔합하여 녹였다. 여기에 PTBP(para-tert butyl phenol) 4.3 g과 폴리디메틸실록산 6.57 g (제조예 1에서 제조한 AP- PDMS(n=34) 5.91 g 및 제조예 2에서 제조한 MBHB-PDMS(m=58) 0.66 g의 흔합액 (증량비 90: 10))을 MCXmethylene chloride)로 용해하여 넣어주었다. 그 다음 TPG(triphosgene) 128 g을 MC에 녹여 pH를 11 이상으로 유지시켜 주면서 1시간 동안 투입하여 반응시킨 다음 10분 뒤에 TEA(triethylamine) 46 g을 넣어 커플링 (coupling) 반웅을 시켰다. 총 반응시간 1시간 20분이 지난 다음 pH를 4로 낮추어 TEA를 제거하였고， 증류수로 3회 세척하여 생성된 중합체의 pH를 6~7 중성으로 맞추었다. 이렇게 얻은 중합체를 메탄올과 헥산 흔합용액에서 재침전시켜 수득한 다음， 이를 120°C에서 건조하여 최종 코폴리카보네이트를 얻었다. 실시예 2 Into the polymerization reaction, 1784 g of water, 385 g of NaOH, and 232 g of BPA bisphenol A) were added, and the mixture was dissolved under N 2 atmosphere. Here, 4.3 g of PTBP (para-tert butyl phenol) and 6.57 g of polydimethylsiloxane (5.91 g of AP-PDMS prepared in Preparation Example 1 (n = 34) and MBHB-PDMS prepared in Preparation Example 2 (m = 58)) 0.66 g of the mixture (extension ratio 90: 10)) was dissolved in MCXmethylene chloride). Then, 128 g of TPG (triphosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 hours, and then 46 g of TEA (triethylamine) was added for coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and hexane mixed solution, which was then dried at 120 ° C. to obtain a final copolycarbonate. Example 2
상기 실시예 1의 코폴리카보네이트 20 중량부 및 제조예 4의 폴리카보네이트 (PC) 80 중량부를 흔합하여， 코폴리카보네이트 조성물을 제조하였다. 실시예 3 20 parts by weight of copolycarbonate of Example 1 and Preparation Example 4 80 parts by weight of polycarbonate (PC) were mixed to prepare a copolycarbonate composition. Example 3
상기 실시예 1의 코폴리카보네이트 40 중량부 및 제조예 4의 폴리카보네이트 (PC) 60 중량부를 흔합하여, 코폴리카보네 0트 조성물을 제조하였다. 실시예 4  40 parts by weight of copolycarbonate of Example 1 and 60 parts by weight of polycarbonate (PC) of Preparation Example 4 were mixed to prepare a copolycarbonate ointment composition. Example 4
상기 실시예 1의 코폴리카보네이트 60 중량부 및 제조예 4의 폴리카보네이트 (PC) 40 중량부를 흔합하여， 코폴리카보네 0트 조성물을 제조하였다. 실시예 5  60 parts by weight of copolycarbonate of Example 1 and 40 parts by weight of polycarbonate (PC) of Preparation Example 4 were mixed to prepare a copolycarbonate composition. Example 5
상기 실시예 1의 코폴리카보네이트 80 중량부 및 제조예 4의 폴라카보네이트 (PC) 20 중량부를 흔합하여, 코폴리카보네 0트 조성물을 제조하였다. 비교예  80 parts by weight of copolycarbonate of Example 1 and 20 parts by weight of polycarbonate (PC) of Preparation Example 4 were mixed to prepare a copolycarbonate ointment composition. Comparative example
상기 실시예 1과 동일한 방법으로 제조하되, 폴리디메틸실록산으로 제조예 3에서 제조한 EU-50 6.57 g을 사용하여， 코폴리카보네이트를 얻었다. 실험예  Prepared in the same manner as in Example 1, using 6.57 g of EU-50 prepared in Preparation Example 3 as polydimethylsiloxane, a copolycarbonate was obtained. Experimental Example
상기 실시예 및 비교예에서 제조한 코폴리카보네이트 또는 코폴리카보네이트 조성물 1 중량부에 대하여， 트리스 (2.4-디 -tert- 부틸페닐)포스파이트 으 050 중량부， 옥타데실 -3-(3 , 5ᅳ디 -tert-부틸 -4- 히드록시페닐)프로피오네이트를 0.010 중량부, 펜타에리스리를테트라스테아레이트를 0.030 중량부 첨가하여， 벤트 부착 Φ 30隱 이축압출기를 사용하여， 펠릿화한 후， JSW (주) N-20C 사출성형기를 사용하여 실린더 온도 300 °C , 금형 온도 80°C로 사출성형하여 시편을 제조하였다. 이하의 방법으로 각 물성을 측정하였다. 050 parts by weight of tris (2.4-di-tert-butylphenyl) phosphite, octadecyl-3- (3, 5) based on 1 part by weight of the copolycarbonate or copolycarbonate composition prepared in Examples and Comparative Examples. 0.010 parts by weight of di-tert-butyl-4-hydroxyphenyl) propionate and 0.030 parts by weight of pentaerythritol tetrastearate were added and pelletized using a vented Φ 30 kV twin screw extruder. The JSW N-20C Injection Molding Machine is used to perform injection molding at a cylinder temperature of 300 ° C and a mold temperature of 80 ° C. Prepared. Each physical property was measured by the following method.
1) 중량 평균 분자량 (Mw) : Agi lent 1200 ser ies를 이용하여 PC 스텐다드 (Standard)를 이용한 GPC로 측정하였다.  1) Weight average molecular weight (Mw): Agi lent 1200 ser ies were measured by GPC using a standard PC (Standard).
2) 저온충격강도: ASTM D256( l/8 inch , Notched Izod)에 의거하여 - 30°C에서 측정하였다. 2) Low temperature impact strength: measured at-30 ° C according to ASTM D256 (1/8 inch, Notched Izod).
3) 저온충격강도: ASTM D256( 1/8 inch , Notched Izod)에 의거하여 - 30°C에서 측정하였다. 3) Low temperature impact strength: measured at-30 ° C according to ASTM D256 (1/8 inch, Notched Izod).
4) 실리콘 함량 (wt%) : NMR 분석을 통하여 실리콘 함량을 측정하였다.  4) Silicon content (wt%): The silicon content was measured by NMR analysis.
5) TD ( T i me-doma i n ) -NMR Fid 실험 : The mini spec mq20 Polymer Research System을 사용하고 표준작동절차서 "SOP-0274-0k Bruker Opt i cs社 Mini spec 표준 작동 절차서 "에 따라 실험 setup 및 f id data를 얻었다. 상기 결과를 하기 표 1에 나타내었으며， TD(Ti me-doma in)-NMR Fid 실험 결과는 도 1에도 나타내었다. 도 1에서， X축은 코폴리카보네이트 조성물 내 실리콘 함량 (중량 %)을 의미하고， Y축은 TD( Timeᅳ domain)— NMR Fi d 실험에서 측정한 Normal i zed Fid intens i ty를 의미한다.  5) TD (Ti me-doma in) -NMR Fid experiment: The setup using the mini spec mq20 Polymer Research System and following the standard operating procedure "SOP-0274-0k Bruker Opt i cs Mini spec standard operating procedure" And f id data was obtained. The results are shown in Table 1 below, and the results of TD (Ti me-doma in) -NMR Fid experiments are also shown in FIG. 1. In FIG. 1, the X axis means silicon content (% by weight) in the copolycarbonate composition, and the Y axis means TD (Time in domain) —Normal Fid intensity measured in an NMR Fi d experiment.
【표 1】  Table 1
Figure imgf000024_0001
상기 표 1 및 도 1에 나타난 바와 같이， 본 발명에 따른 실시예의 경우， X 및 Y가 수학식 1을 만족하고 있는 반면， 비교예의 경우 이를 만족하지 못함을 확인할 수 있었다. 또한， 이에 따라 특히 상온 충격강도에서 차이가 있음을 확인할 수 있었다.
Figure imgf000024_0001
As shown in Table 1 and FIG. 1, in the case of the embodiment according to the present invention, X and Y satisfy Equation 1, whereas the comparative example does not satisfy this. In addition, it was confirmed that there is a difference in the impact strength, especially at room temperature.

Claims

【특허청구범위】 【청구항 1】 0 방향족 폴리카보네이트계 제 1 반복 단위; 및 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위를 포함하는 코폴리카보네이트를 포함하거나 또는 Π ) 상기 코플리카보네이트 및 폴리카보네이트를 포함하는， 코폴리카보네이트 조성물이고, 상기 코폴리카보네이트 조성물은 하기 수학식 1을 만족하는， 코폴리카보네이트 조성물: [수학식 1] 【Patent Claims】 【Claim 1】 0 A first repeating unit based on aromatic polycarbonate; and a copolycarbonate comprising a second repeating unit based on an aromatic polycarbonate having at least one siloxane bond, or Π) a copolycarbonate composition comprising the above-described copolycarbonate and a polycarbonate, and the copolycarbonate composition is as follows: Copolycarbonate composition that satisfies Equation 1: [Equation 1]
1.0682XX + 0.51 < Y < 1.0682 XX + 1.2 1.0682XX + 0.51 < Y < 1.0682XX + 1.2
상기 수학식 1에서， In Equation 1 above,
X는 상기 코폴리카보네이트 및 폴리카보네이트의 총 중량 대비 실리콘 함량 (중량 «을 의미하고, X refers to the silicon content (weight «) relative to the total weight of the copolycarbonate and polycarbonate,
Y는 TD(Time-domain) Fid 실험을 통하여 얻어진 Fid Intensi ty 값을 0.1 msec에서 normal ized 한 값을 의미한다. Y refers to the normalized value of the Fid Intensi ty value obtained through TD (Time-domain) Fid experiment at 0.1 msec.
【청구항 2】 【Claim 2】
제 1항에 있어서， In clause 1,
상기 X는 0.1 내지 20인 것을 특징으로 하는， Characterized in that the X is 0.1 to 20,
코폴리카보네이트 조성물. Copolycarbonate composition.
【청구항 3】 【Claim 3】
저 U항에 있어서， In that U port,
상기 코플리카보네이트 조성물은 하기 수학식 1-1을 만족하는 것을 특징으로 하는, The coplicarbonate composition is characterized in that it satisfies the following equation 1-1,
코폴리카보네이트 조성물: Copolycarbonate composition:
[수학식 1-1] [Equation 1-1]
1.0682XX + 0.60 < Y < 1.0682XX + 1.0 1.0682XX + 0.60 < Y < 1.0682XX + 1.0
상기 수학식 1-1에서, In Equation 1-1 above,
X 및 Y는 청구항 , 1에서 정의한 바와 같다. X and Y are as defined in claim 1.
23 대체용지 (규칙 제 26조) 23 Substitute paper (Rule Article 26)
【청구항 4】 【Claim 4】
제 1항에 있어서， In clause 1,
상기 코폴리카보네이트 조성물은, ASTM D256( l/8 inch, Notched Izod)에 의거하여 23°C에서 측정한 상온충격강도가 750 내지 1000 J/m인 것을 특징으로 하는， The copolycarbonate composition is characterized in that the room temperature impact strength measured at 23 ° C is 750 to 1000 J / m according to ASTM D256 (l / 8 inch, Notched Izod),
코폴리카보네이트 조성물. Copolycarbonate composition.
【청구항 5] [Claim 5]
제 1항에 있어서， In clause 1,
상기 코폴리카보네이트 조성물은, 중량 평균 분자량 (g/mol ) o 1 ,000 내지 100 ,000인 것을 특징으로 하는， The copolycarbonate composition is characterized in that the weight average molecular weight (g/mol) o is 1,000 to 100,000,
코폴리카보네이트 조성물. Copolycarbonate composition.
【청구항 6】 【Claim 6】
제 1항에 있어서, According to clause 1,
상기 방향족 폴리카보네이트계 제 1 반복 단위는 하기 화학식 1로 표시되는 것을 특징으로 하는， The aromatic polycarbonate-based first repeating unit is characterized in that it is represented by the following formula (1):
코폴리카보네이트 조성물 : Copolycarbonate composition:
[화학식 1] [Formula 1]
Figure imgf000026_0001
상기 화학식 1에서,
Figure imgf000026_0001
In Formula 1,
Rl 내지 R4는 각각 독립적으로 수소, Cwo 알킬， d-U) 알콕시 , 또는 할로겐이고， Rl to R4 are each independently hydrogen, Cwo alkyl, d-U) alkoxy, or halogen,
Z는 비치환되거나 또는 페닐로 치환된 Ci-H) 알킬렌， 비치환되거나 또는 d-10 알킬로 치환된 C3-15 사이클로알킬렌， 0, S, SO, S02, 또는 CO이다. Z is unsubstituted or substituted with phenyl Ci-H) alkylene, C 3-15 cycloalkylene unsubstituted or substituted with d- 10 alkyl, 0, S, SO, SO 2 , or CO .
24 대체용지 (규칙 제 26조) 24 Substitute paper (Rule Article 26)
【청구항 7】 【Claim 7】
제 1항에 있어서 In paragraph 1
상기 방향족 폴리카보네이트계 제 1 반복 단위는， 비스 (4- 히드록시페닐)메탄， 비스 (4-히드록시페닐)에테르， 비스 (4- 히드록시페닐)설폰， 비스 (4ᅳ히드록시페닐)설폭사이드, 비스 (4- 히드록시페닐)설파이드， 비스 (4-히드록시페닐)케톤, 1 , 1ᅳ비스(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)프로판， 2， 2-비스 (4-히드록시 -3 , 5-디클로로페닐)프로판, 2 , 2- 비스 (4-히드록시 -3-브로모페닐)프로판， 2， 2-비스 (4-히드록시 -3- 클로로페닐)프로판， 2， 2-비스 (4-히드록시 -3ᅳ메틸페닐)프로판， 2ᅳ 2ᅳ비스 (4- 히드록시 -3， 5-디메틸페닐)프로판 , 1 , 1-비스 (4-히드록시페닐 )-1-페닐에탄, 비스 (4-히드록시페닐)디페닐메탄， 및 (1， 0) -비스[3- ( 0 - 히드록시페닐)프로필]폴리디메틸실록산으로 이루어진 군으로부터 선택되는 어느 하나 이상의 방향족 디을 화합물로부터 유래한 것을 특징으로 하는， 코폴리카보네이트 조성물. The aromatic polycarbonate-based first repeating unit is bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide. Side, 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-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-phenyl From any one or more aromatic diol compounds selected from the group consisting of ethane, bis (4-hydroxyphenyl) diphenylmethane, and (1, 0) -bis [3- ( 0 - hydroxyphenyl) propyl] polydimethylsiloxane A copolycarbonate composition, characterized in that it is derived from a copolycarbonate composition.
【청구항 8】 【Claim 8】
제 1항에 있어세 In paragraph 1
상기 방향족 폴리카보네이트계 제 1 반복 단위는， 하기 화학식 1- 1로 표시되는 것을 특징으로 하는， The aromatic polycarbonate-based first repeating unit is characterized in that it is represented by the following formula 1-1,
코폴리카보네이트 조성물: Copolycarbonate composition:
-1] -One]
Figure imgf000027_0001
Figure imgf000027_0001
【청구항 9】 【Claim 9】
제 1항에 있어서, According to clause 1,
25 대체용지 (규칙제 26조) 상기 하나 이상의 실록산 결합을 갖는 방향족 폴리카보네이트계 제 2 반복 단위는， 하기 화학식 2로 표시되는 반복 단위 및 하기 화학식 3으로 표시되는 반복 단위를 포함하는 것을 특징으로 하는， 25 Substitute paper (Article 26 of the Rules) The aromatic polycarbonate-based second repeating unit having at least one siloxane bond is characterized in that it includes a repeating unit represented by the following formula (2) and a repeating unit represented by the following formula (3):
코폴리카보네이트 조성물: Copolycarbonate composition:
[화학식 2] [Formula 2]
Figure imgf000028_0001
Figure imgf000028_0001
상기 화학식 2에서 , In Formula 2 above,
X은 각각 독립적으로 d- ) 알킬렌이고， Each X is independently d-) alkylene,
R5는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐, 옥시라닐로 치환된 Cwo 알콕시, 또는 Ce-20 아릴로 치환된 d-15 알킬; 할로겐; 알콕시 ; 알릴; ᅳ10 할로알킬; 또는 C6-20 아릴이고, R 5 is each independently hydrogen; d -15 alkyl unsubstituted or substituted with oxiranyl, Cwo alkoxy substituted with oxiranyl, or Ce- 20 aryl; halogen; alkoxy; allyl; ᅳ 10 haloalkyl; or C 6 - 20 aryl,
n은 10 내지 200의 정수이고， n is an integer from 10 to 200,
Figure imgf000028_0002
Figure imgf000028_0002
¾은 각각 독립적으로 d- ) 알킬렌이고， ¾ is each independently d-) alkylene,
Yr 각각 독립적으로 수소, d-6 알킬, 할로겐， 히드록시， d-6 알콕시， 또는 C6-20 아릴이고, Yr is each independently hydrogen, d- 6 alkyl, halogen, hydroxy, d- 6 alkoxy, or C 6-20 aryl,
¾는 각각 독립적으로 수소; 비치환되거나 또는 옥시라닐， 옥시라닐로 치환된 d-H) 알콕시， 또는 C6-20 아릴로 치환된 d-l5 알킬; 할로겐; Cwo 알콕시; 알릴; d-10 할로알킬; 또는 C6-20 아릴이고， ¾ are each independently hydrogen; unsubstituted or oxiranyl, dH) alkoxy substituted with oxiranyl, or dl 5 alkyl substituted with C 6-20 aryl; halogen; Cwo alkoxy; allyl; d- 10 haloalkyl; or C 6-20 aryl ,
m은 10 내지 200의 정수이다. m is an integer from 10 to 200.
【청구항 10] [Claim 10]
26 대체용지 (규칙 제 26조) 저 19항에 있어서, 26 Substitute paper (Rule Article 26) In paragraph 19,
상기 화학식 2로 표시되는 반복 단위는， 하기 화학식 표시되는 것을 특징으로 하는， The repeating unit represented by Formula 2 is characterized in that it is represented by the following formula,
코폴리카보네이트: Copolycarbonate:
[화학식 2-2] [Formula 2-2]
Figure imgf000029_0001
Figure imgf000029_0001
【청구항 11】 【Claim 11】
저 19항에 있어서, In paragraph 19,
상기 화학식 3으로 표시되는 반복 단위는, 하기 화학식 표시되는 것을 특징으로 하는, The repeating unit represented by Formula 3 is characterized in that it is represented by the following formula,
코폴리카보네이트: Copolycarbonate:
Figure imgf000029_0002
Figure imgf000029_0002
27 27
대체용지 (규칙 제 26조) Substitute paper (Article 26 of the rules)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10174194B2 (en) * 2014-12-04 2019-01-08 Lg Chem, Ltd. Copolycarbonate and composition comprising the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3457805B2 (en) * 1996-06-28 2003-10-20 三菱エンジニアリングプラスチックス株式会社 Polycarbonate resin composition
KR20130104317A (en) * 2012-03-13 2013-09-25 제일모직주식회사 Polycarbonate-polysiloxane copolymer and method for preparing the same
US20130309474A1 (en) * 2012-05-16 2013-11-21 Sabic Innovative Plastics Ip B.V. Polycarbonate composition and articles formed therefrom
KR20140116921A (en) * 2012-01-20 2014-10-06 사빅 글로벌 테크놀러지스 비.브이. Articles prepared from thermoplastic compositions, and method of preparing such articles
KR20140117396A (en) * 2012-01-19 2014-10-07 사빅 글로벌 테크놀러지스 비.브이. Polycarbonate-polyester compositions, methods of manufacture, and articles thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3457805B2 (en) * 1996-06-28 2003-10-20 三菱エンジニアリングプラスチックス株式会社 Polycarbonate resin composition
KR20140117396A (en) * 2012-01-19 2014-10-07 사빅 글로벌 테크놀러지스 비.브이. Polycarbonate-polyester compositions, methods of manufacture, and articles thereof
KR20140116921A (en) * 2012-01-20 2014-10-06 사빅 글로벌 테크놀러지스 비.브이. Articles prepared from thermoplastic compositions, and method of preparing such articles
KR20130104317A (en) * 2012-03-13 2013-09-25 제일모직주식회사 Polycarbonate-polysiloxane copolymer and method for preparing the same
US20130309474A1 (en) * 2012-05-16 2013-11-21 Sabic Innovative Plastics Ip B.V. Polycarbonate composition and articles formed therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10174194B2 (en) * 2014-12-04 2019-01-08 Lg Chem, Ltd. Copolycarbonate and composition comprising the same

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