WO2018074822A1

WO2018074822A1 - Polycarbonate resin composition

Info

Publication number: WO2018074822A1
Application number: PCT/KR2017/011478
Authority: WO
Inventors: 이기재; 박정준; 홍무호; 반형민; 황영영
Original assignee: 주식회사 엘지화학
Priority date: 2016-10-20
Filing date: 2017-10-17
Publication date: 2018-04-26

Abstract

The present invention relates to a polycarbonate resin composition which has enhanced fluidity while maintaining excellent mechanical properties of copolycarbonate in which a polysiloxane structure has been introduced to the main chain of polycarbonate.

Description

[Name of invention]

Polycarbonate resin composition

Technical Field

Cross Citation with Related Applications

This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0136731 dated October 20, 2016 and Korean Patent Application No. 10-2017-0134207 dated October 16, 2017. All content disclosed in the literature is included as part of this specification.

The present invention relates to a polycarbonate resin composition capable of improving the fluidity of copolycarbonate having a polysiloxane structure introduced into the main chain of the polycarbonate.

[Technique to become background of invention]

. 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, etc. Applicable to a wide range of fields such as parts. 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 main chain of polycarbonate has been conducted, but most of the technologies have a disadvantage in that the production cost is high, and the chemical resistance or impact strength, in particular, the low temperature impact strength increases, on the contrary, the fluidity decreases. Therefore, the present inventors have provided a polysiloxane structure to the main chain of polycarbonate. As a result of intensive studies on how to increase the fluidity while maintaining the excellent physical properties of the introduced copolycarbonate, as described below, a polycarbonate including a copolycarbonate having a sebacoyl structure in addition to the copolycarbonate having the polysiloxane structure is introduced. It confirmed that the resin composition satisfy | filled the above, and completed this invention.

[Content of invention]

Problem to be solved

The present invention is to provide a polycarbonate composition that can improve the fluidity of the polycarbonate structure in the backbone of the polycarbonate.

[Measures of problem]

In order to solve the above problems, the present invention includes a first copolycarbonate comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3); And

It provides a polycarbonate resin composition comprising; a second copolycarbonate comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (4):

In Chemical Formula 1,

Ri to R ₄ are each independently hydrogen, C _1-10 alkyl, Cwo alkoxy, or halogen,

¾ is Cwo alkylene unsubstituted or substituted with phenyl, cycloalkylene unsubstituted or substituted with ci- ₁₀ alkyl, O, S, SO, SO ₂ , or CO,

[Formula 2]

In Chemical Formula 2,

Each X is independently Ci-w alkylene,

Each R ₅ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; ₂₀ is an aryl, - or C ₆

n is an integer from 10 to 200,

[Formula 3]

In Chemical Formula 3,

Each X ₂ is independently C _1-10 alkylene,

^ Are each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

Are each independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, Q- ₁₀ alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; Cwo alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

m is an integer of ^"10 to 200,

[Formula 4]

In the above formula (4),

Z2 is unsubstituted or phenyl-substituted C _wo alkylene, unsubstituted or substituted with a c _1-10 alkyl substituted by C ₃ - ₁₅ cycloalkylene is, o, s, so, so _2, or CO,

1 is an integer of 1-10. Polycarbonate is prepared by the condensation polymerization of aromatic di-compounds such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, numerical stability, heat resistance and transparency, and are used in exterior materials, automotive parts, building materials, and optics of electrical and electronic products. Applicable to a wide range of fields such as 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, the polycarbonate in which the polysiloxane structure is introduced becomes poor in fluidity, which is one factor that degrades the processability.

Accordingly, the present invention includes a second copolycarbonate having a Sebacoyl structure together with a first copolycarbonate having a polysiloxane structure in the main chain of the polycarbonate, thereby maintaining the physical properties of the copolycarbonate having the polysiloxane structure at the same time. It is possible to improve the melting characteristics.

Hereinafter, a polycarbonate resin composition according to a specific embodiment of the present invention will be described in more detail. First copolycarbonate

The first copolycarbonate according to the present invention means a polymer having a polysiloxane structure introduced into the main chain of the polycarbonate.

The main chain of the polycarbonate is formed by reacting an aromatic diol compound and a carbonate precursor, and specifically means a repeating unit represented by Chemical Formula 1. In the above formula (1), preferably,] to R ₄ are each independently hydrogen, methyl, chloro, or bromo. Also preferably, is straight or branched Cwo alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2, 2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, ¾ is cyclonucleic acid-1,1-diyl, 0, S, SO, S0 ₂ , or CO. Preferably repeating unit represented by the formula

Hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxymethoxyphenyl) 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 ethane, bis (4-hydroxyphenyl) _{diphenylmethane.} And a, oo-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane.

The term “derived from an aromatic diol compound” means that a hydroxyl group of an aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by the formula (1).

For example, when bisphenol A, an aromatic diol compound, and triphosgene, a carbonate precursor, are polymerized, the repeating unit represented by Formula 1 is represented by the following Formula 1-1.

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, One or more kinds selected from the group consisting of dinaphthyl carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformates can be used. Preferably, triphosgene or phosgene can be used. In addition, the polysiloxane structure means a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3.

In Chemical Formula 2, preferably, d) is each independently C ₂ _ ₁₀ alkylene, more preferably C _2-4 alkylene, and 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, iodo, Mesoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each R ₅ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C ₃ 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, each of X ₂ is independently C _2-10 alkylene, more preferably C ₂ 6 alkylene ^: and most preferably isobutylene.

Also preferably, Υ is hydrogen.

Also preferably, R ₆ is each independently hydrogen, methyl, ethyl, propyl,

3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, mesochym, ethoxy, propoxy, allyl, 2,2,2-trifluoro Roethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. . Also preferably, each R ₆ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C ₃ alkyl, most preferably methyl. Also preferably, m is 30 or more, 40 or more, 45 or more, 50 or more, 53 or more, 55 or more, or 56 or more, 70 or less, 65 or less, 63 or less, 62 or less, 61 or less, or 60 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.

2-1]

In Chemical Formula 2-1,

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

[Formula 3-1]

In Chemical Formula 3-1,

The definitions of X 2, Yi, R ₆ and m are as defined above.

The term “derived from said ¹ siloxane compound” means that the hydroxy group and the carbonate precursor of each of the siloxane compounds are reacted to form a repeating unit represented by the above formula (2) and a repeating unit represented by the formula (3). . In addition, the carbonate precursor which can be used for formation of the repeating unit of Formula 2 and 3 is the same as that of the carbonate precursor which can be used for formation of the repeating unit of Formula 1 described above.

In addition, the first copolycarbonate may improve the various physical properties of the copolycarbonate by controlling the content of each repeating unit. The weight ratio between the repeating units may be 1:99 to 99: 1. Preferably it is 3: 97-97: 3, More preferably, it is 5: 95-95: 5. Of the repeating unit The weight ratio is based on 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 the following Formula 2-2:

[

In Formula 2-2, R ₅ and n are as defined above. Preferably, R 5 is methyl.

Also preferably, the repeating unit represented by Chemical Formula 3 is represented by the following Chemical Formula 3-2:

In Formula 3-2, R ₆ and m are as defined above. Preferably, R ₆ is methyl.

In addition, the increase ratio of the total weight of the repeating unit represented by the formula (1), the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) (Formula 1: (Formula 2 and Formula 3)) is 1, : 0.001 to 1: 0.2, more preferably 1: 0.01 to 1: e1. The weight ratio of the repeating unit corresponds to the weight ratio of the aromatic diol 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. The first copolycarbonate has a weight average molecular weight (g / mol) of 1,000 to 100,000, preferably 30,000 to 70,000, and more preferably 50,000 to 60,000. Second Copolycarbonate

The second copolycarbonate is a polymer having a sebacoyl structure, and includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 4.

In Chemical Formula 4, preferably, Zi is straight or branched Cwo alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl , Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z ₂ is cyclonucleic acid-1,1-diyl, O, S, SO, S0 ₂ , or CO.

Preferably, the repeating unit represented by Formula 4 is represented by the following Formula 4-1:

4—1]

In addition, the second copolycarbonate may be prepared by polymerizing a composition including a compound represented by Chemical Formula 4-2, an aromatic dialkyl compound, and a carbonate precursor:

[Formula 4-2]

In Chemical Formula 4-2,

R ^' is hydrogen, OH, C _1-10 alkyl, or halogen, and 1 is as defined above.

In this case, the compound represented by Formula 4-2 is 0.001 parts by weight or more, or 0.01 parts by weight or more, or 01 parts by weight or more, 10 parts by weight or less, 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound. Or 4 parts by weight or less. By adjusting the content of the formula 4-2 in the polymerization step as described above, it is possible to adjust the weight ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (4).

In addition, the aromatic diol compound and the carbonate precursor are as described above in the aromatic diol compound and the carbonate precursor that can be used to form the repeating unit of Formula 1.

In addition, the polymerization is preferably performed by interfacial polymerization, and the polymerization reaction is possible at atmospheric pressure and low silver during interfacial polymerization, and the molecular weight is easily controlled.

The polymerization temperature is 0 ^° C to 40 ^° C, reaction time is preferably 10 minutes to 5 hours. Also, empty: Response of the p _H is preferably maintained at 9 or more or 11 or more.

As a solvent which can be used for the said superposition | polymerization, if it is a solvent used for superposition | polymerization of copolycarbonate in the art, it will not specifically limit, For example, halogenated hydrocarbons, such as methylene chloride and chlorobenzene, can be used.

In addition, the polymerization is preferably carried out in the presence of an acid binder, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or an amine compound such as pyridine may be used as the acid binder.

In addition, in order to control the molecular weight of the copolycarbonate during the polymerization, it is preferable to polymerize in the presence of a molecular weight regulator. Ci- ₂₀ alkylphenol may be used as the molecular weight modifier, and specific examples thereof include p-tert-butylphenol, P-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, nuxadecylphenol, octadecylphenol, and eicosyl. Phenol, docosylphenol or triacontylphenol. 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. The molecular weight modifier is, for example, 0.01 part by weight, 0,1 part by weight, or 1 weight based on 100 parts by weight of the aromatic diol compound. It is more than 10 parts by weight, contained in 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less, preferably 0.1 to 6 parts by weight can be used, the desired molecular weight can be obtained within this range.

In addition, in order to promote the polymerization reaction, reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds and the like Accelerators may additionally be used.

The first copolycarbonate has a weight average molecular weight (g / mol) of 1,000 to 100,000, preferably 30,000 to 70,000, and more preferably 50,000 to 60,000. Polycarbonate resin composition

The polycarbonate resin composition which concerns on this invention contains the above-mentioned 1st copolycarbonate and 2nd copolycarbonate.

Melting characteristics of the polycarbonate resin composition may be adjusted by adjusting a mixing ratio of the first copolycarbonate and the second copolycarbonate. Preferably, in the polycarbonate resin composition, the weight ratio of the first copolycarbonate and the second polycarbonate is 1: 0.1 to 1: 10, black is 1: 0.25 to 1: 5, or 1: 0.5 to 1: 3 , Black may be 1: 5 to 1: 2.5, or 1: 0.5 to 1: 2, or 1: 1 to 1: 2.

That is, it may be possible to simultaneously improve the mechanical properties and melt properties (fluidity) of the polycarbonate resin composition within the preferred weight ratio range. However, when out of the weight ratio range, it is difficult to simultaneously improve the mechanical properties and fluidity of the composition. For example, when the second copolycarbonate is included in the composition in too high a weight ratio, the impact strength at low temperature (eg, −30 ^° C.) of the composition may be sharply reduced. In addition, the polycarbonate resin composition has a weight average molecular weight (g / mol) of 1,000 to 100,000, preferably 30,000 to 70,000, more preferably, 40,000 to 60,000. Also preferably, the polycarbonate resin composition according to the present invention

The impact strength at room temperature measured at 23 ^° C according to ASTM D256 (l / 8 inch, Notched Izod) is 800 to 1100 J / m. More preferably, the room temperature impact strength (J / m) is 820 or more, or 840 or more. In addition, the room temperature impact strength (J / m) is the higher the value is excellent, there is no upper limit, for example, may be 1050 or less, or 1000 or less. Also preferably, the copolycarbonate according to the present invention is a low temperature impact strength measuring device at -30 ^° C based on ASTM D256 (l / 8 inch, Notched Izod)-600 to 1000 J / m. More preferably, the low temperature impact strength (J / m) is 630 or more, or 650 or more. In addition, the low-temperature laminar strength (J / m) is the higher the value is excellent, there is no upper limit, for example, may be 950 or less, or 900 or less. Also preferably, the copolycarbonate according to the present invention has a fluidity of 7 to 30 g / 10 min, measured according to ASTM D1238 (300 ^° C., 1.2 kg conditions). More preferably, the fluidity (g 0 min) is 7.2 or more, 7.3 or more, or 7.4 or more and 18 or less, 15 or less, or 13 or less. Also preferably, the copolycarbonate according to the present invention has a chemical resistance of 18 to 50 min, measured based on the Mini Jig measurement method. More preferably, the chemical resistance (min) is 19 or more, or 20 or more, and 40 or less, 30 or less, or 28 or less. In addition, the polycarbonate resin composition may further include a polycarbonate, wherein the polycarbonate is characterized in that the polysiloxane structure is not introduced into the polycarbonate and the main chain.

Preferably, the polycarbonate includes a repeating unit represented by Formula 5 below:

In Chemical Formula 5,

R to R'4 are each independently hydrogen, Cwo alkyl, C _1-10 alkoxy, or halogen,

Cwo alkylene unsubstituted or substituted with phenyl, c ₃ _ ₁₅ cycloalkylene unsubstituted or substituted with c _1-10 alkyl, o, s, so, so ₂ , or CO. Also preferably, the polycarbonate has a weight average molecular weight of 1,000 to 100,0000 g / mol, more preferably 20,000 to 60,000 g / m. The repeating unit represented by Formula 5 may be an aromatic dialkyl compound and a carbonate The precursor is formed by reaction. 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 ₅ and R _{4 in} Formula 5 are the same as F in R ₄ and Z in Formula 1, respectively.

Also preferably, the repeating unit represented by Chemical Formula 5 is represented by the following Chemical Formula 5-1.

In addition, the polycarbonate resin composition, if necessary, selected from the group consisting of antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, optical brighteners, ultraviolet absorbers, pigments and dyes It may further comprise any one or more. The present invention also provides an article comprising the polycarbonate resin composition. Preferably, the article is an injection molded article.

In the method for producing the article, the polycarbonate 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 next injection molding machine.

【Effects of the Invention】

As described above, the polycarbonate resin composition according to the present invention includes a copolycarbonate having a sebacoyl structure in addition to a copolycarbonate having a polysiloxane structure in the main chain of the polycarbonate, thereby providing excellent physical properties of the copolycarbonate. It is possible to improve the melting properties while maintaining the maximum. [Specific contents to carry out invention]

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples. -PDMS (n = 34)

47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 mmol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 1 part by weight of acidic clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane. Put together 3L flask and reaction 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 (n) of the terminal unmodified polyorganosiloxane thus obtained was found to be 34 by 1 H 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 terminal unmodified polyorganosiloxane, and the mixture was reacted at 90 ^° C. for 3 hours. After completion of reaction, Mibanung siloxane was removed by evaporation under conditions of 12 CTC and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n = 34). AP-PDMS is light yellow oil, and the repeat unit (n) was identified as 34 by NMR using a Varian 500 MHz, and no further purification was necessary. Preparation Example 2 MBHB-PDMS (m = 58)

47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (ll mmol) of tetramethyldisiloxane were mixed, and then the mixture was added 1 part by weight of acidic clay (DC-A3) to 100 parts by weight of octacetylcyclotetrasiloxane. Into a 3L polar flask with 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 58 by ⁱ H NMR.

3-methylbut-3-enyl to the terminal unmodified polyorganosiloxane obtained above.

6.13 g (29.7 mmol) of 4-methylbut-3-enyl 4-hydroxybenzoate and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added for 3 hours at 90 ^° C. I responded. After the reaction was completed, unreacted siloxane Evaporation was performed ^at 120 ^° C and 1 torr. The terminal modified polyorganosiloxane thus obtained was named MBHB-PDMS (m = 58). MBHB-PDMS is a light yellow oil, NMR using a Varian 500MHz confirmed that the repeat unit (m) is 58, no further purification was required. Example 1 (7% PDMS (95: 5): 0.5% SBC PC = 1: 1)

i) manufacture of PC-A

620 g H ₂ 0 620, bisphenol A (BPA) 116.47 g, AP-PDMS 11.66 g prepared in Preparation Example 1 in a 2 L main reactor equipped with a nitrogen purge and a condenser and capable of holding a phase as a 'circulator' , 0.61 g of MBHB-PDMS prepared in Preparation Example 2, 102.5 g of NaOH, and 200 ml of MeCb were added thereto, followed by stirring for several minutes.

Stop nitrogen purging, add 62 g of Triphosgene and 120 g of MeCb to a 1 L isometric bottom flask, dissolve the Triphosgen, and slowly add the dissolved Triphosgen solution to the main reactor where the BPA solution is dissolved. Stirred for 10 minutes. 1.16g of TEA was added as a coupling agent and then stirred into a 40 weight ^_0/0 NaOH aqueous solution after completion of 97g. At this time, the reaction pH was maintained at 11 to 13. In order to complete the reaction, the pH was dropped to 3-4 by adding HC1 to terminate the reaction. Then, the stirring was stopped to separate the polymer layer from the water layer, the water layer was removed, and pure Η ₂ 0 was added again and washed with water for three to five times.

After complete washing with water, only the polymer layer was extracted, and copolycarbonate crystals (PC-A) were obtained by reprecipitation using a nonsolvent using methanol, Η ₂₀ , and the like.

The weight average molecular weight (Mw) of the copolycarbonate (PC-A) measured using GPC (40 ^° C., THF, standard polystyrene) was 55,000 g / mol. ii) manufacturing of PC-B

Nitrogen purge and condenser, equipped with a circle (circulator) 620 g of H ₂ O, 116.47 g of BPA, 0.93 g of sebacoyl chloride, 102.5 g of NaOH, and 200 ml of MeCb were added to a ₂ L main reactor capable of maintaining, followed by stirring for several minutes.

Stop purging nitrogen, add 62 g of Triphosgene and 120 g of MeCl ₂ in a 1 L isometric bottom flask, dissolve the Triphosgen, and slowly press the dissolved Triphosgen solution into the main reactor in which the BPA solution is dissolved. The mixture was stirred for 10 minutes. After stirring into the 40 parts by weight ^_0/0 aqueous solution of NaOH 97 g After completion of the TEA it was added 1.16 g as a coupling agent. At this time, the reaction pH was maintained at 11 to 13. In order to allow sufficient reaction, the pH was dropped to 3-4 by adding HC1 to terminate reaction. Then, the stirring was stopped to separate the polymer layer and the water layer, the water repellent was removed, and pure H ₂ 0 was added again and washed with water for three to five times.

After washing with water, only the polymer layer was extracted and copolycarbonate crystals (PC-B) were obtained by reprecipitation using a nonsolvent using methanol, H ₂ O, and the like.

The weight average molecular weight (Mw) of the copolycarbonate (PC-B) measured using GPC (40 ^° C., THF, standard polystyrene) was 55,000 g / mol. ^: Iii) PC-A and PC-B in heunhap

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 1. Example 2 (7% PDMS (95: 5): 1% SBC PC = 1: 1)

PC-A and PC-B were prepared in the same manner as in Example 1, except that the amount of sebacoyl chloride used in the preparation of PC-B was changed to 1.87 g.

Here, the increased average molecular weight of the PC-B measured using GPC (40 ^° C, THF, standard polystyrene) was 55,200 g / mol.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 1. Example 3 (7% PDMS (95: 5): 3% SBC PC = 1: 1)

PC-A and PC-B were prepared in the same manner as in Example 1, except that sebacoyl chloride was changed to 5.6 g in the preparation of PC-B.

Here, the weight average molecular weight of PC-B measured using GPC (40 ^° C., THF, standard polystyrene) was 55,000 g / mc) I.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 1. Example 4 (7% PDMS (90:10): 1% SBC PC = 1: 1)

PC-A was prepared in the same manner as in Example 1, except that the amount of AP-PDMS used was 11.05 g and the amount of MBHB-PDMS was changed to 1.23 g.

And PC-B was prepared in the same manner as in Example 1, except that the amount of sebacoyl chloride used in the preparation of PC-B was changed to 1.87 g.

Here, the weight average molecular weight of the PC-A measured using GPC (40 ^° C, THF, standard polystyrene) was 55,300 g / mol, the weight average molecular weight of the PC-B was 54,500 g / m.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 1. Example 5 (7% PDMS (90:10): 3% SBC PC = 1: 2)

In the preparation of PC-A, the amount of AP-PDMS used was 11.05 g,

PC-A was prepared in the same manner as in Example 1, except that the amount of MBHB-PDMS was changed to 1.23 g.

In addition, PC-B was prepared in the same manner as in Example 1, except that sebacoyl chloride and the amount of use thereof were changed to L87 g in the preparation of PC-B. Here, the weight average molecular weight of the PC-A measured using GPC (40 ^° C, THF, standard polystyrene) was 55,300 g / mol, the weight average molecular weight of the PC-B was 54,500 g / m. .

The thus prepared PC-A and PC-B were mixed and extruded at a weight ratio of 1: 2. Example 6 (7% PDMS (90:10): 3% SBC PC = 1: 0.5)

And, except that the amount of sebacoyl chloride (sebacoyl chloride) in the preparation of PC-B was changed to 1.87 g, the PC-B was prepared in the same manner as in Example 1.

The PC-A and PC-B thus prepared were mixed and extruded at a weight ratio of 1: 0.5. Comparative Example 1 (7% PDMS (95: 5): NPC = 1: 1)

PC-A and PC-B were prepared in the same manner as in Example 1, except that sebacoyl chloride was not used in the preparation of PC-B.

Here, the weight average molecular weight of the PC-B (Neat PC) measured using GPC (40 ^° C., THF, standard pulley styrene) was 54,900 g / mol.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 1. Comparative Example 2 (3.5% PDMS (95: 5))

In the preparation of PC-A, the amount of AP-PDMS used was 5.5 g, The PC-A was manufactured in the same manner as in Example 1, except that the amount of MBHB-PDMS was changed to 29 g. However, the PC-B was not prepared.

Here, the weight average molecular weight of the PC-A measured using GPC (40 ^° C, THF, standard polystyrene) was 55,200 g / mol.

The PC-A thus prepared was extruded alone. Comparative Example 3 (0.5% SBC PC)

The PC-B according to Example 1 was extruded alone. Reference Example 1 (7% PDMS (90:10): 3% SBC PC = 1: 3)

The PC-Bs were prepared in the same manner as in Example 1, except that the amount of sebacoyl chloride was changed to 1.87 g in the preparation of PC-B.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 3. Reference Example 2 (7% PDMS (90:10): 3% SBC PC = 1 ： 5)

In the preparation of PC-A, the amount of AP-PDMS used was 1L05 g,

The PC-Bs were prepared in the same manner as in Example 1, except that the amount of sebacoyl chloride was changed to 1.87 g in the preparation of PC-B. Here, the weight average molecular weight of the PC-A measured using GPC (40 ^° C, THF, standard polystyrene) was 55,300 g / mol, the weight average molecular weight of the PC-B was 54,500 g / mol.

The PC-A and PC-B thus prepared were mixed and extruded in a weight ratio of 1: 5. Experimental Example

The physical properties were measured by the following method, and the results are shown in Tables 1 and 2 below.

1) Increased average molecular weight (Mw): Agilent 1200 series was measured by GPC using PS standard (Standard).

2) Room temperature and low temperature impact strength: measured at room temperature and -30 ^° C (low temperature) in accordance with ASTM D256 (l / 8 inch, Notched Izod).

3) Melt Index (MI): Measured according to ASTM D1238 (300 ^° C., 1.2 kg conditions).

4) Chemical Resistance (Jig Test): Place 13 mm * 64 mm * l / 8 inch specimen in close contact with Mini Jig (58.5R), place 5 mm * 13 mm cotton in the center, and then NIVEA sunspray 0.5ml on it. After the injection, the contact time of the closely spaced specimens was measured.

Table 1

Example Example Example Example Example Example 1 2 3 4 5 6

Mw (g / mol) 55,400 55,200 55,000 54,900 55,000 55,000 Room temperature Shock strength (J / mol) 850 850 840 850 840 860 Low temperature impact strength (J / mol) 710 670 680 710 640 770

MI (g / 10 min) 7.4 9.2 10.4 9.1 11.2 9.0 Chemical resistance (min) 20 24 22 25 20 29 Table 2

Referring to Tables 1 and 2, the polycarbonate resin compositions obtained in Examples 1 to 6 are copolycarbonates incorporating a polysiloxane structure into the main chain of the polycarbonate and copolycarbonates doped with sebacoyl structures. By including, compared to Comparative Example 2 containing only a copolycarbonate having a polysiloxane structure in the polycarbonate main chain and Comparative Example 1 in which it is mixed with a general polycarbonate, the same level of room temperature and low temperature impact strength. While showing, it can be confirmed that it shows remarkably excellent fluidity and flowability. -

Claims

[Claim]

[Claim 1]

A first copolycarbonate comprising a repeating unit represented by the following Formula 1, a repeating unit represented by the following Formula 2, and a repeating unit represented by the following Formula 3; And

A repeating unit represented by the following formula (1). And a second copolycarbonate comprising a repeating unit represented by Formula 4 below.

Polycarbonate resin composition comprising:

In Chemical Formula 1,

Ri to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Zr is Cwo alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene unsubstituted or substituted with Cwo alkyl, 0, S, SO, S0 ₂ , or CO,

In Chemical Formula 2,

Each Xi is independently C _1-10 alkylene,

Each R ₅ is independently hydrogen; Cw ₅ alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; Cwo alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n is an integer from 10 to 200,

In Chemical Formula 3,

Χ ₂ are each independently Q-io alkylene,

^ Are each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C ₆ — ₂₀ aryl,

Each R ₆ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; Cwo haloalkyl; Or C _6-20 aryl,

m is an integer from 10 to 200,

[Formula 4]

In Chemical Formula 4,

¾ is C 40 alkylene unsubstituted or substituted with phenyl;

Cycloalkylene substituted with Cwo alkyl, O, S, SO, SO2, or CO,

1 is an integer of 1-10.

[Claim 2] ^"

The method of claim 1,

The repeating unit represented by the formula (1) is characterized in that, polycarbonate resin composition:

[Formula 1-1]

[Claim 3]

The method of claim 1,

The repeating unit represented by Formula 2 is represented by the following Formula 2-2, polycarbonate resin composition:

[Claim 4]

The method of claim 3,

R <5> is methyl, Polycarbonate resin composition.

[Claim 5]

The method of claim 1,

n is an integer of 10 to 50, polycarbonate composition.

[Claim 6]

The method of claim 1,

The repeating unit represented by Chemical Formula 3 is represented by the following chemical formula, polycarbonate resin composition:

[Formula 3-2]

[Claim 7]

The method of claim 6,

R ₆ is methyl, polycarbonate resin composition.

[Claim 8]

The method of claim 1,

m is an integer of 30-70, The polycarbonate resin composition.

【Claim ⁹ 】

The method of claim 1,

The first copolycarbonate has a weight average molecular weight of 1,000 to

It is 100,000 g / mol, Polycarbonate resin composition.

[Claim 10]

The method of claim 1,

The repeating unit represented by Formula 4 is represented by the following Formula 4-2, polycarbonate resin composition:

4-2]

[Claim 11]

The method of claim 1,

The second copolycarbonate has a weight average molecular weight of 1,000 to 100,000 g / mol, polycarbonate resin composition.

[Claim 12]

The method of claim 1,

Polycarbonate resin composition comprising the first copolycarbonate and the second copolycarbonate in a weight ratio of 1: 0.5 to 1: 2.

[Claim 13]

The method of claim 1,

A polycarbonate resin composition, further comprising a polycarbonate, wherein a polysiloxane structure is not introduced into the main chain of the polycarbonate.