KR102168679B1 - Copolycarbonate and resin compositin comprising the same - Google Patents

Abstract

The present invention relates to a copolycarbonate having improved chemical resistance while maintaining excellent impact strength at room temperature and low temperature, and a polycarbonate resin composition comprising the same.

Description

Copolycarbonate and a resin composition containing the same TECHNICAL FIELD [COPOLYCARBONATE AND RESIN COMPOSITIN COMPRISING THE SAME}

The present invention relates to a copolycarbonate having improved chemical resistance while maintaining excellent impact strength at room temperature and low temperature, and a resin composition comprising the same.

Polycarbonate resin is manufactured by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and has excellent impact strength, numerical stability, heat resistance, and transparency, and exterior materials of electrical and electronic products, automobile parts, construction materials, and optical parts. And so on.

In order to apply these polycarbonate resins to a wider variety of fields recently, many studies have been attempted to obtain desired physical properties by copolymerizing two or more types of aromatic diol compounds of different structures to introduce units with different structures into the main chain of polycarbonate. .

In particular, studies to introduce a polysiloxane structure into the main chain of polycarbonate are also being conducted, but most of the technologies have a high production cost, and other physical properties such as chemical resistance and fluidity decrease when the impact strength, especially low-temperature impact strength, is increased. There is this.

Accordingly, the inventors of the present invention have studied copolycarbonate which has improved chemical resistance while maintaining excellent impact strength at room temperature and low temperature by overcoming the above disadvantages, and as a result of introducing a specific polysiloxane structure into the main chain of polycarbonate as described below. The present invention was completed by confirming that the copolycarbonate satisfies the above.

The present invention is to provide a copolycarbonate having improved chemical resistance while maintaining excellent impact strength at room temperature and low temperature.

In addition, the present invention is to provide a resin composition containing the copolycarbonate.

In order to solve the above problems, the present invention provides a 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):

[Formula 1]

In Formula 1,

R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the

[Formula 2]

In Chemical Formula 2,

Each X ₁ is independently C _1-10 alkylene,

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

n is an integer from 10 to 200,

[Formula 3]

In Chemical Formula 3,

Each X ₂ is independently C _1-10 alkylene,

Each Y is independently a bond or COO,

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

R ₇ is C _1-15 alkyl substituted with 1 to 3 fluoro,

Each R ₈ is independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, C _6-20 aryl, hydroxy, or halogen,

m and l are each independently an integer of 1 to 200.

Polycarbonate resin is a resin produced by condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene, and has excellent mechanical properties by itself, but needs to simultaneously satisfy several physical properties depending on the application field. In particular, polycarbonate resins can improve certain physical properties by changing some structures, but in most cases, when one of the properties is improved, other properties are deteriorated.

Accordingly, in the present invention, in order to improve chemical resistance while maintaining excellent impact strength at room temperature and low temperature, the repeating units of Formulas 2 and 3 are introduced in addition to the conventional polycarbonate structure including a repeating unit such as Formula 1 Introducing the repeating units such as Formulas 2 and 3 may improve various physical properties of the polycarbonate without deteriorating other properties.

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

Repeating unit represented by Formula 1

The repeating unit represented by Formula 1 forms the basic skeleton of the copolycarbonate resin according to the present invention, and is formed by reacting an aromatic diol compound and a carbonate precursor.

In Formula 1, preferably, R ₁ to R ₄ are each independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is a linear or branched C _1-10 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 is cyclohexane-1,1-diyl, O, S, SO, SO 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-hydroxyl) Roxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 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 -From any one or more aromatic diol compounds selected from the group consisting of phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and a,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane It can be derived.

The meaning of "derived from an aromatic diol compound" means that a hydroxy group of an aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by Formula 1 above.

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

[Formula 1-1]

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, At least one selected from the group consisting of bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate may be used. Preferably, triphosgene or phosgene may be used.

Chemical formula 2 furnace Repeat unit displayed

The repeating unit represented by Formula 2 has a polyorganosiloxane structure, and may be introduced into copolycarbonate to improve various physical properties.

In Formula 2, preferably, each of X ₁ is independently C _2-10 alkylene, more preferably C _2-4 alkylene, and most preferably propane-1,3-diyl.

Also preferably, R ₅ 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 ₅ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 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 It is an integer.

The repeating unit represented by Formula 2 is derived from a siloxane compound represented by Formula 2-1 below.

[Formula 2-1]

In Formula 2-1,

The definitions of X ₁ , R ₅ and n are as defined above.

The meaning of “derived from a siloxane compound” means that the hydroxy group of each of the siloxane compounds reacts with the carbonate precursor to form a repeating unit represented by the respective formula (2). In addition, the carbonate precursor that can be used to form the repeating unit of Formula 2 is as described in the carbonate precursor that can be used to form the repeating unit of Formula 1 described above.

Preferably, the repeating unit represented by Formula 2 is represented by the following Formula 2-2:

[Formula 2-2]

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

Repeating unit represented by Formula 3

The repeating unit represented by Formula 3 has a polysiloxane structure containing Fluorine in the side chain, and is introduced into copolycarbonate to improve chemical resistance.

In Formula 3, preferably, R ₆ 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 ₅ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

In addition, preferably R ₇ is -(CH ₂ ) _p CH _q F _r , in this case, p is an integer of 0 to 10, q and r are each independently an integer of 0 to 3, and q+r is It is 3.

Preferably, the sum of m and l is 30 or more, 35 or more, 40 or more, 45 or more, 46 or more, 47 or more, or 48 or more, 70 or less, 65 or less, 60 or less, 55 or less, 54 or less, or It is an integer of 53 or less.

And, the repeating unit represented by Formula 3 is derived from a siloxane compound represented by Formula 3-1 below.

[Formula 3-1]

In Formula 3-1,

The definitions of X ₂ , Y, R ₆ to R ₈ , m and l are as previously defined.

Preferably, the repeating unit represented by Formula 3 is represented by the following Formula 3-2:

[Chemical Formula 3-2]

In Formula 3-2,

Definitions of R ₆ to R ₇ , and m are as defined above. Preferably, R ₆ is methyl and R ₇ is -(CH ₂ ) ₂ CF ₃ .

Copolycarbonate

The copolycarbonate according to the present invention includes a repeating unit represented by Formula 1, a repeating unit represented by Formula 2, and a repeating unit represented by Formula 3 below. Preferably, the copolycarbonate is a random copolymer.

In addition, the copolycarbonate may improve various physical properties of the copolycarbonate at the same time by adjusting the content of each repeating unit. The weight ratio between the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 having the polyorganosiloxane structure may be 99:1 to 1:99. It is preferably 99:1 to 70:30, and more preferably 99:1 to 80:20. The weight ratio of the repeating unit corresponds to a weight ratio of a siloxane compound, such as a siloxane compound represented by Formula 2-1 and a siloxane compound represented by Formula 3-1.

The copolycarbonate according to the present invention may be prepared by a manufacturing method comprising the step of polymerizing an aromatic diol compound, a carbonate precursor, and two types of siloxane compounds.

The aromatic diol compound, carbonate precursor, and siloxane compound are as described above.

In addition, as the polymerization method, an interfacial polymerization method may be used as an example, and in this case, a polymerization reaction is possible at normal pressure and a low temperature, and molecular weight control is easy. 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, for example, pre-polymerization and then adding a coupling agent and then polymerizing again, and in this case, a high molecular weight copolycarbonate may be obtained.

The materials used for the interfacial polymerization are not particularly limited as long as they can be used for the polymerization of polycarbonate, and the amount of the material may be adjusted as necessary.

As the acid binder, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine may be used.

The organic solvent is not particularly limited as long as it is a solvent commonly used for polymerization of polycarbonate, and halogenated hydrocarbons such as methylene chloride and chlorobenzene may be used as an example.

In addition, the interfacial polymerization is a reaction such as triethylamine, tetra-n-butylammonium bromide, and tertiary amine compounds such as tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds, etc. Additional accelerators can be used.

The reaction temperature of the interfacial polymerization is preferably 0 to 40°C, and the reaction time is preferably 10 minutes to 5 hours. In addition, during the interfacial polymerization reaction, the pH is preferably maintained at 9 or higher or 11 or higher.

In addition, the interfacial polymerization may be performed by further including a molecular weight modifier. The molecular weight modifier may be added before the start of polymerization, during the start of polymerization, or after the start of polymerization.

Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol, and triacontylphenol, preferably p-tert-butylphenol, and in this case, the molecular weight control effect is large.

The molecular weight modifier is, for example, 0.01 parts by weight or more, 0,1 parts by weight or more, or 1 part by weight or more, and includes 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound. And a desired molecular weight can be obtained within this range.

In addition, the copolycarbonate has a weight average molecular weight (g/mol) of 1,000 to 100,000, preferably 10,000 to 50,000, more preferably 20,000 to 40,000, and even more preferably 25,000 to 35,000.

Also preferably, the copolycarbonate according to the present invention has a room temperature impact strength of 700 to 1100 J/m measured in 23 according to ASTM D256 (1/8 inch, Notched Izod). More preferably, the room temperature impact strength (J/m) is 700 or more, or 800 or more. In addition, the room temperature impact strength (J/m) is superior as the value is higher, and thus there is no upper limit, but may be, for example, 1050 or less or 1000 or less.

Also preferably, the copolycarbonate according to the present invention has a low-temperature impact strength of 600 to 1100 J/m measured at -30 according to ASTM D256 (1/8 inch, Notched Izod). More preferably, the low-temperature impact strength (J/m) is 700 or more, or 730 or more. In addition, the low-temperature impact strength (J/m) is excellent as the value is higher, and thus there is no upper limit, but may be, for example, 1050 or less or 1000 or less.

In addition, preferably, the copolycarbonate according to the present invention has a chemical resistance of 8 to 50 min as measured based on Jig strain R 1.0 according to ASTM D543 (Practice B). More preferably, the chemical resistance (min) is 8 or more, 9 or more, or 10 or more, 40 or less, or 30 or less.

Polycarbonate resin composition

In addition, the present invention provides a polycarbonate composition comprising the above-described copolycarbonate and polycarbonate.

The copolycarbonate may be used alone, but the physical properties of the copolycarbonate may be adjusted by using a polycarbonate together if necessary.

The polycarbonate is distinguished from copolycarbonate in that a polysiloxane structure is not introduced into the main chain of the polycarbonate.

Preferably, the polycarbonate contains a repeating unit represented by Formula 4:

[Formula 4]

.

.

In Chemical Formula 4,

And R _'1 to R' ₄ each independently represent a hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z 'is a Beach unsubstituted or phenyl-substituted C _1-10 alkylene, or C _1-10 unsubstituted or substituted with a C _3-15 alkyl cycloalkylene, O, S, SO, SO _2, or CO in .

Also preferably, the polycarbonate has a weight average molecular weight of 1,000 to 100,0000 g/mol, more preferably 10,000 to 35,000 g/mol.

The repeating unit represented by Formula 4 is formed by reacting an aromatic diol compound and a carbonate precursor. The aromatic diol compound and carbonate precursor that can be used are the same as those described for the repeating unit represented by Chemical Formula 1.

Preferably, in the general formula 4 R _'1 to R' _4, and Z 'are the same as R ₁ to R ₄ and Z of the formula (1) described above, respectively.

Also preferably, the repeating unit represented by Formula 4 is represented by the following Formula 4-1.

[Formula 4-1]

.

.

In addition, the polycarbonate resin composition is selected from the group consisting of antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent whitening agents, ultraviolet absorbers, pigments, and dyes, if necessary. Any one or more may be additionally included.

In addition, the present invention provides an article comprising the polycarbonate resin composition. Preferably, the article is an injection molded article.

The manufacturing method of the article is, after mixing the polycarbonate resin composition according to the present invention and the above-described additives as necessary using a mixer, extruding the mixture with an extruder to produce pellets, and drying the pellets. It may include the step of injecting with an injection molding machine.

As described above, the copolycarbonate according to the present invention introduces a specific polysiloxane structure into the main chain of the polycarbonate, thereby maintaining the excellent physical properties of the polycarbonate as much as possible and improving chemical resistance at the same time.

1 is a ¹ H NMR graph of the compound prepared in Preparation Example 2.
2 is a ¹ H NMR graph (top) of the compound prepared in Preparation Example 1, and a ¹ H NMR graph (bottom) of the copolycarbonate of Example 1 prepared using the same.

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Manufacturing example One: AP - PDMS (n=34)

After mixing 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 mmol) of tetramethyldisiloxane, the mixture was mixed with 1 part by weight of acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane. Put together in a 3L flask and reacted at 60°C for 4 hours. After completion of the reaction, it was diluted with ethyl acetate and rapidly filtered using Celite. The repeating unit (n) of the terminal unmodified polyorganosiloxane thus obtained was 34 as a result of ¹ H NMR.

To the obtained terminal unmodified polyorganosiloxane, 4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added and reacted at 90° C. for 3 hours. After completion of the reaction, the unreacted siloxane was removed by evaporation under conditions of 120°C and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n=34). AP-PDMS is a pale yellow oil, and it was confirmed that the repeating unit (n) was 34 through ¹ H NMR using Varian 500MHz, and further purification was not required.

Manufacturing example 2: Si -F- PDMS (m+l=50)

After mixing 35.70 g of the sum of octamethylcyclotetrasiloxane and poly(methyl-trifluoropropyl)dimethylsiloxane and 2.40 g (17.8 mmol) of tetramethyldisiloxane, the mixture was mixed with octamethylcyclotetrasiloxane and poly(methyl- Trifluoropropyl) placed in a 3L flask with 1 part by weight of acid clay (DC-A3) relative to the sum of 100 parts by weight of dimethyl siloxane and reacted at 60° C. for 4 hours. After completion of the reaction, it was diluted with ethyl acetate and rapidly filtered using celite. The repeating unit (sum of m and l) of the thus obtained unmodified polyorganosiloxane was 50 as a result of ¹ H NMR.

In the obtained terminal unmodified polyorganosiloxane, 0.01 g (50 ppm) of Karlstedt's platinum catalyst was added and reacted at 90° C. for 1 hour, and then 4.81 g (35.9 mmol) of 2-allylphenol was added. It was added and further reacted for 3 hours. After completion of the reaction, the unreacted siloxane was removed by evaporation under conditions of 120°C and 1 torr. In this way, a modified polyorganosiloxane having a liquid light yellow transparent property was obtained.

Thereafter, chloroform (CHCl ₃ ) 1,000 mL (liquid basis) was added to a 2,000 mL 3-neck flask capable of refluxing, and 7.1 g of terephthaloyl chloride was slowly dissolved for 1 hour while maintaining a nitrogen atmosphere at room temperature (20 to 26°C). . Then, 25 g of triethylamine was added and reacted for 1 hour, and then 175 g of the modified polyorganosiloxane was added and sufficiently reacted to prepare a compound represented by the above formula, and it was confirmed whether or not it was produced by ¹ H NMR.

Example One

1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved in an N ₂ atmosphere. Here, 4.3 g of PTBP (para-tert butylphenol), 16.7 g of AP-PDMS (n=34) prepared in Preparation Example 1, and 0.17 g of Si-F-PDMS (m+l=50) prepared in Preparation Example 2 The mixed solution (weight ratio 99:1) was dissolved in MC (methylene chloride) and added. Then, 128 g of TPG (triphosgene) was dissolved in MC and added for 1 hour while maintaining the pH above 11 to react, and after 10 minutes, 46 g of TEA (triethylamine) was added to perform a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed 3 times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120° C. to obtain a final copolycarbonate.

Example 2

It was prepared in the same manner as in Example 1, except that the amount of AP-PDMS was changed to 16 g and the amount of Si-F-PDMS was changed to 0.85 g (weight ratio 95:5).

Example 3

It was prepared in the same manner as in Example 1, except that the amount of AP-PDMS was changed to 15.2 g and the amount of Si-F-PDMS was changed to 1.69 g (weight ratio 90:10).

Example 4

It was prepared in the same manner as in Example 1, except that the amount of AP-PDMS was changed to 14.3 g and the amount of Si-F-PDMS was changed to 2.54 g (weight ratio 85:15).

Example 5

Copolycarbonate was prepared in the same manner as in Example 1, except that the amount of AP-PDMS was changed to 15.2 g and the amount of Si-F-PDMS was changed to 1.69 g (weight ratio 90:10). In addition, the copolycarbonate and general PC (Comparative Example 1) having a molecular weight of approximately 29,000 were mixed in a weight ratio of 8:2.

Comparative example One

1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved in an N ₂ atmosphere. Here, 4.86 g of PTBP (para-tert butylphenol) was dissolved in MC (methylene chloride) and added. Then, 128 g of TPG (triphosgene) was dissolved in MC and added for 1 hour while maintaining the pH above 11 to react, and after 10 minutes, 46 g of TEA (triethylamine) was added to perform a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed 3 times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120° C. to obtain a final copolycarbonate.

Comparative example 2

1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved in an N ₂ atmosphere. Here, 4.3 g of PTBP (para-tert butylphenol) and 16.9 g of AP-PDMS (n=34) prepared in Preparation Example 1 were dissolved in MC (methylene chloride) and added. Then, 128 g of TPG (triphosgene) was dissolved in MC and added for 1 hour while maintaining the pH above 11 to react, and after 10 minutes, 46 g of TEA (triethylamine) was added to perform a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed 3 times with distilled water to adjust the pH of the resulting polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120° C. to obtain a final copolycarbonate.

Experimental example

Each physical property was measured by the following method, and the results are shown in Table 1 below.

1) Weight average molecular weight (Mw): Measured by GPC using PS standard using Agilent 1200 series.

2) Room temperature and low-temperature impact strength: In accordance with ASTM D256 (1/8inch, Notched Izod) was measured at room temperature and -30 ℃ (low temperature).

3) Flowability (Melt Flow Rate; MFR): It was measured according to ASTM D1238 (300 ℃, 1.2kg condition).

4) Chemical Resistance (Jig Test): According to ASTM D543 (Practice B), chemical resistance was measured based on Jig strain R 1.0.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Mw
(g/mol) 30,000 30,000 30,000 30,000 28,000 30,000 30,000 Room temperature impact strength
(J/mol) 900 950 980 990 850 870 750 Low temperature impact strength
(J/mol) 850 910 940 950 750 200 600 Chemical resistance
(min) 10 20 22 25 12 3 5

As shown in Table 1, the copolycarbonates prepared in Examples 1 to 5 introduced two types of specific polysiloxane structures into the main chain of the polycarbonate, and thus Comparative Example 1, which is a general polycarbonate, and 1 in the main chain of the polycarbonate. It can be seen that even compared with Comparative Example 2 in which a species polysiloxane structure was introduced, it not only exhibited the same level of impact strength at room temperature and low temperature, but also exhibited very excellent chemical resistance.

Claims (11)

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 3-2:
[Formula 1]

In Formula 1,
R ₁ to R ₄ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is Beach and unsubstituted or phenyl-substituted C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, or CO, the
[Formula 2]

In Chemical Formula 2,
Each X ₁ is independently C _1-10 alkylene,
Each R ₅ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, C _1-10 alkoxy substituted with oxiranyl, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,
n is an integer from 10 to 200,
[Chemical Formula 3-2]

In Formula 3-2,
R ₆ is methyl,
R ₇ is -(CH ₂ ) ₂ CF ₃ ,
m is an integer from 40 to 70.
The method of claim 1,
The repeating unit represented by Formula 1 is a copolycarbonate, characterized in that represented by the following Formula 1-1:
[Formula 1-1]

.
The method of claim 1,
The repeating unit represented by Formula 2 is a copolycarbonate, characterized in that represented by the following Formula 2-2:
[Formula 2-2]

.
The method of claim 1,
n is an integer of 10 to 50, characterized in that, copolycarbonate.
delete delete delete The method of claim 1,
The weight ratio between the repeating unit represented by Chemical Formula 2 and the repeating unit represented by Chemical Formula 3-2 is 99:1 to 1:99.
The method of claim 1,
Copolycarbonate, characterized in that the weight average molecular weight is 1,000 to 100,000 g/mol.
The polycarbonate resin composition comprising the copolycarbonate of any one of claims 1 to 4, 8, and 9, and polycarbonate.
The method of claim 10,
The polycarbonate is a polycarbonate resin composition, characterized in that the polysiloxane structure is not introduced into the main chain of the polycarbonate.

Images