KR20190038118A - Copolycarbonate and article containing the same - Google Patents

Abstract

The present invention relates to copolycarbonate with improved chemical resistance and flowability, and a composition including the same. The copolycarbonate comprises: a first repeating unit represented by chemical formula 1; a second repeating unit represented by chemical formula 2; and a third repeating unit represented by chemical formula 3.

Description

[0001] COPOLYCARBONATE AND ARTICLE CONTAINING THE SAME [0002]

The present invention relates to copolycarbonates and articles containing them, and more particularly to copolycarbonates which are economically produced and simultaneously improved chemical resistance and flow properties, and articles containing same.

The polycarbonate resin is produced by the condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene and has excellent impact strength, numerical stability, heat resistance, transparency and the like. The polycarbonate resin can be used for exterior materials, automobile parts, And so on.

In order to apply this polycarbonate resin to various fields in recent years, many attempts have been made to obtain desired physical properties by copolymerizing aromatic diol compounds having two or more different structures and introducing monomers having different structures into the main chain of the polycarbonate .

Particularly, studies have been conducted to introduce a polysiloxane structure into the main chain of polycarbonate, but most of the technologies have a disadvantage in that the production cost is high and the chemical resistance and fluidity are not simultaneously improved.

The inventors of the present invention have conducted intensive studies in order to overcome the above disadvantages. As a result, the present inventors have confirmed that the copolycarbonate having a specific siloxane compound introduced into the polycarbonate main chain satisfies the above-mentioned condition.

The present invention is to provide a copolycarbonate having improved chemical resistance and flowability at the same time.

The present invention also provides an article comprising the copolycarbonate.

In order to solve the above problems, the present invention provides a copolycarbonate as described below.

A first repeating unit represented by the following formula (1);

A second repeating unit represented by the following formula (2); And

And a third repeating unit represented by the following formula (3): < EMI ID =

[Chemical 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

(2)

In Formula 2,

X ₁ is each independently C _1-10 alkylene,

Y ₁ is each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

R < ₅ > are each 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 of 10 to 200,

(3)

In Formula 3,

X ₂ is C _1-10 alkylene, each independently,

X ₃ each independently is C _1-20 alkylene,

Y ₂ and Y ₃ 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, 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,

m ₁ and m ₂ are each independently an integer of 10 to 200.

The polycarbonate resin is a resin which is produced by the condensation polymerization of an aromatic diol such as bisphenol A and a carbonate precursor such as phosgene. The resin itself has excellent mechanical properties, but it is required to satisfy various physical properties at the same time depending on application fields. Recently, a variety of techniques have been developed for improving specific physical properties by changing a part of the structure of the polycarbonate resin. However, most of the properties of the polycarbonate resin are deteriorated when the physical properties are improved.

Therefore, in order to simultaneously improve the chemical resistance and the flowability, the inventors of the present invention have found that, in addition to the conventional polycarbonate-based recurring units as shown in Formula 1, aromatic polycarbonate-based repeating units having at least one siloxane bond represented by Chemical Formulas 2 and 3 Unit, it is possible to simultaneously improve the chemical resistance and flowability without deteriorating the inherent mechanical properties of the polycarbonate.

Hereinafter, the present invention will be described in more detail.

The first repeating unit represented by formula (1)

The first repeating unit represented by the 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.

[Chemical 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 an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

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 which is 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 first repeating unit represented by formula (1) is at least one selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy- Bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (3-hydroxyphenyl) propyl] polydimethylsiloxane, which is obtained from the group consisting of bis (4-hydroxyphenyl) diphenylmethane, May be derived from any one or more aromatic diol compounds selected.

Derived from the aromatic diol compound means that the hydroxy group of the aromatic diol compound reacts with the carbonate precursor to form the first repeating unit represented by the above formula (1).

For example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the first repeating unit represented by the 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 can be used. Preferably, triphosgene or phosgene can be used.

The second repeating unit represented by the general formula (2)

The second repeating unit represented by the general formula (2) is an aromatic polycarbonate-based repeating unit having at least one siloxane bond, and at least one siloxane compound and a carbonate precursor are reacted and formed. The second recurring unit is used in combination with the third recurring unit represented by the following formula (3) to simultaneously improve the chemical resistance and flowability of the polycarbonate according to the present invention.

(2)

In Formula 2,

X ₁ is each independently C _1-10 alkylene,

Y ₁ is each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

R < ₅ > are each 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 of 10 to 200;

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

Also preferably, Y ₁ is hydrogen.

Also preferably, each R ₅ is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) propyl, fluoro, chloro, bromo, 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.

Preferably, n is at least 45, at least 50, at least 55, at least 56, at least 57, or at least 58, and at most 100, at most 80, at least 75, at least 70, at least 65, at least 64, at most 63, And an integer of 62 or less. More preferably, it is an integer of 45 to 100 or less, or 58 to 62, inclusive.

Preferably, the second repeating unit represented by the formula (2) may be represented by the following formula (2-1): < EMI ID =

[Formula 2-1]

In Formula 2-1, R ₅ and n are as defined above. Preferably, R < ₅ > is methyl.

The second repeating unit represented by the formula (2) is derived from the siloxane compound represented by the following formula (2-A).

[Chemical Formula 2-A]

In the above formula (2-A), the definitions of X ₁ , Y ₁ , R ₅ and n are as defined above.

Means that the hydroxy group of each of the siloxane compounds reacts with the carbonate precursor to form the second repeating unit represented by the formula (2). The term " derived from the siloxane compound " The carbonate precursor that can be used to form the second repeating unit of Formula 2 is as described for the carbonate precursor that can be used to form the first repeating unit of Formula 1 described above.

The method for preparing the siloxane compound represented by the formula (2-A) is shown in the following reaction formula (1).

[Reaction Scheme 1]

In the above Reaction Scheme 1,

X ₁ 'is C _2-10 alkenyl,

X ₁ , Y ₁ , R ₅ and n are as defined above.

The reaction of Scheme 1 is preferably carried out under a metal catalyst. As the metal catalyst, it is preferable to use a Pt catalyst. As the Pt catalyst, an Ashby catalyst, a Karstedt catalyst, a Lamoreaux catalyst, a Spear catalyst, PtCl ₂ (COD) PtCl ₂ (benzonitrile) ₂ , and H ₂ PtBr ₆ may be used. The metal catalyst is used in an amount of 0.001 parts by weight or more, 0.005 parts by weight or more, or 0.01 parts by weight or more, 1 part by weight or less, 0.1 parts by weight or less, or 0.05 parts by weight or less, based on 100 parts by weight of the compound represented by Chemical Formula 5 .

The reaction temperature is preferably 80 to 100 占 폚. The reaction time is preferably 1 hour to 5 hours.

The compound represented by Formula 5 may be prepared by reacting an organosiloxane with an organocyclosiloxane in the presence of an acid catalyst, and adjusting the content of the reaction material to control n and m. The reaction temperature is preferably 50 to 70 占 폚. The reaction time is preferably 1 hour to 6 hours.

As the organosiloxane, at least one selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane and hexaphenyldisiloxane can be used. Examples of the organocyclosiloxane include organocyclotetrasiloxane, and examples of the organocyclosiloxane include octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.

The organosiloxane may be used in an amount of 0.1 parts by weight or more, or 2 parts by weight or more, 10 parts by weight or 8 parts by weight or less based on 100 parts by weight of the organocyclosiloxane.

As the acid catalyst, at least one selected from the group consisting of H ₂ SO ₄ , HClO ₄ , AlCl ₃ , SbCl ₅ , SnCl ₄ and acidic white clay can be used. The acid catalyst may be used in an amount of 0.1 parts by weight or more, 0.5 parts by weight or more, 1 part by weight or more, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane have.

The third repeating unit represented by the general formula (3)

The third repeating unit represented by the formula (3) is an aromatic polycarbonate repeating unit having at least one siloxane bond, and at least one siloxane compound and a carbonate precursor are formed by reaction. The third repeating unit is used in combination with the second repeating unit represented by the above-mentioned general formula (2) to improve the chemical resistance and flowability of the polycarbonate according to the present invention simultaneously. Particularly, since the internal chain length of the PDMS by the repeating unit is increased, the domain size is increased in the polycarbonate, and the chemical resistance can be remarkably improved.

(3)

In Formula 3,

X ₂ is C _1-10 alkylene, each independently,

X ₃ each independently is C _1-20 alkylene,

Y ₂ and Y ₃ 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, 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,

m ₁ and m ₂ are each independently an integer of 10 to 200.

In Formula 3, preferably, X ₂ and X ₃ are each independently C _2-10 alkylene, more preferably C _2-4 alkylene.

Also preferably, Y ₁ is hydrogen.

Also preferably, each R ₆ is independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) propyl, fluoro, chloro, bromo, 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.

Preferably, m ₁ and m ₂ are each independently an integer of 10 or more, or 15 or more, and 100 or less, 80 or less, 75 or less, 70 or less, 65 or less, or 55 or less. More preferably, it is an integer of 10 to 75 or 15 to 35. [

Preferably, the third repeating unit represented by Formula 3 may be represented by the following Formula 3-1:

[Formula 3-1]

In Formula 3-1, R ₆ , m ₁ and m ₂ are as defined above.

The third repeating unit represented by Formula 3 is derived from the reaction product of the siloxane compound of Formula 3-A and aliphatic diacyl chloride.

[Formula 3-A]

In the above formula (3-A), X ₂ and R ₆ are as defined above, and m is as defined for m ₁ and m ₂ .

Aliphatic diacyl chloride to react with the siloxane compound of Formula 3-A is preferably a C _{1- 20} alkyl diacyl chloride, and more preferably from Sebacoyl chloride.

The third repeating unit represented by the formula (3) is derived from a siloxane compound produced by the reaction of two equivalents of a compound of the formula (III-A) with one equivalent of an aliphatic diacyl chloride. This reaction is due to the reactivity of the acyl chloride moiety, and the aliphatic diacyl chloride end acyl chloride reacts with two equivalents of the hydroxy group of the compound of formula 3-A to produce the siloxane compound. And the third repeating unit is derived from the siloxane compound as the reaction product.

Means that the hydroxy group of each siloxane compound and the carbonate precursor react with each other to form the third repeating unit represented by the above formula (3). The carbonate precursor which can be used for forming the third repeating unit of the above formula (3) is as described for the carbonate precursor which can be used for forming the first repeating unit of the above-mentioned formula (1).

The method for preparing the siloxane compound represented by the above formula (3-A) is shown in the following reaction formula (2).

[Reaction Scheme 2]

In the above Reaction Scheme 2,

X ₂ 'is C _2-10 alkenyl,

X ₂ , R ₆ and m are as defined above.

The reaction of Reaction Scheme 2 can be carried out under the same conditions as the reaction conditions of Reaction Scheme 1 described above.

In the present invention, it is possible to more effectively improve the chemical resistance and flowability of the copolycarbonate by adjusting the content of the second repeating unit represented by the formula (2) and the third repeating unit represented by the formula (3).

The weight ratio between the repeating units may be 1:99 to 99: 1. Preferably from 3:97 to 97: 3, from 5:95 to 95: 5, from 10:90 to 90:10, or from 15:85 to 85:15, and more preferably from 20:80 to 80:20. The weight ratio of the repeating units corresponds to the weight ratio of the siloxane compound, for example, the siloxane compound represented by Formula 2-A and the siloxane compound represented by Formula 3-A and the aliphatic diacyl chloride reaction product.

In the present invention, the second repeating unit represented by formula (2) and the third repeating unit represented by formula (3) may be added in an amount of 100 parts by weight based on 100 parts by weight of the total repeating unit (including the first repeating unit represented by formula , 1 to 20 parts by weight, and preferably 3 to 15 parts by weight, or 5 to 12 parts by weight. By the inclusion of the above content range, the chemical resistance and flowability of the copolycarbonate can be improved more efficiently.

The copolycarbonate according to the present invention may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 15,000 to 70,000 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 / Or more, 27,000 g / mol or more, or 28,000 g / mol or more. The weight average molecular weight is 65,000 g / mol or less, 60,000 g / mol or 55,000 g / mol.

The copolycarbonate according to the present invention may have a flowability of 4.7 to 10.0 g / 10 min as measured according to ASTM D1238 (300 ° C, 1.2 kg conditions). Preferably, the flowability is 4.8 or greater, 9 or less, 8 or less, or 7 or less.

The copolycarbonate according to the present invention has a fluidity of about 0.4 to 5 g / 10 min or more as compared with a polycarbonate resin not containing a siloxane bond, and the copolycarbonate according to the present invention realizes excellent moldability. For reference, in the case of flowability, the difference of 0.1 g / 10 min has a great influence on moldability, so that the copolycarbonate according to the present invention shows remarkably excellent moldability.

The chemical resistance of the copolycarbonate according to the present invention measured based on JIG TEST may be 1000 sec or more. Preferably, the chemical resistance may be 1200 sec or more, or 1300 sec or more.

The JIG TEST is a test specimen prepared by using a co-polycarbonate composition, closely attached to a Mini Jig (58, 5R), putting cotton on it, putting a cosmetic product (Nivea line spray) thereon, And the time (sec) at which the play occurred. The JIG TEST is an experimental method designed by the present inventor to measure the chemical resistance of a copolycarbonate by a chemical substance such as a cosmetic, and more specific measuring methods will be described later in the experimental methods of Examples and Comparative Examples.

The present invention also provides a process for preparing a copolycarbonate comprising polymerizing an aromatic diol compound, a carbonate precursor and at least one siloxane compound.

The aromatic diol compound, the carbonate precursor and the at least one siloxane compound are as described above.

In the polymerization, the at least one siloxane compound is present in an amount of at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2.0 wt%, based on 100 wt% Or more, 2.5 wt% or more, 2.5 wt% or more, or 3.0 wt% or more, 20 wt% or less, 10 wt% or less, 7 wt% or less, 5 wt% or less, or 4 wt% or less.

The aromatic diol compound may be used in an amount of 40 wt% or more, 50 wt% or more, 55 wt% or more, 80 wt% or less, 70 wt% or less, By weight or less, or 65% by weight or less. The carbonate precursor may be present in an amount of at least 10 weight percent, at least 20 weight percent, or at least 30 weight percent, and at most 60 weight percent, at most 50 weight percent, and at most 10 weight percent, based on 100 weight percent of the total of the aromatic diol compound, carbonate precursor, Or 40% by weight or less.

As the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction can be carried out at a low temperature under atmospheric pressure, and the molecular weight can be easily controlled. 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 followed by introduction of a coupling agent and then polymerizing again, in which case a high molecular weight copolycarbonate can be obtained.

The materials used in the interfacial polymerization are not particularly limited as long as they can be used for polymerization of polycarbonate, and the amount thereof can be adjusted as needed.

As the acid binding agent, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like or an amine compound such as pyridine can be used.

The organic solvent is not particularly limited as long as it is a solvent usually used for polycarbonate polymerization. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

The interfacial polymerization may be carried out in the same manner as in the reaction for promoting the reaction, such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound Additional accelerators may be used.

The reaction temperature for the interfacial polymerization is preferably 0 to 40 ° C, and the reaction time is preferably 10 minutes to 5 hours. During the interfacial polymerization, the pH is preferably maintained at 9 or more or 11 or more.

In addition, the interfacial polymerization may be carried out by further including a molecular weight modifier. The molecular weight regulator may be added before the initiation of polymerization, during the initiation of polymerization or after initiation of polymerization.

The mono-alkylphenol may be, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecyl Phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol. In this case, the effect of controlling the molecular weight is large.

The molecular weight regulator is included in an amount of 0.01 part by weight or more, 0,1 parts by weight or more, 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 based on 100 parts by weight of the aromatic diol compound And a desired molecular weight can be obtained within this range.

The present invention also provides an article comprising the above-mentioned copolycarbonate.

Preferably, the article is an injection molded article. The article may further include at least one selected from the group consisting of an antioxidant, a heat stabilizer, a photostabilizer, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, a lubricant, an impact modifier, a fluorescent whitening agent, As shown in FIG.

The method of manufacturing the article may be carried out by mixing the additives such as the copolycarbonate and the antioxidant according to the present invention using a mixer and then extruding the mixture into an extruder to produce pellets, As shown in FIG.

As described above, the copolycarbonate having the specific siloxane compound introduced into the main chain of the polycarbonate according to the present invention is characterized in that both chemical resistance and flowability are improved.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are shown to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Manufacturing example

Manufacturing example  One: Of polyorganosiloxane (MB-60)  Produce

(A)

After mixing 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 mmol) of tetramethyldisiloxane, the mixture was mixed with 1 part by weight of acidic clay (DC-A3) relative to 100 parts by weight of octamethylcyclotetrasiloxane The mixture was placed in a 3 L flask and reacted at 60 ° C for 4 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate and rapidly filtered using Celite. The repeating unit (m) of the unmodified polyorganosiloxane of the formula (A) thus obtained was 60 as determined by ¹ H NMR.

To the resulting unmodified polyorganosiloxane were added 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and 6.8 g of Karstedt's platinum catalyst (0.01 g, 50 ppm) was added and reacted at 90 ° C for 3 hours. After completion of the reaction, the unreacted siloxane was removed by effervescence under the conditions of 120 DEG C and 1 torr. The thus obtained end-modified polyorganosiloxane was named MB-60. MB-60 was a pale yellow oil. Varian 500 MHz was used to confirm that the repeating unit (m) was 60 by ¹ H NMR and no further purification was required.

Manufacturing example  2: Of the polyorganosiloxane (SBAP-60)  Produce

(1) AP-30 synthesis

[Chemical Formula B]

42.5 g (142.8 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed and then the acid clay (DC-A3) was added to 1 part by weight of 100 parts by weight of octamethylcyclotetrasiloxane In a 3 L flask and reacted at 60 DEG 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 unmodified polyorganosiloxane thus obtained was found to be 30 by ¹ H NMR.

9.57 g (71.3 mmol) of 2-allylphenol and 0.01 g (50 ppm) of a Karstedt's platinum catalyst were added to the unmodified polyorganosiloxane obtained above and reacted at 90 ° C for 3 hours. After completion of the reaction, the unreacted polyorganosiloxane was removed by effervescence under the conditions of 120 DEG C and 1 torr. The thus obtained end-modified polyorganosiloxane, that is, the polyorganosiloxane represented by the formula (B) was a pale yellow oil, the repeating unit was 30, no further purification was necessary, and the polyorgano The preparation of the siloxane was confirmed by ¹ H NMR and was named AP-30.

(2) Synthesis of SBAP-60

≪ RTI ID = 0.0 &

Sebacic acid (10 g) was diluted with dichloromethane in a round-bottomed flask under nitrogen atmosphere and 0.36 mg of DMF was added. Oxalyl chloride (14.43 g) was then slowly added dropwise and stirred at room temperature for about 4 hours under nitrogen. After that, dichloromethane and DMF were evaporated using a rotary mixer to obtain about 11 g of Sebacic chloride.

Approximately 296 g of the AP-30 prepared above was placed in a round flask and diluted with ethyl acetate. After that, Sebacoyl chloride (11 g) and 23.5 g of pyridine were added, followed by stirring for 24 hours. When the reaction was completed, 1 M HCl was added dropwise until the pH became neutral, and then washed three times with water and ethyl acetate to obtain an organic layer. Ethyl acetate was evaporated using a rotary stirrer to obtain about 290 g of SBAP-60. The preparation of the polyorganosiloxane represented by the formula (C) was confirmed by ¹ H NMR (see Fig. 1), which was named SBAP-60.

Manufacturing example  3: Of the polyorganosiloxane (AP-60)  Produce

Except that 85.0 g (285.6 mmol) of octamethylcyclotetrasiloxane and 4.52 g (33.6 mmol) of tetramethyldisiloxane were used in the same manner as in AP-30 in Production Example 2, 60, which was named AP-60.

Manufacturing example  4: Of polyorganosiloxane (SBAP-Aryl)  Produce

[Chemical Formula D]

23.8 g (80 mmol) of octamethylcyclotetrasiloxane and 1.10 g (8.9 mmol) of tetramethyldisiloxane were mixed with terephthaloyl dichloride prepared using terephthalic acid instead of sebacic acid to obtain AP-17 Was used to prepare a polyorganosiloxane represented by the formula (D), which was named SBAP-Aryl.

Example  And Comparative Example

Example  One

One) Copolycarbonate  Manufacture of resin

620 g of H ₂ O, 116.47 g of bisphenol A (BPA), 0.26 g of MB-60 prepared in Preparation Example 1, 2 g of Production Example 2 (manufactured by Nippon Aerosil Co., Ltd.) were added to a ₂ L main reactor equipped with a nitrogen purge and a condenser, 5.01 g of SBAP-60, 102.5 g of a 40 wt% NaOH aqueous solution and 200 ml of MeCl ₂ were added and stirred for several minutes.

Next, nitrogen purging was stopped, and 62 g of triphosgene and 120 g of MeCl ₂ were added to a 1 L round bottom flask, triphosgene was dissolved and then the dissolved triphosgene solution was slowly added to the main reactor in which the BPA solution was dissolved. When the PTBP And the mixture was stirred for 10 minutes. After the stirring was completed, 97 g of a 40 wt% NaOH aqueous solution was added, and 1.09 g of TEA was added as a coupling agent. At this time, the reaction pH was maintained at 11 to 13. The pH was lowered to 3-4 by the addition of HCl to terminate the reaction over time to allow sufficient reaction to take place. Then, stirring was stopped to separate the polymer layer and the water layer, and then the water layer was removed, and pure H ₂ O was added again, and the water was washed 3 to 5 times.

When the water was completely washed, only the polymer layer was extracted and polymer crystals were obtained by re-precipitation using methanol, H ₂ O, or the like.

At this time, the produced copolycarbonate had a weight average molecular weight of 51,000 g / mol and a total content of polyorganosiloxane of 3.5 wt%. This was pelletized using a Bau Tech small twin screw extruder to produce pellets.

2) Manufacture of injection specimen

0.050 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite was added to 1 part by weight of the prepared copolycarbonate resin, and the mixture was pelletized using a Bau Tech small twin screw extruder. The specimen was injection molded at a cylinder temperature of 300 캜 and a mold temperature of 80 캜 using a molding machine.

Example  2

Except that the total content of the polyorganosiloxane of Production Example 1 and Production Example 2 was changed to 7 wt% (5 wt% of the polyorganosiloxane (MB-60) of Production Example 1 and 2 wt% of the polyorganosiloxane of Production Example 2 By weight of a polyorganosiloxane (SBAP-60) of 95 wt%), to prepare a copolycarbonate resin and its injection specimen.

Example  3

Except that the total content of the polyorganosiloxane of Production Example 1 and Production Example 2 was changed to 12 wt% (5 wt% of the polyorganosiloxane (MB-60) of Production Example 1 and 2 wt% of the polyorganosiloxane of Production Example 2 By weight of a polyorganosiloxane (SBAP-60) of 95 wt%), to prepare a copolycarbonate resin and its injection specimen.

Example  4

Except that the total content of the polyorganosiloxane of Production Example 1 and Production Example 2 was changed to 7 wt% (10 wt% of the polyorganosiloxane (MB-60) of Production Example 1) and 10 wt% of the polyorganosiloxane of Production Example 2 And about 90.5 wt% of polyorganosiloxane (SBAP-60)) to prepare a copolycarbonate resin and an injection specimen thereof.

Example  5

1% by weight of polyorganosiloxane (MB-60) of Production Example 1 and 1% by weight of the polyorganosiloxane of Production Example 2 were obtained in the same manner as in Example 1 except that the total content of the polyorganosiloxane of Production Example 1 and Production Example 2 was changed to 7% And about 10.54 g as a mixture of 99 wt% of polyorganosiloxane (SBAP-60)), to prepare a copolycarbonate resin and its injection specimen.

Comparative Example  One

The same procedure was followed as in Example 1 (3.5 wt%), except that AP-30 of Preparation Example 2 was used in the same amount as the polyorganosiloxane instead of SBAP-60 of Preparation Example 2 to prepare a copolycarbonate resin and its injection Specimens were prepared.

Comparative Example  2

The same procedure as in Example 2 (7.0 wt%) was carried out except that AP-30 of Production Example 2 was used in the same amount as the polyorganosiloxane instead of SBAP-60 of Production Example 2 to prepare a copolycarbonate resin and its injection Specimens were prepared.

Comparative Example  3

The same procedure as in Example 3 (12.0 wt%) was carried out except that AP-30 of Production Example 3 was used in the same amount as polyorganosiloxane instead of SBAP-60 of Production Example 2 to prepare a copolycarbonate resin and its injection Specimens were prepared.

Comparative Example  4

The copolycarbonate resin and its injection sample were prepared by the same method as in Example 2 (7.0 wt%) except that 10.54 g of MB-60 of Production Example 1 alone was used as the polyorganosiloxane.

Comparative Example  5

The copolycarbonate resin and its injection specimen were prepared by the same method as in Example 2 (7.0 wt%) except that 10.54 g of AP-30 was used alone as the polyorganosiloxane.

Comparative Example  6

A copolycarbonate resin and its injection sample were prepared by the same method as Example 2 (7.0 wt%) except that only 10.54 g of SBAP-Aryl of Production Example 4 was used alone as the polyorganosiloxane.

Comparative Example  7

A copolycarbonate resin and its injection specimen were prepared using the same procedure as Example 2 (7.0 wt%), except that AP-60 of Preparation Example 3 was used in the same amounts instead of SBAP-60 of Preparation Example 2.

Experimental Example : Property evaluation

The weight average molecular weights of the resins prepared in the Examples and Comparative Examples were measured by GPC using a PC Standard using an Agilent 1200 series.

The properties of the specimens made of the resins of the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

* Weight average molecular weight (g / mol): Measured using a PC standard using an Agilent 1200 series GPC.

Flowability (MI): Measured according to ASTM D1238 (300 ° C, under 1.2kg condition).

* Room Temperature Impact Strength: Measured at 23 캜 according to ASTM D256 (1/8 inch, Notched Izod).

Low temperature impact strength: measured at -30 占 폚 according to ASTM D256 (1/8 inch, Notched Izod).

* Chemical resistance (JIG TEST): 13mm * 64mm * 1 / 8inch specimen is attached closely to Mini Jig (58, 5R), 5mm * 13mm cotton is put in the center, 0.5ml of Nivea line spray is put on it The time of occurrence of the clearance of the adhered specimen was measured.

division Impact strength at room temperature
(J / m) Low temperature impact strength
(J / m) liquidity
(g / 10 min) Chemical resistance
(sec) Weight average molecular weight
(g / mol) Example 1 814 662 6.5 1,008 51,000 Example 2 828 677 5.8 1,280 51,000 Example 3 836 685 4.9 1,370 51,000 Example 4 831 680 5.4 1,310 51,000 Example 5 823 671 6.1 1,220 51,000 Comparative Example 1 799 642 4.5 512 51,000 Comparative Example 2 821 670 3.2 558 51,000 Comparative Example 3 830 672 2.1 620 51,000 Comparative Example 4 826 672 2.7 600 51,000 Comparative Example 5 810 659 3.6 525 51,000 Comparative Example 6 828 666 5.5 780 51,000 Comparative Example 7 823 680 2.8 1,140 51,000

As can be seen from the above Table 1, when the copolycarbonate according to the present invention is used, it can be confirmed that excellent fluidity and chemical resistance are maintained while maintaining excellent mechanical properties.

In the case of the comparative examples which do not include all the repeating units according to the present invention, there is a problem in that both fluidity and chemical resistance can not be secured at the same time. In the case of Comparative Example 7, the chemical resistance was somewhat high due to the long chain length in the PDMS using AP-60, but it was confirmed that the flowability was remarkably lowered as compared with the Example without the repeating unit of the present invention there was.

Claims (11)

A first repeating unit represented by the following formula (1);
A second repeating unit represented by the following formula (2); And
And a third repeating unit represented by the following formula (3): < EMI ID =
[Chemical 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
(2)

In Formula 2,
X ₁ is each independently C _1-10 alkylene,
Y ₁ is each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,
R < ₅ > are each 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 of 10 to 200,
(3)

In Formula 3,
X ₂ is C _1-10 alkylene, each independently,
X ₃ each independently is C _1-20 alkylene,
Y ₂ and Y ₃ 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, 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,
m ₁ and m ₂ are each independently an integer of 10 to 200.
The method according to claim 1,
The repeating unit represented by the above-mentioned general formula (1) is preferably a repeating unit represented by the following general formula (1): bis (4-hydroxyphenyl) methane, bis Bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4-hydroxyphenyl) sulfone, bis Butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) , Bis (4-hydroxyphenyl) diphenylmethane, and α, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxane. ≪ / RTI > or more of an aromatic diol compound.
The method according to claim 1,
(1) is represented by the following general formula (1-1): < EMI ID =
[Formula 1-1]

.
The method according to claim 1,
Wherein the second repeating unit is represented by the following formula (2-1): < EMI ID =
[Formula 2-1]

In the above formula (2-1), R ₅ and n are as defined in claim 1.
The method according to claim 1,
Wherein n is an integer from 45 to 100. < RTI ID = 0.0 > 25. < / RTI >
The method according to claim 1,
Wherein the third repeating unit is represented by the following formula (3-1): < EMI ID =
[Formula 3-1]

In the above formula (3-1), R ₆ , m ₁ and m ₂ are as defined in claim 1.
The method according to claim 1,
And m ₁ and m ₂ are each independently an integer of from 10 to 75.
The method according to claim 1,
Wherein the weight ratio of the repeating unit represented by the formula (2) to the repeating unit represented by the formula (3) is 1:99 to 99: 1.
The method according to claim 1,
Wherein the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 are contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total repeating units.
The method according to claim 1,
Wherein the copolycarbonate has a weight average molecular weight of from 1,000 to 100,000 g / mol.
An article comprising the copolycarbonate of any one of claims 1 to 10.