KR20140006489A - Method for preparing polysiloxane-polycarbonate copolymer - Google Patents

Abstract

The invention relates to a method for preparing polysiloxane-polycarbonate copolymer, and to manufacture of polysilxane having aromatic hydroxy compounds for both ends, using Lewis acid boron compounds as a catalysta, and to a preparing method of polysiloxane-polycarbonate copolymer with an in-situ process without a separating process of the boron compound.

Description

Production method of polysiloxane-polycarbonate copolymer {METHOD FOR PREPARING POLYSILOXANE-POLYCARBONATE COPOLYMER}

The present invention relates to a process for the preparation of polysiloxane-polycarbonate copolymers. More specifically, the present invention provides a polysiloxane-polycarbonate copolymer in situ without producing a polysiloxane having an aromatic hydroxy compound at both ends using a Lewis acid boron compound as a catalyst and separating the boron compound. It relates to a manufacturing method.

Polycarbonate is a thermoplastic resin having an aromatic polyester bond. Polycarbonate is excellent in mechanical properties, self-extinguishing, dimensional stability, and heat resistance has been increasing the range of applications, such as electrical and electronic product exterior materials, automotive parts. Recently, research has been actively conducted on polycarbonate copolymers having various physical properties by bonding polycarbonate and other kinds of polymers to a polycarbonate backbone. Especially, the polysiloxane-polycarbonate copolymer which introduce | transduced polysiloxane into polycarbonate in order to improve the chemical resistance and impact resistance of polycarbonate is developed.

As polysiloxane polymers for introduction into the polycarbonate backbone, polysiloxanes substituted at both ends with eugenol or 2-allyl phenol have been used.

In the production of the substituted polysiloxane, platinum, which is an expensive heavy metal catalyst, is used. Platinum catalysts include Karstedt platinum catalysts as homogeneous catalysts and platinum metal catalysts adsorbed on activated carbon as non-uniform catalysts, and both catalysts require a separation process after the reaction. Platinum is expensive and residuals in the copolymer of heavy metals are undesirable. In addition, the application of the separation process is undesirable in terms of time and cost in producing the resin.

In this regard, Korean Patent Laid-Open Publication No. 2003-0031882 et al. Discloses a method for producing siloxane copolycarbonate by melt condensation of hydroxyaryl terminated polydiorganosiloxane and dihydroxy compound under a catalyst.

It is an object of the present invention to provide a process for the preparation of polysiloxane-polycarbonate copolymers without separation of the catalysts used in the preparation of polysiloxanes which are reactive at both ends.

It is another object of the present invention to provide a process for preparing polysiloxane-polycarbonate copolymers from low cost polysiloxanes.

Method for producing a polysiloxane-polycarbonate copolymer of one aspect of the present invention comprises the steps of reacting an aromatic dihydroxy compound and a polysiloxane represented by the following formula (4) in the presence of a Lewis acid boron compound (step 1), an aromatic dihydroxy compound and Adding a carbonate precursor (step 2):

≪ Formula 4 >

(Wherein,

Q ₁ to Q ₈ are the same or different and independently from each other hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted A substituted C3-C10 cycloalkyl group, or halogen,

Z is an oxygen, a substituted or unsubstituted C1-C12 alkylene group, a substituted or unsubstituted C3-C12 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, formula 4a or formula 4b,

≪ Formula 4a &

(In the above, R ₁₁ , R ₁₂ are the same or different, independently of each other is a C2-C8 alkylene group, R ₁₃ , R ₁₄ are the same or different, independently of each other hydrogen, halogen, hydroxy group, C1-C10 alkyl group, Alkoxy group of C1-C10, aryl group of C6-C20, Y is a linear or branched aliphatic group of C1-C20 or mononuclear or polynuclear aromatic group of C6-C30, and a is independently an integer of 0-4 )

<Formula 4b>

(In the above, R ₁₅ , R ₁₆ are the same or different, independently of each other is a C2-C8 alkylene group, R ₁₇ , R ₁₈ are the same or different, independently of each other hydrogen, halogen, hydroxy group, C1-C10 alkyl group, C 1 -C 10 alkoxy group, C 6 -C 20 aryl group, X is C 1 -C 10 alkylene group, C 5 -C 20 cycloalkylene group, C 6 -C 30 mononuclear or polynuclear arylene group, b is independently 0- Is an integer of 4)

 m and n are the same or different and independently of each other are integers from 5 to 80).

In one embodiment, Step 1 and Step 2 may be performed in situ .

In one embodiment, the preparation method may not include the step of separating the Lewis acid boron compound.

In one embodiment, the Lewis acid boron compound may be a boron compound including a halogenated aryl group.

In one embodiment, the sum of m and n m + n may be an integer of 15-150.

In one embodiment, the sum m + n of m and n may be an integer of 30-100.

In one embodiment, the Lewis acid boron compound may be added at 1-100 ppm relative to the polysiloxane-polycarbonate copolymer.

In one embodiment, the aromatic dihydroxy compound in step 1 may be added in more than 2 mol per 1 mol of polysiloxane.

In one embodiment, the polysiloxane may be copolymerized at 0.1% -50% by weight in polysiloxane-polycarbonate.

In one embodiment, the carbonate precursor may be phosgene, triphosgene, diaryl carbonate or mixtures thereof.

Another aspect of the present invention, the polysiloxane-polycarbonate copolymer may be prepared by the above production method.

The present invention has the effect of the invention that a polysiloxane-polycarbonate copolymer can be prepared without separation of the catalyst used in the preparation of the polysiloxane having both ends reactive. Moreover, this invention has the effect of the invention which can manufacture the polysiloxane-polycarbonate copolymer which has the outstanding impact resistance, mold release property, and chemical resistance.

The production method of the present invention comprises the steps of producing a siloxane polymer modified with an aromatic dihydroxy compound (or capped at both ends) by reaction of an aromatic dihydroxy compound with a polysiloxane, and introducing the siloxane polymer into the polycarbonate backbone. polysiloxane - a step for producing the polycarbonate copolymer of the process without catalyst separation situ at the same time (in situ ).

To this end, the production method of the present invention uses a Lewis acid boron compound as a catalyst.

In the present specification, 'substituted' in 'substituted or unsubstituted' is C1-C10 alkyl group, C1-C10 alkoxy group, C6-C20 aryl group, halogen, hydroxy group, C5-C20 cycloalkyl group, C7-C20 Arylalkyl group, amine group and the like.

Specifically, the production method of the present invention reacts an aromatic dihydroxy compound with a polysiloxane in the presence of a Lewis acid boron compound (step 1),

It may include the step of adding an aromatic dihydroxy compound and a carbonate precursor (step 2).

Lewis acid The boron compound reacts with the polysiloxane to activate the polysiloxane. As a result, it is possible to catalyze the reaction of the polysiloxane with the aromatic dihydroxy compound.

Lewis Mountain in Step 1 The boron compound is used in a small amount compared to the amount of the final copolymer or resin, the amount does not significantly affect the physical properties of the copolymer or resin. As a result, in step 1, the end of the aromatic dihydroxy compound is modified with polysiloxane, and then copolymerization can be performed without further separation or purification of the Lewis acid boron compound. As a result, the polysiloxane-polycarbonate copolymer or resin synthesized by the method of the present invention has high impact resistance and processability.

The Lewis acid boron compound may be represented by Formula 1, but is not limited thereto.

&Lt; Formula 1 >

(Wherein R ₂₁ , R ₂₂ and R ₂₃ are the same or different and are each independently hydrogen, halogen, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C6-C20 aryl group)

Preferably, the boron compound may be a boron compound including a halogenated aryl group. Specifically, the boron compound may be represented by the following Chemical Formula 2, but is not limited thereto.

(2)

Wherein X is halogen, r is an integer from 1 to 5, s is an integer from 0 to 4, and r + s is 5.

Preferably, the halogenated aryl boron compound may be tris (pentafluorophenyl) borane (B (C ₆ F ₅ ) ₃ ).

The Lewis acid boron compound may be added at 0.0001-0.0020 mol, preferably 0.0001-0.0006 mol to 1 mol of polysiloxane.

The Lewis acid boron compound may be added at 1-100 ppm, preferably 1-15 ppm relative to the final polysiloxane-polycarbonate. Within this range, the catalytic activity can be sufficiently exhibited during the initial reaction of the aromatic dihydroxy compound and the polysiloxane, and since the trace amount is small compared to the amount of the final resin, the physical properties are not affected.

The aromatic dihydroxy compound may be represented by the following Chemical Formula 3, but is not limited thereto.

<Formula 3>

Wherein A is a single bond, a C1-C5 alkylene group, a C1-C5 cycloalkylene group, a C1-C5 alkylidene group, a C5-C10 cycloalkylene group, a C5-C10 cycloalkylidene group,- S-, -SO-, -SO2-, -O- or -CO-,

R ₁ to R ₁₀ are the same or different and each independently represent hydrogen, a hydroxy group, a halogen, an alkyl group of C1-C5 or an aryl group of C6-C20,

At least one of R ₁ to R ₅ is a hydroxy group, and at least one of R ₆ to R ₁₀ is a hydroxy group)

Preferably, A can be a single bond or a linear or branched C 1 -C 5 alkylene group.

Preferably, R ₁ to R ₁₀ may be hydrogen, a hydroxy group or a C1-C5 alkyl group.

Preferably, R ₃ and R ₈ may be hydroxy groups.

Specific examples of the aromatic dihydroxy compound include 2,6,2 ', 6'-tetramethyl-4,4'-biphenol, 2,2-bis- (4-hydroxyphenyl) -propane, 4,4 '-Dihydroxydiphenyl, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, and the like, and the like, but are not necessarily limited thereto.

Preferred as aromatic dihydroxy compounds of step 1 are those compounds having substituents (e.g., C1-C5 alkyl groups or C6-C20 aryl groups) adjacent to the hydroxy group of the biphenol, for example 2,6,2 ' , 6'-tetramethyl-4,4'-biphenol (TMBPA).

In step 1 the aromatic dihydroxy compound may be added at least 2 mol, preferably at least 3 mol, more preferably 3-10 mol, most preferably 3-6 mol, relative to 1 mol of polysiloxane. Within this range, it is possible to reduce the connection of two or more siloxane units in one chain.

In the present invention, the polysiloxane may be a siloxane including two or more hydrogen bonded silicon (H-Si-).

Specifically, the polysiloxane may be represented by the following Chemical Formula 4, but is not limited thereto.

&Lt; Formula 4 >

(Wherein,

Q ₁ to Q ₈ are the same or different and independently from each other hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted A substituted C3-C10 cycloalkyl group, or halogen,

Z is oxygen, a substituted or unsubstituted C1-C12 alkylene group, a substituted or unsubstituted C3-C10 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, formula 4a or formula 4b,

&Lt; Formula 4a &

(In the above, R ₁₁ , R ₁₂ are the same or different and independently of each other an alkylene group of C2-C8,

R ₁₃ and R ₁₄ are the same or different, and are each independently hydrogen, halogen, hydroxy group, alkyl group (eg C1-C10), alkoxy group (eg C1-C10), aryl group (eg C6-C20),

Y is a C1-C20 linear or branched aliphatic group or C6-C30 mononuclear or polynuclear aromatic group,

a is independently an integer from 0-4)

<Formula 4b>

(In the above, R ₁₅ , R ₁₆ are the same or different and independently of each other an alkylene group of C2-C8,

R ₁₇ and R ₁₈ are the same or different, and are each independently hydrogen, halogen, hydroxy group, alkyl group (eg C1-C10), alkoxy group (eg C1-C10), aryl group (eg C6-C20),

X is C1-C10 alkylene group, C5-C20 cycloalkylene group, C6-C30 mononuclear or polynuclear arylene group,

b is independently an integer of 0-4,

m and n are the same or different and independently of each other are integers from 5 to 80)

Preferably, Q ₁ to Q ₈ may be C ₁ -C 10 alkyl groups, more preferably C 1 -C 5 alkyl groups.

Preferably, Z may be oxygen, a C1-C5 alkylene group or a C6-C10 cycloalkylene group.

In the compound of Formula 4, m and n are average degree of polymerization, and m + n may be 15-150. Preferably m + n may be 30-100, more preferably 40-80. In the above range, high flowability, ductility can be increased without increasing the inherent characteristics of polycarbonate, and the processing such as release property can be increased, impact resistance can be improved, and transparency can not be reduced.

The reaction of Step 1 is not particularly limited but is preferably carried out at 10-40 ° C. Within this range, the production rate of the siloxane polymer modified with the aromatic dihydroxy compound is high, and there may be no problems such as side reaction or coloring of the resulting polycarbonate copolymer. Preferably, it may be carried out at 20-25 ℃.

The siloxane polymer modified with the aromatic dihydroxy compound can be prepared by the reaction of step 1.

The production method of the present invention may be carried out in the same reaction vessel in step 1 and step 2 in situ (insitu). That is, the production method of the present invention does not include the step of separating the Lewis acid boron compound, step 1 and step 2 can be carried out continuously.

In the production method of the present invention, the polysiloxane-polycarbonate copolymer is prepared at the same time after the production of the siloxane polymer modified with the aromatic dihydroxy compound.

The aromatic dihydroxy compound and the carbonate precursor may be added 1-4 hours after the addition of the Lewis acid boron compound in step 1 above. Within this range, a siloxane polymer modified with an aromatic dihydroxy compound can be produced sufficiently and can prevent side reactions or decomposition of the polysiloxane.

The aromatic dihydroxy compound of step 2 may be the same as or different from the aromatic dihydroxy compound of step 1 above.

As the aromatic dihydroxy compound of Step 2, a compound represented by Chemical Formula 2 may be used. Preferably, it may be 2,2-bis- (4-hydroxyphenyl) -propane (BPA).

As the carbonate precursor, phosgene, triphosgene, diaryl carbonate or a mixture thereof can be used. The diaryl carbonate may be represented by the following formula (5).

&Lt; Formula 5 >

(Wherein Ar1 and Ar2 are the same or different and are independently of each other an aryl group of C6-C20, or a C6-C20 aryl group substituted with halogen or C1-C6 alkoxy)

Preferably, phosgene or triphosgene may be used as the carbonate precursor.

The carbonate precursor may be included in an amount of 1.0-3.0 mol based on 1 mol of the aromatic dihydroxy compound of Step 2. Within this range, the degree of polymerization can be appropriate to ensure the differentiated physical properties of the polycarbonate copolymer. Preferably it may be included in 1.1-1.8 mol.

The polysiloxane in the reaction of step 2 is copolymerized in a weight ratio of 0.1% -50%, preferably 5% -20%, in the final polysiloxane-polycarbonate.

The reaction of step 2 is not particularly limited, but may be performed at 20-40 ° C. Within this range, the production rate of the siloxane polymer modified with the aromatic dihydroxy compound is high, and there may be no problems such as side reaction or coloring of the resulting polycarbonate copolymer. Preferably at 20-35 ° C.

The solvent in the production method of the present invention is not particularly limited, but an organic solvent used in a conventional interfacial polymerization can be used. For example, methylene chloride can be used.

The production method of the present invention may further include additives such as terminal blockers, antioxidants and the like as necessary. As the terminal encapsulant, o, m or pn-butylphenol, o, m or p-isobutylphenol, o, m or p-tert butyl phenol and the like can be used, but are not limited thereto. Antioxidants include, for example, hydrosulfite, Trimethyl phosphite, triethyl phosphite, distearyl pentaerythritol diphosphite and the like can be used, but are not limited thereto.

The polysiloxane-polycarbonate copolymer prepared according to the present invention may include a unit represented by the following formula (6) and a unit represented by the following formula (7):

(6)

(In the above, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are the same or different and each independently hydrogen, hydroxy group, halogen, alkyl group of C1-C5 or C6- An aryl group of C20;

Q1 to Q8, A, Z, m and n are as defined above)

&Lt; Formula 7 >

(In the above, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are the same or different and each independently hydrogen, hydroxy group, halogen, alkyl group of C1-C5 or C6- An aryl group of C20;

A is as defined above).

In the polysiloxane-polycarbonate copolymer, Chemical Formulas 6 and 7 may be randomly arranged, and the units of Chemical Formula 6 may be copolymerized at 0.1-50% by weight, preferably 5-20% by weight of the copolymer. Can be.

The weight average molecular weight of the polysiloxane-polycarbonate copolymer prepared according to the present invention may be 15,000-40,000 g / mol. Preferably 20,000-30,000 g / mol.

Si content of the polysiloxane-polycarbonate copolymer prepared according to the present invention may be 1-4 wt%.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. It is to be understood, however, that the same is by way of illustration and example only and is not to be construed in a limiting sense.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Example

In the following examples, siloxane oligomer A was used in the compound of Formula 4 wherein Q1 to Q8 are CH3, Z is oxygen, and m + n is 40.

Example  One: Polysiloxane -Polycarbonate Copolymer Preparation

2,6,2 ', 6'-tetramethyl-4,4'-biphenol (TMBPA) (26.5 g, 93.1 mmol), polysiloxane (91.7 g, 31.1 mmol) (siloxane oligomer A), methylene in a glass stirred reactor 800 ml of chloride was added and then stirred. B (C 6 F 5) 3 (0.0033 g, 0.0062 mmol) was added thereto, and the resulting mixture was stirred at 20-25 ° C. for 2 hours. 6000 ml of H 2 O, 2,2-bis (4-hydroxyphenyl) propane (BPA) (1300 g, 5694.5 mmol) and 1248 ml of a 50% aqueous NaOH solution were added and stirred, while maintaining the temperature of the reaction at 20-25 ° C. Stir for 1 hour. After adding 3000 ml of t-butyl phenol (35.8 g, 238.2 mmol) and methylene chloride, 3000 ml of methylene chloride solution containing triphosgene (844.9 g, 8541.8 mmol) was slowly added to the reactor for 1 hour, and the temperature of the solution was Stir for 1 hour while maintaining at 20-25 ° C. Triethylamine (8.4 g, 83.5 mmol) was added and stirred for 2 hours while maintaining the temperature of the reaction at 30-35 ° C. The methylene chloride layer was separated and neutralized by addition of 8000 ml of 10% HCl solution and washed several times with water until the pH reached neutral. The methylene chloride layer was taken and dried using a trimixer (TX-15, Inoue) to obtain a copolymer. DOSY analysis of the prepared copolymer confirmed that the siloxane oligomer is bound to the polycarbonate backbone. Si NMR content was 2.1 wt% as a result of 1 H NMR analysis, and the weight average molecular weight was 21,955 g / mol as a result of GPC analysis.

Example  2: Polysiloxane -Polycarbonate Copolymer Preparation

In Example 1 2,6,2 ', 6'-tetramethyl-4,4'-biphenol (TMBPA) (33.2g, 116.7mmol), polysiloxane (114.9g, 38.9mmol) (siloxane oligomer A), A copolymer was prepared in the same manner except that B (C 6 F 5) 3 (0.0042 g, 0.0078 mmol) was used.

Comparative Example

In the following Comparative Examples, the siloxane oligomers B and C used polysiloxanes represented by the following Chemical Formulas 8 and 9.

(8)

Siloxane oligomer B

&Lt; Formula 9 >

Siloxane oligomer C

Comparative Example  One: Polysiloxane -Polycarbonate Copolymer Preparation

6000 ml of H 2 O, 2,2-bis (4-hydroxyphenyl) propane (BPA) (1300.0 g, 5694.5 mmol) and 1248 ml of a 50% NaOH solution were added to a glass stirred reactor, followed by vigorous stirring and the solution temperature of 20 to 25 Stir for 1 hour while maintaining at ℃. To this was added polysiloxane (129.4 g, 38.7 mmol) (siloxane oligomer B), t-butyl phenol (35.8 g, 238.2 mmol) and 3000 ml of methylene chloride, followed by methylene dissolved in triphosphene (844.9 g, 8541.8 mmol) 3000 ml of chloride solution is slowly added to the reactor for 1 hour and stirred for 1 hour while maintaining the solution temperature at 20-25 ° C. To this, triethylamine (8.4 g, 83.5 mmol) was added and stirred for 2 hours while maintaining the solution temperature at 30 to 35 ° C. After the stirring was completed, the mixture was stirred for 1 hour, and then the organic layer was separated, neutralized by adding 8000 ml of 10% HCl solution, and washed with water several times until pH neutrality was reached. After washing, the solvent of the organic layer was downloaded, and then dried using a trimixer (Inoue Co., TX-15) to obtain a powdered polymer. DOSY analysis of the polymer confirmed that the siloxane oligomer was present in the main chain of the polycarbonate, and the Si content was 2.7 wt% based on 1 H NMR. Gw analysis showed a Mw of 22,619 g / mol.

Comparative Example  2: Polysiloxane -Polycarbonate Copolymer Preparation

In Comparative Example 1, a copolymer was prepared in the same manner except that polysiloxane (105.0 g, 32.6 mmol) (siloxane oligomer C) and t-butyl phenol (41.0 g, 272.9 mmol) were used.

Comparative Example  3

PANLITE L-1225WX (a bisphenol-A linear polycarbonate resin having a weight average molecular weight of 21,000 g / mol) manufactured by TEIJIN, Japan, was used.

Type of polysiloxane Si No.
(m + n) Si content
(weight%) Weight average molecular weight (g / mol) Example 1 Siloxane oligomer A 40 2.1 21,955 Example 2 Siloxane oligomer A 40 2.7 22,560 Comparative Example 1 Siloxane oligomer B 40 2.7 22,619 Comparative Example 2 Siloxane oligomer C 40 2.3 21,858 Comparative Example 3 - - - 21,000

Experimental Example

The polycarbonate resin used for evaluating the properties of the polysiloxane-polycarbonate copolymer of the present invention was a bisphenol-A linear polycarbonate resin having a weight average molecular weight of 21,000 g / mol, and PANLITE L-1225WX of TEIJIN, Japan.

As shown in Table 2, the polysiloxane-polycarbonate copolymer and the polycarbonate resin (PANLITE L-1225WX manufactured by TEIJIN, Japan) were mixed according to the Examples and Comparative Examples, using a twin screw extruder having a diameter of Φ = 45 mm, Processed at 250-300 ° C. to make pellets. The prepared pellets were dried at 120 ° C. for at least 4 hours, and then 10 Oz. Specimens were prepared by injecting at a molding temperature of 290 ° C. and a mold temperature of 70 ° C. in an injection machine.

The prepared specimens were measured for physical properties by the following method, and the results are shown in Table 2 below.

(1) Impact resistance evaluation: Notches were made in 1/8 "Izod specimens and 1/4" Izod specimens by ASTM D256 evaluation method, and evaluated at 25 ° C and -30 ° C.

(2) Workability evaluation: Spiral flow was evaluated by the ASTM D3123 evaluation method at a temperature of 320 ° C. and a thickness of 1 mm.

(3) Evaluation of impact resistance after painting: 50mm (W) × 200mm (L) × 2mm (T) rectangular specimens were immersed in thinner for 2 minutes and dried, and then Dupont Drop Shock Tester was used to increase the weight of 2kg weight by 50cm Free fall at and impact the specimen. Drop test was performed on 15 specimens and classified into four types of deformation failure (ductile deformation / ductile fracture / brittle fracture / complete fracture).

Example Comparative Example One 2 One 2 3 Polycarbonate resin
(weight%) 67 58 58 60 100 Polysiloxane-Polycarbonate (% by weight) 33 42 42 40 - Si content (% by weight) 0.9 0.9 0.9 0.9 - 1/4 "IZOD Impact Strength
(25 ° C) (kgfcm / cm) 66 58 65 58 15 1/8 "IZOD Impact Strength
(25 ° C) (kgfcm / cm) 97 87 88 98 77 1/8 "IZOD Impact Strength
(-30 ° C) (kgfcm / cm) 59 58 57 60 8 Processability
320 ℃ (mm) 143 138 126 124 - Impact resistance after painting 15/0/0/0 14/1/0/0 8/11/1/0 0/11/4/0 0/0/0/15

The polysiloxane-polycarbonate-containing resin prepared using the boron catalyst as shown in the above embodiment shows an impact strength equivalent to that of other polysiloxane-polycarbonates, and a greatly improved impact strength compared to general polycarbonates. In particular, the improvement in impact strength was noticeable at low temperatures. In addition, it shows higher spiral flow than other resins, which means high processing efficiency due to excellent melt flow during processing. Finally, in the impact strength test on the organic coating liquid, almost all of Examples 1 and 2 maintain superior ductility than the comparative objects, and thus have high impact resistance.

Claims (15)

Reacting the aromatic dihydroxy compound with a polysiloxane represented by the following Chemical Formula 4 in the presence of a Lewis acid boron compound (Step 1),
A process for preparing a polysiloxane-polycarbonate copolymer comprising adding an aromatic dihydroxy compound and a carbonate precursor (step 2):
&Lt; Formula 4 >

(Wherein,
Q ₁ to Q ₈ are the same or different and independently from each other hydrogen, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted A substituted C3-C10 cycloalkyl group or halogen,
Z is oxygen, a substituted or unsubstituted C1-C12 alkylene group, a substituted or unsubstituted C3-C10 cycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, formula 4a or formula 4b,
<Formula 4a>

(In the above, R ₁₁ , R ₁₂ are the same or different and independently of each other an alkylene group of C2-C8,
R ₁₃ and R ₁₄ are the same as or different from each other, and are each independently hydrogen, a halogen, a hydroxyl group, an alkyl group of C1-C10, an alkoxy group of C1-C10, an aryl group of C6-C20,
Y is a C1-C20 linear or branched aliphatic group or C6-C30 mononuclear or polynuclear aromatic group,
a is independently an integer from 0-4)
<Formula 4b>

(In the above, R ₁₅ , R ₁₆ are the same or different and independently of each other an alkylene group of C2-C8,
R ₁₇ and R ₁₈ are the same or different and independently from each other are hydrogen, a halogen, a hydroxy group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C20 aryl group,
X is C1-C10 alkylene group, C5-C20 cycloalkylene group, C6-C30 mononuclear or polynuclear arylene group,
b is independently an integer from 0-4)
m and n are the same or different and independently of each other are integers from 5 to 80). The method of claim 1, wherein Step 1 and Step 2 are performed in situ . The method of claim 1, wherein the manufacturing method does not include separating the Lewis acid boron compound. The method for producing a polysiloxane-polycarbonate copolymer according to claim 1, wherein the Lewis acid boron compound is a boron compound containing a halogenated aryl group. The method of claim 1, wherein the sum of m and n, m + n is an integer of 15-150. The method of claim 1, wherein the sum m + n of m and n is an integer of 40-80. The method of claim 1, wherein the Lewis acid boron compound is added at 1-100 ppm relative to the polysiloxane-polycarbonate copolymer. The method of claim 1, wherein the aromatic dihydroxy compound is represented by the following Chemical Formula 3:
(3)

Wherein A is a single bond, a C1-C5 alkylene group, a C1-C5 cycloalkylene group, a C1-C5 alkylidene group, a C1-C5 cycloalkylene group, a C5-C10 cycloalkylidene group,- S-, -SO-, -SO2-, -O- or -CO-,
R ₁ to R ₁₀ are the same or different and each independently represent hydrogen, a hydroxy group, a halogen, an alkyl group of C1-C5 or an aryl group of C6-C20,
At least one of R ₁ to R ₅ is a hydroxy group, and at least one of R ₆ to R10 is a hydroxy group). The method of claim 1, wherein the Lewis acid boron compound is added at 0.0001-0.0020 mol based on 1 mol of the polysiloxane. The method of claim 1, wherein in step 1, the aromatic dihydroxy compound is added in an amount of 2 mol or more based on 1 mol of the polysiloxane. The method of claim 1, wherein the carbonate precursor is a phosgene, a triphosgene, a diaryl carbonate represented by the following Chemical Formula 5, or a mixture thereof:
&Lt; Formula 5 >

(Wherein Ar1 and Ar2 are the same or different and are independently of each other an aryl group of C6-C20, or a C6-C20 aryl group substituted with halogen or C1-C6 alkoxy). The method of claim 1, wherein the polysiloxane-polycarbonate copolymer comprises a unit represented by the following formula (6) and a unit represented by the following formula (7):
(6)

(In the above, R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are the same or different and each independently hydrogen, hydroxy group, halogen, alkyl group of C1-C5 or C6- An aryl group of C20;
A represents a single bond, a C1-C5 alkylene group, a C1-C5 cycloalkylene group, a C1-C5 alkylidene group, a C5-C10 cycloalkylidene group, -S-, -SO-, -SO2-, O- or -CO-,
Q1 to Q8, Z, m and n are as defined in claim 1)
&Lt; Formula 7 >

(In the above, A is a single bond, C1-C5 alkylene group, C1-C5 cycloalkylene group, C1-C5 alkylidene group, C1-C5 cycloalkylene group, C5-C10 cycloalkylidene group,- S-, -SO-, -SO2-, -O- or -CO-,
R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₉ and R ₁₀ are the same or different and each independently represent hydrogen, a hydroxy group, a halogen, a C1-C5 alkyl group or a C6-C20 aryl group Indicates). The method of claim 1, wherein the polysiloxane-polycarbonate copolymer has a weight average molecular weight of 15,000-40,000 g / mol. The method of claim 1, wherein the polysiloxane is copolymerized at 0.1% -50% by weight in the polysiloxane-polycarbonate. A polysiloxane-polycarbonate copolymer prepared by the process of any one of claims 1-14.