KR101489958B1 - Polycarbonate-polysiloxane copolymer and method for preparing the same - Google Patents

Abstract

(상기에서 R¹, R², R³ 및 R⁴는 각각 독립적으로 치환 또는 비치환된 C1-C10 알킬기 또는 치환 또는 비치환된 C6-C18 아릴기이고, *는 폴리카보네이트 단위 연결기이며, 상기 R"는 C4-C20의 지방족 또는 지환족 하이드로카본이고, 상기 폴리카보네이트 단위 연결기로부터 2번째 위치하는 탄소는 알킬기 또는 사이클로알킬기에 의해 모두 치환되어 있고, n은 30 내지 90의 정수임).The present invention relates to a polycarbonate-polysiloxane copolymer containing a polysiloxane unit represented by the following formula
[Chemical Formula 1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group, * is a polycarbonate unit linkage group, and R Quot; is an aliphatic or alicyclic hydrocarbon of C4-C20, the carbon located second from the polycarbonate unit linking group is all substituted by an alkyl group or a cycloalkyl group, and n is an integer of 30 to 90).

Description

POLYCARBONATE-POLYSILYLCANE COPOLYMER AND POLYCARBONATE-POLYSILOXANE COPOLYMER AND METHOD FOR PREPARING THE SAME

The present invention relates to polycarbonate-polysiloxane copolymers and processes for their preparation. More specifically, the present invention relates to a polycarbonate-polysiloxane copolymer which can introduce a polysiloxane having a specific structure to maintain high impact strength and high haze while maintaining high transparency and low haze, and a method for producing the same.

Polycarbonate is a transparent thermoplastic, high performance plastic material that combines the desirable mechanical, optical, thermal and electrical properties. However, polycarbonate requires a higher level of impact strength in order to be used in various applications.

In order to improve the mechanical properties of the polycarbonate, a method of blending with other materials has been proposed. However, in the case of blending with other materials, the phase separation due to the difference in solubility between the materials is often observed, which is a disadvantage that inherent transparency of the polycarbonate is deteriorated. For example, studies have been conducted to physically mix polysiloxane with polycarbonate to improve impact, melt flow, and releasability of polycarbonate. However, in this case, even a small amount of siloxane added results in a significant drop in transparency, which hinders the various color representations of the resins required recently.

On the other hand, in the case of a chemical mixing method, a method of polymerizing two or more kinds of monomers together to improve physical properties has been proposed. In this case, each polymer can have physical properties expressed in a unit, and thus it is used in the synthesis of a high-performance polycarbonate. As one example thereof, it is known that a copolymer of polycarbonate-polysiloxane maintains high transparency while improving high ductility, workability, weather resistance, impact resistance after painting, and the like.

In particular, the polycarbonate-polysiloxane copolymer to which polysiloxane having both terminal ends substituted with aliphatic hydroxyl groups exhibits excellent impact properties, transparency, high ductility and melt flow. However, it has been observed that the decomposition occurs at high temperature.

Under such high temperature molding conditions, carbon dioxide is generated by decomposition, which causes flow marks to be formed in the molded article, becoming opaque, and causing problems such as a decrease in impact strength due to a decrease in molecular weight.

Therefore, it is necessary to develop a polycarbonate-polysiloxane copolymer which can maintain high impact strength while maintaining high transparency and low haze under high temperature molding conditions.

An object of the present invention is to provide a polycarbonate-polysiloxane copolymer and a method for producing the same that can maintain high impact strength while maintaining high transparency and low haze under high temperature molding conditions.

Another object of the present invention is to provide a polycarbonate-polysiloxane copolymer which can be advantageously applied to a thin molded article requiring high temperature molding and a method for producing the same.

One aspect of the present invention relates to a polycarbonate-polysiloxane copolymer containing a polysiloxane unit represented by the following formula (1).

[Chemical Formula 1]

R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C 1 -C 10 alkyl group or a substituted or unsubstituted C 6 -C 18 aryl group,

* Is a polycarbonate unit linking group,

Wherein R "is an aliphatic or alicyclic hydrocarbon of C4-C20, the carbon located second from the polycarbonate unit linking group is all substituted by an alkyl group or a cycloalkyl group,

n is an integer from 30 to 90;

The polycarbonate-polysiloxane copolymer may have a haze change (? H) of 0.5 or less according to the following formula (2). :

[Formula 2]

H = H1-H0

(In the above, ΔH is the haze change, H0 is the initial haze of the copolymer, and H1 is the haze after 10 g of the copolymer has stayed at 320 ° C. for 150 seconds).

The polycarbonate-polysiloxane copolymer may have a weight-average molecular weight change rate within 5% according to the following formula 3:

[Formula 3]

(Mw is the weight average molecular weight after standing at 320 DEG C for 150 seconds and Mwb is the initial weight average molecular weight)

Another aspect of the invention relates to a process for making polycarbonate-polysiloxane copolymers. The method is characterized in that an aromatic dihydroxy compound and a phosgene-based compound are added to a polysiloxane represented by the following formula (2)

(2)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

Wherein R "is a C4-C20 aliphatic or alicyclic hydrocarbon, wherein the carbon atom located second from the hydroxyl group is substituted by an alkyl group or a cycloalkyl group,

and n is an integer of 30 to 90).

The aromatic dihydroxy compound may be added in an amount of 99.9 to 80.0 parts by weight relative to 0.1 to 20.0 parts by weight of polysiloxane.

The polysiloxane may have an acid value change rate (? AV) of 1% or less according to the following formula 1:

[Formula 1]

(AVV is the acid value change rate, AVa is the acid value after leaving 10 g of the polysiloxane at 280 DEG C for 1 hour, and AVb is the initial acid value of the polysiloxane).

The present invention relates to a polycarbonate-polysiloxane copolymer which can maintain an excellent impact strength while maintaining high transparency and low haze even under high temperature molding conditions, and which can be advantageously applied to thin molded articles requiring high temperature molding, and a method for producing the same .

1 is an NMR photograph of the polysiloxane prepared in Production Example 1 of the present invention.
2 is an NMR photograph of the polysiloxane prepared in Production Example 2 of the present invention.

In the present invention, the term "substituted" means a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a carbonyl group, a carbamyl group, a thiol group, A salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or salt thereof, an alkyl group having 1-20 carbon atoms, an alkenyl group having 2-20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an alkoxy group having 1-20 carbon atoms, An aryloxy group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, a cycloalkynyl group having 3 to 30 carbon atoms, or a combination thereof.

The polycarbonate-polysiloxane copolymer of the present invention contains a polysiloxane unit represented by the following formula:

[Chemical Formula 1]

R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C 1 -C 10 alkyl group or a substituted or unsubstituted C 6 -C 18 aryl group,

* Is a polycarbonate unit linking group,

Wherein R "is an aliphatic or alicyclic hydrocarbon of C4-C20, the carbon located second from the polycarbonate unit linking group is all substituted by an alkyl group or a cycloalkyl group,

n is an integer from 30 to 90;

In embodiments, the polysiloxane unit may be represented by the following formula 1-1:

[Formula 1-1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 5 -C 18 cycloalkyl group or a substituted or unsubstituted C 6 -C 18 aryl group,

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 4 -C 18 cycloalkyl group or a substituted or unsubstituted C 5 -C 18 aryl group,

A is a C1-C20 2-4 aliphatic or alicyclic hydrocarbon,

Y is a substituted or unsubstituted C0-C10 alkylene (provided that when C0 is an A-C single bond), C5-C18 cycloalkylene,

X and Z are each independently a C1-C20 2-4 hydrocarbons,

Q is a substituted or unsubstituted C1-C5 alkylene, oxygen, sulfur, sulfur dioxide (SO2), NR (where R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group)

a, b, c, d, e and f are each independently 0 or 1,

(Where a + b + c + d + e = 3, either one of d or e is 0 if any of a, b,

n is an integer from 30 to 90,

* Is a polycarbonate unit linkage.

The polycarbonate-polysiloxane copolymer may be prepared by introducing an aromatic dihydroxy compound and a phosgene-based compound into a polysiloxane having a specific structure and polymerizing.

Polysiloxane

The polysiloxane used in the present invention has a hydroxy group at the end of the silylic acid unit and the second position carbon (hereinafter referred to as? -Position carbon) from the terminal hydroxy is substituted with an alkyl group or a cycloalkyl group .

The R may be an alkyl group, a cycloalkyl group, or an aryl group, and may be connected to a carbon linked to the siloxane (hereinafter referred to as carbon) to form a ring.

In an embodiment, the? -Position carbon and the? -Position carbon may be connected by a linear or branched alkyl group.

In another embodiment, the? -Position carbon and the? -Position carbon may be linked by a cyclic alkyl to have a cyclic structure.

In any case, all of the above-mentioned < RTI ID = 0.0 > p-carbon < / RTI > Therefore, it is possible to suppress the eilimination reaction, which is an alkene formation reaction, which may occur in a hydroxy group connected to the first position carbon (hereinafter referred to as? -Position carbon) from hydroxy.

In embodiments, the polysiloxane used in the present invention is represented by the following formula:

(2)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

Wherein R "is a C4-C20 aliphatic or alicyclic hydrocarbon, wherein the carbon atom located second from the hydroxyl group is substituted by an alkyl group or a cycloalkyl group,

and n is an integer of 30 to 90).

In one embodiment, the polysiloxane of the present invention can be represented by the following Formula 2-1:

[Formula 2-1]

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 5 -C 18 cycloalkyl group or a substituted or unsubstituted C 6 -C 18 aryl group,

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are each independently a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 4 -C 18 cycloalkyl group or a substituted or unsubstituted C 5 -C 18 aryl group,

A is a C1-C20 2-4 aliphatic or alicyclic hydrocarbon,

Y is a substituted or unsubstituted C0-C10 alkylene (provided that when C0 is an A-C single bond), C5-C18 cycloalkylene,

X and Z are each independently a C1-C20 2-4 hydrocarbons,

Q is a substituted or unsubstituted C1-C5 alkylene, oxygen, sulfur, sulfur dioxide (SO2), NR (where R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group)

a, b, c, d, e and f are each independently 0 or 1,

(Where a + b + c + d + e = 3, either one of d or e is 0 if any of a, b,

n is an integer from 30 to 90;

The meaning of 0 in a, b, c, d, e and f means the case where the corresponding group does not exist, and the meaning of 1 in a, b, c, d, it means.

When b is 0, A and A may form an alicyclic ring.

For example, b may be 0, d may be 0, and f may be 1.

In another embodiment, b may be 0, d may be 0, and f may be 0.

When b is 1, a is 1, c is 0, d is 1, and e is 0, then A and A may form an alicyclic ring.

In another embodiment, when a and c are 0 and b is 1, the A carbon and the A carbon may be connected with a linear or branched alkylene. In this case, d and e are one.

Wherein n is an integer of 30 to 90, preferably 35 to 70, more preferably 40 to 65. [ The transparency is excellent in the above range.

For example, the polysiloxane of the present invention may have the following structure:

The polysiloxane may be prepared by reacting a terminal hydrogen siloxane with an aliphatic hydroxyl group derivative.

The aliphatic hydroxyl group derivative may be represented by the following formula (3).

(3)

(Wherein R "is a C4-C20 aliphatic or alicyclic hydrocarbon containing a double bond at the end, and the carbon atom located second from the hydroxyl group is substituted by an alkyl group or a cycloalkyl group).

In an embodiment, the aliphatic hydroxyl group derivative may be represented by the following formula (3-1).

[Formula 3-1]

(Wherein R ⁵ and R ⁶ are each independently hydrogen, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 5 -C 18 cycloalkyl group or a substituted or unsubstituted C 6 -C 18 aryl group ego,

R ⁹ and R ¹⁰ are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C4-C18 cycloalkyl group or a substituted or unsubstituted C5-C18 aryl group,

A is a C1-C20 2-4 aliphatic or alicyclic hydrocarbon,

Y is a substituted or unsubstituted C0-C10 alkylene (provided that when C0 is an A-C single bond), C5-C18 cycloalkylene,

X and Z are each independently a C1-C20 2-4 hydrocarbons,

Q is a substituted or unsubstituted C1-C5 alkylene, oxygen, sulfur, sulfur dioxide (SO2), NR (where R is hydrogen, a substituted or unsubstituted C1-C10 alkyl group)

a, b, c, d, e and f are each independently 0 or 1,

(Provided that any one of d or e is 0 if any one of a, b, c, d and e is 3, a, b or c is 0).

The A comprises a double bond at the end for the hydrosilylation reaction.

The terminal hydrogen siloxane may be represented by the following Formula 4:

[Chemical Formula 4]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C 1 -C 10 alkyl group or a substituted or unsubstituted C 6 -C 18 aryl group, and n is an integer of 30 to 90 to be).

The reaction of the terminal hydrogen siloxane with the aliphatic hydroxyl group derivative may be carried out in the presence of a catalyst. As the catalyst, a conventional catalyst applicable to hydrosilylation may be used. In an embodiment, the catalyst comprises platinum and palladium. Preferred catalysts include H2PtCl6, Pt2 {[(CH2 = CH) Me2Si] 2O} 8, Rh [(cod) 2] BF4, Rh (PPh3) 4Cl, Pt / C, or Pd / But are not limited thereto. The catalyst may be used with a metal content of less than 500 ppm, preferably less than 100 ppm, based on the polysiloxane.

In an embodiment, the terminal hydrogen siloxane may be dissolved in a solvent, and then the catalyst may be added and the aliphatic hydrocarbon derivative may be added dropwise. The reaction temperature may be 50 to 150 ° C, preferably 70 to 130 ° C.

In an embodiment, the equivalent ratio between the terminal hydrogen siloxane and the aliphatic hydroxyl group derivative is preferably 1: 2 to 1: 2.2.

The polysiloxane may have an acid value change rate (? AV) according to the following formula 1 of 1% or less, preferably 0.1% or less, more preferably 0%

[Formula 1]

(AV AV is the acid value change rate, AVa is the acid value after 10 g of the polysiloxane is left at 280 DEG C for 1 hour, and AVb is the initial acid value of the polysiloxane)

Preferably, the polysiloxane does not contain an ether group in the main chain. In this case, it has a high reaction participation rate and has excellent transparency in comparison with the same silicon content.

The polysiloxane unit does not contain an arylene group in the main chain. In this case, it can have a better low-temperature impact strength.

The polycarbonate-polysiloxane copolymer of the present invention can be prepared by adding an aromatic dihydroxy compound and a phosgene-based compound to the polysiloxane represented by the above formula (2)

The above-mentioned phosgene-based compounds may include phosgene, triphosgene, diphosgene, and the like.

The aromatic dihydroxy compound may be added in an amount of 99.9 to 80.0 parts by weight relative to 0.1 to 20.0 parts by weight of polysiloxane. The transparency is excellent in the above range.

The aromatic dihydroxy compound may be represented by the following general formula (5).

[Chemical Formula 5]

(Wherein A is a single bond, a substituted or unsubstituted C1 to C30 linear or branched alkylene group, a substituted or unsubstituted C2 to C5 alkenylene group, a substituted or unsubstituted C2 to C5 alkylidene group, A substituted or unsubstituted C1 to C30 linear or branched haloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, a substituted or unsubstituted C5 to C6 cycloalkenylene group, a substituted or unsubstituted C5 to C6 cycloalkylene group, A substituted or unsubstituted C 1 to C 20 linear or branched alkoxysilyl group, a halogen acid ester group, S or SO ₂ , and R ₁ and R ₂ are each independently a substituted or unsubstituted C 6 to C 30 arylene group, ₂ are the same or different, is a substituted or unsubstituted C1 to C30 alkyl group, or a substituted or unsubstituted C6 to C30 aryl group unsubstituted ring, n ₁ and n ₂ is an integer from 0 to 4, respectively).

Specific examples of the aromatic dihydroxy compound of Formula 5 include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- Phenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 2,2- - (3,5-dichloro-4-hydroxyphenyl) -propane, and the like, but are not limited thereto. Of these, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro- Hydroxyphenyl) -cyclohexane, and the like, and 2,2-bis- (4-hydroxyphenyl) -propane, also referred to as bisphenol-A, is most preferred.

In one embodiment, an aromatic dihydroxy compound may be added to a basic aqueous solution, and then an organic solvent, a polysiloxane represented by the above formula (2) may be added and mixed, and a phosgene compound may be added thereto to effect interfacial polymerization. By applying the interfacial polymerization in this way, remarkably excellent transparency can be secured.

The polycarbonate-polysiloxane copolymer thus prepared contains units of the above formula (1) in its main chain and has excellent transparency and impact resistance at room temperature and low temperature.

The polycarbonate-polysiloxane copolymer may have a haze change (? H) according to the following formula 2 within 0.5, preferably within 0.2, more preferably within 0.1. :

[Formula 2]

H = H1-H0

(In the above, ΔH is the haze change, H0 is the initial haze of the copolymer, and H1 is the haze after 10 g of the copolymer has stayed at 320 ° C. for 150 seconds).

The polycarbonate-polysiloxane copolymer may have a weight-average molecular weight change rate (DELTA Mw) of 5% or less, preferably 4% or less, more preferably 3% or less,

[Formula 3]

(Mw is the weight average molecular weight after standing at 320 DEG C for 150 seconds and Mwb is the initial weight average molecular weight)

The polycarbonate-polysiloxane copolymer may have a silicon content of 2.5% by weight on a 2.1% by weight basis and a haze of 2% or less, preferably 1.99% or less.

The polycarbonate-polysiloxane copolymer may have a weight average molecular weight of 15,000 to 50,000 g / mol, preferably 19,000 to 40,000 g / mol.

The polycarbonate-polysiloxane copolymer of the present invention can maintain excellent impact strength while maintaining high transparency and low haze even under high-temperature molding conditions. Therefore, it can be particularly preferably applied to a thin molded article requiring high-temperature molding, for example, a light guide plate.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Production Example 1

0.5 g of Pt / C (Pt 5% wt, 0.025 g Pt) was added to 300 g of the dimethylsiloxane (0.1 mol, number average molecular weight Mn = 3026) and 270 mL of toluene, and the mixture was stirred and heated to 110 캜 . 27.4 g (0.24 mol) of 2,2-dimethyl-4-penten-1-ol was slowly added dropwise. The reaction solution was stirred for 1 hour and then cooled to room temperature. The reaction product was filtered, and the solvent and the unreacted product were removed under a high-temperature vacuum to obtain 320 g of an oil product. The NMR analysis results are shown in Fig.

Production Example 2

Except that 33.2 g of (2-Methyl Bicyclo [2.2.1] hept-5-en-2-yl) methanol was used in place of 2,2-dimethyl-4-penten- Respectively.

Production Example 3

The procedure of Preparation Example 1 was repeated except that 25 g of the compound represented by the following formula (3-3) was used instead of 2,2-dimethyl-4-penten-1-ol.

The physical properties of the polysiloxanes of Preparation Examples 1 to 3 were measured according to the following methods. The results are shown in Table 1 below.

Polysiloxane molecular weight
(Mn) Initial acid value Acid value change rate
(AV) Production Example 1 3181 35 0 Production Example 2 3229 34 0 Production Example 3 3232 35 0

(1) Number average molecular weight and 1 H-NMR were measured using Ultrashield 300 MHz from Bruker.

(2) Acid value (KOH mg / g): A sample of 1 to 20 g was dissolved in dimethylsulfoxide (50 ml), 0.03 ml to 0.2 ml of a BTB solution was added, and titrated with 0.1 N NaOH solution.

Acid value = ((0.1N-NaOH solution consumption ml) * (0.1N-NaOH solution Factor) * 5.61) / sample amount (g)

(3) Acid value change rate (? AV): The measured acid value was calculated by the following formula (1).

[Formula 1]

(AV AV is the acid value change rate, AVa is the acid value after 10 g of the polysiloxane is left at 280 DEG C for 1 hour, and AVb is the initial acid value of the polysiloxane)

Example 1

A 20 L glass reactor was mixed and stirred with a 50 wt% aqueous solution of NaOH and 7 L of distilled water. Bisphenol-A (1.50 kg) was added thereto. After the temperature of the solution reached 22 ° C or lower, methylene chloride (3 L), t-butylphenol (41.5 g) and 111 g of the polysiloxane prepared in Preparation Example 1 were added and stirred vigorously. A solution of 974 g of triphosgene in 3 L of methylene chloride was added to the solution at a rate of 60 mL / min. When the temperature of the reaction solution dropped below 23 ° C after about 1 hour, triethylamine (7.80 g) was added and the reactor temperature was maintained at 30 ° C or higher. After stirring for 2 hours, the separated organic layer was washed once with a mixture of 6 L of water and 10 mL of 50 wt% NaOH, once with 6 L of water and 60 mL of 35% HCl mixed solution, and with 12 L of distilled water twice.

The organic layer was slowly stirred in an agitator and a methanol solution of the same volume ratio was added over 1 hour to obtain a white precipitate. The precipitate was separated by filtration and dried at 80 DEG C for 12 hours to obtain a final polycarbonate-polysiloxane copolymer of 1.4 kg. As a result of GPC analysis, Mw was 19,800 g / mol.

Example 2

And 113 g of the polysiloxane prepared in Production Example 2 was added thereto. A final 1.5 kg polycarbonate-polysiloxane copolymer was obtained. DOSY and 1 H NMR analysis of the polymer confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, Mw was 20,100 g / mol.

Example 3

And 113 g of the polysiloxane prepared in Preparation Example 3 were added thereto. A final 1.4 kg polycarbonate-polysiloxane copolymer was obtained. DOSY and 1 H NMR analysis of the polymer confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, Mw was 20,500 g / mol.

Comparative Example 1

118 g of the polysiloxane represented by the following formula (2-1) was added thereto, and the same procedure as in Example 1 was carried out. A final 1.5 kg polycarbonate-polysiloxane copolymer was obtained. DOSY and 1 H NMR analysis of the polymer confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, Mw was 21,300 g / mol.

[Formula 2-1]

Comparative Example 2

And 111 g of the polysiloxane represented by the following formula (2-2) was added thereto. A final 1.5 kg polycarbonate-polysiloxane copolymer was obtained. DOSY and 1 H NMR analysis of the polymer confirmed that the siloxane polymer was bonded to the main chain of the polycarbonate. As a result of GPC analysis, Mw was 20,600 g / mol.

[Formula 2-2]

The polycarbonate-polysiloxane copolymer produced by the methods of Examples 1 to 3 and Comparative Examples 1 and 2 was dried at 120 ° C. for 4 hours, Specimens were prepared by injection molding at injection temperature of 250 ~ 290 ℃ and mold temperature of 70 ℃. In the case of high temperature retention test, molding temperature was set to 320 ℃ and mold temperature was 70 ℃ in injection molding machine. After 150 seconds stay in the injection machine, specimen was visually evaluated for presence of gas mark. Respectively.

How to measure property

(1) Weight average molecular weight: Measured on the basis of PS standard (unit: g / mol) using GPC (ViscoTek).

(2) Si content (% by weight): Measured using 300 MHz Ultrasheild NMR of Bruker.

(3) Impact resistance (kgf cm / cm): A notch was formed on 1/4 "and 1/8" Izod samples according to the ASTM D256 evaluation method, and evaluated at room temperature and -20 ° C respectively.

(4) Haze: Haze Meter (YDPO2-0D) manufactured by NIPPON DENSHOKU was used to measure a 2.5 mm thick specimen.

(5) Gas mark: Mark presence or absence was visually observed.

The measurement results are shown in Table 2 below.

Si
No. Si content
(wt%) Molecular Weight
(Mw) Haze Impact Characteristics (IZOD) High temperature retention (320 ° C) 1/4 1/8 1/8
(-20 ° C) Gas
Mark Haze Molecular Weight
(Mw) Example 1 40 2.10 19,800 1.98 39 68 54 none 2.10 19,100 Example 2 40 2.15 20,100 2.01 42 70 53 none 2.05 19,500 Example 3 40 2.05 20,500 1.85 38 67 52 none 1.98 20,000 Comparative Example 1 30 2.02 21,300 1.44 38 68 53 has exist 70.5 17,300 Comparative Example 2 40 2.10 20,600 2.15 40 67 55 has exist 65.8 17.500

Also, as shown in Table 1, it can be seen that Example 1-3 in which the polysiloxane having all of the? -Position carbon atoms were applied showed no significant change in transparency and molecular weight under high temperature molding conditions while maintaining the properties of polycarbonate . On the other hand, in the case of the general linear structure as in Comparative Example 1-2, carbon dioxide is generated through the decomposition reaction of the polysiloxane and the polycarbonate at high temperature molding conditions, leaving a gas mark, and thus the transparency is greatly reduced . Also, the decomposition of the polymer chain was confirmed to be a reduction of the weight average molecular weight of about 3,000.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the embodiments described above are in all respects illustrative and not restrictive.

Claims (6)

A polycarbonate-polysiloxane copolymer containing a polysiloxane unit represented by the following formula (1)
[Chemical Formula 1]

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,
* Is a polycarbonate unit linking group,
Wherein R "is an aliphatic or alicyclic hydrocarbon of C4-C20, the carbon located second from the polycarbonate unit linking group is all substituted by an alkyl group or a cycloalkyl group,
and n is an integer of 30 to 90).
The polycarbonate-polysiloxane copolymer according to claim 1, wherein the polycarbonate-polysiloxane copolymer has a haze change (? H) of 0.5 or less according to the following formula 2:
[Formula 2]
H = H1-H0
(In the above, ΔH is the haze change, H0 is the initial haze of the copolymer, and H1 is the haze after 10 g of the copolymer has stayed at 320 ° C. for 150 seconds).
The polycarbonate-polysiloxane copolymer according to claim 1, wherein the polycarbonate-polysiloxane copolymer is a polycarbonate-polysiloxane copolymer having a weight-average molecular weight change ratio of 5%
[Formula 3]

(Mw is the weight average molecular weight after standing at 320 DEG C for 150 seconds and Mwb is the initial weight average molecular weight)
A process for producing a polycarbonate-polysiloxane copolymer characterized by introducing an aromatic dihydroxy compound and a phosgene-based compound into a polysiloxane represented by the following formula (2)
(2)

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a substituted or unsubstituted C1-C10 alkyl group or a substituted or unsubstituted C6-C18 aryl group,
Wherein R "is a C4-C20 aliphatic or alicyclic hydrocarbon, wherein the carbon atom located second from the hydroxyl group is substituted by an alkyl group or a cycloalkyl group,
and n is an integer of 30 to 90).
5. The method according to claim 4, wherein the aromatic dihydroxy compound is added in an amount of 99.9 to 80.0 parts by weight relative to 0.1 to 20.0 parts by weight of the polysiloxane.
5. The method according to claim 4, wherein the polysiloxane has an acid value change rate (? AV) of 1% or less according to the following formula 1:
[Formula 1]

(AVV is the acid value change rate, AVa is the acid value after leaving 10 g of the polysiloxane at 280 DEG C for 1 hour, and AVb is the initial acid value of the polysiloxane).

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