KR20130074748A - Method of preparing polysiloxane-polycarbonate copolymer - Google Patents

Abstract

PURPOSE: A manufacturing method of polysiloxane [polysiloxane] - polycarbonate copolymer is provided to improve the reaction rate of silicone monomer and secure excellent low temperature-resistance property and flexible rate by adjusting input timing of silicone monomer depending on molecular weight of oligomer property polycarbonate. CONSTITUTION: : A manufacturing method of polysiloxane [polysiloxane] - polycarbonate copolymer comprises the steps of : manufacturing 'oligomer property polycarbonate [oligomeric polycarbonate] with adjusted viscosity average molecular weight of 3,000-20,000 (i), adding and blending hydroxy-terminated siloxane with the manufactured 'oligomer property polycarbonate (ii), and reacting and polymerizing the 'oligomer property polycarbonate and the hydroxy-terminated siloxane under the condition of interfacial reaction (iii). The number average molecular weight injected to the above reaction step (ii) is 2,500-15,000. [Reference numerals] (AA) Input oligomer property; (BB) Input polymer property; (CC,KK) Oligomer property; (DD,LL) Separate heavy liquid; (EE,MM) Polymer property 1; (FF,NN) Polymer property 2; (GG,OO) Washing; (HH,QQ) Catalyst; (II,PP) Assembly, dry; (JJ,RR) Shipment

Description

Method for producing polysiloxane-polycarbonate copolymer {METHOD OF PREPARING POLYSILOXANE-POLYCARBONATE COPOLYMER}

The present invention relates to a method for producing a polysiloxane-polycarbonate copolymer, and more particularly, in the synthesis of a polysiloxane-polycarbonate copolymer, the reaction rate of the silicone monomer by adjusting the timing of addition of the silicone monomer according to the molecular weight of the oligomeric polycarbonate. It relates to a method for producing a polysiloxane-polycarbonate copolymer that can improve the excellent low temperature impact resistance and ductility.

Polycarbonate is widely used for industrial purposes because of its excellent mechanical properties such as tensile strength and impact resistance, and excellent dimensional safety, heat resistance and optical transparency. However, polycarbonate has excellent impact resistance at room temperature, but has a weak point that the impact resistance sharply drops at low temperatures.

In order to remedy this weakness, research on various copolymers continues, and it has been found that polysiloxane-polycarbonate copolymers based on polydimethylsiloxane (PDMS) have relatively good impact resistance at low temperatures.

In general, the synthesis of the polysiloxane-polycarbonate copolymer is largely divided into the initial stage, oligomerization stage, the first stage of polymerization and the second stage of polymerization, and the silicone monomer is introduced in the oligomer stage and reacted with the oligomeric polycarbonate. To form an intermediate. Synthesis of the polysiloxane-polycarbonate copolymer is divided into a heavy liquid constituting a methylene chloride (MC) layer and a hard liquid constituting a water layer as an interfacial reaction, and a reaction is performed between these two interfaces. In addition, in order to narrow the molecular weight distribution of the final product, the synthesis of the polysiloxane-polycarbonate copolymer requires a process of lowering the pH of the initial stage and the oligomerization stage and increasing the water phase to lower the reaction rate. If maintained, the molecular weight distribution of the oligomers will be larger, resulting in a larger molecular weight distribution of the final product.

On the other hand, the higher the molecular weight (number average molecular weight, Mn) of the silicone monomer, the higher the low temperature impact strength and ductility (Ductile rate) at the same content.However, the higher the monomer molecular weight, the lower the reactivity and the lower the pH (eg, Range from 6 to 8) in the oligomerization step, the silicone monomer, which is not properly bound to the polycarbonate oligomer, remains at the intermediate / hard layer interface and is missing from the reaction solution when the heavy liquid is transferred to the next process. These missing silicone monomers reduce the silicone content of the final product, leading to lower physical properties. In addition, as the process proceeds, the missing silicone monomer accumulates in the middle part of the reaction of the oligomerization step, and is mixed irregularly when transferring the heavy / hardening solution to the polymerization stage 1, causing LOT difference and defective products of the final product and Become polluted. On the other hand, in view of the missing silicone monomer, an increase in manufacturing cost is inevitable when more excess silicone monomer is used.

Accordingly, there is a demand for the development of an efficient and economical method for producing a polysiloxane-polycarbonate copolymer capable of dramatically improving the reaction rate of the silicone monomer to impart excellent low temperature impact resistance and ductility to the final product.

US Patent Publication No. 2003/0105226

The present invention is to solve the problems of the prior art as described above, to provide a method for producing a polysiloxane-polycarbonate copolymer which can improve the reaction rate of the silicone monomer and ensure excellent low temperature impact resistance and ductility It is a task.

The present invention comprises the steps of: a) preparing an oligomeric polycarbonate having a viscosity average molecular weight of 3,000 to 20,000; b) adding and mixing hydroxy-terminated siloxane to the prepared oligomeric polycarbonate; And c) reacting the oligomeric polycarbonate with a hydroxy-terminated siloxane under interfacial reaction conditions to polymerize the polysiloxane-polycarbonate copolymer.

In another aspect of the present invention, there is provided a polysiloxane-polycarbonate copolymer prepared by the above method.

In still another aspect of the present invention, there is provided a thermoplastic resin composition comprising a polysiloxane-polycarbonate copolymer and an additive prepared by the above method.

In still another aspect of the present invention, there is provided a molded article prepared from the thermoplastic resin composition.

According to the method for preparing a polysiloxane-polycarbonate copolymer according to the present invention, the reaction rate of the silicone monomer is greatly improved, so that even when the viscosity average molecular weight of the copolymer is kept low, desired properties such as low temperature impact resistance and ductility can be secured. In addition, polysiloxane-polycarbonate copolymers can be synthesized economically without the need for additional processes or reactor fabrication.

1 is a flowchart showing a comparison of a conventional process of introducing a silicone monomer in an oligomerization step and a process of the present invention injecting a silicone monomer in a polymerization step.

Hereinafter, the present invention will be described in more detail. The objects, features and advantages of the present invention will be easily understood by the following embodiments. The present invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and the spirit of the present invention may be sufficiently delivered to those skilled in the art to which the present invention pertains. Therefore, the present invention is not limited by the following exemplary description and embodiments.

As used herein, the term "reaction product" means a material in which two or more reactants are formed by reaction.

In addition, although the terms "first", "second" and the like are used herein to describe a polymerization catalyst, the polymerization catalyst is not limited by these terms. These terms are merely used to distinguish polymerization catalysts from each other. For example, the first polymerization catalyst and the second polymerization catalyst may be the same kind of catalyst or different kinds of catalysts.

In addition, the English letter "R" used to represent hydrogen, a halogen atom and / or a hydrocarbon group, etc. in the chemical formula described herein has a subscript represented by a number, but the "R" is added to such a subscript. It is not limited by. "R" represents, independently of each other, hydrogen, a halogen atom and / or a hydrocarbon group. For example, regardless of whether two or more "R" have the same or different subscripts, these "R" s may represent the same hydrocarbon group or may represent different hydrocarbon groups.

Method for producing a polysiloxane-polycarbonate copolymer according to the present invention comprises the steps of a) preparing an oligomeric polycarbonate having a viscosity average molecular weight of 3,000 to 20,000; b) adding and mixing hydroxy-terminated siloxane to the prepared oligomeric polycarbonate; And c) polymerizing the oligomeric polycarbonate with hydroxy-terminated siloxane under interfacial reaction conditions.

a): Oligomerization  step

This step is to prepare an oligomeric polycarbonate which is used to polymerize with a silicone monomer to form a polysiloxane-polycarbonate copolymer (Si-PC). In this step, the oligomeric polycarbonate is not added without the addition of the silicone monomer. The viscosity average molecular weight (Mv) of is adjusted to 3,000 to 20,000, more preferably to 4,000 to 15,000 levels. Polymerization with a silicone monomer in the state where the viscosity average molecular weight of the oligomeric polycarbonate is less than 3,000 may widen the molecular weight distribution and deteriorate the physical properties, and when the polymerization with the silicone monomer is performed in excess of 20,000, the reactivity may be excessive. Can be degraded.

In one embodiment, the oligomeric polycarbonate is prepared by adding a dihydric phenolic compound to an aqueous alkali solution to form a phenol salt, and then reacting the salted phenol in methylene chloride (MC) or dichloromethane injected with phosgene gas. Can be. For the preparation of oligomers it is desirable to maintain the molar ratio of phosgene to bisphenol in the range of about 1: 1 to 1.5: 1, more preferably about 1: 1 to 1.2: 1. If the molar ratio of phosgene to bisphenol is less than 1, the reactivity may be lowered. If the molar ratio of phosgene to bisphenol is more than 1.5, processability may decrease due to excessive molecular weight increase.

For example, triethylamine (TEA) may be used as the reaction catalyst in forming the oligomer in this step, but is not necessarily limited thereto.

In addition, a monofunctional compound similar to the monomer used for preparing polycarbonate may be used as the molecular weight regulator. Such monofunctional materials include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl Phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) is used.

The reaction in this step is suitably carried out at a pH in the range of 6 to 8 and a temperature in the range of 15 to 40 ° C., and alkali metal hydroxides (eg sodium hydroxide) can be used to adjust the pH of the reaction mixture. If the pH of the reaction mixture is less than 6, there may be a problem that the molecular weight rise of the reaction mixture is lowered or the reaction time is long. You may have a bigger problem.

In one preferred embodiment, the polysiloxane-polycarbonate copolymer prepared according to the present invention comprises a polycarbonate block represented by the following formula (4) as a repeating unit.

[Formula 4]

In Chemical Formula 4,

R ₅ is an alkyl group having 1 to 20 carbon atoms (eg, an alkyl group having 1 to 13 carbon atoms), a cycloalkyl group (such as a cycloalkyl group having 3 to 6 carbon atoms), an alkenyl group (eg, an alkenyl group having 2 to 13 carbon atoms), An alkoxy group (eg, an alkoxy group having 1 to 13 carbon atoms), a halogen atom, or a nitro substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms.

Here, the aromatic hydrocarbon group may be derived from a compound having the structure of the following formula (4a).

[Chemical Formula 4a]

In Chemical Formula 4a,

X is an alkylene group, a linear, branched or cyclic alkylene group having no functional group, or a linear, branched or cyclic alkylene group containing a functional group such as sulfide, ether, sulfoxide, sulfone, ketone, naphthyl, Lt; / RTI > Preferably, X may be a straight, branched or cyclic alkylene group having 3 to 6 carbon atoms.

R ₆ independently represents a hydrogen atom, a halogen atom or an alkyl group, such as a linear, branched or cyclic alkyl group having 3 to 20 carbon atoms (preferably 3 to 6) carbon atoms.

n and m independently represent the integer of 0-4.

The compound of formula 4a is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl )-(4-isobutylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1,1 -Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,10-bis ( 4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy Phenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) nonane, 2,2- Bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane , 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Tan, Resorcinol, Hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-di Hydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5-dichloro-4 -Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, p ' -Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl 4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclo Dodecane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 1,1-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) decane, 1,4 -Bis (4-hydroxyphenyl) propane, 1,4-bis (4- Hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3-chloro-4-hydroxyphenyl ) Propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydrate Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,4 -Bis (4-hydroxyphenyl) -2-methyl-butane, 4,4'-thiodiphenol [bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfide , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzofe , 4,4'-dihydroxy-diphenyl, methyl may be a hydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxy naphthalene, but is not limited thereto. Representative of these is 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other functional dihydric phenols can be found in US Pat. Nos. US 2,999,835, US 3,028,365, US 3,153,008 and US 3,334,154, and the dihydric phenols may be used singly or in combination of two or more. Can be used.

In the case of the carbonate precursor, for example, carbonyl chloride (phosphene), carbonyl bromide, bis halo formate, diphenyl carbonate or dimethyl carbonate may be used as another monomer of the polycarbonate resin.

In one embodiment, the heavy liquid comprising the oligomeric polycarbonate prepared in this step is extracted and separated from the reaction mixture and used in the next step, the polymerization step.

b) and c): silicone Monomer  Input and Polymerization  step

In this step, a polysiloxane-polycarbonate copolymer is formed by adding and mixing a hydroxy-terminated siloxane, which is a silicone monomer, to the oligomeric polycarbonate prepared in step a) and then reacting and polymerizing under an interfacial reaction condition consisting of an aqueous alkali solution and an organic phase. It's a step. In the present invention, unlike the conventional production method of adding a silicone monomer in the oligomerization step, after preparing the oligomeric polycarbonate whose viscosity average molecular weight is adjusted to a certain level first, the silicone monomer is added to form a copolymer. It features.

The mixture of the oligomeric polycarbonate and the hydroxy terminal siloxane may further include a molecular weight regulator, a first polymerization catalyst, a phase transfer catalyst, a pH regulator (eg, NaOH), methylene chloride (MC), and the like. Specifically, the polysiloxane-polycarbonate copolymer can be prepared by adding hydroxy terminal siloxane to the organic phase-aqueous mixture containing the oligomeric polycarbonate, and stepwise introducing a molecular weight modifier, a catalyst and the like.

As the molecular weight modifier, a monofunctional compound similar to the monomer used for preparing polycarbonate as mentioned above may be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. As the polymerization catalyst, for example, triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound represented by the following Chemical Formula 5 may be used.

[Chemical Formula 5]

^{_{(R 7) 4 Q + X}} -

In Formula 5, R ₇ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and X represents a halogen atom or -OR ₈ . Here, R <_8> represents a hydrogen atom, a C1-C18 alkyl group, or a C6-C18 aryl group.

Specifically, the phase transfer catalyst is, for example, [CH ₃ (CH ₂ ) ₃ ] ₄ NX, [CH ₃ (CH ₂ ) ₃ ] ₄ PX, [CH ₃ (CH ₂ ) ₅ ] ₄ NX, [CH ₃ (CH ₂ ) ₆ ] ₄ NX, [CH ₃ (CH ₂ ) ₄ ] ₄ NX, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NX, CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NX have. In the above formulas, X represents Cl, Br or -OR ₈ , wherein R ₈ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.01 to 10% by weight, more preferably 0.1 to 10% by weight, based on the total weight of the mixture of hydroxy terminal siloxane and oligomeric polycarbonate. If the content is less than 0.01% by weight may be less reactive, if the content is more than 10% by weight may precipitate as a precipitate or the transparency may be reduced.

The preferred molecular weight (number average molecular weight, Mn) of the hydroxy-terminated siloxane introduced in this step is 2,500 to 15,000, more preferably 3,000 to 8,000. If the molecular weight of the hydroxy-terminated siloxane is less than 2,500, low-temperature impact resistance and ductility may be lowered. If the molecular weight is excessively higher than 15,000, the reactivity may be poor, causing problems in synthesizing the polysiloxane-polycarbonate copolymer to the desired molecular weight. have.

In this step, the oligomeric polycarbonate and the hydroxy-terminated siloxane are preferably mixed in a weight ratio of 80:20 to 99: 1, and more preferably in a weight ratio of 85:15 to 97: 3. In short, the preferred dosage of hydroxy-terminated siloxane in the preparation of the polysiloxane-polycarbonate copolymer according to the invention is 1 to 20% by weight, more preferably 3 to 15% by weight, based on the total reactants. If the amount of the hydroxy-terminated siloxane is less than 1% by weight, the impact resistance at low temperature may be lowered. If the amount is more than 20% by weight, the physical properties such as fluidity, heat resistance, and transparency may be lowered, and the manufacturing cost is increased and economical. Not preferable in terms of. In the present invention, by maximizing the reaction rate by controlling the timing of the hydroxy terminal siloxane can be exhibited excellent low-temperature impact resistance even when using a relatively low amount of siloxane of 1 to 20% by weight.

The hydroxy terminated siloxane loading and polymerisation of this step is preferably performed in a high pH environment (e.g., in the range of pH 9 to 14). If the pH is less than 9, the reactivity is poor, resulting in unreacted silicon or polysiloxane-polycarbonate. It may not reach the target molecular weight of the copolymer, and if the pH exceeds 14, the molecular weight distribution is widened due to a rapid reaction or a large amount of acid is added to neutralize the cleaning process after the reaction, which is not economically desirable. In other words, the production method of the present invention can effectively complete the reaction without the unreacted silicon monomer after the oligomerization step to homogenize the oligomeric polycarbonate, and the addition of the silicon monomer in the polymerization step of high pH, NaOH enter. .

In one preferred embodiment, the polymerization of the oligomeric polycarbonate with the hydroxy terminated siloxane is carried out stepwise over the first and second stages. Specifically, the first step of polymerization is carried out from a mixture in which an hydroxy terminal siloxane, a first polymerization catalyst, a phase transfer catalyst, a molecular weight regulator, a pH regulator (eg, NaOH), methylene chloride (MC), and the like are added to the oligomeric polycarbonate. Then, the second polymerization catalyst is sequentially added to carry out two steps of polymerization. Here, the second polymerization step can be performed by providing a second polymerization catalyst to the resulting mixture after the first polymerization step is completed.

Preferred viscosity average molecular weights of the polysiloxane-polycarbonate copolymers prepared according to the invention are 15,000 to 30,000, more preferably 17,000 to 22,000. If the viscosity average molecular weight of the copolymer is less than 15,000, the mechanical properties can be significantly reduced, if it exceeds 30,000 may cause problems in the processing of the resin due to the rise of the melt viscosity. In the present invention, by maximizing the reaction rate by controlling the timing of the hydroxy terminal siloxane, even if the viscosity average molecular weight of the copolymer is reduced to a level of 30,000 or less, excellent low-temperature impact resistance and ductility can be secured under the same processing conditions. The moldability improves. As a result, even if the processing temperature is lowered than the viscosity average molecular weight of 30,000, it is possible to form smoothly. have. In addition, it is possible to knead with other resins having poor thermal stability, thereby facilitating further development.

In a preferred embodiment, the polysiloxane-polycarbonate copolymer prepared according to the present invention comprises a hydroxy-terminated siloxane of formula 1a or formula 1 and a polycarbonate block of formula 4 mentioned above as repeating units.

[Formula 1a]

In formula (1a)

R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group. For example, the halogen atom may be Cl or Br, the alkyl group may be an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl or propyl, and the alkoxy group may be an alkoxy group having 1 to 13 carbon atoms such as methoxy, It may be ethoxy or propoxy, the aryl group may be 6 to 10 aryl groups, such as phenyl, chlorophenyl or tolyl.

R ₂ independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a hydrocarbon group or hydroxyl group having 1 to 13 carbon atoms. For example, R ₂ is an alkyl or alkoxy group having 1 to 13 carbon atoms, an alkenyl or alkenyloxy group having 2 to 13 carbon atoms, a cycloalkyl group or a cycloalkoxy group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms or aryl It may be an oxy group, a C7-13 aralkyl group or an alkoxy group, or a C7-13 alkaryl group or an alkaryloxy group.

R ₃ independently represents an alkylene group having 2 to 8 carbon atoms.

m independently represents the integer of 0-4.

n is independently an integer of 30 to 200, preferably an integer of 40 to 170, more preferably an integer of 50 to 120. [

)를 사용할 수 있으나, 반드시 이에 한정되는 것은 아니다.In one embodiment, the hydroxy terminated siloxane of Formula 1a is a silicone monomer of Dow Corning (

) Can be used, but is not necessarily limited thereto.

[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ And m is as defined above in Formula 1a, n independently represents an integer of 15 to 100, preferably an integer of 20 to 80, more preferably an integer of 25 to 60.

A shows the structure of following General formula (2) or (3).

[Formula 2]

In Formula 2,

X is Y or NH-Y-NH, wherein Y is a linear or branched aliphatic group having 1 to 20 carbon atoms, a cycloalkylene group (e.g., a cycloalkylene group having 3 to 6 carbon atoms), or a halogen atom, an alkyl group, alkoxy Or a mononuclear or polynuclear arylene group having 6 to 30 carbon atoms substituted or unsubstituted with a group, an aryl group or a carboxyl group. For example, Y is an aliphatic group substituted or unsubstituted with a halogen atom, an aliphatic group containing oxygen, nitrogen or sulfur atoms in the main chain, or an aryl which may be derived from bisphenol A, resorcinol, hydroquinone or diphenylphenol. It may be a len group, for example, it may be represented by the formula 2a to 2h.

(2a)

[Formula 2b]

[Formula 2c]

(2d)

[Formula 2e]

(2f)

[Chemical Formula 2g]

[Chemical Formula 2h]

(3)

In Formula 3,

R ₄ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms or an aromatic / aliphatic mixed hydrocarbon group, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Here, R ₄ may have a structure containing halogen, oxygen, nitrogen or sulfur in addition to the carbon atom. For example, R &lt; ₄ &gt; may be phenyl, chlorophenyl or tolyl (preferably phenyl).

In one embodiment, the hydroxy terminal siloxane of Formula 1 may be a reaction product of the hydroxy terminal siloxane of Formula 1a (wherein n is an integer of 15 to 100) and an acyl compound.

Here, the acyl compound may have, for example, an aromatic, aliphatic or mixed structure including both aromatic and aliphatic. When the acyl compound is aromatic or mixed, it may have 6 to 30 carbon atoms, and if it is aliphatic, it may have 1 to 20 carbon atoms. The acyl compound may further include a halogen, oxygen, nitrogen or sulfur atom.

In another embodiment, the hydroxy terminal siloxane of Formula 1 may be a reaction product of the hydroxy terminal siloxane of Formula 1a (wherein n is an integer of 15 to 100) and the diisocyanate compound.

Here, the diisocyanate compound may be, for example, 1,4-phenylenediisocyanate, 1,3-phenylenediisocyanate or 4,4'-methylenediphenyl diisocyanate. Isocyanate (4,4'-methylenediphenyl diisocyanate).

In another embodiment, the hydroxy-terminated siloxane of Formula 1 is a reaction product of the hydroxy-terminated siloxane of Formula 1a, wherein n is an integer of 15 to 100, and a phosphorus-containing compound (aromatic or aliphatic phosphate compound). Can be.

Here, the phosphorus-containing compound may be represented by the following Formula 1b.

[Chemical Formula 1b]

In Formula 1b, R ₄ is as defined above in Formula 3, Z independently represents a phosphorus, a halogen atom, a hydroxy group, a carboxyl group, an alkyl group (with 1 to 20 carbon atoms), an alkoxy group or an aryl group.

In one embodiment, a polysiloxane-polycarbonate copolymer is prepared according to the present invention and then the organic phase dispersed in methylene chloride is alkali washed and then separated. Subsequently, the organic phase is washed with 0.1N hydrochloric acid solution, and then washed twice with distilled water. When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted to granulate with a certain amount of pure water in the range of 30 to 100 ° C, preferably in the range of 60 to 80 ° C. If the temperature of the pure water is less than 30 ℃ assembling rate may be very long, the assembly time may be very long, and if the temperature of the pure water exceeds 100 ℃ it may be difficult to obtain the shape of the polycarbonate with a certain size. When the assembly is complete, it is preferable to dry for 5 to 10 hours at 100 to 120 ℃, more preferably first to dry for 5 to 10 hours at 100 to 110 ℃, second to 110 to 120 ℃ for 5 to 10 hours .

According to another aspect of the present invention, there is provided a polysiloxane-polycarbonate copolymer produced by the method of the present invention as described above. The polysiloxane-polycarbonate copolymer of the present invention has a low viscosity average molecular weight and is excellent in workability and moldability, but excellent in low temperature impact resistance and ductility, and thus may be suitably used for various applications.

Accordingly, according to another aspect of the present invention, there is provided a thermoplastic resin composition comprising a polysiloxane-polycarbonate copolymer and an additive prepared by the method of the present invention. As the additive, those commonly added to the thermoplastic resin composition (eg, heat stabilizer, antioxidant, UV stabilizer, flame retardant, mold release agent, etc.) may be used.

In addition, according to another aspect of the present invention, there is provided a molded article prepared from the thermoplastic resin composition. As a processing method used in the production of the molded article, a method commonly used for processing a thermoplastic resin composition, such as extrusion, thermoforming, injection, or the like, may be used.

Example  And Comparative example

Example  One

<Preparation of hydroxy terminal siloxane>

A 100 mL three-necked flask was equipped with a condenser, and 0.03 mol of eugenol and 0.015 mol of polydimethylsiloxane were completely dissolved in 50 mL of chlorobenzene in a nitrogen atmosphere, followed by a platinum catalyst (platinum (0) -1). , 3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added to 0.00364 mmol and refluxed for 24 hours. After removing the solvent of the reacted solution, it was washed with distilled water. The hydroxy terminal siloxane of the following Chemical Formula 6 was prepared by drying in a vacuum oven for 24 hours.

[Formula 6]

<Production of hydroxy terminal siloxane having ester bond>

In a nitrogen atmosphere, 0.4 mol of hydroxy-terminated siloxane having a bond of formula 6 was dissolved in 300 mL of chloroform, and 67 mL of triethylamine (TEA) catalyst was added thereto. 0.2 mol of terephthaloylchloride (TCL) was dissolved in 1,000 mL of chloroform while refluxing the solution, and then slowly added for 1 hour and refluxed for 12 hours. After removing the solvent of the reaction solution, dissolved in acetone (acetone) and washed with hot distilled water. Hydroxy terminal siloxane (number average molecular weight: 4,000) having an ester bond of formula (7) was prepared by drying in a vacuum oven for 24 hours. The peaks of the methylene group of the polysiloxane observed at 2.6 ppm by H-NMR and the hydrogen peak of the benzene ring of TCL observed at 8.35 ppm and the hydrogen peak of the benzene ring of polysiloxane observed at 6.75 to 7.35 ppm It was confirmed.

[Formula 7]

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

An interfacial reaction between bisphenol A and phosgene gas in an aqueous NaOH solution in the presence of methylene chloride prepared an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 2.6 g of p-tert-butylphenol (PTBP) and 275 μl of triethylamine (triethylamine, TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes to obtain a viscosity average molecular weight of 3,000 to 3,000. 400 mL of an 6,000 oligomeric polycarbonate mixture was prepared. 4.5% by weight of hydroxy-terminated siloxane having an ester bond of the above formula (7), 43% by weight of an aqueous solution of 43% by weight of tetrabutyl ammonium chloride (TBACl) dissolved in methylene chloride in the obtained oligomeric polycarbonate mixture, hydroxide 160 g of aqueous sodium solution, 300 g of methylene chloride, and 25 µl of 15% by weight aqueous solution of triethylamine were mixed and reacted for 1 hour to react with the first step of polymerization. Thereafter, 260 µl of triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes. After phase separation, the organic phase having increased viscosity was separated after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then repeatedly washed 2-3 times with distilled water. Washing was complete and the organic phase was assembled at 76 ° C. with a certain amount of pure water. After the assembly was completed, the mixture was first dried at 110 ° C. for 8 hours and secondly at 120 ° C. for 10 hours. The peaks of the methylene group of polysiloxanes observed at 2.6 ppm and 2.65 ppm by H-NMR and the hydrogen peaks of the hydrogen peaks of the benzene ring of TCL and the benzene ring of polysiloxane observed at 6.95 to 7.5 ppm were observed at 8.35 ppm. Confirmed. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example  2

<Preparation of hydroxy terminal siloxane>

Dissolve 0.0666 mol of the hydroxy terminus having a bond of formula 6 in 100 mL of benzene under nitrogen, and then dissolve 1,4-diazabicyclo [2,2,2] -octane (1,4-diazabicyclo [2,2]. , 2] -octane) 6.66 mmol. In the state of refluxing the solution, 0.0333 mol of 4,4-methylene bis (phenyl isocynate) was dissolved in 200 mL of benzene, and then slowly added for 1 hour. The solution above was refluxed for 12 hours. After removing the solvent of the reaction solution, dissolved in acetone (acetone), washed with hot distilled water. Dry in a vacuum oven for 24 hours. As a result, a hydroxy-terminated siloxane (molecular weight: 4,000) having a urethane bond represented by Formula 8 was prepared. In Formula 8, hydrogen bonded to the first carbon of the aliphatic chain adjacent to the terminal phenyl group was found at 2.75 ppm.

[Formula 8]

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

An interfacial reaction between bisphenol A and phosgene gas in an aqueous NaOH solution in the presence of methylene chloride prepared an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 2.6 g of p-tert-butylphenol (PTBP) and 275 μl of triethylamine (triethylamine, TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes to obtain a viscosity average molecular weight of 3,000 to 3,000. 400 mL of an 6,000 oligomeric polycarbonate mixture was prepared. 4.5% by weight of hydroxy-terminated siloxane having a urethane bond of Formula 8, 43% by weight of an aqueous solution of 43% by weight of tetrabutyl ammonium chloride (TBACl) dissolved in methylene chloride in the obtained oligomeric polycarbonate mixture, hydroxide 160 g of aqueous sodium solution, 300 g of methylene chloride, and 25 µl of 15% by weight aqueous solution of triethylamine were mixed and reacted for 1 hour to react with the first step of polymerization. Thereafter, 260 µl of triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes. After phase separation, the organic phase having increased viscosity was separated after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then repeatedly washed 2-3 times with distilled water. Washing was complete and the organic phase was assembled at 76 ° C. with a certain amount of pure water. After the assembly was completed, the mixture was first dried at 110 ° C. for 8 hours and secondly at 120 ° C. for 10 hours. It was confirmed by H-NMR that the peak of the methylene group of polysiloxane observed at 2.65 ppm, the peak of the methoxy group observed at 3.85 ppm, and the hydrogen peak of the benzene ring observed at 7.1 ppm to 7.5 ppm. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example  3

<Preparation of hydroxy terminal siloxane>

A condenser was mounted in a 500 mL three-neck flask, and 0.01 mole of DMS polychem PMS-25 was dissolved in 100 ml of toluene under nitrogen atmosphere, and then 0.01 mole of triethylamine (TEA) catalyst was added thereto. While the solution was refluxed, 0.005 mole of phenyl phosphonic dichloride was slowly added for 1 hour and refluxed for 5 hours. After removing the solvent toluene of the reaction solution, and dried for 24 hours in a vacuum oven to prepare a phosphate-containing hydroxy terminal siloxane (molecular weight: 4,000) of the formula (9).

[Chemical Formula 9]

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

An interfacial reaction between bisphenol A and phosgene gas in an aqueous NaOH solution in the presence of methylene chloride prepared an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 2.6 g of p-tert-butylphenol (PTBP) and 275 μl of triethylamine (triethylamine, TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes to obtain a viscosity average molecular weight of 3,000 to 3,000. 400 mL of an 6,000 oligomeric polycarbonate mixture was prepared. 4.5% by weight of the phosphate-containing hydroxy-terminated siloxane of the formula (9), 43% by weight of an aqueous solution of tetrabutyl ammonium chloride (TBACl), 0.8 mL, sodium hydroxide dissolved in methylene chloride in the obtained oligomeric polycarbonate mixture. 160 g of aqueous solution, 300 g of methylene chloride, and 25 µl of 15 wt% aqueous solution of triethylamine were mixed and reacted for 1 hour to react with the first step of polymerization. Thereafter, 260 µl of triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes. After phase separation, the organic phase having increased viscosity was separated after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then repeatedly washed 2-3 times with distilled water. Washing was complete and the organic phase was assembled at 76 ° C. with a certain amount of pure water. After the assembly was completed, the mixture was first dried at 110 ° C. for 8 hours and secondly at 120 ° C. for 10 hours. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example  4

A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Example 1 except that Dow Corning's hydroxy terminated siloxane BY16-752 (molecular weight: 3,000) was used in an amount of 4.5 wt%. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Example  5

<Preparation of hydroxy terminal siloxane>

In the same manner as in Example 1, a hydroxy-terminated siloxane (number average molecular weight: 4,000) having an ester bond of Formula 7 was prepared.

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

An interfacial reaction between bisphenol A and phosgene gas in an aqueous NaOH solution in the presence of methylene chloride prepared an oligomeric polycarbonate mixture having a viscosity average molecular weight of about 1,000. To the obtained oligomeric polycarbonate mixture, 2.8 g of p-tert-butylphenol (PTBP) and 275 μl of triethylamine (triethylamine, TEA, 15 wt% aqueous solution) were mixed and reacted for 30 minutes. The oligomeric polycarbonate mixture was mixed with 160 g of sodium hydroxide solution, 300 g of methylene chloride, and 25 µl of 15 wt% aqueous solution of triethylamine, followed by one step of polymerization for 1 hour to obtain an average molecular weight of 8,000 to 12,000. Polycarbonate mixtures were prepared. Then, 4.5% by weight of a hydroxy-terminated siloxane having an ester bond of the formula (7), 43% by weight of an aqueous solution of tetrabutyl ammonium chloride (TBACl) dissolved in methylene chloride, 0.8 mL, triethylamine (TEA, 260 μl of 15 wt% aqueous solution) were mixed and reacted for 30 minutes. After phase separation, the organic phase having increased viscosity was separated after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then repeatedly washed 2-3 times with distilled water. Washing was complete and the organic phase was assembled at 76 ° C. with a certain amount of pure water. After the assembly was completed, the mixture was first dried at 110 ° C. for 8 hours and secondly at 120 ° C. for 10 hours. The peaks of the methylene group of polysiloxanes observed at 2.6 ppm and 2.65 ppm by H-NMR and the hydrogen peaks of the hydrogen peaks of the benzene ring of TCL and the benzene ring of polysiloxane observed at 6.95 to 7.5 ppm were observed at 8.35 ppm. Confirmed. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Comparative example  One

The physical properties of 3022PJ Linear polycarbonate (Mv: 21,000) of Samyang Corporation were measured and described in Table 1 below.

Comparative example  2

The physical properties of 3030PJ Linear polycarbonate (Mv: 31,200) of Samyang Corporation were measured and described in Table 1 below.

Comparative example  3

The physical properties of the linear polycarbonate synthesized to have a viscosity average molecular weight of 70,800 were measured and described in Table 1 below.

Comparative example  4

<Preparation of hydroxy terminal siloxane>

In the same manner as in Example 1, a hydroxy-terminated siloxane (number average molecular weight: 4,000) having an ester bond of Formula 7 was prepared.

&Lt; Preparation of polysiloxane-polycarbonate copolymer >

Bisphenol A in aqueous solution and phosgene gas were interfacially reacted in the presence of methylene chloride to prepare 400 mL of an oligomeric polycarbonate mixture having a viscosity average molecular weight of 1,000 to 2,000. 4.5% by weight of hydroxy-terminated siloxane having an ester bond of the above formula (7), 0.8 mL of tetrabutyl ammonium chloride (TBACl), p-tert-butyl dissolved in methylene chloride in the obtained oligomeric polycarbonate mixture Phenol (PTBP) 2.6g, triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes after mixing. The reacted oligomeric polycarbonate mixture was allowed to stand still and layer separation occurred, followed by extracting only the organic phase. The mixture was mixed with 160 g of sodium hydroxide solution, 300 g of methylene chloride, and 25 µl of 15 wt% aqueous solution of triethylamine, and reacted for 1 hour. Thereafter, 260 µl of triethylamine (triethylamine, TEA, 15wt% aqueous solution) was mixed and reacted for 30 minutes. After phase separation, the organic phase having increased viscosity was separated after alkali washing. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution and then repeatedly washed 2-3 times with distilled water. Washing was complete and the organic phase was assembled at 76 ° C. with a certain amount of pure water. After the assembly was completed, the mixture was first dried at 110 ° C. for 8 hours and secondly at 120 ° C. for 10 hours. The peaks of the methylene group of polysiloxanes observed at 2.6 ppm and 2.65 ppm by H-NMR and the hydrogen peaks of the hydrogen peaks of the benzene ring of TCL and the benzene ring of polysiloxane observed at 6.95 to 7.5 ppm were observed at 8.35 ppm. Confirmed. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Comparative example  5

A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Comparative Example 4, except that hydroxy-terminated siloxane (molecular weight: 4,000) having a urethane bond of Formula 7 was used. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Comparative example  6

A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Comparative Example 4, except that the phosphate-containing hydroxy terminal siloxane (molecular weight: 4,000) of Formula 9 was used. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

Comparative example  7

A polysiloxane-polycarbonate copolymer was prepared in the same manner as in Comparative Example 4 except that Dow Corning's hydroxy-terminated siloxane BY16-752 (molecular weight: 3,000) was used. The physical properties of the prepared polysiloxane-polycarbonate copolymer were measured and described in Table 1 below.

As shown in Table 1 above, the polysiloxane-polycarbonate copolymer prepared according to the embodiment is superior to the polysiloxane-polycarbonate copolymer (or linear polycarbonate) prepared according to the comparative example. And Ductile rate.

The performance evaluation method used in the said Example and a comparative example is as follows.

(a) H-NMR (nuclear magnetic resonance spectroscopy): Measured using a Bruker Avance DRX 300.

(b) Viscosity Average Molecular Weight (Mv): The viscosity of the methylene chloride solution was measured at 20 ° C. using an Ubbelohde Viscometer, from which the ultimate viscosity [η] was calculated by the following equation.

^{[η] = 1.23x10 -5 Mv 0} .83

(c) Impact strength: The impact strength was measured at room temperature and -50 ℃ using an impact tester (RESIL IMPACTOR of CEAST).

(d) Ductile rate (ductility) at -50 ° C impact measurement: Ductile specimens / total specimens * 100%.

TEA: triethylamine
PTBP: p-tert-butylphenol
Si-monomer: silicone monomer
PTC cat .: phase transfer catalyst
Catalyst 1: First Polymerization Catalyst
DMW: demineralized water
MC: methylene chloride
Catalyst 2: Second Polymerization Catalyst
BPA-Na: bisphenol A-Na
CDC: phosgene (carbonyldichloride)

Claims (11)

a) preparing an oligomeric polycarbonate having a viscosity average molecular weight of 3,000 to 20,000;
b) adding and mixing hydroxy-terminated siloxane to the prepared oligomeric polycarbonate; And
c) reacting the oligomeric polycarbonate with hydroxy-terminated siloxane under interfacial reaction conditions to polymerize the polysiloxane-polycarbonate copolymer. The method of claim 1,
Method for producing a polysiloxane-polycarbonate copolymer, characterized in that the number average molecular weight (Mn) of the hydroxy terminal siloxane introduced in step b) is 2,500 to 15,000. The method of claim 1,
The method of producing a polysiloxane-polycarbonate copolymer, characterized in that in step b) the oligomeric polycarbonate and the hydroxy terminal siloxane is mixed in a weight ratio of 80:20 to 99: 1. The method of claim 1,
In step b), the oligomeric polycarbonate and the hydroxy-terminated siloxane is a method of producing a polysiloxane-polycarbonate copolymer, characterized in that mixing in a weight ratio of 85: 15 to 97: 3. The method of claim 1,
The step a) is carried out in the range of pH 6 to 8, wherein the steps b) and c) is carried out in the range of pH 9 to 14 method of producing a polysiloxane-polycarbonate copolymer. The method of claim 1,
Method for producing a polysiloxane-polycarbonate copolymer, characterized in that the polymerization in step c) is carried out over the first and second. The method of claim 1,
Method for producing a polysiloxane-polycarbonate copolymer, characterized in that the viscosity average molecular weight of the polysiloxane-polycarbonate copolymer is 15,000 to 30,000. The method of claim 1,
Method for producing a polysiloxane-polycarbonate copolymer, characterized in that the polysiloxane-polycarbonate copolymer comprises a hydroxy terminal siloxane of the general formula (1a) or (1) and a polycarbonate block of the general formula (4) as a repeating unit:
[Formula 1a]

In formula (1a)
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
m is independently an integer of 0 to 4,
n represents an integer of 30 to 200,
[Formula 1]

In Chemical Formula 1,
R ₁ independently represents a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or an aryl group,
R ₂ independently represents a hydrocarbon group or a hydroxyl group having 1 to 13 carbon atoms,
R ₃ independently represents an alkylene group having 2 to 8 carbon atoms,
m is independently an integer of 0 to 4,
n independently represents an integer of 15 to 100,
A represents the structure of the following Chemical Formula 2 or 3,
(2)

In Formula 2,
X is Y or NH-Y-NH, wherein Y is unsubstituted or substituted with a linear or branched aliphatic group, a cycloalkylene group having 1 to 20 carbon atoms, or a halogen atom, an alkyl group, an alkoxy group, an aryl group or a carboxyl group A mononuclear or polynuclear arylene group having 6 to 30 carbon atoms,
(3)

In Formula 3,
R ₄ represents an aromatic or aromatic / aliphatic mixed hydrocarbon group having 6 to 30 carbon atoms, or an aliphatic hydrocarbon group having 1 to 20 carbon atoms,
[Chemical Formula 4]

In Formula 4,
R ₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a halogen atom, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. A polysiloxane-polycarbonate copolymer prepared by the method of any one of claims 1 to 8. A thermoplastic resin composition comprising the polysiloxane-polycarbonate copolymer and additive according to claim 9. A molded article prepared from the thermoplastic resin composition according to claim 10.

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