KR20190062024A - Polymerization of Polycarbonate by using Tumbler Reactor - Google Patents

Abstract

Since the present invention effectively crystallizes a polycarbonate using a tumbler-type reactor, a method of crystallizing the polycarbonate capable of manufacturing the polycarbonate excellent in physical properties by having low reactant loss and a high glass transition temperature is disclosed. According to the present invention, as the polycarbonate is crystallized by using the tumbler-type reactor, the loss of reactants is small, and a crystallization rate is increased, and at the same time, a size of a crystal is refined, thereby being able to manufacture the polycarbonate having a large increase in crystallinity. Therefore, the polycarbonate can be usefully used for exterior walls, bottled water bottles and the like that require high viscosity physical properties.

Description

TECHNICAL FIELD The present invention relates to a method of polymerizing polycarbonate using a tumbler type reactor,

The present invention relates to a polycarbonate polymerization method using a tumbler type reactor, and more particularly, to a polycarbonate polymerization method using a tumbler type reactor, thereby effectively reducing the reactant loss, and having a high glass transition temperature, And a polycarbonate polymerization method using a tumbler type reactor capable of producing the excellent polycarbonate.

A polycarbonate (PC) resin is a representative thermoplastic polymer having an aromatic polycarbonate bond structure and a thermal deformation temperature of about 130 占 폚. Polycarbonate resin has been growing as an important part of engineering plastics due to its excellent heat resistance, impact resistance, mechanical strength, dimensional stability and transparency. It is used for electric / electronic exterior materials, office equipment compact discs, packaging materials, And is widely used in engineering plastics such as automobile bumpers.

Polycarbonate can be polymerized using an interfacial polymerization method and a melt polymerization method, which are typical polycarbonate polymerization methods. The interfacial polymerization method called bisphenol-A and the so-called "phosgene process" using a phosgene gas as a monomer account for most of the polycarbonate processes in the world at present. However, the phosgene process has been limited from the problems of facility safety and environment due to the use of poisonous gas, phosgene, and high operation cost and construction cost due to the use of methylene chloride and water due to adoption of the interfacial polymerization method.

In order to improve the environmental hazard of the phosgene process and the high manufacturing cost, researches on non-phosgene-based processes other than interfacial polymerization have been continuously carried out. In recent years, the polycarbonate production process newly established has been proved to be most efficient by the melt polymerization process, but there is a limit to the production of high molecular weight products due to the limitation of stirring. Solid phase polymerization processes have been attracting attention as a way to overcome the limitations of the production of high molecular weight polycarbonate, which is a weak point of the non-phosgene process by melt polymerization, and many techniques have been introduced to realize this.

In order to achieve solid-state polymerization of amorphous polycarbonate, a process of inducing crystallization in advance is indispensably required. In order to realize the solid phase polymerization of polycarbonate, many conventional techniques are the first step to be solved have.

Among the three methods of PC crystallization, (1) thermal induced crystallization has the advantage of not using a solvent, but takes too long, (2) crystallization using strain induction is a pellet type Not suitable for sample. (3) The crystallization method using a solvent can obtain a sufficient degree of crystallization even in a small amount of solvent in a short period of time to sufficiently perform solid-state polymerization, but the loss ratio of the polycarbonate prepolymer is high. Particularly, in the method of crystallizing by a solvent, when a generally used impeller type reactor is used, there is a problem that a polycarbonate prepolymer is broken due to a direct physical factor such as an impeller, and the yield is lowered.

Korean Patent Registration No. 10-0878453 discloses a method in which a polycarbonate prepolymer is dissolved in a solvent and then a solvent is added to the solution to precipitate the solution. Various solvents are used as the non-solvent, and the crystallized polycarbonate is formed in a powder form. However, it is disadvantageous to use an additional organic solvent in order to dissolve the polycarbonate.

Korean Patent Laid-Open No. 10-2004-0016514 discloses a method of dissolving a polycarbonate prepolymer using a solvent and proceeding crystallization in such a manner that a small amount of the polycarbonate prepolymer is precipitated by adding a small amount to a non-solvent, but an additional process for dissolving polycarbonate Is required.

Korean Patent Registration No. 10-0561743 A method of increasing the molecular weight by using an organic solvent vapor having a large microwave and dipole moment to remove by-products in the solid phase polymerization after crystallizing the polycarbonate prepolymer with acetone is disclosed, but a product having a low molecular weight (<30.000, viscosity average) There is a limit.

Disclosure of the Invention The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a polycarbonate which is low in loss of reactants during crystallization and has a high glass transition temperature To provide a polycarbonate having physical properties.

According to an aspect of the present invention, there is provided a process for producing a polycarbonate resin composition, comprising the steps of: (a) polymerizing an amorphous polycarbonate prepolymer using an aromatic hydroxy compound and an aryl carbonate; (b) surface-crystallizing the amorphous polycarbonate prepolymer using a tumbler type reactor; And (c) subjecting the surface-crystallized polycarbonate prepolymer to solid phase polymerization; &Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; polycarbonate.

Also, the aromatic hydroxy compound is a monomer represented by the following formula (1).

[Chemical Formula 1]

에서 선택되는 그룹을 나타내고, R3 및 R4는 독립적으로 수소원자, 탄소수 1 내지 20의 알킬 그룹, 탄소수 4 내지 20의 사이클로알킬 그룹, 탄소수 5 내지 20의 아릴 그룹 및 탄소수 6 내지 20의 융합고리로부터 선택된다.)Wherein R 1 and R 2 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, a and b are independently an integer of 0 to 4 X is a chemical bond or an oxygen atom, a sulfur atom, a -SO ₂ - group, an aliphatic radical having 1 to 20 carbon atoms, or

And R 3 and R 4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, and a fused ring having 6 to 20 carbon atoms do.)

The step (b) of crystallizing the surface may be performed by impregnating the non-crystalline polycarbonate prepolymer in a non-solvent in a volume ratio of 1: 1 to 5, and then rotating the polymer in a tumbler type reactor for 20 minutes to 3 hours. A method for polymerization of carbonates is provided.

Also, the aromatic hydroxy compound may be 1,1-bis- (hydroxyphenyl) -methane, 1,1-bis- (hydroxyphenyl) -ethane, 1,1- (Hydroxyphenyl) -butane, 1,1-bis- (hydroxyphenyl) -ether, 1,1-bis- (hydroxyphenyl) -ketone, 1,1- (Hydroxyphenyl) -sulfoxide, 1,1-bis- (hydroxyphenyl) -sulfoxide, 1,1-bis (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) -1-phenylethane, 1,6-bis- (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2- Hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2- 2-bis- (3-phenyl-4-hydroxyphenyl) (3-n-propyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3-bromo-4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether,?,? ' (4-hydroxyphenyl) -toluene and?,? '- bis- (4-hydroxyphenyl) -p-diisopropylbenzene,

Wherein the aryl carbonate is selected from the group consisting of diphenyl carbonate, dicyclopentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenetyl carbonate, di (phenylpropyl) carbonate, Di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, butylphenyl-phenyl carbonate, dibutylphenyl carbonate, isobutylphenyl-phenyl carbonate, diisobutylphenyl carbonate, (N-hexylphenyl) carbonate, cyclohexylphenyl-phenyl carbonate, dicyclohexylphenyl carbonate, phenylphenol-phenyl carbonate, phenylphenyl carbonate, Diphenylphenol carbonate, isooctylphenyl-phenyl carbonate, di (N-nonylphenyl) carbonate, cumylphenyl-phenyl carbonate, dicumylphenyl carbonate, naphthylphenyl-phenyl carbonate, dinaphthylphenyl carbonate, di-tert-butylphenyl carbonate, Di (tert-butylphenyl) carbonate, dicumylphenyl-phenyl carbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phenyl carbonate, di (4-phenoxyphenyl) carbonate , 3-pentadecylphenyl-phenyl carbonate, di (3-pentadecylphenyl) carbonate, tritylphenyl-phenyl carbonate and dityrylphenyl carbonate. .

In addition, the step (a) may further comprise a step of reacting the compound of formula (I) with a reducing agent such as sodium hydrogencarbonate, potassium hydroxide, tetraphenylphosphonium tetraphenylborate, tetramethylammonium hydroxide tetraphenyl, sodium hydrogencarbonate, calcium acetate, lithium acetate, lithium hydride, Wherein the polymerization is carried out using at least one member selected from the group consisting of butyl tin oxide, sodium phenolate and hydrogen fluoride as polymerization catalysts.

And the surface-crystallized polycarbonate prepolymer has a crystallinity of 20 to 50%.

According to the present invention, polycarbonate is crystallized by using a tumbler type reactor, the loss of the reactants is small, the crystallization rate is increased, and the size of the crystal is miniaturized, so that the polycarbonate having greatly increased crystallinity can be manufactured , The outer wall of a highway requiring a high viscosity property, and a bottled water bottle

1 is a graph showing a Tm of a polycarbonate prepolymer prepared by the method of Example 1, measured using a differential scanning calorimeter (PERKINELMER, DIAMOND DSC)
FIG. 2 is a graph of Tm of a polycarbonate solid polymer prepared by the method of Example 1, using Differential Scanning Calorimeter (PERKINELMER, DIAMOND DSC).

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as " including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

Conventional polycarbonate resins are synthesized through interfacial polymerization or melt polymerization, but they use a large amount of chemicals and solvents which are harmful to humans and the environment and react at high temperature to cause side reaction and yellowing. Further, it is difficult to synthesize high molecular weight polycarbonate by melt polymerization. Therefore, solid-state polymerization processes have been studied to overcome the problems of the two polymerization processes. However, the polymerization rate is slow due to the polymerization at a rather low temperature and the molecular weight of the polycarbonate resin is limited. In addition, Which is not easily escaped, leads to a reverse reaction, which makes it difficult to obtain a high molecular weight polycarbonate resin. Therefore, a method of synthesizing a polycarbonate prepolymer having a low molecular weight and crystallizing the polycarbonate prepolymer having a low molecular weight has been carried out to obtain a polycarbonate having a high molecular weight while shortening the reaction time by progressing solid-state polymerization. The present inventors have observed that when a crystallization method using a solvent is used, a polycarbonate prepolymer is cracked due to a direct physical factor such as an impeller when a generally used impeller type reactor is used and the yield is lowered. It has been found that when the tumbler type reactor is used, the reactor itself is turned and the crystallization by the solvent is performed purely, and the direct physical impact on the sample is reduced, so that the polycarbonate prepolymer is prevented from being broken, And a polycarbonate resin showing a high viscosity property can be obtained after the solid phase polymerization, and this destruction is completed.

Accordingly, the present invention provides a process for producing a polycarbonate resin composition, comprising: (a) polymerizing an amorphous polycarbonate prepolymer using an aromatic hydroxy compound and an aryl carbonate; (b) surface-crystallizing the amorphous polycarbonate prepolymer using a tumbler type reactor; And (c) subjecting the surface-crystallized polycarbonate prepolymer to solid phase polymerization; &Lt; RTI ID = 0.0 &gt; polycarbonate &lt; / RTI &gt;

Hereinafter, the crystallization process using the tumbler type reactor according to the present invention will be described in detail.

(1) Polycarbonate Prepolymer  And manufacturing method thereof

In the first step of the polycarbonate polymerization process according to the present invention, an amorphous polycarbonate prepolymer is polymerized using an aromatic hydroxy compound and an aryl carbonate.

Preferably, the polycarbonate prepolymer having a repeating unit represented by the following formula (2) can be polymerized by melt-kneading the monomer represented by the following formula (1) and the aryl carbonate.

[Chemical Formula 1]

(2)

에서 선택되는 그룹을 나타내며, R3 및 R4는 독립적으로 수소원자, 탄소수 1 내지 20의 알킬 그룹, 탄소수 4 내지 20의 사이클로알킬 그룹 또는 탄소수 5 내지 20의 아릴 그룹 또는 탄소수 6 내지 20의 융합고리로부터 선택된다.)(Wherein R1 and R2 in the formulas (1) and (2) are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, a and b are independently 0 X is a chemical bond or an oxygen atom, a sulfur atom, -SO ₂ - group, an aliphatic radical having 1 to 20 carbon atoms, or

And R 3 and R 4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, or a fused ring having 6 to 20 carbon atoms do.)

Examples of the monomer represented by Formula 1 include 1,1-bis- (hydroxyphenyl) -methane, 1,1-bis- (hydroxyphenyl) -ethane and 1,1-bis- (hydroxyphenyl) (Propyl) -propane, 1,1-bis- (hydroxyphenyl) -butane, 1,1-bis- (hydroxyphenyl) (Hydroxyphenyl) -sulfone, 1,1-bis- (hydroxyphenyl) -sulfone, 1,1-bis- (hydroxyphenyl) -cyclohexane, Sulfoxide, 1,1-bis- (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) Phenyl-1,6-hexanedione, 2,2-bis- (4-hydroxyphenyl) propane, 2,2- (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis- (3-methoxy- Propane, 2,2-bis- (3-phenyl-4-hydroxy Propane, 2,2-bis (3-n-propyl-4-hydroxyphenyl) propane, 2,2- (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (3-bromo-4-hydroxyphenyl) propane, 2,2- (4-hydroxyphenyl) -2-methylbutane, trans-2,3-bis (4-hydroxyphenyl) -2-butene, ethylene glycol- (4-hydroxyphenyl) -toluene, and?,? '-Bis- (4-hydroxyphenyl) -p-diisopropylbenzene. Examples of the aryl carbonate include diphenyl carbonate, dicyclo Pentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenetyl car (Phenylbutyl) carbonate, p, p'-dinitrodiphenyl carbonate, butylphenyl-phenyl carbonate, dibutylphenyl carbonate, isobutylphenyl-phenyl carbonate, diisobutylphenyl carbonate (n-hexylphenyl) carbonate, n-hexylphenyl-phenyl carbonate, di (n-hexylphenyl) carbonate, N-octylphenyl-phenyl carbonate, n-nonylphenyl-phenyl carbonate, n-octylphenyl-phenyl carbonate, dicyclohexylphenyl carbonate, phenylphenol-phenyl carbonate, diphenylphenol carbonate, Nonylphenyl) carbonate, cumyl phenyl-phenyl carbonate, dicumyl phenyl carbonate, naphthylphenyl-phenyl carbonate, Di (tert-butylphenyl) carbonate, dicumylphenyl-phenyl carbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phenylcarbonate, di (4-phenoxyphenyl) carbonate, 3-pentadecylphenyl-phenylcarbonate, di (3-pentadecylphenyl) carbonate, tritylphenyl-phenylcarbonate and ditertiylphenylcarbonate.

Most preferably, the aromatic hydroxy compound is 2,2-bis (4-hydroxyphenyl) propane represented by the following formula (1a), wherein the aryl carbonate is diphenyl carbonate, and the amorphous The polycarbonate prepolymer may include a repeating unit represented by the following formula (2a).

[Formula 1a]

(2a)

In the step (a), when the polymerization is carried out, sodium hydrogen carbonate, potassium hydroxide tetraphenylphosphonium tetraphenylborate, tetramethylammonium hydroxide tetraphenyl, sodium hydrogencarbonate, calcium acetate, lithium acetate, lithium hydride, magnesium chloride, Butyl tin oxide, sodium phenolate, hydrogen fluoride or the like, and more preferably sodium hydrogen carbonate or potassium hydroxide can be used.

(2) Polycarbonate Prepolymer  Crystallization method

The polycarbonate prepolymer having a repeating unit represented by the above-described formula (2) was impregnated in a non-solvent at a volume ratio of 1: 1 to 5, and then rotated at 100 to 500 rpm for 20 minutes to 3 hours using a tumbler type reactor, The surface of the carbonate prepolymer is crystallized.

In the present invention, the non-solvent may be any non-solvent in which the form of the amorphous polycarbonate prepolymer can be maintained. Preferred examples thereof include water, alcohols, glycols, acetone, etc., Preferably, acetone can be used.

In the present invention, the mixing ratio of the prepolymer and the non-solvent may be preferably 1: 1 to 4, more preferably 1: 1 to 3. When the volume ratio is less than 1: 1, the ratio of the polycarbonate prepolymer is relatively high, so that crystallization may not proceed to the desired degree. When the volume ratio is more than 1: 5, It can be economically disadvantageous to use quantitative cost

On the other hand, the polycarbonate prepolymer impregnated with the non-solvent is rotated at a rate of preferably 100 to 500 rpm, more preferably 200 to 400 rpm, preferably 30 to 2 hours, more preferably 30 Min to 1 hour and 30 minutes. When the rotation speed and the rotation time of the tumbler type reactor are less than the preferable range, the surface crystallization of the polycarbonate prepolymer may not proceed sufficiently. When the rotation speed and the rotation time exceed the above preferable range, The yield may be lowered.

The crystalline polycarbonate prepolymer mixture prepared by the above method has a crystallinity of 20 to 50%, preferably 20 to 40%, more preferably 25 to 40%, and most preferably 25 to 35%.

The yield of the crystalline polycarbonate prepolymer obtained by surface crystallization of the polycarbonate prepolymer using the tumbler type reactor according to the above method is 80 to 95%, preferably 85 to 95%, and most preferably 90 to 95% .

Thereafter, the crystallized polycarbonate prepolymer can be separated by separating the non-solvent and drying the separated crystalline polycarbonate prepolymer by a continuous vacuum drying process or a continuous dehumidification drying process or a continuous hot-air drying process.

(3) Polycarbonate Crystallinity Prepolymer Solid state polymerization

The crystalline polycarbonate prepolymer mixture prepared by the above method is maintained at a temperature of 50 to 200 ° C, preferably 120 to 200 ° C, for a predetermined period of time and subjected to preliminary solid phase polymerization. Through the preliminary solid phase polymerization, the melting temperature of the crystalline polycarbonate prepolymer mixture is increased to 200 ° C, preferably 220 ° C or more. The preliminary solid phase polymerization is terminated and the solid phase polymerization is carried out at a temperature of 180 to 250 ° C, preferably 200 to 230 ° C, for a certain period of time. At this time, the solid phase polymerization proceeds in a nitrogen gas atmosphere or a vacuum state, and phenol is removed in the surface-crystallized polycarbonate prepolymer mixture.

The finally produced polycarbonate may have a glass transition temperature (占 폚) of 150 to 170 占 폚, and preferably 150 to 160 占 폚. If the glass transition temperature is lower than 150 ° C., the viscosity of the resulting polycarbonate may be lowered to deteriorate the physical properties. If the glass transition temperature is higher than 170 ° C., the workability may be deteriorated. The polycarbonate may have a melt flow index of 2 to 10 g / 10 min, preferably 2 to 7 g / 10 min, more preferably 2 to 5 g / 10 min, and most preferably 3 to 4 g / 10 min. The melt flow index is an index showing the workability. When the melt flow rate is less than 2 g / 10 min, the flowability during processing is not good and the defective rate is high or a lot of energy is required. The physical properties may be reduced. The polycarbonate may have a molecular weight of 25,000 to 40,000, preferably 30,000 to 40,000, more preferably 31,000 to 40,000, and most preferably 32,000 to 40,000.

Hereinafter, a specific embodiment of the present invention will be described.

Polycarbonate Prepolymer  Produce

A bisphenol-A and diphenyl carbonate (bisphenol-A / diphenyl carbonate molar ratio = 1.05) and KOH (500 ppb relative to the charged BPA) were charged to a 1 L reaction flask wrapped in a heating mantle. The raw materials were melted while maintaining the temperature of the heating mantle at 180 占 폚, reacted for 30 minutes while stirring, elevated to 210 占 폚 of the heating mantle, and further reacted for 30 minutes. Thereafter, the internal vacuum degree was reduced to 30 torr, 50 torr, and 25 torr, respectively, and 30 dispersion reactions were performed. The vacuum degree in the reactor was reduced to 10 Torr and the temperature of the heating mantle was increased to 230 deg. C, 250 deg. C and 270 deg. C, respectively, for 20 minutes to prepare a polycarbonate prepolymer.

Example

The polymerized polycarbonate prepolymer was pulverized in the above-mentioned manner to obtain a powder form. Powder type polycarbonate prepolymer was impregnated in acetone at a volume ratio of 1: 2 at room temperature. At this time, a non-impeller type tumbler type reactor was used as the reactor. The reactor was rotated at 300 rpm. The powdery polycarbonate prepolymer impregnated with acetone was obtained as a white powder in a crystalline form within 1 minute, and a crystalline polycarbonate prepolymer was obtained after stirring for about one hour. After completion of the reaction, the reaction mixture was filtered through a plate and dried at 70 ° C for one day to remove all the acetone to obtain a crystalline polycarbonate prepolymer. The crystalline polycarbonate prepolymer prepared by the above method was allowed to stand for 5 hours at a flow rate of 45 L / min under a nitrogen flow condition of 160 DEG C, and then allowed to stand for 5 hours at a flow rate of 45 L / min at 190 DEG C for preliminary crystallization . Thereafter, the solid phase polymerization was carried out at a flow rate of 220 L / min at 45 L / min for 20 hours to prepare polycarbonate having a high molecular weight.

.

Comparative Example  One

The polymerized polycarbonate prepolymer was pulverized in the above-mentioned manner to obtain a powder form. Powder type polycarbonate prepolymer was impregnated in acetone at a volume ratio of 1: 2 at room temperature. At this time, an impeller type reactor was used. The powdery polycarbonate prepolymer impregnated with acetone was obtained as a white powder in a crystalline form within 1 minute, and a crystalline polycarbonate prepolymer was obtained after stirring for about one hour. After completion of the reaction, the reaction mixture is filtered through a plate and dried at 70 ° C for one day to remove all the acetone, and then a crystalline polycarbonate prepolymer is obtained. Thereafter, polycarbonate was prepared by solid-phase polymerization according to the method described in the above example. After the reaction, crystallized PC and solvent were separated using a 425 μm sieve and dried at 70 ° C for one day.

Comparative Example  2

A raw material and catalyst were injected into a 20 L SUS reactor heated by thermal oil under the same conditions as in Comparative Example 1. After the raw material was melted, the oil of the outer wall of the reactor was elevated to 210 DEG C while stirring, the internal vacuum degree was gradually reduced to 350 torr for 10 minutes, and then the reaction was performed at 350 torr for 30 minutes. Subsequently, the vacuum was gradually reduced to 300 torr, 250 torr, and 150 torr for 10 minutes, 20 minutes, and 20 minutes, respectively. Again, the heat of reaction in the reactor was increased to 230 DEG C and the reaction was carried out while gradually reducing the pressure in the reactor at 60 torr for 20 minutes. After that, the oil of the reactor was raised to 250 ° C and reacted at 10 torr and 5 torr while being gradually depressurized for 15 minutes. The temperature of the reactor was elevated to 270 ° C. and the reactor was reacted for 15 minutes. The temperature of the reactor was elevated to 300 ° C. and the degree of vacuum in the reactor was maintained at 1 to 2 torr. When the reaction was continued for about 30 minutes, the stirring limit was reached, at which time the reaction was terminated and the product was discharged and processed into pellets to produce a polycarbonate. After the reaction, crystallized PC and solvent were separated using a 425 μm sieve and dried at 70 ° C for one day.

Experimental Example

The properties of the polycarbonate prepared according to the Examples and Comparative Examples were measured by the following methods, and the results are shown in Tables 1 and 2 below.

[Glass transition temperature (Tg)]

The glass transition temperature (Tg) values of the polycarbonate polymers prepared in the Examples and Comparative Examples were measured according to ASTM D3418 using a differential scanning calorimeter (PERKINELMER, DIAMOND DSC).

[Melt Flow Index (MI)]

The melt flow index (MI) for the polycarbonate polymers prepared in the Examples and Comparative Examples was measured at 330 ° C under a load of 2.16 kg using a melt indexer (TOYOSEIKI, F-B01) according to ASTM D1238.

[Crystallinity]

Degree of crystallinity for the Polycarbonate crystal cargo prepared in Examples and Comparative Examples are Differential Scanning Calorimeter (PERKINELMER Co., DIAMOND DSC) heat of fusion (△ Hm) the complete melting heat quantity of the sample crystal and then measured with a castle (100%) (134 J / g) of the polycarbonate. (Crystallinity = (? Hm / 134) * 100)

[yield]

The yields of the polycarbonate crystallites prepared in the Examples and Comparative Examples were determined by weight after crystallization to the weight of the polycarbonate prepolymer before crystallization. Specifically, after crystallization relative to the weight before the crystallization (weight of the input sample), the yield was measured by the weight of PC having a size of 425 μm or more.

 [Number average molecular weight (Mn) and weight average molecular weight (Mw)] [

Polycarbonate polymers prepared in the above Examples and Comparative Examples were melted in tetrahydrofuran (THF) and then measured by GPC (Gel Permeation Chromatography, SCHAMBECK, RI2012A) while flowing at a flow rate of 1 ml / min. At this time, Mixed C and Mixed-D columns were used.

Referring to Tables 1 and 2 and FIGS. 1 and 2, in the case of the polycarbonate resin of the present invention produced using the tumbler type reactor (Example), the glass transition temperature is 150 ° C or more, the melt flow index is low The processability was also excellent. In addition, the yield of the polycarbonate prepolymer was 90% or more, and it was confirmed that effective crystallization proceeded by minimizing the cracking phenomenon by reducing the direct physical influence of the sample contacting the impeller.

On the other hand, polycarbonate (Comparative Example 1) produced by a general impeller-type reactor has a low glass transition temperature and a high melt flow index, indicating that the viscosity and processability are relatively inferior to those of Examples, and polycarbonate prepolymer Yield was also very low at 75%.

As described above, the polycarbonate resin of the present invention (Example 1) manufactured by using the tumbler type reactor and the polycarbonate produced by the general impeller type reactor (Comparative Example 1) have a higher degree of crystallization, There is an advantage that the degree of crystallization is sufficient to polymerize and the loss rate of the polycarbonate prepolymer is low.

On the other hand, in the case of the polycarbonate prepared by the general melt polymerization method (Comparative Example 2), the molecular weight was low and the melt flow index was high, which proved to be undesirable from the viewpoint of workability.

As described above, the polycarbonate of the present invention produced using the tumbler-type reactor has excellent processability and high glass transition temperature and is suitable for products requiring high viscosity properties.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (6)

(a) polymerizing an amorphous polycarbonate prepolymer using an aromatic hydroxy compound and an aryl carbonate;
(b) surface-crystallizing the amorphous polycarbonate prepolymer using a tumbler type reactor; And
(c) solid-phase-polymerizing the surface-crystallized polycarbonate prepolymer;
&Lt; / RTI &gt; The method according to claim 1,
Wherein the aromatic hydroxy compound is a monomer represented by the following formula (1).
[Chemical Formula 1]

Wherein R 1 and R 2 are independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, a and b are independently an integer of 0 to 4 X is a chemical bond or an oxygen atom, a sulfur atom, a -SO ₂ - group, an aliphatic radical having 1 to 20 carbon atoms, or

And R 3 and R 4 are independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, and a fused ring having 6 to 20 carbon atoms do.) The method according to claim 1,
The step (b) of crystallizing the surface is performed by immersing the amorphous polycarbonate prepolymer in a non-solvent in a volume ratio of 1: 1 to 5, and then rotating the polycarbonate prepolymer in a tumbler type reactor for 20 minutes to 3 hours. Lt; / RTI &gt; The method according to claim 1,
The aromatic hydroxy compound is selected from the group consisting of 1,1-bis- (hydroxyphenyl) -methane, 1,1-bis- (hydroxyphenyl) -ethane, 1,1- (Hydroxyphenyl) -butane, 1,1-bis- (hydroxyphenyl) -ether, 1,1-bis- (hydroxyphenyl) ) - cyclohexane, 1,1-bis- (hydroxyphenyl) -sulfone, 1,1-bis- (hydroxyphenyl) 1-bis- (4-hydroxyphenyl) -sulfoxide, 1,1-bis- (4-hydroxyphenyl) (3-methyl-4-hydroxyphenyl) propane, 2,2-bis- (3-ethyl- 4-hydroxyphenyl) propane, 2,2-bis- (3-allyl-4-hydroxyphenyl) propane, 2,2- Bis (3-phenyl-4-hydroxyphenyl) propane, 2, Propane, 2,2-bis- (3-n-propyl-4-hydroxyphenyl) propane, 2,2- Butyl-4-hydroxyphenyl) propane, 2,2-bis- (3-t-butyl- (4-hydroxyphenyl) propane, 2,2-bis- (3-bromo-4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) -2-butene, ethylene glycol-bis (4-hydroxyphenyl) ether,?,? ' Hydroxyphenyl) -toluene and?,? '- bis- (4-hydroxyphenyl) -p-diisopropylbenzene,
Wherein the aryl carbonate is selected from the group consisting of diphenyl carbonate, dicyclopentyl carbonate, dicyclohexyl carbonate, dicycloheptyl carbonate, dibenzyl carbonate, diphenetyl carbonate, di (phenylpropyl) carbonate, Di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, di-tert-butylphenyl carbonate, butylphenyl-phenyl carbonate, dibutylphenyl carbonate, isobutylphenyl-phenyl carbonate, diisobutylphenyl carbonate, (N-hexylphenyl) carbonate, cyclohexylphenyl-phenyl carbonate, dicyclohexylphenyl carbonate, phenylphenol-phenyl carbonate, phenylphenyl carbonate, Diphenylphenol carbonate, isooctylphenyl-phenyl carbonate, di (N-nonylphenyl) carbonate, cumylphenyl-phenyl carbonate, dicumylphenyl carbonate, naphthylphenyl-phenyl carbonate, dinaphthylphenyl carbonate, di-tert-butylphenyl carbonate, Di (tert-butylphenyl) carbonate, dicumylphenyl-phenyl carbonate, di (dicumylphenyl) carbonate, 4-phenoxyphenyl-phenyl carbonate, di (4-phenoxyphenyl) carbonate , 3-pentadecylphenyl-phenyl carbonate, di (3-pentadecylphenyl) carbonate, tritylphenyl-phenyl carbonate and dityrylphenyl carbonate. Polymerization method. The method according to claim 1,
The step (a) may be carried out in the presence of a base such as sodium hydrogencarbonate, potassium hydroxide, tetraphenylphosphonium tetraphenylborate, tetramethylammonium hydroxide tetraphenyl, sodium hydrogencarbonate, calcium acetate, lithium acetate, lithium hydride, magnesium chloride, dibutyl Tin oxide, sodium phenolate, and hydrogen fluoride as polymerization catalysts. The method for crystallizing a polycarbonate according to claim 1, wherein the polycarbonate is a polycarbonate. The method according to claim 1,
Wherein the surface-crystallized polycarbonate prepolymer has a crystallinity of 20 to 50%.

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