KR100358657B1 - A Continuous Process for the preparation of Copolycarbonate resins - Google Patents

Abstract

In accordance with the present invention, the flowability is 1.5 to 2 times higher than that of the existing polycarbonate, and the thin film molding, the complex structured molding, the compact disc (UV), and the ultraviolet (UV) blocking are maintained by maintaining the heat resistance of the general-purpose polycarbonate. It is an object to provide a process for the continuous production of copolycarbonate resins with excellent advantages for use in these required moldings.

The method of the present invention simplifies the production process by dividing the tubular reactors into one and two stages, connects them in series, and continuously synthesizes them, and changes the reaction rate while changing variables such as Reynolds number, material loading rate, and Weber constant. This is accomplished by a novel polymerization process in which the comonomer is introduced completely into the polymer backbone.

Description

A continuous process for the preparation of copolycarbonate resins

The present invention relates to a method for producing a copolycarbonate resin. More specifically, the flowability is 1.5 to 2 times higher than that of the existing polycarbonate, and the thin film molding, the complex structure molding, the compact disc (UV) and the ultraviolet (UV) are maintained by maintaining the heat resistance of the general-purpose polycarbonate. It relates to a process for the continuous production of copolycarbonate resins with excellent advantages for use in moldings requiring blocking.

In general, aromatic polycarbonates are excellent in mechanical properties such as tensile strength and impact resistance, and have been widely used for industrial purposes due to their excellent dimensional safety, heat resistance, and optical transparency. However, it has a disadvantage of poor workability due to its higher melt viscosity when processing than other polymers, and it is difficult to manufacture a complicated structure and a thin molding.

For this reason, there have been many efforts to overcome these problems continuously. However, efforts to lower the viscosity in the molten state while maintaining the advantages of the existing polycarbonate was not a simple problem.

An example of such an attempt was the first use of plastic plasticizers. Plasticizers are generally used together with thermoplastic resins to achieve greater melt flow, but have brittleness (crushing properties), and also have a problem of causing deterioration of existing physical properties.

Next, the flowability could be improved by using a molecular weight regulator of phenols substituted with long aliphatic chains or by forming a low molecular weight polymer, but the original purpose was to lower the Notched Izod Impact Strength and cause brittleness. No results were obtained that correspond to.

Alternatively, the use of bisphenol A derivatives greatly increases the flowability by using bisphenols having aliphatic long chains, but the problem remains in addition to the high cost of raw materials and impact strength.

As another method, a blend with another polymer can be considered. This method could also improve the flowability, but it was not a fundamental solution because it impaired the transparency and other properties of polycarbonate.

As this effort is limited, US Patent No. 3,169,121 to Goldberg et al. Introduces long chain aliphatic ester derivatives into the polymer chain that act as a soft part of a polymer chain consisting of hard bisphenol A. It is described that copolycarbonates with low transition temperature (Tg) and improved flowability can be obtained, and that aliphatic dibasic acid derivatives are suitable as aliphatic ester derivatives.

However, the method presented in this patent requires the use of a pyridine solvent, and there is a problem in the color tone of the final product by using aliphatic dibasic acid chloride which is a colored aliphatic ester derivative. Therefore, there is always a problem of removing the pyridine solvent in the polymer in the manufacturing process, the problem of coloration of the final product, the price of aliphatic dibasic acid chloride, and the supply of bulk raw materials from a commercial point of view. .

Therefore, studies have been continued focusing on raw materials containing long aliphatic chains using an interfacial method to simultaneously solve solvent removal and color problem.

As a suitable material (comonomer), it has been found that aliphatic dibasic acid, which is relatively easy to supply raw materials and is inexpensive, is suitable. Kochanowski, US Pat. No. 4,286,083, one of those who used these raw materials and studied the interfacial method, described two monomers with different reactivity (e.g., bisphenol A and aliphatic dibasic acids). When conducting a phosgenation reaction using a derivative), it is reported that the pH can be completed by adjusting the pH in two steps.

In other words, the aliphatic dibasic acid and bisphenol A are subjected to phosgenation reaction at pH 4.5 to 8, preferably pH 5.5 to 6.5, so that the aliphatic dibasic acid is reacted with bisphenol A while converting the aliphatic dibasic acid to aliphatic dibasic chloride. To 11.5 to complete the oligomerization and polycondensation reactions.

However, only 10% of adipic acid using 10 mol% of the main monomer bisphenol A is introduced into the polymer backbone.

As such, even though the reaction is performed by adjusting the pH in two stages, a large amount of unreacted material is present, and there is a disadvantage in that productivity is lowered compared to the continuous reaction by adopting a batch reaction for pH adjustment.

In addition, efforts have been made by several people to partially improve Kochanosky's methods. One method is to improve the reaction rate by using this base acid as the base salt rather than in the neutral state (US Pat. No. 4,677,183). However, this method also adopts a batch method, and it is necessary to adjust the pH in two stages to increase the reaction rate while minimizing side reactions.

Meanwhile, further efforts have been made by introducing long-chain aliphatic ester derivatives that act as soft parts into the polymer chain, and by using phenol derivatives substituted with paracumyl, isooctyl, and isononyl instead of phenol as end terminators. One method is to obtain improved physical properties (US Pat. Nos. 4,774,315, 4,788,275). However, this method also employs a batch method, and there are still disadvantages of reacting by adjusting the pH in two steps.

Such efforts have resulted in improved polymers due to modification of existing polycarbonates with high viscosity in the molten state during processing. However, the problem of increasing the reaction rate and the difficulty of the production process still need to be solved. Remained. This simplifies the reaction process and requires the adoption of a new polymerization process that completes the backbone introduction of other reactive comonomers.

On the other hand, these aliphatic ester derivatives were introduced into the polymer chain to improve the processability and fluidity of the polycarbonate, but the addition of soft components showed another problem of poor heat resistance. Normal aromatic polycarbonate has a heat resistance (heat deformation temperature) of 135 degrees, but polycarbonate having aliphatic ester derivatives introduced into the polymer chain has a heat resistance of about 110 degrees.

As a method for increasing the heat resistance of aromatic polycarbonates, a technique of introducing polyesters having improved heat resistance by introducing aromatic ester derivatives into a polymer chain has been introduced (US Pat. Nos. 5,010,146 and 5,010,146). 5,010,177, 5,110,895 and Japanese Patent Nos. 56-822, 56-2323, 57-12929, 60-179421, and 63-159467. However, these methods did not solve both heat resistance and fluidity at the same time considering only the heat resistance of polycarbonate.

Conventional techniques require that the pH control be made in two stages while the carbonate precursor (phosgene) is introduced in the phosgenation step in order to react differently reactive monomers (eg, bisphenol A and aliphatic dibasic acid derivatives) with the carbonate precursor. By completing the reaction while reducing the reactants, it was possible to prepare a polyester carbonate with improved fluidity while maintaining the properties of the existing polycarbonate. This was only possible with batch reactions. That is, the pH had to be adjusted in multiple stages using a cylindrical reactor.

In addition, the conventional method used phosgene 1.3-1.5 times or more for the combination of bisphenol A and aliphatic dibasic acid to reduce unreacted substances. However, this is not only an increase in manufacturing costs, but also a large amount of HCl (hydrochloric acid) causes a decrease in pH, which is undesirable to increase the molecular weight during oligomerization and polycondensation reaction.

However, the present inventors have continued efforts to overcome these limitations, and as a result, the viscosity in the molten state during processing is lower than that of the conventional general-purpose polycarbonate, so that the processing is easy, and the heat resistance maintains the heat resistance of the conventional general-purpose polycarbonate. We have found a method of producing copolyester carbonate with excellent physical properties which is superior in terms of productivity and quality uniformity, which uses a tube-type reactor to simplify the production process (for example, In contrast to the reaction in which the pH is divided into two stages using a general batch reactor in the form of a cylinder, the tubular reactor is divided into one and two stages, and connected in series and continuously synthesized.), Reynols Number The reaction rate of the polymer can be increased by increasing the reaction rate by changing the parameters such as the material velocity (Linear Velosity) and the Weber Number (Weber Number). In may be achieved by the novel polymerization process to completely introduced.

Accordingly, a first object of the present invention is to provide a method for continuously producing a copolycarbonate suitable for producing a molded article having a thin and complicated structure.

It is a second object of the present invention to provide a continuous method for producing a resin of copolycarbonate having excellent color without unreacted material in the phosgenation reaction and excellent physical properties such as UV blocking property.

The third object of the present invention is to use two tubular reactors in succession, instead of using a general batch reaction in which pH control is multistage during the phosgenation reaction. It is an object of the present invention to provide a method for continuously producing a copolycarbonate resin having superior and uniform product quality.

A fourth object of the present invention is to provide a continuous method for producing a copolycarbonate resin that can increase the reaction rate without using unreacted phosgene economically (minimizing the use of phosgene).

1 is a diagram illustrating a process for phosgenation reaction using first and second tubular reactors, and oligomerization and polycondensation reactions using a reactor in the form of a general cylinder.

<Description of the symbols for the main parts of the drawings>

10 --- first tube reactor 20 --- second tube reactor

30,40 --- Cylindrical reactor 50 --- Pump

The present invention is a continuous production method of copolycarbonate resin is made from dihydric phenol, aliphatic dibasic acid, aromatic dibasic acid and carbonate precursor and molecular weight adjusting agent to control the molecular weight, productivity by overcoming the difference in the reactivity of the monomers by pH control It is characterized in that the use of two tubular reactors in series to maximize the.

That is, the present invention is the primary reaction of aliphatic dibasic acid salts and aromatic dibasic salts in the second tubular reactor in the pH range lower than the pH range of the phosgene and the first tubular reactor to convert the basic acid salts to the basic acid chloride. After the phosgenation reaction, the basic acid chloride produced in the above reaction is introduced into the first tube reactor, and the bisphenol A-salt and the phosgene, which are the main monomers, are added and continuously reacted. And simultaneously adding a catalyst to the first tubular reactor to perform a secondary phosgenation reaction;

Performing a oligomerization reaction by transferring a reaction product of the phosgenation reaction using the tubular reactor to an oligomerization reactor and adding a molecular weight regulator and a catalyst; And

The step of conducting the polycondensation reaction by putting the organic solvent layer separated from the reaction product of the oligomerization reaction is completed into the polycondensation reactor, the first and second tubular reactors are connected in series to perform the reaction in a continuous manner It is characterized in that the continuous production method of the copolycarbonate resin.

The dihydric phenols used in the present invention may include all substances derived from compounds represented by the following structural formulas.

In the above structural formula, X may have no alkyl group or functional group, or may have functional groups such as sulfide, ether, sulfoxide, sulfone or ketone or linear, branched or cyclic alkyl group,

R ₁ and R ₂ are hydrogen, a halogen atom, a linear, branched or cyclic alkyl group,

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

Preferred X is a linear, branched or cyclic alkyl group structure containing 1 to 10 carbon atoms.

Suitable examples of dihydric phenols include the following.

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 [aka bisphenol A], 2,2-bis (4-hydroxyphenyl) 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) methane, lesosi , Hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl 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) cyclonucleic acid, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclonucleic acid, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclonucleic acid, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane, 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-hydrate 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-hydroxy Phenyl) 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'-di Hydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydro quinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene.

Other dihydric phenols are described in detail in US Pat. Nos. 2,999,835, 3,028,365, 3,153,008, 3,334,154, and 4,131,575 and the like. Various dihydric phenols used herein can be used alone or in combination with each other.

In addition, examples of aliphatic dibasic acids, which are one of important monomers used in the present invention, may include all substances derived from the following structural formulas.

In the above structure, A may be a linear, branched and cyclic aliphatic alkyl group having no functional group, or may have a linear, branched or cyclic aliphatic alkyl structure including functional groups such as sulfide, ether, sulfoxide or sulfone. Preferred structure of A for giving high polyolefin flexibility is a linear aliphatic alkyl group containing 6 to 20 carbon atoms.

Representative examples of aliphatic dibasic acids that can be used as comonomers important in the present invention are as follows.

Malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2-ethyl-2-methylsuccinic acid, 2,3-dimethylsuccinic acid, meso-2 , 3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4-dimethylglutaric acid, 3,3-dimethylglutaric acid , Adipic acid, 3-methyladipic acid, 2,2,5,5-tetramethylhexanedioic acid, pimalic acid, subbeic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, 1,11-undecanoic acid , Hexadecanoic acid, decanoic acid or tetracoic acid.

In addition, saturated aliphatic base acids such as branched and cyclic dibasic acids and dibasic acids of unsaturated aliphatic can also be used, and these substances can be used in combination. The small chain length of the double aliphatic alkyl group is difficult to prepare a desired level of copolycarbonate when introduced into the main chain on a divalent phenol basis. Therefore, it is effective that the alkyl group has 6 or more carbon atoms than adipic acid, and sebacic acid or dodecanoic acid can sufficiently satisfy the desired level of physical properties. Therefore, the most suitable raw materials are sebacic acid or dodecanoic acid in consideration of raw material price and physical property satisfaction.

The content can be determined in consideration of the flowability while maintaining the basic physical properties, 3 to 30 mol% is suitable for the main monomer divalent phenol. This is because the amount of the molar% may vary depending on the chain length of the aliphatic base acid, and the physical properties may also vary depending on the content. If the content is less than 3 mol%, the effect of high flow is less, and if it exceeds 30 mol%, the polycarbonate falls far below the basic mechanical properties. Preferably 5-20 mol% is the most suitable.

Another important monomer used in the present invention is, for example, aromatic dibasic acids, terephthalic acid, isophthalic acid or mixtures thereof. Or terephthaloyl chloride, isophthaloyl chloride in the form of their halides may be used, but monomers are expensive and careful attention is required for storage and use.

The content of the aromatic dibasic acid salt used in the present invention is suitably 5 to 20 mol% based on the dihydric phenol which is the main monomer. If it is 5 mol% or less, the heat resistance of the general-purpose polycarbonate will not be shown, whereas if it is 20 mol% or more, it will not show high fluidity. Especially preferably, it is 10-15 mol%.

On the other hand, the carbonate precursor used in the present invention is generally advantageous to phosgene (for example, carbonyl chloride) commonly used in solution and interfacial methods, in addition to carbonyl bromide, bis halo formate, diphenyl carbonate or Dimethyl carbonate and the like can also be used. It is also possible to use them in combination.

As the molecular weight regulator, a monohydric phenol, which is a monofunctional phenolic compound similar to a known material, that is, a monomer used for preparing polycarbonate, is used. Suitable examples of such molecular weight modifiers include p-isopropyl phenol, p-tert-butyl phenol, p-cumyl phenol, p-isooctyl phenol or p-isononyl phenol, which are phenol-based derivatives. In addition, various kinds of substances such as aliphatic alcohols can be used. The amount of the molecular weight modifier used is preferably 1 to 5 mol%, preferably 1.5 to 3 mol%, based on the dihydric phenol.

The catalyst used in the present invention uses amines catalysts which are also generally known. Commonly used catalysts include tertiary alkyl amines, for example triethylamine. Meanwhile, tetraethyl ammonium chloride, which is a halogen salt of quaternary ammonium, can be used, and amidine or guanidine can also be used. The amount of the catalyst used is 0.25 to 5 mol%, preferably 0.5 to 2.5 mol%, based on the dihydric phenol.

In general, in the case of homo polycarbonate, the phosgenation reaction using one monomer can be prepared at a certain pH range in one step. In addition, in the case of preparing a branched polycarbonate using two different monomers having the same functional group (hydroxy group) (for example, bisphenol A, 1,1,1-tris (4-hydroxyphenyl) ethane) It is possible to manufacture in the pH range.

However, for the production of branched polycarbonates using monomers that do not have the same functional groups (eg bisphenol A, trimellitic acid) the pH control must be adjusted in two stages.

The monomers used in the present invention (eg, bisphenol A, dicarboxylic acid) have different functionalities (eg, hydroxy groups, ester groups) from different reactivity, so that the monomers (eg, bisphenol A, dicarboxylic acid) have a different pH range in one step. It is difficult to complete the reaction without reactants. Therefore, in the phosgenation reaction, two different pH ranges should be selected to complete the reaction.

According to the method of the present invention, since the reactivity with aliphatic dibasic acid is relatively inferior to the dihydric phenol, the first phosgenation reaction is performed at a lower pH range in the first tubular reactor using the second tubular reactor. .

At this time, the pH range of the second tubular reactor is preferably 7.0 to 9.0, more preferably in the range of 7.5 to 8.5, the aliphatic dibasic acid is first reacted with a carbonate precursor to convert the aliphatic dibasic acid salt to aliphatic dibasic acid chloride. Subsequently, the secondary phosgenation reaction takes place with divalent phenol, a main monomer, and a carbonate precursor in a first tubular reactor having a pH range of 9.5 to 13, preferably 10.5 to 12.5.

If the passage time (for example, residence time) of the first tubular reactor is longer than necessary, the anhydride production increases, which may cause deterioration of the physical properties of the final product, but the reaction time should be well controlled. Reaction with the carbonate precursor in the first tubular reactor is converted to the carbonyl chloride form, thereby completely eliminating side reactions.

A detailed response to this is described in US Pat. No. 3,318,950. If necessary, in the case of using a second tubular reactor, an amine catalyst may be used to further promote the reaction of the base acid salt.

According to the present invention, copolycarbonates having a flowability of 1.5 times or more within the same molecular weight range by irregularly introducing aliphatic dibasic acids and aromatic dibasic acids having 8 to 20 carbon atoms into the general polycarbonate backbone consisting of bisphenol A Could get

After the phosgenation reaction, the oligomerization reaction and the polycondensation reaction are continuously performed using a reactor in the form of a general cylinder. Here, the number of reactors may be limited as needed, but considering the uniformity of productivity and quality, it is also preferable to use several reactors.

1 of the accompanying drawings shows a process for the phosgenation reaction using the first and second tubular reactors, and oligomerization and polycondensation reactions using the reactor in the form of a general cylinder, which is made through these three steps The copolycarbonates according to the invention are made in a continuous manner, which makes the pH adjustment in the phosgenation step simpler than in a conventional batch reaction system and in which the product quality is constantly managed.

The method of the present invention will be described in more detail with reference to the accompanying drawings.

The present invention uses two tubular reactors each having a constant inner diameter and tube length instead of the general reactor, and in the second tubular reactor 20 of FIG. 1, aliphatic dibasic and aromatic dibasic materials are converted into dibasic chloride form. Minimize the use of carbonate precursors, especially phosgene materials, while maximizing the conversion of phosgenation in the first tubular reactor (10), the main tubular reactor, resulting in maximum productivity and product quality uniformity in terms of overall reaction. Becomes.

That is, the present invention is an aliphatic dibasic acid salt (DA-Na), for example sebarate (SCA-Na), which is a raw material prepared in the second tubular reactor 20 having an inner diameter of 3.5 mm and a tube length of 8 m. Aromatic dibasic salts (DA-Na), for example terephthalic acid salts (TPA-Na) and an organic solvent, for example methylene chloride (MC), are added simultaneously with a carbonate precursor such as phosgene (CDC). It is charged at a flow rate of 0.5 to 2.0 kg / h, preferably 1.0 to 1.5 kg / h. At this time, it is important to maintain the pH in the second tubular reactor 20 to 7.0 to 9.0.

Reynolds number of the second tube reactor 20 is preferably 20,000 to 50,000, preferably 30,000 to 45,000, the number of webbers 25,000 to 40,000, preferably 30,000 to 38,8. Cloth is suitable. In addition, the reaction flow rate is suitably 1 to 3 m / sec, preferably 1.5 to 2.5 m / sec. The residence time in the second tubular reactor 20 is 5 to 10 seconds, preferably 6 to 8 seconds.

Most of the material produced through the second tubular reactor is converted from this base salt to the base acid chloride form, and in part, only one side thereof is converted to the base acid chloride. Less than 10%.

If necessary, the above-mentioned tertiary amines or quaternary amines can be added as a catalyst in order to promote the reaction of this basic acid with phosgene.

According to the present invention, a divalent phenol such as bisphenol A-salt (BPA-Na) and an organic solvent such as methylene chloride (MC) are the first having an inner diameter of 15 mm and a tube length of 30 m. 5-20 kg / h, preferably 10-15 kg, of carbonate precursor phosgene (CDC) is introduced into the tubular reactor 10 while allowing the basic acid chloride produced in the second tubular reactor 20 to be introduced. Feed at a flow rate of / h. At this time, it is important to maintain the pH in the first tubular reactor 10 to 9.5 to 13.

Reynolds number of the first tubular reactor 10 is suitable for 40,000 to 80,000, preferably 50,000 to 70,000, Weber number 30,000 to 50,000, preferably 35,000 to 45,000 is suitable Do. In addition, the reaction flow rate is 3 to 6 m / sec, preferably 3.5 to 5 m / sec. The residence time in the first tubular reactor 10 is suitably 8 to 20 seconds, preferably 10 to 17 seconds.

According to the method of the present invention, in the case of the first tubular reactor 10, the temperature of the reactants after the phosgenation reaction is maintained at 25 to 30 ° C. using a heat exchanger. The molecular weight of the resulting material is 500 to 2,000, preferably 1,000 to 1,500. LC analysis showed that no unreacted or sub-reactant remained. In the case of using the conventional batch reactor, even if the pH control in two stages, the unreacted substance is present, so the problem of reuse of the unreacted substance has always occurred.

As described above, the reaction product after the phosgenation reaction using the tubular reactor is transferred to the oligomerization reactor 30, which is a general reactor, by using a pump 50, in which a molecular weight regulator, for example, p-tert-butyl phenol Is added according to the desired final molecular weight (based on dihydric phenol) and a catalyst, for example triethylamine (TEA), is added to make the molecular weight 2,000 to 5,000, preferably 3,000 to 4,000.

After the oligomerization reaction, the organic solvent layer and the water layer are separated to introduce an organic phase into the polycondensation reactor 40, and the concentration is 10 to 20% by weight, preferably 10 to 15% by weight, using 33% by weight of the organic solvent. % Sodium hydroxide solution is added to maintain the water phase ratio (aqueous volume / total volume) of 15 to 30%, preferably 20 to 25%, while maintaining the pH at 10 to 14, preferably 12 to 13.

In addition, although one reactor may be used in the polycondensation step, several reactors may be used continuously. However, since the degree of polymerization is finally determined according to the amount of the catalyst, the catalyst may be added in several stages. In the present invention, it is preferable to add the catalyst divided into two stages in order to lead the efficient reaction while continuing the entire reaction.

After completion of the polycondensation reaction, the organic solvent methylene chloride (MC) and distilled water are used for alkali washing and then separated. Subsequently, the organic phase is washed with 0.1 N hydrochloric acid (HCl) solution, followed by three successive washings with distilled water. When the aqueous layer separated after alkali washing was confirmed by unreacted basic acid by liquid chromatography, the unreacted product was not detected but was completely reacted with the polymer backbone.

On the other hand, when the cleaning is completed, the concentration of the organic phase in which the copolycarbonate is dissolved is adjusted to perform granulation at 40 to 60 ° C, preferably 45 to 55 ° C. When the assembly is complete, it is dried for 10 hours at 100 ℃, 5 hours at 110 ℃, 2 hours at 120 ℃. After the drying process, the copolycarbonate was analyzed. NMR, thermal analysis (Tg), melt flow index (MFI), viscosity average molecular weight (Mv), and residual oligomer amount in the polymer were measured, indicating that the reaction was completed. The melt flow index of the copolycarbonate also showed a flowability of 1.5 to 2 times in the same molecular weight range as the conventional general-purpose polycarbonate, and the processing temperature was about 20 ° C. lower than that of the conventional polymer.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following Examples.

Example 1

Raw material sebarate prepared in the second tubular reactor 20 having an inner diameter of 3.5 mm and a tube length of 8 m (SCA-Na: a solution made by dissolving 7 kg of sebacic acid in 42.5 L in a 5.6 wt% NaOH solution) and terephthalic acid Salt (TPA-Na: a solution made by dissolving 5 kg of terephthalic acid in 42.5 L in a 5.6 wt% NaOH solution) and methylene chloride (MC) were added, and phosgene was added at a flow rate of 1.2 kg / h. At this time, the pH in the second tubular reactor 10 was maintained at 8.2.

Most of the material produced through the second tubular reactor 10 is converted from the base salt to the base acid chloride form, and in part, only one side is converted into the base acid chloride. Less than 5%.

Subsequently, the bisphenol A-salt (BPA-Na: a solution made by dissolving 75 kg of bisphenol A in 425 L in a 5.6 wt% NaOH solution) and methylene chloride (MC) in a first tube type having an inner diameter of 15 mm and a tube length of 30 m. The phosgene was introduced at a flow rate of 12.8 kg / h while being introduced into the reactor 10 while allowing the basic acid chloride produced in the second tubular reactor 20 to be introduced. At this time, the pH in the first tubular reactor 10 was maintained at 12.1.

In the case of the first tubular reactor 10, the reactants after the phosgenation reaction were maintained at 25 to 30 ° C. using a heat exchanger. The molecular weight of the material produced at this time was 1,500.

The reactants after the phosgenation reaction were transferred to the oligomerization reactor 30 using a pump 50. In the reactor 30, 1.5 mol% (based on divalent phenol) of p-tert-butyl phenol as a molecular weight regulator and triethylamine (TEA) as a catalyst were added so that the molecular weight was 3,000.

After the oligomerization is completed, the organic solvent layer and the water layer are separated, the organic phase is added to the polycondensation reactor 40, and the concentration is maintained at 15% by weight with an organic solvent. The water phase ratio (aqueous volume / total volume) was set to 25% while maintaining the ratio.

After completion of the polycondensation reaction, the organic solvent was washed with alkali methylene chloride and distilled water, and then separated. Subsequently, the organic phase is washed with 0.1 N hydrochloric acid (HCl) solution, and then washed repeatedly with distilled water two or three times. When the initial washing is performed by mixing alcohol with about 35% by weight of distilled water, This reacted base acid can be thoroughly washed.

On the other hand, when the washing was completed, the concentration of the organic phase in which the copolycarbonate was dissolved was adjusted to granulate at 48.5 ° C. When the granulation was completed, it was dried for 10 hours at 100 ℃, 5 hours at 110 ℃, 2 hours at 120 ℃.

The reactivity of these basic acids was confirmed by 1 H-NMR. As a result, unreacted basic acids were not detected and were completely reacted with the polymer backbone. The physical properties of the copolycarbonate thus obtained are shown in Table 1 below.

<Evaluation Items>

Unreacted (%): Measured using Liquid Chromatography HP 1100.

Viscosity average molecular weight: After measuring the intrinsic viscosity in methylene chloride solvent (20 ℃), convert to the viscosity average molecular weight.

Melt index: measured according to ASTM D-1238.

HDT: measured by ASTM-648

Anhydride: measured by Bruker Avance 400 NMR.

Examples 2 to 8

In the same manner as in Example 1, as the aliphatic dibasic acid salt, sebacic acid salt (SCA-Na), dodecanoate (DDDA-Na: 5.6 wt% NaOH solution in 47 L, and 3.8 kg of dodecanoic acid were used. Content of the aromatic dibasic acid salt, terephthalic acid salt (TPA-Na) and isophthalic acid salt (IPA-Na: a solution made by dissolving 7.5 kg of isophthalic acid in 42.5 L of 5.6 wt% NaOH solution). Copolycarbonate was synthesized by use. The phosgenation reaction time and pH in the first tubular reactor and the second tubular reactor are shown in Table 1. As a result of the unreacted analysis, it was found that the base acid was mixed in the polymer main chain. The measurement results of the physical properties of the copolycarbonates thus obtained are shown in Table 1 below.

Examples 9-10

Copolycarbonate was synthesized in the same manner as in Example 1, but using a mixture of terephthalic acid salt (TPA-Na) and isophthalic acid salt (IPA-Na) as aromatic dibasic acid salts as shown in Table 1 below. The phosgenation reaction time and pH in the first tubular reactor and the second tubular reactor are shown in Table 1. Physical properties of the obtained copolycarbonates are shown in Table 1 below.

Comparative Example 1

Synthesis was carried out using the same material as in Example 1, but synthesized in a batch manner according to the existing method.

That is, the pH was phosgenated at 6.4, and the pH was subsequently raised to 11.2 to complete the oligomerization and polycondensation reactions. After completion of the polycondensation reaction, the organic solvent was washed with alkali methylene chloride and distilled water, and then separated. Subsequently, the organic phase was washed with hydrochloric acid (HCl) solution, and then washed with distilled water continuously. The reactivity of these basic acids was confirmed by 1H-NMR, the reaction rate of these basic acids showed a reaction rate of about 90 to 93%. After the washing was completed, the concentration of the organic phase was constantly adjusted in the same manner as in Example 1, and granulated at 48 ° C. After the granulation was completed, the resultant was dried at 100 ° C. for 10 hours, 110 ° C. for 5 hours, and 120 ° C. for 2 hours.

The physical property measurement results for the copolycarbonate thus obtained are shown in Table 2 below.

Comparative Example 2

Synthesis using the same material as in Example 1, but using a pH of 11.6, bisphenol A salt, sebacic acid, terephthalic acid, phosgene, and p-tert-butylphenol as a molecular weight regulator as shown in Table 2 below After the phosgenation reaction was carried out by regulation, an oligomerization reaction and a polycondensation reaction were performed subsequently. As a result of the reaction, sebacic acid was hardly incorporated into the polymer main chain. At high pH, the reaction of bisphenol A and phosgene was better than that of basic acid and phosgene.

The physical property measurement results for the copolycarbonate thus obtained are shown in Table 2 below.

Comparative Example 3

Synthesis was performed using the same material as in Example 1, but the pH of step 1 was adjusted using bisphenol A salt, sebacic acid, terephthalic acid, phosgene, and p-tert-butylphenol as a molecular weight modifier at 7.2 as shown in Table 2 below. After the phosgenation reaction was carried out by regulation, an oligomerization reaction and a polycondensation reaction were performed subsequently. As a result of the reaction, sebacic acid was considerably incorporated into the polymer main chain, but as a result of the reaction at a low pH, there was little incorporation into the remaining molecular chains of bisphenol A, and the molecular weight did not increase to obtain a copolycarbonate of a desired physical property.

The physical property measurement results for the copolycarbonate thus obtained are shown in Table 2 below.

The present invention uses two tubular reactors each having a constant inner diameter and a tube length instead of a general cylinder type reactor, and the aliphatic monomers which have an absolute effect on the flowability in the second tubular reactor affect the maintenance of basic acid and heat resistance. Aromatic dibasic acid is converted to this basic acid form with maximum conversion, but minimal use of carbonate precursors, in particular phosgene, as a whole and complete phosgenation reaction in the first tubular reactor, the main tubular reactor . In addition, the aromatic dibasic acid salt compensates for the decrease in heat resistance due to aliphatic dibasic salts, while maintaining the heat resistance, and when melted, the fluidity increases by 1.5 to 2 times compared to the conventional polycarbonate, and the physical properties are almost the same. Polycarbonates can be prepared.

Copolycarbonate resins can be used in a variety of applications such as optical discs, films and optical fibers, such as external storage devices for personal mobile communication devices, laptops and desktop computers, voice recording, video storage and information storage.

Claims (9)

Performing a primary phosgenation reaction in which the aliphatic dibasic acid salt and the aromatic dibasic acid salt and the phosgene are reacted in a second tube reactor to convert the aliphatic dibasic acid salt and the aromatic dibasic acid salt into dibasic acid chloride; Reacting the dibasic acid chloride with bisphenol A-salt and phosgene in a first tubular reactor to continuously carry out a second phosgenation reaction; Transferring the reaction product to an oligomerization reactor to perform an oligomerization reaction under a molecular weight regulator and a catalyst; And separating the organic solvent layer from the reaction product of the oligomerization reaction and performing a polycondensation reaction of the separated organic solvent layer in a polycondensation reactor, wherein the first tubular reactor and The second tubular reactor is connected in series, the pH of the second tubular reactor is a continuous method of producing a copolycarbonate resin lower than the pH of the first tubular reactor. The method of claim 1, wherein the aliphatic dibasic acid salt is used in an amount of 3 to 30 mol% based on the dihydric phenol, which is a main monomer. The method of claim 1, wherein the aromatic dibasic acid salt is used in an amount of 5 to 20 mol% based on the dihydric phenol, which is a main monomer. The method of claim 1, wherein the pH range of the second tubular reactor is 7.0 to 9.0, the pH range of the first tubular reactor is 9.5 to 13. The continuous flow of copolycarbonate resin according to claim 1, wherein the flow rate of phosgene into the second tubular reactor is 0.5 to 2.0 kg / h, and the flow rate of phosgene into the first tubular reactor is 5 to 20 kg / h. Manufacturing method. The method of claim 1, wherein the reaction flow rate in the second tubular reactor is 1 to 3 m / sec, and the reaction flow rate in the first tubular reactor is 3 to 6 m / sec. The method of claim 1, wherein the reaction residence time in the second tubular reactor is 5 to 10 seconds, and the residence time in the first tubular reactor is 8 to 20 seconds. The method according to claim 1, wherein the molecular weight modifier is a monohydric phenol, the amount is 1 to 5 mol% based on the dihydric phenol, the catalyst is a tertiary amine or a quaternary amine, the amount is based on the dihydric phenol A continuous method for producing a copolycarbonate resin of 0.25 to 5 mol%. The method of claim 1, wherein the concentration of the organic solvent layer separated in the polycondensation reaction step is 10 to 20% by weight, and 33% by weight of sodium hydroxide solution is further added to the organic solvent layer to maintain a pH of 10 to 14 Continuous production method of copolycarbonate resin.